ELEMENTS OF

X-RAY DIFFRACTION
ADDISON -WESLEYMETALLURGY
ADDISON-WESLEY MET SERIES
ALL URG Y SERIES

COHEN, Consulting
MORRIS COHEN, Consulting Editor
Editor

Cullity-ELEMENTS
Cidlity ELEMENTS OF X-RAY DIFFRACTION

GUy-ELEMENTS
Guy ELEMENTS OF PHYSICAL METALLURGY

Norton-ELEMENTS
Norton ELEMENTS OF CERAMICS

Schuhmann-METALLURGICAL
Schuhmann METALLURGICAL ENGINEERING
VOL. I:
I: ENGINEERING PRINCIPLES

Wagner-
Wagner THERMODYNAMICS OF ALLOYS
 ELEMENTS OF

X-RAY DIFFRACTION

by
by
B. D. CULLITY
Associate Professor
Associate Professor of
of Metallurgy
Metallurgy
University
University of
of Notre
Notre Dame

ADDISON-WESLEY PUBLISHING
PUBLISHIKG COMPANY, INC.
READING, MASSACHUSETTS
READING,
 Copyright
Copyright 19/i6
1956
ADD1SON-WESLEY PUBLISHING COMPAN",
ADDISON-WESLEY COMPANY, Inc.
Prltltrd
Printed ni the
trI the l"nited
United StateR
States of
of Amprlea
America

RESERVED.
ALL RIGHTS RESERV),;U. THIS BOOK, OR PARTS THERE-
OF, MAY NOT BE REI'ROIH
OF, !\fAY CED IS'
REI'RODl ("ED FORM WITHOUT
IN ANY }'ORM
WRITTEN I'ERlIUSSION
WRIT'r)';N PUBLISHERS
PERMISSION OF THE Pl"BLIRHERS

LIbrary
Library of
of Congresl<
Congress Catalog
Catalog No 56-10187
56-10137
 PREFACE
PREFACE

X-ray
X-ray diffraction
diffraction is is aa tool
tool forfor the
the investigation
investigation of of the
the fine structure of
fine structure of
matter.
matter. ThisThis technique
technique had its
its beginnings
beginnings in
in von Laue's
Laue's discovery
discovery in
in 1912
1912
that
that crystals
crystals diffract
diffract x-rays,
x-rays, the the manner of of the
the diffraction
diffraction revealing
revealing the the
structure
structure of of the
the crystal.
crystal. At first,
first, x-ray diffraction was used
x-ray diffraction used onlyonly forfor the
the
determination of
determination of crystal
crystal structure.
structure. Later
Later on, on, however,
however, other other uses
uses werewere
developed,
developed, and today today the the method is is applied,
applied, not not only
only to to structure
structure deter-deter-
mination,
mination, but to to such
such diverse
diverse problems
problems as as chemical
chemical analysis
analysis and stress stress
measurement,
measurement, to
to the
the study
study of
of phase equilibria
phase equilibria and the
the measurement of
of
particle size,
particle size, to
to the
the determination
determination of
of the
the orientation
orientation of
of one
one crystal
crystal or
or the
the
ensemble
ensemble of of orientations
orientations in in aa polycrystalline
polycrystalline aggregate.
aggregate.
purpose of
The purpose of this
this book is is to
to acquaint
acquaint the the reader
reader who has has no previous
previous
knowledge of
knowledge of the
the subject
subject withwith the the theory
theory of of x-ray
x-ray diffraction,
diffraction, the the experi-
experi-
mental
mental methods involved, involved, and the the main applications.
applications. Because Because the the author
author
is
is a
a metallurgist,
metallurgist, the majority of
the majority of these
these applications
applications are are described
described in in terms
terms
of
of metals
metals and alloys.
alloys. However,
However, little
little or
or no modification
modification of
of experimental
experimental
method is is required
required for the ex~f
for the examinatiorrof nonmetallic
nonmetallic materials,
materials, inasmuch
as
as the
the physical
physical principles
principles involved
involved do not not depend
depend on on the
the material
material investi-
investi-
gated.
gated. ThisThis book should should therefore
therefore be be useful
useful to to metallurgists,
metallurgists, chemists,
chemists,
physicists,
physicists, ceramists,
ceramists, mineralogists,
mineralogists, ete., etc., namely,
namely, to all who use
to all use x-ray
x-ray diffrac-
diffrac-
tion
tion purely
purely as as aa laboratory
laboratory tool tool for
for the sort of
the sort of problems
problems already
already mentioned.
mentioned.
Members of of this
this group,
group, unlike
unlike x-ray
x-ray crystallographers,
crystallographers, are are not
not normally
normally
concerned
concerned with with the determination of
the determination of complex
complex crystalcrystal structures.
structures. For this
this
reason
reason the
the rotating-crystal
rotating-crystal method and space-group
space-group theory, theory, the
the two chief
chief
tools
tools in
in the
the solution
solution of of such
such structures,
structures, are are described
described only briefly.
only briefly.
This
This is
is a
a book of
of principles
principles and methods intended
intended for
for the
the student,
student, and
not
not aa reference
reference book for for the
the advanced research research worker.
worker. Thus no metal- metal-
lurgical data
lurgical data areare given
given beyond
beyond those those necessary
necessary to to illustrate
illustrate thethe diffraction
diffraction
methods involved.
involved. For For example,
example, the the theory
theory and practicepractice of of determining
determining
preferred
preferred orientation
orientation are
are treated
treated in
in detail,
detail, but
but the
the reasons
reasons for
for preferred
preferred
orientation,
orientation, the
the conditions
conditions affecting
affecting its
its development,
development, and actual
actual orien-
orien-
tations
tations found
found in in specific
specific metals
metals and alloys alloys areare not
not described,
described, because
because these these
topics
topics are
are adequately
adequately coveredcovered in in existing books. In
existing books. In short,
short, x-ray
x-ray difirac-
diffrac-
tion
tion is
is stressed
stressed rather
rather thanthan metallurgy.
metallurgy.
The book is is divided
divided into into three
three main parts: parts: fundamentals,
fundamentals, experimental
experimental
methods,
methods, and applications.
applications. The subject subject of of crystal
crystal structure
structure is is approached
approached
through,
through, and based based on, on, the
the concept
concept of of the point lattice
the point lattice (Bravais
(Bravais lattice),
lattice),
because the
because the point
point lattice
lattice of
of a
a substance
substance is
is so
so closely
closely related
related to
to its
its diffrao-
diffrac-
v
vi
VI PREFACE

tion pattern.
tion pattern. entire book
The entire book isis written
written inin terms
tenns ofof the
the Bragg
Bragg law
law and
can be
can be read
read without
without any
any knowledge
knowledge of of the
the reciprocal
reciprocal lattice.
lattice. (However,
(However, aa
brief treatment
brief treatment ofof reciprocal-lattice
reciprocal-lattice theory
theory is
is given
given in
in an
an appendix
appendix for
for those
those
wish to
who wish to pursue
pursue the
the subject
subject further.)
further.) The methods
methods of of calculating
calculating the
the
intensities of
intensities of diffracted
diffracted beams are
are introduced
introduced early
early in
in the
the book
book and used
used
throughout.
throughout. Since aa rigorous
Since rigorous derivation
derivation of
of many
many of
of the
the equations
equations for
for dif-
dif-
fracted intensity
fracted intensity is too
is too lengthy
lengthy and complex
complex aa matter
matter for
for aa book
book of
of this
this
kind, II have
kind, have preferred
preferred aa semiquantitative
semiquantitative approach
approach which,
which, although
although itit does
does
not furnish
not furnish aa rigorous
rigorous proof of the
proof of the final result,
final result, at least
at least makes it physically
it physically
reasonable.
reasonable. This preference
This preference is based
is based on
on my conviction
conviction that
that it
it is
is better
better
for aa student
for student to
to grasp
grasp the
the physical
physical reality
reality behind
behind aa mathematical
mathematical equation
equation
than to
than to be
be able to glibly
able to glibly reproduce
reproduce an
an involved
involved mathematical
mathematical derivation
derivation
of whose
of whose physical
physical meaning
meaning he is only
he is only dimly
dimly aware.
aware.
Chapters on
Chapters on chemical
chemical analysis by diffraction
analysis by diffraction and fluorescence
fluorescence have
have been
been
included because
included because of the present
of the present industrial
industrial importance of these
importance of these analytical
analytical
methods.
methods. In
In Chapter
Chapter 77 the diffractometer, the
the diffractometer, the newest instrument for
newest instrument dif-
for dif-
fraction experiments, is
fraction experiments, is described
described in in some detail;
detail here
;
the material
here the material on the
various kinds
various kinds of of counters
counters and their their associated
associated circuits
circuits should
should be be useful,
useful,
not only
not only to those engaged
to those engaged in in diffraction
diffraction work,
work, but
but also
also to
to those
those working
working
with radioactive tracers
with radioactive tracers oror similar
similar substances
substances who wish wish to
to know how their their
measuring
measuring instruments
instruments operate.
operate.
Each chapter
chapter includes
includes a set of
a set of problems.
problems. Many Many of of these
these have been
chosen
chosen to to amplify
amplify and extend
extend particular topics
particular topics discussed
discussed in
in the
the text,
text, and
as
as such they fonn
such they form an an integral
integral partpart of
of the
the book.
book.
Chapter 18
Chapter 18 contains
contains an an annotated
annotated list list of
of books
books suitable
suitable for
for further
further study.
study.
The reader
reader should
should become
become familiar
familiar withwith atat least
least a a few
few of
of these,
these, as
as he pro-
pro-
gresses through
gresses through thisthis book,
book, in in order
order that
that hehe may
may know where to to turn
turn for
for
additional
additional infonnation.
information.
Like
Like any author of
any author of a
a technical
technical book,
book, II am greatly
greatly indebted
indebted to to previous
previous
writers
writers onon this
this and allied
allied subjects.
subjects. I
I must also
also acknowledge
acknowledge my gratitude
gratitude
to two of
to two of my
my fonner
former teachers
teachers at at the
the Massachusetts
Massachusetts Institute
Institute of of Technology,
Technology,
Professor
Professor B. B. E.
E. Warren
Warren and and Professor
Professor JohnJohn T. T. Norton:
Norton: they
they will
will find
find many
many
an echo
echo of their own lectures
of their lectures in in these
these pages.
pages. Professor
Professor Warren has kindly kindly
allowed me to
allowed to use
use many
many problems
problems of of his
his devising,
devising, and the the advice and
encouragement
encouragement of
of Professor
Professor Norton
Norton has
has been
been invaluable.
invaluable. My colleague
colleague at at
Notre Dame, Professor G. C.
Notre Dame, Professor G. C. Kuczynski, Kuczynski, has
has read
read the
the entire
entire book as
as it
it was
written,
written, andand his
his constructive
constructive criticisms
criticisms have
have been
been most helpful.
helpful. II would
also
also like
like to
to thank
thank the
the following,
following, eacheach of of whom has has read
read one
one or or more chap-
chap-
ters
ters and offered
offered valuable
valuable suggestions:
suggestions: Paul
Paul A.
A. Beck,
Beck, Herbert
Herbert Friedman,
Friedman,
S.
S. S.
S. Hsu, Lawrence Lee,
Hsu, Lawrence Lee, Walter
Walter C. C. Miller,
Miller, William Parrish,
Parrish, Howard
Pickett,
Pickett, and
and Bernard
Bernard Waldman. I
I am also
also indebted
indebted to
to C.
C. G.G. Dunn for for
the loan of illustrative material and to many graduate
the loan of illustrative material and to many graduate students, August students, August
 PREFACE vii
Vll

Freda
Freda inin particular,
particular, who have helped
helped with the preparation of
the preparation of diffraction
diffraction
patterns.
patterns. Finally
Finally but not perfunctorily,
perfunctorily, II wish to
to thank Miss Rose Kunkle
for
for her
her patience
patience and diligence
diligence in
in preparing the typed
preparing the typed manuscript.
manuscript.

B. D. CULLITY
B.
Notre Dame,
Dame, Indiana
March,
March, 1956
 CONTENTS
ceNTENTS
FUNDAMENTALS

CHAPTER 1
1 .F
PR.PERTIEH OF X-RAYS
PROPERTIES 1
1

1-]
1-1 Int1oduction
Introduction 1
1

1-
1-22 Eleetromagnctie radiation
Electromagnetic radiation 1
1

1-3
1-3 continuoUH spectrum
The continuous spectrum . 4
4
1-4
1-4 characteriHtir spectrum
The characteristic Hpectrum 6
1-5
1-5 Absorption
Absorption . 10
1--6
1-6 Filters
Filters 16
16
1-7
1-7 Production of
Production of x-rays
x-rays 17
1 -s
J -8 Detection of
Detection of x-rays
x-rays 23
23
11 99 Hafety precautions
Safety precautions . 25
25

C'HAPTER 2
CHAPTER 2 TH]O~
THE GEOMETRY
GEOMETUY OF CRYSTALS 29
J2-J
^2-1 Introduc,tion
Introduction . 29
29
./2-2
J2-2 Lattiees
Lattices . 29
2-3
2-3 Crystal Hystems
Crystal systems 30
30
h-4
^2-4 Symmetry
Symmetry 34
2-5
2-5 Primitive
Primitive and nonprimitive
nonprimitive cells
cells 36
36
2-6
2-6 Lattiee
Lattice direetions
directions and planes *
planes ../ . 37
37
J
2-7
2-7 Crystal
Crystal strueture
structure J 42
42
2-S
2-8 Atom sizes
sizes and roordination
coordination 52
52
2-9
2-9 Crystal shape
Crystal shape 54
2-10
2-10 Twinned crystals
crystals . 55
2-11
2-11 The stereographic
stereographic projeetion
projection . . 60

CHAPTER 3
CHAPTEU 3 DIFJo'RACTlON DIRECTIONS OF DIFFRACTED BEAMS
DIFFRACTION I: THE DmECTIONS 7H
78

3-1
3-1 Intl'Oduction
Introduction . .78
7H
3-2
3-2 Diffraction
Diffraction f. 79
.J3-3
'

^3-3 The Bragg

Bragg law'
law -
*
. M
84
3-4
3-4 X-ray speetroseopy
X-ray spectroscopy H5
85
3-5
3-5 Diffmetion
Diffraction dirertions
directions -
HH
88
3-6
3-6 Diffraction
Diffraction methods . 89
3-7
3-7 Diffraction under nonidcal
Diffraction nonideal conditions
conditions . 96

CHAPTER 4
4 DIFFRACTION II: DIFFRACTED BEAMS
II: THE INTENSITIES OF DIFFRA<-'TED . 104
4-1
4-1 Introduetion
Introduction 104
4-2
4-2 Seattering
Scattering by
by an
an electron
electrons ,;' . . 105
105
4-3
4-3 Scattering by
Scattering by an atom.
atom _/
/ >, . 108
108
4-4
4-4 Scattering
Scattering by
by aa unit cell */
unit cell . 111
Ill
ix
 CONTENTS
CONTENTS

l-5 Some useful

useful relations
relations . 118
118
4-5
l-6
4-6
Some
Structure-factor calculations
Structure-factor calculations
.

^
.,/',
J
118
118
'1:-7
4-7 Application to
Application to powder
powder method
method ' 123
123
l-8
4-8 Multiplicity factor
Multiplicity factor 124
124
4-9
4-9 Lorentz factor
Lorentz factor 124
124
'1:-10
1-10 Absorption factor
Absorption factor 129
129
'1:-11
4-11 Temperature factor
Temperature factor 130
130
4-12
4-12 Intensities of
Intensities of powder
powder pattern
pattern lines
lines 132
132
4-13
4-13 Examples of
Examples of intensity
intensity calculations
calculations 132
132
4-14
4-14 Measurement of
Measurement of x-ray
x-ray intensity
intensity 136
136

EXPERIMENTAL METHODS
EXPERIMENTAL METHODS

,PTER 55
LPTER LAUE PHOTOGRAPHS 138
138

5-1
5-1 Introduction
Introduction 138
138
5-2
5-2 Cameras
Cameras . 138
138
5-3
5-3 Specimen holders
Specimen holdeI'fl 143
143
5-4
5-4 Collimators
Collimators .
.144
144
5-5
5-5 TheshapesofLauespo~
The shapes of Laue spots . 146
146

~PTER 6
kPTER 6 POWDER PHOTOGRAPHS . .149
149
6-1
6-1 Introduction
Introduction . 149
149
6-2
6-2
6-3
6-3
6-4
6-4
Debye-Scherrer method
Debye-Scherrer
Specimen
method
Specimen preparation
Film
preparation
Film loading
loading
....
. .
.
149
149
153
153
154
154
6-5
6-5 Cameras
Cameras for
for high
high and
and low
low temperatures
temperatures 156
156
...
.

6-6
6-6 Focusing
Focusing cameras
cameras . 156
156
6-7
6-7 Seemann-Bohlin
Seemann-Bohlin camera
camera . 157
157
6-8
6-8 Back-reflection
Back-reflection focusing
focusing cameras
cameras . . .160
160
6-9
6-9 Pinhole
Pinhole photographs
photographs . 163
163
6-10
6-10 Choice
Choice of
of radiation
radiation . .165
165
6-11
6-11 Background
Background radiation
radiation . 166
166
6-12
6-12 Crystal
Crystal monochromators
monochromators . 168
168
6-13
6-13 Measurement
Measurement of of line
line position
position 173
173
6-14
6-14 Measurement
Measurement of of line
line intensity
intensity . 173
173

VPTER 7
~PTER 7 DIFFRACTOMETER
DlFFRACTOMETER MEASUREMENTS
MEASUREMENTS 177
177
7-1
7-1
7-2
7-2
7-3
7-3
Introduction
Introduction
General
General features
X-ray
features
optics
.

.... .
.
177
177
177
177
184
184
X-ray optics
...
. . . -

7-4
7-4 Intensity
Intensity calculations
calculations . 188
188
7-5
7-5 Proportional
Proportional counters
counters 190
190
...
. . .
.

7-6
7-6 Gf'iger
Geiger counters
counters . . .193
193
7-7 Scintillation
Scintillation counters 201
201
7-7 counters
....
-

...
.

7-8
7-8 Scalers
Sealers .
.202
202
7-9
7-9 Ratemeters
Ratemeters . -
206
206
7-10
7-10 Use
Use of
of monochromators
monochromators . 211
211
 CONTENTS
CONTENTS xi
XI

APPLICATIONS
APPLICATIONS

CHAPTER 88
CHAPTER ORIENTATION OF
ORIENTATION SINGLE CRYSTALS
OF SINGLE CRYSTALS .
215
215
.....215
. .

8-1
8-1 Introduction
Introduction . .
215 215
8-2
8-2 Back-reflectionLaue method
Laue method 215
8-3
8-3
Back-reflection
Transmission Laue
Transmission Laue method
method '
.

....... 229
.

. 229
8-4
8-4 Diffractometer method
Diffractometer . 237
237
8-5
8-5 Setting aa crystal
Setting crystal in
in aa required
required orientation
orientation . 240
240
8-6
8-6 Effect of
Effect of plastic
plastic deformation
deformation .
242
242
8-7
8-7 Relative orientation
Relative orientation of
of twinned
twinned crystals
crystals 250
250
8-8
8-8 Relative orientation
Relative orientation of
of precipitate
precipitate and matrix
matrix . . .
256
256

CHAPTER 99 THE STRUCTURE OF POLYCRYSTALLINE AGGREGATES .

259
259
9-1
9-1 Introduction
Introduction .
259
259

CRYSTAL SIZE
9-2
9-2 Grain
Grain size
size 259
259
9-3
9-3 Particle size
Particle size . 261
261

CRYSTAL PERFECTION
9-4
9-4 Crystal perfection
Crystal perfection . .... 263
263
9-5
9-5 Depth of
Depth of x-ray
x-ray penetration
penetration . .
269
269

CRYSTAL ORIENTATION
9-6
9-6
9-7
9-7
General
General
Texture of
Texture of wire
.

and rod
wire and rod (photographic
(photographic method)
method)
.272
. . .
272
276
9-8
9-8 Texture
Texture of
of sheet
sheet (photographic
(photographic method)
method) 280
9-9
9-9 Texture of
Texture of sheet
sheet (diffractometer
(diffractometer method)
method) . . 285
9-10
9-10 Summary
Summary . . 295

CHAPTER 10
10 THE DETERMINATION OF CRYSTAL STRUCTURE . . . 297
HH
10-1 Introduction
Introduction . . 297
297
10-2
10-2 Preliminary
Preliminary treatment
treatment of of data
data . . . 299
10-3
10-3 Indexing patterns
Indexing patterns of
of cubic
cubic crystals
crystals 301
10-4
10-4 Indexing patterns
Indexing patterns of
of noncubic
noncubic crystals
crystals (graphical
(graphical methods)
methods) 304
10-5
10-5 Indexing
Indexing patterns
patterns ofof noncubic
noncubic crystals
crystals (analytical
(analytical methods)
methods) . .311
311
10-6
10-6 The effect
effect of
of cell
cell distortion
distortion on the
the powder
powder pattern
pattern .
. . . 314
10-7
10-7 Determination
Determination of of the
the number of of atoms inin a
a unit
unit cell
cell . .316
316
10-8
10-8 Determination
Determination of of atom positions
positions . 317
10-9
10-9 Example
Example ofof structure ....
structure determination
.

determination . . 320

CHAPTER 1111 PRECISE PARAMETER MEASUREMENTS

PARAMETER MEASUREMENTS. ... 324
....
.

11-1
11-1 Introduction
Introduction 324
11-2
11-2
11-3
Debye-Scherrer cameras
Debye-Scherrer cameras ....
Back-reflection focusing camems
.... 326
333
1 1-3 Back-reflection focusing cameras
11-4
11-4 Pinhole
Pinhole cameras
cameras 333
333
11-5
11-5 Diffractometers
Diffractometers 334
11-6
11-6 Method
Method ofof least
least squares
squares .335
335
xii
Xll CONTENTS
11-7
11-7 Cohen's method
Cohen's .... 338
338
11-8
11-8 Calibration
Calibration method . . 342
342

12
CHAPTER 12 PHASE-DIAGRAM DETERMINATION . . . 345
345
12-1
12-1 Introduction
Introduction . 345
345
12-2
12-2 General principles
General principles . . 346
346
12-3
12-3 Solid solutions
Solid solutions . 351
351
12-4
12-4 Determination of
Determination of solvus
solvus curves
curves (disappearing-phase
(disappearing-phase method)
method) 354
354
12-5
12-5 Determination of
Determination of solvus
solvus curves
curves (parametric
(parametric method)
method) 356
356
12-6
12-6 Ternary systems
Ternary systems 359
359

CHAPTER 13
13 ORDER-DISORDER TRANSFORMATIONS 363
363
13-1
13-1 Introduction
Introduction . 363
13-2
13-2 Long-range order
Long-range in AuCus
order in AuCu3 363
363
13-:-3
13-3 Other examples
Other examples of
of long-range
long-range order
order 369
369
13-4
13-4 Detection of
Detection of superlattice lines
superlattice lines 372
13-5
13-5 Short-range order and clustering
Short-range order clustering 375
375

CHAPTER 14
14 CHEMICAL ANALYSIS BY DIFFRACTION 378
14-1
14-1 Introduction
Introduction 378
378

QUALITATIVE ANALYSn;
QUALITATIVE ANALYSIS
14-2
14-2 Basic principles
Basic principles 379
14-3
14-3 Hanawalt
Hanawait method 379
14-4
14-4 Examples
Examples ofof qualitative
qualitative analysis
analysis 383
14-5
14-5 Practical
Practical difficulties
difficulties 386
14-6
14-6 Identification
Identification of
of surface
surface deposits
deposits 387
QUANTITATIVE ANALYSIS (SINGLE
(SINGLE PHASE)
PHASE)
14-7
14-7 Chemical
Chemical analysis
analysis by
by parameter
parameter measurement 388
388

QUANTITATIVE ANALYSIS (MULTIPHASE)

(MULTIPHASE)
14-8
14-8 Basic
Basic principles
principles . . . 388
14-9
14-9 Direct
Direct comparison
comparison method . . . 391
]14-10
4-10 Internal
Internal standard
standard method . . . 396
14-11
14-11 Practical
Practical difficulties
difficulties . . . 398

CHAPTER 15
15 CHEMICAL ANALYSIS BY FLUORESCENCE 402
15-1
15-1 Introduction
Introduction . ... 402
15-2
15-2 General
General principles
principles . 404
...
. .

15-3
15-3 Spectrometers.
Spectrometers 407

....
.

15-4 Intensity
Intensity and resolution
resolution . . . 410
15-5
15-5 Counters.
Counters 414
.... ...
.

15-6
15-6 Qualitative
Qualitative analysis
analysis 414
15-7'
15-7 Quantitati~e
Quantitative analysis
analysis ... . . 415
15-8
15-8 Automatic spectrometers
spectrometers . . 417
15-9 Nondispersive
Nondispersive analysis
analysis ..... . 419
1IHO
15-10 Measurement of of coating
coating thickness
thickness 421
 CONTENTS xiii
xiil

CHAPTER 16
16 CHEMICAL ANALYSIS BY ABSORPTION . . . 423
HH
16-1 Introduction
Introduction . . . ... 423
16-2
16-2 Absorption-edge
Absorption-edge method . . ... 424
16-3
16-3 Direct-absorption
Direct-absorption method (monochromatic
(monochromatic beam)
beam) . 427
427
16-4
16-4 Direct-absorption
Direct-absorption method (polychromatic
(polychromatic beam)
beam) 429
16-5
16-5 Applications
Applications . . 429
CHAPTER 17
17 STRESS MEASUREMENT . ... 431
431
17-1
17-1 Introduction
Introduction . 431
431
17-2
17-2 Applied
Applied stress
stress and residual
residual stress
stress . . 431
431
17-3
17-3 Uniaxial
Uniaxial stress
stress . . 434
434
17-4
17-4 Biaxial
Biaxial stress
stress . 436
436
17-5
17-5 Experimental
Experimental technique
technique (pinhole
(pinhole camera)
camera) 441
441
17-6
17-6 Experimental
Experimental technique
technique (diffractometer)
(diffractometer) 444
444
17-7
17-7 Superimposed
Superimposed macrostress
macrostress and microstress
microstress 447
447
17-
17-8X Calibration
Calibration 449
449
17-9
17-9 Applications
Applications 451

CHAPTER 18
18 SUGGESTIONS FOR FUltTHER
FURTHER STuDY
STUDY . 454
18-1
18-1 Introduction
Introduction 454
454
18-2 Textbooks . 454
18-3
18-3 Reference books
Reference books . 457
18-4
18-4 Periodir.als
Periodicals 458

ApPENDIXES
APPENDIXES

APPENDIX I1 LATTICE GEOMETRY . 459

AI-l
Al-1 Plane
Plane spacings
spacings 459
AI-2
Al-2 Cell
Cell volumes . . 460
460
AI-3
Al-3 Interplanar
Interplanar angles
angles . . . 460
APPENDIX 22 THE RHOMBOHEDRAL-HEXAGONAL TRANSFORMATION 462
APPENDIX
APPENDIX 3
3 WAVELENGTHS (IN
(IN ANGSTROMS)
ANGSTROMS) OF SOME CHARACTERISTIC
EMISSION
EMISSION LINES AND ABSORPTION EDGES . . . 464
APPENDIX 44 MASS ABSORPTION COEFFICIENTS AND DENSITIES . 466
APPENDIX 55 VALUES OF SIN!
siN 2 (J
8 . 469
469

APPENDIX 66 QUADRATIC
QUADRATIC FORMS OF MILLER INDICES
INDICES . . . 471
471

APPENDIX 77 VALUES OF (SIN

(SIN (J)/,A
0)/X . . . 472
APPENDIX 88 ATOMIC SCATTERING
SCATTERING FACTORS . 474
APPENDIX 99 MULTIPLICITY
MULTIPLICITY FACTORS FOR POWDER PHOTOGRAPHS .
*
. 477
APPBNDIX 10 LoRENTZ-POLARIZATION
APPENDIX 10 LORENTZ-POLARIZATION FACTOR 478
478

APPENDIX 11
11 PHYSICAL
PHYSICAL CONSTANTS
CONSTANTS . . 480
480
xiv
XIV CONTENTS

APPENDIX 12
12 WEIGHTS, 1953
INTERNATIONAL ATOMIC WEIGHTS, 1953 481
481

APPENDIX 13
13 CRYSTAL STRUCTURE DATA . 482
482

APPENDIX 14
14 ELECTRON AND NEUTRON DIFFRACTION 486
486
...
Al4-1
A14-1 Introduction
AI4-2
AI4-3
Introduction .
A14r-2 Electron
.

Electron diffraction
diffraction
Neutron diffraction
A14-3 Neutron diffraction
...
....
.

.
. 486
486
486
487
487

APPENDIX 15
15 THE RECIPROCAL LATTICE . 490
....
.

Al5-1
A15-1 Introduction
AI5-2
AI5-3
Introduction
A15-2 Vector
Vector multiplication
multiplication
A15-3 The reciprocal
reciprocal lattice
lattice .
.

.
......
.490
490
490
491
491
A15-4 Diffraction
AI5-4 Diffraction and the
the reciprocal
reciprocal lattice
lattice . 496
496
AI5-5
A15-5 The rotating-crystal
rotating-crystal method . 499
499
AI5-6
A15-6 The powder
powder method . 500
AI5-7
A15-7 The Laue method . 502

...
. .

ANSWERS TO SELECTED PROBLEMS . 506

INDEX
INDEX. 509
 CHAPTER
CHAPTER 1 1

PROPERTIES OF
PROPERTIES OF X-RAYS
X-RAYS

1-1 Introduction.
1-1 Introduction. X-rays were
X-rays were discovered
discovered in
in 1895
1895 by
by the
the German
German
physicist Roentgen
physicist Roentgen and
and were
were so
so named
named because
because their
their nature
nature was unknown
was unknown
at the
at the time.
time. Unlike
Unlike ordinary
ordinary light,
light, these
these rays
rays were
were invisible,
invisible, but
but they
they
traveled in
traveled in straight
straight lines
lines and
and affected
affected photographic
photographic film
film in
in the
the same way
as light.
as light. On the other hand, they
the other hand, they were
were much more penetrating than light
penetrating than light
and could easily pass through
and could easily pass through the
the human body, wood, quite
body, wood, quite thick
thick pieces of
pieces of
metal, and
metal, and other
other "opaque"
"opaque" objects.
objects.
It is not always necessary
It is not always necessary toto understand a thing
thing in
in order
order to
to use
use it,
it, and
x-rays
x-rays were
were almost
almost immediately put
immediately put to
to use
use by physicians and,
by physicians and, somewhat
later, by
later, by engineers,
engineers, who wished wished to to study
study the
the internal
internal structure
structure of of opaque
opaque
objects. By
objects. By placing placing a
a source
source of
of x-rays
x-rays on
on one side
side of
of the
the object.
object and photo-
photo-
graphic
graphic film
film on
on the
the other,
other, a
a shadow picture,
picture, or
or radiograph,
radiograph, could
could be
be made,
made,
the less
the less dense
dense portions
portions of of the
the object
object allowing
allowing aa greater
greater proportion
proportion of of the
the
x-radiation to
x-radiation to pass
pass through
through thanthan thethe more dense.
dense. In In this
this way the the point
point
of fracture
of fracture in in aa broken
broken bonebone or the position
or the position of of aa crack in in a metal
metal casting
casting
could
could be located.
be located.
Radiography
Radiography was thus thus initiated
initiated without any precise understanding
any precise understanding of
the
the radiation
radiation used, used, because
because it it was not until until 1912 that the exact nature of of
x-rays
x-rays waswas established.
established. In In that
that year
year thethe phenomenon
phenomenon of of x-ray
x-ray diffraction
diffraction
by
by crystals
crystals was was discovered,
discovered, and this this discovery
discovery simultaneously
simultaneously proved proved the the
wave nature
nature of of x-rays
x-rays andand provided
provided a new method for for investigating
investigating the the
fine
fine structure
structure of of matter.
matter. Although
Although radiography
radiography is is a very
very important
important tool tool
in
in itself
itself and has has a a wide
wide field
field of
of applicability,
applicability, it it is
is ordinarily
ordinarily limited
limited inin the
the
1
internal
internal detail
detail it it ean
can resolve,
resolve, or or disclose,
disclose, to to sizes
sizes of of the order of 10- em.
the order of 10"" 1 cm.
Diffraction,
Diffraction, on on thethe other
other hand,
hand, can indirectly
indirectly reveal
reveal details
details of of internal
internal
8
structure of the order
structure of the order of 10~~ of 10- 8 cm in
in size,
size, and it
it is
is with this
this phenomenon,
phenomenon,
and
and itsits applications
applications to to metallurgical
metallurgical problems,
problems, thatthat this
this book is is concerned.
concerned.
The properties of
properties of x-rays x-rays and the
the internal
internal structure
structure of
of crystals
crystals are here
described in the
described in the first first two chapters
chapters as
as necessary
necessary preliminaries to
preliminaries to the dis-
dis-

cussion of the diffraction of x-rays

cussion of the diffraction of x-rays by crystals by crystals which follows.
follows.

1-2
1-2 Electromagnetic radiation. We
Electromagnetic radiation. We know today
today that x-rays
x-rays are
are elec-
elec-

tromagnetic
tromagnetic radiation
radiation of
of exactly
exactly the
the same
same nature
nature as
as light
light but
but of
of very
very much
much
shorter
shorter wavelength.
wavelength. The The unit
unit ofof measurement
measurement in in the
the x-ray
x-ray region
region is
is the
the
angstrom (A), equal to
to 10-
10~ 88 em, and
and x-rays used
used in
in diffraction
diffraction have
have wave-
wave-
angstrom (A), equal cm, x-rays
lengths
lengths lying
lying approximately
approximately in in the
the range 0.5-2.5A, whereas
range O.5-2.5A, whereas the
the wavelength
wavelength
of
of visible
visible light
light is
is of
of the
the order
order of
of 6OOOA.
6000A. X-rays
X-rays therefore
therefore occupy
occupy thethe
11
 2 PROPERTIES OF
PROPERTIES OF X-RAYS
X-RAYS [CHAP.
[CHAP. 1
1

Frequenl'Y Wavelength
(l'yeles / see) in milhmicrons

10 23
1022 10-5
10 21 Gamma-raYR
10-4 1 X unit
1020 10- 3
1019 10- 2
10 18 10- 1 I angstrom
x-ray~

10 11 1 1 llulhmlrron
1016
10 15
ultmv;o,'1 10
10 2
Visihle J 10 3 1 mic'ron
10 14
10 13 Infrared 0'
10 6
10 12
lOll Hhort radIO waveR 10
10 7 1 {'Plltnllrt(,J"
1010
10 9
10 8
10 9 1 lllPter
1010
UlJBroad(,RSbnm 1011
11 megacycle
megarycle 10_ U!handlU 10 12 1 kIlolllPter
10 13
Long radIO wave" IOU
11 kilocycle
kiloC'ycle 10
IQl3
1015
102
1016
10

FIG.
FIG. 1-1.
i-i. The ele('tl'Omagnetie
electromagnetic speetrum.
spectrum. The boundaries het\\"ecn
between regions
regions are
are
arbitrary, since no
arbitrary, since no sharp
sharp upper
upper or
or lower
lower limitf'
limits ('an
can be aSHigned.
assigned. (F.
(F. W. Sears,
Sears, OIl/iI'S,
Optics,
3rd
3rd ed.,
ed., Addison-Wesley
Addison- Wesley Publishing
Publishing Company,
Company, Inl'.,
Inc., Cambridge,
Cambridge, Mass.,
Mass., H14!l)
1949 )

region
region between
between gamma
gamma and ultraviolet
ultraviolet rays
rays in
in the
the complete
complete eleetromag-
electromag-
netic
netic spectrum
spectrum (Fig. 1-1). Other
(Fig. 1-1). Other units
units sometimes used to measure x-ray
x-ray
wavelength
wavelength are
are the X unit
the X unit (XC)
(XU) and thethe kilo
kilo X unit (kX =
unit (kX XU).**
= 1000 XU).
The
The X X unit
unit is
is only
only slightly
slightly larger
larger than the
the angstrom,
angstrom, the exact relation
being
bemg
kX = 1.00202A.
1lkX= 1.00202A.

It
It is
is worth
worth while
while to
to review
review briefly
briefly some properties
properties of of electromagnetic
electromagnetic
waves.
waves. Suppose monochromatic beam of
Suppose aa monochromatic of x-rays,
x-rays, i.e.,
i.e., x-rays
x-rays of of a
a single
single

wavelength, is
wavelength, is traveling
traveling -in the x
in the x direction
direction (Fig. 1-2). Then
(Fig. 1-2). Then it it has
has asso-
asso-
ciated with it
ciated with it an
an electric
electric field
field EE in,
in, say,
say, the
the yy direction
direction and,
and, at at right
right angles
angles
to
to this,
this, a
a magnetic
magnetic field
field H the zz direction.
H inin the direction. If If the
the electric
electric field
field isis ('on-
con-
fined to
fined to the
the xy-plane
xy-plane as
as the
the wave
wave travels
travels along,
along, the
the wave
wave is
is said
said to
to be
be plane-
plane-
polarized.
polarized. (In(In aa completely
completely unpolarized
unpolarized wave,
wave, the electric field
the electric field vector
vector E E
and hence the
and hence the magnetic
magnetic field
field vector
vector H
H can
can assume
assume all
all directions
directions in
in the
the

* For
For the
the origin
origin of
of these
these units,
units, see Sec. 3-4.
see Sec. 3-4.
1-2]
1-2] ELECTROMAGNETIC
ELECTROMAGNETIC RADIATION
RADIATION 3
z
yz-plane.) The
t/2-plane.) The magnetic
magnetic field
field isis of
of
no concern
no concern to
to us
us here
here and
and wewe need
need
not consider
not consider it further.
it further. H y
In the
In the plane-polarized
plane-polarized wave
wave con-
con-
sidered,
sidered, E
E is
is not
not constant
constant with
with time
time
but varies
but varies from
from aa maximum in
maximum in the
the
+y direction
+y direction through
through zero
zero to
to aa maxi-
maxi-
mum in in the
the - yy direction
direction and
and back
back
again, at
again, at any
any particular
particular point
point inin ------------ x
= 0.O. At
say xx =
space, say At any
any instant
instant ofof FIG. 1-2.
FIG. Electric and
1-2. Electric and magnetic
magnetic
space,
fields
fields associated
associated with
with aa wave
wave moving
moving
time, say t = 0,
time, say t 0, E varies
varies in
in the
the same
same in in the
the j-direction.
x-direction.
fashion with
fashion with distance
distance along
along thex-axis.
the x-axis.
If both
If both variations
variations areare assumed
assumed to to be
be sinusoidal,
sinusoidal, they
they may be expressed
expressed in
in
the one
the one equation
equation
E = - lA (1-1)
(1-1)
Asin27r(-

where A
where =
= amplitude
amplitude of
of the wave, X\ =
the wave, = wavelength,
wavelength, and v
II =
= frequency.
frequency.
The variation
The of E is
variation of is not
not necessarily
necessarily sinusoidal,
sinusoidal, but
but the
the exact
exact form of
of the
the
wave matters
matters little;
little; the
the important
important feature
feature is
is its
its periodicity. Figure 1-3
periodicity. Figure
shows the variation
shows the variation ofof E graphically.
graphically. The wavelength
wavelength and frequency are
frequency are
connected
connected by
by the
the relation
relation cc
X - -,
\ = -. (1-2)
(1-2)
II
V

c = velocity light = 3.00

10
where c
where velocity of of light 3.00 X 10 10 10 em/sec.
cm/sec.
Electromagnetic
Electromagnetic radiation,
radiation, such
such as
as a beam of
of x-rays,
x-rays, carries
carries energy,
energy, and
the rate
the rate of
of flow
flow ofof this
this energy through
energy through unit
unit area
area perpendicular
perpendicular to the direc-
tion of
tion of motion
motion of of the
the wave isis called
called the
the intensity
intensity I.
I. The average
average value ofof

the
the intensity
intensity is
is proportional
proportional to
to the
the square
square of
of the
the amplitude
amplitude of
of the wave,
wave,
2
i.e.,
i.e., proportional
proportional to to A 2.
. In
In absolute
absolute units,
units, intensity
intensity isis measured in in

ergs/cm 22/sec, but

ergs/cm /sec, but this this measurement is
is a difficult
difficult one and is
is seldom carried
carried
out;
out; most
most x-ray
x-ray intensity
intensity measurements are are made on a a relative
relative basis
basis in
in

+E +E

i r---~L--~~-----yX

-E

(a)
(a) (b)
(b)

FIG. 1-3. The

FIG. 1-3. of E,
variation of
The variation E, (a) with t at
(a) with tat aa fixed value of
fixed value of x and (b)
x and with xx at
(b) with at
aa fixed
fixed value
value of
of t.
t.
44 PROPERTIES OF
PKOPERTIES OF X-RAYS
X-RAYS [CHAP.
[CHAP. 1 1

arbitrary units,
arbitrary units, such
such as
as the
the degree
degree of
of blackening
blackening of
of aa photographic
photographic film
film
exposed
exposed to
to the
the x-ray
x-ray beam.
beam.
An accelerated
An accelerated electric
electric charge
charge radiates
radiates energy.
energy. The
The acceleration
acceleration may,
may,
of course,
of course, be
be either
either positive
positive or
or negative,
negative, and
and thus
thus aa charge
charge continuously
continuously
oscillating about
oscillating about some
some mean
mean position
position acts
acts as
as an
an excellent
excellent source
source of electro-
of electro-
magnetic radiation.
magnetic radiation. Radio
Radio waves,
waves, for
for example,
example, are
are produced
produced by
by the
the oscil-
oscil-
lation of charge back and forth
lation of charge back and forth in
in the
the broadcasting antenna,
broadcasting antenna, and
and visible
visible

light by
light by oscillating
oscillating electrons
electrons in
in the
the atoms
atoms ofof the
the substance
substance emitting
emitting the
the
light. In
light. In each
each case,
case, the
the frequency
frequency of of the
the radiation
radiation isis the
the same
same asas the
the fre-
fre-
quency of
quency of the
the oscillator
oscillator which
which produces
produces it.it.
Up to
Up to now we we have
have been
been considering
considering electromagnetic
electromagnetic radiation
radiation as wave
as wave
motion in
motion in accordance
accordance withwith classical
classical theory.
theory. According
According to to the
the quantum
quantum
theory, however,
theory, however, electromagnetic
electromagnetic radiation
radiation can can also
also bebe considered
considered as as aa
stream of
stream of particles
particles called
called quanta
quanta or or photons.
photons. Each photon photon has
has associated
associated
with it
with it an
an amount
amount of of energy
energy hv, where hh is
hll, where is Planck's
Planck's constant (6.62 X
constant (6.62 10-27
X 10~ 27

erg sec).
erg -sec). A link
link is
is thus
thus provided
provided between
between the
the two viewpoints,
viewpoints, because
because
we can
we can use
use the
the frequency
frequency of of the
the wave motion
motion to to calculate
calculate thethe energy
energy ofof
the photon.
the photon. Radiation
Radiation thus
thus has
has a
a dual
dual wave-particle character,
wave-particle character, and
and we
will use
will use sometimes
sometimes one one concept,
concept, sometimes
sometimes the the other,
other, toto explain
explain various
various
phenomena, giving
phenomena, giving preference
preference inin general
general toto the classical
the classical wave theory when-
theory when-
ever
ever itit is
is applicable.
applicable.

1-3
1-3 The
The continuous
continuous spectrum.
spectrum. X-rays X-rays are
are produced
produced when any any electri-
electri-

cally
cally charged particle of
charged particle of sufficient
sufficient kinetic
kinetic energy
energy is is rapidly
rapidly decelerated.
decelerated.
Electrons
Electrons are
are usually
usually used
used for
for this
this purpose,
purpose, the
the radiation
radiation being
being produced
produced
in an
in an x-ray
x-ray tube
tube which
which contains
contains a
a source
source of
of electrons
electrons and two metal elec-
elec-

trodes.
trodes. The high voltage
high voltage maintained
maintained across
across these
these electrodes,
electrodes, some tens
tens
of
of thousands
thousands of of volts, rapidly
volts, rapidly draws the
the electrons
electrons to
to the anode,
anode, or target,
target,
which
which they
they strike
strike with
with very
very high
high velocity.
velocity. X-rays
X-rays are produced at
are produced at the
the
point
point of
of impact
impact and
and radiate
radiate in
in all
all directions.
directions. If
If e
e is
is the charge
charge on the elec-
elec-

tron (4.80 X 10-

tron (4.80 esu)
esu) and 1) the
the voltage
voltage (in
(in esu)*
esu)* across
across the electrodes,
10
10~10 and 'l) electrodes,
then the kinetic energy (in
then the kinetic energy (in ergs) ergs) ofthe
of *the electrons
electrons on impact
impact is
is given
given byby the
the
equation
equation
KE =- e'l) tmv
eV == \mv*, 2, (1-3)
(1-3)

28
where m is
where is the
the mass
mass ofof the
the electron (9.11 X 10-
electron (9.11 10~28 gm) and vv its
gm) its velocity
velocity
just
just before
before impact.
impact. At a
a tube
tube voltage
voltage of
of 30,000
30,000 volts
volts (practical
(practical units),
units),
this
this velocity
velocity is
is about
about one-third
one-third that
that of
of light.
light. Most of
of the
the kinetic
kinetic energy
energy
of
of the
the electrons
electrons striking
striking the
the target
target is
is converted
converted into
into heat,
heat, less
less than
than 11 percent
percent
being
being transformed
transformed into
into x-rays.
x-rays.
When
When thethe rays
rays coming
coming from
from the
the target
target are
are analyzed,
analyzed, they
they are
are found
found toto
consist
consist of
of aa mixture
mixture of
of different
different wavelengths,
wavelengths, and
and the
the variation
variation of
of intensity
intensity

** 11 volt
volt (practical units) =
(practical units)
= Th
^fo volt
volt (esu),
(esu).
 1-3)
1-3] THE CONTINUOUS SPECTRUM
THE CONTINUOUS SPECTRUM 5
6r-----r-----.-----.------.----~----~

5
i'
'8
:::l
Q)

.~ 4
ell

!
-~
rn
Z
ril
3

-Eo-<
Z
,...
~
2

><

1.0 2.0

(angstroms)
WAVELENGTH (angstroms)
FIG. 1-4.
FIG. 1-4. X-ray
X-ray spectrum
spectrum of molybdenum as
of molybdenum as a
a function of
of applied
applied voltage
voltage (sche-
(sche-
matic).
matic). Line
Line \\idths
widths not
not to
to scale.
scale.

with
with wavelength
wavelength is is found
found to to depend
depend on the tube voltage. voltage. Figure
Figure 1-41-4
shows
shows the kind of
the kind of curves
curves obtained.
obtained. The intensity intensity is is zero up up to a certain
to a certain
wavelength,
wavelength, called called thethe short-wavel(}1J1lthJimil
short-wavelengthjimit (ASWL), (XSWL), increases
increases rapidly
rapidly toto aa
maximum
maximum and and tnenthen decreases.
decreases, with with no sharp
sharp limit
limit on the long long wavelength
wavelength
side..* When the
side the tube
tube voltage
voltage is is raised,
raised, thethe intensity
intensity of of all
all wavelengths
wavelengths
increases,
increases, andand bothboth thethe short-wavelength
short-wavelength limit limit and the position
position of of the
the max-
max-
imum
imum shiftshift to to shorter wavelengths. We are
shorter wavelengths. are concerned now now with the
with the
smooth
smooth curve.s
curves in in Fig.
Fig. 1-4,
1-4, those
those corresponding
corresponding to to applied voltages of
applied voltages of

20
20 kv
kv or or less
less in in the
the case
case ofof aa molybdenum
molybdenum target. target. The The radiation repre- repre-
sented
sented by by such
such curves
curves is
is called
called heterochromatic,
heterochromatic, continuous,
continuous, or white
or white radia-
radia-
tion,
tion,
since
since it
it is
is made
made up,
up, like
like white
white light,
light, of
of rays
rays of
of many
many wavelengths.
wavelengths.
The
The continuous spectrum is
continuous spectrum is due
due toto the
the rapid
rapid deceleration
deceleration of of the
the electrons
electrons
hitting
hitting the
the target since,
target since, as
as mentioned
mentioned above,
above, any
any decelerated
decelerated charge
charge emits
emits
energy. Not
Not every
every electron
electron is
is decelerated
decelerated in
in the
the same
same way,
way, however;
however; some
some
energy.
are
are stopped
stopped in
in one
one impact
impact and
and give
give up
up all
all their
their energy
energy at
at once,
once, while
while others
others
are
are deviated
deviated this this way
way andand that
that by by the
the atoms
atoms of of the
the target,
target, successively
successively
losing
losing fractions
fractions of
of their
their total
total kinetic
kinetic energy
energy until it
until it is
is all
all spent.
spent. Those
Those
electrons
electrons which
which are are stopped
stopped in
in one
one impact
impact will
will give
give rise to
rise to photons
photons of
of

maximum
maximum energy,energy, i.e.,i.e., to
to x-rays
x-rays of
of minimum
minimum wavelength.
wavelength. Such
Such electrons
electrons
transfer
transfer allall their energy e'l)
their energy eV into
into photon
photon energy
energy and and wewe maymay write
write

e'lJ = h"max,
6 OF X-RAYS
PROPERTIES OF [CHAP.
[CHAP. 11
cc he
he
XSWL = - - =-,
"max e'O
12,400
12,400
XSWJ, = -y- (1-4)
(1-4)

This equation
equation gives
gives the
the short-wavelength
short-wavelength limit limit (in
(in angstroms)
angstroms) as as aa func-
func-
tion
tion ofof the
the applied voltage Y
applied voltage V (in
(in practical
practical units).
units). If an electron
If electron is is not
not
completely
completely stopped
stopped in in one
one encounter
encounter but but undergoes
undergoes a a glancing
glancing impact
impact
which only
only partially
partially decreases
decreases its its velocity,
velocity, then
then only
only a
a fraetion
fraction of
of its
its energy
energy
e'O
eV isis emitted
emitted as as radiation
radiation and the the photon produced
photon produced has energy
energy less
less than
than
hpmax- In terms of
h"max. of wave motion,
motion, the the corresponding x-ray
corresponding x-ray has
has a
a frequency
frequency
lower than "maxv max and a a wavelength
wavelength longer longer than XSWL.XSWL- The totality
totality ofof these
these
wavelengths, ranging
wavelengths, ranging upward upward from XSWL,
ASWL, constitutes
constitutes the
the continuous
continuous spec-
spec-
trum.
We now see see why
why the
the curves
curves of of Fig.
Fig. 1-4 become higher higher and shift
shift to
to the
the
left
left as
as the
the applied voltage
applied voltage is
is increased,
increased, since
since the
the number of
of photons
photons pro- pro-
duced perper second
second and the the average
average energy
energy perper photon
photon are
are both increasing.
increasing.
The total
total x-ray
x-ray energy
energy emitted
emitted per per second,
second, which is is proportional
proportional to to the
the
area
area under one of of the
the curves
curves of of Fig. 1-4,
Fig. 1-4, also
also depends
depends on
on the
the atomic
atomic num-
ber Z of
ber of the
the target
target and on the the tube
tube current
current i, i, the
the latter
latter being
being aa measure
measure of of
the
the number of of electrons
electrons perper second
second striking
striking the
the target.
target. This
This total
total x-ray
x-ray
intensity
intensity isis given
given byby
lcoDt
/cent spectrum = AiZV"',
spectrum = AlZV, (1-5)
(1-5)

where A isis a proportionality

proportionality constant
constant and m is is a
a constant
constant with
with a a value
value of
of
about 2.2. Where large amounts of
large amounts of white radiation are
white radiation are desired,
desired, it it is
is there-
there-
fore necessary to
fore necessary to use
use aa heavy
heavy metal
metal like
like tungsten
tungsten (Z = 74)
(Z = 74) as
as aa target
target and
as
as high
high a voltage
voltage as
as possible. that the
possible. Note that material of
the material of the
the tar
target
t
aff~cts
et affects
the intensity
the intensit but
bu not thg. wftV dfin fi^h distribution
it ntjon Ooff the cont.inJlQJUs. SIlec-
t.hp..p.ont.iniiniia spec-
trum.
trum,

characteristic spectrum.
1-4 The characteristic spectrum. When the the voltage
voltage onon an
an x-ray
x-ray tube
tube
is raised
is raised above
above aa certain
certain critical
critical value,
value, characteristic
characteristic of of the
the target
target metal,
metal,
sharp intensity maxima appear
sharp intensity appear at certain wavelengths,
at certain wavelengths, superimposed
superimposed on on
the continuous
the continuous spectrum.
spectrum. Since
Since they
they are
are so
so narrow
narrow and
and since
since their
their wave-
wave-
lengths are
lengths are characteristic
characteristic ofof the
the target
target metal
metal used,
used, they
they are
are called charac-
called charac-
teristic lines.
teristic These lines
lines. These lines fall
fall into
into several
several sets,
sets, referred
referred toto as
as K,K, L,
L, M,
M,
etc.,
etc., in
in the
the order
order of
of increasing wavelength,
increasing wavelength, all
all the
the lines
lines together forming
together forming
the characteri8tic spectrum
the characteristic spectrum of of the
the metal
metal used
used as as the
the target.
target. ForFor aa molyb-
molyb-
denum target the K lines
target the lines have
have wavelengths
wavelengths of of about
about 0.7A,
0.7A, the
the L lines
lines
about 5A,
about SA, and thethe M lines
lines still
still higher
higher wavelengths.
wavelengths. Ordinarily
Ordinarily only
only the
the
K lines
lines are
are useful
useful in
in x-ray
x-ray diffraction,
diffraction, the
the longer-wavelength
longer-wavelength lines lines being
being
too easily
too easily absorbed.
absorbed. There are are several
several lines
lines in the K
in the K set,
set, but
but only
only the
the
1-4)
1-4] THE CHA.RA.CTERISTIC
CHARACTERISTIC SPECTRUM 77
three
three strongest
strongest are
are observed in
in normal diffraction
diffraction work.
work. These are
are the
the
ctz, and Kfh,
Kal! Ka2, Kfa, and for
for molybdenum
molybdenum their
their wavelengths
wavelengths are:
are:

Kal: O.70926A,
0.70926A,
Ka 2
Ka2: : O.71354A,
0.71354A,
K{jl: O.63225A.
0.63225A.

The al and a22 components

i components have wavelengths
wavelengths so so close
close together
together that
that they
they
are
are not always
always resolved
resolved as as separate
separate lines;
lines; ifif resolved,
resolved, theythey are
are called
called the
the
doublet and,
Ka doublet and, ifif not resolved, simply the Ka
resolved, simply Ka. line.
line** Similarly, K&\ is
Similarly, K{jl is

usually
usually referred
referred to to as
as the
the K{j line, with
K@ line, with the
the subscript
subscript dropped.
dropped. Ka\ Kal is is

always
always about twicetwice asas strong
strong as Ka2, while
as Ka%, while thethe intensity
intensity ratio
ratio of Kat to
of Ka\ to
Kfli depends
K{jl depends on atomic number but averages averages aboutabout 5/1. 5/1.
These characteristic
characteristic lines
lines may
may be seen seen in
in thethe uppermost
uppermost curvecurve of of Fig.
Fig.
1-4.
1-4. Since
Since the
the critical
critical KK excitation voltage, i.e.,
excitation voltage, i.e., the
the voltage
voltage necessary
necessary to to
excite K
excite K characteristiC'
characteristic radiation,
radiation, is is 20.01
20.01 kv for for molybdenum,
molybdenum, the the KK lines
lines
do not
not appear
appear inin the
the lower
lower curves
curves of of Fig.
Fig. 1-4.
1-4. An increase
increase in in voltage
voltage
above thethe critical
critical voltage
voltage increases
increases the intensities of
the intensities of the
the characteristic
characteristic
lines
lines relative
relative to
to the
the continuous
continuous spectrum
spectrum but but does does not
not change
change their
their wave-
wave-
lengths.
lengths. Figure
Figure 1-5 shows the
the spectrum
spectrum of
of molybdenum
molybdenum at
at 35
35 kv on aa
compressed
compressed vertical
vertical scale
scale relative
relative to
to that
that of
of Fig.
Fig. 1-4;
1-4;
the
the increased
increased voltage
voltage
has shifted
shifted the
the continuous spectrum to
continuous spectrum to still
still shorter
shorter wavelengths
wavelengths and in- in-
creased the intensities
creased the intensities of the K
of the K lines
lines relative
relative to to the
the continuous
continuous spectrum
spectrum
but has
has not
not changed
changed their
their wavelengths.
wavelengths.
The intensity
intensity ofof any
any characteristic
characteristic line, line, measured above the the continuous
continuous
spectrum, depends
spectrum, depends both
both on the
the tube
tube current
current i
i and the
the amount by which
by
the
the applied voltage
applied voltage V exceeds
exceeds the
the critical
critical excitation
excitation voltage
voltage for
for that
that line.
line.

For aa K line,
line, the
the intensity
intensity is
is given
given by by
IIK
Kline = Bi(V -- V K)n,
line = Bi(V K)
n
,
(1-6)
(1-6)

where
where B isis a proportionality constant,
a proportionality constant, V K the
VK K excitation
the K excitation voltage,
voltage, and
nn aa constant
constant with
with a
a value
value of
of about
about 1.5.
1.5. The intensity
intensity of
of a characteristic
characteristic
line
line can
can be
be quite
quite large:
large: for
for example,
example, inin the
the radiation
radiation from a a copper
copper target
target
operated
operated at
at 30
30 kv,
kv, the
the Ka line
line has
has an intensity
intensity about 90 times
times that
that of
of the
the
wavelengths immediately
wavelengths immediately adjacentadjacent to
to it
it in
in the
the continuous
continuous spectrum.
spectrum. Be-
sides
sides being
being very
very intense,
intense, characteristic
characteristic lines
lines are
are also
also very
very narrow,
narrow, most of of
them less than O.OOIA
less than 0.001A wide
wide measured at
at half
half their
their maximum intensity,
intensity,
as
as shown in in Fig. 1-5. The existence
Fig. 1-5. existence of
of this
this strong
strong sharp Ka line
sharp Ka. line is
is what

makes aa great
great deal
deal of
of x-ray
x-ray diffraction
diffraction possible,
possible, since
since many
many diffraction
diffraction
experiments
experiments require
require the use of
the use of monochromatic or or approximately
approximately mono-
chromatic
chromatic radiation.
radiation.

* The wavelength
wavelength of of an unresolved Ka doublet
an unresolved doublet is
is usually
usually taken
taken as
as the
the weighted
weighted
average
average of of the
the wavelengths
wavelengths ofof its components, Kal
its components, Kai being
being given
given twice
twice the
the weight
weight
of Ka%, since
of Ka2, since it
it is
is twice
twice as
as strong.
strong. Thus the
the wavelength
wavelength ofof the
the unresolved
unresolved Mo Ka
line is t(2
line is 0.70926 +
J(2 X 0.70926 0.71354) =
+ 0.71354) = 0.71069A.
0.71069A.
8 PROPERTIES OF X-RAYS [CHAP.
[CHAP. 11

K",
Ka

60

50

S
'8
:::l
II>
> 40
.5
.~
40

!....
Eo<
.....
rn
- -<O.OOIA
*-<0.001A

1 30
Z
r..:l
Eo<
Z
.....

20
20
KfJ

10

(
~ .... ,
o '--
0.2
0.2 0.4
0.4 0.6
0.6 0.8
0.8 1.0
1.0

WAVELENGTH (angstroms)
(angstroms)

FIG.
FIG. 1-5.
1-5. Spectrum
Spectrum of
of Mo at
at 35
35 kv (schematic).
(schematic). Line
Line widths
widths not
not to
to scale.
scale.

The characteristic
characteristic x-ray
x-ray lines
lines were
were discovered
discovered by
by W. H. Bragg
Bragg and
systematized
systematized byby H. G.G. Moseley.
Moseley. The latter
latter found
found that
that the
the wavelength
wavelength of
of
any
any particular
particular line
line decreased
decreased as
as the
the atomic
atomic number of of the
the emitter
emitter increased.
increased.
In particular,
particular, he
he found
found a a linear
linear relation
relation (Moseley's
(Moseley's law)
law) between thethe
square root of
square root of the
the line
line frequency"
frequency v and the atomic number Z:
the atomic Z :

v; == C(Z
C(Z -- CT), er),
(1-7)
(1-7)

where C and CT are

where are constants.
<r constants. This
This relation
relation is
is plotted
plotted in
in Fig.
Fig. 1--6
1-6 for
for the
the
KOl
Kail and LOll lines,
Lai lines, the
the latter
latter being
being the
the strongest
strongest line
line in
in the
the L series.
series. These
curves
curves show,
show, incidentally, that L lines
incidentally, that lines are
are not
not always
always ofof long
long wavelength:
wavelength :

the LOll
the Lai line
line of
of a
a heavy
heavy metal
metal like
like tungsten,
tungsten, for
for example,
example, hashas about thethe
same wavelength
wavelength as
as the
the KOl line of copper, namely
Ka\t line of copper, namely about about 1.5A.
1.5A. The
1-4)
1-4] THE CHARACTERISTIC SPECTRUM 9
X (angstroms)

3.0 2.5 2.0 1.5 1.0 0.8 0.7

80 I T I I I T
W
70

60

w
50

u
40
s

30

20 -

10~
10 ____ ~ __ ~ ____ ~ ____ ~ ____ ~
I
____ ~

1.0
1.0 1.2
1.2 1.4
1.4 1.6
1.6 1.8
1.8 2.0 2.2 X 109
2.2 9

v'; (ser-!)
FIG.
FIG. 1-6.
1-6. Moseley's
Moseley's relation between V;
relation between \/v and Z for
for two
two characteristic
characteristic lines.
lines.

wavelengths
wavelengths ofof the
the characteristic
characteristic x-ray
x-ray lines
lines of
of almost
almost all
all the
the known ele- ele-
ments have been precisely measured, mainly
precisely measured, mainly by by M. Siegbahn
Siegbahn and his
his
associates,
associates, and a tabulation of
a tabulation of these
these wavelengths
wavelengths for
for the
the strongest
strongest lines
lines
of the K and L series
of the series will
will be
be found
found M shell
in
in Appendix
Appendix 3.
3.

While the
the continuous s~~s
cQntinuoi^s_srjex;truri^js
caused
caused by the rapid dece~erat.ion_qL
byjthe T^^^^dej^tignj)^
erectrons-bj_~~e
electrons by the..~~.!g~tL
targe t~.
the ~rig!!l_9f_
origin of
t
;

lli8 Characteristic ^spectrum lies in the

at~~ of the target_~~!e:~al.A~lf.
atoms__j3i_tl^_taj^J)_jrnaterial itself.

T'o
To understand
understand this phenomenon, it
this phenomenon, it

is
is enough
enough to to consider
consider an atom as as con-
con-
sisting
sisting of
of a
a central
central nucleus
nucleus surrounded
surrounded
by
by electrons
electrons lying
lying in
in various
various shells
shells
(Fig. 1-7).
(Fig. 1-7). If
If one
one of
of the
the electrons
electrons
bombarding
bombarding the the target
target has
has sufficient
sufficient
kinetic
kinetic energy,
tron
tron out
energy, it
it can
can
the K shell,
of the
out of
knock an elec-
elec-

shell, leaving the

leaving
FIG. ^
FlG 1-7. Electl'Onic
Elec tronic transitions
transitions in
in
the an at0 m (schematic).
an atom (schematic). Emission
Emission PI'OC-
proc-
atom inin an excited, high-energy state.
an excited, high-energy state, esses
esses indicated by arrows.
indicated by arrows.
10
10 PROPERTIES OF
PROPERTIES OF X-RAYS
X-RAYS [CHAP.
[CHAP. 1
1

One of
One of the
the outer
outer electrons
electrons immediately
immediately falls
falls into
into the
the vacancy
vacancy in the K shell,
in the shell,
emitting energy
emitting energy in
in the
the process,
process, and
and the
the atom
atom is
is once
once again
again in
in its
its normal
normal
energy state.
energy state. The
The energy
energy emitted
emitted is in the
is in the form of radiation of aa definite
of radiation of definite
wavelength and is,
wavelength is, in
in fact, characteristic K radiation.
fact, characteristic radiation. K
The Jff-shell vacancy may
K-shell vacancy may be
be filled
filled by
by an electron
electron from any
anyone of the
one of the
outer shells,
outer shells, thus
thus giving
giving rise
rise toto aa series
series of lines; Ka
of K lines; K
KeY. and K{3 lines,
and K& lines, for
for
example, result
example, result from
from the
the filling
filling of
of aa K-shell
K-shell vacancy
vacancy byby an electron from
an electron
the
the LOT M
L or M shells,
shells, respectively.
respectively. It It is
is possible
possible to to fill
fill aa 7-shell
K-shell vacancy
vacancy either
either
from the
from the L or M
or M shell,
shell, so
so that
that oneone atom of of the
the target emitting Ka
target may be emitting
be KeY.
radiation while
radiation while its its neighbor
neighbor is is emitting
emitting Kfi\ K{3; however,
however, it it is
is more probable
probable
that aa jf-shell
that K-shell vacancy
vacancy will will be
be filled
filled byby an L electron
electron than by M
by an M elec-elec-
tron, and
tron, and the
the result
result is is that
that the Ka
the KeY. lineline is stronger
is stronger than the K$
the K{3 line.
line. It It
also follows
also follows that
that it it is
is impossible
impossible to to excite
excite one one K line line without
without exciting
exciting allall
the others.
the others. L characteristic
characteristic lines lines originate
originate in in aa similar
similar way:
way: an electron
electron
is knocked
is knocked outout of of the
the L shell
shell and the the vacancy
vacancy is is filled
filled by
by an electron
electron from
some outer
some outer shell.
shell.
We now see see why
why there
there should
should be be aa critical
critical excitation
excitation voltage
voltage forfor charac-
charac-
teristic radiation. K radiation,
teristic radiation. radiation, for for example,
example, cannotcannot be be excited
excited unless
unless the
the
tube voltage
tube voltage is is such
such that
that thethe bombarding
bombarding electrons electrons have enough enough energy
energy
to knock
to knock anan electron
electron out out of the K shell
of the shell ofof aa target
target atom.
atom. If If WWKK isis the
the
required to
work required to remove aa K electron,electron, thenthen the the necessary
necessary kinetic
kinetic energy
energy
of the electrons
of the electrons is is given
given by by
!mv
ynxr2 = = TVWK- K. (1-8)
(1~8)

It
It requires less energy
requires less energy to to remove
remove an L electron electron than a K electron, electron, since
the
the former
former is
is farther
farther from the the nucleus;
nucleus; it it therefore follows that the L excita-
therefore follows excita-
tion voltage is
tion voltage is less
less than
than thethe K and that that K characteristic
characteristic radiation
radiation cannot
be produced
be produced without
without L, L, M,M, etc.,
etc., radiation
radiation accompanying
accompanying it. it.

1-5
1-6 Absorption.
Absorption. Further
Further understanding
understanding of of the
the electronic
electronic transitions
transitions
which
which can
can occur
occur in
in atoms can
can be
be gained by considering
gained by considering not only
only the inter-
inter-
action
action of
of electrons
electrons and atoms,
atoms, but also
also the
the interaction
interaction of
of x-rays
x-rays and atoms.
When x-rays
x-rays encounter
encounter anyany form of of matter,
matter, they
they are
are partly
partly transmitted
and partly
partly absorbed.
absorbed. Experiment
Experiment shows that that the
the fractional
fractional decrease in in
the
the intensity
intensity I
7 of
of an
an x-ray
x-ray beam as
as it
it passes through any homogeneous
passes through any homogeneous
substance
substance isis proportional
proportional toto the
the distance traversed, x.
distance traversed, x. In differential
differential form,
form,
dI
--J-/.AC,
1= p.dx, (1-9)
(1-9)

where the
the proportionality
proportionality constant
constant II- is
is called
called the
the lnear
/u linear absorption
absorption coeffi-
coeffi-

cient
cient and is
is dependent
dependent on
on the
the substance
substance considered,
considered, its
its density,
density, and the
wavelength
wavelength ofof the
the x-rays.
x-rays. Integration
Integration ofof Eq. (1-9) gives
Eq. (1-9) gives
{.
4-
-
= Ioe-I'x,
/or**, (1-10)
(1-10)
where 10 =
/o = intensity
intensity ofof incident
incident x-ray
x-ray beam and Ix Ix = intensity
= intensity of
of trans-
trans-
~itted
mitted beam after
after passing
passing through thickness x.
through aa thickness x.
1-51
1-5] ABSORPTION 11
11

linear absorption
The linear coefficient /zp. is
absorption coefficient is proportional
proportional to
to the
the density
density p, which
p, which
that the
means that the quantity p./p isis aa constant
quantity M/P constant of
of the
the material
material and
and independent
independent
of its
of its physical
physical state
state (solid,
(solid, liquid,
liquid, or
or gas).
gas).
This latter
This latter quantity,
quantity, called
called the
the
mass absorption
mass absorptioncoefficient, is the
the one
one usually
coefficient, is usually tabulated.
tabulated. Equation
Equation (1-10)
(1-10)
may then
may then be
be rewritten
rewritten inin aa more
more usable
usable form
form: :

I Ix = Ioe-<P./p)pz I (1-11)
(1-11)

Values of
Values of the
the mass
mass absorption
absorption coefficient p./ p are
coefficient /i/p are given
given in
in Appendix
Appendix 44 for
for
various characteristic
various characteristic wavelengths
wavelengths used
used in
in diffraction.
diffraction.
It is occasionally
It is occasionally necessary
necessary to
to know the
the mass absorption
absorption coefficient
coefficient of
of aa
substance containing
substance containing more
more than
than one
one element.
element. Whether the
the substance
substance is
is aa
mechanical mixture,
mechanical mixture, aa solution,
solution, or
or aa chemical
chemical compound,
compound, and whether
whether itit
is in
is in the
the solid,
solid, liquid,
liquid, or
or gaseous
gaseous state,
state, its
its mass absorption coefficient is
absorption coefficient is
simply
simply the
the weighted average
weighted average of
of the
the mass absorption
absorption coefficients
coefficients of
of its
its

constituent elements. If
constituent elements. If WI, w2 etc.,
Wi, W2, etc., are
,
the weight
are the weight fractions of elements
fractions of elements
1, 2, etc.,
1, 2, etc., in
in the
the substance
substance and (p./ph, (p./ph, etc.,
(M/P)I, (M/p)2j etc., their
their mass absorption
absorption
coefficients, then the
coefficients, then the mass absorption
absorption coefficient of the
coefficient of the substance
substance isis given
given
by
by
~ == WI
- Wl ((~) + + W2 ((~) +
-J -J 2
+ .... . .
(1-12)
(1-12)
..

p PIP

4 X lO-H
The way
way inin which thethe absorption critical energy W K
coefficient
coefficient varies
varies with
absorption
with wavelength
wavelength \ for ejection of K
('lectroll from nickel
gives
gives the
x-rays
x-rays
the clue
and
and
clue toto the
atoms.
atoms.
the interaction
The
interaction of
lower
lower curve
curve
of
\ /
1/
of
of Fig. 1-8 shows
Fig. 1-8
nickel
shows this
nickel absorber;
this variation
variation for
for aa
I~ .........
absorber; it it is
is typical
typical of
of all
all

materials.
materials. The curvecurve consists
consists of
of two
two
I
I
I
r---
similar
similar branches
branches separated
separated by by a
a sharp
sharp
()
400
discontinuity
discontinuity called
called anan absorption
absorption I
edge.
edge. Along
Along each
each branch
branch thethe absorp-
absorp- SOl )
tion
tion coefficient
coefficient varies
varies with
with wave-
length
length approximately
approximately according
according toto aa / K absorption
..- edge

relation
relation of
of the
the form
form
::I.: Q, IOO
/ /
~
M

P
= kA 3 Z 3 , (1-13)
II / ~~2.0
= aa constant,
o 0.5
0.5 1.0
1.0 1.5
1.5 2.0 2.
2.
where
where kk = constant, with
with aa different
different
}.X (angstroms)
(angstroms)
value
value for
for each branch of
each branch of the
the curve,
curve,
= atomic FIG.
FIG. 1-8.
1-8. Variation with wave-
Variation wave-
and
and Z = atomic number ofof absorber.
absorber.
length
length of
of the
the energy
energy per
per x-ray
x-ray quantum
quantum
Short-wavelength
Short-wavelength x-rays
x-rays are
are there-
there- and of the mass
of the mass absorption
absorption coefficient
coefficient
fore highly penetrating
fore highly penetrating and are
are of
of nickel.
nickel.
12
12 PROPERTIES OF X-RAYS
PROPERTIES OF X-RAYS [CHAP.
[CHAP. 11

termefl hard,
termed while long-wavelength
hard, while long-wavelength x-rays
x-rays are
are easily
easily absorbed
absorbed and
and are
are said
said
to be
to 80ft.
be soft. .
Matter absorbs
Matter absorbs x-rays
x-rays in
in two
two distinct
distinct ways,
ways, byby scattering
scattering and
and by
by true
true
absorption, and
absorption, and these
these two
two processes
processes together
together make
make upup the
the total
total absorption
absorption
measured by
measured by the
the quantity J.I./p. The
quantity M/P- 8cattering of
The scattering of x-rays
x-rays by
by atoms
atoms isis similar
similar
in
in many ways
many ways to to the
the scattering
scattering of of visible
visible light
light by by dust
dust particles
particles in in the
the air.
air.
It takes place
It takes place in
in all
all directions,
directions, and
and since
since the
the energy
energy in
in the
the scattered
scattered beams
beams
does not
does not appear
appear in in the
the transmitted
transmitted beam, beam, it it is,
is, so
so far
far as as the
the transmitted
transmitted
beam is
beam is concerned,
concerned, said to be
said to be absorbed.
absorbed. The phenomenon
The phenomenon of scattering
of scattering
will be
will be discussed
discussed in in greater
greater detail
detail in in Chap.
Chap. 4; 4; itit is
is enough
enough to to note
note herehere
that, except
that, except for the very
for the very light
light elements,
elements, it it is
is responsible
responsible for for only
only aa small
small
fraction of
fraction of the
the total
total absorption.
absorption. True True absorption
ab8orption is is caused
caused by by electronic
electronic
transitions within
transitions within the the atom and and is is best
best considered
considered from the the viewpoint
viewpoint of of
the quantum
the quantum theory theory of of radiation.
radiation. Just Just as as an electron
electron of of sufficient
sufficient energy
energy
can knock aa K electron,
can knock electron, for for example,
example, out out ofof an atom and thus thus cause
cause the the
emission of
emission of K characteristic
characteristic radiation,
radiation, so so also
also can an incident incident quantum
quantum of of
x-rays, provided
x-rays, provided it
it has
has the
the same minimum amount of
of energy
energy WK.
WK- In
In the
the
latter case,
latter case, the the ejected
ejected electron
electron is is called photoelectron and the
called aa photoelectron the emitted
emitted
characteristic radiation
characteristic radiation is
is called
called fluore8cent
fluorescent radiation.
radiation. It
It radiates
radiates in all
in all
directions and has
directions and has exactly theexactly the same wavelength
wavelength as
as the
the characteristic
characteristic radia-
radia-
tion 'caused
tion caused by by electron
electron bombardment
bombardment. of of aa metal
metal target.
target. (In (In effect,
effect, an an
atom with
atom with aa #-shell
K-shell vacancy always emits
vacancy always emits K radiation
radiation no matter how the
matter the
vacancy
vacancy was was originally
originally created.)
created.) This phenomenon phenomenon is is the x-ray
x-ray counter-
counter-
part
part ofof the photoelectric effect
the photoelectric effect in in the
the ultraviolet
ultraviolet regionregion of of the spectrum;
spectrum;
there, photoelectrons
there, photoelectrons can
can be
be ejected
ejected from the
the outer shells of a metal atom
shells
by
by the action of
the action of ultraviolet
ultraviolet radiation,
radiation, provided
provided the the latter
latter has a wavelength
wavelength
less than
less than a a certain
certain critical
critical value.
value.

say that
To say that thethe energy
energy of of the
the incoming
incoming quanta quanta must exceed a certain certain

value W
value is equivalent
WK equivalent saying
K is to
to saying that
that the
the wavelength
wavelength must be less
less than
than a a
certain
certain value
value XK,
X#, since
since the
the energy per
energy per quantum quantum is
is h"
hv and wavelength
wavelength is
is

inversely
inversely proportional
proportional to to frequency.
frequency. These relations relations may be written

hc
he
W K = h"K = -, (1-14)
XK
where
where "K V K and
and XK \K areare the
the frequency
frequency and wavelength,wavelength, respectively,
respectively, of of the
the
K absorption
K absorption edge. edge. N ow consider
Now consider the the absorption
absorption curve of of Fig.
Fig. 1-8
1-8 in light
in light
of
of the
the above.
above. SupposeSuppose that that x-rays
x-rays of of wavelength
wavelength 2.5A 2.5A are are incident
incident on on aa
sheet of
sheet of nickel
nickel and and thatthat this
this wavelength
wavelength is is continuously
continuously decreased.decreased. At At
first
first the
the absorption coefficient is about
about 180
180 cm
cm 22/ gm, but but as
as the
the wavelength
wavelength
absorption coefficient is /gm,
decreases,
decreases, the the frequency
frequency increases
increases and and so so does
does thethe energy
energy per per quantum,
quantum,
as shown by
as shown by the
the upper curve,
upper curve, thus
thus causing
causing the
the absorption
absorption coefficient
coefficient to
to
decrease,
decrease, since
since the
the greater
greater the
the energy
energy of
of aa quantum
quantum the
the more
more easily
easily it it

passes through
passes through an
an absorber.
absorber. When
When the
the wavelength
wavelength is
is reduced
reduced just
just below
below
1-5)
1-5] ABSORPTION 13
13

the
the critical
critical value A#, Ax, which is is l.488A
1.488A for for nickel,
nickel, the the absorption
absorption coefficient
coefficient
suddenly
suddenly increases
increases about eightfold eightfold in in value.
value. True absorptionabsorption is is now oc- oc-
curring
curring and a a large
large fraction
fraction of of the
the incident
incident quanta
quanta simplysimply disappear,
disappear, their their
energy
energy beingbeing converted
converted into into fluorescent
fluorescent radiation
radiation and the the kinetic
kinetic energy
energy
of
of ejected photoelectrons.
ejected photoelectrons. Since
Since energy
energy must be conserved
conserved in
in the
the process,
process,
it
it follows
follows that that the
the energy
energy per per quantum
quantum of of the
the fluorescent
fluorescent radiation
radiation must
be
be less
less than that that of of the
the incident radiation, or
incident radiation, or that
that the wavelength Ax
the wavelength \K ofof
the K absorption
the absorption edge edge must be
be shorter
shorter than that
that of
of any
any K characteristic
characteristic
line.
line.

AB
As the
the wavelength
wavelength of of the
the incident
incident beam is is decreased
decreased below below Ax,Xx, thethe ab-
ab-
sorption
sorption coefficient begins to
coefficient begins to decrease
decrease again,again, even
even though
though the the production
production
of K fluorescent
of fluorescent radiation
radiation and photoelectrons
photoelectrons is is still
still occurring.
occurring. At a a wave-
length
length of of l.OA,
l.OA, forfor example,
example, the the incident
incident quanta
quanta have more than enough enough
energy to
energy to remove an electron electron from the the K K shell
shell of of nickel.
nickel. But thethe more
energetic
energetic the the quanta become, the
quanta become, greater is
the greater is their
their probability
probability of passing
of passing
right through
right through the
the absorber,
absorber, with
with the
the result
result that
that less
less and less
less of
of them take
take
part
part in
in the
the ejection
ejection of
of photoelectrons.
photoelectrons.
If
If the
the absorption
absorption curve curve of of nickel
nickel is is plotted
plotted forfor longer
longer wavelengths
wavelengths than
2.5A, i.e.,
2.5A, i.e., beyondbeyond the
the limit
limit of
of Fig.
Fig. 1-8,1-8, other
other sharp
sharp discontinuities
discontinuities will
will be

found.
found. These These are are thethe L, M, N, etc., absorption
L, M, N, etc., absorption edges; edges; in
in fact,
fact, there
there are
are
three closely
three closely spaced spaced Ledges
L edges (Lj, (L ,
I Ln,Ln, and L m
I/m), ), five
five M
M edges,
edges, etc.
etc. Each
of
of these
these discontinuities
discontinuities marks the the wavelength
wavelength of of the
the incident
incident beam whose
quanta
quanta have just just sufficient
sufficient energy
energy to eject an L,
to eject L, M, M, N, N, etc.,
etc., electron
electron from
the
the atom.
atom. The right-handright-hand branch branch of of the
the curve
curve of of Fig. 1-8, for
Fig. 1-8, for example,
example,
lies
lies between
between the the K and L absorptionabsorption edges; edges; inin this
this wavelength
wavelength regionregion inci-
inci-

dent
dent x-rays
x-rays havehave enough
enough energyenergy to to remove L, L, M,
M, etc.,
etc., electrons
electrons from nickel nickel
but
but not not enough
enough to remove K
to remove K electrons.
electrons. Absorption-edge
Absorption-edge wavelengthswavelengths
vary
vary with
with the
the atomic
atomic number of
of the
the absorber
absorber in
in the
the same way,
way, but but not
quite
quite as
as exactly,
exactly, as
as characteristic
characteristic emission
emission wavelengths,
wavelengths, that
that is, according
is, according

to
to Moseley's
Moseley's law. law. Values
Values of the K and L absorption-edgc
of the absorption-edge wavelengths
wavelengths
are
are given
given in in Appendix
Appendix 3. 3.

The measured
measured values values of of the
the absorption
absorption edges edges can can be be used
used to to construct
construct
an energy-level
an energy-level diagram diagram for
for the
the atom,
atom, which in
in turn
turn can
can be
be used
used in
in the
the
calculation
calculation of of characteristic-line
characteristic-line wavelengths.wavelengths. For example, example, if we take
if take
the
the energy
energy of of the
the neutral
neutral atom as as zero,
zero, then
then the
the energy
energy of of an ionized
ionized atom
(an
(an atom in in an
an excited
excited state)
state) willwill be be some positive
positive quantity,
quantity, since
since work
must be be done
done to to pull
pull an electron
electron away away from the the positively
positively charged
charged nucleus.
nucleus.
If
If aa K electron
electron is is removed,
removed, work equal equal to WKK must be
to W be done and the the atom
is
is said
said to to bebe in the K energy
in the energy state.state. energy W
The energy WKK maymay be be calculated
calculated
from
from the the wavelength
wavelength of
of the
the K
K absorption edge
absorption edge by by the
the use
use of
of Eq.
Eq. (1-14).
(1-14).
Similarly,
Similarly, the
the energies
energies of
of the
the L, M,
L, M, etc.,etc., states
states can
can be
be calculated
calculated from the
wavelengths
wavelengths of
of the
the L, M, etc., absorption
L, M, etc., absorption edges edges and the
the results
results plotted in
plotted in
the form
the form of
of an energy-level
energy-level diagram diagram for
for the
the atom (Fig. 1-9).
(Fig. 1-9).
14
14 PROPERTIES OF X-RAYS
PROPERTIES OF X-RAYS [CHAP,
[CHAP. 1

KK state (K electron
state (A' electron removed)
removed)

.: Ka Kf) emission
.g
~
'"
>(

""
:::.::
:2
0
E-<
<
.....
0
>< WL L state (L electron
state (L electron removed)
remo\'ed)
V
~
~
Z .:
~ g
~ La
'"
>(

"'
...::i

M
M state electron removed)
(M electron

M Ma

11',\ N state
state (N
(N electron removed)
4A'
\'alencf'
valence electron
electron rerno\'ed
removed

o neutral atom

FIG,
FIG. 1-9.
1-9. Atomic
Atomic energy
energy levels
levels (schematic).
(schematic). Excitation
Excitation and emission processes
processes
indicated
indicated by
by arrows.
arrows. (From
(From Structure
Structure of
of Metals,
Metals, by
by C,
C. S.
S. Barrett,
Barrett, McGraw-Hili
McGraw-Hill
Book
Book Company,
Company, Inc.,
Inc., 1952.)
1952.)

Although
Although this
this diagram
diagram isis simplified,
simplified, in
in that
that the substructure of
of the
the L,
L,
M, etc.,
M, etc., levels
levels is
is not
not shown,
shown, it
it illustrates
illustrates the
the main principles.
principles. The arrows
show
show the transitions of
the transitions of the atom, and their
the atom, their directions
directions are therefore just
just
the
the opposite
opposite of
of the arrows in
the arrows in Fig.
Fig. 1-7,
1-7, which shows the transitions
transitions of
of the
the
electron. Thus,
electron. Thus, if
if a K electron
a K electron is
is removed from
from anan atom (whether
(whether by anan
incident
incident electron
electron or
or x-ray),
x-ray), the
the atom
atom is
is raised
raised to
to the
the KK state.
state. If
If an elec-
elec-

tron
tron then
then moves
moves from
from the
the LL to
to the K level
the K level to
to fill
fill the
the vacancy,
vacancy, the atom
atom
undergoes
undergoes aa transition
transition from
from thethe KK to
to the
the LL state.
state. This
This transition
transition isis accom-
accom-
panied by
panied by the
the emission
emission of
of Ka
Ka characteristic
characteristic radiation
radiation and
and the
the arrow
arrow indi-
indi-

cating
cating Ka
Kot emission
emission is
is accordingly
accordingly drawn
drawn from
from the
the KK state
state to
to the
the LL state.
state.

Figure
Figure 1-9
1-9 shows
shows clearly
clearly how how the
the wavelengths
wavelengths of of characteristic
characteristic emission
emission
lines can be
lines can be calculated,
calculated, since
since the
the difference
difference in
in energy
energy between
between two
two states
states
will equal hll, where
will equal hv, where II
v is
is the
the frequency
frequency of
of the
the radiation
radiation emitted
emitted when
when the
the
1-5]
1-5] ABSORPTION 15
15

atom goes
goes from one state
state to
to the other.
other. Consider thethe Kat
Kai characteristic
characteristic
line,
line, for example. The "L level"
for example. level" of
of an atom is
is actually
actually a group
group of of three
three
closely
closely spaced
spaced levels
levels CLI,
(Li, Ln,
Ln, and Lm),
LIU), and the emission
emission of of the Kat line
the Kai line
is due to
is K --+> Lm transition.
to a K transition. The frequency
frequency 11K",!
VK ai of
of this
this line
line is
is there-
there-
fore
fore given
given by the equations
by the equations

hJlKa,
hi> K<*I = WK - WLulI

hllKa, = hllK - hllLlI1I

1 1 11
--=----, (1-15)
(1-15)
X/,111

where the subscripts K and Lm refer

the subscripts refer to
to absorption
absorption edges
edges and the
the subscript
subscript
Kat
Kai to
to the
the emission
emission line.
line.

Excitation
Excitation voltages
voltages can bebe calculated
calculated by
by aa relation similar to
relation similar to Eq.
Eq. (1--4).
(1-4).
K radiation,
excite K
To excite radiation, for
for example,
example, inin the
the target
target of
of an x-ray
x-ray tube,
tube, the
the bom-
barding
barding electrons
electrons must have energy equal to
energy equal WK> Therefore
to WK. Therefore

he
e'OK = K =
= lJ'K W
= hllK = - , .

XK*
he
i.
he
'OK=-' '

eXK
e\ K

12,400
12,400
VK = - - , (1-16)
(1-16)
XK
where VVKK is the K excitation
is the excitation voltage
voltage (in practical units)
(in practical units) and \K
XK is
is the K
the K
absorption
absorption edge
edge wavelength
wavelength (in (in angstroms).
angstroms).
Figure
Figure 1-10
1-10 summarizes
summarizes some of of the
the relations
relations developed
developed above.
above. This
This
curve gives
gives the
the short-wavelength
short-wavelength limitlimit of
of the
the continuous
continuous spectrum
spectrum as as a
function
function ofof applied
applied voltage.
voltage.
Because ofof the
the similarity
similarity be-
be- 30
tween Eqs. (1-4)
Eqs. (1-4) and (1-16),
(1-16), \
the
the same curve
curve also
also enables
enables usus 25
to
to determine the
tation
tation voltage
the critical
critical exci-

voltage from the

exci-
the wave- ~20
\
length
length of
of an absorption
absorption edge.
edge. \\
the
FIG.
FIG. 1-10.

tube
1-10.
the voltage
tube and the
limit
limit of
of the
Relation
Relation between
voltage applied
applied toto an
between
an x-ray
the short-wavelength
x-ray
short-wavelength
the continuous
continuous spectrum,
spectrum,
5
"" .......
~ --.
-
and between the the critical
critical excita-
excita- o
tion voltage of
tion voltage of any
any metal
metal and
and the
the
o 0.5
0.5 1.0
1.0 1.5
1.5 2.0
2.0 2.5
2.5 3.0
3.0

wavelength
wavelength ofof its
its absorption
absorption edge.
edge. >.X (angstroms)
(angstroms)
16
16 PROPERTIES OF
PROPERTIES OF X-RAYS
X-RAYS [CHAP.
[CHAP. 1
1

Ka

E-< ~
Z /1

--
/ I
r"'l / I /
I
U
...... /
/
/ I

/
I
I

;;.. 0 r"'l

-
I
E-< u /
/

-
00 I
Z Z /

r"'l 0 V
/
'Ka
A'a

zE-<
- t: ~
0
00
CQ
KfJ
I
-< I
00 I
00
-<
.... I

....
- ~~~
1.2
1.2 1.4
1.4

~
X
1---

1.6
(angstroms)
(angstroms)
1.6 1.8
1.8 1.2
1.2
KfJ

1.4
1.4
'--

1.6
1.6

~ (angstroms)
X (angstroms)
1
--1.8
1.8

(a) filter
(a) No filter (b) Nickel
(b) Nickel filter
filter
FIG.
FIG. 1-11.
1-11. Comparison
Comparison of of the
the spectra
spectra of
of copper
copper radiation (a) before
radiation (a) before and
and (b)
(b)
after passage through
after passage through a
a nickel
nickel filter
filter (schematic).
(schematic). The dashed line
line is
is the mass ab-
ab-
sorption
sorption coefficient
coefficient of
of nickel.
nickel.

1-6
1-6 Filters.
Filters. Many
Many x-ray x-ray diffraction
diffraction experiments
experiments require require radiation
radiation
which
which is is as
as closely
closely monochromatic as
as possible.
possible. However,
However, the beam from
an
an x-ray
x-ray tube
tube operated
operated at
at aa voltage
voltage above VVK
K contains not only
only the strong
strong
Ka line
line but
but also the weaker K{3
also the Kft line
line and the continuous spectrum. spectrum. The The
intensity
intensity of
of these
these undesirable
undesirable components
components can be decreased relative to the
the
intensity
intensity of
of the
the Ka line
line by passing
by passing the
the beam through
through a
a filter
filter made of
of aa
material whose K
material whose K absorption
absorption edge edge lies
lies between the Ka and KfJ
Kfl wave-
lengths
lengths of of the
the target
target metal.
metal. SuchSuch aa material
material willwill have
have an an atomic number 11
atomic number
or
or 22 less
less than
than that
that of of the
the target
target metal.
metal.
AA ftiter
filter so
so chosen
chosen willwill absorb
absorb the the K{3Kfi component
component much much more more strongly
strongly
than
than thethe Ka
Ka component,
component, because
because of
of the
the abrupt change
abrupt change in
in its
its absorption
absorption
coefficient
coefficient between
between these
these two
two wavelengths.
wavelengths. The The effect
effect ofof filtration
filtration is shown
is shown

in
in Fig. 1-11,
Fig. 1-11, in
in which
which the
the partial spectra
partial spectra of
of the
the unfiltered
unfiltered and
and filtered
filtered

beams
beams from
from aa copper target (Z
copper target (Z = = 29)
29) areare shown
shown superimposed
superimposed on on aa plot
plot
of
of the
the mass
mass absorption
absorption coefficient
coefficient of
of the
the nickel
nickel filter
filter (Z
(Z == 28).
28).
The
The thicker
thicker the
the filter
filter the
the lower
lower the the ratio
ratio of
of intensity
intensity of of KfJ
Kft toto KaKa in in the
the
transmitted
transmitted beam.beam. But But filtration
filtration is is never
never perfect,
perfect, of
of course,
course, no
no matter
matter
how
how thick
thick the
the filter,
filter, and
and oneone must
must compromise
compromise between between reasonable
reasonable sup- sup-
pression
pression of
of the
the KfJ component
Kfi component and
and the
the inevitable
inevitable weakening
weakening of
of the
the Ka
Ka
component
component which
which accompanies
accompanies it.
it. In
In practice
practice it
it is
is found
found that
that a
a reduction
reduction
1-7)
1-7] PRODUCTION OF X-RAYS
PRODUCTION OF X-RAYS 17
17

TABLE 1-1
TABLE 1-1

FILTERS FOR
FILTERS FOR SUPPRESSION OF K/3 RADIATION
SUPPRESSION OF RADIATIONKP
Filter thickneu for
Incident beam /(Ka) 500
Target Filter I (Ka) I(K{J) = - ] I(Ka} trans.
I (K{3) in trans. beam I(Ka) incident

mg/cm2 in.
Mo Zr 3.9 75 0.0045 0.27
Cu NI 5.6 19 0.0001 O.~
Co Fe 5.7 14 0.0007 0.44
Fe Mn 5.7 13 0.0007 0.43
Cr V 5.1 11 0.0007 0.44

in the
in the intensity
intensity of
of the
the KOI line
Ka line to
to about
about half
half its
its original
original value will decrease
value will decrease
the ratio
the of intensity
ratio of intensity of to Ka
Kp to
of K& KOI from
from about
about ^ inin the t
the incident
incident beam toto
about ~ in
about -gfa in the
the transmitted
transmitted beam
beam; this
this level
level is
;
is sufficiently
sufficiently low
low for
for most
most
purposes. Table
purposes. Table 1-1 shows the
1-1 shows the filters
filters used
used in
in conjunction
conjunction with
with the
the com-
com-
target metals,
mon target metals, the
the thicknesses
thicknesses required,
required, and the
the transmission
transmission factors
factors
for the
for KOI line.
the Ka line. Filter
Filter materials
materials are
are usually
usually used
used in
in the
the form of of thin
thin foils.
foils.
If it is
If it not possible
is not possible to
to obtain
obtain aa given
given metal
metal in
in the form of
of a stable foil,
foil, the
the
oxide
oxide of of the
the metal
metal may
may be
be used.
used. The powdered
powdered oxide is
is mixed with
with aa
suitable
suitable binder
binder and
and spread
spread on
on a
a paper backing,
paper backing, the
the required
required mass of metal
per
per unit
unit area
area being
being given
given in
in Table
Table 1-1.
1-1.

1-7
1-7 Production
Production of of x-rays.
x-rays. We have seen seen thatthat x-rays
x-rays are produced
produced
whenever
whenever high-speed
high-speed electrons
electrons collide
collide with a
a metal target.
target. Any x-ray
x-ray
tube
tube must
must therefore
therefore contain
contain (a)(a) a
a source
source of
of electrons,
electrons, (b)
(6) a high
high acceler-
acceler-
ating
ating voltage,
voltage, and and (c) (c) aa metal
metal target.
target. Furthermore,
Furthermore, since since most of of the
the
kinetic
kinetic energy
energy of
of the
the electrons
electrons is
is converted
converted into
into heat in
in the target,
target, the
the
latter
latter must
must be be water-cooled
water-cooled to to prevent
prevent its
its melting.
melting.
All
All x-ray
x-ray tubes
tubes contain
contain two two electrodes,
electrodes, an an anode
anode (the(the metal target)
target)
maintained,
maintained, with
with few
few exceptions,
exceptions, at
at ground potential,
ground potential, and
and a
a cathode,
cathode,
maintained at
maintained at aa high
high negative
negative potential,
potential, normally
normally of of the
the order
order of
of 30,000
30,000
to
to 50,000
50,000 volts
volts for
for diffraction
diffraction work.
work. X-ray
X-ray tubes
tubes may
may be
be divided
divided into
into two
two
basic
basic types, according
types, according to
to the
the way
way in
in which
which electrons
electrons are
are provided:
provided: filament
filament
tubes,
tubes, in which the
in which the source
source ofof electrons
electrons is is aa hot
hot filament,
filament, and and gas
gas tubes,
tubes, in in

which
which electrons
electrons are are produced
produced by by the
the ionization
ionization of
of a
a small
small quantity
quantity of
of gas
gas
in
in the
the tube.
tube.
Filamen~
Filament tubes,
tubes, invented
invented by by Coolidge
Coolidge in in 1913,
1913, are
are by by far
far the more
the more
widely
widely used
used\..\ They
They consist
consist of
of an
an evacuated
evacuated glass envelope
glass envelope which
which insulates
insulates
the
the anode
anode at at one
one end
end from
from the
the cathode
cathode at at the
the other,
other, the
the cathode being aa
cathode being
tungsten
tungsten filament
filament and
and the
the anode
anode a
a water-cooled
water-cooled block
block of
of copper
copper con-
con-
taining the
taining the desired
desired target
target metal
metal as
as aa small
small insert
insert at
at one
one end.
end. Figure
Figure 1-12.
1-12
 ......

18
00

PROPERTIES OF X-RAYS
"tl
FIG. 1-12. Sealed--<>ii nonshockproof filament x-ray tube. (Courtesy of Machlett Laboratories, Inc.) l:C
o
"tl
trl
l:C
glass ~
trl
tungsten filament U1

,/,// ///
o
"l

,~
~>
cooling water #// //
><
U1

to transformer

target /// & 9'

ij'/ // /ff/

[CHAP.
beryllium window x-rays metal focusing cup
;.
~
FIG. 1-13. Cross section of sealed-off filament x-ray tube (schematic).

1
1-7)
1-7] X-EAY8
PRODUCTION OF X-RAYS 19
19

is
is a
a photograph
photograph of of such
such a a tube,
tube, and Fig. Fig. 1-13 shows its its internal
internal construc-
construc-
tion.
tion. One leadlead of of the
the high-voltage
high-voltage transformer
transformer is is connected
connected to to the
the fila-
fila-

ment and the the other

other to to ground,
ground, thethe target
target being
being grounded
grounded by by its
its own cooling-
cooling-
water
water connection.
connection. The filament filament is is heated
heated by filament current
by a filament current of of about
33 amp
amp and emits emits electrons
electrons which are rapidly drawn to
are rapidly to the
the target
target byby thethe
high voltage
high voltage across
across the
the tube.
tube. Surrounding
Surrounding the
the filament
filament is
is a small
small metal
cup maintained at
cup maintained at the
the same high high (negative)
(negative) voltage
voltage as as the
the filament:
filament: it it

therefore
therefore repels
repels the
the electrons
electrons and tends
tends to
to focus
focus them into
into a
a narrow region
region
of
of the
the target,
target, called
called thethe focal
focal spot.
spot. X-rays
X-rays are are emitted
emitted from the the focal
focal
spot
spot in
in all
all directions
directions and escape
escape from the
the tube
tube through
through two or
or more win-
dows in in the
the tube
tube housing.
housing. Since
Since these
these windows must be
be vacuum tight
tight
and yetyet highly
highly transparent
transparent t.o to x-rays,
x-rays, they
they are are usually
usually made of of beryllium,
beryllium,
aluminum,
aluminum, or or mica.
mica.
Although
Although one might think that
might think that an x-rayx-ray tubetube would operate
operate only only from
aa DC source,
source, since
since the
the electron
electron flmv
flow must occur occur onlyonly inin one
one direction,
direction, it. it is
is

actually possible to
actually possible to operate
operate a a tube from an AC source source such
such asas a a transformer
transformer
because
because of of thethe rectifying properties of
rectifying properties of the
the tube
tube itself.
itself. Current
Current exists
exists
during
during the
the half-cyrIe
half-cycle in
in which the
the filament
filament is
is negative
negative with respect
respect to
to the
the
target; during
target; during the
the reverse
reverse half-cycle
half-cycle the
the filament
filament is
is positive,
positive, but
but no elec-
elec-
trons
trons cancan flowflow since
since onlyonly the
the filament
filament is is hot
hot enough
enough to to emit
emit electrons.
electrons.
Thus aa simple
simple circuit
circuit such
such as
as shown in
in Fig.
Fig. 1-14
1-14 suffices
suffices for
for many
many installa.-
installa-
tions, alt.hough
tions, although more elaborate
elaborate circuits, containing rectifying
circuits, containing rectifying tubes, tubes, smooth-
ing
ing capa<"itors,
capacitors, and voltage voltage stabilizers,
stabilizers, are are often
often used,
used, particularly
particularly when
the
the x-ray intensity must.
x-ray intensity must be be kept
kept constant
constant withinwithin narrow limits. limits. In
In Fig.
Fig.
1-14, the
1-14, the \"oltage
voltage applied
applied to to the
the tube
tube is is controlled
controlled by by the
the autotransformer
autotransformer
whi('h
which controls
controls the the voltage
voltage applied
applied to to thethe primary
primary of of the
the high-voltage
high-voltage
transformer.
transformer. The voltmeter voltmeter shown measures measures the the input
input voltage
voltage but but may
may
be
be ealibrated,
calibrated, if if desired,
desired, to to read
read the
the output
output voltage
voltage applied
applied to
to the
the tube.
tube.

,,-ray
\-ray tub!'
tube

ri'ISZil ~
filament
filament
~~~~ transformer
high-voltage transformer 000000000
M AK Q-0-0-0 Q.ooo Q Q Q Q Q,Q Q .*

filament
filament
rheostat
rheostat
ground
ground

autotransformer
autotransformer """'"",,,onnC''''''''''
f 0000001)1)0
"
110
110 volts
volts AC

110 volts AC

FIG.
FIG. 1-14.
1-14. Wiring
Wiring diagram
diagram for
for self-rectifying
self-rectifying filament
filament tube.
tube.
 ~

20
aluminum-foil aluminum ('opper glass
copper
window, x-rays cathode coohng fins
I
I ~

PROPERTIES OP X-RAYS
o
."

~
o
"!I

~~
to transformer

needle yalye

to yscuum pump

FIG. 1-15. Cross section of Eras x-ray tube (schematic).

o
c

g;.

[CHAP.
-"

1
1-8)
1-8] DETECTION OF X-RAYS 23
23

electrons
electrons

x-rays

anode
t.arget
target
mptai
metal
fO('ai spot.

FIG.
FIG. I-Hi.
1-16. Redurtion
Reduction in
in apparent
apparent FIG. 1-17. S('hematirdrawingsoftwo
FIG. 1-17. Schematic drawings of two
size
size of
of fOl'al
focal flpOt.
spot. typef\
types of
of rotating
rotating anode for
for high-power
high -power
x-ray
x-rav tubes.
tubes.

Hince
Since an x-rayx-ray tuhe
tube isis lesR
less than 1 pen'ent efficient
percent efficient in producing x-rays
in producing x-rays
and Hinel'
since the
the diffraction
diffraction of of x-rayH
x-rays by by crystals
crystals is
is far
far less
less efficient
efficient than
than this,
this,
it
it follows
follows that
that the
the intensities
intensities of of diffracted
diffracted x-ray
x-ray beams are are extremely
extremely low.
low.
In fact,
fact, it
it may
may require
require asas much as as several
several hours
hours exposure
exposure to to a
a photographic
photographic
film
film inin order
order to to dl'tect
detect them at at all.
all. Constant efforts
efforts areare therefore
therefore being
being
made t.o to increase
increase thethe intensity
intensity of
of the
the x-ray
x-ray source.
source. One solution
solution to
to this
this
problem
problem is
is the
the rotating-anode
rotating-anodc tuiJe.
tube, in
in which rotation
rotation of
of the
the anode con-
con-
tinuously
tinuously brinl!;s
brings fresh
fresh target.
target metal
metal intointo the
the focal-spot
focal-spot areaarea and so so allows
allows
aa greater powE'r
greater power input input without
without l'xce:sive
excessive heating
heating of
of the
the anode.
anode. Figure
Figure 1-17
1-17
shows two designs designs that
that have been used successfully;
successfully; the
the shafts
shafts rotate
rotate
through
through vaeuum-tight
vacuum-tight seals seals in the tube
in the tube housing.
housing. SuehSuch tubes
tubes can operate
operate
at
at a a power level
power level 5 5 to
to 10
10 times
times higher than
higher than that that of
of a
a fixed-focus
fixed-focus tube,
tube, with
with
corresponding redu<"t.ions
corresponding reductions in in exposure
exposure time.time.

1-8
1-8 Detection
Detection ofof x-rays.
x-rays. The principal
principal means used used toto detect
detect x-ray
x-ray
beams areare fluorescent
fluorescent screens,
screens, photographic
photographic film,
film, and ionization
ionization devices.
devices.
Fluorescent
Fluorescent screens are made of
screens are of a
a thin
thin layer
layer of
of zinc
zinc sulfide,
sulfide, containing
containing
aa trace
trace of
of nickel,
nickel, mounted on a a cardboard
cardboard backing.
backing. (nder
Under thethe action
action of
of
x-rays,
x-rays, this
this compound
compound fluoresces
fluoresces in
in the
the visible
visible region,
region, i.e.,
i.e., emits
emits visible
visible
light,
light, in
in this
this case
case yellow
yellow light.
light. Although
Although most diffracted
diffracted beams are are too
too
weak to to be
be detected
detected byby this
this method,
method, fluorescent
fluorescent sel'Cens
screens are
are widely
widely used
in
in diffraction
diffraction work toto loeate
locate the position of
the position of the
the primary
primary beam when adjust- adjust-
ing
ing apparatus.
apparatus. A fluorescing crystal may
fluorescing crystal may also be used
also be used in
in conjunction
conjunction with
aa phototube;
phototube; thethe combination,
combination, ealled
called a a scintillation
scintillation counter,
counter, isis aa very
very
sensitive
sensitive detector
detector of
of x-rays.
x-rays.
24
24 PROPERTIES OF
PROPERTIES OF X-RAYS
X-RAYS [CHAP.
[CHAP. 1
1

(a)
(a)
Photographic film
Photographic film is affected
is affected by
by
x-rays in
x-rays in much
much the
the same way
same way as
as by
by
visible light,
visible light, and
and film
film isis the
the most
most
widely used
widely used means
means of
of recording
recording dif-
dif-
fracted x-ray
fracted x-ray beams.
beams. However, the
However, the
emulsion on
emulsion on ordinary film isis too
ordinary film too
thin to
thin to absorb
absorb much
much of
of the
the incident
incident
x-radiation, and
x-radiation, and only
only absorbed
absorbed x- x-
rays can
rays can be
he effective
effective in
in blackening
blackening
the film. For this reason,
the film. For this reason, x-ray
x-ray films
films
are made
are made with
with rather
rather thick
thick layers
layers of
of
emulsion on
emulsion on both
both sides
sides in order
in to
order to
increase the
increase the total
total absorption.
absorption. The
The
(h)
(h) grain size
size is also
is also made large
large for
for the
the
grain
purpose: this
same purpose: this has
has the
the unfor-
unfor-
t.unate consequence
tunate that x-ray
eonsequcnee that x-ray films
films
are grainy,
are grainy, not resolve
do not finc de-
rcsolve fine de-
K edge of A' edge of
tail, and cannot stand much
cannot stand mueh enlarge-
enlarge-
silver
bromine tail,

(0.48A).
(0.92A) mcnt.
ment.
V Because the
Because the mass absorption co-
absorption co-
efficient of any
efficient of any substance varies with
substance varies with
wavelength,
wavelength, it follows that
it follows that film
film sen-
sen-
sitivity,
sitivity, i.e.,
i.e., the amount of blacken-
of blacken-
ing
ing caused by x-ray beams of
by x-ray of the
the
same int.ensity,
intensity, depends
depends on on their
their

(c) wavelength.
wavelength. This should he
be borne
borne
Ib
lh mind whenever whitc white radiation is is

reeorded
recorded photogruphieally;
photographically; for for one
one
thing,
thing, this
this sensitivity
sensitivity variation al- al-

ters
ters the
the effective
effective shapeshape of of the (:on-
con-
tinuous
tinuous speetrum.
spectrum. Figure Figure 1-18(a)
l-18(a)
~ shows
shows thethe intensity
intensity of
of the
the cont.inu-
continu-

--
ous
ous spe('trum
spectrum as function of
as aa funetion of wave-
wave-
length
length and (b)
and (b) the variation of film
the variation of film

I
""r---. sensith'ity.
sensitivity. This This latter curve is
latter curve is

merely aa plot plot of of the

the mass ahsorp-
mass absorp-
() llii 1 1 II 1 [)5
1 211 merely
tion
tion eoeffi('ient
coefficient of of silver
silver bromide,
bromide,
11X (angHtroms)
(angstroms)
the
the aetive
active ingredient
ingredient of of the
the emul-
emul-
FIG. I-Is'
FIG. 1-18. Relation
Relation between
between film film sion, and is
sion, and is marked
marked hy by diseontinui-
discontinui-
sensitivity
sensitivity und and effeetive
effective shupe
shape of of con-
con-
ties at
tics at thc
the K K absorption
absorption edgesedges of of
tinuous ~pe(tlum
tinuous spectrum (schematir):
(schematic): (u) (a) con-
con-
tinuous silver
silver and
and hromine.
bromine. (Xote, (Note, inciden-
inciden-
tinuousspectrum
spectrum fl'om from aa tungsten
tungsten tal'get
target
at
at 4040 kv;
kv; (b)
(b) film
film sensitivity;
sensitivity; (c)
(c) blark-
black- tally,
tally, how
how muehmuch more more sensitive
sensitive thethe
ening rUl've for spertrum
ening curve for spectrum shown
shown in
in (Il).
(a). film
film is
is to
to t.he
the KA' radiation
radiation from
from cop-
cop-
1-91
1-9] SAFETY PRECAUTIONS
SAFETY PRECAUTIONS 25
25

per than
per than to
to the
the KK radiation
radiation from from molybdenum,
molybdenum, other other things
things being
being equal.)
equal.)
Curve (c) of
Curve (c) of Fig. Fig. 1-18
1-18 shows
shows the
the net
net result, namely
result, namely the
the amount
amount of film
of film
blackening caused
blackening caused by by the
the various
various wavelength
wavelength components
components of the continu-
of the continu-
ous spectrum,
ous spectrum, or or what
what might
might be be called
called thethe "effective
"effective photographic
photographic in- in-
tensity" of
tensity" of the
the continuous
continuous spectrum.
spectrum. These These curves
curves areare only
only approximate,
approximate,
however, and
however, and in practice itit is
in practice is almost
almost impossible
impossible to to measure
measure photographi-
photographi-
cally
cally the
the relative
relative intensities
intensities of
of two
two beams
beams of
of different
different wavelength.
wavelength. On
On the
the
other hand,
other hand, thethe relative
relative intensities
intensities of of beams
beams of of the same wavelength
the same wavelength can can
be accurately
be accurately measured
measured by by photographic
photographic means, means, and and such
such measurements
measurements
are described
are described in in Chap.
Chap. 6. 6.
Ionization devices
lonization devices measure
measure the the intensity
intensity of of x-ray
x-ray beams
beams by by the
the amount
amount
of ionization they
of ionization they produce produce in
in a
a gas.
gas. X-ray quanta
X-ray quanta can
can cause
cause ionization
ionization
just as
just as high-speed
high-speed electrons
electrons can,can, namely,
namely, by by knocking
knocking an an electron
electron outout ofof aa
gas molecule
gas molecule and leaving
leaving behind
behind a
a positive
positive ion.
ion. This phenomenon
phenomenon can
can be
be
made the
made the basis
basis of of intensity
intensity measurements
measurements by by passing
passing the x-ray
the x-ray beam
through aa chamber
through chamber containing
containing aa suitable
suitable gas gas and two electrodes
electrodes having
having aa
constant potential
constant potential difference
difference between
between them. them. The electronselectrons are attracted
are attracted
to the
to the anode
anode andand thethe positive
positive ions ions toto the
the cathode
cathode and aa currentcurrent is is thus
thus
produced
produced in
in an
an external
external circuit.
circuit. In
In the
the ionization
ionization chamber,
chamber, this
this current
current is
is

constant for
constant for a constant x-ray
a constant x-ray intensity,
intensity, and the the magnitude
magnitude of of the
the current
current
is aa measure
is measure of the x-ray
of the x-ray intensity.
intensity. In In the Geiger counter
the Geiger counter and proportional
proportional
counter,
counter, this
this current
current pulsates,
pulsates, and the
the number of
of pulses
pulses per
per unit
unit of
of time is is

proportional
proportional to
to the
the x-ray intensity.
x-ray intensity. These deviees
devices are
are diseussed
discussed more
fully
fully in Chap. 7.
in Chap. 7.

In
In general,
general, fluoreseent
fluorescent screens
screens are are used today
today onlyonly forfor the deteetion
detection of of

x-ray beams, while photograph,ic

x-ray beams, while photographic film
film and the
the various
various forms of
of counters
permit
permit both detection and measurement of
both detection of intensity.
intensity. Photographic
Photographic film film
is the most widely
is the most widely used used method of
of observing
observing diffraction
diffraction effeets,
effects, because it
it

can
can record
record a a number of of diffracted
diffracted beams at one timeat one time and their relative
their relative
positions
positions in in space
space and the film
and the film cancan be be used as as a basis
basis for
for intensity
intensity measure-
measure-
ments if
ments if desired.
desired. Intensities
Intensities can can be measured much more rapidly rapidly withwith
counters,
counters, and and these
these instruments
instruments are are becoming
becoming more and more popular popular for for
quantitative
quantitative work.
work. However,
However, they
they record
record only
only one diffracted beam at a
diffraeted
time.
time.

1-9
1-9 Safety
Safety precautions.
precautions. The The operator
operator ofof x-ray
x-ray apparatus
apparatus is is exposed
exposed
to
to two
two obvious
obvious dangers,
dangers, electrie
electric shock
shock and
and radiation
radiation injury,
injury, but both ofof
these
these hazards
hazards can
can be
be reduced
reduced toto negligible proportions
negligible proportions by
by proper
proper design
design of
of
equipment
equipment andand reasonable
reasonable care
care on
on the
the part
part of
of the
the user.
user. Nevertheless,
Nevertheless, itit is
is

only prudent for the x-ray

only prudent for the x-ray worker
worker to
to be
be continually
continually aware
aware of
of these
these hazards.
hazards.
The danger of
The danger of electric
electric shock
shock isis always
always present
present around
around high-voltage
high-voltage appa-
appa-
ratus. The anode end of most
ratus. The anode end of most x-ray x-ray tubes
tubes is
is usually
usually grounded and
grounded and there-
there-
fore safe, but
fore safe, but the
the cathode
cathode end
end is
is a
a source
source of
of danger.
danger. GasGas tubes
tubes and
and filament
filament
26
26 PROPERTIES OF X-RAYS [CHAP.
[CHAP. 1
1

tubes of
tubes of the
the nonshockproof
nonshockproof variety
variety (such
(such as
as the
the one
one shown in in Fig.
Fig. 1-12)
1-12)
be so
must be so mounted that
that their
their cathode
cathode end
end is
is absolutely
absolutely inaccessible
inaccessible to
to
the user
the user during
during operation;
operation; this
this may
may be
be accomplished
accomplished byby placing
placing the
the cathode
cathode
end below
end below aa table
table top,
top, in
in aa box,
box, behind
behind aa screen,
screen, etc.
etc. The installation
installation
should be
should be so
so contrived
contrived that
that it is
it is impossible
impossible for for the
the operator
operator to to touch
touch the the
high-voltage
high-voltage parts parts without
without automatically disconnecting
automatically disconnecting the
the high voltage.
high voltage.
Shockproof sealed-off
Shockproof sealed-off tubestubes areare also
also available:
available: thesethese are are encased
encased in in aa
grounded
grounded metal
metal covering,
covering, and
and an
an insulated, shockproof
insulated, shockproof cable
cable connects
connects the
the
cathode end
cathode end to to the
the transformer.
transformer. Being Being shockproof,
shockproof, such a tube has the
such a tube has the
advantage that
advantage that it it need
need not not bebe permanently
permanently fixed fixed inin position
position but but maymay be be
set up
set up inin various
various positions
positions as as required
required for for particular
particular experiments.
experiments.
radiation hazard
The radiation hazard is is due
due toto the
the fact
fact that
that x-rays
x-rays can can kill
kill human tis- tis-
sue; in fact,
sue; in fact, it it is
is precisely
precisely thisthis property
property which is is utilized
utilized in in x-ray
x-ray therapy
therapy
for the
for the killing
killing of of cancer
cancer cells.
cells. The biological
biological effects
effects of of x-rays
x-rays include
include burns
bums
(due
(due to
to localized
localized high-intensity
high-intensity beams),
beams), radiation
radiation sickness
sickness (due
(due to
to radia-
radia-
tion received
tion received generally
generally by by the
the whole
whole body),
body), and,
and, at at Iia lower
lower level
level of of radia-
radia-
tion intensity, genetic
tion intensity, genetic mutations.
mutations. The burns bums are are painful
painful and may may be be
difficult,
difficult, if
if not
not impossible,
impossible, to
to heal.
heal. Slight exposures
Slight exposures to
to x-rays
x-rays are
are not
not
cumulative,
cumulative, but but above aa certain level called
certain level called thethe "tolerance
"tolerance dose,"dose," they they
do have
have aa cumulative
cumulative effect effect and can can produre
produce permanent
permanent injury. injury. The
x-rays
x-rays used
used in diffraction are
in diffraction particularly harmful
are particularly because they
harmful because they have rela- rela-
tively
tively long
long wavelengths
wavelengths and are are therefore
therefore easily
easily absorbed
absorbed by by the body.
the body.
There
There is is no
no excuse
excuse today
today forfor receiving
receiving serious
serious injuries
injuries as as early
early x-ray
x-ray
workers
workers did did through
through ignorance.
ignorance. There There would probablyprobably be be no accidents
accidents if if

x-rays
x-rays were
were visible
visible and produced
produced an immediate
immediate burning sensation, but
burning sensation,
they
they are
are invisible
invisible and bums burns maymay not not bebe immediately
immediately felt. felt. If
If the body
the body
has
has received
received general
general radiation
radiation above
above the
the tolerance
tolerance dose,
dose, thE'
the first
first noticeable
noticeable
effect will
effect will be be a a lowering
lowering of of the
the white-blood-cell
white-blood-cell count, count, so so periodic
periodic bloodblood
counts
counts areare advisable
advisable jf if there
there isis any
any doubt
doubt about the
the general
general level
level of
of in-
in-
tensity
tensity in
in the
the lIiboratory.
laboratory.
The safest
safest proredure
procedure for for the experimenter to
the experimenter to follow
follow is: is: first,
first, toto locate
locate
the primary
the primary beam from the
from the tube tube with
with aa small
small fluorescent
fluorescent screen
screen fixed
fixed to
to
the
the end
end ofof a a rod
rod and thereafter
thereafter avoidavoid it;it; and second,
second, to to make sure sure that
that hehe
is
is well
well shielded
shielded by by lead
lead or or lead-glass
lead-glass screens
screens from the radiation scattered
the radiation scattered
by
by the
the camera
camera or or other
other apparatus
apparatus which may may be be in
in the
the path
path of of the
the primary
primary
beam.
beam. Strict
Strict and and constant attention to
constant attention to these
these precautions
precautions will will ensure
ensure
safety.
safety.

PROBLEMS

1-1.
1-1. What is is the
the frequency
frequency (per
(per second)
second) and
and energy
energy per
per quantum
quantum (in(in ergs)
ergs) of
of
x-ray
x-ray beams
beams of wavelength O.71A
of wavelength 0.71 A (Mo and l.54A
Ka) and
(Mo Ka) 1.54A (Cu
(Cu Ka)?
Ka)l
1-2.
1-2. Calculate
Calculate the
the velocity
velocity and
and kinetic
kinetic energy
energy with
with which the
the electrons
electrons strike
strike
the
the target
target of
of an
an x-ray
x-ray tube
tube operated
operated atat 50,000
50,000 volts.
volts. What isis the
the short-wavelength
short-wavelength
 PROBLEMS
PROBLEMS 27
27

limit of
limit of the
the continuous
continuous spectrum emitted
spectrum emitted and the maximum
and the maximum energy
energy per
per quantum
quantum
of radiation?
of radiation?
1-3. Graphically
1-3. Graphically verify
verify Moseley's
Moseley's law
law for
for the K{31 lines
the K($\ lines of
of Cu,
Cu, Mo, and W.
Mo, and W.
1-4. Plot
1-4. Plot the
the ratio
ratio of
of transmitted
transmitted to
to incident
incident intensity
intensity vs. thickness of
vs. thickness of lead
lead
sheet for
sheet for Mo Ka radiation
Mo Kot radiation and
and aa thickness
thickness range
range of
of 0.00
0.00 to 0.02 mm.
to 0.02 mm.
1-5. Graphically
1-5. Graphically verify
verify Eq. (1-13) for
Eq. (1-13) for aa lead
lead absorber
absorber and Mo
Ka, Rh
and Mo Kot, Ka, and
Rh Ka, and
Ag Ka radiation.
Ag Karadiation. (The
(The mass
mass absorption
absorption coefficients
coefficients of
of lead
lead for
for these
these radiations
radiations
are 141,
are 141, 95.8,
95.S, and
and 74.4,
74.4, respectively.)
respectively.) From
From the
the curve,
curve, determine
determine the
the mass
mass ab-
ab-
sorption coefficient
sorption coefficient of
of lead
lead for
for the
the shortest
shortest wavelength
wavelength radiation
radiation from
from a
a tube op-
tube op-
erated at 60,000
erated at 60,000 volts.
volts.
1-6. Lead
1-6. Lead screens
screens for
for the
the protection
protection of
of personnel
personnel in
in x-ray
x-ray diffraction
diffraction laboratories
laboratories
are usually
are usually at
at least mm
least 1I mm thick.
thick. Calculate
Calculate the
the "transmission
"transmission factor"
factor" (/trans.
(Itran //incident)
[Incident) .!
of such
of such aa screen
screen for
for Ka, Mo Kot,
Cu Kot, Ka, and thethe shortest
shortest wavelength
wavelength radiation
radiation from
from aa
tube operated
tube operated at
at 60,000
60,000 volts.
volts.
1-7. (a)
1-7. (a) Calculate
Calculate thethe mass
mass and linear
linear absorption
absorption coefficients
coefficients of of air
air for Cr Ka
for Cr
radiation. Assume that
radiation. that air
air contains
contains 80 1'0 percent
percent nitrogen
nitrogen and 20 20 percent
percent oxygen
oxygen
by weight,
by weight. (b)(b) Plot
Plot the
the transmission
transmission factor
factor ofof air for Cr Ka radiation
air for radiation and aa path
path
length of
length of 0 to
to 20
20 cm.
cm.
1-8. A sheet
1-8. of aluminum 11 mm thick
sheet of thi('k reduces
redu('es the
the intensity
intensity ofof aa monochromatic
x-ray beam to
x-ray to 23.9 percent of
23.9 percent of its
its original
original value.
value. What is is the
the wavelength
wavelength of of the
the
x-rays?
x-rays?
1-9.
1-9. Calculate the K
Calculate the K excitation
excitation voltage
voltage of of copper.
copper.
1-10. Calculate the
1-10. Calculate the wavelength
wavelength of the Lm absorption
of the absorption edge
edge of molybdenum.
of molybdenum.
1-11. Calculate the
1-11. Calculate the wavelength
wavelength of of the
the Cu Ka\Kal line.
line.
1-12.
1-12. Plot
Plot the
the curve
curve shown in Fig. 1-10 and save it
in Fig. it for
for future reference.
reference.
1-13.
1-13. What voltage
voltage must be be applied
applied to to aa molybdenum-target
molybdenum-target tube tube in
in order
order
that
that the
the emitted
emitted x-rayf:;
x-rays excite
excite K
A' fluorescent
fluorescent radiation
radiation from a piece
piece of
of copper
copper placed
placed
in
in the
the x-ray
x-ray beam?
beam? What is is the
the wavelength
wavelength of of the
the fluorescent
fluorescent radiation?

In
In Problems 14 and 15
Problems 14- 15 take
take the
the intensity
intensity ratios of Ka to
ratios of to K{3
K@ in unfiltered
unfiltered radia-
tion Table 1-1.
from Table
tion from 1-1.

1-14.
1-14. Suppose
Suppose that that It a ni(~kel
nickel filter
filter is
is required
required to to produce
produce an intensity intensity ratio of of

Cu Ka to to Cu K{3 of 100/1
K/3 of 100/1 in in the
the filtered
filtered beam. Calculate
Calculate the thickness of of the
the fil-
fil-

ter
ter and
and the
the transmisRion
transmission factor factor for
for the
the euCu Ka line.
line. (J.I./
(JJL/P p of
of nickel
nickel forfor Cu K{3 Kft ra-
ra-

diation == 286
diation 286 cm 2 Y/gm.)
gin.)
1-15.
1-16. Filters
Filters for
for CoCo K K radiation
radiation are are usually
usually made of of iron
iron oxide
oxide (Fe203)
(Fe 2 03) powder
powder
rather than
rather than iron
iron foil.
foil. If
If a
a filter
filter contains
contains 5 mg Fe20a/cm2,
Fe 2 3 /cm
2
, what is
is the transmission
transmission
factor
factor for
for the
the CoCo KaKa line?
line? WhatWhat is is the
the intensity
intensity ratio
ratio of of CoCo KaKa to Co K{3
to Co KQ inin the
the
filtered
filtered beam?
beam? (Density
(Density of Fe220a3 == 5.24
of Fe 5.24 gm/cm
3
/i/P of
gm/cm3 , Jl./p
,
of iron
iron for Co Ka
for Co Ka radiation
radiation
== 59.5 cm22/gm,
59.5 cm M/P of
/gm, Jl./p of oxygen
oxygen for for CoCo KaKa radiation
radiation = = 20.2, pt/P of
20.2, Jl./p of iron
iron for Co KfJ
for Co Kfi
radiation = 371,
radiation = JJL/P of
371, J.I./p of oxygen
oxygen for for CoCo K{3
K0 radiation =
radiation = 15.0.) 15.0.)
1-16.
1-16. What
What is is the
the power
power input
input to to an
an x-ray
x-ray tube
tube operating
operating at at 40,000
40,000 volts
volts and
and
aa tube
tube current
current of of 25 ma? If
25 rna? If the
the power
power cannot
cannot exceed
exceed this
this level,
level, what
what is
is the
the maxi-
maxi-
mum
mum allowable
allowable tubetube current
current at at 50,000
50,000 volts?
volts?
1-17.
1-17, A A copper-target
copper-target x-ray x-ray tube
tube is is operated
operated at at 40,000
40,000 volts volts and
and 25 25 rna.
ma. TheThe
efficiency
efficiency ofof anan x-ray
x-ray tubetube is is so
so low
low that,
that, for
for all
all practical
practical purposes,
purposes, one one maymay as-as-

sume that all the input energy

sume that all the input energy goes goes into
into heating
heating the
the target.
target. If
If there
there were
were no
no dissi-
dissi-
28
28 PROPERTIES OF X-RAYS [CHAP.
[CHAP. 1
1

pation
pation ofof heat
heat by
by water-cooling,
water-cooling, conduction,
conduction, radiation,
radiation, etc.,
etc., how long
long would it
it

take
take aa lOO-gm
100-gm copper target to
copper target to melt?
melt? (Melting
(Melting point
point of copper =
of copper = 1083C,
1083C, mean
specific heat =
specific heat
= 6.65
6.65 cal/mole/oC,
cal/mole/C, latent
latent heat
heat ofof fusion
fusion == 3,220
3,220 cal/mole.)
cal/mole.)
1-18. Assume that
1-18. that the
the sensitivity
sensitivity of x-ray
of film is proportional to
x-ray film is proportional to the
the mass ab-
ab-
sorption
sorption coefficient
coefficient of
of the
the silver
silver bromide in
in the
the emulsion
emulsion for
for the
the particular
particular wave-
length
length involved.
involved. What,
What, then,
then, is
is the
the ratio
ratio of
of film sensitivities to
film sensitivities Kat and Mo Kat
to Cu Ka Ka
radiation?
radiation?
 CHAPTER
CHAPTER 22

THE GEOMETRY
THE GEOMETRY OF
OF CRYSTALS
CRYSTALS

2-1 Introduction.
2-1 Introduction. Turning
Turning from
from the
the properties
properties ofof x-rays,
x-rays, we must now
we must now
consider the
consider the geometry
geometry andand structure
structure of
of crystals
crystals in
in order
order toto discover
discover what
what
there isis about
there about crystals
crystals in
in general
general that
that enables
enables them
them to to diffract
diffract x-rays.
x-rays. We We
must also
must also consider
consider particular
particular crystals
crystals of
of various
various kinds
kinds and
and how
how the
the very
very
large
large number of
number of crystals
crystals found
found in
in nature
nature are
are classified
classified into
into aa relatively
relatively
small
small number of groups.
number of groups. Finally,
Finally, we will
will examine
examine the
the ways
ways in
in which
which the
the
orientation of
orientation of lines
lines and
and planes
planes inin crystals
crystals can
can be
be represented
represented in in terms
terms ofof
symbols or
symbols or in
in graphical
graphical form.
form.
crystal may
A crystal may bebe defined
defined as
as aa solid
solid composed
composed of
of atoms arranged
arranged in in aa pat-
pat-
tern periodic
tern periodic in
in three
three dimensions.
dimen8ions. As such,such, crystals
crystals differ
differ in
in aa fundamental
fundamental
way from
way from gases
gases and
and liquids
liquids because
because the the atomic
atomic arrangements
arrangements in in the
the latter
latter
do not
do not possess
possess the
the essential
essential requirement
requirement of
of periodicity.
periodicity. Not all all solids
solids are
are
crystalline, however;
crystalline, however; some
some are amorphous, like glass,
are amorphous, like glass, and do not have
not have any
any
regular interior arrangement
regular interior arrangement of of atoms.
atoms. is, in
There is, in fact,
fact, no
no essential
essential
difference between an amorphous
difference between an amorphous solid
solid and a liquid,
liquid, and the former is
is

often referred to as an "undercooled liquid."

often referred to as an "undercooled liquid."

2-2
2-2 Lattices.
Lattices. In
In thinking
thinking about
about crystals,
crystals, it it is
is often
often convenient to ig- ig-
nore the,
nore the, actual
actual atoms
atoms composing
composing the
the crystal
crystal and their
their periodic
periodic arrange-
arrange-
ment
ment in in space,
Space, andand to to think
think instead
instead of of aa set
set of
of imaginary
imaginary points points which has has
aa fixed
fixed relation
relation in in space
space to
to the
the atoms of
of the
the crystal
crystal and may be regarded
regarded
as
as aa sort
sort of of framework
framework or or skeleton
skeleton on which the the actual
actual crystal
crystal is is built
built up.
up.
This
This setset ofof points
points can
can be
be formed
formed as
as follows.
follows. Imagine
Imagine space
space to
to be divided
divided
by
by three
three sets
sets ofof planes,
planes, thethe planes
planes in in each
each setset being
being parallel
parallel and equallyequally
spaced.
spaced. This
This division
division of
of space
space will
will produce
produce a set
set of
of cells
cells each
each identical
identical in in
size, shape,
size, shape, and
and orientation
orientation to
to its
its neighbors.
neighbors. Each
Each cell
cell is is aa parallelepiped,
parallelepiped,
since
since its
its opposite
opposite faces
faces are parallel and
are parallel and each
each face
face isis a
a parallelogram._
parallelogram.^ The The
space-dividing
space-dividing planes planes will
will intersect
intersect each each other
other inin aa set
set ofof lines
lines (Fig.
(Fig. 2-1),
2-1),
and
and these
these lines
lines in
in turn
turn intersect
intersect in in the
the set
set of
of points
points referred
referred to to above.
above. A A
set
set of
of points
points so so formed
formed hashas an an important
important property:
property: it consti.tutes a point
it constitutes a point
lattice, which is defined as an array of points in
lattice, which is defined as an array of points
in 8pace
space so so arranged
arranged that that each
each
point has identical 8urroundings.
point has identical surroundings. By
By "identical
"identical surroundings"
surroundings*' we
we mean
mean
that
that the
the lattice
lattice of of points,
points, when
when viewed
viewed in in aa particular
particular direction
direction fromfrom oneone
lattice point, would have
lattice point, would have exactly exactly the
the same
same appearance
appearance when
when viewed
viewed in
in the
the
same direction from
same direction from any any other
other lattice
lattice point.
point.
Since
Since allall the
the cells
cells ofof the
the lattice
lattice shown
shown in Fig. 2-1
in Fig. 2-1 areare identical,
identical, we we may
may
choose anyone,
choose any one, for
for example
example the
the heavily
heavily outlined
outlined one,
one, as
as a
a unit
unit cell.
cell. The
The
29
29
 30
30 THE
THE GEOMETRY
GEOMETRY OF
OF CRYSTALS
CRYSTALS [CHAP. 22
[CHAP.

FIG. 2-1.
FIG. 2-1. A point
A point lattice.
latti!'e.

size and
size and shape
shape ofof the
the unit
unit cell
cell can
('an inin turn
turn be he described
des('ribed by by the
the three
three vec-vec-
tors a,
tors* a, b,
b, and cc drawn
and drawn fromfrom oneone corner
corner of of the
th(' cell
cell taken
taken as as origin
origin (Fig.
(Fig.
2-2). These
2-2). These vectors
vectors define
define the
the cell
cell and are called the
are called the crystallographic
crystallographic axes axes
of the cell.
of the cell. They
They maymay also
also he
be described
described in
in terms
terms of
of their
their lengths
lengths (a,
(a, b,
6, c)
c)
and the angles
and the angles between
between them (a, {3,
(a, ft 7). -y). These lengths
lengths and angles
angles are the
the
lattice constants or
lattice constants or lattice parameters of
lattice parameters of the
the unit
unit cell.
cell.

Note
Note that
that the vectors a,
the vectors b, c
a, b, c define,
define, not not only
only the
the unit
unit cell, but also the
cell, but

whole
whole point
point lattice
lattice through
through the
the translations
translations provided
provided by by these vectors.
In other words,
In other words, the
the whole
whole set
set of
of points
points in
in the
the lattice
lattice can be produced
produced by by
repeated
repeated action
action of
of the
the vectors
vectors a, b,
a, b, c
c on one lattice
lattice point
point located at
at the
the
origin,
origin, or,or, stated
stated alternatively,
alternatively, the the
vector
vector coordinates
coordinates of of any
any point
point in in the
the
lattice are Pa,
lattice are Pa, Qb, Qb, and Rc,
/fc, where
P,
P, Q, and R are
Q, and are whole numbers. It
whole numbers. It
follows that the
follows that the arrangementarrangement of
of
points
points inin a a point
point lattice
lattice isis absolutely
absolutely
periodic
periodic in three dimensions, points
in three dimensions, points
being
being repeated
repeated at at regular
regular intervals
intervals
along
a~------------ ___
along anyany line
line one
one chooses
chooses to to draw
draw
through
through the the lattice.
lattice. FIG. 2-2.
FIG. 2-2. unit cell.
A unit cell.

2-3
2-3 Crystal
Crystal systems.
systems, <J.n
(jn dividing
dividing space
space by
by three
three sets
sets of
of planes, we can
planes, we can
of
of course
course produce
produce unit
unit cells
cells of
of various
various shapes,
shapes, depending
depending on how we ar-
on how we ar-

range
range the
the planes,:) For example, ifif the
planesT) For example, the planes
planes in
in the
the three sets are all equally
three sets are all equally

* Vectors
Vectors are
are here
here represented
represented byby boldface
boldface symbols.
symbols. The
The same symbol in
same symbol in italics
italics

stands
stands for
for the
the absolute
absolute value
value of
of the
the vector.
vector.
 2-3)
2-3] CRYSTAL SYSTEMS
CRYSTAL SYSTEMS 31
31

TABLE 2-1
TABLE 2-1

SYSTEMS AND
CRYSTAL SYSTEMS
CRYSTAL AND BRAVAIS
BRAVAIS LATTICES
LATTICES

(The symbol
(The ~ implies
symbol ^ implies nonequality
nonequnlity byby reason
reason of
of symmetry.
symmetry. Accidental
Accidental equality
equality
may occur,
may occur, as
as shown
shown by
by an
an example
example in
in Sec.
Sec. 2-4.)
2-4.)
Bravais Lattice
System Axials lengths and angles
lattice symbol
I
Simple P
Cubic Three equal axes at right angles
Body-centered I
II = I) = r, a=~=Y=9OO
Face-centered F
Three axes at right angles, twa equal Simple P
Tetragonal II = b '" l', a=~=Y=9OO Bady-centered I

Simple .P
Orthorhambic Three unequal axes at right angles Body-centered I
<I ~ Ii # c, a = ~ = Y = 900 Base-centered C
Face-centered F
Three equal axes, equally Inclined
Rhombohedral * II= b = c, a=~=Y*9ao
Simple p
Two equal coplanar axes at l:ZOO,
Hexagonal third axis at right angles Simple P
II = b # c, a = ~ = 90a , ')' = 121f
Three unequal axes,
one pair not at right angles
Simple P
Monoclinic Base-centered C
II ~ b ~ c, a=Y=9OO;O~

Three unequal axes, unequolly inclined

Triclinlc
and nane at right angles Simple P
II ~ I) # c, a#~#Y#9ao

* Also
Also called
called trigonal.
trigonal.

spaced
spaced andand mutually
mutually perpendicular,
perpendicular, the the unit
unit cell
cell is
is cubic.
cubic. In this this case the
vectors a,
vectors a, b, b, c
c are
are all
all equal
equal and at
at right angles
right angles to
to one another,
another, or a= = bb == cc
and
and aa =
= {j =
= 'Y
7 = 90.
90. By
By thus
thus giving special
giving special values to the axial
axial lengths
lengths
and
and angles,
angles, we we can can produce
produce unit unit cells
cells of of various
various shapes
shapes and and therefore
various
various kinds
kinds of
of point lattices,
point lattices, since
since the
the points
points of
of the lattice
lattice are
are located
located atat
the cell corners.
the cell corners. It
It turns
turns out
out that
that only
only seven
seven different
different kinds
kinds of
of cells
cells are
are
necessary
necessary to to include
include all all the
the possible
possible point
point lattices.
lattices. These
These correspond
correspond to to
the seven crystal
the seven crystal systems systems into
into which
which all
all crystals
crystals can
can b~
be classified.
classified. These
These
systems
systems are are listed
listed in in Table
Table 2-1.2-1.
Seven
Seven different
different point point lattices
lattices can
can be be obtained
obtained simply
simply by by putting
putting points
points
at the corners
at the corners of
of the
the unit
unit cells
cells of
of the
the seven
seven crystal
crystal systems.
systems. However,
However,
there
there are
are other
other arrangements
arrangements of of points
points which
which fulfill
fulfill the
the requirements
requirements of of aa
point lattice, namely,
point lattice, namely, that
that each
each point
point have
have identical
identical surroundings.
surroundings. The
The
French
French crystallographer
crystallographer Bravais Bravais worked
worked on on this
this problem
problem and and inin 1848
1848
demonstrated
demonstrated that
that there
there are
are fourteen
fourteen possible point
possible point lattices
lattices and
and no
no more;
more;
this
this important
important result result is commemorated by
is commemorated by our
our use
use of of the terms BravaiB
the terms Bravais
32
32 THE GEOMETRY
THE GEOMETRY OF
OF CRYSTALS
CRYSTALS [CHAP. 22
[CHAP.

HIMPLE
SIMPLE BODY -CENTERED FACE-C
BODY-CENTERED 'ENTERED
FACE-CENTERED
1

('{TRW (P)
CUBIC (P) CUBIC' (/)
CUBIC (1) CVBI(' (F)
CUBIC (P)

SIMPLE BOD
BODY CENTERED
-CENTERED
Y-( SIMPLE BODY-CENTERED
TETRAGONAL TETRAGONAL ORTHORHO:\IBJ(' ORTHORHOMBIC
ORTHORHOMBIC
(P)
(P) (1)
(/) (P)
(P) (I)
(/)

BASE-CENTERED FACE-CENTERED RHOMBOHEDRAL

RHOI\IBOHEDRAL HEXAGONAL
ORTHORHO:-'1BIC
ORTHORHOMBIC 1

ORTHORHOMBIC
ORTHORHOI\1BIC (ll)
(/?) (P)
(C)
(O (F)
(F)

SIMPLE BASE-CENTERED TRICLlNIC

TRICLINIC (P)
(P)
MONOCLINIC (Pl ~IONOCLINJ('
MONOCLINIC 1

(P) (')
(C)

FIG.
FIG. 2-3.
2-3. The fourteen
fourteen BraYais
Bravais lattices.
lattices.

lattice and point

lattice and point lattice
lattice as
as synonymous.
synonymous. For example,
example, ifif a
a point
point is
is placed
placed
at the center of
at the center of each
each cell
cell of
of a
a cubic
cubic point lattice, the
point lattice, the new array
array of points
of points
also
also forms
forms aa point
point lattice.
lattice. Similarly,
Similarly, another
another point
point lattice
lattice can
can be
be based
based
2-3]
2-3] CRYSTAL SYSTEMS 33
33

on a cubic unit cell cell having

having lattice
lattice points
points atat each corner
corner and in in the
the center
center
of
of each face.
face.
The fourteen Bravais latticeslattices are
are described
described in in Table 2-1 and illustrated
illustrated
in
in Fig.
Fig. 2-3,
2-3, where the the symbols
symbols P, P, F, I, etc.,
F, /, etc., have thethe following
following meanings.
meanings.
We must first first distinguish
distinguish between simple,
simple, or primitive, cells
or primitive, cells (symbol
(symbol P
or R) and nonprimitive
or R) nonprimitive cells
cells (any
(any other
other symbol): primitive cells
symbol): primitive cells have only
only
one lattice
lattice point
point perper cell
cell while
while non primitive have more than one.
nonprimitive one. A lattice
lattice
point
point inin the
the interior
interior of
of a
a cell
cell "belongs"
"belongs" to to that
that cell.
cell, while
while one
one in
in a
a cell
cell face
face
is
is shared by by two cells
cells and one at at a
a corner
corner isis shared
shared by by eight.
eight. The numbeI
number
of
of lattice
lattice points
points per
per cell
cell is
is therefore
therefore given
given byby

--
Nf
N, Nc
Nc
N == N,
N + 2-+ 8' ,
(2-1;
(2-1 ;

2 8

where N, N =
t
= number of of interior points, N,
interior points, N/ = = number of points on faces,
of points faces,
and N Ncc == number of points on corners.
of points corners. Any Any cell
cell containing
containing lattice
lattice points
points
on the
the corners
corners only
only isis therefore
therefore primitive,
primitive, whilewhile one
one containing
containing additional
additional
points
points in
in the
the interior
interior or
or on faces
faces is
is nonprimitive.
nonprimitive. The symbols F and I/
symbols
refer
refer toto face-centered
face-centered and body-centered
body-centered cells, respectively, while
cells, respectively, A, B,
while A, B,
and C refer
refer to base-centered cells,
tqjmse-centered cells, centered
centered on one pair
pair of
of opposite
opposite faces
faces
A, B,
A, or C.
B, or (The A face
C. (111e face isis the
the face
face defined
defined by by the
the band
b and c c axes,
axes, etc.)
etc.) The
symbol
symbol R is is used especially
especially for for the
the rhombohedral system. system. In In Fig.
Fig. 2-3,
2-3,
axes
axes ofof equal
equal length
length in in a a particular
particular system
system are are given
given the
the same symbol
symbol to to
indicate
indicate their
their equality,
equality, e.g.,
e.g., the
the cubic
cubic axes
axes are
are all
all marked a, a, the
the two equal
equal
tetragonal
tetragonal axesaxes are
are marked a and the the third
third one
one c,
c, etc.
etc.
At first
first glance,
glance, the
the list
list of
of Bravais
Bravais lattices
lattices in
in Table
Table 2-12-1 appears
appears incom-
incom-
plete.
plete. Why not,not, for
for example,
example, a a base-centered
base-centered tetragonal
tetragonal lattice?
lattice? The
full
full lines
lines in
in Fig. 2-4 delineate
Fig. 2-4 delineate such such a a cell,
cell, centered
centered on the the C face, but we
face, but
see
see that the same array
that the array of of lattice
lattice points
points can be be referred
referred to to the
the simple
simple
tetragonal
tetragonal cellcell shown by by dashed lines, lines, soso that
that the
the base-centered
base-centered arrange-
arrange-
ment of of points
points isis not
not a a new lattice.
lattice.

"
-~I
1
1
1
1
I
I
1
I /
,I

---~
a~--------~~-------.~
FIG.
FIG. 2--4.
2-4. Relation
Relation ofof tetragonal
tetragonal C FIG.
FIG. 2-5.
2-5. Extension
Extension of
of lattice points
lattice points
lattice
lattice (full
(full lines)
lines) to tetragonal P lat-
to tetragonal iat- through
through space
space by
by the
the unit
unit cell
cell vectors
vectors
tice
tice (dashed
(dashed lines).
lines). a, b, c.
a, b, c.
34
34 THE GEOMETRY OF
OF CRYSTALS
CRYSTALS [CHAP. 2
[CHAP. 2

The lattice
lattice points
points in in a
a nonprimitive
nonprimitive unitunit cell
cell can bebe extended
extended through
through
space
space by
by repeated
repeated applications
applications of
of the
the unit-cell
unit-cell vectors
vectors a,
a, b,
b, cc just
just like
like those
those
of
of aa primitive
primitive cell.
cell. We may regard
may regard the
the lattice
lattice points
points associated
associated with
with aa
unit cell
unit cell as
as being
being translated
translated one by
by one
one or
or as
as a group.
group. In either
either case, equiv-
case, equiv-
alent
alent lattice
lattice points
points inin adjacent
adjacent unit
unit cells
cells are
are separated
separated by by one of of the
the vectors
vectors
a, b, c,
a, b, c, wherever these
these points happen
points happen to
to be
be located
located in
in the
the cell
cell (Fig.
(Fig. 2-5).
2-5).

2-4 Symmetry, I Both Bravais

2-4 Symmetry. i Bravais lattices
lattices andand the
the real
real crystals
crystals which
which are are
built
built upup on them exhibit
exhibit various
various kinds
kinds of of symmetry.
symmetry. A body body or or structure
structure
is
is said
said to
to be
be symmetrical
symmetrical when its its component
component parts parts areare arranged
arranged in in such
such
balance,
balance, so so to speak, that
to speak, that certain
certain operations
operations can be performed
performed on the the body
body
which will
will bring
bring it
it into
into coincidence
coincidence with with itself.
itself. These areare termed symmetry
symmetry
operations.
operations. /For
/For example,
example, if
if a
a body
body is
is symmetrical
symmetrical with
with respect
respect to
to aa plane
plane
passing
passing through
through it,
it, then reflection
reflection of
of either
either half
half of
of the
the body
body in
in the
the plane
plane
as
as in
in a
a mirror
mirror will
will produce
produce a a body
body coinciding
coinciding with the the other
other half.
half. Thus a a
cub has
cub Qhas SE''''
ir
ral planes
se -ral planes of
of symmetry,
symmetry, one
one of
of which is
is shown in
in Fig. 2-6(a).
Fig. 2-6(a).
There are are in
in all
all four
four macroscopic*
macroscopic* symmetrysymmetry operations
operations or or elements:
elements:
reflection,
reflection, rotation,
rotation, inversion,
inversion, and rotation-inversion.
rotation-inversion. A body
body has has n-fold
n-fold
rotational
rotational symmetry
symmetry about about an axis axis if
if a rotation of
a rotation 360 In
of 360 /n brings
brings it
it into
into
self-coincidence.
self-coincidence. Thus aa cube has aa 4-fold 4-fold rotation
rotation axisaxis normal
normal to to each
each
face,
face, a a 3-fold
3-fold axis
axis along
along each
each body
body diagonal,
diagonal, and 2-fold2-fold axes
axes joining
joining the the
centers of
centers of opposite edgesJ
opposite edgesf Some of
of these
these are
are shown in
in Fig.
Fig. 2-6(b)
2-6 (b) where
where
the
the small plane figures
small plane figures (square,
(square, triangle,
triangle, and ellipse)
ellipse) designate
designate the the various
various

(a) (h)
(b) (r) (1I)
(ci)

FIG. 2-6. Some symmetry

FIG, 2-6. elements of
symmetry elements of aa cube,
cube. (a)
(a) Reflection
Reflection plane.
plane. AI Al be-
be-
A 2
comes A%. (b) Rotation
(b) Rotation axes.
axes. 4-fold
4-fold axis: Al becomes
axis: A\ becomes A^A 2 ; 3-fold
3-fold axis: Al becomes
axis: A\ becomes
Aa; 2-fold
AZ\ 2-fold axis: Al becomes A*,
axis: AI A 4 (r) Inversion center.
(c) Inversion renter. AIAl becomes A2. (d)
becomes A%. (d) Rota-
Rota-
tion-inversion axis.
tion-inversion axis. 4-fold
4-fold axis: Al becomes
axis: AI AI'; inversion
becomes A\\ inversion center: AI' becomes
center: A\ A 2
becomes A*.

*
So
So called
called to
to distinguish
distinguish them from
from certain
certain microscopic
microscopic symmetry
symmetry operations
operations
with which
with are not
which we are not concerned
concerned here.
here. The macrosopic
macrosopic elements
elements can
can be
be deduced
deduced
from the
from the angles
angles between
between the
the faces of aa well-developed
faces of weU-developed crystal,
crystal, without
without any
any knowl-
knowl-
edge of
edge of the
the atom arrangement
arrangement inside
inside the
the crystal.
crystal. The microscopic
microscopic symmetry
symmetry ele-
ele-
ments, on
ments, on the
the other
other hand,
hand, depend
depend entirely
entirely on
on atom
atom arrangement,
arrangement, and
and their
their pres-
pres-
ence cannot
ence cannot be
be inferred
inferred from
from the
the external
external development
development of
of the
the crystal.
crystal.
 2-4)
2-4] SYMMETRY
SYMMETRY 35

kinds of
kinds of axes.
axes. ' In
In general,
general, rotation
rotation axes
axes maymay be 1-, 2-,
be 1-, 2-, 3-,
3-, 4-,
4-, or 6-fold. AA
or 6-fold.
I-fold axis
1-fold axis indicates
indicates nono symmetry
symmetry at at all,
all, while
while aa 5-fold
5-fold axis
axis oror one
one of
of higher
higher
degree
degree than
than 6
6 is
is impossible,
impossible, in
in the
the sense
sense that
that unit
unit cells
cells having
having such
such sym-
sym-
metry
metry cannot
cannot be
be made
made to
to fill
fill up space
up space without
without leaving
leaving gaps.
gaps.
AA body has
body an inversion
has an inversion center
center ifif corresponding
corresponding points
points of of the
the body
body are
are
located at equal
I'ocated at equal distances
distances from
from the
the center
center onon aa line
line drawn
drawn through
through thethe
center.
center. A Abody having
body having an
an inversion
inversion center
center will
will rome
come into
into coincidence
coincidence
with itself
with itself ifif every
every point
point in
in the body isis inverted,
the body inverted, or or "reflected,"
"reflected," inin the
the
inversion center.
inversion center. A Acube has
cube has such
such a
a center
center at
at the
the intE'rsection
intersection of
of its
its body
body
diagonals [Fig.
diagonals [Fig. 2-6(c)].
2-6(c)]. Finally, aa body
Finally, body may may havehavc aa rotation-inversion
rotation-inversion
axis, either 1-, 2-, 3-, 4-,
axis, either 1-, 2-, 3-, 4-, or 6-fold.or 6-fold. If
If it
it has
has an
an n-fold
n-fold rotation-inversion
rotation-inversion

axis, it can
axis, it can bebe brought
brought intointo coincidence
coincidence with itself by
with itself by a rotation .of
a rotation 360 0 In
of 360/n
about the
about the axis
axis followed
followed by by inversion
inversion in in aa center
center lying
lying on the axis. ) Figure
on the axis. ;
Figure
2-6(d) illustrates
2-6(d) illustrates thethe operation
operation of of aa 4-fold
4-fold rotation-inversion
rotation-inversion axis axis on
on aa cube.
cube.
/Now,
^Now, the
the possession
possession of
of a
a rertain
certain minimum set
set of
of symmetry
symmetry elements
elements
is aa fundamental
is fundamental property propert.y of of each
each crystal
crystal system,
systcm, and one one system
system is is dis-
dis-
tinguished
tinguished from
from another
another just
just as
as much by
by its
its symmetry
symmetry elements
elements as
as by
by the
the
values of
values of its
its axial
axial lengths
lengths and and angles'*
angles:? InIn fact,
fact, these
these are
are interdependent
interdependent
The minimum number
The number of of symmetry elements possessed
symmetry elements possessed by by each
each crystal
crystal
system
system is
is listed
listed in
in Table
Table 2-2.
2-2.
{
f Some rrystals
crystals may possess
possess more
more than
than the
the
minimum
minimum symmetry
symmetry elements
elements required
required by
by the
the system
system to whic'h
which they
they belong,
belong,
but
but none
none maymay havehave less.'
less.)
Symmetry
Symmetry operations
operations applyapply not only to
not only to the
the unit
unit cellsjshown
cells]shown in in Fig.
Fig. 2-3)
2-3J
considered
considered merely
merely as
as geometric shapes,
geometric shapes, hut
but also
also to
to the point
point lattices
lattices asso-
asso-
ciated
ciated with them. The latter
with them. latter (~ondition
condition rules
rules out the possibility
possibility thatthat the
the
cubic system,
cubic system, for
for example,
example, (~ould
could include
include a base-centered
base-centered point
point lattice,
lattice,
since
since such
such an array of
an array of points
points would
would notnot have the minimum set set ofof sym-
metry elements required
metry elements required by by the
the cubic
cubic system, namdy
system, namely four a-fold
3-fold rotation
rotation

axes. Ruch
axes. Such aa lattice
lattice would
would be be classified
classified inin the
the tetragonal
tetragonal system,
system, whichwhich
has no a-fold axes
has no 3-fold axes and and in
in which
which accidental
accidental equality
equality of
of the a and c
c axes
axes is
is

TABLE 2-2
TABLE 2-2
ELEMENTS
SYMMETRY ELEMENTH
SYMMETRY

System
System Minimum
Minimum symmetry
symmetry elements
elements

Cubic
Cubic Four
Four 33 --fold
fold rotation
rotation axes
axes

One - inversion) axis

Tetragonal
Tetragonal One 4-fold
4 -fold rotation
rotation (or
(or rotation
rotation -inversion) axis

Three
Three perpendicular rotation -- inversion)
Orthorhombic perpendicular 22--fold
fold ratation
rotation (or
(or rotation inversion) axe.
Orthorhombi c axes

One - inversion) axis

Rhombohedral
Rhombohedral One 33--fold
fold rotation
rotation (or
(or rotation
rotation -Inversion) axis

Hexagonal One
One 66--fold
fold rotation
rotation (or rotation--inversion)
(or ratation inversion) axis
axis
Hexagonal
Monoclinic
Monoclinic One
One 22--fold
fold rotation
rotation (or rotation--inversion)
(or rotation Inversion) axl.
axis

Triclinlc
Triclinic None
None
36
36 THE GEOMETRY OF CRYSTALS [CHAP. 2
[CRAP. 2

allowed;
allowed; asas mentioned before,
before, however,
however, thisthis lattice
lattice is
is simple,
simple, not base-
not base-
centered,
centered, tetragonal.
tetragonal.
Crystals
Crystals in
in the
the rhombohedral (trigonal)
(trigonal) system
system can bebe referred
referred to
to either
either
aa rhombohedral or or aa hexagonal lattice.~ Appendix
hexagonal lattice.^ Appendix 2
2 gives
gives the
the relation
relation
between
between these
these two lattices
lattices and the
the transformation
transformation equations
equations which allowallow
the
the Miller
Miller indices
indices ofof a. plane (see
a. plane (see Sec.
Sec. 2-6)
2-6) to
to be
be expressed
expressed in
in terms
terms of
of
either
either set
set of axes.
of axes.

2-6
2-5 Primitive
Primitive and nonprimitive
nonprimitive cells. cells. In any
any point
point latticelattice a unit unit cell cell

may
may be be chosen
chosen in in an infinite
infinite number of of ways
ways and may may contain
contain one one or or more
lattice points per
lattice points per cell.
cell. It
It is
is important
important to to note
note that
that unit
unit cellscells do not not "exist"
"exist"
as
as such in in a a lattice:
lattice: theythey areare a a mental construct
construct and can accordingly accordingly be be
chosen
chosen at at our
our convenience.
convenience. The conventional conventional cells cells shown in in Fig.
Fig. 2-3 are are
chosen
chosen simply
simply for for convenience
convenience and to to
conform to to the
the symmetry
symmetry elements
elements E _---~-~;
of
of the
the lattice.
lattice.
.".~ , ,
'1
# / / I
Any of
Any of the
the fourteen
fourteen Bravais
Bravais lattices
may
may be be referred
referred to to a a primitive
lattices

primitive unit unit c

;, I

"I'
,," , -_ . .., /'
,/'

,
B"'---1
, -1/- - -
'
"
I '
cell.
cell. For example,
example, the the face-centered
face-centered
I _- ,-,J
;
cubic
cubic lattice
lattice shown in in Fig. 2-7 may
Fig. 2-7 may ~~-'~~,' ,,"
be
be referred
referred to to the primitive cell
the primitive cell indi-
indi- J, I ~

'rut" +----.Jt
cated
cated byby dashed
dashed lines.
lines. latter cell
The latter cell
,~"
,
is
is rhombohedral,
rhombohedral, its its axial
axial angle
angle a is
60,
is
'"
A~------------- a ~ __
60, and each each of of its
its axes
axes is is 1/0
l/\/2
times
times the the length
length of of the
the axes
axes of of the
the
FIG. 2-7.
FIG. 2-7. Fare-rentel'ed
Face-centered rubic cubic point
point
cubic cell.
cubic cell. Each cubic
cubic cell cell has
has four
four lattire
lattice referred
referred to to rubir
cubic and rhombo-
lattice
lattice points
points associated
associated with with it, it, each
each hedral cells.
hedral cells.

rhombohedral
rhombohedral cell cell has
has one,one, and the
the
former
former has,has, correspondingly,
correspondingly, four four times
times thethe volume of of the the latter.
latter. Never-
theless,
theless, it
it is
is usually
usually more convenient
convenient to
to use
use the
the cubic
cubic cell
cell rather
rather than
than the
the
rhombohedral one one because
because the the former
former immediately
immediately suggests suggests the
the cubic
cubic
symmetry
symmetry which which the the lattice
lattice actually
actually possesses.
possesses. Simiiarly,
Similarly, the other ce'n-
the other cen-
tered
tered nonprimitive
nonprimitive cells cells listed
listed in in Table
Table 2-1 2-1 are
are preferred
preferred to to the
the primitive
primitive
cells
cells possible
possible in in their
their respective
respective lattices.
lattices.

If
If nonprimitive
nonprimitive lattice lattice cells
cells areare used,
used, thethe vector
vector from from the the origin
origin to to any any
point in
point in the lattice will
the lattice will now have have components
components which which are are nonintegral
nonintegral mul-
tiples
tiples ofof the
the unit-cell
unit-cell vectors
vectors a, a, b,b, c.
c. The position
position of of anyany lattice point in
lattice point in aa
cell
cell may
may be be given
given in in terms of its coordinates;
of its coordinates] if if the
the vector
vector from from the the origin
origin
of
of the unit cell
the unit cell toto the
the given
given point
point has has components
components xa, xa, yb, yb, ZC, where x,
zc, where x, y, y,
and Zz areare fractions,
fractions, then
then the
the coordinates
coordinates of
of the
the point
point are
are x
x y
y z.
z. Thus,
Thus,
point
point A in in Fig. 2-7, taken
Fig. 2-7, taken as as the
the origin,
origin, hashas coordinates
coordinates 000 while while points points
B,
Bj C,C, and D, D, when referred
referred to to cubic
cubic axes,
axes, have coordinates
coordinates 0 ! !, !f 0 !,
Off, f ,

and if if 0, respectively.
0, respectively. Point
Point E has
has coordinates!
coordinates f \ ! 1
1 and
and is
is equivalent
equivalent
2-6)
2-6] LATTICE DIRECTIONS AND PLANES 37
37

to point D,
to point Z), being
being separated
separated from it it by
by the
the vector
vector c. c. The coordinates
coordinates of of
equivalent points in
equivalent points in different
different unit
unit cells
cells can always
always be made identical identical by by
the
the addition
addition or subtraction of
or subtraction of a a set
set ofof integral
integral coordinates;
coordinates; in in this
this case,
case,
subtraction
subtraction of of 00 1 1 from ! ! 1
f ^ 1 (the
(the coordinates
coordinates of
of E)
E) gives
gives ^ !f 0 (the
! (the
coordinates
coordinates of of D).
D).
Note that
that thethe coordinates
coordinates of of a body-centered
body-centered .point,point, for for example,
example, are are
always!
always | ^ ^ ! ! no matter whether the
the unit
unit cell
cell is
is cubic, tetragonal,
cubic, tetragonal, or
or ortho-
ortho-
rhombic,
rhombic, and whatever its its size.
size. The coordinates
coordinates of of aa point position, such
point position, such
as !
as ^ !
^ !,
\, may
may also
also be regarded
be regarded as an operator
as an operator which,
which, when "applied"
"applied" to to a a
point
point atat the origin, will
the origin, will move or or translate
translate it it toto the position!\ !\ !,
the position \, the
the
final
final position
position beingbeing obtained by by simple
simple addition
addition of of thethe operator
operator ! \!\! \
and thethe original
original position
position 0 0 O. In this
000. this sense,
sense, the positions 0000,
the positions 0 0, !\ !\ !\
are
are called
called thethe "body-centering
"body-centering translations,"
translations," since since they
they will
will produce
produce the the
two point
point positions characteristic of
positions characteristic of aa body-centered
body-centered cell cell when applied
applied toto
aa point
point atat the
the origin.
origin. Similarly,
Similarly, the
the four
four point positions
point positions characteristic
characteristic of
of aa
face-centered
face-centered cell, namely
cell, namely 0 0 0,
0, 0 ! !,
\ ^, \ ! 0 !,
^, and ! !
\ \ 0,0, are
are called
called the
the
face-centering
face-centering translations.
translations. The base-centering
base-centering translations
translations depend depend on
which
which pair
pair of
of opposite
opposite faces
faces are
are centered;
centered; if
if centered
centered on the
the C face,
face, for
for
example,
example, theythey are
are 000, !
0, \ \ ! o.
0.

2-6 Lattice
Lattice directions
directions and planes.
planes. The direction
direction of of any
any line
line inin a a lat-
lat-
tice
tice may
may be be described
described by by firs.t
first drawing
drawing a a line
line through
through the the origin parallel
origin parallel
to
to the
the given
given line
line and then
then giving
giving thethe coordinates
coordinates of of any point on the
any point the line
line
through
through the the origin.
origin. Let
Let the
the line
line pass
pass through
through the the origin
origin ofof the
the unit
unit cell
cell

and any point having

any point coordinates u v
having coordinates w, where these
v W, these numbers are are not
not neces-
neces-
sarily
sarily integral.
integral. (This line will
(This line will also pass through
also pass through the points 2u 2v
the points 2v 2w,
2w,
3u 3v
3u 3v 3w,
3w, etc.)
etc.) Then [UVW]
[uvw], , written
written in
in square
square brackets,
brackets, are
are the
the indices
indices
of
of the
the direction
direction of of the
the line.
line. They
They are are also
also the
the indices
indices of of any
any line
line parallel
parallel
to
to the
the given line,
given line, since
since the
the lattice
lattice is
is infinite
infinite and the
the origin
origin may be
may be taken
taken
at
at any point.
any point. Whatever the
the values
values of
of u,
i/,v, w, they
v, w, they are
are always
always converted
converted
to
to a set of
a set of smallest
smallest integers
integers byby multi-
multi-
plication
plication oror division
division throughout:
throughout: thus,thus, [233]
[233]

[! ! 1], [112],
[||l], [112], and [224]
[224] all
all represent
represent
[100]
[111]

the direction, but

the same direction, but [112]
[112] is is the
the [001]

preferred
preferred form. Negative indices
form. Negative indices areare
written
written with
with a a bar
bar over
over the
the number,
number,
e.g., [uvw].
e.g., [uvw]. Direction
Direction indices
indices are
are illus-
illus- c
trated
trated inin Fig.
Fig. 2-8.
2-8.
[210]
Direction~ related
related byby symmetry
symmetry are are
Direction^
called
called directions
directions of of a form, and aa set
a form, set HO
of
of these
these arefJepresented
are|Pepresented by by the
the indices
indices [100]
of
of one
one ofof them enclosed
enclosed in in angular
angular '[120]

bracAts;
bracHts; for for example,
example, thethe four
four body
body FI~~-8.
Fib/^-8. IndicesIndices of
of directions.
directions.
38
38 THE GEOMETRY
THE GEOMETRY OF
OF CRYSTALS
CRYSTALS 2
[CHAP. 2
[CHAP.

diagonals of
diagonals of aa cube,
cube, [111],
[Ill], [ill], [TIl], and
[lT1), [TTl], and [Til],
[TIl), may all
may all be
be represented
represented
by the symbol
by the symbol (111).
(111).
The orientation
The orientation of
of planes
planes in
in aa lattice
lattice may
may also
also be
be represented
represented sym-
sym-
bolically, according
bolically, ac('ording to
to aa
system popularized
system popularized by
by the
the English
English crystallographer
crystallographer
Miller. In
Miller. In the
the general
general case,
case, the
the given
given plane
plane will
will be
be tilted
tilted with
with respect
respect to
to
the crystallographic
the crystallographic axes,
axes, and,
and, since
since these
these axes
axes form aa convenient
convenient frame
frame
of reference,
of might describe
referenee, we might deseribe the
the orientation
orientation of
of the
the plane
plane by
by giving
giving the
the
actual distances,
actual distances, measured
measured from the the origin,
origin, at
at which itit intercepts
intercepts the
the
three axes.
three axe::;.Better still,
Better still, by
by expressing
expre::;sing these
these distances
distances as
as fractions
fractions of
of the
the
axial lengths,
axial lengths, we can
can obtain
obtain numbers which areare independent
independent of
of the
the par-
par-
ticular axial
ticular axial lengths
lengths involved
involved in
in the
the given
given lattice.
lattice. But aa difficulty
difficulty then
ari::;es
arises the given
when the given plane
plane is
is parallel
parallel to
to aa certain
certain crystallographic
crystallographic axis,
axis,
because such
because such aa plane
plane does not intercept
does not intercept that
that axis,
axis, i.e.,
i.e., its
its "intercept"
"intercept" cancan
only
only be
be described
described as
as "infinity."
"infinity." To avoid
avoid the
the introduction
introduction of
of infinity
infinity into
into
the description
the description of
of plane
plane orientation, can use
orientation, we can use the
the reciprocal
reciprocal of
of the
the frac-
frac-
tional intercept,
tional intercept, this
this reciprocal
reciprocal being
being zero
zero when the
the plane
plane and axis
axis are
are
parallel.
parallel. We
We thus
thus arrive
arrive at
at a
a workable
workable symbolism
symbolism for
for the
the orientation
orientation of
of a
a
plane in
plane in aa lattice,
lattice, the
the Miller
Miller indices, are defined
indices, which are defined as
as the
the reciprocals
reciprocals of
of
the fractional intercepts
the fractional which the
intercepts which the plane
plane makes
makes with
with the
the crystallographic
crystallographic axes.
axes.
For example,
For example, if if the
the Miller
Miller indices
indices of of aa plane
plane are
are (AW), written in
(hkl) , written in paren-
paren-
theses, then the
theses, then the planeplane makes fractional
fractional intercepts
intercepts of
of l/h, l/k, l/l
I/A, I/A*, \/l with
with the
the
axes, and, if the axial lengths
axes, and, if the axial lengths are
are a, IJ,
a, 6, c,c, the
the plane
plane makes actual
actual intercepts
intercepts
of a/A,
of a/h, b/k,
b/k, c/l, as shown in
c/l, as in Fig.
Fig. 2-9(a). Parallel to
2-9(a). Parallel to any plane in
any plane any lat-
in any lat-

tice,
tice, there
there is
is a whole set
a whole set of
of parallel
parallel equidistant
equidistant planes,
planes, one of
of which passes
passes
through
through thethe origin;
origin; the
the Miller
Miller indices (hkl) usually
indices (hkl) usually refer
refer to
to that
that plane
plane inin
the
the set
set which
which is is nearest
nearest the
the origin,
origin, although
although they they may be be taken as referring
as referring
to
to any
any other
other plane
plane inin the
the set
set or
or to
to the
the whole set set taken together.
together.
We may
may determine
determine the the Miller
Miller indices
indices of of the plane
plane shown in in Fig.
Fig. 2-9(b)
2-9 (b)
as
as follows:
follows :

1--11 /11 ----..J a 1A 2A 3A 4A

(a)
(a) (b)
(b)

FIG. 2-9.
FIG. 2-9. Plane
Plane designation by Miller
designation by Miller indices.
indices.
 2-6]
2-6] DIRECTIONS AND
LATTICE DIRECTIONS
LATTICE AND PLANES
PLANES 39
39

Axial lengths
Axial lengths 4A
4A SA
8A 3A
3A
Intercept lengths
Intercept lengths 2A
2A 6A
6A 3A
3A
3~
Fractional intercepts
Fractional intercepts !
I 4
4
11

{~
2 1"3" 1
1
Miller indices
Miller indices I
44 33
16

Miller indices
Miller indices are
are always
always cleared
cleared of of fractions,
fractions, asas shown
shown above.
above. AsAs stated
stated
earlier, if a plane is parallel
earlier, if a plane is parallel to
to aa given axis,
given axis, its
its fractional
fractional intercept
intercept on
on that
that
axis is taken as infinity
axis is taken as infinity and
and the
the corresponding
corresponding Miller
Miller index
index is
is zero.
zero. If aa
If

plane cuts
plane cuts aa negative
negative axis,
axis, the
the corresponding
corresponding index
index isis negative
negative and
and isis writ-
writ-
ten with a bar over it.
ten with a bar over it. PlanesPlanes whose
whose indices
indices are
are the
the negatives
negatives of
of one
one
another are parallel and lie on opposite
another are parallel and lie on opposite sides
sides of
of the
the origin, e.g., (210)
origin, e.g., (210) and
and
(210).
(2lO). The planes
planes (nh
(nh nk
nk nl) are parallel
nl) are parallel to
to the
the planes
planes (hkl) and have
(hkl) and have 1/n
lin
the spacing.
the spacing. The
The same
same plane
plane may
may belong
belong to
to two different sets,
different sets, the Miller
the Miller
indices of
indices of one
one set
set being
being multiples
multiples of
of those
those of
of the
the other;
other; thus
thus the
the same plane
p'lane
belongs to
belongs to the
the (210)
(210) set
set and
and the
the (420)
(420) set,
set, and,
and, in fact,
in fact, the planes
the planes of
of the
the
(210) set
(210) set form
form every
every second
second plane
plane in
in the
the (420)
(420) set.
set. jjn
I In the
the cubic
cubic system,
system,
it is
it is convenient
convenient toto remember
remember that
that aa direction
direction [hkl] is '-iiways
[hkl] is perpendicular
always perpendicular
to aa plane (hkl)
to of the
(hkl) of
plane the same
same indices,
indices, but
but this
this is
is not
not generally
generally true
true in
in other
other
systems. Further familiarity
systems. Further familiarity withwith Miller
Miller indices
indices can be be gained
gained from
from aa
study
study of Fig. 2-10.
of Fig. 2-10.
A slightly
slightly different
different system
system of plane indexing
of plane indexing isis used in in the hexagonal
hexagonal
system.
system. The
The unit
unit cell
cell of
of a
a hexagonal
hexagonal lattice is
lattice is defined
defined by
by two equal
equal and
and
coplanar
coplanar vectors
vectors al ai and a2,a 2 at
at 120 to one another,
,
0 to
another, and a thirdthird axis
axis c at
c at
right
right angles
angles [Fig.
[Fig. 2-l1(a)].
2-11 (a)]. The complete
complete lattice
lattice is
is built
built up,
up, as usual,
usual, by

L. HfeocH

fJw (100) (200) (110)

(110)

(flo)
(110)
(lll)
(111) (102)
(102)

FIG.
FIG. 2-10.
2-10. Miller
Miller indices
indices of
of lattice
lattice planes.
planes.
40
40 THE GEOMETRY OF CRYSTALS [CHAP. 2
[CHAP.

[001]
[001]

(0001) [011)
[Oil]

(1210)
(1100)
(1100)-

:"-'rI!II-- [OlO]
[010]

'

[100]
'[210]
(1011)
(a)
(a) (b)
(b)

FIG.2-11.
FIG. 2-11. (a)
(a) The hexagonal
hexagonal unit
unit cell
cell and
and (b)
(b) indices
indices of
of planes
planes and
and dil'eetions.
directions.

repeated
repeated translations
translations of of the points at
the points at the
the unit
unit cell
cell corners
corners by by thethe vectors
vectors
aI, a2 c.
EI, a2, ,
c. Some of of the
the points
points soso generated
generated areare shown in in the
the figure,
figure, atat the
the
ends ofof dashed lines,
lines, in in order
order toto exhibit
exhibit the
the hexagonal
hexagonal symmetry
symmetry of of the
lattice,
lattice, which has a 6-fold 6-fold rotation
rotation axis parallel to
axis parallel to c.
c. The third axis a3,
third axis a3 ,

lying
lying in
in the
the basal
basal plane
plane of
of the
the hexagonal
hexagonal prism,
prism, is
is so
so symmetrically
symmetrically related
related
to EI and a2
to al a2 that
that itit is
is often
often used
used inin conjunction
conjunction with the the other
other two.
two. Thus
the
the indices
indices of of aa plane
plane in
in the
the hexagonal system,
hexagonal system, called
called Miller-Bravais
Miller-Bra vais
indices,
indices, refer
refer t%ur
to four axes
axes and are
are written
written (hkil).
(hkil). The index
index i
i is
is the
the recipro-
recipro-
cal
cal of
of the
the fractional
fractional il1tercept
iiltercept on the a3
on the a 3 axis.
axis. Since
Since the
the intercepts
intercepts of of a
plane
plane on al
ai and a2
a 2 determine
determine its
its intercept
intercept on a3,
a 3 the
the
,
value
value of
of i
i depends
depends on
the
the values
values ofof hand
h and k. k. The relation
relation isis

h +
h + k == -i.
-i. (2-2)
(2-2)

Since ii is
Since is determined by by hand
h and k, it
A;, it is
is sometimes replaced
replaced by by a a dot and
the
the plane symbol
plane symbol written
written (hkl).
(hk-l). However,
However, this
this usage
usage defeats
defeats the pur-
the pur-
pose
pose for
for which Miller-Bravais
Miller-Bra vais indices
indices were devised, namely,
devised, namely, to
to give
give similar
similar
indices
indices to
to similar
similar planes.
planes. For example,example, thethe side planes of
side planes of the
the hexagonal
hexagonal
prism in
prism in Fig.
Fig. 2-11 (b) are
2-1 l(b) are all
all similar
similar and symmetrically
symmetrically located,
located, and theirtheir
relationship
relationship is
is clearly
clearly shown in
in their
their full
full Miller-Bravais
Miller-Bra vais symbols: (1010),
symbols: (10K)),
(0110),
(OlTO), (1100),
(TlOO), (1010),
(T010), (0110),
(OTlO), (1100).
(iTOO). On thethe other
other hand,
hand, the abbreviated
the_abbreviated
symbols
symbols of
of these
these planes,
planes, (10-0), (01-0), (11-0), (10-0), (01-0), (1'10)
(100), (010), (110), (100), (010), (11-0)
do not immediately
immediately suggest suggest this
this relationship.
relationship.
Directions
Directions in in aa hexagonal
hexagonal lattice
lattice are
are best
best expressed
expressed in in terms
terms of the three
of the three
basic vectors all
basic vectors ai, a2,
a 2,
and c.
c. Figure
Figure 2-11
2-1 (b)
l(b) shows
shows several
several examples
examples of of
both plane and direction
both plane direction indices.
indices. (Another system, involving
(Another system, involving four
four indices,
indices,
is
is sometimes usedused to
to designate
designate directions.
directions. The required
required direction
direction is is broken

up
up into
into four
four component
component vectors,
vectors, parallel to all
parallel to ai, a2,
a 2 a3,
aa, and c
,
c and so so chosen
chosen
that
that the
the third
third index
index is is the
the negative of
negative of the the sum of
of the first two. Thus
the first two.
 2-6)
2-6] LATTICE DIRECTIONS AND PLANES 41
41

[100], for example,

[100], for example, becomes
becomes [2110],[2TIO], [210]
[210] becomes
becomes [1010],[1010], [010]
[010] becomes
becomes
[1210], etc.)
[T210], etc.)
In any
In any crystal
crystal system
system there there areare sets
sets of
of equivalent
equivalent latticelattice planes
planes related
related
by symmetry.
by symmetry. These are
are called
called planes
planes ofof a
a form,
form, and the
the indices
indices of any
of any
one plane,
one plane, enclosed
enclosed in braces I)M/},
in braces hkl}, stand
stand forfor the
the whole
whole set.
set. InIn general,
general,
planes of
planes of aa form
form have
have the the same spacing
spacing butbut different
different Miller
Miller indices.
indices. For For
example,
example, the
the faces
faces of
of a
a cube, (100), (010), (100), (010),
cube, (100), (010), (TOO), (OTO), (001), (001), and (001),
(001),
are planes
are planes of of the
the form {100}, POOl, since
since all
all of
of them may be be generated
generated from
anyone
any by operation
one by operation of of the
the 4-fold
4-fold rotation
rotation axes
axes perpendicular
perpendicular to to the
the cube
cube
faces. In
faces. In the
the tetragonal
tetragonal system,system, however,
however, onlyonly the the planes
planes (100),
(100), (010),
(010),
(100), and (OTO)
(TOO), (010) belong
belong to to the
the form
form |100);
1100}; the the other
other two planes,
planes, (001)
(001)
and (OOT),
and (001), belong
belong to to the
the different
different form lOOI}; the
form {001) ;
the first
first four
four planes
planes men-
tioned are
tioned related by
are related by aa 4-fold
4-fold axis
axis and thethe last
last two by by aa 2-fold axis. *
2-fold axis.*
Planes of
Planes of aa zone
zone are
are planes
planes which
which areare all
all parallel
parallel to to one
one line,
line, called
called the
the
zone axis,
zone axis, and
and thethe zone,
zone, i.e.,
i.e., the
the setset of
of planes,
planes, is is specified
specified by
by giving
giving the
the
indices of
indices of the
the zone
zone axis.
axis. Such Such planes
planes [001]
[001]

may have
may have quite
quite different indices and
different indices and zone (11) (210)
(110) (210)
spacings,
spacings, the
the only requirement
only requirement being being (210)

UOO) \
their parallelism to
their parallelism to a a line.
line. Figure
Figure
2-12
2-12 shows some examples. examples. If the c
If the

axis of
axis of aa zone
zone has indices [uvwj,
has indices then tIfIMMIhllHMi8fiIMItiflA
[uvw], then
,(100)

any
any plane belongs to
plane belongs to that
that zone
zone whose
indices (hkl)
indices (hkl) satisfy
satisfy the
the relation
relation

hu + kv +
+ kv Iw =
+ lw = O. 0. (2-3)
(2-3)

(A
(A proof
proof ofof this
this relation
relation is
is given
given in in
Section
Section 4 4 of
of Appendix 15.)
Appendix 15.) Any Any two
nonparallel
nonparallel planes
planes are planes of
are planes of a
a zone
zone
since
since they are both
both parallel to their
line
line of
they are
of intersection.
intersection.
parallel
If
If their
to their
their indices
indices

FIG.
FIG, 2-12. All shaded
2-12, All shaded planes
planes in
in the
the
are (/hfci/i) and (h2k2~)'
are (hlkJld (h^kj^j then the in- in-
cubic
cubic lattice
lattice shown
shown are
are planes
planes of
of the
the
dices
dices of
of their
their zone axis [uvw]
zone axis [uvw] are
are given
given zone
zone [(01).
[001].
by
by the
the relations
relations

u = kl12 - k2lJ,

v = ll~ - 12hlJ (2-4)

(2-4)

W ==
W hlk2
/&1/T2 - ~kJ'
h?jk\.

** Certain
Certain important
important crystal
crystal planes
planes are
are often
often referred to by
referred to by name without
without any
any
mention
mention of of their
their Miller
Miller indices.
indices. Thus, planes
Thus, planes of
of the
the form
form 11111
111(
in
in the
the
|
cubic
cubic sys-
sys-
tem
tem areare often
often called
called octahedral
octahedral planes,
planes, since
since these
these are
are the
the bounding
bounding planes
planes of
of an
octahedron.
octahedron. In the hexagonal
In the hexagonal system,
system, the
the (0001)
(0001) plane
plane is
is called
called the
the basal
basal pll!.ne,
plane,
planes
planes ofof the
the form
form {10101
{1010) are
are called
called prismatic
prismatic planes,
planes, and
and planes
planes ofof the
the form {lOll}
1011 { )

are
are called
called pyramidal
pyramidal planes.
planes.
42
42 THE GEOMETRY
THE GEOMETRY OF
OF CRYSTALS
CRYSTALS [CHAP. 22
[CHAP.

"~





(10)

(21)~
(11 )

(4f)~
(13)
(13)

FIG. 2-13.
FIG. Two-dimf'IlHional lattice,
2-13. Two-dimensional !attic'c, showing
sho,,-ing that
that lines
line:-- of
of lowest
lowest indices
iudic'';, have
hay,
the greatest
the greatest spacing
Rpac'ing and
and the
the greatest
greatest density
density ofof lattice
Jattic'p points.
pOllltS.

The various
The various sets
sets of
of planes
plan('1:) in
in aa lattice
latti('(' have \'ariou~ values
haye various \:aitleH of
of interplanar
int('l'planal'
spacing.
spacing. The planes
planes of
of large
large Hpa('ing
spacing haw
have low indieer-;
indices and pasH
pass throu~h a
through a
high density
high density of
of lutti('('
lattice points,
points, w}wl'eas
whereas the
the "pwrsp
reverse is
is trup
true of
of planer-;
planes of
of small
small
spacing,
spacing. Figure 2-13 illustrates
Figure 2-13 ilIustratPIl this this for
for a It two-dimensional lattice, latticc, and
it
it is equally tru('
is equally true in thr('c dimensions.
in three dimensions. The Thc intpl'pianar
interplanar spac'ing
spacing d mpas-
hkl , meas-
rf^./,

ured at
ured right angles
at right angles to
to the
the pi alll'S
planes, , is
is a function
function both of the plau('
plane indiees
indices
(hkl)
(hkl) and
and the
the lattiee constants (u,
lattice constants (a, IJ, c, 0, 1').
a, (3,
r, Ct,
/>, 7). ThE'
The exact relation
relation de-de-
pends on the crystal
pends on the crystal system system iuvolwd
involved and for
for the ('ubi('
cubic system
system tak('s
takes on
the relativE'ly simplE'
the relatively simple form
a
(Cubic) d hk i
= (2-5)
(2-5)
-^-JL===.
In
In the
the tetragonal
tetragonal Rystem
system the
the spaeing
spacing equation
equation naturally
naturally involves both
both
aa and c sinee
and since
c these
these are
are not
not genemlly equal:
generally equal :

a
(Tetragonal) dUl =
h ki = _ r- 2 2 2 2 2 (2-fi)
(2-0)
(Tetragonal)
v h +k +I (a / (' )

Interplanar spac'in~
Interplanar spacing equations
equations for
for all
all systC'ms
systems are /.!;iven
given in in Appmdix
Appendix 1. 1 .

2-7
2-7 Crystal
Crystal structure.
structure. So So far
far WE'
we have
have disclIsspd
discussed topiC's
topics from
from thpthe field
field

of
of mathematical
mathematical (geometrzcal)
(geometrical) crystallograp~y
crystallography and
and have said
said praetieally
practically
nothing
nothing about.
about actual
actual crystals
crystals and
and tile
the atoms
atoms ofof whieh
which they
they are
are ('om posed.
composed.
In
In fart,
fact, all
all of
of the
the above
above was
was well
well known
known long
long before
before the
the discovery
discovery of
of x-ray
x-ray
diffraction, i.e., long
diffraction, i.e., long before
before there
there was
was any
any certain
certain knowledge
knowledge of
of the
the interior
interior
arrangements
arrangements of of atoms
atoms in
in crystals.
crystals.
It
It is
is now
now time
time to to describe
describe the
the structure
structure of of some
some actual
actual crystals
crystals andand to
to
relate this structure to the point lattices, crystal
relate this structure to the point lattices, crystal systems, systems, and
and symmetry
symmetry
 2-7)
2-7] CRYSTAL STRUCTURE
CRYSTAL STRUCTURE 43
43

elements discussed
elements discussed above.
above. The
The cardi-
cardi-
nal principle
nal principle of
of crystal
crystal structure
structure isis
the atoms
that the
that atoms of
of aa crystal
crystal are
are set
set in
in
space either
space either on
on the points of
the points of aa Bravais
Bravais
lattice or
lattice or in
in some
some fixed
fixed relatio'fl
relation those
f.() those
to

points. It
points.
follows from
It follows from this this th tl. the ~he
atoms of a crystal will
atoms of a crystal will be arranged be arranged Bee
BCC FCC
FCC
periodically in
periodically in three
three dimensions
dimensions and and FIG. 2-14.
FIG. Strurtures of
2-14. Structures of some
some com-com-
that this
that this arrangement
arrangement of of atoms
atoms will will mon mon metals.
metals. Body-centered
Body-centered cubic: cubic: a- a-
exhibit many
exhibit many of of thethe properties
properties of of aa Fe, Fe, Cr,Cr, Mo, Mo, V, V, etc.;
etc.; face-centered
fare-rentered
Bravais lattice,
Bravais lattice, in in particular
particular many many of cubic: 7-Fe,
of cubic: 'Y-Fe, Cu,Cu, Pb,
Pb, Ni, etc.
Ni, etc.
its symmetry
its symmetry elements.
elements.
The simplest
The simplest crystals
crystals one one can can imagine
imagine are are those
those formed by by placing
placing atomsatoms
of the
of the same
same kind
kind on on thethe points
points of of aa Bravais
Bravais lattice.
lattice. Not all all such
such crystals
crystals
exist but,
exist but, fortunately
fortunately for for metallurgists,
metallurgists, many many metals metals crystallize
crystallize in in this
this
simple fashion,
simple fashion, and
and Fig.
Fig. 2-14
2-14 shows
shows two common structures
structures based
based on
on the
the
body-centered cubic
body-centered cubic (BCC) (BCC) and
and face-centered
face-centered cubic
cubic (FCC)
(FCC) lattices.
lattices. The
The
former has
former has two
two atoms
atoms per per unitunit cell
cell andand the
the latter
latter four,four, asas we can can find
find by by
rewriting Eq. (2-1)
rewriting Eq. (2-1) in terms in terms of
of the
the number of
of atoms,
atoms, rather
rather than
than lattice
lattice

points, per
points, per cell
cell and
and applying
applying it it to
to the unit cells
the unit cells shown.
shown.
The next
The degree of
next degree of complexity
complexity is is encountered
encountered when two or or more atoms atoms
of
of the
the same
same kind
kind are are "associated
"associated with" with" eacheach point
point of of a Bravais lattice,
a Bravais lattice, as as
e"emplified
exemplified by by thethe hexagonal
hexagonal close-packed
close-packed (HCP) (HCP) structure common to to
many
many metals.
metals. This structure is
This structure is simple
simple hexagonal
hexagonal and is is illustrated
illustrated in in

Fig.
Fig. 2-15.
2-15. There
There are
are two
two atoms
atoms per
per unit
unit cell,
cell, as
as shown in
in (a),
(a), one at
at 00 0
and
and the other at
the other at i! \ !| (or (or atat !\ if !, f which is
,
is an equivalent
equivalent position).
position).
Figure 2-15(b)
Figure 2-15(b) shows
shows the
the same
same structure
structure with
with the
the origin
origin of
of the unit cell
cell

shifted
shifted so so that
that thethe point
point 1
1 0 0 in
in the
the new cell
cell is
is midway
midway between the atoms
at
at 1
1 00 and and i! \ !| in in (a),
(a), the
the nine
nine atoms shown in in (a)
(a) corresponding
corresponding to to the
the
nine atoms
nine atoms marked
marked with
with an
an X
X in
in (b).
(b). The '
"association"
'association" of
of pairs
pairs of
of atoms
atoms
with
with the the points
points of of a a simple
simple hexagonal
hexagonal Bravais Bravais lattice
lattice is is suggested
suggested by by the
the
dashed lines in (b).
dashed lines in (b). Note, however, Note, however, that
that the
the atoms
atoms of
of aa close-packed
close-packed
hexagonal
hexagonal structure
structure do do notnot themselves
themselves form form aa point
point lattice,
lattice, thethe surround-
surround-
ings at i i3 t.
ings ofof an
an atom
atom at at 000 being being different
different from those of an atom at
from those of an atom ^.
Figure
Figure 2-15(c)
2-15(c) showsshows still still another
another representation HCP
representation of the HCP structure:
of the structure:
the
the three
three atoms
atoms in in the
the interior
interior of of the
the hexagonal
hexagonal prism prism areare directly
directly aboveabove
the
the centers
centers of of alternate
alternate triangleJj
triangles in in the
the base
base and,
and, if if repeated
repeated through
through space space
by
by the
the vectors
vectors al
ai and
and a2,
a 2
,
would
would rusd
alsd form
form aa hexagonal
hexagonal array
array just
just like
like

the
the atoms
atoms in in the
the layers
layers above
above and and below.
below.
The HCP
The HCP structure
structure is is so so called
called because
because it it isis one
one of of the
the two two ways
ways in in

which
which spheres
spheres can
can be
be packed together
packed together in
in space
space with
with the
the greatest
greatest possible
possible
density
density and and still
still have
have aa periodic
periodic arrangement.
arrangement. Such Such an an arrangement
arrangement of of
spheres
spheres in
in contact
contact is
is shown
shown in
in Fig. 2-15(d).
Fig. 2-15(d). If
If these
these spheres
spheres are
are regarded
regarded
 4444 THEGEOMETRY
THE GEOMETRYOF
OFCRYSTALS
CRYSTALS [CHAP. 2
P I
0
I

I
I

P p

I
/

(a)
(a) (h)

(e)
(c)

FIG.
FIG. 2-15.
2-15. The
The hexagonal
hexagonal close-packed
close-packed structure,
structure, shared
shared by
by Zn,
Zn, Mg,
Mg, He,
Be, a-Ti, etc.
etc. a-Ti,

as
as atoms,
atoms, then
then the
the resulting
resulting picture
picture ofof an
an HCP metal
metal isis much
much closer
closer to
to
HCP
physical reality
physical reality than
than isis the
the relatively
relatively open structure ~uggested by the
open structure the
suggested by
drawing of
drawing of Fig.
Fig. 2-15(c),
2-15(c), and
and this
this isis true,
true, generally,
generally, of
of all
all crystals. On the
crystals. On the
other
other hand,
hand, itit may
may be
be shown
shown that
that the
the ratio
ratio of
of cc to a in an HCP structure
structure
to a in an HCP
formed
formed of ofspheres
spheresinin contact
contactisis Ui33
1 whereas the
.633 whereas thec/acia ratio
ratio ofofmetals
metalshaving
having
this
this structure
structure varies
varies from
from about
about 1.58
1.58 (Be)
(Be) to
to 1.89
1.89 (Cd).
(Cd). As As there
there isis no
no
reason
reason toto suppose
suppose that
that the
the atoms
atoms inin these
these crystals
crystals areare not
not inin contact,
contact, itit
'followsthat
'follows theymust
thatthey must be beellipsoidal
E'llipsoidal ininshape
shaperather
ratberthanthanspherical.
spherical.
The FCC
The FCC structure
structure isis an
an equally
E'qually close-packed
dose-packed arrangement.
arrangement. Its Its rela-
rela-
tion theHCP
tiontotothe HCPstructure
structurE'isisnot
notimmediately
immediatelyobvious,
obvious,but butFig.
Fig.2-16
2-16shows
shows
that
thatthetheatoms
atomson onthe
the (111)
(111)planes
planesofofthetheFCC
FCCstructure
structureare arearranged
arrangedininaa
hexagonal pattern
hexagonal pattern just
justlike
like the
the atoms
atomsononthe the (0002)
(0002)planes
planes ofof the
the HCP
HCP
structure. The
structure. Theonly
onlydifference
differencebetween
betweenthe thetwotwostructures
structuresisisthe theway
wayinin
which
whichthesethesehexagonal
hexagonalsheets
sheetsofofatoms
atomsare arearranged
arrangedabove aboveone oneanother.
another.
InInananHCP
Hepmetal,
metal,thetheatoms
atomsininthe thesecond
secondlayerlayerareareabove
abovethethehollows
hollowsinin
 2-71
2-7] CRYSTAL STRUCTURE
CRYSTAL STRUCTURE 45
45

i
HID

[001]

HEXAGONAL CLOSE-PACKED
HEXAGONAL CLOSE-PACKED

FIG.
FIG. 2-16.
2-16. Comparison
Comparison of
of FCC
FCC and HCP structmes.
and HCP structures.
46
46 THE GEOMETRY OF CRYSTALS [CHAP. 2
[CHAP.

CD CD

j; CD
HH
b

FIG. 2-17. The structure

FIG. 2-17. structure of
of a-uranium. (C.
(C. W. Jacob and B.
B. E.
E. Warrl'n,
Warren, J.A.C.S
J.A.C.S
69,2588,
59, 2588, 1!137.')
1937.')

the
the first
first layer
layer and the atoms in in the
the third
third laYf'r
layer are
are above the the atoms in in the
the
first
first layer,
layer, so so that
that the
the layer
layer stacking
stacking sequencc
sequence ('an can be be summarized as as
A B A B A B . ... The first
. . . . first two atom laYf'rs layers of of an FCC metalmetal are put. down
are put
in
in the
the same way, way, but the the at.oms
atoms of of the
the third
third layer
layer are
are pla('ed
placed in in the
the hollows
hollows
of
of the
the se('ond
second layer
layer and not.
not until
until t.hf'
the fourth
fourth layer
layer does
does a
a posit.ion
position repeat.
repeat.
FCC stacking
stacking therefore
therefore has the
the sequenee
sequence ABC
A B C ABC
A B (' ....
... . Thesf'
These st.ac'k-
stack-
ing
ing schemes are
are indicat.ed
indicated in
in thf'
the plan
plan views
views shown in
in Fig.
Fig. 2-
2-1Hi.
(>.

Another example
example of of the
the "assoeiation"
"association" of of more than one one atom with with eacheach
point
point of
of aa Bravais
Bravais lattice
lattice is
is given
given by by uranium.
uranium. The structure
structure of
of the
the form
stable at
stable at room temperature,
temperature, a-uranium,
a-uranium, is is illustrated
illustrated in in Fig.
Fig. 2-17 by by plan
plan
and elevation
elevation drawings.
drawings. In
In sueh
such drawings,
drawings, the
the height
height of
of an
an atom (ex-
(ex-
pressed
pressed as
as a
a fraction
fraction of
of the
the axial
axial length)
length) above
above the
the plane
plane of
of the
the drawing
drawing
(which
(which includes
includes the origin of
the origin of the
the unit
unit cell
cell and two of of the
the eell
cell axes)
axes) is is given
given
by
by the
the numbers marked on each
each atom. The Bravais
Bravais lattice
lattice is
is base-centered
base-centered
orthorhombie,
orthorhombic, centered centered on the the (' C face,
face, and Fig. Fig. 2-17 shows how the the atoms
occur
occur in in pairs through
pairs through the
the structure,
structure, each
each pair
pair associated
associated with
with aa lattice
lattice
point.
point. There are
are four
four atoms per
per unit
unit cell,
cell, located
located at
at 0 1,
Or/-}, 0 fj
Y y t,
f ,

1 (1 +
\ (\ + y} T>y) t, and 1 (1
i (2 -
"~
y)
y) T1-. Here we have an example
example of
of a
a variable
variable
parameter
parameter y y in
in the
the atomic coordinates.
coordinates. Crystals Crystals often
often contain
contain suchsuch vari-
vari-
able parameters, which may
able parameters, may have any
any fractional
fractional value
value without
without destroying
destroying
any
any of of the
the symmetry
symmetry elements
elements of of the
the structure.
structure. A quite
quite different
different sub- sub-
stance
stance might
might have exactly
exactly the
the same structure
structure as
as uranium except
except for
for slightly
slightly
different
different values
values of of a, 6, c,
a, b, c, and y. y. For uranium yy is 0.105 0.005.
is 0.105 0.005.
Turning to
Turning to the
the crystal
crystal structure
structure of of compounds
compounds of of unlike
unlike atoms,
atoms, we find find
that
that the
the structure
structure is is built
built up up on
on the
the skeleton
skeleton of
of a
a Bravais
Bravais lattice
lattice but
but that
that
certain
certain other
other rules
rules must be be obeyed,
obeyed, precisely
precisely because
because there there are are unlike
unlike
atoms present.
present. Consider,
Consider, for
for example,
example, a
a crystal
crystal of
of A",By
A E
x y which
which might
might be be
an ordinary
ordinary chemical
chemical compound,
compound, an intermediate phase of relatively
intermediate phase of relatively fixed fixed
composition
composition in in some alloy
alloy system,
system, or or an ordered
ordered solid
solid solution.
solution. Then the the
arrangement
arrangement of
of atoms in
in A",By
A E
x y must satisfy
satisfy the following conditions:
the following conditions:
2-71
2-7] CRYSTAL STRUCTURE 47
47

oO Cs+
CB+

e cr

(010)
[010]

(a)
(a) CsC!
CsCl (b)
(b) NaC!
NaCl

FIG. 2-18. The structures

FIG. 2-18. structures of
of (a)
(a) CsCI
CsCl (common
(common toto CsBr, NiAl, ordered
CsBr, NiAl, ordered ,a-brass,
/3-brass,
ordered
ordered CuPd,
CuPd, etc.)
etc.) and (b)
(b) NaCI
NaCl (common
(common toto KCl,
KC1, CaSe,
CaSe, PbTe,
Pbf e, etc.).
etc.).

(1)
(1) Body-,
Body-, face-,
face-, oror base-centering
base-centering translations,
translations, if if present,
present, must begin begin
and end on on atoms of of the kind. For example,
the same kind. example, if
if the
the structure
structure is
is based
based
on
on aa body-centered
body-centered Bravais
Bravais lattice, then it
lattice, then it must be be possible
possible to to gogo from an
A atom, say,
atom, say, to
to another A atom by
by the
the translation
translation lll.
^ ^ f .

(2)
(2) The set set of
of A atoms in in the
the crystal
crystal and the the set
set ofof B atoms must sep- sep-
arately possess
arately possess the
the same symmetry
symmetry elements
elements as
as the
the crystal
crystal as as a a whole,
whole,
since
since inin fact
fact they
they make up up the
the crystal.
crystal. In particular, the
In particular, the operation
operation of of
any symmetry
any symmetry element
element present
present must bring
bring a
a given atom,
given atom, A for
for example,
example,
into
into coincidence
coincidence with anotheranother atom of of the
the same kind, kind, namely
namely A.
Suppose
Suppose we consider
consider thethe structures
structures of of a a few
few common crystals crystals in in light
light
of
of the
the above requirements.
requirements. Figure Figure 2-18
2-18 illustrates
illustrates the
the unit
unit cells
cells of
of two
ionic
ionic compounds,
compounds, CsCI CsCl and NaCI.
NaCl. These structures,
structures, both both cubic,
cubic, areare com-
mon to to many
many other
other crystals and,
crystals and, wherever
wherever they occur,
they occur, are
are referred
referred to
to as
as
"
the
the "CsCI
"CsCl structure"
structure" and the the "N
"NaClaCI structure."
structure. In
In considering
considering aa crystal
crystal
structure,
structure, one of of the
the most important
important things things to to determine is is its
its Bravais

lattice, since that

lattice, since that isis the
the basic
basic framework on which the the crystal
crystal is is built
built and
because,
because, as
as we shall
shall see
see later,
later, it
it has
has a profound
profound effect
effect on the
the x-ray
x-ray diffrac-
diffrac-
tion pattern
tion pattern of of that
that crystal.
crystal.
What is is the
the Bravais
Bravais lattice
lattice of of CsCI?
CsCl? FigureFigure 2-18(a)
2-1 8 (a) shows that that the
unit cell contains
unit cell contains two atoms,
atoms, ions
ions really,
really, since
since this
this compound
compound is is com-

pletely ionized
pletely ionized even in
in the
the solid
solid state:
state: a
a caesium ion
ion at
at 000 and a chlo-
chlo-
rine ion at
rine ion at lll.
^ \ \ The Bravais
. Bravais lattice
lattice is obviously
is obviously not not face-centered,
face-centered, but
we note
note that
that the
the body-centering translation III
body-centering translation \ \ \ connects
connects two atoms. atoms.
However,
However, these
these are
are unlike
unlike atoms and the
the lattice
lattice is
is therefore
therefore not
not body-
body-
48
48 THE GEOMETRY OF CRYSTALS 2
[CHAP. 2
[CHAP.

centered. It
centered. It is,
is, by
by elimination,
elimination, simple
simple cubic.
cubic. If one wishes,
If one wishes, one
one may
think of both
think of both ions,
ions, the
the caesium
caesium at at 000 and thethe chlorine
chlorine at ! ! !,
at \ \ ^, as
as be-
be-
ing
ing associated
associated with
with the
the lattice
lattice point
point at
at 000.
0. It
It is
is not
not possible, however,
possible, however,
to associate
to anyone
associate any caesium ion
one caesium ion with
with any
any particular
particular chlorine
chlorine ion
ion and re-
re-
fer to them
fer to them as CsCI molecule;
as aa CsCl molecule; the
the term
term "molecule"
"molecule" therefore
therefore has
has no
no real
real
physical significance
physical significance in
in such
such aa crystal,
crystal, and
and the
the is true
same is true of
of most inor-
inor-
ganic compounds
ganic compounds andand alloys.
alloys.
Close inspection
Close inspection ofof Fig.
Fig. 2-18(b)
2-18(b) will
will show that
that the
the unit
unit cell
cell of
of NaCl
NaCI
contains 88 ions,
contains ions, located
located as
as follows:
follows:
4
4 Na+
Na + at
at 000,
0, !\ !\ 0, !\ 0 !,
0, |, and 0 !
\ !
\

4 CI-
4 Cl~ at
at !\\\,
! !, 00 !, 0 !\ 0, and!
\, 0, 0 O.
and ^00.

The sodium
The ions are
sodium ions clearly face-centered,
are clearly face-centered, and we note
note that
that the
the face-center-
face-center-
ing
ing translations
translations (0
(0 0 0, ! !0,
0, \ \ 0, \ ! !, ! !),
0 \, 0 \ ^), when applied
applied to
to the
the chlorine
chlorine
ion at
ion ! !,
at !\\\, will
will reproduce
reproduce all all the
the chlorine-ion positions. The Bravais
chlorine-ion positions.
lattice of NaCl
lattice of N aCI isis therefore
therefore face-centered
face-centered cubic.
cubic. The ion positions, inci-
ion positions, inci-
dentally,
dentally, may
may be written in
be written in summary
summary form as:
as:

44 Na
Na+4 at
at 000
"

+
+ face-centering translations
face-centering translations

44 Cl-
Cl~ at \ !\ !\ +
at ! + face-centering
face-centering translations.
translations.

Note also
Note also that
that in
in these,
these, as
as in
in all
all other
other structures,
structures, the
the operation
operation ofof any
any
symmetry
symmetry element
element possessed
possessed by by the
the lattice
lattice must bring
bring similar
similar atoms or
or
ions into coincidence.
ions into coincidence. For example,
For example, in
in Fig. 2-18(b),
Fig. 2-18(b), 90
90 rotation
rotation about
the 4-fold [010]
the 4-fold 1 ! into
[010] rotation
rotation axis
axis shown brings
brings the
the chlorine
chlorine ion
ion at
at 0 1 \ into
coincidence
coincidence with
with the
the chlorine ion at
chlorine ion at ! 1 1, the
^11, the sodium ionion at
at 0 11
1 1 with

the
the sodium
sodium ionion at
at 11 1
1 1,
1, etc.
etc.

Elements
Elements and and compounds
compounds oftenoften have
have closely
closely similar
similar structures.
structures. Figure
Figure
2-19
2-19 shows
shows the unit cells
the unit cells of
of diamond and the the zinc-blende
zinc-blende form of of Zn8.
ZnS.
Both are face-centered
Both are face-centered cubic.
cubic. Diamond has
has 8
8 atoms per
per unit
unit cell, lo-
cell, lo-

cated
cated at
at
+
000 + face-centering
face-centering translations
translations

1 i I +
111 + face-centering
face-centering translations.
translations.

The
The atom
atom positions
positions in
in zinc
zinc blende
blende are
are identical
identical with
with these,
these, but
but the
the first
first

set of
set of positions
positions is
is now occupied
occupied byby one
one kind
kind of
of atom (8)
(S) and the
the other
other byby
aa different
different kind
kind (Zn).
(Zn).
Note that
Note that diamond and a a metal
metal like
like copper
copper have quite
quite dissimilar
dissimilar struc-
struc-
tures, although
tures, although both
both are
are based
based on
on aa face-centered
face-centered cubic
cubic Bravais
Bravais lattice.
lattice.

To distinguish
distinguish between
between these
these two,
two, the
the terms
terms "diamond cubic"
cubic" and "face-
"face-
centered cubic" are usually used.
centered cubic'' are usually used.
2-7]
2-7] CRYSTAL STRUCTURE 51
51

oCr oO Fe
eMo C position
position

<

(8.)
(a) (b)
(b)

FIG.
FIG. 2-21.
2-21. Structure
Structure of
of solid
solid solutions:
solutions: (a)
(a) Mo in
in Cr (substitutional);
(substitutional) (b)
(b) C in
in ;

a-Fe
a-Fe (interstitial).
(interstitial).

on the
the lattice
lattice of of the
the solvent,
solvent, while while in in the
the latter,
latter, solute
solute atoms fit fit into
into the
the
interstices of
interstices of the
the solvent
solvent lattice.
lattice. The interesting
interesting feature
feature of
of these
these struc-
struc-
tures is
tures is that
that the solutesolute atoms are are distributed
distributed more or or less
less at
at random. For For
example,
example, consider
consider a 10 10 atomic percent percent solution
solution of
of molybdenum
molybdenum in
in chro-
chro-
mium,
mium, which has a BCC structure. structure. The molybdenummolybdenum atoms can can occupy
occupy
either
either the comer corner or or body-centered
body-centered positionspositions of
of the
the cube
cube in
in a
a random,
random, ir- ir-

regular manner,
regular manner, and a small
small portion
portion of
of the
the crystal might
crystal might have
have the
the appear-
appear-
ance of of Fig.
Fig. 2-21(a).
2-21 (a). Five adjoining adjoining unit unit cells
cells are
are shown there, there, contain-
contain-
ing
ing a total
total of of 29 atoms,
atoms, 3 3 of
of which are are molybdenum.
molybdenum. This This section
section of of the
the
crystal
crystal therefore
therefore contains
contains somewhat more than
than 10
10 atomic
atomic percent
percent molyb- molyb-
denum, but the
denum, the next
next fivefive cells
cells would probably
probably containcontain somewhat less. less.

Such a structure
structure does does not not obeyobey the
the ordinary
ordinary rules
rules of
of crystallography:
crystallography:
for
for example,
example, the right-hand cell
the right-hand cell ofof the
the group
group shown does does notnot havehave cubic
cubic
symmetry,
symmetry, and one
one finds
finds througl)out
throughout the
the structure
structure that
that the
the translation
translation
given by
given by one one of the unit
of the unit cell vectors may
cell vectors may begin
begin on on an an atom of of one
one kind
kind
and end on an atom of of another
another kind. kind. All that can
All that can be be said
said ofof this
this structure
structure
is that it
is that is Bee
it is BCC on on the average, and experimentally
the average, experimentally we find that it
find that displays
it displays

the x-ray diffraction

the x-ray diffraction effects proper to
effects proper to aa Bee
BCC lattice.
lattice. This is
This is not
not surpris-
surpris-
ing since
ing since the the x-ray
x-ray beam used used to to examine
examine the the crystal
crystal is is so
so large
large compared
compared
to the
to the size
size of of a unit
unit cell
cell that
that it it observes,
observes, so to speak,
so to speak, millions
millions of of unit
unit cells
cells
at the
at the same time time and so so obtains
obtains only only anan average "picture"
average "picture" of
of the
the structure.
structure.
The above remarks remarks apply apply equally
equally well well to to interstitial
interstitial solidsolid solutions.
solutions.
These formform whenever
whenever the the solute
solute atom is is small
small enough
enough to to fit into the
fit into the sol-
sol-
vent lattice
vent lattice without
without causing
causing too too much distortion.
distortion. Ferrite,Ferrite, thethe solid
solid solu-
solu-
tion of
tion of carbon
carbon in in a-iron,
a-iron, is is aa good
good example.
example. In In thethe unit
unit cell
cell shown in in
Fig.
Fig. 2-21
2-21 (b),
(b), there
there are
are two kinds
kinds of
of "holes"
"holes" in
in the
the lattice:
lattice: one
one at
at | l
! 0
(marked
(marked ) .) and equivalent positions
equivalent positions in
in the
the centers
centers of
of the
the cube
cube faces
faces and
and
edges,
edges, and one
one at
at 1
J 0 l (marked
^ (marked x) x) and equivalent positions.
equivalent positions. All
All the
the
evidence at
evidence at hand points points to to the
the fact
fact that
that thethe carbon
carbon atoms atoms in in ferrite
ferrite are
are
located in
located in the
the holes
holes at at flo! f and equivalent positions.
equivalent positions. On the
the average,
average,
nowever, no
however, no more than than about
about 11 of of these
these positions
positions in in 500
500 unit
unit cells
cells isis occu-
occu-
2-8]
2-8] ATOM SIZ,,;t;
SIZES AND COORDINATION 53
53

the
the distance
distance of
of closest
closest approach
approach in
in the
the three
three common met.al
metal stnt('tures:
structures:

Va
BCC == - a , '

v2
V2
FCC = - aa,
2
>
(2-7)
(2-7)

HCP = a (hetween
(l)etwcen atoms in
in basal
basal plane),
plane),

=
J a2
"3
\ 3 + 4"4
cc 2 (het.wpen
(between atom in
and
and nC'ighbors
in hasal
basal plane

neighbors ahove
above or
plane
bC'low).
or below).

Values
Values ofof the
the distanC'e
distance ofof closeHt.
closest approach,
approach, togC'ther with HlP
together with the ('rYHtal
crystal struc'-
struc-
tures
tures and lat.tie('
lattice paramet.ers
parameters of of t.ht' plements, arp
the elements, are t.ahulat.ed
tabulated in in Appendix
Appendix 13. 13.

To a.a first.
first approximation,
approximation, t.il('the Hize
size of
of an atom is is aa ('onst.ant.
constant. In In ot.her
other
words,
words, anan iron
iron at.om
atom hashas the
the same size whether it.
size whpt.her it occur:,;
occurs inin pure
pure iron,
iron, an
intennediat.e
intermediate phasC',
phase, oror aa Holid
solid solution
solution This is
is aa YPrY
very useful
useful faet
fact toto re-
re-
member when investigating
investigating unknown erystal crystal structures,
structures, for for it
it enablelS
enables \II-;
us
to predict roughly
to predict roughly how large
large a a hole
hole isis neecssary
necessary in in aa proposed
proposed Htruet.ure
structure t.o to
accommodate aa given given at.om.
atom. More precisely,
precisely, it. isis known that.
it, that the
the Hize
size of
of
an atom has has a a slight. dl'pcndcnce
slight dependence on it.s
its coordmat1'on
coordination number,
number, whieh
which is
is t.he
the
number of of nearest.
nearest neighbors
neighbors of of thp
the given
given at,om
atom andarid whieh
which depends
depends on on
cryst.al
crystal st.ruct.ure.
structure. The coordinat.ion
coordination number of
of an
an at.om
atom in
in th('
the FCC or
or
HCP st.ructures
structures is is 12,
12, in
in BCC 8,
8, and in
in diamond {'uhie
cubic 4.
4. The Hmaller
smaller
the
the coordinat.ion
coordination numher,
number, the the smallpr
smaller the the volume oeC'upi('d
occupied by by aa giV('n
given
atom,
atom, and the the amount of of eont.raetion
contraction t.o to he expl'ct.cd
be expected with decreas('
with decrease in in co-
co-
ordination
ordination numnpr
number is is found t.oto be:
be:

Change
Change ill
in eoordination
coordination Hizc
Size ('olltrartion,
contraction, pcr('eut
percent

12 - S8
12 ---+ 33
12
12 -> 6
---+ 6 44
12
12 -> 4
---+ 12

This means,
means, forfor example,
example, that
that the
the diameter of of an iron
iron at.om
atom is is greater
greater if
if

the
the iron
iron is
is dissolved
dissolved in in FCC copper
copper than
than ifif it
it exists
exists in
in a
a crystal
crystal ofof BCC
a-iron. If
a-iron. If it
it were dissolved
dissolved inin copper,
copper, its
its diameter
diameter would be be approximately
approximately
2.48/0.97, or
2.48/0.97, or 2.56A.
2.56A.
The size
size of
of an atom in in a crystal
crystal also
also depends
depends on whether its binding is
its binding is

ionic, covalent, metallic,

ionic, covalent, metallic, or
or van der
der Waals,
Waals, and on its
its state
state of
of ionization.
ionization.
The more electrons
electrons are
are removed from from a a neutral
neutral atom the the smaller
smaller it be-
it be-

comes,
comes, as
as shown strikingly
strikingly for
for iron,
iron, whose atoms and ions
ions Fe,
Fe, Fe++,
"
Fe" 4 have
"
Fe+++ have diameters
diameters of 1.66, and 1.34A,
L34A, respectively.
"

of 2.48,
2.48, 1.66,
1 1

respectively.
54
54 THE GEOMETRY
THE GEOMETRY OF
OF CRYSTALS
CRYSTALS [CHAP. 22
[CHAP.

2-9 Crystal
2-9 Crystal shape.shape. We We have have said said nothing
nothing so so farfar about
about the the shape
shape of of
crystals, preferring
crystals, preferring to
to concentrate
concentrate instead
instead on
on their
their interior
interior structure.
structure.
However, the
However, the shape
shape of of crystals
crystals is, is, toto the
the layman,
layman, perhapsperhaps their their most
most char-char-
acteristic property,
acteristic property, and and nearly
nearly everyone
everyone isis familiarfamiliar with with the the beautifully
beautifully
developed flat
developed flat faces
faces exhibited
exhibited by by natural
natural minerals
minerals or or crystals
crystals artificially
artificially
grown
grown from
from aa supersaturated
supersaturated salt
salt solution.
solution. In
In fact,
fact, it
it was
was with
with aa study
study
of these
of these facesfaces and
and the
the angles
angles between
between them
them that
that the
the science
science of
of crystallog-
crystallog-
raphy began.
raphy began.
Nevertheless, the
Nevertheless, the shape
shape of crystals isis really
of crystals really aa secondary
secondary characteristic,
characteristic,
since itit depends
since depends on, on, andand is is aa consequence
consequence of, of, the interior arrangement
the interior arrangement of of
atoms. Sometimes
atoms. Sometimes the the external
external shape shape of of aa crystal
crystal is rather obviously
is rather obviously re- re-
lated to
lated to itsits smallest
smallest building
building block,block, the the unit cell, as
unit cell, as inin the
the little
little cubical
cubical
grains
grains of
of ordinary
ordinary table
table salt
salt (NaCI
(NaCl has
has a
a cubic
cubic lattice)
lattice) or
or the
the six-sided
six-sided
prisms of
prisms of natural
natural quartz quartz crystals
crystals (hexagonal
(hexagonal lattice).lattice). In In many other other
cases, however,
cases, however, the
the crystal
crystal and
and its
its unit
unit cell
cell have
have quite
quite different
different shapes;
shapes;
gold, for example, has a cubic lattice, but
gold, for example, has a cubic lattice,
but natural
natural gold gold crystals
crystals are are octa-
octa-
hedral in
hedral in form,
form, i.e.,
i.e., bounded
bounded by by eight
eight planes
planes of of the
the form {111}. IIll}.
An important
An important fact fact about
about crystal
crystal facesfaces was known long long before
before therethere waswas
any knowledge
any knowledge of crystal of crystal interiors.
interiors. It
It is
is expressed
expressed as
as the
the law
law of
of rational
rational
indices,
indices, which
which states
states that that thethe indices
indices of of naturally
naturally developed
developed crystal crystal facesfaces
are always composed
are always composed of small of small whole
whole numbers, rarely
numbers, rarely exceeding exceeding 3 or
or 4.
4.

Thus,
Thus, faces
faces of of the
the formform {100{
100 I, {1l11,
} ,
111
{ } ,
{11001,
{
iTOO ) ,
{210 \, etc.,
{
210 ) , etc., are observed but
are observed but
not
not such
such faces
faces as as {5101,
(510}, {7191,
{719}, etc. etc. We know today today that that planes
planes of of low
low
indices
indices havehave the the largest
largest density
density of of lattice
lattice points,
points, and it it is
is a law of of crystal
crystal
growth
growth that
that such
such planes
planes develop
develop at
at the
the expense
expense of
of planes
planes with high
high indices
indices

and few
and few lattice
lattice points.
points.
To
To aa metallurgist,
metallurgist, however, however, crystalscrystals with well-developed
well-developed faces faces are in in

the
the category
category of
of things
things heard
heard of
of but
but rarely
rarely seen.
seen. They
They occur occasionally
occasionally
on
on the
the free
free surface
surface of of castings,
castings, in in some electrodeposits,
electrodeposits, or or under other
conditions
conditions of no of no external
external constraint.
constraint. To aa metallurgist,
metallurgist, a crystal
crystal is is most

usually a "grain,"
usually a "grain," seen through seen through aa microscope
microscope in
in the
the company
company of
of many
other grains on a polished
other grains on a polished section. section. If
If he
he has
has an isolated
isolated single
single crystal, it
crystal, it

will
will have
have been been artificially
artificially grown grown either either fromfrom the melt,
the melt, and thus have the
and thus have the
shape
shape of of the
the crucible
crucible in in which
which it it solidified,
solidified, or or byby recrystallization,
recrystallization, and and
thus
thus have
have the shape of
the shape of the
the starting
starting material,
material, whetherwhether sheet, sheet, rod,rod, or wire.
or wire.
The
The shapes
shapes of
of the
the grains
grains in
in a
a poly crystalline
polycrystalline mass
mass of
of metal
metal are
are thethe re-
re-

sult
sult ofof several
several kindskinds of of forces,
forces, all all ofof which
which are are strong
strong enoughenough to to counter-
counter-
act
act the
the natural
natural tendency
tendency of of each
each grain grain to to grow
grow with with well-developed
well-developed flat flat

faces.
faces. The result is
The result is aa grain roughly
grain roughly polygonal polygonal in
in shape
shape with
with no
no obvious
obvious
aspect
aspect of of crystallinity.
crystallinity. Nevertheless,
Nevertheless, that that grain
grain is is aa crystal
crystal and and justjust asas
"crystalline"
"crystalline" as, as, for
for example,
example, aa well-developed
well-developed prism prism of
of natural
natural quartz,
quartz,
since
since the
the essence
essence of of crystallinity
crystallinity is is a a periodicity
periodicity of of inner
inner atomic
atomic arrange-
arrange-
ment
ment andand not not any regularity of
any regularity of outward
outward form. form.
2-10J
2-10] TWINNED CRYSTALS
CRYSTA.LS 55

2-10 Twinned
2-10 crystals. crystals have two parts
Some crystals
crystals. parts symmetrically
symmetrically
related to one
related to one another.
another. These, called
These, called twinned crystals,
crystals, are
are fairly
fairly common
both in
both in minerals
minerals and in
in metals
metals and alloys.
alloys.
relationship between
The relationship between the
the two parts
parts ofof aa twinned
twinned crystal
crystal is
is described
described
by the symmetry
by the symmetry operation
operation which will
will bring
bring one
one part
part into
into coincidence
coincidence
with the
with the other
other or
or with an extension
with an extension of
of the
the other.
other. kinds of
Two main kinds of
twinning are
twinning are distinguished,
distinguished, depending
depending onon whether
whether the
the symmetry
symmetry opera-
opera-
tion is
tion (a) 180
is (a) rotation about
180 rotation about an axis,
axis, called
called the
the twin
twin axis,
axis, or (b) reflec-
or (6) reflec-
tion across
tion across aa plane,
plane, called
called the
the twin
twin plane. plane on
plane. The plane on which
which the
the two
parts
parts of
of a
a twinned
twinned crystal
crystal are
are united
united is
is called
called the
the composition plane.
composition plane. In
In
the case
the case of
of aa reflection
reflection twin,
twin, the
the composition
composition plane
plane mayor
may or may not
not coin-
coin-
cide
cide with
with the
the twin
twin plane.
plane.
Of most interest to metallurgists,
interest to metallurgists, who deal
deal mainly with
mainly with FCC,
FCC, BCC,
BCC,
and HCP structures,
and structures, are the following
are the kinds of
following kinds of twins:
twins:
(1) Annealing twins,
(1) Annealing twins, such
such as
as occur
occur in
in FCC metals FCC
metals and alloys
alloys (Cu, Ni,
(Cu, Ni,
a-brass, AI, etc.),
a-brass, Al, etc.), which
which have
have been
been cold-worked
cold-worked and then
then annealed
annealed to
to
cause recrystallization.
cause recrystallization.
(2) Deformation twins,
(2) Deformation twins, such as as occur
occur in in deformed HCP metals metals (Zn,
(Zn,
Mg,
Mg, Be,Be, etc.)
etc.) and BCC metals
metals (a-Fe,
(a-Fe, W,
W, etc.).
etc.).
Annealing
Annealing twins twins inin FCC metalsmetals are are rotation twins, in
rotation twins, in which thethe two
parts
parts are
are related
related by
by a
a 180
180 rotation
rotation about a twin
twin axis
axis of
of the
the form (111).
(111).
Because
Because of of the
the high symmetry
high symmetry of
of the
the cubic
cubic lattice,
lattice, this
this orientation
orientation rela-
rela-
tionship
tionship is
is also
also given
given by by a
a 60
60 rotation
rotation about the
the twin axis
axis or
or by
by reflec-
reflec-
tion
tion across
across the 111 plane
the 1111}
{ j plane normal
normal to to the
the twin axis.
axis. InIn other
other words,
words, FCC
annealing
annealing twinstwins may
may also
also bebe classified
classified as as reflection
reflection twins.
twins. The twin plane plane
is also the composition
is also the composition plane. plane.
Occasionally,
Occasionally, annealing
annealing twinstwins appear
appear under the microscopemicroscope as as in
in Fig.
Fig.
2-22 (a) , with one part of a
2-22 (a), with one part of a grain (E) grain (B) twinned
twinned with respect
respect to
to the
the other
other
part (A).
part (A). The two
two parts
parts areare in
in contact
contact on on the
the composition
composition plane
plane (111)
(111)
which
which makes
makes aa straight-line
straight-line trace
trace on on the
the plane
plane ofof polish.
polish. More common,
common,
however,
however, is is the
the kind
kind shown in in Fig. 2-22 (b). The grain
Fig. 2-22(b). grain shown consists
consists ofof
three parts:
three parts: twotwo parts
parts (A(Ai1 and A 2) 2 ) of
of identical
identical orientation
orientation separated
separated by by a
third part (B)
third part (B) which
which isis twinned
twinned withwith respect
respect to to AA\1 and A 22 B is
. is known as

aa twin
twin band.
band.

(a)
(a) (b) (c)

FIG. 2-22. Twinned

FIG. 2-22. Twinned grains:
grains: (a)
(a) and (b) FCC annealing
and (b) annealing twins;
twins; (c)
(c) HCP defor-
defor-
mation
mation twin.
twin.
56
56 THE GEOMETRY
THE GEOMETRY OF
OF CRYSTALS
CRYSTALS [CHAP. 22
[CHAP.

C A B C

PLAN OF CRYSTAL
PLAN OF CRYHTAL PLAN OF TWIN
PLAN OF TWIN

FIG. 2-23.
FIG. 2-23. Twin band
Twin band in
in FCC
FCC lattice.
lattice. Plane
Plane of
of main
main drawing
drawing isis (110).
(110).
2-10)
2-10] TWINNED CRYSTALS
TWINNED CRYSTALS 59
59

'~
twinnin

.
twinning
shear
shear

~
::c ~ 0
0

I

~
I
I 0
t.I

.~
0

')

ya / /'
,
,
,, 0 2( , ",~
;R /-
; /

~/
'
, /

1,./ ;
,
~ 7~
/

So ~
0
0r'\ c

211]
![211]

~C (1012)
(1012)

0
0
b t~in plane
twin plane

c
~
N
n 0
b

'-J

~
;"000 . a2

~
I

~
~ L.- V ~A121O), ~I

J<:1/
PLAN OF
OF CRYSTAL
CRYSTAL
.......
4~al
c

OF TWIN
PLAN OF
al

1
aa

2-24.
FIG. 2-24.
FIG. Twin band
Twin band in Hep lattice.
in HCP lattice. Plane of
Plane of main
main drawing
drawing is is (1210).
(1210).
60
60 THE GEOMETRY OF CRYSTALS 2
[CHAP. 2

are said
are said to
to be
be first-order,
first-order, second-order,
second-order, etc.,
etc., twins
twins of
of the
the parent
parent crystal A.
crystal A.
all these
Not all these orientations
orientations are
are new.
new. InIn Fig.
Fig. 2-22
2-22(b), example, B may
for example,
(b), for may
be regarded
be regarded as
as the
the first-order
first-order twin
twin of All and A
of AI, as the
A22 as the first
first order
order twin
twin
of B. -4-2
of B. is therefore
A2 is therefore the
the second-order
second-order twin
twin of Al but
of AI but has
has the
the same orien-
orien-
tation as
tation as A
At.i.

2-11 The stereographic

2-11 stereographic projection.
projection. Crystal
Crystal drawings
drawings made inin perspec-
perspec-
tive or
tive or in
in the
the form of
form of plan
plan and elevation,
elevation, while
while they
they have
have their
their uses,
uses, are
are
not suitable
not suitable for
for displaying
displaying the
the angular
angular relationship
relationship between
between lattice
lattice planes
planes
and
and directions. frequently we are
directions. But frequently are more interested
interested in
in these
these angular
angular
relationships than
relationships than in
in any
any other
other aspect
aspect of
of the
the crystal,
crystal, and we then
then need
need aa
kind of
kind of drawing
drawing on which
which the
the angles between planes
angles between planes can
can be
be accurately
accurately
measured and
measured and which
which willwill permit
permit graphical
graphical solution
solution of of problems
problems involving
involving
such
such angles.
angles. The stereographic projection fills
stereographic projection fills this
this need.
need.
The orientation
orientation of of any plane in
any plane in a crystal
crystal can
can be be just
just asas well
well represented
represented
by
by the
the inclination
inclination of
of the
the normal
normal to
to that
that plane
plane relative
relative to
to some reference
reference
plane
plane as
as by
by the
the inclination
inclination of
of the
the plane
plane itself.
itself. All
All the
the planes
planes in
in aa crystal
crystal
can thus be
can thus represented by
be represented by aa set
set ofof plane
plane normals radiating
radiating from some one
point
point within
within the
the crystal.
crystal. If
If a reference
reference sphere
sphere is
is now described
described about
about
this point, the
this point, plane normals
the plane will intersect
normals will intersect the
the surface
surface of of the
the sphere
sphere in in aa
set
set of points called
of points POle8. This procedure
called poles. procedure is is illustrated
illustrated in Fig. 2-25,
in Fig. 2-25, which
is
is restricted
restricted to to the {100}I planes
the \100 planes of of a cubic
cubic crystal.
crystal. The pole
pole of of a plane
plane
represents,
represents, by by its
its position
position on
on the
the sphere,
sphere, the
the orientation
orientation of
of that
that plane.
plane.
A plane
plane maymay also
also bebe represented
represented by by the
the trace
trace the
the extended
extended plane plane makes
in
in the
the surface
surface of of the
the sphere,
sphere, as
as illustrated
illustrated in
in Fig. 2-26,
Fig. 2-26, where the
the trace
trace
ABCDA represents
represents the plane whose pole
the plane is PI.
pole is PI. This
This trace
trace is
is a
a great circle,
great circle,
i.e.,
i.e., aa circle
circle ofof maximum diameter,
diameter, if if the
the plane
plane passes
passes through
through the the center
center
of
of the
the sphere.
sphere. A plane
plane not
not passing through
passing through the
the center
center will
will intersect
intersect the
the
sphere
sphere in
in a
a small
small circle.
circle. On a ruled
ruled globe,
globe, for
for example,
example, the
the longitude
longitude lines
lines

100
100

010 t - - - t - - L 1 r - + - - - - f 010
010

100
100 M
FIG.
FIG. 2-25.
2-25. 100 I poles
{{1001 poles of
of a
a cubic
cubic FIG.
FIG. 2-26.
2-26. Angle
Angle between
between two planes.
planes.
crystal.
crystal.
2-11)
2-1 1J 8TEREOGRAPHIC PROJECTION
THE STEREOGRAPHIC 61
61

(meridians)
(meridians) are are great
great circles,
circles, while
while the
the latitude
latitude lines,
lines, except
except the
the equator,
equator,
are
are small
small circles.
circles.

The angle
angle a between two planes planes is
is evidently
evidently equal
equal toto the
the angle
angle between
between
their
their great
great circles or to
circles or to the
the angle
angle between their
their normals (Fig.
(Fig. 2-26).
2-26). But
this
this angle,
angle, inin degrees,
degrees, can alsoalso be
be measured on the the surface
surface ofof the
the sphere
sphere
along
along the
the great circle KLMNK connecting
great circle connecting the poles PI
the poles PI and P 22 of of the
the two
planes, if
planes, if this
this circle
circle has
has been
been divided
divided into
into 360 equal parts. The measure-
equal parts. measure-
ment of of an angle
angle hashas thus
thus been
been transferred
transferred from
from the planes themselves
the planes themselves
to
to the
the surface
surface ofof the
the reference
reference sphere.
sphere.
Preferring, however, to
Preferring, however, to measure angles
angles on a a flat
flat sheet
sheet of paper rather
of paper rather
than on the the surface
surface ofof aa sphere,
sphere, we find
find ourselves
ourselves inin the
the position
position ofof the
the

,
projection plane

-
basic circle

reference
reference
sphere
sphere

\
point of
projection

4
observer
observer

SECTION THROUGH
AB AND PC

I---"*--?'IB

FiG.
FIG. 2-27.
2-27. The stereographic
stereographic projection.
projection.
62
62 THE GEOMETRY
THE GEOMETRY OF
OF CRYSTALS
CRYSTALS [CHAP. 22
[CHAP.

geographer
geographer who wants
who wants to to transfer
transfer aa map map of of the
the world
world from from aa globe
globe to to aa
page
page of
of an
an atlas.
atlas. Of
Of the
the many
many known
known kinds
kinds of
of projections,
projections, he
he usually
usually
chooses aa more
chooses more or or less
less equal-area
equal-area projection
projection so that countries
so that countries of of equal
equal area
area
will be
will be represented
represented by by equal
equal areasareas on on the
the map.
map. In In crystallography,
crystallography, how- how-
ever, we
ever, we prefer
prefer the the equiangular
equiangular stereographic
stereographic projection
projection since since it it preserves
preserves
angular relationships faithfully
angular relationships faithfully although distorting although distorting areas.
areas. It
It is
is made by
made by
placing
placing aa plane
plane of
of projection
projection normal
normal to
to the
the end of
of any
any chosen
chosen diameter
diameter
of the
of the sphere
sphere and and usingusing the the other
other end of that diameter
of that diameter as as the
the point
point of of
projection.
projection. In Fig. In Fig. 2-27
2-27 the
the projection
projection plane plane is
is normal
normal to
to the
the diameter
diameter
AB, and
AB, and the the projection
projection is is made from from thethe point
point B. B. If If aa plane
plane hashas itsits pole
pole
at P,
at P, then
then the the stereographic
stereographic projection projection of of P is is at
at P',P', obtained
obtained by by draw-
ing the
ing line BP and
the line and producing
producing it it until
until it
it meets
meets the the projection
projection plane. plane. Al- Al-
ternately stated,
ternately stated, the the stereographic
stereographic projection
projection of of the poTe P is
the pole is the
the shadow
cast by
cast by P on on thethe projection
projection plane plane when aa light light source
source is is placed
placed at at B.B. The
observer, incidentally,
observer, incidentally, views
views the
the projection
projection from the
the side
side opposite
opposite the
the
light
light source.
source.
plane NESW
The plane N ESW is is normal
normal to to AB and passes passes through
through the the center
center C. C.
It therefore cuts
It therefore cuts the the sphere
sphere in in half
half and its its trace
trace in in the
the sphere
sphere is is a great
great
circle. 1This
circle. his great
great circle
circle projects
projects to to form the basic circk
the basic circle N'E'S'W
N' E'S'W' on the the
projection, and
projection, and allall poles
poles on on the
the left-hand hemisphere will project
left-hand hemisphere will project within
within
this basic
this basic circle.
circle. Poles Poles on on the
the right-hand
right-hand hemisphere
hemisphere will wiII project
project outside
outside
this
this basic circle, and
basic circle, those near
and those near B will will have projections
projections lying lying at very large
at very large
distances
distances from from the the center.
center. If
If we wish wish to to plot
plot such poles, poles, we move the
point
point of projection to
of projection to A and the projection plane
the projection plane to to B and distinguish
distinguish
the
the new set set of points so
of points so formed
formed by by minus signs,signs, thethe previous
previous set set (projected
(projected
from B)
from being
B) being marked with
with plus
plus signs.
signs. Note that
that movement of
of the pro-
pro-
jection plane
jection plane along along AB or
or its
its extension
extension merely
merely alters
alters the
the magnification;
magnification;
we usually
usually make it it tangent
tangent to to the
the sphere,
sphere, as as illustrated,
illustrated, but we Can can also
also
make it it pass through
pass through the
the center
center of
of the
the sphere,
sphere, for
for example,
example, in
in which case
the
the basic
basic circle
circle becomes
becomes identicalidentical with the the great circle N
great circle NESW.
ESW.
A lattice
lattice planeplane in
in a
a crystal
crystal is
is several
several steps
steps removed from its its stereo-
stereo-
graphic projection,
graphic projection, and it
it may be worth-while
may be worth-while at
at this
this stage
stage to
to summarize
these
these steps:
steps:
(1) The plane
(1) plane C is is represented
represented by its normal CPo
by its CP.
(2)
(2) The normal normal CP is is represented
represented by by its pole P,
its pole P, which is is its
its intersec-
intersec-
tion
tion with
with the the reference
reference sphere.sphere.
(3)
(3) The pole pole P is is represented
represented by by its
its stereographic
stereographic projectionprojection P'. P'.
After
After gaining
gaining some
some familiarity
familiarity with
with the
the stereographic
stereographic projection,
projection, the
student
student will will bebe able
able mentally
mentally to
to omit
omit these
these intermediate
intermediate steps
steps and he will
will

then
then refer
refer to to the
the projected
projected point point pI P' asas the
the pole
pole of of the
the plane
plane C C or,
or, even
more
more directly,
directly, as
as the
the plane
plane C itself.
itself.

Great
Great circles
circles on on thethe reference
reference sphere sphere project
project as as circular
circular arcs arcs on the the pro-
pro-
jection
jection or, or, if
if they pass
they pass throughthrough the
the points
points A and BB (Fig. 2-28),
(Fig. 2-28), as
as straight
straight
2-11)
2-11] THE STEREOGRAPHIC
THE STEREOGRAPHIC PROJECTION
PROJECTION 63
63

lines
lines through
through the center
center of
of the
the projection.
projection. Projected
Projected great
great circles
circles always
always
cut the basic
basic circle
circle in diametrically
diametrically opposite
opposite points,
points, since
since the
the locus
locus of
of a
a
great
great circle
circle on
on the sphere
sphere isis a
a set
set of
of diametrically
diametrically opposite
opposite points.
points. Thus
Thus
the great circle ANBS in
great circle in Fig.
Fig. 2-28 projects
projects as
as the
the straight line N'S'
straight line N'S' and
and
AWBE as W'E';
AWBE WE'\ the great circle NGSH,
great circle NGSH, which is is inclined
inclined toto the
the plane
plane of
of
projection,
projection, projects
projects as
as the
the circle arc N'G'S'.
circle arc N'G'S'. IfIf the
the half
half great
great circle WAE
circle W AE
is
is divided into
into 18 equal
equal parts
parts and thesethese points
points of of division
division projected
projected onon
WAE' we obtain a graduated
W'AE', , graduated scale,
scale, at
at 10
10 intervals,
intervals, on on the
the equator
equator ofof
the basic circle.
circle.

N'

basic
circle

S'
FIG. 2-28.
FIG. 2-28. Stereographic projection
Stereographic projection of
of great
great and
and small
small circles.
circles.
64
64 THE GEOMETRY or
OP CRYSTALS [CHAP. 2
[CRAP.

FIG. 2-29. Wulff

FIG. 2-29. Wulff net
net drawn to 2 intervals.
to 2 intervals.

Small
Small circles
circles on
on the
the sphere
sphere also
also project
project asas circles,
circles, but their
their projected
projected
center
center does
does not
not coincide
coincide with
with their
their center
center onon the
the projection.
projection. For example,
example,
the circle AJEK whose center
the circle center P lies on AW
P lies AWBE BE projects
projects as AJ'E'K'. Its
as AJ'E'K'. Its
center
center onon the projection is
the projection at C,
is at C, located
located at
at equal
equal distances
distances from A and E',
',

but
but its projected center
its projected center is
is at P', located
at P', located an equal
equal number of of degrees
degrees (45
(45
0

in
in this
this case)
case) from
from A and E'.
E'.
The device
device most usefuluseful in
in solving
solving problems
problems involving
involving the the stereographic
stereographic
projection
projection is
is the
the Wulff
Wulff net
net shown in
in Fig.
Fig. 2-29.
2-29. It
It is
is the
the projection
projection ofof aa
sphere
sphere ruled
ruled with
with parallels
parallels of
of latitude
latitude and longitude
longitude on
on a
a plane parallel
plane parallel
to
to the
the north-south
north-south axis axis of
of the
the sphere.
sphere. The latitude
latitude lines
lines on
on aa Wulff net
net
are
are small
small circles
circles extending from side
extending from side to to side
side and the longitude
the longitude lines
lines (merid-
(merid-
ians)
ians) are
are great
great circles
circles connecting
connecting the the north
north and south poles of
south poles of the
the net.
net.
2-11)
2-11] THE STEREOGRAPHIC PROJECTION 65

PROJECTION

Wulff net

FIG.
FIG. 2-30.
2-30. Stereographir
Stereographie projection
projection superimposed
superimposed on Wulff
Wulff net
net for
for measurement
of
of angle between poleR.
angle between poles.

These nets
nets are
are available
available in in various
various sizes,
sizes, one of of IS-cm
18-cm diameter
diameter giving
giving an
accuracy
accuracy of
of about one degree,
degree, which is
is satisfactory
satisfactory for
for most problems;
problems;
to
to obtain
obtain greater
greater precision,
precision, either
either a a larger
larger net net or
or mathematical
mathematical calculation
calculation
must be be used.
used. Wulff nets
nets are
are used
used by by making
making the the stereographic projec-
stereographic projec-
tion
tion on tracing paper
tracing paper and with the
the basic
basic circle
circle of
of the
the same diameter
diameter as
as
that
that ofof the
the Wulff net;net; the projection is
the projection is then
then superimposed
superimposed on the
the Wulff
net
net and pinned
pinned at at the
the center
center so so that
that itit is
is free
free to
to rotate
rotate with
with respect
respect to to the
the
net.
net.
To return
return to to our
our problem
problem of of the
the measurement of of the
the angle
angle between
two crystal planes,
crystal planes, we saw in
in Fig.
Fig. 2-26 that
that this
this angle
angle could
could be measured
on the
the surface
surface ofof the
the sphere along
sphere along the
the great
great circle
circle connecting
connecting the the poles
poles of
of
the
the two planes.
planes. This measurement can can also
also bebe carried
carried out
out on the the stereo-
stereo-
graphic
graphic projection
projection if, if, and only
only if,
if, the projected poles
the projected poles lie
lie on a great
great circle.
circle.

In
In Fig. 2-30,
Fig. 2-30, for
for example,
example, the
the angle
angle between the
the planes
planes* A and B or C
or
and D can be be measured directly, simply by
directly, simply by counting counting the
the number of
of de-
de-
grees separating
grees separating them along
along the
the great
great circle
circle on which they
they lie.
lie. Note that
that
the angle C-D equals
the angle equals the angle E-F,
the angle E-F, there being the
there being the same difference
difference in in
latitude
latitude between C and D as as between E and F. F.
If
If the
the two poles
poles dodo not
not lie
lie on
on aa great
great circle,
circle, then
then the
the projection
projection is is rotated
rotated
relative
relative toto the
the Wulff
Wulff netnet until
until they
they do lie
lie on a great
great circle, where the
circle, w.here the de-
de-

* We are
are here
here using
using the
the abbreviated
abbreviated terminology
terminology referred to above.
referred to above.
66 PROJECTION N

)V~--------------4---------------~E

(a)
(a)

FIG. 2-31. (a)

FIG. 2-31. (a) Stereo-
Stereo-
graphic
graphic projection
projection ofof poles
poles
PI and P 22 of
Pi and of Fig.
Fig. 2-26.
2-26. (b)(b)
Rotation
Rotation of of projection
projection toto put
put
poles
poles on
on same great
great circle
circle of
of Wulff (b)
(b)
poles = 30.
net.
net. Angle
Angle between
between poles = 30.
2-11]
2-11] THE STEREOGRAPHIC PROJECTION 67
sired
sired angle
angle measurement can then be made. Figure Figure 2-31 (a) (a) is
is a projec-
a projec-
tion
tion of
of the poles PI
the two poles PI and P 22 shown in perspective in
in perspective in Fig.
Fig. 2-26,
2-26, and the the
angle between them is
angle is found by by the
the rotation
rotation illustrated
illustrated in in Fig.
Fig. 2-31 (b).
2-3 l(b).
This
This rotation
rotation ofof the projection
projection is is equivalent
equivalent to to rotation
rotation of of the
the poles
poles on
latitude
latitude circles
circles of
of aa sphere
sphere whose north-south
north-south axisaxis isis perpendicular
perpendicular to to the
the
projection plane.
projection plane.
As shown in in Fig.
Fig. 2-26,
2-26, a a plane
plane maymay bebe represented
represented by by its
its trace
trace inin the
reference
reference sphere.
sphere. This trace trace becomes a a great
great circle
circle in
in the
the stereographic
stereographic
projection.
projection. Since
Since every
every point
point on this
this great circle is
great circle is 90
90 from the the pole
pole ofof
the plane, the
the plane, the great
great circle
circle may
may be be found byby rotating
rotating the the projection until
projection until
the
the pole falls on the
pole falls the equator
equator bf 'of the
the underlying
underlying Wulff
Wulff netnet and tracing
tracing that
that
meridian
meridian which cuts cuts the
the equator
equator 90 90 from
from the pole, as
the pole, as illustrated
illustrated in in Fig.
Fig.
2-32. If
2-32. If this
this is
is done for for two poles,
poles, as
as in
in Fig.
Fig. 2-33,
2-33, thethe angle
angle between the
corresponding
corresponding planes
planes may may also
also bebe found from the the angle
angle of of intersection
intersection of of
the
the two great
great circles corresponding to
circles corresponding to these
these poles;
poles; it it is
is in
in this
this sense
sense that
that
the
the stereographic
stereographic projection
projection is is said
said to
to be angle-true.
angle-true. This method of of an-

gle measurement is
gle is not
not as
as accurate,
accurate, however,
however, asas that
that shpwn
shpwn in in Fig.
Fig. 2-31(b).
2-3 l(b).

FIG.
FIG. 2-32.
2-32. Method of
of finding
finding the
the trace
trace of
of a
a pole
pole (the pole P2'
(the pole P 2 in
in Fig.
Fig. 2-31).
'
2-31).
68
68 THE GEOMETRY OF CRYSTALS [CHAP. 2
[CHAP. 2

PROJECTION N

Pi

Wr-------~~----~----~~r_------~E

FIG.
FIG. 2-33.
2-33. Measurement of
of an angle
angle between two poles (Pi and P 22 of
poles (p] of Fig.
Fig. 2-2ti)
2-26)
by
by measurement of
of the
the angle
angle of
of interseetion
intersection of
of the
the corresponrling
corresponding traces.
traces.

PROJECTION

s
FIG. 2-34.
FIG. 2-34. Rotation of
Rotation of poles
poles about
about axis of
NS axis of projection.
projection.
2-11)
2-11] THE STEREOGRAPHIC PROJECTION
THE STEREOGRAPHIC PROJECTION 69
69

We often
We often wish
wish to
to rotate
rotate poles
poles around
around various axes. We
various axes. We havehave already
already
seen that
seen that rotation
rotation about
about an
an axis
axis normal
normal to
to the
the projection
projection isis accomplished
accomplished
simply by
simply by rotation
rotation of
of the
the projection
projection around
around the
the center
center of
of thethe Wulff
Wulff net.
net.
Rotation about
Rotation about an
an axis
axis lying
lying in
in the
the plane
plane of
of the
the projection
projection isis performed
performed
by, first,
by, first, rotating
rotating the axis about
the axis about the
the center
center of
of the
the Wulff
Wulff net
net until
until itit coin-
coin-
cides with
cides with the
the north-south
north-south axis
axis if it
if it does
does not not already
already do do so,
so, and,
and, second,
second,
moving
moving the
the poles
poles involved
involved along
along their
their respective
respective latitude
latitude circles
circles the re-
the re-
quired
quired number
number of
of degrees.
degrees. Suppose Suppose it
it is
is required
required to
to rotate
rotate the
the poles
poles Al
A\
and BI
and BI shown
shown in in Fig.
Fig. 2-342-34 by by 60 60 about
about the the NS axis, axis, thethe direction
direction of of mo-
mo-
tion being
tion being from from W to to E on on the the projection.
projection. Then AI Then A 1 moves to A22 along
moves to A along
its latitude
its latitude circlecircle as as shown.
shown. #1, B1, however,
however, can can rotate
rotate only only 40 40 before
before
finding itself
finding itself at
at the
the edge
edge of of the
the projection;
projection; we must then then imagine
imagine it to move
it to
20 in
20 in from
from the the edge
edge to to the
the point
point B[ B~ on on thethe other
other sideside of of the
the projection,
projection,
staying always
staying always on on itsits own latitude
latitude circle.circle. The final final position
position of of this
this pole
pole
on
on the
the positive
positive side
side of
of the
the projection
projection is
is at
at B
B2 diametrically
2 diametrically opposite opposite B~.
B\.
Rotation about
Rotation about an an axis
axis inclined
inelined to to thethe plane
plane of of projection
projection is is accomplished
accomplished
by compounding
by compounding rotations rotations about about axes axes lyinglying in and perpendicular
in perpendicular to to the
the
projection plane.
projection plane. In In this
this case,
case, thethe givengiven axis axis must first first be rotated
rotated intointo
coincidence with
coincidence with one one or or the
the other
other of of thethe two latter latter axes,
axes, the the given
given rota-
rota-
tion performed,
tion performed, and and the the axisaxis thenthen rotated
rotated back to to its
its original
original position.
position.
Any movement of
Any the given
of the given axis axis must be be accompanied
accompanied by by a similar move-
ment
ment of of all
all the
the poles
poles on
on the
the projection.
projection.
For
For example,
example, we may may be be required
required to to rotate
rotate AI A 1 about BI Bl by by 4040 in in aa
clockwise
clockwise direetion
direction (Fig. (Fig. 2-35).
2-35). In (a) (a) the
the polepole toto be rotated Al and the
}
A and the
rotation
rotation axis axis BIBI are
are shown in in their
their initial
initial position.
position. In (b) (b) the projection
projection
has
has been
been rotated
rotated to to bring
bring Bl
BI to
to the
the equator
equator of
of a Wulff net.
net. A rotation of
of

48
48 about
about the the NS axis axis of of the
the net net brings
brings Bl
BI to
to the
the point
point B
B2 2 at
at the center
of
of the
the net;
net; at at the
the same time time Al AI must go go to to A2A 2 along
along a parallel
parallel of latitude.
latitude.

The rotation
rotation axis axis is
is now perpendicular
perpendicular to
to the
the projection
projection plane, and the
plane, the
required
required rotation
rotation of of 40 brings A22 to
40 brings A to A33 along
A along a circular path
a circular path centered
centered
on B 22 . The operations
on .
operations which which brought
brought B1 BI to B 2 must now be reversed
to B2 reversed in in

order
order to return B2
to return B 2 to to its
its original
original position. Accordingly, B2
position. Accordingly, B 2 isis brought
brought to to
B3
JBs and
and A3
A% to
to A 4 ,
A*, by by aa 48
48 reverse
reverse rotation
rotation about the NS axis
axis of
of the
the net.
net.

In
In (c)
(c) the
the projection
projection has
has been
been rotated
rotated back to
to its
its initial
initial position,
position, construc-
tion
tion lines
lines have
have been
been omitted,
omitted, and only only the the initial
initial and
and final
final positions
positions of of the
the
rotated pole are shown.
rotated pole are shown. During During its
its rotation
rotation about
about Bt,
B^ AI Al moves
moves along
along
the
the small
small circle
circle shown.
shown. This This circle
circle is is centered
centered at at CC onon thethe projection
projection and and
not
not at at its
its projected
projected center center B BI.1 ToTo find find C C wewe useuse thethe fact
fact that
that all points
all points
on
on the
the circle
circle must
must lie lie at equal angular
at equal angular distances
distances from from B 1 ; in
BI] in this
this case,
case,
measurement
measurement on on aa Wulff
Wulff net net shows
shows that that bothboth Al and A4
AI and A are are 7676 fromfrom B B\.
1
Accordingly,
Accordingly, we
we locate
locate any
any other
other point,
point, such
such as
as D,
D, which
which is
is 76
76 from
from BlI
B\,
and
and knowing center C.
knowing three three points
points on on thethe required
required circle, circle, wewe cancan locate
locate its its center C.
70
70 THE GEOMETRY OP
THE GEOMETRY OF CRYSTALS
CRYSTALS [CHAP. 22
[CHAP.

40

48

(b)

------------~--------~E

s
(a)
(a) (c)
(c)

FIG.
FIG. 2-35.
2-35. Rotation
Rotation of
of a
a pole
pole about
about an
an inclined
inclined axis.
axis.
2-111
2-11] THE 8TEREOGRAPHIC PROJECTION
THE 8TEREOGRAPHIC PROJECTION 71
71

In dealing
In dealing with
with problems
problems of of crystal
crystal orientation
orientation aa standard projedion isis
lltandard projection
of very
of very great
great value,
value, since
since it shows
it shows atat aa glance
glance the
the relative
relative orientation
orientation ofof
all the
all the important
important planes
planes inin the
the crystal.
crystal. Such
Such aa projection
projection isis made
made by
by se-
se-
lecting some
lecting some important
important crystal
crystal plane
plane of
of low
low indices
indices as
as the
the plane
plane of
of pro-
pro-
jection [e.g.,
jection [e.g., (100),
(100), (110),
(110), (111),
(111), or
or (0001)]
(0001)] and
and projecting
projecting the
the poles
poles of
of
various crystal
various crystal planes
planes onto
onto the the selected
selected plane.
plane. The
The construction
construction of of aa
standard projection
standard projection of
of aa crystal
crystal requires
requires aa knowledge
knowledge of of the
the interplanar
interplanar
angles
angles for
for all
all the
the principal
principal planes
planes of
of the
the crystal.
crystal. AA set
set of
of values
values applicable
applicable
to all
to all crystals
crystals in
in the
the cubic
cubic system
system isis given
given in
in Table
Table 2-3,
2-3, but
but those
those for
for
crystals
crystals of
of other
other systems
systems depend
depend on
on the
the particular
particular axial
axial ratios
ratios involved
involved
and must
and must be
be calculated
calculated for
for each
each case
case by
by the
the equations
equations given
given in
in Appendix
Appendix 1.
1.
Much time
Much time can
can be
be saved
saved in
in making
making standard
standard projections
projections by
by making
making use
use
of the
of the zonal
zonal relation:
relation: the
the normals
normals to
to all
all planes
planes belonging
belonging to
to one
one zone
zone are
are
coplanar and
coplanar and at at right
right angles
angles toto the
the zone
zone axis.
axis. Consequently,
Consequently, the the poles
poles
of planes
of planes of
of aa zone
zone will
will all
all lie
lie on
on the
the same
same great
great circle
circle on the
the projection,
projection,
and the
and the axis
axis of
of the
the zone
zone will
will be
be at
at 90
90 from this
this great
great circle.
circle. Furthermore,
Furthermore,
important planes usually
important planes usually belong belong to
to more than one zone
zone and their poles
their poles
are therefore
are therefore located
located at
at the
the intersection
intersection of
of zone
zone circles.
circles. It
It is
is also
also helpful
helpful
to remember
to remember that
that important
important directions,
directions, which in
in the
the cubic
cubic system
system are
are
normal to
normal to planes
planes of
of the
the same indices, are
indices, are usually
usually the
the axes
axes of
of important
important
zones.
zones.
Figure
Figure 2-36(a) shows the
2-36 (a) shows the principal
principal poles
poles of
of a cubic
cubic crystal
crystal projected
projected on
the
the (001) plane
(001) plane of
of the
the crystal or,
crystal or, in
in other
other words,
words, a standard (001)
(001) projec-
projec-
tion.
tion. The
The location
location of the 1100
of the {100} I cube poles
poles follows
follows immediately
immediately from Fig.
Fig.
2-25.
2-25. To locate
locate the
the 1110 I poles
{110} poles we first
first note from Table 2-3 that they
they
must
must lie
lie at
at 45
45 from {100}I poles,
from 1100 poles, which areare themselves 90 90 apart.
apart. InIn

100
100 100
100

no 110
111

1)10 Oil

no no

100 100
(a) (b)

FIG. 2-36.
FIG. 2-36. Standard
Standard projections
projections of
of cubic
cubic crystals,
crystals, (a)
(a) on (001) and
on (001) and (b)
(b) on
on (011).
(Oil).
72
72 OF CRYSTALS
THE GEOMETRY OF
THE CRYSTALS [CHAP. 2
[CHAP. 2

TABLE 2-3

INTERPLANAR ANGLES (IN BETWEEN

(IN DEGREES) IN CUBIC CRYSTALS BETWEEN
I
hlklld AND
FORM \hik\li\
OF THE FORM
PLANES OF AND h2k2121 I
IhJk]IJI
I h2k2121
100 110 III 210 211 221 310

100 0
90
110 45 0
90 60
90
111 54.7 35.3 0
90 70.5
109.5
210 26.6 18.4 39.2 0
63.4 50.8 75.0 36.9
90 71.6 53.1
211 35.3 30 19.5 24.1 0
65.9 54.7 61.9 43.1 33.6
73.2 90 56.8 48.2
90
221 48.2 19.5 15.8 26.6 17.7 0
70.5 45 54.7 41.8 35.3 27.3
76.4 78.9 53.4 47.1 39.0
90
310 18.4 26.6 43.1 8.1 25.4 32.5 0
71.6 47.9 68.6 58.1 49.8 42.5 25.9
90 63.4 45 58.9 58.2 36.9
77.1
311 25.2 31.5 29.5 19.3 10.0 25.2 17.6
72.5 64.8 58.5 47.6 42.4 45.3 40.3
90 80.0 66.1 60.5 59.8 55.1
320 33.7 11.3 61.3 7.1 25.2 22.4 15.3
56.3 54.0 71.3 29.8 37.6 42.3 37.9
90 66.9 41.9 55.6 49.7 52.1
321 36.7 19.1 22.2 17.0 10.9 11.5 21.6
57.7 40.9 51.9 33.2 29.2 27.0 32.3
74.5 55.5 72.0 53.3 40.2 36.7 40.5
90
331 46.5 13.1 22.0
510 11.4
511 15.6
711 11.3

Largely from R.
Largely R. M. Bozorth, Rev. 26,
Phys. Rev.
Bozorth, Phys. 26, 390
390 (1925);
(1925); rounded
rounded
off to the
off to the nearest
nearest 0.1.
0.1.
2-111
2-11] THE STEREOGRAPHIC PROJECTION
THE STEREOGRAPHIC PROJECTION 73
73

~il'!.o _ _Too_ _ ~5JO

[112)
[112]
zone

mi]
1110]

.121
i31
.i22
oiJ2 .i~1
[001] -i3,
zone
zone

.
013 012 013 032 021 031

..
011
-115
[100)
[100] // II~ 123
el33
.132
103 151 150
zone
zone -'22

-112 131
102

e ..
-213 -'21
203

212
"' -1:31
J~
101
-'221
.31t

302 -211 -331
-!21

201
-Joll
301

'0'
-511

'ID;----~--."O
100

FIG. 2-37.
FIG. 2-37. Standard
Standard (001)
(001) projection
projection of
of a cubic
cubic crystal.
crystal. (From
(From Structure of
of
Metals, by C.
Metals, by C. S.
S. Barrett,
Barrett, McGraw-Hill Book Company,
Company, Inc.,
Inc., 1952.)
1952.)

this
this way
way we locate locate (011),
(Oil), for
for example,
example, on the the great
great circle
circle joining
joining (001)
(001)
and
and (010)
(010) and
and at
at 45
45 from each.
each. After
After all
all the
the {11O}
{110} poles
poles are plotted,
plotted,
we can
can find
find the
the {Ill}
{
111 poles
} poles atat the
the intersection
intersection of of zone circles.
circles. Inspection
Inspection
of
of a
a crystal
crystal model
model or
or drawing
drawing or
or use
use of
of the zone relation
relation given
given by Eq.
by JEq.
(2-3)
(2-3) will
will show
show that
that (lll),
(111), for
for example,
example, belongsbelongs to
to both the zone [101]
[101]
and
and the
the zone
zone [011].
[Oil]. The pole
pole ofof (111)
(111) is is thus located
located at at the intersection
of
of the
the zone
zone circle
circle through (010),
through (OlO), (101), (101), and (010)
(010) and the zone circlecircle

through (100),
through (TOO), (Oil), (OIl), and (100).
(100). This location
location may be
be checked by
by meas-
urement
urement of of its
its angular
angular distance
distance fromfrom (010)(010) or (100), which should be
or (100),
54.7.
54.7. The The (011)
(Oil) standard
standard projection
projection shown
shown in
in Fig.
Fig. 2-36(b)
2-36(b) is is plotted
plotted in
the
the same
same manner.
manner. Alternately,
Alternately, it
it may
may be
be constructed
constructed by
by rotating
rotating all
all the
the
poles
poles in
in the
the (001) projection
(001) projection 45
45 to
to the
the left
left about
about the
the NS
NS axis
axis of
of the
the pro-
pro-
jection,
jection, since
since this
this operation
operation willwill bring
bring the (Oil) pole
the (011) pole to to the
the center.
center. In In
both
both ofof these
these projections symmetry
projections symmetry symbols symbols have
have been
been given
given each
each pole
pole
in
in conformity
conformity with with Fig. 2-6(b), and
Fig. 2-fj(b), and it it will
will be be noted
noted thatthat the
the projection
projection
itself
itself has
has thethe symmetry
symmetry of
of the
the axis
axis perpendicular
perpendicular to
to its
its plane,
plane, Figs.
Figs. 2-36(a)
2-36(a)
and (b) having 4-fold
and (b) having 4-fold and and 2-fold
2-fold symmetry, respectively.
symmetry, respectively.
74
74 THE GEOMETRY OF CRYSTALS [CHAP. 2
[CHAP.

1010
Jl20

1130

.
T530, i021

. .
ii21 -ioll fill
1211
oito
ii22 1112
.0~21

.oill
.O~21
.
ii24 .iOll
.io, ...
.
~1I4
.2103
.ito.
.2201

d20
.'
1321
1321
Oi12
.Oill
0113..
..
_0114
OilS
-jQtS

hil
. 53TO

.' .0001

.
1211 0
i2T4 i212
.li05 .OtiS
_. -,i04 .OI~1)1i3
2311
-,102 1103 .Iois .oli2 foil 320

0 2201
-1101
no.
'2203
.
2ii4
-,oi...
'loT3
ioTs .
.
IIf4
00223

.IOi2
02023 .
. ..
2112 1122

2iil 1251
1121

loio

FIG. 2-38. Standard (0001)

FIG. 2-38. (0001) projection
projection for
for zinc
zinc (hexagonal,
(hexagonal, cia
= 1.86).
c/a = 1.86). (From
(From
Structure of
Structure Metals, by
of Metals, by C.
C. S.
S. Barrett,
Barrett, McGraw-Hill Book Company,
Company, Inc.,
Inc., 1952.)
1952.)

Figure
Figure 2-37
2-37 is
is a
a standard
standard (001)(001) projection
projection of of aa cubic
cubic crystal
crystal with
with con-
con-
siderably
siderably more detail
detail and a a few
few important
important zoneszones indicated.
indicated. A standard
standard
(0001)
(0001) projection
projection ofof a
a hexagonal
hexagonal crystal
crystal (zinc)
(zinc) is
is given
given inin Fig.
Fig. 2-38.
2-38.
It
It is
is sometimes
sometimes necessary
necessary to to determine
determine the Miller indices
the Miller indices ofof a given
given
pole on aa crystal
pole projection, for
crystal projection, for example
example the pole A in
the pole in Fig.
Fig. 2-39("8.),
2-39(a), which
applies to
applies to a
a cubic crystal. If
cubic crystal. If aa detailed
detailed standard
standard projection
projection is is available,
available,
the
the projection
projection with the the unknown pole pole can be superimposed on it
be superimposed it and itsits

indices
indices will
will be
be disclosed
disclosed by by its
its coincidence
coincidence with with one
one of
of the
the known polespoles
on the
the standard. Alternatively, the
standard. Alternatively, the method illustrated
illustrated inin Fig.
Fig. 2-39 may may
be
be used.
used. pole A defines
The pole defines a a direction
direction in in space,
space, normal to to the
the plane
plane
(hkl) whose indices
(hkl) indices are
are required,
required, and this this direction
direction makes angles
angles p, p, IT, Tr <r,

with the
the coordinate
coordinate axes
axes ., b, c.
a, b, c. These angles
angles are
are measured on the the pro-
pro-
jection as
jection as shown in in (a).
(a). Let
Let the
the perpendicular
perpendicular distance
distance between
between the the ori-
ori-
gin
gin and thethe (hkl) plane nearest
(hkl) plane nearest the origin be
the origin be d [Fig.
[Fig. 2-39(b)),
2-39(b)], and let let the
the
direction
direction cosines
cosines of
of the
the line
line A be be p,p, q,
g, T.
r. Therefore
Therefore

d
d d d
p = cosp
cosp = - , q = COS a
cos IT =-, T == COST"'-'
cos r
alh
o/fc' blk
bjk ell
 2-111
2-11] THE
THE STEREOGRAPHIC
STEREOGRAPHIC PROJECTION
PROJECTION 75
75

c:

~~--~~----_a
100
100

(a)
(a) (b)
(b)

FIG. 2-39.
FIG. 2-39. Determination of
Determination of the
the Miller
Miller indices
indices of
of aa pole.
pole.

h:k:l =
h:k:l pa:qb:rc.
= pa:qb:rc. (2-8)
(2-8)

For the
For the cubic
cubic system
system we have have the
the simple
simple result
result that
that the
the Miller
Miller indices
indices
required
required are
are in
in the
the same
same ratio
ratio as
as the
the direction
direction cosines.
cosines.
The lattice
The lattice reorientation
reorientation caused
caused by by twinning
twinning cancan be
be clearly
clearly shown
shown onon
the stereographic
the stereographic projection.
projection. In In Fig.
Fig. 2-40
2-40 the
the open
open symbols
symbols are the 1100}
are the 100}
{

poles of
poles of aa cubic
cubic crystal projected on
crystal projected on the (001) plane. If
(OOl)jplane. this crystal
If this crystal is
is

FCC, then
then one
one of
of its possible twin
twin planes is (IT1),
is represented
represented on the
FCC, its possible planes (111),
projection
projection both
both by by its
its pole
pole and
and its
its trace.
trace. The cube poles
poles ofof the twin
twin
formed
formed by by reflection
reflection in
in this
this plane
plane are
are shown as
as solid
solid symbols;
symbols; these poles
poles
are
are located
located by by rotating
rotating thethe projection
projection on a a Wulff netnet until
until the pole
pole of
of the
twin
twin plane
plane lies
lies on
on the
the equator,
equator, after
after which the cube poles
poles of
of the crystal
crystal
can
can be
be moved
moved alongalong latitude
latitude circles
circles ofof the
the net
net toto their
their final
final position.
position.
The
The main
main principles
principles of
of the
the stereographic
stereographic projection
projection have now been pre-
pre-
sented,
sented, and
and we
we will
will have
have occasion
occasion to
to use
use them later
later in
in dealing
dealing with various
practical
practical problems
problems in in x-ray
x-ray metal-
metal- 100
100
lography.
lography. The
The student
student is
is reminded,
reminded,
however,
however, that that aa mere
mere reading
reading of of this
this
section
section is is not
not sufficient
sufficient preparation
preparation
for
for such
such problems.
problems. In In order
order to to gain
gain
real familiarity
real familiarity with
with the
the stereographic
stereographic
010 010
projection,
projection, he he must
must practice,
practice, with with
Wulff
Wulff net net andand tracing
tracing paper,
paper, the the
operations
operations described
described above
above and
and solve
solve
problems
problems of of the
the kind
kind given
given below.
below.
Only
Only in
in this
this way
way will
will he
he be
be able
able to
to
read
read and
and manipulate
manipulate the
the stereo-
stereo- (111)
graphic
graphic projection
projection withwith facility
facility andand twin plane
twin plane 100
100
think
think in in three
three dimensions
dimensions of of what
what is is FIG.
FIG. 2-40.
2-40. Stereographic
Stereographic projection
projection
represented
represented in in two.
two. of
of an FCC crystal
an FCC crystal and
and its
its twin.
twin.
76
76 THE GEOMETRY
THE GEOMETRY OP
OF CRYSTALS
CRYSTALS [CHAP. 22
[CHAP.

PROBLEMS
PROBLEMS

2-1. Draw
2-1. Draw the the following
following planes
planes andand directions
directions inin aa tetragonal
tetragonal unitunit cell:
cell: (001),
(001),
(011), (113), [110], [201],
(Oil), (113), [110], [201], [I01]._ [IOl].
2-2. Show
2-2. Show by by means
means of of aa (110) sectional drawing
(110) sectional drawing that that [111]
[111] isis perpendicular
perpendicular to to
(111)
(111) in
in the
the cubic
cubic system,
system, but
but not,
not, in
in general,
general, in
in the
the tetragonal
tetragonal system.
system.
W. In
2-3. In aa drawing
drawing of of aa hexagonal
hexagonal prism,
prism, indicate
indicate the the following
following planes
planes and
and di-
di-
rections: (1210),
rections: (1210), (1012),
(1012), (T011),
(1011), [110], [Ill], [021].
[110], [111), [021].
2-4. Derive
2-4. Derive Eq. Eq. (2-2)
(2-2) of
of the
the text.
text.
w. Show
2-5. Show that
that the
the planes (110),
planes (110), (121), and (312)
(121), and belong to
(312) belong to the
the zone
zone [111]^
[111].
2-6. Do
2-6. Do thethe following
following planes
planes allall belong
belong to to the
the same
same zone:
zone: (110), (311), (132)?
(110), (311), (132)1
If so,
If so, what
what is is the
the zone
zone axis?
axis? GiveGive the
the indices
indices of
of any
any other
other plane
plane belonging
belonging toto this
this
zone.
zone.
2-7. Prepare
2-7. Prepare aa cross-sectional
cross-sectional drawing
drawing of an HCP structure
of an structure which
which will
will show
show that
that
all atoms do
all atoms do not not have
have identical
identical surroundings
surroundings and therefore
therefore do
do not
not lie
lie on
on a point
a point
lattice.
lattice.
2-8. Show
2-8. Show that cia for
that c/a for hexagonal
hexagonal closeclose packing
packing of of spheres
spheres is is 1.633.
1.633.
2-9. Show
2-9. Show thatthat thethe HCP structure
structure (with cia =
(with c/a = 1.633)
1.633) and the the FCC structure
structure
are equally
are equally close-packed,
close-packed, and and that the BCC structure
that the structure is is less
less closely
closely packed
packed
than either
than either ofof the
the former.
former.
2-10. The
2-10. The unitunit cells
cells ofof several orthorhombic crystals
several orthorhombic crystals are are described
described below.
below.
What is is the
the Bravais lattice of
Bravais lattice of each
each and how do you you know?

(a) Two atoms

(a) atoms of of the
the same kindkind per per unit
unit cell
cell located
located at 0, ! 0 t.
at 0 IJ 0, \.
(b) Four atoms
(6) Four atoms
of
of the
the same kind
kind per
per unit
unit cell
cell located
located at
at 00 z,z, 0 ! z, O!
J z, f (! +
(^ + z),
z),

00 (i +
00(| + 2). z).
(c) Four atoms of the same kind
(c) Four atoms of the
kind perper unit cell located at x Y
unit cell z, ix fi
y z, z, (!
y z, J + x)
( x)+
(!
(I -
- Y)
y) z,
*, (!
(I - x)
-*)(* (! ++ Y)
y) z.
*
(d)
(d) Two atoms
atoms of of one kind A located
one kind located atat too,
J 0, 0 it;J J; and two atoms of of another
another
kind B located
kind located at at 001, \, i\\! o.0.
2-11.
2-11. Make aa drawing,
drawing, similar
similar to
to Fig.
Fig. 2-23,
2-23, of
of a (I12)
(112) twin inin a BCC lattice
lattice

and
and show
show the
the shear
shear responsible
responsible for
for its
its formation.
formation. Obtain the magnitude
magnitude ofof the
the
shear
shear strain
strain graphically.
graphically.
2-12.
2-12. Construct
Construct aa Wulff
Wulff net,
net, 18
18 em
cm inin diameter
diameter and
and graduated
graduated at 30 intervals,
at 30 intervals,
by
by the
the use
use of
of compass, dividers,
compass, dividers, and
and straightedge only.
straightedge only. Show
Show all
all construction
construction lines.
lines.

In
In 80me
some of
of the
the following
following problems,
problems, the the coordiMte8
coordinates of
of a
a point
point on
on a
a 8tereographic
stereographic pro-
pro-
jection
jection are
are given
given inin term8 of its
terms of its latitude
latitude and
and longitude,
longitude, measured from
measured the center
from the center of
of the
the

projection.
projection.
Thus, the N pole
Thus, the N pole is
is BOON, OOE,
90N, 0E, the
the E
E pole
pole is
is OON, BOoE,
0N, 90E, etc.
etc.

2-13. Plane A
2-13. Plane A isis represented
represented onon aa stereographic
stereographic projection
projection by
by aa great
great circle
circle

passing
passing through the Nand
through the N and SS poles
poles and
and the
the point
point OON, 70W. The
0N, 700W. The pole
pole of plane B
of plane B
isis located at 30 oN, 5O
located at 30N, 50W. o W.

(a) Find
(a) Find the
the angle
angle between
between the
the two
two planes.
planes.
(b) Draw
(b) Draw the
the great
great circle
circle of plane BB and
of plane and demonstrate
demonstrate that
that the
the stereographic
stereographic
projection
projection is
is angle-true
angle-true by
by measuring
measuring with
With aa protractor
protractor the
the angle
angle between
between
the great circles
the great circles of
of AA and
and B.
B.
 PROBLEMS 77
77

i-14. Pole
2-14. A, whose
Pole A, whose coordinates
coordinates are
are 20N, 50 0E, is
200N, 50E, to be
is to be rotated
rotated about
about the
the
axes described
axes described below.
below. In each
In each case,
case, find
find the
the coordinates
coordinates of
of the
the final
final position
position of
of
pole
pole A and
A and show the
the path
path traced
traced out
out during
during its
its rotation.
rotation.
(a)
(a) 100 rotation
100 rotation about the NS axis,
about the axis, counterclockwise
counterclockwise looking from N to
looking from S.
to 8.
(b)
(b) 60
60 rotation
rotation about
about an
an axis
axis normal
normal to
to the
the plane
plane of
of projection,
projection, clockwise
clockwise to
to
the observer.
the observer.
60 rotation
(c) 60
(c) rotation about
about an inc~lined axis
an inclined B, whose
axis B, whose coordinates
coordinates are
are 108, 30 0W,
10S, 30W,
clockwise to the
clockwise to the observer.
observer.
i-16.
2-16. Draw aa standard
standard (111)
(111) projection
projection of
of aa cubic
cubic crystal,
crystal, showing
showing all
all poles
poles of
of
the form
the form {1001,
100} {1101,
{ ,
10 {
{IIll the important
(111) and the
1 1 ,
important zone
zone circles
circleR between
between them.
them. Com-
pare with
pare with Figs.
Figs. 2-36(a)
2-36(a) Il.nd (b).
and (b).
i-16.
2-16. Draw a
a standard
standard (001) projection of
(001) projection of white
white tin
tin (tetragonal, cia =
(tetragonal, c/a 0.545),
= 0.545),
Rhowing
showing all poles
all poles of
of the
the form {0011,
001
1 1
{IOOI.
100
, {
{1I01,
1 10
) , { {Olll,
01 1
) ,
{1111
(
1 1
1 , {
the important
and the important
1 )

zone
zone circles between
between them.
circles them. Compare
Compare withwith :I<'ig. 2-36(a).
Fig. 2-36(a).
i-17. Draw aa standard
2-17. (0001) projection
standard (0001) projection of
of beryllium
beryllium (hexagonal,
(hexagonal, c/a = 1.57),
cia = 1.57),
showing
showing all
all poles
poles of
of the
the form {2ITol,
{2l70j, {lOrOI,
{lOTO}, {2ITII,
{2TTl|, {lOTI
(10Tl| I and
and the
the important
important
zone
zone circles between them.
circles between them. Compare
Compare withwith Fig.
Fig. 2-3R.
2-38.
i-18.
2-18. On a a standard
standard (001) projection of
(001) projection of a cubic crystal,
a cubic crystal, in the orientation
in the of
orientation of
Fig. 2-36
Fig. (a) , the
2~36(a), pole of
the pole of aa certain plane has
certain plane has coordinates
coordinates 53.3S, 26.6E. What
53.3S, 26.6E.
are its Miller
are its Miller indices?
indices? Verify your answer
Verify your answer by by comparison
comparison of of measured angles
angles
with those
with those given
given in Table 2-3.
in Table 2-3.
i-19.
2-19. Duplicate
Duplicate the the operations
operations shown in in Fig.
Fig. 2-40
2-40 and thusthus find
find the
the locations
locations
of
of the
the cube
cube poles
poles ofof aa (ITl)
(TTl) reflection
reflection twin
twin inin a a cubic
cubic crystal.
crystal. What are
are their
their
coordinates?
coordinates?
i-20.
2-20. Show thatthat the
the twin
twin orientation
orientation found
found in in Prob.
Prob. 2-2- 199 can
can also
also be
1be obtained
obtained
by
by

(a) Reflection
(a) Reflection in
in a
a {1121
1112) plane.
plane. Which one?
one?
(6) 180
(b) 180 rotation
rotation about
about aa (111)
(ill) axis.
axis. Which one?
one?
(c) 60
(c) 60 rotation
rotation about a (111)
about a (ill) axis.
axis. Which one?
one?

In (c), show the

In (c), the paths
paths traced
traced out
out by
by the
the cube
cube poles
poles during
during their
their rotation.
rotation.
 CHAPTER
CHAPTER 33

DIFFRACTION I:
DIFFRACTION I: THE DIRECTIONS OF
THE DIRECTIONS DIFFRACTED BEAMS
OF DIFFRACTED BEAMS

Introduction.
3-1 Introduction.
3-1 After our
After our preliminary
preliminary survey
survey of
of the
the physics
physics of
of x-rays
x-rays
and the
and the geometry of crystals,
geometry of crystals, we
we can
can now
now proceed
proceed to
to fit
fit the
the two
two together
together
and discuss
and discuss the
the phenomenon
phenomenon of of x-ray
x-ray diffraction,
diffraction, which
which isis an
an interaction
interaction
of the
of the two.
two. Historically, this
Historically, this isis exactly
exactly the the way
way this field of
this field of science
science de-de-
veloped.
veloped. For
For many years, mineralogists
many years, mineralogists and
and crystallographers
crystallographers had
had accumu-
accumu-
lated knowledge
lated knowledge about about crystals,
crystals, chiefly
chiefly by by measurement
measurement of of interfacial
interfacial
angles, chemical analysis,
angles, chemical analysis, and
and determination
determination of
of physical properties.
physical properties. There There
was little knowledge of interior structure,
was little knowledge of interior structure, however, although however, although some
some very
very
shrewd guesses
shrewd guesses hadhad beenbeen made, namely, that crystals
made, namely, that crystals were built up
were built up byby
periodic repetition
periodic repetition of of some
some unit,
unit, probably
probably an an atom or or molecule,
molecule, and that that
these units
these units were
were situated
situated some some 11 or or 2A apart.
apart. On the the other
other hand,
hand, there
there
were indications,
were indications, but but onlyonly indications,
indications, that that x-rays
x-rays might
might be be electromag-
electromag-
netic waves
netic waves about
about 1 1 oror 2A in in wavelength.
wavelength. In In addition,
addition, the the phenomenon
phenomenon
of diffraction
of diffraction was was well
well understood,
understood, and it it was known that diffraction,
diffraction, as as
of
of visible
visible light
light by
by a
a ruled
ruled grating,
grating, occurred
occurred whenever wave motion en-
countered
countered a a set
set ofof regularly
regularly spacedspaced scattering
scattering objects,
objects, provided
provided that the the
wavelength
wavelength of
of the
the wave motion
motion was of
of the
the same order
order of
of magnitude
magnitude as the
the
repeat
repeat distance
distance between
between the the scattering
scattering centers.
centers.
Such
Such was was the state of
the state of knowledge
knowledge in
in 1912
1912 when the German physicist physicist
von
von Laue
Laue tooktook up up the
the problem.
problem. He reasoned
reasoned that,
that, ifif crystals
crystals were com-
posed
posed of
of regularly spaced
regularly spaced atoms
atoms which
which might
might act
act as
as scattering
scattering centers for
for
x-rays, and if
x-rays, and if x-rays x-rays were
were electromagnetic
electromagnetic waves of
of wavelength
wavelength about
equal
equal to to the
the interatomic
interatomic distance distance in in crystals,
crystals, then
then it it should be possible
possible to to
diffract x-rays by means
diffract x-rays by means of crystals. of crystals. Under his
his direction, experiments
direction, experiments to
to
test
test this
this hypothesis
hypothesis were were carried
carried out:out: aa crystal
crystal of of copper
copper sulfate
sulfate was
was setset
up in the path of a narrow beam of x-rays
up in the path of a narrow beam of x-rays and photographic plate and a
a photographic plate was
arranged to
arranged to record
record the the presence
presence of of diffracted
diffracted beams,
beams, if if any.
any. The The very
very
first
first experiment
experiment was was successful
successful and and showed
showed without
without doubt that x-rays
doubt that x-rays
were
were diffracted
diffracted by by the
the crystal
crystal outout of of the
the primary
primary beam beam to to form
form aa pattern
pattern
of
of spots
spots on on the
the photographic
photographic plate. plate. TheseThese experiments
experiments proved, proved, at at one
one
and
and the
the same
same time,
time, the
the wave
wave nature
nature of
of x-rays
x-rays and
and the
the periodicity
periodicity of
of the
the
arrangement
arrangement of
of atoms
atoms within
within aa crystal.
crystal. Hindsight
Hindsight is
is always
always easy
easy and
and
these
these ideas
ideas appear
appear quite simple to
quite simple to us
us now,
now, when
when viewed
viewed fromfrom the the vantage
vantage
point
point of
of more
more than
than forty years'
forty years' development
development of
of the
the subject,
subject, but
but they
they were
were
not
not atat all
all obvious
obvious in in 1912,
1912, and
and von
von Laue's
Laue's hypothesis
hypothesis and
and its
its experimental
experimental
verification
verification mustmust stand
stand as as aa great
great intellectual
intellectual achievement.
achievement.
78
78
 3-2)
3-2] DIFFRACTION
DIFFRACTION 79
79

The account
The account of of these
these experiments
experiments was was read
read with
with great
great interest
interest byby two
two
English physicists,
English physicists, W.
W. H.
H. Bragg
Bragg and
and his
his son
son W.
W. L.
L. Bragg.
Bragg. The
The latter,
latter,
although only
although only aa young
young student
student at at the
the time
time-it was still
it was still the
the year
year 1912
1912-
successfully analyzed
successfully analyzed the
the Laue
Laue experiment
experiment and
and was
was able
able to
to express
express the
the
necessary
necessary conditions
conditions for
for diffraction
diffraction in
in a
a somewhat
somewhat simpler
simpler mathematical
mathematical
form than that
form than that used
used by
by von
von Laue.
Laue. He He also
also attacked
attacked the
the problem
problem of of crystal
crystal
structure
structure with
with the
the new
new tool
tool of
of x-ray
x-ray diffraction
diffraction and,
and, in
in the
the following year,
following year,
solved the structures
solved the structures of
of NaCI, KCI,
NaCl, KC1, KBr, KBr, and
and KI,
KI, all
all of
of which
which have
have the
the
N aCI structure; these
NaCl structure; these were were the
the first
first complete crystal-structure
complete crystal-structure determina-
determina-
tions ever
tions ever made.
made.

3-2 Diffraction.
3-2 Diffraction. Diffraction
Diffraction is due
is due essentially
essentially toto the
the existence
existence of of cer-
cer-
tain phase
tain phase relations
relations between
between two
two or waves, and it is advisable,
or more waves, and it is advisable, at at
the start,
the start, to
to get
get aa clear
clear notion
notion of
of what
what is
is meant by by phase
phase relations.
relations. Con-
sider aa beam
sider beam of of x-rays,
x-rays, such as beam 11 in
such as in Fig.
Fig. 3-1,
3-1, proceeding
proceeding from from left
left to
to
right.
right.
For
For convenience
convenience only,
only, this
this beam is
is assumed to
to be plane-polarized
plane-polarized
in order
in order that
that wewe may
may draw
draw the
the electric
electric field vector E always
field vector always in in one
one plane.
plane.
We maymay imagine
imagine this
this beam toto be
be composed
composed of of two equal
equal parts,
parts, ray
ray 22 and
and
ray 3,
ray 3, each
each of
of half
half the
the amplitude
amplitude of
of beam 1.
1. These two rays,
rays, on
on the
the wave
wave
front AA', are
front AA', are said to be
said to completely in
be completely or in
phase or
in phase in step;
step; i.e.,
i.e., their
their electric-
electric-
field
field vectors
vectors have the same magnitude
have the magnitude and direction
direction at
at the same instant
instant
at any point
at any point x
x measured
measured along
along the
the direction
direction of
of propagation
propagation of
of the wave.
A wave front
wave front is
is a
a surface
surface perpendicular
perpendicular to
to this
this direction
direction of
of propagation.
propagation.
A H

A' 8'
FIG. 3-1.
FIG. 3-1. Effect
Effect of
of path
path difference
difference on
on relative
relative phase.
phase.
80
80 I: THE
DIFFRACTION II
DIFFRACTION THE DIRECTIONS DIFFRACTED BEAMS
OF DIFFRACTED
DIRECTIONS OF BEAKS [CHAP. 33
[CHAP.

Now consider
Now consider an
an imaginary
imaginary experiment,
experiment, inin which
which ray
ray 33 isis allowed
allowed to
to
continue in aa straight
continue in straight line
line but
but ray
ray 22 is
is diverted
diverted by
by some
some means
means intointo aa
curved path before
curved path before rejoining
rejoining ray
ray 3.
3. What
What isis the
the situation
situation on on the
the wave
wave
front BB' where
front BB' where both
both rays
rays are
are proceeding
proceeding inin the
the original direction? On
original direction? On
this front,
this the electric
front, the electric vector
vector of
of ray
ray 22 has
has its
its maximum
maximum value
value at
at the
the instant
instant
shown, but that
shown, but that of
of ray
ray 33 isis zero.
zero. The
The two
two rays
rays are
are therefore
therefore out
out of
of phase.
phase.
If we add
If we add these
these two
two imaginary components
imaginary components of
of the
the beam
beam together,
together, we
we find
find
that beam
that beam 1 1 now has
has the
the form
form shown
shown in
in the
the upper right
upper right of
of the
the drawing.
drawing.
If the
If the amplitudes
amplitudes ofof rays
rays 22 and
and 33 are
are each
each 11 unit,
unit, then
then the
the amplitude
amplitude of of
beam at the
beam 11 at the left
left is
is 22 units
units and that
that of
of beam
beam 11 at
at the
the right
right is
is 1.4 units, if
1.4 units, if
a sinusoidal
a sinusoidal variation
variation of
of with xx is
E with is assumed.
assumed.
conclusions may
Two conclusions may be be drawn from this this illustration
illustration: :

(1) Differences
(1) Differences in in the
the length
length of of the
the path
path traveled
traveled leadlead to to differences
differences in in
phase.
phase.
(2) The
(2) The introduction
introduction of of phase
phase differences
differences produces
produces aIi change
change in in ampli-
ampli-
tude.
tude.
The greater
The greater the the path
path difference,
difference, the the greater
greater the
the difference
difference in in phase,
phase, sincesince
the path
the path difference,
difference, measured
measured in in wavelengths,
wavelengths, exactly exactly equals
equals thethe phase
phase
difference, also
difference, also measured
measured in wavelengths. If
in wavelengths. the diverted
If the diverted path path ofof ray
ray 22 in in
Fig. 3-1 were a quarter wavelength
Fig. 3-1 were a quarter wavelength longer longer than
than shown,
shown, the
the phase
phase differ-
differ-

ence would
ence would be be aa half
half wavelength.
wavelength. The two rays rays would then then be be completely
completely
out
out of
of phase
phase on on the
the wave frontfront BB' and beyond, beyond, and they they would therefore
therefore
annul
annul each
each other, since at
other, since at any
any point
point theirtheir electric
electric vectors
vectors would be be either
either
both
both zero
zero or or of
of the
the same magnitude
magnitude and opposite opposite in direction. If
in direction. If the dif- dif-

ference
ference in in path
path length
length were
were made three
three quarters
quarters of
of a wavelength
wavelength greater
greater
than
than shown,
shown, the the two rays rays would be be one complete
complete wavelength
wavelength out of of phase.
phase,
aa condition it
ir + +
condition indistinguishable
indistinguishable from being
being completely
completely in
in phase
phase since
since
cases
cases the
the two
two waves
waves wouldwould combine
combine to to form a beam of of amplitude
amplitude 2 \
just
just like
like the
the original
original beam.
beam. We may
may conclude
conclude that
that two rays
rays are
pletely
pletely in
in phase
phase whenever
whenever their
their path lengths
path lengths differ
differ either
either by
by zero
zero or . >

whole number of wavelengths.

whole number of wavelengths.
Differences
Differences in the path
in the path length
length of of various
various raysrays arise
arise quite
quite naturally
naturally v
we consider
consider how a a crystal
crystal diffracts
diffracts x-rays.
x-rays. FigureFigure 3-2 shows aa section
3-2 shows section
crystal,
crystal, itsits atoms
atoms arranged
arranged on aa set set of of parallel planes A.,
parallel planes A, B,5, C,
C, D,D,
normal
normal to to the
the plane
plane of of the
the drawing
drawing and spaced spaced aa distance
distance d' d' apart.
apart. Ase Ass
that
that aa beam of of perfectly
perfectly parallel,
parallel, perfectly
perfectly monochromatic x-rays x-rays of of vv\v

length
length AX is
is incident
incident on
on this
this crystal
crystal at
at an
an angle
angle 0,
0, called
called the
the Bragg
Bragg a,
a,

where
where (J is is measured
measured between
between the the incident
incident beam beam andand the the particular
particular cr; cr;

planes
planes under
under consideration.
consideration.
We
We wish
wish to to know
know whether
whether this this incident
incident beam beam of of x-rays
x-rays willwill be
be diffrd
diffrd

by
by the
the crystal and,
crystal and, if
if so,
so, under
under what
what conditions.
conditions. A
A. diffracted
diffracted beam
beam m~
me
defined
defined as
as a
a beam
beam comp08ed of
composed of largeaa large number
number of
of 8cattered
scattered rays
rays mutually .
mutuaUy
forcing one another.
forcing one another. Diffraction
Diffraction is,
is, therefore, essentially a
therefore, essentially a scattering-
scattering-
3-21
3-2| DIFFRACTION 83
We have here here regarded
regarded a diffracted
diffracted beam as as being built up
being built up of of rays
rays scat-
scat-
tered
tered by by successive
successive planes planes of of atoms within the the crystal.
crystal. It
It would be be aa
mistake to
mistake to assume,
assume, however,
however, that that a a single
single plane
plane of of atoms A would diffract diffract
x-rays
x-rays just just asas the
the complete
complete crystal does but less
crystal does less strongly.
strongly. Actually,
Actually, the the
single plane of
single plane of atoms would produce, produce, not not only
only thethe beam in in the
the direction
direction l' 1'

as
as the
the complete
complete crystal
crystal does,
does, but also
also additional
additional beams in
in other
other directions,
directions,
some of of them not not confined
confined to to the plane of
the plane of the
the drawing.
drawing. These additional additional
beams do not exist in
not exist in the
the diffraction
diffraction from the the complete
complete crystal precisely
crystal precisely
because
because the the atoms in in the
the other
other planes
planes scatter
scatter beams which destructively
destructively
interfere
interfere with those those scattered
scattered by by the
the atoms in in plane
plane A, A, except
except in in the
the direc-
direc-
tion
tion 1'.
7
I .

At first
first glance,
glance, the.the. diffraction
diffraction of of x-rays
x-rays by by crystals
crystals and the the reflection
reflection of of
visible
visible light
light byby mirrors
mirrors appear
appear very
very similar,
similar, since
since in both phenomena
in both phenomena the the
angle
angle of of incidence
incidence is is equal
equal to to the
the angle
angle of of reflection.
reflection. IItt seems
seems that that we
might
might regardregard the the planes
planes of of atoms as as little
little mirrors
mirrors which "reflect" "reflect" the the
x-rays.
x-rays. Diffraction
Diffraction and reflection,
reflection, however,
however, differdiffer fundamentally
fundamentally in in at
at
least
least three
three aspects:
aspects:
(1) The diffracted
(1) diffracted beam from a a crystal
crystal is is built
built up up ofof rays
rays scattered
scattered by by
all the atoms of
all the of the
the crystal
crystal which lie
lie in
in the
the path
path of
of the
the incident
incident beam.
beam.
reflection of
The reflection of visible
visible light
light takes
takes place
place in in a thin surface
a thin surface layer
layer only.
only.
(2)
(2) The diffraction
diffraction of
of monochromatic x-rays
x-rays takes
takes place only
place only at at those
those
particular
particular anglesangles of
of incidence
incidence which satisfy
satisfy the
the Bragg
Bragg law.
law. The reflection
reflection
of
of visible
visible light
light takes
takes place
place atat any
any angle
angle of of incidence.
incidence.
(3)
(3) The reflection
reflection of of visible
visible light
light byby aa good
good mirror
mirror is is almost
almost 100 percent
100 percent
efficient.
efficient. The intensity
intensity of of a
a diffracted
diffracted x-ray
x-ray beam is is extremely
extremely small small com-
pared to
pared to that
that ofof the
the incident
incident beam.
beam.
Despite
Despite these these differences,
differences, we often often speak
speak of of "reflecting
"reflecting planes"planes" and
"reflected beams" when we really
"reflected really mean diffracting
diffracting planes
planes and diffracted
diffracted
beams.
beams. This This is is common usage usage and,
and, from now on,
on, we will
will frequently
frequently use use
these
these terms
terms without
without quotation
quotation marks but
but with
with the
the tacit
tacit understanding
understanding that
that
we really
really mean diffraction
diffraction and not not reflection
reflection.....
*

To sum up, up, diffraction

diffraction is is essentially
essentially a a scattering phenomenon in
scattering phenomenon in which
aa large
large number of
of atoms cooperate.
cooperate. Since
Since the
the atoms are
are arranged
arranged period- period-
ically on
ically on a a lattice,
lattice, thethe rays
rays scattered
scattered by by them have definite definite phase
phase relations
relations
between
between them; them these
;
these phase
phase relations
relations areare such that that destructive
destructive interference
interference
occurs in
occurs in most
most directions
directions of of scattering,
scattering, but in in a few directions
directions constructive
constructive
interference
interference takes takes place
place and diffracted
diffracted beams are are formed.
formed. The two essen- essen-
tials
tials are
are a a wave motion
motion capable
capable of of interference
interference (x-rays)
(x-rays) and a a set
set ofof periodi-
periodi-
cally
cally arranged
arranged scattering
scattering centers
centers (the
(the atoms of of a a crystal)
crystal)..

...* For
For the
the sake
sake of
of completeness,
it
it should
completeness,should be
be mentioned
mentioned that
that x-rays be totally
x-rays can be totally
re~ected
reflected by by aa solid
solid surface, just
like
like visible
surface, just visible light
light by
by a
a mirror,
mirror, but
but only
only at
at very
very
small
small angles
angles of
of incidence
incidence (below
(below about
about one
one degree).
degree). This phenomenon is
This phenomenon is of
of little
little

practical
practical importance
importance in
in x-ray
x-ray metallography
metallography andand need
need not
not concern
concern us
us further.
further.
84
84 DIFFRACTION I: THE
DIFFRACTION i: DIRECTIONS OF
THE DIRECTIONS DIFFRACTED BEAMS
OF DIFFRACTED BEAMS [CHAP. 33
[CHAP.

3-3 The
3-3 The Bragg
Bragg law.
law. Two geometrical
Two geometrical facts
facts are
are worth
worth remembering:
remembering:
(1)
(1) The
The incident
incident beam,
beam, the
the normal
normal to
to the
the reflecting
reflecting plane,
plane, and the
and the dif-
dif-
fracted beam
fracted beam areare always
always coplanar.
coplanar.
The angle
(2) The
(2) angle between
between the the diffracted
diffracted beam
beam and
and the
the transmitted
transmitted beam beam
is always
is always 26. This isis known
28. This known as as the
the diffraction
diffraction angle,
angle, and
and itit is
is this
this angle,
angle,
rather than 6,8, which
rather than which isis usually
usually measured
measured experimentally.
experimentally.
As previously stated,
As previously stated, diffraction
diffraction in
in general occurs only
general occurs only when
when the the wave-
wave-
length of the
length of the wave motion
motion is
is of
of the
the same
same order
order of
of magnitude
magnitude as
as the
the repeat
repeat
distance between
distance between scattering
scattering centers.
centers. ThisThis requirement
requirement follows
follows from
from the
the
Bragg law.
Bragg law. Since
Sinre sin cannot exceed
sin 8 cannot exceed unity,
unity, we
we may write
write
n>.
n\
sin 8 < l.
- == sin0<l. (3-2)
(3-2)
2d'
2rf'

Therefore, nX
Therefore, n\ must be
must be less
less than 2d'. For diffraction,
than 2d'. diffraction, the
the smallest
smallest value
value of
of
is 1.
n is
n 1. (n = 0 corresponds
(n corresponds to
to the
the beam diffracted
diffracted in
in the
the same direction
direction
as the
as the transmitted
transmitted beam.
beam. It cannot be
It cannot be observed.)
observed.) Therefore
Therefore the
the condi-
condi-
tion for
tion for diffraction
diffraction at
at any
any observable
observable angle
angle 28
26 is
is

x << 2d'.
X 2d'. (3-3)
(3-3)

For most
For most sets of crystal
sets of planes dd'r is
crystal planes is of
of the
the order
order of
of 3A or
or less,
less, which
whicli means
that Xcannot
that X cannot exceed
exceed about
about 6A. crystal could
6A. A crystal could not possibly
possibly diffract
diffract ultra-

violet radiation, for

violet radiation, for example,
example, of wavelength about 5ODA.
of wavelength 500A. On the the other
hand,
hand, if
if X
X is
is very small,
very small, the
the diffraction
diffraction angles
angles are
are too small to be con-
be
veniently
veniently measured.
measured.
The Bragg
Bragg law
law may
may be
be '''Iritten
written in in the form

d'
>.X == 22 -- sin
sin 8.
6. (3-4)
(3-4)
n
Since
Since the
the coefficient of >.
coefficient of X is
is now unity,
unity, we can consider
consider a reflection
reflection of
of any
any
order
order as
as aa first-order
first-order reflection
reflection from planes,
planes, real
real or
or fictitious, spaced at a
fictitious, spaced

distance lin
distance 1/n ofof the
the previous
previous spacing.
spacing. This turns out to be a real real con-

venience,
venience, so
so we set
set d
d =
= d'in
d'/n and write
write the
the Bragg
Bragg law in
in the form

I>. = 2d sin 8 I. (3-5)

(3-5)

This
This form
form will
will be
be used
used throughout
throughout thisthis book.
book.
This
This usage
usage is
is illustrated
illustrated by
by Fig.
Fig. 3-3.
3-3. Consider
Consider the
the second-order
second-order 100
100 re-
re-

flection* shown
flection shown in in (a).
(a). Since
Since it
it is
is second-order,
second-order, the
the path
path difference
difference ABC
ABC
between
between rays
rays scattered
scattered by by adjacent
adjacent (100)
(100) planes
planes must
must bebe two
Jwo whole
whole wave-
wave-

*This
This means
means the
the .reflection
^reflection from
from the
the (100)
(100) planes.
planes. Conventionally,
Conventionally, the
the Millpr
Miller
indices
indices of
of aa reflecting
reflecting plane hkl, written
plane hkl, written without
without parentheses,
parentheses, stand
stand for
for the
the r'e-
re-
fleeted
flected beam
beam from
from the
the plane
plane (hkl).
(hkl).
3-41
3-4] X-RAY SPECTROSCOPY 85
85

(200)

(100)

(a) (b)

FIG.
FIG. 3-3.
3-3. Equivalen('e
Equivalence of
of (a)
(a) a
a lieeond-ordel' 100 refieetion
second-order 100 reflection and (b)
(b) a first-order
first-order
200 reflertion.
reflection.

lengths.
lengths. If If there
there is is no real plane of
real plane of atoms between
between the the (100) planes, we
(100) planes,
can
can always
always imagine
imagine one one asas in
in Fig.
Fig. 3-3(b),
3-3 (b), where the the dotted
dotted plane
plane midway
midway
between the the (100) planes forms
(100) planes forms partpart of
of the
the (200)
(200) set
set ofof planes.
planes. For the the
same reflection
reflection asas in
in (a),
(a), the
the path difference DEF between rays
path difference rays scattered
scattered
by
by adjacent
adjacent (200) planes is
(200) planes is now onlyonly one whole wavelength,
wavelength, so so that
that this
this
reflection can properly
reflection properly be
be ('aIled
called a
a first-order
first-order 200 reflection.
reflection. Similarly,
Similarly,
300,
300, 400,
400, etc.,
etc., rE'fle<'tions
reflections are
are E'quivulltnt
equivalent to to reflections
reflections of of the
the third,
third, fourth,
fourth,
etc.,
etc., orders from t.he
orders from the (100) planes. In
(100) planes. In gen('ral,
general, an nth-order
nth-order reflection
reflection
from (hkl) plancli
from (hkl) planes of of spadng
spacing d' d may
f

may b('be ('onsidered

considered as as aa first-order
first-order reflection
reflection
from
from thethe (nh
(nh nk nl) planes
nl) planes of
of spadng
spacing d =
= d'/n.
d' /n. Note that
that this
this convention
convention
is
is in
in ac('ord
accord with
with thethe definition
definition of of Miller indices since
Miller indices since (nh nl) are
(nh nk nl) are the
the
Miller indices of
Miller indices of planes paraIlpl
planes parallel to
to the
the (hkl) planes
(hkl) planes but
but with
with lin
1/n the
the spacing
spacing
of
of the
the latter.
latter.

3-4
3-4 X-ray spectroscopy. Exp('rimentaIly,
X-ray spectroscopy. Experimentally, thethe Bragg
Bragg Jaw
law can
can be
be uti-
uti-
lized
lized in
in two ways.
ways. By By using
using x-rays
x-rays of
of known wavelength
wavelength X X and measuring
measuring
6, we can
fJ, can determine
determine the the spacing
spacing d of of various
various planes
planes in
in a
a crystal:
crystal: this
this is
is

8tructure analysis and is

structure analysi8 is the
the subject,
subject,
in
in one
one way
way oror another,
another, of of the
the greater
greater
part
part ofof this
this book.
book. Alternatively,
Alternatively, we
ean
can use
use a
a crystal
crystal with planes of
with planes of known
spacing
spacing d,d, measure fJ,
0, and thus deter-
deter-
mine thethe wavelength
wavelength X
X of
of the
the radia-
radia-
tion
tion used: this is
used: this is x-ray 8pectro8copy.
x-ray spectroscopy.
The essential
essential features
features of of an x-ray
x-ray
spectrometer
spectrometer are
are shown in
in Fig.
Fig. 3-4.
3-4.
X-rays
X-rays from
from the
the tube
tube T are
are incident
incident
on
on a crystal C which may
a crystal may be be set
set at
at
any desired
any desired angle angle to
to the
the incident
incident FIG.
FIG. 3-4.
3-4. The
The x-ray
x-ray spectrometer.
spectrometer.
86
86 DIFFRACTION i:
DIFFRACTION I: THE
THE DIRECTIONS
DIRECTIONS OF DIFFRACTED BEAMS
OF DIFFRACTED BEAMS [CHAP. 33
[CHAP.

beam by
beam by rotation
rotation about
about an
an axis
axis through
through 0,
0, the
the center
center of
of the
the spectrometer
spectrometer
circle. D
circle. is an
D is an ionization
ionization chamber
chamber or or some
some form
form of of counter
counter which
which measures
measures
the intensity
the intensity of
of the
the diffracted
diffracted x-rays;
x-rays; it can
it can also
also bebe rotated
rotated about
about 0 and and
set at
set at any
any desired
desired angular
angular position.
position. The crystal crystal is is usually
usually cut
cut or or cleaved
cleaved
so that aa particular
so that particular set set of
of reflecting
reflecting planes
planes of of known spacing
spacing is is parallel
parallel toto
its surface,
its surface, as
as suggested
suggested by by the
the drawing.
drawing. In
In use,
use, the
the crystal
crystal is
is positioned
positioned
so that its
so that its reflecting
reflecting planes
planes make some particularparticular angle
angle 6fJ with
with thethe incident
incident
beam,
beam, and and D is
is set
set at
at the
the corresponding
corresponding angle angle 2fJ.
26. The intensity
intensity of of the
the
diffracted beam is
diffracted is then
then measured
measured and its wavelength
its wavelength calculated
calculated from the
the
Bragg law,
Bragg law, this
this procedure
procedure beingbeing repeated
repeated for for various
various angles
angles 6.fJ. ItIt is
is in
in this
this
way that curves
way that curves such such asas Fig.
Fig. 1-5
1-5 and the the characteristic
characteristic wavelengths
wavelengths tabu- tabu-
lated in
lated in Appendix
Appendix 33 were were obtained.
obtained. W. H. Bragg Bragg designed
designed and used the the
first x-ray
first x-ray spectrometer,
spectrometer, and the the Swedish
Swedish physicist
physicist Siegbahn
Siegbahn developed
developed it it
into an
into an instrument
instrument of of very
very high
high precision.
precision.
Except for
Except for one
one application,
application, the the subject
subject of of fluorescent
fluorescent analysis
analysis described
described
in Chap. 15,
in Chap. 15, we are
are here
here concerned
concerned with
with x-ray
x-ray spectroscopy
spectroscopy only
only in so
in so
far as
far as it
it concerns
concerns certain
certain units
units ofof wavelength.
wavelength. Wavelength
Wavelength measurements
made in in the
the way
way justjust described
described are are obviously
obviously relative,
relative, and their
their accuracy
accuracy
is no greater
is no greater than
than the
the accuracy
accuracy with
with which the
the plane spacing
plane spacing of
of the
the crystal
crystal
is known.
is known. For a cubic
For cubic crystal
a crystal this
this spacing
spacing can
can be
be obtained
obtained independently
independently
from aa measurement
from measurement of its density.
of its density. For any crystal,
any crystal,
weight of
weight of atoms in
in unit
unit cell
cell
Density ==
Density
- - ,
>

volume of
of unit
unit cell
cell

ZA
};A
p== - ,
p ,
(3-6)
(3-6)
NV
where pp = density };A =
= sum of
3
where density (gm/cm
(gm/cm 3 ), ), SA of the
the atomic weights
weights of
of the
atoms
atoms inin the
the unit
unit cell,
cell, N
N =
= Avogadro's number,
Avogadro's number, and V =
= volume of
of unit
cell (cm 3
3
cell (cm ).). NaCI,
NaCl, for
for example,
example, contains
contains four
four sodium atoms and four
four chlo-
chlo-
rine
rine atoms
atoms per
per unit
unit cell, so that
cell, so that

SA == 4(at.
};A 4(at. wt Na)
Na) +
+ 4(at.
4 wt CI).
(at. Cl).

If
If this
this value
value is
is inserted
inserted into
into Eq.
Eq. (3-6),
(3-6), together
together with Avogadro's
Avogadro's number
and the
the measured
measured valuevalue of
of the
the density,
density, the
the volume of of the unit cell V can
unit cell
be
be found.
found. Since
Since NaCI
NaCl isis cubic,
cubic, the
the lattice
lattice parameter
parameter a is is given
given simply
simply byby
the
the cube
cube root of V.
root of V. From this this value
value ofof aa and the the cubic
cubic plane-spacing
plane-spacing
equation
equation (Eq.
(Eq. 2-5),
2-5), the spacing of
the spacing of any
any set
set of
of planes
planes can
can be
be found.
found.
In
In this
this way, Siegbahn
way, Siegbahn obtained
obtained aa value
value of
of 2.814A
2.8 14 A for
for the
the spacing
spacing of
of the
the
(200) planes
(200) planes of
of rock
rock salt,
salt, which he could
could use
use as
as a basis
basis for
for wavelength
wavelength
measurements.
measurements. However,
However, he able to
he was able to measure wavelengths
wavelengths in in terms
terms
of
of this
this spacing
spacing much
much more accurately
accurately than
than the
the spacing
spacing itself
itself was known,
known,
in
in the sense that
the sense that he
he could
could make relative
relative wavelength
wavelength measurements accurate accurate
3-4)
3-4] X-RAY SPECTROSCOPY
X-RAY 8PECTRO8COPY 87
87

to
to six
six significant
significant figures
figures whereas the the spacing
spacing in
in absolute
absolute units
units (angstroms)
(angstroms)
was known only only to four. It
to four. It was therefore
therefore decided
decided to to define
define arbitrarily
arbitrarily
the (200)
(200) spacing
spacing ofof rock salt
salt as
as 2814.00
2814.00 X X units
units (XU),
(XU), this
this new unit
unit being
being
chosen to be as nearly
nearly asas possible
possible equal
equal toto O.OOIA.
0.001A.
Once a particular
particular wavelength
wavelength was determined
determined in in terms
terms ofof this
this spacing,
spacing,
the spacing
spacing ofof a given
given set
set of
of planes
planes in
in any
any other
other crystal
crystal could
could be
be measured.
measured.
Siegbahn
Siegbahn thus measured the the (200)
(200) spacing
spacing ofof calcite,
calcite, which he he found
found more
more
suitable
suitable as a standard crystal,crystal, and thereafter
thereafter based
based all
all his
his wavelength
wavelength
measurements on this this spacing.
spacing. Its Its value
value is 3029.45 XU. Later
is 3029.45 Later on,
on, the
the
kilo
kilo X unit (kX)
unit (kX) was introduced,
introduced, a thousand times
a times as as large
large asas the
the X unit
unit
and
and nearly
nearly equal
equal to
to an angstrom.
angstrom. The kX unit unit is
is therefore defined by
therefore defined by the
the
relation
relation
(200) plane spacing of of calcite
calcite
11 kX = = (200) plane spacing . (3-7)
(37);
V
3.02945
On this
this basis,
basis, Siegbahn
Siegbahn and his his associates
associates made very very accurate
accurate measure-
measure-
ments ofof wavelength
wavelength in in relative (kX) units
relative (kX) units and these
these measurements
measurements form form
the basis
basis of
of most published
published wavelength
wavelength tables.
tables.
It
It was found laterlater that
that x-rays
x-rays could
could bebe diffracted
diffracted by
by aa ruled
ruled grating
grating
such as
as is
is used in
in the
the spectroscopy
spectroscopy of of visible
visible light, provided that
light, provided that the
the angle
angle
of
of incidence
incidence (the
(the angle
angle between the the incident
incident beam and the the plane
plane of
of the
the
grating) is
grating) kept below the
is kept critical angle
the critical angle for
for total reflection. Gratings
total reflection. Gratings thus
thus
offer
offer a means of making absolute
of making wavelength measurements,
absolute wavelength independent
measurements, independent
of any
of knowledge
any knowledge of
of crystal
crystal structure.
structure. By a
a comparison
By comparison of
of values
values so
so ob-
ob-
tained with
tained with those
those found by by Siegbahn
Siegbahn from
from crystal diffraction,
crystal diffraction, it
it was
was pos-
pos-
sible to
sible to calculate
calculate the
the following relation between
following relation between thethe relative
relative and absolute
absolute
units:
units:

11 kX =
1 kX = 1.00202A
1.00202A I (3-8)
(3-8)

This conversion
This conversion factor
factor was decided
decided on
on in
in 1946
1946 by
by international
international agreement,
agreement,
and it was recommended that,
it that, in
in the
the future,
future, x-ray
x-ray wavelengths
wavelengths andand the
the
lattice parameters
lattice parameters ofof crystals
crystals be
be expressed
expressed inin angstroms.
angstroms. If If V in
in Eq.
Eq. (3-6)
(3--6)
for the
for the density
density of
of aa crystal
crystal is
is expressed
expressed inin A33 (not in kX
(not in kX3)
3
and the
) and the currently
currently
accepted value
accepted value of
of Avogadro's
Avogadro's number inserted,
inserted, then
then the
the equation
equation becomes
becomes
1. 660202;A
1.66020S4
p=
P = (3-9)
(3-9)
V
The distinction between kX and A is
distinction between is unimportant
unimportant if if no
no more
more than
than
about three
about three significant
significant figures
figures are
are involved.
involved. InIn precise
precise work,
work, on
on the
the other
other
hand, units
hand, units must
must be
be correctly
correctly stated,
stated, and on
on this
this point
point there
there has
has been
been con-
con-
siderable confusion
siderable confusion in
in the
the past.
past. Some
Some wavelength
wavelength values
values published
published prior
prior
to about
to about 1946
1946 are stated to
are stated to be in angstrom
be in angstrom units
units but
but are
are actually
actually in
in kX kX
units.
units. Some crystallographers
Some crystallographers have
have used
used such
such aa value
value as
as the
the basis
basis for
for aa
.-'"
'~~.'
'88; I: THE
DIFFRACTION II
DIFFRACTION DIRECTIONS OF
THE DIRECTIONS DIFFRACTED BEAMS
OF DIFFRACTED BEAMS [CHAP. 33
[CHAP.

precise
precise measurement of
measurement of the
the lattice
lattice parameter
parameter of of aa crystal
crystal and
and the
the result
result
has been
has been stated,
stated, again
again incorrectly,
incorrectly, inin angstrom
angstrom units.units. Many
Many published
published
parameters are
parameters are therefore
therefore inin error, and itit isis unfortunately
error, and unfortunately notnot always
always easy
easy
to determine
to determine which
which ones
ones are
are and
and which
which ones
ones areare not.
not. The
The only
only safe
safe rule
rule
to follow,
to follow, in
in stating
stating aa precise
precise parameter,
parameter, isis to
to give
give the
the wavelength
wavelength of
of the
the
radiation used
radiation used in
in its
its determination.
determination. Similarly,
Similarly, anyany published
published table
table of
of
wavelengths
wavelengths can
can be
be tested
tested for
for the
the correctness
correctness of
of its
its units
units by
by noting
noting the
the
wavelength given
wavelength given for
for aa particular
particular characteristic
characteristic line, eu Ka\
line, Cu for example.
Kat for example.
The wavelength
The wavelength of
of this
this line
line is
is 1.54051A
1.54051A or
or 1.53740
1.53740 kX.
kX.

3-6 Diffraction
3-5 Diffraction directions.
directions. What determines determines the the possible
possible directions,
directions,
i.e., the possible angles
i.e., the possible angles 20,
28, in
in which
which a
a given crystal
given crystal can
can diffract
diffract a beam
a beam ofof
monochromatic x-rays?
monochromatic x-rays? Referring
Referring to to Fig.
Fig. 3-3,
3-3, we see that various diffrac-
see that various diffrac-

tion angles
tion 28}, 20
angles 20i, 2822 , 20
,
2833 , ...
,
can be
can be obtained
obtained from the the (100)
(100) planes
planes byby
using aa beam
using beam incident
incident at at the
the correct
correct angle
angle 0i,
81 822 , 0s,
83 , and producing
producing ,

first-, second-,
first-, third-, ... order
second-, third-, . . order reflections.
. reflections. But diffraction
diffraetion can
can also
also be
be
produced by
produced by the
the (110)
(110) planes,
planes, the the (111)
(111) planes,
planes, thethe (213)
(213) planes,
planes, and so so
on. obviously need
on. We obviously need aa general
general relation
relation which will wiII predict
predict the
the diffrac-
diffrac-
tion angle
tion angle for
for any
any setset ofof planes.
planes. ThisThis relation
relation isis obtained
obtained by by combining
combining
the Bragg
the Bragg lawlaw and
and thethe plane-spacing
plane-spacing equation
equation (Appendix
(Appendix 1)
1) applicable
applicable to
to
the particular
the crystal
particular crystal involved.
involved.
For
For example,
example, if the crystal
if the crystal is is cubic, then
cubic, then

).,X =
= 2d sin
sin 8
and
and
1
1 (h
(ft
22 +
+ k2 +
fc
2
+ 12) I
2
}

d2 a2
Combining
Combining these
these equations,
equations, we have
have
).,2
X2
sin 2 =-
sin2 8 = -
(h
(h
22 + k2 + 2
+ 12 ). l
2
). (3-10)
(3-10)
4a22
This
This equation
equation predicts,
predicts, for
for a
a particular
particular incident
incident wavelength).,
wavelength X and a par-
par-
ticular
ticular cubic crystal of
cubic crystal of unit
unit cell size a,
cell size a, all
all the possible
possible Bragg
Bragg angles
angles at
at
which
which diffraction
diffraction can
can occur
occur from
from the planes (hk1).
the planes (hkl). For (110)
(110) planes,
planes, for
for
example,
example, Eq.
Eq. (3-10)
(3-10) becomes
becomes
).,2
sin 2 8110 = -.
2a2
If
If the
the crystal
crystal is
is tetragonal,
tetragonal, with axes a
with axes and c,
a and c, then
then the
the corresponding
corresponding gen-
gen-
eral equation is
eral equation is
).,2
sin2 8 = -
+ k2 +- , (h2 (3-11)
12)
44 aa22 cc22
and
and similar
similar equations
equations can
can readily
readily be
be obtained
obtained for
for the
the other
other crystal
crystal systems.
systems.
3-6]
3-6] DIFFRACTION METHODS 89
89

. These
These examples
examples show thatthat the
the directions
directions inin which aa beam of of given
given wave-
wave-
length
length is diffracted
is diffracted byby aa given
given setset of
of lattice
lattice planes
planes is is determined
determined by by the
the
crystal
crystal system
system to
to which the
the crystal
crystal bel~ngs
belongs and its
its lattice
lattice parameters.
parameters. In
In
short, diffraction
short, diffraction directions
directions are
are determined
determined solely
solely by
by the
the shape
shape and
and size
size of
of the
the
unit cell.
unit cell. This
This isis an
an important
important point
point and so so is
is its
its converse:
converse: all all we can
can pos-
pos-
sibly
sibly determine
determine about
about an
an unknown crystal
crystal byby measurements of
of the
the direc-
direc-
tions of
tions of diffracted
diffracted beams are are the
the shape
shape and size size of
of itsits unit cell. We will
unit cell. will
find, in the next chapter,
find, in the next chapter, that
that the
the intensities
intensities of
of diffracted
diffracted beams are
are deter-
deter-
mined by by the
the positions
positions of
of the
the atoms within
within the
the unit
unit cell,
cell, and itit follows
follows that
that
measure intensities
we must measure intensities ifif we are
are toto obtain
obtain any any information
information at at allall
about positions. We will
about atom positions. will find,
find, for
for many
many crystals,
crystals, that that there
there are
are
particular atomic
particular arrangements which reduce
atomic arrangements reduce the the intensities
intensities of of some dif-dif-
fracted beams to
fracted to zero.
zero. InIn such
such a case, there
a case, there isis simply diffracted beam
simply no diffracted
at the
at the angle predicted by
angle predicted by an
an equation
equation of of the
the type
type ofof Eqs.
Eqs. (3-10) (3-11).
(3-10) and (3-11).
It is in
It is in this
this sense that equations
sense that equations of of this
this kind
kind predict
predict all possible diffracted
all possible diffracted
beams.
beams.

3-6 Diffraction methods.

3-6 Diffraction Diffraction
Diffraction can occur
occur whenever the
the Bragg
Bragg
law, >. =
law, X = 2d sin
sin 8,
0, is
is satisfied.
satisfied. This equation
This puts very
equation puts very stringent condi-
stringent condi-
tions >.
on X and 8
tions on 6 for
for any
any given crystal. With monochromatic radiation,
given crystal. radiation,
an
an arbitrary
arbitrary setting
setting of
of a
a single
single crystal
crystal in
in aa beam of x-rays will
of x-rays will not in gen-
not in gen-
eral
eral produce any
produce any diffracted
diffracted beams.
beams. Some way
way of
of satisfying
satisfying the
the Bragg
Bragg law
must bebe devised,
devised, and this
this can
can be
be done by continuously varying
by continuously varying either
either >.X
or
or 8
6 during
during the
the experiment.
experiment. The ways
ways in
in which these
these quantities
quantities are
are varied
varied
distinguish
distinguish the
the three
three main diffraction
diffraction methods:

8
Laue method Variable
Variable Fixed
Rotating-crystal
Rotating-crystal method Fixed Variable
Variable (in
(in part)
part)
Powder method Fixed
Fixed Variable
Variable

The Laue method was the the first

first diffraction
diffraction method everever used,
used, and it it re-
re-

produces
produces von Laue's
Laue's original
original experiment.
experiment. A beam of radiation, the
of white radiation,
continuous
continuous spectrum
spectrum from an x-rayx-ray tube,
tube, is
is allowed
allowed toto fall
fall on a fixed
fixed single
single
crystal.
crystal. The Bragg angle
Bragg angle 8
6 is
is therefore
therefore fixed
fixed for
for every
every set
set of
of planes
planes in
in the
crystal,
crystal, and each
each set
set picks
picks out
out and diffracts
diffracts that
that particular wavelength
particular wavelength
which satisfies the
which satisfies the Bragg
Bragg law for for the
the particular
particular values of d
values of d and 8 involved.
involved.
Each diffracted
diffracted beam thus
thus has a a different
different wavelength.
wavelength.
There
There are
are two variations of
two variations the Laue me~hod,
of the method, depending
depending on the the relative
relative
positions of source, crystal,
positions of source, crystal, and film (Fig. 3-5).
film (Fig. 3-5). In each,
each, the
the film
film is
is flat
flat

and
and placed
placed perpendicular
perpendicular toto the
the incident
incident beam. The film film in the trans-
in the trans-
mission
mission Laue
Laue method
method (the
(the original
original Laue method)
method) is is placed
placed behind the the crys-
crys-
tal
tal so
so as
as to
to record
record the diffracted in
the beams diffracted in the
the forward direction.
direction. This
90
90 DIJ'l'RACTION
DIFFRACTION I:i: THE DIRECTION8 BEAMS
DIRECTIONS OF DIFFRACTED BEAKS [CHAP. 3
[CHAP.

(a)
(a) (b)
(b)

FIG. 3-5.
FIG. 3-5. (a)
(a) Transmission
Transmission and
and (b)
(b) back-reflection
back-reflection Laue methods.
methods.

method is is so
so called
called because
because the
the diffracted
diffracted beams are partially transmitted
are partially transmitted
through
through the
the crystal.
crystal. In the
the back-reflection
back-reflection Laue method the
the film
film is placed
is placed

between
between the
the crystal
crystal and the
the x-ray source,
x-ray source, the
the incident
incident beam passing through
passing through
hole in
aa hole in the
the film,
film, and thethe beams diffracted
diffracted in
in a
a backward direction
direction are
are
recorded.
recorded.
In
In either
either method,
method, the the diffracted
diffracted beams fonn
form an array
array of
of spots
spots on the
the
film as
film as shown in
in Fig.
Fig. 3-6.
3-6. This array
array of
of spots
spots is
is commonly
commonly called
called a pat-
pat-
tern,
tern, but
but the
the tenn
term isis not
not used inin any
any strict
strict sense
sense and does
does not
not imply
imply any
any
periodic
periodic arrangement
arrangement of of the
the spots.
spots. On the
the contrary,
contrary, the
the spots
spots areare seen
seen
to
to lie
lie on
on certain
certain curves,
curves, asas shown byby the
the lines
lines drawn on the photographs.
the photographs.

(a)
(a) (b)

FIG.
FIG. 3-6.
<H*. (a)
(a) Transmil8ion
Transmission and (b) back-reflection
and (b) back-reflection Laue patterns of
Laue patterns of an
an alumi-
alumi-
num crystal
crystal (cubic).
(cubic). Tungsten radiation, 30
Tungsten ntdiA.tin'l, 30 kv,
kv, 19
19 Ina.
ma.
3-6)
3-6] DIFFRACTION METHODS 91
91

Z.A.

(a)

(b)
(b)

FIG. 3-7.
FIG. 3-7. Location
Location of
of Laue spots
spots (a)
(a) on ellipses
ellipses in
in transmission
transmission method and (b)
(b)
on hyperbolas
hyperbolas in
in back-reflection
back-reflection method. (C =
(C = crystal,
crystal, F = film,
film, Z.A.
= zone
Z.A. = zone
axis.)
axis.)

These
These curves
curves are
are generally
generally ellipses
ellipses oror hyperbolas
hyperbolas for for transmission patterns
transmission patterns
[Fig. 3-6(a)]
[Fig. 3-6(a)] and hyperbolas
hyperbolas for
for back-reflection
back-reflection patterns [Fig. 3-6(b)].
patterns [Fig. 3-6(b)].
The spots
spots lying
lying onon anyone
any one curve
curve are
are reflections
reflections from planes
planes belonging
belonging
to
to one
one zone.
zone. This
This isis due to
to the
the fact
fact that
that the
the Laue reflections
reflections from planes
planes
of
of a
a zone
zone all
all lie
lie on
on the
the surface
surface ofof an imaginary
imaginary cone whose axis
axis is
is the
the zone
axis. As shown in
axis. in Fig.
Fig. 3-7(a),
3-7 (a), one
one side
side of
of the
the cone
cone is
is tangent
tangent to
to the
the trans-
trans-
mitted beam, and the
mitted beam, the angle
angle ofof inclination",
inclination <f>of
of the
the zone axis
axis (Z.A.)
(Z.A.) toto the
the
transmitted
transmitted beam is is equal
equal to
to the
the semi-apex
semi-apex angleangle of
of the
the cone.
cone. A film
film
placed
placed as intersects the
as shown intersects the cone
cone inin an imaginary
imaginary ellipse passing through
ellipse passing through
the
the center
center ofof the
the film,
film, the
the diffraction
diffraction spots
spots from planes
planes of
of aa zone
zone being
being
arranged
arranged on this this ellipse.
ellipse. When the the angle",
angle exceeds
exceeds 45,
<t> 45, aa film
film placed
placed
between the
between the crystal
crystal and the the x-ray
x-ray source
source to to record
record the
the back-reflection
back-reflection pat-pat-
tern
tern will
will intersect
intersect the
the cone
cone in
in a hyperbola,
hyperbola, as shown in Fig.
as in Fig. 3-7(b).
3-7 (b).
92
92 I: THE
DIFFRACTION i:
DIFFRACTION THE DIRECTIONS DIFFRACTED BEAMS
OF DIFFRACTED
DIRECTIONS OF BEAKS [CHAP. 33
[CHAP.

Z.A.

1""""--'=----
7'

FIG. 3-8.
FIG. Stereographic projection
3-8. Stereographic projection FIG. 3-9.
FIG. 3-9. Rotating-crystal method.
Rotating-crystal method.
of transmission Laue
of transmission Laue method.
method.

fact that
The fact that the
the Laue reflections
reflections from planes
planes of of a zone
zone lie
lie on the
the surface
surface
of
of aa cone
cone can can bebe nicely
nicely demonstrated
demonstrated with with thethe stereographic
stereographic projection.
projection.
In Fig.
In Fig. 3-8,
3-8, the crystal is
the crystal is at the center
at the center of of the reference sphere,
the reference sphere, the the incident
incident
beam 7I enters
enters at at the left, and the
the left, the transmitted
transmitted beam T leaves leaves at at the
the right.
right.
point representing
The point representing the the zone
zone axis
axis lies on the
lies on the circumference of the basic
of the
circle
circle and the the poles
poles of of five
five planes
planes belonging
belonging to to this zone, PI
this zone, to P 5 , lie
PI to ,
lie on

the
the great
great circle
circle shown.
shown. The direction direction of of the
the beam diffracted
diffracted by by anyone
any one
of
of these
these planes,
planes, forfor example
example the plane P 22 , can be found as
the plane ,
follows. I,
as follows. ,
D2
7, P 2 , D2
(the
(the diffraction
diffraction direction
direction required),
required), and T T are
are all coplanar. Therefore D2
all coplanar. 7> 2
lies
lies on
on the
the great
great circle through I,
circle through 7, P 2
2 , and T.
,
T. The angleangle between I7 and P2 P2
is
is (90
(90 - 9), and D2
0), and 7) 2 must lie lie at
at an equal
equal angular
angular distance
distance on the other
side
side ofof P 22 , as
,
as shown.
shown. The diffracteddiffracted beams so found, DI
so found, D\ to to DZ>5 , are seen
,

to
to lie
lie on
on aa small
small circle,
circle, thethe intersection
intersection with the the reference
reference sphere
sphere of a cone
whose
whose axis
axis is is the
the zone
zone axis.
axis.
The positions
positions of of the
the spots
spots on the the film,
film, for
for both the transmission and the
back-reflection
back-reflection method,method, depend depend on on the
the orientation
orientation of of the crystal
crystal relative
relative
to
to the
the incident
incident beam, beam, and the the spots
spots themselves
themselves become distorted distorted and
smeared
smeared out out if if the
the crystal
crystal has has been
been bent
bent or twisted in
or twisted in any
any way.
way. These
facts
facts account
account for for the
the two main uses uses ofof the
the Laue methods: the determina-
tion of
tion of crystal
crystal orientation
orientation and the the assessment
assessment of of crystal
crystal perfection.
perfection.
In the rotating-crystal method a
the rotating-crystal a single
single crystal
crystal isis mounted with one of of
its
its axes,
axes, oror some important
important crystallographic
crystallographic direction, normal to
direction, normal to a a mono-
chromatic
chromatic x-ray x-ray beam.
beam. A cylindrical
cylindrical film film is placed around it
is placed it and the

crystal
crystal isis rotated
rotated aboutabout the the chosen
chosen direction,
direction, the the axis
axis of
of the
the film
film coinciding
coinciding
with
with thethe axis
axis ofof rotation
rotation of of the
the crystal (Fig. 3-9).
crystal (Fig. 3-9). As As the
the crystal
crystal rotates,
rotates,
3-6]
3-6] DIFFRACTION METHODS 93

^m^mm
^'S'lililtt

FIG.
FIG. 3-10.
3-10. Rotating-crystal
Rotating-crystal pattern
pattern of
of a
a quartz
quartz crystal
crystal (hexagonal)
(hexagonal) rotated
rotated
about its
its c
c axis.
axis. Filtered
Filtered ropper
copper radiation.
radiation. (The
(The streaks
streaks are
are due to
to the
the white
white radi-
radi-
ation
ation not
not remo\"ed
removed by by the
the filter.)
filter.) (Courtesy
(Courtesy of B. E.
of B. E. Warren.)
Warren.)

a particular
particular set set of
of lattice
lattice planes will, for
planes will, for an instant,
instant, make the the correct
correct
Bragg
Bragg angleangle for reflection of
for reflection of the
the monochromatic incident incident bE'am,beam, and at at
that
that instant
instant a reflected
reflected beam will will bebe formed.
formed. The reflected reflected beams are are
again
again located
located on imaginary
imaginary conescones but now the the cone
cone axesaxes coincide
coincide with
with thethe
rotation
rotation axis.
axis. result is
The result is that
that the
the spots
spots on thE'
the film,
film, when the
the film
film is
is

laid
laid out
out flat,
flat, lie
lie on imaginary
imaginary horizontal
horizontal lines,
lines, as
as shown in
in Fig.
Fig. 3-10.
3-10.
Since
Since the crystal is
the crystal is rotated
rotated about only only oneone axis,
axis, thethe Bragg
Bragg angleangle does
does not
not
take
take on all all possible
possible values
values between
between 0 and 90
90 for
for every
every set
set of
of planes.
planes. Not
every
every set,
set, therefore,
therefore, is is able
able to
to produce
produce a a diffracted
diffracted beam;beam sets
;
perpendicular
sets perpendicular
or
or almost perpendicular to
almost perpendicular to the
the rotation
rotation axisaxis are
are obvious
obvious examples.
examples.
The chief use of
chief use of the
the rotating-crystal
rotating-crystal method and its
its variations
variations is is in
in the
the
determination of
determination of unknown crystal structures,
crystal structures, and for
for this
this purpose
purpose it
it is
is

the
the most powerful
powerful tool
tool the
the x-ray crystallographer
x-ray crystallographer has
has at
at his
his disposal.
disposal. How-
ever,
ever, the
the complete
complete determination
determination of of complex
complex crystal
crystal structures
structures is is a
a subject
subject
beyond
beyond the
the scope
scope of
of this
this book and outside
outside the
the province
province of
of the
the average
average
metallurgist
metallurgist who uses uses x-ray
x-ray diffraction
diffraction as as a a laboratory
laboratory tool. tool. For this
this
reason the
reason the rotating-crystal
rotating-crystal method will
will not
not be
be described
described in
in any
any further
further
detail,
detail, except
except forfor aa brief
brief discussion
discussion in Appendix 15.
in Appendix 15.
In the powder method,
the powder method, the the crystal
crystal to to be examined is is reduced
reduced to to aa very
very
fine powder and placed
fine powder placed in
in a
a beam of
of monochromatic x-rays.
x-rays. Each particle
particle
of
of the
the powder
powder is is a
a tiny
tiny crystal
crystal oriented
oriented at at random with respect respect toto the
the inci-
inci-
dent beam. Just
dent Just by chance,
by chance, some of
of the
the particles
particles will
will be
be correctly
correctly oriented
oriented
so that
so that their
their (100) planes, for
(100) planes, for example,
example, can can reflect
reflect the the incident beam.
incident beam.
particles will
Other particles will be
be correctly
correctly oriented
oriented for
for (110) reflections,
(110) reflections, and so
so on.
on.
The result
result is is that
that every
every set
set of
of lattice
lattice planes
planes will
will be
be capable
capable of
of reflection.
reflection.
The mass of of powder
powder is is equivalent,
equivalent, in fact, to
in fact, to a a single
single crystal
crystal rotated,
rotated, notnot
about oneone axis,
axis, but
but about
about all
all possible
possible axes.
axes.
Consider
Consider one one particular
particular hkl hkl reflection.
reflection. One or or more particles
particles of powder
of powder
will,
will, by chance, be
by chance, be so
so oriented
oriented that their (hkl)
that their (hkl) planes
planes make the correct
the correct
94
94 DIFFRACTION I:
1 THE DIRECTIONS OF DIFFRACTED BEAMS
1 [CHAP. 3
3

(a)

FIG.3-11.
FIG. 3-11. Formation of
of a diffracted
diffracted cone
cone of
of radiation
radiation in
in the
the powder
powder method.

Bragg
Bragg angle
angle for for reflection;
reflection; Fig. Fig. 3-11
3-11 (a)(a) shows one one plane
plane in in this
this set
set and
the
the diffracted
diffracted beam formed. formed. If If this
this plane
plane is is now rotated
rotated about the the incident
incident
beam as as axis
axis inin such a way that
a way that 8 6 is
is kept
kept constant,
constant, then the the reflected
reflected beam
will
will travel
travel over
over the the surface
surface of of a a cone
cone as as shown in in Fig.
Fig. 3-11(b),
3-1 l(b), thethe axis
axis ofof
the
the cone
cone coinciding
coinciding with with the the transmitted
transmitted beam. beam. This This rotation
rotation doesdoes notnot
actually
actually occur
occur in in the
the powder method, but the
powder method, presence of
the presence of aa large
large number
of
of crystal particles having
crystal particles having all
all possible
possible orientations
orientations is
is equivalent
equivalent to
to this
this
rotation,
rotation, since
since among
among these
these particles
particles there
there will
will be
be a
a certain
certain fraction
fraction whose
whose
(hkl) planes make the
(hkl) planes the right
right Bragg
Bragg angle angle with
with thethe incident
incident beam and which
at
at the
the same time time lie lie in
in all
all possible
possible rotational
rotational positions about the
positions the axis
axis ofof
the
the incident
incident beam. The hkl hkl reflection
reflection from a a stationary
stationary mass of powder
of powder
thus
thus hashas thethe form of of a a cone
cone of of diffracted radiation, and aa separate
diffracted radiation, separate conecone is is

formed for for each

each set set ofof differently
differently spacedspaced lattice
lattice planes.
planes.
Figure
Figure 3-123-12 shows four four such
such cones
cones and also also illustrates
illustrates the the most common
powder-d.iffraction
powder-diffraction method.
method. In
In this,
this, the
the Debye-Scherrer
Debye-Scherrer method, method, a narrow
strip
strip of
of film
film is
is curved
curved into
into a
a short
short cylinder
cylinder with the
the specimen
specimen placedplaced oJi op
its
its axis
axis and the the incident
incident beam directed directed at at right angles
right angles to
to this
this axis.
axis. The
cones
cones of of diffracted
diffracted radiation
radiation intersect
intersect the the cylindrical
cylindrical stripstrip ofof film
film in
in lines
lines
and,
and, when the
the strip
strip is
is unrolled
unrolled and laid
laid out
out flat,
flat, the
the resulting
resulting pattern has
pattern has
the
the appearance
appearance of
of the
the one
one illustrated
illustrated in
in Fig. 3-12(b).
Fig. 3-12(b). Actual
Actual patterns,
patterns,
produced
produced by by various
various metal metal powders,
powders, are are shown in in Fig.
Fig. 3-13.
3-13. Each diffrac- diffrac-
tion
tion line
line isis made up up of
of a
a large
large number of
of small
small spots,
spots, each
each from a
a separate
separate
crystal
crystal particle,
particle, the the spots
spots lying
lying so so close together that
close together that they they appear
appear as as a a
continuous line. line. The lines
lines are
are generally curved,
generally curved, unless
unless they
they occur
occur exactly
exactly
at
at 2826 = 90 when they
== 9(}0
they willwill be
be straight.
straight. From the the measured position position of of a
given
given diffraction
diffraction line
line on
on the
the film,
film, 8
6 can
can be
be determined,
determined, and, knowing X, we
and, knowing >.,
can calculate
calculate the the spacing
spacing d
d of
of the
the reflecting
reflecting lattice planes which
lattice planes which produced
produced
the
the line.
line. >

Conversely,
Conversely, if if the
the shape
shape and size size ofof the
the unit
unit cell
cell of
of the
the crystal
crystal areare known,
known,
we can predict
predict the the position
position of
of all
all possible
possible diffraction
diffraction lines
lines on
on the
the film.
film. The
line
line of
of lowest
lowest 28 28 value
value is produced by
is produced by reflection
reflection from planes of
from planes of the
the greatest
greatest
3-6]
3-6] DIFFRACTION METHODS 96
95

(a)
point where
incident beam
enters (26 = 180) -/ 26 =
\

(h)
(b)

FIG. 3-12. Debye-Scherrer

Debye-Scherrer powder
powder method: (a)(a) relation
relation of film to
of film to specimen
specimen and
and
incident
incident beam;
beam; (b) appearance of
(b) appearance of film
film when laid
laid out
out flat.
flat.

28 = 1800
26 = 26 =

T
(a)
(a)

ii

(b)

(c)

FIG. 3-13.
FIG. 3-13. Debye-Scherrer powder
Debye-Scherrer powder patterns
patterns of
of (a)
(a) copper
copper (FCC),
(FCC), (b)
(b) tungsten
tungsten
(BCC), and
(BCC), (c) zinc (HCP).
(c) zinc (HCP). Filtered
Filtered copper
copper radiation,
radiation, camera diameter *
camera diameter - 5.73
5.73
em.
cm.
96
96 i: THE DIRECTIONS OF DIFFRACTED BEAMS
DIFFRACTION I: [CHA.p.3
[CHAP. 3

spacing.
spacing. In the the cubiccubic system,
system, for for example,
example, d is is aa maximum when
(h +
(h 22 + k22 ++ l2)2 ) isis a minimum,
I minimum, and the the minimum vJl.lue v#lue of of this
this term is is 1,
1,

corresponding
corresponding to
to (hkl) equal
(hkl) equal to
to (100).
(100). The 100
100 reflection
reflection is
is accordingly
accordingly
the
the oneone of
of lowest
lowest 2IJ 20 value.
value. The next next reflection
reflection will indices hkl
will have indices hkl corre-
corre-
sponding
sponding to
to the
the next
next highest
highest value
value of
of (h 2
(h +
2
+ k
k 22
+ 2
l2), namely
+ ), namely 2,
/ 2, in
in which
which
case (hkl)
case (hkl) equals
equals (110),(110), and so so on.
on.
The Debye-Scherrer
Debye-Scherrer and other other variations
variations of of the
the powder
powder method are are very
very
widely used, especially
widely used, especially in
in metallurgy.
metallurgy. The powder
powder method is,
is, of course,
of course,
the only method that
the only that can be employed
employed when aa single single crystal
crystal specimen
specimen is is

not
not available,
available, and this this isis the
the case
case more often often than
than notnot inin metallurgical
metallurgical
work.
work. The method is is especially
especially suited
suited for for determining
determining latticelattice parameters
parameters
with high
high precision
precision and for for the
the identification
identification of of phases,
phases, whetlier
whetrier they they occur
occur
alone
alone or or in
in mixtures such as as polyphase
polyphase alloys,
alloys, corrosion
corrosion products,
products, refrac-refrac-
tories,
tories, and rocks.
rocks. These and other other uses
uses ofof the
the powder
powder method will will be be fully
fully
described
described in in later
later chapters.
chapters.
Finally,
Finally, the
the x-ray
x-ray spectrometer
spectrometer can can bebe used
used asas a a tool
tool inin diffraction
diffraction anal- anal-
ysis.
ysis. This instrument is
is known as
as a diffractometer
diffractometer when it
it is
is used
used with
with
x-rays
x-rays of
of known wavelength
wavelength to
to determine
determine the
the unknown spacing
spacing of
of crystal
crystal
planes,
planes, and as as a spectrometer
spectrometer in in the
the reverse
reverse case,
case, when crystal planes of
crystal planes of
known spacing
spacing are used to determine unknown wavelengths.
are used to determine wavelengths. The diffrac- diffrac-
tometer
tometer is is always
always used used with
with monochromatic radiation radiation and measurements
measurements
may
may be be made on either either single
single crystals
crystals oror polycrystalline
polycry stalline specimens;
specimens in ; in the
the
latter
latter case,
case, it it functions
functions much like like a a Debye-Scherrer
Debye-Scherrer camera camera in in that
that the the
counter
counter intercepts
intercepts and measures measures only only a a short
short arcarc ofof anyone
any one eone cone of of dif-
dif-
fracted
fracted rays.
rays.

3-7 Diffraction
Diffraction under
under nonideal
nonideal conditions.
conditions. Before
Before going
going any
any further,
further,
it
it is important to
is important to stop
stop and consider
consider with
with some care
care the
the derivation
derivation of the
of the
Bragg
Bragg law
law given
given in
in Sec.
Sec. 3-2
3-2 in
in order
order to
to understand
understand precisely
precisely under
under what
what
conditions
conditions it it is
is strictly
strictly valid.
valid. In In our
our derivation
derivation we assumed certain ideal
certain ideal
conditions, namely
conditions, namely a perfect crystal
perfect crystal and
and an
an incident
incident beam composed
composed of of
perfectly parallel
perfectly parallel and strictly
strictly monochromatic
monochromatic radiation.
radiation. These conditions
These conditions
never actually
never exist, so
actually exist, determine the
so we must determine the effect
effect on
on diffraction
diffraction ofof vari-
vari-
ous kinds
ous kinds ofof departure
departure from from thethe ideal.
ideal.
In particular,
In particular, thethe way
way inin which
which destructive
destructive interference
interference isis produced
produced in in
all directions except
all directions except those
those ofof the
the diffracted
diffracted beams is is worth
worth considering
considering in in
detail, both
some detail, both because
because it it is
is fundamental
fundamental to to the
the theory
theory ofof diffraction
diffraction
because it
and because it will
will lead
lead us
us to
to aa method for for estimating
estimating the
the size
size of
of very
very small
small
crystals. We will
crystals. will find
find that
that only
only the
the infinite
infinite crystal
crystal isis really
really perfect
perfect and
and
that small
that small size
size alone,
alone, ofof an
an otherwise
otherwise perfect
perfect crystal,
crystal, can be considered
can be considered aa
crystal imperfection.
crystal imperfection.
condition for
The condition for reinforcement
reinforcement used used in Sec. 3-2
in Sec. 3-2 is
is that
that the
the waves
waves in-
in-
volved must differ
volved differ in path length,
in path length, that
that is,
is, in
in phase,
phase, byby exactly
exactly anan integral
integral
3-7)
3-7J DIFFRACTION UNDER NONIDEAL CONDITIONS 97
97

number of of wavelengths.
wavelengths. But suppose suppose that that thethe angle
angle 9 9 in
in Fig.
Fig. 3-2
3-2 is
is such
such
that
that the
the path
path difference
difference for for rays
rays scattered
scattered by by the
the first
first and second planes
second planes
is
is only
only a a quarter
quarter wavelength.
wavelength. These rays rays do not annul one another but, but,
as we saw in
as in Fig. 3-1, simply
Fig. 3-1, simply unite
unite to
to form aa beam of of smaller
smaller amplitude
amplitude
than that
that formed by by two rays rays which are are completely
completely in in phase.
phase. How then
does
does destructive
destructive interference
interference take place? The answer lies
take place? in the
lies in the contribu-
contribu-
tions
tions from planes deeper
planes deeper in
in the
the crystal.
crystal. Under the
the assumed conditions,
conditions,
the
the rays
rays scattered
scattered by by the
the second
second and third third planes
planes would also also be a quarter
quarter
wavelength
wavelength out out of
of phase.
phase. But this this means that that thethe rays
rays scattered
scattered by by the
the
first
first and third
third planes
planes areare exactly
exactly halfhalf a a wavelength
wavelength out out ofof phase
phase and would
completely
completely cancel cancel oneone another.
another. Similarly,
Similarly, the the rays
rays from the the second and
fourth planes, third
fourth planes, third and fifthfifth planes,
planes, etc.,
etc., throughout
throughout the the crystal,
crystal, are
are com-
pletely
pletely outout ofof phase;
phase; thethe result
result is is destructive
destructive interference
interference and no diffracted
diffracted
beam. Destructive interference is
Destructive interference is therefore
therefore just just as as much a a consequence
consequence
of
of the
the periodicity
periodicity of
of atom arrangement
arrangement as
as is
is constructive
constructive interference.
interference.
This isis an extreme example.example. If If the path difference
the path difference between rays rays scat-
scat-
tered by
tered by the
the first
first two planes
planes differs
differs only slightly
only slightly from an integral
integral number
of
of wavelengths,
wavelengths, then then thethe plane
plane scattering
scattering a a ray
ray exactly
exactly out out ofof phase
phase with
the
the ray
ray from the
the first
first plane
plane will
will lie
lie deep
deep within
within the
the crystal.
crystal. If
If the
the crystal
crystal
is
is so
so small
small that
that this
this plane
plane does
does not
not exist,
exist, then complete
complete cancellation
cancellation of
of all
all

the
the scattered
scattered rays rays will
will not
not result.
result. It
It fbllows
follows that that there
there is is a connection
connection
between the the amount of of "out-of-phaseness"
"out-of-phaseness" that that cancan be be tolerated
tolerated and the the
size of
size of the
the crystal.
crystal.
Suppose,
Suppose, for example, that
for example, that thethe crystal
crystal has has a a thickness
thickness tt measured in in aa
direction perpendicular to
direction perpendicular to a a particular
particular set set ofof reflecting
reflecting planes
planes (Fig.
(Fig. 3-14).
3-14).
Let there
there be be (m(m + 1) +planes in
1) planes in this
this set.
set. We will
will regard
regard the the Bragg
Bragg angle
angle 9 6
as
as a variable
variable and call call 9BOB thethe angle
angle A A'
which exactly
exactly satisfies
satisfies thethe Bragg
Bragg law
for the
for the particular
particular values
values of of >.X and d d
involved,
involved, or
or

>.X =
= 2d sin
sin 9B.
6B . o
In Fig.
Fig. 3-14,
3-14, rays
rays A,
A, D,
D, ... , M M make
. . .
,

exactly
exactly this
this angle OB with
angle fJB with the
the re-
re-
flecting planes. Ray
flecting planes. Ray D',
D', scattered
scattered by by
the
the first plane below
first plane below the surface, is
the surface, is

therefore
therefore one wavelength
wavelength out
out of
of phase
phase
with A'i
A'; and ray
ray M', scattered by
M', scattered by the
the
mth plane
plane below
below the
the surface,
surface, is
is m
wavelengths
wavelengths out
out of
of phase
phase with
with A'.
A'.

Therefore, at
Therefore, at aa diffraction
diffraction angle m
angle 2fJ B,
20#,
rays A', D',
rays A', D', .... , M'
. .are
are,
completely
completely FIG.
FIG. 3-14.
3-14. Effect
Effect of
of crystal
crystal size
size on
on
in
in phase
phase and unite
unite to
to form a a diffracted
diffracted diffraction.
diffraction.
98 DIFFRACTION I:
i: THE DIRECTIONS OF DIFFRACTED BEAMS [CHAP. 3
[CHAP. 3

beam of of maximum amplitude,

amplitude, i.e.,
i.e., a beam of of maximum intensity, intensity, since
since thethe
intensity
intensity is is proportional
proportional to to the
the square
square of of the
the amplitude.
amplitude.
When we consider
consider incident
incident rays
rays that make Bragg Bragg angles
angles onlyonly slightly
slightly
different
different from 8B, 0#, we find
find that
that destructive
destructive interference
interference is is not complete.
complete.
Ray
Ray B, B, for
for example,
example, makes a slightly larger angle
slightly larger angle 8 1 , such
0i, such that
that ray ray L' L'
from
from the
the mth plane
plane below the
the surface
surface is
is (m
(m +
+ 1) wavelengths
1) wavelengths out
out of
of phase
ph6.se
with
with B',
B', the
the ray
ray from the the surface
surface plane.
plane. This means that that midway
midway in in the
the
crystal
crystal there
there is
is a plane scattering
plane scattering a ray
ray which is
is one-half
one-half (actually,
(actually, an
integer plus one-half) wavelength
integer plus one-half) wavelength out
out of
of phase
phase with
with ray
ray B'
B' from the
the surface
surface
plane.
plane. These rays
rays cancel
cancel one another,
another, and so
so do the
the other
other rays
rays from sim-
sim-
ilar
ilar pairs
pairs of
of planes throughout
planes throughout the
the crystal,
crystal, the
the net
net effect
effect being
being that
that rays
rays
scattered
scattered by by the
the top
top half
half of
of the
the crystal
crystal annul
annul those
those scattered
scattered by by the bottom
the bottom
half. intensity of
half. The intensity of the
the beam diffracted
diffracted at at an angle
angle 28 20i1 isis therefore
therefore zero.zero.
It
It is
is also
also zero
zero atat an angle
angle 282022 where 822 is is such
such that.
that ray ray N' from the the mth
plane
plane below the the surface
surface is is (m
(m - 1) 1) wavelengths
wavelengths out out of phase with
of phase with ray ray C'C'
from the
the surface plane. It
surface plane. It follows
follows that
that the
the diffracted
diffracted intensity
intensity at at angles
angles
near 2fe, but not
near 28B, not greater
greater than 28 26 1 or
1or less
less than 28 is not
2022 , is
,
not zero but has
zero but has a a
value
value intermediate
intermediate between zero zero and the the maximum intensity intensity of of the
the beam
diffracted at
diffracted at an angle
angle 28B.
20s- The curve
curve of of diffracted
diffracted intensity
intensity VS. vs. 2828 will
will
thus
thus have the the form of of Fig.
Fig. 3-15(a)
3-15(a) in in contrast
contrast to to Fig. 3-15(b),
Fig. 3-15(b), which illus-
illus-

trates
trates the
the hypothetical
hypothetical case case ofof diffraction
diffraction occurring
occurring only only at at the
the exact
exact Bragg
Bragg
angle.
angle.
The width of of the
the diffraction
diffraction curve
curve of of Fig.
Fig. 3-15(a)
3-1 5 (a) increases
increases as as the
the thick-
thick-
ness of
ness of the
the crystal
crystal decreases.
decreases. The width
width B is
is usually measured,
usually measured, in
in radians,
radians,
at
at an intensity
intensity equal
equal toto half
half the
the maximum intensity.
intensity. As a a rough
rough measure
measure

Imax-

!llllax-- B

202 20i 288

20*
2
20 8 - - _
.. 2
20- 8 -

(a)
(a) (b)
(b)

FIG.
FIG. 3-15.
3-15. Effect
Effect of
of fine
fine particle
particle size
size on
on diffraction
diffraction curves
curves (schematic).
(schematic).
3-71
3-7] DIFFRACTION UNDER
DIFFRACTION UNDER NONIDEAL
NONIDEAL CONDITIONS
CONDITIONS 99
99

of
of B, we
we can
J5,
can take
take half
half the
the difference
difference between
between the
the two
two extreme
extreme angles
angles at
at
which the
which the intensity
intensity isis zero,
zero, or
or
B = f (20i
- 20 2 ) = 0i
- 2.

The path-difference
The path-difference equations
equations for
for these
these two
two angles
angles are
are

2t sin 01 = (m + 1)X,
sin O22 =
2t sin
2t (m -
= (m l)X.
- 1)X.
By subtraction
By subtraction we
we find
find
(sin 0i sin 2)
= X,

n \
+ fO2) sin //) \
i
/)
CM
21 cos ( 0
1 ~"T~
. (01
2\
sm 1
i ^1
I
O2)\ =
- ^2 X.
= X.)
(/> 2
2 / \ 2
2 /

But 0i
But and O22 are
01 and are both
both very
very nearly
nearly equal
equal to
to 0#, so that
OB, so that
01
0i + 02O2 ==
+ 20B
200 (approx.)
(approx.)
and
and
( 01 -2 02) = (01 - O2)
sin
sin f
^J
= f 2 j (approx.).
(approx.).

Therefore
Therefore
01 - 02)
2t (
2t[ 2 cos OBB ==
-) cos X,
X,

t =
t =--- (3-12)
(3-12)
B
JS cos
cos OB
SB

A more
more exact
exact treatment.
treatment of
of the
the problem
problem gives
gives

0.9X
, .
t =--- _*_. (3-13)
(3-13)
B cos
cos OB
BR

which
which is is known as as the
the Scherrer formula. It
Scherrer formula. is used to estimate the particle
It is particle
size of very small crystals
size of very small crystals from
from the
the measured width of of their
their diffraction
diffraction
curves.
curves. What is is the
the order
order of
of magnitude
magnitude of of this
this effect? Suppose X == 1.5A,
effect? Suppose). 1.5A,
dd = l.OA, and 8 = 49.
LOA, and = 49. ThenThen for
for aa crystal
crystal 1 1 mm in diameter the
in diameter the breadth
breadth
B, due to the small crystal effect
J5, due to the small crystal
effect alone,
alone, would be aboutabout 2 2 X 10~77 radian
X 10-
(0.04
(0.04 sec),
sec), or
or too small to
too small to be
be observable.
observable. Such Such aa crystal
crystal would
would contain
contain
some
some 10 107 parallel
7
parallel lattice
lattice planes
planes ofof the
the spacing
spacing assumed
assumed above.
above. However,
However,
ifif the
the crystal
crystal were
were only
only 500A thick, it
500A thick, it would
would contain
contain only
only 500
500 planes,
planes, and
and
3
the
the diffraction
diffraction curve
curve would
would be be relatively
relatively broad,
broad, namely about 44 X
namely about X 10-
10~~3

radian
radian (0.2).
(0.2).
Nonparallel
Nonparallel incident
incident rays,
rays, such
such as B and CC in
as Band in Fig.
Fig. 3-14,
3-14, actually
actually exist
exist
in any
in any real
real diffraction
diffraction experiment,
experiment, since
since the
the "perfectly parallel
"perfectly parallel beam"
beam"
100
100 I: THE
DIFFRACTION i:
DIFFRACTION DIRECTIONS OF
THE DIRECTIONS DIFFRACTED BEAMS
OF DIFFRACTED BEAMS [CHAP. 33
[CHAP.

assumed in
assumed in Fig. 3-2 has
Fig. 3-2 has never
never been
been produced
produced inin the
the laboratory.
laboratory. As
As will
will
be shown
be shown in
in Sec.
Sec. 5-4,
5-4, any
any actual
actual beam
beam of
of x-rays
x-rays contains
contains divergent
divergent and
and
convergent rays
convergent rays as
as well
well as
as parallel
parallel rays,
rays, so
so that
that the
the phenomenon
phenomenon of of dif-
dif-
fraction at angles
fraction at angles not
not exactly
exactly satisfying
satisfying the
the Bragg law
Bragg law actually
actually takes
takes
place.
place.
Neither is
Neither is any
any realreal beam
beam ever ever strictly
strictly monochromatic.
monochromatic. The usual usual
"monochromatic"
"monochromatic" beam is
is simply
simply one
one containing
containing the
the strong
strong Ka component
component
superimposed on
superimposed on the
the continuous
continuous spectrum.
spectrum. But But. thethe Ka line line itself
itself hashas aa
width of
width of about O.OOlA
about 0.001 A and this this narrow
narrow range range of of wavelengths
wavelengths in the nom- in the
inally monochromatic
inally monochromatic beam is is aa further
further cause cause of of line
line broadening,
broadening, i.e., i.e., of
of
measurable diffraction
measurable diffraction at at angles
angles close,
close, butbut notnot equal,
equal, to to 20#, since for
20B, since for each
each
value of
value there is
of AA there is aa corresponding
corresponding value value of of 8. (Translated into
O. (Translated int.o terms
termi> of of
diffraction line
diffraction line width,
width, aa range
range of of wavelengths
wavelengths extending extending over O.OOIA
over 0.001 A leads
leads
to an
to an increase
increase in in line
line width,
width, for for XA = = 1.5A
1..5A and 80 = = 45, of about 0.08
-l,r'jO, of 0.08
over the
over the width
width one one would
would expect
expeet if if the
the Incident
ineident beam were were strictly
strietly mono-
chromatic.) Line
chromatic.) Line broadening
broadening due to to this
this natural
natural "spectral
"sp('(tral width" width" is IS
proportional
proportional to tan to tan 80 and
and becomes
becomes quite
quite notieeable
noticeable aH
as 0
8 approaehes
approaches 90.
90.
Finally, there
Finally, there is is aa kind
kind of of crystal
crystal
imperfection known as
imperfection mosaic struc-
as mosaic struc-
ture which
ture which is is possessed
possessed by by all real
all real

crystals
crystals to to aa greater
greater or or lesser
lesser degree
degree
and
and which
which has has aa decided
decided effect effect on
diffraction phenomena. IItt is
diffraction phenomena. is a a kind
of
of substructure
substructure into into which a a "single"
"single"
crystal
crystal is is broken
broken up up and is is illustrated
illustrated
in
in Fig.
Fig. 3-16
3-16 in in an enormously
enormously ex- ex-
aggerated
aggerated fashion.
fashion. A crystal
crystal with
mosaic
mosaic structure
structure does does notnot have its its
atoms arranged on a perfectly regular FIG. 3-1
FIG. 3-K). The mosaic
Ii. The mosaic Htl'U('ture
structure of of
atoms arranged on a perfectly regular
aa real
real ('rystal.
crystal.
lattice
lattice extending
extending from one one side
side of of the
the
crystal to
crystal to the
the other;
other; instead,
instead, the the lattice
lattice is is broken up up into
into a number of of tiny
tiny
blocks,
blocks, each
each slightly
slightly disoriented
disoriented one one from another.
another. The size size of of these
these blocks
blocks
is
is of
of the
the order
order of of 1 OOOA , while
1000A, while the the maximum angle angle of of disorientation
disorientation be- be-
tween
tween them may vary
may vary from
from aa very
very small
small value
value to
to as
as much as
as one degree,
degree,
depending
depending on on the crystal. If
the crystal. If this
this angle
angle is is E, then diffraction
,
diffraction of.,a of ^a parallel
parallel
monochromatic
monochromatic beam from from aa "single" crystal
"single" crystal will
will occur not only
only at at an
angle
angle of
of incidence
incidence UB
0# but
but at
at all
all angles
angles between OR
8s and OR
OR +
+ E.
c. Another
effect of
effect of mosaic
mosaic structure
structure is is toto increase
increase the the intensity
intensity of of thethe reflected
reflected beam
relative
relative to
to that theoretically calculated
that theoretically calculated for
for an ideally
ideally perfect crystal.
perfect crystal.
These,
These, then,then, areare some examples
examples of of diffraction
diffraction under nonideal nonideal conditions,
conditions,
that
that is,
is, of
of diffraction
diffraction as as it
it actually
actually occurs.
occurs. We should should not not regard
regard thesethese as as
"deviations"
"deviations" from from thethe Bragg
Bragg law, law, andand we will will not
not asas long
long as as we remember
that
that this
this lawlaw is is derived
derived for for certain
certain ideal ideal conditions
conditions and and that that diffraction
diffraction is is
3-71
3-7] DIFFRACTION UNDER NONIDEAL CONDITIONS 101
101

....
~ crystal
crystal
Z
~
-
Z

liqUId or
liquid or amorpholls solid
amorphous solid

(a)
(a)

. \.----.. /.
monatomic gas

/~
~~ "------'
o HO
90 180
180
DIFFRAC TION (KCATTEHINU)
DIFFRACTION (SCATTERING)
(1))
(1)) ANGLE 28
AXGLE 28 (d('gree~)
(degrees)

FIG.
FIG. 3-17.
3-17. (a)
(a) i-)cattering
Scattering by by an FIG. 3-18. Comparative
FIG. 3-IS. Comparative x-ray
x-ray scat-
scat-
atom.
atom, (b)
(b) Diffraction by aa crystal.
Diffraction by crystal. tering by ('rystalline
tering by crystalline solids,
solids, amorphous
amorphous
solids,
solids, Iiqui(ls,
liquids, and monatomir
monatomic gases
gases
(schematie).
(schematic).

only
only aa special
special kind
kind of
of scattering.
scattering. ThisThis latter
latter point
point cannot
cannot bebe too
too strongly
strongly
emphasized.
emphasized. A single single atom scatters
scatters an incident
incident beam of x-rays
of x-rays in in all
all

directions
directions in space, but
in space, but a a large
large number of of atoms arranged
arranged in in aa perfectly
perfectly
periodic
periodic array
array in in three dimensions to
three dimensions to form a crystal
crystal scatters
scatters (diffracts)
(diffracts)
x-rays
x-rays in
in relatively
relatively few
few directions,
directions, as as illustrated
illustrated schematically
schematically in in Fig.
Fig. 3-17.
3-17.
It
It does
does soso precisely
precisely because
because the the periodic
periodic arrangement
arrangement of of atoms causes
destructive interference of
destructive interference of the
the scattered
scattered rays
rays in
in all
all directions except those
directions except those
predicted
predicted by by the
the Bragg
Bragg law,law, and
and in
in these
these directions
directions constructive
constructive inter-
inter-
ference
ference (reinforcement) occurs. It
(reinforcement) occurs. It is
is not
not surprising,
surprising, therefore,
therefore, that
that meas-
urable
urable diffraction
diffraction (scattering)
(scattering) occurs
occurs at
at non-Bragg angles
non-Bragg angles whenever any
any
crystal imperfection
crystal imperfection results
results in
in the
the partial
partial absence
absence of
of one or
or more of
of the
the
necessary conditions for
necessary conditions for perfect perfect destructive
destructive interference
interference at
at these
these angles.
angles.
102
102 I: THE
DIFFRACTION i:
DIFFRACTION THE DIRECTIONS DIFFRACTED BEAMS
OF DIFFRACTED
DIRECTIONS OF BEAlIS [CHAP. 33
[CHAP.

These imperfections
These imperfections are
are generally
generally slight
slight compared
compared to
to the
the over-all
over-all regularity
regularity
of the
of the lattice,
lattice, with
with the
the result
result that
that diffracted
diffracted beams
beams are
are confined
confined to
to very
very
narrow angular
narrow angular ranges
ranges centered
centered on the angles
on the angles predicted
predicted by
by the
the Bragg
Bragg law
law
for ideal
for ideal conditions.
conditions.
This relation
This relation between
between destructive
destructive interference
interference andand structural
structural periodicity
periodicity
can be further
can be further illustrated
illustrated by
by a
a comparison
comparison of
of x-ray
x-ray scattering
scattering by solids,
by solids,
liquids, and gases (Fig.
liquids, and gases (Fig. 3-18). 3-18). The
The curve
curve of
of scattered
scattered intensity
intensity VB.
vs. 26
26 for aa
for
crystalline solid is almost zero everywhere
crystalline solid is almost zero everywhere except except at
at certain
certain angles
angles where
where
high sharp
high sharp maxima
maxima occur:
occur: these
these are
are the
the diffracted
diffracted beams.
beams. BothBoth amorphous
amorphous
solids and
solids and liquids
liquids have
have structures
structures characterized
characterized by by anan almost
almost complete
complete
lack of
lack of periodicity
periodicity and and aa tendency
tendency to to "order"
"order" onlyonly in
in the
the sense
sense that
that the
the
atoms are
atoms are fairly
fairly tightly
tightly packed
packed together
together andand show
show aa statistical
statistical preference
preference
for aa particular
for particular interatomic
interatomic distance;
distance; thethe result
result isis an x-ray
x-ray scattering
scattering curve
curve
showing nothing
showing nothing more
more than
than one
one or
or two broad
broad maxima. Finally,
Finally, there
there are
are
the monatomic
the monatomic gases,
gases, which
which have
have no no structural
structural periodicity
periodicity whatever;
whatever; in in
such gases,
such gases, the
the atoms
atoms areare arranged
arranged perfectly
perfectly at at random and their their relative
relative
positions change
positions change constantly
constantly withwith time.
time. The corresponding
corresponding scattering
scattering
curve shows
curve shows no
no maxima, merely
maxima, merely a
a regular
regular decrease
decrease of
of intensity with in-
intensity with in-
crease in scattering angle.
crease in scattering angle.

PROBLEMS

3-1.
3-1. Calculate
Calculate thethe "x-ray
"x-ray density"
density" [the
[the density
density given
given byby Eq.
Eq. (3-9)]
(3-9)] of
of copper
copper
to
to four
four significant
significant figures.
figures.
3-2.
3-2. A transmission
transmission LaueLaue pattern
pattern is
is made ofof a cubic
cubic crystal
crystal having
having a lattice
lattice

parameter
parameter of
of 4.00A.
4.00A. The x-ray
x-ray beam is
is horizontal.
horizontal.
_
The [OTO]
[OlO] axis
axis of
of the crystal
crystal
points
points along
along the
the beam towards
towards the
the x-ray
x-ray tube,
tube, the [100] axis
the [TOO] axis points
points vertically
vertically up-
up-
ward,
ward, and
and the
the [001]
[001] axis
axis is
is horizontal
horizontal and parallel
parallel to
to the photographic
photographic film.
film. The

film
film is
is 5.00
5.00 cm from
from the
the crystal.
crystal.

(a) What is
(a) is the
the wavelength
wavelength ofof the
the radiation
radiation diffracted
diffracted from the (310)
(3TO) planes?
planes?
(b) Where will the 310 reflection strike the
(6) Where will the 310 reflection strike
the film?
film?

3-3.
3-3. A A back-reflection
back-reflection LaueLaue pattern
pattern isis made
made of of aa cubic
cubic crystal
crystal inin the
the orientation
orientation
of
of Prob.
Prob. 3-2.
3-2. ByBy means
means of
of a
a stereographic projection
stereographic projection similar
similar to
to Fig.
Fig. 3-8,
3-8, show
show that
that
the
the beams
beams diffracted
diffracted byby the
the planes
planes (120),
(120), (123),
(T23), and
and (121),
(121), all
all of
of which
which belong
belong to
to
the
the zone
zone [210],
[210], lie
lie on
on the
the surface
surface ofof aa cone
cone whose
whose axis
axis is
is the
the zone
zone axis.
axis. What
What isis
the angle q, between
the angle <f>between thethe zone
zone axis
axis and
and the
the transmitted
transmitted beam?
beam?
W.
3-4. Determine
Determine the the values
values ofof 28
20 and (hkl) for
and (hkl) for the
the first
first three
three lines
lines (those
(those of
of low-
low-
est
est 28
26 values)
values) on
on the powder patterns
the powder patterns of
of substances
substances with
with the
the following structures,
following structures,
the
the incident
incident radiation
radiation being
being CuCu Ka:
Ka:

(a) Simple
(a) Simple cubic (a =
cubic (a = 3.00A)
3.00A)
(6) Simple
(b) Simple tetragonal
tetragonal (a 2.00A, cc == 3.00A)
(a == 2.00A, 3.00A)
(c)
(c) Simple tetragonal (a 3.00A, cc == 2.00A)
Simple tetragonal (a === 3.00A, 2.00A)
(d) Simple
(d) Simple rhombohedral (a =
rhombohedral (a = 3.00A, a=
3.00A, Or! = 80)
80)
 PROBLEMS 103
103

3-5.
3-6. Calculate
Calculate the breadth B (in
the ereadth (in degrees
degrees of
of 28), due to
26), due to the
the small
small crystal
crystal effect
effect
alone,
alone, of
of the
the powder pattern
powder pattern lines
lines of
of particles
particles of
of diameter
diameter 1000,
1000, 750, 500,
750, 500, and 250A.
250A.
Assume 86 = = 45
45 and X X =
= I.5A.
1.5A. For particles
particles 250A in in diameter,
diameter, calculate
calculate thethe
breadth B for
breadth for (J =
= 10,
10, 45,
45, and BO.
80.
W.
3-6. Check thethe value
value given
given in
in Sec.
Sec. 3-7 for
for the
the increase
increase inin breadth
breadth ofof aa diffrac-
diffrac-
tion line due to
tion line to the
the natural
natural width of of the
the Ka emission
emission line.
line. (Hint: Differentiate
(Hint: Differentiate
the
the Bragg
Bragg law
law and find
find an expression
expression for
for the
the rate
rate of
of change
change ofof 28
26 with
with X.)
X.)
 CHAPTER 4

DIFFRACTION II:
II: THE INTENSITmS
INTENSITIES OF DIFFRACTED BEAMS

4-1
4-1 Introduction.
Introduction. As stated earlier, l~~
stated earlier, ^.he positions
positions of of the atom!;
atoms in in the
unit
unit cell
cell affect
affect thethe intensities
intensities but not the directions directions of of the diffracted
diffracted beams.
That this
this must be so so may be seen seen by by considering
considering the two structures
structures shown
in
in Fig.
Fig. 4-1.
4-1. Both are are orthorhombic with two atoms of of the
the same kind per per
unit
unit cell,
cell, but thethe one on the left left is is base-centered
base-centered and the the one on the the right
right
body-centered. Either is
body-centered. is derivable
derivable from the the other
other by by a simple
simple shift
shift of of

ope atom by
OJre by the vector lc. ^c.
(/ C~)I~.!3ider
Consider reflections
reflections from the (001) planes which are
(001) planes are shown i~. p!:9file in
in profile in
Pig.
Ftg. 4-2.
4-2. For the
the base-centered
base-centered lattk'e lattice shown in in (a),
(a), suppose
suppose that that thethe
Bragg
Bragg law is is sati!;fied
satisfied for
for the particular
particular values values of of X
X and 9 6 employed.
employed. This
means thatthat thethe path difference ABC between rays
path difference rays l' 1' and 2' 2' is
is one wave-

length,
length, so
so that
that rays
rays l'
1' and 2'
2' are
are in
in phase
phase and diffraction
diffraction occurs
occurs in
in the
direction
direction shown. Similarly,
Similarly, in
in the
the body-centered
body-centered lattice
lattice shown in
in (b),
(b),
rays
rays l'
1' and 2'
2' are
are in
in phase,
phase, since
since their
their path
path difference
difference ABC is
is one wave-
length.
length. However,
However, in in this
this case,
case, there
there is is another planeplane of of atoms midwaymidway
between the the (001) planes,
(001) planes, and the
the path
path difference
difference DEF between rays
between rays l' 1'

and 3'3' is
is exactly
exactly half
half of
of ABC,
ABC, or
or one half
half wavelength.
wavelength. Thus rays
rays l'
1' and
3'
3' are
are completely
completely out out of phase and annul each other.
of phase other. Similarly,
Similarly, ray ray 4' 4'
from thethe next plane
plane down (not shown)
(not shown) annuls ray 2',
ray 2', and so
so on throughout
throughout
the
the crystal.
crystal. There is is no 001
001 reflection
reflection from the the body-centered lattice.~
body-centered latticeTJ
This example
example shows how a simple rearrangement
simple rearrangement of
of atoms withIn
within the the
unit
unit cell
cell can eliminate
eliminate a a reflection
reflection completely.
completely. More generally,
generally, the
the in-
in-
tensity
tensity of
of a diffracted
diffracted beam is
is changed,
changed, not necessarily
necessarily to
to zero, by
zero, by any any
change
change in in artomic
atomic positions,
positions, and,and, conversely,
conversely, we can only only determine atomic
positions
positions by by observations
observations of of diffracted
diffracted intensities.
intensities. To est.ablish
establish an exact exact
relation between atom position
relation position and intensityintensity is
is the main purpose
purpose of
of this
this
chapter.
chapter. The problem
problem is
is complex
complex because
because of
of the
the many
many variables
variables involved,
involved,
and we willwill have to to proceed
proceed stepstep by by step:
step we will
: will consider
consider how x-rays x-rays areare
scattered
scattered first
first by a single electron,
by single electron, then by
by an atom,
atom, and finally
finally byby all
all the
the

I
c I
~-----
,- 0

...,.
"
,$
(a)
(a) (b)
(b)

FIG.4-1.
FIG. 4-1. (a)
(a) Base-centered
Base-centered and (b)
(b) body-centered
body-centered orthorhombic
orthorhombic unit
unit cells.
cells.

104
104
4-21
4-2] SCATTERING BY AN ELECTRON
SCA'ITERING 105
r i

II'

(a)
(a) (b)
(b)

FIG.
FIG. 4-2.
4-2. Diffraction
Diffraction from thethe (001)
(001) planes
planes of
of (a)
(a) base-centered
base-centered ancl
and (b)
(b) body-
body-
centered orthorhombir Jlltti('eR.
centered orthorhombi(' lattices.

atoms in
in the
the unit
unit cell.
cell. We will
will apply
apply these
these results
results to
to the powder method
the powder
of
of x-ray
x-ray diffraction
diffraction only,
only, and,
and, to
to obtain
obtain an expression
expression for
for the
the intensity
intensity of
of a
a
powder pattern
powder pattern line,
line, we will
will have to
to consider
consider aa number of of other
other factors
factors
which affect
affect the
the way
way inin which aa crystalline
crystalline powder
powder diffracts
diffracts x-rays.
x-rays.

4-2 Scattering
Scattering by by an electron.
electron. Wee haY(~
W have seen
seen in
in Chap.
Chap. 1 that a~
1 that
aq| x-ray
x-ray
beam is js an electromagnetic
electromagnetic wave characterized
characterized by
by an electric
electric field
field whose
strength
strength varies
varies sinusoidally
sinusoidally with t'imeattime at anyone point in
any one point in the
the beam..
beam., BUice
Sipce
aneiec'iric
anVlectric field
field exert!:?
exerts a force 0;;
a forep on a ebarg(,cCpartide
a Charged particle such
such as
as an electron,.the
electron^lhe
o~lnating electric fiel~
oscillating electric field of
of an
an '"x-ray
x-ray beam will will set
set any
any electron
electron it it encounters
encounters
into
into oscillatory
oscillatory motion about.
about its
its mean P9!!ttion.,
position.}
\NO";-
Wow an an acceTerating
accelerating or or dece!e~~ting
decelerating electro~ emits ~n
electron emits an el~c~ro~_~g.netic
electromagnetic
wave.
wave. We have already already seen
seen an example
example of
of thIS
this 'phenomenon
phenoinejionjn In the
the ?f.-ray
x-ray
tUDe,
tube, where x-rays
x-rays are
are emitted'
emitted because
because of
of the
the rapid
rapid decelerati~n
deceleration of
of the
the
electrons
electrons striking
striking the
the target.
target. Similarly,
Similarly, an electron'
electron which has
has been set
set
into
into oscillation
oscillation by by an x-ray
x-ray beam is
is continuously accelerating
continuously accelerating and de-
de-
celerating
celerating during
during itsits motion and therefore
therefore emits electromagnet.~<l. .iY.ave.
emits an electromagnetic, .wjave.
In this
this sense,
sense, an electron
electron is is said
said toto scatter
scatter x-rays,
x-rays, the
the scattered
scattered beam being being
simply "the
simplY ITie beam radiatoo
radiated by by the
the electroii' under the~aciioii
electron '!nder)p.e action of of th~
the incident
incident
beain.
beam. The scattered
scattered beam has has the
the same wavelength frequency .as
wavelength and frequency as
toe
the incident
incident beam and is is said
said to be coherent
to be coherent with
with it,
it, since
since there
there isis a definite
definite
relationship betweenilie "phase
piIase of of the
lite scatteredheam
scattereHbeam 'aiicf'tJiii'o(the
anJTEat of the inci-
relationship T>etwee7fT1ie
deiif'Deatn
denFfieam \vhichwhich produced
produced it. \
t _._ .....-.... - -.
it. """'
inci-

Although
Although x-raysx-rays are
are scattered
scattered in in all
all directions
directions by by an electron,
electron, the in- in-

tensity of
tensity of the
the scattered
scattered beam dependsdepends on t.he the angle
angle of
of scattering,
scattering, in in a way
which was firstfirst worked out by J.
out by J. J.
J. Thomson. He found that that the
the intensity
intensity
I/ of
of the
the beam scattered
scattered by by a a single
single electron
electron ofof charge
charge e e and mass m, m, atat a
(I;stance
^stance rr from
from thethe electron,
electron, is is given
given by by

sin
2
a, (4-1)
(4-1)
106
106 II: THE
DIFFRACTION II
DIFFRACTION INTENSITIES OF
THE INTENSITIES
: DIFFRACTED BEAMS
OF DIFFRACTED BEAMS [CHAP. 44
[CHAP.

where /o
where 10 == intensity
intensity of
of the
the incident beam, ce == velocity
incident beam, velocity of
of light,
light, and
and
aex = angle between
= angle between the
the scattering
scattering direction
direction and
and the
the direction
direction of
of accelera-
accelera-
tion of the
tion of the electron.
electron. Suppose the
Suppose the incident
incident beam
beam isis traveling
traveling,in the direc-
in the direc-
tion
tion Ox (Fig.
Ox 4-3) and
(Fig. 4-3) and encounters
encounters anan electron
electron at O. We
at 0. We wish
wish to
to know
know the
the
scattered intensity
scattered intensity at
at P
P in
in the
the xz
xz plane
plane where
where OP
OP is
is inclined
inclined at
at aa scattering
scattering
angle of
angle of 26 to the
20 to the incident
incident beam.
beam. AnAn unpolarized
unpolarized incident
incident beam,
beam, such
such as
as
that issuing
that issuing from
from an
an x-ray tube,
x-ray tube, has
has its
its electric
electric vector
vector E in
in a
a random
random
direction in
direction in the
the yz plane. This
yz plane. This beam
beam may
may bebe resolved
resolved into
into two
two plane-
plane-
polarized components,
polarized components, having
having electric
electric vectors
vectors Eyy and
E Ez where
and E where
2

E2 = Ey2 + Ez2.
the average,
On the Elly will
average, E will be
be equal
equal to E z, since
to E, since the
the direction of E is
direction of is perfectly
perfectly
random. Therefore
random. Therefore
Ey2 == E zz22 = E2
= !E2.
2
E, .

The intensity
intensity of
of these
these two components
components of
of the
the incident
incident beam is
is proportional
proportional
to the
to the square
square of
of their
their electric
electric vectors,
vectors, since
since E measures the
the amplitude
amplitude of
of
the
the wave and
wave and the
the intensity
intensity of
of aa wave is proportional
proportional to
to the
the square
square of
is of its
its
amplitude.
amplitude. Therefore
Therefore
101/
IQ V
= lozZ =
= IQ = !lo.
2^0-

component of
The yy component of the incident beam accelerates
the incident the electron
accelerates the electron in
in the
direction Oy. It
direction Oy. therefore gives
It therefore gives rise
rise to
to a scattered
scattered beam whose intensity
intensity
at P is
at is found
found from Eq. (4-1)
from Eq. (4-1) to be
to be

2 2 4
r ra c

since ex
since a = 4YOP
^yOP == 1(/2.
w/2. Similarly,
Similarly, the
the intensity of the scattered z
intensity of z com-

ponent
ponent is
is given by
given by

a =
since ex
since = 11'/2
r/2 - 20. 20. The total
total scattered
scattered intensity
intensity at P isis obtained
at P obtained by
by
Bumming
summing the
the intensities
intensities of
of these
these two scattered
scattered components:
components:

Ip
IP == Ipy
Ip v +
+ IIppz z

44
ee
== 224
-r-r-r (101/
rme
r'm'c'
(7o + loz cos2 20)
hz C08 20)
2

4
e \
= //o
(
~ -^
/o 2o
cos 2^
2
)
r
2
m 2 4
c \2 2 /

+ cos2
(4--2)
^V
4-21
4-2] SCATTERING BY
SCATTERING BY AN
AN ELECTRON
ELECTRON 107
107
\

E
hVL -
~,
e
~ .. 0
--~~----~-------y
befofr impact
before lIupa('t

::e:
h"2

x after HUpD ~t
aftl'r impart P

FIG. 4-3.
FIG. 4-3. Coherent scattering
Coherent seattering ofx-
of x- FIG. 4-4.
FIG. 4-4. Elastic collision
Elastic eollision of
of photon
photon
rays by aa single
rays by single electron.
eleetl'On. electron (Compton
and electron (Compton effect).
effect).

This
This is the
is the Thomson equation equation for for the
the scattering
seattering of of an x-ray
x-ray beam by by aa
single electron. If
single electron. the values
If the values of of the constants e,
the constants e, r,
r, m,
m, and c are inserted
c are inserted
into this
into this equation,
equation, it will be
it will he found
found thatthat the
the intensity
in.ten.sity of of the
the scattered
scattered beam
is only
is only aa minute
minute fraction
fract.ion of of the
t.he intensity
int.ensity of of the
the incident
incident beam. The equa- equa-
ti~n also
tion also shows
shows thatthat the the scattered
scattered intensity
intensity decreases
decreases as as the
the inverse
inverse square
square
of the
of the distance
distance from from the the scattering
scattering atom, atom, as as one
one \vould
would expect,
expect, and that that
the scattered
the scattered beam is is stronger
stronger in in forward
forward or or backward directions
directions than than in in aa
direction at
direction right angles
at right angles to to the
tIle incident
incident beam.
beam .
.. The Thomson equation equation gives gives thethe absolute
absolute intensity
intensity (in ergs/sq em/sec)
(in ergs/sq cm/sec)
of
of thethe scattered
scattered beam in terms of
in terms of the
the absolute intensity of
absolute intensity of thethe incident
incident
beam.
beam. These These absolut.e
absolute intensities
intensities are are bot.h
both diffi('ult
difficult to to measure and difficult difficult

to
to caleulate,
calculate, so
so it
it is
is fortunate
fortunate that
that relative
relative values
values are
are sufficient
sufficient for
for our
purposes
purposes in
in practically
practically all
all diffraction
diffraction problems.
problems. In most cases,
cases, all
all factors
factors
in
in Eq. (4-2)
Eq. (4-2) except except the
the last
last are
are constant
constant during
during the
the experiment
experiment and can
be omitted.
be omitted.* This This lastlast factor,
factor, ^(1 +!(l + cos
cos
2
2 28),
26), is
is called
called the
the polarization
polamation
f!!E!E; this
factor; this isis aa rather
rather unfortunate
unfortunate term because, because, as as we have just just seen,
seen, this
this
factor enters the equation
factor enters the equation simply because simply because the
the incident
incident beam is
is unpolarized.
unpolarized.
The polarization
polarization factor factor is is common to to all
all intensity
intensity calculations,
calculations, and we
will
will use use itit later
later inin our
our equation
equation for for the
the intensity
intensity of of a a beam diffracted
diffracted by by aa
crystalline
crystalline powder.powder.
There
There is is another
another and quite quite different
different way way in in which an electron
electron can scatter scatter

x-rays, and
x-rays, and that
that isis manifested
manifested in the Compton
in the Compton effect.
effect. This effect,
effect, discovered

by A.
by A. H. H. Compton
Compton in in 1923,
1923, occurs
occurs whenever x-rays x-rays encounter loosely loosely
bound or or free
free electrons
electrons and can can be be best
best understood by by considering
considering the
incident
incident beam, beam, not not as as a a wave motion,
motion, but but as as aa stream of of x-ray
x-ray quanta
quanta or or
photons,
photons, each
each of
of energy
energy hIll.
hvi. When such
such a
a photon
photon strikes
strikes a
a loosely
loosely bound
electron,
electron, the the collision
collision is is an
an elastic
elastic one one like
like that
that ofof two billiard
billiard balls
balls (Fig.
(Fig.
'.\ The electron
electron is is knocked
knocked aside aside and the the photon
photon is
is deviated
deviated through
through
Jigle 28.
.ngle 26. Since
Since somesome of of the
the energy
energy of of the
the incident
incident photonphoton is is used in in

,riding kinetic
/iding kinetic energy energy for
for the
the electron,
electron, the
the energy
energy h"2
hv 2 of
of the photon
photon
lOB
108 DIFFRACTION II! INTENSITIES OF DIFFRACTED BEAMS
II: THE INTENSITIES [CHAP. 44
[CHAP.

after impact
after impact is
is less
less than
than its
its energy
energy hv\ before impact.
hill before impact. The wavelength
wavelength
of the
).22 of
X the scattered
scattered radiation
radiation is
is thus
thus slightly
slightly greater
greater than the
the wavelength
wavelength
of the
).1 of
Xi the incident
incident beam,
beam, the
the magnitude
magnitude of of the
the change
change being
being given
given by
by the
the
equation
equation
AX(A) = X2 - Xl = 0.0243 (1 - cos 28). (4-3)
The increase
The increase in
in wavelength
wavelength depends
depends only
only on
on the
the scattering
scattering angle,
angle, and it
it
varies from
varies from zero
zero in
in the
the forward
forward direction
direction (26
(28 =
= 0)0) toto 0.05A
0.05A inin the
the extreme
extreme
backward direction
backward direction (20 =
(28 = 180).
180).
Radiation so
Radiation so scattered
scattered is is called
called Compton
Compton modified
modified radiation,
radiation, and,
and, be-be-
sides having
sides having its
its wavelength
wavelength increased,
increased, it it has
has the
the important
important characteristic
characteristic
i"Ui phase
that its
that phase has
has no
no fixed
fixed relation to the
relation to th:e phase
phase of
of the
the incident
incident beam.
beam. For For
this reason
this reason it is also
it is also known as as incoherent
incoherent radiation.
radiation. It cannot take
It cannot take part
part
in diffraction
in diffraction because
because its its phase
phase isis only
only randomly
randomly related
related to to that
that of
of the
the inci-
inci-
dent beam
dent beam and cannot therefore produce
cannot therefore produce any any interference effects. Comp-
interference effects. Comp-
ton modified
ton modified scattering cannot be
scattering cannot be prevented,
prevented, however,
however, and it it has
has the
the
undesirable effect
undesirable effect of darkening the
of darkening the background
background of diffraction patterns.
of diffraction patterns.
-:It
[It should be noted
should be noted that
that the
the quantum
quantum theorytheory cancan account
account for both the
for both the
c(j}erent
coherent and and the
the incoherent
incoherent scattering, whereas the
scattering, whereas the wave theory
theory isis only
only
applicable
applicable to to the former. In
the former. In terms
terms ofof the
the quantum theory, coherent
quantum theory, coherent scat-
scat-
tering
tering occurs
occurs when an incident
incident photon
photon bounces
bounces off
off an electron
electron which is so
is so
tightly
tightly bound
bound that
that it
it receives
receives no momentum from the
the impact.
impact, The scat-
scat-
tered
tered photon
photon therefore
therefore hashas the
the same ep.ergy,
energy, and hence hence wavelength,
wavelength, as as itit

had
had before
before

4-3 Scattering
4-3 Scattering by by anan atom.
atom. \ When an
1 an x-ray
x-ray beam encounters
encounters an atom, atom,
each
each electron
electron in in it
it scatters
scatters part
part of
of the
the radiation
radiation coherently
coherently in
in accordance
accordance
with
with thethe Thomson equation.
equation. One might might also
also expect
expect thethe nucleus
nucleus to to take
take
part
part in
in the
the coherent
coherent scattering,
scattering, since
since it
it also
also bears
bears a
a charge
charge and should
should be
capable
capable of
of oscillating
oscillating under
under the
the influence
influence of
of the
the incident
incident beam. I However,
beam,} However,
the
the nucleus
nucleus has has an
an extremely
extremely large
large mass relative
relative to to that
that of of the
tne electron
electron
and cannot
cannot be be made to
to oscillate
oscillate to
to any appreciable
any appreciable extent;extent; in
in fact,
fact, the
the
rhomson equation shows that the
Thomson equation shows that the intensity of intensity of coherent
coherent scattering
scattering is
is in-
in-

versely
versely proportional
proportional to to the square of
the square of the
the mass of of the
the scattering
scattering particle.
particle.
The net effect is
net effect is that
that coherent
coherent scattering
scattering by by an atom is is due onlyonly to
to the
the
electrons
electrons contained
contained in in that
that atom.
atom.
The following
following question
question then then anses;
arises: isis the
the wave scattered
scattered by by an atom
simply
simply the the sum of of the
the waves scattered
scattered by by its
its component
component electrons?
electrons? More
precisely,
precisely, doesdoes anan atom of of atomic
atomic number Z, Z, i.e.,
i.e., an
an atom containing
containing Z
electrons,
electrons, scatter
scatter a a wave whosewhose amplitude
amplitude is
is Z times
times the
the amplitude
amplitude of of
the
the wave scattered
scattered by a
a single
by single electron?
electron? The answer
answer is
is yes,
yes, if
if the
the scatter-
scatter-
ing
ing isis in
in the
the forward
forward direction
direction (28 = 0), because
(20 = 0), because the the waves
waves scatterec'
scattered . by
1
"

by
all
all the
the electrons
electrons of of the
the atom are are then
then inin phase
phase and
and the
the amplitudes
amplitudes 0o ff all all
the
the scattered
scattered waves
waves can can bebe added
added directly.
directly.
4-3]
4-3] SCATTERING BY AN ATOM 119
It9

This isis not true

true for
for other
other directions
directions of of scattering.
scattering. frhe
iThe fact
fact that
that the
the
electrons
electrons of of an atom are are situated
situated atat different
different points
points in
in space
space introduces
introduces
differences
differences in in phase
phase between the the waves scattered
scattered by different electrons.1
by different electrons:^
Consider
Consider Fig.Fig. 4-5,
4-5, inin which,
which, for
for simplicity,
simplicity, the the electrons
electrons are
are shown as as
points arranged
points arranged around the the central
central nucleus.
nucleus. The waves scattered
scattered in in the
the
forward
forward direction
direction by electrons A and
by electrons B are exactly':'m
and_J^are ~ on...a...wave
exactly* in phase on_a_3Kave
front
front such as XX', because each wave has
as XX', has traveled
traveled the
the same distance
distance
before
before and after
after scattering.
scattering. The other
other scattered
scattered waves shown in'
in' the
the .fig-
'fig-

ure, however,
ure, however, have a
a path
path difference
difference equal
equal to
to (CB
(CB - AD)
AD) and are
are thus
thus
somewhat out out of phase along
of phase along a a wave front
front such as YY',
such as YY', the
the path
path differ-
differ-
ence
ence being
being less
less than one wavelength.
wavelength. Partial
Partial interferenc~
interference occurs
occurs between
between
the
the waves scattered
scattered by by A and B, 5, with
with thethe result
result that
that the
the net
net amplitude
amplitude of of
the
the wave scattered
scattered in in this
this direction
direction isis less
less than that
that of
of the
the wave scattered
scattered
by
by the
the same electroDs
electrons in in the
the forward
forward direction.
direction.
JA
I A quantity
quantity /, f, the
the atomic
atomic scattering factor, is
scattering factor, is used
used to
to describe
describe thethe "effi-
"effi-

cIency"
ciency" of of scattering
scattering of of aa given
given atom in in a given direction. It
given direction. It is
is defined
defined
as
as a
a ratio
ratio of
of amplitudes:
amplitudes :

amplitude
amplitude of
of the
the wave scattered by an atom
scattered by
f=
/ = .
amplitude
amplitude of
of the
the wave scattered
scattered by
by one electron
electron f I
From what has has been. said already,~t
been* said already, lit is
is clear that f/ =
clear that = Z for
f or any
any atom
scattering
scattering in
in the
the forward
forward directioIll
direction^ As 8 increases, however,
increases, however, the
the waves
scattered by
scattered by individual
individual electrons
electrons become more and more out
out of phase and
of phase
f/ decreases.
decreases. The atomic scattering
scattering factor
factor also
also depends
depends on the
the wavelength
wavelength
of
of the
the incident beam at
incident beam: at a
: a fixed
fixed value
value of 0, f
of 8, f will
will be
be smaller
smaller the
the shorter
shorter the
the

X'

FIG.
FIG, 4-5.
4-5. X-ray
X-ray scattering
scattering by
by an
an atom.
atom.
110
110 DIFFRACTION IIII: THE
DIFFRACTION THE INTENSITIES
: DIFFRACTED BEAMS
OF DIFFRACTED
INTENSITIES OF BEAMS [CHAP. 44
[CHAP.

wavelength, since
wavelength, since the
the path
path differ-
differ-
ences
ences will
will be
be larger
larger relative
relative to
to the
the
wavelength, leading
wavelength, leading to
to greater
greater in-
in-
terference between
terference between the
the scattered
scattered
beams. The actual
beams. The actual calculation of /f
calculation of 20
involves sin 8 rather than 8,
involves sin 6 rather than 6, so
so that
that
the net
the net effect
effect is that /f decreases
is that decreases as as fell
the quantity
the quantity (sin (sin 0)/X
8)/X increases!
increasesj
Calculated values
Calculated values of of /f for
for various
varIOUS 10
atoms and
atoms and various
various values
values of of (sin
(sin 0)/X
O)/X
are tabulated
are tabulated in in Appendix
Appendix 8, 8, and
and aa
curve showing
curve showing the the typical
typical variation
variation
of j, in this case for copper, is given
of/, in this case for copper, is given
in Fig.
in Fig. 4-6.
4-6. Note Note again
again that that thethe
curve begins
curve begins at at the
the atomic
atomic numbernumber
of copper,
of copper, 29, 29, and
and decreases
decreases to to very
very
Ilow I f .. h b k The atomic
4-6. The
FIG. 4-6.
FIG. atomic scattering
scattering fac-
fac-
ow va ues or scattering
values for scattermg m t e ac - tor
in the back- tor of
of copper.
copper.
ward direction
ward direction (0 near 90)
(0 near 90) or or for
for
very short wavelengths.
very short wavelengths. Since
Since the
the intensity of
intensity of aa wave is is proportional
proportional to to
the square of its
the square of its amplitude, amplitude, a
a curve
curve of
of scattered
scattered intensity
intensity f~m
fit)m an
an atom
atom
can be
can be obtained
obtained simply simply by by squaring
squaring the the ordinates
ordinates of of aa curve
curve suchsuch a&a& Fig.
Fig.
4-{3.
4-6. (The resulting curve closely
(The resulting curve closely approximates approximates the
the observed scattered
scattered in-
in-

tensity
tensity per atom of
per atom of aa monatomic
monatomic gas, gas, asas shown in Fig.
in Fig. 3-18.)
3-18.)
The
The scattering
scattering just just discussed,
discussed, whose amplitude amplitude is is expressed
expressed in in terms
terms of of

the
the atomic
atomic scattering
scattering factor,
factor, is is coherent,
coherent, or or unmodified,
unmodified, scattering,
scattering, which
which
is
is the
the only
only kind
kind capable
capable of
of being
being diffracted.
diffracted. On the other hand,
hand, incoherent,
incoherent,
or
or Compton modified,
Compton modified, scattering
scattering is
is occurring
occurring at
at the
the same time.
time. Since
Since thethe

latter is
latter is due
due to to collisions
collisions of of quanta
quanta with loosely loosely bound electrons,
electrons, its its in-
in-

tensity relative to
tensity relative to that
that of of the
the unmodified
unmodified radiationradiation increases as as the
the pro-
pro-
portion
portion of
of loosely
loosely bound
bound electrons
electrons increases.
increases. The
The intensity
intensity of
of Compton

modified
modified radiation
radiation thus thus increases
increases as as the
the atomic number Z
atomic number Z decreases.
decreases. It It

isis for this reason

for this reason that
that it
it is
is difficult
difficult to
to obtain
obtain good
good diffraction
diffraction photographs
photographs
ofof organic
organic materials,
materials, which which contain
contain lightlight elements
elements such such asas carbon,
carbon, oxygen,
oxygen,
and hydrogen, since the
and hydrogen, since the strong Compton strong Compton modified
modified scattering
scattering from
from these
these
substances darkens the
substances darkens the background background of
of the
the photograph
photograph and
and makes
makes it
it diffi-
diffi-

cult to
cult to see
see the
the diffraction
diffraction lineslines formed
formed by by the unmodified radiation. It
the unmodified radiation. It is
is

also
also found
found that that the the intensity
intensity of of the
the modified
modified radiation increases as the
radiation increases as the
quantity
quantity (sin 0)/X increases.
(sin O)/X increases. The The intensities
intensities of of modified
modified scattering
scattering and and of of
unmodified
unmodified scattering
scattering therefore
therefore vary vary in in opposite
opposite ways Z
ways with Z and with
with and with
(sin 8)/X.
(sin0)/X. ,
i
To summarize'JWE,~n
To summarize,|when aa monochromatic monochromatic beam beam of x-rays strike~
of x-rays strikes,anan atom,
atom,
two
two scattering processes,
scattering processes occ'l!r,
occur 4 Tightly
Tightly bound
bound electron.tarEl..etl!!~o
electrons are jet, into oscIl-
pscTP"
lation
lation andand radiate
radiate x-rays
x-rays ofof the
the sa.rii~
saiffi wavelength
wavelength as
as that
that of
of the
the i~
incident
 SCATTERING BY AA UNIT
SCATTERING BY UNIT CELL
CELL hl
incident beam
incident beam

absorbing substance
absorbing substance

."'~t ,om,. -----;7 ~

fluorescent x-rays

/ transmitted beam electrons

scattered x-rayM '-1_ _ -JI____""I
rl___.1. .-----,1 Compton recoil
Compton rel'Oii photoelectrons
photoelectrons

unmodified Compton modified

modIfied electrons
eic('trons
unmodified Compton
(coherent)
(coherent) (in('oherpnt)
(incoherent)

FIG. 4-7.
FIG. 4-7. Effects
Effects produced
produced by
by the
the passage
passage ofof x-rays
x-rays through
through matter.
matter. (After
(After
N. F.
N. F. M.
M. Henry,
Henry, H.
H. Lipson,
Lipson, and
and W. A.
A. Wooster,
Wooster, The Interpretation
Interpretation of
of X-Ray
X-Ray Dif-
Dif-
fraction Photographs,
fraction Photographs, Macmillan,
Macmillan, London,
London, 1951.)
1951.)

beam. More loosely

beam. loosely bound electrons
electrons scatter
scatter part
part ofof the
the incident
incident beam
and slightly
and in-crease its
slightly increase wave1eii~h in
its wavelength in the
the process,
proces.s., the exact thE}
exact amount
amount" ofof
iilc~ase depending
increase de~nd}I!gj~n ~he scattering
on the angle. The !5?!fD~
scattering angle. former isj~ called
called coherent
coherent
or
or unmodified scattering and the
unmodified scattering the latter
latter incoherent
incoherent oror modified; both kinds
modified both kinds
all
;

occur simultaneously
occur simultaneously andand in directions. If
in all directions. If the
the atom is is a part
part of a large
large
group
group of
of atoms
atoms arra~d
arranged 'in
in space Tn
spaceTh ii.
a regular
Tegular periodic
periodic fashion as in
in a crys-
crys-
tal, then another phenomenon occurs. The coherently
tal, then another phenomenon occurs. coherently scattered radiation
from
from all
all the
the atoms
atoms undergoes
undergoes reinforcement
reinforcement in in certain directions and.
certain directions and can-
cellation
cellation inin other directions, t~us
other directions, thus producing
producing ditrracted
diffracted beams.
beams. 1?jffratigR
Djttjw^p^
is, essentially, relworced coherent
is, essentially, reinforced scattering. ,I ~
coherent scattering. ^1
We are
are now in in aa position
position to summarize, from th~
to summarize, the preceding
preceding sections and
from
from Chap.
Chap. 1,1, the
the chief
chief effects
effects associated
associated with the passage
passage of x-rays
x-rays through
through
matter.
matter. ThisThis isis done
done schematically
schematically in in Fig. 4-7. The incident
Fig. 4-7. incident x-rays
x-rays are
assumed to
assumed to be
be ofof high
high enough
enough energy,
energy, i.e.,
i.e., of
of short
short enough
enough wavelength,
wavelength,
to
to cause
cause the
the emission
emission ofof photoelectrons
photoelectrons andand characteristic
characteristic fluorescent
fluorescent radia-
radia-

tion. The
tion. The Compton
Compton recoil
recoil electrons
electrons shown
shown in
in the
the diagram
diagram are
are the
the loosely
loosely

Z
bound
bound electrons
giving
electrons knocked
rise
rise to
to
knocked out
Compton
Compton
of the
out of
modified
modified
the atom
atom by
radiation.
radiation.
by x-ray
x-ray quanta,
quanta, the
the interaction
interaction

W <Cattering
Scattering by by aa unit
unit celL
cell. To
To arrive
arrive at
at an
an expression
expression for for the
the in-
in-

tensity
tensity of
of aa diffracted
diffracted beam,
beam, we
we must
must now
now restrict
restrict ourselves
ourselves to
to aa considera-
considera-
tion
tion of
the
r~d
of the
the atoms
ranged in
the coherent
atoms making
coherent scattering,
making up
in aa periodic
up
scattering, not
the
the crystal.
crystal.
fashion in
not from

in space
from an
'The
The
an isolated
mere
mere
isolated atom,
fact
fact that
that
atom, but
the
the
but from
atoms
atoms
from all
are
all

are Ar- ,r-

space means
mftans that
that the
the scattered
scattered radiation
radiation isis
periodic fashion
~
nowjeverely
limited to
limited~to certain
certain definite
definite directions
directions and
and isis now
now referred
referred to
to
as
as aa set
set of
of diffracted
diffracted beams.
beams. 'The
'The directions
directions ofof these
these beams
beams are are fixed
fixed by
by
112
112 DIFFRACTION
DIFFRACTION II: THE INTENSITIES
II THE OF DIFFRJ.'
INTENSITIES OF
: DIFFRA' p. 4
P. 4

2'2'
-(MO)
l'
o
l c

l
I

3
I~ -I
I-x-I
FIG. 4-8. The effect
effect of
of atom pOHition
position on
on the
the phase
phase difference
difference between
between diffracted
diffracted
rays.
rays.

the Bragg
Bragg law,-,Iwhich
law, Avhich is, is, in
in a sense,
sense, a a negative
negative lu,,".
law. If If the
the Bragg
Bragg law law isis not
not
satisfied, no. diffracted
satisfied, ,!lO. diffracted beam ean can oec'ur;
occur; however,
however, the the Bragg
Bragg law law may may be be
satisfied
satisfied for a certain
certain setset of of atomic planes
planes and yet yet no diffraction
diffraction may may occur,
occur,
as in
in the example
example givengiven at at the beginning of
the beginning of this chapter, because
this chapter, because of of aa
particular arrangement of
particular arrangement of atoms within the unit
within the cell [Fig.
unit cell 4-2(b)].
[Fig. 4-2(b)].
. Vssuming
\.ssumin that that the
the Bragg
Bra law law isis satisfied,
satisfied, we wish wish to to find the intensity
find the intensity
at the frftftm
oMhhe beam diffracted
diffracted by by "a fgrgjgjjis
crystal as fijnrtinn nf fl.tnrjijvisit.inn
.

fl osition. Since Since

the crystal
the crystal is
is merely
merely aa repetition
repetition of of the
the fundamental
fundamental unit unit cell, it is
rell, it is enough
enough
to consider
to consider the the way
way in in which the the arrangement
arrangement of of atoms
atoms within
within aa single
single
unit cell
unit cell affects
affects the
the diffracted
diffracted intensity.\
intensity \
Qualitatively, the
Qualitatively, the effect
effect is is similar
similar to*the
to'the scattering
scattering from from ar^ au atom,
atom, dis- dis-
cussed in
cussed in the
the previous sectio~. [There
previous section. /There we found found thatthat phase
phase differences
differences
occur in
occur in the
the waves scattered
scattered by by thejndividual
the individual plentrnns
electrons, for for any
any direction
direction
the ~treme forward f~;~\'ard direction.
j

of scattering
of scattering except
except the.extreme direction. Similarly,
Similarly, the the waves
waves
scattered by
scattered by the
the individual
individual atoms atoms of of aa unit
unit cell
cell are
are not
not necessarily
necessarily in in phase
phase
except in
except in the
the forward direction,!
direction" and and we must now now determine
determine how the the
phase difference
phase difference depends
depends on on the
the arrangement
atrangement of of the
the atoms.
atoms.
(This problem
|This problem is is most
most simply
simply approached
approached by by finding
finding thethe phase
phase difference
difference
between waves
between waves scattered
scattered by hy anan atom
atom at at the
the origin
origin andand another
another atom atom whosewhose
position isis variable
position variable in the xx direction
in the direction only.
only.) For convenience.
\ For convenieJ!.ce. consklex*an
cons4lex..an
~thogon~:~~mit cell,
orjJvjgoriaJunit cell, aa section
section of of which
which isis shown
shown in in Fig.
Fig. 4-8. ~m
4-8. Taice.aiDm
A
^as as the
the Ol'lgm
origm^and and let
let diffraction
diffraction occur
occur from
from the
the (hOO)~lanes
(AOO) planes shown shown as as
~yy hnftsJiTthe
heavy hoes iU1i1e-drawing:1
drawings This
This means
means that
that the
the Bragg
Bragg iaw
law is
is satisfied
satisfied for
for
this
this
^
reflection
reflection and
and that
that '1', Ithe path
5522'iV$he path difference
difference between ray
between
... ray 2' 2'_*.and ray
and
f.
t~y I IM.I ........

~Y
. ..
_
' .

|/
t I .
^^ ( )

-
'1'
5522'i' MeN == 2rf/,
== MCN 2dhOO sin (J == X.
00 sin X.
 4-4)
4-4] SCATTERING BY AA UNIT
SCATTERING BY UNIT CELL
CELL 113
113

From the
From the definition
definition of
of Miller
Miller indices,
indices,
aa
dhOO == AC
AC == --.
nh

How isis this

How this reflection
reflection affected
affected by
by x-rays
x-rays scattered
scattered in in the
the same
same direction
direction
by
by atom
atom B,
B, located
located at
at aa distance
distance xx from
from A?
Al Note
Note that
that only
only this
this direction
direction
need be
need be considered
considered sincesince only
only in
in this
this direction
direction isis the
the Bragg
Bragg law
law satisfied
satisfied
for the AGO
for the hOO reflection.
reflection. Clearly,
Clearly, the
the path
path difference
difference between
between ra%._
ray 3'
3' and.
and
~;
ray
----
1', 8
6 3 '1',
ray 1', 3 'i>,
. will
will be
be less
less than
than by simple proportion
X; by simple proportion

AB X
it
it is
is found
found to
to be
be

AC
AC
= - (X).
(X) =
83 '1' = RBS = - (X)
alh
a/ft
(X).
_
...

Phase differences
Phase differences may
may bebe expressed
expressed in
in angular
angular measure
measure as
as well
well as
as in
in
wavelength: two
wavelength: two rays,
rays, differing
differing in path length
in path length by
by one
one whole
whole wavelength,
wavelength,
are said
are said to
to differ
differ in
in phase
phase by
by 360,
360, or
or 2?r
271" radians.
radians. If If the
the path
path difference
difference is
is

8,
6, then
then the
the I~hase
'phase difference
difference cP
jjn_in radia!l~j~ .Kiy_~.!l_ by
8
IjJ =
= -
- (271").
(27T). .

'" X .
The
The use
use of
of angular
angular measure is convenient
measure is because it
convenient because it makes the expression
expression
of phase differences independent of wavelength,
of phase differences independent of wavelength, whereas the use of a path
path
difference to describe a phase difference
difference to describe a phase difference is
is meaningless
meaningless unless the wave-
length is
length is specified.
specified.
The
The phase
phase difference,
difference, then,
then, between thethe wave scattered by B and
by atom Band
that
that scattered
scattered byby atom A atat the
the origin
origin is
is given
given by
by

83'1'
5vi' 271"hx
2irhx \^
cP3'1' =- (271") = --.
~ a
If
If the
the position
position of
of atom B i~is specified
atom B specified by
by its
its fractional
fractional coordinate u == -
coordinate u = ,,

a
then
then the
the phase
phase difference
difference becomes
becomes

cPa' I' = 271"hu.

This
This reasoning
reasoning may
may be
be extended
extended to
to three
three dimensions,
dimensions, as
as in
in Fig.
Fig. 4-9,
4-9, in
in

xyz
atom B
which atom
which B has
has actual coordinates xx yy zz or
actual co()rdinates or fractional coordinates - - ~-
fractional coordinates:!!.
abc
a o c
equa~
equal toto u
u vv w,
w, respectively.
respectively. WeWe then
then arrive
arrive atat the
the following
following important
important
relation
relation for
for the
the phase
phase difference
difference between
between the
the wave
wave scattered
scattered by
by atom B
atom B
and
and that
that scattered
scattered byby atom
atom A
A at
at the
the origin,
origin, for
for the
the hkl
hkl reflection:
reflection:

cP ". 2r(hu
--:---..
kv +
+ hnJ.
faL^bJm). (4-4)
(4-4)

This
This relation
relation is
is general
general and
and applicable
applicable to
to aa unit
unit cell
cell of
of any
any shape.
shape.
114
114 DIFFRACTION II:
II THE INTE,NSITIES
:
INTENSITIES OF DIFFRACTED BEAMS [CRA.P.
[CHAP. 44

FIG.
FIG. 4-9.
4-9. The three-dimensional
three-dimensional analogue
analogue of
of Fig.
Fig. 4-8.
4-8.

,t!Iese
These two waves may differ, differ, not only
only in
in phase, but also in
phase, jbut^also in amp!Jt.!llje
amplitude if if

atom B and the the atomat--the-

atonTstr-trre otiginare-or different
ongih"^l^^d^fferent kinds.
kinds. In
In that
that case,
case,
v.re
v .ie amplitudes
amplitudes ofof these
these waveS-are-give;;-
waves are given, relathreto
relative to the
the amplitude
amplitude of of the
the
scattered by
wave scattered by a single
single electron,
electron, by by the
the appropriate
appropriate values
values of I, the
of /, the
atomic scattering
scattering factor.-
factor.
We now seesee that
that the problem of
the problem of scattering
scattering from a a unit
unit cell
cell resolves
resolves itself
itself
into
into one of of adding
adding waves of of different phase and amplitude
different phase amplitude in
in order
order to
to find
find
the
the resultant
resultant wave. Waves scatteredscattered by by all
all the
the atoms of of the unit cell,
the unit cell,

including the one at

including at the
the origin,
origin, must be be adde~.
added. The most convenient
convenient way way
of carrying out this
of carrying this summation is by expressing
is by each wave as
expressing each as A
& complex
complex
exponential
exponential function.
function.

+E

II

-E

\
,,
..... .-
FIG. 4-10.
FIG. 4-10. addition
The addition of sine waves
of sine wa,'es of
of different
diffe-tent phase
phase and
and amplitude.
amplitude.
 4-4) SCATTERING BY
SCATTERING UNIT CELL
BY AA UNIT CELL
4-4] 117
117

2i

A3

~-2
-2t

FIG. 4-11.
FIG. 4-11. Vector
Vector addition
addition of
of waves.
waves. FIG. 4-12.
FIG. 4-12. AA wave
wave vector
vector in
in the
the
romplex plane.
complex plane.

The two
The two waves
waves shown
shown as
as full
full lines
lines in
in Fig.
Fig. 4-10
4-10 represent
represent the
the variations
variations
in electric field intensity
in electric field intensity E with
with time
time t
t of
of two
two rays
rays on
on any
any given
given wave
wave front
front
in a diffracted x-ray beam.
in a diffracted x-ray beam. Their
Their equations
equations may be
be written
written

EI
EI = A\
= Al sin
sin (2irvt c/>1),
(27rllt - ^i), (4-5)
(4-5)

E = AA22 sin
E22 = sin (2","t - c/>2).
(2wt - $2). (4-6)
(
4 ~^)

These waves
These waves are of the
are of the same frequency
frequency IIv and therefore
therefore of
of the
the same wave-
same wave-
length
length A, but differ in amplitude A and in
A, but differ in amplitude
in phase
phase 41. The dotted
dotted curve
curve </>.

shows
shows their
their sum
sum E 33 , which
which is
is also
,
also a
a sine
sine wave,
wave, but of different
different amplitude
and
and phase.
phase.
Waves
Waves differing
differing in in amplitude
amplitude and phase phase may also also be added by represent-represent-
ing
ing
them
them as
as vectors.
vectors. In
In Fig.
Fig. 4-11,
4-11, each
each component
component wave is
is represented
represented
by which
by aa vector
vector whose whose length
length is is equal
equal to to the
the amplitude
amplitude of of the wave and and which
is
is inclined
inclined to to the
the x-axis
:r-axis atat anan angle
angle equal
equal to to the phase
phase angle.
angle. The The ampli-
ampli-
tude
tude andand phasephase of of the
the resultant
resultant wave wave is is then found
found simply
simply by adding adding the the
vectors
vectors by by the
the parallelogram
parallelogram law.
law.
This
This geometrical
geometrical construction
construction may may be be avoided
avoided by by use
use of of the
the following
following
analytical treatment,
analytical treatment,
in
in which
which complex
complex numbers
numbers are
are used
used to
to represent
represent the
the
vectors.
vectors. A A complex number
number is
is the
the sum
sum of
of aa real
real andand an imaginary
anjmaginary
num-
num-
complex
ber, such ~s (a + bi), where aa and
ber, such as (a + 6z), where
and b6 areare real
real and
andjt i = = v'=t
V-il isis imaginary.
imaginary.
Such
Such numbers
numbers may may be
be plotted
plotted in
in the
the "complex
"complex plane,"
plane," in
in which
which real num-
real num-

bers
bers are
are plotted
plotted as
as abscissae
abscissae and
and imaginary
imaginary numbers
numbers as
as ordinates.
ordinates. Any
Any
point
point
inin this
this plane
plane or
or the
the vector
vector drawn
drawn from
from the
the origin
origin to
to this
this point
point then
then
represents
represents aa particular
particular complex
complex number number (a (a ++ bi).
bi).
To find
To find an
an analytical expression
analytical expression for
for aa vector
vector representing
representing aa wave, wave, we we
draw
draw thethe wave
wave vector
vector in
in the
the complex
complex plane
plane as
as in
in Fig.
Fig. 4-12.
4-12. Here
Here again
again
the
theamplitude
amplitudeand andphase
phaseof of the
the wave
waveisisgiven
given by by A,
A, thethelength
length of ofthe
thevector,
vector,
and C/>, the
and 0, the angle angle between
between the
the vector
vector and
and the
the axis
axis of
of real
real numbers.
numbers. The
The
analytical expression for
for the
the wave
wave is
is now
now the
the complex
complex number
number (A
(A cosc/> +
cos <t> +
analytical expression
iA sin
iA sin c/,
</>),
since
since these
these two
two terms
terms are
are the
the horizontal
horizontal and
and vertical
vertical components
components
 DIFFRACTION II:
II THE INTENSITIES OF DIFFRACTED BEAMS
:
[CHAP. 4
[CHAP.

md ON of
tnd of the
the vector.
vector. Note that that multiplication
multiplication of of a
a vector
vector byby ii
Jtates
jtates itit counterclockwise
counterclockwise by by 90 90; 0 ; thus multiplication by ii converts
multiplication by converts thethe
horizontal
horizontal vector
vector 2 into
into the
the vertical
vertical vector
vector 2i.
2i. Multiplication
Multiplication twice twice byby i,
i,

by ii2 =
2 =
that
that is,
is, by - 1,
1, rotates
rotates a vectorvector through
through 180 0 or or reverses
reverses its
its sense;
sense;
thus
thus multiplication
multiplication twice
twice by
by ii converts
converts the the horizontal
horizontal vectorvector 22 into
into the
the
horizontal
horizontal vector
vector - 2 pointing
pointing in
in the
the opposite
opposite direction.
direction.
If
If we write
write down the
the power-series
power-series expansions
expansions of of ee iz , cos
ix
x, and sin
cos x sin x,
x, we , y

find
find that
that
cos x +
ee iix% == cos + ii sin
sin x (4-7)
(4-7)
or
or
Ae'" ==
Ae* = A coscos q, + + Ai sinsin q,.
4.
<t>
(4-8)
(4-8)

Thus thethe wave vector

vector may
may be expressed
expressed analytically
analytically byby either
either side
side of
of
Eq. (4-8).
Eq. (4-8). The expression
expression on
on the
the left
left is
is called
called a
a complex exponential
complex exponential
function.
function.
Since
Since the intensity of
the intensity of aa wave isis proportional
proportional to to the
the square
square ofof its
its ampli-
ampli-
2
tude,
tude, we now needneed an expression
expression forfor A 2, the
the square
square ofof the
the absolute
absolute value
,
value
of
of the
the wave vector.
vector. When a a wave is is expressed
expressed in in complex
complex form,
form, this
this quan-
quan-
tity
tity is
is obtained
obtained by
by multiplying
multiplying thethe complex
complex expression
expression for
for the
the wave by by
its complex
its complex conjugate,
conjugate, which is is obtained
obtained simply
simply by by replacing
replacing ii byby -i. i.

Thus,
Thus, the
the complex
complex conjugate
conjugate of Ae'"* is
of Ae Ae-'''.
is Ae~ *. We have
l
have
l

\Ae
l
*\
2
= Ae +Ae-* = A 2
l
,
(4-9)
(4-9)

which is
is the
the quantity
quantity desired.
desired. Or,
Or, using
using the
the other
other form
form given
given by
by Eq.
Eq. (4-8),
(4-8),
we have
(cos q, + = A 2 (cos2
<) = A2(COS q, + sin 2 q,) = AA2.2
2 2
A (cos + ii sin 4)A(cos q, - ii sin
sin q,)A(cos sin q,)
< + sin <t> </>)
== .

We retwn
return now to to the
the problem
problem of of adding
adding the
the scattered
scattered waves
waves from
from each
each
of
of the
the atoms in in the
the unit
unit cell.
cell. The amplitude
amplitude ofof each
each wave isis given by the
given by the
appropriate
appropriate value of f/ for
value of for the
the scattering
scattering atom considered
considered and thethe value
value
of
of (sin 0)/X involved
(sin (J)/'lI. involved inin the
the reflection.
reflection. The phase
phase of
of each
each wave isis given
given by
by
Eq. (4-4) in
Eq. (4-4) in terms
terms of the hkl
of the hkl reflection
reflection considered
considered and the uvw
and the uvw coordinates
coordinates
of
of the
the atom.
atom. Using Using our previous relations,
our previous relations, we can
can then
then express
express any
any scat-
scat-
tered
tered wave in in the
the complex exponential
complex exponential form
form

(4-10)
(4-10)

The resultant
resultant wave scattered
scattered by
by ~~U.h~"atoms
alljbhe atoms of
of the
the unit
unit cell
cell is
is called
called the
the
structure factor and is
structure factor is designated"by
designated by the
the sym.fioT
symBol F.F. If
It" is ootained by simply
obtained by simply is"

adding
adding together
together all
all the
the waves scattered by the
scattered by the individual atoms> If
individual atoms;' If a
a
unit
unit cell
cell contains
contains atoms 1,
1, 2, 3, ... , N,
2, 3, N, with
with fractional
fractional coordinates
coordinates
. . .
,

Ul
Ui Vl
vi Wi, u 2 V2
!!, U2 v 2 W2,
tt? 2
, MS Va
Ua *>3 Wa, ... and atomic scattering
MS, scattering factors
factors ft,
/i, 12, fa,
/2 /a, ,
,
. . .
,

then
then the
the structure
structure factor
factor for
for the hkl reflection
the hkl reflection is
is given
given by
by
F == fte 21ri (/u.u+kvl+lwl) +
^ !2e2l'i(kuz+kvz+lwz)
y e + fa e2l'i(kua+kv.+lw.) + .. '.
2*i(hu2+kvi+lwti i /
g 2iri(Au3-H;i>s-f Iwi)
i
. . .
 4-4]
4-4]

This equation

the

.4

The
equation may

tude of
)y
ay a

jugate*

reflection

differing
that
that the
as
here
here of
the

Bragg
phase of
of the
a single

IFI
|/P|

The intensity
=-
=

intensity of
direction
-
may be written

the summation extending

F is,
and phase
is, in

of the
extending over
in general,
general, a

Equation (4-11)
crystallography,
crystallography, since
reflection from a
We have found
differing in
in
the phase
as A and B in
of these
the crystal
crystal
exactly
exactly equal
Bragg law,
in
in phase
phase,

in Fig.

as
as

equal to
law, the
phase and so
these
a complex

amplitude of

direction predicted
!lquare of
multiplying
the
multiplying the
jugate) Equation
of the
of the

the beam
predicted by by

the expression

since it

found the
phase,

Fig. 4-8,
these rays
SCATTERING BY A UNIT CELL

written more compactly

compactly as

over all

it permits

a knowledge
knowledge of
the resultant
scattered
scattered
phase difference
difference between
4-8,
rays becoming
there
there
to the
the rays
is
is
N
N

of the

by
by

constant
constant
as

\~* f e2 ... (hu,,+A:v.. +lw,,>

'"
F hkl -- ."
Z^Jn
11

resultant wave. l..!!s

the resultant
the resultant
resultant wave in
single electron.
t .,.:atio
ratio of
i of amE!itud~~
amplitudes

amplitude
in terms
Like the
elect ron.~Like
**"
--
:\
fn

all the

complex number,
the atoms of
number, and it
{Its absolute
termsofr the
the atomic

the wave scattered

----------------
amplitude
amplitude of

the
amplitude.Q!
square of the amplitude

(4-11) is
of the
or

scattered by

beanL diffracted
the Bragg
Bragg law
oQiiejresul^^^
expression given
given for
by all

is
is

for F in
is therefore
therefore a

individual
between rays

becoming increasingly
was
the Bragg
rays scattered
so are
sets of
these two sets
when
Bragg angle
scattered by
are the
of rays
the rays
rays there
we
rays
for
for

angle 8B.
by all
OB-
all the

rays scattered
there is
of the

all the

the wave scattered

the unit

tne amplItude
unit cell.
it expresses

amplitude of
atomic scattering
scattering factor

the atoms of

in Eq.
by one
scattered by

diffracted .l;>~
by all the

Eq. (4-1
a very
very important
permits aa calculation
calculation of
the atomic positions.

individual
scattered
scattered
every
every
increasingly out
unit
unit
out of
considered
considered
In
In the
the atoms
scattered by
is a
a definite
by all
cell.

expresses both the

absolute value IFI|F| gives
of the

of a

the atoms of
proe.~;tfoilal

4-11)
a unit

one electron
electron
the amplitude
gives the
the wave
j, 1]1'
factoFJT 1 IS
|^'|

unit cell
cell

of the

important relation
of the

positions.
scattered wave by
resultant scattered
atoms
by adding
in
by
by
cell.
cell.

of phase

A
all the
the
any
any
There
phase as

in
in the
the atoms
phase difference
definite phase
amplitude
the ampli-

the unit
simply
proportional simply
the resultaIl!J~~~~nd IFI2 |F|
1) by
2

by its
is
ampli-
scattered
wa/ve^scaTEered
aennoo as
is~definect

unit cell
to
to

relation in
the intensity
intensity of

adding together
in the unit
two
is
as we go
diffraction
diffraction
the direction
is

at
at
predicted by
direction predicted
the crystal
crystal are
atoms B,
as

cell in

IFj2",
|f|
^obtained
its complex
2
,

is obtained ITy
complex con-
in x-ray
of any

together waves,
unit cell.
cell.

atoms,
no
117
117

~4-11)
14-11)

in a
the
the
by
con-
x-ray
any hkl

question
go deeper
deeper in
angles
angles

B, but between
difference which depends
by the
are exactly

depends on
hkl

waves,
Note
atoms, suchsuch
question
in
not
the
exactly

the
the relative
relative positions
positions of atoms A and B in
of atoms in the
the unit
unit cell
cell and which is is given
given
by
by Eq.
Eq. (4-4).
(4-4).

Although
Although itit is
is more
more unwieldy,
unwieldy, the
the following
following trigonometric
trigonometric equation
equation may
may be
be
used
used instead
instead of
of Eq.
Eq. (4-11):
(4-11):
N
N
F=
F = L ! ..[COB 2r(hu"
Z/n[cOS 2ir(7Wn + kVn +
+ lev,. lw +
+ lw,.)
n) I 2v(hu +
+ i sin 2r(hu"
SU1 kVn +
+ lev,.
n + lw,.)].
lWn)].
11

One
One such
such term
term must
must be
be written
written down for
for each
each atom inin the
the unit
unit cell.
cell. In
In general,
general,
the
the summation
summation will
will be
be a
a complex
complex number
number of
of the
the form
form

F == a +
+ ib,
ib,
118
118 DIFFRACTION II:
III THE INTENSITIES OF DIFFRACTED BEAMS [CHAP. 4
[CHAP.

where
where
N
......
<* a =
a = "EJ
1
N
.. cos
/n 2ir(hu .. +
cos 21r(hu + lev n +
kv .. + lw
Jw ..
n ), n ),

N
JV
= L i"
bb = /n sin 27r(/m n +
sin 21r(hu" ^ ..n
+ lev + lw,,),
lw n ),
11

IFI2 =-
\F\
2
(a
(a + ib)(a - ib)
ib)(a - ib)
= a22 + b
= &2
2

.

Substitution
Substitution for
for a and b gives
gives the
fe the final
final form of
of the
the equation:
equation:

IFI2
\F\* = [ft cos
= 2r(hui +
cos 271'(hul fan +
+ kVl + lWl) +
+ i2
/ cos 2r(Atii +
cos 271'(hUl ^2) +
fa* + lW2)
+ kV2 + ... ]2 2
[/i Ztin) 2 ]

+
+ [ft sin
[/i 2ir(hui +
sin 271'(hul + kVl +
+ lWl) + sin 271'(hu2 +
+ h sinkvi kv +
+ kV2 Iw +
+ lW2)
Iwi) + ... ]2.
/, 2ir(fctt2 2 2) -]
2
-

Equation
Equation (4-11)
(4-11) is easier to
is much easier to manipulate, compared to
manipulate, compared to this
this trigonometric
trigonometric
form,
form, particularly
particularly if
if the
the structure
structure is
is at
at all
all complicated,
complicated, since
since the
the exponential
exponential
form
form is
is more compact.
compact.

4-5 Some useful relations.

relations. In calculating
calculating structure
structure factors by com-
factors by
plex exponential functions,
plex exponential functions, many particular
particular relations
relations occur often
often enough
enough
to
to be worthwhile stating
stating here.
here. They may
They may be verified
verified by
by means of
of Eq.
Eq.
(4-7).
(4-7).

(a)
(a) e
vi
e",i = eari
e*
Ti
=
== e""i
e
5iri
= -1,
-1,
(b) ec*'
27ri = e**<
4ri = " = + 1,
= e667ri
(fc) +1,
nTl = n
(c)
(c) general, e
In general, e nri = (-1)",
( l) where n is
is any
any integer,
integer, ,

(d)
(d)
nvi
een7r =
= e- nTl
where n
e~~ nr ., where
,
n is
is any
any integer,
integer,

(e)
(e)
lx
ee lZ + = 22 cos
e~ z =
+ e-' cos x.
lx
z.

4-6
4r-6 Structure-factor
Structure-factor calculations.
calculations. Facility
Facility in
in the
the use
use of Eq. (4-11)
of Eq. (4-11) can
be gained
gained only
only by
by working
working out
out some actual
actual examples,
examples, and we shall
shall con-
con-
sider
sider a few such problems
problems here
here and again
again in
in Chap.
Chap. 10.
10.
(a)
(a) The simplest
simplest case
case is
is that
that of
of a
a unit
unit cell
cell containing
containing only
only one atom atat
the origin,
origin, i.e.,
i.e., having
having fractional
fractional coordinates
coordinates 000. Its Its structure
structure factor
factor is
is

F = je2r
= /e .(O) = /
2Tl(0) j
and
F22 ==/j2.
F 2
.

F2 is
F2 independent of h,
is thus independent of
A, k, and l and is
is the
the same for
fc, for all
all reflections.
reflections.
I

(b)
(6) Consider now the
the base-centel'f'd
base-centered cell
cell discussed
discussed at
at the
the beginning
beginning of
of
this
this chapter
chapter and shown inin Fig.
Fig. 4-1(0.).
4-1 (a). It
It has
has two atoms of
of the
the same kind
kind
per
per unit cell
cell located
located at
at 00 O,and
0,and J J O.0. ii
F = je2r i(O) + je2riC h/2+k/2)
j[1 + ert(Hkl].
=/[I
4-6)
4-6] STRUCTURE-FACTOR CALCULATIONS Ih
1U
This expression
expression may
may be evaluated without
without multiplication
multiplication byby the
the complex
complex
conjugate, (h +
since (h
conjugate, since + k)
fc) is
is always
always integral,
integral, and the
the expression for F ~
expression for ig

thus real
real and not complex.
complex. If If hand
h and k are both even or
are both fc or both
both odd, Le.,
odd, :Te.,
"unmixed,"
"unmixed," then
then their
their sum is is always
always even
even and elTl(Hk)
e* l(h+k} has
has the
the value
value 1.
1.

Therefore
Therefore
F == 2j2/ for h and k
for hand k unmixed;
unmixed;
F2 == 4f2.
F2 4/
2
.

On the
the other
other hand,
hand, if
if hand
h and k k are
are one
one even
even and one
one odd,
odd, i.e.,
i.e., "mixed,"
"mixed,"
then
then their
their sum is
is odd and e
e 7rt ^ +/r)
(h+k) has
7rl
the value
has the value -1.
1. Therefore
Therefore

F == 0 for h and k
for hand k mixed;
mixed;
F2 ==
F2 o.
0.

Note that,
that, in
in either
either case,
case, the
the value
value of the 1index
of the index has
I has no effect
effect on the
the struc-
struc-
ture
ture factor.
factor. For example,
example, the
the reflections
reflections 111, 112, 113,
111, 112, 113, and 021,
021, 022, 023
022, 023
all
all have the the same value
value ofof F, namely 2f. Similarly,
F, namely 2/. Similarly, the
the reflections
reflections 011,
Oil,
012,013,
012, 013, and 101, 101, 102,
102, 103
103 allall have a a zero
zero structure
structure factor.
factor.

(c) The structure

(c) structure factor
factor ofof the
the bo..Qy:-centered
hody-ppntfifpH eel! ahnwn In
r,el] shown Fig. 4-1(b~
ill. Fig. 4-1 (b^
may
may alsoalso be
be calculated.
calculated. This cell cell has
has two atoms of of the
the same kind located
located
at 000 and lll. f | |.
(O) + je
F == je
F fe
27r
27n(0)
+ Se 22iri(h/2+k/2+l/2)
"i(h/2+k/2+Z/2)

= j[l + e"t(HHI)].
F == 2f
2f (h +
when (h +k+ + l) is even;
I) is
even;

F =
F22 = 2
4f2.
4/ .

F == 0
F when (h
(h + k + 1) is odd;
I) is
odd;
F2 = o.
We had previously concluded
had previously concluded fromfrom geometrical
geometrical considerations
considerations thatthat the
the
base-centered cell
base-centered cell would produce
produce a
a 001
001 reflection
reflection but
but that
that the
the body-centered
body-centered
cell
cell would
would not.
not. This
This result
result is
is in
in agreement
agreement withwith the
the structure-factor
structure-factor equa-
equa-
tions
tions for
for these two cells.
these two cells. A detailed
detailed examination
examination of of the
the geometry
geometry ofof all
all

possible
possible reflections,
reflections, however,
however, would be be aa very
very laborious process compared
laborious process compared
to
to the
the straightforward
straightforward calculation
calculation of of the
the structure
structure factor,
factor, a calculation
calculation
2
that
that yields
yields a a set
set of
of rules
rules governing
governing thethe value
value of
of F fOJ" all
F2 for all possible
possible values
values of
of
cWIie
otene indices.
indices.

(d) A face-centered
(d) face-centered cubic
cubic cell,
cell, such
such as as that
that shown in in Fig.
Fig. 2-14,
2-14, may
no~
now be be considered.
considered. Assume it it to
to contain
contain four
four atoms of of the
the same kind,
kind,
located
located atat 000, l ! 0,
0, | f 0, \ ! 0 i,and
|, and 0 l i.
\ \.
F= fe 2ri (O) + fe2'n (h{2+k/2) + fe2riCh{2+1/2) + ie2ri (k/Hl/2)
= i[l + e'l'i(Hk) + e'l'iCHl) + e'l"(1:+1)].
\20
t20 DIFFRACTION II:
II THE INTENSITIES OF DIFFRACTED BEAMS
: [CHAP. 4
[CHAP.

If
If h,
A, k, and lI are
fc, are unmixed,
unmixed, then all (h +
three sums (h
all three + k), (h +
ft), (h + l), (fc +
Z), and (k + l)
are
are even integers,
integers, and each term inin the
the above equation
equation has the value 1. 1.

= 4f
F= 4f for
for unmixed indices;
indices;
'V

^ ~)
V;
F == 16f2.
2
pt2 16/
2
'I'" *>. i ,"" I<
^
If
If h, k, and l are
ft, /c,
are mixed,
mixed, then
Z then the
the sum of
of the
the three
three exponentials
exponentials isis -1,1,

whether two ofof the

the indices
indices are
are odd and one even,
even, or
or two even and one odd.odd.
Suppose
Suppose for
for example,
example, that
that hand
h and l are
are even and k is
I is odd,
odd, e.g.,
e.g., 012.
012. Then
F == /(I +
f(1 - 11 -f 11 - 1)
1) =
= 0,
0, and no reflection
reflection occurs.
occurs.

F == 0 for
for mixed indices;
indices;

F2 == 0
pt2

Thus,
Thus, reflections
reflections will
will occur
occur forfor such
such planes
planes as as (111),
(111), (200),
(200), and (220) but
(220) but
not
not for
for the planes (H)Q),
the planes (210), (112),
(100), (210), (112), etc.
etc.
The reader
reader may
may have noticed
noticed in in the
the previous examples that
previous examples that some of of the
the
information
information given given was not
not used in
in the
the calculations.
calculations. In (a),
(a), for
for example,
example,
"he
the cell
cell was said
said to
to contain
contain onlyonly one atom,
atom, but the the shape
shape of of the
the cell
cell was

not specified;
not specified; in
in (b)
(6) and (c), the cells were described
(c), the cells were described as
as orthorhombic
orthorhombic and
in (d) as
in (d) as cubic,
cubic, but this this information
information did did not enter
enter intointo the
the structure-factor
structure-factor
calculations.
calculations. This illustrates
illustrates thethe important
important point that the
point that the structure factor
structure factor
is
is independent
independent of of the shape and size
the shape size of
of the
the unit
unit cell.
cell. example, any
For example, any body-
body-
centered cell
centered cell will
will have missing
missing reflections
reflections for for those planes which have
those planes
(h +
(h + k+ + l)I) equal
fc
equal to to an odd number,
number, whether the the cell
cell is
is cubic,
cubic, tetragonal,
tetragonal,
or
or orthorhombic.
orthorhombic. The rules rules we have have derived
derived in in the
the above
above examples
examples are are
therefore
therefore of of wider
wider applicability
applicability than
than would at
at first
first appear
appear and demonstrate
demonstrate
the
the close
close connection between the
connection between the Bravais lattice of
Bravais lattice of aa substance
substance and its its

diffraction
diffraction pattern.
pattern. They They are
are summarized in
in Table 4-1.
4-1. These rules
rules are
are
subject
subject to to some qualification,
qualification, since since some cells cells maymay contain
contain more atoms
than the
the ones
ones given
given in
in examples (a) through
examples (a) through (d), (d), and these
these atoms may may be be
in such positions that
in such positions that reflections
reflections normally
normally present
present are are now missing.
missing. For
example,
example, diamond has has a a face-centered
face-centered cubic cubic lattice,
lattice, butbut itit contains
contains eight
eight
TABLE 4-1
4-1

Bravais lattice Reflections present Reflections absent

Simple all none

Base-c:entered h and k unmixed hand k mixed
Body-centered (h + k + l) even (h + k + /) odd
Face-centered h, k, and 1 unmixed h, k, and 1 mixed

* These
These relations apply to
relations apply to a
a cell
cell centelocd the C face.
centered on the face. If
If reflections
reflections are
are present
present
h and l are
only when hand
only are unmixed,
unmixed, 01'
I or when k k and l are
are unmixed,
unmixed, then the cell
I cell is
is cen-
cen-
tered
tered on the B or
on the or A face,
face, respectively.
respectively.
4-6]
4-6] STRUCTURE-FACTOR CALCULATIONS 121
121

carbon
carbon atoms per per unit
unit cell.
cell. All
All the
the reflections present have unmixed
reflections present
indices,
indices, but reflections
reflections such as as 200,
200, 222,
222, 420,
420, etc.,
etc., are
are missing.
missing. The fact
fact
that
that the
the only
only reflections present have unmixed indices
reflections present proves that the lat-
indices proves lat-

tice
tice is
is face-centered,
face-centered, while
while the extra
extra missing
missing reflections
reflections are
are a clue
clue to
to the
the
actual atom arrangement
actual arrangement in
in this
this crystal.
crystal.
(e)
(e) This point
point may
may bebe further
further illustrated
illustrated by
by the
the structure
structure of NaCI
of NaCl
(Fig. 2-18).
(Fig. 2-18). This
This crystal
crystal has
has aa cubic
cubic lattice
lattice with 4 Na and 4
4 Cl
Cl atoms
per
per unit
unit cell,
cell, located as follows:
located as follows:

Na 000 f |
.!O.!
|
2 2 o!!
Off
CI
Cl HI
1.! 1
2" 2 2" 00 i OfO !OO
fOO
In
In this
this case,
case, the
the proper
proper atomic
atomic scattering
scattering factors
factors for
for each
each atom must be
inserted
inserted in
in the
the structure-factor
structure-factor equation:
equation :

F = fNa e21ri (O)+ fNae21ri (h/2+k/2) + fNa e21rt (h/2+1/2) + fNae21ri(k/2+1/2)

+ fCle 2",(h/2H/2+1/2) + fCle 27ri (I/2) + fCle 21ri (k/2) + fCle 21f i(h/2)
F
F fNa[! +
= /Na[l + e",(hH) + e",(h+l) + e 1r (k+l))
e

+ fCI[e .. i(hH+I) ++ e"il + 7

+ e",k
e'*e* +
+ e ...h).
lk

As
As discussed
discussed inin Se~.
Sec?. 2-7,
2-7, the
the sodium-atom positions
positions are
are related
related by
by the
the
face-centering translations
face-centering translations and so are the chlorine-atom positions.
so are the chlorine-atom positions. When-
ever
ever aa lattice
lattice contains
contains common translations,
translations, the
the corresponding
corresponding terms in in
the
the structure-factor
structure-factor equation
equation can
can always
always be
be factored
factored out,
out, leading
leading to
to con-
con-
siderable
siderable simplification.
simplification. In In this
this case
case we proceed
proceed as
as follows:
follows :

F=
F = /Natl
fNa[1 +
+ e'Jl"(h+k) + e 1fi (h+l) + e 1ri (k+l))
+ fCle 1ri (h+k+l)[l- +. e .... (-h-k) + e ... (-h-l) + e1ri (-k-I).
The signs
signs of
of the
the exponents
exponents in
in the
the second bracket may
second bracket may be
be changed,
changed, by
by rela-
rela-

tion (d)
tion (d) of
of Sec.
Sec. 4-5.
4-5. Therefore
Therefore

F = [I + e 1f i(h+k) + e 1ri (h+l) + e"'Ck+I)ffNa + fCleriCHk+l)).

,
Here the
the terms
terms corresponding
corresponding to
to the
the face-centering
face-centering translations
translations appear
appear in
in
the
the first
first factor.
factor. These terms
terms have already
already appeared
appeared in
in example (d), and
example (d),
they
they were found to
were found to have a
a total
total value
value of
of zero
zero for
for mixed indices
indices and 44 for
for
unmixed indices.
indices. This shows at
This shows at once
once that
that N aCI has
NaCl has a
a face-centered
face-centered lattice
lattice
and that
that
= 0 for
F = for mixed indices;
indices;

F2 = O.
122
122 DIFFRACTION II
DIFFRACTION II: THE INTENSITIES OF
THE INTENSITIES
: DIFFRACTED BEAMS
OF DIFFRACTED BEAMS [CHAP. 44
[CHAP.

For unmixed
For unmixed indices,
indices,
F = 4[fNa + leteTi(h+HI)].
FF -= 4(/ N +
4(fNa +/ci)
let) if (h + kk ++ l) is even;
(h + even;if is

fF22 == 16(/
16(/Na + let)2.
Na +/Cl)
2
.

F -= 4(/
'F 4(fNa - let) if (h +
Na - /ci) + k ++ 9l) is odd;
odd; if (ft fc is

FF22 -
= 16(/
16(/Na ~
Na - ICl)2.

In this
In this case,
case, there
there are
are more
more than
than four
four atoms per
per unit
unit cell, but
cell, but the
the lattice
lattice
is still face-centered.
is still introduction of
face-centered. The introduction of additional
additional atoms has has not
not elim-
elim-
inated any
inated any reflections
reflections present
present in
in the
the case
case of
of the
the four-atom
four-atom cell,
cell, but
but it
it has
has
decreased some
decreased some inin intensity.
intensity. For
For example,
example, the 111 reflection
the 111 reflection now involves
involves
the difference,
the difference, rather than the
rather than the sum,
sum, ofof the
the scattering
scattering powers
powers of of the
the two
two
atoms.
atoms.
(f) One other
(/) other example
example ofof structure
structure factor
factor calculation
calculation will
will be given
given here.
here.
close-packed hexagonal
The close-packed hexagonal cell
cell shown in Fig.
in Fig. 2-15
2-15 has two atoms of the
of the
same kind
same kind located
located atat 000 and t i J. i.
F =
F = le2-rri(O)
fe
2iri(0) + le 2-n (h/3+2k/3+1/2)
+ e2nl (h+2k)/3+1I2
- 1[1
= fM _|_ e J ].

For
For convenience, put [(h +
convenience, put 2/c)/3 +
+ 2k)/3 + l/2] == g.
[(h 1/2] g.

/(I +
F == 1(1 + e2 "..,). 2
e ').

Since g may
may have
have fractional
fractional values,
values, such as ^-, i,
as t, $, t,
^, etc.,
etc., this
Since g this expression
expression
is
is still
still complex. Multiplication
complex. Multiplication by
by the
the complex
complex conjugate,
conjugate, however,
however, will
will

give
give the
the square
square of
of the
the absolute
absolute value
value of
of the
the resultant
resultant wave amplitude
amplitude F.
F.

IFI2 ==//2(1 ++ e2".i"')(l

|F|
a 2
(l)(1 +
+ e-2....')
e
2 g c-"
2't
')

== 12(2
2
/ (2 +
+ ee22vi
".i,* +
+ e-
<T22Tl
".\g).
*).

By relation (e)
By relation (e) of
of Sec.
Sec. 4-5,
4-5, this
this becomes

IFI2 = j2(2
|F|
2
/ + 2
+ 22 cos
cos 2rg)
(22*0)

== j2[2
2
/ [2 +
+ 2(2
2(2 cos
-
*g - 1)]
cos2 rg
2
1)]

= j2(4 cos 2 rg)

= 4f cos2 r ( h +3 2k +2
l)
= 0 when (h +
when (h + 2k)
2fc) is
is a
a mUltiple
multiple of
of 3 and l is
3 and is odd.
odd. I
4-71
4-7] APPLICATION TO POWDER METHOD 123
123

It
It is
is by
by these
these missing
missing reflections,
reflections, such as
as 111,
11-1, 113,
11-3, 221,
22-1, 223,
22-3, that
that aa
hexagonal
hexagonal structure
structure is
is recognized
recognized asas being close-packed. Not all
being close-packed. all the
the re-
re-
flections present have the
flections present the same structure
structure factor.
factor. For example,
example, if (h +
if (h + 2k)
2k)
is
is a multiple
multiple of
of 3
3 and 1 is
is
I even,
even, then

\
I

3
--
+ + _I) __
( h + 2k
/h

o
2k l\
h - )
2
2t/
= nn,
'
where n is
is an integer,'
integer;

cos irn =
cos'll'"n = 1, 1 ,

cos 2
cos 2 'll'"n
trn = 1,
= 1 ,

|F|
2 = 4/
2
.

When all
all possible
possible values of h,
values of h, k,
k, and 1 are
are considered,
considered, the results may be
the results 7 be
summarized as
as follows:
follows:

h + 2k IFI2
3n
3" odd 0
371
3w
3n 11
even
odd
4r
4/
3f22
2

3/
3 1
311 even /(2
2
A?1

4-7
4-7 Application
Application to powder method.
to powder method. Any Any calculation
calculation of of the
the intensity
intensity ofof
aa diffracted
diffracted beam must always always begin with the
begin with the structure
structure factor.
factor. The re-
re-
mainder of of the
the calculation,
calculation, however,
however, varies
varies with
with the particular diffraction
the particular diffraction
method involved.
involved. For the
the Laue method,
method, intensity
intensity calculations
calculations are
are soso
difficult that
difficult that they
they are
are rarely
rarely made,
made, since
since each
each diffracted
diffracted beam has has aa differ-
differ-
ent
ent wavelength
wavelength and blackens
blackens the
the film
film byby aa variable
variable amount,
amount, depending
depending
on both
both the
the intensity
intensity and the
the film
film sensitivity
sensitivity for
for that
that particular
particular wave-
length.
length. The factors
factors governing
governing diffracted
diffracted intensity
intensity in
in the
the rotating-crystal
rotating-crystal
and powder
powder methods are are somewhat similar,
similar, in
in that
that monochromatic radia-
radia-
tion
tion is
is used
used in
in each,
each, but
but they
they differ
differ in
in detail.
detail. The remainder
remainder of
of this
this chapter
chapter
will
will be devoted to to the powder method,
the powder method, sincesince it
it is
is of
of most general
general utility
utility
in metallurgical
ill metallurgical work.
work.

- -
~apowde~n: --- ---
There ^re_six_factorsaffecting
are six factors affecting the
lines on a powder pattern:

(1)
- the relative
-- ---
intensity of
relative intensity of the
the diffraction
diffraction
---.----. -
(1) polarization
polarization factor,
factor,
(2)
(2) structure
structure factor,
factor,
(3)
(3) multiplicity
multiplicity factol",
factor,
(4)
(4) Lorentz
Lorentz factor,
factor,
(5)
(5) absorption
absorption factor,
factor,
(6)
(6) temperature
temperature factor.'
factor^
The first
first two ofof these
these have already
already been
been described,
described, and the others will
the others will be
discussed
discussed in in the following sections.
the following sections.
124
124 II: THE
DIFFRACTION II
DIFFRACTION THE INTENSITIES
: DIFFRACTED BEAMS
OF DIFFRACTED
INTENSITIES OF BEAMS [CHAP. 4
[CHAP. 4
4-8 Multiplicity
4-8 Multiplicity factor.
factor. Consider
Consider the the 100100 reflection
reflection from
from aa cubiccubic lat-
lat-
tice. In
tice. In the
the powder
powder specimen,
specimen, somesome of of the
the crystals
crystals will
will be
be so so oriented
oriented thatthat
r~flection can
reflection can occur
occur fromfrom their
their (100)
(100) planes.
planes. OtherOther crystals
crystals of of different
different
orientation may
orientation may be be inin such
such aa position
position thatthat reflection
reflection cancan occur
occur fromfrom their
their
(010) or (001) planes.
(010) or (001) planes. Since
Since all
all these
these planes
planes have
have the
the same
same spacing,
spacing, the the
beams diffracted
beams diffracted by by them
them all
all form
form part
part of
of the
the same
same cone.
cone. Now
N ow consider
consider
the 111 reflection.
the 111 reflection. ThereThere are
are four
four sets
sets ofof planes
planes ofof the
the form
form {111)
1111} which
which
have the same spacing
have the same spacing but but different
different orientation, namely, (111),
orientation, namely, (111), (111), (111),
(lIT), and
(111), and (ill),
(111), whereas
whereas there
there are are only
only three
three sets of the form (100).
sets of the form \100}.
Therefore, the
Therefore, the probability
probability that that {1111111} planes
planes will
} will be
be correctly
correctly oriented
oriented for for
reflection isis ft the
reflection the probability
probability that that {100}
1100} planes
planes will
will bebe correctly
correctly oriented.
oriented.
It follows
It follows that
that the
the intensity
intensity of of the
the III
1 reflection will
11 reflection be ft that
wiII be that ofof the
the 100
100
reflection,
reflection, other
other things
things being
being equal.
equal.
This relative
This relative proportion
proportion of of planes
planes contributing
contributing to to the
the same reflection
reflection
enters the
enters the intensity
intensity equation
equation as as thethe quantity
quantity p, the multiplicity
p, the multiplicity factor,
factor,
which may
which may be be defined
defined as as the
the number of of different
different planes
planes in in aa form
form having
having
the same
the same spacing.
spacing. Parallel
Parallel planes
planes with with different
different Miller
Miller indices,
indices, such
such as as
(100) and (100),
(100) and (TOO), are
are counted
counted separately
separately as
as different
different planes, yielding
planes, yielding num-
bers which
bers which areare double
double those
those given
given in in the
the preceding
preceding paragraph.
paragraph. Thus the the
multiplicity factor
multiplicity factor for the 1100}
for the planes of a cubic crystal
{100} planes of a cubic crystal is 6
is 6 and for the
for the
III
{111}I} planes
planes 8.8.
The
The value
value ofof p depends on
p depends on the
the crystal
crystal system:
system: in in a tegragonal
tegragonal crystal,
crystal,
the
the (100)
(100) and
and (001)
(001) planes
planes do not not have
have the the same spacing,
spacing, so so that
that the value
of p for
of p {100}I planes
for 1100 planes is is reduced
reduced to to 4 and the the value for for 10011 planes to 2.
{001} planes 2.

Values
Values of of the
the multiplicity
multiplicity factorfactor as as aa function
function of hkl and crystal
of hkl crystal system
system
are
are given
given in in Appendix
Appendix 9. 9.

4-9
4-9 Lorentz
Lorentz factor.
factor. We must now consider consider certain
certain trigonometrical
trigonometrical fac- fac-
tors
tors which
which influence
influence the
the intensity
intensity of
of the
the reflected
reflected beam. Suppose
Suppose there is
is

incident on a crystal
incident on a crystal [Fig. [Fig. 4-13(a)]
4-13 (a)] a narrow beam of
of parallel
parallel monochro-
matic
matic rays,
rays, and let the"
and let the" crystal
crystal be be rotated
rotated at at a uniform angular
angular velocity
velocity
about
about an an axis through 0 and normal
axis through normal to to the drawing,
the drawing, so that aa particular
so that particular
set
set of
of reflecting
reflecting planes,
planes, assumed for for convenience to to be parallel
parallel toto the
the crys-
crys-
tal
tal surface,
surface, passes
passes through
through the the angle
angle 6B,fe, at
at which thethe Bragg
Bragg law is is exactly
exactly
satisfied.
satisfied. As mentioned
mentioned in in Sec.
Sec. 3-7,
3-7, the
the intensity
intensity ofof reflection
reflection is is greatest
greatest
at
at the
the exact
exact Bragg
Bragg angle
angle butbut still
still appreciable
appreciable at at angles
angles deviating
deviating slightly
slightly
from
from thethe Bragg angle,
Bragg angle, so
so that
that a
a curve
curve of
of intensity
intensity VS.
vs. 26
20 is
is of
of the
the form
form
shown
shown in in Fig.
Fig. 4-13(b).
4-13 (b). If
If all
all the
the diffracted
diffracted beams
beams sent
sent out
out by
by the
the crystal
crystal
as it
as it rotates
rotates through
through thethe Bragg
Bragg angle
angle areare received
received onon aa photographic
photographic film film
or
or in
in aa counter,
counter, the
the total
total energy
energy of
of the
the diffracted
diffracted beam
beam can
can be
be measured.
measured.
This
This energy
energy is is called
called thethe integrated
integrated intensity
intensity of of the
the reflection
reflection andand is is given
given
by the area
by the area underunder the
the curve
curve of
of Fig.
Fig. 4-13(b).
4-13 (b). The
The integrated
integrated intensity is
intensity is

of
of much
much moremore interest
interest than
than the the maximum
maximum intensity,
intensity, since
since the former is
the former is
4-9J
4-9] LORENTZ FACTOR 125

28/1
DIFFRACTION ANGLE 28
26
(a)
(a) (b)
(b)

FIG.
FIG. 4-13.
4-13. Diffraction
Diffraction by
by a
a crystal
crystal rotated
rotated through
through the
the Bragg
Bragg angle.
angle.

characteristic
characteristic of of the
the specimen
specimen whilewhile thethe latter
latter is
is influenced
influenced byby slight
slight adjust-
adjust-
ments ofof the
the experimental
experimental apparatus.
apparatus. Moreover,
Moreover, in in the
the visual
visual comparison
comparison
of
of the
the intensities
intensities of of diffraction
diffraction lines,
lines, it
it is
is the
the integrated
integrated intensity
intensity of of the
the
line
line rather
rather than
than the
the maximum intensityintensity which the the eye
eye evaluates.
evaluates.
The integrated
integrated intensity
intensity of of aa reflection
reflection depends
depends on on the
the particular
particular value
value
of BB involved,'even
of 8B involved, even though
though all
all other
other variables
variables are
are held
held constant.
constant. We can
can
find
find this
this dependence by considering,
dependence by considering, separately, separately, two aspects
aspects of
of the
the diffrac-
diffrac-
tion
tion curve:
curve: the
the maximum intensity
intensity and the the breadth.
breadth. When the the reflecting
reflecting
planes
planes make an
an angle
angle BB 8B with
with the
the incident
incident beam,
beam, the
the Bragg
Bragg law
law is
is exactly
exactly
satisfied
satisfied and the the intensity
intensity diffracted
diffracted in' in the
the direction
direction 28B26s is
is aa maximum.
But some energy
energy is is still
still diffracted
diffracted in in this
this direction
direction when the the angle
angle ofof inci-
inci-

dence
dence differs
differs slightly
slightly from 8B, fe, land
(and thethe total
total energy
energy diffracted
diffracted inin the
the direc-
direc-
tion 20# as
tion 28B as the
the crystal
crystal is is rotated
rotated through
through the the Bragg
Bragg angle
angle is
is given
given byby the
the
value
value of / m ax of
of Imax of the
the curve
curve ofof Fig.
Fig. 4-13(b).
4-13(b). tThe'value
^The value of / ma x therefore
of Imax therefore
depends on
depends on the
the angular
angular rangerange of of crystal
crystal rotation
rotation over
over which the the energy
energy
diffracted
diffracted inin the
the direction
direction 28B20 is is appreciable.l
appreciable.) In Fig. Fig. 4-14(a),
4-14(a), thethe dashed
lines
lines show thethe position
position of of the
the crystal
crystal after
after rotation
rotation through
through a a small
small angle
angle

1~2
2,

l'
C 2' 2'
91 D 9:!

A\-a--JB

I----------Na---------I

(a)
(a)
(b)
(b)

FIG.
FIG. 4-14.
4-14. Scattenng
Scattering in
in a
a fixed
fixed direction
direction during
during crystal
crystal rotation.
rotation.
 126
126 DllITRACTION
DIFFRACTION II:
II! THE INTENSITIES OF DllITRACTED
DIFFRACTED BEAMS [CHAP.
[CHAP. 4

~
A0 from thethe Bragg position. The incident
Bragg position. incident beam and the the diffracted
diffracted beam
under consideration
consideration now make unequal angles with the reflecting
unequal angles planes,
reflecting planes,
the former making
making an angle
angle tit
0i =
= 8B
OB +
+ MJ
A0 and the latter
latter an angle
angle 822 =
OB - !J.9.
8B A0. The situation
situation on an atomic scale
scale is
is shown inin Fig. 4-14(b).
Fig. 4-14(b). Here
we need only
only consider
consider a single
single plane
plane of
of atoms,
atoms, since
since the
the rays
rays scattered
scattered byby
all
all other
other planes
planes are
are in
in phase
phase with the corresponding
corresponding raysrays scattered
scattered by
by the
the
first plane. Let a equal
first plane. equal the
the atom spacing
spacing inin the plane and Na the
the plane the total
total
length
length* * of
of the plane.
the plane. The difference in path
difference in path length
length for rays l' and 2'
for rays 1' 2'

scattered
scattered byby adjacent
adjacent atoms is is given
given by
by
5 r2 =
&1'2''= AD -- CB
= a cos
= cos 82 -
62 a cos
cos 81
B\

= a[cos
= a[cos (8B
(Bs - !J.9) - cos (8B
A0) - cos (SB + !J.8)].
A0)].

By
By expanding
expanding thethe cosine
cosine terms and setting sin !J.8
setting sin A0 equal
equal to A0, since
to 1l.8, since the
the
latter
latter is
is small,
small, we find:
find:

&1'2' = 2aA0 sin

$i> 2 = 2a!J.O
' sin 8B,
0#,

and the path difference

the path difference between the the rays
rays scattered
scattered byby atoms at at either
either end
of the
of the plane
plane is
is simply
simply N times
times this
this quantity.
quantity. When the
the rays
rays scattered
scattered by
by
the
the two end atoms are are (N +
(N + 1) wavelengths
1) wavelengths out of
of phase,
phase, the
the diffracted
diffracted

intensity will
intensity will be
be zero.
zero. (The
(The argument
argument here
here is
is exactly
exactly analogous
analogous to to that
that
used in Sec. 3-7.)
used in Sec. 3-7.) The condition for zero
condition for zero diffracted
diffracted intensity
intensity is therefore
is therefore

2JVaA0 sin
2Nall.9 sin OB = (N
B = (N +
+ 1)"-,
1)X,
or
or

!J.O
(N
(AT + 1)"-
1)X
A0 = .
2Na sin
sin 8B
6B

This equation
equation gives
gives the
the maximum angular angular range
range ofof crystal
crystal rotation
rotation over over
which appreciable energy will
appreciable energy will be
be diffracted
diffracted in in the
the direction
direction 28B.20#. Since
Since
I/max
max depends
depends on this this range,
range, we can conclude that that I/ max is
is proportional
proportional to to
l/sin
I/sin 8B.
0fl. Other things
things being equal, I/ max is
being equal, is therefore
therefore large
large at
at low scatter-
scatter-
ing
ing angles
angles and small
small inin the
the back-reflection
back-reflection region.
region.
The breadth of of the
the diffraction
diffraction curve
curve varies
varies in in the
the opposite
opposite way, being
way, being
larger at
larger at large
large values
values of
of 28B,
20#, as
as was shown in
in Sec.
Sec. 3-7,
3-7, where the
the half-
half-
maximum breadth B was found to to be
be proportional
proportional to
to l/cos
I/cos 8B.
BB. The inte-
inte-
grated intensity
grated intensity of
of the
the reflection
reflection is
is given by
given by the
the area
area under the
the diffraction
diffraction
curve and is is therefore proportional to
therefore proportional to the product I/ maxB,
the product ma x-B, which is is in
in tum
turn
proportional
proportional to
to (l/sin 9B)(1/cos
(l/sin0#)(l/cos0B) OB) or
or to
to l/sin
I/sin 28B.
26 (:hus,
B (Thus,
. as
as a crystal
a crystal
is
is rotated
rotated through
through thethe Bragg
Bragg angle,
angle, the
the integrated
integrated intensity
intensity ofof aa reflection,
reflection,
which is is the quantity
quantity of of most experimental
experimental interest,
interest, turns
turns out
out to be greater
to be greater

** If
If the
the crystal
crystal isis larger
larger than
than the
the incident beam, then
incident beam, then NNaa is
is the
the irradiated
irradiated length
length
of
of the
the plane;
plane; if
if it is smaller,
it is smaller, Na is
is the
the actual
actual length
length of
of the
the plane.
plane.
4-9)
4-9] LORENTZ FACTOR 127
127

for
for large
large and.
and small
small values
values of 200 than for
of 28B for intermediate values,
values, other things
things
being equal.
being equal.
The preceding
preceding remarks apply apply just just asas well
well to
to the powder method as
the powder as they
they
do to
to the
the case
case of
of a rotating crystal,
rotating crystal, since
since the
the range
range of
of orientations
orientations available
available
among
among the the powder
powder particles,
particles, some satisfying
satisfying thethe Bragg
Bragg law exactly,
exactly, some
not
not soso exactly,
exactly, areare the equivalent of
the equivalent of single-crystal
single-crystal rotation.
rotation.
However,
However, in in the
the powder
powder method,
method, a second geometricalgeometrical factor
factor arises
arises when
we consider
consider that ~he integrated
thatfyhe integrated intensity
intensity of of a reflection
reflection atat any particular
any particular
Bragg
Bragg angle
angle depends
depends on the the number of particles oriented
of particles oriented at at or
or near that
that
angle.'"
angled This number is is not
not constant
constant even though though thethe particles
particles are
are oriented
oriented
completely
completely at at random. In Fig. 4-15
In Fig.
aa reference
reference sphere
sphere of
of radius
radius rr is
is drawn

around
around the powder specimen
the powder specimen located
located
at O.
at particular hkl
0. For the particular hkl reflec-
reflec- I
I
tion
tion shown,
shown, ON is
is the
the normal to
to this
this I
I
set
set of planes in
of planes in one particle
particle of of thethe I
I
Suppose that
powder. Suppose that the
the range
range of

jJ-
powder. of I

angles
angles near near the
the Bragg
Bragg angleangle over over
reflection is
which reflection is appreciable
appreciable is is M.
A0.
Then,
Then, for for this
this particular
particular reflection,
reflection,
only
only those particles will
those particles will be
be in in a a re-
re-
flecting position
flecting position which have the
the ends
ends
of
of their
their plane
plane normals lying lying in
in aa band
FIG. 4-15.
4-15. The distribution
distribution of plane
of plane
of width rM
of width rA0 on the the surface
surface of of thethe
normals
normals forfor aa particular cone of
particular cone of re-
re-
sphere.
sphere. Since
Since the particles are
the particles are as-as- flected rays.
flected rays.
sumed to to be
be oriented
oriented at at random,
random, the the
ends
ends of of their
their plane
plane normals will will be be uniformly
uniformly distributed
distributed over
over the
the surface
surface
of
of the
the sphere;
sphere; the
the fraction
fraction favorably
favorably orientedoriented forfor a
a reflection
reflection will
will be
be given
given
by
by the
the ratio
ratio of
of the
the area
area ofof the strip to
the strip to that
that ofof the
the whole sphere. If
whole sphere. /j,N is
If AAT is

the
the number of of such particles and N the
such particles the total
total number,
number, thenthen

llN
AAT r/j,8
rA0 . 2111'
2nr sin
sin (90 - B)
(90 - 8B) M
A0 cos
cos 8B
6B
=---
N 4rr2 2

The number of of particles

particles favorably
favorably oriented
oriented forfor reflection
reflection is
is thus
thus propor-
propor-
tional to
tional to cos
cos 8BB and is
is quite
quite small
small for
for reflections
reflections in
in the
the backward direction.
direction.
In assessing
assessing relative
relative intensities,
intensities, we do not not compare
compare the the total
total diffracted
diffracted
energy
energy in
in one
one cone
cone of
of rays
rays with
with that
that in
in another
another but
but rather
rather the
the integrated
integrated
intensity
intensity per
per unit
unit length
length ofof one
one diffraction
diffraction line
line with
with that
that of
of another.
another. For
example,
example, in in the
the most common arrangement
arrangement of of specimen
specimen and film, film, the
the
Debye-Scherrer
Debye-Scherrer method,
method, shown in in Fig.
Fig. 4-16,
4-16, the
the film
film obviously
obviously receives
receives a
greater proportion of
greater proportion of a diffraction
diffraction cone
cone when the the reflection
reflection is
is in
in the
the forward
or
or b(l.ckward direction than it
backward direction it does
does near
near 28 = 90.
20 == 90. Inclusion
Inclusion ofof this
this effect
effect
128 DIJ'l'RACTlON
DIFFRACTION II: OF DIII'I'RACTED
II! THE INTENSITIES 011' BEAMS
DIFFRACTED BEAKS [CHAP.
[CHAP. 4

R sin 20/i

FIG.
FIG. 4-16.
4-16. Intersection
Intersection of
of cones
cones of
of diffracted
diffracted rays
rays with
with Debye-Scherrer
Debye-Scherrer film.
film.

thus
thus leads
leads to
to aa third
third geometrical
geometrical factor
factor affecting
affecting the
the intensity
intensity of
of a reflec-
reflec-
tion.
tion. The length
length of
of any
any diffraction
diffraction line
line being
being 2rR
2vR sin
sin 28B,
20s, where R is
is the
the
radius
radius of
of the
the camera,
camera, the
the relative
relative intensity per
intensity per unit
unit length
length of
of line
line is
is pro-
pro-
portional to
portional to 1/ sin 28B.
I/sin 20B.
In
In intensity
intensity calculations,
calculations, the
the three
three factors just discussed
factors just discussed are
are combined
into
into one
one and called
called the
the Lorentz
Lorentz factor.
factor. Dropping
Dropping the
the subscript
subscript on the
the
Bragg angle,
Bragg angle, we have:
have:

Lorentz factor =
Lorentz factor == (_1_)
(
sin
(cos 8) (_1_) = cos 8 =
Vsin 28
207 \
) [
sin
cos 6
sin
} [
/ Vsin 28
207
I
CO80
sin
2
2 28
28 4 sin
1 .1

2
sin cos
2 86 cos 8

This
This in
in tum
turn is
is combined with
with the
the polarization
polarization factor
factor t(1 +
+ cos
cos 2 28)
26)
2
of
of
Sec.
Sec. 4-2 to
to give
give the
the combined Lorentz-
Lorentz- ~ ...
polarization factor
polarization factor which,
which, with con- "'~! 50
with a con-
stant
stant factor of t
factor of -^ omitted,
omitted, is given
is by + ~
given by
,...c "iiJ
= 40
Lorents-polarization
Lorentz-polarization factor
factor = ^
o
+
1 + cos
1 2
cos2 28
26 5|
CSJ

sin
sin'2
2
86 cos
cos 8
6 3

Values ofof this factor are

this factor are given
given inin
Appendix
Appendix 10 and p~otted
plotted in
in Fig.
Fig. 4-17 10
as a function
function of 6. <.The
of 8. (jhe over-all
over-all effect
effect
of these geometrical
of these geometrical factors
factors is
is to
to de-
de- o~O----~4~5------00~
crease
crease the
the intensity
intensity of
of reflections
reflections at
at 45 90
intermediate
intermediate angles compared
angles compared to
to those
those BRAGG ANGLE 6 (degrees)
(J (degrees)
in
in forward
forward or
or backward directions.
directions. FIG.4-17. Lorentz-polarization factor.
FIG. 4-17. Lorentz-polarization factor.
4-10]
4-10] ABSORPTION FACTOR 129
129

(a)
(a) (h)
(h)

FIG.
FIG. 4-18.
4-18. Absorption
Absorption in
in Debye-Scherrer
Debye-Scherrer specimens:
specimens: (a)
(a) general
general case,
case, (b)
(b) highly
highly
absorbing
absorbing specimen.
specimen.

4-10 Absorption
Absorption factor.
factor. Still
Still another factorfactor affecting
affecting the the intensities
intensities of of
the
the diffracted
diffracted rays
rays must be considered,
considered, and that
that is
is the
the absorption
absorption which
takes
takes place
place inin the
the specimen
specimen itself.
itself. The specimen
specimen in in the
the Debye-Scherrer
Debye-Scherrer
method has the the form of of aa very
very thin
thin cylinder
cylinder of powder placed
of powder placed on on the
the camera
axis,
axis, and Fig.
Fig. 4-18(11.)
4-1 8 (a) shows the
the cross
cross section
section of
of such
such a
a specimen.
specimen. For
the
the low-angle
low-angle reflection
reflection shown, absorption
shown, absorption of
of aa particular
particular ray inray in the
the inci-
inci-
dent beam occursoccurs along
along a
a path
path suoh
such as
as AB;
AB] at
at 5
B aa small
small fraction
fraction of
of the
the
incident
incident energy
energy is
is diffracted
diffracted by
by a
a powder particle,
powder particle, and absorption
absorption of
of this
this
diffracted
diffracted beam occurs occurs along
along the path BC.
the path BG. Similarly,
Similarly, for for a a high-angle
high-angle
reflection, absorption
reflection, absorption of
of both
both the
the incident
incident and diffracted
diffracted beams occurs
occurs
along
along a
a path
path such
such as
as (DE +
(DE + EF). EF). The net
net result
result is
is that
that the
the diffracted
diffracted
beam is is of
of lower intensity than one would expect
lower intensity expect for for a a specimen
specimen of of no
absorption.
absorption.
A calculation
calculation of of this effect shows that
this effect that the
the relative
relative absorption
absorption increases
increases
as 6 decreases,
as (J decreases, for
for any given cylindrical
any given cylindrical specimen. specimen. That this
this must be be so
so
can
can bebe seen
seen from Fig. Fig. 4-18(b)
4-1 8 (b) which applies
applies to
to a
a specimen (for
specimen (for example, example,
tungsten)
tungsten) of of very
very highhigh absorption.
absorption. incident beam is
The incident is very
very rapidly
rapidly
absorbed, and most of
absorbed, of the
the diffracted
diffracted beams originate originate in in the
the thin
thin surface
surface
layer
layer on the the left
left side
side ofof the
the specimen
specimen \backward-reflected
,-f
backward-reflected beams then then
undergo
undergo very very little
little absorption,
absorption, but but forward-reflected
forward-reflected beams have to pass
to pass
through
through the the whole specimen
specimen and are are greatly
greatly absorbed.
absorbed.^ Actually, the
'\ Actually, the
forward-reflected
forward-reflected beams in in this
this case
case come almost
almost entirely
entirely from the the top
top and
bottom edgesedges of of the
the specimen.
specimen.* This This difference
difference in in absorption
absorption betweenbetween
* The powder
powder patterns
patterns reproduced
reproduced in in Fig.
Fig. 3-13
3-13 show this
this effect.
effect. The lowest-
lowest-
angle
angle line
line in
in each pattern is
each pattern is split
split in
in two,
two, because
because the
the beam diffracted
diffracted through
through the
the
center of
center of the
the specimen
specimen isis so
so highly
highly absorbed.
absorbed. ItIt is
is important
important toto keep
keep the possi-
the possi-
bility
bility of
of this phenomenon in
this phenomenon in mind when examining
examining Debye-Scherrer
Debye-Scherrer photographs,
photographs,
or
or split
split low-angle
low-angle lines may be
lines may be incorrectly
incorrectly interpreted
interpreted as
as separate
separate diffraction
diffraction lines
lines
from two different sets of
different sets planes.
of planes.
130
130 DIFFRACTION II: THE
DIFFRACTION III INTENSITIES OF
THE INTENSITIES DIFFRACTED BEAMS
OF DIFFRACTED BEAMS [CHAP. 44
[CHAP.

high-6 and
high-0 and low-0
10w-6 reflections
reflections decreases
decreases as
as the
the linear
linear absorption
absorption coefficient
coefficient
of the specimen
of the specimen decreases,
decreases, but
but the
the absorption
absorption is
is always
always greater
greater for
for the
the
10w-6 reflections.
low-0 reflections. (These
(These remarks
remarks apply
apply only
only to
to the
the cylindrical
cylindrical specimen
specimen
used in
used the Debye-Scherrer
in the Debye-Scherrer method.
method. The
The absorption
absorption factor
factor has
has an
an entirely
entirely
different form
different form for
for the
the flat-plate
flat-plate specimen
specimen used
used in
in aa diffractometer,
diffractometer, as
as will
will
be shown
be shown in Sec. 7-4.)
in Sec. 7-4.)
Exact calculation
Exact calculation ofof the
the absorption
absorption factor
factor for
for aa cylindrical
cylindrical specimen
specimen isis
often difficult,
often difficult, so
so it
it is
is fortunate
fortunate that
that this
this effect
effect can
can usually
usually be
be neglected
neglected in
in
the calculation
the calculation ofof diffracted
diffracted intensities,
intensities, when the
the Debye-Scherrer
Debye-Scherrer method
is used.
is used. Justification
Justification ofof this
this omission
omission will
wiII be
be found
found inin the
the next
next section.
section.

4-11 Temperature
4-11 Temperature factor. So far
factor. far we have considered
considered aa crystal
crystal as
as aa
collection of
collection of atoms located
atoms located atat fixed
fixed points
points in
in the
the lattice.
lattice. Actually,
Actually, the
the
atoms undergo
atoms undergo thermal
thermal vibration
vibration about
about their
their mean positions
positions even atat the
the
absolute zero
absolute of temperature,
zero of temperature, and the
the amplitude
amplitude of
of this
this vibration
vibration increases
increases
as the
as the temperature
temperature increases.
increases. In aluminum at
In at room temperature,
temperature, the the
average displacement
average displacement of
of an
an atom from its
its mean position
position is
is about 0.17
0.1 7 A,
A,
which is
which is by
by nono means negligible,
negligible, being
being about
about 66 percent
percent of of the
the distance
distance of of
clpsest approach
closest approach of of the
the mean atom positions
positions in in this
this crystal.
crystal.
"Thermal agitation
^Thermal agitation decreases
decreases thethe intensity
intensity of of aa diffracted
diffracted beam because because
it has the effect of
it has the effect of smearingsmearing out
out the
the lattice
lattice planes;\atoms
planes;* atoms can
can be regarded
regarded
as lying no longer
as lying longer on on mathematical planes planes but rather rather in in platelike
platelike regions
regions
of iiI-defined thickness.
of ill-defined thickness. Thus the the reinforcement
reinforcement of scattered at
of waves scattered the
at the
Bragg
Bragg angleangle byby various
various parallel planes, the
parallel planes, the reinforcement
reinforcement which is is called
called a
diffracted
diffracted beam,beam, is is not
not asas perfect
perfect asas itit is
is for
for a crystal
crystal with fixed fixed atoms.
This
This reinforcement
reinforcement requiresrequires that
that the
the path
path difference,
difference, which is
is a
a function
function
of
of the
the plane spacing
plane spacing d, d, between waves scattered
scattered by
by adjacent
adjacent planes
planes be an
integral
integral number of
of wavelengths.
wavelengths. Now the
the thickness
thickness of
of the platelike
platelike
"planes"
"planes' in
'
which the
in which the vibrating
vibrating atoms lie lie is,
is, on thethe average,
average, 2u, 2?/, where

u is
is the
the average displacement
average displacement of
of an atom from its
its mean position.
position. Under
these
these conditions
conditions reinforcement
reinforcement is is no longer perfect,
longer perfect, and it
it becomes more

imperfect as the ratio u/d increases,

imperfect as the ratio u/d increases, i.e., i.e., as
as the
the temperature
temperature increases,increases,
since
since that increases u,
that increases u, or
or as
as 8 increases,
increases, since since high-O
high-0 reflections
reflections involve
involve
planes
planes of low d
of low d value.
value. (Thus
TThus the the intensity
intensity of of a diffracted
diffracted beam decreases decreases
as
as the
the temperature
temperature is is raised,
raised, and,
and, forfor a a constant
constant temperature,
temperature, thermal
vibration
vibration causes
causes a a greater
greater decrease
decrease in in the
the reflected intensity at
reflected intensity at high
high angles
angles
than
than at at low
low angles.
angles. )/
The temperature
temperature effect effect and the the previously
previously discussed
discussed absorption
absorption effect effect
in
in cylindrical
cylindrical specimens
specimens therefore
therefore depend
depend on
on angle
angle in
in opposite
opposite ways
ways and,
and,
to
to aa first
first approximation,
approximation, cancel
cancel each
each other.
other. In
In back reflection,
reflection, for
for exam-
ple,
ple, the
the intensity
intensity of of aa diffracted
diffracted beam is is decreased
decreased very very little
little by by absorption
absorption
hut
but very greatly
very greatly by by thermal
thermal agitation,
agitation, while
while in
in the
the forward
forward direction
direction the
reverse
reverse is is true.
true. The two effects
effects do not not exactly
exactly cancelcancel one other at
one other at all
all
 4-11)
4-11] TEMPERATURE FACTOR 131
131

angles;
angles; however,
however, if if the comparison
comparison of of line
line intensities
intensities is is restricted
restricted to to lines
lines
not
not differing
differing too too greatly
greatly in 6 values,
in fJ values, thethe absorption
absorption and temperature
temperature effects
effects
cll.n
can be safelysafely ignored.
ignored. This is.ais. a fortunate
fortunate circumstance,
circumstance, since both of
since both of
these
these effects
effects areare rather
rather difficult
difficult to to calculate
calculate exactly.
exactly.
It should
It should be be noted here here that
that thermal vibrationvibration of of the
the atoms of of aa crystal
crystal
does
does notnot cause
cause any broadening
any broadening of
of the
the diffraction
diffraction lines; they
lines; they remain
remain sharp
sharp
right
right up up to
to the
the melting
melting point, point, but
but their
their maximum intensity
intensity gradually de-
gradually de-
creases.
creases. It It is
is also
also worth noting noting that
that the
the mean amplitude
amplitude of
of atomic vibra-
vibra-
tion is
tion is not
not a a function
function of of the
the temperature
temperature alone alone but but depends
depends also also on the the
elastic constants of
elastic constant.s of the crystal.
the crystal. At anyAt any given
given temperature,
temperature, the the less
less "stiff"
"stiff"
the
the crystal,
crystal, the the greater
greater the the vibration
vibration amplitude
amplitude 1l. u. This
This means that that u u
is
is much greater
greater at at any
any on!'one temperature
temperature for for a a soft,
soft, low-melting-point
low-melting-point metal metal
like lead than it
like lead it i8
is for,
for, say,
say, t.ungsten.
tungsten. Substances
Substances with with low melting points
melting points
have quite
quite large
large values
values of u even at
of Ii at room temperature
temperature and therefore therefore yield
yield
rather
rather poorpoor back-reflection
back-reflection photographs.photographs.
The thermal
thermal vibration
vibration of of atoms has has another
another effect
effect on diffraction
diffraction pat-pat-
terns.
terns. Besides
Besides decreasing
decreasing the
the intensity
intensity of
of diffraction
diffraction lines,
lines, it
it causes
causes some
general
general eoherent scattering in
coherent scattering in all
all directions.
directions. This
This is called temperature-
is called temperature-
diffuse scattering;
diffuse scattering; it
it contributes
contributes only
only to
to the
the general
general background of
background of thethe
pattern
pattern and its
its intensity gradually
intensity gradually in('reases
increases with
with 28.
26. Contrast
Contrast between
between
lines
lines and background
background naturally naturally suffers,
suffers, so so this
this effect
effect is is aa very
very undesirable
undesirable
one,
one, leading
leading in in extreme
extreme cases cases to to diffraction
diffraction lines lines in in the
the back-reflection
back-reflection
region
region scarcely
scarcely distinguishable
distinguishable from the the background.
background.
In
In thethe phenomenon
phenomenon of of temperature-diffuse
temperature-diffuse scattering scattering we have another another
example,
example, beyond beyond those alluded to
those alluded to inin Sec.
Sec. 3-7,
3-7, of of scattering
scattering at at non-Bragg
non-Bragg
angles.
angles. Here again again it it is not surprising
is not surprising that that such
such scattering
scattering shouldshould occur,
occur,
since
since the the displacement
displacement of of atoms from their their mean positions
positions constitutes
constitutes a a
kind
kind of of crystal
crystal imperfection
imperfection and leads leads to to a a partial
partial breakdown of of the
the con-
con-
ditions
ditions necessary
necessary for perfect destructive
for perfect destructive interference
interference between between rays rays scat-
scat-
tered
tered at at non-Bragg
non-Bragg angles. angles.
The effect
effect of of thermal
thermal vibration
vibration also also illustrates
illustrates what has has beenbeen called
called
"
"the
"the approximate
approximate law
law of
of conservation
conservation of
of diffracted
diffracted energy."
energy. This
This law
states
states thatthat the
the total energy
total energy diffracted
diffracted by a
a particular
by particular specimen specimen under par-
par-
ticular
ticular experimental
experimental conditions conditions is is roughly
roughly constant.
constant. Therefore,
Therefore, anything
anything
done to to alter
alter the physical condition
the physical condition of of the
the specimen
specimen does does notnot alter
alter the
the total
total
amount of of diffracted
diffracted energy energy but but only
only its distribution in
its distribution in space.
space. This This "law"
is not at
is not at all
all rigorous,
rigorous, but but it it does
does prove
prove helpful
helpful in in considering
considering many many diffrac-
diffrac-
tion
tion phenomena.
phenomena. For example, example, at at low
low temperatures
temperatures there there is is very
very little
little

background
background scatteringscattering due to
to thermal
thermal agitation
agitation and the
the diffraction
diffraction lines
lines
are
are relatively intense;
relatively intense; if
if the
the specimen
specimen is
is now heated
heated to
to a
a high temperature,
high temperature,
the
the lines
lines willwill become quite quite weak and the the energy
energy which which is is lost
lost from
the
the lines
lines willwill appear
appear in
in a
a spread-out
spread-out form
form as
as temperature-diffuse
temperature-diffuse scat- scat-
tering.
tering.
 132
132 DIFFRACTION IIII: THE
DIFFRACTION THE INTENSITIES
: DIFFRACTED BEAMS
OF DIFFRACTED
INTENsITIES OF BEAMS [CHAP.44
[CHAP.

4-12 Intensities ofofpowder

4-12 Intensities powderpattern lines. We
pattemlines. are now
We are now inin aa position
position to
to
gather together
gather together
the
the factors
factors discussed
discussed in
in preceding
preceding sections
sections into
into an
an equation
equation
for the
for the relative
relative intensity
intensity ofofpowder
powderpattern
pattern lines:
lines:

1=
(1
1 + C0s22g>
IFI 2pY +22 cos
2 28))
,
, (4-12)
(4-12)
sin 68cos
\ sin cos68/

where II == relative
where relative integrated
integrated intensity
intensity (arbitrary units), FF == structure
(arbitrary units), structure
factor, p
factor, p
= =
multiplicity
multiplicity factor,
factor, and
and 68 = Bragg
Bragg angle.
angle. In
In= arriving
arriving at this
at this
equation,
we have
equation, we have omitted
omitted factors
factors which
which are
are constant
constant for all lines of
for all lines of the
the
pattern. For
pattern.
For example,
example, all all that
that isis retained
retained of of the
the Thomson
Thomson equation equation (Eq. (Eq.
4-2)
4-2)
is
is the
the polarization
polarization factor
factor (1
(1 ++ cos
cos
22
28),
26), with
with constant
constant factors,
factors, such
such
as the
as the intensity
intensity of of the
the incident
incident beam beam and and the the charge
charge and and mass
mass of of the
the elec-
elec-
tron,
tron,
omitted.
omitted. The
The intensity
intensity of
of aa diffraction
diffraction line
line is
is also
also directly
directly propor-
propor-
tional to
tional to the
the irradiated
irradiated volume volume of of the
the specimen
specimen and and inversely
inversely proportional
proportional
to the
to the camera
camera radius,
radius, but but these
these factors
factors are are again
again constant
constant for for all
all diffraction
diffraction
lines and
lines and may may be neglected. Omission
be neglected. Omission of of the
the temperature
temperature and and absorption
absorption
factors means
factors means that that Eq. Eq. (4-12)
(4-12) is is valid
valid onlyonly for for the Debye-Scherrer method
the Debye-Scherrer method
and then
and then only only for for lines
lines fairly
fairly close
close together
together on the the pattern;
pattern; this this latter
latter
restriction is
restriction is not
not as as serious
serious as as itit may
may sound.
sound. EquationEquation (4-12) (4-12) is is also
also re-re-
stricted to
stricted to the
the Debye-Scherrer
Debye-Scherrer method because of
of the particular
particular way in
in

which
which the the Lorentz
Lorentz factorfactor was was determined;
determined; other other methods,
methods, such such as those
as those
involving focusing
involving focusing cameras,
cameras, will
will require
require a
a modification
modification of
of thethe Lorentz
Lorentz
factor
factor givengiven here.
here. In
In addition,
addition, the
the individual
individual crystalscrystals making
making up thethe
powder
powder specimen
specimen must must have have completely
completely random orientations orientations if if Eq.
Eq. (4-12)
(4-12)
is
is to
to apply. Finally,
apply. Finally, it
it should
should be
be remembered that this
this equation
equation gives
gives the
the

relative integrated
relative integrated intensity,
intensity, i.e., i.e., the
the relative
relative area area under the the curve
curve of of in-
in-

tensity VB. 28.

tensity vs. 20.
It
It should
should be be noted
noted that that "integrated
"integrated intensity"intensity" is is not really intensity,
not really intensity,
since
since intensity
intensity is
is .expressed
-expressed in
in terms
terms of
of energy
energy crossing
crossing unit
unit area
area perper unit
unit
of
of time.
time. A A beam
beam diffracted
diffracted by aa
by powderpowder specimen
specimen carries
carries aa certain
certain amount
amount
of
of energy
energy per per unit
unit timetime and and one one could
could quitequite properly
properly refer refer to to the
the total
total

power
power of
of the
the diffracted
diffracted beam.
beam. If
If this
this beam
beam is
is then
then incident
incident on on aa measuring
measuring
device, such as photographic film, for for aa certain
certain length
length of of time
time and and ifif aa
device, such as photographic film,
curve of diffracted
curve of diffracted intensity intensity VB.
vs. 2826 is
is constructed
constructed from
from the
the measurements,
measurements,
then
then the
the areaareaunder
under this this curve
curve gives
gives the total energy
the total energy in in the
the diffracted
diffracted beam.beam.
This is the quantity
This is the quantity commonly commonly referred
referred to
to as
as integrated
integrated intensity.
intensity. AA
more descriptive
more descriptive term
term would
would be
be "total
"total diffracted
diffracted energy,"
energy," but
but the
the term
term
lIintegrated
"integrated intensity"
intensity" has has been
been too too long
longentrenched
entrenched in in the
the vocabulary
vocabulary of of
x-ray diffraction
x-ray diffraction to to be
be changed
changed now.
now.

4-13 Examples of
4-13 Examples of intensity calculations. The
intensity calculations. The use
use of
of Eq. (4-12) will
Eq. (4-12) will

be illustrated by the calculation

be illustrated by the calculation of
ofthe
the position
position and
and relative
relative intensities
intensities ofof
4-131
4-13] EXAMPLES
EXAMPLES OF INTENSITY CALCULATIONS
OF INTENSITY CALCULATIONS 133
133

the diffraction
the diffraction lines
lines on
on aa powder
powder pattern
pattern of
of copper,
copper, made
made with
with Cu Ka
eu Ka.
radiation. The
radiation. The calculations
calculations are
are most
most readily
readily carried
carried out
out in
in tabular
tabular form,
form,
as in
as in Table
Table 4-2.
4-2.
TABLE 4-2
TABLE 4-2

1 2 3 4 5 6 7 8

+ k2 + f2 sin 2 9 sinS (A-I)

line likl li2 sin9 9 A feu
1 111 3 0.1365 0.369 21.70 0.240 20.0
2 200 4 0.1820 0.426 25.2 0.277 18.7
3 220 8 0.364 0.602 37.0 0.391 15.6
4 311 11 0.500 0.706 44.9 0.459 14.0
5 222 12 0.546 0.738 47.6 0.479 13.7
6 400 16 0.728 0.851 58.3 0.553 12.4
7 331 19 0.865 0.929 68.3 0.604 11.7
8 420 20 0.910 0.951 72.0 0.618 11.4

1 9 10 11 12 13 14

1 + cos 2 29 Relative integrated intensity

line F2 p
sin 2 9 cos9 Calc. Calc. Obs.
1 6400 8 12.10 6.20 X 105 10.0 s
2 5600 6 8.50 2.86 4.6 m
3 3890 12 3.75 1.75 2.8 m
4 3140 24 2.87 2.16 3.5 s
5 3000 8 2.75 0.66 1.1 w
6 2460 6 3.18 0.47 0.8 w
7 2190 24 4.75 2.50 4.0 vs
8 2000 24 5.92 2.96 4.8 vs

Remarks:
Remarks:
Column ;:: 2: Since
Since copper
copper is
is fuce-centered
face-centered ('ubic,
cubic, F is is equal
equal to
to 4fc.1l
4/Cu forfor lines
lines of
of un-
mixed
mixed indices
indices and
and zero
zero for
for lines
lines of
of mixed indices.
indices. The reflecting
reflecting plane
plane indices,
indices, all
all

unmixed,
unmixed, are
are written
written down in
in this
this column in
in order
order of
of increasing
increasing values
values of
of (h
(h
2
2 -f- +
+ Z ), from
kfc 22 + (2),
2
from Appendix
Appendix 6.
6.

Column 4: 4: For
For aa cubic
cubic crystal,
crystal, values
values of sin 2 0
of sin 6 are
are given by Eq.
given by Eq. (3-10):
2
(3-10) :

}..2
sin
sm"0 = 4~
20 = (h 2
j-gC/r +
-h k
/r2 +
-h l2).
r;.

In
In this
this case, X = 1.542A
case, }.. 1.542A (eu Ka) and a =
(Cu Ka) = 3.615A (lattice
(lattice parameter
parameter ofof copper).
copper).
Therefore, multiplication
Therefore, multiplication of
of the
the integers
integers in
in column 3
3 by}..2/4a
by X 2
/4a =
22 = 0.0455 gives
gives the
the
values of
values sin2 0 listed
of sin listed in
in column 4. In this
this and similar
similar calculations,
calculations, slide-rule
2
4. slide-rule
accuracy
accuracy is is ample.
ample.
Column
Column 6: 6: Needed
Needed toto determine
determine the
the Lorentz-polarization
Lorentz-polarization factor factor and (sin
(sin O)/}".
0)/X.
Column 7:
Column 7: Obtained
Obtained from
from Appendix
Appendix 7.
7. Needed to
to determine
determine leu.
/ Cu -

Column
Column 8: 8: Read
Read from
from the
the curve
curve of
of Fig.
Fig. 4-6.
4-6.
Column
Column 9: 9: Obtained
Obtained from
from the relation F2
the relation F 2 == 16/eu 2
16/Cu2 -

Column
Column 10: 10: Obtained
Obtained from
from Appendix
Appendix 9. 9.
 134
134 DIFFRACTION IIII: THE
DIFFRACTION :THE INTENSITIES DIFFRACTED BEAMS
OF DIFFRACTED
INTENSITIES OF BEAMS [CHAP. 44
[CHAP.

Column 11:
Column 11:Obtained
Obtainedfrom
from Appendix
Appendix 10.
10.
Column 12:
Column 12:These
These values
values are
arethe
the product
productofofthe
the values
values inin columns 10, and
columns9,9, 10, and 11.
11.
Column 13:
Column 13:Values
Valuesfrom
from column
column 1212recalculated
reralrulated to give
to an
give the firRt line anarbitrary
the first line arbitrary
intensity of 10.
intensity of 10.
Column 14:
Column 14: These
These entries
entries give
give the
the observed intem~ities, visually
observed intensities, visually estimated
estimated ac-ac-
cording
cording to
to the
the following simple
following simple scale,
scale, from
from the
the pattern
pattern shown
shown in
in Fig.
Fig. 3-13(s)
3-1 3(a)
(vs = very strong, s == strong,
(vs = very strong, s
strong, m medium, ww == weak).
m == medium, weak).

The agreement
The agreement. obtained
obtained here
here between
bet.ween observed
observed and
and calculated
ealculated intensities
in1iensities
is satisfactory.
is satisfactory. For For example,
(>xample, lineslines 11 and
and 22 areare observed
observed to to be
be of
of strong
strong
and medium
and medium intensity,
intensity, their
their respective
respeeti\"e calculated
ealculated intensit.ics being
intensities being 10 10 and
and
4.6. Similar
4.0. Similar agreement
agreement can can bebe found
found by by comparing
comparing the the intensities
intensities of of any
any
pair of neighboring lines in
pair of neighboring lines
in the
the pattern.
pattern. Note,Note, however,
howewr, that the com-
that the com-
parison
parison
must
must be
be made
made between
between lines
lines which
which are
are not
not too
too far
far apart:
apart: for
for exam-
exam-
ple, the calrulated intensity of
ple, the calculated intensity
of line
line 22 is
is greater
greater than
than that
that of
of line
line 4,
4, whereas
whereas
line 4 is
line 4 is observed
observed to
to be
be stronger
stronger than
than line
line 2.
2. Similarly,
Similarly, thp
the Rtrongest
strongest lines
lines

on the pattern
on the pattern are
are lines
lines 7
7 and
and 8,
8, while
while ealeulations
calculations show
show lim'
line 1 to
to
1

be strongest. Errors
be strongest. Errors of
of this
this kind
kind arise
arise from the
the omission
omission of
of the
the absorption
absorption
and temperature
and temperature factors
factors from
from thethe calculation.
caleulation.
A more
more complicated
complicated structure
structure may may now be be considered,
considered, namely
namely that that of
of
the
the zinc-blende
zinc-blende form
form of ZnS, shown in Fig.
of ZnS, in Fig. 2-19(b).
2-19(b). This form of ZnR is
This form of ZnS is
cubic
cubic and
and has
has a
a lattice
lattice parameter
parameter of of 5.41A.
5.41A. We will will ealculatr
calculate thethe relatiw
relative
intensities
intensities ofof the
the first
first six
six lines
lines onon aa pattern
pattern made wit.h with euCu Ka radiation.
radiation.

As
As always, ZnS hall
always, the
the first
first step
step is is to
to work
work out.
out thethe struet,ure
structure faetor.
factor. ZnS has
four
four zinc
zinc and
and four
four sulfur
sulfur at.oms
atoms per per unit
unit eell,
cell, loeat.ed
located inin the following
following posi-
posi-
tions:
tions:
'Zn: \ \ i
'Zn: tt
\ ++ facc-eentering
face-centering translationR,
translations,

s:S: 0 0 0 +
+ fare-ccntering
face-centering translations.
translations.

Since
Since the structure is
the structure is face-centered,
face-centered, wewe know
know that
that the
the struct ure factor
structure factor

will be
will be zero
zero for
for planes
planes ofof mixed
mixed indices.
indices. WcWe also know,
also know, from example
from example (e)
(e)

of
of Sec.
Sec. 4-6,
4-6, that
that the
the terms
terms in
in the
the structure-factor
structure-factor equation
equation corresponding
corresponding
to
to the
the face-centering
face-centering translations
translations cancan be
be factored
factored out
out and
and the
the equation
equation for
for

unmixed
unmixed indires
indices written
written down
do\vn at
at once:
once:

F = 4[fs + izne(.-,/2) (Hk+l'].

IFI2 is obtained
|F|
2
obtained by
is by multiplication
multiplication of
of the
the above
above by
by its complex
complex conjugate:
conjugate: its

IFI2 = 16[fs + fZn e (h+k+/l][fs + fZne-( .. ,/2)(h+k+/)].

(n/2)

This
This equation
equation reduces
reduces to
to the
the following
following form:
form:

1F12
2
|F| 16 [1S2
== 16 I/!,
2
++fzn
/Zn2 +
2
+ 2fs1zn
2/s/Zn cosi
cos *-
(h(h ++ kk++ l) ].
J
4-13)
4-13] EXAMPLES OF INTENSITY CALCULATIONS 135
135

Further simplification
simplification is possible for
is possible for various
various special
special cases:
cases:

IFI2
\F\
2 =
= 16(fs2
16(/s
2
+ fzn
/Zn2)
2
) when (h
(h + kk +
+ l) is odd;
I) is odd; (4-13)
(4-13)

(h +
+k+
IFI2
\F\
2= 16(18
= - /Z n) 2
16(/s - Jzn)2 when (h + l)1} is
is an odd multiple
multiple of
of 2;
2; (4-14)
(4-14)

IFI2
|^|
2 =
= 16(1s
16(/s + fZn)2
/zn)
2
(h + k
when (h k + I) is
l) is an even
even multiple
multiple of
of 2.
2. (4-15)
(4-15)

The intensity
intensity calculations
calculations are
are carried
carried out
out in
in Table
Table 4-3,
4-3, with
with some
some columns
columns
omitted for
for the sake of
the sake of brevity.
brevity.

TABLE 4-;1
4-3

I 2 3 4 5 6
Line ,,1., e sine (A-I) h ./Zn
A
--
I III 14.30 0.161 11.5 24.2
2 200 16.6 0.185 11.0 23.2
3 220 23.8 0.262 9.5 20.0
4 311 28.2 0.307 8.9 18.5
5 222 29.6 0.321 8.6 18.0
6 400 34.8 0.370 8.1 16.7

1 7 8 9 10 11

1 + cos 2 29 Relative intensity

line /<,,2
I'
sin 2 e cos9 Colc. Obs.

I 11490 8 30.1 10.0 vs

2 2380 6 21.9 1.1 w
3 13940 12 9.72 5.9 vs
4 6750 6.65 3.9 vs
5 1410 2: I 6.00 0.2 vw
6 9850 4.24 0.9 w

Remarks:
Remarks:
Columns
Columns 5 5 and (j: These \'aluc~
6: These values are
are read
read f!'Om
from scattel'ing-fartol'
scattering-factor ('urves
curves plotted
plotted
from the
the datu
data of of Apppndix
Appendix S.
8.

Column 7: 7: 1F12
\F\~ is
is obtain cd by
obtained by the
the use
use of
of Eq.
Eq. (4-13), (4-14), or
(4-13), (4-14), (4-15), depE'nrling
or (4-15), depending
on the
the parti('ular
particular valueR of hkl
values of hkl im'ol\cd.
involved. ThuR,
Thus, Eq. (4-13) if'
Eq. (4-13) for the III
is used for 111 re-
re-

flection
flection and
and Eq. (4-15)) for
Eq. (4-15 for the 220 reflection.
the 220 reflection.
Columnl!
Columns 10 10 and
and 11: 11: The agreement
agreement ohtained
obtained herehere between calculated
calculated and ob-
served intensities iR
served intensities is again
again satiRfa(tory.
satisfactory. In In thiR
this case,
case, the
the agreement
agreement is is good
good when
any pail'
any pair of
of lines
lines if'
is ! compared,
compared, becauRe
because of
of the
the limited
limited range
range of
of 8
6 values
values involved.
involved.
------------
One further
further remark
remark on on intensity
intensity ealrulations
calculations is
is necessary.
necessary. In In the powder
the powder
method,
method, two
two Ret.s
sets of
of planes
planes with
with different
different Miller
Miller indices
indices can
can reflect
reflect to
to the
the
same point
point on
on the
the film:
film: for
for example,
example, the
the planes (HI)
planes (411) and (330)
(330) in
in the
(h + k2 +
2 2
('ubic
cubic system,
system, since
since they
they have
have the value of
the same value of (h 22 + k + l2) and hence I )

the
the same spal'ing, or the planes
spacing, or the planes (501)(501) and (431)
(431) of
of the
the tetragonal
tetragonal system,
system,
 1"0
JLJO DIFFRACTION IIII: THE
DIFFRACTION INTENSITIES OF
THE INTENSITIES
: DIFFRACTED BEAMS
OF DIFFRACTED BEAMS [CHAP. 44
[CHAP.

since they
since they have
have the
the same values
same values of
of (h? +
2
and If. In
(h2 + fck22)) and In such
such aa case,
case, the
. the
intensity
intensity of
of each
each reflection
reflection must
must be
be calculated
calculated separately,
separately, since
since in
in general
general
the two
the two will
will have
have different
different multiplicity
multiplicity and
and structure factors, and
structure factors, and then
then
added to
added to find
find the
the total
total intensity
intensity of
of the
the line.
line.

4-14 Measurement
4-14 Measurement of of x-ray
x-ray intensity.
intensity. In In the
the examples
examples just
just given,
given, the
the
observed intensity was estimated
observed intensity was estimated simply by simply by visual
visual comparison
comparison of
of one
one line
line

with another.
with another. Although
Although this this simple
simple procedure
procedure is is satisfactory
satisfactory inin aa sur-
sur-
prisingly large
prisingly large number
number of of cases,
cases, there
there are
are problems
problems in which a more precise
in which a more precise
measurement of
measurement of diffracted
diffracted intensity
intensity is necessary. Two
is necessary. Two methods
methods are are in
in
general
general use
use today
today for
for making
making such
such measurements,
measurements, one
one dependent
dependent on
on the
the
photographic effect
photographic effect of
of x-rays
x-rays and
and the
the other
other on
on the
the ability
ability of
of x-rays
x-rays to
to ionize
ionize
gases
gases and
and cause
cause fluorescence
fluorescence of
of light
light in
in crystals.
crystals. These
These methods
methods have
have
already
already been
been mentioned
mentioned briefly
briefly in
in Sec.
Sec. 1-8
1-8 and will
will be
be described
described more fully
fully
in Chaps.
in Chaps. 66 and
and 7,
7, respectively.
respectively.

PROBLEMS

By adding
4-1. By
4-1. adding Eqs. (4-5) and (4-6)
Eqs. (4-5) and simplifying
(4-6) and simplifying the
the sum,
sum, show that E 3a,
show that ,

the resultant of these

the resultant of these two
two sine
sine waves,
waves, is
is also
also a
a sine
sine wave,
wave, of
of amplitude
amplitude

[Ai +
Aa3 == [A12
A + AA222* +
+ 2AIA2 fa -- .p2)1~
cos (.pI
2
2A,A 2 cos )] <*> 2

and
and of
of phase
phase
= tan" -;AI
.
1
sin fa + Az sin 92
</> 3 ^ ,

AI COS fa + A COS 02
,

4-2.
4-2. Obtain
Obtain the
the same
same result
result by
by solving
solving the
the vector
vector diagram
diagram ofof Fig. 4-11 for
Fig. 4-11 for the
the
right-angle triangle of which
right-angle triangle of which Aa
A 3 is
is the
the hypotenuse.
hypotenuse.
W.
4^3. Derive
Derive simplified
simplified expressions
expressions forfor F2
F2 for
for diamond,
diamond, including
including the rules
rules gov-
gov-
erning
erning observed
observed reflections.
reflections. This
This crystal
crystal is
is cubic
cubic and contains
contains 8 carbon atoms per
per
unit
unit cell, located in the following positions:
cell, located in the following positions:

000
000 HO $0i OH
011
ill
Hi Hi Hi Hi
iiI
H.
4-4. A
A certain
certain tetragonal
tetragonal crystal
crystal has
has four
four atoms
atoms of
of the
the same
same kind
kind per unit cell,
per unit cell,

1, !i 0 1,i, !\ 0 i,f, 0 IH-

at 0 iH.
located at
located l-
(a) Derive
(a) Derive simplified
simplified expressions for F2.
expressions for F2 .

(b) What
(b) What is
is the
the Bravais
Bravais lattice
lattice of
of this
this crystal?
crystal?
(c) What
(c) What are
are the
the values of F2
values of F2 for
for the
the 100,
100, 002, 111, and
002, 111, Oil reflections?
and 011 reflections?

W.
4-6. Derive
Derive simplified
simplified expressions for F2
expressions for F2 for
for the
the wurtzite
wurtzite form
form of
of ZnS,
ZnS, includ-
includ-
ing the rules governing observed
ing the rules governing observed reflections.
reflections. This
This crystal
crystal is
is hexagonal
hexagonal and
and con-
con-
tains 22 ZnS
tains ZnS per
per unit
unit cell,
cell, located
located in
in the
the following positions:
following positions:

Zn: 000, i
Zn:000, Hi
i 1,
S:OOI,lii.
S:OOf,Hi
 PROBLEMS 137
Note thatthat these
these positions translation, which may be
positions involve a common translation, be factored
factored
out
out ofof the
the structure-factor
structure-factor equation.
equation.
4.-6.
4-6. In In Sec.
Sec. 4-9,
4-9, in
in the part devoted to
the part to scattering
scattering when the the incident
incident and srat-
scat-
tered
tered beams make unequal unequal angles
angles with
witli the
the reflecting planes, it
reflecting planes, it is
is stated
stated that
that
"rays
"rays scattered
scattered by by all
all other
other planes
planes are
are in
in phase
phase with the corresponding
corresponding raysrays scat-
scat-
tered by
tered by the
the first
first plane."
plane." Prove this. this.
4.-7.
4-7. Calculate
Calculate thethe position
position (in
(in terms
terms ofof 8)
6) and the
the integrated
integrated intensity
intensity (in
(in rela-
rela-
tive
tive units)
units) ofof the
the first
first five
five lines
lines on the Debye pattern of
Debye pattern of silver with Cu Kat
silver made with Ka
radiation.
radiation. Ignore
Ignore the
the temperature
temperature and absorption
absorption factors.
factors.
4-8.
4-^8. A Debye-Scherrer
Debye-Scherrer pattern
pattern ofof tungsten
tungsten (BCC)
(BCC) isis made with Cu Ka Kat radia-
radia-
tion.
tion. The first first four
four lines
lines on this
this pattern
pattern were observed to to have the
the following
following 8 8
values:
values:
Line 86
1
1 20.3
20.3
2 29.2
33 36.7
4 43.6

Index
Index these
these lines
lines (i.e.,
(i.e., determine the the Miller indices of
Miller indices of each refiertion
reflection byby the
the use
use
of Eq.
of (3-10)
Eq. (3-10) and Appendix
Appendix 6)
6) and caleulate
calculate their
their relative
relative integrated
integrated intensities.
intensities.
4-9.
4-9. A Debye-Scherrer
Debye-Scherrer pattern
pattern isis made of of gray
gray tin,
tin, which has the the same struc-
struc-
ture
ture asas diamond,
diamond, with Cu Ka Kat radiation.
radiation. What are are the
the indices
indices of
of the
the first
first two lines
lines
on the
the pattern,
pattern, and what is is the
the ratio
ratio of
of the
the integrated
integrated intensity
intensity of
of the
the first
first to
to that
that
of
of the
the second?
second?
4.-10.
4-10. A Debye-Scherrer
Debye-Scherrer patternpattern isis made of of the
the intermediate phase InSb with
intermediate phase
Cu KaKat radiation.
radiation. ThisThis phase
phase hashas the
the zin!'-blende
zinc-blende strurture
structure and a lattice parameter
a lattice parameter
of 6.46A. What are
of 6.46A. are the
the indices
indices ofof the
the first
first two lines
lines on the pattern, and what is
the pattern, is

the ratio of
the ratio of the
the integrated
integrated intensity
intensity of of the
the first
first to
to the
the second?
second?
4.-11.
4-11. Calculate
Calculate thethe relative
relative integrated
integrated intensities
intensities of of the
the first
first six
six lines
lines of
of the
the
Debye-Scherrer pattern
Debye-Scherrer pattern of
of zinc,
zinc, made with
with Cu Kat
Ka radiation.
radiation. The indices
indices and ob-
served
served 8 6 values
values ofof these lines are:
these lines are:

Line
Line hkl
hkl 86
1 002 18.8
2 100 20.2
3 101 22.3
4 102 27.9
5 110, 103 36.0
6 004 39.4

(Line 5
(Line 5 is
is made upup of
of two unresolved
unresolved lines
lines from planes
planes of
of very
very nearly
nearly the
the same
spacing.)
spacing.) Compare
Compare your
your results
results with
with the
the intensities
intensities observed
observed in
in the
the pattern
pattern
shown inin Fig.
Fig. 3-13(b).
3-13(b).
 CHAPTER 5

LAUE PHOTOGRAPHS

B-1
6-1 Introduction.
Introduction. The experimental
experimental methods used in in obtaining
obtaining diffrac-
diffrac-
tion
tion patterns
patterns willwill bebe described
described in in this
this chapter
chapter and the the two following
following ones.ones.
Here we areare concerned with the Laue method only only from the the experimental
experimental
viewpoint;
viewpoint; its its main applications
applications will will & Be dealt
dealt with in in Chap.
Chap. 8. 8.

Laue photographs
photographs are are the easiest
easiest kind of of diffraction pattern to
diffraction pattern to make and
require
require only
only the
the simplest
simplest kind of of apparatus.
apparatus. White radiation radiation is is necessary,
necessary,
and the
the best
best source
source is is aa tube with a heayy-metal
heavy-meta! target, target, such
such as as tungsten,
tungsten,
SJQce
since the
the intensity
intensity of of the
the continuous
continuous spectrum
spectrum is proportional to
is proportional to the
the atomic
atomic
number of of the
the target
target metal.
metal. Good patterns patterns can can also
also bebe obtained
obtained with
radiation
radiation from other other metals,
metals, such as as molybdenum
molybdenum or or (opper.
copper. Ordinarily,
Ordinarily,
the
the presence
presence of of strong
strong characteristic
characteristic components,
components, such such as as WW Lai,
I.-a), Cu Ka,Ka,
Mo Ka,
Ka, etc.,
etc., in in the radiation'
radiation used,
used, does not complicatecomplicate the the diffraction
diffraction

pattern in
pattern in any
any way way or or introduce
introduce difficulties
difficulties inin its
its interpretation.
interpretation. Ruch Such a a
component will
component will only
only be reflected
reflected if if a
a set.
set of planes in
of planes in the
the ('rystal
crystal happens
happens to to
be oriented
oriented in just such a way
in just way that the the Bragg
Bragg law is is satisfied
satisfied forfor that
that com-
ponent,
ponent, and then the the only
only effect
effect will
will be thethe formation
formation of of a Laue spot spot ofof
exceptionally
exceptionally high high intensity.
intensity.
The specimen
specimen used used in in the
the Laue method is is aa single
single crystal.
crystal. This
This maymay
mean an isolated
isolated single
single crystal
crystal or or one particular
particular crystal
crystal grain,
grain, not not too
too
small,
small, in
in a
a polycrystalline aggregate. The only
polycrystalline aggregate. only restriction
restriction 011 on the
the size
size of
of aa
crystal
crystal in
in a polycrystalline
polycrystalline mass is is that
that itit must be no smaller smaller than than thethe
incident
incident x-ray
x-ray beam,
beam, if if the
the pattern
pattern obtained
obtained is is to
to correspond
correspond to to that
that crystal
crystal
alone.
alone.
Laue spots
spots are are often
often formed by by overlapping
overlapping reflections
reflections of of different
different
orders.
orders. For example,
example, the the 100,
100, 200,
200, 300,
300, ... reflections
. .reflections are
. are all
all superimposed
superimposed
since
since the
the corresponding
corresponding planes, planes, (100),
(100), (200),
(200), (300),
(300), ...... areare all
all parallel.
parallel.
The first-order
first-order reflection
reflection is is made up up of radiation of
of radiation of wavelength
wavelength )., X, the
the
second-order of of ),/2,
X/2, the
the third-order
third-order of
of ),/3, etc.,
X/3, etc., down to
to ).SWL,
XSWL, the
the short-
short-
wavelength
wavelength limit
limit of of the
the continuous
continuous spectrum.
spectrum.
The position
position of of any
any Laue spot spot is
is unaltered
unaltered by by aa change
change in in plane
plane spacing,
spacing,
since the only
only effect
effect ofof such
such a change
change is
is to
to alter
alter the
the wavelength
wavelength of of the
the
diffracted beam. It It follows
follows that
that two crystals
crystals of
of the
the same orientation
orientation and
crystal
crystal structure,
structure, but of of different
different lattice
lattice parameter,
parameter, will produce identical
will produce identical
Laue patterns.
patterns.

B-2
5-2 Cameras. Laue cameras are are so
so simple
simple to
to construct
construct that
that home-
made models are found inin a great many
great many laboratories.
laboratories. Figure
Figure 5-1
5-1 shows
shows
typical transmission
a typical transmission camera,
camera, in
in this
this case
case a
a commercial
commercial unit,
unit, and
and Fig.
Fig.
138
138
5-2J
5-2] CAMERAS
CAMERAS 139
139

FIG. 5-1. Transmission

FIG. 5-1. Transmission Laue
Laue camera.
camera. Specimen
Specimen holder
holder not
not shown. (Courtei<~'
(Courtesy
of
of General
General ElectriC'
Electric Co.,
Co., X-Ray
X-Ray Department.)
Department.)

5-2
5-2 illustrates
illustrates itsits essential
essential parts.
parts. A is
is the
the collimator,
collimator, a device used to
produce
produce a
a narrow
narrow incident
incident beam made up
up of
of rays
rays as
as nearly
nearly parallel
parallel as pos-
pos-
sible;
sible; it
it usually
usually consists
consists of
of two pinholes
pinholes in
in line,
line, one in
in earh
each of
of two lead
disks set
disks set into
into the
the ends
ends of of the
the collimator
collimator tuhe.
tube. c:(7 isis the single-erystal
single-crystal
specimen supported
specimen supported on
on the
the holder
holder B.
B. F
F is
is the
the li~ht-tight
light-tight film
film holdt'r, or
holder, OJ"
cassette,
cassette, made of
of aa frame,
frame, a
a removable I-l)~
metal
metal back, F
back, and a a sheet
sheet of of opaque
opaque
paper;
paper; the the film,
film, usually
usually 4 4 by
by 55 in.
in. in
in
A ('
size,
size, is
is sandwiched
sandwiched between
between the
the metal
metal
back and the paper. S
the paper. S isis the
the beam
s
13
stop, designed
stop, designed to
to prevent
prevent the
the trans-
trans-
mitted
mitted beam from from striking
striking the the film
film
and causing
causing excessive blackening. A
excessive blackening. 5-2. Transmi~~ion
FIG. 5-2.
FIG. Transmission Laue Laue camera.
camera.
140
140 LAUE PHOTOGRAPHS
LAUE PHOTOGRAPHS [CHAP. 55
[CHAP.

small copper
small copper disk,
disk, about
about 0.5
0.5 mm
mm thick,
thick, cemented
cemented on
on the
the paper
paper film
film cover
cover
serves very
serves well for
very well for this
this purpose:
purpose: it stops
it stops all
all but
but aa small
small fraction
fraction of of the
the
beam
beam transmitted
transmitted through
through the
the crystal,
crystal, while
while this
this small
small fraction
fraction serves
serves to
to
record
record the
the position
position of
of this
this beam
beam on
on the
the film.
film. The
The shadow
shadow of
of aa beam
beam stop
stop
of this
of this kind
kind can be seen
can be seen in
in Fig.
Fig. 3-6(a).
3-6(a).
The Bragg angle 8 corresponding
The Bragg angle corresponding to to any
any transmission
transmission Laue
Laue spot
spot isis found
found
very simply from the relation
very simply from the relation
Tl
tan 20
tan 28 =-,
= -> (5-1)
(5-1)
D
where r\
where Tl = distance
= distance of of spot
spot from
from center
center ofof film
film (point
(point of
of incidence
incidence of of trans-
trans-
mitted beam)
mitted beam) and and D =
= specimen-to-film
specimen-to-film distance
distance (usually
(usually 5
5 cm). Adjust-
cm). Adjust-
ment of
ment of the
the specimen-to-film
specimen-to-film distance distance is is best
best made by by using
using aa feeler
feeler gauge
gauge
of the
of the correct
correct length.
length.
The voltage
The voltage applied
applied to to the
the x-ray
x-ray tube
tube hashas aa decided
decided effect
effect on the the appear-
appear-
ance of
ance of aa transmission
transmission Laue Laue pattern.
pattern. It I t is
is of
of course
course true
true that
that the the higher
higher
the tube
the tube voltage,
voltage, thethe more
more intense
intense thethe spots,
spots, other
other variables,
variables, suchsuch as as tube
tube
current and
current and exposure
exposure time,time, being
being held
held constant.
constant. But there there is is still
still another
another
effect due
effect due to to the
the fact that the
fact that the continuous
continuous spectrum
spectrum is is cut
cut off
off sharply
sharply on on
the
the short-wavelength
short-wavelength side
side at
at a
a value
value of
of the
the wavelength
wavelength which
which varies
varies in-
in-

versely as
versely as the tube voltage
the tube voltage [Eq. [Eq. (1-4)].
(1-4)]. Laue spots
spots near the the center of of aa
transmission pattern
transmission pattern are are caused
caused by
by first-order
first-order reflections
reflections from planes
planes in-
in-

clined
clined at at very
very small
small Bragg
Bragg angles
angles to to the
the incident
incident beam. Only Only short-wave-
length
length radiation
radiation can can satisfy
satisfy the the Bragg
Bragg law for for such
such planes,
planes, butbut if if the
the tube
tube

voltage is
voltage is too
too low
low to to produce
produce the the wavelength
wavelength required,
required, the corresponding
corresponding
Laue
Laue spotspot will
will not
not appear
appear on on the pattern. It
the pattern. It therefore
therefore follows
follows that there
is
is a
a region
region near
near the
the center
center of of the
the pattern
pattern which is is devoid of of Laue spotsspots and
that
that thethe size
size of
of this
this region
region increases
increases as
as the
the tube
tube voltage
voltage decreases.
decreases. The
The
tube
tube voltage
voltage therefore
therefore affects
affects not
not only
only the
the intensity
intensity of
of each spot,
spot, but also
also
the number of
the number of spots.
spots. This
This is
is true
true also
also of
of spots
spots far
far removed from
from the center
center
of
of the
the pattern;
pattern; somesome of of these
these areare due
due toto planes
planes so so oriented
oriented and and of of such a a
spacing that
spacing that they they reflect
reflect radiation
radiation of
of wavelength
wavelength close
close to
to the
the short-wave-
short-wave-
length
length limit,
limit, and
and such
such spots
spots willwill be
be eliminated
eliminated by by aa decrease
decrease in in tube
tube voltage
voltage
no
no matter
matter how how long
long the
the exposure.
exposure.
AA back-retiection
back-reflection camera camera is is illustrated
illustrated in in Figs.
Figs. 5-3
5-3 and
and 5-45-4... Here
Here the the
cassette
cassette supports
supports both both the the film
film and
and the
the collimator.
collimator. The The latter
latter has has aa re-re-

duced
duced section
section at at one
one end
end which
which screws
screws into
into thethe back
back plate
plate ofof the
the cassette
cassette
and
and projects
projects aa short
short distance
distance in in front
front of
of the
the cassette
cassette through
through holesholes punched
punched
in
in the
the film
film and
and its
its paper
paper cover.
cover.
The
The Bragg
Bragg angleangle 8 for for anyany spot
spot onon aa back-reflection
back-reflection pattern
pattern may may be be
found
found from
from thethe relation
relation
o T2
tan
tan (180 - 20) == -,
(180 - 29) -> (5-2)
(5-2)
D
 5-2)
6-2] CAMERAS
CAlIERAS 141
141

FIG. ~3. Back - re ec tion L

Back-reflection Laue camera. The
aue camera. The specimen
specimen holder
holder shown
shown permits
permits
f L
spe<'imen, "
t
tm
the incident h 1
vertical adjustment of th6
beam. The
the incident beam.
the Spedme
The specimen \ as We
specimen shown
well
shown is
as rotation
" as rotation about
about an
an axis
** parallel
Pail to to
is aa coarse-grained polycrystalline one,
coarse-grained polycrystaJline one
positioned so
poBitioned so that
that only
only aa single,
single, selected
selected grain
grain will
will be
be struck
struck by
by the
the incident
incident beam!
beam.
FIG. ~4.
FIG. 5-4. Back-reflection
Back-reflection Laue camera
Laue camera (schematic).
(schematic).

where rr22 == distance

where distance ofof spot
spot from
from center
center ofof film and D == specimen-to-film
film and D specimen-to-film
distance
distance (usually
(usually 33 cm).
cm). InIn contrast
contrast toto transmission
transmission patterns,
patterns, back-reflec-
back-reflec-
tion
tion patterns
patterns may
may have
have spots
spots as
as close
close to
to the
the center of the
center of the film
film as
as the
the size
size
of the colhmator
of the collimator permits.
permits. Such
Such spots
spots areare caused
caused by by high-order
high-order over-
over-
lapping reflections
lapping reflections from
from planes
planes almost
almost perpendicular
perpendicUlar to to the
the incident
incident beam
beam.
bmce
Sinceeach
eachdiffracted beam isisformed
diffracted beam formed ofofaa number
numberofofwavelengths
wavelengths, thethe only
only
effect ofaa decrease
effect of decrease inin tube
tube voltage
voltage isis toto remove
remove one
one oror more
more short-wave-
short-wave-
length components
ength componentsfrom
from some
someofofthe
the diffracted
diffractedbeams.
beams. The Thelonger
longerwave-
wave-
lengths will still
lengths will still be
be diffracted,
diffracted, and
and the
the decrease
decrease inin voltage will not, in
voltage will not in '

general,remove
general, removeany
anyspots
spotsfrom
fromthe
thepattern.
pattern.
Transmission patterns
Transmission patterns can
canusually
usually bebe obtained
obtainedwith
with much
much shorter
shorterex-
ex-
posures than
posures than back-reflection
hack-reflection patterns.
patterns. For For example,
example, with
with aa tungsten-
tungsten-
targettube
target operatingatat3030kv
tubeoperating kvand
and2020mamaandandan
an aluminum crystal about
aluminum crystal about
1
1mm
mmthick,
thick,the
therequired exposureisisabout
requiredexposure about5 5minmininintransmission
transmissionandand
30 mm
30 min inback
in backreflection.
reflection. This
Thisdifference
differenceisisdue
duetotothe
thefact
factthat
thatthe
theatomic
atomic
scattering factor/ fdecreases
scatteringfactor decreasesasasthe
thequantity (sin 6) I>"increases,
quantity(sin0)/A increases,and
andthis
this
142
142 LAUE PHOTOGRAPHS
LAUE PHOTOGRAPHS [CHAP. 55
[CHAP.

quantity isis much

quantity much larger
larger inin back
back reflection
reflection than
than inin transmission.
transmission. Trans-
Trans-
mission patterns
mission patterns are
are also
also clearer,
clearer, in
in the
the sense of having
sense of having greater
greater contrast
contrast
between the
between the diffraction
diffraction spots
spots and
and the
the background,
background, since
since the
the coherent
coherent
scattering,
scattering, which
which forms
forms the
the spots,
spots, and
and the
the incoherent
incoherent (Compton
(Compton modified)
modified)
scattering,
scattering, which contributes
which contributes to to the
the background,
background, vary vary in in opposite
opposite waysways
with (sin 8)/)".
with (sin 0)/X. The The incoherent
incoherent scattering
scattering reaches
reaches its
its maximum
maximum value
value in
in

the back-reflection region,

the back-reflection region, as as shown
shown clearly
clearly in
in Fig. 3-6(a)
Fig. 3-6(a) and
and (b);
(b); it
it is
is

in this
in this region
region alsoalso that
that the the temperature-diffuse
temperature-diffuse scatteringscattering is most intense.
is most intense.
In both
In both Laue
Laue methods,
methods, the the short-wavelength
short-wavelength radiation radiation in in the
the incident
incident
beam will
beam will cause
cause mostmost specimens
specimens to emit K fluorescent
to emit fluorescent radiation.
radiation. If If this
this
becomes troublesome
becomes troublesome in in back
back reflection,
reflection, it it may
may be be minimized
minimized by by placing
placing aa
filter of
filter of aluminum
aluminum sheet sheet 0.010.01 in.
in. thick
thick inin front
front of of the
the film.
film.
If necessary,
If necessary, the the intensity
intensity of of aa Laue spotspot may be be increased
increased by by means
means
of an
of an intensifying
intensifying screen,
screen, as as used
used in in radiography.
radiography. This This resembles
resembles aa fluores-
fluores-
cent screen
cent screen in in having
having an an active
active material
material coated
coated on an inert inert backing
backing such such
as cardboard,
as cardboard, the
the active
active material
material having
having the
the ability
ability to
to fluoresce
fluoresce in
in the
the
visible region under
visible region under the actionthe action of
of x-rays.
x-rays. When such
such a
a screen
screen is
is placed
placed
with its
with its active
active face
face inin contact
contact withwith the film (Fig.
the film (Fig. 5-5), the film
5-5), the film is
is blackened
blackened
not only
not only byby thethe incident
incident x-rayx-ray beam but but also
also by by the
the visible
visible light
light which
which
the screen
the screen emits
emits under
under the the action
action of of the
the beam.
beam. Whereas fluorescentfluorescent screens
emit yellow light,
emit yellow light, intensifying
intensifying screens
screens are are designed
designed to to emit
emit blue
blue light,
light,
which
which is more effective
is more effective thanthan yellow
yellow in in blackening
blackening the film. Two kinds of
the film. of
intensifying
intensifying screens
screens are
are in
in use
use today,
today, one
one containing
containing calcium tungstate
tungstate
and
and the
the other
other zinc
zinc sulfide
sulfide with
with a a trace
trace ofof silver;
silver; the
the former is is most effective
effective
at
at short
short x-ray wavelengths
x-ray wavelengths (about (about 0.5A or
or less),
less), while the latter
latter can be
used
used at
at longer wavelengths.
longer wavelengths.
An intensifying
intensifying screen
screen should
should not be used if if it
it is
is important
important to record
fine detail in the Laue
fine detail in the Laue spots, spots, as
as in
in some studies
studies of
of crystal
crystal distortion,
distortion, since
since
the
the presence
presence of of the
the screen
screen willwill cause
cause thethe spots
spots toto become more diffuse than
diffuse than

paper s('reen
screen
film / back plate
plate
emulsion
film base

diffracted
beam D
Rrtive
r (a)
(a) (b)
(b)
active side
side
of
of screen
screen
FIG.
FIG. iHl.
5-6. Effect
Effect of
of double-coated
double-coated film
film
on appearance of
on appearance of Laue
Laue spot:
spot: (a)
(a) section
section
FIG. 5-5.
FIG. 5-5. Arrangement
Arrangement ofof film
film and
and through
through diffracted
diffracted beam
beam and
and film;
film; (b)
(b)
intensifying
intensifying screen
screen (exploded
(exploded view).
view). front
front view
view of
of doubled
doubled spot
spot on
on film.
film.
5-31
5-3] SPECIMEN HOLDERS 143

they
they would ordinarily
ordinarily bp.bo. Each particle
partir}p of
of thp
the srreen
screen whi('h
which is is strurk by
struck by
x-rays
x-rays emitR
emits light
light in all dlrp('tions
in all directions and thNefore
therefore hlackens
blackens thethe film
film outside
outside
the region
region blaC'kl'ned
blackened by by the
the diffracted
diffracted b{'am
beam itsl'lf,
itself, as
as suggP!'ted
suggested in in Fig.
Fig. 5-5.
5-5.
This effert
effect is
is aggraYUted
aggravated hy
by the
the fud
fact that
that most x-my
x-ray film
film is
is douhl{'-('oat.ed,
double-coated,
the two layer!oi
the layers ofof emulsion
emulsion hping
being sf'parated
separated by by an appreciahle
appreciable thI('kness
thickness of
of
film
film basl'.
base. EYen
Even when an inf,pnsifymg
intensifying screen
screen is
is not
not used,
used, double-('oated
double-coated
film causes til(>
film eauseH the size
size of
of ua dlffraetion
diffraction !'pot
spot formed by by an obliquely
obliquely incident
incident
beam to
heam to be larger than the
be larger the eross
cross Ae('tion
section ofof the
the l)('am it.Al'lf; in
beam itself; in extreme

cases, an apparent
('ases, apparent douhling
doubling of of the
the diffrartion
diffraction spot
spot I"('sults,
results, us as shown in in
Fig.5-H.
Fig. 5-0.

5-3
5-3 Specimen
Specimen holders.holders. BefoJ'e Before going
going into into thf'
the question
question of of Kpe('imen
specimen
holdNs,
holders, we might
might ronsider
consider tllP
the spe('imen
specimen itsf'lf
itself 01wiouAly,
Obviously, a
a spp('imen
specimen forfor
transmission method mW'lt
the transmission must have low low enough ah'lorpt.ion
enough absorption to
to transmit
transmit the
the
diffrart.ed b'ams;
diffracted beams; in pra('tice, this
in practice, this means that that relatiwly
relatively thi(k
thick sperimens
specimens
of
of a
a light
light element
element like
like aluminum may
may be
be uspd
used hut
but that
that the
the thi('kness
thickness of of a
a
fairly
fairly hea\'y
heavy element.
element likf'like ('oppel"
copper must.must b('be redu('pd,
reduced, by hy {t.rliing,
etching, forfor example,
example,
to
to a
a few thousandth!'
thousandths of of an inch inch On t.lw
the other
other hand,
hand, thethe spf'('imen
specimen must
not hI'
be too
too thin
thin oror the
the difTm,etf'd intensity will
diffracted intensity be too
will be too low,
low, Aim''
since the
the intensity
intensity
of a diffraet.ed
of It diffracted heam beam is is proportional
proportional t.o to t.he
the yoJume
volume of of diffraeting
diffracting material.
material.
In the
the ha('k-rl'fie(,tion
back-reflection method, method, there there IH is no restrietion
restriction on the the specimen
specimen
thickness
thickness and quite massive Hpecimf'ns
quite massiye specimens may may he be I'xamined,
examined, sinc'e
since the
the dif-
dif-
fraded
fracted hpams
beams originat.e
originate in in only
only a a thin
thin surfac'e
surface layer
layer of
of the
the Hp('eimen.
specimen. This
This
difference
difference between thf' the t.wo
two mtthods
methods may may be stat'dstated in in another
another wayway and
one which iA is well
well worth remrmbering:
remembering: any any information
information about
about aa thick
thick
spE'eimen
specimen obtained
obtained by
by t.hl'
the baek-refiection
back-reflection method applies
applies only to
only to a a
thin
thin surfaee
surface layer
layer of
of that
that sp('eimen,
specimen,
whereas information
information rec'orded
recorded on a
transmission
transmission patternpattern is is representative
represent at ive
of
of the
the eompletc thickness of
complete thickness of the
the speei-
speci-
men,
men, simply
simply because
because the the transmission
transmission
specimen
specimen must necessarily necessarily be be thin
thin

enough to
enough to transmit
transmit diffraeted
diffracted heams beams
from allall parts
parts of of its
its cross
cross section.
section.* *
There is is aa large variety
large variety of
of specimen
specimen
holders
holders in in use,
use, each suited to
each suited to some
pa.rticular purpose.
particular purpose. The simplest
simplest
consists
consists of of aa fixed
fixed post
post to to which the the
specimen
specimen is
is attached
attached with
with wax or
or

plasticine. A
plasticine. A more elaborate
elaborate holderholder is is
FIG* 5-7. Goniometer with
required when it
required it is
is necessary
necessary to to set
set aa rotation axes, (Courtesy of

crystal in
crystal in some particular
particular orientation
Supper
orientation Co,)

See
'

See Sec.
Sec. 9-5
9-5 for
for further
further discussion
discussion of
of this
this point.
point.
144
144 LAUE PHOTOGRAPHS [CHAP. 5
[CHAP. 5

relative
relative to to the
the x-ray
x-ray beam. In this this case,
case, a three-circle
three-circle goniometer
goniometer is used
is used

(Fig. 5-7) it
(Fig. 5-7); ;
it haS
has three
three mutually
mutually perpendicular
perpendicular axes axes ofof rotation,
rotation, two hori-hori-
zontal
zontal and one vertical,
vertical, and is so constructed that
is so that the crystal,
crystal, cemented
to
to the
the tip
tip of
of the
the short
short metal rod at at the
the top,
top, isis not displaced
displaced in in space
space by by
any of
any of the
the three
three possible
possible rotations.
rotations.
In
In the
the examination
examination of of sheet
sheet specimens,
specimens, it it is
is frequently
frequently necessary
necessary to to
obtain
obtain diffraction
diffraction patterns
patterns from various points on the
various points the surface,
surface, and this this
requires
requires movement of of the specimen,
specimen, between exposures,exposures, in in two directions
directions
at
at right
right angles
angles inin the
the plane
plane ofof the
the specimen
specimen surface,
surface, this
this surface
surface being per-
being per-
pendicular
pendicular to to the
the incident x-ray beam. The mechanical
incident x-ray mechanical stagestage from a a
microscope
microscope can be be easily converted to
easily converted to this
this purpose.
purpose.
IItt is
is often
often necessary
necessary to to know exactly
exactly where the the incident
incident x-ray
x-ray beam
strikes
strikes thethe specimen,
specimen, as, as, for
for example,
example, when one wants to to obtain
obtain a pattern
a pattern
from aa particular
particular grain,
grain, or
or a particular
particular partpart of of a
a grain,
grain, inin a poly crystalline
a polycrystalline
mass.
mass. This is is sometimes a rather difficult matter in
rather difficult in a back-reflection
a back-reflection
camera because of of the
the short
short distance
distance between the the film
film and the the specimen.
specimen.
One method is is to project aa light
to project light beam through
through the
the collimator
collimator and observe
observe
its
its point
point of
of incidence
incidence on the
the specimen
specimen with a
a mirror
mirror or
or prism
prism held
held near
near the
the
collimator.
collimator. An even simpler simpler method is
is to
to push
push a
a stiff
stiff straight
straight wire
wire through
through
the
the collimator
collimator and observeobserve where it it touches
touches the the specimen
specimen with with a a small
small
mirror,
mirror, of
of the
the kind used
used by dentists,
by dentists, fixed
fixed at
at an angle
angle to
to the
the end
end of
of a
a rod.
rod.

6-4 Collimators.
Collimators. Collimators of
Collimators of one
one kind or or another
another are are used
used inin all
all

varieties
varieties of
of x-ray cameras,
x-ray cameras, and it
it is
is therefore
therefore important
important to
to understand
understand their
their
function and to
function to know what they they can and cannot do. do. To "collimate"
"collimate"
means, literally,
means, literally, t.o
to "render
"render parallel,"
parallel," and the
the perfect
perfect collimator
collimator would
would
produce
produce a
a beam composed
composed of
of perfectly parallel
perfectly parallel rays. rays. Such a
a collimator
collimator
does
does not exist, and the
not exist, the reason,
reason, essentially,
essentially, lies
lies in
in the
the source
source of of the
the radia-
radia-
tion,
tion, since
since every source
every source emits
emits radiation
radiation in
in all
all possible directions.
possible directions.
Consider the
Consider the simplest
simplest kind
kind ofof collimator
collimator (Fig. 5-8), consisting
(Fig. 5-8), consisting of of two
circular apertures of
circular apertures of diameter
diameter d separated
d separated by distance u,
by a distance u, where u is is

large
large compared
compared to to d.
d. If
If there
there isis a
a point
point source
source of of radiation
radiation at at S,
S, then
then all
all

the
the rays in the
rays in the beam from the the collimator
collimator areare nonparallel,
nonparallel, and the the beam is is

conical
conical in
in shape
shape with
with a a maximum angle angle of divergence fJl
of divergence f$\ given
given byby the
the

"r. I
====~.tl=====:
t : -v====-u_-_-_-_-_-_ -1-\:1

FIG. 5-8.
FIG. 5-8. Pinhole
Pinhole collimatol'
collimator and small
small source.
source.
5-4)
5-4] COLLIMATORS 145
equation Pl d/2
equation
tan-
t
tan
Hi
= d/2
= -,
2 vv
where vv is
is the distance
distance of
of the
the exit
exit pinhole
pinhole from the
the source. Since Pl is
source. Since is 1

always
always very
very small,
small, this
this relation
relation can be
be closely
closely approximated
approximated byby the
the equa-
equa-
tion
tion
d
fJl ==
ft i -- radian.
radian. (5-3)
(5-3)
vv
Whatever we do to decrease fJl
to decrease 0\ and therefore
therefore render
render the the beam more
nearly parallel
nearly parallel will
will at
at the
the same time decrease
decrease the
the energy
energy of
of the
the beam. We
note also
also that
that the
the entrance
entrance pinhole
pinhole serves
serves no function
function when the
the source
source is
is

very small,
very small, and may
may be omitted.
be omitted.
No actual
actual source
source is is aa mathematical
mathematical point,
point, and,
and, inin practice,
practice, we usually
usually
have to
to deal
deal with x-ray
x-ray tubes which have focal focal spots
spots ofof finite
finite size,
size, usually
usually
rectangular
rectangular inin shape.
shape. The projected
projected shape
shape of
of such a a spot,
spot, at
at aa small
small target-
target-
to-beam angle,
angle, isis either
either a a small
small square
square or
or aa very
very narrow line line (Fig.
(Fig. 1-16),
1-16),
depending
depending on the the direction
direction of of projection.
projection. Such sources
sources produce
produce beams
having
having parallel,
parallel, divergent,
divergent, and convergent
convergent rays.
rays.
Figure
Figure 5-9 illustrates
illustrates thethe case
case when thethe projected
projected source
source shape
shape isis square
square
and of
of such a height
height h thatthat convergent
convergent rays
rays from the the edges
edges of of the
the source
source
cross
cross at
at the
the center
center of of the
the collimator
collimator and thenthen diverge.
diverge. The maximum
divergence
divergence angle
angle is is now given
given by
by
2d
fJ2 =
($2 = - radian,
radian,
,.
(5-4)
(5-4)
u

and the
the center
center of
of the
the collimator
collimator may
may be
be considered
considered as
as the
the virtual
virtual source
source of
of
these
these divergent
divergent rays.
rays. The beam issuing
issuing from the
the collimator
collimator contains
contains not
not
only
only parallel
parallel and divergent
divergent rays
rays but
but also
also convergent
convergent ones,
ones, the
the maximum
angle
angle of
of convergence
convergence being
being given
given by
by

d
a = --radian
radian, (5-5)
(5-5)
u+w
u + w '
('

I-------------v------------

FIG.
FIG. 5-9.
5-9. Pinhole
Pinhole collimator
collimator and large source. S =
large source. = source, (7 =
source, C = crystal.
crystal.
146
146 LAUE PHOTOGRAPHS
LAUE PHOTOGRAPHS [CHAP. 55
[CHAP.

where
where w isis the
w the distance
distance of
of the
the crystal
crystal from
from the
the exit
exit pinhole.
pinhole. The
The size
size of
of
the source
the source shown
shown in
in Fig. 5-9
Fig. 5-9 is given
is given by
by
/2u \
(5-6)
(5-6)
-d(--l).
\u /

In practice,
In practice, vv is
is very
very often
often about
about twice
twice as
as large
large as u, which
as u, which means
means that
that the
the
conditions illustrated
conditions illustrated inin Fig. 5-9 are
Fig. 5-9 are achieved
achieved when thethe pinholes
pinholes are
are about
about
one-third the
one-third the size
size of
of the
the projected
projected source. If the
source. If the value
value of
of hh is
is smaller
smaller than
than
that given
that given by
by Eq.
Eq. (5-6),
(5-6), then
then conditions
conditions will
will be
be intermediate
intermediate between
those shown
those shown in
in Figs. 5-8 and 5-9;
Figs. 5-8 5-9; as
as hh approaches
approaches zero, the maximum
zero, the
divergence angle
divergence angle decreases
decreases from
from the
the value
value given by Eq.
given by Eq. (5-4)
(5-4) to that
to that given
given
by Eq.
by Eq. (5-3)
(5-3) and
and the
the proportion
proportion of
of parallel
parallel rays
rays in
in the
the beam and the
the max-
imum convergence
convergence angle both approach
angle both approach zero.
zero. When h exceeds exceeds thethe value
value
given by Eq. (5-6),
given by Eq. (5-6), none
none of
of the
the conditions
conditions depicted
depicted in
in Fig.
Fig. 5-9 are
are changed,
changed,
and the
and the increase
increase in the size
in the size ofof the
the source
source merely
merely represents
represents wasted energy.energy.
When the the shape
shape of of the
the projected
projected source
source is is aa fine
fine line,
line, the
the geometry
geometry of of
the beam
the beam varies
varies between
between two extremes
extremes in in two mutually
mutually perpendicular
perpendicular
planes. In
planes. In aa plane
plane at at right
right angles
angles to
to the
the line
line source,
source, thethe shape
shape isis given
given byby
Fig. 5-8,
Fig. 5-8, and in
in a
a plane
plane parallel
parallel to
to the
the source
source by
by Fig.
Fig. 5-9.
5-9. Aside from the
the
component which
component which diverges
diverges in in the
the plane
plane ofof the
the source,
source, thethe resulting
resulting beam
is shaped
is shaped somewhat
somewhat like
like a
a wedge.
wedge. Since
Since the
the length
length of
of the
the line source
line
greatly
greatly exceeds
exceeds the
the value
value given by Eq.
given by Eq. (5-6),(5-6), a large
large fraction
fraction of
of the x-ray
x-ray
energy
energy is
is wasted
wasted with
with this
this arrangement
arrangement of
of source
source and collimator.
collimator.
The extent
extent of of the
the nonparallelism
nonparallelism of of actual
actual x-rayx-ray beams may be illus- illus-

trated by taking, as typical

trated by taking, as typical values, values, d
d =
= 0.5
0.5 mm,
mm, u =
= 5
5 cm,
cm, and w =
= 3 cm.
Then Eq.
Eq. (5-4)
(5-4) gives
=
gives {322 = 1.15
1.15 and Eq. Eq. (5-5)
(5-5) gives
=
gives a = 0.36. These
a 0.36. These
values
values may
may of of course
course bebe reduced
reduced by by decreasing
decreasing the size size of
of the pinholes,
pinholes, forfor
example,
example, but but this
this reduction
reduction will will be
be obtained
obtained at at the
the expense
expense of of decreased
energy
energy inin the
the beam and increased
increased exposure
exposure time.time.

6-6
6-5 The shapes
shapes ofof Laue spots.
spots. We will
will see
see later
later that Laue spots spots be-
come smeared out if the reflecting
come smeared out if the reflecting crystal crystal is
is distorted.
distorted. Here,
Here, however,
however,
we are
are concerned
concerned with the the shapes
shapes of of spots
spots Qbtaioe!L.gom
obained__from perfect, perfect, undis-
undis-
torted
torted crystals.
crystals. These
These shapes
shapes are greatly infl~nced
are greatly influenced by by the nature
nature of of the
incident
incident beam,
beam, i.e.,
i.e., by
by its
its convergence
convergence or divergence, and it
or divergence, it is
is important
important
to
to realize
realize this
this fact,
fact, or
or Laue spots
spots ofof "unusual" shape shape may be erroneously
erroneously
taken
taken as evidence of
as evidence of crystal
crystal disto~tion.
distortion. .
Consider
Consider the the transmission
transmission case case first,
first, and assume that the crystal crystal isis thin

and larger
larger than
than the
the cross
cross se~tion
section of
of the
the primary
primary beam at
at the point
point of
of inci-
inci-

dence. If
dence. If this
this beam is is mainly divergent,
mainly divergent, which is
is the
the usual
usual case
case in
in practice
practice
(Fig.
(Fig. 5-8
5-8 oror 5-9),
5-9), then
then aa focusing
focusing action
action takes
takes place
place on diffraction.
diffraction. Figure
Figure
5-10
5-10 isis a
a section
section through
through the the incident
incident beam and any any diffracted
diffracted beam;beam; thethe
incident beam,
incident beam, whose cross
cross section at any point
section at any point is
is circular,
circular, is
is shown issuing
issuing
5-5)
5-5] THE SHA.PES
SHAPES 01'
OF LAUE SPOTS 147
147

c
,.,
/--;.
--- - ...
---

----..
--,.,--
R
H
- ellllT.(ll-------~----
---------tII-
- -- - - -- - ~

FIG.
FIG. 5-10.
5-10. FocuHing
Focusing of
of diffra(terl
diffracted heam
beam in
in the
the transmission
transmission Laue method.
method. ,Ii
S == T

source,
source, C =
= rrystal,
crystal, F =
= f()('al
focal point.
point.

from a smaH small source,

source, real real oror virtual.
virtual. Each ray ray ofof the
the .nddent
incident beam which
lies
lies in
in the plane of
the plane of the
the drawing
drawing strikes
strikes thethe reflecting
reflecting lattice
lattice planes
planes ofof the
the
crystal
crystal at at aa slightly
slightly different
different Bragg angle,
Bragg angle, this
this angle
angle being
being a
a maximum t .
i
'

A and decreasing progressively

decreasing progressively toward
toward B.
B. The lowermost
lowermost rays
rays are
are there-
there-
fore
fore deviated
deviated throughthrough a a greater angle 26
greater angle 28 than
than thethe upper
upper ones,ones, with
with thethe
result that
result that thethe diffra('ted
diffracted beam convergesconverges to
to a
a focus
focus at
at F.
F. This is
is true
true
only (J
only of thethe rays
rays in in the
the plane
plane of of the
the drawing;
drawing; thosethose inin a
a plane
plane at at right
right angles
angles
continue
continue to to diverge after diffraction,
diverge after diffraction, with
with the
the result
result that
that th'
the diffracted
diffracted
beam is is ellipti(:al
elliptical in in cross
cross section.
section. The film film intersects
intersects different
different diffracted
diffracted
beams at at dl,Terent
diJerent distances
distances fromfrom thethe ('ryst.al,
crystal, so so elliptical
elliptical spots
spots ofof various
various
sizes
sizes are
are observed,
observed, as as shown in in Fig. 5-11. This
Fig. 5-11. This is is not
not a a sket('h
sketch of of a
a Laue
pattern
pattern but but an an illustration
illustration of of spot
spot size
size and shape
shape as as a a function
function of of spot
spot
position in
position in one
one quadrant
quadrant of of the
the film.
film. Not'
Note that.
that the
the spots
spots are are all
all elliptical
elliptical
with
with their
their minor axes axes aligned
aligned in in aa radial direction and that
radial direct.ion that spot.!'!
spots near
near thethe
center
center and edge edge of
of the
the pattern
pattern are
are thicker
thicker than
than those
those in
in intermediate
intermediate posi-
posi-
tions,
tions, thethe latter
latter being being formro
formed by by beams np,.'l.r
near their
their focal point. Spots
focal point. Spots
having
having the the shapes
shapes illustrated
illustrated are are fairly
fairly common,
common, and Fig. 3-6(a) is
Fig. 3-6(a) is an

example.
example.
In
In back
back reflection,
reflection, no focusing o(~-
no focusing oc- _
curs
curs and a a divergent
divergent incident incident beam
intinues to
1ntinues
ter
to diverge
ter diffraction.
1e spots are
..* near
diverge in
diffraction. Back-reflection
le spots are therefore
near the
I they
in all
all directions

therefore more or
the center
they become
center of
directions
Back-reflection

of the
or less
less
pat-
the pat-
become increasingly
,
-----t--.-
1
increasingly
ward the the edge,
edge, due to to the
the
~nce of
.>nce of the
the rays
rays on
on the
the
)r
)r axes
axes of of the
the ellipses
ellipses
18.tely
lately radial.
radial. Figure
Figure FIG.
FlG 5-11.
^_ 1L Shape
.
shape of of transmission
transmission
,11.1.
.al. I,aue
Laue spots
spots as
as a
a function
function of position.
of position.
148
148 LAUE PHOTOGRAPHS [CHAP. 5
[CHAP. 5

PROBLEMS

6-1.
5-1. A transmission
transmission Laue pattern
pattern isis made of of an aluminum crystalcrystal with 4O-kv
40-kv
tungsten
tungsten radiation.
radiation. The film film is
is 55 cm from the the crystal.
crystal. How close close to
to the
the center
center
of
of the
the pattern
pattern can
can Laue spots
spots be formed by by reflecting planes of
reflecting planes of maximum spacing,
spacing,
namely (111), and those
namely (111), those of
of next
next largest
largest spacing,
spacing, namely
namely (200)?
(200)?
6-2.
6-2. A transmission
transmission Laue pattern
pattern isis made of of an aluminum crystal
crystal with
with a a speci-
speci-
men-to-film
men-to-film distance
distance of of 5
5 cm.
cm. The (111)
(111) planes
planes ofof the
the crystal
crystal make an angle angle ofof
~o
3 with
with the
the incident
incident beam. What minimum tube tube voltage
voltage is
is required
required to
to produce a
produce a
111 reflection?
111 reflection?
6-3. (a) A back-reflection
6-3. (a) back-reflection Laue pattern
pattern is is made of of an aluminum crystal
crystal at at 50
50
kv.
kv. The (111) planes make an angle
(111) planes angle ofof 88 0 with
with the
the incident
incident beam. What orders orders
of
of reflection
reflection are present in
are present in the
the beam diffracted
diffracted byby these
these planes?
planes? (Assume
(Assume that that
wavelengths
wavelengths larger
larger than
than ? 0 A are
are too
too weak and too too easily
easily absorbed
absorbed by air to
by air to regis-
regis-
ter the film.)
ter on the film.)

(6) What orders

(b) orders ofof the
the 111
111 reflection
reflection are
are present
present ifif the
the tube
tube voltage
voltage isis reduced
reduced
. ) 40
'

40 kv?
) kv?
 CHAPTER 66

POWDER PHOTOGRAPHS

6-1
6-1 Introduction.
Introduction. powder method of
The powder of x-ray
x-ray diffraction
diffraction was de- de-
vised
vised independently
independently in in 1916 by by Debye
Debye and Scherrer Scherrer in in Germany
Germany and in in
1917 by
1917 by Hull
Hull in in the
the United
United States.
States. It It is
is the
the most generally
generally useful
useful of of all
all

diffraction
diffraction methods and, and, when properly
properly employed,
employed, can can yield
yield a
a great
great dealdeal
of
of structural
structural information
information about the the material
material under investigation.
investigation. Basi-
Basi-
cally,
cally, this
this method involves
involves the the diffraction
diffraction of of monochromatic x-rays x-rays by by a
powder specimen.
powder specimen. In this
this connection,
connection, "monochromatic" usually
usually means
the
the strong
strong K K characteristic
characteristic component
component of of the
the general
general radiation
radiation from an
x-ray
x-ray tube
tube operated
operated above the the K excitation potential of
excitation potential of the
the target
target rnate-l
mate-]
rial.
rial. "Powder" can can mean eithereither an actual, physical
actual, physical powder powder held
held together
together I
with
with a a suitable
suitable binder
binder or or any
any specimen
specimen in in polycrystalline
polycrystalline form. form. The
method is is thus
thus eminently
eminently suited for metallurgical
suited for metallurgical work, work, since
since single
single crys-
crys-
tals
tals are
are not
not always
always available
available to to the
the metallurgist
metallurgist and such such materials
materials as as
polycrystaIIine
polycrystalline wire, wire, sheet,
sheet, rod,
rod, et.c.,
etc., may
may be examined nondestructively
nondestructively
without
without any any special
special preparation.
preparation.
There
There are are three
three main powderpowder methods in in use,
use, differentiated
differentiated by by the
the rela-
rela-
tive
tive position
position of of the
the specimen
specimen and film: film:
(1) method. The film
Debye-Scherrer method.
(1) Debye-Scherrer film is placed on
is placed on the
the surface
surface ofof aa cylin-
cylin-
der
der and
and the specimen on
the specimen on the
the axis
axis ofof the
the cylinder.
cylinder.
(2) method. The film,
Focusing method.
(2) Focusing film, specimen,
specimen, and x-ray x-ray source
source are
are all piaced
all placed

on
on the
the surface
surface of of a
a cylinder.
cylinder.
(3)
(3) Pinhole method. The film
Pinhole method. film isis flat,
flat, perpendicular
perpendicular to to the
the incident
incident x-ray
x-ray
beam,
beam, and located
located at
at any
any convenient
convenient distance
distance from the
the specimen.
specimen.
In
In all
all these
these methods,
methods, the the diffracted
diffracted beams lie lie on
on the
the surfaces
surfaces ofof cones
cones
whose axesaxes lie
lie along
along the
the incident
incident beam or
or its
its extension;
extension; each
each cone
cone of
of rays
rays
is
is diffracted
diffracted fromfrom a a particular
particular set
set of
of lattice
lattice planes.
planes. In
In the
the Debye-Scherrer
Debye-Scherrer
and focusing
focusing methods,
methods, only only a a narrow stripstrip ofof film
film isis used
used and the the recorded
recorded
diffraction
diffraction pattern
pattern consists
consists of of short
short lines
lines formed by by the
the intersections
intersections of of the
the
cones
cones of of radiation
radiation withwith thethe film.
film. In
In the pinhole method,
the pinhole method, the the whole cone cone
intersects
intersects thethe film
film toto form a a circular
circular diffraction
diffraction ring. ring.

6-2
6-2 Debye-Scherrer
Debye-Scherrer method.
method. A typical
typical Debye
Debye camera
camera isis shown in in

Fig. ~
Fig. 1. It
6-1. It consists
consists essentially
essentially of
of a
a cylindrical
cylindrical chamber with
with aa light-tight
light-tight
cover,
cover, aa collimator
collimator to
to admit
admit and define
define the
the incident
incident beam,
beam, aa beam stop
stop to
to
confine
confine and stop
stop the
the transmitted
transmitted beam,
beam, a
a means for
for holding
holding the
the film
film
tightly
tightly against
against the
the inside
inside circumference
circumference of of the
the camera,
camera, and a a specimen
specimen
holder that
holder that can
can be
be rotated.
rotated.
149
149
150
150 POWDER PHOTOGRAPHS
POWDER PHOTOGRAPHS [CHAP. 66
[CHAP.

FIG. 6-1.
FIG. 6-1. Debye-Scherrer camera,
Debye-Scherrer camera, with
with cover
cover plate
plate removed.
removed. (Courtesy of
(Courtesy of
North American
North American Philips
Philips Company,
Company, Inc.)
Inc.)

Camera
Camera diameters
diameters vary vary from about about 55 to to about
about 2020 cm.
cm. The The greater
greater the
the
diameter,
diameter, the
the greater
greater the
the resolution
resolution or
or separation of a partieular
separation of a particular pair of pair of
lines on
lines on the
the film.
film. In In spectroscopy,
spectroseopy, resolving
resolving power
power is is the
the power
power of of dis-
dis-
tinguishing between
tinguishing between two two components
components of of radiation
radiation which
whieh have
have wavelengths
wavelengths
very close together
very close together and and isis given
given by 'AI ~A, where
by X/AX, where AX ~A isis the
the difference
differenee be-
be-
tween the
tween the two wavelength~ and
two wavelengths and XAisis their
their mean
mean value;
value; inin crystal-structure
crystal-strueture
analysis, we
analysis, we may
may take
take resolving
resolving power
power as as the
the ability
ability to
to separate
separate diffraction
diffraetion
lines from
lines from sets
sets ofof planes
planes of of very
very nearly
nearly the the same
same spacing,
spacing, or or as
as the
the value
value
of d/ ~d. ** Thus,
of d/M. Thus, ifif SS isis the
the distance
distanee measured
measured on on the
the film
film from
from aa particular
partieular
diffraction line
diffraction to the
line to the point
point where
where thethe transmitted
transmitted beambeam would
would strike
strike the
the
film (Fig.
film 6-2), then
(Fig. 6-2), then
SS == 2dR
28R
*
*Resolving
Resolving power
power is often
often defined
is defined by
by the
the quantity ~A/A, which
quantity AX/X, which is the
the reciprocal
reciprocal
is
of that given
of that given above.
above. However, the
However, power of
the power of resolving
resolving two
two wavelengths
wavelengths whichwhich are
are
nearly alike isis aa quantity
nearly alike quantity which
which should
should logically increase as
logically increase ~A, the
as AX, the difference
difference be-
be-
tween
tween the
the two
two wavelengths
wavelengths toto be
be separated,
separated, decreases.
decreases. This
This isis the
the reason
reason for
for the
the
definition given
definition given in
in the
the text.
text. The same
The same argument
argument applies
applies to
to interplanar
interplanar spacings
spacings d.d.
6-2J
6-2] DEBYE-SCHERRER METHOD
DEBYE-SCHERRER METHOD 151
151

and
and flS =
AS = #A20,
Rfl28, (6-1)
(6-1)

where R
where R isis the
the radius
radius ofof the camera. Two
the camera. Two sets
sets of
of planes
planes of
of very
very nearly
nearly
the same
the same spacing
spacing willwill give
give rise
rise to
to two
two diffracted
diffracted beams
beams separated
separated byby aa
small angle
small angle A20; for aa given
fl20; for givpn value
value of
of A20, Eq. (6-1)
fl20, Eq. shows that
(O-I) shows that AS, the
flS, the
separation
separation of
of the
the lines
lines on
on the
the film,
film, increases
increases with
with R.
R. The
The resolving
resolving power
power
may be
may be obtained
obtained by
by differentiating
differentiating the
the Bragg
Bragg law:*
law:*
= 2d
XX = sin 0
2d sin , /~----------- /

dO
d0 -1
-1
/ :\8
R
- = - tan
tan 0.
O. , (6-2)
(6-2) \
dd d
d
,

20 ..i.
But
But
dS
_
=-.
dO6 ~
2R
Therefore
Therefore

dS -2R
2R ^
FIG. 6-2. ^
1G ^"^'
' Geometry
eome^ ry of the Debye-
- == --tanO.
an '.

0, Scherrer
Scherrer method. Hection through
Section through
dd
dd d
d film and one
film one diffraction
diffraction cone.
cone. l:S
^
d -2R
Hesolving power
Resolving power =
=- =
= - - tan
tan 0,
0, (6-3,
(6-3,
fld
Arf flS
AS
where d
where d is
is the
the mean spacing
spacing of of the
the two setssets ofof planes,
planes, fld the difference
Ad the difference inin
their
their spacings,
spacings, and flS AS the the separation
separation of of two diffraction
diffraction lines
lines which appear
appear
just resolved
just resolved on on the
the film.
film. Equation
Equation (6-3) Jlh,Qws shows that the...r.c&.l.lY.ing
the rcsolyjng powerpower
increases
increases with
with the
the size
size of of the
the camera;
camera; thisthis increased
increased resolution
resolution is is obtained,
obtained,
however,
however, at at the
the cost
cost of of increased
increased exposure
exposure time, time, and the the smaller cameras
are
are usually preferred
usually preferred for
for all
all but
but the
the most .complicat.ed
complicated patterns.
patterns. A camera
diameter
diameter of of .5.73
5.73 em
cm isis often used and will
often used will beJo1;lnd
be found suitahle
suitable forfor most work.
This particular dia~ete!J-.~CLmtl
This particular diameter, .equal to"ij1O to 1/10 the the number of of degrpcs
degrees in in a radian,
radian,
facilitates
facilitates ealculation,
calculation, since
since 0, (in qegrees)
0, (in degrees)
is
is obtained
obtained simply
simply by
by multipli-
multipli-
cation
cation ofof S
S (in
(in em)
cm) byby 10, 10, excppt
except for certain corre~eions
for certain corrections necessary
necessary in in pre-
pre-
cise work. Equation
cise work. Equation (6-3) (6-3) also
also shows that
that the
the resolving power
resolving power of a given
given
camera
camera increases
increases with
with 0, 0, being
being directly
directly proportional
proportional to to tan O. 0.

The increased
increased exposure
exposure time time requirpd
required by by an increase
increase in camera diameter
in camera diameter
is
is due
due not
not only
only toto the
the decrease
decrease in intensity "f
in intensity <rf the diffracted
diffracted beam with
with
increased
increased distance
distance from
from the specimen, but al;~
the specimen, also to the partial
partial absorption
absorption
of
of both
both thethe incident
incident andand diffracted
diffracted beams
beams by by the
the air
air in
in the
the camera.
camera. For For
example,
example, Prob.
Prob. 1-7
1-7 and
and the
the curves
curves of
of Fig.
Fig. 6-3
6-3 show
show that,
that, in
in aa camera
camera of
of
19
19 em
cm diameter
diameter (about
(about the the largest
largest in in common
common use), use), the
the decrease
decrease in in in-
in-

tensity
tensity duedue to
to air
air absorption
absorption is is about
about 20 20 percent
percent for Cu Ka
for Cu Ka radiation
radiation andand
about
about 52 52 percent
percent for
for Cr
Cr Ka
Ka radiation.
radiation. This
This decrease
decrease in
in intensity
intensity may
may be
be

* A
A lower-case
lower-case roman
roman dd is
is used
used throughout
throughout this
this book
book for
for differentials
differentials in
in order
order to
to
avoid
avoid confusion
confusion with
with the symbol dd for
the symbol for distance
distance between
between atomic
atomic planes.
planes.
152
152 POWDER PHOTOGRAPHS [CHAP. 6
[CHAP. 6

avoided by by evacuating
evacuating the camera or Zl00
by filling it with a light gas such as
as
o
.....
by filling it light gas 'Xl
hydrogen
hydrogen or or helium during during the the ex- ex- ~
..... 75
,-!;
posure.
posure. 00
Z
Correct
Correct design
design of of the
the pinhole
pinhole system
system
which collimates
collimates the the incident
incident beam is is
pa50
Eo<
important,
important, especially
especially when weak dif- dif- Eo<
fracted
fracted beams must be recorded. recorded. The
Z
r.."l 25
exit
exit pinhole
u
pinhole scatters
scatters x-rays
x-rays in in all
all di-
di- p::
'rections,
rections, and these these scattered
scattered rays, rays, if if !l: o~__~____~__~~__~
not prevented
prevented from striking striking the film, film, o 55 10
10 15
15 20
can
can seriously PATH LENGTH (em)
seriously increase
increase the intensity
intensity
(cm)
FIG.
FIG. 6-3.
6-3. Absorption
Absorption of of CuKa
Cu Ka andand
of
of the
the background.
background. A "guarded-
"guarded-
Cr Ka radiation
radiation by by air.
air.
pinhole"
pinhole" assembly
assembly which practically practically
eliminates
eliminates this this effect
effect is is shown in in Fig.
Fig. 6-4,
6-4, where the the divergent
divergent and con- con-
vergent rays
vergent rays in
in the incident
incident beam are
are ignored
ignored and only
only the
the parallel
parallel com-
ponent
ponent is is shown.
shown. The collimator collimator tube tube is is extended
extended a a considerable
considerable distance
distance
beyond
beyond the the exit
exit pinhole
pinhole and constricted
constricted so so that the end A is
that the is close
close enough
enough
to
to the
the main beam to to confine
confine the the radiation
radiation scatteredscattered by by thethe exit
exit pinhole
pinhole
to
to a very
very narrow angular angular rangerange and yet yet not not dose
close enough
enough to to touch
touch thethe
main beam and be itself itself a cause of of further
further scattering.
scattering. The heam beam stop stop is
is

usually
usually a thick piece of
thick piece of lead
lead glass placed behind
glass placed behind aa fluorescent
fluorescent screen,
screen, thethe
combination allowing
allowing the transmitted beam to
the transmitted to be
be "iewpd
viewed with with safety
safety when
adjusting
adjusting the camera in
in front
front of
of the
the x-ray
x-ray tube.
tube. Back scatter
scatter from
from thethe
stop
stop is
is minimized by extending
by extending the
the hearn-stop
beam-stop tube
tube backward and con-
con-
stricting
stricting itsits end B. B. Another reason reason for for extending
extending the collimator and
the collimator and
beam-stop
beam-stop tubes
tubes as
as close
close to
to the
the specimen
specimen as
as possible
possible is
is to
to minimize
minimize the
the
extent
extent toto which the primary beam is
the primary scattered by air, as it
is scattered by air, as it passes through passes through
the camera.
the camera. Both tubes are tapered to
are tapered interfere as
to interfere as little
little asas possible
possible with
with
low-angle and high-angle
low-angle high-angle diffracted
diffracted beams. beams.
Some cameras
cameras employemploy rectangular
rectangUlar slits slits rather
rather than pinholes to
than pinholes define
to define
the beam,
the beam, the the long edp;es of
long edges of the
the slits being parallel
slits being parallel to to thethe axis
axis ofof the
the speci-
speci-

ramera hody
I'perimen

L-__~__~~--A B------__ beam Rtop

~~~

fluorescent
screen

FIG. 6-4.
FIG. 6-4. Design of
Design of collimator
collimator and beam stop
stop (schematic).
(schematic).
6-3)
6-3] SPECIMEN PREPARATION 153
153

men. The use of of slits

slits instead
instead of pinholes decreases
of pinholes decreases exposure
exposure time by in-
time by in-
creasing
creasing the
the irradiated
irradiated volume ofof the
the specimen,
specimen, but requires
requires more accurate
accurate
positioning
positioning of
of the
the camera relative
relative to
to the
the source
source and produces
produces diffraction
diffraction
lines
lines which are
are sharp only along
sharp only along the
the median line
line of
of the
the film.
film.

6-3
6-8 Specimen
Specimen preparation.
preparation. Metals and alloys alloys may may be be converted
converted to to
powder by filing
powder by filing or, or, if
if they
they are
are sufficiently brittle, by
sufficiently brittle, by grinding grinding in
in aa small
small
agate
agate mortar.
mortar. In In either
either case,
case, the the powder
powder should should be be filed
filed or
or ground
ground as as
fine
fine as possible, preferably
as possible, preferably to pass a 325-mesh
to pass 325-mesh screen,screen, in order
in order to to produce
produce
smooth,
smooth, continuous
continuous diffraction
diffraction lines. lines. The screened powder is
screened powder is usually
usually an- an-
nealed
nealed in in evacuated
evacuated glass glass or or quartz
quartz capsules
capsules in in order
order to to relieve
relieve thethe strains
strains
due to
to filing
filing oror grinding.
grinding.
Special
Special precautions
precautions are are necessary
necessary in in screening
screening two-phase
two-phase alloys.alloys. If a
If
small,
small, representative
representative sample sample is is selected
selected from an an ingot
ingot forfor x-ray
x-ray analysis,
analysis,
then that
then that entire
entire sample
sample must be be ground
ground or or filed
filed to pass through
to pass through the the screen.
screen.
The common method of of grinding
grinding until
until an amount sufficient
sufficient for
for the
the x-ray
x-ray
specimen
specimen has
has passed
passed the
the screen,
screen, the
the oversize
oversize being rejected,
being rejected, may may lead
lead to
to
very
very erroneous
erroneous results.
results. One phase
phase of
of the
the alloy
alloy is
is usually
usually more brittle
brittle than
than
the other, and that
the other, that phase
phase will will more easilyeasily be be ground
ground into into fine
fine particles;
particles; if if

the grinding
the grinding and screening
screening are
are interrupted
interrupted at
at any point,
any point, then
then the
the material
material
remaining on the
remaining the screen
screen will will contain
contain lessless ofof the
the more brittle
brittle phase
phase thanthan thethe
original
original sample
sample whilewhile the the undersize
undersize will will contain
contain more,more, and neither
neither will will be
representative.
representative.
The final
final specimen
specimen for for the
the Debye
Debye camera
camera should should be be inin the
the form
form of of aa thin
thin
rod,
rod, 0.5
0.5 mm or or less
less inin diameter
diameter and about about 1 1 cm long.
long. There are are various
various
ways
ways of of preparing
preparing such such a a specimen,
specimen, one one of of the
the simplest
simplest beingbeing to to coat
coat thethe
powder
powder on
on the
the surface
surface of
of a
a fine
fine glass
glass fiber
fiber with
with a
a small
small amount of
of glue
glue or or
petroleum jelly.
petroleum jelly. Other
Other methods consist
consist in
in packing
packing the
the powder
powder into
into aa thin-
thin-
walled
walled tube
tube made of of a a weakly
weakly absorbing
absorbing substance
substance such such as as cellophane
cellophane or or
lithium
lithium borate
borate glass,
glass, or
or in
in extruding
extruding a
a mixture
mixture of
of powder
powder and binder
binder
through
through a a small
small hole.
hole. Polycrystalline
Polycrystalline wires wires maymay be be used
used directly,
directly, but but
since
since they
they usually
usually exhibit
exhibit some preferredpreferred orientation,
orientation, the the reSUlting
resulting diffrac-
diffrac-
tion
tion pattern
pattern must be be interpreted
interpreted with with that
that fact
fact in
in mind (Chap.
(Chap. 9). 9). Strongly
Strongly
absorbing
absorbing substances
substances may produce split
may produce split low-angle
low-angle lines (see Sec.
lines (see Sec. 4-10);
4-10);
if
if this
this effect
effect becomes
becomes troublesome,
troublesome, it it may
may be be eliminated
eliminated by by diluting
diluting the the
substance
substance involved
involved with with some weakly weakly absorbing
absorbing substance,
substance, so so that
that thethe
absorption coefficient of
absorption coefficient of the
the composite
composite specimen
specimen is is low.
low. Both flour flour and
cornstarch
cornstarch have have beenbeen used used for for this
this purpose.
purpose. The diluent diluent chosen
chosen should
should
not
not produce any
produce any strong strong diffraction
diffraction lines
lines of
of its
its own and too
too much of
of it
it

should
should notnot bebe used,
used, or
or the
the lines
lines from
from the
the substance
substance being
being examined will
will

become spotty.
spotty.
After
After the specimen rod
the specimen rod is is prepared,
prepared, it it is
is mounted in in its
its holder
holder so so that
that itit

will
will lie accurately
lie accurately along along the
the axis of the
axis of the cameracamera when the
the specimen
specimen holder
holder
154
154 POWDER
POWDER PHOTOGRAPHS
PHOTOGRAPHS [CHAP. 66
[CHAP.

is rotated.
is rotated. (Rotation
fRotation ofof the
the specimen
specimen during
during the
the exposure
exposure isis common
common prac-
prac-
tice but not
tice but not an
an intrinsic
intrinsic part
part of
of the
the powder
powder method;
method; its
its only
only purpose
purpose isis to
to
produce continuous,
produce continuous, rather
rather than
than spotty,
spotty, diffraction
diffraction lines
lines by
by increasing
increasing the
the
number of
number of powder
powder particles
particles in
in reflecting
reflecting positions.
positions. \ |

6-4 Film
6-4 Film loading. Figure 6-5
loading. Figure 6-5 illustrates
illustrates three
three methods
methods of of arranging
arranging
the film strip
the film strip in
in the
the Debye
Debye method.
method. The
The small
small sketches
sketches on
on the
the right show
right show
the loaded film in relation
the loaded film in relation to the to the incident
incident beam,
beam, while
while the
the films
films laid
laid out
out
flat are
flat are indicated
indicated on on the
the left.
left. InIn (a),
(a), aa hole
hole is punched
is punched in the center of the
in the center of the
film so
film so that
that the
the film
film may
may bebe slipped
slipped over
over the
the beam
beam stop;
stop; the
the transmitted
transmitted
beam thus leaves
beam thus leaves through
through the
the hole
hole in
in the
the film.
film. The pattern
pattern isis symmetrical
symmetrical
on either
on either side,
side, and
and the
the 68 value
value ofof aa particular
particular reflection
reflection is
is obtained
obtained by by
measuring
measuring U,
U, the
the distance
distance apart
apart of
of two diffraction
diffraction lines
lines formed by
by the
the
same cone
same cone of
of radiation, using the
radiation, and using the relation
relation
40R
4BR =
= U.
U.
Photographic film
Photographic film always
always shrinks
shrinks slightly
slightly during
during processing
processing and drying,
drying,
and this shrinkage effectively changes
and this shrinkage effectively changes the
the camera radius.
radius. The film-shrink-
film-shrink-
age error
age error may
may bebe allowed
allowed forfor by
by slipping
slipping the
the ends
ends of
of the film under
the film under metal
metal
knife-edges which cast a sharp
knife-edges which cast a sharp shadow near
near each
each end of
of the
the film.
film. In
In this
this

way, aa standard
way, standard distance
distance isis impressed
impressed on on the film
the film which will shrink in the
will shrink in the
same
same proportion as the
proportion as the distance between aa given
distance between given pair
pair of diffraction
of diffraction lines.
lines.
If
If the
the angular separation 40
angular separation K of
40* of the
the knife-edges
knife-edges inin the camera is is known,
known,
either
either by
by direct
direct measurement or
or by
by calibration
calibration with a substance of
of known
lattice parameter, then
lattice parameter, then the
the value
value of
of 0 for
for a
a particular
particular reflection
reflection may be
obtained
obtained by simple proportion:
by simple proportion:
o
6 U
-=-,
OK llK
where UK
where UK is
is the
the distance
distance apart
apart of
of the
the knife-edge
knife-edge shadows on the film. film.

Figure 6-5(b)
Figure 6-5(b) illustrates
illustrates a
a method of
of loading
loading the film
film which is
is just
just the
reverse of the previous
reverse of the previous one. one. Here the
the incident
incident beam enters
enters through
through thethe
hole in the film, and
hole in the film, and 0 is obtained from
is obtained from the
the relation
relation

- 4S)R ~
(27T - 48)R
(211' ^ V.
V.

Knife-edges
Knife-edges may may also
also be
be used
used in
in this
this case
case as
as aa basis
basis for
for film-shrinkage
film-shrinkage cor- cor-
rections.
rections.
The
The unsymmetrical,
unsymmetrical, or or Straumanis,
Straumanis, method
method of of film
film loading
loading is is shown
shown in in
Fig.
Fig. 6-5(c).
6-5 (c). Two
Two holes
holes are
are punched
punched in
in the
the film
film so
so that
that it
it may
may be
be slipped
slipped
over
over both
both the
the entrance
entrance collimator
collimator and
and the
the beam
beam stop.
stop. Since
Since itit is
is possible
possible
to
to determine
determine from
from measurements
measurements on on the
the film
film where
where thethe incident
incident beambeam en-en-
tered the film
tered the film circle
circle and
and where
where the
the transmitted
transmitted beambeam left
left it,
it, no
no knife-edges
knife-edges
are required to
are required to make
make the
the film-shrinkage
film-shrinkage correction.
correction. The point X
The point X (28 =
(20 =
6-4)
6-4] FILM LOADING 155
155

5 4 2 1 12 45
(a)

knife-edge
shadow

211
26 211

e
1122 :13 44 55 j5 4
4 a 2 1

(bl
IDll rr 0 11 I J(II l" "--~-

- 2'11
-
211 211

((')
(c)

FIG.
FIG. 6-5.
6-5. Methods of
of film
film loading
loading in
in Debye
Debye cameras.
cameras, Corresponding
Corresponding lines
lines
have the same numbers in
have the in all
all films.
films.

180),
180), where thethe incident
incident beam f'ntered,
entered, is
is halfway
halfway bf'tw('en
between the
the measured
positions
positions of lines .~,,~;
of lines 5,5; similarly,
similarly, th(' point. Y (28
the point = 0), where the
(26 = 0), the trans-
trans-
mitted
mitted beam left,
left, is
is halfway
halfway between
between lines
lines 1,1.
1,1. The difference
difference between
the positions of
the positions of X and Y gives
gives lV,
W, and 8 6 is
is found by
by proportion:
proportion :

28
29
_ S
~
8
7'If' W
Unsymmetrical
Unsymmetrical loading
loading thus provides for
thus provides for the
the film-shrinkage
film-shrinkage correction
correction
without
without calibration
calibration ofof the
the camera or or knowledge
knowledge of of any
any camera dimension.
dimension.
The shapes
shapes of
of the
the diffraction
diffraction lines
lines in Fig. 6-5 should
in Fig. should be noted.
noted. The low-low-
angle
angle lines
lines are
are strongly
strongly curved
curved because
because they
they are
are formed by
by cones
cones of
of radia-
radia-
tion
tion which
which have
have a a small
small apex angle 48.
apex angle 48. The same isis true
true of
of the
the high-angle
high-angle
lines.
lines, although naturally
although naturally theythey are
are curved
curved in
in the
the opposite
opposite direction.
direction. Lines
Lines
for
for which 4840 is
is nearly equal
nearly equal to
to 180
180 are
are practically straight.
practically straight. This
This change
change
of
of line
line shape
shape with
with change
change inin 8
6 may
may also
also be
be seen
seen in
in the
the powder photographs
powder photographs
shown in Fig. 3-13.
in Fig. 3-13.
156
156 POWDER
POWDER PHOTOGRAPHS
PHOTOGRAPHS [CHAP. 66
[CHAP.

6-6 Cameras
6-6 Cameras for
for high
high and
and low
low temperatures.
temperatures. Metallurgical investiga-
Metallurgical investiga-
tions frequently
tions frequently require that the
require that the crystal
crystal structure
structure of
of aa phase
phase stable
stable only
only
at high
at high temperature
temperature be
be determined.
determined. InIn many
many cases,
cases, this
this can
can be
be accom-
accom-
plished
plished by quenching
by quenching the the specimen
specimen at at aa high
high enough
enough rate rate to to suppress
suppress the the
decomposition
decomposition of
of the
the high-temperature
high-temperature phase phase and
and then
then examining
examining the
the
specimen in
specimen an ordinary
in an ordinary cameracamera at at room
room temperature.
temperature. In In other
other cases,
cases, the the
transformation
transformation into into the
the phases
phases stable
stable at
at room
room temperature
temperature cannot
cannot be
be sup-
sup-
pressed, and
pressed, and aa high-temperature
high-temperature camera camera is is necessary
necessary in in order that the
order that the
specimen may
specimen may be be examined
examined at at the
the temperature
temperature at which the phase
at which the phase in ques-
in ques-
tion is
tion is stable.
stahle.
The design
The design of of high-temperature
high-temperature Debye Debye cameras
cameras variesvaries almost
almost from from
laboratory to
laboratory to laboratory.
laboratory. They They all all involve
involve aa small
small furnace,
furnace, usually
usually of of the
the
electric-resistance type,
electric-resistance type, to to heat
heat thethe specimen
specimen and aa thermocouple
thermocouple to to meas-
meas-
ure its
ure its temperature.
temperature. The main design design problem
problem is to keep
is to keep the the film
film cool
cool
without too
without too great
great an an increase
increase in in the
the camera diameter;
diameter; this this requires
requires water-
water-
cooling of
cooling of the
the body
body of of the
the camera
camera and/or
and/or the the careful
careful placing
placing of of radiation
radiation
shields between
shields between the the furnace
furnace and and the
the film,
film, shields
shields soso designed
designed that that they
they willwill
not interfere
not interfere with
with the
the diffracted
diffracted x-ray
x-ray beams. The furnace
furnace which
which sur-
sur-
rounds the
rounds the specimen
specimen must also also bebe provided
provided with with aa slot
slot of of some kind kind to to
permit the passage of
permit the passage of the incident the incident and diffracted
diffracted beams.
beams. If
If the
the specimen
specimen
is susceptible
is susceptible to to oxidation
oxidation at high temperatures,
at high temperatures, means of of evacuating
evacuating the the
camera or
camera of filling
or of filling it it with
with an inert inert gas
gas must be provided;
provided; alternately,
alternately, the the
powder
powder specimen
specimen may may be be sealed
sealed in in aa thin-walled
thin-walled silicasilica tube.
tube. Because of of
the
the small
small size
size ofof the
the furnace
furnace in in aa high-temperature
high-temperature camera, camera, the tempera-tempera-
ture
ture gradients
gradients in
in it
it are
are usually
usually quite
quite steep,
steep, and special
special care must be taken
to
to ensure
ensure that
that thethe temperature
temperature recorded
recorded by
by the thermocouple
thermocouple is
is actually
actually
that
that of of the
the specimen
specimen itself.
itself. Since
Since the
the intensity
intensity of
of any
any reflection
reflection is
is de-

creased
creased by by an
an increase
increase in
in temperature,
temperature, the
the exposure
exposure time required
required for
for a a
high-temperature
high-temperature diffraction
diffraction pattern
pattern is
is normally
normally rather
rather long.
long.
Debye
Debye cameras
cameras are are also
also occasionally
occasionally requiredrequired forfor work at temperatures
temperatures
below
below roomroom temperature.
temperature. Specimen Specimen cooling cooling is is usually
usually accomplished
accomplished by
running aa thin
running thin stream
stream of of coolant,
coolant, such as as liquid
liquid air,
air, over the specimen
specimen
throughout
throughout the the x-ray
x-ray exposure.
exposure. The diffraction diffraction pattern
pattern of of the
the coolant
coolant will will

also
also bebe recorded
recorded but but this
this is is easily
easily distinguished
distinguished from that of of a crystalline
a crystalline
solid,
solid, because
because the typical pattern
the typical pattern of of aa liquid
liquid contains
contains onlyonly one one oror two veryvery
diffuse
diffuse maxima in contrast to
in contrast to the
the sharp
sharp diffraction
diffraction lines
lines from
from aa solid.
solid. Scat-
Scat-
tering from the
tering from the liquid
liquid will,
will, however,
however, increase
increase thethe background
background blackening
blackening
of
of the
the photograph.
photograph.

6-6
6-6 Focusing cameras. Cameras
Focusing cameras. Cameras inin which
which diffracted
diffracted rays
rays originating
originating
from
from anan extended
extended region
region of
of the
the specimen
specimen all
all converge
converge to
to one
one point
point on
on the
the
film
film are
are called
called focusing
focusing cameras.
cameras. The
The design
design of
of all
all such
such cameras
cameras is
is based
based
on
on the
the following
following geometrical
geometrical theorem
theorem (Fig.
(Fig. 6-6):
6-6) all
all angles
angles inscribed
inscribed in
: in aa
 6-7)
6-7] SEEKA.NN-BOHLIN CAMERA
8EEMANN-BOHLIN CAMERA 157
157

- -,
----~--
\,
_- - - - 2<>,
S -- ,

6-6.
FIG. 6-6.
FIG. Geometry of
Geometry of focusing
focusing cameras.
cameras.

circle and
circle based on
and based on the
the same
same arc
arc SF are
are equal
equal toto one
one another
another and equal
equal to
to
half the
half the angle
angle subtended
subtended at the center
at the center by the same arc.
by the arc. Suppose
Suppose that
x-rays proceeding
x-rays proceeding in
in the
the directions
directions SA and SB encounter a powder speci-
powder speci-
men located
located on
on the arc AB. Then the
the arc the rays
rays diffracted
diffracted by
by the (hkl)
(hkl) planes
planes
at points A and
at points and B will
will be
be deviated
deviated through
through the
the same angle
angle 28. But these
26.

deviation
deviation angles
angles 29
26 are
are each
each equal
equal to
to (180
(180
0 - a),
a), which means that the
the
diffracted rays
diffracted rays must proceed along
proceed along AF and BF,
BF, and come to
to a focus at
at FF
on
on aa film
film placed along
placed along the
the circumference
circumference of
of the
the circle.
circle.

6-7
6-7 Seemann-Bohlin
Seemann-Bohlin camera. camera. This This focusing
focusing principle
principle is is utilized
utilized in the
Seemann-Bohlin
Seemann-Bohlin camera
camera shown in
in Fig.
Fig. 6-7.
6-7. The slit
slit S
S acts as aa virtual
virtual
line
line source
source of
of x-rays,
x-rays, the
the actual
actual source
source being
being the
the extended
extended focal
focal spot
spot on
the target
the target T
T of
of the
the x-ray
x-ray tube.
tube. Only converging
Only converging rays rays from
from the
the target
target can
can
enter
enter this
this slit
slit and,
and, after
after passing
passing it, it, they diverge to
they diverge to the
the specimen
specimen AB.
(Alternatively,
(Alternatively, if
if aa tube
tube with
with a
a fine-line
fine-line focal
focal spot
spot is
is available,
available, the
the slit
slit

may be eliminated
may be eliminated and
and exposure
exposure time
time shortened
shortened by designing
by designing the
the camera
camera
to
to use
use the
the focal
focal spot
spot itself
itself asas aa source
source of of divergent
divergent radiation.)
radiation.) For For aa par-
par-
ticular
ticular hkl
hkl reflection,
reflection, each
each ray
ray is
is then
then diffracted
diffracted through
through the
the same
same angle
angle
26, with
with thethe result
result thatthat all
all diffracted
diffracted rays rays from
from various
28, various parts
parts of of the
the spec-
spec-
imen converge
imen converge to to aa focus
focus at
at F.
F. As
As in
in any powder method,
any powder method, the
the diffracted
diffracted
beams
beams lie lie on
on the
the surfaces
surfaces of of cones
cones whose
whose axes axes are
are coincident
coincident withwith thethe inci-
inci-

dent beam; in this

dent beam; in this case, case, aa number
number ofof incident
incident beams
beams contribute
contribute to
to each
each
reflection and
reflection and aa diffraction
diffraction line line is
is formed
formed by by the
the intersection
intersection of of aa number
number
of cones with
of cones with the the film.
film. As
As in
in the
the Debye-Scherrer
Debye-Scherrer method, method, aa diffraction
diffraction

line is
line is in
in general
general curved,
curved, the the amount
amount of of curvature
curvature depending
depending on on the
the par-
par-
158
158 PHOTOGEAPHS
POWDER PHOTOGRAPHS [CHAP. 6
[CHAP. 6

A B

film

FIG.
FIG. 6-7.
6-7. Seemann-Bohlin forusing
focusing ramera.
camera. Only one hkl
Only one hkl reflertion
reflection is
is shown.

ticular
ticular value
value of
of 86 involved. Figure 6-8
involved. Figure 0-8 showH
shows a a typical
typical powder
powder pattern
pattern
made with this
this camera.
camera.
The ends
ends of the film
of the film strip
strip are
are covered
covered by
by knife-edges
knife-edges M M and N, N, which
cast reference shadows on the
cast reference the film.
film. The value of (J
value of 6 for
for any
any diffraetion
diffraction line
line
may
may be
be found
found from the distance r;,
the distance U, measured on the
the film,
film, from the
the line
line to
to
the
the shadow ofof the
the lmy-angle knife-edge N,
low-angle knife-edge N, by by HHe
use of
of the
the relation
relation

4(JR
46R = U + arc SARN.
*rcSABN. (6-4)
(6-4)

In practice,
practice, 8 is is found
found by by calibrating
calibrating the
the eamera
camera with
with aa standard
standard sub-
sub-
stance of
stalJce of known lattiee parameter, such
lattice parameter, such as
as NaCI,
NaCl, rather
rather than
than by
by the
the use
use
of Eq.
of Eq. (6-4).
(6-4). Several
Several patterns
patterns are prepared
are prepared of of the
the same standard
standard with
with
radiations of
radiations of different
different wavelength,
wavelength, in in order
order to
to obtain
obtain diffraction
diffraction lines
lines at
at a
a
large number of
large of 28
26 positions.
positions. Line
Line positions
positions are
are measured on each each film,
film,
as well
as well asas the
the total
total length
length of
of the
the film
film between the knife-edge shadows M
the knife-edge M
and N. Because of of variable
variable film
film shrinkage,
shrinkage, these
these films
films will
will generally
generally have
unequal
unequal lengths.
lengths. The lengthlength of
of one is taken
one is taken as
as aa standard,
standard, and a a multiply-
multiply-
ing
ing factor
factor isis found for each of
for each of the
the other
other films
films which will
will make itsits length
length
equal to
equal to the
the standard
standard length.
length. This
This factor
factor is
is then
then applied
applied to the U value
to the value
of
of each
each diffraction
diffraction line.
line. The corrected of U are
values of
corrected values are then plotted against
then plotted against
calculated
calculated values
values ofof 86 to
to obtain
obtain a a calibration
calibration curve
curve for
for the
the camera.
camera.

FIG.
FIG. 6-8.
6-8. Powder pattern
pattern of
of tungsten,
tungsten, made in in aa Seemann-Bohlin
Seemann-Bohlin camera,
camera, 8.4
8.4
em
cm inin diameter.
diameter. This
This camera covers
covers a 28 range
a '}jJ range of
of 92
92 to
to 166.
166. High-angle
High-angle end of
of
film
film at
at left.
left. Filtered
Filtered copper
copper radiation.
radiation. (Courtesy
(Courtesy ofof John
John T.
T. Norton.)
Norton.)
6-7]
6-7] SEEMANN-BOHLIN CAMERA
SEEMANN-BOHLIN CAMERA 159
159

AA similar
similar procedure
procedure is is then
then followed
followed when
when an an "unknown"
"unknown" specimen
specimen is is
being
being examined.
examined. A correction
correction factor
factor is
is found
found which
which will
will convert
convert the
the meas-
meas-
ured film
ured film length
length of the unknown
of the unknown to to the
the standard
standard length.
length. This
This factor
factor is
is
then applied
then applied toto each measured U value
each measured value before
before finding
finding the
the corresponding
corresponding
ovalue
value from
from the
the calibration
calibration curve.
curve.
If more accuracy
If more accuracy is is desired
desired than
than this
this graphical
graphical method
method can
can give,
give, the
the
calibration data
calibration data can
can bebe handled
handled analytically.
analytically. Equation
Equation (6-4)
(6-4) is
is written
written
in the
in thc form
form
= K 1U
0=K + K22 ,
U+K 1 ,

where KI
where and K
KI and are constants.
K22 are eonstants. The values
values of
of these
these constants
constants are
are then
then
determined by
determined by the
the method of of least
least squares
squares (see
(see Sec.
Sec. 11-6). the
ll-()). Once the
constants are
constants are known,
known, this
this equation
equation can
can be
be used
used to
to calculate
calculate 0, or aa table
0, or table
of corresponding
of corresponding 0 and U
(T values
values can
can be
be constructed.
constructed.
differentiating Eq.
By differentiating
By (G-4), we obtain
Eq. (0-4), obtain
dU
dO
dd =
= -.
411
4R
This relation
This relation may be
may be combined
comhined with
with Eq.
Eq. (G-2) to give
((5-2) to give
dU 411
4R
= - -tanO.
tan 6.
dd
dd dd
d 411
4R
Resoh'ing power =
Resolving power = - =
= - - tan O. (6-5)
M
I1d AU
MJ
6. (6-5)

The resolving
resolving power,
power, or or ability
ability to to separate
separate diffraction
diffraction lines
lines from planes
planes
of almost the
of almost the same spacing,
spacing, is
is therefore
therefore twice
twice that
that of
of a Debye-Scherrer
Debye-Scherrer
camera of of the
the same radius.
radius. In addition,
addition, the exposure
exposure time is is much shorter,
shorter,
because
because of of the
the fact
fact that
that a a much larger specimen
larger specimen is
is used (the arc AB of
(the
Fig. 6-7 is
Fig. 6-7 is of
of the
the order
order ofof 1 1 cm)
cm) and diffracted
diffracted rays
rays from a considerable
volume of material
of material are are all
all brought
brought to
to one focus.
focus. The Seemann-Bohlin
camera
camera is, therefore, very useful in studying complex diffraction
is, therefore, very useful in studying complex diffraction patterns,
patterns,
whether they
whether they are
are due to to aa single
single phase
phase oror to
to a mixture of of phases
phases such as as
occur
occur inin alloy
alloy systems.
systems.
For
For metallurgical
metallurgical work,work, this
this camera has the the further
further advantage
advantage that aa
massive
massive polycrystalline specimen may be used as
polycrystalline specimen as well
well as a powder.
powder. For
example,
example, aa metallographic
metallographic specimen,
specimen, mounted in in the usual I-in. 1-in. diameter

bakelite mount for

bakelite for microscopic
microscopic examination,
examination, can be fastened to the cir- cir-

cumference
cumference of of the
the camera and used used directly.
directly. When a a flat
flat specimen
specimen placed
placed
tangentially to
tangentially to the
the camera
camera circle
circle is is substituted
substituted for
for aa curved specimen,
specimen, the
focusing
focusing action
action of
of the
the camera is
is slightly
slightly decreased
decreased but not objectionably
objectionably
so,
so, while
while the
the advantage
advantage of
of being
being able
able to
to examine
examine the
the same area of
of the
specimen
specimen both both with
with the
the microscope
microscope and with
with x-rays
x-rays is
is obvious.
obvious. It
It is
is
160
160 POWDER
POWDER PHOTOGRAPHS
PHOTOGRAPHS [CHAP. 66
[CHAP.

worth noting
worth noting also
also that
that both
both methods
methods ofof examination,
examination, the
the optical
optical and
and the
the
x-ray, provide
x-ray, provide information
information only
only about the surface
about the surface layer
layer of
of the
the specimen,
specimen,
since the
since the x-ray
x-ray method here
method here involved
involved is is of
of the
the reflection,
reflection, andand not
not the
the trans-
trans-
mission, type.
mission, type.
A powder
A powder specimen
specimen may may also also bebe used
used in in this
this camera
camera by by fixing
fixing aa thin
thin
layer
layer of
of the
the powder
powder to
to a
a piece
piece of
of paper
paper with
with glue
glue or
or petroleum jelly.
petroleum jelly. The
paper is
paper is then
then curved
curved andand heldheld against
against the the camera circumference
circumference by by an
attachment provided
attachment provided with the with the camera.
camera. Whether the
the specimen
specimen is
is in
in the
the
massive or
massive or powder
powder form,form, smoother
smoother diffraction
diffraction lines can
lines can be obtained by
obtained by
oscillating the
oscillating the specimen
specimen aboutabout the the camera
camera axis.axis.
the debit
On the debit side,
side, the
the Seemann-Bohlin
Seemann-Bohlin camera camera has has the
the disadvantage
disadvantage that that
the reflections
the reflections registered
registered on on the
the film
film cover
cover only
only aa limited
limited range
range ofof 26
28 values,
values,
particularly on
particularly the low-angle
on the low-angle side; side; for
for this
this reason,
reason, it it is
is better
better toto make aa
preliminary
preliminary surveysurvey of
of the
the whole
whole pattern
pattern with
with aa Debye
Debye camera,
camera, reserving
reserving
the focusing
the focusing camera
camera for for aa closer
closer study
study of of certain
certain portions.
portions. Some investiga-
investiga-
tors use
tors use aa set
set of
of three
three Seemann-Bohlin
Seemann-Bohlin cameras, cameras, designed
designed to to cover
cover practically
practically
the whole
the whole range
range of of 26
28 values
values in in overlapping
overlapping angular
angular ranges.
ranges.
Diffraction lines
Diffraction lines formed in in aa Seemann-Bohlin
Seemann-Bohlin camera are are normally
normally
broader than
broader than those
those inin aa Debye-Scherrer
Debye-Scherrer pattern. pattern. The focused line is,
focused line is, in
in aa
sense, an
sense, image of
an image of the
the slit,
slit, and decreasing
decreasing the the slit opening will
slit opening will decrease
decrease
the line
the line breadth
breadth but but increase
increase the the exposure
exposure time. time. The line line breadth
breadth in- in-
creases
creases as as 2628 i?ecomes
Becomes smaller,
smaller, since
since at
at low
low 28
26 values
values the
the diffracted
diffracted rays
rays
strike the film
strike the film at
at aa very low angle.
very low angle. This effect effect isis aggravated
aggravated by by the
the double-
double-
emulsion film
emulsion normally used
film normally used for for x-ray
x-ray diffraction.
diffraction. In special
special cases,
cases, it
it may

pay
pay to
to use
use single-emulsion
single-emulsion film
film at
at the
the cost
cost of
of increased
increased exposure
exposure time.
time.

6-8
6-8 Back-reflection
Back-reflection focusing
focusing cameras.
cameras. The most precise precise measurement
of
of lattice parameter
lattice parameter is
is made in
in the
the back-reflection
back-reflection region,
region, asas discussed in in
greater detail in Chap.
greater detail in Chap. 11. 11. The most suitable
suitable camera for
for such measure-
ments
ments is is the
the symmetrical
symmetrical back-reflection
back-reflection focusing
focusing camera illustrated
illustrated inin
Fig.
Fig. 6-9.
6-9.
It
It employs
employs thethe same focusing
focusing principle
principle as as the
the Seemann-Bohlin camera, camera,
but
but the
the film
film straddles
straddles the the slit
slit and the
the specimen
specimen is is placed
placed diametrically
diametrically
opposite the
opposite the slit.
slit. Means are are usually
usually provided
provided for
for slowly
slowly oscillating
oscillating the
specimen through
specimen through a
a few
few degrees
degrees about
about the
the camera axis
axis in
in order
order to
to produce
produce
smooth
smooth diffraction
diffraction lines.
lines. A typical film, punched
typical film, punched in
in the
the center
center to
to allow
the
the passage
passage of
of the
the incident
incident beam,
beam, is
is shown in
in Fig.
Fig. 6-10.
6-10. The value of
of 86

for
for any
any diffraction
diffraction line
line may
may be
be calculated
calculated from the
the relation
relation

(41r - 86)R =
(4T - 88)R
= V,
V, (6-6)
(6-6)

where V
where V isis the
the distance
distance on
on the
the film
film between corresponding
corresponding diffraction
diffraction lines
lines
on
on either
either side
side of
of the
the entrance
entrance slit.
slit.
6-8)
6-8] BACK-REFLECTION FOCUSING CAMERAS 161
161

film

FIG. 6-9.
6-9. Symmetrical
Symmetrical back-reflection
back-reflection focusing
focusing camera.
camera. Only
Only one hkl reflec-
one hkl reflec-
tion
tion is
is shown.

Differentiation
Differentiation of
of Eq.
Eq. (6-6)
(6-6) gives
gives

A0
--'ft- (6-7)
(6-7)
4R \2/
where ~(V /2) is
A(F/2) is the
the separation
separation on
on the
the film
film of
of two reflections
reflections differing
differing in
in
Bragg angle by
Bragg angle by ~(J.
A0. Combination of
of this
this equation
equation with
with Eq.
Eq. (6-2) shows
(6-2) shows
that
d 4R
Resolving power == - ==
Resolving power tan
tan 8.
M
~d ~(Vn)
6.

A(F/2)
The resolving
resolving power
power of this camera
of this camera is is therefore the same as
therefore the as that
that of
of a
a
Seemann-Bohlin camera of of the
the same diameter.
diameter.
In the
In the pattern
pattern shown in in Fig.
Fig. 6-10, pairs of
6-10, two pairs of closely
closely spaced lines can
spaced lines can
be seen,
be lines 11 and 22 and lines
seen, lines lines 44 and 5.
5. Each pair
pair is
is aa doublet
doublet formed
formed byby
321 i

65-t
6 5 4 321
3 2 1

FIG. 6-10.
FIG. 6-10. Powder photograph
Powder photograph of tungsten made
made in
of tungsten in aa symmetrical
symmetrical back-reflec-
back-reflec-
tion focusing
tion focusing camera,
camera, 4.00
4.00 in.
in. in
in diameter.
diameter. Unfiltered
Unfiltered copper
copper radiation.
radiation.
162
162 POWDER
POWDER PHOTOGRAPHS
PHOTOGRAPHS [CHAP. 66
[CHAP.

reflection
reflection from one
from one set
set of
of planes
planes ofof the
the two
two components,
components, Ka\ and Ka^
Kal and Ka2,
which make
which make upup Ka radiation. These
Ka radiation. These component
component lines
lines are
are commonly
commonly foundfound
to be
to be resolved,
resolved, or
or separated,
separated, in
in the
the back-reflection
back-reflection region.
region. (The
(The ft(3 lines
lines in
in
this
this photograph are
photograph are not
not resolved
resolved since
since K/3 radiation consists
K{3 radiation consists only
only of
of aa
single wavelength.)
single wavelength.) To determine
determine the
the conditions
conditions under
under which
which a given
given
camera can
camera can separate
separate two
two components
components of of radiation
radiation which
which have
have almost
almost the
the
same wavelength,
same wavelength, we must use
use the
the spectroscopic
spectroscopic definition
definition of
of resolving
resolving
power, namely
power, XI <lA, where AX
namely X/AX, is the
<lA is the difference
difference between
between thethe two wave-
wave-
lengths and
lengths and XA is
IS their value. For Cu Ka radiation,
their mean value. radiation, these
these wave-
lengths are
lengths are: :

A(CU Ka2)
\(CuKa 2
= 1.54433A
1. 54433A
)

A(CU Kal) = 1.54051

X(Cu#a!) 1.54051 A

~A =
AX = 0.00382A
Therefore
Therefore
A
X 1.542
1.542
= =
= 404.
<lA
AX 0.00382

The resolving
The resolving power
power of
of the
the camera must exceed this
this value,
value, for the partic-
for the partic-
ular reflection
ular reflection considered, if the
considered, if the component
component lines
lines are
are to
to be
be separated
separated on
the film.
the film.
By
By differentiating the Bragg
differentiating the law, we obtain
Bragg law, obtain

X =
A = 2d sin
sin e,
0,

de
d<9 1 tan
tan
---=--,
e
tan
tan e
dA
dX cos e
2d cos S 2d sin
sin e
A
X tan e
tan S
(6-8)
(6-8)
<lA
AX <le
A0

Substitution
Substitution of
of Eq. (0-7) gives
Eq. (6-7) gives
A
X -4R tan ()
4J?tan0
Resolving power =
Resolving power
= - = ----
= (6-9)
(6-9)
<lA
AX <l(Y /2)
A(7/2)

The negative
negative sign
sign here can be
here can be disregarded;
disregarded; it it merely
merely means that an in- in-

crease
crease inin AX causes
causes a a decrease
decrease inin V /2, since
F/2, since the latter
latter is
is measured from the

center
center ofof the
the film.
film. Equation (6-9) demonstrates that
Equation (G-9) that the
the resolving
resolving power
power
increases
increases with
with the
the camera
camera radius with e,
radius and with 6, becoming
becoming very very large
large near
near 90.
90.
This latter
This latter point
point is
is clearly
clearly evident
evident in
in Fig.
Fig. G-lO,
6-10, which shows a
a greater
greater
separation
separation of of the
the higher-angle
higher-angle 400400 refledions
reflections asas compared
compared to to the 321 re-
re-

flections.
flections.
By
By use
use ofof Eq. (6-9),, we can
Eq. (G-g) can calculate
calculate the
the resolving
resolving power,
power, for
for the
the 321
321
reflections,
reflections, of
of the
the camera used
used to
to obtain
obtain Fig.
Fig. 6-10.
6-10. The
The camera
camera radius
radius is
is
6-9]
6-9] PINHOLE PHOTOGRAPHS 163
163

2.00
2.00 in.,
in., and the mean 8 6 value for
for these
these reflections
reflections is
is about
about 65.7.
65.7. Th('
The
line
line breadth at at half
half maximum intensity
intensity is
is about O.Oo!
0.04 rm.
cm. The two ('om-
com-
ponent
ponent lines
lines ofof the doublet willwill he
be clearly
clearly resolved
resolved onon thp
the film
film if
if their
their

separation is
separation is twiee
twice their
their breadth.
breadth. Therefore
Therefore

~ (~)
0-= 2(0.04) = 0.08 ('m,
2(0.04) = cm,

X
X (-1)(2.00)(2.54)(tan
(4) (2.00) (2.54) (tan (i5.7)
05.7)
-- = = 5n3.
= 5(8.
~X
AX (0.08)
(0.08)

Aim'e
Since this
this yalue
value excepds
exceeds the
the resolving
resolving power
power ofof o!04,
404, found ahoY('
above to to be
be
n('('('ssary
necessary for resolution of th(' ('U
for resolution of the Cu KO/ douhlet,
Ka expect thi~
doublet, we would expect this douhlet
doublet
to
to he
be resolved
resolved for
for the
the 321
321 refl(,(,tion,
reflection, and sueh
such is
is seen
seen to be the
to he the rase
case inin
Fig. (>-10. At ~ome
Fig. (j-1O. some lower
lower angle,
angle, this
this would not
not he
be true
true and t.he
the two ('om-
com-
ponents would m('rl?;e
ponents merge into
into aa single,
single, unresolved
unresolved linE'.
line. Th('
The faet
fact that
that resolu-
resolu-
tion
tion ofof the KO/
Ka doublet
doublet normally occurs only
normally O('("UI"S only in
in the
the haek-refleetion
back-reflection region
region
('an
can he seen from tthe
be se'en h(' Dehye
Debye photographs
photographs reprodu('ed
reproduced in in Fig.
Fig. 3-13.
3-13.

6-9 Pinhole photographs.

photographs. When monochromatic radiation radiation is is us('(}
used to to
examine'
examine a polycryst.alline spe('imen
poly crystalline specimen in
in a
a Laue
Latie camera,
camera, the
the result
result is
is called,
called,
for
for no particularly
particularly !,:ood
good reason,
reason, a
a pinhole'
pinhole photograph.
photograph. Either Either a a trans-
trans-
mission or a buek-r<>fleC'tion
or a back-reflection ('ame'ra
camera may be used.
may be used. A typieal transmission
typical transmission
photograph,
photograph, made of of fine-grained
fine-grained aluminum sheet,
sheet, isis shown in in Fig.
Fig. 6-11.
6-11.
The pinhole
pinhole method has has thethe ad-ad-
yant.age
vantage thatthat an e'nt.ire'
entire De'hye
Debye ring, ring,
and not just aa part
not just purl. of it, is
of it, is recorded
recorded
on the film.
on the film. On t.he othe'r hand,
the other hand, the the
range of
range of 86 values
values which
whi('h are' recorded
are recorded
is rather
is limited: either
rather limited low-angle or
either low-angle
: or
high-angle
high-angle re'flect ions
reflections may
may be
be ob-
ob-
tained, but
tained, hut not
not those
those inin the
the median
median

:FIG.
FIG. 6-11.
6-11. Transmission pinhole
Transmission pinhole
photograph
photograph of an
of an aluminum
aluminum sheetsheet
specimen. :Filtered
specimen. copper radiation.
Filtered copper radiation.
(The diffuse
(The diffuse circular
circular band
band near
near thethe
center is
center is caused
caused by by white
white radiation.
radiation.
nonuniform blackening
The nonuniform blackening of of thethe
Debye rings
Debye rings isis due to preferred
due to preferred orien-
orien- :FIG. 6-12.
FIG. 6-12. Angular relationships
Angular relationships in
in
tation in
tation in the
the specimen;
specimen; see
see Chap.
Chap. 9.)
9.) the pinhole
the pinhole method.
method.
164
164 POWDER PHOTOGRAPHS
POWDER PHOTOGRAPHS [CHAP. 66
[CHAP.

range of
range of 68 (see
(see Fig.
Fig. 6-12).
6-12). In In the
the transmission
transmission method,
method, the
the value
value of
of 8 for
for
aa particular reflection isis found
particular reflection found from
from the
the relation
relation
U
U
tan 21?
tan 28 == - , .
(6-10)
(6-10)
2D
2D
where
where U == diameter
U diameter of
of the"
the' Debye
Debye ring and D
ring and D == specimen-to-film
specimen-to-film dis-
dis-
tance. The corresponding
tance. The corresponding relation
relation for
for the
the back-reflection
back-reflection method
method is
is

V
tan (*
tan (11' -
- 28) = -,
28) = >
(6-11)
(6-11)
2D
where
where = diameter
V = diameter of
of the
the Debye
Debye ring.
ring. The distance D is
The distance is usually
usually of
of the
the
order of 33 to
order of to 55 cm.
cm.
Powder specimens
Powder specimens may may be be prepared
prepared simplysimply by by spreading
spreading aa bit bit ofof the
the
powder
powder mixed
mixed with
with a
a binder
binder on
on a
a glass
glass slide
slide or
or a
a small
small piece
piece of
of paper.
paper.
However, the
However, the greatest
greatest utility
utility of of the
the pinhole
pinhole method in in metallurgical
metallurgical work
lies in
lies in thethe fact
fact that
that massive,
massive, polypolycrystalline specimens
crystalline specimens may be be used.
used. In In
back reflection,
back reflection, mounted metallographic specimens
metallographic specimens may be
be examined di-
di-

rectly, while
rectly, while thethe transmission
transmission method is is of
of course
course restricted
restricted to to wire
wire andand
sheet specimens
sheet specimens which are
are not
not too
too highly absorbing.
highly absorbing.
There is
There is an optimum specimen
an optimum specimen thickness
thickness for for the
the transmission
transmission method, method,
because the
because the diffracted
diffracted beams will will bebe very
very weak or entirely absent
or entirely absent if if the
the
specimen
specimen is is either
either too thin (insufficient
too thin (insufficient volume of of diffracting
diffracting material)
material) or or
too
too thick
thick (excessive absorption). As will
(excessive absorption). will be shown in Sec. 9-9,
in Sec. 9-9, the speci-
speci-
men thickness
thickness which produces produces the the maximum diffracted diffracted intensity
intensity is is given
given
by 1/
by I/M, IJ., where
where IJ.
M is
is the
the linear
linear absorption
absorption coefficient
coefficient of
of the specimen.
specimen. In-
In-
spection
spection of
of Eq. (1-10)
Eq. (1-10) shows that
that this
this condition
condition can also
also be stated as
as
follows:
follows: a a transmission
transmission specimenspecimen is
is of
of optimum
optimum thickness
thickness when the inten-
sity
sity of of the the beam transmitted
transmitted through
through the the specimen
specimen is 1/c, or about t, of
is l/e, ,
of
the
the intensity
intensity of
of the
the incident
incident beam. Normally
Normally this
this optimum
optimum thickness is
is

of the order
of the order of a of a few
few thousandths
thousandths of
of an inch.
inch. There is
is one way, however,
way, however,
in
in which
which aa partial partial transmiHsion
transmission patternpattern can be obtained from a thick
specimen
specimen and and thatthat is is by
by diffraction
diffraction from an edge edge (Fig. 6-13). Only
(Fig. 6-13). Only the
upper
upper half half of the pattern
of the pattern is is recorded
recorded on the the film,
film, but that is all that
that is all that is is

necessary
necessary in in many
many applications.
applications. The same technique technique has also also been used
been used
in
in some
some Debye-Scherrer
Debye-Scherrer cameras. cameras.
The pinholepinhole method is is used
used inin studies
studies of of preferred
preferred orientation,
orientation, grain grain
size,
size, and
and crystal
crystal perfection.
perfection. With aa back-reflection
back-reflection camera,
camera, fairly
fairly precise
precise
parameter
parameter measurements
measurements can can bebe made
made by by this
this method.
method. PrecisePrecise knowledge
knowledge
of
of the
the specimen-to-film
specimen-to-film distance
distance D
D is
is not
not necessary,
necessary, provided
provided the
the proper
proper
extrapolation
extrapolation equation equation is
is used
used (Chap.
(Chap. 11)
1 1) or
or the
the camera
camera is
is calibrated.
calibrated. The
The
calibration
calibration is is usually performed
usually performed for
for each
each exposure, simply
exposure, simply by by smearing
smearing aa
thin
thin layer
layer of
of the
the calibrating powder
calibrating powder over
over the
the surface
surface of
of the
the specimen;
specimen; in
in

this
this way,
way, reference
reference lines lines ofof known
known 88 value
value areare formed
formed on on each
each film.
film.
6-101
6-10] CHOICE OF RADIATION 165
165

specnnen
specimen
film
film

(a)
(a) (b)
(b)

FIG. 6-13. Transmission

FIG. 6-13. pinhole method
Transmission pinhole method for
for thick
thick specimens:
specimens: (a)
(a) section
section through
through
incident
incident beam;
beam; (b)
(b) partial pattern obtained.
partial pattern obtained.

When thethe pinhole

pinhole method is is used
used for parameter measurements,
for parameter measurements, the the film
film
or
or specimcn,
specimen, or or both,
both, isis moved during
during thethe exposure
exposure to produce smooth,
to produce smooth,
continuous
continuous diffraction
diffraction lines.
lines. By
By rotating
rotating oror oscillating
oscillating the
the film
film about
about the the
axis
axis of
of the
the incident
incident beam,
beam, thethe reflections
reflections from each each reflecting particle or
reflecting particle or
grain
grain are
are smeared out
out along
along the
the Debye
Debye ring.
ring. The specimen
specimen itself
itself may
may be
be
rotated
rotated about
about thethe incident
incident beam axis axis or
or about any any axis parallel to
axis parallel to the
the
incident
incident beam,
beam, or
or translated
translated back and forth
forth in
in any
any direction
direction in
in a
a plane
plane
parallel to
parallel to the
the specimen
specimen surface.
surface. Such movements increaseincrease thethe number
of
of grains
grains in
in reflecting positions and allow
reflecting positions allow aa greater
greater proportion
proportion of of the
the total
total
specimen
specimen surface
surface t.o
to take part in
take part in diffraction,
diffraction, thu8
thus ensuring
ensuring that
that the
the informa-
informa-
tion
tion recorded
recorded onon the
the film
film is
is representative
representative of of the
the surfacc
surface as
as a
a whole.
whole. Any Any
camera
camera inin whi('h
which the
the specimen
specimen can can be soso moved duringduring the
the exposure
exposure thatthat
the
the incident
incident beam traverses
traverses a a large part of
large part of its
its surface
surface is called an integrating
is called integrating
camera.
camera.

6-10
6-10 Choice
Choice of
of radiation.
radiation. With any
any of
of th(' powder methods described
the powder described
above,
above, the
the investigator
investigator must choose
choose the
the radiation
radiation best
best suited
suited to
to the
the prob-
prob-
lem at
lem at hand.
hand. InIn making
making this
this choi('e,
choice, the
the two most important
important considera-
considera-
tions
tions are:
are :

(1) The characteristic

(1) characteristic wavelength
wavelength usedused should
should not be shorter
not be shorter than
than the
the
K absorption
K edge
absorption edge of
of the
the specimen,
specimen, or
or the
the fluorescent
fluorescent radiation
radiation produced
produced
will
will badly
badly fog
fog the
the film.
film. In
In the
the ('ase
case ofof alloys
alloys or
or compounds,
compounds, itit may
may be
difficult
difficult or
or impossible
impossible to
to satisfy
satisfy this
this ('ondition
condition for
for every
every element
element in
in the
the
specimen.
specimen.

(2) The Bragg

(2) Bragg law
law shows
shows that
that the
the shorter
shorter the
the wavelength,
wavelength, the
the smaller
smaller
the
the Bragg angle
Bragg angle for
for planes
planes of
of a
a given
given spacing.
spacing. Decreasing
Decreasing the
the wavelength
wavelength
wiII
will therefore
therefore shift
shift every
every diffraction
diffraction line
line to
to lower
lower Bragg
Bragg angles
angles and increase
increase
the
the total
total number ofof lines
lines on the
the film,
film, while
while increasing
increasing the
the wavelength will
wavelength will
have
have the
the opposite
opposite effect.
effect. The choice
choice of
of a
a short
short or
or a
a long
long wavelength de-
wavelength de-
pends on the particular problem
pends on the particular problem involved.
involved.
 166
166 POWDER PHOTOGRAPHS
POWDER PHOTOGRAPHS [CHAP. 66
[CHAP.

The characteristic
The characteristic radiations
radiations usually
usually employed
employed in
in x-ray
x-ray diffraction
diffraction are
are
the following:
the following:
MoKa:
MoKa: 0.711A
0.711A
CuKa:
CuKa: 1.542
1.542
CoKa:
CoKa: 1.790
1.790
FeKa:
YeKa: 1.937
1.937
CrKa:
CrKa: 2.291
2.291

In each
In each case,
case, the
the appropriate
appropriate filter
filter is used
is used toto suppress
suppress the K{3 component
the K/3 component
of the radiation.
of the radiation. All
All in
in all,
all, Cu
Cu K
Ka a radiation
radiation is
is generally
generally the
the most
most useful.
useful.

It cannot be employed
It cannot be employed with
with ferrous
ferrous materials, however,
materials, however, since
since it
it will
will cause
cause
fluorescent radiation
fluorescent radiation from from the
the iron
iron in
in the
the specimen; instead,
specimen; instead, Co
Co Ka,
Ka, Fe
Fe Ka
Ka
or Cr
or Cr Ka radiation should
Ka radiation should be be used.
used.
Precise lattice-parameter
Precise lattice-parameter measurements
measurements require that there
require that there be be aa num-
num-
ber of
ber of lines
lines in
in the
the back-reflection
back-reflection region,
region, while
while some specimens
some specimens may yield yield
only
only one
one or
or two.
two. This
This difficulty
difficulty may
may be
be avoided
avoided by
by using
using unfiltered
unfiltered radia-
radia-

tion, in
tion, in order
order to
to have K{3 as
have Kfi as well
well asas Ka lines
lines present,
present, andand by
by using
using an an alloy
alloy
target.
target.
For
For example,
example, if
if a
a 50
50 atomic
atomic percent
percent Fe-Co alloy
alloy is
is used
used as
as a
a tar-
tar-

get,
get,
and
and no
no filter
filter is
is used
used in
in the
the x-ray
x-ray beam,
beam, the
the radiation
radiation will
will contain
contain the
the

Fe Ka, Fe
Fe Ka, K{3, Co Ka,
Fe K0, Ka, and and Co K/3 K{3 wavelengths,
wavelengths, sincesince each
each element
element will will
emit its
emit its characteristic
characteristic radiation
radiation independently.
independently. Of course, course, special targets
special targets
can be used
can be used only only with
with demountable
demountable x-ray
x-ray tubes.
tubes.

6-11 Background
Background radiation.
radiation. A good
good powder
powder photograph
photograph has has sharp
sharp in-in-

tense
tense lines
lines superimposed
superimposed on on a background of
a background of minimum intensity.
intensity. How-
ever,
ever,
the
the diffraction
diffraction lines
lines themselves
themselves vary
vary in
in intensity,
intensity, because of
of the
the struc-
struc-

ture of
ture of the
the crystal itself,
crystal itself, and
and an appreciable
appreciable background
background intensity
intensity may
exist,
exist,
due
due to
to a
a numher
number of
of causes.
causes. The two effects
effects together
together may cause
cause thethe
weakest
weakest diffraction
diffraction line
line to
to be
be almost
almost invisible
invisible in
in relation
relation to the background.
background.
This
This background intensity is
background intensity is due
due toto the
the following
following causes:
(1) Fluorescent radiation
radiation emitted
emitted by the
the specimen. It
specimen. It cannot
cannot be be too
too
(1) Fluorescent by
strongly emphasized
strongly emphasized that that the
the characteristic
characteristic wavelength
wavelength used
used should
should be
be

longer than the K absorption edge

longer than the K absorption edge of the specimen, in order to prevent
of the specimen, in order to prevent
the
the emission
emission of of fluorescent
fluorescent radiation.
radiation. Incident
Incident radiation
radiation so so chosen, how-
chosen, how-

ever, will
ever, will not
not completely
completely eliminate
eliminate fluorescence,
fluorescence, sincesince the short-wavelength
the short-wavelength
components of
components of the
the continuous
continuous spectrum
spectrum will will also excite K
also excite K radiation
radiation in in the
the
specimen.
specimen. For For example,
example, suppose
suppose aa copper specimen is
copper specimen is being
being examined
examined
with
with CnCuKaKa radiation
radiation of of wavelength
wavelength 1.542A 1.542A fromfrom aa tube
tube operated
operated at at
30
30 kv.
kv. Under
Under thesethese conditions
conditions the the short-wavelength
short-wavelength limit limit isis 0.413A.
0.413A. The The
KK absorption
absorption edge edge of
of copper
copper is
is at
at ] .380A.
1.380A. The
The Ka
Ka component
component of
of the
the
incident radiation will
incident radiation will not
not cause
cause fluorescence,
fluorescence, but but all
all wavelengths
wavelengths betweenbetween
0.413
0.413 and will. If
1.380A will.
and 1.380A If aa nickel
nickel filter
filter is
is used
used to to suppress
suppress the the K{3
K/3 com-
com-
ponent of
ponent of the
the incident
incident beam,
beam, it
it will
will also
also have
have the
the desirable
desirable effect
effect of
of reducing
reducing
6-111
6-11] BACKGROUND RADIATION
BACKGROUND RADIATION 167
167

the intensity
the intensity of
of some of
some of the
the short
short wavelengths
wavelengths which which causecause fluorescence,
fluorescence,
but
but it will not,
it will not, of of course,
course, eliminate
eliminate them them completely,
completely, particularly
particularly in in the
the
wavelength
wavelength region region near
near O.6A,
0.6A, where
where the
the intensity
intensity of
of the
the continuous
continuous spec-
spec-
trum isis high
trum high and and thethe absorption
absorption coefficient
coefficient of of nickel
nickel rather
rather low.low.
It is
It is sometimes
sometimes possible possible to to filter
filter part
part of of the
the fluorescent
fluorescent radiation
radiation from from
the specimen
the specimen by placing by placing the
the proper
proper filter
filter over
over the
the film.
film. For
For example,
example, if if
aa steel
steel specimen
specimen is is examined
examined with with copper
copper radiation,
radiation, which is not generally
which is not generally
advisable, the
advisable, the situation
situation may may be be improved
improved by by covering
covering the the film
film with
with alu-
alu-
minum foil,
minum foil, because
because aluminum
aluminum has has aa greater
greater absorption
absorption for for the
the fluorescent
fluorescent
Fe KOL
Fe radiation contributing
Ka radiation contributing to to the
the background
background than than forfor thethe Cu Ka radia- radia-
tion forming
tion forming the the diffraction
diffraction lines.
lines. In In fact,
fact, thethe following
following is is aa good
good general
general
rule to
rule to follow:
follow: if if it
it is
is impossible
impossible to to use
use aa wavelength
wavelength longer longer than than thethe K
absorption
absorption edge edge of
of the
the specimen,
specimen, choose
choose one
one which is
is considerably
considerably shorter
shorter
and cover
and cover the film with
the film with aa filter.
filter. Sometimes the the air air itself
itself will
will provide
provide
sufficient filtration.
sufficient filtration. Thus excellent patterns of
excellent. patterns of aluminum can be be obtained
obtained
with CuKa
with radiation, even
Cu Ka radiation, even though
though this this wavelength
wavelength (1.54A) (1.54A) is is much
shorter
shorter than than the
the K absorption
absorption edge edge of
of aluminum (6.74A), simply
(6.74A), simply because because
the
the Al Al Ka radiation excited
radiation excited has
has such
such a
a long wavelength
long wavelength (8.34A) (8.34A) that
that it is
it is
almost completely
almost completely absorbed absorbed in in aa few
few centimeters of air.
centimeters of air.

(2) Diffraction of
(2) Diffraction of the contmuous spectrum.
the continuous spectrum. Each crystal crystal in in aa powder
powder
specimen
specimen forms forms aa weak Laue pattern, pattern, because
because of of the
the continuous
continuous radiationradiation
component of
component the incident
of the incident beam.beam. This This is is of
of course
course true true whether
whether or not not
that particular crystal
that particular crystal is is in
in the
the correct
correct position
position to to reflect
reflect the characteristic

component
component into
into the
the Debye
Debye ring.
ring. Many
Many crystals
crystals in
in the specimen
specimen are there-
fore
fore contributing
contributing only
only to
to the
the background
background of
of the photograph
photograph and notnot to to
the
the diffraction
diffraction ring, ring, and the
the totality
totality of
of the
the Laue patterns
patterns from all
all the
the
crystals
crystals is is aa continuous
continuous distribution
distribution of of background radiation. If
background radiation. If the inci-
inci-

dent
dent radiation
radiation has has been
been so chosen that
so chosen that veryvery little
little fluorescent
fluorescent radiation is
is

emitted,
emitted, then
then diffraction
diffraction of
of the
the continuous
continuous spectrum
spectrum is
is the largest
largest single
single
cause
cause of of high
high background
background intensity
intensity in in powder
powder photographs.
photographs.
(3)
(3) Diffuse
Diffuse scattrring
scattering fromfrom the the specimen
specimen itself.itself.

(a) Incoherent (Compton modified)

Incoherent (Compton modified) scattering.
scattering. This kind of
(a) of scat-
scat-
tering
tering becomes
becomes more intense intense as as the atomic
the number of the specimen
of the specimen
decreases.
decreases. .
(6) Coherent
(b) Coherent scattering.
scattering.
(i) Temperature-diffuse scattering. This
(i) Temperature-diffuse scattering.
This formform is is more intense
intense
with
with softsoft materials
materials of of low
low melting
melting point.point.
(ii)
(ii)
Diffuse
Diffuse scattering
scattering due
due to
to various
various kinds
kinds of of imperfection
imperfection in in

the
the crystals.
crystals. Any Any kind
kind of
of randomness
randomness or
or strain
strain will
will cause
cause such
such
scattering.
scattering.
(4)
(4) Diffraction
Diffraction and and scattering
scattering fromfrom other
other thanthan the
the specimen
specimen material.
material.
(a)
(a) Collimator
Collimator and
and beam
beam stop.
stop. This
This kind
kind of
of scattering
scattering can
can bebe mini-
mini-
mized by
mized by correct correct camera
camera design,
design, as
as discussed
discussed in
in Sec.
Sec. 6-2.
6-2.
168
168 POWDER
POWDER PHOTOGRAPHS
PHOTOGRAPHS [CHAP. 66
[CHAP.

(b) Specimen
(b) Specimen binder,
binder, support,
support, oror enclosure.
enclosure. TheThe glue
glue oror other
other
adhesive used
adhesive to compact
used to compact the the powder
powder specimen,
specimen, the
the glass
glass fiber
fiber to
to
which the
which the powder
powder isis attached,
attached, or
or the
the glass
glass or
or fused-quartz
fused-quartz tube
tube in
in
which
which it
it is
is enclosed
enclosed all
all contribut.e
contribute to
to the
the background
background of
of the
the photo-
photo-
graph, since
graph, since these
these are
are all
all amorphous substances. The
amorphous substances. The amount
amount ofof
these materials should
these materials should be
be kept
kept to
to the
the absolute
absolute minimum.
minimum.
(c) Air.
(c)
Air. Diffuse
Diffuse scattering
scattering from
from the
the air
air may
may be
be avoided
avoided by
by evacu-
evacu-
ating the
ating the camera
camera or
or filling it with
filling it with aa light
light. gas
gas such
such as
as hydrogen
hydrogen or
or
helium.
helium.

6-12 Crystal
6-12 Crystal monochromators.
monochromators. The The purest
purest kind
kind ofof radiation
radiation to to use
use in
in
a diffraction experiment is radiation
a diffraction experiment is radiation which
which has
has itself
itself been
been diffracted,
diffracted, since
since
it is
it is entirely monochromatic. * If
entirely monochromatic.* If aa single
singh' crystal
crystal is
is set
SE't to
to reflect
reflect the
the strong
strong
component of
Ka component of the
the general
general radiation
radiation fromfrom an an x-ray
x-ray tube and this this reflected
reflected
beam is
beam is used as the
used as the incident
ineident beam in in aa diffraction
diffraetion camera,
camera, thenthen the
the causes
eauses ofof
background radiation
background radiation listed
listed under
under (1)(I) and (2) (2) above can
ean be completely
completely elimi-
elimi-
nated. Since
nated. the other
Since the other causes
causes of of background
background scattering
scattering areare less
less serious,
serious, the
the
use of
use of crystal-monochromated
crystal-monochromated radiation radiation produces
produees diffraction
diffraction photographs
photographs of of
remarkable clarity.
remarkable clarity. There
There areare two kinds
kinds of of monochromators in in use,
use, depend-
depend-
ing
ing onon whether the reflecting
whether the crystal is
reflecting crystal is unbent or or bent and cut.
An unbent
unbent crystal
crystal is
is not
not a
a very
very efficient
efficient reflector,
reflector, as can be be seen from
Fig.
Fig. 6-14.
6-14. The beam from
from an
an x-ray
x-ray tube
tube is
is never composed
composed only
only of parallel
parallel
rays, even
rays, even when defined
defined by
by a
a slit
slit or
or collimator,
collimator, but contains a large
large pro-
pro-
portion of convergent and
portion of convergent and divergent divergent radiation.
radiation. When the crystal
crystal is
is set
set

at the correct Bragg angle for the parallel

at the correct Bragg angle for the parallel component component of
of the incident beam,
it
it can
can reflect
reflect only
only that
that component
component and none of of the
the other
other rays,
rays, with
with thethe

** This
This statement
statement requires
requires some
some qualification.
qualification. When a a crystal
crystal monoehromator
monochromator
is
is set
set to
to diffract
diffract radiation
radiation of of wavelength
wavelength X X from
from aa partiCUlar
particular set set of
of planes,
planes, thenthen
these
these same planes will
same planes will also
also diffract
diffract radiation
radiation of of wavelength
wavelength X/2 A/2 and X/3 A/3 in in the
the
second
second andand third
third order, respectively,
order, respectively, and
and at
at exactly
exactly the
the same angle
angle 2(J.
26. These
components
components of of submultiple
submultiple wavelength
wavelength are are of
of relatively
relatively low low intensity
intensity when
when the the
main
main component
component is
is Ka
Ka characteristic
characteristic radiation
radiation but,
but, even
even so,
so, their
their presence
presence is
is un-

desirable
desirable whenever
whenever precise calculations of
precise calculations of the
the intensity
intensity diffracted
diffracted by the specimen
by the specimen
must
must be be made.
made. The
The submultiple components
submultiple components may may be
be eliminated
eliminated from
from the
the beam
beam
from
from thethe monochromator
monochromator by by reducing
reducing the the tube
tube voltage
voltage to to the
the point
point where
where these
these
wavelengths
wavelengths are are not
not produced.
produced. If If the
the main
main component
component is Cu Ka
is Cu Ka radiation,
radiation, thisthis
procedure
procedure is
is usually impractical
usually impractical because
because of
of the
the decrease
decrease in
in intensity
intensity attendant
attendant on
on
aa reduction
reduction in in tube
tube voltage
voltage to to 16
16 kv
kv (necessary
(necessary to to eliminate
eliminate the the X/2
A/2 and
and X/3
A/3 com-
com-
ponents).
ponents). Usually,
Usually, aa compromise
compromise is is made
made by by operating
operating at at aa voltage
voltage just
just insuffi-
insuffi-

cient
cient toto generate
generate the the X/3
A/3 component
component (24 (24 kvkv for
for copper
copper radiation)
radiation) and and by
by using
using aa
crystal which has, for a certain set of planes, a negligible reflecting power for
crystal which has, for a certain set of planes, a negligible reflecting power
for the
the
)./2
A/2 component.
component. Fluorite (CaF22) is
Fluorite (CaF ) is such
such aa crystal,
crystal, the
the structure
structure factorfactor for
for the
the 222
222
reflection
reflection being
being much
much lessless than
than for
for thethe 111.
111. The The diamond
diamond cubic cubic crystals,
crystals, silicon
silicon
and
and germanium,
germanium, are
are even
even better,
better, since
since their
their structure
structure factors
factors for
for the
the 222
222 reflec-
reflec-
tion
tion are
are actually
actually zero.
zero.
6-12]
6-12] MONOCHROMATORS
CRYSTAL MONOCHROMATORB 169
169

result
result that the reflected
reflected beam is is of
of
very
very low intensity
intensity although
although it it is
is itself
itself

perfectly parallel, at
perfectly parallel, at least
least inin the
the plane
plane
of
of the
the drawing.
drawing. In a plane at
a plane at right
right
angles,
angles, the reflected
reflected beam may con- con- ---_
tain
tain both convergent
convergent and divergent divergent ;;~~~=~~
radiation.
radiation.
A large gain in
large gain in intensity
intensity may may be be
FIG.
FIG. 6-14.
6-14. Monochromatic reflec- reflec-
obtained
obtained by by using
using a bent
bent and cut cut crys-
crys- tion
tion when the the incident
incident beam is is non-
non-
tal, operates on
tal, which operates on the
the forusing
focusing parallel.
parallel.
principle illustrated in
principle illustrated in Fig.
Fig. C)-I
6-15.5. A
line
line source
source of of x-rays,
x-rays, the
the focal
focal line
line on the
the tube target,
target, isis located
located at at S per-
per-
pendicular
pendicular to
to the
the plane
plane of
of the
the drawing.
drawing. The crystal
crystal AB is
is in
in the
the form
form of
of aa
rectangular
rectangular plateplate and has
has aa set
set of
of reflecting planes parallel
reflecting planes parallel to
to its
its surface.
surface.
It
It is
is elastically
elastically bent
bent into
into a a circular
circular form so so that
that the
the radius
radius of of curvature
curvature of of
the plane through
the plane through Cis
C is 2R == ell!;
CM; in
in this
this way,
way, all
all the
the plane
plane normals
normals are
are
made to to pass through 111,
pass through M, which
which is is located
located onon the
the same circle,
circle, of radius R,
of radius J?,

as
as the source S.
the source S. If
If the
the face
face of of the
the ('rystal
crystal isis then cutcut away
away behind the the
dotted line to
dotted line to a radius of
a radius 72, then
of R, then allall rays
rays diverging
diverging from the the source
source S willwill
encounter
encounter the the lattice
lattice planes
planes at at the
the same BraggBragg angle,
angle, since
since thethe angles
angles
SDM,
SDM, SCM,SCM, and SEM are are all
all equal
equal to to one
one another,
another, being
being inscribed
inscribed on the the
same arcarc SM,
SM, and have the the value
value ('/1'/2
(ir/2 - 8).
8).
When the the Bragg
Bragg angle
angle is is adjusted
adjusted to to that
that required
required forfor reflection
reflection ofof the
the
KOI
Ka component
component of of the
the inrident
incident beam, beam, thenthen a a strong
strong monochromatic beam

D ('

focusing
circle

M
FIG.
FIG. 6-15.
6-15. Focusing
Focusing monochromator
monochromator (reflection
(reflection type).
type).
 170
170 POWDER PHOTOGRAPHS
POWDER PHOTOGRAPHS [CHAP. 66
[CHAP.

will be
will be reflected
reflected byby the
the crystal.
crystal. Moreover,
Moreover, since since thethe diffracted
diffracted rays
rays all
all
originate
originate on
on aa circle
circle passing through
passing through the
the source
source S,
S, they
they will
will converge
converge to
to aa
focus at F, located
focus at F, located on
on the
the same
same circle
circle as
as S
S and
and at
at the
the same
same distance
distance from
from
in much
C, in
C, much thethe same
same wayway as
as inin the
the focusing
focusing cameras
cameras previously
previously discussed.
discussed.
In practice the crystal
In practice the crystal is
is not
not bent
bent and
and then
then cut
cut as
as described
described above,
above, but
but
the unbent crystal, usually of
the unbent crystal, usually of quartz, quartz, is
is first
first cut
cut to
to aa radius
radius of
of 2R
2R and
and then
then
bent against
bent against aa circular
circular form
form of of radius
radius R.R. ThisThis procedure
procedure willwill produce
produce the the
same net
same net result.
result. TheThe value
value of required for the diffraction of a particular
of 68 required for the diffraction of a particular
wavelength XA- from
wavelength from planes
plancs of spacing dd isis given
of spacing given byby the
the Bragg
Bragg law:
la,,,:
XA- == 2rfsin0.
2d ::;in 8. (6-12)
(0-12)

The source-to-crystal
The source-to-crystal distance
distance 8C, which equals
8C, which equals the
the crystal-to-focus
cryr,;tal-to-focus dis-
dis-
tance CF,
tance is given
CF, is given by
by
SC = 2R cos
= 2fl cos
(-
8)-
(~ -- 0V (fi-13)
(0-13)

By combining
By combining Eqs.
Eqs. (6-12)
(6-12) and
and (0-13),
(6-13), we obtain
obtain
A-
SC = R-
= R-- (6-14)
(0-M)
d
d

For
For reflection of
reflection of eu radiation from the
Cu Ka radiation the (10
(10-1) 1) planes
plane::; ofof quartz,
quartz, the the
distance 8C
distance SC is is 14.2
14.2 emcm forfor a value of
a value of RK ofof 30 cm.
em.
The
The chief
chief value
value of of the
the focusing
focusing monochromator lies lies inin the factfact that
that allall

the
the monochromatic
monochromatic rays rays in
in the
the incident
incident beam arf'
are utilized
utilized and the diffracted
diffracted
rays
rays from
from aa considerable
considerable area area of of thethe crystal
crystal surface
surface are all all brought
brought to to a a
focus.
focus. This
This leads
leads to
to a
a large
large concentration
concentration of
of energy
energy and a considerable
considerable
reduction
reduction in in exposure
exposure time compared to
time compared to the
the unbent-crystal
unbent-crystal monochromator
first
first described.
described. However,
However, the the latter
latter doesdoes produce
produce a semi parallel beam of
semiparallel of
radiation, and, even though
radiation, and, even though it is of very it is of very low intensity,
intensity, such a beam is
is r{'-
re-

quired
quired inin some
some experiments.
experiments.
If
If the
the monochromating
monochromating crystal crystal is is bent
bent but not cut, cut, some
some concentration
concentration
of
of energy
energy willwill bebe achieved
achieved inasmuch
inasmuch \LS p,s the
the reflected
reflected beam will
beam will be
be con-
con-
vergent,
vergent, butbut it it will
will not
not converge
converge to to aa perfect
perfect foeus.
focus.
The
The focusing
focusing monochromator
monochromator is
is best
best used
used with
with powder
powder cameras
cameras especially
especially
made
made to to take
take advantage
advantage of
of the
the particular
particular property
property of
of the
the reflected
reflected beam,
beam,
namely
namely its
its focusing
focusing action.
action. Figure
Figure 6-16(a)
0-10(a) shows
shows the
the best
best arrangement.
arrangement.
AA cylindrical
cylindrical camera
camera is is used
used with
with the the specimen
specimen and and film
film arranged
arranged on on the
the
surface of
surface of the
the cylinder. Low-angle
cylinder. Low-angle reflections
reflections are
are registered
registered with
with the
the cam-
cam-
era
era placed
placed in position C,
in position C, in
in which
which case case the specimen D
the specimen D must
must be be thin
thin enough
enough
to be examined ill transmission.
to be examined in transmission. High-angle High-angle reflections
reflections are
are obtained
obtained by
by
back reflection with the camera
back reflection with the camera in position C", in position C', shown
shown dotted,
dotted, and
and the
the

specimen at
specimen D In
at D'.
1
In the
. the latter
latter case,
case, the the geometry
geometry of of the
the camera
camera isis exactly
exactly
similar
similar toto that
that of of the
the Seemann-Bohlin
Seemann-Bohlin camera, camera, the the focal point F
focal point F of
of the
the
6-12]
6-12] CRYSTAL MONOCHROMATORS 171
171

2()

,,
(h)
(h) '}"
'/"

FIG. 6-16. Cameras UReci

used wIth
with focusing
focusing monochromatofH'
monochromators (a) (a) focw-!ing
focusing cameras;
cameras;
(b) Debye-Scherrer and flut-film
(b) Dehye-15('}l('rrer flat-film ('amems
cameras Only Only one diffracted
diffracted beam iH is Hhown
shown in
in
ea('h
each case. (After A. (luini('r,
case. (AftRr X-ray Crystallographic
(Juinier, X-ray f'r!Jstallographir Technology,
Technology, Hilger
Hilger and Watts,
Watts,
Ltd.,
Ltd., London,
London, 1952)
1952)

monoehromati('
monochromatic bf'um beam tt(,ting
acting as as a a virtual
virtual souree
source of of divergent
divergent radiation.
radiation.
In either
either ('ase,
case, the
the diffra(ted
diffracted rays
rays from the
the specimen
specimen are
are focused
focused on
on the
the
film
film for
for all hkl rpfieetions;
all hkl reflections; the
the only requirf'ml'nt
only requirement is
is that
that the
the film
film be
be loeated
located
on a eirele pusHing thl'Ough
circle passing through the the spf'('imen
specimen and the point F.
the point F.
A Dehye-Heherrcr
Debye-Scherrer Or
or flut-film eampra may
flat-film camera may also be also bf' used
used with
with a a fo('using
focusing
mono<~hromator, if
monochromator, if tllf' in('idpnt-hf'am collimator
the incident-beam collimat.or is is rl'mowd.
removed. Figure
Figure
f>-lU(b)
6-1 6(b) shows sueh such an arrangf'ml'nt,
arrangement, where where D is is the
the speeimen,
specimen, E is iH aa
Debye
Debye camera,
camera, and PP' is is the
the position
position where aa flat. film may
flat film may be be placed.
placed.
In npith('l"
In neither ('asf', how('wr, is
case, however, is the ahove-mentioned fm'using
the above-mentioned requirement
focusing requirement
satisfif'd,
satisfied, withwith thl' result that
the result that no morl' than one
more than one diffracted
diffracted beam,beam, corre-
corre-
sponding t.o
sponding one particular
to one partil'ular hkl reflection, can
hkl reflection, can bebf' focused
foeusro on on the
the film
film at the
at the
samp time.
same time.
A bent
bent crystal
crystal maymay also
also be he used
used inin transmission
transmisHion as as aa focusing
focusing mono-
chromator. It
chromator. It must be be thin
thin enough
enough to to transmit
transmit aa largelarge fraction
fraction of of the
the
incident radiation
incident radiation and have aa set
arid have set ofof reflecting planes at
reflecting planes right angles
at right angles to to its
its
surface; mica
surface; miea is is often
often used.
used. In In Fig.
Fig. 6-17,
fH7, the the line
line ACBA('B represents
represents the the
crystal, bent
crystal, bent toto aa radius
radius 2/2,
2R, itsits center
center ofof curvature
curvature located
located at at M. ThreeThree
of itH transverse
of its transverse reflecting
refleeting planes
planes are shown. If
arf' shown. radiation converging
If radiation converging to to
K were incident
A' ineident on on these
these planes
planes and and reflected
reflected at at the
the points
points //, H, C,C, and G,
and (/,
the reflected
the reflected radiation
radiation would
would converge
converge to to aa perfect
perfect focusfocus at at F,F, all
all the
the
points
points mentioned
mentioned being
being on
on aa focusing
focusing circle
circle of
of radius
radius R centered
centered at
at O.
0.
the reflecting
But the reflecting planes
planes dodo notnot actually
actually extend
extend out out ofof the
the crystal
crystal surface
surface
in the
in the wayway shown in in the drawing and reflection
the drawing reflection must occur occur at at the
the points
points
172
172 POWDER PHOTOGRAPHS 6
[CHAP. 6
[CHAP.

_ fo('usmp;
focusing
('JT('It>
circle

Fw.6--17.
FIG. 6-17. Fo('using monoohromator
Focusing mono('hromatol' (transmission type).
(transmission type).

D, C, and E.
D, C, K. Fnder
Under these
these conditions
conditions thethe reflected
reflected rays
rays from all
all parts
parts of
the
the crystal
crystal do not
not ('onverge
converge to
to a
a perfect
perfect focus
focus at
at F.
F. Nevertheless there is
is

sufficient
sufficient concentration
concentration of of diffracted
diffracted energy
energy in
in a very
very narrow region
region near
F to
to make this
this device
device a quite
quite efficient
efficient and usable monochromator. The
crystal-to-focus
crystal-to-focus distance
distance CF is
is given
given byby
= 2R cos
CF = cos 8.
0. (fi--15)
(0-15)

Combination of of this
this equation
equation with the Bragg law will
the Bragg will give
give the bending
bending
radius
radius required
required for
for specific applications.
specific applications.
The use
use ofof a
a monochromator produces produces a a change
change in in the
the relative
relative intensities
intensities
of
of the
the beams diffracted
diffracted by by the
the specimen. Equation
specimen. Equation (4-12), (4-12), for
for example,
example,
was derived
derived for for the
the completely unpolarized
completely unpolarized incident
incident beam obtained from
the x-ray
x-ray tube.
tube. Any
Any beam diffracted
diffracted by a crystal, however,
by crystal, however, becomes par-
par-
tially polarized
tially polarized by by the
the diffraction
diffraction process itself,
process itself, which means that the
beam from a crystalcrystal monochromator is
is partially polarized
partially polarized before
before it
it reaches
the specimen.
specimen. Under these these circumstances,
circumstances, the the usual
usual polarization
polarization factor
factor
(1
(1 + cos
cos 22 28)/2, which is
20)/2, is included
included in
in Eq. (4-12),
Eq. (4-12), must be replaced
replaced by the
by
factor
factor (1 (I ++ cos
cos 22
2a
2 cos
cos
2
2 28)/(1
20)/(l + + cos
cos
2
2 2a),
2a), where 2a is
is the
the diffraction
diffraction
angle
angle in
in the
the monochromator [Fig. C}-16(b)].
[Fig. 6-16(b)]. Since
Since the
the denominator
denominator in
in
this
this expression
expression is
is independent
independent of
of 8,
0, it
it may
may be
be omitted;
omitted; the
the combined
Lorentz-polarization
Lorentz-polarization factor factor for for a a Debye-Scherrer
Debye-Scherrer camera and crystal- crystal-
monochromated radiation radiation is therefore (1
is therefore +
(1 + cos
2
cos2 2a cos
2
cos2 28)/sin 22 cos 8.
20) /sin 8 cos 6.
6-14)
6-14] MEASUREMENT OP
OF LINE INTENSITY 173
173

FIG.
FIG. 6-18.
6-18. Film-measuring device.
Film-measuring device. (Courtesy
(Courtesy of General Electric
of General Co., X-Ray
Electric Co., X-Ray
Department.)
Department.)

6-13
6-13 Measurement of of line
line position.
position. The solution
solution of of any
any powder pho-
powder pho-
tograph begins
tograph begins with
with the
the measurement of
of the
the positions
positions of
of the
the diffraction
diffraction
lines the film.
lines on the film. A device
device of of the
the kind
kind shown in in Fig.
Fig. 6-18 is is commonly
commonly
used
used for
for this
this purpose.
purpose. It
It is
is essentially
essentially a
a box with
with an opal-glass
opal-glass plate
plate on
top,
top, illuminated
illuminated from below,
below, on
on which the
the film
film to
to be
be measured is
is placed.
placed.
On top
top of
of the
the glass plate
glass plate is
is a
a graduated
graduated scale
scale carrying
carrying a
a slider
slider equipped
equipped
with
with a a vernier
vernier and cross-hair;
cross-hair; the cross-hair is
the cross-hair is moved overover the
the illuminated
illuminated
film
film from oneone diffraction
diffraction line
line toto another
another and theirtheir positions
positions noted.
noted. The
film
film is
is usually
usually measured
measured without
without magnification.
magnification. A low-power
low-power hand lens lens
may
may be
be of
of occasional
occasional use,
use, but
but magnification greater
magnification greater than
than 2 or
or 3
3 diameters
diameters
usually
usually causes
causes the line to
the line to merge
merge intointo the
the background
background and become invisible, invisible,
because of
because of the
the extreme
extreme graininess
graininess of
of x-ray
x-ray film.
film.

6-14
6-14 Measurement of of line
line intensity.
intensity. Many
Many diffraction
diffraction problems
problems re-re-
quire
quire an accurate
accurate measurement of
of the
the integrated intensity,
integrated intensity, or
or the
the breadth
at
at half
half maximum intensity,
intensity, of of a
a diffraction
diffraction line
line on aa powder
powder phot'Jgraph.
photograph.
For this
this purpose
purpose it
it is
is necessary
necessary to
to obtain
obtain a
a curve
curve of
of intensity vs. 28
intensity V8. 26 for
for
the
the line
line in
in question.
question.
The intensity of an
intensity of an x-ray
x-ray beam may may bebe measured by by the
the amount of of
blackening
blackening it
it causes
causes on
on aa photographic
photographic film.
film. The photographic density
photographic density D, D,
or
or blackening,
blackening, of a film
of a film is
is in
in turn
turn measured by by the
the amount of of visible
visible light
light
174
174 POWDER PHOTOGRAPHS
POWDER PHOTOGRAPHS [CHAP. 66
[CHAP.

it will
it will transmit
transmit and
and isis defined
defined by
by the
the relation
relation
10
/0
D == Iog
loglO
10 --,
yI
,

where /10 = intensity

where intensity of
of aa beam
beam of
of light
light incident
ineident on
on the
the film and /I == inten-
film and inten-
sity of the transmitted beam.
sity of the transmitted beam. For
For most
most x-ray films,
x-ray films, the
the density
density is
is directly
directly
proportional to
proportional to the
the exposure
exposure upup to
to aa density
density of
of about
about 1.01.0 (which
(which corre-
corre-
sponds to
sponds to 10
10 percent
percent transmission
transmission of
of the
the incident
incident light).
light.). Here,
Here, "exposure"
"exposure"
is defined
is defined by
by the
the relation
relation
Exposure
Exposure =
=:' (intensity
(intensity of
of x-ray
x-ray beam)
beam)(time).
(time).

Since the
Since the time
time is constant
is constant for
for all
all the
the diffraction
diffraction lines
lines on
on one
one film,
film, this
this means
means
that the
that the photographic
photographic density
density is directly
is direet.Iy proportional
proportional toto the
the x-ray
x-ray in-
in-
tensity.
tensity.
Density is
Density is measured
measured by by means of of aa microphotometer.
microphotometer. There There are are sev-
sev-
eral forms
eral forms of
of such
such instruments,
instruments, the
the simplest consisting
simplest consisting of
of a
a light
light source
source
and an
and an arrangement
arrangement of of lenses
lenses and slits slits which allows narrow beam of
allows aa narrow of
light to pass through
light to pass through the x-raythe x-ray film
film and strike
strike a
a photocell
photocell or
or thermopile
thermopile
connected
connected to to aa recording
recording galvanometer.
galvanometer. Since Rince thethe current
current through
through the the
galvanometer is
galvanometer is proportional
proportional to to thethe intensity
intensity of of the.
the. light
light striking
striking thethe
photocell, the
photocell, the galvanometer deflection 8
galvanometer deflection S is
is proportional
proportional to to the
the transmitted
transmitted
light intensity
light intensity /. I.
The light
light beam is
is rectangular
rectangular in in cross
cross section,
section, normally
normally about 3 mm mm
high
high and
and 0.1
0.1 mm wide.
wide. With movement of
of the
the film,
film, this
this beam is is made toto
traverse
traverse the
the film
film laterally, crossing
laterally, crossing one
one diffraetion
diffraction line
line after
after another [Fig.
[Fig.
6-19(a)].
6-19(a)]. The resulting
resulting galvanometer
galvanometer record record [Fig.
[Fig. 6-19(b)]
6-1 9(b)] shows gal- gal-
vanometer
vanometer deflection
deflection as as ordinate
ordinate and distancedistance along
along the film as abscissa,
abscissa,
the
the latter
latter being
being increased
increased by by aa fador
factor of of about 5 5 in
in order to spreadspread thethe
lines out.
lines out. The line
line A at
at the
the top
top of
of the
the record
record marks zero deflection
deflection of the
the
galvanometer;
galvanometer; the the line
line BB atat the
the bottom marks the the maximum galvanometer
galvanometer
deflection
deflection 8 S0 when .the the light
light beam passespasses through
through an unexposed
unexposed portionportion ofof
the
the film,
film, a
a portion
portion which
which hashas been
been shielded
shielded from all all scattered x-rays. SoQ is
scattered x-rays. S is

therefore
therefore constant
constant and proportional
proportional to to the
the incident
incident light intensity 10 , In
light intensity 7 . In
this
this way
way thethe readings
readings are are correded
corrected for for the
the normal background
background fog fog ofof

unexposed film.
unexposed film. The density
density of of any
any exposed
exposed partpart ofof the film
film isis then ob-
ob-
tained
tained from
from the
the relation
relation
10
/0
-- =
So
SQ
Dr, == 10glO
D Iog 10 - = IOglO-'
i i
logio
I1 So
Finally,
Finally, aa curve
curve is
is constructed
constructed of of x-ray
x-ray intensity
intensity as
as aa function
function ofof 28
26 [Fig.
[Fig.
6-19(c)].
6-19(c)]. Such
Such aa plot
plot is
is seen
seen to
to consist
consist of
of a
a number
number of
of diffraction
diffraction peaks
peaks
superimposed
superimposed on on aa curve
curve ofof slowly
slowly varying
varying background
background intensity,
intensity, due
due toto
fluorescent
fluorescent radiation,
radiation, diffraction
diffraction of of the
the continuous
continuous spectrum,
spectrum, Compton
Compton
6-14]
6-14] MEASUREMENT OF LINE INTENSITY 175
175

... >(a)

~
o
....
r-.----------------------,
---i
t;
t1 t
,'{
,,I

1~o 8 11
I

o~ L -_____________________,

'21)
20
DJ~TAN(
DISTANCE'E AL01'\U FILM l(Yj>)
ALONCJ l<'lLl\l Xli)
(h) 1C)

FIG. 6-19. Mp.:J,HUI"emt'llt

FIG. 6-19. Measurement of of line
line mtenslty
intensity with
with a a mwrophotometl'l
microphotomctci (Hl'hcmatit')
(schematic)
(a)
(a) film;
film; (h)
(b) galmIloml'tI'r recoul, (l')
galvanometei 1'('('oul, x-iay llIt1'llHII.y
(c) l\-WY intensity ('urY('
curve

scatterinjl"
scattering, et.r.,
etc., URas pl'E'viomdy
previously dil'l('ul'lsed,
discussed. A ('ontmuous
continuous harkgrotUld
background linl' line
is
is drawn in in hl'low
below earheach peak,
peak, aftt'r
after wh)('h measurements of
which ml'ltsuJ'(-UU'Ut.s of UI(' illtc'gruh-d
the integrated
intemlit.y
intensity and th(' breadth 11
the hrl'adt.h K utat half
half maximum iut.(-llslty intensity ('un can hl'
be made.
Not.e
Note that.
that thl'
the int.l'grat<>d
integrated intl'nsit.y
intensity is jl,1\'en by
is given by t.hethe Hhuded area, IlleUI$UI'(>U
shaded lLJ'(>U, measured
above
above the
the barkgl'ound,
background. A mil:l'Ophotometel'
microphotorneter record
1'('('01'(1 of
of an a('t.ual
actual paft,l'rn
pattern is is

shown in in FIg
Fig (i - 20.
(>-20.

In
In very
very pre('ise
precise work,
work, or when the the line
line densit.y
density ex('eeds
exceeds a vulue value of 1.0, it
of 1.0, it

is
is no longer
longer safe
safe to
to assume that
that the
the demlity
density 18
is proportiunal
proportional to
to tlJ('
the x-ray
x-ray
exposure
exposure 111l$tend,
Instead, earheach film
film I$houlU
should he be ('alihrat.ed
calibrated hy by ('xI)()Hing
exposing a st.rip
strip nl'ar
near
its
its edgl'
edge t.o
to a ronstant-intcnsity
constant-intensity x-rayx-ray heam
beam for
for im'rcasing
increasing amount.s
amounts of
of t.lme
time
so that
80 that a serieR
series of of stepwiRe
stepwise inrreasing
increasing exposures
exposures 11' is1 ohtained.
obtained. The exart exact
rl'latiol1
relation h('tw('l'11
between densitydensity and x-ray
x-ray ('XPOHIU'('
exposure ('an can 1.11('
then 11 he'
be dl'it-nnim-d
determined l'X- ex-
perimcntu.lly,
perimentally.

1*10. 6-20.
l'IG. 6-20. Powder pattern
pattern of
of quartz
quartz (above) corresponding ml('rophotom-
(above) and ('orre!!}Jonding mirrophotom-
eter
eter trare (below). (J.
trace (below), Ballard, H. I.
(J. W. Ballard, I. ORhry,
Oshry, and n. II H('hrenk,
II. II Schrcrik, C.
T. S.
S. Bur
Mines R.I.
Mines R. I. ,;'520.
520. CourteRy
Courtesy ofof IT.
U. R.
S. BuJ'C>uu
Bureau ofof Mines.)
Mines.)
176
176 POWDER
POWDER PHOTOGRAPHS
PHOTOGRAPHS [CHAP. 66
[CHAP.

PROBLEMS
PROBLEMS

6-1. Plot
6-1. Plot aa curve
curve similar
similar to to that
that ofof Fig.
Fig. 6-4 showing the
6-4 showing the absorption
absorption of Fe Ka
of Fe Ka
radiation
radiation by by air.
air. Take
Take the
the composition
composition of
of air
air as
as 80
80 percent
percent nitrogen
nitrogen and
and 20
20 per-
per-
cent oxygen,
cent oxygen, byby weight.
weight. If If aa 1-hr
l-hr exposure
exposure in in air
air isis required
required to to produce
produce aa certain
certain
diffraction line
diffraction line intensity
intensity in in aa 19-cm-diameter
19-cm-diameter camera camera with with FeFe Ka
Ka radiation,
radiation, what
what
exposure is
exposure is required
required to to obtain
obtain the the same
same line
line intensity
intensity withwith the
the camera
camera evacuated,
evacuated,
other conditions
other conditions being
being equal?
equal?
6-2. Derive
6-2. Derive an an equation
equation forfor thethe resolving
resolving power
power of of aa Debye-Scherrer
Debye-Scherrer cameracamera
for two
for two wavelengths
wavelengths of of nearly
nearly the the same
same value,
value, inin terms
terms of !lS, where
of AS, where SS is is defined
defined
by Fig.
by Fig. 6-2.
6-2.
6-3. For
6-3. For aa Debye
Debye pattern
pattern made
made in in aa 5.73-crn-diameter
5.73-cm-diameter camera camera with Cu Ka radi-
with Cu radi-
ation, calculate
ation, calculate thethe separation
separation of of the
the components
components of the Ka doublet
of the doublet in in degrees
degrees
and in
and in centimeters
centimeters for for e = 35, 60,
10, 35,
= 10, 60, and
and 85.
85.
6-4.
6-4. What is
is the
the smallest
smallest value
value of
of e
6 at
at which
which the Cr Ka doublet
the doublet will
will be
be resolved
resolved
in aa 5.73-cm-diameter
in 5.73-cm-diameter Debye Debye camera?
camera? Assume that that thethe line
line width
width is 0.03 cm and
is 0.03 and
that the
that the separation
separation must be be twice
twice thethe width
width for
for resolution.
resolution.
6-6. A powder
6-5. powder pattern
pattern ofof zinc
zinc isis made in in aa Debye-Scherrer
Debye-Scherrer camera 5.73 5.73 cm in in
diameter with
diameter radiation.
with Cu Ka radiation.
Calculate the
(a) Calculate
(a) the resolving
resolving power
power necessary
necessary to
to separate
separate the
the 11.0 10.3 diffrac-
11.0 and 10.3 diffrac-
tion lines.
tion lines. Assume thatthat the
the line
line width isis 0.03
0.03 cm.
cm.
Calculate the
(b) Calculate
(b) the resolving
resolving power
power of
of the
the camera used,
used, for
for these
these lines.
lines.
(c) camera diameter is
(c) What minimum camera diameter
is required
required to
to produce
produce resolution
resolution of
of these
these
lines?
lines?

(See
(See Fig.
Fig. 3-l3(c),
3-13(c), whichwhich shows these these lines unresolved from one another. They
lines unresolved They
form
form the
the fifth
fifth line
line from
from the
the low-angle
low-angle end.)end.)
6-6.
6-6. A transmission
transmission pinhole
pinhole photograph
photograph is is made of of copper with Cu Ka radia-
copper with radia-
tion.
tion. The film measures
The film measures by 44 by 5
5 in.
in. What is
is the
the maximum specimen-to-film
specimen-to-film dis-dis-

tance
tance which
which can can bebe used
used and still
still have thethe first
first two Debye
Debye rings
rings completely
completely re-
re-

corded
corded onon the
the film?
film?
6-7.
6-7. A powder is made with Cu Ka radiation.
powder pattern
pattern of of iron
iron is radiation. Assume that
the
the background
background is is due
due entirely
entirely to to fluorescent
fluorescent radiation
radiation from the specimen.
specimen. The
maximum intensity
intensity (measured
(measured above the the background)
background) of of the weakest line line on the
the
pattern
pattern is
is found
found to
to be
be equal
equal to
to the
the background intensity
background intensity itself
itself at that angle.
angle. If
If

the
the film
film is
is covered
covered withwith aluminum foil foil 0.0015
0.0015 in.in. thick,
thick, what will
will be the ratio
ratio of
of

max for
I/max for this
this line
line to
to the
the background
background intensity?
intensity?
6-8.
6-8. A microphotometer
microphotometer record record of of a a diffraction
diffraction line
line shows the following
following gal-
gal-
vanometer
vanometer deflections:
deflections:

Position of
Position of Light
Light Beam Deflection
Deflection

On
On unexposed
unexposed film
film 5.0
5 cm
.cm
On
On background,
background, just
just to
to left
left of
of line
line 3.0
3.0
On
On background,
background, just
just to
to right
right of
of line
line 3.2
3.2
On
On center
center of
of diffraction
diffraction line
line 1.2
1 2.

Assume
Assume that
that x-ray
x-ray intensity
intensity is
is proportional
proportional to
to photographic
photographic density.
density. Calculate
Calculate
the
the ratio of I7max
ratio of max for
for the
the diffraction
diffraction line
line (measured
(measured above
above the
the background)
background) to
to the
the
intensity of the background at the same Bragg
intensity of the background at the same Bragg angle. angle.
 CHAPTER
CHAPTER 77

DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETER MEASUREMENTS

1-1 Introduction.
7-1 Introduction. The The x-ray
x-ray spectrometer,
spectrometer, briefly briefly mentioned
mentioned in in Sec.
Sec.
3-4, has had a long and uneven
3-4, has had a long and uneven history history in
in the
the field
field of
of x-ray
x-ray diffraction.
diffraction. It
It

was first
was first used
used by by W.W. H. H. and
and W.W. L. L. Bragg
Bragg in their early
in their early work on x-ray
work on x-ray
spectra and
spectra and crystal
crystal structure,
structure, butbut itit then
then passed
passed into into aa long
long period
period of of rela-
rela-
tive disuse
tive disuse during
during which
which photographic
photographic recording
recording in in cameras
cameras was the the most
most
popular method
popular method of of observing
observing diffraction
diffraction effects.
effects. The The few few spectrometers
spectrometers in in
use were
use were all
all home
home made and
and confined
confined largely
largely to
to the
the laboratories
laboratories of
of research
research
physicists. In
physicists. In recent
recent years,
years, however,
however, commercially
commercially made instruments instruments
(based mainly
(based mainly on on aa design
design developed
developed by by Friedman about about 1943)
J943) have
have be- be-
come available,
come available, and and their
their use is growing
use is growing rapidly
rapidly because
because of of certain
certain par-par-
ticular advantages
ticular advantages which which theythey offer
offer overover filmfilm techniques.
techniques. Initially
Initially aa
research tool,
research tool, the
the x-ray
x-ray spectrometer
spectrometer has has now become an instrument instrument for for
control and analysis
control and analysis in
in a
a wide
wide variety
variety of
of industrial
industrial laboratories.
laboratories.
Depending
Depending solelysolely onon the
the way
way itit is used, the
is used, the x-ray
x-ray spectrometer
spectrometer is is really
really
tW.0
two instruments:
instruments:
s (1)
./ (1) An instrument
instrument for for measuring
measuring x-rayx-ray spectra
spectra by by means of of a crystal
crystal of of
known
known structure.
structure.

(2) An instrument
(2) instrument for for studying
studying crystalline
crystalline (and (and noncrystalline)
noncrystalline) mate-
rials by measurements
rials by measurements of
of the
the way
way in
in which
which they
they diffract
diffract x-rays
x-rays ofof known
wavelength.
wavelength.
The term 6pectrometer
The term spectrometer has has been,
been, and stillstill is,
is, used to to describe
describe both
both instru-
instru-

ments,
ments, but, properly, it
but, properly, it should
should be be applied
applied only only to to the first
first instrument.

The
The second
second instrument
instrument has has been
been aptly
aptly called
called a a diffractometer:
diffractometer: this this is
is a
a term
of
of quite
quite recent
recent coinage
coinage but
but one
one which
which serves
serves well
well to
to emphasize
emphasize the par-
par-
ticular use
ticular use toto which
which the
the instrument
instrument is
is being put,
being put, namely,namely, diffraction
diffraction anal-
anal-
ysis
ysis rather
rather than spectrometry. In
than spectrometry. In this
this chapter,
chapter, the the design
design and
and operation
operation
of diffractometers will
of diffractometers will be
be described
described with with particular
particular reference
reference to to the
the com-
com-
mercial
mercial models
models available.
available.

1-2
7-2 General features. In
General features. In aa diffraction
diffraction camera,
camera, the the intensity
intensity of of aa dif-
dif-

fracted beam is measured

fracted beam is measured through through the
the amount
amount of
of blackening
blackening it
it produces
produces
on photographic film,
on aa photographic film, aa microphotometer
microphotometer measurement
measurement of of the
the film
film being
being
required
required to
to convert
convert "amount
"amount of
of blackening"
blackening" into
into x-ray
x-ray intensity.
intensity. In
In the
the
diffractometer,
diffractometer, the intensity of
the intensity of aa diffracted
diffracted beam
beam isis measured
measured directly,
directly,
_either
.either byby means
means of
of the
the ionization
ionization it
it produces
produces in
in aa gas
gas or
or the
the fluorescence
fluorescence
177
177
 178
178 DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETER MEASUREMENTS [CRAP. 77
[CHAP.

it produces
it produces in in aa solid.
solid. As As we we saw
saw in in Sec. 1-5, incident
Sec. 1-5, incident x-rayx-ray quanta
quanta can can
eject
eject electrons
electrons from
from atoms
atoms and
and thus
thus convert
convert them
them into
into positive
positive ions.
ions. If
If

an x-ray
an x-ray beambeam isis passed
passed intointo aa chamber
chamber containing
containing aa gas gas andand two two elec-
elec-
trodes, one
trodes, one charged
charged positively
positively and and the the other
other negatively,
negatively, then then the the ejected
ejected
electrons
electrons will
will be drawn
be drawn to
to the
the positive
positive electrode
electrode (the anode)
(the anode) and
and the
the posi-
posi-
tive ions to the negative electrode
tive ions to the negative electrode (the cathode). (the cathode). A
A current
current therefore
therefore
exists in
exists the external
in the external circuit
circuit connecting
connecting anode anode to to cathode.
cathode. Under Under special
special
conditions, which
conditions, which are are described
described later later in in detail,
detail, this current
this current can can bebe caused
caused
to surge
to surge or or pulse
pulse rather
rather thanthan be be continuous;
continuous; each each pulse
pulse results
results fromfrom the the
ionization caused
ionization caused by by aa single
single entering
entering x-ray x-ray quantum.
quantum. By By use
use of of thethe
proper
proper external
external circuit,
circuit, the
the number
number of
of current
current pulses
pulses produced
produced per
per unit
unit
of time
of time can can be be counted,
counted, and and this
this number
number is is directly
directly proportional
proportional to to thethe
intensity
intensity of
of the
the x-ray
x-ray beam
beam entering
entering the
the gas
gas chamber.
chamber. Appropriately,
Appropriately,
this device
this device is is called
called aa counter,
countpT, and and two varieties
varietieH are are inin common use, use, thethe
proportional
proportional counter
counter and
and the
the Geiger
Geiger counter.
counter. In
In another
another type,
type, the
the scintil-
scintil-

lation counter,
lation counter, incident
incident x-ray
x-ray quanta
quanta produce
produce flashes
flashes or or scintillations
scintillations of of
fluorescent blue
fluorescent blue light light in
in a
a crystal
crystal and t.hese
these light
light flashes
flashes are
are converted
converted into
into
current pulses
current pulses in in aa phototube.
phototube.
Basically, aa diffractometer
Basically, diffractometer is is designed
designed somewhat like like aa Debye-Scherrer
Debye-Scherrer
camera,
camera, exceptexcept that that aa movable counter replaces
movable counter replaces the strip
the strip of film. In
of film. In both
both
instruments,
instruments, essentiallyessentially monochromatic
monochromatic radiation radiation is used and the x-ray
is used and the x-ray
detector
detector (film (film or counter) is
or counter) placf'd on the
is placed the circumference of of a cirele
circle cen-

tered
tered on on thethe powder
powder specimen.
specimen. The essential essential features
features of of a diffractometer
are
are shown
shown in in Fig.
Fig. 7-1.
7-1. A powder
powder specimen
specimen C,
C, in
in t.he
the form of
of a flat
flat plate,
plate,
is
is supported
supported on
on a
a table
table H,
H, which can he
be rotated
rotated about an axis"O
axis*0 peJ-pen-
perpen-
dicular
dicular to to the
the plane
plane ofof the
the drawing.
drawing. The x-ray x-ray source is S, the line
is S, line focal
focal

spot
spot on
on the
the target
target TT of
of the
the x-ray tube;
x-ray tube; S is
is also
also normal to
to the plane
plane of the
drawing
drawing and
and therefore
therefore parallel
parallel to
to the
the diffractometer
diffractometer axis
axis O.
0. X-rays
X-rays di-
di-

verge
verge from
from this
this source
source and
and are
are diffracted
diffracted by
by the
the specimen
specimen to
to form a con-
con-
vergent
vergent diffracted
diffracted beam which comes comes to focus at
to a focus at the slitslit F F andand then
enters the counter
enters the counter G. G. A
A and B
B are
are special
special slits
slits which define
define and
and collimate
the incident and diffracted
the incident and diffracted beams. beams.
The
The receiving
receiving slits slits and
and counter
counter are are supported
supported on on the carriage E,
the carriage E whieh
y
which
may
may be be rotated
rotated about about the axis 0 and
the axis and whose
whose angular
angular position
position 28 may
26 may be be
read
read on on the
the graduated
graduated scale scale K. K. The The supports
supports E E and H
and H are mechanically
are mechanically
coupled
coupled so so that
that aa rotation
rotation of of the
the counter
counter through
through 2x 2x degrees
degrees is is automatically
automatically
accompanied
accompanied by by rotation
rotation of of the
the specimen
specimen throughthrough xx degrees.
degrees. This This cou-cou-
pling
pling ensures
ensures that
that the
the angles
angles of
of incidence
incidence on,
on, and
and reflection
reflection from,
from, the
the flat
flat

specimen
specimen will
will always
always be
be equal
equal to
to one
one another
another and
and equal
equal to
to half
half the
the total
total
angle
angle of of diffraction,
diffraction, an an arrangement
arrangement necessarynecessary to to preserve
preserve focusing
focusing con- con-
ditions. The
ditions. The counter
counter may may be
be power-driven
power-driven at
at aa constant
constant angular
angular velocity
velocity
about
about the the diffractometer
diffractometer axis axis oror moved
moved by by hand
hand to to any
any desired
desired angular
angular
position.
position.
7-21
7-2] GENERAL FEATURES 179

_/- -------- -------,

ddlml'tolll!'!!'1
('U 1'1('

1\-

FKJ i7 I,
FIG 1. X-ray
X-ray IhfTra('toll1eteJ
difTrartoinetei (~('hemlitJ(')
(schematic)

Figures i7-2
FigurPIl - '2 and 77-3-3 ilIust
illustratera t (' two ('umm('n'ial
commercial inst mment Il, Ba~i('ully,
instruments. Basically,
both adhE'l'l'
adhere to to thp
the dE'llign prin('iplE'~
design principles des('rihe(l
described ahoye,
above, hut but they
they differ
differ in
in
detail
detail undand in in pu~it ioning:
positioning: III
in t hp
the OE'neral
(General Elpl'tri('
Electric unit,
unit, thE'
the diffrlu'tometer
diffract ometer
UXiH
axis iHis ,,('rtieul
vertical lindand th('
the ('ountf'J'
counter mO\'(,H moves in in Ita horizolltllI
horizontal plull(',
plane, whf'reas
whereas thethe
UXiH
axis ofof the
the XOJ't'll'O
Xorelco unit unit isi/.; horizontal
horizontal and the the l'ountpl'
counter moyes
moves in a wrtielll
in II vertical
plane,
plane.
Th(,
The wayway in in ",hidl
which II a (hffra('tom('tf'1'
diffract ometer ill is u~('d
used to to m('!l.SUI'('
measure II a diffrlt<'tion
diffraction pat-pat-
tern depends
tern depends on the
the kind of ei!'('uit
of circuit used IlHpd to
to measurE'
measure thp
the rate
rate of
of prodll(,tion
production
of PUIHE:'H
of pulses in in th(,
the ('mlllt('\', The pul~('
counter. 'I'll(' pulse mh' rate mlly
may he be m(,llImrpd
measured in t\\o diffprt'nt
in 1\\0 different
\\u)'s:
uuys:
(1)
(1) ThE'
The HIlCl'ession
succession of of ('urrent
current pullles pulses ill is ('onwrtpd
converted into into a stpad~' l'url'l'nt,
a steady current,
whil'h
which is is measured on a
a meter called a counting-rate meter, !'ulihrated
mef,e!' ('!tll('d It (,OIl1ltl1lg-rat(' m('/n, calibrated in in
1!U('h
such unit.s
units usas ('OuntH
counts (pulsell)
(pulses) p('r per s('('ond,
second. Hm'h Such II a !'ireuit gives a ('ontinuou~
circuit givPIl continuous
indi('at.ion
indication of of x-ray
x-ray intenllity.
intensity.
(2) The puIHPs
(2) pulses of of ('url'('nt
current un' are ('ount
counted ('d ('I('('t I'OnieulIy ill
electronically in ua ('in'uit
circuit ('ullpd
called II.
a
sealer, and the
lICalcT, the U\'prage
average ('ollIlting
counting I'II.tp rate i~ obtained ~imply
is ohtuined simply hy by dh'idmg
dividing the
numher
number of of pulHeH
pulses ('ounted
counted by by the the ttime
imp spent
spent in in ('ounting,
counting. ThiH This operation
operation
is
is P8sentially
essentially dil!<'ontinuolIH
discontinuous ht'('uuse
because of of the'
the timp
time spent
spent in in ('Ollllting,
counting, and a
sealing
scaling rir('uit
circuit ('an not he'
cannot be IIHed
used to to folIow continuous rhang('~
follow ('ontinuous changes in in x-ray
x-ray in-
in-
t.enHit.y.
tensity.
Corl'E:'l:!ponding
Corresponding to to these
these two kindH kinds of of meaHllring
measuring ('in'lIits,
circuits, t.here
there UI'('
are two
ways
ways in in which thp the diffraetion
diffraction patternpattl'rn of of an unknown suh8f:m('e substance mlly may h('
be
ohtained
obtained with with a diffrurtometer:
diffract ometer:
 180
180 DIFFRACTOMETER MEASUREMENTS [CHAP. 7
[CHAP. 7

FIG.
FIG. 7-2.
7-2. General Electric
Electric diffractometer.
diffractometer. (Courtesy
(Courtesy of
of General
General EleC'tric
Electric Co.,
Co.,
X-Ray Depart~ent.)
X-Ray Department.)
7-2]
7-2] GENERAL FEATlTItES
GENERAL FEATURES 181
181

'
' '

7-3. Norelco
FIG. 7-3.
FIG. Norelro diffractometer.
diffractometer. InIn this
this particular
parti('ular photograph,
photograph, the
the specimen
speeimen
holder for
holder for aa thin
thin rod
rod specimen
;.;pe('imen is
is shown
shown instead
instead of
of the
the usual
usual holder
holder for
for aa flat
flat plate
plate
specimen. X-ray
specimen. X-ray tube
tube not
not shown.
shown. (Courtesy
(Courtesy of
of North
North American
American Philips
Philips Co.,
Co., Inc.)
Ine.)
 182
Ig2 DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETER MEASUREM~;NTS [CHAP. 77
[CHAP.

(1) Continuous.
(1)
The counter
Continuous. The counter isis set
set near 2(J == 0 and
near 26 and connected
connected to
to aa
counting-rate meter.
counting-rate meter. The
The output
output. ofof this
this circuit
eire'uit iH fed into a fast-acting
is fed into a fast-acting
automatic recorder
automatic recorder of
of the
the kind
kind used
used to
t.o record
record temperature
temperature changes
changes as
as
measured by
measured by aa thermocouple.
thermo('ouple. The
ThE' counter
count.er isis then
then driven
driven at. a constant
at a constant,
angular velocity
angular velocity through
through increasing
increasing values
valul's of
of 20 until the
28 until the whole
wholl' angular
angular
range isis "scanned."
range "seanned." At At the
t.he same
saml' time,
time, the
t.he paper
pap('r chart
('hart on
on the
t.he recorder
recorder
moves at
moves at. aa constant
eonst.ant speed,
speed, so
so that
t.hat distances
distam'l's along
along the
the length
length ofof the
t.hl' chart
chart
are proportional
are proportional toto 26. The result
28. The result isis aa chart,
('hart, such
such as
as Fig.
Fill:. 7-4,
7-4, which gives
which gives
aa record
record of
of counts
counts per
per second
seeond (proportional
(proportional to
to diffracted
difTra('ted intensity)
intE'nHity) !'s. dif-
vs. dif-

fraction angle
fraction angle 26.
28.
(2)
(2)
Jntcrmzttent.
Intermittent. The counter
The ('ount.er isis connected
wnn{'('ted to t.o aa sealer
scaler and
and set
set at
at aa fixed
fixed
value of
value of 26 for aa time
28 for time sufficient
suffi('ient to
to make
make an an accurate
ae('urate count
count ofof the
the pulses
pulscs
obtained from
obtained from the
thf' counter.
counter. TheThe counter
(ount.er is
is then
thl'n moved
mO\'ed toto aa new angular
angular
position
position and
and the
the operation
operation repeated.
repeated. The
The wholl'
whole range
range of
of 28
26 is
is C'O\'ered
covered in
in

this fashion,
this and the
fashion, and the curve
C'urvc of
of intensity
intensity vs. is finally
2(J is
!'S. 26 finally plotted
plottl'd by
hy hand.
hand.
When the the continuous
('ontinuous background
ba('kground betweenbet\\w'n diffraction
diffradion lines lines isis being
}wing meas-
meas-
ured,
ured, the
the ('ounter
counter may
may be
be moved in
in stE'PH
steps of
of several
several degrees,
degrees, but
but df'tprmina-
determina-
tions of
tions of line
line profile
profile maymay require
require measurements
mpasurpments of of intensity
intenfiity at at angular
angular
intervals as
intervals as small
small as aH 0.01 'fhi" method of
0.01 0. This
. of obtaining
ohtaining aa diffraction
diffraetion pattern
pattern
is much
is much slower
slower thanthan that
that involving
involving Iia rate rate meter and automatic recorder reeorder
but it yields
but it yields more precise measurempnts
more precise measurements of of intf'nsity.
intensity.
There is
There is aa fundamental
fundamental differenee
difference he tween thp
between the oppration
operation of a powder powder
camera
camera andand aa diffraetometer.
diffractometer. In In aa ('amera,
camera, all all diffraction
diffraction lines lines are reeorded
recorded
simultaneously,
simultaneously, and and variations
variations in in the
the intensity
intensity of of the imident.
incident x-rayx-ray beam
during
during the
the exposure
exposure can
can ha\'e
have no effc(t
effect on relati\'('
relative line
line intensities.
intensities. On
the
the other
other hand,
hand, with
with a
a diffractometer,
diffractometer, diffra('tion
diffraction lines
lines are
are recorded one
after
after the
the other,
other, and and itit is
is therefore
therefore imperatIve
imperative to to kl'ep
keep the inc'idcnt-beam
incident-beam
intensity
intensity constant
constant when relative
relative line
line intensities
intensities must he
be measured accu-
accu-
rately.
rately. Since
Since the
the usual
usual variations
variations in
in line
line voltage
voltage arc
are quite
quite appreciable,
appreciable,
the
the x-ray
x-ray tube
tube circuit
circuit ofof aa diffractometer
diffractometer must inelude include a voltagevoltage stabilizer
stabilizer

and
and aa tube-current
tube-current stabilizer,
stabilizer, unless
unless a
a monitoring
monitoring system
system is
is used (see (see
Sec.
Sec. 7-8).
7-8).
The
The kind
kind of of specimen
specimen used used depend~
depends on on thethe form
form and and amount
amount of of material
material
available.
available. Flat Flat metal
metal sheet
sheet or or plate
plate maymay be
be examined
examined dIrectly;
directly; however,
however,
such
such materials
materials almost
almost always
always exhibit
exhibit preferred
preferred orientation
orientation and and this this fact
fact
must
must bebe kept
kept in
in mind
mind in
in assessing
assessing relative
relative intensities.
intensities. This
This is
is also
also true
true of
of
wires,
wires, which
which are
are best
best examined
examined by cementing
by cementing a
a number
number of
of lengths
lengths side
side by
by
side
side to
to aa glass
glass plate.
plate. ThisThis plate
plate is is then
then inserted
inserted in in the
the specimen
specimen holder holder
so that
so that thethe wire
wire axes
axes are are atat right angles
right angles to
to the
the diffractometer
diffractometer axis.
axis.

Powder specimens
Powder specimens are
are best
best prepared by
prepared by placing placing the
the powder
powder in
in a
a recess
recess in
in

aa glass
glass or
or plastic plate, compacting
plastic plate, compacting it
it under
under just
just sufficient
sufficient pressure
pressure to
to
cause
cause cohesion
cohesion without
without use use of of aa binder,
binder, and and smoothing
smoothing off off the
the surface.
surface.
Too much pressure
Too much pressure causes
causes preferred
preferred orientation
orientation of
of the
the powder particles.
powder particles.
Alternately,
Alternately, the the powder
powder may may be be mixed
mixed with with aa binder
binder and and smeared
smeared on on the
the
 7-2]
~
(wb) 3TVDS A1ISN31NI

GEKKRAL FEATURES
o
~
l;I;2

I
A~~m~tic~IY recorded diffraction pattern of tungsten powder. Unfiltered copper radiation, 25 kv, 20 rna. Different
slits used for the front-reflection region (above) ami the back-reflection region (below). The weak tungsten Wi lines are due to a ~

183
small amount of tungsten contamination in the x-ray tube. after 3750 hours of use. (Courtesy of North American Philips Co., Inc.) Co:)
 184
184 DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETER MEASUREMENTS [CHAP. 77
[CHAP.

surface of
surface of aa glass
glass slide.
slide. The powder
The powder shouldshould be be ground
ground extremely
extremely fine, fine, to
to aa
size of 10 microns
size of 10 microns or or less,
less, ifif relative
relative line line intensities
intensities are are to to bebe accurately
accurately
reproducible; since
reproducible; sinee the the flat flat specimen
specimen isis not not rotated
rotated as as aa Debye-Scherrer
Debye-Scherrer
specimen
specimen is, is, the
the only
only way ' .... ay of
of obtaining
obtaining an
an adequat.e
adequate number
number of particles
of particles
having
having the
the corred
correct orient.ation
orientation for
for reflection
reflection is
is to
to reduee
reduce their
their average
average size.
size.

Surface
Surface roughnessroughness also
also has
has aa marked
marked effeet
effect on
on relative
relative line
line int.ensities.
intensities. If
If

the surface
the surface is
is rough,
rough, as
as in
in the
the ease
case of
of aa eoarse
coarse powder ('ompact,
powder compact, and
and the
the
linear absorption
linear absorption coefficient
eoefficient high, high, the the intensities
intensities of of low-angle
low-angle reflections
reflections
will be abnormally
will be abnormally low, because low, beeause of
of the
the absorption
absorption of
of the
the diffraeted
diffracted rays in
rays in
each projecting
each projecting portionportion of of the
the surface.
surfa('e. The only
The only wayway to avoid this effe('t
to avoid this effect

is to
is to use
use aa flat-surfaced
flat-surfa('ed compact ('ompaet of of very
very fine
fine powders
powders or or aa specimen
specimen with with
aa polished
polished surface.
surfa('e.
not. enough
If not
If enough powder
powder is is available
available for for aa flat
flat specimen,
spe('imen, aa thin-rod
thin-rod speci-
spe('i-
men of
men of the
the kind
kind used
used in in Debye-Scherrer
Debye-S(,herrer cameras cameras may may be used; it
be used ; it is
is mounted
mounted
on the
on the diffractometer
diffractometer axis axis and and continuously
eontinuousl:v rotated rotated by by aa small
small motor
motor
(sec Fig.
(see Fig. 7-3). 7-3). However,
However, the
the use
use of
of su('h
such a
a limall
small spp('imen
specimen should
should be
be
avoided if
avoided if possible,
possible, sincesinep it it leads
leads to to intensities
intensities very very muchmu('h lower
lower thanthan those
those
obtainable with
obtainable with aa flat,
fiat specimen.
sppeimen.
Ringle-(,rystal spc('im'ns
Single-crystal specimens may may also also be be examined
examined in in aa diffractometer
diffra('tometer by by
mounting the
mounting the crystal crystal on
on a
a three-cirde
three-circle goniometer,
goniometer, su('h
such as
as that
that shown in
in

Fig. 5-7, ",hieh will allow

Fig. 5-7, which will allow independent independent rotation
rotation of
of the
the sp'('imen
specimen and
and coun-
coun-
ter
ter about
about thp the diffra('tometer
diffractometer axis. axis.
A diffraetometer
diffractometer may may be be uspd
used forfor measurements at at high
high or or low
low tempera-
tempera-
tures
tures by by surrounding
surrounding the the speC'imen
specimen with with the the appropriate
appropriate heating heating or or eooling
cooling
unit..
unit. Ruth Such an an adaptation
adaptation of of the instrument is
the instrument is mu('h
much easiereasier with the the dif-
dif-

fractometer than
fractomet.er than with
with a a camera
camera because
because of of the
the generally
generally larger larger amount of of

free
free working
working spaee around t.he
space around the spetimen
specimen in in the
the formpr.
former.
In
In thethe suecepding
succeeding sections,
sections, the
the various
various parts
parts of
of the diffractometer will
the diffraetometer will

be
be des('ribed
described in in greater
greater detail.
detail. This
This summary
summary of
of the
the general
general features of
of

the
the instrument
instrument is is enough
enough to
to show its
its prineipal
principal advantage
advantage over the powder
powder
camera:
camera: the the quantitative
quantitative measur,ementmeasurement of of line
line position
position and intensity intensity is is

made in one
made in one operation operat.ion with
with aa diffraetometer,
diffractometer, whereas
whereas the same
same measure-
measure-
ment
ment with with filmfilm technique
technique requires requires three three stepssteps (recording
(recording the the pattern
pattern on on
film,
film, making
making aa mierophotometer
microphotometer record record of of thethe film,
film, and conversion of
and conversion of

galvanometer
galvanometer deflections deflections to to intensities)
intensities) and and leads
leads to anto an over-all result
over-all result

which is
which is generally
generally of of lower
lower accuracy.
accuracy. This This superiority
superiority of of the
the diffractometer
diffractometer
isis reflected
reflected in in the
the much
much higher higher cost cost of of the
the instrument.,
instrument, aa cost cost due
due notnot only
only
to
to t.he
the precision
precision machining
machining necessary
necessary in
in its
its mechanical
mechanical parts
parts but
but also
also toto
the
the expensive
expensive circuits
circuits needed
needed to
to stabilize
stabilize the
the power
power supply
supply and
and measure
measure
the
the intensity
intensity of of diffracted
diffracted beams. beams.

7-3 X-ray optics.

7-3 X-ray optics. The
The chief
chief reason
reason for
for using
using aa flat
flat specimen
specimen isis to
to take
take
advantage of the focusing
advantage of the focusing action
action described
described in
in Sec.
Sec. 6-6
6-6 and
and so
so increase
increase the
the
7-31
7-3] X-RAY
X-HA Y OPTICS
OPTICS 185
185

iffract omc'tor circle

fO(,UHllIg
('Ire\(>
L--

\
\ '1)('('JIJI!'lI
F \ lIoflllal
\

(a)
(a)

FIG. 7-5.
FIG. 7-5. Fc)('usin~ geometry
Focusing geometry for
for flat
flat specimens
spe('imen;; in
iII (a)
(a) forward
forwarci reflection
reflection and
(11)
(h) lJ:wk reflection.
hack Irfle('tion.

int.ensity of
intensity of weak diffracted
weak diffra('ted beams toto aa point
point where they
they can
ran he
he accurately
a('curately
measured.
measured. Figure
Figure 7-5
7-5 Hhows
shows how this
this is
is done,
done. For any
any position
position of the
of the
e()lInt.er,
counter, the
the reeeiying
receiving slit
slit F and dIP
the x-ray
x-ray source
source S are
are always
always loeated
located on
on
the difTractometer
the difTraet.omef('r circle,
cirele, which
which means that
that. the
the face
faee of t.he specimen,
of the speeimen, be-
be-
('ause of
cause of its
it.s mechanical
meehanieal coupling
eoupling with with thethe counter,
('ounter, is is always
always tangent
t.angent, to t.o aa
foeusing
focusing eirele
circle ('ent.ered
centered on
on the
the normal
normal to
to t.he
the speeimen
specimen and passing through
passing through
F and
and S. foem;in!!; eirele
$. The focusing circle isis not.
not of'
of ('onst.ant
constant Hize size hut inereases in
but increases radius
in radius
as the angle
as the angle 20
26 deereases,
decreases, as
as indieated
indicated in
in Fig.
Fig. i-5.
7-5. Perfect,
Perfect focusing
focusing at at F
requires t.hat the
requires that the specimenspeeimen be
be euryed
curved to
to fit
fit the foeusing eircle,
focusing circle, but.
but that is
is

not practical bee'ause of

not practical because of the changing the ehanging radiuH
radius of
of euryatnre
curvature of
of the ein-Ie.
circle.

This
This ineyitably
inevitably causes causes some broadening
broadening of of the
the diffraeted
diffracted heam
beam at F but
not.
not t.o
to any
any objeetionable
objectionable degree,degree, so so long
long as as the
the divergence
divergence of of the
the incident
incident
hram
beam is is not
not t.oo
too large.
large.
The
The line
line souree
source .-; $ extrnds
extends eonsiderahly
considerably ahove above and below the the plane
plane of of
thr
the drawing
drawing of of Fig. 7-5 and emit.s
Fig. 7-5 emits radiation
radiation in in allall direetions,
directions, but the foe us-
but the focus-
ing
ing deserihed
described ahove above requires
requires that
that allall rays
rays in in the
the ineident
incident beam be be parallel
parallel
to
to the
the plane
plane of of the
the drawing.
drawing. This conditioncondition is is realized
realized as dosely
closely as pos- pos-
sible experimentally by
sible experimentally by passing
passing the the incident
incident beam through through a SollerSoller slitslit

(Fig. 7-0), slit

(Fig. 7-6), slit A in in Fig. 7-1, which contains
Fig. 7-1, contains aa set set of
of closely
closely spaced,
spaced, thin
metal
metal plates parallel to
plates parallel to the
the plane
plane ofof the
the diffractomet.er
diffractometer circle. circle. These plates plates
remove
remove aa large proportion
large proportion of
of rays
rays inclined
inclined to
to the
the plane
plane of
of the diffractometer
diffractometer
circle and
circle and still
still allow
allow the
the use
use ofof aa line
line source
source of of considerable
considerable length.
length. Typical
Typical
dimensions
dimensions of of aa Soller
Soller slit
slit are:
are: length
length of of plates
plates 32 32 mm,
mm, thickness
thickness of of
plates
plates 0.05
0.05 mm,
mm, clear
clear distance
distance between
between plates
plates 0.43
0.43 mm.
mm. At
At either
either end
end of
of
the
the slit
slit assembly
assembly are are rectangular
rectangular slits slits a and b,
a and 6, the
the entrance
entrance slitslit aa next
next toto
the
the source
source being narrower
narrower than
than the
the exit
exit slit b.
slit b. The
The combination
combination of
of slits
slits
being
and
and plates
plates breaks
breaks up up the
the incident
incident beam beam into into aa set set of
of triangular
triangular wedges
wedges of of
radiation, as indicated
radiation, as indicated in
in Fig.
Fig. 7-6.
7-6. There
There are,
are, of
of course,
course, some
some rays,
rays, not
not
shown
shown in in the
the drawing,
drawing, which
which diverge
diverge in in planes
planes perpendicular
perpendicular to to the
the plane
plane
 -

186
~

t:;$

DIFFRACTOMETER MEASUREMENTS
....
"'lI

~
~
~
l".2
'"'l
ta
is::
~
~
~l".2
Z
;1
r

FIG. 7-6. Soller slit (schematic). For Rimplicity. only three metal plates are shown; actual Soller slits contain about a dozen. ~

TJ

[CHAP. 7
G
6

c3

G
03

o
>-
:-<'
"""
7-3J
7-3] X-RAY
X-RAY OPTICS
OPTICS 187
187

incident-beam ~hlH
llI(,IC\!'nl-i){'UIIl slits

S
specimen

*--
iecei\ ing slit

/
; :^_
,.^ . - to
10 counter
('olllllpr
7-7.
FIG. 7-7.
FIG. Arrangement of
Arrangement of slits
slits in
in diffractometer.
diffractometer.

of the
of the plates,
plates, these rays
and these rays cause
cause the
the wedges
wedges ofof radiation
radiation to
to merge
merge into
into
one another
one another aa short distance away
short distance away from the
the exit
exit slit.
slit. However,
However, the
the long,
long,
elosely spaced
closely spa('ed plates
platpH do restrict
rpstriet this
this unwanted divergence
divergence toto an angle
angle of
of
about 1..1)0.
about Rlits a and bb define
1.5. Slits define the
the divergence
divergen('e of
of the
the incident
incident beam in
in the
the
plane of
plane of the
the diffractometer
diffractometer circle.
eirele. The slits commonly available
slits commonly available have
divergen('p angles
divergence angles ranging
ranging from
from very
very small values up
small values up to about 4.
to about In the
-10. In the
forward-refiection region, Ita divergence
forward-reflection region, divergence angle
angle of 1 is
of 1 is sufficient because of
sufficient because of
the
the low inclination of
low inclination thp specimen
of the specimen surface
surface to to the incident
incident beam,
beam, but in in
baek refieetion an increase
back reflection increase in in divergence
divergence angleangle to to 33 or -1 will
or 4 will increase
increase the
diffracted
diffracted intensity.
intensity. But ifif line
line intensities
intensities areare to be compared
to be compared over the
whole
whole range
range of of 28,
26, the
the same diverg<>nce
divergence must be used throughout throughout and the
specimen
specimen must be be wider
wider than
than the
the beam at at all
all angles.
angles.
The beam diffracted
diffracted by by the
the specimen
specimen passes
passes through
through another Soller-slit
Soller-slit
assembly
assembly and the the receiving slit F before
receiving slit before entering
entering the the counter.
counter. Since the
receiving
receiving slit
slit defines
defines the
the width of of the
the beam admitted to the counter, counter, an
increase
increase in
in its
its width
width will
will increase
increase thethe maximum intensity
intensity of of any
any diffraction
diffraction
line
line being
being measured but
but at
at the
the expense
expense of
of some loss
loss of
of resolution.
resolution. On the
other
other hand,
hand, the
the relative
relative integrated
integrated intensity
intensity of
of a diffraction
diffraction line
line is
is inde-

pendent
pendent ofof slit
slit width,
width, which is is one
one reason
reason for
for its
its greater
greater fundamental im-
portance.
portance. *
* Figure 7-7 illustrates the
Figure 7-7 illustrates the relative
relative arrangement
arrangement of
of the various

**A
A number of of things
things besides
besides slit
slit width (e.g.,
(e.g., x-ray
x-ray tube rurrent)
current) will
will change
change
the
the integrated
integrated intensity
intensity ofof a
a single
single diffrartion
diffraction line.
line. The important
important thing
thing toto note,
note,
however,
however, is is that
that aa rhange
change inin anyone
any one of of the
the operating
operating variables
variables changes
changes the inte-
inte-
grated
grated intensities
intensities of
of all
all diffraction
diffraction lines
lines in
in the
the same ratio
ratio but ran can produce
produce very
very
unequal
unequal efferts
effects on
on maximum intensities.
intensities. Thus,' if I/i//2
Thus, 'if II I 2 is
is the
the ratio
ratio of
of the inte-
inte-
grated intensities of
grated intensities of two lines
lines measured with a a rertain
certain slit and MIIM2
slit width and Mi/M 2 the
ratio
ratio of
of their
their maximum
maximum intensities,
intensities, then
then another
another measurement
measurement with aa different different
slit
slit width
width will
will result
result in
in the
the same ratio 11112
same ratio I\/h for
for the
the integrated
integrated intensities,
intensities, but
but the
the
ratio
ratio of
of the
the maximum
maximum intensities
intensities will
will now,
now, inin general,
general, differ from M1IM
differ from Af i/Af2
2.
188
188 DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETER MEASUREMENTS [CHAP. 77
[CHAP.

slits in aa typical
slits in typical diffractometer
diffractometer andand shows
shows thethe passage
passage of of aa few
few selected
selected
rays
rays from
from source
source to
to counter.
counter.
Because of
Because of the
the focusing
focusing ofof the
the diffracted
diffracted rays
rays andand thethe relatively
relatively large
large
radius
radius of of the
the diffractometer
diffractometer circle,
circle, about
about 15
15 em
cm in
in commercial
commercial instruments,
instruments,
aa diffractometer
diffractometer can can resolve
resolve very
very closely
closely spaced
spaced diffraction
diffraction lines.
lines. Indica-
Indica-
tive of this is the fact that resolution
tive of this is the fact that resolution of
of the
the Cu
Cu Ka
Ka doublet
doublet can
can be
be obtained
obtained
at 20
at 28 angles
angles as as low
low asas about
about 40.
40. Such
Such resolution
resolution can can only
only be be achieved
achieved
with aa correctly
with correctly adjusted
adjusted instrument,
instrument, and and it is necessary
it is necessary to so align
to so align the
the
component parts
component parts that
that the
the following
following conditions
conditions are are satisfied for all diffrac-
satisfied for all diffrac-
tion angles
tion angles: :

(1) line source,

(1) line source, specimen
specimen surface, and receiving-slit
surface, and receiving-slit axis axis are
are all
all parallel,
parallel,
(2)
(2) the
the specimen
specimen surface
surface coincides
coincides with
with the
the diffractometer
diffractometer axis,
axis, and
and
(3)
(3) the
the line
line source
source and
and receiving
receiving slit
slit hoth
both lie
lie on
on the
the diffractometer
diffractometer circle.
circle.

7-4 Intensity
7-4 Intensity calculations.
calculations. The calculation calculation of of the
the relative
relative integrated
integrated
intensities
intensities of
of beams
beams diffracted
diffracted by
by a
a powder
powder .specimen
specimen in
in a
a diffractometer
diffractometer
follows the
follows the general
general principles
principles de- de-
scribed in
scribed in Chap.
Chap. 4, 4, but
hut thethe details
details of of
the calculation
the calculation depend depend on on thethc form
of the
of the specimen.
specimen.
The useuse of of aa fiat-plate
flat-plate specimen,
specimen,
making
making equalequal angles with the
angles with the incident
incident .. '"
and
and diffracted
diffracted beams,beams, not not only
only pro-pro- " "

duces
duces focusing
focusing as as described
described aboveabove but but
makes
makes the the absorption
absorption faetor
factor inde-
inde- FIG.
FIG. 7-11..
7-*- Diffrartion
Diffraction from from a a fiat
flat

plate:
late: ineident
id nt andan d dlf'frueted
diffmcted beamsbeams
pendent
pendent of
this
of the
the angle
angle 8.0. We can can prove
t
prove f
have ^ f
aa thickness
thickness of
of 1
f 1 em
cm inin a
a dire('tioll
direction
this by calculating the effect of absorp-
, i i i rr i

by calculating the effect of absorp- normal

normfll to t() the
the plane
plane of
()f the drawing.
drawing .

tion in the
tion in the specimen
specimen on on the
the intensity
intensity
of
of the
the diffracted
diffracted beam, beam, and, and, since
since this effect will
this effect will come up up again
again in in later
later

parts of this book,

parts of this book, we will
will make our
our calculation
calculation quite general.
quite general. In Fig.
Fig. 7-8,
7-8,
2
the incident
the incident beam has intensity
has intensity 10
7 (ergs/cm 2
(ergs/cm /ec),/sec), is
is 1
1 cm
em square
square in
in cros.s
cross

section,
section, andand is is incident
incident on on the
the powder
powder plate
plate at at an
an angle
angle a. a. We consider
consider
the
the energy
energy diffracted
diffracted fromfrom this this heam
beam by by aa layer
layer of the powder
of the powder of length
of length 1 /

and thickness dx,

and thickness dr, located
located at depth xx below
at aa depth below the the surface.
surface. Since Since thethe inci-
inci-

dent
dent beam
beam undergoes
undergoes absorption
absorption by by the
the specimen
specimen over over the the path
path length
length
(AB}
AB,
AB, thethe energy
energy incident
incident per per second
second on on the
the layer
layer considered
considered is I e~^
is Ioe-P.(AB)

(ergs/sec),
(ergs/sec), where
where J.I.M is
is the
the linear
linear absorption
absorption coefficient
coefficient of of the
the powder
powder com- com-
pact.
pact. Let
Let a
a be
be the
the volume
volume fraction
fraction of
of the
the specimen
specimen containing
containing particles
particles
having
having the the correct
correct orientation
orientation for for reflection
reflection of of the
the incident
incident beam, beam, and and bb
the
the fraction
fraction of of the
the incident
incident energy energy which
which is
is diffracted
diffracted by
by unit
unit volume.
volume.
Then
Then thethe energy
energy diffracted
diffracted by by thethe layer
layer considered,
considered, which which has has aa volume
volume
IIdx,
dx, isis given
given by by ablloe-P.(AB)
aW/ e~" u *' dx.
}

dx. But
But this
this diffracted
diffracted energy
energy is
is also
also de-
de-
creased by absorption, by a factor of (BC , since
e-p.(BC) since the
the diffracted
diffracted rays
creased by absorption, by a factor of e~~ \ rays
 7-4]
7-4] INTENSITY CALCULATIONS
INTENSITY CALCULATIONS 189
189

have aa path
have path length of BC
length of BC in
in the
the specimen.
specimen. The
The energy
energy flux
flux per
per second
second in
in
the diffracted
the diffractedbeam outside
beam outside the
the specimen,
specimen, i.e.,
i.e., the
the integrated
integrated intensity,
intensity, isis
therefore given by
therefore given by
dID
dID == ablI
ablIoc- (AB+BC} dx
c-l'cAB+BC') dx (ergs/sec).
(ergs/sec). (7-1)
(7-1)
But
But
11 xx xx
l=-.-. AB=-. BC=-
sm aa
sin sin aa
sin sin ft(j
sin
Therefore,
Therefore,
dID = ~oab e-I'I(l/sin "'+l/sin
in /J) dx.
(3) dj (7-2)
(7_ 2)
sm a.a
sn
For the
For the particular
particular specimen
specimen arrangement
arrangement used
used in
in the
the diffractometer,
diffractometer,
aa = ^/3 = 0, ande,
and the
the above
above equation
equation becomes
becomes
Ioab m 99 dx
dID = - - e- 2l'Ilsln dx. _
(7-3)
(7 3)
sin 6e
sin

The total
The total diffracted
diffraeted intensity
intensity is
is obtained
obtained byby integrating
integrating over
oYer an infinitely
infinitely
thick specimen
specimen:
thick :

ID =
ID =
I=O
x
I='"
j Ioab
dID = - .
21-'
(7-4)

Here 7 b,
Here 10, and I-' are constant for
6, and M are constant
,
for all reflections (independent
all reflections of e)
(independent of 8) and we
we
may regard a
with e,
may also
also regard a as
as constant.
constant. Actually,
Actually, a varies
varies with but this
0, but this variation
variation
is already taken
is already taken Care
care ofof by
by the
the cos
cos0 e portion
portion of the Lorentz factor (see
Lorentz factor (see
Sec.
Sec. 4-9)
4-9) and
and need
need not
not concern
concern us
us here.
here. We conc'lude
conclude that the absorption
absorption
factor, 1/21-', is independent of of e for
for a flat
flat specimen
specimen making
making equal
equal angles
angles
factor, l/2/i, is independent
with
with the
the incident
incident and
and diffracted
diffracted beams,
beams, provided
provided the specimen
specimen fills
fills the
the
incident
incident beam at at all
all angles
angles and is
is effectively
effectively of infinite
infinite thickness.
thickness. *
*
This
This

** The
1

The criterion
'

criterion adopted for "infinite

adopted for "infinite thiekness"
thickness" depend"
depends on the sensitivity
sensitivity of
of our
pur
intensity
intensity
measurements
measurements or
or on
on what we regard
regard aR
as negligible
negligible diffrarted
diffracted intensity.
intensity.
For
For example,
example, we we might
might arbitrarily
arbitrarily but but quite
quite reu!iunahly
reasonably define
define infinite
infinite thieknes8
thickness asas
that thickness t whieh
that thicknei:!s which aa spc('imen
t specimen mustmust have
have in in order
order that
that the
the intensity
intensity diffracted
diffracted
by
by aa thin layer on
thin layer on the
the back
back side
side be T ^Vo off the
be r<f()() tne intensity
intensity diffraeted
diffracted by
by aa thin
thin layer
layer
on
on the
the front
front side.
side. Then,
Then, from
from Eq.
Eq. (7-3)
(7-3) we
we have
have
= 0) = e2"t/slIl
(at xx = ~l
dID
dip (at = t/Bm 9e =
^ = 1000
]0()0
dID
d!D (at
(at x=
x -= t)
from
from which
which
sin e
.

3.45
3. 45 sin 8
t =_ - - - - .
jJ.M

This
This expression shows that "infinite thickness," for
expression shows that "infinite thickness,"
for aa metal
metal specimen,
specimen, isis very
very
small indeed. For example,
small indeed. For example, suppose suppose aa specimen
specimen of
of nickel
nickel powder
powder is
is being
being ex-
ex-
amined
amined withwith eu KOL radiation
Cu Ka radiation atat e 8 values
values approaching
approaching 90. 90. The The density
density ofof the
the
powder
powder compact
compact may may bebe taken
taken asas about
about 0.60.6 the
the density
density of of bulk
bulk nickel,
nickel, which
which isis
of t
8.9 gm/cm
8.9 33, leading to a value
value of jJ. for
for the
the compact of
of 263
263 cm
cm" 1
-I. The
The value
value of t
gm/cm leading ~ 2
,
to a of M compact .

isis therefore
therefore 1.31
1.31 X 10 2 em,
X 10- cm, or
or about
about fivefive thousandths
thousandths of of an
an inch.
inch.
190
190 DIFFRACTOMETER MEASUREMENTS [CHAP. 7
[CHAP. 7

independence
independence of of 86 is
is due to
to the
the exact
exact balancing
balancing of of two opposing
opposing effects.
effects.

When 86 is is small,
small, the
the specimen
specimen area irradiated
irradiated byby an incident
incident beam of of fixed
fixed
cross section is
cross section is large,
large, but the
the effective
effective depth
depth ofof x-ray penetration is
x-ray penetration is small;
small ;

when 8 is is large,
large, the
the irradiated
irradiated area
area is
is small,
small, but the penetration
penetration depthdepth isis

relatively large.
relatively large. The net
net effect
effect is
is that
that the
the effective
effective irradiated
irradiated volum('
volume iH
is

constant
constant and independent.
independent of
of 8.
6. Absorption
Absorption occurs
occurs in
in any case, however,
any case, however,
and the
the larger
larger the
the absorption
absorption ('oefficient
coefficient ofof the
the specimen,
specimen, the the lmn'r
lower thethe in-
in-
tensity
tensity of
of the
the diffracted
diffracted heams,
beams, other
other things being equal.
things being equal. The important.
important
fact to
fa('t to note
note isis that
that absorption
absorption decreases
decreases thethe intensities
intensities of of all
all diffral'ted
diffracted
beams by by th('
the same factor
factor and therefore does not.
therefore does not enter
enter int.o
into the>
the ('ulculation
calculation
of rrZatil'r
of intensities. This mean~
relative intensities. means thatthat Eq.
Eq. (-1-12)
(4-1 2) for
for the
the relatiyc
relative integrated
integrated
intensity
intensity of of aa diffral'tion
diffraction line
line from a powder specimen,
a powder specimen, namely,
namely,

') (1 + 28) .
I = IFI-p -
cos
COS
2
2 20
(-1---12)
sm 22 8
sin 6 {'os
cos 88

needs
needs only
only the
the insertion
insertion of
of a
a temperature
temperature factor
factor t.o
to make itit preciHe,
precise, for
for the
the
case
case of
of a
a flat
flat specimen
specimen examined in
in a
a diffractometer.
diffractometer. As it
it stands,
stands, it.
it may
may
still
still be
be uspd
used toto calculate
calculate the
the approximate
approximate relative
relative intensities
intensities ofof two adja-
adja-
cent
cent lines
lines on
on the pattern, hut
the pattern, but the
the caleulated
calculated intensity
intensity ofof the
the highN-angle
higher-angle
line, relative to
line, relative to that
that of
of the
the lower-angle
lower-angle one,
one, will
will always
always bebe somewhat too too
large because of
large because of the
the omission
omission of of the
the t.empcrature
temperature faetor.
factor.
When thethe specimen
specimen used
used in in the
the diffractometer
diffractometer has has the
the form of of aa thin
thin
rod,
rod, no focmsing
focusing occurs
occurs and thpthe inl'jdent-hpam
incident-beam stitH
slits are
are ('hoHPn
chosen t.o prodlH'p
to produce
aa thin,
thin, essentially
essentially parallel
parallel heam.
beam. The x-ray geometry is
x-ray geometry is thC'n
then pntirely
entirely
equivalent
equivalent to
to that
that of
of a
a Debye-Scherrer
Debye-Scherrer ('amefa
camera equipped
equipped with
with slits,
slits, and
Eq. (4-12) applies,
Eq. (4-12) applies, with exactly
exactly the
the samp
same limitations
limitations as
as mentioned in
in
Aec.4-12.
Sec. 4-12.

7-5 Proportional
7-6 Proportional Counters.
counters. Proportional,
Proportional, Geiger,
Geiger, and scint.illation
scintillation
counters
counters may
may be used
used to
to detect,
detect, not
not only
only x-
x- and 'Y-radiation,
7-radiation, but but also
also
charged
charged particles
particles such
such as as electrons
electrons oror a-particles,
a-particles, and the the design
design of
of the
the
counter and associated
associated circuits
circuits depends
depends to to some extent
extent on what.what is
is to
to bf'
be
detected.
detected. Here we are are concerned
concerned only
only with
with counters
counters forfor the
the dete('tion
detection ofof
x-rays
x-rays of
of the
the wavelengths
wavelengths commonly
commonly employed
employed in in diffraction.
diffraction.
Consider thethe device
device shown in in Fig.
Fig. 7-9,
7-9, consisting
consisting ofof aa {'ylindrie'al
cylindrical metal
metal
shell
shell (the
(the cathode)
cathode) filled
filled with a a gas
gas and containing
containing a a fine
fine metal
metal wire
wire (the
(the
anode)
anode) running
running along
along itsits axis.
axis. Suppose there is
Suppose there is a
a constant potential dif-
constant potential dif-
ference of about 200
ference of 200 volts
volts between
between anode and cathode.cathode. One end end of
of the
the
cylinder
cylinder is
is covered
covered with
with aa window material,
material, such
such as
as mica
mica or
or beryllium,
beryllium, of
of
high transparency
high transparency to
to x-rays.
x-rays. Of the
the x-rays
x-rays which
which enter
enter the
the cylinder,
cylinder, a a
small
small fraction
fraction passes right through,
passes right through, but
but the
the larger part
larger part is
is absorbed
absorbed by
by the
the
gas,
gas, and this
this absorption
absorption is is accompanied
accompanied by by the
the ejection
ejection of of photoelectrons
photoelectrons
 7-5J
7-5] PROPORTIONAL COUNTERS
PROPORTIONAL COUNTERS 191
191

and Compton
and Compton recoil
recoil electrons
electrons from
from cathode \lIre
anod(' insulator
llISUiatof
the atoms
the atoms of
of the
the gas.
gas. The
The net
net result
result \
isis ionization
ionization of of thethe gas, producing x-raYH
gas, producing
electrons, which
electrons, which move move underunder the the in- in- /'I::::::==:;:::::=~
fluence of
fluence of the
the electric
electric field
field toward
toward wmdo\l
the wire
the wire anode,
anode, and and positive
positive gas gas ions,
ions, to
detector
which move toward
which move toward the the cathode
cathode shell.
shell. ('Jr('l11t
circuit

At aa potential
At potential difference
difference of of about
about +
200 volts,
200 volts, allall these
these electrons
electrons and and ionsions
will be
will be collected
collected on on thethe electrodes,
electrodes,
and, ifif the
and, the x-ray
x-ray intensity
intensit.y is is constant,
constant, F'10. ?7-9.
FlG _ g Gas
Gas counter
eounter (proportional
( pro p rtional
there will
there will be be aa small
small constant
constant currentcurrent orGeiger)or Geiger) and and basic
basiccirruitronnertions.
circuit connections,
of the
of the order
order of 10-12
of 10~ 12 amp or
amp or less less
through
through the
the resistance
resistance R
R\.I This
This current is
current is aa measure of of thethe x-ray
x-ray in- in-
tensity.
tensity. When operated
operated in
in this
this manner,
manner, this
this device
device is
is called
called an
an ionization
ionization
chamber. It
chamber. It was
was usedused in in thethe original
original BraggBragg spectrometer
spectrometer but but is is now
obsolete
obsolete for
for the
the measurement
measurement of
of x-ray
x-ray intensities
intensities because
because of
of its
its low
low sensi-
sensi-
tivity.
tivity.
The same instrument, however,
same instrument, however, can be made madp to to act
act as proportwnal
as aa proportional
counter if
counter the voltage
if the voltage is is raised
raised to to thethe neighborhood
neighborhood of 600 t.o 900
of 600 to 900 volts.
volts.
A new
new phenomenon
phenomenon now occurs, namely, multiple
occurs, namely, multiple ionization or "gas
ionization or "gas ampli-
ampli-
fication."
fication." The electric-field intensity is
electric-field intensity is now so so high
high that the the eleetrons
electrons
produced
produced by by thethe primary
primary ionization
ionization are are rapidly
rapidly accelerated toward the the
wire
wire anode
anode and and at at anan ever
ever increasing
increasing rate rate of of acceleration,
acceleration, since the field field

intensity
intensity increases
increases as
as the
the wire
wire is
is approached.
approached. The electrons
electrons thus acquire
acquire
enough
enough energy
energy to to knock
knock electrons
electrons out out ofof ot.lier
other gas gas atoms,
atoms, and these in in tum
turn
cause
cause further
further ionization
ionization and so so on,on, until
until the
the number of
of atoms ionized by
the
the absorption of aa single x-ray quantum is some 10
1033 to
to 10
10 55 times as as large
large
absorption of single x-ray quantum is

as
as the
the number
number ionizedionized in in an
an ionization
ionization chamber. As a a result
result of of this
this ampli-
ampli-
fication
fication aa veri.table
veritable avalanche
avalanche of
of electrons
electrons hits
hits the
the wire and
and causes
causes an
an easily
easily
detectible pulse of
detectible pulse of current current in
in the
the external
external circuit.
circuit. This pulse
pulse leaks away
away
through the large
through the large resistance RIresistance Rl but
but not before
before the
the charge momentarily
charge momentarily
added to
added to the
the capacitor
capacitor C Cit has
has beenbeen detected
detected by by the
the ratemeter
ratemeter or or scaling
scaling
circuit connected to
circuit connected Ci. At
to CI. At thethe samesame timetime the positive
the positive gas gas ions move
ions move to to
the
the cathode
cathode but but at at aa much
much lower lower rate rate because
because of of their
their larger
larger mass. This
mass. This
whole
whole process,
process, whichwhich is is extremely
extremely fast, fast, isis triggered
triggered by by thethe absorption
absorption of of
one
one x-ray
x-ray quantum.
quantum.
We
We cancan define
define aa gasgas amplification
amplification factor factor A A as as follows:
follows if : n is
if n is the
the number
number
of
of atoms
atoms ionized
ionized by by one
one x-ray
x-ray quantum,
quantum, then
then An
An is
is the
the total
total number
number
ionized
ionized by by the
the cumulative
cumulative process
process described
described above.
above. Figure
Figure 7-10
7-10 shows
shows
schematically
schematically how
how the
the gas amplification
gas amplification factor
factor varies
varies with
with the
the applied
applied
voltage. At
voltage. At the
the voltages
voltages used used in in ionization chambers, A
ionization chambers, A == 1; 1; i.e.,
i.e., there
there
isis no gas amplification,
no gas amplification, since
since the
the electrons
electrons produced
produced by by the
the primary
primary ioniza-
ioniza-
192
192 DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETER MEASUREMENTS [CHAP, 77
[CHAP.

(()12

1011 n g:low
glow
l()
p:; uu.,('harg:{'
discharge
O 10 10
0 10"' -T
t-'
E-I
lOiI (;Plg:Pr ('Ollllt{'l' I
('orona
corona
:;: (()~s
< I : discharge
dlH('harp;('
.... 10
^
^
~ lO'
O
0
~
7

lOti
1()
;--:--1
I

I
I
I

I
I
I

prop' Irt :ollal

:-r.
r<
~
!().10:'
('ount{'I I a \'alanell('
: avalanche
;;; KM
E 10 1
I
I rl'g:HlIl
region
:::i J():l
* I
0... io
i
^ H) 2
IOlllzatlO1l
10
('halllhrr I
1 - - - - - - -I - -, - - - -
I ,

YOLTA(;E
VOLTAC5E

FIG. 7-10.
FIG. Effect of
7-10. Effect of voltage
voltage on
on the
the gas
gas amplification
amplification factor.
fartor. (H. Friedman,
(H. Friedman,
Proc. /.#.#.
Proc. I.R.E. 37,791,
37, 791, 1949.)
1949.)

tion
tion do not acquire
do not acquire enough
enough energy
energy to to ionize
ionize other
othpr atoms.
atoms. But when the thp
voltage is raised into the
voltage is raised into the proportional proportional ('ounter
counter region,
region, A becomes of
of the
the
5
order of
order of 10 3
3
10 toto 10
]05. .

The current pulse in

current pulse in the anode wire
the anode wire is
is normally
normally expressed
expressed in in t.erm!>
terms of of the
the
momentary
momentary change change of voltage in
of voltage the wire,
in the wirp, and this
this ehangp
change is of the order
is of order
of
of aa few
few millivolts.
millivolts. The proportional
proportional eounter
counter receives
receives itsits name from thp the
fact
fact that
that thethe size
size ofof this
this pul!>e,
pulse, for
for aa given
given applit'd
applied voltagt',
voltage, is is directly
directly pro-pro-
portional to
portional n, tht'
to n, the number of of ions
ions formed by by the
the primary
primary ionization
ionization process,
process,
and this number is
and this is in
in turn
turn proportional
proportional to
to the
the energy
energy of
of the x-ray
x-ray quantum
quantum
absorbed.
absorbed. Thus, Thus, if if absorption
absorption of of aa eu
Cu Ka quantum
quantum (hv = 9,000 ev)
(hv = 9,000 ev) pro-
pro-
duces
duces a a voltage pulse
voltage pulse of
of 1.0
1 .0 mv,
mv, t.hen
then absorption
absorption of
of a Mo Ka quantum
quantum
(hv = 20,000
(hv 20,000 ev)ev) will
will produce
produce a a pulse
pulse of
of (20,000/9,000)(1.0) =
(20,000/9 ,000) (1.0) = 2.2 my. mv.
The proportional
proportional counter
counter is
is essent.ially
essentially a very
very fast
fast eounter;
counter; i.e., it
i.e., it can

resolve separate pulses

resolve separate pulses arriving arriving at
at a
a rate
rate as
as high
high as
as 10 6 per
per seeond.
second. It can
do
do this
this becausp
because eacheach avalanche
avalanche is confined to
is confined to an extremely
extremely narrow region
region
of
of the
the wire,
wire, 0.1
0.1 mm or or less,
less, and doesdoes not
not spread
spread longitudinally
longitudinally along along thethe
counter
counter tube.
tube. ThisThis is is an important
important feature
feature of of the process
process and one to which w hich r

we will
will return
return inin the
the next
next section.
section.

By
By inserting
inserting sperial
special cin'uits
circuits between
between aa proportional
proportional counter
counter and the the measuring
measuring
instrument
instrument (scaler
(sealer 01'
or ratemeter),
ratemeter), it
it is
is possible
possible to
to take
take advantage
advantage of
of the fart
fact that
the
the sizes
sizes of
of the
the pulses
pulses produced
produced are
are inversely
inversely proportional
proportional to
to the
the wavelengths
wavelengths of
of
the
the x-rays
x-rays producing
producing them.
them. For For example,
example, oneone such
such eircuit
circuit allows
allows only
only pulses
pulses
larger
larger than
than aa certain
certain selected
selected size
size to
to pass
pass and
and discriminates
discriminates against
against smaller
smaller ones;
ones;
it
it is
is called a pulse-height
called a pulse-height discriminator.
discriminator. If If two
two such
such circuits
circuits are
are used
used together,
together, one
one
7-6J
7-6] GEIGER COUNTERS
GEIGER COUNTERS 193
193

set to pass
set to pass only
only those
those pulses
pulses larger
larger than Vi
than ~'l volts
volts and
and the
the other
other only
only those
those larger
larger
than ^2
than volts, then
V 2 volts, then the
the difference
difi'erenee between
between their
their two
two outputs
outputs isis due
due only to pulses
only to pulses
having sizeR in
having sizes in the
the V\- to VVvolt
V 1- to V2-volt range.
range. This
This subtraction
subtraction may
may be be done
done electroni-
electroni-
cally,
cally, in
in whi('h
which case
case the
the eomposite
composite eireuit
circuit is
is ealled
called aa single-channel pulse-height
single-channel pulse-height
analyzer.
analyzer.
Such aa device
Such deviee allows
allows aa proportional
proportional counter
counter to to bebe operated
operated under
under essentially
essentially
monoehromatic conditions.
monochromatic ('onditions. For
For example,
example, ifif aa diffraction
difi'ra('tion pattern
pattern is
is being
being obtained
obtained
with copper
with ('opper radiation,
raciiation, the
the analyzer
analyzer can
can be
he set
Ret to
to pass
pass only
only pulses
pulses due
due to eu Ka
to Cu Ka
radiation and
radiation and reject
reJeet those
thos(' due
due to
to other
other wavelengths,
wavelengths, such su('h as
as Cu K{3, fluorescent
Cu Kft, fluorescent
radiation from
radiation the specimen,
from the RpeeJnWlI, white
white radiation,
radiation, etc.
ete.

7-6 Geiger
7-6 Geiger counters.
counters. If t Iw voltage
If the \"oJtagp on on aa proportional
proport ional counter countpr is is in-
in-
creased
creased some hundreds of
of volts,
volts, it
it will
will ad
act as
as a
a Geiger
Geiger ("ounter.
counter. The exact
exact
operating voltage
operating voltage is is determined
dptt'rmilwd in in the followingfollowing way. wa:v. The counter is is
exposed to
exposed t.o aa beam
heam of x-rays
of x-rays of constant
of ("onstant intensityintensity and connected ('onnected to an to
appropriatf' circuit
appropriate ("ir("uit which
whieh will will measure its its counting
("ounting rate, ratf', i.e., i.r., the
the rate
ratf' ofof
production of
production of current
("IIl"l"f'nt pulses
pulsps in in the
t hf' external
extprnal circuit.("ireuit. The applied applied voltage
voltage
is then
is tlH'n gradually
gradually increasedinereased from zero, zero, and the the counting
('ounting rate rate is is found to to
vary with
vary wit II voltage
volt age in in the
t hp manner shown in in Pig. 7-11. No counts
Fig. 7-11. ('ounts areare ob-oh-
tained below
tained bplow aa ('('rtain
certain minimum voltage voltagr ('aIled the starting
called the starting voltage,* voltage, * but
above this
above this value
value the thp ('ounting
counting rate rate increases
inerpases rapidly rapidly with with voltage voltage until until
tthe
hp threshold
thrpshold of of thethp (;eiger rpgion
Geiger region is
is rpaehed.
reached. In
In this
this rpgion.
region, ('aIled
called the
the
T >lateau,
plateau, the
the ("ounting
counting rajp
rate is
is almost
almost ,~_
^
I
pat('all
plateau
indeppnrient of
independent of volta!!:e.
voltage. At voltagps voltages ;:: I 0\ PI

Ibeyond I1(' Pplateau,

)e:von d tthe Iateau, tthe h e ("()untpr
counter gops goes i..,.& il(lltagpi
(

-l!Lg(l! _ _ _ _--"'1
.:.:--=:..;-:.:'
..:1.:.
i^

intI) a stat!'
into a state I)f
of ("ontinuouH
continuous dis(,harge.
discharge. '-'
p \\ t \ continuous
(()tltllllIOU~

A Gpigpr
Geiger rOllnter
piat<'all,
counter is
normally
is oppratC'd

at
operated on
an
on HIP:::
oYPr\,o!tagC'
the ~
,....,
;--;
4 4 1^^
thl(',hold;
\ oltagt"
'

I
dl,dl:ugt'

plateau, normally at overvoltage

of
of ahout
about tOO 100 volts,
volts, i.p.,i.e., atat 100
100 volts
volts
:---
c: "pt'ratllll!, I oltal!,p

highpr
higher thanthan threshold.
threshold. The platpau plateau APPLIMI) \()LTA(JK
has
has aa finite
finite slop<',
slope, ahout.about 0.05 0.05 pC'r-per-
. . . , , FIG.
PIG. 7-11. Effp(,t.
Effect of of yoltage
voltage on
cent /yolt, w!tieh
cent/volt, which means that that the
the OPPl"-
oper- eountll1g for ('on~tant.
ountmg ratp rato for (>onstant x-ray in _
x . ray In-
.
(

ating yoltage
ating voltage must
must be
be HtabilizC'd
stabilized if
if the
the tensity.
tensity,
eounting
counting ratp rate isis toto h{'
be accumtely
accurately pro- pro-
portional
portional to to x-ray
x-ray inten::;ity.
intensity. (Thp
(The same same is is true ofof proportional
proportional (ounter::;.) counters.)
No exactexact figures
figures ('an
can hC'
be gi\"(.'n
given for
for t.he
the st.arting
starting voltage,
voltage, thrpshold
threshold voltage,
voltage,
and
and lengt
length h of
of platpau
plateau of
of GeigPr ('onntprs,
Geiger counters, asas tllesp
these drppnd
depend on
on su('h
such variables
variables
as
as ('ountpr
counter dimensions
dimensions and and naturr
nature of of the
the gas gas mixt.ure,
mixture, but fhp the operat.ing
operating

** Pu!;;('!; are produ(,ed

Pulses ar(' produced helow/hiR
below /his voltage,
voltage, but
but they
they areare too
too RIllall
small toto be
be ('ounted
counted
hy
by the
the IIlea~UI"lIIg
measuring (inuit
circuit (s('aler
(sealer or
or ratemeter).
ratemeter). Below
Below the
the starting
starting voltage,
voltage, the
the
counter i~
counter is a('ting
acting asas aa proportional
proportional ('ounter
counter and
and the
the pulses
pulses are
are much
much smaller
smaller than
than
those
those produ('eo
produced in in the
the Ceiger
(Jeiger region.
region. Rinee
Since thf'
the measuring
measuring eir('uit
circuit used
used with
with aa
Geiger counter iR
Geiger ('ounter is df'signed
designed to to operate
operate only
only on
on puls(,R
pulses larger
larger than
than aa ('ertain
certain size,
size,
usually
usually 0.25
0.25 volt, no pulses
volt, 110 pulses are
are ('ouuted
counted atat voltageI'
voltages les;;
less than
than the
the starting
starting voltage
voltage
194
194 DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETER MEASUREMENTS ICHAP. 77
[CHAP.

voltage of
voltage of most
most counters
counters isis commonly
commonly found
found toto lie
lie in
in the
the range
range of
of 1000
1000 to
to
1500 volts.
1500 volts. ItIt should
should be
be noted
noted that
that some
some counters
counters cancan be
be permanently
permanently
damaged if
damaged if subjected,
subjected, even
even for for brief
brief periods, to voltages
periods, to voltages high
high enough
enough to
to
cause aa continuous
cause continuous discharge.
discharge.
There are
There are several
several important
important differences
differences between
hetween the
the action
action of
of aa Geiger
Geiger
counter and that
counter and that of
of aa proportional
proportional counter:
counter:
(1) The absorption
(1) absorption of of an
an x-ray
x-ray quantum
quantum anywhere
anywherf' within
within the
tllf' volume
of a Geiger
of a Geiger counter
counter triggers
triggers an avalanche
avalanche that
that extends
extends oyer
over the whole
the whole
length of the
length of the counter.
counter.
(2) The gas
(2) gas amplification
amplifleation factor factor of of aa Geiger
Geiger counter
count.er is is therefore
therefore much
8 9
larger, about
larger, about 10 lOll toto 10
10 (see
9 (see Fig.
Fig. 7-10),
7-10), and so so is the
is the voltage
voltage pulsepulse in in the tllf'
wire, now about
wire, about 11 to to 10
10 volts.
volts. This This means that that lessless amplification
amplifieation is is needed
in the
in the external
external circuit.
('if{'uit. (Pulses
(Pulses from from either
either kindkind of of counter
count('r are ar(' always
always
amplified
amplified before
before being
being fed
fed to
to a
a sealer
sealer or
or ratemeter.)
ratemeter.)
(3) At
(3) At aa constant
eonstant applied
applied voltage,
voltage, all all Geiger
Geiger pulses
pulses are are of
of the
th(' same size, siz(',
independent
independent of
of the
the energy
energy of
of the
the x-ray quantum
x-ray quantum that
that caused
caused the
the primary
primary
ionization.
ionization. '\-ra~
x .
qlLalltlllli
ra> (iuantimi

t-== =~-~ ']--

These differences
These differences are are illustrated
illustrated a],,,,, ]'1'1/ hm-
absorbed ]1('1'1'

schematically
schematically in
in Fig.
Fig. 7-12.
7-12. The ab-
ab-
sorption of
sorption an x-ray
of an x-ray quantum
quantum in in aa
proportional counter produces
proportional counter produces aa very very
I'I{()I'OHTIO"\AL ('Ol
pHU])()lrn()NAL ( NT K
, n ;'\TEH ,,
localized radial column of
localized radial ot ions
ions andana
,-1:1\ qliall! 11111
electrons. In
electrons. In aa Geiger counter, on the
Geiger counter, the
al""II)("I iH"11'
other hand, the
other hand, the applied
applied voltage
voltage is is so

~ ~.~ ~ ~ ~. ~ : ~: ~ -~nr
so

high that
high
ionized
that not
ionized but
not only
but others
only are
others are
are some atoms
are raised
raised to to ex-
ex-
[_____________ TI
cited
cited states
states and caused
caused to to emit
emit ultra-
ultra- (;EH;EH
r.KKiKK ('Or:\TEH
'orvrat
<

violet
violet radiation.
radiation. These ultraviolet
ultraviolet FIG.
FIG. 7-12.
7-12. Differenc'es
Differences in the extent
photons then
then travel
travel throughout
throughout the
the of
of ionization
ionization betwE'en
between proportional
proportional ane! and
photons
counter Gei!!:er
Geiger ('ounterR.
counters. Each pluR plus (or (or minm;)
minus)
counter at at the
the speed
speed of
of light,
light, knock-
. ,, Hymbol
symbol reprE'RentH
represents a largclarge number of ol
ing
mg electrons
electrons out out of of other
other gas gas atoms
.

positiye ionR
positive kms (or (or electron!').
ele( trons)
,
.

and
and outout of
of the
the eathode
cathode shell.shell. All
All the
the
electrons
electrons so produced trigger other avalanches,
so produeed trigger other avalanches, and the net result result is is that

one
one tremendous
tremendous avalanche
avalanche of of electrons
electrons hits hits the whole If'ngt.h length of the anode
of the anode
wire whenever an
wire whenever an x-ray
x-ray quantum
quantum is is absorbed
absorbed anywhere
anywhere in in the tube.

All
All these
these electrons
electrons hit hit thethe wire
wire inin less
less than a a microseeond,
microsecond, but the slowly slowly
moving
moving positive
positive ionsions require
require about about 200 200 microseconds to to reaeh
reach the cathode.
This
This means
means thatthat thethe electron
electron avalanche
avalanche in in aa Geiger
Geiger l'ounter
counter leaves
leaves behind
it
it a
a cylindrical
cylindrical sheath
sheath of
of positive
positive ions
ions around
around the
the anode wire.
wire. The presence
presence
of
of this
this ion
ion sheath
sheath reduces
reduces the the electric
electric field
field between it it and the wire below

the
the threshold
threshold value necessary to
value necessary to produce
produce aa GeigerGeiger pulse.
pulse. UntilUntil this this ion
sheath
sheath has has moved far far enough
enough away away from
from the
the wire,
wire, the
the counter is
is insensitive
insensitive
to
to entering
entering x-ray quanta. If
x-ray quanta. If these
these quanta
quanta are are arriving
arriving at at aa veryvery rapid rapid
7-6)
7-6] GEIGER COUNTERS
6EIGER COUNTERS 195
195

(a)
{oj II a a a A TIME
TIME
a n. R

O
(b)

TIME
TIl\IE

TIME
TI:\1E
()~------~----~~~---------+--------------------~

normal pube
r.l amplItude
o
(d) ~ --~--------

...:1 ',-- mput

input Rcnsitivity
sensitivity
o of
of detp(,j,or
detector (,lff'lIit
:> circuit

-dead time (<1--1

-dead I TIME
time t,-:--
/,/ *-|

I_r!'soiYlng tIme
resolving /s

recovery tune
recovery time I, - - - -
/,

FIG.
FIG. 7-13.
7-13. Dependence
Dependence of
of pulRe
pulse amplitude
amplitude on pulse
pulse spacing.
spacing.

rate,
rate, itit follows
follows that
that not
not everyone
every one will
will cause
cause a separate
separate pulse
pulse and the coun-
ter
ter will
will become
become "choked."
"choked." This This places
places an upper
upper limit
limit on the rate rate at
which
which entering
entering quanta
quanta can can bebe accurately
accurately counted without losses. losses. This
limit
limit isis much lower
lower than
than that
that ofof a
a proportional
proportional counter,
counter, since
since the positive
positive
ions
ions produced
produced by by aa discharge
discharge are are very
very localized
localized inin the proportional
proportional counter
and
and dodo not
not render
render the
the rest
rest of
of the
the counter
counter volume insensitive.
insensitive.
The
The way way inin which
which pulses
pulses occur
occur inin a
a Geiger
Geiger counter
counter is is worth examining
examining
in
in some detail. It
some detail. It must be be remembered that that the
the arrival
arrival ofof x-ray
x-ray quanta
quanta
in
in the
the counter
counter isis random in in time.
time. Therefore
Therefore pulse production
pulse production in
in the coun-
ter
ter is
is also
also random
random in in time,
time, and
and a
a curve
curve showing
showing the
the change
change in
in voltage
voltage ofof
the
the anode
anode wirewire with
with time
time would
would have
have thethe appearance
appearance of
of Fig.
Fig. 7-13(a).
7-13 (a).
During
During each each pulse,
pulse, the
the voltage
voltage rises
rises very
very rapidly
rapidly toto aa maximum and then
196
196 DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETER MEASUREMENTS [CHAP. 77
[CHAP.

decreases more
decreases more slowly
slowly to
to its
its normal
normal value.
value. All pulses
All pulses have
have the
the same
same ampli-
ampli-
tude and
tude and are
are spaced
spaced atat random
random timetime intervals.
intervals.
But ifif the
But the rate
rate of
of pulse
pulse production
production is is so
so high
high that
that two
two successive
successive pulses
pulses
occur too
occur too closely
closely together, it is
together, it is found
found that
that the
the second
second one
one has
has less
less than
than
normal amplitude,
normal amplitude, as as indicated
indicated in in Fig.
Fig. 7-13(b)
7-13(b) onon enlarged
enlarged voltage-time
voltage-time
scales. If
scales. If the
the interval
interval between
between pulses pulses becomes
becomes smaller
smaller than that that shown
shown in in
(b),
(b), then
then the
the amplitudc
amplitude of
of the
the second
second pulse
pulse bpcomPH
becomes still
still smaller,
smaller, as
as shown
shown
in (c).
in (c). Figure
Figure 7-13(d)
7-13(d) sums sums up up aa number
numher of of curves
curves of of this
this kind;
kind; i.e.,i.e., it
it is
is
a superposition
a superposition of
of a
a number of
of curyCS
curves like
like (b)
(b) and (c),
(c), and it
it shows the
the
amplitude which
amplitude which any any given
given pulse
pulse will will have
have when it it follows
follows the the initial
initial pulse
pulse
at the
at the time
time interval
interval indicated
indicated by by itsits position
position on the the time axis. This
axis. This de-de-
crease in
crease pube height
in pulse height with with decrease
decrease in in pulse
pulse spacing
spacing has has been correlated
correlated
with the
with the phenomena
phenomena occurring occurring in in the
the counter
counter as as follows.
foIlowH. When the the ava-
ava-
lanche of
lanche of electrons
eleetronH hits hits the
the anode
anode wire wire to to form the the initial
initial pulse,
pulse, the the voltage
voltage
rapidly builds
rapidly builds up up to to its
its maximum value value and then then decays
decays more slowly slowly to to
zero as
zero as the
the charge
chargf' on on the ~wire leaks
the wire leakH away.
tLway. But, But, as as stated
stated above,
aboye, the the posi-
posi-
tive ion
tive ion sheath
sheath left left behind
bphind reduces
reduces the field strength
the field Htrength between it it and the the
wire. The field
wire. field strength
strength increases
increases as as thethe ions
ions move away away from the the wire,
wire,
and
and thethe time
time at at which
which the the field
field reaches
rmches the tllJ'f~shold value
the threshold value marks theVhid the't\nd
of the dead
of the dead time time til,
,/,
during
during which
which thp
the counter
counter is
is absolutely
absolutely insensitive
insensitive to
to
entering quanta. The arrival
entering quanta. arrival of of the
the ionion sheath
shpath at at the
the cathode
cathode restores the
restores the
field
field toto its
its normal
normal strengthstrength and marks the pnd of
the end the rccollcry
of the recovery tim!'time trr Be-
t .

tween
tween id id and ir tr the
the field
field isis ahove threshold but
above threshold but notnot yetyet back to to normal;
normal;
during
during this this interval
interval entering
entering quantaquanta can can cause
cause pulses,
pulses, hut but theythey willwill not

have
have the the full
full amplitude
amplitude eharaeteristic
characteristic of of tht'
the applied
applied voltagc.
voltage. The recov-
ery time,
ery time, at
at whieh
which the
the pulses
pulses regain
regain their
their full
full amplitude,
amplitude, is
is fixed
fixed by by the
counter
counter design and gemrally is
is of
of the
the order
order of
of 2
2 X 10-
10~ 44 sec.
sec. However,
However,
design generally
the
the detecting
detecting eircuit circuit ('an can usually
usually deted detect pulsespulses smaller
smaller than maximum
amplitude,
amplitude, and we ('an
can therefore
therefore speak
speak of
of the
the resolving
resolving timetime ts of
ts of the counter-
circuit
circuit combination,
combination, defined
defined ,by
,by the
the time
time after
after the
the initial
initial pulse
pulse at at which a
following
following pulsepulse can
can first
first be
be detected.
detected.
If
If the
the arrival,
arrival, and absorption,
absorption, of of entering
entering quantaquanta were absolutely
absolutely periodicperiodic
in
in time,
time, thethe maximum counting counting rate rate without losses losses would be given given simply
simply
by lit..
by \/t 8 . But even even if if their
their average
average rate rate of of arrival
arrival is greater than lit.,
is no greater l/t 8,

some successive
successive quanta quanta may may be be spaced
spaced less less than t.8 apart
t apart because of of their
randomness
randomness in time. It
in time. It follows
follows that that counting
counting losseslosses willwill occur
occur at at rates
rates
less than 1/t8
less than \/t 8 and that that thethe losses
losses will will increase
increase as as the
the rate
rate increases,
increases, as
shown
shown in in Fig.
Fig. 7-14.
7-14. Here Here "quanta
"quanta ahsorbed absorbed per per second"
second" are are directly
directly
proportional
proportional to
to the
the x-ray
x-ray intensity,
intensity, so
so that
that this
this curve
curve has an important
important
bearing
bearing on on diffractometer
diffractometer measurements,
measurements, since since itit shows the the point
point at which
the
the observed
observed countingcounting rate
rate is
is no
no longer proportional
longer proportional to
to the
the x-ray
x-ray intensity.
intensity.
The
The straight
straight line
line shows the
the ideal
ideal response
response which can
can be obtained
obtained with aa
proportional
proportional counter
counter at
at the
the rates
rates shown.
shown.
7-6)
7-6] GEIGER COUNTERS
GEIGER COUNTERS 197
197
501Kl
5000 r-
pro)lortumal

o%;
9 40!Nl
~
'l.
~

s: 3000
'-"
IJIl1itll'halllh('r
(;l'lgl'l ('ollllh'r

~lII~ll'-rhalll
single-chain hl'r
her
Ol'll1;l'r
CJcieer ('ouuter
counter

----'---~-.---'--------'-
IOlHl
1000 :lOOO
2000 300n
3000 40()(l
4000 500t)
5000
<ll'At\TA
QUANTA ABi40HBEI>
ABSOHBKI) PER
PKK i4E( 'O.!\'J)
SECOND
FIG,
FIG. 7-14.
7-14. The effect
effect of
of counting rate on counting
counting rate counting lOSseR
losses (Rchematic).
(schematic).

Since
Since thethe resolving
resolving time of of th!:'
the ordinary
ordinary Geiger
Geiger count!:'r
counter is is of
of the
the order
order
of 10-
of 10~ 44 sec,
sec, eounting-rat!:'
counting-rate curves curves should
should be be lin!:'ar
linear up up to
to about
about 10,000
10,000 cps
cps
(counts
(counts per per second)
second) if
if th!:'
the arrival
arrival of
of quanta
quanta were
were periodic
periodic in
in time, How-
time. How-
ever, counting losses
ever, counting losses areare observed
observed to to begin
begin at at much
mueh lower
lower rates,
rates, namely,
namely,
at aa few
at few hundred counts ('ounts per per second,
seeond, as as shown
shown in in Fig.
Fig. 7-14.
7-14, In In the
the multi-
multi-
chamber counter
chamber counter the the counting
eounting rate rate isis linear
linear up up toto more
mort' thanthan 1000 cps;
1000 cps;
such a counter has
such a counter has a number of chambers
of chambers side side byby side, elteh with
side, each with its
its own
own
anode wire,
anode wire, and one (~hamber can
one chamber ran therefore
therefore register
regist.er aa count
count. while
while another
another
one is
one is in
in its
it.s insensitive
insensitive period.
period. (The (The proportional
proportional counter,
('ounter, much much faster
faster
than either
than either of of these,
these, has has aa linear
linear counting
counting curve('urve upup to to about
about 10,000
10,000 cps.
cps.
I ts resolving
Its resolving time time is is less
less than
than aa microsecond;
microsecond; this this is
is the
the time
time required
required for
for
an electron
an electron avalanche
avalanche to to hit
hit the
the wire,
wire, immediately
immediately after after which
which thethe pro-
pro-
portional counter
portional counter isis ready
ready to to register
register another
another pulse,
pulse, since
since thethe positive
positive ions
ions
formed produce
formed produce no no interference.)
interference.)
The particular
The particular counting
counting rate rate where
where losses
losses begin
begin with
with aa particular
particular Geiger-
Geiger-
counter-scaler combination
counter-scaler combination must must be be determined
determined experimentally,
experimentally, and and this
this
can be
can be done
done as as follows.
follows. Position
Position the the counter
counter to to receive
receive aa strong
strong diffracted
diffracted
beam, and
beam, and insert
insert inin this
this beam
beam aa sufficient
sufficient number
number of of metal
metal foils
foils of
of uniform
uniform
thickness to
thickness to reduce
reduce the the counting
counting rate rate almost
almost to to the
the cosmic
cosmic background.
background.
(Cosmic rays,
(Cosmic rays, because
because of of their
their high
high penetrating
penetrating power,power, passpass right
right through
through
the walls of the counter and continually
the walls of the counter and continually produce
produce aa few few counts
counts perper second.)
second.)
Measure the
Measure the counting
counting rate, rate, remove
remove one one foil,
foil, measure
measure the the counting
counting rate,
rate, and
and
continue in
continue in this
this manner
manner until until all
all the
the foils
foils have
have beenbeen removed.
removed. Since Since each
each
198
198 DIFFRACTOMETER MEASUREMENTS
DIFPRACTOMETER MEASUREMENTS [CHAP. 77
[CHAP.

/
/
10,000
10,000

"-
Co .~ 50-h peak ""'"""-4Ir--......=----
.::
w[.il
Hf-<
<
<S
c.::
tf

v
-
;t;
......
;t;
;...,

"
!::::)
~
;...
1000
1000

~
r.,::
'L
a:I
CQ
O
0

100~----~----~----~----~----~----~----J
o 22 4 (j S 10
10 12 14
NF:\IHEH OK FOIL;';
Nt'MHKK OF REMOVED
FOILS HE:\IO\'ED
FIG.
FIG. 7-15.
7-15. Calibration
Calibration curves
curves of
of a
a Illultichamber
multichamber Ueiger
Geiger counter foJ'
for two values
of
of the x-ray tube
the x-ray tube peak
peak voltage.
voltage. Cu Ka
C'u A'a radiation.
radiation. Nickel foils, 0.01 mm
foils, each 0.01
thick,
thick, used
used as
as absOIbers.
absorbers.

foil
foil produces
produces thethe same fractional
fractional absorption
absorption of of the
the energy
energy in('ident
incident on it, it,

aa plot
plot of
of observed
observed counting
counting raterate (on (on a a logarithmic
logarithmic s('ale) vs. number of
scale) I'S. of
foils
foils removed fromfrom the the beam (on (on a a linear
linear scale)
scale) willwill be
be linear
linear up up toto the
the
point
point where
where losses
losses begin
begin and willwill in in fact
fact resemble Fig. Fig. 7-14.
7-14. A curve of of
this
this kind
kind is
is shown in in Fig.
Fig. 7-15.
7-15. Once the the length
length of of the
the linE'ar
linear portion
portion ofof
the
the ealibration
calibration curve
curve hali
has beE'n
been determined,
determined, it it iHis best
best toto make all all further
further
measurements
measurements in in this
this region.
region. Of Of ('ourse,
course, thethe losses
losses attendant
attendant on very very high
high
counting
counting rates
rates ean
can be
be determined
determined from
from the
the calibration
calibration curve
curve and
and used to
to
correct
correct the
the observed
observed rate,rate, but it
it is
is usually
usually safer
safer to
to reduce
reduce the
the intensity
intensity of
of aa
very strong beam,
very strong beam, by by means
means of
of foils
foils of
of known
known absorption,
absorption, to
to aa point
point where
where
the
the observed
observed ('ounting
counting rate rate is
is on
on the the linear
linear portion
portion of of the
the curve.
curve.

Figure 7-15
Figure 7-15 also
also shows
shows that
that the the range
range of of linearity
linearity of of aa ('ounting
counting raterate
curve
curve is
is dependent
dependent on
on the
the x-ray
x-ray tube
tube voltage
voltage and
and is
is shorter
shorter for
for lower
lower voltages.
voltages.
The
The reason
reason for
for this
this dependence
dependence is is the
the fact
fact that
that the
the x-ray
x-ray tube
tube emits
emits charac-
charac-
teristic x-rays not continuously
teristic x-rays not continuously but
but only
only in
in bursts
bursts during
during those
those times
times when
when
 7-6)
7-6] GEIGER COUNTERS
GEIGER COUNTERS 199
199

the tube
the tube voltage
voltage exceeds
exceeds the
the critical
critical
excitation voltage of the
voltage of the target
target mate-
mate- 50
excitation
rial. Suppose,
rial. Suppose, for for example,
example, that that aa ~ 40
copper target (excitation voltage = ~
copper target (excitation voltage =
9 kv)
9 kv) is
is operated
operated at
at a
a peak voltage
peak voltage r"'l
of 50 kv.
of 50 kv. Then, Then, if
if the
the wave form
wave form isis ~
like that shown in
like that shown in Fig. 7-16, Cu Fig. 7-16, eu Ka Ka _
radiation will be emitted during the ~
radiation wiII be emitted during the
time intervals
time intervals ^2 and t^
tlt2 and tat. butbut notnot
during t2ta.
during < 2 fe- But ifif the
But the peak
peak voltage
voltage () L--o----o--......JI.----\---...L.
is decreased
is decreased to to 25
25 kv,kv, Cueu Ka Ka emission
emission I-~ eyrie-I critical
-
-\ cycle -I rrltI('al excitation
exritation
is limited
limited to to the
the shorter
shorter time time intervals
intervals \'oltage
voltage
is
TIME
ttste and 177t",.
5 G and
t / 8< If the
If the x-ray
x-ray intensity
intensity is is
volt-
.

FIG. 7-16.
FIG. 7-16. Variation of
Variation of tube
tube volt-
made the
made the same same at at both
both voltages
voltages by by age with
age with time time forfor aa full-wave
full-wave rectified
rectified
adjusting the
adjusting the tube
tube current,
current, then then it fol- x-ray
it fol- x-ray tube
tube (schematic).
(schematic).
lows that
lows that the the same
same number
number of of Cueu Ka
quanta are
quanta are bunched
bunched into into shorter
shorter timestimes at at the
the lower
lower tube tube voltage
voltage than than atat
the higher.
the higher. Lowering
Lowering the
the tube
tube voltage
voltage therefore
therefore decreases
decreases the
the average
average
time interval
time interval between between quanta quanta entering
entering the the Geiger counter during
Geiger counter during each each
half-cycle and
half-cycle and may may cause counting losses
cause counting losses to occur at rates at which no
to occur at rates at which no
losses
losses are produced at
are produced at higher
higher tube voltages. It
tube voltages. It follows
follows thatthat aa counter
counter cali-cali-
bration
bration curvecurve applies
applies only only to to measurements made at at voltages
voltages not not less
less than
than
the
the voltage
voltage at at which
which the the calibration
calibration was performed. performed.
One
One otherother aspect aspect of of Geiger-counter
Geiger-counter operation operation deserves
deserves mention,
mention, and
that
that is is the
the method
method used used to to prevent
prevent the the discharge
discharge actuated by by the absorp-
absorp-
tion of
tion of one
one quantum
quantum from
from continuing
continuing indefinitely.
indefinitely. If
If the counter is is filled
filled

with
with a a single
single gas gas such
such as
as argon,
argon, the
the positive
positive argon
argon ions
ions on reaching
reaching the
the
cathode
cathode are are ableable to to eject
eject electrons
electrons from
from the
the cathode material.
material. These
These
electrons
electrons are are accelerated
accelerated to to the
the anode
anode and initiate initiate another chain of of ioniza-
ioniza-
tion,
tion, with
with the
the result
result that
that a
a continuous
continuous discharge
discharge is
is set
set up
up in
in the counter,
counter,
rendering
rendering it incapable of
it incapable of counting
counting any any entering
entering quantaquanta afterafter the first first one.
one.
This discharge may
This discharge may be prevented be prevented or
or "quenched"
"quenched" if
if an
an external
external circuit
circuit is
is

used which abruptly

used which abruptly lowers the voltagelowers the voltage on
on the
the counter
counter after
after each
each pulse
pulse
to
to aa value
value below below that that necessary
necessary to to maintain
maintain aa dischargedischarge but but high
high enough
enough
to
to clear
clear all all ions
ions from
from the the gas.
gas. As As soon
soon as as the
the ions
ions areare neutralized
neutralized at at the
the
cathode,
cathode, the the high voltage is
high voltage is reapplied
reapplied and and the the counter
counter is again
is again sensitive.
sensitive.

To
To avoid
avoid the the necessity
necessity for for aa quenching
quenching circuit, circuit, counters
counters have have beenbeen designed
designed
which
which are are self-quenching
self-quenching by
by virtue
virtue of
of the
the gas
gas mixture
mixture they
they contain.
contain. To To
the
the main
main gas gas in in the
the counter,
counter, usually
usually argonargon or krypton, is
or krypton, is added
added aa small small
proportion
proportion of
of "quench
"quench gas," gas," which
which is
is either
either aa polyatomic
polyatomic organic
organic vapor,
vapor,
such
such as as alcohol,
alcohol, or or aa halogen,
halogen, such such as as chlorine
chlorine or or bromine.
bromine. As As its name
its name

implies,
implies, the
the quench gas
quench gas plays plays the
the role
role of
of the
the quenching
quenching circuit
circuit used
used with
with
single-gas counters
single-gas counters and
and prevents
prevents the
the initial
initial avalanche
avalanche of
of ionization
ionization from
from
200
200 DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETER MEASURJ<;M ~;NTS [CHAP. 77
[CHAP.

becoming aa continuous
becoming continuouH discharge.
diHcharge. In
In an
an argon-chlorine
argon-chlorine counter,
counter, for
for exam-
exam-
ple, ionized
ple, ionized argon atoms acquire
argon atoms acquire electrons
eleet.rons from
from chlorine
chlorine molecules
molecules byby
collision, forming
collision, forming neutral
neutral argon
argon atoms
atoms andund ionized
ionized chlorine
chlorine molecules.
molecules.
The latter
The latter are
are merely
mprcly neutralized
neutralized on
on reaching
reuehing the
the cathode
eathode and
and do
do not
not re-
re-
lease electrons
lease aH argon
clectronH as argon ions
ions do.
do. Most counters counters used used today
today are are ofof the
the
self-quenching variety.
self-quenching variety.
efficiency of
The efficiency of aa Geiger
Geiger or or proportional
proportional counter ('OlUlter and and its its associated
associated
circuits is
circuits is given
given by by thethe product
produet. of of two efficiencies,
dfieieneiclS, that that of of quantum
quantum ab- ab-
sorption
sorption and that
that of
of quantum
quantum det.ed,ion.
detection. The absorption efficiency de-
ahsorption e'ffiei!'ney de-
pends on
pends on the
the absorption
ahsorption coefficient
eocfficimt and thiekneHH of thickness tIl(' counter
of the eounter window,
window,
both of
both of which
which should
Hhould be be as as small
small as as possible,
pOHHible', and on the absorption
on the ahHorption coeffi-
('oeffi-
cient of
cient the counter
of the counter gas gas and the the length
lpngth of of the the counter,
('ounter, bothhoth of of which
whi('h should
be as
be as large
large as as possible.
possible. The detection detection efficiency
effi('ieney of of aa Geiger
Geiger counter,
('ounter, as aR we
have seen,
have seen, depends
depends on the th(' counting
counting rate rate and is is effectively
effeetively 100 100 percent
percent at at
low rates;
low rates; with
with aa proportional
proportional counter counter this this efficiency
effiei('ney is is near
n('u1' 100 pereent
100 percent
at any
at any rate
rate likely
likely toto be eneountered in
be encountered in diffraction
diffra('tion experiments.
experimentH. The The' over-
over-
all efficiency
all efficiency of of either
either counter
counter at at low rates
rateH is is therefore
thNefore determined by hy the
the
absorption efficieney,
absorption efficiency, whieh
which is
is commonly
commonly about
about GO
60 to
to 80 per('ent.
percent.
absorption efficiency,
The absorption effieien('y, however,
however, is iH "pry
very much mu('h dependent
d('pe'ndpnt on the the'
x-ray wavelength,
x-ray wavelength,
determine the
determine the amount
the
the
amount. of
kind
kind
..
of
of
of radiation
gas used,
gas used,
radiation absorbed
and
ahsorbed in
its
its prpsHurp,
pressure,
in aa counter
sinee
since
countpr of
thesp
these
of given
fae/OJ's
factors
p;iwn length.
length.
Figure 7-17
Figure 7-17 shows how the the amount absorbed depends depends on wuv('\mgth
wavelength for for
the two gases
the gases most
mm,t often
often used us('d inin x-ray eounterH. Note
x-ray counters. Notl:' that
that a a krypton-
krypton-
filled
filled count.er
counter has has high
high Hl:'nsitivity
sensitivity for for
all
all the
the charaetpristi('
characteristic radiationH
radiations nor- nor-

mally used
mally used in in diffraction
diffraction but but that
that an Mo A
1\101\", ('uA"
argon-filled
argon-filled counter
counter is is sensitive
sensitive only only :::c IOOr--,..---L.--'----r::>-L---,--::;oo-L---,
KM)
0::
to
to the
the longer
longer wavPlen!!,ths.
wavelengths. ThiH latter ~
This latter
characteristic
characteristic may advantageous ~ so -
may be advantap;<'ous
in
in some circumstaneeH.
circumstances. For example, example, ;.0;
if
if a
a diffraction
diffraction pattern
pattern i.s
is made with ~ IiO __ _
with
filtered
filtered radiation
radiation from a a copppr
copper tur- tar- ~
get, use
get, use of of an argon-filled
argon-filled counter will
counter w ill 5t
r

~ 401---+--
produce
produce semimonochromatic condi- <
condi-
tions,
tions, in in that
that the the counter
counter will will be l--
radiation r;
;.0; 20
highly
highly sensitive
sensitive to to euCu Ka radiation ~--+--+-
and relatively
relatively insensitive
insensitive to to the
the short
short P::
wavelength
g; 0':-o--:::-'::---L.--L....-..,..2.LO----...I
wavelength radiation
radiation which
which formsforms the the 05 10 1.5 2.0 25
most intense
intense part part ofof the eontinuous
continuous WAVELENGTH
WAVELENGTH (A) (A)
spectrum.
spectrum. The diffraction
diffraction background
background
7-17. Absorption
FIG. i-Ii. Absorption of of x-rays
x-rays inin
will
will therefore
therefore be be lower
lower than than if if a a
aa lO-em
10-cm path path length
length of of krypton
krypton andand
krypton-filled counter
counter had been
been argon, e:teh
krypton-filled argon, each at at aa pressure
pressure of of 65
65 emcm
used.
used. Hg.
Hg.
7-7]
7-7] SCINTILLATION COUNTERS 201
201

7-7
7-7 Scintillation
Scintillation counters.
counters. This type type of of counter
counter utilizes
utilizes thethe ability
ability ofof
x-rays
x-rays to to cause
cause certain
certain substances
substances to to fluoresce
fluoresce visible
visible light.
light. The amount
of
of light
light emitted is proportional to
is proportional to the x-ray
x-ray intensity
intensity and can be measured
by
by means of
of a phototube.
phototube. Since
Since the
the amount of
of light
light emitted
emitted is is small,
small, a a
special
special kind of
of phototube
phototube called
called a photomuUiplier
photomultiplier has to
to be
be employed
employed in
in
order
order toto obtain
obtain a a measurable
measurable current
current output.
output.
The substance
substance generally
generally used
used toto detect
detect x-rays
x-rays is is aa sodium iodide
iodide crystal
crystal
activated
activated with a small amount of
a small of thallium.
thallium. It emits
It emits blue light under
blue light under
x-ray
x-ray bombardment. The crystal crystal is is cemented to to the
the face
face ofof a photo-
a photo-
.multiplier
.multiplier tube,tube, as as indicated
indicated in in Fig.
Fig. 7-18,
7-18, and shielded
shielded from externalexternal lightlight
by
by means of of aluminum foil. foil. A flash
flash ofof light
light is produced in
is produced in the
the crystal
crystal forfor
every
every x-ray
x-ray quantum
quantum absorbed,
absorbed, and this this light
light passes
passes intointo thethe photomulti-
photomulti-
plier
plier tube and ejects ejects a a number of of electrons
electrons from the the photocathode,
photocathode, vhich vhich
is
is aa photosensitive
photosensitive material
material generally
generally made of of a caesium-antimony
caesium-antimony inter- inter-
metallic
metallic compound.
compound. (For (For simplicity,
simplicity, only only one of of these
these electrons
electrons is is shown

in
in Fig. 7-18.)
Fig. 7-18.) The emitted
emitted electrons
electrons are
are then
then drawn to
to the
the first
first of
of several
several
metal
metal dynodes,
dynodes, each
each maintained
maintained at
at a
a potential
potential about 100
100 volts
volts more posi-
posi-
tive
tive than the preceding one,
the preceding one, the
the last
last one being
being connected
connected to
to the
the measuring
measuring
circuit.
circuit. On reaching
reaching the the first
first dynode,
dynode, each electron
electron from the photocathode
the photocathode
knocks two electrons,
electrons, say,say, out
out ofof the
the metal
metal surface,
surface, as as indicated
indicated in in the
the
drawing.
drawing. These are are drawn to to the
the second dynodedynode where each each knocks out out
two more electrons
electrons and so so on.
on. Al'tually,
Actually, the the gain
gain at at each
each dynode
dynode may may
be
be 4 4 or
or 55 and there
there are usually at
are usually at least
least 10 dynodes. If
10 dynodes. If the
the gain per dynode
gain per dynode
5 10 =
10 =
is
is 55 and there
there areare 1010 dynodes,
dynodes, thenthen thethe multiplication
multiplication faetor factor is is 5 10 7
10 7
.

Thus the the absorption

absorption of of one
one x-ray
x-ray quantum
quantum in in thethe crystal
crystal results
results in in the
the
collection
collection of of a
a very large number of
very large of electrons
electrons at at the
the final
final dynode,
dynode, producing
producing
aa pulse
pulse about
about as as large
large asas a
a Geiger
Geiger pulse,
pulse, i.e.,
i.e., of
of the
the order
order of of volts.
volts. Further-
Further-
more,
more, the
the whole
whole process requires
process requires less
less than
than a
a mierosecond,
microsecond, so
so that
that a
a scintil-
scintil-
lation
lation counter
counter can can operate at
at rates
rates as
as high as
as 10
10 55 counts
counts per second
second without
without
operate high per
losses.
As in
in the proportional counter,
the proportional counter, the pulses produced
the pulses produced in in aa scintillation
scintillation
counter have sizes proportional
counter have sizes proportional to
to the
the energy
energy of
of the
the quanta
quanta absorbed.
absorbed.

dYIl()d("~
dynodes vacuum
photocathode
\

light

x-ray::;

~'--- .,.--
rrystal
crystal photomultiplier
photoniultiplicr tub!.'
tube

FIG. 7-]8.
FIG. 7-18. Scintillation
Scintillation counter
counter (schematic).
(schematic). Electrical
Electrical conne('tions
connections not
not shown.
shown.
202
202 DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETER MEASUREMENTS [CHAP. 7
[CHAP. 7
But the
But the pulse
pulse size
size corresponding
corresponding to
to aa certain
certain quantum
quantum energy
energy isis much
much
less sharply
less sharply defined
defined thanthan in in aa proportional
proportional counter;
counter; i.e., i.e., scintillation-
scintillation-
counter pulses produced by
counter pulses produced by x-ray quantax-ray quanta of
of aa given
given energy
energy have
have aa mean
mean
size characteristic
size characteristic of
of that
that energy,
energy, but
but there
there is
is also
also a
a fairly
fairly wide
wide distribu-
distribu-

tion of pulse
tion of pulse size
size about
about thisthis mean.
mean. As As aa result,
result, itit isis difficult
difficult toto discriminate
discriminate
between x-ray quanta
between x-ray quanta of of different
different energies
energies on
on the
the basis
basis of
of pulse size.
pulse size.
The efficiency
The of aa scintillation
efficiency of scintillation counter
counter approaches
approaches 100 percent
100 percent overover the
the
whole range
whole range ofof x-ray
x-ray wavelengths,
wavelengths, shortshort and long,
and long, because all incident
because all incident
x-ray quanta
x-ray quanta areare absorbed
absorbed in in the
the crystal.
crystal. Its Its chief
chief disadvantage
disadvantage is is its
its
rather high
rather high background
background count;count; aa so-called
so-called "dark
"dark current"
current" of of pulses
pulses isis pro-
pro-
duced even
duced even when
when nono x-ray quanta are
x-ray quanta are incident
incident on on thethe counter.
counter. The The main
main
source of
source of this
this dark
dark current
current is is thermionic
thermionic emission
emission of of electrons
electrons from from the
the
photocathode.
photocathode.

7-8 Sealers.
7-8 Scalers. A A sealer
scaler is is an
an electronic
electronic device
device whichwhich counts
counts each each pulsepulse
produced
produced by by the
the counter.
counter. Once
Once the
the number of
of pulses
pulses over
over a
a measured
measured
period of
period of time
time is is known,
known, the the average
average counting
counting rate rate is is obtained
obtained by by simple
simple
division. If the rate of pulse
division. If the rate of pulse production production were
were always low,
always low, say say aa few
few counts
counts
per second,
per second, the the pulses
pulses could
could be be counted
counted satisfactorily
satisfactorily by by aa fast mechanical
fast mechanical
counter, but
counter, but such devices cannot
such devices cannot handle
handle highhigh counting
counting rates. It
rates. It is there-
is there-

fore
fore necessary
necessary to to divide,
divide, or or scale down, the
scale down, the pulses
pulses by by a known factor before
factor before
feeding
feeding them them to to thethe mechanical counter. As its
mechanical counter. its name implies,
implies, the scaler sealer
fulfills this latter
fulfills this latter function.
function. There There are are two main kinds, kinds, the binarybinary scaler,
sealer,
in
in which
which the the scaling
scaling factor
factor is is some powerpower of 2, and the decade scaler,
of 2, sealer, in in

which it
which it is
is aa power
power of
of 10.
10.
We will
will consider
consider scaler sealer operation
operation only only in in terms of of binary
binary scalers
sealers but
the
the principles
principles involved
involved are
are applicable
applicable to
to either
either type.
type. A typical
typical binary
binary
scaler
sealer hashas several
several scaling
scaling factors
factors available
available at
at the
the turn of
of a switch,
switch, ranging
ranging
from 2
from 2 (=(= 1) 1) to
to about
about 214
14
2 (= (= 16384).
16384). The scaling scaling circuit
circuit is is made up up of of a
number of identical
number of identical "stages" "stages" connected
connected in
in series,
series, the
the number of
of stages
stages
n
being equal to
being equal to n n where
where 22n is is the
the desired
desired scaling
scaling factor.
factor. Each stage stage is is com-

posed of
posed of aa number
number of of vacuum
vacuum tubes,tubes, capacitors,
capacitors, and and resistors
resistors so so connected
connected
that
that only
only one
one pulse
pulse of of current
current is is transmitted
transmitted for for every
every two two pulses
pulses received.
received.
Since
Since thethe output
output of of one stage is
one stage is connected
connected to to thethe input
input of of another,
another, this this

division
division by two is
by two is repeated
repeated as as many
many times
times as as there
there are are stages.
stages. The The output
output
of
of the
the last
last stage
stage may may be connected to
be connected to aa mechanical
mechanical counter counter which which will will

register
register one
one count
count for
for every pulse
every pulse transmitted
transmitted to
to it
it byby the
the last
last stage.
stage. Thus,
Thus,
N pulses
ifif N pulses fromfrom aa counter
counter are are passed
passed through
through aa circuit circuit of of nn stages,
stages, only only
NN/2/2 nn will
will register
register on
on the
the mechanical
mechanical counter.
counter.
There
There areare twotwo waysways of of using
using aa scaler
sealer to to obtain
obtain an an average
average counting
counting rate: rate :

counting
counting for afor a fixed
fixed time
time and
and counting
counting aa fixed
fixed number
number of
of pulses.
pulses. In
In the
the
first method, the
first method, the sealer scaler is
is turned
turned on
on for
for aa time
time tt and
and then
then shut
shut off.
off. If
If the
the
mechanical counter then shows NQ counts,
mechanical counter then shows No counts, the
the number
number of
of input pulses
input pulses
7-8]
7-8] SCALERS
8CALER8 203
203

must
must have
have been
been
AT = N (2
n
) + a, (7-5)
(7-5)
n
where
where aa is is an
an integer
integer ranging
ranging from from 0 up up to (2 - 1).
to (2n 1). The
The integer
integer a a gives
gives
the number
the number of of pulses
pulses still
still "in
"in the
the circuit"
circuit" whenwhen the the input
input pulses
pulses werewere shutshut
off,
off, and
and its
its value
value is is found
found by by noting
noting which
which of of several
several neonneon interpolation
interpolation
lamps connected to
lamps connected to the several
several stages
stages are are still
still on.
on. As indicated
indicated in in Fig.
Fig.
7-19
7-19 for
for aa scale-of-16
scale-of-16 circuit,
circuit, therethere isis aa neon
neon lamp
lamp connected
connected to
to each
each stage
stage
n~
and the number opposite opposite each lamp lamp is is 22n - 1 where
where nn is
1
is the
the number
number of of the
the
stage.
stage. The The initial
initial pulse
pulse entering
entering aa stage
stage turns
turns the
the lamp
lamp on
on and
and the
the second
second
pulse
pulse turns
turns it it off.
off. Since
Since the second entering entering pulse pulse causes
causes a a pulse
pulse to to bebe
transmitted to the next stage, stage, the lamp
lamp on that
that stage
stage goesgoes on
on at the
at the samesame
time that the lamp lamp on the preceding preceding stage stage goesgoes out.out. The integer
integer a a is
is

therefore givengiven by by the sum of

of the
the numbers opposite lighted neon
opposite lighted neon lamps. lamps.
The total
The total count
count shown in in Fig.
Fig. 7-19,
7-19, forfor example,
example, is is N 18(16) +
N == 18(16) + (2 (2 + + 4)4)
=
= 294. the total
total number of of counts
counts is is known,
known, the the average
294. Once the average counting
counting
rate isis given
given simply
simply by by N It.
N/t.
In
In the second method of of scaling
scaling (counting
(counting a a fixed
fixed number of of pulses),
pulses),
the mechanical counter is is replaced
replaced by by an electric
electric timer.
timer. The timer timer is is con-
con-
nected to
nected to the circuit
circuit in in such a a way
way that
that it it starts
starts when the the scaler
sealer is is started
started
and stops
stops at the instant a pulse pulse is is transmitted
transmitted from the the last
last stage.
stage. For
For
example,
example, if if the
the timer
timer is is connected to to a 1O-stage scaler,
10-stage sealer, it
it will
will stop
stop when
when
10
exactly
exactly 1024 (= (= 2 10 )) pulses
pulses have have entered
entered the the first
first stage, because at
stage, because that
at that
instant the
instant the tenth
tenth stage
stage willwill transmit
transmit its its first pulse; the
first pulse; the average
average counting
counting
rate is
rate is then
then given
given by by the
the quotient
quotient of of 1024
1024 and the the time
time shown
shown on on the
the timer.
timer.
Such aa circuit
Such circuit requires
requires no interpolation
interpolation since since no no counts
counts remain
remain in in the
the circuit
circuit
at the
at the instant
instant thethe final
final stage
stage transmits
transmits its its pulse
pulse to to the
the timer;
timer; i.e.,
i.e., all
all thethe
neon lights
neon lights are off.
are off. The total number of
total of counts,
counts, whichwhich must must be be aa power
power
of 22 in
of in aa binary
binary sealer,
scaler, is is selected
selected by by aa switch
switch which
which connects
connects the the timer
timer to to
any desired
any desired stage,
stage, thus
thus making
making that that stage
stage thethe final
final stage
stage andand short-circuit-
short-circuit-
ing the
ing the remainder.
remainder.
Because the
Because the arrival
arrival of of x-ray quanta in
x-ray quanta in the
the counter
counter is is random
random in in time,
time,
the accuracy
the accuracy of of aa counting
counting rate rate measurement is is governed
governed by by the
the laws
laws of of
probability. Two counts
probability. counts of of the
the same
same x-rayx-ray beam
beam for for identical
identical periods
periods of of
time will
time will not
not be
be precisely
precisely the the same
same because
because of of the
the random
random spacingspacing between
between
lllterpolatlOll
interpolation (,\
x v

numbers ~~^
~
numbers - \i)
mechanical
mechanical
counter

input
pulses

7-19. Determination
FIG. 7-19.
FIG. Determination of
of sealer
scaler counts.
counts.
204
204 DIFFRACTOMETER MEASUREMENTS [CHAP. 7
(CHAP. 7

pulses,
pulses, even
even though
though the
the counter
counter and scaler
sealer are
are functioning pedectly.
functioning perfectly.
Clearly,
Clearly, the
the accuracy
accuracy of
of a
a rate
rate measurement of
of this
this kind improves
improves as
as the
the
time
time of
of counting
counting is
is prolonged,
prolonged, and it
it is
is therefore
therefore important
important to
to know how
long
long to
to count
count in
in order
order to
to attain
attain a specified
specified degree
degree of
of accuracy.
accuracy. The prob-
prob-
able error
able error* inin a
a single
single count
count of
of NN pulses,
pulses, relative
relative to
to an average
average value
value
obtained
obtained byby a
a great many repetitions
great many repetitions of
of the same counting
counting operation, is
operation, is

given
given by
by
67
67
EN =
EN = VN = percent,
percent, (7-6)
(7-6)

so
so long
long as N isis fairly
as N fairly large.
large. For some ofof the
the total
total counts
counts obtainable
obtainable from
aa binary
binary scaler, this expression
sealer, this expression gives
gives the
the following
following errors:
errors:

Total number of Percent

pulses counted probable error
256 (= 28) 4.2
512 (= 29) 3.0
1024 (= 210) 2.1
2048 (= 211) 1.5
4096 (= 212) 1.0
8192 (= 213) 0.7
16384 (= 211) 0.5

Note that
Note that the
the error
error depends
depends only
only on the the number of pulses counted
of pulses counted and not not
on
on their
their rate,
rate, which
which means that that high
high rates
rates and low rates
low can be
rates can be measured
measured
with
with the
the same accuracy,
accuracy, if if the
the counting
counting times
times are chosen to
are chosen produce the
to produce the
same
same total
total number of of counts
counts in in each
each measurement. It It also
also follows
follows that
that
the
the second
second scaling
scaling method outlinedoutlined above,
above, in
in which thethe time
time is is measured

for
for aa fixed
fixed number of of counts,
counts, is is generally
generally preferable
preferable to to the
the first,
first, since
since it
it

permits
permits intensity
intensity measurements of
of the
the same precision
precision of
of both
both high-
high- and
and
low-intensity
low-intensity beams.
beams.
Equation
Equation (7-6)
(7-6) is is valid
valid only
only when the the counting
counting rate
rate due to to the
the radiation
radiation
being
being measured
measured is
is large
large relative
relative to
to the
the background. (Here "background"
background. (Here "background"
means thethe unavoidable
unavoidable background
background counting
counting rate
rate measured with with the
the x-ray
x-ray
tube shut
tube shut off,off, and not
not the
the "diffraction
"diffraction background"
background" at
at non-Bragg
non-Bragg angles
angles
due
due toto any
any ofof the
the several
several causes
causes listed
listed in
in Sec.
Sec. 6-11
6-11 and ofof which fluorescent
fluorescent
radiation
radiation is is usually
usually the the most important.
important. The unavoidable
unavoidable background
background is is

due
due toto cosmic
cosmic rays
rays and
and may
may be be augmented,
augmented, in in some laboratories,
laboratories, by by stray
stray

** The probable
probable error
error is that
that which is
is just as
is just as likely to be
likely to be exceeded
exceeded as
as not.
not. Three
times
times the probable error
the probable error isis a
a somewhat more usefuluseful figure,
figure, as
as the
the probability
probability that
that
this
this will
will be
be exceeded
exceeded is
is only 0.04. Thus,
only 0.04. Thus, if
if a
a single
single measurement gives 1000 counts,
gives 1000 counts,
then
then the
the probable is 67/ y'IOOO = 2.1
error is
probable error 2.1 percent
percent or
or 21
21 counts.
counts. Then the the prob-
prob-
67/^/1000
ability
ability is 0.5 that
is 0.5 that this
this count
count lies
lies in
in the
the range Nt 21,
range Nt where N
21, where Nt is
t is the
the true
true number
of
of counts,
counts, while
while the
the probability
probability is 0.96 that
is 0.96 that the
the measured
measured value
value lies
lies in
in the
the range
range
N t 63.
t 63.
7-8]
7-8] SCALERS
SCALER8 205
205

radiation
radiation from nearby
nearby radioactive
radioactive material;
material; it it may
may be rather
rather high,
high, if
if aa
scintillation
scintillation counter isis used,
used, because of of the
the dark current
current ofof this
this counter.)
counter.)
Suppose
Suppose a a measurement is is required
required of of the
the diffraction
diffraction background,
background, always
always
rather low,
rather low, in
in the
the presence
presence ofof a
a fairly
fairly large
large unavoidable
unavoidable background.
background. In In
these
these circumstances,
circumstances, Eq.Eq. (7-6)
(7-6) does
does not apply.
apply. Let NTV be
be the
the number of
of
pulses
pulses counted in
in a given
given time with the
the x-ray
x-ray tube on,
on, and N
Nb b the
the number
counted
counted inin the
the same time
time with the tube off.
the tube off. Then N Nbb ('ounts
counts areare due toto
the
the unavoidable
unavoidable background
background and (N
(N - N
Nb)b) to
to the
the diffraction
diffraction hackground
background
being
being measured,
measured, and the the relative
relative probable
probable error
error inin (N
(N - N b) is
Nb) is

E *-x*
EN =
-Kb =
07V'N
67VN +
percent.
ercent
N
+ Nb b
(7-7)
^7T~ P
-~7^ - N
(N
-
(7-7)
(N - Nb)
b)

Comparison
Comparison of of Eqs. (7-0) and (7-7)
Eqs. (7-6) (7-7) shows that that longer
longer counts
counts must be be
made when the the unavoidable
unavoidable hackground
background is is ofof comparable
comparable intensityintensity to to
the
the radiation
radiation being
being measured than than when the the unavoidable
unavoidable background
background is is

completely negligible by
completely negligible by comparison,comparison, if
if the
the same accura('y
accuracy is
is to
to be
be obtained
obtained
in
in both
both measurements.
As indicated
indicated in Sec. 7-2,
in Sec. 7-2, the the integrated
integrated intensity
intensity of of aa diffraction
diffraction lineline
may
may be
be measured with
with a
a scaler
sealer by determining
by determining the
the average ('ounting
average counting rate
rate
at
at several
several angular positions of
angular positions of the
the counter.
counter. The line line profile,
profile, thethe curve
curve of of
intensity
intensity VS. vs. 28,
26, isis then
then plotted
plotted on on graph
graph paper,
paper, and the the area
area under
under thethe
curve,
curve, and above the the continuous
continuous background,
background, is is measured with with a a planimeter.
planimeter.
To obtain
obtain the
the same relative
relative a('curacy
accuracy of of both
both thethe line profile and the
line profile the adja-
adja-
cent
cent background,
background, all all measurements should should be be made by by counting
counting a a fixed
fixed
number of of pulses.
pulses. Three other other methods of of measuring
measuring integrated
integrated intensities
intensities
have been
been used,
used, allall of
of which utilize
utilize thethe int.egrating properties of
integrating properties of the
the scaling
scaling
circuit to
circuit to replace
replace the
the curve
curve plot.ting
plotting and planimeter
planimeter measurement:
(1) The line
(1) line is
is scanned
scanned from from oneone side
side toto the
the other
other atat aa constant
constant angular
angular
rate,
rate, the
the scaler
sealer being
being started
started at
at the
the beginning
beginning of
of the
the scan
scan and stopped
stopped at at
its
its end.
end. The total total number of of counts
counts registered
registered by by the
the scaler,
sealer, minus the
the
number of of counts
counts due to to the background, is
the background, is then
then proportional
proportional to to the
the in-
in-

tegrated
tegrated intensity
intensity of of the
the line.
line. All
All lines
lines on thethe pattern
pattern must be measured
with
with thethe same receiving
receiving slitslit and the the same scanning
scanning rate.rate. The background
background
adjacent
adjacent to, to, and on eithereither side
side of,of, the
the line
line may
may be measured by by the
the same
procedure,
procedure, i.e.,i.e., by scanning at
by scanning at the
the same rate rate over
over the
the same angular
angular range,
range,
or
or by counting at
by counting at aa fixed position for
fixed position for the
the same time required
required to to scan
scan the
the
line.
line.

(2) The counter

(2) counter is is moved stepwise
stepwise acrossacross thethe line
line and maintained in in
each
each position
position for
for the
the same length
length of
of time,
time, the
the scaler
sealer being operated
being operated con-
con-
tinuously
tinuously except
except when changingchanging counter positions. The total
counter positions. total count
count accu-
accu-
mulated
mulated by by the
the scaler,
sealer, minus the
the background correction,
background correction, is
is again propor-
again propor-
tional
tional toto the
the integrated
integrated intensity.
intensity. A wide receiving receiving slitslit is
is used,
used, and the the
206
206 DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETER MEASUREMENTS [CHAP. 77
[CHAP.

angular interval
angular interval between
between counter
counter positions
positions isis so
so chosen
chosen that
that the
the overlap
overlap
between adjacent
between adjacent settings
settings of of the slit isis negligibly
the slit negligibly small
small and
and constant
constant and
and
never coincides
never coincides with
with the
the maximum
maximum intensity
intensity of of the
the line
line being
being measured.
measured.
(3) A
(3) A receiving
receiving slit
slit isis used
used which
which isis wider
wider than
than the
the line
line being
being measured.
measured.
The slit isis centered
The slit centered on on the
the line
line and
and aa count
count made
made for
for aa given time. The
given time. The
background is measured by
background is measured by counting counting at
at a
a position adjacent
position adjacent to
to the
the line
line

with the same slit for the same

with the same slit for the same length length of
of time.
time.
Because
Because all these
all these methods
methods involve
involve counting
counting for for aa fixed
fixed time,
time, the the back-
back-
ground and
ground and low-intensity
low-intensity portionsportions of of the
the diffraction line are measured
diffraction line are measured
with less
with less accuracy
accuracy than than thethe high-intensity
high-intensity portions.
portions. The counting counting time time
should be
should be chosen
chosen so that the
so that the low
low intensities
intensities areare measured
measured to to the
the accuracy
accuracy
required by
required by the
the particular
particular problem
problem involved;
involved; it it will
will then
then follow
follow thatthat thethe
high
high intensities
intensities are
are measured
measured with
with unnecessarily
unnecessarily high
high accuracy,
accuracy, but
but that
that
is unavoidable
is unavoidable in in fixed-time
fixed-time methods such such asas these.
these.
The integrating
The integrating ability
ability of of aa sealer
scaler is
is also
also put
put to to use
use inin x-ray
x-ray tube
tube moni-
moni-
tors. In
tors. In Sec.
Sec. 7-2
7-2 it it was
was mentioned
mentioned thatthat thethe incident-beam
incident-beam intensity
intensity had had
to be
to be maintained
maintained absolutely
absolutely constant
constant in in aa diffractometer
diffractometer and that that this
this
constancy required
constancy required tube
tube current
current and voltage
voltage stabilizers.
stabilizers. These
These stabilizing
stabilizing
circuits are
circuits are not
not needed
needed if if an
an extra
extra counter
counter and sealer scaler areare available
available to to
"watch," or
"watch," or monitor,
monitor, the the tube
tube output.
output. The monitor counter may be posi-
counter be posi-
tioned to
tioned to receive
receive the the direct
direct beam,
beam, suitably
suitably filtered
filtered to to reduce
reduce itsits intensity,
intensity,
from another window of
from another the x-ray
of the x-ray tube,
tube, oror an
an auxiliary crystal may be
auxiliary crystal be set
set
to
to diffract
diffract aa portion
portion of the beam used
of the used in
in the
the diffractometer
diffractometer into the monitor
the monitor
counter.
counter. In
In either
either case,
case, every
every intensity
intensity measurement with the diffrac- diffrac-

tometer
tometer is is made by by starting
starting the the diffractometer
diffractometer scaler sealer and monitor scaler sealer
simultaneously
simultaneously and
and stopping
stopping both
both when the
the monitor scaler
sealer has registered
registered
aa constant number of
constant number counts N.
of counts N. InIn this
this way,
way, every
every intensity
intensity measurement
is
is made in in terms
terms of of the
the same amount of of energy
energy incident
incident on the specimen,
specimen,
and
and variations
variations in
in tube
tube output
output have no effect.
effect.

7-9
7-9 Ratemeters.
Ratemeters. The counting-rate
counting-rate meter,meter, as as its
its name implies,
implies, is is a

device which indicates the average

device which indicates the average counting counting rate
rate directly
directly without requir-
requir-
ing,
ing, as
as in
in the
the scaler-timer
sealer-timer combination,
combination, separate measurements of
separate measurements of the
the
number of
number of counts
counts andand the
the time.
time. It It does
does this
this byby a circuit
circuit which,
which, in effect,
in effect,

smooths out
smooths out the
the succession
succession of of randomly
randomly spacedspaced pulses
pulses from
from thethe counter
counter
into
into aa steady
steady current,
current, whose
whose magnitude
magnitude is is proportional
proportional to the average average
rate of
rate of pulse
pulse production
production in in the
the counter.
counter.
The heart of
The heart of aa ratemeter
ratemeter circuit
circuit is is a
a series
series arrangement
arrangement of of aa capacitor
capacitor
and
and resistor.
resistor. To To understand
understand the the action
action of of aa ratemeter,
ratemeter, we we must
must review
review
some
some ofof the
the properties
properties of
of such
such a
a circuit,
circuit, notably
notably the
the way
way in
in which
which the
the
current
current and
and voltage vary
voltage vary with
with time.
time. Consider
Consider the
the circuit
circuit shown
shown in
in Fig.
Fig.
7-2O(a),
7-20(a), inin which
which the switch S
the switch S can
can be be used
used either
either to connect a
to connect a to
to cc and
and thus
thus
apply a voltage
apply a voltage to to the
the capacitor,
capacitor, or
or to
to connect
connect bb to
to cc and
and thus
thus short-circuit
short-circuit
7-9)
7-9] RATEMETERS 207
207

r"l
~ O.63l' f----'~......."r
~
e O.37V f-----:~--"I..

0<--_ _ _'--_ _ _ _ _ _ __
I--RC--I
TIME
(a) (b)

FIG. 7-20.
7-20. The capacitor-resistor
capacitor-resistor circuit.
circuit.

the
the capacitor
capacitor and resistor.
resistor. When a is is suddenly
suddenly connected
connected to to c,
c, the
the voltage
voltage
across
across the
the capacitor
capacitor reaches
reaches its
its final
final value
value V not instantaneously
instantaneously but only only
over
over a period of
a period of time,
time, and at at aa rate
rate which dependsdepends on the resistance R
the resistance Rand
and
the
the capacitance
capacitance C, C, as
as shown in
in Fig. 7-20(b).
Fig. 7-20(b). The product
product of
of Rand
R and C has
has
the dimensions
the dimensions of
of time (seconds,
time (seconds, in
in fact,
fact, if
if R is
is in
in megohms
megohms and C in
in micro-
micro-
farads), and it
farads), it may
may be be shown that that the
the voltage
voltage across
across thethe capacitor
capacitor reaches
reaches
63 percent of
63 percent of its
its final
final value
value in in aa time
time given
given by by RC,
RC, known as the time
as the time
constant of
constant of the
the circuit.
circuit. The time
time required
required to to reach
reach 99 percent of
99 percent of its
its final
final

value is
value is 4.6RC.
4.6RC. Conversely,
Conversely, if if the
the fully
fully charged
charged capacitor,
capacitor, bearing
bearing a
charge Q
charge Q = = CV,
CV, is is suddenly
suddenly shorted
shorted through
through the the resistor
resistor byby connecting
connecting
bb to
to c,
c, the
the charge
charge doesdoes notnot immediately
immediately disappear
disappear but but leaks
leaks away
away at at a rate
rate
dependent
dependent on
on the
the time
time constant.
constant. The charge
charge dropsdrops to
to 37
37 percent
percent of
of its
its

initial
initial value
value in in aa time
time equal
equal to
to RC and to
to 1
1 percent
percent in
in a time
time equal
equal to to
4.6RC.
A complete
complete ratemeter
ratemeter circuit
circuit consists
consists of of two parts.
parts. The first first isis a pulse-
pulse-
amplifying
amplifying and pulse-shaping
pulse-shaping portion portion which
which electronically
electronically converts
converts the
the
counter pulses,
counter pulses, which vary
vary in
in amplitude
amplitude and shape
shape from counter
counter to
to counter,
counter,
into
into rectangular
rectangular pulsespulses of of fixed
fixed dimensions
dimensions in in voltage
voltage and time. time. These
pulses
pulses are are then
then fedfed into
into the
the second portion, which
second portion, which is is the
the measuring
measuring circuitcircuit
shown in in Fig.
Fig. 7-21,
7-21, a a circuit
circuit basically
basically pulse
pulse input
input c
similar
similar to to that
that of of Fig.
Fig. 7-20(a)
7-20 (a) and and ~/"'-----1-'
having
having a a time constant R
time constant 2 C2 S,
#2^2- $, b
shown as as a simple
simple switch,
switch, is is actually
actually C2
an
an electronic
electronic circuit
circuit which
which connects
connects a R2
to
to c c each
each time
time a pulse arrives
a pulse arrives and then then
connects
connects b b toto c c immediately
immediately after-
after-
wards.
wards. A constantconstant charge charge is is thus
thus
added to the
to the capacitor
capacitor for each pulse
for each pulse F IG 7
pIG.. -21.
7.21. M . portion
easunng
Measuring port'Ion 0off
received
received and this this charge
charge leaks
leaks away
away raremerer
ratemeter circuit.
circuit.
208
208 DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETER MEASUREMENTS [CHAP. 77
[CHAP.

through the
through the resistor
resistor until,
until, at
at equilibrium,
equilibrium, the
the rate
rate of
of addition
addition of
of charge
charge isis
just
just balanced
balanced by
by the
the rate
rate of
of leakage.
leakage. The
The rate
rate of
of charge
charge leakage
leakage is simply
is simply
the current
the current through
through thethe microammeter
microammeter M, M, which
which therefore
therefore indicates
indicates the
the
rate of
rate of pulse
pulse production
production in
in the
the counter
counter and,
and, in
in turn,
turn, the
the x-ray
x-ray intensity.
intensity.
The circuit
The circuit usually
usually contains, in addition
contains, in addition to
to the
the indicating
indicating meter,
meter, aa chart
chart
recorder
recorder which
which produces
produces a
a continuous
continuous record
record of
of the
the intensity.
intensity.
Even when
Even when the the x-ray
x-ray intensity
intensity is is constant
constant (constant
(constant average average counting
counting
rate), the spacing
rate), the spacing of of the
the counter
counter pulses
pulses is
is random
random in
in time,
time, which
which means
means
that the
that the counting
counting rate rate actually
actually varies
varies with time over short periods.
with time over short periods. The The
ratemeter responds
ratemeter responds to to these
these statistical
statistical fluctuations
fluctuations in the in the counting
counting rate,
rate,
and its
and its response
response speedspeed is is greater
greater the the smaller
smaller the the timetime constant.
constant. This This fol-
fol-
lows from
lows from thethe discussion
discussion of of the
the capacitor-resistor
capacitor-resistor circuit: circuit: any any change
change in in
the pulse
the pulse rate
rate causes
causes aa changechange in in the
the current
current through
through the the circuit,
circuit, but
but the
the
latter change
latter change always
always lags lags behind
behind the the former;
former; the the amount of of lag
lag is
is less
less for
for aa
small time
small time constant
constant than than for for aa large
large one.
one. Random fluctuations fluctuations in in the
the
counting
counting rate
rate are
are therefore
therefore more evident
evident with a
a small
small time
time constant,
constant, be-
be-
cause
cause the
the current
current in
in the
the circuit
circuit then
then follows
follows the
the changes
changes in
in counting
counting rate
rate
more closely.
more closely. This This feature
feature is is illustrated
illustrated in in Fig.
Fig. 7-22,7-22, which
which shows the the
automatically recorded
automatically recorded output output of ratemeter
of a ratemeter when the counter is receiving
the counter is receiving
a constant-intensity
a constant-intensity x-ray x-ray beam.
beam. The large large fluctuations
fluctuations at at the
the left
left have
have
been reduced
been reduced in in magnitude
magnitude by by successive increases in
successive increases in the
the time constant,
constant,
effected
effected byby changing
changing the value of
the value of C 2 2. . Evidently, aa single
Evidently, single reading
reading of of the
the
position
position of of the
the indicating
indicating meter needle needle or or the
the recorder
recorder pen pen of of a ratemeter
ratemeter
may
may be
be seriously
seriously in
in error,
error, and more so
so at
at low time constants than at high.
high.
In
In Sec.
Sec. 7-87-8 we saw that that the the error
error in in a counting-rate
counting-rate measurement de- de-
creased
creased as as the
the number of of counts
counts increased.
increased. Now it it may be shown that a

ratemeter
ratemeter acts acts asas if if it
it counted
counted for for a time 2R 2 C2 in
2 ('2,
,
in the sense that the
accuracy
accuracy of
of any single
any single readingreading is
is equivalent
equivalent to a count made with a scalersealer
for a time
for a time 2R C
22 22 . Therefore,
Therefore, the
the relative
relative probable
probable error
error in
in any single
any single
ratemeter
ratemeter reading
reading is is given
given by by the
the counterpart
counterpart of of Eq.Eq. (7-6),
(7-G), namely
namely by by
C7
67
E ==
E V2nR C
; percent,
percent, (7-8)
(7-8)
\/2nR22 22

where
where n n is
is the
the average
average counting
counting rate.
rate. This equation
equation alsoalso shows that the
probable
probable error
error is
is less
less for
for high
high counting
counting rates
rates than for
for low,
low, when
when the time
constant
constant remains
remains the the same.
same. ThisThis is is illustrated
illustrated graphically
graphically in in Fig.
Fig. 7-23,
7-23,
which
which shows
shows how how thethe recorded
recorded fluctuations
fluctuations in in the counting rate decrease
the counting decrease
as
as the
the rate
rate itself
itself isis increased.
increased.
The
The most
most useful
useful feature
feature of
of aa ratemeter
ratemeter is is its
its ability
ability toto follow changes in
follow changes in

the average counting

the average counting rate, rate, aa function
function which
which the
the scaler
sealer is
is totally
totally unable
unable to
to
perform,
perform, since
since aa change
change in in the
the average
average counting
counting raterate occurring
occurring during
during the
the
time a count is being made with
time a count is being made with a sealer a scaler will
will go entirely
go entirely undetected.
undetected. It
It isis
this
this feature
feature of
of aa ratemeter
ratemeter which
which is is so
so useful
useful in in diffractometry. A
diffractometry. A diffrac-
diffrac-
7-9]
7-9] RATEMETERS 209
209

11\ !'I'll!!:!' ('OUlltlll!!: ral!'

--------- -------
FIG. 7-22.
7-22. Effcrt
Effect of
of time eonstant
constant (T.C.)
(T.C.) on recorded
recorded fluctuations
fluctuations in
in counting
counting
rate
rate at
at constant
constant x-ray
x-ray intensity
intensity (srhematir).
(schematic). Time eonstants
constants ('hanged
changed abruptly
abruptly at
at
(T.C.)i <
times shown. (T.C.h (T.C.) 2 <
< (T.C.h < (T.C.)3.
(T.C.) 3 .

tion
tion pattern
pattern can be be scanned from one end to to the
the other,
other, and the the moving
moving
counter aut.omatically
automatically t.ransmits,
transmits, through
through thethe ratemeter,
ratemeter, a continuous
continuous
record
record ofof the intensity it
the int.ensity it observes
observes as as the
the diffraction
diffraction angle
angle isis changed.
changed. On
the
the other
other hand,
hand, the ratemeter is
the rat.emet.er is less
less accurate
accurate than t.he the scaler, both because
sealer, both
of
of the
the unayoidable
unavoidable statistical
statistical flurtuations
fluctuations inin its
its output.
output and because
because of of the
the
errors
errors inherent
inherent in in its
its indieating
indicating or or recording
recording instruments.
instruments.
As mentioned earlier,
earlier, a a large
large time
time constant
constant smooths out out fluctuations
fluctuations in in
the
the average counting
average counting ratE'
rate by in(,reasing
by increasing the
the response
response time
time to
to changes
changes in in
rate.
rate. But when aa sharp sharp diffraction
diffraction line
line is
is being scanned,
being scanned, the
the average
average
counting
counting rate
rate is
is ('hanging rapidly
changing rapidly and we would like
like the
the ratemeter
ratemeter to
to indi-
indi-
cate
cate this
this l'hange
change as
as accurately
accurately as
as possible.
possible. From this
this point.
point of
of view
view aa short
short
response
response time,
time, produl'ed
produced by by a a small
small time constant, is
time constant, is required.
required. A rate- rate-
meter must t.herefore
therefore be be designed
designed with
with these
these two conflicting
conflicting factors
factors in
in

TIl\IE
TIME

FIG.
FIG. 7-23.
7-23. Effe(t
Effect of
of average
average counting
counting rate
rate on recorded
recorded fluctuation!!
fluctuations in
in counting
counting
rate,
rate, for a fixed
for It fixed time
time constant
constant (schematic).
(schematic). X-ray
X-ray intensity
intensity changed
changed abruptly
abruptly at
at
times
times shown.
shown.
210
210 DIFFRACTOMETER MEASUREMENTS
DIFFRACTOMETBR MEASUREMENTS [CHAP. 77
[CHAP.

mind, and
mind, and the
the time
time constant
constant should
should be
be chosen
chosen large
large enough
enough to
to smooth
smooth out
out
most of the
most of the statistical
statistical fluctuations
fluctuations and
and yet
yet small
small enough
enough to
to give
give aa reason-
reason-
ably short
ably short response
response time.
time.
Most commercial
Most commercial ratemeters
ratemeters have
have several
several scales
scales available
available to
to cover
cover var-
var-
ious ranges
ious of x-ray
ranges of x-ray intensity
intensity (100,
(100, 1000,
1000, and
and 10,000
10,000 cps
cps for
for full-scale
full-scale
deflection of the recorder pen,
deflection of the recorder pen, for
for example).
example). Smaller
Smaller time
time constants
constants are
are
used with
used with the
the higher
higher scales,
scales, just
just asas short
short counting
counting times
times are
are used
used with
with aa
scaler when
sealer when the
the counting
counting rate
rate is high. In some instruments,
is high. In some instruments, the time con-
the time con-
stant appropriate
stant appropriate to to each
each scale
scale is
is fixed
fixed by
by the manufacturer,
the manufacturer, and
and in
in others
others
the operator
the operator cancan select anyone
select any one of of several
several time
time constants,
constants, ranging
ranging from
from
about 0.5
about 0.5 to 15 sec,
to 15 sec, by
by switches
switches which
which insert
insert the
the proper
proper capacitance
capacitance in
in the
the
circuit. The
circuit. The proper
proper time
time constant
constant to to use is, of
use is, of course,
course, not
not unrelated
unrelated to
to the
the
scanning speed,
scanning speed, for
for aa fast
fast scan
scan demands aa fast fast response
response from the
the ratemeter
ratemeter
and therefore
and therefore aa short
short time
time constant.
constant. A time
time constant
constant which is
is too
too large
large
for the
for the scanning
scanning speed
speed used will slightly
used will slightly shift
shift the
the peaks
peaks of
of diffraction
diffraction lines
lines
in the
in the direction of the
direction of the scan
scan and lower
lower their
their maximum intensity
intensity and,
and, be-
be-
cause of
cause of its
its excessive
excessive smoothing
smoothing action,action, may actually actually obliterate
obliterate weak dif- dif-
fraction
fraction lines
lines and
and cause
cause them to
to go
go unnoticed.
unnoticed. In
In choosing
choosing a
a time
time constant,
constant,
it is
it is therefore
therefore better
better to to err
err on
on thethe short side. A
short side. A good
good rule
rule toto follow
follow is is to
to
make the
make the time
time constant
constant less than half the time width of the receiving
less than half the time width of the receiving slit,slit,
where the
where the time
time width
width is is defined
defined as as the
the time
time required
required for for the
the slit to travel
slit to travel
its
its own
own width.
width. For For example,
example, if if a 0.2 slit
a 0.20 slit is
is used at at a scanning
scanning speed speed of of
2/min, =
(60) = 6 sec,
2/min, then then the
the time
time width
width of of thethe slit
slit isis (0.2/2)
(0.2/2) (60) sec, and the the
time
time constant
constant should therefore be
should therefore be less
less than 3 3 sec.
sec. The same rule rule can be be
used
used to to find
find the
the proper
proper slit
slit width
width for
for a given
given scanning
scanning speed
speed when the time
time
constant
constant is is fixed.
fixed.
The
The relation
relation between
between the the x-ray
x-ray intensity,
intensity, i.e.,
i.e., thethe average
average counting
counting rate, rate,
and
and the deflection of
the deflection of the
the indicating
indicating meter needle
needle or
or recorder pen
pen is
is linear
linear
for
for some
some ratemeters
ratemeters and logarithmic
logarithmic for for others.
others. The exact relation relation may
be found
be found by by a
a calibration
calibration procedure
procedure similar
similar to
to that used for
for the Geiger
Geiger
counter and scaler, as
counter and sealer, as outlined outlined in
in Sec.
Sec. 7-8.
7-8. A number of
of identical
identical metal
foils are placed in a strong
foils are placed in a strong diffracteddiffracted beam entering
entering the counter and these
these
are
are withdrawn
withdrawn one one by by one,
one, with
with the the counter
counter in a fixed position.
in a fixed position. After After
each
each withdrawal,
withdrawal, the counting rate
the counting rate is is measured accuratelyaccurately with with aa scaler,
sealer,
and
and the
the ratemeter
ratemeter operated
operated for for a time at
a time at least
least equal
equal to to the
the scaling
scaling time,
time,
the
the recording
recording chartchart speed
speed being selected to
being selected to give
give a a trace of of reasonable

length. An average
length. average straight
straight line
line isis then
then drawn
drawn through
through each each trace,
trace, in in such
such
aa way
way as
as to
to make
make the
the positive
positive and
and negative
negative fluctuations
fluctuations as
as nearly
nearly equal
equal as
as
possible.
possible. (Figure
(Figure 7-23
7-23 shows
shows a
a portion
portion of
of a
a calibration
calibration run
run made
made in
in this
this
way.)
way.) Finally,
Finally, the distances of
the distances of these
these straight
straight lineslines from
from the the chart
chart zero
zero are
are
plotted against
plotted against the
the corresponding average
corresponding average counting counting rates
rates as
as determined
determined by
by
the scaler,
the sealer, and
and the
the calibration
calibration curve
curve so
so obtained
obtained is
is used
used as
as aa basis
basis f6l'
for* future
future
intensity
intensity measurements
measurements with with the
the ratemeter-recorder
ratemeter-recorder combination. combination.
7-101
7-10] USE OF MONOCHROMATORS 211
211

7-10 Use of of monochromators. Some research problems, notably

research problems, notably the the
measurement of of diffuse
diffuse scattering
scattering at at non-Bragg
non-Bragg angles,
angles, require
require a a strictly
strictly
monochromatic incident incident beam if if the
the effects
effects to be measured are
to be are not
not to be
to be
blotted
blotted outout by by the
the continuous spectrum.spectrum. In such a case, case, the
the focusing
focusing
crystal
crystal monochromator described described in Sec. 6-12 may
in Sec. may be used in in conjunction
conjunction
with
with a a diffractometer
diffractometer in in the
the manner shown in in Fig.
Fig. 7-24.
7-24. Rays Rays from the the
physical
physical line
line source
source S on the
the x-ray
x-ray tube
tube target
target T are
are diffracted
diffracted by
by the
the bent
bent
and cut crystal M to
cut crystal to aa line
line focus
focus at at S',
S', located
located on the the diffractometer
diffractometer circle,circle,
and then diverge to
then diverge to the
the specimen
specimen C. C. After
After diffraction
diffraction from the the specimen,
specimen,
they
they are
are again
again focused
focused at at F,
F, the
the counter
counter receiving
receiving slit.
slit. The diffractometer
diffractometer
geometry is
geometry is therefore
therefore identical
identical withwith that
that shown in in Fig.
Fig. 7-1 but but with
with the
the
important difference that
important difference that thethe rays
rays incident
incident on the the specimen
specimen are are mono-
chromatic
chromatic and issue issue from the the virtual source S',
virtual source S', the
the focal
focal line
line ofof the
the mono-
chromating
chromating crystal.crystal.
There is is another
another method of of operating
operating under essentially
essentially monochromatic
conditions,
conditions, a a method peculiar
peculiar to to the diffractometer, and that
the diffractometer, that is by the
is by the
use of Ross filters,
use of filters, also
also called balanced filters.
called balanced filters. This method depends depends on
the fact that
the fact that the the absorption
absorption coefficients
coefficients of
of all
all substances
substances vary
vary in
in the
the same
way
way with
with wavelength; i.e.,
wavelength; i.e., they they are
are proportional
proportional to
to >.3,
X
3
,
as
as shown by Eq.
by Eq.
(1-13).
(1-13). If
If filters
filters are
are made of
of two substances
substances differing
differing in
in atomic number
by
by one,
one, and their their thicknesses
thicknesses adjusted
adjusted so so that
that they
they produce
produce the the same ab- ab-
sorption for a particular
sorption for a particular wavelength,wavelength, then
then they
they will
will have the
the same absorp-
absorp-
tion
tion for
for all
all wavelengths
wavelengths except except those
those lying
lying inin the
the narrow
narrow wavelength
wavelength region region
between
between the the K K absorption
absorption edges edges of of the
the two substances.
substances. This This region
region isis

called
called the
the passpass band of of the
the filter combination. If
filter combination. If these
these filters
filters are
are placed
placed
alternately
alternately in in a a heterochromatic
heterochromatic x-ray x-ray beam,
beam, i.e.,
i.e., aa beam containing
containing rays rays
of
of different
different wavelengths,
wavelengths, then then thethe difference
difference between the the intensities
intensities trans-
trans-
mitted
mitted in in each case is
each case is due onlyonly to to wavelengths
wavelengths lying lying iI, in the
the pass
pass band.
band.

7'

FIG.
FIG. 7-24.
7-24. Use of crystal
Use of crystal monorhromator
monochromator with
with diffrartometel.
diffractometer.
212
212 DIFFRACTOMETER MEASUREMENTS [CHAP. 7
[CHAP. 7

When the the pass

pass band is is chosen
chosen to to include
include a a strong
strong characteristic
characteristic component component
of
of thethe spectrum,
spectrum, then
then the
the net
net effect
effect is
is that
that of
of a
a strong
strong monochromatic
beam.
beam.
isolation of
The isolation of euCu Ka radiation
radiation may may be taken as as an f'xample.
example. Its Its
wavelength
wavelength is is 1.542A,
1.542A, which which means that that cobalt
cobalt and nickel nickel can be used as as
filter
filter materials
materials sincf'since theirtheir K K absorption
absorption edges edges (1.608(1.608 and 1.488A, respec-
1.488A, respec-
tively)
tively) effectively
effectively bracketbracket the the Cu Ka line. line. Their
Their linear
linear absorption
absorption coeffi- coeffi-

cients
cients IJ. M are
are plotted
plotted in
in Fig.
Fig. 7-25(a),
7-25 (a), which shows that
that balancing
balancing can
can be
obtained by
obtained by making making the
the nickel
nickel filt.er
filter somewhat thinner
thinner than the
the cobalt
cobalt one.
one.
When their thicknesses x are
their thicknesses are adjusted
adjusted to to the
the eorrect
correct ratio,
ratio, then MN^NI ==
then IJ.N1XNi
MCO^CO except
IJ.CoXCo except in in the pass band,
the pass band, and aa plot plot of of IJ.X vs. >.
px V8. X has the the appearanee
appearance
of
of Fig.
Fig. 7-25(b).
7-25(b). Sinee =
/LT = -
Since J.l.:r In 1,:11
In /x //0 , the
,
the transmission
transmission factors factors I;x/I/V/oo
(ratio
(ratio of
of transmittro
transmitted to
to incident
incident intensity)
intensity) of
of the
the two filters
filters are
are now equal
equal
for
for all all wavelengths
wavelengths exrept except those those in in the pass band,
the pass band, whiehwhich is is only
only O.12A
0.1 2A

wide.
wide. At each each angle
angle 28 20 atat which
which the the intensity
intensity is is to
to bebe measured with with the the
diffractometer,
diffractometer, first first oneone filter
filter and then then the other is
the other placed in
is placed in thf'
the diffracted
diffracted
beam beforebefore it it enters
enters the counter. Th>
the ('ountf'r. The intensity
intensity of of thethe diffracted
diffracted beam
passing through
passing through each each filter
filter isis then
then measured,
measured, and the the difference
difference in in the
the
measurements gives gives the
the diffract.ro
diffracted intensity
intensity of
of only
only the
the Cu Ka
A'a line
line and
the
the relatively
relatively weak wavelengths wavelengths immediatelyimmediately adjacent adjacent to to it it inin the
the passpass
band.
band.
should be
IItt should be emphasized
emphasized that that the the beam enteringentering the the counter
counter is is never
never
physically
physically monoehromatic,
monochromatic, as as itit is
is when a a crystal
crystal monochromator is is used.
used.
Radiation
Radiation with with a a great
great many
many wavelengths
wavelengths enters enters the the counter
counter when either either
filter is
filter is in place, hut
in place, but every
every wavelength
wavelength transmitted
transmitted by by one one filter
filter has
has thethe
same intensity
intensity as
as that
that transmitted
transmitted by
by the
the other
other filter, exeept
filter, except those
those wave-
lengths
lengths lyinglying in in the
the passpass band,
band, and these these areare transmitted
transmitted quite quite unequally
unequally
by
by thethe two filters.
filters. Therefore,
Therefore, when the the intensity
intensity measured with with one one filter
filter

is
is subtracted
subtracted from that that measured with with thethe other
other filter,
filter, the the difference
difference is is

zero
zero for for every
every wavelength
wavelength except except those
those in
in the
the pass
pass band.
band.
In
In practice, balancing of
practice, balancing of the
the filters
filters isis carried
carried out out by by inserting
inserting two foils foils

of
of approximately
approximately the
the same thickness
thickness into
into suitable
suitable holders
holders which
which can
can be
be
slipped
slipped into into place
place in thein the beam enteringentering the counter. One foil
the counter. foil isis always
always
perpendicular to
perpendicular to thf'the x-ray
x-ray beam,beam, while while thethe other
other may may be be rotated
rotated about about
axis at
an axis at right
right angles
angles to to the
the beam;
beam; in in this
this way
way the the second
second foil foil maymay be be in-
in-

clined
clined to the beam at
to the at such
such an angle angle that
that its
its effective
effective thickness
thickness x
x equals
equals
the
the thickness
thickness required
required for for balancing.
balancing. Perfect balancing at
Perfect balancing at all
all wavelengths
wavelengths
outside
outside the the pass
pass band is is not
not possible, although it
possible, although it may
may be be approached
approached quite quite
closely, because n does not vary exactly as X and because the
closely, because IJ. does not vary exactly as 3
>.3 and because the magnitude
magnitude
of the K absorption
of the absorption jump jump (ratio(ratio of of absorption
absorption coefficients
coefficients for for wavelengths
wavelengths
just shorter
just shorter and just just longer
longer than than the the K edge)
edge) is is not
not exactly
exactly the the same
same for for
all
all elements.
elements.
 -~

7-10]
~

~ -lOOOi
eu Ko.
r ('U Ko.

..:::.. :
<-:s. f
~
.....
MDLl^KX) XOLIxIHOSHV HVMXTI :{(MIO -

...... I -('0

USE OF MONOCHROMATORS
~

-- ~~~
~

ttl
;.-; 20(HI- o
pas~ 'OJ
o
...:s. hand is:

-E~ Xl
~
on
:=
~
- - ('0
=a
1000, o
~
;.-;
1
~
=a
!XI
____ ~_L _______ L
O'_~ __ L -L_ _- L
OJ 10 I,j 20 OJ 10 l,j 20
~ (angstrom-) ~ (angstroms)
la! (hi
II

5
^

1
FIG, 7-25, Ross filters for Cu Ka radiation: (a) absorption coefficients of filter materials;
,0

-3

c3
g

<u
c
o

O
8

(b) jJ.X values after balancing.

213
to.:)
.-
~
214 DIFFRACTOMETER MEASUREMENTS [CHAP. 7
[CHAP. 7

PROBLEMS

7-1. A powder
7-1. powder specimen
specimen in in the form of of a rectangular
rectangular plateplate has a a width of of 0.5
0.5
in.,
in., measured in in the
the plane
plane of
of the
the diffractometer
diffractometer circle,
circle, which hashas aa radius
radius ofof 5.73
5.73
in.
in. If
If it
it is
is required
required that
that the
the specimen
specimen entirely
entirely fill
fill the
the incident
incident beam at at all
all angles
angles
and that
that measurements must be made to to angles
angles as as low
low asas 28
26 == 10,
10, what
what is is the
the
maximum divergence angle (measured
divergence angle (measured in
in the
the plane
plane of
of the
the diffractometer
diffractometer circle)
circle)
that
that the
the incident
incident beam may may have?
7-2.
7-2. Prove the the statement
statement made in Sec. 7-4
in Sec. 7-4 that
that the
the effective
effective irradiated
irradiated volume
of
of aa flat
flat plate
plate specimen
specimen inin a
a diffractometer
diffractometer is is constant
constant and independent
independent of of 8.
6.

7-3.
7-3. In measuring
measuring thethe maximum intensity
intensity ofof a a certain
certain diffraction line with
diffraction line with a a
scaler,
sealer, 2048
2048 pulses
pulses were
were counted
counted inin 1.9
1.9 sec.
sec. When the the "diffraction
"diffraction background"
background"
aa few degrees
degrees away
away from the the line
line was measured,
measured, 2048 pulses were counted
2048 pulses counted in in 182182
seconds.
seconds. The average counting
average counting rate
rate determined
determined over
over a
a long period
long period of
of time
time with
with
the
the x-ray
x-ray tube
tube shut
shut off
off was 2.2
2.2 cps.
cps.

(a) What is
(a) is the
the ratio
ratio of
of the
the maximum intensity
intensity of
of the
the line
line to
to that
that of
of the
the "dif-
"dif-
fraction
fraction background"?
background"?
(b)
(6) What isis the
the probable
probable error
error in
in each
each of
of these
these intensities?
intensities?
(c)
(c) How long
long must the
the "diffraction
"diffraction background"
background" be be counted
counted in
in order
order to
to obtain
obtain
its
its intensity
intensity with
with the
the same accuracy
accuracy as
as that
that of
of the
the diffraction
diffraction line?
line?

7-4. (a) Calculate

7-4. (a) Calculate the the ratio
ratio of
of the
the effective
effective thicknesses
thicknesses of
of cobalt
cobalt and nickel
nickel
filters
filters when they
they are
are balanced
balanced forfor all
all wavelengths except Cu Ka. (Obtain
wavelengths except (Obtain anan av-
av-
erage
erage value
value applicable
applicable to
to a
a wavelength range extending
wavelength range extending from about
about 0.5A
0.5A to
to about
about
2A.)
2A.)
(b)
(6) When the the filters
filters are
are balanced,
balanced, calculate
calculate the
the ratio
ratio of
of the
the intensity of Cu Ka
intensity of
radiation
radiation transmitted
transmitted by by the
the nickel
nickel filter
filter to
to that
that transmitted
transmitted byby the
the cobalt
cobalt filter,
filter,

assuming
assuming the the same incident
incident intensity
intensity in
in each
each case.
case. The effective thickness of
effective thickness of the
the
nickel
nickel filter
filter is 0.00035 in.
is 0.00035 in.
 CHAPTER 8

ORIENTATION OF SINGLE CRYSTALS

8-1 Introduction.
Introduction. Much ofof our understanding
understanding of of the
the properties
properties of poly-
of poly-
crystalline
crystalline materials
materials has been gained by studies
gained by studies ofof isolated
isolated single crystals,
single crystals,
since
since such studies
studies permit
permit measurement of of the properties of
the properties of the
the individual
individual
building blocks
building blocks inin the
the composite
composite mass. Because single single crystals
crystals are
are usually
usually
anisotropic, research of
anisotropic, research of this
this kind
kind always
always requires
requires accurate
accurate knowledge
knowledge of of
the
the orientation
orientation of of the
the single crystal
single crystal test
test specimen
specimen in
in order
order that
that measure-
ments may be be made along
along known crystallographic
crystallographic directions
directions or or planes.
planes.
By
By varying
varying the
the crystal
crystal orientation,
orientation, we can obtain
obtain data
data on
on the
the property
property
measured (e.g.,
(e.g., yield
yield strength,
strength, electrical
electrical resistivity,
resistivity, corrosion
corrosion rate)rate) as
as aa
function
function ofof crystal
crystal orientation.
orientation.
In
In this
this chapter
chapter thethe three
three main x-ray
x-ray methods of of determining
determining crystal
crystal
orientation
orientation will
will be described:
described: thethe back-reflection
back-reflection Laue method,method, the the trans-
trans-
mission Laue method,
method, and the
the diffractometer
diffractometer method. It
It is
is also
also con-
con-
venient toto treat
treat here
here the
the question
question of
of crystal
crystal deformation
deformation and the
the measure-
measure-
ment ofof this
this deformation
deformation by by x-ray
x-ray methods. Finally,
Finally, the the subject
subject of of rela-
rela-
tive
tive crystal
crystal orientation
orientation is
is discussed,
discussed, and methods are
are given
given for
for determining
determining
the
the relative orientation of
relative orientation of two naturally
naturally associated
associated crystals,
crystals, suchsuch asas the
the
two parts
parts of
of a
a twin or
or a
a precipitated crystal
precipitated crystal and its
its parent phase.
parent phase.

8-2 The back-reflection

back-reflection Laue method. As mentioned in in Sec.
Sec. 3-6,
3-6, the
the
Laue pattern
pattern of of aa single
single crystal
crystal consists
consists of of aa set
set ofof diffraction
diffraction spots
spots onon the
the
film
film and the positions of
the positions of these
these spots
spots depend
depend on on the
the orientation
orientation of of the
the crys-
crys-
tal.
tal. This is is true
true of of either
either Laue method,
method, transmission
transmission or or back-reflection,
back-reflection,
so
so either
either can
can be used to
be used to determine
determine crystal
crystal orientation.
orientation. However,
However, the the back-
reflection method is
reflection is the
the more widely
widely used
used ofof the
the two because
because it it requires
requires no
special preparation of
special preparation of the
the specimen,
specimen, which may may be be ofof any
any thickness,
thickness,
whereas
whereas thethe transmission
transmission method requires requires relatively
relatively thin
thin specimens
specimens of of low
absorption.
absorption.
In
In either
either case,
case, since
since the
the orientation
orientation of of the
the specimen
specimen is is to
to be determined
from the
the location
location of of the
the Laue spots
spots on the film, it
the film, it is
is necessary
necessary to to orient
orient
the
the specimen
specimen relative
relative to to the
the film
film in in some known manner. The single
single
crystal
crystal specimens
specimens encountered
encountered in in metallurgical
metallurgical work are are usually
usually in in the
the
form of
of wire,
wire, rod,rod, sheet,
sheet, or
or plate,
plate, but
but crystals
crystals ofof irregular
irregular shape
shape must occa- occa-
sionally
sionally bebe dealt
dealt with.
with. Wire oror rod
rod specimens
specimens are best mounted with
are best
their
their axis
axis parallel
parallel to
to one
one edge
edge of
of the
the square
square or
or rectangular
rectangular film;
film; a fiducial
fiducial
mark on on the
the specimen surface,
specimen surface, for
for example
example on
on the
the side
side nearest
nearest the
the film,
film,
then fixes
fixes the
the orientation
orientation of of the
the specimen completely.
specimen completely. It
It is
is convenient
convenient to
to
215
215
216
216 ORIENTATION OF
ORIENTATION SINGLE CRYSTALS
OF SINGLE CRYSTALS [CHAP. 88
[CHAP.

ZA

~-l.
}<'IG. 8-1.
FIG. IntRrsc('tion of
Intersection of aa conical
eonieal array
array of
of diffracted
difi'J'aetRd with aa film
beams with film placed
plaecd
in the
in the back-reflection
baek-rdlcetioll position.
position. (' =
C F=
I'rystal, F
= crystal, film, Z.A =
= film, zone axis.
= zone axis.

sheet or
mount sheet or plate
plat.e specimens
sperimens with
with their
their plane
plane parallel
parallel to
to the
the plane
plane of
of
the film
the film and
and one
one edge
('dge of
of the
1.he sheet
sheet or
or plate
plate parallel
parallel to
to an edge
edge ofof the
the film.
film.
Irregularly shaped
Irregularly shap('d crystals han' fiducial
C'rystals must have fidueilll marks on their
t h('ir surface
surfa('e which
whi('h
will definitely fix th('ir orientation relatiye to that of the film.
will definitely fix their orientation relative to that of the film.
problem now is
The problem is to
to determine
determine the the orientation
orientation of of the
the ('rystal
crystal from the thE'
position
position of
of the
the baek-r('fil'dion
back-reflection Laue spot
spots s on the
the film.
film. If
If wo wp wish(>d,
wished, ,n'
we
could determinl' thE'
could determine Bragg angle
the Bragg angle (J (,Ol'respondiu!!,
corresponding to to ea('h
each Laue spot spot from
Eq. (5-2),
Eq. (5-2), butbut thatthat would
would h(, be no help help in in ilh'nt
identifyingifyill!!, tthe
hp planes
planes producing
produeing
that
that spot,
spot, sin('t'
since thl'
the wuyt'length
wavelength of
of til('
the diffra('tpcl
diffracted "pam
beam is
is unknown. We
Wl'
ran, howE'\'E'f,
can, however, dE'tE'fmine
determine th('
the orientation
orientation of
of th{'
the normal to th('
the plan{'s
pianos eaus-
caus-
ing
ing each
each spot,
spot, bE'('ause
because the plane normal al\\'a~'s
the plane always hispds bisects th{'the anglp
angle h('twE'l'n
between
in('id('nt
incident and and diffraeted
diffracted beams.beams. The dirt'(,tionHdirections of of th('
tho plane
piano normals l'an can
th('n
then bl'bo plotted
plotted on
on a
a sterl'ographie projl'(tion,
steroographic projection, the angles
angles bet\Y(,l'n
between th('m
thorn
measured,
measured, and and the the planes
planes identifi('d
identified by by eomparison
comparison with a list list of known

int('rplanar
interplanar anglesangleH fur
for the
the l'rystal
crystal imolwd.
involved.
Our first
first prohlE'm,
problem, therefore,
therefore, is is to
to deriY{',
derive, f!'Omfrom tllP the meaHured
measured position position of
each
each difira('tion
diffraction spot spot on
on the
the film,
film, the
the position
position on a
:t stl'rl'ographi('
stereographic projl'etion
projection
of
of the
the pole
pole of
of thE'
the plane l'ausing
plane causing that
that spot.
spot. In doing
doing this
this it
it isis \wlpful
helpful to
recall
recall that
that allall ofof the
the planes
planes of
of onE'
one zone reflect
reflect beams whil'h
which li('
lie on th('tho sur-
fa('e
face ofof a a ('one
cone whosewhoso axis axis is is th('
tho zon('
zono axisaxis nndand whosp whoso Hpmi-apex
somi-apox angle is angle is

equal
equal to
to the
the anglt'
angle cp
<t>
at
at ",hic'h
which tht'
tho zonE'
zono axiH
axis is
is inc'lined
inclined to
to the transmitted
beam
beam (Fig. 8-1). If
(Fig. 8-1). If cp do('s
doos not
<t>
not E'xef'ed
exceed 45, 45, thE' cone will
tho ('onE' will not not intersect
intersect aa
film
film placE'd
placed in
in th('
tho hu('k-rf'fif'l'tion
back-reflection region;
region; if
if cp
< li('s
lies hetw('('n
between 45
45 and
and 00,
90, the
the
cone
cone int('rsE'cts
intersects thE' tho film
film in in aa hYPE'rhola;
hyperbola; and, and, if
if cf>
</> {'quaIs
oquals 90, 00, t.hE'
the intE'rs(,(,tion
intersection
is
is a
a straight
straight line line passing
passing through
through th(' tho in('iclf'Ilt
incident bE'am. beam. (If (If cf> exeeE'ds
</> exceeds 90,90,
the
the cone
cone shifts
shifts to to aa position
position below
below the
tho transmitted
transmitted heam
beam and
and intersects
intersects
the
the lower
lower half
half of of the
the film,
film, asas may
may he be sc('n
soon by by viewing
viewing Fig, Fig. 8-18-1 upside
upside down.)
down.)
Diffrartion spots on a hark-reflection
Diffraction spots on a back-reflection Laue Laue film
film therefore
therefore lie
lie onon hyper-
hyper-
8-21
8-2] THE LAl'E METHOD
BAr'K-REFLECTIO),; LAUE
THE BACK-REFLECTION METHOD :!Ii
217

II
111111
film

('01'111'1 cut
[ornri tor
!'llttOI'
identification
Ull'l1tlll('ullOI1

S( I, Iii K

Fid S 2 Locution oi buck-ieflertion hnuo spot. Note that 7 =- 1)0

0.

holas or
bolas 01' sll':lIghl
straight lines,hnPH, and the t 11<' distance
dU.,I.a1H'P of an~' hyperbola
of any h~'I)(,l'hola from
froIll theI II{' center
('('ntN
of tllP film iH a IlIpa~lIJ'(' of
of the film is a measure of the inclination III(' IIwlinallOIl of
of til('
the zonp
zone axiH.
axis.
In
In FiJ!,.
Fig. S 8 :!2 til('
the film
film is is \\ie\\ed
i('\\('d from tllP the {,I'yslal.
crystal. COOl'liinat('
Coordinate axes arl' are
spt
set upup su('h
such Ithathat til('
the lII('id('nl
incident h('am beam PI'o('!'!'d:-
proceed* alollg the z-axi~ in t hl' din'C'-
along til{' z-axis in the direc-
tion
tion ()z Oz aIld
and tthe 1)(' ,r-
.r- and lI-a).('H
//-axes hl' he m in till'
the plan('
plane of of tthe
II(' film.
film. 'I'll('
The heam beam l'P-re-
flp('jpd
flected by by til('
the plalH'
plane SIIO\\,I1
shown Ht l'ikpH thp
strikes the film
film atat S.
S. 'I'll{' I1ol'IIlal
The normal to thiH I'pfl('d-
to this reflect-
in!!:
ing plam'
plane is is ('X
(\\ and tilt, plane It~I'Jj
the plam' itself iHis IU';Hunwd
assumed to to 1J('lonJ,!;
belong to to Ii a zonE'
zone \\hose
\\hose
axi~
axis he'S
lies inin thl'
the y:-plarl<'.
//; -plane.
If
If \\,p imagine tllI~
we imaginl' this plall('
plane to rolat('
rotate ahout th(' zone
about the
axis.
axis, it will pass
it will pass throll!!,11
through all all thp
the pOHillOIlH
positions nt at whil'h
which planl'l<
planes of of this
this zon('
zone in in an

actual
actual ('\'ystal
crystal miJ!,ht
might lip. lie. During tlll~
f)l\J'iIlJ!, this rotation,
rotation, tlJ('the plam'
plane normal would ('ut
cut
th('
the film
film inin thp
the Ht.rai!!,ht
straight Iml' line AB aIHI and til('
the I'efipl'lpd
reflected hl'am
beam in in the hYP(,l'hola
hyperbola HK.
AB iH is tll('rpfol'P
therefore til(' the lo('uS
locus of of platH'
plane normal int('I'Hl'('tions
intersections with th(' the filmfilm and

HK
If K till'
the l()('us
locus of of difTm,('t
diffracted l'1i bpam
beam int ('1'SPI't ions. The plaTH'
intersections. plane \\ hil'h refie<'1s
\\hich reflects a a
beam to to S,
N, for
for exampl(',
example, has aa normal whi('h which intl'l'~e('ts
intersects til('the film
film at at N, N, sim'p
since
the
the inei<i('nt
incident hearn,beam, planpplane normal,
normal, and and diffl'al'tpd
diffracted Iwam beam arp are ('oplanar.
coplanar. Rim'p Since
til('
the orientation
orientation of of thp
the plam'
plane normal in in spa('p
space ('an
can hl' be d('s('ribpd
described by by it.s
its angular
angular
coordinatp~
coordinates "y 7 and
and ", 6, til('
the prohll'm
problem i:-l is to
to detNminp
determine "y7 and" and 6 from
from tthe hp m('aslll'pd
measured
coordinatl's
coordinates J'x and and II// of
of th('
the diffl'a('tion
diffraction :-Ipot,spot ..,S on
on thl'
the film.
film.

AA graphi('ul
graphical mpthodmethod of of doin!!:
doing this was dp\'ised
this WUI:! devised hy by nrminger
(Ireninger who who deyel-
devel-
oped
oped aa ehurt chart whieh,
which, when when pla(,pd
placed on on thl'
the film,
film, giwsgives dir('('tiy
directly the the "y7 and"
and 5
l'oordinat.l's
coordinates ('orrl'spomlin!!:
corresponding to
to any
any diffradion
diffraction spot.
spot. To
To plot
plot :su('h
such aa ('hart,
chart,
we
we notp
note fromfrom Fig.Fig. 8-28-2 thnt
that

J'
jc == OS
OK Hin
sin p., /x, lJU =
= ()S
OS COl:!
cos p.,
M, and OS =
and OS = 0('
OC t.an
tan 20',
2a,
 218
218 ORIENTATION OF SINGLE CRYSTALS [CHAP. 8
[CHAP. 8

where OC === D === specimen-film

specimen-film distance.
distance. The angles
angles JI. and ju tI are ob-
<r are ob-

tained
tained from 'Y
7 and a
d as
as follows:
follows:

CF tan a
FN CFtan 8 tan a
tan 6
tan =-
JI. =
tan M =
= = --,
=
FO CF sin
sin 'Y
7 sin
sin 'Y
7

ON ( FN) (
tan tI == OC
OC == \sin
sin M/
1 )
CF cos
p. \CF
(CF tan
Y == \ sin
cos 'y/ p.
a) (CF cos1
\CF cos 'Y
)
sin M / 7

tan a
tan 5
=----
sin
sin p. cos
/icos '7
Y

With these
these equations,
equations, the the position
position (in (in terms
terms of x and y)
of x y) of
of any
any diffraction
diffraction
spot can be
spot can plotted for
be plotted for given
given values
values of 7 and a
of 'Y d and any any desired
desired specimen-
specimen-
film distance D.
film distance D. The result result is is the
the Greninger chart,
Greninger chart, graduatedgraduated at
at 2
2 inter-
inter-
vals
vals shown in in Fig.
Fig. 8-3.
8-3. The hyperbolas running
hyperbolas running from left
left to
to right
right are are
curves
curves of of constant
constant 'Y, 7, and anyone
any one of
of these
these curves
curves is
is the
the locus
locus of
of diffraction
diffraction
spots planes of
spots from planes of aa zone
zone whose axis axis isis tilted
tilted away
away from the the plane
plane of of the
the
film
film byby the
the indicated
indicated angle angle 'Y. 7. If points having
If points having the the same value value of of a d are
are
joined together,
joined together, another
another set set ofof hyperbolas
hyperbolas running
running from top top toto bottom is is

obtained.
obtained. The lower half of
lower half of the
the chart
chart contains
contains a a protractor
protractor whose use
use
will
will bebe referred
referred to to later.
later. Greninger
Greninger charts charts should
should have dark dark lines
lines on a a
transparent background
transparent background and are
are best
best prepared
prepared as
as positive prints
positive prints on photo-
photo-
graphic film.
graphic film.

In
In use,
use, the
the chart
chart is is placed
placed over over the
the film
film with
with its
its center
center coinciding
coinciding with with
the film
the film center
center and with with the the edges
edges of of chart
chart and film film parallel.
parallel. The '7Y and
aS coordinates
coordinates corresponding
corresponding to to any
any diffraction
diffraction spotspot areare then
then read
read directly.
directly.
Note thatthat use
use ofof the
the chart
chart avoids
avoids any any measurement of
of the
the actual
actual coordinate
coordinate
distances
distances x x and yy of of the
the spot.
spot. The chart chart gives
gives directly,
directly, not the x
not the x and y y
coordinates
coordinates of of the
the spot,
spot, but
but the
the angular
angular C()ordinates
coordinates 'Y
y and
and a
d of
of the
the normal
normal to
to

the plane causing

the plane causing the the spot.
spot.
Knowing
Knowing the the '7 Y and a 8 coordinates
coordinates of of any
any plane
plane normal,
normal, for example CN
for example
in
in Fig.
Fig. 8-2,
8-2, we can can plot
plot the
the pole
pole of of the plane on
the plane on aa stereographic
stereographic projection.
projection.
Imagine
Imagine a a reference
reference sphere
sphere centered
centered on
on the
the crystal
crystal in
in Fig.
Fig. 8-2
8-2 and tangent
tangent
to
to the
the film,
film, and let
let the
the ,projection
projection plane plane coincide
coincide with
with the
the film.
film. The point
point
of
of projection
projection is
is taken
taken as
as the
the intersection
intersection of
of the
the transmitted
transmitted beam and the
the
reference sphere. Since the plane normal CN intersects
reference sphere. Since the plane normal intersects the the side
side ofof the
the
sphere
sphere nearest
nearest the the x-ray
x-ray source,
source, the projection must be
the projection be viewed
viewed from that that
side
side and the the film
film "read"
"read" fromfrom thatthat side.
side. In In order
order toto know,
know, after
after processing,
processing,
the
the orientation
orientation the the film
film had during during the
the x-ray exposure,
x-ray exposure, the
the upper
upper right-
right-
hand comer
corner of the film
of the film (viewed
(viewed from
from the
the crystal)
crystal) is
is cut
cut away
away before
before it it is
is

placed
placed in
in the
the cassette,
cassette, as
as shown in
in Fig.
Fig. 8-2.
8-2. When the
the film
film is
is read,
read, this
this
8-2]
8-2] THE BACK-REFLECTION LAUE METHOD 219
219

6 20

'Y =
7 20
= 20

7 = 10

7=0

.........- - - - - 2lJ
21) -------I~~

FIG.
FIG. S-3.
(S-3. Gl"enill~el"
(jreniiifter char
chait t for
for the
the !loiution
solution of
of bark-reflertion
back-reflection Laue patternll,
patterns,
l"epl"o<iu("t'd
reproduced ill in the
the CO/Teet
correct !lizr for a
size fOI" a I'pe('imrn-to-film distance D of
specimen-to-film di!ltam'e of 3
3 I'm.
cm.

cut
cut ('orner
corner must
must therefor'
therefore b'
be at
at the
the upper
upper left,
left, as
as shown in in Fig.
Fig. 8-4(a).
8-4(a).
The angles 7 and
angles 'Y and 0,6, reud
read from
from the
the chart,
chart, are
are then
then laid
laid out
out on thethe projection
projection
us
as indicated
indicated inin Fip;.
Fig. 8-4(h).
8-4 (b). Xote
Note that
that the
the underlying
underlying Wulff
Wulff net
net must bebe
oriented
oriented so
so that
that its
its meridians
meridians run run from
from side
side to
to side,
side, not
not top
top to
to bottom.
bottom.
The reason
reason for
for this
this is
is the
the fact
fact that
that diffraction
diffraction spots
spots which lie lie on curves
curves of
of
constant
constant 'Yy come from planes
from planes of
of a
a zone,
zone, and the
the poles
poles of
of these
these planes
planes must
220
220 ORIENTATION OF SINGLE
SINGLE CRYSTALS 8
[CHAP, 8
[CHAP.

('ut corner
cut (x.:,I'.:....Il(>_T_ _ _ _ _ ......!.y
y_ _ _ _ _ _ _--,
film

"0/
~.1 "' ... ~ ,. ,r .,,"'\

""'j,JIJ'/,lh'l ~.1ll~l \.\\~\

fa I

\ I'Ho.lEt"l'I():\
RO.JI-XTION

(h)
(b)

FIG,
P'IG. S-4,
<S-4. Use of
of the
the Greninger
Greninger ('hart
chart to
to plot
plot the
the pole
pole of
of a
a reflecting
reflecting plane
plane on
on aa
stereogl'aphic
stereographic projectioll,
projection. Pole
Pole l' m (b)
1' III (b) is
is the
the pole
pole of
of the
the plane
plane ('ausIng
causing dIffraction
diffraction
spot
spot 1 1 in
in (a),
(a).
8-21
8-2] BACK-REFLECTION LAUE METHOD
THE BACK-REFLECTION 221
221

therefore
therefore lie on
lie on aa great
great circle
circle on
on the
the
projection.
projection. The "f,a coordinates cor-
7,6 coordinates cor-
responding to
responding to diffraction
diffraction spots
spots on thethe
lower half
lower
simply by
simply
half ofof thethe film
hy reversing
film are
reversing the
are obtained
oht.ained
the Greninger
Greninger
2
e_ :!
e----._
I - J.
/
--'l-i--~--
-- -
chart end
chart end for
for end.
end.
This procedure
This proeedure may be be illustrated
illustrated
by determining
dpt,t'fmining the the orientation
orientation of of the
the !l
by
aluminum crystal
aluminum crystal whose
whose back-reflec-
bark-r('fi(>('- o

I

tion Laue
tion pattern is
1.I1U(' pattern iR shown in in Fig.
Fig.
3-H(b). Fig. Fig. 8-58-5 isis aa tracing
tra('ing of
of this
this II
3-(>(b)-
photograph, showing
photograph, showing the th(' more im- im-
portant spots
portant numhered for
spots numbered for reference.
reference.
.10
Tht' poles
The poles ofof the
t h(' planes
plant's causing
('ausing these
these
numhered spots
numbered spots are ar' plotted
plotted stereo-
stereo-
graphieally in
graphically in Fig.
Fig. 8-{i
8-0 byhy the
the method
of
of Fig.
Fig. 8-4 and and areare shown as as solid
solid
Fw.
FIG. S-5. Selected ciiffl"lwtioll
X-5. l'Ieierted diffraction SPOt.
spots'I
('in'leH.
circles.
of haek-l"rfi('c'tIOIl
of back-reflection Laue pattern
pattern of of an
aluIllilluIll rl'yRtal. trac'ed
aluminum crystal, traced from Fig. Fig.
\
a-t.i(h).
3-6(b).

S
FIG. S-6.
8-6. Hter'eogmphir
Stereographic pr'ojcetioll corresponding to
projection ('OI'1'cRponcling to bac'k-refiertion
back-reflection patter'n
pattern of
of
Fig.
Fig. S-5.
8-5.
222
222 ORIENTATION OF
ORIENTATION SINGLE CRYSTALS
OF SINGLE CRYSTALS [CHAP. 88
[CHAP.

The problem
The problem now now isis to to "index"
"index" these these planes,
planes, i.e., i.e., to to find
find theirtheir Miller
Miller
indices,
indices, and
and so
so disclose
disclose the
the orientation
orientation of
of the
the crystal.
crystal. With
With the
the aid
aid of aa
of
Wulff net,
Wulff net, great
great circles
circles are
are drawn
drawn through
through the the various
various sets sets of of poles
poles corre-
corre-
sponding to
sponding to thethe various
various hyperbolas
hyperbolas of of spots
spots on on the the film.film. These These greatgreat
circles connect
circles connect planes planes of of aa zone,
zone, andand planes
planes lyinglying at at their
their intersections
intersections are are
generally
generally of
of low
low indices,
indices, such
such as
as II
j
00
100 I,
} ,
{11O
{110}, j, {1111,
{
11 1 and
and
} , {112J.
{112}. The
The axes
axes
of the
of the zones
zones themselves
themselves are are alsoalso ofof low
low indices,
indices, so so it it. is
is helpful
helpful to to locate
locate
these
these axesaxes on
on the
the projection.
projection. They They are
are shown
shown as
as open
open circles
circles in
in Fig. 8-6,
Fig. 8-6,
P A being the
PA being the axis axis of
of zone
zone A,
.4, PBP B the
the axis
axis of
of zone
zone B,
B, et
etc.c. We then
then measure
measure
the angles
the angles between
between important
important poles poles (zone(zone intersections
interseetions and and zone zone axes)
axes)
and try
and try toto identify
identify the the poles
poles by by comparison
('omparison of these measured angles
of these measured angles with
with
those calculated
those calculated for for cubic
cubic crystals
crystals (Table(Table 2-3). 2-3). The The method is essentially is essentially
one of
one of trial
trial and error. We note,
and error. note, for for example,
example, that that the angles P A - PB,
the angles PB ,
PAA _ - 5' and
5', an
?
d p PB - 5' 5' araree all
all 90.
90. This This suggests
suggests that that one one or or more of of these
these
poles might
poles might be 1100 1 or
be |100| {IIO l. since
or {110}, sinee the the angle
angle between two {100} {lOO 1 poles
poles
or between
or between two two jllOj poles is
{1101 poles is 90.
90. Suppose
Suppose we tentatively tentatiw'ly assume that that
PA,
PA, PB,P B , and
and 5'
5' are
are all
all IIOO}
J100} poles.
poles.* * Then P E
< whieh
which lies
lies on
on the
the great
great
circle between PAA and
circle between and P B and and at at an angular
angular distance
distam'e of of 45 from each,
.t,ljo from each.
must be
must be aa {11O}
j
pole.
10} pole.
1 We then
then turn
turn our
our at.tention
attention to
to zone C
(' and find
find that
that
the
the distance
distance between
between pole
pole ()'
6' and either
either pole
pole 5'
5' or
or P
PR E is
is also
also 45.
45. But
reference
reference to to a
a standard
standard projection,
projection, such
such as
as Fig. 2-3i,
Fig. 2-37, shows that
that there
there is
is

no important pole
no important pole located midway located midway on
on the
the great
great circle
circle hetwe('n
between lIOO},
{100},
which
which we have have identified
identified with with 5', 5', and 11lO {110}, I. ",hieh
which w(' we have identifiedidentified
with
with PH. PR. Our originaloriginal assumption
assumption is is therefore
therefore wrong.wrong. We therefore therefore make
aa second
second assumption,
assumption, which is is consistent
consistent with the angles angles measured so so far,
far,

namely that
namely that 5' 5' is
is a {100! pole,
a {IOOI pole, as as before,
before, but that P A and P B are {lIO} {110}

poles. PE:
poles. PE must then then be be a {100} pole
a POO} pole and (i' & a {1l0}
{110} pole. pole. We can check
this
this assumption by
assumption by measuring measuring the
the angles
angles in
in the
the triangle a - b - 5'.
triangle 5'. Both
a and b are
a and b are found found to
to be
be 5.)0
55 from 5',
5', and il
71 from each other,
other, which con-
clusively
clusively identifies
identifies a and bas b as {Ill}
{111} poles.
poles. We note also,also, from a
a standard
projection,
projection, that that a a {Ill}
{111} polepole must lie lie on a a great
great circle
circle between {100} {
100 and
j

(110),
{110}, which
which agrees
agrees with
with the
the fact
fact that
that a,
a, for
for example,
example, lies
lies on the great
great
circle
circle between
between 5', 5', assumed to
to be
be 1100},
{100}, and P
PB,B, assumed to be 111O}.
{110}-
Our
Our second
second assumption
assumption is is therefore
therefore shown to to be correct.
correct.

* The reader
1 i

reader may detect an

may detect an apparent
apparent error
error in
in nomenclature here. here. Pole
Pole 5'5' for
for
example,
example, is is assumed
assumed to to be
be aa {I 00 I pole
{100} pole and
and spot
spot 55 on
on the
the diffraction
diffraction pattern
pattern is is

assumed, tacitly,
assumed, tacitly, to
to be
be due
due to
to aa 100
100 reflection.
reflection. But
But aluminum
aluminum is
is face-centered
face-centered
cubic
cubic and
and we we know
know thatthat there
there is
is no
no 100
100 reflection
reflection from
from such
such aa lattice,
lattice, since
since hkl
hkl
must
must bebe unmixed
unmixed for for diffraction
diffraction toto occur.
occur. Actually,
Actually, spot
spot 5,5, if
if our
our assumption
assumption is is

correct,
correct, is
is due
due to
to overlapping
overlapping reflections
reflections from
from the
the {200}, {4001, {6001, etc.,
(200), {400}, (600), etc., planes.planes.
But
But these
these planes
planes areare all
all parallel
parallel and
and are represented on
are represented on the
the stereographic
stereographic projec-
projec-
tion
tion by
by one
one pole,
pole, which
which is is conventionally
conventionally referred
referred to
to as 100}I. The
as {100 The corresponding
{ corresponding
.

diffraction spot is
diffraction spot is also
also called,
called, conventionally
conventionally but but loosely,
loosely, the
the 100
100 spot,
spot.
8-2)
8-2] THE BACK-REFLECTION LAUE METHOD 223
223

1\

FIG. S-7.
FIG. 8-7. Rtereogl'aphic
Stereographic projection
projection of
of Fig. 8-6 with
Fig. /'1-6 with Jloles
poles identifit'<l.
identified.

Figure 8-7
Figure 8-7 shows the the st-enographic
stereographic proje<"tion
projection in a more complete
in II complete form,form,
with
with all
all poles
poles of
of the
the type
type 1100},
{100}, IllD},
{110}, and 11111
{111} located
located and identified.
identified.
Note that
that it it was not not necessary
necessary to to index
index allall the
the observed
observed diffraction
diffraction spots
spots
in
in order
order to to detE'rmine
determine the the crystal orientation,
crystal orientation, which is
is specified
specified completely,
completely,
in
in fart,
fact, byby the
the locations
locations of of any
any two 1100 {
100 1 poles
} poles on the the projection.
projection. The
information
information given given in
in Fig.
Fig. 8-7
8-7 is
is therefore
therefore all
all that
that is
is commonly
commonly required.
required.
Occasionally, however,
Occasionally, however, we may
may wish
wish to
to know the
the Miller
Miller indices
indices of of a
a par-
par-
tieular
ticular diffraction
diffraction spot spot on
on the
the film, spot
film, spot 11
11 for
for example.
example. To find
find these
these
indices,
indices, we note note that
that pole
pole 11'
IT isis located
located 35 35 from (001) (001) on the the great
great circle
circle
passing through
passing through (001) (001) and (111).
(111). Referenee
Reference to
to a
a standard projection
projection and
aa table
table ofof interplanar
interplanar anglesangles shows that
that its
its indices
indices are
are (112).
(112).
As mentioned
mentioned above, above, the the stereographic
stereographic projeetion
projection of of Fig.
Fig. 8-7 is is a com-

plete description
plete description of
of the
the orientation
orientation of
of the
the crystal.
crystal. Other methods of
of
description
description are
are also
also possible.
possible. The crystal
crystal to
to which Fig.
Fig. 8-7 refers
refers had the
the
form of of aa square
square plate
plate and was mounted with its its plane
plane parallel
parallel toto the
the plane
plane
of
of the
the film
film (and
(and the
the projection)
projection) and its
its edges parallel
edges parallel to
to the
the film
film edges,
edges,
which are are inin tum
turn parallel
parallel to the NS and ElY
to the EW axesaxes of of the
the projection.
projection. Since Since
the
the (001) pole is near the center of
(001) pole is near the center of the projection,t.he projection, which corresponds
corresponds to to
224
224 ORIENTATION OF
ORIENTATION SINGLE CRYSTALS
OF SINGLE CRYSTALS [CHAP. 88
[CHAP.

the specimen
the specimpn normal,
normal, and
and the
t.he (010)
(010) pole
pole near
near the
thp edge
edge of
of the
the projection
projection
the K
Y

and approximately
and approximately midway
midway between
bptwpen the E and
and *SS poles,
poles, we
we may
may very
very
roughly describe
roughly des('rihe the
the crystal
('Ioystal orientation
orientation asas follows:
follows: one
one set
set of
of cube
('ubp planes
planes
is approximately
is approximatply parallel
parallel to tilt' surface
to the surface of
of the
the plate
plat.e while
whi\P another
anothpI' set
set
passes diagonally
passes diagonally through
through the
the plate
plate and
and approximately
upproximutply at
at right
right angles
anglps to
to
its surfu('e.
its surface.
Anothpr method
Another method of of description
dt's('ription may may be be used
ul'pd whenwhen only only one one direction
direction in in
thc crystal is of physi('ul
the crystal is of physical significance, signifi('an<'p, su('h
such as
as t
thehp pIat
plate e normal
normal in
in tIl('
the pres-
pres-
ent case.
ent ease. For For example,
examplp, we we maymay wish wish to to make
make aIt compression
rompl'('i.;sion test test ofof this
this
crystal, with
crystal, with the tilt' axis
axis of of compression
('ompression normal normal to the plate
to the plate :-;urfa('c.
surface. We are
are
then interested
then interestpd in in the
tl1<' orientation
orientation of of the ('r~'stal rplatiw to the compression
the crystal relative to the ('ompression
axis (plate
axis (plate normal)
normal) or, or, stated
stated inversely,
inwrsely, in in thethp orientation
orientation of of the
the compres-
('ompres-
sion axis
sion axis relative
relatiye to to certain
certain directions
dire<"tjons of of low indicesinrii('es in in the ('rystal. Now
thp crystal. Xow
inspection
inspection of
of a
a standard
standard projretion
projection su('h
such a:,;
as Fig.
Fig. :2-~(j(a)
2-36(a) shows that
that parh
each
half of
half of the
the reference
refrrpnce spheresphere is is covered
('owred by by 24
2-1- similar
similar and equivalent
eqlliyulpllt spherical
sphpri('al
triangles, each
triangles, eaeh having
haying 1100 f100}, I, : 110),
110 I. and 11111 as
1 j
1 1 as its
1 1 ,"('rtiers The
its vertices Thr plate
plate
normal will
normal will fall
fall inin one
on(' ofof these
th('/:ie triangles
triangles and it is is necessary
nN'('/:iSary to
it to draw only only
onp of
one them in
of them in order
order to to describe
de::>eriiJr the the precise
prp('ise location
location of of thethe normal.
normal. In In
Fig. 8-7,
Fig. 8-7, the
the plate
plate normal lies
lies in
in the
the (001)-(101)-(111)
(001)-(101)-(1 Jl) triangle'
triangle whieh
which is
is

redra\\"n
redrawn in Fig.in Fig. 8-8
8-8 in
in the
the ('onwntional
conventional orientation,
orientation, as
as though
though it
it form'd
formed
part of
part of aa (001)
(001) standard projE'('tion. To locate
standard projection. 10{'at(' the thE' plate
plate normal on on this
this
new drawing, w(' meUHure
new drawing, we measure the angles the anglpfl hetwepn
between the ('ent
center ('I' of t h('
the projeetioll
projection
in Fig. 8-7
in Fig. 8-7 and and th('the three
three adjaeent
adjacent polE'S. LE't
poles. Let thpl'e
these angleH
angles h(' be POOl,
pooi, PIOI,
Pioi,
and
and PJlI'
pin- These These anglps
angles a1"C are then us('d used to to dptermiIlP
determine the three three ar('s
arcs shown
in Fig. 8-8.
in Fig. 8-8. Thes('These are are ('in'le
circle ares,arcs,
but
but they
they arp are not centered on the
not ('ente1"'<1 the ('or-
cor-
responding
responding poles; poles; rather,
rather, ea('h
each one is
is

the
the loemi
locus of of points
points lo('atl'd
located at
at an equal
equal
angular distunee
angular distance from the the pole pole in- in-
Pili
"olved
volved and and their
their interseetion
intersection there- there-
fore
fore locates
locates the the dpflired
desired point.point. An
alternatp
alternate method of
of arriving
arriving at
at Fig.
Fig.
8-8
8-8 from
from Fig.Fig. 8-7 8-7 ('onsiHts
consists simplysimply in in
rotating
rotating the the whole
whole projeetion,
projection, polps poles
. 1 - - - - - + + - - - - - - : / - 1111
and
and plate
plate normal
normal together.
together, from from the the
orientation
orientation shown shown in Fig. 8-7
in Fig. 8-7 to to that
that
of
of aa standard
standard (001) (001) projection.
projection.
Similarly, the
Similarly, the orientation
orientation of of aa
single-crystal
single-crystal
scribed
scribed in
axis
.

axis in
Note
.
in terms
xl
in the
the unit
.
wire
wire
terms of
,
or
or
of the
unit stereographic
A
rod
rod may
the location
may
location of
, .
be
be

triangle.
,

stenographic triangle. angle is

de-
de-
of its
its
,
FIG.
ff?P
FIG. IHI.
graphic
orientation.
8-8. Use
hic triangle
tHan
orientation. The
angle ig the
^
.
Use of
e to
The point
normal^
normal
of the

.
the unit
t() deseribe
A
point inside
to
to the
&*
^
unit stereo-

inside the
the single
stereo-
('rystal
the tri-
gingle crys-
l

tn-
cryg
.

Note that that this this method

method does does not not tal
plate whose
tal plate whose orientation
orientation is is shown
shown
completply
completely describe describe the the orientation
orientation in
in Fig.
Fig. 8-7.
8-7.
8-21
g-2] THE
THE BACK-REFLECTION LAUE METHOD
BACK-REFLECTION LAUE METHOD 225
225

of the
of the crystal,
crystal, since
since it allows
it allows one
one rotational
rotational degree
degree ofof freedom
freedom about
about the
the
specimen
specimen axis.
axis. This
This is
is of
of no
no consequenee,
consequence, however,
however, when
when we
we are
are only
only
interested in
interested in the
the value
value of of some
some measured
measured physical
physical or
or mechanical
mechanical property
property
along
along a
a partirular
particular direetion
direction in
in the'
the rrYHtal.
crystal.

There arc
There alternate ways
:lfC alternate ways of of manipulating
manipulating both both the the Gremnger
Gremnger chart chart and and the the
stercographie projertion,
stereographic projection, and
and the
the partieubr
particular method used
used is
is purely
purely a matter
matter of
of
pcn;oual preferen("e
personal preference For
For examplr.
example, wc
we lIlay
may ignore
ignore the
the individual
individual spots
spots on
on the
the film
film
and focus
and forus ourour attention
attention instead instead on on the
til(' various
yarious hyperbolas
hyperbolas on whirh they
OIl which they lie. lie. The
spots
spots on
on one
one hyperbola
hyperbola MC
are dur
due to
to refi(!etiolll-l
reflections from planCR
planes of
of one
one zonr
zone and,
and, hy
by means
of the
of the Greninger
Ureninger chart, ehal"t. we wc can
('an plot
)llot directly
direetIy the the axis
axil'1 of
of this
thil'1 zone
zonl' without
without plottingplotting
the poles
the Jloles ofof any
any of of the
thc planes
plancs belonging
helonginJ!, to to it.
it. The procedure
procedure is is illustrated
illustrated in in Fig.
Fig.
S-9. Keeping
S-9. Kceping the the centers
ecnters of of film
film and chart ehalt coincident,
c'oin("iciellt, we rotute the
WI' rotate the film film about
this center
this c'enter until
untIl aIt particular
partie'ular' hyperbola
hyper'hola of of spots
RJlots coincides
eoiueides with with aII curve
eurve of of constant
constant
'7Y on the chart,
011 the ('hart, as ILS in
in (a).
(a). The amount ulllount of of rotation
rotutioll required
required is is read
reael from the the inter-
inter-
Reetioll of
section of aa vertical
verti('al pencil
)ll'ncil line,
line. previously
preyiously ruled I'ull'd through
through the thc center
('enter of of the
the filmfilm and
parallel to
parallel to one
one edge,
edgr. with\\"Ith thetitr protractor
protm("tor of of the
the Greninger
Greninger chart. ('hart. Suppose
Ruppose this this
angle is
angle iK e.
E. Then the the projection
projectIon is ~taicc\ by
IS mtftted hy thethe same
salllc angle
angle cE withwith respect
respect to to the
the
unc\rrlying Wulff
underlying W ulfT net l}('t and
anrl thetht' ~zojueaxis
z~M?'axis is is 'plotted
j

plotted on the the vertical

vertic'al axisaxiR of of the
the pro-pro-
jeetion at
jection at :tn angle' 7
an angle fl~om,e 'circumference,
'Y {wm&e (irrllmferellre. as ILR in
III (h).
(b). (:'\otr that
(Note zone A itself
that zone itReif
is l"{'prcsentr(1 by
is represented ~J'r:
hy aIt greatyrcle cle located
lo('ated at at anan angle
:tngle'Y ahoye the
7 above center of
the center of the
the pro-pro-
Jertion. However,
jection. tlWp ottin!!. of
Howryer. tlprpK)tting of the
titr zone circle
circle is is not ordinarily
orciinarily necessary
neresRary sillce since
the zone
the zone axis adequately rrpl'eRrnts
axis adequately represents the whole zOllr.)*
the whole zone.)* Proreeding
Proceeding in in thiR way,
this way,
plot the
we plot polrs of
the poles all the
of all thl' important
important zones zone:; and,
and. hy by thethe method of of Fig.
Fig. H-4, 8-4, the the
pole
pole of the planr
of the plane cauRing
causing the thc mORt important spot
most important spot or OJ' 8p01.<;
spots on the the pattern.
pattern. (The (The
latter
latter arc,
are, lik(>
like spot
spot 5 5 of Fig. ioI-5.
of Fig. S-5, of of hIgh
high illtelltlity.
intensity, at at the
the inteJ'se(>tion
intersection of of a number
of
of hypcrholns.
hyperbolas, :mrl
and well
well separated
separated from their
their neighhort;.)
neighbors.) The pointR
points so ohtained
1'10 obtained
are
are ulways
always of
of 10""
low inclireR
indices anrl
and ('all
can usually
usually be indexed
indexed without difficulty.
difficulty.
An alternatr
alternate mrthodmethod of of inclrxill~
indexing plotted poles depend~
plotted ]lolr!" depends on haying having available a
set
set of
of detailrc\ standard ]lJ'ojel'tioll~
detailed Rtan(\nJ'c\ projections in in It a numhPl'
number of of orientations,
orientations, su('h such as {100 {100(, I,
(
/110
110|,I. and /1111
(
11 1
1
foJ'
for ('uhi(' crystals. It
cubic crystals. It isis also
also a trial
trial and error error method and may
he
be illustrated
illustrated with with J'eft'rence
reference to to Fig
Fig S-6.S-6. First,First, a a prominent
prominent zone iR is sele(ted
selected and
an aSRumption
assumption is
is mlule
made as
as to
to its
its indi('es.
indices, for
for example.
example, we might
might aSsume
assume that zone
B iRis a a (100)
(100) zone.
zone. This
This assuIllption
assumption it;
is then
then tested
tested by
by (It)
(a) rotating
rotating the projection
projection
about
about its its ('enter
center untiluntil PIIPH lieslies on the the equator
equator of of the
the Wulff net and the ends of of the
llOne
zone rirC'lc
circle C'oineicie
coincide "ith uith the N and SA> JloieR
the Nand poles of of the
the net,
net, and (b) (b) rotating
rotating all all the im- im-
portant points
portant points on the projection
the projection about the
the NS-axis
MS-axis of
of the
the net until
until PPBB lies
lies at the
eenter
center ILnd the
and the zone
zone rirrie
circle at
at the
the cil'('umference.
circumference. The new projection
projection is
is then super-
super-
imposed
imposed on aa {100 (100)I standard
standard projection
projection and rotated about the center until all all

points
points on the the projection
projection coin(ide
coincide with
with those
those on the
the standard.
standard. If
If no such coinri- coinci-
dence
dence is obtained, another
is ohtained, another standard
standard projection
projection is is tried.
tried. For the particular
particular case

* Note that,
that, when a a hyperbola
hyperbola of of Rpots
spots is
is lined
lined up
up with aa horizontal
horizontal hyperbola
hyperbola
on
on the
the chart
chart as
as in
in Fig.
Fig. 8-9(a),
8-9(a), the
the vertical
vertical hyperbolas
hyperbolas cancan be used to to measure the
the
difference
difference in
in angle
angle 5 for
for any
any a
two
two spots
spots and
and that
that this
this angle
angle is
is equal
equal to
to the
the angle be-
angle be-
tween
tween thethe planes
planes causing
causing those
those spots,
spots, just
just as
as the
the angle
angle between
between two
two poles
poles lying
lying
on
on aa meridian
meridian of
of aa Wulff
Wulff net
net is
is given
given by
by their
their difference
difference in
in latitude.
latitude.
226 ORIENTATION
ORIENTATION OF SINGLE CRYSTALS
SINGLE CRYSTALS [CHAP. 8
[CHAP. 8

cut corner

row of .spots
from planes of
zone A

(b)

FIG. 8-9.
FIG. 8-9. Use of the
of the Greninger chart
Greninger chart to
to plot
plot the
the axis
axis of
of aa zone
zone of
of planes
planes on
on the
the
stereographic projection.
stereographic projection. P A is
PA is the
the axis
axis of
of zone A.
zone A.
8-21
8-2] THE BACK-REFLECTION LAUE METHOD
BACK-REFLECTION LAUE 227
227

o film s

referen('!'
Kphert' ",
~ D

/
/

prnJ!'rtion
plaIlt'
plane
-u---------ol

FIG. 8-10. Relation

FIG. 8-10. Relation between
between diffrartion
diffraction flpot
spot Sand
8 and stereographic projection P
stereographic projection
of
of the
the plane
plane causing
causing the
the spot.
spot, for
for baek
back reflection.
reflection.

of
of Fig. 8-6, a coincidenee
Fig. 8-6, coincidence would be obtained obtained onlyonly on a a {1101
{
1 1 standard.
standard, since
1
PB
since PB
is
is actually
actually a {1101
( 110) pole.
pole. Om'eOnce a a match hashas been
been found,
found, the
the indires
indices ofof the
the unknown
poles are given
poles are given simply
simply by by the
the indices
indices ofof the
the poles
poles on
on the
the standard
standard withwith whirh
which they
they
coincide.
coincide.
In the
In the absence of of aa Greninger
Greninger chart,
chart, thethe pole
pole rorresponding
corresponding to to any observed
any observed
Laue spot
spot maymay be
be plotted
plotted by by means of of an easily
easily constructed
construrted "stereographic ruler."
"stereographic ruler."
The construction
construction of of the ruler is
the ruler is based
based onon the
the relations
relations shown in Fig. 8-10.
in Fig. 8-10. This
This
drawing
drawing is
is a
a section
section through
through the
the incident
incident beam OC and
and any
any diffracted
diffracted beam CS.
CS.
Here itit is
is convenient
convenient to to use
use the
the plane normal ON' rather
plane normal than ON and
rather than and toto make the
the
projection from T,
projection the intersection
T, the intersection of of the
the reference
reference sphere with the
sphere with the incident
incident beam.
beam.
projection of
The projection of the
the pole
pole N' is is therefore
therefore at P. From the
at P. the measured
measured distance
distance OS
of the
of the diffraction
diffraction spot from the
spot from the center
center ofof the
the film,
film, we can
can find
find the
the distance
distance PQ ofof
the projected
the projected pole
pole from the the center
center ofof the
the projection,
projection, since
sinre
= OC tan
OS = (180 0 -
tan (180 - 20) = D tan
'lfJ) = (180 0 -
tan (180 - 'lfJ)
26) (8-1)
(8-1)
and

PQ = TQtan
= TQ -~)
tan (45 0 ~ = 2r tan
f ) = 2rt.an (45
0
- n (8-2)
(8-2)

where D isis the

the specimen-film
specimen-film distance and rr the
distance and the radius
radius of
of the
the reference
reference sphere.
sphere.
value of
The value of rr is
is fixed
fixed by
by the
the radius
radius R of
of the
the Wuiff
Wulff net
net used,
used, since
since the
the latter
latter equals
equals
the radius
the of the
radius of the basic
basic circle
circle of
of the
the projection.
projection. We note
note that, if the
that, if the pole
pole of
of the
the
228
228 OP SINGLE CRYSTALS
ORIENTATION 01' [CHAP. 8
[CHAP, 8

PROJJtX'TION
PROJECTION N

II'

L. _ _ _ _ _ _ _ _ _ _ _ .J

FIG.
FIG. 8-11. Use of
8-11. rRC of a
a sten'ographi(' ruler to
stereographic ruler to plot
plot thE'
the pole
pole of a ref:le('tlIl~
of II reflecting plane
plane on a
a
stereographic
stereographic proje('tion
projection ill
in the back- reflection Laue method. Pol('
the blu'k-refle(,tion Pole l'1' if!
is the
the pole
pole
of the
of the plane
plane causing
causing diffra('tion
diffraction f!pot
spot 1.
1 .

plane
plane were
were in
in its
its extrcme
extreme positiou at JI,
position at M, then
then it... projE''<'tiou
its projection would hE' at V.
he at U. The
point
point U thereforc
therefore lies
lies on the
the basic
basic ('ir('le
circle of
of the
the proje(,tiou,
projection, aud
and l'lJ
UQ if!
is the
the radius
radius R
of the
of the basic
basic circle.
circle. Be('aUMe
Because the
the trilluglE's
triangles TFQ TUQ aUII TMC aI'P
and T.UC are similar,
similar, ftR == 2r
2r and

PQ == R tan
tan (45
^45
-- :).
-)
(~-3)
(8-3)

The ruler
ruler is
is constru('ted
constructed by by mllrkinl(
marking off,
off, from
from a a (,(,l1tral point, aa M(,llle
central point, scale ofof centi-
centi-
meters
meters by by which
which the the distan('e
distance 08 ON may
may bebe mcafolured.
measured. The du;tan('p distance P(J PQ (,o/Tcspond-
correspond-
ing to
ing to each
each distanre
distance OS is is then
then ('Illculated
calculated from Eqs. (~-I) Ilnd
Eqs. (S-l) and (><(S 3),
3), Illld
and marked
off
off from the the center
center ofof the
the ruler
ruler in in the
the opposit('
opposite dire('tioll.
direction. COITCl'lpoudiug
Corresponding gfllc!ua-gradua-
tions
tions areare given
given thethe SIlme
same number and the the reMult
result is is the
the rull"
rulei showu
shown ill Fig. s-
in Fig. 11,
8-11,
which
which alsoalso illustrate!!
illustrates the
the method of of using
using it.
it. [Calc'ulation
[Calculation of
of th('
the yurioull
various llilltllllCCII
distances
PQ call
can bebe Ilvoided
avoided by by use
use ofof the
the Wulff
Wulff net
net it.'ielf.
itself. Fig.
Fig. X-IO
8-10 IIhows
shows that
that tht'
the polepole
of
of the
the reflecting
reflecting plane
plane is is located
located at at an angle
angle (J 6 from the the cd~e
edge of of th('
the proJc('tioll,
projection, and
6 is
(J is given
given for
for each
each distance
distance OS by by Eq. (8-1). Th('
Eq. (X-I). The rult'r
ruler isis laid
laid IIlol1/!;
along thcthe equator
equator
of
of the
the Wulff
Wulff net,
net, its
its center
center ('oinciding
coinciding with
with tht'
the net
net ('cnter,
center, und
and the distance PQ
the disttm('e PQ
corresponding
corresponding to to each
each angle
angle (J 6 is
is marked off off with
with thc the help
help ofof the
the angular
angular 1I('ule
scale on on
the
the equator.]
equator.]
From the the ('hoi('e
choice ofof plane
plane normal
normal made in in Fig. 8-10, it
Fig. X-IO, it iM
is upplmmt
apparent that that thethe pro-pro-
jection
jection mUllt
must bc be vicwed
viewed from the the side
side oppollite
opposite the the x-ray
x-ray !l()urrc.
source. This
This requires
requires
that the
the film
film be read
read from that that sidc
side also,
also, i.c.,
i.e., with
with itMits ('ut
cut ('omer
corner in in the
the upper
upper right-
right-
hand position.
position. The projection
projection ill is then
then pla('ed
placed overover thcthe film,
film, illuminated
illuminated f/'Om from be- be-
low,
low, as as shown in in Fig. 8-11. With the
Fig. X-ll. the center
center of of the
the ruler
ruler ('oinciding
coinciding with with thethe cen-cen-
ter
ter ofof the
the projection,
projection, the the rulcr
ruler isis rotated until its
rotated until its edge
edge passes
passes through
through a a parti('ular
particular
8-31
8-3] TRANSMISSION LAUE METHOD 229
diffraction spot. The distance 08 is
diffraction spot. as
is noted and the corresponding
corresponding polepole plotted
plotted as
as
shown,
shown, on the other side side ofof center and at at the corresponding
corresponding distance
distance PQ.
PQ. This
procedure is
procedure is repeated
repeated forfor each important
important diffraction
diffraction spot,
spot, after
after whirh
which the
the projec-
projec-
tion
tion is
is transferred
transferred toto a Wulff net and the poles poles indexed by by either
either of
of the
the methods
previously
previously described.
described. Note that
that this
this proredure
procedure gi,'es
gives a projertion of
a projection of the
the crystal
crystal
from the
the side
side opposite
opposite the
the x-ray
x-ray sourre,
source, whereas the
the Greninger
Oreninger ('hart
chart gives
gives aa pro-
pro-
jection of
jection of the crystal aR
the rrystal as seen
seen from the the x-ray
x-ray Hourc'e.
source. A ('rystal
crystal orientation
orientation can,
can,
of
of course,
course, be desrrihed just as
described just as well
well from one side
side as
as the
the other,
other, and either
either projer-
projec-
tion
tion can
can be made to to ('oine'ide
coincide with
with the
the other
other by
by aa umo
180 rotation
rotation ofof the
the projection
projection
about its
its EW-axis. Although simple
Although simple to
to use
use and c'onstruet,
construct, the
the stereographir
stereographic ruler
ruler
is
is not
not as
as a('rurat('
accurate asas the
the Greninger
Greninger ('hart
chart in
in the
the solution
solution ofof hark-refie(,tioll patternR.
back-reflection patterns.

Th(>
The methods of of det'rmining
determining and descrihing
describing crystal
crystal orientation
orientation have
be('n pn's('nted
been presented hpr('
here exclusiwly
exclusively in
in tPfms
terms of
of ('ubic
cubic crystals, be('/luse
('rystals, because these
these
are
are the
the simplest
simplest kind t.oto ('on sideI' and thp
consider the most frequently
frequently encountered.
encountered.
Thesp
These methods arpare quitp
quite general.
general, howey('f,
however, und
and ('an
can he
be applied
applied to
to a
a C'rystal
crystal
of
of any
any sy!'tem
system u!' long a!'
as long as it!'
its intl'rplanar
interplariar angl('s
angles aI''
are known.

8-3 Transmission Laue method. Gi"en Given a spp('im'n

specimen of of sufficient
sufficiently I:\' low
absorpt
absorption, ion. aa transmission Lam' pattern ('an
Laue pattern can bp
be ohtainl'd
obtained and used,used, in
in much
tht'
the samp
same wayway us as a bu('k-refi'C'tion Laup
a back-reflection pattprn, to
Laue pattern, to r('\'eal
reveal the
the orientation
orientation
of
of tthe
h' ('ryst al.
crystal.
In
In ('ither
either Luup
Laue method,
method, the the diffra(,tion
diffraction spots
spots on the the film,
film, due to to the the
planes
planes of of aa singl('
single zone in in thp
the ('rystal,
crystal, always
always lielie on aa eurve
curve whic'h
which is is some

kind of of c'olliC'
conic s('C'tion.
section. When the the film
film is
is in
in the
the transmission position, this
transmission position, this
('ur\'(>
curve is is aa ('omplete
complete ellipse
ellipse for
for Huffi(:ientIy
sufficiently small
small "alues
values ofof cp, the
</>,the angle
angle be- be-
twepn
tween the the zonp
zone axis
axis und
and the
the tram,mitted
transmitted bpambeam (Fig.
(Fig. 8-1:2).
8-12). For somewhat
largPI'
larger \'ulups
values of of cp, the
</>,
the ellipse
ellipse is
is incompletp beeaw;p of
incomplete because of the
the finite
finite size
size ofof the
the
film.
film. When cp =
Whpn = 4.3,
45, the
the C'UI'Y('
curve be('omes
becomes u parabola, when cp exceeds 45,
a parabola, </> 45, aa

/
~ .'.'
, : ::--:-:- ::
('

F
,
8-12. Illtel'~ertioll
FIG. S-12. Intersection of a roniral
of II. conical flrray
array of
of diffracted beams with
diffracted beams with aa film
film plared
placed
in
in the
the transmission = crystal, F =
position. C = C'l'ystal,
transmission position. = film, Z.A. =
film, Z.A.
= zone
zone axis.
axis.
230
230 ORIENTATION OF
ORIENTATION OF SINGLE
SINGLE CRYSTALS
CRYSTALS [CHAP. 88
[CHAP.

Z A

FIG. R-13. Relation

FIG. 8-13, Relation between
between plane
plane normal
normal orientation
onentatlOlI and diffraction
dIffractlO1l spot posi-
spot posi-
tion
tion in
in the
the transmission
transmission Laue method.

hyperbola, and when 4> = 90

hyperbola, = 90,
</>
0
, aa straight
straight line. line. In all
all eases,
cases, thC'the eurve
curve
passes through
passes through the
the central
central spot
spot formed by
by the
the transmitt('d
transmitted beam.
The angular
angular relationships
relationships involved
involved in in thethe transmission
transmission Laue method
are
are illustrated
illustrated in in Fig.
Fig. 8-13.
8-13. Here aa reference
reference sphere
sphere is is described about

the
the crystal
crystal at
at C,
C, the
the incident
incident beam entering
entering the
the sphere
sphere at
at I/ and the trans-
mitted
mitted beam leayingleaving at
at O.
0. The film
film is
is placed tangent
placed tangent to
to the sphere
sphere at 0, 0,
and itsits upper right-hand
upper right-hand corner, corner, viewed from the
the crystal,
crystal, is
is rut
cut off
off for
identification
identification of of its
its position
position during
during the the x-ray
x-ray exposure.
exposure. The beam reflected reflected
by
by the
the lattice
lattice plane
plane shown strikes
strikes the
the film
film at
at R,
R, and the
the normal to this
this
plane
plane intersects
intersects the
the sphere
sphere at
at P.
P.
Suppose
Suppose we consider
consider diffraction
diffraction from a a zone
zone of of planes
planes whose axis axis lies
lies in
in

the
the yz-plane
jyz-plane at
at an
an angle
angle 4> to
to
<t>
the
the transmitted
transmitted (or incident)
(or incident) beam. If
If aa
single plane
single plane of
of this
this zone
zone is
is rotated
rotated so
so that
that its
its pole, initially
pole, initially at
at A,
A, travels
along
along thethe great circle APEBW
great cin'le APEBWA, A, then
then it will pass
it will pass through
through all all the orienta-

tions
tions inin which planes
planes ofof this
this zone
zone might
might occuroccur in in anan actual
actual crystal.
crystal. During
During
this
this rotation,
rotation, the
the diffraction
diffraction spot
spot on the
the film, initially
film, initially at
at D, would travel
D,
along
along thethe elliptical
elliptical path
path DROD shown shown by by the
the dashed
dashed line.
line.

Any particular
Any particular orientation
orientation of
of the
the plane,
plane, such
such as
as the
the one
one shown
shown in in the
drawing,
drawing, is
is characterized
characterized by particular
by particular values
values of
of 4>
<t>
and
and 5, 6, the
the angular
angular co- co-
8-3]
8-3] TRANSMISSION LAUE METHOD 231
o 10
10 20 30

40

50

10
60

FIG.
FIG. S 14. Leonhardt chart
(S-14. chart for
for the
the solution
solution of
of tran!'missioll
transmission Laue patterns,
patterns, re-
re-
produ('cd
produced in the COITe('t
in the correct size
size for
for aa specimen-to-film
specimen-to-film distan('e
distance of of 33 ('m.
cm. The dashed
dashed
lines
lines are
are lines
lines of constant cP, and the
of ('onstant </>, the solid
solid lim's
lines are
are linet;;
lines of stant ~.
constant
of ('011 5. (Courte!'J
(Courtesy
of
of C.
C. G. Dunn.)
Dunn.)

ordinates
ordinates of of its
its pole.
pole. These
These coordinates
coordinates in in turn,
turn, for a given
for It given crystal-film
crystal-film
distance D (=
distance CO),
(= TO), determine
determine the
the X,y
x,y coordinates
coordinates of
of the
the diffraction
diffraction spot
spot
R on thethe film.
film. From the the spot position
spot position we can
can therefore
therefore determine the
the
plane orientation,
plane orientation, and one
one way
way of
of doing
doing this
this is
is by
by means of
of the
the Leonhardt
chart
chart shown in in Fig.
Fig. 8-]
8-14.4.
This chart
chart is
is exactly
exactly analogous
analogous to to the
the Greninger
Greninger chart chart for
for solving
solving back-
back-
reflection
reflection patterns
patterns and is
is used
used in
in precisely
precisely the
the same way.
way. It
It consists
consists of
of aa
grid composed
grid composed of
of two sets
sets of
of lines:
lines: the
the lines
lines of
of one
one set
set are
are lines
lines of
of constant
constant cP
<t>

and correspond
correspond to to the
the meridians
meridians on on aa Wulff
Wulff net,net, and the the lines
lines of of the
the other
other
are
are lines
lines of constant ~5 and correspond
of constant correspond to
to latitude
latitude lines.
lines. By
By means of
of this
this
chart,
chart, the
the pole
pole of
of a
a plane causing any particular
plane causing any particular diffraction
diffraction spot may
spot may be be
plotted stereographically.
plotted stereographically. The projection
projection plane plane is
is tangent
tangent to
to the
the sphere
sphere
at
at the
the point
point /I of Fig. 8-13
of Fig. 8-13 and the projection is
the projection is made from from the pbint O.
the point 0.
This requires
requires that
that the
the film
film be
be read
read from the
the side
side facing the crystal,
facing the crystal, i.e., i.e.,
232
232 ORIENTATION OF
ORIENTATION OF SINGLE
SINGLE CRYSTALS
CRYSTALS [CHAP. 88
[CHAP.

}'r

('u(, ('orl)('r
FILM
FILl\[

1010 20 30

40
'0

''''. '0

10.
"0

.0
X

(a)

PROJECTION
PRO.m< '1'10:-\ .\ tIIHlprlYlIlg
underlying
Wulff Ilpj
Wulff net

II' ~--E==t----+-+-+-!-+-I-+-++-HH--+-+-===~-I fI'

(h)

FIG. 8-15.
FIG. oS-I5. l~ se of
Use of the
the Leonhardt
Leonhardt chart
chart to
to plot
plot the
the pole
pole of
of aa plane
plane on
OIl aa stereo-
stcreo-
graphic projection.
graphic projection. Pole
Pole in (b)
I' in
1' (h) isis the
the pole
pole of
of the
the plane
plane causing
('uusing diffraction
diffrartion spot
spot
1 in
1 in (a).
(a).
8-3]
8-3] TRANSMISSION LAUE
TRANSMISSION METHOD
LAUE METHOD 233
233

FILM
Ellipse of spots from
plant' of zone A
10 20 / JO

cut cornel

(a)
(a)

(b)

FIG. S-16.
FIG. S-J6. Use of the
of the Leonhardt chart
Leonhardt chart to
to plot
plot the
the axis
axis of aII zone
of zone of
of planes
planes on the
on the
projection.
projection. PAis
PA the axis
is the axis of
of zone A.
zone A.

with the
with the cut
cut corner
('orner at
at the
the upper
upper right. Figure
right. Figure 8-15
8-15 shows
shows how the the pole
pole
corresponding
corresponding to
to a
a particular spot.
particular spot is
is plotted
plotted when
when th('
the film
film and
and chart
chart are
are
in the
in the parallel
parallel position.
position. An alternate
alternate way way of
of using
using the
the chart is to
chart is to rotate
rotat.e
it about
it about its
its center
center until
until aa line
line of
of constant
constant <p coincides
coincides with
<t> with aa row
row ofof spots
spots
from planes
from planes of
of aa single
single zone,
zone, asas shown
shown in in Fig.
Fig. 8-16;
8-lG; knowing
knowing <p and
and the
the
rotation angle
rotation angle 6,E, we
we can
can then
then plot
plot the
the axis
axis of
of the
the zone
zone directly.
directly.
234
234 ORIENTATION OF SINGLE CRYSTALS [CHAP. 8
[CHAP. 8

reference
sphere

T
!

f------

() film
film /?

FIG.
FIG. S-17.
8-17. Relation
Relation between diffrartion spot Sand
diffraction spot S and 8tereol!:raphir
stereographic proje(tlOn
projection P
of
of the
the plane
plane rausing
causing the
the spot.
spot, in
in transmission
transmission..

.\

(
\/---------,
~ film I
I I
1I

I
L ________ ---lI

L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _---l

FIG. 8-1s'
8-18. Use ofof a
a stereographic
stereographic ruler
ruler to
to plot
plot the pole of
the pole of a
a reflerting plane on
reflecting plane on
a stereographic projection in
stereographic projection in the
the transmission
transmission Laue
Laue method. Pole I'
method. Pole 1' is
is the
the pole
pole of
of
the
the plane
plane causing
causing diffraction
diffraction spot
spot I. 1 .
8-3)
8-3] TRANSMISSION LAUE METHOD 235
235

A stereographic
stereographic ruler
ruler may
may be constructed
constructed for
for the
the transmission
transmission method
and it will give
it will give greater
greater accuracy
accuracy of plotting
of plotting than the
the Leonhardt chart,
chart,
particularly
particularly when the angle <p approaches
the angle approaches 90.
<t> 90. Figure
Figure 8-17,
8-17, which is is a
a
section
section through
through the
the incident
incident beam and any
any diffracted
diffracted beam,
beam, shows that
that
the
the distance
distance of
of the
the diffraction
diffraction spot
spot from the
the center
center of
of the
the film
film is
is given by
given by

os
OS == D tan
tan 28.
20.

The distance
distance of
of the pole of
the pole of the
the reflecting plane from the
reflecting plane the center
center of
of the pro-
the pro-
jection is
jection is given
given by
by

PQ = R tan 45 - -
(
V 2

Figure
Figure 8-18
8-18 illustrates
illustrates the use of
the use of a
a ruler
ruler constructed
constructed according
according to to these
these equa-
equa-
tions.
tions. In this case,
In this case, the projection is
the projection is made on a plane located
a plane located on the the same
side
side ofof the
the crystal
crystal as as the
the film
film and,
and, accordingly,
accordingly, the the film
film must be read read with
its
its cut
cut corner
corner in in the
the upper
upper left-hand
left-hand position.
position.
Whether the the chart
chart or or the
the ruler
ruler is is employed
employed to plot the
to plot poles of
the poles of reflecting
reflecting
planes,
planes, they
they are
are indexed
indexed in in the
the same way way as back-reflection patterns.
as back-reflection patterns. For
example,
example, the the transmission
transmission Laue pattern pattern shown in in Fig.
Fig. 8-19
8-19 in in the
the form
of
of a
a tracing yields
tracing yields the
the stereographic projection
stereographic projection shown in
in Fig.
Fig. 8-20.
8-20. The
solid
solid symbols
symbols in in the
the latter
latter are
are the poles of
the poles of planes
planes responsible
responsible for for spots
spots on
the film
the film and areare numbered accordingly;
accordingly; the the open
open symbols
symbols are are poles
poles derived
derived
by
by construction.
construction. (The
(The reader
reader will
will note
note that
that the
the poles
poles of
of planes responsible
planes responsible
for
for observed
observed spots
spots on on a transmission film
a transmission film areare allall located
located near
near thethe edge
edge ofof
the
the projection,
projection, sincesince such
such planes
planes must necessarily
necessarily be inclined at
be inclined at small
small
angles
angles to
to the
the incident
incident beam.
beam. The reverse
reverse is
is true
true of
of back-reflection
back-reflection pat-
pat-
terns,
terns, as
as inspection
inspection of
of Fig.
Fig. 8-6
8-6 will
will show.)
show.) The solution
solution of
of Fig.
Fig. 8-20
hinged
hinged on on the identification of
the identification of the
the zone
zone axesaxes P PA,A, P B, and Pc.
PB, PC. Measure-
ment showed that that the the stereographic
stereographic triangletriangle formed by by these
these axes
axes had
sides
sides equal
equal to
to 35
35 (P
(P A -
- P B
B ),
), 45
45 (P
(P B
B -
- Pc),
PC), and 30
30 (Pc
(P c
-
- P A
PA), ), which
identified
identified P A , PB,
,PB, and Pc
PC as
as 12111, 1100\,
{211}, {100}, and 11101 poles, respectively.
{110} poles, respectively.
Now the the transmission
transmission patternpattern shown in in Fig.
Fig. 8-19
8-19 and the back-reflection
the back-reflection
pattern
pattern shown in in Fig.
Fig. 8-5
8-5 were
were both
both obtained
obtained from the the same crystal
crystal in in the
the
same orientation relative to
orientation relative to the
the incident
incident beam. The corresponding corresponding pro- pro-
jections, Figs. 8-20
jections, Figs. 8-20 and 8-7, 8-7, therefore
therefore referrefer to to a a crystal
crystal of of the
the same orien-
orien-
tation.
tation. But
But these
these were
were made from from opposite
opposite sides sides ofof the
the crystal
crystal and so so
appear completely
appear completely dissimilar.
dissimilar. However,
However, a
a rotation
rotation of
of either
either projection
projection
by
by 180
180 about
about its EW-axis will
its EW-&xis will make it it coincide
coincide withwith thethe other,
other, although
although
no attempt
attempt has has been
been made to to make the the indexing
indexing of of one projection
projection con- con-
sistent
sistent with
with that
that ofof the
the other.
other.
236
236 ORIENTATION OF
ORIENTATION OF SINGLE
SINGLE CRYSTALS
CRYSTALS [CHAP. 88
[CHAP.

'.
I
----', . . . :2 /
/
----^ 3

I
I
I \
\ ,4
\

I
I
I
/
\ I ti I
"
'Jf..-I_---~
__ _ - ,
,
,

~) - '/ ,v

------- I

"

FIG.
FIG. 8-19.
8-19. Transmission Laue pattern
pattern of
of an aluminum crystal,
crystal, traced
traced from
from Fig.
Fig.
3-6(a).
3-6 (a). Only
Only selected
selected diffraction
diffraction spots
spots are
are shown.
shown.

FIG. 8-20.
FIG. 8-20. Stereographic projection
Stereographic projection corresponding
corresponding to
to transmission
transmission pattern
pattern of
of
Fig. 8-19.
Fig. 8-19.
8-4)
8-4] DIFFRACTOMETER METHOD
DIFFRACTOMETER METHOD 237
237

8-4 Diffractometer
8-4 Diffractometer method. method. Still Still another
another methodmethod of of determining
determining crys- crys-
tal orientation involves the
tal orientation involves the use
use of of the
the diffractometer
diffractometer and and aa procedure
procedure radi- radi-
cally
cally different
different from that
that of
of either
either Laue
Laue method.
method. With
With the
the essentially
essentially
monochromatic radiation
monochromatic radiation used used in in the
the diffractometer,
diffractometer, aa single single crystal
crystal will
will
produce
produce aa reflection
reflection only
only when its
its orientation
orientation is
is such
such that
that a
a certain
certain set
set of
of
reflecting
reflecting planesplanes is
is inclined
inclined to
to the
the incident
incident beam
beam at
at an
an angle
angle 6
6 which
which satis-
satis-

fies the
fies the Bragg
Bragg law law for for that
that set set ofof planes
planes and the the characteristic
characteristic radiation radiation
employed. But
employed. But when the the counter,
counter, fixed fixed in in position
position at at thethe corresponding
corresponding
angle 20,
angle 26, discloses
discloses that that aa reflection
reflection is is produced,
produced, then then the the inclination
inclination of of the
the
reflecting planes
reflecting planes to to any
any chosen
chosen line line oror plane
plane on the the crystal
crystal surface
surface is is known
from the
from the position
position of of the
the crystal.
crystal. Two kinds kinds of of operation
operation are are required:
required:
(1)
(1) rotation
rotation of
of the
the crystal
crystal about
about various
various axes
axes until
until aa position
position is found
is

for which
for which reflection
reflection occurs,occurs,
(2) location
(2) location of of the
the polepole of of the
the reflecting
reflecting planeplane on aa stereographic
stereographic projec- projec-
tion from
tion from the the known angles angles of of rotation.
rotation.
diffractometer method has
The diffractometer has many
many variations,
variations, depending
depending on the the par-
par-
ticular kind
ticular kind of of goniometer
goniometer used used to to hold
hold and rotate rotate the the specimen.
specimen. Only Only one
of these
of these variations
variations will will be be described
described here, here, that
that involving
involving the the goniometer
goniometer
used in the
used in the reflectionrefleetion method of determining preferred orientation, since
of determining preferred orientation, since
that is
that is thethe kindkind mostmost generally
generally available
available in metallurgical
in metallurgical laboratories.
laboratories.
This specimen
This specimen holder, holder, to to be be described
described in in detail
detail in in Sec.
Sec. 9-9, 9-9, needs
needs veryvery
little
little modification
modification for for useuse withwith single crystals, the
single crystals, the chief
chief one being being an in- in-
crease
crease in in the
the width
width of the primary
of the primary beam slits slits inin a direction
direction parallelparallel to the the
diffractometer
diffractometer axis axis in in order
order to to increase
increase the the diffracted
diffracted intensity.
intensity. This type type
of
of holder
holder provides
provides the
the three
three possible
possible rotation
rotation axes
axes shown in
in Fig.
Fig. 8-21:
8-21 :one
coincides
coincides with with the the diffractometer
diffractometer axis, axis, the
the second (AA')
(A A') lies
lies in
in the plane
plane
of the
of incident beam I/ and diffracted
the incident diffracted beam D and tangent tangent to the specimen specimen
surface,
surface, shown here
here as
as a
a flat
flat plate,
plate, while
while the
the third
third (BB')
(BB )
r
is
is normal to the
specimen
specimen surface.
surface.
Suppose
Suppose the the orientation
orientation of of a a cubic crystal is
cubic crystal is to
to be determined.
determined. For such
crystals it is convenient
crystals it is convenient to use to use the
the l111} planes
{111) planes as
as reflectors;
reflectors; there are
four sets of
four sets of these
these and their their reflecting
reflecting power power is is usually
usually high. high. First, First, the
the 28 26
value
value for for the
the 111 111 reflection
reflection (or, (or, ifif desired,
desired, the the 222 reflection)
reflection) is is computed
computed
from
from thethe known spacing spacing of the II
of the 11} planes
{111} planes and the the known wavelength wavelength of
the
the radiation
radiation used. used. The counter counter is is then
then fixed
fixed in in this
this 26 28 position.
position. The
specimen
specimen holder holder is is now rotatedrotated about about the the diffractometer
diffractometer axis axis until
until its
its sur-

face,
face, and the
the rotation
rotation axis
axis A
AA',A', is
is equally
equally inclined
inclined to the incident
incident beam
and
and thethe diffracted
diffracted beam, beam, or
or rather,
rather, to
to the
the line
line from crystal
crystal to
to counter with
which the
which the diffracted
diffracted beam, beam, when formed,
formed, will
will coincide.
coincide. The specimen
specimen
holder
holder is is then
then fixed
fixed in in this
this position,
position, no further further rotation
rotation about the diffrac- diffrac-

tometer axis being required.

tometer axis being required. Then, by Then, by rotation
rotation about the axis
axis BB
BB',f
,one
edge of the specimen
edge of the specimen or or a
a line
line drawn on
on it
it is
is made parallel
parallel to the diffrac-
diffrac-

tometer
tometer axis. axis. This This is is the
the initial
initial position
position illustrated
illustrated in in Fig.
Fig. 8-2l.
8-21.
238
238 SINGLE CRYSTALS
ORIENTATION OF SINGLE 8
[CHAP. 8
[CHAP.

crystal is
The crystal is then
then slowly
slowly rotated
rotated
about the
about axes A
the axes AA' BB' until
A and BE''
until an
indication of
indication of aa reflection
reflection is observed
is observed
on the
on the counting-rate
counting-rate meter.
meter. Once aa
reflecting position
reflecting position of of the
the crystal
crystal has
has
been found,
been found, we know that that thethe normal
normal
to one
to one set
set ofof (111!
/1111 planes
planes coincides
coincides I
with the
with line CN
the line that is,
CN, that
9
is, lies
lies in
in the
the
plane of
plane of the
the diffractometer
diffractometer circle circle and
and
bisects the
bisects the angle
angle between
between incident
incident
and diffracted
and diffracted beams.
beams. The pole pole of
of ,,
,
these diffracting
these diffracting planes
planes may may now be be
'B'
plotted stereographically,
plotted stereographically, as as shown in in
Fig. 8-22.
Fig. projection is
8-22. The projection is made
on aa plane
on plane parallel
parallel to to the
the specimen
specimen FIG. 8-21.
FIG. 8-21. Crystal rotation
rotation axes
axes
Crystal
surface, and with
surface, with the
the MS-axis
NS-axis of of the
the forfor the
the diffractometer
diffractometer method of of de-
de-
projection parallel
projection parallel to to the reference termining
the reference orientation.
termining orientation.
edge or line
edge or mentioned above.
line mentioned above. When
the crystal
the crystal is is rotated
rotated {3 degrees
degrees about
about BB' from its its initial
initial position,
position, the
projection
projection is is also
also rotated
rotated {3 degrees
degrees about its its center.
center. The direction
direction CN,CAT,
which might
which might be called the
be called the normal
normal to to "potential" reflecting planes,
"potential" reflecting planes, is
is repre-
repre-

PROJECTION
PROJECT 10K

11" E

FIG. 8-22. Plotting

FIG. 8-22. Plotting method used
used when determining
determining crystal
crystal orientation
orientation with
with the
the
diffractometer.
diffractometer. (The
(The directions
directions of
of the
the rotations
rotations shown here
here correspond
correspond to
to the
the
directions of
directions of the
the arrows
arrows in
in Fig.
Fig. 8-21.)
8-21.)
8-4)
8-4] DIFFEACTOMETER METHOD
DIFFRACTOMETER 239
sented
sented by by the pole N
the pole N', which is is initially
initially atat the
the center
center of of the projection but
f
,
the projection but
which moves 'Yy degrees degrees alongalong a a radius
radius when the the crystal
crystal is is rotated
rotated 'Y y degrees
degrees
about A AA'.
A'.
What we are are trying
trying to to do,
do, essentially,
essentially, is to make N
is to N' coincide
coincide withwith a
f
a
{Ill}
{
111 pole
J pole and so
so disclose
disclose the
the location
location of
of the
the latter
latter on
on the
the proj ection.
projection. The
search
search may may be be made by by varying
varying 'y Y continuously
continuously for for fixed
fixed values
values of of {j 4
4 or
or 5
5
apart;
apart; the
the projection
projection is
is then
then covered
covered point by point
point by point along along a
a series
series of
of radii.
radii.
It
It is
is enough
enough to to examine one one quadrant
quadrant in in this
this way
way since
since there
there will
will always
always
be atat least
least one {Ill} {111} polepole in
in anyone
any one quadrant.
quadrant. Once one
one pole has
pole has been
been
located,
located, the the search
search for for the
the second is is aided
aided byby the
the knowledge
knowledge that that itit must

be
be 70.5
70.5 from the the first.
first. Although
Although two {Ill} {111) poles
poles are are enough
enough to to fix
fix the
the
orientation
orientation of of the
the crystal,
crystal, a a third
third should
should be be located
located as as a a check.
check.
Parenthetically, it
Parenthetically, it should
should be be noted
noted that
that the positioning of
the positioning of the
the crystal
crystal
surface
surface and the the axis
axis A AA'
A' at at equal
equal angles
angles to to the
the incident
incident and diffracted
diffracted
beams is is done only only for for convenience
convenience in in plotting
plotting the the stereographic
stereographic projec- projec-
tion.
tion. There is is no question
question of of focusing
focusing when monochromatic radiation
radiation is
is

reflected
reflected from an undeformed undeformed single crystal,
single crystal, and the
the ideal
ideal incident
incident beam
for
for the determination of
the determination of crystal
crystal orientation
orientation is is aa parallel beam, not
parallel beam, not a a di-
di-
vergent
vergent one.
one.
In
In the
the hands of of an experienced
experienced operator,operator, the the diffractometer
diffractometer method is is

faster
faster than either
than either Laue method. Furthermore,
method. Furthermore, it it can
can yield
yield results
results of of
greater
greater accuracy
accuracy if if narrow slits slits areare used
used to to reduce
reduce the the divergence
divergence of of the
the
incident
incident beam, beam, although
although the the use use of of extremely
extremely narrownarrow slits slits will
will make it it

more difficult
difficult to to locate
locate the the reflecting positions of
reflecting positions of the
the crystal.
crystal. On the the other
other
hand,
hand, the the diffractometer
diffractometer method furnishes furnishes no permanent
permanent record record of of the
the
orientation
orientation determination,
determination, whereas whereas Laue patterns patterns may may be be filed
filed away
away for for
future reference. But what is
future reference. is more important,
important, the
the diffractometer
diffractometer method
does
does not not readily
readily disclose
disclose the the state
state of perfection of
of perfection of the
the crystal,
crystal, whereas
whereas a a
Laue pattern yields
pattern yields this
this kind
kind of
of information
information at
at aa glance,
glance, as
as we will
will see
see in
in
Sec.
Sec. 8--6,
8-6, and in in many
many investigations
investigations the the metallurgist
metallurgist is just as
is just as much inter-
inter-
ested
ested in in the
the relative
relative perfection
perfection of
of a
a single crystal
single crystal as
as he
he is
is in
in its
its orientation.
orientation.
All
All things
things considered,
considered, the the Laue methods are are preferable
preferable when only only occa-
occa-
sional orientation determinations
sional orientation determinations are required, or are required, or when there
there is is any
any doubt
as
as toto the perfection of
the perfection of the
the crystal.
crystal. When the the orientations
orientations of of large
large num-
bers
bers of of crystals
crystals have to to bebe determined
determined in in a a routine
routine manner,
manner, the the diffrac-
diffrac-
tometer method is is superior.
superior. In
In fact,
fact, this
this method was developed developed largelylargely
for just such
for just such an an application
application during during World War II, II, when the the orientation
orientation of of
large
large numbers of of quartz
quartz crystals
crystals had to to bebe determined.
determined. These These crystals
crystals
were
were usedused in in radio transmitters to
radio transmitters to control,
control, through
through theirtheir natural
natural frequency
frequency
of
of vibration,
vibration, the
the frequency
frequency of
of the
the transmitted
transmitted signal.
signal. For
For this purpose
this purpose
quartz
quartz wafers
wafers had to
to be
be cut
cut with
with faces
faces accurately parallel
accurately parallel to
to certain
certain crys-
crys-
tallographic
tallographic planes, planes, and the
the diffractometer
diffractometer was used
used to
to determine
determine the
the
orientations of these
orientations of these planes planes in
in the crystal.
the crystal.
240
240 ORIENTATION OF SINGLE CRYSTALS 8
[CHAP. 8
[CHAP.

8-6 Setting
8-5 Setting aa crystal
crystal in
in aa required
required orientation.
orientation. Some x-ray
x-ray investiga-
investiga-
tions require
tions that aa diffraction
require that diffraction pattern
pattern bebe obtained
obtained of
of aa single
single crystal
crystal
having aa specified
having specified orientation
orientation relative
relative to
to the
the incident
incident beam. To obtain
obtain
this orientation,
this orientation, the
the crystal
crystal is mounted in
is in aa three-circle
three-circle goniometer
goniometer like
like
that shown in
that in Fig.
Fig. 5-7,
5-7, whose arcs
arcs have been
been set
set at
at zero,
zero, and its
its orienta-
orienta-
tion is
tion is determined
determined by,
by, for
for example,
example, the
the back-reflection
back-reflection Laue method. A A
projection of
projection of the
the crystal
crystal is
is then
then made,
made, and from this
this projection
projection the
the goni-
goni-
ometer rotations
ometer rotations which
which will
will bring
bring the
the crystal
crystal into
into the
the required
required orientation
orientation
are determined.
are determined.
For example,
For example, suppose
suppose itit is
is required
required to
to rotate
rotate the
the crystal
crystal whose orienta-
orienta-
tion
tion is given
is by Fig.
given by Fig. 8-7
8-7 into
into aa position
position where [Oil] points along
[all] points along the
the inci-
inci-
dent beam and [100]
dent points horizontally
[100] points horizontally to
to the
the left, i.~., into
left, i.e., into the
the standard
standard
orientation shown by
(all) orientation
(Oil) by Fig.
Fig. 2-36
2-36(b) if the
(b) if the latter
latter were
were rotated
rotated 9090
about the
about the center.
center. The initial
initial orientation
orientation (Position
(Position 1) is shown in
1) is in Fig.
Fig. 8-23
by the
by the open
open symbols,
symbols, referred
referred to NSEW-axes. Since (011)
to NSEW-&xes. is to
(01 1) is to be
be brought
brought
to the
to the center
center of
of the
the projection
projection and (100)
(l00) to
to the
the left
left side,
side, (010)
(010) will
will lie
lie on
on
the vertical axis
the vertical axis of
of the projection when the
the projection the crystal
crystal is in its
is in final position.
its final position.
The first
first step
step therefore is to
therefore is to locate
locate aa point
point 9090 away
away from (all)
(Oil) on the
the
great circle joining
great circle joining (010)
(010) to (Oil), because this
to (all), this point
point must coincide with
the north pole
the north pole of
of the
the final projection. This
final projection. This is
is simply
simply a construction point;
a construction point;

FIG. 1'1-23.
FIG. 8-23. Crystal
Crystal rotation
rotation to
to produce
produce specified
specified orientation.
orientation. Positions
Positions 11 and 2
2
are
are indicated
indicated by
by open symhols, position
open symbols, position 3
3 by
by shaded
shaded symbols,
symbols, and
and position
position 4 by
by
solid
solid symbols.
symbols.
8-5]
8-5] SETTING A CRYSTAL IN A
A REQUIRED ORIENTATION 241
241

in
in the
the present
present case case it it happens
happens to to coincide
coincide with the the (OIl)
(Oil) pole, but gen-
pole, but gen-
erally it
erally it is
is ofof no crystallographic
crystallographic significance.
significance. The projection
projection is is then
then
rotated
rotated 22 22 clockwise
clockwise about the the incident-beam
incident-beam axis axis to bring this
to bring point
this point
onto the
the vertical
vertical axis axis of of the underlying
underlying Wulff net. net. (In
(In Fig. 8-23, the
Fig. 8-23, the
latitude
latitude and longitude
longitude lines lines ofof this
this net
net have been omitted for for clarity.)
clarity.) The
crystal is
crystal is now in in Position
Position 2, 2, shown by by open
open symbols
symbols referred
referred to to N'S'E'W'-
N'S'E'W-
axes.
axes. The next rotation rotation is is performed
performed about the
the E'W'-axis,
.EW-axis, which requires
requires
that
that the
the underlying
underlying Wulff
Wulff net
net be
be arranged
arranged with
with its
its equator
equator vertical
vertical so
so that
that
the
the latitude
latitude lines
lines will
will run from top top to
to bottom.
bottom. This rotation,
rotation, of
of 38,
38, moves
all
all poles
poles along
along latitude
latitude lines,
lines, shown as as dashed smallsmall circles,
circles, and bringsbrings
(Oil) to
(011) to the
the N'-pole,
N'-pole, and (100) (100) and (011) (Oil) to the E'W'-axis
to the E'W'-'dxis of of the
the projec-
projec-
tion,
tion, asas indicated
indicated by by the
the shaded symbols
symbols (Position
(Position 3).3). The final
final orienta-
orienta-
tion is obtained
tion is obtained by by a 28 rotation
a 28 rotation about the N'S'-axis, with
the JV'S'-axis, with the equator
the equator
of
of the
the underlying
underlying Wulff net net now horizontal;
horizontal the
;
poles move to
the poles to the positions
the positions
shown by by solid
solid symbols
symbols (Position
(Position 4). 4).
The necessity
necessity for for selecting
selecting a a construction
construction point point 9090 from (011) (Oil) should
should
now be evident. If
be evident. If this point, which here
this point, here happens
happens to be (OIl),
to be (Oil), isis brought
brought
to
to the N'-pole, then
the Af'-pole, then (011)
(Oil) and (100) (100) must of of necessity
necessity lie lie on the
the E'W'-axis;
SW-axis;
the
the final rotation about N'S'
final rotation N'S' will
will then
then move the the latter
latter to to their
their required
required
positions without
positions without disturbing
disturbing the
the position
position of
of the
the (011)
(Oil) pole,
pole, since
since [OIl]
[Oil]
coincides
coincides with the N'S'-axis.
the N'$'-axis.
order of
The order of these
these three
three rotations
rotations is is not
not arbitrary.
arbitrary. The stereographic
stereographic
rotations
rotations correspond
correspond to
to physical
physical rotations
rotations on the
the goniometer
goniometer and must be be
made in in such
such a a way
way that.
that one
one rotation
rotation does
does not
not physically
physically alter
alter the
the position
position
of
of any
any axis
axis about
about which which a a subsequent
subsequent rotation
rotation is is t.o
to be
be made. The goni- goni-
ometer used here here was initially
initially set
set with the the axis
axis ofof its
its uppermost
uppermost arc arc hori-
hori-
zontal
zontal and coincident
coincident with with the primary beam,
the primary beam, and with with thethe axis
axis ofof the
the
next
next arc horizontal and at
arc horizontal at right
right angles
angles to to the
the incident
incident beam. The first first

rotation
rotation about the the beam axis axis there-
there-
fore
fore did
did notnot disturb
disturb the the position
position of of
the
the second
second axis (the E'W'-axis)
axis (the UW-axis),, and
neither
neither of of the
the first
first two rotations
rotations dis-dis-

FIG.
FIG. 8-24.
8-24. Back-reflection
Back-reflection Laue pat-
Laue pat-
tern
tern of
of an aluminum crystal.
crystal. The in-
in-
cident
cident beam is parallel to
is parallel to [011],
[Oil], [OIl]
[Oil]
points vertically
points vertically upward,
upward, and
and [100]
[100] points
points
vertically
vertically to
to the
the left.
left. Tungsten
Tungsten radia-
radia-
tion, 30
tion, 30 kv,
kv, 19
19 ma,
ma, 40
40 min exposure,
exposure, 55 cm
specimen-to-film
specimen-to-film distance.
distance. (The
(The shadow
shadow
at
at the
the bottom is is that
that of
of the
the goni-
goni-
ometer
ometer which
which holds
holds thethe specimen.)
specimen.)
242
242 BINGLE CRYSTALS
ORIENTATION OF SINGLE (ClJIA.,. 88
[CHAP.

turbed the
turbed the position
position of
of the
the third
third axis
axis (the
(the vertical N'B'-axis). Whether or
vertical WS'-axis). or
not the
not the stereographic
stereographic orientations
orientations are
are performed
performed inin the
the correct
correct order
order makes
a great
a great difference
difference in
in the
the rotation
rotation angles
angles found,
found, but
but once
once the
the right
right angles
angles
are determined
are determined by the
by the correct stereographic
correct stereographic procedure,
procedure, the
the actual
actual physical
physiClll
rotations on
rotations on the
the goniometer
goniometer may
may be
be performed
performed in
in any
any sequence.
sequence.
back-reflection Laue
The back-reflection Laue pattern
pattern of
of an
an aluminum crystal
crystal rotated
rotated into
into
the orientation
the orientation described
described above
above is in Fig.
is shown in Fig. 8-24.
8-24. Note that
that the
the
arrangement of
arrangement of spots
spots has
has 2-fold
2-fold rotational
rotational symmetry
symmetry about
about thethe primary
primary
beam, corresponding
beam, corresponding to
to the
the 2-fold
2-fold rotational
rotational symmetry
symmetry of
of cubic
cubic crystals
crystals
about their (110) axes. (Conversely,
about their (110) axes. (Conversely, the
the observed
observed symmetry
symmetry of
of the
the Laue
pattern of a crystal
pattern of a crystal ofof unknown structure
structure is
is an
an indication
indication of
of the
the kind
kind of
of
symmetry possessed by
symmetry possessed by that
that crystal.
crystal. Thus the
the Laue method can can be
be used
used
as an
as an aid in the
aid in the determination
determination of
of crystal
crystal structure.)
structure.)
There is another
There is another method ofof setting a crystal
setting a in aa standard
crystal in standard orientation,
orientation,
which does
which not require
does not require either
either photographic
photographic registration
registration of
of the
the diffraction
diffraction
pattern or
pattern or stereographic
stereographic manipulation of the
manipulation of the data.
data. It depends on
It depends on the
the fact
fact
that the
that the diffracted beams formed in
diffracted beams in the
the transmission
transmission Laue method are
are so
so
intense, for
intense, for aa crystal
crystal ofof the
the proper
proper thickness,
thickness, that the spots
that the spots they
they form on a a
fluorescent
fluorescent screen
screen are
are visible
visible inin aa dark room.
room. The observer merely rotates
observer merely rotates
the
the crystal
crystal about
about the various arcs
the various of the
arcs of the goniometer
goniometer until the pattern
until the pattern cor-
cor-
responding
responding to to the
the required
required orientation
orientation appears
appears on the
the screen.
screen. Obviously,
Obviously,
he must be
he must be able
able toto recognize
recognize this pattern when it
this pattern it appears,
appears, butbut a a little
little

study
study of
of aa few
few Laue
Laue photographs
photographs made of of crystals
crystals in
in standard
standard orientations
orientations
will
will enable
enable him to to do
do this.
this. The necessity
necessity for
for working
working in in a
a darkened
darkened room
may
may bebe avoided
avoided by by use
use of
of a a light-tight
light-tight viewing box, if
viewing box, if the job of
the job of crystal
crystal
setting
setting occurs
occurs sufficiently
sufficiently often
often to justify its
to justify its construction.
construction. This This box en-
en-
closes
closes the
the fluorescent
fluorescent screen
screen which
which thethe observer
observer views
views through
through a a binocular
binocular
eyepiece
eyepiece set
set in
in the
the wall
wall ofof the
the box,
box, either
either directly
directly along
along thethe direction
direction ofof
the
the transmitted
transmitted beam,
beam, or
or indirectly
indirectly in
in a
a direction
direction at
at right angles
right angles by by means
of
of a
a mirror
mirror oror a
a right-angle
right-angle prism.
prism. For x-rayx-ray protection,
protection, the the optical
optical system
system
should
should include
include lead
lead glass,
glass, and the
the observer's
observer's hands should
should be
be shielded
shielded
during manipulation of
during manipulation of the
the crystal.
crystal.

8-6
8-6 The effect
effect of
of plastic
plastic deformation.
deformation. Nowhere have x-ray x-ray methods
been
been more fruitful
fruitful than
than in
in the study of
the study of plastic
plastic deformation.
deformation. The way way inin
which aa single
single crystal
crystal deforms
deforms plastically
plastically isis markedly
markedly anisotropic,
anisotropic, and
almost
almost all
all of
of our
our knowledge
knowledge of of this
this phenomenon
phenomenon has has been
been gained
gained byby x-ray
x-ray
diffraction
diffraction examination
examination of of crystals
crystals atat various
various stages
stages during
during plastic
plastic defor-
defor-
mation.
mation. At the the out.set
outset we can
can distinguish
distinguish between
between twotwo kinds
kinds of
of deforma-
deforma-
tion,
tion, that
that of
of the
the crystal
crystal lattice
lattice itself
itself and
and that
that of
of the
the crystal
crystal as
as aa whole.
whole.
This distinction is
This distinction is worth
worth while
while because
because crystal deformation,
crystal deformation, defined
defined as
as aa
change
change in
in the
the shape
shape of
of the
the crystal
crystal due
due to
to lattice
lattice rotation,
rotation, can
can occur
occur with
with
or
or without
without lattice
lattice deformation,
deformation, defined
defined as
as the
the bending
bending and/or
and/or twisting
twisting ofof
8-6)
8-6] THE EFFECT OF PLASTIC DEFORMATION 243
243

originally
originally flat flat lattice
lattice planes.
planes. On the otherother hand, hand, lattice
lattice deformation
cannot occur without some deformation of of thethe crystal
crystal as as aa whole.
whole.
A crystal
crystal lattice
lattice can therefore
therefore behave in in two quitequite different
different waysways during
during
plastic deformation it
plastic deformation: : it can simply
simply rotate
rotate without undergoing
undergoing deformation
deformation
itself, or it
itself, or it can become bent and/or and/or twisted.
twisted. Laue photographs
photographs can easily easily
decide
decide between these these two possibilities.
possibilities. In
In thethe Laue method,method, any any change
change
in
in the orientation of
the orientat.ion of the
the reflecting
reflecting planes
planes is is accompanied
accompanied by by aa correspond-
correspond-
ing change
ing change in
in the
the direction
direction (and wavelength)
(and wavelength) of
of the
the reflected
reflected beam. In
fad,
fact, Laue refle(tion
reflection of
of x-rays
x-rays is
is oft.en
often compared
compared to
to the
the refledion
reflection of
of visible
visible
light
light byhy a
a mirror.
mirror. If
If t.he
the latti('e
lattice simply
simply rotates
rotates during
during deformation, then
deformation, then
Lam'
Laue patt.E'rns
patterns madE'
made hefore
before and after
after will
will merely
merely show a
a ehange
change in
in the
the
position
position of
of the
the diffra(,tion
diffraction SPOt.IS, ('orresponding
spots, corresponding to
to t.he
the ('hange
change in
in orientation
orientation
of
of the lattice, hut
the latti('p, but thethe spots themselves will
spots themlSplV('s will remain
remain sharp.sharp. On the the other
other
hand, if thE'
hand, if the lat.ti('E'
lattice is hent
is bent or twisted,
or twisted, the the Laup spots
Laue spots will he('ome
will become smeared
out
out into
into strE'aks
streaks hecause
because of the continuous chanj!;e
of the change in in orientation
orientation of of the
the
reflecting planE'S,
reflecting just alS
planes, just as aa spot
spot of of light
light rpflccted
reflected hy by aa flat
flat mirror
mirror hecomes
becomes
elongated wllPn
elongated when the the mirror is is curved.
curved.
A (-lassie
classic E'xamplE'
example of of l'limple
simple lattice
lattice rotation
rotation during
during crystal
crystal deformation
is
is afford('(l
afforded hy by the
the tE'nl'lilp
tensile elongation
elongation of of long
long eylindrical
cylindrical single
single metal crystals.
crystals.
When l'lu('h
such a a ('rystal
crystal is is E'xtended
extended plastieally,
plastically, Laue photog"aphs
photographs of of the
the
cent.er
center sedion
section made l)('fore before and aftpr after the
the extE'nsion
extension show that that thethe lattice
lattice
has bE'en
has been rotatE'd
rotated hutbut not not dE'formpd.
deformed. Yet the the ('rYlStal
crystal it.self
itself has
has undergone
undergone
considerable
considerable deformation
deformation as as pyidence
evidence by by its
its ('hange
change in
in shape-it
shape it has has be-be-
pomE'
come longer
longer and t hinnpr.
thinner. How this
this occurs
occurs is
is !'mggE'sted
suggested by Fig.by Fig. 8-25.
8-25.
Thp initial form of
The initial of thc'
the ('rystal
crystal is is IShown
shown in in (a),
(a), with
with the potential slip
the potential slip
planes
planes SE'E'n
seen in
in profilp.
profile. Thp
The applipd
applied tpnsilp
tensile for('Pl'l
forces ('an
can hp
be rp:;olved
resolved intointo

__ bendmg
^ bonding
.

r, , ___ rotlitlOn
\ '
\

bonding

t
,
?

(al (b)
(b) (e)
Co

P'iG. 8-25.
FIG. 8-25. Slip in
Hlip in tension
tension (schemati(').
(schematic).
244 ORIENTATION OF SINGLE CRYSTALS [CHAP. 8
[CHAP. 8

shearing
shearing forces
forces parallel
parallel to to these
these slip planes and tensile
slip planes tensile forces
forces normal to to
them. The normal normal forces forces have no effect, effect, but the the shearing
shearing forcesforces cause
cause
slip to
slip to occur,
occur, and the the crystal
crystal would,
would, as as a result,
result, assume the the shape
shape shown
in
in (b)
(b) if
if the
the ends
ends were not
not constrained
constrained laterally.
laterally. However,
However, the grips of
the grips of
the
the tensile
tensile machine keep keep the
the ends
ends of
of the
the crystal aligned, causing
crystal aligned, causing bending bending
of
of the
the crystal
crystal lattice
lattice nearnear eacheach grip,
grip, as as indicated
indicated in in (c),
(c), which illustrates
illustrates
the
the appearance
appearance of
of the
the crystal
crystal after
after considerable
considerable extension.
extension. Note that.
that thethe
lattice of
lattice of the
the central portion has
central portion has undergone
undergone reorientation
reorientation but not
not dist.or-
distor-
tion.
tion. This
This reorientation
reorientation clearly clearly consists
consists in in a a rotation
rotation whi('hwhich makes the the
active
active slip plane more nearly
slip plane parallel to
nearly parallel to the
the tension
tension axis.
axis.

Analysis
Analysis of of the
the Laue patterns patterns yields
yields further informat.ion about the
further information the
deformation
deformation process.
process. The changes changes in in orientation
orientation which o('cur occur in in the
the cen-
cen-
tral
tral section
section cancan be be followed
followed stereographically,
stereographically, either either by by plotting
plotting the the before
before
and after orientations of
after orientations of the
the crystal
crystal on a a fixed
fixed proje('t,ion
projection plane, plane, or or byby
plotting
plotting the the before
before and after after orientations
orientations of of the
the specimen
specimen axis axis inin the
the unit
unit
stereographic
stereographic triangle.
triangle. latter method is
The latter is the
the more common one one and
is
is illustrated
illustrated by Fig.
by Fig. 8-26,8-26, which
which applies
applies to
to a
a fa(,f'-eentered
face-centered ('ubi('
cubic ('rystal.
crystal.
The initial position of
initial position of the
the tension
tension axis
axis isis represf'nted hy
represented by point point 1.
1. After
After
successive
successive extensions,
extensions, the
the position
position of
of this
this axis
axis is
is found to
to be
be at.
at point.s
points
2,
2, 3,
3, 4,4, ... ; i.e.,
. . .
i.e.,
;
the
the axisaxis moves
along
along a a great
great circle passing through
circle passing through
the
the initial position and the
initial position the direction
direction
[101],
[T01], which is is the
the direction
direction of of slip.
slip.
During
During this this extension
extension the the active
active slip
slip
plane
plane is (111). We can
is (111). can conclude
conclude that that
the
the lattice
lattice reorientation
reorientation occurs occurs in in such
such
way that
aa way that both
both the the slip plane and
slip plane
the
the slip ef------
slip direction
direction in in t.hat plane rotate
that plane rotate
001
toward
toward the the axis
axis of of tension.
tension. This This
process
process becomes more complicated
complicated at at
later
later stages
stages of
of the
the deformation,
deformation, and
the
the interested
interested readerreader is is referred
referred to to
books on crystal
books crystal plasticity
plasticity for for further
further ~hJl
slip plulIl'
plane -NAiii
details.
details. Enough
Enough has has beenbeen saidsaid here
here
FIG. 8-26. Lattice
FIG. 8-26. Lattice rotation
rotation during
to
to indicate
indicate the the way way in in which
which x-ray
x-ray during
slip
slip inin elongation
elongation of of FCC metal metal crys-
crys-
diffraction
diffraction may may be be applied
applied to to this
this
tal.
tal.
particular
particular problem.
problem.
One other
other example
example of of lattice
lattice reorientation
reorientation during during slip slip may
may be be given
given in in
order
order toto illustrate
illustrate the alternate method of
the alternate plotting the
of plotting the data.
data. In In Fig. 8-27,
Fig. 8-27,
the successive
successive orientations
orientations which a a cylindrical
cylindrical magnesium
magnesium crystal crystal assumes
assumes
during plastic
during plastic torsion
torsion are
are plotted
plotted on
on a
a fixed
fixed projection
projection plane parallel to
plane parallel to the
the
specimen
specimen axis
axis (the
(the axis
axis of
of torsion).
torsion). Since
Since the
the poles
poles of
of reflecting planes
reflecting planes
are
are found to to move along along latitude
latitude circles
circles on on the projection, it
the projection, it follows
follows thatthat
8-6)
8-6] THE EFFECT OF PLASTIC DEFORMATION 245
245
N
-SPECIMEN
-- SPECIMEN AXIS

I __ -
-r---
I

--- --- _L _____ ----

I

s
o INITIAl /l. AFTER TWIST OF 22 0
AFTER TWIST OF gO X AFTER TWIST OFOF 11
11
0

FIG. 8-27. Change

FIG. 8-27. Change in in lattice
lattice orientation
orientation during plastic torsion
during plastic torsion of
of a
a magnesium
magnesium
crystal.
crystal. The active
active slip plane is
slip plane is (0001),
(0001), the
the basal plane of
basal plane of the
the hexagonal
hexagonal lattice.
lattice.
(S.
(S. S.
S. Hsu and
and B.
B. D.
D. Cullity,
Cullity, Trans. A.I.M.E. 200,
Trans. A.I.M.E. 200, 305,
305, 1954.)
1954.)

the
the lattice
lattice reorientation
reorientation is is mainly
mainly one of of rotation
rotation about the the specimen
specimen axis.
axis.
Some lattice
lattice distortion
distortion alsoalso occurs,
occurs, since
since special
special x-rayx-ray methods reveal
reveal
that
that twisting
twisting of of the
the lattice
lattice planes
planes takes
takes place,
place, but the the main feature
feature of of the
the
deformation
deformation is is the
the lattice
lattice rotation
rotation described
described above.
above. Similarly,
Similarly, in in the
the
plastic
plastic elongation
elongation of of single
single crystals,
crystals, itit should
should not
not be be supposed
supposed that
that abso-
abso-
lutely
lutely no lattice
lattice deformation occurs.occurs. Here again
again the feature is
the main feature is lattice
lattice
rotation,
rotation, but sensitive
sensitive x-ray
x-ray methods will will always
always show some bending bending or or
twisting
twisting ofof lattice
lattice planes,
planes, and in in some cases
cases this
this lattice distortion may
lattice distortion may be
so severe that
so severe that ordinary
ordinary Laue patterns
patterns will
will reveal
reveal it.it.

A good example
good example of
of severe
severe lattice
lattice distortion
distortion is
is afforded
afforded by those
by parts of
those parts of
aa single-crystal
single-crystal tension
tension specimen immediately
specimen immediately adjacent adjacent to
to the
the grips.
grips. As
mentioned earlier,
earlier, these portions of
these portions of the
the crystal
crystal lattice
lattice are
are forced
forced toto bend
during elongation
during elongation of
of the
the specimen,
specimen, and Laue photographs
photographs made of
of these
these
sections
sections will
will accordingly
accordingly show elongated spots.
elongated spots. If
If the
the bending
bending is
is about a
single axis, the Miller indices of the
single axis, the Miller indices of the bending bending axis
axis can usually
usually be
be determined
246
246 ORIENTATION OP SINGLE CRYSTALS
OF SINGLE 8
[CHAP. 8
[CHAP.

(a)
(a) Transmission
Transmission (b)
(b) reflection
Back reflection

FIG. 8-28.
FIG. 8-28. Laue photographs
Laue photographs of
of aa deformed
deformed aluminum crystal.
crystal. Specimen-to-
Specimen-to-
film distance
film distance 3
3 em, tungsten radiation,
cm, tungsten radiation, 30
30 kv.
kv.

stereographically;
stereographically; each Laue streak
each Laue streak is plotted as
is plotted as an arc arc representing
representing the the
range
range of
of orientation
orientation of
of the
the corresponding
corresponding lattice
lattice plane,
plane, and a rotation
rotation axis
axis
which will account
which will account for for the directions of
the directions of these
these arcs
arcs on on the
the projection
projection is is

found. The angular

found. angular lengths
lengths of
of the
the arcs
arcs are
are a
a measure of
of the
the amount of
of
bending
bending which
which has has occurred.
occurred. In
In measuring
measuring the the amount of of bending
bending by by
this
this method,
method, it
it must
must be
be remembered that
that the
the wavelengths
wavelengths present
present in
in the
incident
incident beam do do not cover an infinite
not cover infinite range.
range. There is is no radiation
radiation of of
wavelength
wavelength shorter
shorter than
than the
the short-wavelength
short-wavelength limit,
limit, and on the
the long-
long-
wavelength
wavelength side side thethe intensity
intensity decreases
decreases continuously
continuously as as the
the wavelength
wavelength
increases:
increases.- This means that,
This that, for
for a
a given degree
given degree of
of lattice
lattice bending,
bending, some
streaks may
Laue streaks may not
not be
be as
as long
long as
as they might
they might be if
if a
a full
full range
range of of wave-
lengths
lengths were
were available.
available. The amount of
of bending
bending estimated from the
the lengths
lengths
of
of these
these streaks
streaks would
would therefore
therefore be smaller than that
be smaller that actually present.
actually present.
Transmission
Transmission and back-reflection
back-reflection Laue patterns patterns made from the the same
deformed
deformed region usually
region usually differ
differ markedly
markedly in
in appearance.
appearance. The photographs
photographs
in
in Fig.
Fig. 8-28
8-28 were
were made,
made, under
under identical
identical conditions,
conditions, of of the
the same regionregion ofof a
deformed aluminum crystal having
crystal having the
the same orientation
orientation relative
relative to
to the
the
incident
incident beam for for each
each photograph.
photograph. Both show elongated
elongated spots, spots, which
are
are evidence
evidence of of lattice bending, but
lattice bending, but the
the spots
spots areare elongated
elongated primarily
primarily in in a
radial
radial direction
direction on on the transmission pattern
the transmission pattern while
while on
on the
the back-reflection
back-reflection
pattern
pattern they
they tend
tend toto follow
follow zone
zone lines.
lines. The term term asterism
asterism (from(from the the Greek
aster
aster == star)
star) was used
used initially
initially to
to describe
describe the
the starlike
starlike appearance
appearance of of a
transmission pattern
transmission pattern such
such as
as Fig. 8-28 (a)
Fig. 8-28 (a), but, but it
it is
is now used
used to
to describe
describe any
any
form ofof streaking,
streaking, radial
radial or
or nonradial,
nonradial, on either kind
either kind of of Laue photograph.
photograph.
The striking
striking difference
difference between these photographs is
these two photographs is best
best under-
under-
stood by considering a very general case. Suppose a crystal is so deformed
stood by considering a. very general case. Suppose a. crystal is so deformed
8-6] THE EFFECT OF PLASTIC
PLASTIC DEFORMATION 247
247

film

.1

FIG. 8-29. Effect

FIG. 8-29. Effect of
of lattice
lattice distortion
distortion FIG. 8-30. Effect
FIG. 8-30. Effect of
of lattice
lattice distortion
distortion
on the shape of
the shape of a
a transmission
transmission Laue on the shape of
the shape of a
a back-reflection
back-reflection Laue
spot.
spot. CN isis the
the normal
normal toto the
the reflect-
reflect- spot. CN is
spot. is the
the normal toto the
the reflecting
reflecting
ing
ing plane.
plane. plane.
plane.

that
that thethe normal to to aa particular
particular set set ofof reflecting
reflecting lattice
lattice planes
planes describes
describes a
small
small cone
cone ofof apex angle 2E;
apex angle 2e; i.e., i.e., in
in various
various parts
parts of
of the
the crystal
crystal the
the normal
deviates
deviates by by an angle
angle E
c in
in all
all directions
directions from
from its
its mean position.
position. This is
is

equivalent
equivalent to
to rocking
rocking a
a flat
flat mirror
mirror through
through the
the same angular range
angular range and, and,
as
as Fig.
Fig. 8-29 shows,
shows, the
the reflected
reflected spot spot S is is roughly
roughly elliptical
elliptical on a film
film placed
placed
in
in the
the transmission
transmission position.
position. When the
the plane
plane normal rocks
rocks through
through thethe
angle
angle 2E
2c in
in the
the plane ACN,
plane ACN, the
the reflected
reflected beam moves through
through an angle
angle 4E,
4c,
and
and thethe major
major axis
axis of
of the
the ellipse
ellipse is
is given
given approximately by t(AC) when
approximately by 4E(AC)
26 is
28 is small.
small. On the the other
other hand,
hand, when the the plane
plane normal rocksrocks through
through the
the
angle
angle 2E
2e in
in a
a direction
direction normal to
to the
the plane
plane of
of reflection
reflection ACN, the
the only
only
effect
effect isis to
to rock
rock the
the plane
plane of of reflection
reflection through
through the same angle 2c about
angle 2E
the
the incident
incident beam.
beam. The minor axis axis of of the
the elliptical
elliptical spot
spot isis therefore
therefore given
given
by 2E(AS)
by 2e(AS) ~ 2E(AC)
2e(AC) tan
tan 28
26 ~ 2E(AC)28.
2e(AC)26. The shape
shape of
of the
the spot
spot is
is charac-
charac-
terized
terized by by the
the ratio
ratio
Major
Major axis axis 4E(AC) 1
----=-.
Minor axis axis 2E(AC)28
2e(AC)26 86
26 = 10,
For 28 10, the
the major
major axis
axis is
is some 12
12 times
times the
the length
length of
of the
the minor axis.
axis.
248
248 ORIENTATION OF SINGLE CRYSTALS [CHAP. 8
[CHAP. 8

In the
the back-reflection
back-reflection region,
region, the situation
situation is is entirely
entirely different
different and the the
spot S is
spot is roughly
roughly circular,
circular, as
as shown in in Fig.
Fig. 8-30.
8-30. Both axes of of the
the spot
spot
subtend an angle
angle ofof approximately
approximately 4E 4c atat the
the crystal.
crystal. We may therefore
therefore
conclude
conclude that
that the
the shape
shape ofof aa back-reflection
back-reflection spotspot isis more directly
directly related
related
to
to the
the nature
nature ofof the
the lattice
lattice distortion
distortion than is is the shape
shape of of a
a transmission
transmission
spot
spot since,
since, in
in the
the general
general case,
case, circular
circular motion of of the
the end of of the
the reflecting
reflecting
plane normal causes
plane causes circular
circular motion of of the
the backward-reflected
backward-reflected beam but but
elliptical
elliptical motion of of the
the forward-reflected
forward-reflected beam. For this reason, the
this reason, back-
the back-
reflection
reflection method is is generally
generally preferable
preferable forfor studies
studies of of lattice
lattice distortion.
distortion.
It
It must not
not be supposed,
supposed, however,
however, that
that only
only radial
radial streaking
streaking is possible on
is possible

transmission patterns. The direction

transmission patterns. direction ofof streaking
streaking depends
depends on the orienta-
orienta-
tion of the axis
tion of axis about which the the reflecting planes are
reflecting planes are bent and if, if, for
for exam-
ple,
ple, they
they are
are bent only
only about an axisaxis lying
lying inin the plane ACN of
the plane of Fig.
Fig. 8-29,
8-29,
then the
the spot
spot will
will be elongated
elongated in in a
a direetion
direction at right angles
at right angles to
to the
the radius
radius
AS.
^

\x
t"IlIml(pd
enlaiged
\\ LallP
Laue hpot
spot ---,..
spot ---e
Laue ~pot ^^ \\
-

Deb\ e a ic -

J)oteut13J
potential _____ ---/
-*-
'

D('hye
Debye nUl(
ring I/

(a) e
(a) ndt'forllled
Undeformed (Ty~taI
crystal (l>) Deformed cnstal
FIG.
FIG. 8-31.
8-31. Formation of
of Debye
Debye arcs
arcs on
on Laue
Laue patterns
patterns of
of deformed
deformed crystals.
crystals.

One feature
feature ofof the
the back-reflection pattern of
back-reflection pattern of Fig.
Fig. 8-28
8-28 deserves
deserves some
comment, namely, the short
comment, namely, short arcs,
arcs, concentric
concentric with
with the
the film
film center,
center, which
pass
pass through
through many
many of of the
the elongated
elongated Laue spots.
spots. These areare portions
portions ofof
Debye
Debye rings,
rings, such asas one might
might expect
expect on a a pinhole photograph made of
pinhole photograph of a
a
polycrystalline
polycrystalline specimen
specimen with with characteristic
characteristic radiation
radiation (Rec.
(Sec. (i-9).
6-9). With
aa polycrystalline
polycrystalline specimen
specimen of of random orientation
orientation a a complete
complete Debye
Debye ring
ring
is
is formed,
formed, because the the normals to to any particular set
any particular set of planes (hkl)
of planes (hkl) have
all
all possible
possible orientations
orientations in in space;
space; in
in aa deformed single crystal, the
single crystal, the same
normals are restricted to
are restricted to a finite
finite range
range ofof orientations
orientations with the the result
result that
that
only
only fragments
fragments of of Debye
Debye rings
rings appear.
appear. We may may imagine
imagine a a circle
circle on the
the
film
film along
along which a a Debye
Debye ring
ring would form if if a polycrystalline specimen
a polycrystalline specimen
were used,
used, as
as indicated
indicated inin Fig. 8-31. If
Fig. 8-31. If a
a Laue spot
spot then
then becomes enlarged
enlarged
as a result
result of lattice deformation and spreads
of lattice spreads over
over the potential Debye
the potential Debye
ring,
ring, then a short
short portion
portion of of a
a Debye
Debye ring
ring will
will form.
form. It It will be much
will be
darker than the Laue spot, spot, since
since the
the characteristic radiation** which
characteristic radiation which
* In Fig.
Fig. 8-28(b),
8-28(b), the
the characteristic
characteristic radiation
radiation involved
involved is
is tungsten
tungsten L radiation.
radiation.
The voltage
voltage used (30
(30 kv)
kv) is
is too
too low
low to
to excite
excite the K lines
the K lines of
of tungsten
tungsten (excitation
(excitation
voltage
voltage = = 70 kv)
kv) but
but high
high enough
enough to
to excite
excite the
the L lines
lines (excitation voltage =
(excitation voltage =1212
kv).
kv).
8-6J
8-6] THE EFFECT
THE EFFECT OF PLASTIC DEFORMATION
OF PLASTIC DEFORMATION 249
249

1111'/1'1 : : ; : : . . . - - - - - - . [1/1'1/'1-------
BE:,\T
HKXT POLYGOMZKD
POLH:O:,\!ZED

FIG. 8-32.
FlG. 8-32. Reflection of
Reflection of white
white radiation
radiation by bent
by bent and
and polygonized
polygonized lattices
lattices
(schematic) .
(schematic).

forms
forms it is
it is much more more intense
intense than than thethe wavelengths
wavelengths immediately
immediately adjacent
adjacent
to
to it in
it in thethe continuous
continuous spectrum.spectrum. In In fact,
fact, ifif the
the x-ray
x-ray exposure
exposure is is not
not
sufficiently long,
sufficiently long, only only the
the Debye
Debye arc~
arcs may
may be
be visible
visible on
on the
the film,
film, and the
the
observer may
observer may be be led
led to to erroneous
erroneous conclusions
conclusions regarding
regarding the the nature
nature andand
extent of
extent of thethe lattice
lattice deformation.
deformation.
With these
With these facts
facts inin mind,
mind, re-examination
re-examination of of the
the patterns
patterns shown in in Fig.
Fig.
8-28 leads
8-28 leads to to the
the following
following conclusions:
conclusions:
(1)
(1) Since
Since the the asterism
asterism on on the
the transmission
transmission pattern pattern is is predominantly
predominantly
radial,
radial, lattice
lattice planes
planes inclined
inclined at
at small
small angles
angles to
to the incident
incident beam are bent bent
about
about a a number of of axes,
axes, in
in such
such a
a manner that their
their plane
plane normals are
are

confined to
confined to aa small
small cone
cone in in space.
space.
(2)
(2) Since
Since the the asterism
asterism on on the
the back-reflection
back-reflection pattern pattern chiefly
chiefly follows zone
lines,
lines, the
the major portion
major portion of
of planes
planes inclined
inclined at
at large
large angles to the incident
angles
beam
beam are are bent bent about
about aa singlesingle axis.
axis. However,
However, the the existence
existence of of Debye arcs arcs
shows
shows that
that there
there are
are latent
latent Laue spots
spots of
of considerable
considerable area superimposed
superimposed
on
on the
the visible
visible elongated
elongated spots, spots, and that that a a small
small portion
portion of of the planes
planes
referred to
referred to are
are therefore
therefore bent bent about
about aa number of of axes.
axes.
On annealing
annealing aa deformeddeformed crystal crystal at at aa sufficiently
sufficiently highhigh temperature,
temperature, one one
of
of the
the following
following effects
effects is
is usually produced:
usually produced:
(1) Polygonization. If
(1) Polygonization. If thethe deformation
deformation is is not too severe,severe, plastically
plastically
bent
bent portions
portions of
of the
the crystal
crystal break
break up
up into
into smaller
smaller blocks,
blocks, which
which are
are strain-
strain-
free and
free and disoriented
disoriented by approximately
by approximately the
the same
same total
total amount
amount (never
(never more
more
than a few
than a few degrees) degrees) as
as the
the bent
bent fragment
fragment from
from which
which they
they originate, as
originate, as
suggested
suggested by Fig.by Fig. 8-32.
8-32. (The
(The term
term "polygonization"
"polygonization" describes
describes the
the fact
fact
that
that aa certain
certain crystallographic
crystallographic direction direction [uvw] [uvw] forms
forms partpart ofof an
an arc
arc before
before
annealing and
annealing and part part of
of aa polygon afterwards.)
polygon afterwards.) Moreover, Moreover, the
the mean
mean orienta-
orienta-
tion
tion ofof the
the blocks
blocks is is the
the same
same as as that
that of of the
the parent
parent fragment.
fragment. The The effect
effect

of polygonization on a
of polygonization on a Laue pattern Laue pattern is
is therefore
therefore to
to replace
replace an
an elongated
elongated
Laue
Laue streak
streak (from (from the the bent
bent lattice)
lattice) withwith aa rowrow of of small
small sharp
sharp spots
spots (from
(from
the
the individual
individual blocks)blocks) occupying
occupying the the same
same position
position on on the
the film,
film, provided
provided
each
each block
block is is sufficiently
sufficiently disoriented
disoriented from from its its neighbor
neighbor so so that
that the
the beams
beams
250
250 ORIENTATION OF
ORIENTATION SINGLE CRYSTALS
OF SINGLE CRYSTALS [CHAP 88
[CHAP

:a)
FIG. 8-33.
FIG. 8-33. Enlarged
Enlarged transmission
transmission Laue
Laue
spots from
spots from aa thin
thin crystal
crystal of
of silicon
silicon fer-
fer-
rite (a-iron
rite (a-iron containing
containing 3.3
3.3 percent
percent silicon
silicon
(b) in solid
in solid solution)
solution): (a)
(a) as
: as bent
bent to
to aIi radius
radius
of f
of f in.,
in., (b)
(b) after
after annealing
annealing 1010 min
min atat
950C, (c)
950C, (c) after
after annealing
annealing 44 hr
hr at
at 1300C.
300C.1

(C. G.
(C. G. and F.
Dunn and F. W. Daniels, Trans.
Daniels, Trans.
(e)
(c) A.I.M.E. 191,
A.I.M.E. 191, 147,
147, 1951
1951 ))

reflected
reflected by adjoining
by adjoining blocks
blocks are
are resolved
resolved one
one from another.
another. Figure 8-33
Figure 8-a3
shows an example
shows an example of polygonization
of polygonization in
in aa crystal
crystal of
of silicon
silicon ferrite.
ferrite.
(2) Recrystalhzalion.
(2) Recrystalltzation. If If the
the deformation
deformation is is severe
severe enough,
enough, the
the crystal
crystal
may recrystallize
may recrystallize into
into aa new set of strain-free
set of strain-free grains
grains differing
differing completely
completely
in orientation
in orientation from
from the
the original
original crystal.
crystal. The appearance
appearance ofof the
the diffraction
diffradion
pattern
pattern then
then depends
depends on
on the
the size
size of
of the
the new grains
grains relative
relative to
to the cross-
the cross-
sectional area
sectional area of
of the
the incident
incident x-ray
x-ray beam. The appearance
appearance ofof such
such pat-
pat-
terns is
terns is discussed
discussed and illustrated
illustrated in
in Sec.
Sec. 9-2.
9-2.

8-7 Relative
8-7 Relative orientation
orientation of of twinned
twinned crystals.
crystals. In this this and the the next
next sec-
sec-
tion
tion we shall consider, not single
shall consider, not single crystals, crystals, but
but pairs
pairs of
of crystals
crystals which are
are
naturally associated
naturally associated one one with
with another
another in in certain
certain particular
particular ways.
ways. Twinned
crystals
crystals are
are obvious examples of
obvious examples of such
such pairs:
pairs: the
the two parts
parts of of the twin have
different orientations, but
different orientations, but there
there is is aa definite
definite orientation
orientation relationship
relationship be-
tween
tween thethe two.
two. Furthermore,
Furthermore, the the two parts parts are
are united on a plane, plane, the
composition plane,
composition plane, which
which is
is also
also fixed
fixed and invariable,
invariable, not merely
merely a random
surface
surface of of contact
contact suchsuch asas that
that between two adjacent adjacent grains
grains inin a poly-
poly-
crystalline
crystalline mass.
mass. Twinned crystah;
crystals therefore
therefore present
present a twofold problem,
problem,
that
that ofof determining
determining the the orientation
orientation relationship
relationship and that of of determining
determining
the
the indices
indices ofof the
the composition
composition plane. plane.
The orientation relationship is
orientation relationship is established
established by by finding
finding the orientation
orientation of of
each part of the
each part of the twin twin and plotting
plotting the
the two together
together on the same stereo-
stereo-
graphic
graphic projection.
projection. Determination
Determination of of the
the composition-plane
composition-plane indices indices re-
re-

quires
quires a a knowledge
knowledge of of how to to plot
plot the
the trace,
trace, oror line
line of
of intersection,
intersection, of of one
plane
plane in in another,
another, andand we must digressdigress at at this
this point
point toto consider
consider that
that problem.
problem.
~pose
Suppose that,that, onon the
the polished
polished surface
surface of of a twinned grain,grain, the trace
trace of
of the
composition
composition plane plane makes an
an angle
angle aa with some reference
reference line
line NS
NS,
t
as
as shown
in
in Fig.
Fig. 8-34(a).
8-34(a). Then,Then, if if we make the the projection
projection plane
plane parallel
parallel to the
plane
plane of
of polish,
polish, the
the latter
latter will
will be
be represented
represented by by the
the basic
basic circle
circle of
of the pro-
pro-
jection
jection and
and any
any directions
directions in
in the
the plane
plane of
of polish by diametrically
polish by diametrically oppositeopposite
points
points on on the
the basic
basic circle.
circle. Thus,
Thus, in in Fig.
Fig. 8-34(b), the N-
8-34 (b), the AT- and
and S-poles
$-poles repre-
repre-
sent the reference line
sent the reference line NS and NS and the
the points
points A and B,
B, located
located at
at an angle
angle aa
8-7J
8-7] RELATIVE ORIENTATION
RELATIVE TWINNED CRYSTALS
OF TWINNED
ORIENTATION OF CRYSTALS 251
251

N
I
I referenre
I,"' hne
I

trace of
('Olll)lOhltIOU
composition
plaup
plane

(a)
(a) (h)
FIG,
FIG. R-34.
8-34. Projection
Projection of
of the
the trace
trace of
of a
a plane
plane in
in a
a surface,
surface.

N and S,
from Nand S, represent
represent the trace.
trace. Note thatthat the diameter ACB does
the diameter does not
not
represent
represent the trace;
trace; AACB
('B represents
represents a plane
plane perpendicular
perpendicular to
to the
the plane
plane of of
polish which could have caused the
polish the observed
observed trace,
trace, but
but so
so could
could the
the in-
in-
planes ADB, AFB,
clined planes AFB, and AGB. AGB, Evidently
Evidently anyany number of planes
of planes
could have caused
caused the observed trace,
trace, and all
all we can
can say
say with
with certainty
certainty is is
that the
that the pole
pole of
of the
the composition plane
composition plane lies
lies somewhere on
on the
the diameter
diameter HK,
HK,
where H and K
Hand K are
are 90
9(}0 from the
the trace
trace direction
direction AA,B.
,B. HK isis called
called aa trace
trace
normal.
normal.
To fix
fix the
the orientation
orientation of of the
the composition
composition plane
plane requires
requires additional
additional infor-
infor-
mation which can be be obtained
obtained byby sectioning
sectioning the
the twinned
twinned grain
grain by
by another
another
AT
^^-

A,
dll'l'C'tlOn A,
direction B
H
\

threctlOll ('

(a)
(a) (h)
(b)

FIG, 8-35.
FIG. 8-35, Projection of
Projection of the
the trace
trace of
of aa plane
plane in
in two
two surfaces.
surfaces,
 8
252
252 ORIENTATIONOF
ORIENTATION SINGLECRYSTALS
OFSINGLE CRYSTALS [CHAP.
[CHAP. 8
plane and determiningthe thetrace
tracedirection new
direction in this newplane.
in this plane. Supposethe
Suppose the
plane and determining
section is made through a line WE, chosen
chosen for
for convenience
convenience totobebeatatright
right
section is made through a line WE,
angles to NS, and that the new
new planeplane of
of polish (Plane
(Plane 2) 2)makes
makes anan angle
angle 4cf>
angles to NS, and that the polish
with the original one (Plane 1), asas shown
shown in
in Fig. 8-35(a).
8-35(a). ItItisisnow
now con-
con-
with the original one (Plane 1), Fig.
venienttotouse
venient usethe edge WEasasaareference
theedge WE referencedirection.
direction. Let Letthe tracesofofthe
thetraces the
-
compositionplaneplaneininsurfaces
surfaces1 1and and22make makeangles (equaltoto9090 0 - a)a)
anglesofofft{3(equal
composition
and withthe
and7l'with theedge WE. Then,
edge WE. Then, ififthe the stenographic
stereographic projection
projection plane
plane isis
again made parallel tosurface
surface 1,1,surface
surface22isisrepresented
representedby byaagreat
greatcircle
circle
again made parallel to
through
through
Wand
W IE and at an
and E and at an angle angle cf>
#> from
from the
the circumference
circumference [Fig.
[Fig. 8-35(b)].
8-35(b)J.

Thetrace
The traceofofthe
thecomposition
compositionplaneplane ininsurface
surface 11isisthen
thenrepresented
represented by by A,B
A,B
as before and thethe same
same trace
trace inin surface
surface 2by 2 both
by the direction C, both angles ft{3
the direction C, angles
as before and

(e)(c)AAand
andBB

parts,AA
twinned
FIG8-36.
FIG. 8-36 Back-reflection
Back-reflectionLaue
Lauephotographs
photographsofoftwo twoparts, and
andB,B,ofofa atwinned
crystal
crystal
of copper.
of copper.
Tungsten
Tungsten radiation,
radiation,3030kv, 20
kv, 20rna.
ma. Film
Filmcovered
coveredwith
withO.Dl-in.-
0.01-m.-

intensityofofKKfluorescent
thick fromspecimen.
thickaluminum reducethe
aluminumtotoreduce theintensity fluorescentradiation
radiationfrom specimen.
8-7J
8-7J RELATIVE OUIESTATJOS
UELATIVJ<: TWINNED ('UYKTALK
ORIENTATION OF TWlSNJ-:D CRYSTALS 253
253

and 'Y y hE'illg

being mE'asul'E'd
measured from thE' edge lr,f..'.
the E'dge \V,K. Two nonparallPl
nonparallel lines
lines inin the
unknown ('omposit
composition ion plune
plane X -Y at'('
are now known,
known, namE'ly
namely the dil'ection 1,B
direction ...A,B
direction C.
and the dirertion C. A grt'ut
great ('in'lE' through B,
circle drawn through B, C,
(\ and A therefol'('
therefore
deK('rihE's
describes thE'the orientation
orientation of of plum'
plane X, -Y, and Px PA' is
is itll
its polp.
pole.
An appli(,lltion
application of of this
this mE'thod
method is is ufi'OI'd('d
afforded hy by anneulinJl,
annealing twins
twins in in ('opper,
copper.
The hark-refle(,tion
back-reflection Laue Lane phot.oJl,raphs
photographs of Fig. 8-3(;
of Fig. 8-30 wel'E'
were ohtainE'd
obtained from a
large Jl,l'ILin
larg(' grain ('ontaining
containing a a twin hand:
band; by by tlhifting
shifting thethe spE'('imen
specimen in in its
its own

plune
plane IIpt w('('n exposlII'(,S,
between exposures, tht' the in('id('nt
incident heumbeam was madt' made to to fall
fall first
first on one

purt
part of of th('
the twin
twin [putt('rn
[pattern (n)],(a)], then on thc the oth('1' part [patt('rn
other part [pattern (b)],
(b)], and
finally
finally on ('n('h
each SHip
side of of thE'
the ttrace
ru('(' of
of tIl('
the ('ompotlition
composition planeplane [pattE'rn
[pattern (r)],
(c)].
The luttpr photograph is
latter photograph is thcl'('fol'p
therefore a <louhl('
double pattern
pattern of both pnrttl
of both parts of of t.he
the
twin togpther.
together.
'1'h('
The ori('ntat ions d('rh'('d
orientations derived (!'Om
from pattprns
patterns (a)(a) and (b) (b) ar('
are tlhown
shown in in Fig,
Fig.
8-3i,
8-37, and ('prtain polcs of
certain poles of pu('h part of
each part of thp
the twin arc are sl't'n
seen toto ('oinridE', pur-
coincide, par-
ti(,ttlarly
ticularly tthe hp (111)
(111) pol('
pole in in the
the 10wcI'
lower l'ight
right quadrant.
quadrant. ThetleThese ('oin('idE'm'('s
coincidences
are also
Ul'(' also c\'id('nt
evident in in Fig. 8-3()(<0 in
Fig. R-3Ii(') in th(
the form of of ('oin('ident.
coincident LuuE'
Laue spots.
spots. By
m('atluring
measuring tthe h(' dirE'(,tions
directions of ot tIl('
the ttrace
ra('e of
of th('
the l'omposition
composition plane plane X in in t.wo
two
smfa(,PK,
surfaces, thc the OI'ipntation
orientation of of X was dE'tE'rminpd,
determined, as as shown in in the
the proje('tion.
projection.
P
l>xx is
is found to to roin('id('
coincide WIth with tt\('
the (111) polc rommon
(111) pole common t.o to E'1\('h
each pltrt
part ofof t.hE'
the

FIG,
FIG. 8--37.
8-37. Projection
Projection of
of part
part A (open
(open symbols)
symbols) and part B (solid
and part (solid symbols)
symbols) of
of
aa twin
twin in
in copper,
copper, made from
from Figs,
Figs. 8-36(a)
8-36(a) and
and (b).
(b).
254
254 ORIENTATION OF SINGLE CRYSTALS [CHAP. 8
[CHAP.

twin,
twin, thus
thus disclosing
disclosing the the indices
indices of of the
the composition
composition plane. plane. By the the methods
described
described in in Sec. 2-11, it
Sec. 2-11, it may
may also also be be shown that that the the two partsparts of of the
the twin
are
are related
related by by reflection
reflection in this same (111)
in this plane. The twinning
(111) plane. twinning plane plane
(the plane
(the plane of
of reflection)
reflection) in
in copper
copper is
is therefore
therefore shown to
to be identical
identical with
the
the composition
composition plane. plane.
Similar
Similar problems
problems arise arise in in studies
studies of of plastic
plastic deformation.
deformation. For example, example,
we may
may wish
wish to
to find
find the
the indices
indices of
of slip
slip planes responsible for
planes responsible for the
the observable
observable
slip
slip lines
lines onon a a polished
polished surface.
surface. Or we may may wish wish to to identify
identify the the composi-
composi-
tion
tion plane
plane of of a deformation
a deformation twin. twin. The simplest procedure, if
simplest procedure, if it
it cancan bebe
used,
used, isis to
to convert
convert the the test
test specimen
specimen into into grains
grains largelarge enough
enough so so that
that the the
orientation of
orientation of any
any selected
selected graingrain can can be be directly
directly determined
determined by by one of of the
the
Laue
Laue methods.
methods. The polished specimen is
polished specimen is then
then strained plastically to
strained plastically to pro-
pro-
duce
duce visible
visible slip
slip lines
lines or or deformation
deformation twins. twins. The orientation
orientation of of a a grain
grain
showing
showing such such traces
traces is is determined and the the directions
directions of of these
these traces
traces are are
measured.
measured. If If traces
traces areare measured on two surfaces, surfaces, the
the method of
of solution
solution
is
is identical
identical withwith thatthat described
described above for for twinned
twinned copper.
copper. If If traces
traces are are
measured only only on one plane,
plane, then
then the
the trace
trace normals
normals are
are plotted
plotted on a
a stereo-
stereo-
graphic
graphic projection
projection of of the
the grain;
grain; the the crystal
crystal orientation
orientation and the the trace
trace nor- nor-
mals
mals areare rotated
rotated into into some standard standard orientation
orientation and superimposed
superimposed on aa
detailed
detailed standard projection.projection. Intersection
Intersection of of thethe normals with certain
with certain
poles of
poles of the
the standard
standard will will then
then disclose
disclose the the indices
indices of of the
the planes
planes causing
causing the the
observed
observed traces.
traces.
But it it may
may happen
happen that that the the grain
grain size size is is too
too small
small to to permit
permit a a deter-
deter-
mination
mination of of grain
grain orientation.
orientation. The problem problem is is now much more difficult, difficult,
even
even when trace trace directions
directions are measured on
are measured on two surfaces.
surfaces. The first first step
step
is
is to
to plot
plot the
the trace
trace normals corresponding
corresponding to
to the
the traces
traces on
on both
both surfaces;
surfaces;
these normals will
these normals will be be straight
straight lines lines forfor the
the traces
traces on on the
the surface
surface on which
the
the projection
projection is
is being
being made and great
great circles
circles for
for the
the traces
traces on
on the
the other
other
surface. standard (h1k1l
surface. A standard 1 ) projection
(/hWi) projection is
is then
then superimposed
superimposed on the
the pro-
pro-
jection
jection of
of the
the trace
trace normals,
normals, and a
a rotation
rotation is
is sought
sought which
which will
will bring
bring
Ihlkllil poles into
[h\kili poles
}
into coincidence
coincidence with with the the intersections
intersections of of straight
straight and curved
trace normals. If such
trace normals. If such coincidence
coincidence cannot cannot be found, an (h2k2l2)
be found, (h^h) standard
standard
projection is
projection is tried,
tried, and so so on.
on. If If the
the traces
traces in in either plane have more than
either plane than
one direction, it
one direction, it will
will bebe helpful
helpful to to note
note how many many different
different directions
directions are are
involved.
involved. For example, example, if if there
there are are more than than three
three different
different directions
directions in in
one grain of
one grain of aa cubic
cubic metal,
metal, the the traces
traces cannotcannot be be caused
caused by by f{100}
l00} planes;
planes;
if
if more than four four directions
directions are are observed,
observed, both both 11001{100} and 1111} {111} planes
planes
are
are ruled
ruled out;
out; and so so on.
on.
Up
Up to to this
this point
point we have been been concerned
concerned with with the problem of
the problem of finding
finding
the
the indices
indices of of planes causing
planes causing certain
certain observed
observed traces, generally
traces, generally in
in aa grain
grain
of
of known orientation.
orientation. The same problem problem may may be be solved
solved in in reverse:
reverse: given given
traces
traces inin two surfaces
surfaces of of a a plane
plane of of known indices indices (hkl)(hkl\, the
the orientation
orientation of of
the
the crystal
crystal may may be found without
without using x-rays.
using x-rays. The trace
trace normals
normals are
are
8-7]
8-7] RELATIVE ORIENTATION OF TWINNED CRYSTALS 255
N

FIG.
FIG. S-3S.
8-38. Determination
Determination ofof crystal
crystal orientation
orientation of
of ('opper
copper from traces
traces of
of two
known twin
twin planes
planes in
in one surface.
surface.

plotted on one
plotted one sheet
sheet of paper and on
of paper on this
this is
is superposed
superposed a a standard projec-
standard projec-
tion
tion showing only lhkll planes.
showing only {hkl\ planes. By By trial
trial and error,
error, a
a rotation
rotation is
is found
found
which will the I{hkl\
will make the hkll poles
poles fall
fall on
on the
the observed trace
trace normals.
normals.
By
By the
the same method,
method, crystal
crystal orientation
orientation can can also be determined
also be determined fromfrom
two nonparallel
nonparallel traces
traces of
of planes
planes of
of known indices
indices in
in one
one surface.
surface. In In this
this
way,
way, it
it is
is sometimes possible
possible toto determine
determine the the orientation
orientation of of a
a single
single grain
grain
in
in a
a polycrystalline
polycrystalline mass when the the grain
grain size
size is
is too
too small
small to permit direct
to permit direct
x-ray
x-ray determination.
determination. For example,
example, we may may use use the
the fact
fact that
that annealing
annealing
256
256 ORIENTATION OF SINGLE CRYSTALS 8
[CHAP. 8
[CHAP.

twins in
twins in copper
copper have
have {111}
/1111 composition
composition planes
planes to
to determine
determine the
the orienta-
orienta-
tion of
tion of the
the grain
grain shown
shown in
in Fig.
Fig. 8-38
8-38(a), twin bands have formed on
(a), where twin
two
two different {111}
different /1111 planes
planes ofof the
the parent
parent grain.
grain. The trace tracc normals
normals are are
plotted
plotted in
in Fig. 8-38 (b)
Fig. 8-38(b), , and
and on
on this
this is
is placed
placed a
a standard
standard (001)
(001) projection
projection
containing only
containing /1111 poles.
only (111) poles. If If the
the standard
standard is is rotated
rotated about
about its
its center
('enter
to the
to the position
position shown,
shown, then
then it
it is
is possible
possible by by aa further
further rotation
rotation about
about the the
axis AB to
axis to bring
bring the
the {111}
/1111 poles
poles ofof the
the standard,
standard, shown by by open
opf'n symbols,
symbols,
to positions
to positions lying
lying onon trace
trace normals,
normals, shown by by solid
solid symbols.
symbols. The solid solid
symbols therefore
symbols therefore show an an orientation
orientation of the crystal
of the crystal which will acc'ount
will account
for the
for the observed
observed traces. Fnfortunately, itit is
traces. Unfortunately, is not
not the
the only
only one
one: the
the orienta-
:orienta-
tion found
tion found by by reflecting
reflecting the
the one
one shown in in the
the plane
plane of proje('t.i~n is
of projection is also
also aa
possible solution. A choice
possible solution. choice between
bf'tween thesethese two possibilities
possibilitieR can
can bebe made
only by
only by sectioning
sectioning thethe crystal
crystal so as to
so as to expose tra('e directions
expose trace dirC'rtions in
in aa second
I'lerond
surface.
surface.

8-8 Relative orientation

8-8 Relative orientation of of precipitate
precipitate and matrix.matrix. WhenWhcn aa superl'latu-
supersatu-
rated
rated solid
solid solution preeipitates aa second phase,
solution precipitates phase, the latter frequently
the latter frequently
takes
takes thethe form
form of of thin plates which lie
thin plates lie parallel
parallel to to certain planes of
certain planes of lowlow
indices
indices in
in the
the matrix.
matrix. The matrix
matrix plane
plane on which
which the
the pr('cipitate
precipitate plateplate
lies
lies is called the
is called the habit plane and its
habit plane indices always
its indices refer to
always refer the lattice
to the lattice of of the
the
matrix. There is
matrix. There is also
also a a definite orientation relationship
definite orientation relationship between the the lattice
lattice
of
of the
the precipitate
precipitate and that that ofof the
the matrix.
matrix. Both of of thC'se
these effet'ts
effects result
result from

tendency of
aa tendency of the
the atomic
atomic arrangement
arrangement in in the preeipitate to
the precipitate to conform as as
closely
closely asas possible
possible to to the
the atomic
atomic arrangement
arrangement in in thc
the matrix
matrix atat the
the interface
interface
between
between the two. For
the two. For example, pre('ipitation of
example, precipitation of an
an HCP phase
phase from an
FCC solid
solid solution
solution often
often occurs
occurs in in such
such a a way
way that
that the
the hasal (0001) plane
basal (0001) plane
of
of the
the precipitate
precipitate is
is parallel
parallel t,o
to a
a (111) plane
(111) plane of
of the
the matrix,
matrix, since
since on both
of
of these
these planes
planes the
the atoms have a
a halll\ planl' '-".
hexagonal
hexagonal arrangement.
arrangement.
Relations
Relations of of this
this kind
kind are
are illustrated
illustrated
on an atomic
on an atomic scale
scale in
in Fig.
Fig. 8-39.
8-39. In In
this hypothetical case
this hypothetical case the the habit
habit plane
plane
is (HO) and
is (110) and the
the lattice
lattice relationship
relationship is is

such
such that
that the
the plane
plane (010)(010) ofof the
the pre-
pre-
cipitate
cipitate isis parallel
parallel to to the
the plane
plane (110)
(110)
of
of the
the matrix;
matrix; the the direction [100] in
direction [100] in
the
the former plane is
former plane is parallel
parallel to to the
the
direction [110]
direction [110] inin the
the latter,
latter, or,
or, in
in the
the
usual
usual shorthand
shorthand notation,
notation,
!J
a2
aa a)
,!/)a1
a2~
a.~
~IATRIX
MATRIX PRECIPITATE
UNIT CELL UNIT CELL
where
where the
the subscripts p and
subscripts p and m refer
refer to
to FIG.
FIG. 8-39.
8-39. Matrix-precipitate
Matrix-precipitate rela-
rela-
precipitate
precipitate and matrix, respectively.
matrix, respectively. tionship.
tionship.
8-8]
8-8] ORIENTATION OF
RELATIVE ORIENTATION
RELATIVE PRECIPITATE AND
OF PRECIPITATE AND MATRIX
MATRIX 257
257

= =

FIG. X-40.
FIG. S-40. Wirimanstatten structure
Widmanstatten structure (schematic).
(schematic). matrix has
Cubic matrix has (100)
11001
habit.
habit. Top grain
Top grain is
if; intersected
mterReeted parallel
pamllel to
to I 100).
{
JOOI.

If
If aa certain
eertain solidsolid solution
solution has has an Ihldl habit plane,
\hkl\ habit plane, thenthen precipitation
precipitation
can
can of
of eourst'
course tah
take plact'
place on
on all
all plant's
planes of
of tht'
the form I hkll.
\hkl\. Thus one grain
one grain
may
may ('ontain
contain sets
sets of
of precipitate plates having
precipitate plates having quite quite difft'J't'nt
different orit'ntations.
orientations.
When sueh such a a grain
grain is is seetioned,
sectioned, the the thin
thin preeipitate
precipitate plates plates appear
appear as
needieR on th(> plane of polish
needles on the plane of polish resulting resulting in
in a strueture
structure sueh
such aH
as that shown
in Fig. 8-40
in Fig. 8-40 in in a a highly
highly idealized
idealized form.
form. This is called a IV idmanstatten
is called a Widmanstatten
structure. It
structure. is very
It i:-; very often
often the the produet
product of of nucleation
nucleation and growth growth rea('tions,
reactions,
sueh
such as as precipitation
precipitation and and eute{'toid
eutectoid dceomposition.
decomposition. Romewhat
Somewhat similarsimilar

structures ar(>
structures are also
also observed
observed as as tht'
the result
result ofof the martensitic reaction and and
oth('l'
other diffusionl('ss
diffusionless transformations.
transformations. (There (There are are some s('condary
secondary differences,
differences,
howevpr:
however: martpnHitt'
martensite often takes the
often takes the form of of net'dles
needles aH as well as plates
plates and
the
the indict's
indices of of its
its habit
habit planeplane areare oftt'n
often irrational,
irrational, c.g.,e.g., (259),
(259), and may even, even,
as in the
as in the case
case of of Ft'-C
Fe-C martensite,
martensite, ehangechange with composition.)
composition.)
The crystallographic
crystallographic problems problems prC'sented
presented by by such struetures
structures are vPry very
much the the same
same as as those described in
those deseribed Sec. 8-7,
in Sec. 8-7, except
except that the plates plates of the
second
second phasephase almost.
almost alwaysalways differ
differ inin crystal
crystal structure
structure from from the matrix,
matrix,
unlike
unlike the
the t\\'o
two parts
parts of
of a
a twin
twin or
or the
the material
material on
on eitht'r
either side
side of
of aa slip
slip plane.
plane.
Thc habit
The habit plane plane is
is identified
identified by
by the
the methods
methods previously
previously described
described for
for the
the
identifieation
identification of
of slip
slip or
or twinning planes.
twinning planes. The
The orientation
orientation relationship
relationship is is

easily detPrmined
easily determined if
if a
a single precipitate
single precipitate plate plate can
can be
be found
found which
which is
is large
large

enough to
enough to pPrmit
permit dett'rmination
determination of of its
its orit'ntation
orientation by by one
one of of the
the Laue
Laue
methods.
methods. Ordinarily,
Ordinarily, however,however, the precipitate is
the precipitate is so
so fine
fine that
that this
this method
method
cannot
cannot be applied and
be applied and somesome variant
variant of of the
the rotating-crystal
rotating-crystal method must
method must
be
be used.
used.
258
258 ORIENTATION OF
ORIENTATION SINGLE CRYSTALS
OF SINGLE CRYSTALS [CHAP. 88
[CHAP.

PROBLEMS
PROBLEMS

8-1. A
8-1. A back-reflection
back-reflection Laue
Laue photograph
photograph is
is made
made of of an
an aluminum
aluminum crystal
crystal with
with
aa crystal-to-film
crystal-to-film distance of 33 cm.
distance of cm. When viewed
viewed from
from thethe x-ray
x-ray source,
source, the
the Laue
Laue
spots have
spots have the
the following
following ^-coordinates,
x,y-coordinates, measured
measured (in(in inches)
inches) from
from the
the center
center of
of
the film
the film: :

xx yy xx yy
---
+0.26 +0.09 -0.44
-0.44 +1.24
+1.24
+0.45 +0.70 -1.10
-1.10 +1.80
+
+1.25
1.25 +1.80 -1.21 +0.40
+
+1.32
1.32 +0.40 -1.70
-1.70 +1.19
+0.13
+0.13 -1.61
-1.61 -0.76 -1.41
+0.28
+0.28 -1.21 -0.79 -0.95
+0.51
+0.51 -0.69 -0.92 -0.26
+0.74
+0.74 -0.31
Plot these
Plot these spots
spots on
on aa sheet
sheet of
of graph
graph paper
paper graduated
graduated inin inches.
inches. By means of of aa
Greninger chart,
Greninger chart, determine
determine the
the orientation
orientation of
of the
the crystal,
crystal, plot
plot all
all poles
poles of
of the
the form
form
{1001, {1101, and
(100), (110), and (111),
{1111, and
and give
give the
the coordinates
coordinates ofof the
the {100J
/1001 poles
poles in
in terms
terms of
of
latitude
latitude and longitude
and longitude measured
measured from
from thethe center
center of
of the
the projection.
projection.
8-2. A transmission
8-2. transmission Laue
Laue photograph
photograph is is made ofof an aluminum crystal
crystal with
with aa
crystal-to-film
crystal-to-film distance
distance of
of 55 cm.
cm. To an observer
observer looking through
looking through the
the film
film toward
the x-ray
the x-ray source, the spots
source, the spots have
have the
the following
following ^-coordinates
x,y-coordinates (in(in inches)
inches): :

x y
y x y
y
--- ---
+0.66
+0.66 +0.88
+0.88 -0.10 +0.79
+0.94
+0.94 +2.44 -0.45 +2.35
+
+1.24
1.24 +0.64 -0.77 +1.89
+ 1.36
+1.36 +0.05 -0.90 +1.00
+ 1.39
+1.39 +1.10 -1.27 +0.50
+0.89
+0.89 -1.62 -1.
-1.75 75 +1.55
+ 1.02
+1.02 -0.95 -1.95 +0.80
+ 1.66
+1.66 -1.10 -0.21 -0.58
-0.59 -0.28
-0.85 -1.31
-1.40 -1.03
-1.55 -0.36
Proceed
Proceed as as in
in Prob.
Prob. 8-1,
8-1, but
but use
use a
a stereographic
stereographic ruler ruler to
to plot
plot the poles
poles of reflecting
reflecting
planes.
planes.
8-3.
8-3. Determine
Determine the the necessary
necessary angular
angular rotations
rotations about (a) (a) the
the incident
incident beam
axis, (b)
axis, (6) the
the east-west
east-west axis,
axis, and (c)
(c) the
the north-south
north-south axis
axis to
to bring
bring the crystal
crystal of
Prob.
Prob. 8-2
8-2 into
into the
the "cube
"cube orientation," i.e.,
orientation/' i.e., that
that shown by
by Fig.
Fig. 2-36(a).
2-36(a).
8-4. reference to
8-4. With reference to Fig.
Fig. 8-35 (a) , ifif fJft == 120,
8-35(a), 120, 'Y 135, and q, == 100,
y == 135, <t> 100,
what areare the
the coordinates
coordinates (in(in terms
terms of of latitude
latitude and longitude)
longitude) of of the pole
pole of the
composition
composition plane?
plane?
8-5.
8-6. Precipitate
Precipitate plates
plates in
in a
a cubic
cubic matrix
matrix form form aa Widmanstiitten
Widmanstatten structure.
structure. The
traces
traces ofof the
the plates
plates in
in the
the plane
plane of
of polish
polish lie
lie in
in three
three directions
directions in
in one particular
particular
grain,
grain, making
making azimuthal angles of
azimuthal angles of 15, 64, and
15, 64, 113, measured clockwise from
and 113, from aa
"vertical" NS
"vertical" NS reference
reference line.
line. Determine
Determine the the indices
indices ofof the
the habit
habit plane
plane and
and the
the
orientation of the matrix grain (in
orientation of the matrix grain (in terms terms of
of the coordinates
the coordinates of
of its
its (100 I poles).
{100} poles).
 CHAPTER 99

THE STRUCTURE OF POLYCRYSTALLINE AGGREGATES

9-1 Introduction.
Introduction. In the the previous
previous chapter
chapter we were concerned
concerned withwith the
the
orientation
orientation and relative
relative perfection
perfection of of single
single crystals.
crystals. But the the single
single metal
metal
crystal
crystal is,is, after
after all,
all, somewhat of of a
a laboratory
laboratory curiosity;
curiosity; thethe normal way way inin
which metals and alloys alloys are
are used is is in
in the
the form of of polycrystalline
polycrystalline aggregates,
aggregates,
composed of
composed of a great
great many
many individual
individual crystals
crystals usually
usually of of microscopic
microscopic size.size.
Since thethe properties
properties of of such aggregates
aggregates are are of of great
great technological
technological impor-
impor-
tance,
tance, they
they have been intensively
intensively studied
studied in in many ways. In
many ways. In such
such studies
studies
the two most useful useful tE:'chniques
techniques are are microscopic
microscopic examination
examination and x-ray x-ray
diffraction,
diffraction, and the wise investigator
investigator willwill use
use them both;both; one complements
complements
the other,
other, and both together
together can provide
provide a a great
great deal
deal of
of information
information about
about
the structure
structure of of an aggregate.
aggregate.
The properties
properties (mechanical,
(mechanical, electrical,
electrical, chemical,
chemical, etc.)etc.) of
of aa single-phase
single-phase
aggregate
aggregate are are determined by by two factors:
factors:
(1) the properties
(1) properties ofof aa single
single crystal
crystal of of the
the material,
material, and
(2)
(2) the way way inin which the the single
single crystals
crystals are are put
put together
together to to form thethe
composite
composite mass.
In
In this
this chapter
chapter we willwill be concerned with the the second factor,
factor, namely,
namely, thethe
structure of
structure of the
the aggregate,
aggregate, usingusing this
this term in in its broadest sense
its broadest sense toto mean
the
the relative
relative size, perfection, and orientation
size, perfection, orientation of of the
the grains
grains making
making up up the
the
aggregate.
aggregate. Whether these
these grains
grains are
are large
large or
or small,
small, strained
strained or
or unstrained,
unstrained,
oriented at
oriented at random or or in
in some preferred
preferred direction,
direction, frequently
frequently has very very
important
important effects
effects on the
the properties
properties of
of the
the material.
material.
If the
If the aggregate
aggregate contains
contains more than one one phase,
phase, itsits properties
properties naturally
naturally
depend
depend on the
the properties
properties of
of each
each phase
phase considered
considered separately
separately and and on thethe
way
way these
these phases
phases occur
occur in
in the
the aggregate.
aggregate. Such a
a material
material offers
offers wide
structural possibilities since,
structural possibilities since, inin general,
general, thethe size, perfection, and orienta-
size, perfection, orienta-
tion of
tion of the
the grains
grains of
of one
one phase
phase may
may differ
differ from
from those
those ofof the
the other
other phase
phase oror
phases.
phases.
CRYSTAL SIZE
9-2 Grain size.
size. The size of the
size of the grains
grains inin aa polycrystalline
poly crystalline metal
metal oror
alloy
alloy has
has pronounceO
pronounced effects
effects on
on many
many of
of its
its properties,
properties, the
the best
best known
being the
being the increase
increase in in strength
strength and hardness
hardness which
which accompanies
accompanies aa decrease
decrease
in grain
in grain size.
size. This
This dependence
dependence of of properties
properties on
on grain
grain size the meas-
size makes the meas-
urement of of grain
grain size
size aa matter
matter ofof some importance
importance in in the
the control
control of
of most
m,etal forming
mjetal operations. ~
forming operations.
grain sizes
The grain sizes encountered
encountered in in commercial
commercial metals
metals and alloys
alloys range
range from
from
about 10-
about 10"" 1 to
1
10~4 cm.
to 10-4 cm. These
These limits
limits are,
are, of
of course,
course, arbitrary
arbitrary and repre-
repre-
259
259
260
260 THE STRUCTURE
THE STRUCTURE OF POLYCRYSTALLINE AGGREGATES
OF POLYCRYSTALLINE AGGREGATES [CHAP. 99
[CHAP.

sent rather
sent rather extreme
extreme values;
values; typical
typical values
values fall
fall into
into aa much
much narrower
narrower range,
range,
namely, about
namely, 10-22 to
about 10~ to 10~
10-33 cm
em TheThe most
most accurate
accurate method
method of
of measuring
measuring
grain size
grain size in
in this range isis by
this range by microscopic
microscopic examination;
examination; the
the usual
usual procedure
procedure
is to determine
is to determine thethe average
average number
number ofof grains
grains per
per unit
unit area
area of
of the
the polished
polished
section and
section and report
report this
this inin terms
terms of
of an
an "index
"index number"
number" established
established by
by the
the
American Society
American Society for
for Testing
Testing Materials.
Materials. The
The equation
equation
= 2N - 1
nn =

relates n,
relates the
n, the number of
number of grains
grains per
per square
square inch
inch when
when viewed
viewed at
at aa magnifi-
magnifi-
cation of
cation 100 X,
of 100 X, and
and N,
TV, the
the ASTM
ASTM "index
"index number"
number" or
or "grain-size
"grain-size
number."
number."
Although x-ray
Although x-ray diffraction
diffraction is decidedly
is decidedly inferior
inferior to
to microscopic
microscopic examina-
examina-
tion in
tion the accurate
in the accurate measurement of
measurement of grain
grain size,
size, one
one diffraction
diffraction photograph
photograph
can yield
can yield semiquantitative
semiquantitative information
information about
about grain
grain size, together with
size, together with infor-
infor-
mation about
mation about crystal
crystal perfection
perfection and orientation. A
and orientation. A transmission
transmission or or back-
back-
reflection pinhole
reflection pinhole photograph
photograph made with with filtered
filtered radiation
radiation isis best.
best. IfIf the
the
back-reflection method
back-reflection method is is used,
used, the
the surface
surface ofof the
the specimen
specimen (which
(which need
need
not be
not be polished)
polished) should
should bebe etched
etched toto remove any any disturbed
disturbed surface
surface layer
layer
which might
which might bebe present,
present, because
because most
most ofof the
the diffracted
diffracted radiation
radiation originates
originates
in aa thin
in thin surface
surface layer
layer (see
(see Sees. 9-4 and 9-5)
Sees. 9-4 9-5)..
*

. The nature
nature of the changes
of the produced in
changes produced in pinhole photographs by
pinhole photographs progres-
by progres-
sive
sive reductions
reductions in in specimen
specimen graingrain size
size is
is illustrated
illustrated in
in Fig.
Fig. 9-1. The gov-
gov-
erning
erning effect
effect here
here is
is the
the number of
of grains
grains which take part
part in
in diffraction.
diffraction.
This number is
This number is in
in turn
turn related
related to to the
the cross-sectional
cross-sectional area of of the incident
~eam,
beam, and
and its
its depth
depth of
of penetration
penetration (in (in back reflection)
reflection) or the specimen
specimen
tEJ.cknes~
thickness OIl transmission).
(in transmission). When the
the grain
grain size
size is
is quite
quite coarse,
coarse, as
as in
in
Fig.
Fig. 9-1(a),
9-1 only
(a), only aa few
few crystals
crystals diffract
diffract and the
the photograph
photograph consists of a
set
set of
of superimposed
superimposed Laue
Laue patterns,
patterns, one
one from
from each
each crystal,
crystal, due to the white
radiation
radiation present.
present. A somewhat finer finer grain
grain size
size increases
increases the number of of
Laue
Laue spots,
spots, and
and those
those which
which lie
lie on
on potential Debye rings
potential Debye rings generally generally are
more intense than
more intense than the the remainder,
remainder, because
because they they are
are formed by by the strong
strong
characteristic
characteristic component
component of
of the
the incident
incident radiation.
radiation. Thus,
Thus, the suggestion
suggestion
of aa DebYf;
of Debye ring ring begins
begins to to appear,
appear, as as in
in (b).
(b). When the the grain
grain size
size isis further
further
reduced,
reduced, the
the Laue
Laue spots merge
spots merge into
into aa general background
general background and
and only
only Debye
Debye
rings
rings are
are visible,
visible, as
as in
in (c).
(c). These
These rings
rings are
are spotty, however,
spotty, however, since
since not
not
enough crystals are
enough crystals are present present in
in the
the irradiated
irradiated volume
volume of
of the
the specimen
specimen to to
reflect
reflect to
to all
all parts of the
parts of the ring. ring. A
A still
still finer
finer grain
grain size
size produces
produces- the
the smooth,
smooth,
continuous
continuous Debye Debye rings rings shown
shown in in (d).
(d).
Several
Several methods
methods have have been
been proposed
proposed for for the
the estimation
estimation of of grain
grain size
size
purely
purely in
in terms
terms of
of various geometrical
various geometrical factors.
factors. For
For example,
example, an
an equation
equation
may
may be be derived
derived which which relates
relates the
the observed
observed numbernumber of of spots
spots on on aa Debye
Debye
ring to
ring to the
the grain
grain sizesize and
and other
other such
such variables
variables as as incident-beam
incident-beam diameter,
diameter,
multiplicity
multiplicity of of the reflection, and
the reflection, and specimen-film
specimen-film distance.distance. However,
However, many many
approximations are involved and the
approximations are involved and the resulting equation resulting equation is
is not
not very
very accu-
accu-
9-31
9-3] PARTICLE
PARTICLE SIZE
SIZE 261
261

(a) (b)

Ie)
(c) (d)
(d)

FIG.9-1.
FIG. 9-1. Back-reflection
Back-reflection pinhole
pinhole patterns
patterns ofof recrystallized
recrystallized aluminum specimens;
specimens;
grain
grain size
size decreases
decreases in
in the
the order
order (a),
(a), (b),
(b), (c),
(c), (d).
(d). Filtered
Filtered copper
copper radiation.
radiation.

rate.
rate. The The best
best way
way to to estimate
estimate grain
grain size
size by
by diffraction
diffraction is is to obtain a set set
of
of specimens having
specimens having known ASTM grain-size
grain-size numbers,
numbers, and to prepare
prepare
from
from these
these a a standard
standard set set of
of photographs
photographs of of the kind shown in in Fig.
Fig. 9-1.
9-1.
The
The grain-size
grain-size number of
of an
an unknown specimen
specimen of
of the same material is
is

then
then obtained
obtained simply by matching
simply by matching its
its diffraction
diffraction pattern
pattern with
with one
one of
of the
the
standard
standard photographs,
photographs, provided
provided both
both are
are made
made under
under identical
identical conditions.
conditions.
II ~
32ia, the
the grain
g ra ni size
s ze ireaches
reaches aa value
value somewhere
somewhere in
in the
the range
range 10~33 to
10- to
10-4 4
10"" cm,cm, the
the exact
exact value
value depending
depending on
on experimental
experimental conditions,
conditions, the
the Debye
Debye
rings
rings lose their spotty
lose their spotty character
character andand become
become continuous.
continuous. Between
Between this this
value
value and
and 10-
10~ 5
5
cm
cm (I000A)
(1000A), , no
no change
change occurs
occurs in
in the
the diffraction
diffraction pattern.
pattern.
At about 10-
At about 10~55 cmcm the
the first
first signs
signs of
of line
line broadening,
broadening, due due toto small
small crystal
crystal
3
size, begin
size, begin
to
to be
be detectable.
detectable. There
There is
is therefore
therefore aa size
size range,
range, from
from 10-
10~~3
(or 10""" ) to
(or 10-4)
4
10~~5 cm,
to 10-
5
cm, where
where x-ray
x-ray diffraction
diffraction is is quite
quite insensitive
insensitive toto varia-
varia-
tions in grain
tions in grain size.size., I

9-3
9-3 Particle
Particle size.
size. When
When thethe size
size of
of the
the individual
individual crystals
crystals is
is less
less than
than
about 10- 56
cm (I000A),
about 10~~ cm (1000A), the
the term
term "particle
"particle size"
size" is
is usually
usually used.
used. As
As we
we
262
262 THE STRUCTURE
THE STRUCTURE OF POLYCRYBTALLINE AGGREGATES
OF POLYCRYSTALLINE AGGREGATES (CRAP, 99
[CHAP.

saw in
saw in Sec.
Sec. 3-7,
3-7, crystals
crystals in
in this
this size
size range
range cause
cause broadening
broadening of
of the
the Debye
Debye
rings,
rings, the
the extent
extent of
of the
the broadening being
broadening being given
given by
by Eq.
Eq. (3-13):
(3-13) :

O.9X
BB == ^L,
--, (3-13)
(3-13)
t cos (J
*COS0
where B
where B == broadening
broadening of of diffraction
diffraction line line measured
measured at at half its maximum
half its maximum
intensity (radians)
intensity (radians) and t and t =
= diameter
diameter of
of crystal particle.
crystal particle. All
All diffraction
diffraction
lines have
lines have aa measurable
measurable breadth,
breadth, eveneven when when the the crystal
crystal size
size exceeds 1000A,
exceeds 1000A,
due to
due to such
such causes
causes as as divergence
divergence of of the
the incident
incident beam and size
beam and size ofof the
the sam-
sam-
ple (in
ple (in Debye
Debye cameras)
cameras) and and width
width of of the
the x-ray
x-ray source
source (in
(in diffractometers).
diffractometers).
The breadth
The breadth B in in Eq.
Eq. (3-13)
(3-13) refers,
refers, however,
however, to to the extra breadth,
the extra breadth, or or
broadening,
broadening, due
due to
to the
the particle-size
particle-size effect
effect alone.
alone. In
In other
other words,
words, B is
is

essentially
essentially zero
zero when
when the
the particle
particle size
size exceeds
exceeds about 1000A.
1000A.
The chief
The chief problem
problem in in determining
determining particle
particle size size from line
line breadths
breadths is is to
to
determine B from
determine from thethe measured
measured breadthbreadth B BM
M of of the
the diffraction
diffraction line.
line. Of Of the
the
many methods
many methods proposed,
proposed, Warren's
Warren's is is the
the simplest.
simplest. The unknown is is mixed
mixed
with
with a
a standard
standard which
which has
has a
a particle
particle size
size greater
greater than 1000A,
1000A, and
and which
which
produces a diffraction
produces a diffraction line
line near
near that
that line
line from the
the unknown which
which is
is to be
to be
used in the determination.
used in the determination. A diffraction pattern
diffraction pattern is
is then
then made of
of the
the mix-
mix-
ture in
ture in either
either a Debye camera
a Debye camera or, or, preferably,
preferably, aa diffractometer.
diffractometer. This This pat-pat-
tern will contain
tern will contain sharp
sharp lines
lines from the the standard and broad lines lines from
from the the
unknown, assumed
unknown, assumed to to consist
consist of of very
very fine particles. Let B$
fine particles. Bs be the the meas-
meas-
ured breadth, at
ured breadth, at half
half maximum intensity,intensity, of of the
the line
line from the standard.

Then
Then B is is given,
given, not
not simply
simply by
by the
the difference
difference between BM and B
BM s , but by
5$, by
the
the equation
equation R2 _ _ 2
r> 2 r>
(9-1)
(This
(This equation
equation results
results from
from thethe assumption
assumption that that the diffraction diffraction line line has

the
the shape
shape of
of an
an error
error curve.)
curve.) Once B has been obtained from Eq.
Eq. (9-1),
(9-1),
it
it can
can be
be inserted
inserted into
into Eq. (3-13)
Eq. (3-13) to
to yield
yield the
the particle
particle size
size t. /. There are
several
several other
other methods
methods of
of finding
finding B
B from BM;
BM', comparedcompared with Warren's
method,
method, they
they are
are somewhat
somewhat more accurateaccurate and considerably
considerably more intricate. intricate.

The experimental difficulties

The experimental difficulties involved
involved in
in measuring
measuring particle particle size
size from
line
line broadening
broadening increase
increase with
with the
the size
size of
of the
the particle
particle measured. Roughly
measured. Roughly
speaking,
speaking, relatively
relatively crude
crude measurements suffice suffice in in the the range range 0-500A, 0-500A, but but
very
very good
good experimental
experimental technique
technique is is needed in in the the range range 5DO-1000A.
500-1000A. The The
maximum size size measurable
measurable by by line
line broadening
broadening has usually usually been placed placed at
1000A,
1000A, chiefly
chiefly asas aa result
result ofof the
the use
use of of camera
camera techniques. techniques. Recently, Recently,
however,
however, thethe diffractometer
diffractometer has has been
been applied
applied to to thisthis problem
problem and and the the upperupper
limit
limit has
has been
been pushed
pushed to
to almost
almost 2000A.
2000A. .Y....;;e--:ry::,.....;c;.:;a~re;.;:f..:;;u:..l_w~o~r~k:-w~as~re":'g_w_
Very careful work was jgcmired red
and
and back-reflection
back-reflection lines were .eIXlP19ye~1.sinQe
lines were -employed, since ~uQl.!
such lines
lines exhibit
exhibit the
the largest
largest
~ie' broadening, a~
pSrtictePSize broadening, as sh<?~~.?y
shown by Eq Eq*,. C3-:lQ}.
(SHIS). -. ,.
From
From the
the above
above discussion
discussion it it might
might be
be inferred
inferred that
tha^
line
line broadening
broadening is is

chiefly used
chiefly used toto measure
measure the
the particle
particle size
size of
of loose
loose powders
powders rather
rather than
than the
the
9-4]
9-4] CRYSTAL PERFECTION 263
263

size
size of
of the individual
individual crystals
crystals in in a solid
solid aggregate./
aggregate.! That is is correct.
correct. At-
tempts
tempts have been made to apply apply Eq. (3-13) to
Eq. (3-13) to the broadened
broadened diffraction
diffraction
lines
lines from very
very fine-grained
fine-grained metal specimens
specimens and so
so determine the
the size
size of
of
the individual
individual grains.
grains. Such determinations
determinations are
are never
never very reliable,
very reliable, how-
ever,
ever, because the the individual
individual grains
grains of of such a material
material are are often
often nonuni-
nonuni-
formly strained,
formly strained, and this
this condition,
condition, as
as we shall
shall see
see in
in the
the next
next section,
section,
can also
also broaden the the diffraction
diffraction lines;
lines; an uncertainty
uncertainty therefore
therefore exists
exists as
as
to the exact cause of
to the exact cause of the
the observed
observed broadening.
broadening. On the other
the other hand,
hand, the the
individual crystals which make up
individual crystals up aa loose
loose powder
powder of of fine
fine particle
particle size
size can
can
often
often be assumed to to be
be strain-free,
strain-free, provided
provided the material
material involved
involved is is a

brittle (nonplastic)
brittle (nonplastic) one,one, and all all the
the observed
observed broadening
broadening can confidently
confidently
be ascribed
ascribed to to the particle-size effect.
the particle-size effect. (But
(But note that that loose,
loose, unannealed
metal
metal powders,
powders, produced
produced by by filing,
filing, grinding,
grinding, ballball milling,
milling, etc.,
etc., almost
always
always contain
contain nonuniform strain.) strain.) The.
The. chief
chief applications
applications of of the
the line-
line-

broadening
broadening method have been in
in the
the measurement of
of the
the particle
particle size
size of
of
such materials
materials as as carbon blacks, catalysts,
blacks, catalysts, and industrial
industrial dusts.
dusts.
'Another x-ray method of
JAnother x-ray
of measuring
measuring the size size ofof small
small particles
particles deserves
some mention, although
mention, although a
a complete description
complete description is
is beyond the
beyond scope of
the scope of this
this
book. This is
book. is the
the method of of small-angle scattering.
small-angle scattering. It
It is
is a
a form of
of diffuse
diffuse
scattering
scattering very
very near
near the
the undeviated transmitted
transmitted beam, beam, i.e.,i.e., at
at angles
angles 28 20
ranging
ranging from 0 up up to roughly 22 or
to roughly or 3.
3. From the the observed
observed variation
variation of of
the
the scattered
scattered intensity
intensity VS. vs. angle
angle 28,20, the
the size,
size, and to to some extent
extent thethe shape,
shape,
of
of small particles can be
small particles be determined,
determined, whether they they are
are amorphous
amorphous or or crys-
crys-
talline.
talline. Small-angle
Small-angle scattering
scattering has has also been used to
also been to study precipitation
study precipitation
effects
effects in
in metallic
metallic solid
solid solutions.
solutions. \
|

CRYSTAL PERFECTION
9-4
9-4 Crystal perfection. Of the
Crystal perfection. the many
many kinds
kinds of of crystal
crystal imperfection,
imperfection, the the
one
one we areare concerned
concerned withwith here
here is
is nonuniform strain because it
strain because it is
is so
so charac-
charac-
teristic
teristic of the cold-worked
of the cold-worked state
state of
of metals
metals and alloys.
alloys. When a a polycrystal-
polycrystal-
line piece of
line piece of metal
metal is plastically deformed,
is plastically deformed, for for example
example by by rolling,
rolling, slip
slip
occurs
occurs in in each
each grain
grain and the the grain
grain changes
changes itsits shape,
shape, becoming
becoming flattened
flattened
and elongated
elongated in in the
the direction
direction ofof rolling.
rolling. The change
change inin shape
shape of of anyone
any one
grain
grain isis determined
determined not not only
only by
by the
the forces
forces applied
applied to to the piece as
the piece as a a whole,
whole,
but
but also
also byby the
the fact
fact that
that each
each grain
grain retains
retains contact
contact on itsits boundary
boundary sur- sur-
faces
faces with
with allall its
its neighbors.
neighbors. Because of of this
this interaction
interaction between grains, grains,
aa single
single grain
grain inin aa polycrystalline
polycrystalline mass is is not free to
not free to deform in in the
the same
way
way as
as an
an isolated
isolated single crystal
single crystal would,
would, if
if subjected
subjected to
to the
the same deforma-
tion by
tion rolling.
by rolling. As a
a result
result of
of this
this restraint
restraint by
by its
its neighbors,
neighbors, a
a plastically
plastically
deformed
deformed graingrain inin aa solid
solid aggregate
aggregate usually
usually hashas regions
regions ofof its
its lattice
lattice left
left

in
in an elastically
elastically bent
bent or
or twisted
twisted condition
condition or,
or, more rarely,
rarely, in
in a
a state
state of
of
uniform
uniform tension
tension or compression. The metal
or compression. metal is then
is then said
said to contain residual
to contain residual
264
264 THE STRUCTURE
THE STRUCTURE OF POLYCRYSTALLINE AGGREGATES
OF POLYCRYSTALLINE AGGREGATES [CHAP. 99
[CHAP.

(Such stress
stress. (Such stress is is often
often called
called "internal
"internal stress"
stress" but the term
but the term is is not
not
very
very informative
informative since
since all
all stresses,
stresses, residual
residual or
or externally
externally imposed,
imposed, are
are
internal. The
internal. The term term "residual
"residual stress"
stress" emphasizes
emphasizes thethe fact
fact that
that thethe stress
stress
remains after
remains after all all external
external forces
forces are are removed.)
removed.) Stresses
Stresses of
of this
this kind
kind are
are
also called
also called microstresses
microstresses since since they
they vary
vary from oneone grain
grain to
to another,
another, or or from
from
one part
one part of of aa grain
grain to to another
another part, part, on
on aa microscopic scale. On the
microscopic scale. the other
other
hand,
hand, the
the stress
stress may
may be
be quite
quite uniform
uniform over
over large
large distances;
distances; it
it is
is then
then re-
re-

ferred to
ferred to asas macrostress.
macrostress. CHYSTAL LATTICE
CRYSTAL DIFFRACTION
DIFFHACTJON
The effect
The effect of of strain,
strain, bothboth uniform
uniform LINE
LJ:,\E
and nonuniform,
and nonuniform, on on thethe direction
direction of of
x-ray reflection
x-ray reflection is is illustrated
illustrated in in Fig.
Fig.
portion of
9-2. A portion
9-2. of an
an unstrained
unstrained grain grain
~Idor
appears in
appears in (a)
(a) onon the
the left,
left, and the the set
set
of transverse
of
has
transverse reflecting
has everywhere
everywhere its
reflecting planes
planes shown
its equilibrium
equilibrium spac- spac-
IIIIIII NO STRAIN
STHAI.'J
ing
ing do.
d . The diffraction
diffraction line
line from these
these
(a)
(a)
planes appears
planes appears on on the right. If
the right. the
If the
grain is
grain is then
then given
given aa uniform
uniform tensile
tensile
strain at
strain at right
right angles
angles to to the
the reflecting
reflecting
planes, their
planes, their spacing
spacing becomes larger larger
than ddo, and
than >
and the the corresponding
corresponding dif- dif-
fraction
fraction line
line shifts
shifts to lower angles
to lower angles but
does not otherwise change,
does
in
change, as shown IIIIIII
in (b).
(b). This line
This Rhift is
line shift the basis
is the basis ofof
UNIFORM STRAIN
the
the x-ray
x-ray method for for the
the measurement
of
of macrostress,
macrostress, as as wiII
will bebe described
described
in
in Chap.
Chap. 17. 17. In
In (r)
(c) the
the grain
grain is is bent

and
and the
the strain
strain is is nonuniform;
nonuniform on the
;
the
top
top (tension)
(tension) side side thethe plane
plane spacing
spacing
exceeds
exceeds do, d on,
on the
the bottom (compres- (compres-
NONTNIFORM ;;;THAI:\l
STRAIN '20-
sion) side it
sion) side it is
is less
less than
than do,
,
d andand some-
some- NO:,\[':,\IFOHM
where (c)
where in in between
between it it equals
equals do.
d We .
(c)

may FIG. 9-2.

9-2. Effect of lattice
lattice strain
may imagine
imagine thisthis grain
grain toto be
be com-
on Debye-line
Debye-line width and position.
position.
posed
posed ofof a
a number of of small
small regions
regions in
in
.!ach
jach ofof which
which the
the plane
plane spacing
spacing isis substantially
substantially constant but different different
from
from the
the spacing
spacing inin adjoining
adjoining regions.
regions. These regions
regions cause the various
sharp
sharp diffrartion
diffraction lines
lines indicated
indicated on thethe right
right ofof (c)
(c) by
by the
the dotted curves.
curves.
The sum of of these
these sharp
sharp lines,
lines, each
each slightly
slightly displaced
displaced from
from the other,
other, isis the

broadened
broadened diffraction
diffraction line
line shown by by the
the full
full curve
curve and,
and, of of course,
course, thethe
broadened lineline is
is the
the only
only one
one experimentally
experimentally observable.
observable. We can find find aa
relation
relation between the
the broadening
broadening produced
produced and the the nonuniformity
nonuniformity of the of the
strain
strain by
by differentiating
differentiating thethe Bragg
Bragg law.
law. We obtainobtain
Ad
b = A20 = -2-tanO
-2 tan0, (9-2)
(9-2)
dd '
9-4)
9-4] CRYSTAL PERFECTION
CRYSTAL PERFECTION 265
265

where
where bb is
is the
the
broadening due
broadening due to
to aa fractional
fractional variation
variation in
in plane
plane spacing
spacing
/ld/d.
Ad/d. This equation
This equation allows
allows the
the variation
variation in
in strain,
strain, Ad/d, to
to be ad/d,
be calculated
calculated
from the
from the observed
observed broadening.
broadening. This
This value
value ofof Ad/d, however, ad/d,
however, includes
includes
both tensile
both tensile and
and compressive
compressive strain
strain and
and must
must bebe divided
divided by
by two
two to
to obtain
obtain
the
the maximum tensile
maximum tensile strain
strain alone,
alone, or
or maximum
maximum compressive
compressive strain
strain alone,
alone,
if these
if these two
two are
are assumed
assumed equal.
equal. The
The maximum
maximum strain
strain so
so found
found can
can then
then
be multiplied
be multiplied by
by the
the elastic modulus E to
elastic modulus to give the maximum
give the maximum stress
stress present.
present.
For example,
For example,

(ad) == ~.
/Ad\ Eb
(Max.
(Max. tens. stress)
tens, stress) = E . (max.
(max. tens,
-
strain) =
tens. strain) (E)Ci) \~)
= (E)(?) "A ~*'
d/
\ a 44tan9
tan B

When an an annealed
annealed metal
metal or or alloy
alloy is is cold
cold worked,
worked, its its diffraction
diffraction lines lines
become broader.
become broader. This This isis aa well-established,
well-established, easily easily verified experimental
verified experimental
fact, but
fact, but itsits explanation
explanation has has been
been aa matter of of controversy.
controversy. Some investi- investi-
gators have
gators have feltfelt that
that the
the chief
chief effect
effect of of cold
cold work is is toto fragment
fragment the the
grains to
grains to aa point
point where
where their
their small
small sizesize alone
alone is is sufficient
sufficient to to account
account for for
all the
all the observed
observed broadening.
broadening. Others Others have concluded that that thethe nonuni-
nonuni-
formity of
formity of strain
strain produced
produced by by cold
cold work is is the
the major
major cause
cause of of broadening,
broadening,
with grain
with grain fragmentation
fragmentation possibly
possibly aa minor contributing
contributing cause. cause. Actually,
Actually,
it is
it is impossible
impossible to to generalize,
generalize, inasmuch as as different
different metals
metals and alloys alloys may
behave
behave quitequite differently.
differently. By By advanced
advanced methods of of mathematical analysis,analysis,
it is
it is possible
possible to to divide the ohserved
divide the observed change
change in in line
line shape produced by
shape produced by cold
cold
work
work intointo two parts,parts, one
one due to to fine particle size
fine particle size and the other
the other due to
to
nonuniform
nonuniform strain. strain. When this this isis done,
done, it it is
is found,
found, for example,
for example, that in
that in

alpha
alpha brassbrass containing
containing 30 30 percent
percent zinczinc the observed broadening broadening is due is due
almost
almost entirely
entirely to to nonuniform
nonuniform strain,
strain, while
while in in thoriated
thoriated tungsten
tungsten (tung-(tung-
sten
sten containing
containing 0.75 0.75 percent
percent thorium oxide) oxide) it it is
is due both to to nonuniform
strain
strain andand finc
fine particle
particle size.
size. But no exampleexample is is known where all all the
the
observed broadening can
observed broadening can be ascribed be ascribed to
to fine
fine particle
particle size.
size. In fact,
fact, it
it is
is

difficult to imagine
difficult to imagine how cold
cold work could
could fragment
fragment the grains
grains to the
degree
degree necessary
necessary to to cause
cause particle-size
particle-size broadening
broadening without at the same
time
time introducing
introducing nonuniform
nonuniform strains,
strains, in in view of of the veryvery complex
complex forces forces
that must act on anyone
that must act on any one grain of grain of an aggregate
aggregate no matter how simple
simple the the
forces applied to the
forces applied to the aggregateaggregate as
as aa whole.
whole.
The broadening
broadening of of aa diffraction
diffraction line line byby cold
cold work cannot cannot always
always be
observed by simple
observed by simple inspectioninspection of
of aa photograph
photograph unless some
some standard
standard is
is

available for comparison.

available for comparison. However,
However, the
the separation
separation of
of the Ka
KOI. doublet
doublet
furnishes
furnishes aa very very good
good "internal
"internal standard."
standard." In In the
the back-reflection
back-reflection region, region,
an annealed metal
an annealed metal produces aproduces a well-resolved
well-resolved doublet,
doublet, one one component
component due due
to KOI.l radiation and
to Kai radiation and the other the other to
to K0I.2.
Ka 2 - For
For aa given
given set
set of
of experimental
experimental
conditions,
conditions, the the separation
separation of of this
this doublet
doublet on on the
the film
film is
is constant
constant and and inde-
inde-
pendent of the
pendent of the amount amount of
of cold
cold work.
work. But
But as
as the
the amount
amount of
of cold
cold work
work
is
is increased,
increased, the the broadening
broadening increases,
increases, untiluntil finally
finally thethe twotwo components
components
266
266 THE
THE STRUCTURE
STRUCTURE OF POLYCRYSTALLINE AGGREGATES
OF POLYCRYSTALLINE AGGREGATES [CHAP. 99
[CHAP.

of the
of the doublet
doublet overlap
overlap to
to such
such an
an extent
extent that
that they
they appear as
appear as one
one unresolved
unresolved
line. An
line. unresolved Ka
An unresolved Ka doublet
doublet can can therefore
therefore be be taken
taken as as evidence
evidence of of
cold work,
cold work, ifif the the samesame doublet
doublet is is resolved
resolved when when the the metal
metal is is in
in the
the an-
an-
nealed condition.
nealed condition.
We areare now in in aa position
position to to consider
consider some some of of the
the diffraction
diffraction effects
effects
associated with
associated with the the processes
processes of recovery, recrystallization,
of recovery, recrystallization, and grain grain growth.
growth.
When aa cold-worked
cold-worked metal metal or or alloy
alloy is is annealed
annealed at at a low temperature,
temperature,
recovery takes place;
recovery takes place; at a at a somewhat higher temperature, recrystallization;
higher temperature, recrystallization;
and at
and at aa still
still higher
higher temperature,
temperature, grain grain growth.
growth. Or at at aa sufficiently
sufficiently highhigh
constant temperature,
constant temperature, these these processes
processes may be regarded regarded as as occurring
occurring con-con-
secutively in
secutively in time.
time. Recovery
Recovery is is usually
usually defined
defined as as a process
process involving
involving
changes in
changes in certain
certain properties
properties withoutwithout any any observable
observable change change in in micro-
micro-
structure, while
structure, while recrystallization
recrystallization produces produces an easily easily visible
visible structure
structure of of
grains, which
new grains, which then then growgrow at at thethe expense
expense of of one another during during thethe
grain-growth stage.
grain-growth stage.
above is
The above is aa highly
highly oversimplified
oversimplified description
description of of some very very complex
complex
processes
processes which
which are
are not
not yet completely
yet completely understood.
understood. In
In particular,
particular, the the
exact nature
exact nature of of recovery
recovery is is still
still rather obscure. It
rather obscure. It seems clear,clear, however,
however,
that some form of
that of polygonization
polygonization takes takes placeplace during
during recovery
recovery and may, may,
in fact,
in fact, constitute
constitute the the most important
important part part of that process.
of that process. (Polygoniza-
(Polygoniza-
tion can
tion can occur
occur in the individual
in the individual grainsgrains of of an aggregate
aggregate just just asas in
in aa single
single
crystal. The structure
crystal. structure so produced is
so produced is called
called a substructure,
substructure, and the
smaller units into
smaller units into whichwhich aa grain breaks up
grain breaks up are
are called
called subgrains. Subgrain
subgrains. Subgrain
boundaries
boundaries can can be be made visible under the
visible under the microscope
microscope if if the proper
proper etching
etching
technique
technique is
is used.)
used.) In
In some metals
metals and alloys,
alloys, recovery
recovery appears
appears to
to overlap
overlap
recrystallization
recrystallization (in (in temperature
temperature or or time),
time), while
while in others it
in others it is
is quite
quite sepa-
sepa-
rate.
rate. It
It isis usually
usually associated
associated with a
a partial
partial relief
relief of
of residual
residual stress,
stress, on
both
both a a microscopic
microscopic and a macroscopic
macroscopic scale, scale, without any
any marked change
change
in
in hardness.
hardness. Since Since microstress
microstress is is the
the major
major cause of of line
line broadening,
broadening, we
usually
usually findfind that
that the the broad diffraction
diffraction lines lines characteristic
characteristic of of cold-worked
metal partially sharpen
metal partially sharpen during recovery.during recovery. When recrystallization
recrystallization occurs, occurs,
the lines attain
the lines attain their their maximum sharpness
sharpness and the
the hardness decreases decreases
rather
rather abruptly.
abruptly. During
During grain grain growth,
growth, the the lines
lines become increasingly
increasingly
spotty
spotty as as the
the grain
grain size size increases.
increases.
The nature
nature of of these
these changes
changes is is illustrated
illustrated for for alpha
alpha brassbrass containing
containing
30 weight
weight percent
percent zinc zinc by by thethe hardness
hardness curve curve and diffraction
diffraction patterns
patterns of of
Fig.
Fig. 9-3.
9-3. The hardness
hardness remains remains practically
practically constant,
constant, for for an annealing
annealing
period
period of of oneone hour,
hour, untiluntil a a temperature
temperature of of 200C
200 C is is exceeded,
exceeded, and then
decreases
decreases rapidly
rapidly with
with increasing temperature,
increasing temperature, as
as shown in
in (a).
(a). The dif-
dif-

fraction pattern
fraction pattern in
in (b)
(b) exhibits
exhibits the
the broad
broad diffuse
diffuse Debye
Debye lines
lines produced
produced by by
the cold-rolled,
cold-rolled, un annealed
unannealed alloy.
alloy. These lines
lines become somewhat narrower
for
for specimens annealed at
specimens annealed at 100
100 and 200C, 200 C, and the the Ka Ka doublet
doublet becomes
partially
partially resolved
resolved at
at 250C.
250C. At 250,
250, therefore, the recovery process
therefore, the recovery process
9--4]
9-4] CRYSTAL PERFECTION 267
267

(b) Asrolled (e) 1 hour at

~ 120

1100

~ 80

~ 60
Z
~ 40
~ W~~--~~--~~
100o
UK) 200 300 400 500
500

ANNEALlNG TE:vlPERATllRE
ANNEALING (O
TEMPERATURE ("(')
(a)
(a) Hardness
Hardness ('urve
curve (d)
(d) 1
1 hOlll
houi at
tit 4:;0"('
4f>0"('

FIG.
FIG. 9-3.
9-3. Changes
Changes in
in hardness and diffraction
diffraction liner;
lines of
of 70-30 hraRR
brass ISpe('imens,
specimens,
reduced in
reduced in thickness
thickness by
by 90
90 percent
percent by
by rold
cold rolling,
rolling, and anne:til'd foi 1 hour at
annealed f(ll at the
the 1

temperatures
temperatures mdicated
indicated min (a).
(a), (b),
(b), (r),
(c), and (d)
(d) urI'
are ]lUltionK
poitions of bu!'k-rdleetion
of back-reflection

pinhole patterns
pinhole patterns of
of specimens
specimens annealed ut at the
the temperatuI'Ps
temperatures stated
stated (filtered
(filtered ('op-
cop-
per
per radiation).
radiation).

appears
appears to to be
be l'luhstantially
substantially complete
complete in in one hour and rp('rystuJlization
recrystallization IS is

just
just beginning,
beginning, as as evidenced
evidenced by by th'
the drop
drop in in RO('kwell
Rockwell B hardness from
98
98 to
to 90.
90. At 300C
300 C the the diffra('tion
diffraction lines
lines aI''
are quite
quite l'lharp
sharp and tJH' the douhlpts
doublets
completely resolved, as
completely resolved, as shown in in (c).
(c). Ann'aling
Annealing at at t'mpNutures
temperatures above
300C caUl'les
300C causes thethe lines
lines toto hecome
become incrpasin/l:ly
increasingly spotty,
spotty, indieating
indicating that that the
the
newly recrystallized
newly recrystallized grainsgrains are
are inerpasing
increasing in
in siz'.
size. The pattern
pattern of
of a speci-
speci-
men anneal'd
annealed at at 450C,
450C, when the the hardneKs
hardness had droppeddropped to:nto 37 HOf'kwell
Rockwell B, B,
appears
appears in
in (d).
(d).
Diffraetom'ter
Diffract ometer measurements mad' made on the the same spe(~im('ns
specimens disclose
disclose
both
both more,
more, and leHs,
less, information.
information. Rome
Some automatically
automatically recorded profiles
profiles
of
of the
the 331
331 line,
line, the
the outer
outer ring
ring of
of the
the patterns
patterns shown in
in Fig. 9-3,
Fig. 9-3, are
are repro-
repro-
duced
duced inin Fig.
Fig. 9-4.
9-4. It
It is
is mu('h
much easier
easier to
to follow
follow changes
changes in
in line
line shape
shape by by
means of of theRe
these eurves
curves than by by inl'lpection
inspection of of pinhole
pinhole photographs.
photographs. Thus
the
the slight
slight sharpening
sharpening of of the
the line
line at
at 200C
200 C is is clearly
clearly evident
evident in in the diffrac-
diffrac-
tometer
tometer record,
record, and
and so
so is
is the
the doublet
doublet resolution
resolution which oceurs
occurs at
at 250C.
250 C.
But note
note that
that the
the diffractometer
diffractometer cannot "spe" "see" thethe spotty
spotty diffraction
diffraction lines
lines
caused
caused byby coarse
coarse grains.
grains. There is
is nothing
nothing in
in the
the diffractometer
diffractometer records
records
268
268 THE STRUCTURE
THE STRUCTURE OF
OF POLYCRYSTALLINE AGGREGATES
POLYCRYSTALLINE AGGREGATES [CHAP. 9
[CHAP. 9

I
x;

o
o.....

135
135 134 133 132
132 131
131 130 129
129
20 (degrees)
IS (kp;rees)

FIG. 9-4.
FIG. 9--4. Diffractometer traces
Diffractometer traces of
of the
the 331
331 line
line of
of the
the cold-rolled
cold-rolled and
and annealed
annealed
70-30 brass
70-30 brass specimens
specimens referred
referred to
to in Fig.
in 9--3.
Fig. 9-3. Filtered copper
Filtered copper radiation.
radiation. Loga-
Loga-
rithmic intensity
rithmic intensity scale. All curves
scale. All curves displaced
displaced vertically
vertically by
by arbitrary
arbitrary amounts.
amounts.
9-51
9-5| DEPTH OF X-RAY PENETRATION
Pl<~NETHATION 269
269

FIG 9-5.9--5. Back-reflection

Buek-J"cfic(tlUn pinhole
pmholc
pat.term, of
patterns l'oal'A(,-~Jainl'd lecrystal-
of coarse-grained JI'('ry~tal
Ir Zl,<I copper.
lized l T llfilt{'fl,d coppei
(oPllE'r. Vnfiltered ('OPI)(') ra-
ra-
dmtwll
diation (a)
(a) from surface ~round on
Aurfn('(' ground a
011 a
ht>lt sandei
belt sandt')
, (h) nftt'r removal
(1)) after
,
remoyal of
of 0.003
0.003
III fiom
in flOm this hy etching.
AUlfa('t' by
thi,; suiface t'khing.

(a) (b)

made at at 300
300 and
and 450C
450C which
whi('h wouldwould immediately
immE'chatply .suggest
Hup;p;m;t. that
t.hat the
thE' speci-
Hpe('i-
men annealed
annealed at at. 450
450CO had the
the ('uarHE'f
coarser p;rain .sIze,
grain size, hut
hut thili
this faet
fact it-;
is quitE'
quite
eVIdent in
evident in the
thp pinhole
pinhole patterns
patt('rns shown in Figs. 9-3(')
in Figs. 9-3 (c) and (d).(d).
It always he
It must always he remembered
rememb('r('d that that aa hack-reflection
ha('k-r'flr-etion photograph
phntograph is is
r('prE'sentative of
representative of only
only aa thin
thin surface
smiuce layer
layer ofof the
thE' specimen.
spE'C'imen. For example,
E'xamplE',
Fip;. 9-5
Fig. 9-5(a) was obtained
(a) was ohtained fromfrom aa piecepie('e of
of copper
('opper and exhibits
exhibit.s unresolved
unresolved
doublets in
doublets the high-angle
in the high-angle region.
rE'gion. The Th(' unexperienced
ull('xpcrienc('d observer
observer might might
eon('lude
conclude thatthat. this
this material
mat.erial was highly highly ('old worked. What t.h(
cold worked. x-ray
the x-ray
"sees" ~8
"sees" is eold
cold work'd,
worked, but
but it
it .sees
sees only
only to
to a
a limIted
limited deptl.. A('tually,
depth. Actually, the the
bulk of
bulk of this
this specimen
specimen is
is in
in the
the annealed eondition,
condition, but the
the surfaee
surface from
which the
which the x-ray pattern was made had had 0.002
x-ray pattern 0.002 in.in. removed
remow'd by by grinding
p;rinding
helt. sander
on aa belt sander aft('r
after annealing.
annealing. This treatment
treatment eold
cold worked the
the surface
surface
to
to aa considerable
considerable depth.
depth. By By sU(~cessive
successive etehing
etching treatments and diffraction
diffraction
patterns
patterns made after after each
each E'tch,
etch, the the change
change in in stnI('ture
structure of of the
the eold-worked
cold-worked
layer
layer (muld
could be followed as
be followed as a a function
function of of depth
depth helowbelow the the surfa('E'.
surface. Not
until
until aa total
total ofof 0.003
0.003 in.
in. had been removed did the diffraction
did the diffraction pattern
pattern be- be-
come characteristic
characteristic of of the
the bulk of of the
the material;
material; spe see Fig.
Fig. 9-5(b),
9-5 (b), where the
spotty
sf>otty lines
lines indieate
indicate a coarse-grained,
coarse-grained, re('rystaliized
recrystallized struetur'.
structure.

9-6
9-6 Depth
Depth ofof x-ray
x-ray penetration.
penetration. Observations of of thili
this kind suggest
suggest that
it
it might
might be well
well to
to consider
consider in
in some detail
detail the
the general
general problem of
problem of x-ray
x-ray
penetration.
penetration. Most metallurgical specimens
metallurgical specimens stronglystrongly ahliorh
absorb x-rays,
x-rays, and
the
the intensity
intensity of
of the
the incident
incident beam is
is reduced
reduced almost to
to zero
zero in
in a very
very short
short
distance
distance below
below the
the surface.
surface. The diffracted
diffracted beams th'refore
therefore originate
originate
chiefly
chiefly in a thin
in a thin surface
surface layer
layer whenever a reflection
reflection technique,
technique, as as opposed
opposed
to
to aa transmission
transmission technique,
technique,* * isis used,
used, i.e.,
i.e., whenever a a diffraction
diffraction pat.tern
pattern

* Not even
even in
in transmission
transmission methods,
methods, however,
however, isis the
the information
information on a a diffrac-
diffrac-
tion
tion pattern
pattern truly
truly representative
representative of of the
the entire
entire cross
cross section
section ofof the
the specimen.
specimen. Cal-Cal-
culations
culations such
such as
as those
those given
given in
in this
this section
section show that
that aa greater
greater proportion
proportion of of the
the
total
total diffracted
diffracted energy originates in
energy originates in a
a layer
layer ofof given
given thickness
thickness on on the
the bark
back side
side of
of
the
the specimen (the
specimen (the side
side from
from which
which the
the transmitted
transmitted beam leaves)
leaves) than
than in
in a
a layer
layer
of
of equal
equal thickness
thickness on
on the
the front
front side.
side. IfIf the
the specimen
specimen isis highly
highly absorbing,
absorbing, a a trans-
trans-
mission
mission method
method can be just
can be just as
as non-representative
non-representative of of the
the entire
entire specimen
specimen as
as aa back-
back-
reflection method, in
reflection method, in that
that most
most of
of the
the diffracted
diffracted energy
energy will
will originate
originate in
in aa thin
thin
surface layer.* See
surface layer!' See Prob.
Prob. 9-5.
9-5.
270 THE STRUCTURE OF POLYCRYSTALLINE AGGREGATES [CHAP. 9
[CHAP. 9

is
is obtained
obtained in in a
a back-reflection
back-reflection camera of of any
any kind,
kind, a Seemann-Bohlin
camera or or a
a diffractometer
diffractometer as as normally
normally used.
used. We have just just seen how a
back-reflection
back-reflection pinhole photograph of
pinhole photograph of aa ground
ground surface
surface discloses
discloses the cold-
cold-
condition of
worked condition of aa thin
thin surface
surface layer
layer and givesgives no information what-
ever
ever about the
the bulk
bulk ofof the material below that
the material that layer.
layer.
These
These circumstances
circumstances naturally pose
naturally pose the
the following
following question:
question: what is is the
the
effective
effective depth
depth of
of x-ray penetration?
x-ray penetration? Or, Or, stated
stated in
in a
a more useful
useful manner,
manner,
to
to what depth
depth of
of the
the specimen
specimen docs
does the
the information
information in in such a diffraction
diffraction
pattern
pattern apply?
apply? This
This question
question has
has no precise
precise answer
answer because
because the
the intensity
intensity
of
of the
the incident
incident beam doesdoes not
not suddcnly
suddenly become zero zero atat anyone
any one depth but
depth but
rather
rather decreases
decreases exponentially with distaD(~e
exponentially with distance below the the surface.
surface. However,
However,
we can
can obtain
obtain an answer
answer which,
which, although
although not precise, is
not precise, is at
at least
least useful,
useful, in
in
the
the following
following way.
way. Equation (7-2) gives
Equation (7-2) gives the
the integrated
integrated intensity
intensity dif-
dif-

fracted
fracted byby an infinitesimally
infinitesimally thin
thin layer located at
layer located at a depth
depth x below the the
surface
surface as
as

dID
d//>
= ~oab e-l'x(l/8in
= e-^ (1/8in a+l/8in & dx,
+ 1/8in IJ)
dx, (7-2)
(7-2)
sm a
sin 0/

where thethe various

various symbols
symbols areare defined
defined in in Sec.
Sec. 7-4.
7-4. This expression,
expression, inte-
inte-
grated
grated over
over any
any chosen
chosen depth
depth of
of material, gives
material, gives the
the total
total integrated
integrated in-
in-
tensity
tensity diffracted
diffracted by
by that
that layer,
layer, but only
only in
in terms of
of the
the unknown constants
constants
1/o, a, and b.
0 , a, b. However,
However, these
these constants
constants wiII
will cancel
cancel out
out if
if we express
express the
the
intensity
intensity diffracted
diffracted by
by the
the layer
layer considered
considered as
as a
a fraction
fraction of
of the
the total
total inte-
inte-
grated
grated intensity diffracted by
intensity diffracted by aa specimen
specimen of infinite thickness.
of infinite thickness. (As
(As we
saw in in Sec.
Sec. 7-4,
7-4, "infinite
"infinite thickness"
thickness" amounts to to only
only aa few
few thousandths
thousandths
of
of an inch
inch for
for most metals.)
metals.) Call
Call this
this fraction
fraction Gxx Then .

X-X
[
dlD
G
J
JlfrSL - =
r
1
- e- x(ll * ina + llB{nf
i
.
(9-3)

Jx

This expression permits us

expression permits us to
to calculate
calculate the fraction Gx
the fraction x of
of the
the total
total dif-
dif-
fracted
fracted intensity
intensity which is is contributed
contributed by by aa surface layer of
surface layer depth x.
of depth x. If
If
we arbitrarily
arbitrarily decide
decide that
that aa contribution
contribution from thisthis surface
surface layer
layer ofof 95
95 per-
per-
(or 99 or
cent (or or 99.9 percent) of
99.9 percent) of the
the total
total is
is enough
enough so so that
that we can can ignore
ignore
the contribution
contribution from the the material below that
material below that layer,
layer, then
then x x is
is the
the effective
effective
depth
depth ofof penetration.
penetration. We then then know that
that the
the information
information recorded
recorded on on the
the
diffraction
diffraction pattern (or,
pattern (or, more precisely,
precisely, 95
95 percent
percent of
of the
the information)
information)
refers
refers to
to the
the layer
layer of depth x
of depth x and not
not to
to the
the material
material below
below it.it.

In the case
case of
of the
the diffractometer,
diffractometer, 0/ = fJ == 8,
a = 8, and Eq.
Eq. (9-3)
(9-3) reduces
reduces toto

Gx = (1
- (9-4)
9-5)
9-5] DEPTH OP
OF X-RAY PENETRATION 271
271

which shows that

which that the
the effective
effective depth
depth 1.0
of penetration
of penetration decreases
decreases as
as 6fJ decreases
decreases
therefore varies
and therefore varies from one
one diffrac-
diffrac-
o.g
tion line
tion line to
to another.
another. In back-reflec-
In back-reflec-
tion cameras,
tion cameras, a = 90,
= 90 0 , and
06
G.x =
G [1 -
= [1 - e-llx (l+1/8in (j)j, (9--5)
(9-5)
~ Gr

04
where ft 2fJ -
= 20
fJ = 90 0
- 90.
example, the
For example, the conditions
conditions appli-
appli-
cable to the
cable to the outer
outer diffraction
diffraction ring
ring 02
of Fig.
of Fig. 9-5 are Mp. = 473
9-5 are 473 cm-
cm"" l and
1

26 =
2fJ = 136.7
136.7.0
By using
By using Eq.
Eq. (9-5),
(9-5), we
can construct
can construct the
the plot of Grx as
plot of as func-
func- o
() 03
0') 1.0
1.0 1.5
1.5 2.0
tion of xx which is
tion of is shown inin Fig.
Fig. 9-6.
9-6.
x (th"IIRandth~ of
x (thousandths of an inch)
Inch)
We note that 95
note that percent of
95 percent of the
the infor-
infor-
mation on on the
the diffraction
diffraction pattern
pattern re- re- FIG. 9--6.
FIG. 9-6. fraction G",
The fraction G x of the
of the

fers
fers to a depth
to a of
of only about 0.001
0.001 in.
in.
total
total diffracted
diffracted intensity contributed
intensity contributed
depth only
by a surface
by surface layer
layer of de~th x,
of depth for
x, for
lt
It is
is therefore
therefore not
not surprising
surprising thatthat the
the = 473 em-I, = 136.7,
p. = cm" 2fJ26 = 136.7, and nor-
1
M and nor-
,

pattern of
pattern of Fig.
Fig. 9--5(a)
9-5 (a) discloses only mal
discloses only mal incidence.
incidence.
the
the presence
presence of
of cold-worked
cold-worked metal,
metal,
since
since we found by by repeated
repeated etching
etching treatments
treatments that that the
the depth
depth of of the
the cold-
cold-
worked layer
layer was about 0.003
0.003 in.
in. Of course,
course, the infonnation
information recorded
recorded on
the
the pattern
pattern is
is heavily weighted
heavily weighted in
in terms of
of material
material just
just below
below the
the surface;
surface;
thus
thus 95 percent of
95 percent of the
the recorded
recorded information
information appliesapplies to to a depth
depth ofof 0.001
0.001 in.,
in.,

but
but 5050 pen'ent of that
percent of that information
information originates
originates in in the first
first 0.0002
0.0002 in.
in. (Note
(Note
that
that an effective
effective penetration
penetration of of 0.001
0.001 in. in. means that that aa surface
surface layer
layer only
only
one
one grain
grain thick
thick isis effeetively
effectively contributing
contributing to to the
the diffraction
diffraction pattern
pattern ifif the

specimen
specimen has an ASTM grain-size grain-size number of of 8.)
8.)
Equation (9-4) ('an
Equation (9-4) be put
can be put into
into the
the following
following fonn,form, which is is more suitable
suitable
for
for calcqlation:
calculation:
2p.x =
-^-
- - = In In
(1) 1
= Kx
sin
sin fJ
6 1 - Gx '

Kx sin B
x == - - -
x
2p.

Similarly,
Similarly, we can
can rewrite
rewrite Eq.
Eq. (9-5)
(9-5) in
in the
the fonn
form

p.X
M.T (1 ++ _.1
(l
\
-^}
sm fJ
) == In ( V)
sin /3/
In
1 -- G
Gj (
\1
K
1 ) == Kx,
x
x ,

Kx sin
Kx sin fJ ft
x =
x=
p.(l +
+ sin fJ)
sin/3)
272 THE STRUCTURE OF POLYCRYSTALLINE AGGREGATES [CHAP. 9
[CHAP. 9

TABLE ~1
9-1

G~ 0.50 0.75 0.90 0.95 0.99 0.999

K:t 0.69 1.39 2.30 3.00 4.61 6.91

Values
Values of Kx corresponding
of K:e corresponding to to various
various assumed values of Gx are
of G;e are given
given in in

Table 9-1.9-1.
Calculations
Calculations of of the
the effective
effective depth
depth of penetration can be
of penetration be valuable
valuable in in
many
many applications
applications of of x-ray
x-ray diffraction.
diffraction. We may may wish to to make the effective
effective
depth
depth of of penetration
penetration as large as
as large as possible
possible in in some applications.
applications. Then aa
and p ft in
in Eq.
Eq. (9-3)
(9-3) must be
be as
as large
large as
as possible,
possible, indicating
indicating the
the use of
of high-
high-
angle lines,
angle lines, and p.
^ as
as small
small as
as possible,
possible, indicating
indicating short-wavelength
short-wavelength radia-
radia-
tion.
tion. Other
Other applications
applications may may demand very very little
little penetration,
penetration, as as when we
wish
wish infonnation,
information, e.g., e.g., chemical
chemical composition
composition or
or lattice
lattice parameter,
parameter, from a
very
very thin
thin surface
surface layer.
layer. Then we must make M large, by using
Po large, by using radiation
radiation
which is is highly absorbed,
highly absorbed, and a
a and p small, by
small, by using using a
a diffractometer
diffractometer at
at
low
low values
values of of 29. By
20.* By these
these means the depth
the depth of penetration
of penetration can often be
can often be
made surprisingly
surprisingly small. instance, if
small. For instance, if a steel
steel specimen
specimen is is examined in in a
a
diffractometer
diffractometer with with euCu KaKa. radiation,
radiation, 95 percent
percent of of the
the infonnation
information afforded
afforded
by
by the
the lowest
lowest angle line of
angle line of ferrite
ferrite (the
(the 110 line at
110 line 26 =
at 2fJ = 45)
45) applies
applies to to a
depth of
depth of only
only 9 9 X 10-10~ 55 in.
in. There
There are
are limits,
limits, ofof course,
course, to redu(~ing the
to reducing the
depth
depth of of x-ray
x-ray penetration,
penetration, and when infonnationinformation is is required
required from very very
thin surface films,
thin surface films, electron
electron diffraction
diffraction isis a
a far
far more suitable
suitable tool
tool (see
(see Appen-
Appen-
dix
dix 14).
14).

CRYSTAL ORIENTATION
9-6
9-6 General.
General. Each grain grain in
in a polycrystalline aggregate
a polycrystalline aggregate normally
normally haR
has
aa crystallographic
crystallographic orientation
orientation different
different from thatthat of of its
its neighbors.
neighbors. Con-
sidered
sidered as as a a whole,
whole, the orientations of
the orientations of all
all the
the grains
grains maymay be randomly
randomly
distributed in
distributed in relation
relation toto some selected
selected frame
frame of of reference,
reference, oror they
they may
may
tend toto cluster,
cluster, to
to a
a greater
greater or
or lesser
lesser degree,
degree, about some particular
particular orienta-
orienta-
tion
tion oror orientations.
orientations. Any Any aggregate
aggregate characterized
characterized by by the
the latter
latter condition
condition
is said to
is said to have a preferred orientation,
a preferred orientation, oror texture,
texture, which may
may be
be defined
defined
simply
simply as
as a condition
condition in
in which
which the
the distribution
distribution of
of crystal
crystal orientations
orientations is
is

nonrandom.
There areare many
many examples
examples of of preferred
preferred orientation.
orientation. The individual
individual crys-
crys-
tals
tals in
in a
a cold-drawn
cold-drawn wire,
wire, for
for instance, are so oriented
instance, are so oriented that
that the
the same crystal-
crystal-
lographic direction [uvw]
lographic direction [uvw] in
in most
most ofof the
the grains
grains isis parallel
parallel oror nearly parallel
nearly parallel

* Some of
of these
these requirements
requirements may
may bebe contradictory.
contradictory. For
For example,
example, in
in measur-
measur-
ing
ing the
the lattice
lattice parameter
parameter ofof a
a thin
thin surface
surface layer
layer ,,;th
with aa diffractometer,
diffractometer, we mUllt
must
compromise
compromise between
between the
the low
low value
value of
of 9
6 required
required for
for shallow
shallow penetration
penetration and
and the
the
high
high value
value of
of 9 required
required for
for precise
precise parameter
parameter measurements.
measurements.
9-6]
9-6] CRYSTAL ORIENTATION GENERAL
CRYSTAL ORIENTATION GENERAL 273
273

to the
to the wire
wire axis.
axis. In cold-rolled
In cold-rolled sheet,
sheet, most
most of
of the
the grains
grains are
are oriented
oriented with
with
aa certain
certain plane
plane (hkl) roughly
(hkl) roughly parallel
parallel to
to the
the sheet
sheet surface,
surface, and
and aa certain
certain
direction [uvw] in
direction [uvw] in that
that plane
plane roughly
roughly parallel
parallel to
to the
the direction
direction in
in which
which the
the
sheet was rolled.
sheet rolled. These are
These are called deformation textures.
called deformation textures. Basically,
Basically, they
they
are due
are due toto the
the tendency,
tendency, already
already noted
noted in
in Sec.
Sec. 8-6,
8-6, for
for aa grain
grain to
to rotate
rotate
during plastic
during plastic deformation.
deformation. There considered the
There we considered the rotation
rotation of of aa single
single
erystal subjected to tensile
crystal subjected to tensile forces, forces, but
but similar
similar rotations
rotations occur
occur for
for each
each
grain of
grain of an
an aggregate
aggregate as as aa result
result of of the
the complex
complex forces
forces involved,
involved, with the
with the
result that aa preferred
result that preferred orientation
orientation of of the
the individual
individual grains
grains is is produced
produced by by
the deformation
the deformation imposed
imposed on on the
the aggregate
aggregate as as aa whole.
whole.
When aa cold-worked
cold-worked metal metal or or alloy,
alloy, possessed
possessed of of aa deformation
deformation texture,texture,
is recrystallized
is recrystallized by by annealing,
annealing, the the new grain grain structure
structure usually
usually has has a pre-pre-
ferred orientation
ferred orientation too, too, often
often different
different from from that that ofof the
the cold-worked
cold-worked mate-
rial. This
rial. This isis called
called an annealing texture
an annealing texture or recrystallization texture,
or recrystallization texture, and two
kinds are
kinds are usually
usually distinguished,
distinguished, primary primary and secondary,
secondary, depending
depending on on the
the
recrystallization process
recrystallization process involved.
involved. Such textures
textures are
are due to
to the
the influence
influence
which the
which the texture
texture of of the
the matrix
matrix has has on on thethe nucleation
nucleation and/orand/or growth
growth of of
the new grains
the grains in that matrix.
in that matrix.
Preferred orientation
Preferred orientation can can also
also exist.
exist in in castings,
castings, hot-dipped
hot-dipped coatings,
coatings,
evaporated films,
evaporated films, electrodeposited
electrodeposited layers, layers, etc.
etc. Nor is it confined to metal-
is it confined to metal-
lurgical products:
lurgical products: rocks,
rocks, natural
natural and and artificial
artificial fibers
fibers and sheets,
sheets, and similar
similar
organic
organic or inorganic aggregates
or inorganic aggregates usually usually exhibit
exhibit preferred orientation. In
preferred orientation.
fact, preferred orientation
fact, preferred orientation is generally the
is generally the rule,
rule, not the exception,
not the exception, and the
preparation
preparation of of an
an aggregate
aggregate with with a a completely
completely random crystal crystal orientation
orientation
is
is a
a diffieult
difficult matter.
matter. To a a certain
certain extent,
extent, however,
however, preferred
preferred orientation
orientation
in
in metallurgical
metallurgical products
products ean can be be controlled
controlled by by the
the proper
proper operating
operating con-
ditions. For
ditions. For example,
example, some control
control of
of the
the texture
texture of
of rolled
rolled sheet
sheet is
is possible
possible
by
by the
the correct
correct choice
choice of
of degree
degree of
of deformation, annealing
deformation, annealing temperature,
temperature,
and
and annealing
annealing time.
time.
The industrial
industrial importance
importance of of preferred
preferred orientation
orientation lies lies in
in the effect,
effect, often
very marked,
very marked, which
which it
it has
has on
on the
the over-all,
over-all, macroscopic properties of
macroscopic properties of mate-
rials.
rials. Given the fact
Given the fact that that most single crystals
single crystals are
are anisotropic,
anisotropic, i.e., have
i.e.,
different properties in different
different properties in different directions, directions, it
it follows
follows that that an aggregate
aggregate
having
having preferred
preferred orientation
orientation must also also have directional
directional properties
properties to to a a
greater
greater or or lesser
lesser degree.
degree. Such properties properties are are usually
usually objectionable.
objectionable. For
example,
example, in in the
the deep
deep drawing
drawing of of sheet
sheet the the metal should
should flow flow evenly
evenly in all all

directions,
directions, but but this
this will
will not
not occur-
OCCUF if if the
the metal has a high high degree
degree of of preferred
preferred
orientation,
orientation, sincesince the
the yield point, and in
yield point, in fact
fact the
the whole flow flow stress
stress curve

of the
of the material,
material, will
will then
then differ
differ in
in different
different directions
directions in
in the
the sheet.
sheet. More
rarely,
rarely, the
the intended
intended use
use of
of the
the material
material requires
requires directional
directional properties,
properties,
and
and then
then preferred
preferred orientation
orientation is is desirable.
desirable. For example, example, the steel steel sheet
used
used forfor transformer
transformer cores cores must undergo repeated
undergo repeated cycles cycles of
of magnetization
magnetization
and
and demagnetization
demagnetization in in use,
use, requiring
requiring aa high high permeability
permeability in in the direction
direction
274
274 THE STRUCTURE
THE STRUCTURE OF POLYCRYSTALLINE AGGREGATES
OF POLYCRYSTALLINE AGGREGATES [CHAP. 99
[CHAP.

of the
of the applied
applied field.
field. Since
Since single
single crystals
crystals of
of iron
iron are
are more
more easily
easily mag-
mag-
netized in
netized in the
the [100]
[100] direction
direction than
than inin any
any other,
other, the
the rolling
rolling and
and annealing
annealing
treatments given
treatments given the
the steel
steel sheet
sheet are
are deliberately
deliberately chosen
chosen toto produce
produce aa high
high
degree
degree of
of preferred orientation,
preferred orientation, in
in which
which as
as many grains
grains as
as possible
possible have
have
their [100] directions
their [100] directions parallel
parallel to
to aa single
single direction
direction in
in the
the sheet,
sheet, in
in this
this case
case
the rolling
the rolling direction.
direction.
It should be noted
It should be noted that
that preferred
preferred orientation
orientation is
is solely
solely aa crystallographic
crystallographic
condition and
condition and has
has nothing
nothing to
to do
do with grain
with grain shape
shape as disclosed by
as disclosed by the
the micro-
micro-
scope. Therefore,
scope. Therefore, the
the presence
presence or
or absence of preferred
absence of preferred orientation
orientation cannot
cannot
be disclosed
be disclosed by
by microscopic
microscopic examination.
examination. ItIt is
is true
true that
that grain
grain -shape
.shape is
is
affected
affected by the
by the same
same forces
forces which
which produce
produce preferred
preferred orientation;
orientation; thus
thus
grains
grains become flattened
become flattened by
by rolling,
rolling, and rolling is usually
rolling is usually accompanied
accompanied byby
preferred orientation,
preferred but aa flattened
orientation, but flattened shape
shape is
is not
not in
in itself
itself direct
direet evidence
evidence
of preferred
of preferred orientation.
orientation. Only
Only x-ray
x-ray diffraction
diffraction can give
give such
such evidence.
evidence.
This fact
This fact is most
is most apparent
apparent in in recrystallized
recrystallized metals,
metals, which may have an an
equiaxed
equiaxed microstructure
microstructure and,
and, at
at the
the same time,
time, a
a high degree
high degree of
of preferred
preferred
orientation.
orientation.
At various
At various places
places in in this
this book,
book, we have already already noted
noted that
that aa pinhole
pinhole
photograph
photograph made of
of a
a polycrystalline specimen
polycrystalline specimen with
with characteristiC'
characteristic radia-
radia-
tion consists of concentric
tion consists of concentric Debye rings. Debye rings. We have
have more or
or less
less tacitly
tacitly
assumed that
assumed that these
these rings
rings areare always
always continuous and of of constant
constant intensity
intensity
around
around their circumference, but actually
their circumference, actually such rings rings are
are not formed unless
the individual
the individual crystals
crystals in in the
the specimen
specimen have completely
completely random orienta- orienta-
tions.
tions.** IfIf the
the specimen
specimen exhibits preferred orientation,
exhibits preferred orientation, the the Debye
Debye rings
rings
are
are of
of nonuniform
nonuniform intensity
intensity around their their circumference
circumference (if (if the preferred
preferred
orientation is
orientation is slight),
slight), or or actually
actually discontinuous
discontinuous (if (if there
there isis a high
high degree
degree
of
of preferred orientation).
preferred orientation). In
In the
the latter
latter case,
case, certain
certain portions
portions of
of the Debye
Debye
ring
ring are
are missing
missing because
because the the orientations
orientations which would reflect reflect to those

parts
parts of
of the
the ring
ring are
are simply
simply not
not present
present in
in the
the specimen.
specimen. Nonuniform
Debye rings
Debye rings can
can therefore
therefore be
be taken as
as conclusive
conclusive evidence
evidence for for preferred
preferred
orientation,
orientation, and by analyzing
by analyzing the
the nonuniformity
nonuniformity we can determine the
kind and degree of preferred orientation
kind and degree of preferred orientation present. present.
Preferred
Preferred orientation
orientation is is best
best described
described by by means of of a pole figure. This
pole figure. This
is
is aa stereographic
stereographic projection
projection which shows the the variation
variation in in pole
pole density
density
with
with pole
pole orientation
orientation for for a a selected
selected set set ofof crystal
crystal planes.
planes. This method of
describing
describing textures
textures was first first used
used by by the
the German metallurgist
metallurgist Wever in in
1924,
1924, and its
its meaning
meaning can can best
best be illustrated by
be illustrated by the
the following
following simple
simple ex-
ex-
ample. Suppose we have
ample. Suppose have aa very very coarse-grained
coarse-grained sheet sheet ofof a cubic
cubic metal
containing only
containing only 10
10 grains,
grains, and that
that we determine
determine the
the orientation
orientation of
of each
of these 10
of these 10 grains
grains by by one
one of
of the
the Laue methods.
methods. We decide
decide to
to represent
represent
the
the orientations
orientations of of all
all ofof these
these grains
grains together
together by by plotting
plotting the
the positions
positions ofof

* See
1

See the
the next
next section
section for
for one exception to
one exception to this
this statement.
statement.
9-6J
9-6] CRYSTAL ORIENTATION: GENERAL
CRYSTAL ORIENTATION: GENERAL 275
275

R.D
R.D RD
RD

TD TD
T D f-----:-1f----~T D TDK
T D t-;--+----+.-'i'i-rl----+:.....,..jT.D

raj
(a) (h)
(b)

FIG. 9-7.
FIG. 9-7. (100) pole
(100) pole figures
figures for
for sheet
sheet material,
material, illustrating
illustrating (a)
(a) random
random orienta-
orienta-
tion
tion and
and (b) preferred
(b) preferred orientation.
orientation. R.D.
R.D. (rolling
(rolling dirertion)
direction) and
and T.D.
T.D. (transverse
(transverse
direction) are
direction) are reference
reference directions
dirertions in
in the
the plane
plane of
of the
the sheet.
sheet.

their {100
their I
poles
{100J poles on aa single
on single stereographic
stereographic projection,
projection, with with the the projection
projection
plane parallel
plane parallel to
to the
the sheet
sheet surface.
surface. Since
Since each
each grain
grain has
has three
three {1100
100} I poles,
poles,
there will be
there will be aa total
total ofof 33 X 10 10 = = 30 poles
poles plotted
plotted on the projection. If
the projection. If

the grains
the grains have
have aa completely
completely random orientation,
orientation, thesethese poles
poles will
will bebe dis-
dis-
tributed uniformly*
tributed uniformly over over the projection, as
the projection, as indicated
indicated in in Fig.
Fig. 9-7 (a).
(a). But
if preferred orientation
if preferred orientation is is present,
present, the
the poles
poles will
will tend to
to cluster
cluster together
together
into
into certain
certain areas
areas of of the
the projection,
projection, leaving
leaving other
other areas
areas virtually
virtually unoc-
cupied. For example,
cupied. For example, this
this clustering might
clustering might take
take the
the particular
particular form shown
in Fig. 9-7(b).
in Fig. 9-7(b). This
This is
is called
called the
the "cube
"cube texture,"
texture/' because each grain grain isis

oriented with its (100) planes

oriented with its (100) planes nearly parallelnearly parallel to
to the
the sheet
sheet surface
surface and the
the
[001]
[001] direction
direction in in these
these planes
planes nearly
nearly parallel
parallel toto the
the rolling
rolling direction.
direction. (This (This
simple texture, which may
simple texture, which may be described bybe described by the
the shorthand notation (100)(100)
[001],
[001], actually
actually forms
forms as as a a recrystallization
recrystallization texture
texture in in many face-centered
face-centered
cubic
cubic metals
metals andand alloys
alloys under
under suitable conditions.) If
suitable conditions.) If we had chosenchosen to to
construct
construct aa (111)
(111) polepole figure,
figure, by by plotting
plotting only
only {1111
{111) poles,
poles, the resulting
the resulting
pole
pole figure
figure would
would looklook entirely
entirely different
different from
from Fig.
Fig. 9-7(b)
9-7 (b) forfor the
the same
same pre-
pre-
ferred
ferred orientation;
orientation; in in fact,
fact, it it would
would consist
consist of of four
four "high-intensity"
"high-intensity" areas areas
located
located near
near thethe center
center of of each
each quadrant.
quadrant. This This illustrates
illustrates the the fact
fact that
that
the
the appearance
appearance of of aa pole
pole figure
figure depends
depends on on the
the indices
indices of of the
the poles
poles plotted,
plotted,
and that
and that the
the choice
choice of of indices
indices depends
depends on on which
which aspect
aspect of of the
the texture
texture one one
wishes to
wishes to show
show most
most clearly.
clearly.

If the
* If the orientation
orientation isis random,
random, there
there will
will be
be equal
equal numbers
numbers of of poles
poles inin equal
equal
areas
areas onon the
the surface
surface of
of aa reference
reference sphere
sphere centered
centered on on the
the specimen.
specimen. ThereThere will
will
not
not bebe equal numbers, however,
equal numbers, however, on
on equal
equal areas
areas of
of the
the pole
pole figure,
figure, since
since the
the stereo-
stereo-
graphic
graphic projection
projection is
is not
not a.rea.-true.
area-true. This
This results,
results, for
for randomly
randomly oriented
oriented grains,
grains,
in
in an
an apparent
apparent clustering
clustering of poles at
of poles at the
the center
center ofof the
the pole
pole figure,
figure, since
since distances
distances
representing
representing equal
equal angles
angles areare much
much smaller
smaller inin this
this central
central region
region than
than inin other
other
parts of the pole figure.
parts of the pole figure.
276
276 THE STRUCTURE OF POLYCRYSTALLINE AGGREGATES [CHAP. 9
[CHAP. 9

Naturally,
Naturally, when the the grain
grain size
size is is small,
small, as as itit normally
normally is, is, separate
separate deter-
deter-
mination of of the
the orientations
orientations of of a a representative
representative number of of grains
grains is is out
out ofof
the question,
question, so
so x-ray
x-ray methods are
are used in
in which the
the diffraction
diffraction effects
effects
from thousands of of grains
grains are are automatically
automatically averaged. averaged. The (hkl)(hkl) pole
pole
figure
figure of
of a fine-grained
fine-grained material
material is
is constructed
constructed by analyzing
by analyzing the
the distribu-
distribu-
tion of
tion of intensity
intensity aroundaround the the circumference
circumference of of the
the corresponding
corresponding hkl hkl Debye
Debye
ring.
ring. There are
are two methods of
of doing this,
doing this, the
the photographic
photographic and the
the dif-
dif-
fractometer
fractometer method. The photographic photographic method is
is qualitative
qualitative and, al-
and, al-

though
though affording
affording sufficient
sufficient accuracy
accuracy for for many purposes, it
many purposes, it is
is rapidly
rapidly being
being
made obsolete
obsolete by by the
the more accurate
accurate diffractometer
diffractometer method. method. Both methods
are described
described in in the following
following sections.
sections.
Although
Although only only a pole pole figure
figure cancan provide
provide a a complete
complete description
description of of pre-
pre-
ferred
ferred orientation,
orientation, some information information can can be obtained
obtained simplysimply by by aa com-
parison of
parison of calculated
calculated diffraction
diffraction lineline intensities
intensities with with those
those observed
observed with with a a
Debye-Scherrer
Debye-Scherrer camera or diffractometer. As stated
or a diffractometer. stated in in Sec.
Sec. 4-12,
4-12, rela-
rela-
tive
tive line
line intensities
intensities are are given
given accurately
accurately by by Eq. (4-12) only
Eq. (4-12) only when the the
crystals
crystals of
of the
the specimen
specimen have completely
completely random orientations.
orientations. Therefore
Therefore
any
any radical
radical disagreement
disagreement between observed observed and calculated intensities is
calculated intensities is

immediate evidenceevidence of of preferred

preferred orientation
orientation in
in the
the specimen,
specimen, and, and, from
the nature of of the
the disagreement,
disagreement, certain certain limited
limited conclusions
conclusions can can usually
usually be be
drawn concerning
concerning the nature of
the nature of thethe texture.
texture. For example,
example, if if aa sheet
sheet
specimen
specimen is is examined in in the
the diffractometer
diffractometer in in the
the usual
usual way
way (the (the specimen
specimen
making
making equal equal angles
angles with with thethe incident
incident and diffracted
diffracted beams),
beams), then then the the
only
only grains
grains which can contribute contribute to to the hkl reflection
the hkl reflection are are those
those whose
whose
(hkl) planes
(hkl) planes are parallel to
are parallel to the
the sheet
sheet surface.
surface. If If the
the texture
texture is is such
such that
that
there
there areare very
very few such such grains,
grains, the the intensity
intensity of of the hkl reflection
the hkl reflection will will bebe
abnormally
abnormally low. low. Or aa given given reflection
reflection may may be be of abnormally high
of abnormally high inten-
inten-
sity,
sity, which would indicate indicate thatthat the corresponding planes
the corresponding planes werewere preferen-
preferen-
tially
tially oriented
oriented parallel
parallel or
or nearly parallel
nearly parallel to
to the
the sheet
sheet surface.
surface. As an an
illustration,
illustration, the
the 200 diffractometer
diffractometer reflection
reflection from
from a
a specimen
specimen having having the
the
cube texture
texture is is abnormally
abnormally high, high, and from this this factfact alone
alone it it is possible to
is possible to
conclude that
conclude that there
there is is a preferred
preferred orientation
orientation of of (100) planes parallel
(100) planes parallel to to
the sheet
the sheet surface. However, no conclusion
surface. However, is possible as to
conclusion is possible as to whether or not whether or not
there is
there is aa preferred
preferred direction
direction in in the
the (100) plane parallel
(100) plane parallel to to some
some reference
reference
direction on the
direction the sheet
sheet surface.
surface. Such Such information
information can can be be obtained
obtained only only by by
making aa pole
making pole figure.
figure.

9-7 The texture

9-7 texture ofof wire
wire and rodrod (photographic
(photographic method).
method). As As mentioned
mentioned
in the previous section, cold-drawn
in the previous section, cold-drawn wirewire normally
normally has
has aa texture
texture inin which
which aa
certain crystallographic
certain crystallographic direction [uvw] in
direction [uvw] in most
most of
of the
the grains
grains is
is parallel,
parallel,
or nearly
or nearly parallel,
parallel, toto the
the wire
wire axis.
axis. Since
Since aa similar
similar texture
texture isis found
found inin
natural and artificial
natural artificial fibers, it is
fibers, it is called fiber texture
called aa fiber texture and
and thethe axis
axis of
of the
the
wire is
wire is called
called the
the fiber axis. Materials
fiber axis. Materials having
having aa fiber
fiber texture
texture have
have rota-
rota-
9-7)
9-7] THE
THE TEXTURE
TEXTURE OF WIRE AND
OF WIRE AND ROD
ROD (PHOTOGRAPHIC
(PHOTOGRAPHIC METHOD)
METHOD) 277
277

F.A

Debye
.Debye
nng
ring

reflection
circle

"V.
" reference
referenee
sphere
sphere

FIG. 9-8.
FIG. Geometry of
9-8. Geometry of reflection
reflection from
from material
material having
having aa fiber
fiber texture.
texture. F.A.
F.A. =
=
fiber axis.
fiber axis.

tional
tional symmetry
symmetry about about an axis in the
axis in the sense that all
sense that all orientations
orientations about this this
axis
axis areare equally probable.
equally probable. A fiber
fiber texture
texture is
is therefore
therefore to be
be expected
expected in
in

any
any material
material formed
formed by
by forces
forces which have rotational
rotational symmetry
symmetry about a
line,
line, for
for example,
example, in
in wire
wire and rod,
rod, formed by drawing,
by drawing, swaging,
swaging, or extru-
sion.
sion. LessLess common examples examples of of fiber
fiber texture
texture are are sometimes found in in sheet

formed
formed by simple compression,
by simple compression, in
in coatings
coatings formed by
by hot-dipping, electro-
hot-dipping, electro-
deposition,
deposition, and
and evaporation,
evaporation, and in
in castings
castings amongamong the columnar crystals
crystals
next
next to to the
the mold wall.
wall. The fiber fiber axis
axis in in these
these is is perpendicular
perpendicular to the plane plane
of
of the
the sheet
sheet oror coating,
coating, and parallel
parallel to to the
the axis
axis ofof the columnar crystals.crystals.
Fiber
Fiber textures
textures vary vary in in perfeetion,
perfection, i.e., i.e., in
in the scatter
scatter of of the direction

[uvw] about
[uvw] about the
the fiber
fiber axis,
axis, and both single single and double fiber textures
fiber textures have
been
been observed.
observed. Thus,Thus, cold-drawn
cold-drawn aluminum wire has a single
wire has a single [111]
[111] texture,
texture,
but
but copper,
copper, alsoalso face-centered
face-centered cubic, cubic, has a double [Ill] [111] + + [100]
[100] texture;
texture;
i.e., in drawn copper wire there
i.e., in drawn copper wire
there are
are two sets sets ofof grains,
grains, the fiber
fiber axis of of one
set
set being
being [111]
[111] and that that ofof the
the other
other set set [100].
[100].
The
The onlyonly crystallographic
crystallographic problem problem presented
presented by by fiber
fiber textures is is that

of
of determining
determining the
the indices
indices [uvw]
[uvw] of
of the
the fiber
fiber axis,
axis, and
and that
that problem
problem is
is best
best
approached
approached by by considering
considering the
the diffraction
diffraction effects
effects associated
associated with
with an
an ideal
ideal
case,
case, forfor example,
example, that that of of aa wire
wire ofof a a cubic
cubic material
material having
having aa perfect
perfect [100]
[100]
fiber
fiber texture.
texture. Suppose
Suppose we
we consider
consider only
only the
the III
111 reflection.
reflection. In
In Fig.
Fig. 9-8,
9-8,
the
the wire
wire specimen
specimen is
is at
at C
C with
with its
its axis
axis along
along NS,
NS, normal
normal to
to the
the incident
incident
beam Ie.
beam 1C. C CPP isis the
the normal
normal to to aa setset ofof (111)
(111) planes.
planes. Diffraction
Diffraction from from
these planes
these planes can
can occur
occur only
only when
when they
they are
are inclined
inclined to
to the
the incident
incident beam
beam
 278
278 THE STRUCTURE
THE STRUCTURE OF
OF POLYCRYSTALLINE AGGREGATES
POLYCRYSTALLINE AGGREGATES [CHAP. 99
[CRAP.

F A.
FA. F.A
F.A

I reflect ion circle

pi
I
I

(u) (b)

FIG. 9-9. Perfect [100] fiber

Perfect [100] fiber texture:
texture: (a) (1 11) pole
(a) (111) pole figure; (b) location
figure; (h) location of
of reflect-
reflect-
ing
ing plane
plane normals.
normals.

at
at anan angle
angle 8 which satisfies
satisfies the
the Bragg
Bragg law,
law, and thisthis requires
requires that
that the the (111)
(111)
pole
pole lielie somewhere on the circle PUV,
the circle PUV, since since then
then thethe angle
angle between
between the the
plane
plane normal and the incident incident beam will will always
always be be 9090 0 - 8. 6. For
For this
this
reason, PUQV is
reason, is called the reflection
called the reflection circle.
circle. If
If the
the grains
grains of of the
the wire
wire had
had
completely
completely random orientations,
orientations, then then (111)
(111) poles
poles would
would lie lie at
at all
all positions
positions
on the reflection circle, and
reflection circle, and thethe 111 reflection would
111 reflection consist of
would consist of the com-
the com-
plete Debye
plete Debye ring ring indicated
indicated in in thethe drawing.
drawing. But But if if the
the wire
wire hashas aa perfect
perfect
[100] fiber texture,
[100] fiber texture, thenthen the
the diffraction
diffraction patternpattern produced
produced by by aa stationary
stationary
specimen
specimen is
is identical
identical with
with that
that obtained
obtained from
from a
a single crystal rotated
single crystal rotated about about
the axis
the axis [100],
[100], because
because of of the
the rotational
rotational symmetry
symmetry of of the
the wire.
wire. DuringDuring
this rotation,
this rotation, the the (111)
(111) pole
pole is
is confined
confined to to the
the small
small circle PAQB, all
circle PAQB, all points
points
of which
of which make aa constant angle
constant =
angle pp = 54.7 54.7 with
0 with the
the [100]
[100] direction
direction N. N. Dif-Dif-
fraction can
fraction can now occur occur only
only when
when the the (111)
(111) pole
pole lies
lies at
at the
the intersections
intersections
of the
of the reflection
reflection circle
circle and
and the
the circle PAQB. These
circle PAQB. These intersections
intersections are are located
located
at P and
at and Q, Q, and
and thethe corresponding
corresponding diffraction
diffraction spots
spots at at /?Rand
and T, T, atat an
an
azimuthal angle
azimuthal angle aa from
from aa vertical
vertical lineline through
through the the center
center of of the
the film.
film. TwoTwo
other spots,
other not shown,
spots, not shown, areare located
located in in symmetrical
symmetrical positions
positions on on thethe lower
lower
half of
half of the film. If
the film. If the
the texture
texture isis not not perfect,
perfect, each
each ofof these
these spots
spots will
will
broaden peripherally
broaden peripherally into into an
an arc
arc whose length isis aa function
whose length function of of the
the degree
degree
:>f scatter
^f scatter in in the
the texture.
texture.
By solving
By solving thethe spherical
spherical triangle
triangle IPN, lPN, we we can
can find
find the
the following
following general
general
relation between
relation between the the angles
angles p,P, 0,8, and
and a:a:
cos pp
cos == cos
cos B(J cos
cos a.
a. (9-6)
(9-6)

rhese angles
These angles are
are shown
shown stereographically
stereographicaIIy in
in Fig.
Fig. 9-9,
9-9, projected
projected on
on aa plane
plane
lorma} to
lormal to the
the incident
incident beam.
beam. The (111)
The (111) pole
pole figure
figure in
in (a)
(a) consists
consists simply
simply
9-7]
9-7] THE TEXTURE OF WIRE AND ROD (PHOTOGRAPHIC'
(PHOTOGRAPHIC M}<,THOD)
METHOD) 279
of
of two arcs
arcs which are are the pathspaths traced
traced out
out by fill} pole~
by /111} poles during
during rot.ation
rotation
of
of a single
single cryRtal
crystal about [100]. [100]. In In (b),
(b), this pole figure
this pole figure has
has h('en
been superposed
superposed
on a projection
projection of of the reflection (~irde
the reflertion circle in
in order
order toto find
find the
the locations
locations of of the
the
reflecting plane
reflecting plane normals. Radii
Radii drawn through
through these
these point.s (p, Q.
points (P, Q, P', P',
and Q')
Q') then enable
enable the
the angle
angle ex
a to
to be
be measured and the
the appearance
appearance of
of the
the
diffraction pattern to
diffraction pattern to he predicted.
be predicted.
An unknown fiber fiber axil'!
axis is is identified
identified
by measuring
by measuring the
the angle
angle ex
a on thethe
film
film and obtaining
obtaining p p from Eq. Eq. (9-6).
(9-6).
When thisthis isis done for
for a numher of
a number of dif-
dif-

ferent hkl reflections,

ferent hkl reflections, a a set
set of p values
of p values
is
is ohtained
obtained from which the the indices
indices

[uvw] of
[uvw] of the
the fiber
fiber axis
axis eancan he be det.er-
deter-
mined.
mined. The procedureprocedure will will bE'
be illus-
illus-

trated reference to
trated with reference to the
the diffraction
diffraction

pattern of
pattern of drawn aluminum wire wire
shown in in Fig.
Fig. 9-10.
9-10. The fir~t
first step
step isis

to
to index
index thethe incomplete Debye
incomplete Debye rings. rings.
Values of 6 for
of (J for each
each ring
ring are
are calculated
calculated
from measurement~
measurements of of ring
ring diameter,
diameter,
and hkl indices
indices areare assigned
assigned by by the
the use
use FIG.
FIG. 9-10.
9-10. Tramunission pinhole
Transmission pinhole
of
of Eq.
Eq. (3-10) Appendix n.
(3-10) and Appendix 0. In
In pattern
pattern of of rold-drawn
cold-drawn aluminum wire, wire,
this
this way wire axiH
wire axis vertieu\. Filtered
Filtered eopper
way thethe inner
inner ring
ring isis identified
identified as
vertical. copper
as
radIatIOn.
radiation, (The
(The radial
radial RtreakR
streaks near
near
aa 111
111 reflection
reflection and the the outer
outer one one asas
the
the center
center are
are formed by by the
the white
white
200.
200. The angle angle ex a is
is then
then measured ra.c:hation
radiation in in the
the inCident
incident beam.)
beam.)
from aa vertical
vertical lineline through
through the the center
center
of
of the
the film
film toto the
the center
center of of ea(~h
each strong
strong Debye
Debye are.arc. The average
average values
values ofof
these
these angles
angles are
are given below, together
given below, together with
with t.he
the calculated
calculated value~
values of
of p:
p:

Line hkl
hkl ex (J

Inner
Inner 111
111 69 19.3
19.3 70
Outer 200 52 22.3
22.3 55

The normals
normals to to the
the (111)
(111) and (200)
(200) planes
planes therefore
therefore make angles
angles ofof 70
70
and 55,
55, respectively,
respectively, with
with the
the fiber
fiber axis.
axis. We can
can determine the the indices
indices
[uvw]
[uvw] of
of this
this axis
axis either
either by
by the
the graphical
graphical construction
construction shown in in Fig.
Fig. 8--8
8-8 or
or
by inspection of
by inspection of a
a table
table of
of interplanar
interplanar angles.
angles. InIn this
this case,
case, inspection
inspection ofof
Table 2-3 shows that
Table 2-3 that [uvw]
[uvw] must be be [111],
[111], since
since the
the angle
angle between (111) (111)
and (111)
(111) is 70.5 and that
is 70.5 that between (111)(111) and (100)
(100) isis 54.7,
54.7, and these
these
values
values agree
agree with
with the
the values
values of
of p given
p given above within
within experimental
experimental error.
error.
The fiber axis of
fiber axis of drawn aluminum wire is therefore
wire is therefore [111].
[111]. There isis some

scatter of
scatter of the
the [Ill]
[111] direction
direction about
about the
the wire
wire axis, however,
axis, however, inasmuch as
as
the
the reflections
reflections onon the
the film
film are
are short
short arcs
arcs rather
rather than
than sharp spots.
sharp spots. If
If we
280
280 POLYCRYSTALLINE AGGREGATES
THE STRUCTURE OF POLYCRYSTALLINE 9
[CHAP. 9
[CHAP.

wish, this
wish, this can
can be
be taken
taken into
into account
account by measuring
by measuring thethe angular
angular range
range ofof
a
a for each
for each arc
arc and
and calculating
calculating the
the corresponding
corresponding angular
angular range
range of p. A
of p.
(111) pole
(111) pole figure
figure ofof the
the wire
wire would
would thenthen resemble
resemble Fig.
Fig. 9-9
9-9(a) except that
(a) except that
the two
the two curved
curved lines
lines would
would bebe replaced
replaced by by two curved
curved bands,
bands, each
each equal
equal
in width
in width toto the
the calculated
calculated range
range ofof pp for
for the
the (111)
(111) poles.
poles.
One other
One other aspect
aspect ofof fiber
fiber textures
textures should
should be be noted.
noted. InIn materials
materials having
having
a fiber
a fiber texture,
texture, thethe individual
individual grains
grains havehave aa common crystallographic
crystallographic
direction parallel
direction parallel toto the
the fiber
fiber axis
axis but
but they
they cancan have any
any rotational
rotational posi-
posi-
tion about that axis. It
tion about that axis. It followsfollows that
that the
the diffraction
diffraction pattern
pattern of
of such
such mate-
mate-
rials will
rials will have
have continuous
continuous DebyeDebye rings
rings ifif the
the incident
incident x-ray
x-ray beam is is parallel
parallel
to the
to the fiber
fiber axis.
axis. However,
However, thethe relative
relative intensities
intensities of
of these
these rings
rings will
will not
not
be the
be the same
same asas those
those calculated
calculated for
for aa specimen containing randomly
specimen containing randomly oriented
oriented
grains. Therefore,
grains. Therefore, continuous
continuous Debye
Debye ringsrings are not, in
are not, in themselves,
themselves, evi- evi-
dence for
dence for aa lack
lack of
of preferred
preferred orientation.
orientation.

9-8 The
9-8 The texture
texture of of sheet
sheet (photographic method). The texture
(photographic method). texture of of rolled
rolled
sheet,
sheet, either
either as
as rolled
rolled or
or after
after recrystallization,
recrystallization, differs
differs from that
that of
of drawn
wire in having
wire in having lessless symmetry.
symmetry. There is is no longer
longer a a common crystallo-crystallo-
graphic
graphic direction
direction about
about which
which the
the grains
grains can
can have any
any rotational
rotational position.
position.
Sheet textures can therefore
Sheet textures can therefore be
be described
described adequately only
adequately only by by means of
of aa
pole figure,
pole figure, since
since only this gives
only this gives a complete map
a complete map of the distribution of
of the distribution of
crystal
crystal orientation.
orientation.
The photographic
photographic method of of determining
determining the pole figure
the pole figure of of sheet
sheet isis quite
quite
similar
similar toto the
the method just just described
described for for determining
determining wire wire textures.
textures. A
transmission pinhole camera is
transmission pinhole is used,
used, together
together with general
general radiation
radiation con- con-
taining
taining aa characteristic
characteristic component.
component. The sheet sheet specimen,
specimen, reduced in in thick-
thick-
ness
ness by etching
by etching to
to a
a few
few thousandths
thousandths of
of an inch,
inch, is
is initially
initially mounted per-
per-
pendicular
pendicular to
to the
the incident
incident beam with
with the
the rolling
rolling direction
direction vertical.
vertical. The
resulting
resulting photograph
photograph resembles
resembles tha.ttha,t of
of a a drawn wire:
wire: it it contains
contains DebyeDebye
rings
rings of
of nonuniform
nonuniform intensity
intensity and the
the pattern
pattern is
is symmetrical
symmetrical about a a
vertical line through
vertical line through the
the center
center of
of the
the film.
film. However,
However, if
if the
the sheet
sheet is
is now
rotated
rotated by,
by, say,
say, 10
10 about
about thethe rolling
rolling direction
direction and another
another photograph
photograph
made,
made, the
the resulting
resulting pattern
pattern .will
.will differ
differ from the the first,
first, because
because the the texture
texture
of
of sheet
sheet does
does notnot have
have rotational
rotational symmetry
symmetry about the the rolling
rolling direction.
direction.
This new pattern
pattern will
will not
not bebe symmetrical
symmetrical about a vertical vertical line, line, and the the
regions of
regions of high
high intensity
intensity on the the Debye
Debye ringsrings will
will not
not have the the same azi- azi-
muthal positions
positions as they had in
as they in the
the first
first photograph.
photograph. Figure Figure 9-119-11 illus-
illus-

trates
trates this
this effect
effect for
for cold-rolled aluminum. To determine
cold-rolled aluminum. determine the the complete
complete
texture
texture ofof sheet,
sheet, itit is
is therefore
therefore necessary
necessary to to measure the the distribution
distribution of of
orientations
orientations about
about thethe rolling
rolling direction
direction by making
by making several
several photographs
photographs
with
with the
the sheet
sheet normal
normal at at various
various angles
angles to to the
the incident
incident beam.
beam.
Figure
Figure 9-12
9-12 shows
shows thethe experimental
experimental arrangement
arrangement and defines defines the the angle
angle
"ft between
between thethe sheet
sheet normal and the the incident
incident beam.
beam. The intensityintensity of of the
the
9-8]
9-8] THE TEXTURE
THE TEXTURE OF
OF SHEET
SHEET (PHOTOGRAPHIC
(PHOTOGRAPHIC METHOn)
METHOD) 281
281

f4?if
VHP j
[ji

fr
>: ! v

%/miffim '^1 ,, i
^ i(

';
;igvj
,v
% r
\
,
I

^^;*^/^K
,

^"MJ/I \A/
''/^ l"^"

FIG. 9-11. Transmission pinhole

FIG. 9-11. pinhole patterns
patterns of
of cold-rolled
cold-rolled alUmmum
aiummum sneet,
sneet, rOilIng
roiling
direction
direction vertical:
vertical: (a)
(a) sheet normal parallel to incident
parallel to incident beam;
beam; (b)
(b) sheet
sheet normal
normal atat
30
30 toto incident
incident beam (the(the specimen
specimen has been
been rotated
rotated clockwise
clockwise about
about the
the rolling
rolling
direction,
direction, as
as in
in Fig. 9-12). Filtered
Fig. 9-12). Filtered copper
copper radiation.
radiation.

diffracted
diffracted rays
rays in
in anyone
any one Debyc
Debye cone is is decreased
decreased by by absorption
absorption inin the
the
specimen by an amount which depends depends on the
the angle {3,
angle 0, and when {3 is not
ft is not

zero the
zero the rays going to
rays going to the left
left side
side of the film
of the undergo more
film undergo absorption
more absorption
than
than those
those going
going to
to the
the right.
right. For this
this reason
reason itit is
is often
often advisable
advisable to
to make
make
measurements only
measurements only on the right
right side
side of
of the
the film,
film, particularly
particularly when
when ft is
{3 is
large.
large.
The
The usual
usual practice
practice is
is to
to make photographs
photographs at at about
about 10 10 intervals
intervals from
from
ft
= to =
{3 = 0 to ft{3 = 80,
80, and to
to measure thethe intensity
intensity distribution
distribution around
around aa par-
par-
film RD
TD

~
-C'~:'(\
I,
\
I
"- I I
~h('l't
sheet
normal
llurmal
TD
TD \ I
\
\

'- J
FIG. 9-12.
FIG. 9-12. Section through
Section through sheet
sheet
specimen and
specimen and incident
incident beam
beam (specimen
(specimen FIG. 9-13.
FIG. 9-13.Measurementofazimuthal
Measurement of azimuthal
thickness exaggerated).
thickness exaggerated). Rolling
Rolling direc-
direc- position of high-intensity
position of high-intensity arcs
arcs on aa
on
tion normal
tion normal to plane ofof drawing.
to plane drawing. Debye ring. ft{3 == 40,
Debye ring, 40, R.D.
R.D. == rolling
rolling
T.D. == transverse
T.D. transverse direction.
direction. direction.
direction.
282
282 THE STRUCTURE OF POLYCRYSTALLINE AGGREGATES [CHAP. 9
[CHAP. 9

R.D.

T.D. + ==i TD.

FIG.
FIG. 9-14.
9-14. Method of of plotting
plotting reflecting
reflecting pole
pole positions
positions for
for nonzero
nonzero values
values of
of
(3.
ft. Drawn for
for 8 = 10
6 = 10 and (3 = 40.
ft = 40.

ticular
ticular Debye
Debye ringring on each photograph. The procedure
each photograph. procedure for plotting the
for plotting the
pole figure
pole figure from these
these measurements will
will be illustrated
illustrated here
here for
for an idealized
idealized
case
case like
like that
that shown in in Fig.
Fig. 9-13,
9-13, where the the intensity
intensity ofof the
the Debye
Debye ringring is
is

constant
constant overover certain
certain angular ranges
angular ranges and zero
zero between them. The range
range
of
of blackening
blackening of of the
the Debye
Debye arcs arcs is
is plotted
plotted stereographically
stereographically as as a a range
range ofof
reflecting pole positions
reflecting pole positions along along the
the reflection
reflection circle,
circle, the
the azimuthal
azimuthal angle
angle a
on the
the film
film equal
equal to to the
the azimuthal
azimuthal angle
angle a on the
the projection. Although
projection. Although
the reflection circle is
reflection circle is fixed
fixed inin space
space (see
(see Fig. 9-8 where S(W
Fig. 9-8 SCN is is now thethe
rolling
rolling direction
direction of
of the
the sheet
sheet specimen),
specimen), its
its position
position on the
the projection
projection
varies
varies with the the rotational
rotational position
position (3 of of the
the specimen,
specimen, since
since the projection
the projection
plane
plane is
is parallel
parallel to
to the
the surface
surface of
of the sheet
the sheet and rotates
rotates with
with it.
it.

When (3 = = 0,
ft0, the
the reflection
reflection circle
circle isis concentric
concentric withwith the
the basic
basic circle
circle of
of
the
the projection
projection and 8 degrees inside
degrees inside it, asit, as shown in
in Fig. 9-14, which is
Fig. 9-14, which is

drawn for for 8 = = 10.

10. When the the specimen
specimen is is then
then rotated,
rotated, forfor example
example by by
40
40 inin t.he
the sense
sense shown in in Fig.
Fig. 9-12,
9-12, thethe new position
position ofof the
the reflection
reflection circle
circle
is
is found by rotating
by rotating two or
or three
three points
points on on the
the 0 .reflection
.reflection circle
circle bvbv 40
40
9-8J
9-8] 6HEET (PHOTOGRAPHIC
THE TEXTURE OF SHEET (PHOTOGRAPHIC METHOD) 283
283

to
to the
the right
right along
along latitude
latitude lines
lines and drawing
drawing circle
circle arcs,
arcs, centered
centered on the the
equator
equator or or its
its extension,
extension, through
through these points. This new position
these points. position of of the
the
reflection
reflection circle
circle is
is indicated
indicated by by the arcs ABCDA
the arcs ARCDA in in Fig.
Fig. 9-14;
9-14; since
since in
in this
this
example
example {3 exceeds
exceeds 8, 0, part
part of of the reflection
reflection circle, namely CDA,
circle, namely CD A, lieslies in
in the
back hemisphere.
hemisphere. The arcs arcs in in Fig.
Fig. 9-13 are are first plotted on the
first plotted the 0 reflec-
reflec-
tion
tion circle,
circle, as
as though
though the the projection
projection plane plane were stillstill perpendicular
perpendicular to to the
the
incident
incident beam,
beam, and then rotated rotated to to the right
right along
along latitude
latitude circles
circles onto
onto
the 40
40 reflection
reflection circle.
circle. Thus,
Thus, arc arc MINI
M\N\ in Fig. 9-13 becomes M2N2
in Fig. M 2 A^2 and
then,
then, finally, M3 7V3 inin Fig.
finally, MaNa Fig. 9-14.
9-14. Similarly,
Similarly, Debye
Debye arc arc U I VI is
U\Vi is plotted
plotted as as
U aVa, lying
U^Vz, lying on the
the back hemisphere.
hemisphere.
The texture
texture ofof sheet
sheet isis normally
normally such that that two planes
planes of of symmetry
symmetry exist,exist,
one normal to to the
the rolling
rolling direction
direction (R.D.)(R.D.) and one normal to to the
the trans-
trans-
verse
verse direction
direction (T.D.).
(T.D.). For thisthis reason,
reason, arc -M 3 W 3 may be reflected
arc MaNa reflected in in
the
the latter plane to
latter plane to give
give the
the arcarc M M^N^4N4, thus helping
helping to to fill
fill out the pole
the pole
figure.
figure. These symmetry
symmetry elementselements are are also
also the justification for
the justification plotting
for plotting
T
the arc U
the arc t a F 3 as
3 Va as though
though it it were situated
situated on the front front hemisphere,
hemisphere, since since
reflection
reflection inin the
the center
center of of the
the projection
projection (to bring it
(to bring it to
to the
the front
front hemi-
sphere)
sphere) and successive
successive reflections
reflections in in the
the two symmetry
symmetry planesplanes will
will bring
bring it it

to
to this
this position anyway. If
position anyway. If the
the diffraction patterns indicate
diffraction patterns indicate that that these
these
symmetry
symmetry planes
planes areare not present,
present, then these these short
short cuts
cuts in plotting may
in plotting may
not be used.
used.
By
By successive
successive changes
changes in in {3,0, the
the reflection
reflection circle
circle can
can be be made to to move
across
across the
the projection
projection and so so disclose
disclose thethe positions
positions of reflecting poles.
of reflecting poles. With
the
the procedure
procedure described,
described, however,
however, the the regions
regions near the N
near the Nand and S poles
poles ofof
the
the projection
projection will
will never be be cutcut byby a reflection
reflection circle.
circle. To explore
explore these
these
regions,
regions, we must rotate rotate thethe specimen
specimen 90 90 0 in
in its
its own plane,
plane, so so that
that thethe
transverse
transverse direction
direction is is vertical,
vertical, and take take a photograph with {3
a photograph @ =~ 50.
5.
Figure
Figure 9-15
9-15 shows what might might result
result from a a pole
pole figure
figure determination
determination
involving
involving measurements at
at {3 =
= 0,
0, 20,
20, 40,
40, 60,
60, and 80 0 (R.D. vertical) and
(R.D. vertical)

R.D R.D

1------I--------lT.D .
T.D.

T.D.
FIG. 9-16.
FIG. 9-16. Hypothetical
Hypothetical pole
pole figure
figure
FIG.
FIG. 9-15.
9-15. Plotting
Plotting a pole figure.
a pole figure. derived
derived from
from Fig.
Fig. 9-15.
9-15.
284
284 THE
THE STRUCTURE
STRUCTURE OF POLYCRYSTALLINE AGGREGATES
OF POLYCRYSTALLINE AGGREGATES [CHAP. 99
[CHAP,

{J =
= 55 (T.D.
(T.D. vertical).
vertical). The
The arcs
arcs in
in Fig.
Fig. 9-14
9-14 areare replotted
replotted here
here with
with the
the
same symbols,
same symbols, and
and the
the arcs
arcs E\Fi and E
E1Fl and E2F2
2 F 2 lie
lie on
on the
the 55 reflection
reflection circle
circle
with the transverse
with the transverse direction
direction vertical.
vertical. The
The complete
complete setset of
of arcs
arcs defines
defines
areas of
areas of high
high pole
pole density
density and,
and, by reflecting
by reflecting these
these areas
areas in in the
the symmetry
symmetry
planes
planes mentioned
mentioned above,
above, we arrive
arrive at
at the
the complete pole figure
complete pole figure shown shown in in
Fig.
Fig. 9-16.
9-16. R.D
R.D
In practice,
In practice, the the variation
variation of of inten-
inten-
sity around
sity around aa DebyeDebye ringring is is not
not abrupt
abrupt
but gradual,
but gradual, as Fig. as Fig. 9-11
9-11 demon-
strates. This
strates. This is is taken
taken into into account
account
by plotting
by plotting ranges
ranges in in which the the in-in-
tensity is
tensity is substantially
substantially constant,
constant, and
T.D
no more
no more than than four
four such
such ranges
ranges are are
usually required,
usually required, namely,
namely, zero, zero, weak,
weak,
medium,
medium, and
and strong.
strong. The result
result is
is

a pole
a pole figure
figure in in which
which various
various areas,
areas,
distinguished by
distinguished by different
different kinds kinds of of
cross-hatching, represent
cross-hatching, represent various
various de-
de-
grees of
grees of pole
pole density
density from zero zero to to aa FIG. 9-17.
FIG. 9-17. (Ill) pole figure
(111) pole figure ofof re-
re-
maximum. Figure Figure 9-17 is is aa photo- crystallized 70-30
photo- crystallized 70--30 brass, <letermined
brass, determined
the photographic
by the photographic method. (R. (R.. M.
graphically determined pole
graphically determined pole figure
figure in in by Brick, Trans. A .l.M.E. 137,
Brick, Trans. A.I.M.E. 137, 193,
193, 1940,)
1940.)
which this
which this hashas been done. It
been done. It repre-
repre-
sents the primary
sents the primary recrystallization
recrystallization texture texture of of 70-30 brass
brass which has been
cold-rolled to
cold-rolled to aa 99
99 percent
percent reduction
reduction in in thickness and then annealed at at
400C
400C for for 3030 minutes.
minutes.
The texture
texture of of sheet
sheet is is often
often described
described in in terms of of an "ideal
"ideal orientation,"
orientation,"
i.e.,
i.e., the
the orientation
orientation of
of aa single crystal
single crystal whose poles
poles would lie
lie in
in the high-
high-
density regions
density regions of
of the
the pole figure.
pole figure. For example,
example, in
in Fig.
Fig. 9-17 the solid
solid
triangular symbols
triangular symbols mark the
the positions
positions of
of the
the 11111 poles
Jill} poles of
of a single crys-
single crys-
tal
tal which has has its
its (113)
(113) plane parallel to
plane parallel to the
the plane
plane of of the sheet and the
[211]
[211] direction
direction in in this
this plane
plane parallel
parallel to to the
the rolling
rolling direction.
direction. This orienta- orienta-
tion,
tion, when reflected
reflected in in the
the two symmetry
symmetry planes planes normal to the rolling
to the rolling and
transverse
transverse directions,
directions, willwill approximately
approximately account for for all
all the high-density
high-density
regions
regions on on thethe pole
pole figure.
figure. Accordingly,
Accordingly, this this texture
texture has been called called a

(113) [211]
(113) [2ll] texture.
texture. The actual actual polepole figure,
figure, however,
however, is is a far
far better de-
scription
scription of of the texture than
the texture than any, statement of
any statement of an ideal
ideal orientation,
orientation, since
the
the latter
latter is is frequently
frequently not
not very
very exact
exact and gives
gives no information about the
degree
degree of
of scatter
scatter of
of the
the actual
actual texture
texture about
about the
the ideal
ideal orientation.
orientation.
The inaccuracies
inaccuracies of of photographically
photographically determined pole pole figures
figures areare due
to
to two factors:
factors:

(1)
(1) intensity
intensity "measurements"
"measurements" made on
on the
the film
film are
are usually
usually only
only visual
visual
estimates, and
estimates, and
9-9]
9-9] THE TEXTURE
THE OF SHEET
TEXTURE OF SHEET (DIFFRACTOMETER
(DIFFRACTOMETER METHOD)
METHOD) 285
285

(2) no
(2) no allowance
allowance is is made
made for
for the
the change
change inin the
the absorption
absorption factor
factor with
with
changes
changes in
in {3 and
and
ft a.
a. This
This variation
variation in
in the
the absorption
absorption factor
factor makes
makes it
it very
very
difficult to relate
difficult to relate intensities
intensities observed
observed on on one
one film
film to
to those
those observed
observed on on
another,
another, even
even when
when the
the exposure
exposure time
time is
is varied
varied for
for different
different films
films in
in an
an
attempt to
attempt to allow
allow for
for changes
changes inin absorption.
absorption.

9-9 The texture

9-9 texture of
of sheet
sheet (diffractometer
(diffractometer method).
method). In recent
In recent years
years
methods have
methods have been
been developed
developed for
for the
the determination of pole
determination of pole figures
figures with
with
the diffractometer.
the diffractometer. These
These methods are
are capable
capable of
of quite
quite high
high precision
precision
because
because
(1) the
(1) the intensity
intensity of of the
the diffracted
diffracted raysrays isis measured quantitatively
quantitatively with with
a counter,
a counter, and and
(2) either
(2) either the the intensity
intensity measurements are are corrected
corrected forfor changes
changes in in ab-
ab-
sorption, or
sorption, or the
the x-ray
x-ray optics
optics are
are so
so designed
designed that that the the absorption
absorption is constant
is constant
and no
and no correction
correction is is required.
required.
For reasons
For reasons given given later,
later, two different
different methods must be used to to cover
cover
the whole
the whole pole pole figure.
figure.
The first
The first of of these,
these, called
called the
the transmission
transmission method, method, is is due to to Decker,
Decker,
Asp,
Asp, and
and Harker,
Harker, and
and Fig.
Fig. 9-18
9-18 illustrates
illustrates its
its principal
principal features.
features. To deter-
deter-
mine an
mine an (hkl) pole figure,
(hkl) pole figure, the
the counter
counter is
is fixed
fixed in
in position
position at
at the
the correct
correct
angle 26
angle 28 to to receive
receive the hkl reflection.
the hkl reflection. The sheet specimen, in
sheet specimen, in aa special
special
holder,
holder, is
is positioned initially
positioned initially with
with the
the
rolling direction
rolling direction vertical
vertical and and coinci-
coinci- sp!'cilllPn /
specimen
dent
dent with
with the the diffractometer
diffractometer axis, axis,** Debye ( 11
1
I
normal /
normal/
/
and
and with
with the plane of
the plane of the
the specimen rinll: 1<> /.)0
specimen
I /
bisecting
bisecting the the angle between the
angle between the inci-
inci-
dent
dent and
and diffracted
diffracted beams.
beams. The speci- speci- 'PP(,1Il11'1l
men holder
holder allows allows rotation
rotation of of the
the
specimen
specimen about about the the diffractometer
diffractometer diffractometer
axis
axis and
and about
about a a horizontal
horizontal axis axis nor-
nor- axis
aXIS

mal
mal to to the the specimen
specimen surface.
surface. Al-
Al-
though
though it it isis impossible
impossible to to move the the
counter
counter
counter around
around the the Debye
Debye ringring and so
so
explore
explore the the variation
variation in in diffracted
diffracted in- in-

tensity around
tensity around this ring,this ring, we can ac-
ac-
FIG.
FIG. 9-18.9-18. Transmission
Transmission method
complish
complish essentially
essentially the the same thingthing for
for pole-figure
pole-figure determination.
determination. (After (After
by
by keeping
keeping the the counter
counter fixed
fixed and ro- ro- A.
A. H. Geisler,Geisler, "Crystal
"Crystal Orientation
Orientation
tating
tating the
the specimen
specimen in in its
its own plane.
plane. and Pole Pole Figure
Figure Determination"
Determination" in in

This
This rotation,
rotation, combinedcombined with with the the Modem
Modern Research
Research TechniquesinPhysical
Techniquesin Physical
other rotation about
other rotation about the the diffractom-
diffractom- Metallurgy, American Society
Metallurgy, Society for for Met-
als,
als, Cleveland,
Cleveland, 1953.)
1953.)
eter
eter axis,
axis, moves
moves the the pole
pole of the (hkl)
of the (hkl)

* For
For simplicity,
simplicity, the
the method
method is
is described
described here
here only
only in
in terms
terms of
of a
a vertical-axis
vertical-axis
diffractometer.
diffractometer.
286
286 THE STRUCTURE
THE STRUCTURE OF
OF POLYCRYSTALLINE AGGREGATES
POLYCRY8TALLINE AGGREGATES [CHAP. 99
[CHAP,

FIG, 9-19.
FIG. 9-19. Specimen holder
Specimen holder used
used in
in the
the transmission
transmission method,
method, viewed
viewed from
from trans-
trans-
mitted-beam
mitted-beam side. (Courtesy
side. (Courtesy of
of Paul
Paul A.
A. Beck.)
Beck.)

reflecting plane
reflecting plane over
over the
the surface
surface of
of the
the pole
pole figure,
figure, which
which is
is plotted
plotted on
on aa
projection plane
projection plane parallel
parallel to
to the
the specimen
specimen plane,
plane, as
as in
in the
the photographic
photographic
method. At
method. At each
each position
position of
of the
the specimen,
specimen, the
the measured
measured intensity
intensity of
of the
the
diffracted beam,
diffracted beam, after
after correction
correction for
for absorption,
absorption, gives
gives aa figure
figure which
which is
is pro-
pro-
portional to the
portional to the pole
pole density
density at
at the
the corresponding
corresponding point
point onon the
the pole
pole figure.
figure.
Figure 9-19
Figure 9-19 shows the kind
shows the kind of
of specimen
specimen holder
holder used
used for
for this
this method.
method.
The
The method
method of
of plotting
plotting the
the data
data is
is indicated
indicated in
in Fig.
Fig. 9-20.
9-20. The
The angle
angle aIX
measures the
measures the amount
amount of of rotation
rotation about
about the
the diffract
diffractometer axis;* it isis
ometer axis;* it
zero
zero when
when the
the sheet
sheet bisects
bisects the
the angle
angle between
between incident
incident and
and diffracted
diffracted
beams.
beams. The positive
The positive direction
direction of
of aIX isis conventionally
conventionally taken
taken as
as counter-
counter-
clockwise. The
clockwise. angle 6~ measures
The angle measures thethe amount
amount byby which
which the
the transverse
transverse
direction isis rotated
direction rotated about
about the
the sheet
sheet normal
normal out
out of
of the
the horizontal
horizontal plane and
plane and
*
a is the conventional symbol for this angle, which is measured in a horizontal
IX is the conventional symbol for this angle, which is measured in a horizontal
plane.
plane. It should not be confused with the angle aIX used in Sec. 9-8 to measure
Itshould not be confused with the angle used in Sec. 9-8 to measure
azimuthal positions
azimuthal positions in
in aa vertical
vertical plane.
plane.
9-9)
9-9] THE TEXTURE OF SHEET (DIFFRACTOMETER METHOD) 287
R.D.

re!~~:ll;g~~:_t~_~_
reflecting-
plane
nurmal
*-) /
TD
T.D.l---+----+-~~f:::::4-!~~-~
T.D.

. : I dIllraC'tollletf'r
diffrartometer
-0 I
+a r:)
:0:-
I
aXIH
axis

, " ll'
I ex

sheet
nurmal

(a)
(a) (b)
(b)

FIG.
FIG. 9-20.
9-20. Angular
Angular relationships
relationships in
in the
the transmission pole-figure method (a)
transmission pole-figure (a) in
in
spare
space and (b)
(b) on the
the stereographic
stereographic projection.
projection. (On
(On the
the projection,
projection, the
the position
position of
of
the
the refleeting
reflecting plane
plane normal
normal is
is shown for
for 0 = 30
5 = 30 and ex = -30.)
a = 30.)

is
is zero
zero when the the transverse
transverse direction
direction is is horizontal.
horizontal. The reflecting plane
reflecting plane
normal bisects
bisects the
the angle
angle between incident incident and diffracted
diffracted beams,
beams, and re- re-
mains fixed
fixed in
in position
position whatever the the orientation
orientation of of the
the specimen.
specimen. To plot plot
the
the pole
pole ofof the
the reflecting plane on the
reflecting plane the pole
pole figure,
figure, we note
note that
that itit coincides
coincides
initially,
initially, when ex
a and 06 are
are both zero,
zero, with the
the left
left transverse
transverse direction.
direction. A
rotation
rotation of of the
the specimen
specimen by
by 0
d degrees
degrees in
in its
its own plane
plane then
then moves the
the pole
pole
of
of the
the reflecting
reflecting plane
plane 0 8 degrees
degrees around the the circumference
circumference of of the
the pole
pole figure,
figure,
and aa rotation
rotation of of -exa degrees
degrees about the the diffractometer
diffractometer axis axis then
then moves
it a degrees
it ex degrees from the
the circumference
circumference along
along a radius.
radius. To explore
explore the pole
the pole
figure,
figure, it
it is
is convenient
convenient to
to make intensity readings
intensity readings at
at intervals
intervals of
of 5
5 or
or 10
10
of
of - exa for
for aa fixed
fixed value
value of of 0:
d: the
the pole figure
pole figure is
is thus
thus mapped
mapped out
out along
along a a
series
series ofof radii.
radii.** ByBy this
this procedure
procedure the
the entire
entire pole figure
pole figure can be
be deter-
deter-
mined except
except forfor a region at
a region at the
the center
center extending
extending from about ex a = = _50 50
to a =
to ex = -90;90; in
in this
this region
region not
not only
only does
does the
the absorption
absorption correction
correction be-
be-
come inaccurate
inaccurate but but the
the frame
frame of of the
the specimen
specimen holder
holder obstructs
obstructs the
the dif-
dif-

fracted
fracted x-ray
x-ray beam.
An absorption
absorption correction
correction is is necessary
necessary in in this
this method because
because variations
variations
in a cause
in ex cause variations
variations in in both
both thethe volume of of diffracting
diffracting material
material and thethe
path length
path length of
of the
the x-rays
x-rays within
within the
the specimen.
specimen. Variations
Variations in
in 0
6 have no
effect.
effect. We cancan determine
determine the the angular dependence
angular dependence of
of the
the absorption
absorption factor
factor

** The chart
chart shown in in skeleton
skeleton form in in Fig.
Fig. 9-20(b)
9-20(b) is
is useful
useful for
for this
this purpose.
purpose.
It
It isis railed
called aa polar
polar stereographic
stereographic net, because it
net, because it shows the
the latitude
latitude lines
lines (circles)
(circles)
and
and longitude
longitude lines
lines (radii)
(radii) of
of a
a ruled
ruled globe
globe projected
projected on aa plane
plane normal to to the
the polar
polar
NS-axis.
NS-axis. In In the
the absence
absence of of such
such aa net,
net, the
the equator
equator or
or central
central meridian
meridian of of a
a Wulff
net
net cancan be
be used
used to
to measure the angle a.
the angle a.
288
288 THE STRUCTURE OF
THE STRUCTURE POLYCRYSTALLINE AGGREGATES
OF POLYCRYSTALLINE AGGREGATES [CHAP. 99
[CHAP.

by aa method
by method similar
similar to
to that
that used
used for
for the
the reflection
reflection case
case considered
considered inin Sec.
Sec.
2
7-4. The
7-4. The incident
incident beam
beam inin Fig. 9-21 has
Fig. 9-21 intensity 710 (ergs/cm
has intensity (ergs/cm 2/sec)
/sec) and
is 1 cm
is 1 em square
square inin cross
cross section.
section. It It isis incident
incident on on aa sheet
sheet specimen
specimen of of thick-
thick-
ness
ness tt and linear
linear absorption
absorption coefficient
coefficient p, /J., and
and the
the individual
individual grains
grains of
of this
this
specimen
specimen are
are assumed
assumed to
to have
have a
a completely
completely random
random orientation.
orientation. Let
Let aa
be the
be the volume
volume fraction
fraction ofof the
the specimen
specimen containing
containing grains
grains correctly
correctly oriented
oriented
for reflection
for reflection of of the
the incident beam, and bb the
incident beam, the fraction
fraction ofof the
the incident
incident energy
energy
diffracted
diffracted by by unit
unit volume.
volume. Then the
the total
total energy
energy per per second
second in
in the
the dif-
dif-

fracted
fracted beam outside the specimen, originating
outside the specimen, originating in
in a layer
layer of
of thickness
thickness dx
located at
located at aa depth
depth x,x, is
is given
given byby
dID = ab(DB)I (AB+BC} dx
ab(DB)Ioe-P.(AB+BC') dx (ergs/sec),
dID Q e- (ergs/sec),
where
where
1
1 x t- x
t

DB=---- AB
AB = =---- and Be =
BC = ----
+ a)a)
.

COS (8 - a)
cos (0 a) cos
COS (8 - a)
(0 a) cos
COS (8
(0 +
By substitution,
By substitution, we obtain
obtain
abl
a ^oo ,^ Q (8+a)e-p.x[l/c08
,>, _
=
dID = e-P.t/C08
C
ffi
(8-a)-I/c08
(0-a)-l/cos (8+a)J
(0+a)J dx. (9-7)
J^.
cos
COS (8 - a)
(0 a)

(Only clockwise rotation

(Only clockwise rotation of
of the
the specimen
specimen about the the diffractometer
diffractometer axis,
axis,
i.e., rotation
i.e., rotation in the sense
in the usually designated
sense usually designated byby -a, is considered here.
a, is here.

-
However,
However, in in these
these equations
equations and in Fig. 9-21,
in Fig. the proper
9-21, the proper sign
sign has already
already
been
been inserted,
inserted, and the
the symbol
symbol a stands
stands for
for the
the absolute value of
of this
this angle.)
angle.)
If put a == 0 in
If we put in Eq. (9-7)
Eq. (9-7) and integrate
integrate from x =
= 0 to x =
= t, we obtain /,

the
the total
total diffracted
diffracted energy per second,
energy per second, the
the integrated intensity,
integrated intensity, for
for this
this
position
position of
of the
the specimen:*
specimen:*

IDCa
ID ( a =
= 0)
0)
=
abtlo
-
= _ _- e-P.t/C08
e- tlco 8.
cos
COS08
'. (9-8)
(9-8)

When aa is
is not
not zero,
zero, the
the same integration
integration gives
gives

_
ID(a = a)
ID ( a = a ) == -
abl o{e-P.t/co8
1

/J.[cos - a)/cos
(8-a)
(0 a) _ e-P.tlco8
e n

+
+ a)
(8+a)]

-~ 1]
.
.
(9-9)
(9-9)
M[COS (8(0 - a)/COS (8
(0 a) 1]

** In Sec.
Sec. 6--9
6-9 mention
mention was made of of the
the fact
fact that
that the
the diffracted
diffracted beams in in any
any
transmission
transmission method
method werewere of
of maximum intensity
intensity when thethe thickness
thickness of of the
the speci-
speci-
men was made equal equal to I/M. This
to 1//J.. This result
result follows
follows from
from Eq. (9-8). If
Eq. (9--8). put 8 == aa
If we put
== 0,
0, then
then the
the primary
primary beam will be incident
will be incident on the specimen
the specimen at
at right
right angles (see
angles (see
Fig. 9-21), as
Fig. 9--21), as in
in the
the usual
usual transmission
transmission pinhole
pinhole method,
method, and our
our result
result will
will apply
apply
approximately
approximately to to diffracted
diffracted beams formed
formed at small ~ngles
at small angles 28.
20. The intensity
intensity ofof
such
such aa beam is is given
given by
by
ID
ID == ahtIoe-I't.
By
By differentiating
differentiating this
this expression
expression with
with respect to t and
respect to and setting
setting the
the result
t equal to
result equal to
zero,
zero, we
we can
can find that ID
find that ID is
is a maximum when tt == 1//J..
a maximum 1 //*.
9-9)
9-9] THE TEXTURE OF
OP SHEET (DIFFRACTOMETER
(DIFFRACTOMETER METHOD)
METHOD) 289
289

~
~ 1 () , . . . . . ; ; : : - - - - - - - - - - - - ,
o
t: 0.8
:<
..... 06
;.."
g 04
E-<
~ 02

8~ 0'---'---'-_.1.--<---'_-'----"'---'
0 -)()
-10 -20 -30 -40 -.')0
-50 -60 -70 -80
ANGLE
ROTATION AN<tLE aa (degrees)
(degrees)

FIG.
FIG. 9-22.
9-22. Yariation
Variation of
of the
the correr-
correc-
tion factor R with
tion fartor with a for
for clockwise
clockwise rota-
rota-
FIG. 9-21.
9-21. Path length
length and irrarli-
irradi- tion
tion from the
the zero position, p,t
zero position. = 1.0,
pi = 1.0,
aterl
ated volume in
in the
the transmission
transmission method. o
6 == 19.25.
19.25.

We are
are interested
interested only
only in
in the
the ratio
ratio of
of these
these t.wo
two integrated
integrated intensities,
intensities,
namely,
namely,
ID(a ~ a)
a = cos
COB 0[e-pl/co8 e-p l/ co8 (8+0)]
= D
R =
ID(a
J
a
= 0)
D (a = 0)
=
=
* e
..
(8-0) -

'[cos (0
",ie-pI/coB 8[COS (6 +
- a) /cos (0
(6 - a)/ros + a)a) - 1]
^
- 1]: (9-10)
(9-10) :

A plot
plot ofof R VB.
vs. a is is given
given inin Fig.
Fig. 9-22 for for typical
typical values
values involved
involved in in the
the 111
111
reflection
reflection from aluminum with with eu Cu Ka radiation,
radiation, namely,
namely, pi p,t = 1.0
= 1.0 and
o
6 = = 19.25.
19.25. This This plotplot shows
shows that
that the
the integrated
integrated intensity
intensity of of the
the reflection
reflection
decreases
decreases as increases in
as a increases in t.he
the clockwise
clockwise direction
direction from zero, zero, even
even forfor aa
specimen
specimen containing
containing randomlyrandomly oriented
oriented grains.
grains. In
In the
the measurement of of
preferred
preferred 'orientation,
orientation, it it is
is therefore
therefore necessary
necessary to divide each
to dil'ide each measured in- in-
tensity
tensity by by the
the appropriate value of
appropriate value of the
the correction
correction factor
factor 7? R inin order
order to to
arrive
arrive at at aa figure
figure proportional
proportional to to the
the pole
pole density.
density. From the the way
way inin which
the
the correction factor R was derived,
correction factor derived, it it follows
follows that
that we must measure the the
integrated intensity of
integrated intensity of the
the diffracted
diffracted beam. To do this this with
with a a fixed
fixed counter,
counter,
the
the counter
counter slits
slits must be be as
as wide
wide as as the
the diffracted
diffracted beam for for all
all values
values of of a
so that
so that thethe whole
whole width width ofof the
the beam can can enter
enter the
the counter.
counter. The ideal ideal
incident
incident beam for this method is
for this is a parallel one.
a parallel one. However,
However, a divergent
divergent
beam may may be
be used
used without
without too
too much error,
error, provided the
provided divergence is
the divergence is not
not
too
too great.
great. There is
is no question
question of
of focusing
focusing here:
here: if
if the
the incident
incident beam is
is

divergent,
divergent, the
the diffracted
diffracted beam will
will diverge
diverge also
also and very
very wide
wide counter
counter
slits will
slits will be
be required
required to to admit its its entire
entire width.
width.
The value
value of pt used
of p,t used in in Eq.
Eq. (9-10)
(9-10) must be be obtained
obtained by by direct
direct measure-
measure-
ment,
ment, since
since it
it is
is not
not sufficiently
sufficiently accurate
accurate to
to use
use a tabulated
tabulated value
value of
of I/o
M
together
together with
with the
the measured
measured thickness
thickness t of
of
t the
the specimen.
specimen. To determine
determine
p,t we use
pi use a strong
strong diffracted
diffracted beam from any any convenient
convenient material
material and meas-meas-
ure
ure its
its intensity
intensity when the the sheet specimen is inserted
sheet specimen is inserted in in the diffracted beam
the diffracted
290
290 THE STRUCTURE OP POLYCRYSTALLINE AGGREGATES
STRUCTURE OF [CHAP. 9
[CRAP. 9

a = _90
8 = ;+90
difi'ra('toll1eter:
-1 a
/
/B
axis I I
: / +a
counter RD. I
I
"',
,
'.
-' ~u

-_..f:'Ia
C------ ___ A'

sourre

FIG.
FIG. 9-23.
9-23. Reflection
Reflection method for
for pole-figure
pole-figure determination.
determination.

and again
again when it it is
is not.
not. The value of pt is
of IJ.t is then obtained from the the general
general
absorption
absorption equation,
equation, I I, == /o^~"
t Ioe-I't,
M
',
where 10 7 and // It are
are the
the intensities
intensities inci-
inci-
dent
dent on and transmitted
transmitted by by the
the sheet
sheet specimen,
specimen, respectively.
respectively.
As already
already mentioned,
mentioned, the the central part of
central part of the pole figure
the pole figure cannot
cannot be be cov-
cov-
ered by
ered by the
the transmission
transmission method. To explore explore this this region
region we must use use a a
reflection
reflection method,
method, one in in whiC'h
which thethe measured diffracted
diffracted beam issues issues from
that
that side
side ofof the
the sheet
sheet onon whiC'h
which thethe primary
primary beam is is incident.
incident. The reflec- reflec-
tion method here
tion here described
described was developed
developed by by Schulz.
Schulz. It It requires
requires aa special
special
holder
holder which allows allows rotation
rotation of of the
the specimen
specimen in in its
its own planeplane about
about an an
axis
axis normal to its surface
to its surface and about
about a a horizontal
horizontal axis; these axes
axis; these axes are
are shown
as BB' and A
as AA'A in
1
in Fig.
Fig. 9-23.
9-23. The horizontal
horizontal axis axis AAA'A' lies
lies in the specimen
in the specimen
surface and is
surface is initially
initially adjusted,
adjusted, by by rotation
rotation aboutabout the the diffractometer
diffractometer axis, axis,
to make equal
to equal angles
angles with
with the
the incident
incident and diffracted
diffracted beams.
beams. After
After this
this
is done,
is done, no further
further rotation
rotation about
about the the diffractometer
diffractometer axis axis isis made.
made. Since Since
the axis A
the axis AA' remains in
A' remains in aa fixed position during
fixed position during the the other
other rotations
rotations of of the
the
specimen,
specimen, the
the irradiated
irradiated surface
surface of
of the
the specimen
specimen is
is always tangent
always tangent to
to a
a
focusing
focusing circle
circle passing through
passing through the
the x-ray
x-ray source
source and
and counter
counter slits.
slits. A
divergent beam may
divergent may therefore
therefore be be used
used since
since the the diffracted
diffracted beam will will con-
con-
verge
verge to
to a
a focus
focus at
at the
the counter
counter slits.
slits. Figure
Figure 9-24
9-24 shows
shows a
a specimen
specimen holder
holder
for the
for the reflection
reflection method.
method.
When the the specimen
specimen is is rotated
rotated about
about thethe axisaxis AAA', the axis
A', the axis BB' normal
normal
to the
to the specimen
specimen surface
surface rotates
rotates inin aa vertical
vertical plane,
plane, but eN, the
but CAT, the reflecting
reflecting
plane normal,
plane normal, remains
remains fixed
fixed in
in aa horizontal
horizontal position
position normal
normal to to AAA'.
A'. The
rotation angles
rotation angles a and 66 are are defined
defined in in Fig.
Fig. 9-23.
9-23. The angle angle a is is zero
zero when
9-9]
9-9] THE TEXTURE OF SHEET (DIFFRACTOMETER METHOD)
METHOD) 291
291

FIG.
FIG. 9-24.
9-24. Specimen
Specimen holder
holder used
used in
in the
the reflection
reflection method,
method, viewed
viewed from re-
re-
flected-beam
flected-beam side.
side. (Courtesy
(Courtesy of
of Paul
Paul A.
A. Beck.)
Beck.)

the
the sheet
sheet is
is horizontal
horizontal and has has aa value
value of of _90 90 when the the sheet
sheet is is in
in the
the
v:ertical position
vertical position shown in
in the
the drawing.
drawing. In this
this position
position of
of the
the specimen,
specimen,
the
the reflecting
reflecting plane
plane normal is is at
at the
the center
center of of the
the projection.
projection. The angle angle 6 5

measures
measures the
the amount by
by which the
the rolling
rolling direction
direction is
is rotated
rotated away
away from
the
the left
left end of
of the axis A
the axis AA'
A' and has aa value value of of +90
+90 for for the
the position
position illus-
illus-

trated.
trated. With these these conventions
conventions the the angles
angles a
at and ~
5 may be plotted
plotted on the
the
pole figure
pole figure in
in the
the same way
way as
as in
in the
the transmission
transmission method [Fig. 9-20(b)].
[Fig. 9-20(b)].
The great
great virtue
virtue ofof the
the reflection
reflection method is is that
that no absorption
absorption correc-
correc-
tion
tion is
is required
required for
for values
values of
of a
at between _90
90 and about -40,
40, i.e., up
i.e., up toto
about
about 5050 from
from the
the center
center of
of the
the pole figure.
pole figure. In
In other
other words,
words, a specimen
specimen
whose grains
grains have a a completely
completely random orientation orientation can be rotated rotated over
this
this range
range of a values
of at values without
without any any change
change in in the
the measured intensity
intensity of of the
diffracted
diffracted beam. Under these
these circumstances,
circumstances, the
the intensity
intensity of
of the dif-
dif-

fracted
fracted beam is
is directly proportional
directly proportional to
to the
the pole density
pole density in
in the
the specimen,
specimen,
without
without anyany correction.
correction. The constancy
constancy of of the
the absorption
absorption factor
factor is is due

essentially to the narrow

essentially to the narrow horizontal
horizontal slit
slit placed
placed in
in the
the primary
primary beam-
beanr at
at D
(Fig. 9-23).
(Fig. 9-23). The vertical
vertical opening
opening in
in this
this slit
slit is
is only
only about 0.020
0.020 in.
in. in
in
height, which
height, which means that
that the
the specimen
specimen is
is irradiated
irradiated only
only over a
a long
long nar-
row
row rectangle
rectangle centered
centered on the the fixed axis AA'.
fixed axis A A'. It It can be shown that a
292
292 THE STRUCTURE
THE STRUCTURE OF POLYCRYSTALLINE AGGREGATES
OF POLYCRYSTALLINE AGGREGATES (CHAP. 99
[CHAP.

RD.
RD.

/200
~~~~:r300
41Kl
-500
-'liOO

500
400
300-
2(KJ

.. ~
FIG. 9-25.
FIG. 9-2.'). (111) pole
(Ill) pole figure
figure of
of cold-rolled
cold-rolled 70-30 brass,
bntflR, determined
by the
by the dif-
dif-
fractometer method.
fractometer method. (H. P. R.
Hu, P.
(H. Hu, Sperry, and P.
R. Sperry, P. A. Beck, Trans. A.LM.E.
A. Beck, A.1.M.E.
194, 76, 1952.)
194,76, 1952.)

change
change in in absorption
absorption does does occur,
occur, as as the
the specimen
specimen is rotated about A
is rotated A.1',
A',
but
but itit is
is exactly
exactly canceled
canceled by a change
by change in
in the
the volume of
of diffracting
diffracting material,
material,
the
the net
net result
result being
being a a constant
constant diffracted
diffracted intensity
intensity for for a random specimen
specimen
when a lies
when lies between
between -90 90 0 and about
about -40 40. 0 To achieve
achieve this
this condition,
condition,
the
the reflecting
reflecting surfacc
surface of of the
the specimen
specimen must be adjusted adjusted to accurately
accurately coin-
cide with
cide with the the axis
axis A A' for
for all
all values
values of
of a
a and o.
5. This adjustment
adjustment is is ex-

tremely important.
tremely important.
It
It is
is evident
evident that that the
the transmission
transmission and reflectionreflection methods complementcomplement
one
one another
another in in their
their coveragc
coverage of of the
the pole
pole figure.
figure. The usual practice
practice is is to
to
use
use the
the transmission
transmission method to to cover
cover thethe range
range of of a from 0 to to - 50
50 and
the
the reflection
reflection method
method from from -40 40 0 toto _90 90. 0 This produces
produces an overlap
overlap of
10
10 0 which
which is is useful
useful in in checking
checking the the accuracy
accuracy of of one method against against the
other,
other, and necessary
necessary in in order
order to to find
find a a normalizing
normalizing factor factor for
for one set set of
of
readings
readings which
which will
will make them agree
agree with
with the
the other
other set
set in
in the region
region of
of
overlap.
overlap.
When this this is
is done,
done, the
the numbers which are are proportional
proportional to pole pole density
density
can then
then be be plotted
plotted on the
the pole figure
pole figure at
at each
each point
point at
at which a measure-
ment was made. made. ContourContour lineslines are
are then
then drawn at at selected
selected levels
levels con-
necting points
necting points of
of the
the same pole density,
pole density, and
and the
the result
result is
is a
a pole
pole figure such
figure
as that
as that shown in in Fig. 9-25,
Fig. 9-25, which
which represents
represents the
the deformation
deformation texture
texture ofof
70-30
70-30 brass
brass cold-rolled
cold-rolled to to aa reduction
reduction in in thickness
thickness of of 95
95 percent.
percent. The
numbers attached
attached to to each
each contour
contour lineline give
give the the polepole density
density in in arbitrary
arbitrary
9-9]
9-9] THE TEXTURE
THE OF SHEET
TEXTURE OF SHEET (DIFFRACTOMETER
(DIFFRACTOMETER METHOD)
METHOD) 293
293

units. AA pole
units. pole figure
figure such
such as as this
this isis far far more
more accurate
accurate than than any any photo-
photo-
graphically
graphically determined
determined one,
one, and
and represents
represents the
the best
best description
description available
available
today of
today of the
the kind
kind and and extent
extent of of preferred
preferred orientation.
orientation. The The accuracy
accuracy ob- ob-
tainable with
tainable with thethe diffractometer
diffractometer method method isis sufficient
sufficient to to allow
allow investigation,
investigation,
with some
with some confidence,
confidence, of of possible
possible asymmetry
asymmetry in in sheet
sheet textures.
textures. In In most
most
sheet, no asymmetry
sheet, no asymmetry of of texture
texture is
is found
found (see Fig.
(see Fig. 9-25),9-25), but
but it
it does
does occur
occur
when sheet
when sheet isis carefully
carefully rolledrolled in in thethe same
same direction,
direction, i.e., i.e., without
without any any
reversal end
reversal end forfor end
end between
between passes. passes. In such sheet,
In such sheet, the texture has only
the texture has only
one reflection
one reflection plane plane of of symmetry,
symmetry, normal normal to to thethe transverse
transverse direction;
direction; the the
plane normal
plane normal to to the
the rolling direction isis no
rolling direction no longer
longer aa symmetry
symmetry plane. plane.
In Fig.
In Fig. 9-25,
9-25, the the solid
solid triangular
triangular symbols symbols representing
representing the the ideal
ideal orienta-
orienta-
tion (110)
tion (110) [lT2][l12jlie approximately in
lie approximately in the
the high-density
high-density regions regions of of the
the pole
pole
figure.
figure. But
But here
here again
again the
the pole
pole figure
figure itself
itself must
must be
be regarded
regarded as
as a
a far
far
better description
better description of of the
the texture
texture than than any any bare
bare statement
statement of of anan ideal
ideal orien-
orien-
tation. A
tation. A quantitative
quantitative pole pole figure
figure of of this
this kind
kind has has about the the same
same relation
relation
to an
to an ideal
ideal orientation
orientation as as anan accurate
accurate contour contour map map of of aa hill
hill has
has to to aa state-
state-
ment of
ment of thethe height,
height, width,
width, and and length
length of of. the
the hill.
hill.
Geisler has
Geisler has recently
recently pointed
pointed out out two sources sources of of error
error in in the
the diffractometer
diffractometer
method,
method, both ofboth of which
which can
can lead
lead to
to spurious intensity
spurious intensity maxima on the
on the pole
pole
figure if the investigator
figure if the investigator is
is not
not aware
aware of
of them:
(1) When an pole figure is being
being determined,
determined, the
(1) an (h1k1l
(AiMi) 1) pole figure is the counter
counter is is set
set
at
at the
the appropriate
appropriate angle angle 28 26 to receive Ka radiation reflected from the
to receive radiation reflected from the
(h1k1l
(hikili)1) planes.
planes. But But atat some position
position of of the
the specimen,
specimen, there there may be be another
another
set of
set planes, (h2k2~)'
of planes, (/^tt), so so oriented
oriented that that they
they can reflect reflect a component
component of of the
the
continuous
continuous spectrumspectrum at at the
the same angle angle 28. 26. the (~k2~)
If the
If (hjtj,^) planes
planes have a
high
high reflecting
reflecting power,power, thisthis reflection
reflection may may be so so strong
strong thatthat it it may be taken

for
for an fcjJMi reflection
an hlklll reflection of of thethe Ka wavelength.
wavelength. Apparently Apparently the only only sure
way
way of
of eliminating
eliminating this
this possibility
possibility is
is to
to use
use balanced
balanced filters.
filters.

(2)
(2) TheThe crystal
crystal structure
structure of of the
the material
material being being investigated
investigated may be such
that
that aa set set of of planes, (hakal
planes, (h 3 kM, a ), has
has very nearly
very nearly the
the same
same spacing
spacing as as the
(h1k1l 1) planes.
(hikili) planes. The Ka reflections
reflections of
of these
these two sets
sets will
will therefore occur

at
at very
very nearly
nearly the the same
same angle
angle 28. 26. If If the
the counter
counter is is set
set to
to receive
receive the the hlklll
hik^i
reflection, then there is a
reflection, then there is a possibility possibility that
that some
some of
of the
the hakala
feaMs reflection
reflection may
may
also be received, especially in
also be received, especially in the transmission the transmission method
method for
for which
which a
a wide
wide
receiving
receiving slit slit is
is used.
used. The The best best wayway out out of of this
this difficulty
difficulty is is to
to select
select another
another
reflection, A 4 4 4 well
reflection, h.k.l., fc / well separated
, separated from from its its neighbors,
neighbors, and and construct an
construct an
A4 4 /4 pole
h.k.l.
fc
pole figure
figure instead
instead of of anan h1k1l
ftiMi- 1. (It (It isis not
not advisable
advisable to to attempt
attempt to to
exclude
exclude the the unwanted
unwanted hakala hjc^ reflection
reflection by by narrowing
narrowing the the slits.
slits. If this
If this isis

done,
done, then
then the
the counter
counter may
may not
not receive
receive the
the entire
entire hlklll
hik^i diffracted
diffracted beam,
beam,
and
and ifif all
all ofof this
this beam
beam isis not not received,
received, Eq. Eq. (9-10)
(9-10) will will nono longer
longer give give thethe
correct
correct value
value of of R.
R. If If aa narrow
narrow receiving
receiving slit
slit must
must be
be used,
used, then
then the
the varia-
varia-
tion of R
tion of R with
with aa mustmust be be determined
determined experimentally.
experimentally. This This determination
determination
requires
requires aa specimen
specimen of
of the
the same
same material
material as
as that
that under
under investigation,
investigation, with
with
294
294 THE STRUCTURE OF POLYCRYSTALLINE AGGREGATES [CHAP. 99
[CHAP.

the
the value of
same value of \d and aa perfectly
p.t and perfectly random orientation
orientation of
of its
its constituent
constituent
grains.)
grains.)
other point
One other point about
about pole-figure
pole-figure determinations
determinations should
should be mentioned,
mentioned,
that is
and that is the
the necessity
necessity for
for integrating
integrating devices
devices when the
the grain
grain size
size of
of the
the
specimen
specimen is
is large,
large, as
as in
in recrystallized
recrystallized metals
metals and alloys.
alloys. With such
such speci-
speci-
mens, the
mens, the incident
incident x-ray
x-ray beam will
will not
not strike
strike enough
enough grains
grains to
to give
give aa good
good
statistical average
statistical average of
of the
the orientations
orientations present.
present. This
This is
is true
true of
of both methods,
methods,
the photographic
the photographic and thethe diffractometer.
diffractometer. With coarse-grained
coarse-grained specimens
specimens
it is
it is therefore
therefore necessary
necessary toto use
use some kind
kind of
of integrating
integrating device,
device, which will
will

the specimen
move the specimen back
back and
and forth,
forth, or
or in
in aa spiral,
spiral, in
in its
its own plane
plane and so
so
expose aa larger
expose larger number of
of grains
gT!l.ins to
to the
the incident
incident beam.
Pole-figure determination
Pole-figure is by
determination is by no means aa closed
closed subject,
subject, and varia-
varia-
tions and improvements
tions improvements are
are constantly
constantly being
being described
described in
in the
the technical
technical
literature.
literature. most interesting
The most interesting among
among these
these are
are devices
devices for
for the
the auto-
auto-
matic plotting
matic plotting of
of pole
pole figures
figures by
by the
the diffractometer
diffractometer method. .In these de-
Jn these de-
vices,
vices, the
the specimen
specimen is
is slowly
slowly rotated
rotated about
about the
the various
various axes
axes by
by a
a mechan-
ical drive,
ical drive, and the output of
the output the counter-ratemeter
of the counter-ratemeter circuit
circuit is
is fed
fed to
to a
recorder whose chart
recorder chart isis driven
driven inin synchronism
synchronism withwith the
the rotation
rotation of the
of the
specimen.
specimen. The chartchart may
may bebe either
either of
of the
the simple
simple strip variety, or
strip variety, or even aa
circular pole-figure
circular pole-figure chart
chart onon which
which the
the recorder prints selected
recorder prints levels of
selected levels of
pole
pole density
density at the proper
at the proper positions.
positions. The time
time is probably not
is probably not far off when
far off
most pole
pole figures
figures will
will be
be determined
determined in in an automatic
automatic or or semi-automatic
semi-automatic
manner, at
manner, at least
least in
in the
the larger laboratories.
larger laboratories.

TABLE 9--2
9-2

Appearance
Appearance of
of diffraction
diffraction lines
lines Condition
Condition of
of specimen
specimen

Continuous
Continuous Fine-gralned
Fine-grained (or
(or coarse-grained
coarse-grained and
cold-worked)
cold-worked)

Spotty
Spotty Coarse-grained
Coarse-grained
Narrow
Narrow (1)
(1) Strain-free
Strain -free

Broad
Broad (1)
(1) Residual
Residual stress
stress and possibly
possibly small
small particle
particle
size
size (if specimen is
(if specimen is aa solid
solid aggregate)
aggregate)
Small
Small particle
particle size
size (if
(if specimen
specimen is
is a
a
brittle
brittle powder)
powder)
Uniform
Uniform intensity
intensity Random orientation
orientation (2)
(2)

Nonuniform
Nonuniform intensity
intensity Preferred
Preferred orientation
orientation

Notes:
Notes:
(1)
(1) Best
Best judged
judged by
by noting
noting whether
whether oror not the Ka doublet
not the doublet is
is resolved
resolved in
in back
back re-
re-
flection.
flection.

(2) Or possibly
(2) Or possibly presence
presence of
of aa fiber
fiber texture,
texture, if
if the
the incident
incident beam
beam isis parallel to the
parallel to the
fiber
fiber axis.
axis.
9-10)
9-10] SUMMARY; PROBLEMS
SUMMARY; PROBLEMS 295
295

9-10 Summary.
9-10 Summary. In this
In this chapter
chapter we
we have
have 'considered
'considered various
various aspects
aspects
of the
of the structure
structure of
of polycrystalline
polycrystalline aggregates and the
aggregates and the quantitative
quantitative effects
effects
of variations
of variations in
in crystal
crystal size,
size, perfection, and orientation
perfection, and orientation on
on the
the diffraction
diffraction
pattern.
pattern. Although aa complete
Although complete investigation
investigation ofof the
the structure
structure of aggre-
of an aggre-
gate requires
gate requires aa considerable
considerable amount
amount of
of time
time and
and rather
rather complex apparatus,
complex apparatus,
the very
the very great
great utility
utility of the simple
of the simple pinhole
pinhole photograph
photograph should
should notnot be over-
be over-
looked. It
looked. It is
is surprising
surprising how much information
information an experienced observer
experienced observer
can obtain
can obtain simply
simply by by inspection
inspection of of aa pinhole
pinhole photograph,
photograph, without any any
knowledge of
knowledge of thethe specimen,
specimen, i.e.,
i.e., without
without knowing
knowing itsits chemical
chemical identity,
identity,
crystal structure,
crystal structure, or or even
even whether
whether it it is
is amorphous
amorphous or or crystalline.
crystalline. The
latter point
latter point can
can be be settled
settled at
at aa glance,
glance, since
since diffraction
diffraction lines
lines indicate
indicate crys-
crys-
tallinity
tallinity and
and broad
broad haloes
haloes an
an amorphous
amorphous condition.
condition. If
If the
the specimen
specimen is
is

crystalline,
crystalline, the
the conclusions
conclusions that
that can
can be
be drawn from the
the appearance
appearance of
of the
the
lines are
lines are summarized
summarized in in Table
Table 9-2.
9-2.

PROBLEMS

9-1.
9-1. cold-worked polycrystalline
A cold-worked polycrystalline piece
piece of
of metal,
metal, having
having aa Young's
Young's modulus of
of
psi, is
30,000,000 psi,
30,000,000 is examined with radiation. A diffraction
with Cu Ka radiation. diffraction line
line occurring
occurring at
at
28 == 150
28 is observed
150 is observed to
to be
be 1.28 degrees 28
1.28 degrees 28 broader
broader than
than the
the same line
line from aa
recrystallized specimen. If
recrystallized specimen. this broadening
If this broadening is is assumed to to be due to to residual
residual micro-
micro-
stresses varying from
stresses varying from zero
zero toto the
the yield
yield point both in
point both in tension
tension and compression,
compression,
what is
what is the
the yield point of
yield point the material?
of the material?
9-2. If
9-2. If the
the observed broadening given
observed broadening given in Prob. 9-1
in Prob. is ascribed
9-1 is ascribed entirely
entirely toto a
a frag-
frag-
mentation
mentation of
of the
the grains
grains into
into small
small crystal particles,
crystal particles, what is
is the
the size
size of
of these
these par-
par-
ticles?
ticles?
9-3.
9-3. For
For given
given values
values of 6 and /J., which results
of (J /x, results in
in aa greater
greater effective
effective depth
depth ofof
x-ray
x-ray penetration,
penetration, a a back-reflection
back-reflection pinhole
pinhole camera or or aa diffractometer?
diffractometer?
9-4. Assume that
9-4. that the
the effective
effective depth
depth of of penetration
penetration of of an x-ray
x-ray beam is is that

thickness of material which contributes

thickness of material which contributes 99 percent 99 percent of
of the
the total
total energy
energy diffracted
diffracted
by
by anan infinitely
infinitely thick
thick specimen.
specimen. Calculate
Calculate the the penetration
penetration depth depth in in inches for
for a
low-carbon
low-carbon iteel
steel specimen
specimen under
under the
the following
following conditions:
conditions:
(a)
(a) Diffractometer;
Diffractometer; lowest-angle
lowest-angle reflection;
reflection; Cu Ka radiation.
radiation.

(6) Diffractometer;
(b) Diffractometer; highest-angle
highest-angle reflection;
reflection; Cu Ka radiation.
radiation.

(c) Diffractometer;
(c) Diffractometer; highest-angle
highest-angle reflection;
reflection; Cr KaKa radiation.
radiation.

(d) Back-reflection
(d) Back-reflection pinhole
pinhole camera;
camera; highest-angle
highest-angle reflection;
reflection; Cr Ka radiation.
radiation.
9-6.
9-6. (a)
(a) A transmission
transmission pinhole photograph
pinhole photograph is
is made of
of a sheet
sheet specimen
specimen of of

thickness t and linear

thickness t linear absorption
absorption coefficient
coefficient /J..
p. Show that
that the fraction
fraction of
of the total
total
diffracted
diffracted energy
energy in in anyone
any one reflection
reflection contributed
contributed by by a layer
layer ofof thickness w is is

given
given byby
_ tt(x+(t x)/6O6 2ff\T0 nw(l l/cos 29) I]
w=
TTT I? J

where
where :z;x is
is the distance to
the distance to the
the side
side of
of the
the layer
layer involved,
involved, measured from
from the
the side
side
of the specimen
of the specimen on on which
which the
the primary
primary beam is
is incident.
incident.
296
296 THE STRUCTURE OF POLYCRYSTALLINE AGGREGATES [CHAP. 9
[CHAP.

(b) A transmission
(b) transmission pinhole
pinhole photograph
photograph is is made ofof a
a sheet
sheet ofof aluminum 0.50.5 mm
thick with Cu Kat
thick Ka radiation.
radiation. Consider
Consider onlyonly the III111 reflection
reflection which occurs
occurs at
at
26 =
28 = 38.4.
38.4. Imagine
Imagine the
the sheet
sheet to
to be divided
divided into
into four
four layers,
layers, the
the thickness
thickness of
of
each being
being equal
equal to
to one-fourth
one-fourth ofof the
the total
total thickness. Calculate W
thickness. Calculate W for
for each layer.
layer.
9-6. A transmission
9-6. transmission pinhole
pinhole pattern
pattern isis made with Co KO/. Ka radiation
radiation of
of an iron
iron
wire
wire having
having an almost
almost perfect
perfect [110]
[110] fiber
fiber texture.
texture. The wirewire axis
axis is
is vertical.
vertical. How
many high-intensity maxima will
many high-intensity will appear
appear on th'l the lowest-angle
lowest-angle 110110 Debye
Debye ring
ring and
what areare their
their azimuthal
azimuthal angles
angles on the
the film?
film?
 CHAPTER 10
10

THE DETERMINATION OF CRYSTAL STRUCTURE

10-1 Introduction.
Introduction. Since Since 1913,
1913, when W. L. L. Bragg
Bragg solved
solved thethe struc-
struc-
ture of N aCI, the structures
ture of NaCl, the structures of of some five
five thousand
thousand crystals, organic
crystals, organic and
inorganic,
inorganic, have
have been
been determined.
determined. This
This vast
vast body
body of
of knowledge
knowledge is is of
of funda-
funda-
mental importance
mental importance in in such fields
fields as as crystal
crystal chemistry,
chemistry, solid-state physics,
solid-state physics,
the biological
and the biological sciences because, to
sciences because, to aa large
large extent,
extent, structure determines
structure determines
properties and the
properties the properties
properties of of aa substance
substance are are never
never fully
fully understood
understood
until its
until its structure
structure is known. In
is known. In metallurgy,
metallurgy, aa knowledge
knowledge of of crystal
crystal struc-
struc-
ture is
ture is aa necessary
necessary prerequisite
prerequisite to to any
any understanding
understanding of of such phenomena
phenomena
as plastic deformation,
as plastic deformation, alloy alloy formation,
formation, or or phase
phase transformations.
transformations.
work of
The work of structure determination goes
structure determination goes onon continuously
continuously since since there
there
is
is no dearth
dearth of of unsolved
unsolved structures.
structures. New substances substances are constantly being
are constantly being
synthesized,
synthesized, and the the structures
structures of many old
of many old ones
ones are
are still
still unknown. In
In
themselves
themselves crystal
crystal structures
structures varyvary widely
widely in in complexity:
complexity: the the simplest
simplest can
be
be solved
solved in in aa few
few hours,
hours, while
while thethe more complex
complex may may require
require months or or
even
even years
years for for their
their complete
complete solution.
solution. (Proteins
(Proteins form a notable notable e"ample
example
of the
of the latter
latter kind;
kind; despite
despite intensive
intensive efforts
efforts of of many
many investigators,
investigators, their their
structure
structure has has not
not yet yet been
been completely
completely determined.)
determined.) Complex Complex structures
structures
require
require complex
complex methods of solution, and structure
of solution, structure determination in in its
its

entirety
entirety is is more properly
properly the the subject
subject of of a book than of of aa single
single chapter.
chapter.
All
All we cancan do do here
here is is to
to consider
consider some of of the
the principles
principles involved
involved and how
they
they can
can be applied to
be applied to the
the solution
solution of of fairly
fairly simple
simple structures.
structures. Moreover,
Moreover,
we will
will confine
confine our our attention
attention to to the
the methods of of determining
determining structure
structure from
powder
powder patterns
patterns alone,alone, because
because suchsuch patterns
patterns are are the
the kind most often often en-en-
countered
countered by by the
the metallurgist.
metallurgist.
The basic
basic principles
principles involved
involved in in structure
structure determination have already already
been
been introduced
introduced in in Chaps.
Chaps. 3 3 and 4. 4. We saw there there that
that the
the crystal
crystal struc-
struc-
ture
ture of a substance
of It substance determines
determines the the diffraction
diffraction pattern
pattern of of that
that substance or, or,
more specifically,
specifically, that
that the
the shape
shape and size
size of
of the
the unit
unit cell
cell determines the
angular
angular positions
positions of of the
the diffraction lines, and the
diffraction lines, the arrangement
arrangement of of the
the atoms
within
within thethe unit
unit cell
cell determines
determines the the relative
relative intensities
intensities of of the lines. It
the lines. It may
be
be worthwhile
worthwhile to to state
state this
this again
again in
in tabular
tabular form:
form :

Crystal
Crystal structure
structure Diffraction
Diffraction pattern
pattern

Unit
Unit cell
cell +-+
<- Line
Line positions
positions
Atom positions
positions <-> Line
+-+ Line intensities
intensities
297
298
298 THE DETERMINATION
THE DETERMINATION OF CRYSTAL STRUCTURE
OF CRYSTAL STRUCTURE 10
[CHAP. 10
[CHAP.

Since structure
Since structure determines
determines the
the diffraction
diffraction pattern,
pattern, itit should
should be
be possible
possible to
to
go in the
go in the other
other direction
direction and
and deduce
deduce the
the structure
structure from
from thethe pattern.
pattern. ItIt isis
possible, but not in any
possible, but not in any direct
direct manner.
manner. Given
Given aa structure,
structure, we
we can
can calculate
calculate
its diffraction
its diffraction pattern
pattern inin aa very
very straightforward
straightforward fashion,
fashion, and examples
and examples of
of
such calculations
such calculations were
were given
given in
in Sec.
Sec. 4-13;
4-13 j but
but the
the reverse
reverse problem,
problem, that
that
of directly
of directly calculating
calculating the
the structure
structure from
from the
the observed
observed pattern, has never
pattern, has never
been solved,
been solved, for
for reasons
reasons to
to be
be discussed in Sec.
discussed in Sec. 10-8.
10-8. The
The procedure
procedure
adopted
adopted is
is essentially
essentially one
one of
of trial
trial and
and error.
error. On
On the
the basis
basis of
of an
an educated
educated
guess, aa structure
guess, structure is assumed,
is assumed, its its diffraction
diffraction pattern
pattern calculated,
calculated, and and thethe
calculated pattern
calculated pattern compared compared with
with the
the observed
observed one.
one. If
If the
the two
two agree
agree in in
all detail,
all detail, thethe assumed
assumed structure
structure is is correct;
correct j if not,
if not, the process
the process is repeated
is repeated
as often
as often as as is
is necessary
necessary to to find
find the the correct
correct solution.
solution. The The problem
problem is is not
not
unlike that
unlike that ofof deciphering
deciphering aa code, code, and and requires
requires of of the
the crystallographer
crystallographer the the
same qualities possessed
same qualities possessed by by a
a good
good cryptanalyst,
cryptanalyst, namely,
namely, knowledge,
knowledge,
perseverance, and
perseverance, and notnot aa little
little intuition.
intuition.
The determination
The determination of of anan unknown structure structure proceeds
proceeds in in three
three majormajor
steps:
steps:
(1) The
(1) The shape
shape and and size
size ofof thethe unit
unit cell
cell are
are deduced from from the the angular
angular
positions
positions of
of the
the diffraction
diffraction lines.
lines. An assumption
assumption is
is first
first made as
as to
to which
which
of the seven
of the seven crystal
crystal systems
systems the
the unknown structure
structure belongs
belongs to,
to, and then,
then,
on
on the
the basis
basis of this assumption,
of this assumption, the
the correct
correct Miller
Miller indices
indices are assigned
assigned to
each reflection.
each reflection. This
This step
step is
is called
called "indexing
"indexing the
the pattern"
pattern" and is
is only
only
possible
possible whenwhen the the correct
correct choice
choice of of crystal
crystal system
system has been made. Once
this is
this is done,
done, the the shape
shape of of the
the unit
unit cell
cell isis known (from (from the the crystal
crystal system),
system),
and
and its size is
its size is calculable
calculable from from the the positions
positions and Miller Miller indices
indices of of the
the dif-
dif-

fraction
fraction lines.
lines.
(2)
(2) The
The number
number of of atoms
atoms per per unit
unit cell
cell is
is then
then computed
computed from the shape shape
and
and size
size ofof the
the unit
unit cell,
cell, the
the chemical
chemical composition
composition of
of the specimen,
specimen, and its
its

measured density.
measured density.
(3)
(3) Finally,
Finally, the the positions
positions of of the
the atoms within within the the unit
unit cell
cell are
are deduced
deduced
from
from thethe relative
relative intensities
intensities of of the
the diffraction
diffraction lines.lines.

Only
Only whenwhen these
these threethree steps
steps have have been accomplished is
been accomplished is the
the structure
structure
determination
determination complete.complete. The
The third
third step
step is
is generally
generally the
the most
most difficult,
difficult,

and
and there
there areare many
many structures
structures which
which are
are known
known only
only incompletely,
incompletely, in
in the
the
sense
sense that
that this
this final
final step
step has
has not
not yet
yet been
been made.
made. Nevertheless,
Nevertheless, aa knowl-
knowl-

edge of
edge of the
the shape
shape and and size
size of
of the
the unit
unit cell,
cell, without
without any any knowledge
knowledge of of atom
atom
positions,
positions, is is inin itself
itself ofof very
very great
great value
value in in many
many applications.
applications.
The
The average
average metallurgist
metallurgist is is rarely,
rarely, if if ever,
ever, called
called uponupon to to determine
determine an an
unknown
unknown crystal structure. If
crystal structure. If the
the structure
structure is is at
at all
all complex,
complex, its its deter-
deter-
mination
mination is is aa job
job for
for aa specialist
specialist in
in x-ray
x-ray crystallography,
crystallography, who
who can
can bring
bring
special techniques,
special techniques, both
both experimental
experimental and
and mathematical,
mathematical, to
to bear
bear on
on the
the
problem.
problem. The
The metallurgist should,
metallurgist should, however, however, know
know enough
enough about
about structure
structure
10-2]
10-2] PRELIMINARY TREATMENT OF DATA 299
299

determination
determination toto unravel
unravel any
any simple
simple structures
structures he he may
may encounter
encounter and,
and,
what isis more important,
important, he
he must be
be able
able to
to index
index the
the powder
powder patterns
patterns of
of
substances of known structure,
substances of structure, as
as this
this is
is a
a routine
routine problem
problem in
in almost
almost all
all

diffraction
diffraction work.
work. The procedures given below
procedures given below for
for indexing patterns are
indexing patterns are
applicable
applicable whether
whether the
the structure
structure is
is known or or not,
not, but
but they
they are
are of
of course
course
very
very much easier
easier to apply if
to apply if the
the structure
structure is is known beforehand.
beforehand.

10-2
10-2 Preliminary
Preliminary treatmenttreatment of of data.
data. The powder
powder pattern
pattern of of the
the un-un-
known is is obtained
obtained with with a a Debye-Scherrer
Debye-Scherrer camera or
or a
a diffractometer,
diffractometer, the the
object being
object being to
to cover
cover as
as wide
wide an angular
angular rangerange of
of 20
26 as
as possible.
possible. A camera
camera
such
such asas the Seemann-Bohlin, which records
the Seemann-Bohlin, records diffraction
diffraction lineslines over
over onlyonly a a
limited
limited angular
angular range,range, is is of
of very
very little use in
little use in structure
structure analysis.
analysis. The speci- speci-
men preparation
preparation must ensure ensure random orientationorientation of of the
the individual
individual par- par-
ticles
ticles of powder, if
of powder, if the
the observed
observed relative
relative intensities
intensities of of the
the diffraction
diffraction lineslines
are
are to
to have any any meaning
meaning in in terms of of crystal
crystal structure.
structure. After After thethe pattern
pattern
is
is obtained,
obtained, the
the value
value of
of sin
sin 2
2
8
6 is
is calculated
calculated for
for each
each diffraction
diffraction line;
line; this
this
2
set of sin 0 values is the
set of sin 2 6 values is the raw material for the determination of cell size
material for the determination of cell size
and shape.
shape.
Since
Since the problem of
the problem of structure
structure determination
determination is is one
one of of finding
finding a a struc-
struc-
ture which will
ture will account
account for for all
all the
the lines
lines on the the pattern,
pattern, in in both position
position
and intensity,
intensity, the the investigator
investigator must make sure sure at at the
the outset
outset thatthat thethe ob-
ob-
served
served pattern
pattern does
does not
not contain
contain any
any extraneous
extraneous lines.
lines. The ideal
ideal pattern
pattern
contains
contains lineslines formed
formed by x-rays of
by x-rays of aa single
single wavelength,
wavelength, diffracted
diffracted only only by by
the
the substance
substance whose structure structure is is to
to be
be determined.
determined. There There are are therefore
therefore
sources of
two sources of extraneous
extraneous lines: lines:
(1) Diffraction of
(1) Diffraction of x-rays having wavelengths
x-rays having wavelengths different from that
different from that of
of the prin-
the prin-

cipal component
cipal component of
of the
the radiation.
radiation. If
If filtered
filtered radiation
radiation is
is used,
used, then
then Ka
radiation
radiation is is the
the principal component,
principal component, and characteristic
characteristic x-rays
x-rays of
of any
any
other
other wavelength
wavelength may produce extraneous
may produce extraneous lines.lines. The chiefchief offender
offender is is
K{3 radiation,
Kf$ radiation, which is
is never
never entirely
entirely removed by
by a
a filter
filter and may
may be
be aa
source of
source of extraneous
extraneous lines lines when diffracted
diffracted by by lattice
lattice planes
planes of of high
high reflect-
reflect-

ing power.
ing power. The presence presence of of K{3lines
K0 lines on aa patternpattern cancan usually
usually be be revealed
revealed
by
by calculation,
calculation, since since if if aa certain
certain setset ofof planes
planes reflect
reflect K{3 radia,tion at
K/3 radiation at an
angle 813,
angle fy, theythey must also
also reflect
reflect Ka radiation
radiation at
at an angle
angle Oaa (unless
(unless a ex-
Oa ex-
ceeds
ceeds 90),
90), and one
one angle
angle may may be
be calculated
calculated from the
the other.
other. It
It follows
follows
from
from the
the Bragg
Bragg law law that
that
2
X
(XKa:) sin2813 =
( XK13
sin2 a,
sin2 0a ,
(10-1)
(10-1)

where
where X# XKaa 2
2
/xKl2 has
/Xx/3 has a a value
value near 1.2 for
near 1.2 for most radiations.
radiations. If
If it
it is
is sus-
sus-
pected
pected that
that a
a particular
particular line
line is
is due
due to
to KfJ radiation, multiplication
K$ radiation, multiplication of
of its
its

sin
sin 2
2
8 value
value by XKa 2
2 /XKl
by X/r a /A#0
2
will
will give
give a value
value equal,
equal, or
or nearly equal,
nearly equal, to
to the
the
300
300 THE DETERMINATION OF CRYSTAL STRUCTURE [CHAP. 10
(CHAP. 10

2
value
value of of sin
sin2 8 for some Ka line
8 for line on the the pattern,
pattern, unless
unless thethe product
product exceeds
exceeds
unity.
unity. The K0 K{3line
line corresponding
corresponding to given Ka line
to a given line is
is always
always located
located atat a
smaller
smaller angle
angle 2fJ26 and has lower lower intensity.
intensity. However,
However, since since Ka and Kfl K{3
lines
lines (from
(from different planes) may
different planes) may overlap
overlap on the the pattern,
pattern, Eq. Eq. (10-1)
(10-1) alone
alone
can
can only
only establish
establish the possibility that
the possibility that a given
given line
line isis due to K{3 radiation,
to Kft radiation,
but
but itit can
can never prove that
never prove that it it is.
is. Another possible
possible source
source of of extraneous
extraneous
lines is
lines is LL characteristic
characteristic radiation
radiation from tungsten tungsten contamination
contamination on the the
target
target of
of the
the x-ray tube, particularly
x-ray tube, particularly if
if the
the tube is
is old.
old. If
If such
such contamina-
contamina-
tion is suspected,
tion is suspected, equations
equations suchsuch as as (10-1)
(10-1) can be set set up
up toto test
test the
the possi-
possi-
bility
bility that
that certain
certain lines
lines are
are due to
to tungsten
tungsten radiation.
radiation.
(2) Diffraction by
(2) Diffraction substances other
by substances other than the the unknown. Such substances
substances
are
are usually impurities
usually impurities in
in the
the specimen
specimen but may
may also
also include
include the
the specimen
specimen
mount or or badly
badly aligned
aligned slits. Careful specimen
slits. Careful preparation and good
specimen preparation good ex-
ex-
perimental technique
perimental technique will
will eliminate
eliminate extraneous
extraneous lines
lines due
due toto these
these causes.
causes.
2
For reasons
reasons to to be discussed
discussed in in Chap.
Chap. 11,11, the
the observed
observed values
values of of sin
sin 2 8
always
always contain
contain small
small systematic
systematic errors.
errors. These
These errors
errors areare not
not large
large enough
enough
to
to cause
cause anyany difficulty
difficulty in
in indexing patterns of
indexing patterns of cubic
cubic crystals,
crystals, butbut they
they can
can
seriously
seriously interfere
interfere with
with thethe determination
determination of of some noncubic
noncubic structures.
structures.
best method of
The best of removing
removing such such errors
errors from the the data
data is is to
to calibrate
calibrate thethe
camera or or diffractometer
diffractometer with with a a substance
substance of of known lattice parameter,
lattice parameter,
mixed with the the unknown. The differencedifference between the the observed
observed and calcu-calcu-

O.!K)/j
0.008 -

o (K16
...
1:rr. 0 (K14 /
-1

() 002

o
o () 22 0.4
0.4 () 6
6 O,/j
0.8 1
1 0

~1II2
sm 2 /I lobsen'"d)
(observed)

FIG. to--1.
10-1. An example
example of
of a
a correction
correction curve
curve for
for sin
sin 22 8
6 values.
values.

2
lated
lated values ofof sin
sin 2 8 for
for the standard substance
substance gives
gives the
the error
error in
in sin
sin 2 8,
2
6,
and this
this error
error can be plotted
plotted as
as aa function
function of
of the
the observed
observed values
values of
of sin
sin 2 8,
2
6.

Figure
Figure 10-1 shows a correction
correction curve of of this
this kind,
kind, obtained
obtained with
with a par-
a par-
ticular
ticular specimen
specimen and a particular Debye-Scherrer
particular Debye-Scherrer camera.
camera.* The
The errors
errors
represented
represented byby the
the ordinates
ordinates of
of such a a curve
curve can
can then be applied
then be applied to
to each
each
2
of
of the
the observed values
values of of sin
sin 2 8
6 for
for the
the diffraction
diffraction lines
lines of
of the unknown
the unknown
substance.
substance. For the the particular
particular determination
determination represented
represented byby Fig.
Fig. 10-1,
10-1,
the
the errors
errors shown areare to
to be subtracted
subtracted fromfrom the
the observed values.
observed values.

* For the shape

shape of
of this
this curve,
curve, see
see Prob.
Prob. 11-5.
11-5.
10-3)
10-3] INDEXING PATTERNS
INDEXING PATTERNS OF
OF CUBIC
CUBIC CRYSTALS
CRYSTALS 301
301

10-3
10-3 Indexing
Indexing patterns
patterns of of cubic
cubic crystals.
crystals. A A cubic
cubic crystal
crystal gives
gives dif-
dif-
2
fraction
fraction lines
lines whose
whose sin
sin2 (J6 values
values satisfy
satisfy the
the following equation,
following equation, obtained
obtained
by
by combining
combining the Bragg law
the Bragg law with
with the
the plane-spacing
plane-spacing equation
equation for
for the
the cubic
cubic
system:
system:
2 2 2
sin B sin B X
(1~2)

(h? +
Since the sum sum 8s == (h 2 + kk22 + + l2)2 ) isis always
I
always integral
integral and A /4a2 iss aa con-
and ")..2/4a
2 2
i con-
stant
stant forfor anyone
any one pattern,
pattern, the the problem
problem of of indexing
indexing the
the pattern
pattern of
of a
a cubic
cubic
substance isis one of of finding
finding a set set of of integers
integers 8s whichwhich will will yield
yield a a constant
constant
quotient when divided one by
quotient by one into
into the
the observed
observed sin
sin 22 (J
6 values.
values. (Certain
(Certain
integers,
integers, such as 7, 15, 23, 28, 31,
7, 15, 23, 28, 31, etc., etc., are
are impossible
impossible because they cannot
because they cannot
be formed by by the sum of of three
three squared
squared integers.)
integers.) Once Once the the proper
proper integers
integers
8s are
are found,
found, the indices hkl
the indices hkl ofof each line line cancan be be written
written down by by inspection
inspection
or tabulation in
or from the tabulation in Appendix
Appendix 6. 6.

The proper
proper integers
integers 8s can be determined
determined by by means of of the
the C and and D scales scales
of
of an ordinary
ordinary slideslide rule,
rule, which permit permit simultaneous
simultaneous division division of of one
one setset ofof
numbers by by another,
another, if if the
the quotient
quotient is
is constant.
constant. Pencil
Pencil marks
marks correspond-
correspond-
2
ing
ing to
to the sin
sin2 (J values of of the first
first five
five or or six
six lines
lines on
on the
the pattern
pattern are placed
are placed
on the D scale.scale. A single setting
single setting of
of the
the C scale
scale is
is then
then sought which will
sought which will
bring
bring a set of integers
a set of integers on the
on the C scale
scale into into coincidence
coincidence with with all the pencil
all the pencil
marks on
marks the D scale.
on the Because of
scale. Because the systematic
of the systematic errors errors mentioned
mentioned earlier, earlier,
these coincidences are
these are never
never exact,
exact, but but theythey are are usually
usually close
close enough
enough to to per-
per-
mit selection
mit selection of of the
the proper
proper integer,
integer, particularly
particularly if if the
the C C scale
scale is is shifted
shifted
slightly from line
slightly line toto line
line toto compensate
compensate for for the
the systematic
systematic errors errors in in sin
sin22 6.(J. If
If
a set
a set of
of integers
integers satisfying
satisfying Eq. Eq. (10-2)
(10-2) cannotcannot be be found,
found, then then the the substance
substance
involved does
involved does notnot belong
belong to to the
the cubic
cubic system,
system, and and other
other possibilities
possibilities (tetrag-
(tetrag-
onal, hexagonal,
onal, hexagonal, etc.) etc.) must be
be explored.
explored.
The following
The following example
example will will illustrate
illustrate the the steps
steps involved
involved in in indexing
indexing the the
pattern of
pattern of aa cubic
cubic substance
substance and finding finding its its lattice
lattice parameter.
parameter. In In thisthis
particular example, Cu Ka radiation
particular example, radiation was was used used andand eight
eight diffraction
diffraction lines lines
were observed.
were observed. Their Their sin sin22 (J values
values are are listed
listed in in the
the second
second columncolumn of of
Table 10-1.
Table 10-1. By By means
means of of aa slide
slide rule,rule, the the integers
integers s8 listedlisted in in the
the third
third
column were
column were found
found to to produce
produce the the reasonably
reasonably constant constant quotients
quotients listed listed in in
the fourth
the fourth column,
column, when when divided
divided into into the the observed
observed sin values. The
sin22 (} values. The
fifth column
fifth column listslists the
the lattice
lattice parameter
parameter calculated calculated from from each each lineline position,
position,
and the sixth
and the sixth column
column gives gives thethe Miller
Miller indices
indices of of each
each line.
line. The The systematic
systematic
22
error in
error sin22 6(} shows
in sin shows up up asas aa gradual
gradual decrease
decrease in in the
the value
value of 2
/4a , and
of X)..2/4a ,
and aa
gradual increase
gradual increase in in the
the value
value of a, as
of a, as 8() increases.
increases. We We shall
shall findfind in in Chap.
Chap. 11 11
that the
that the systematic
systematic error error decreases
decreases as as (} increases;
increases; therefore
therefore we we cancan select
select
the value
the value of of aa for
for the
the highest-angle
highest-angle line, line, namely,
namely, 3.62A,3.62A, as as being
being the the mostmost
accurate of
accurate of those
those listed.
listed. Our Our analysis
analysis of of line
line positions
positions therefore
therefore leads leads to to
302
302 THE DETERMINATION OF CRYSTAL STRUCTURE [CHAP. 10
[CHA.P. 10

TABLE 10-1
TA.BLE 10-1

1 2 3 4 5 6
X2
Line sin 2 9 8 = (11 2 + k2 + (2) a(A) hkl
41.12

1 0.140 3 0.0466 3.57 111

2 0.185 4 0.0463 3.58 200
3 0.369 8 0.0462 3.59 220
4 0.503 11 0.0457 3.61 311
5 0.548 12 0.0456 3.61 222
6 0.726 16 0.0454 3.62 400
7 0.861 19 0.0453 3.62 331
8 0.905 20 0.0453 3.62 420

the
the conclusion
conclusion thatthat the
the substance
substance involved,
involved, copper
copper in in this
this case,
case, is
is cubic
cubic in
in
structure
structure with a a lattice
lattice parameter
parameter of of 3.62A.
3.62A.
We can also also determine
determine the the Bravais
Bravais lattice
lattice of
of the
the specimen
specimen by by observing
observing
which lines
lines are
are present
present and which absent.
absent. Examination of
of the
the sixth
sixth col-
col-
umn of of Table to-I10-1 shows that that all
all lines
lines which have mixed odd and even even
indices,
indices, such as as 100,
100, 110,
110, etc.,
etc., are
are absent
absent from the the pattern.
pattern. Reference
Reference to to
the
the rules
rules relating
relating Bravais
Bravais lattices
lattices to
to observed
observed and absent
absent reflections, given
reflections, given
in
in Table 4-1, 4-1, shows that that thethe Bravais
Bravais lattice
lattice of
of this
this specimen
specimen is is face-
face-
centered.
centered. We now have certain
certain information
information aboutabout thethe arrangement
arrangement of of
atoms within
within thethe unit
unit cell,
cell, and itit should
should bebe noted
noted that
that we have had to to make
use
use of
of observed
observed lineline intensities
intensities in order to
in order to obtain
obtain this
this information.
information. In In
this particular case,
this particular case, the
the observation
observation consisted
consisted simply
simply in in noting which
noting which
lines
lines had zero
zero intensity.
intensity.
Each of of the
the four
four common cubic cubic lattice
lattice types is recognizable
types is recognizable by by aa charac-
charac-
teristic
teristic sequence
sequence of
of diffraction
diffraction lines,
lines, and these
these in
in turn
turn may
may be
be described
described
by
by their sequential 8s values:
their sequential values:

Simple cubic:
Simple cubic: 1, 2, 3,
1, 2, 3, 4,
4, 5, 6, 8,
5, 6, 8, 9,
9, 10,
10, 11,
11, 12, 13, 14,
12, 13, 16,
14, 16, ...
Body-centered
Body-centered cubic:
cubic: 2, 4, 6, 8, 10, ]2, 14,
2, 4, 6, 8, 10, 12, 14, 16, 16, ...
Face-centered cubic:
Face-centered cubic: 3,4,8,
3, 4, 8, 11,
11, 12, ]6, ...
12, 16, ...
cubic:
Diamond cubic: 3,8,
3, 8, 11,
11, 16,
16, ...
...

information is
The same information is tabulated
tabulated inin Appendix
Appendix 66 and
and shown graphically
graphically
in Fig.
in Fig. 10-2, in the
10-2, in the form
form ofof calculated
calculated diffraction
diffraction patterns.
patterns. The
The calcula-
calcula-
tions are
tions are made for eu Ka radiation
for Cu radiation and
and aa lattice parameter aa of
lattice parameter of 3.50A.
3.50A.
positions of
The positions of all
all the
the diffraction
diffraction lines
lines which
which would
would bebe formed
formed under
under
these conditions
these conditions are
are indicated
indicated as
as they
they would
would appear
appear onon aa film
film oror chart
chart of
of
the length
the length shown.
shown. (For
(For comparative
comparative purposes,
purposes, the
the pattern
pattern ofof aa hexagonal
hexagonal
close-packed structure
close-packed structure is also
is also illustrated,
illustrated, since
since this
this structure
structure is
is frequently
frequently
10-3) INDEXING PATTERNS OF CUBIC CRYSTALS 303
CUlm' HEXAGONAL
r -______________~A~ ______________~
~
hody- f:1('e- rlose-
SIID"lc centered ccntered dlltillond purked
29 = 0 _ _

HI
100

2 110
Ml
lOO
3 111 002
101
4 200
) 210
102
(j 211

S 220 110
9 3UO, 221 1U3
]( I ;310 20U
11 311 112
201
12 222 004
13 320 2U2
14 321
104

It; 400
17 410,322 2U3

IS 41 L 330
21U
19 21 1

11-4
2( ) 420

211 = 180-

FIG. 10-2.
FIG. 10-2. Calculated diffraction
Calculated diffraction patterns
patterns for
for various
various lattices.
lattices, 8
s h~2
= ti + kk 2 +
+ 2
+ [2.
I
2
.

encountered
encountered among metals
among metals and
and alloys.
alloys. The line
line positions
positions are
are calculated
calculated
for CuKa
for radiation, aa =
eu Ka radiation, = 2.50A,
2.50A, and
and c/a = 1.633,
cia = 1.633, which
which corresponds to
corresponds to
the close
the close packing
packing of
of spheres.)
spheres.)
Powder patterns of cubic
patterns of cubic substances
substances can
can usually
usually be
be distinguished
distinguished at
at aa
glance
glance from
from those
those of
of noncubic
noncubic substances,
substances, since
since the latter patterns nor-
the latter patterns nor-
304
304 THE DETERMINATION OF
THE DETERMINATION CRYSTAL STRUCTURE
OF CRYSTAL STRUCTURE 10
[CHAP. 10
[CHAP.

mally contain
mally contain many
many more
more lines.
lines. In
In addition,
addition, the
the Bravais
Bravais lattice
lattice can
can usu-
usu-
ally
ally be
be identified
identified by inspection:
by inspection: there
there is
is an
an almost
almost regular
regular sequence
sequence of
of
lines in
lines in simple
simple cubic
cubic and
and body-centered
body-centered cubic
cubic patterns,
patterns, but
but the
the former
former
contains almost
contains almost twice
twice as
as many lines,
many lines, while
while aa face-centered
face-centered cubic
cubic pattern
pattern
is characterized
is characterized by by aa pair
pair of
of lines,
lines, followed
followed byby aa single
single line,
line, followed
followed byby aa
pair, another
pair, another single
single line,
line, etc.
etc.
The problem
The problem of of indexing
indexing aa cubic
cubic pattern
pattern isis of
of course
course very
very much sim-sim-
plified
plified if
if the
the substance
substance involved
involved is
is known to
to be
be cubic
cubic and if
if the
the lattice
lattice

parameter is
parameter is also
also known.
known. The simplestsimplest procedure
procedure thenthen is
is to
to calculate
calculate the
the
value of (>.2/4a
2
value of (\ /4a ) 2
2
) and
and divide
divide this
this value
value into
into the
the observed
observed sin
sin
2
2 8
6 values
values to
to
obtain the
obtain the value
value of of ss for
for each
each line.
line.

There is
There is one
one difficulty
difficulty that
that may
may arise
arise in
in the
the interpretation
interpretation of of cubic
cubic powder
powder pat-
pat-
terns,
terns, and
and that
that is
is due
due to
to a
a possible ambiguity
possible ambiguity between
between simple
simple cubic
cubic and body-
body-
centered cubic
centered cubic patterns.
patterns. ThereThere isis aa regular
regular sequence
sequence of of lines
lines in
in both
both patterns
patterns up up
to the
to the sixth
sixth line;line; the
the sequence
sequence thenthen continues
continues regularly
regularly inin body-centered
body-centered cubic cubic
patterns, but
patterns, but is is interrupted
interrupted in in simple
simple cubic
cubic patterns
patterns sincesince s8 = = 77 isis impossible.
impossible.
Therefore, if
Therefore, if>.X is
is so
so large,
large, or
or a so
so small, that six
small, that six lines
lines or
or less
less appear
appear on the the pattern,
pattern,
the two
the two Bravais
Bravais lattices
lattices are indistinguishable. For
are indistinguishable. For example,
example, suppose
suppose that that the
the
substance involved is
substance involved is actually
actually body-centered
body-centered cubiccubic but but the
the investigator
investigator mistakenly
mistakenly
indexes it
indexes it as
as simple
simple cubic, assigning the
cubic, assigning value ss == 11 to
the value to the
the first
first line,
line, s 8 == 22 to
to the
the
second line, etc.
second line, etc. He thus thus obtains
obtains a value of >. /4a
a value of X 2
2 / 4a twice as large
2 twice
2
as large as the true
as the true one,
one,
and
and a a value
value of of a which is
a which is 1/ y2 times
l/\/2 times the
the true
true one.one. This
This sort
sort of
of difficulty can be
difficulty can be
avoided simply by
avoided simply by choosing choosing a
a wavelength
wavelength short
short enough
enough to
to produce
produce at
at least
least seven
lines
lines on
on the
the pattern.
pattern.

10-4
10-4 Indexing
Indexing patterns
patterns ofof noncubic
noncubic crystals
crystals (graphical
(graphical methods).
methods). The
problem of
problem of indexing
indexing powder
powder patterns
patterns becomes more difficult
difficult as
as the
the number
of
of unknown parameters
parameters increases.
increases. There is is only
only one unknown parameter
parameter
for
for cubic
cubic crystals,
crystals, the
the cell
cell edge
edge a,
a, but noncubic
noncubic crystals
crystals have two or
or more,
more,
and
and special graphical
special graphical and analytical techniques
analytical techniques have had to
to be
be devised
devised in
in
order
order to
to index
index the
the patterns
patterns of
of such
such crystals.
crystals.
The tetragonal
tetragonal system
system will
will be
be considered
considered first.
first. The plane-spacing
plane-spacing equa-
equa-
tion
tion for
for this
this system
system involves parameters, a
involves two unknown parameters, a and c:c:

2 2 2
I h + k I

-5-
2 2
+T
2
(10--3)
(10-3)
d a c

This
This may
may be
be rewritten
rewritten in
in the
the form
form

-i = - 2 (h
1 1 [2 ++ k2) ++ -
_ l2]
- ,
dd22 -![(*
*")
a2 L (c/a)2
(c/o)
 10-4)
10-4] NONCUBIC
NON CUBIC CRYSTALS (GRAPHICAL
(GRAPHICAL METHODS)
METHODS) 305
or
or

+ ~] .
2
r i i
2 log = log a -- log
log d = 2 log log [(h
(h
22 +
+ k2 ) +
2
)
(cia) 2
(10--4)
(10-4)
L (c/a) J

Suppose
Suppose we now write
write Eq.
Eq. (10--4)
(10-4) for
for any
any two planes
planes of
of a
a tetragonal
tetragonal crys-
crys-
tal,
tal, distinguishing
distinguishing the
the two planes
planes by
by subscripts 1 and 2,
subscripts 1 2, and then
then subtract
subtract
the equations. We obtain
the two equations. obtain

22 log
log d
- 2 log
d,1 - 2 log d
= -- log
d 22 = (V +
log (hI
2
l
+ kl 22 )
[
L
fc, ) + - 112]
+ -2
(cia)
(c/a)
2

L
^
+ log [r (h2 2 + k2 2) +
+- 122]1
-A-
-2 .fc 2
2
)
(cia)
(c/arj
.
(10-5)

This
This equation
equation shows that that the
the difference between the
difference between the 2 2 log
log dd values
values for for any
any
two
two planes
planes is
is independent
independent of
of a
a and depends
depends only
only on
on the
the axial
axial ratio
ratio cia
c/a and
the
the indices
indices hk1 hkl of of each
each plane.
plane. ThisThis fact fact was used used by by Hull
Hull and Davey Davey as as
the
the basis
basis forfor a a graphical
graphical method of
of indexing
indexing the
the powder patterns
powder patterns of
of tetrag-
tetrag-
onal
onal crystals.
crystals.
construction of
The construction of aa Hull-Davey
Hull-Davey chart chart is is illustrated
illustrated in in Fig.
Fig. 10-3.
10-3. First,
First,
the variation of
the variation of thethe quantity
quantity [(h [(/i
22 ++ k22 )) + 2
+ 12/(cla)2]
l
/(c/a)
2
with
with cia c/a is
]
plotted
is plotted

on
on two-range
two-range semilogsemilog paperpaper for particular values
for particular values of hkl. Each set
of hk1. set of
of indices
indices
hkl,
hkl, as
as long
long as
as they correspond
they correspond to
to planes
planes of
of different
different spacing,
spacing, produces a
produces a
different
different curve,
curve, and when 1
I =
= 0 the
the curve
curve is
is a
a straight
straight line
line parallel
parallel to
to the
the
c/a axis.
cia axis. Planes
Planes of of different
different indices
indices but but the
the same spacing,
spacing, such such as as (100)
(100)
and (010),
(010), areare represented
represented by by the
the same curve curve on the the chart,
chart, which is is then
then
marked with with the indices of
the indices of either
either one one ofof them,
them, in in this
this case
case (100).
(100). [The
[The
chart shown is
chart is for
for a a simple
simple tetragonal
tetragonal lattice;lattice; one one forfor a a body-centered
body-centered
tetragonal
tetragonal latticelattice is is made simply simply by by omitting
omitting all all curves
curves for for which
which
(h +
(h + k
k +
+ I)1) is
is an odd number.]
number.] A single-range logarithmic
single-range logarithmic d
d scale
scale is
is then
then
constructed;
constructed; it
it extends
extends over
over two ranges
ranges of
of the [(h
the [(h + 2
2
+ k
k 2
2
)
) ++ 2
12/(cla)2]
/(c/a)
2
Z ]

scale
scale and runs runs in in the
the opposite
opposite direction,
direction, since since the the coefficient
coefficient of of loglogd d in
in

Eq. (10--4)
Eq. (10-4) is is -2 timestimes thethe coefficient
coefficient of of log
log [(h
22 + kk22 )) +
[(h +
2
+ 12/(cla)2].
/(c/a)
2
This
This
I ].

means thatthat thethe d d values

values of of two planes,
planes, for for aa given
given cia c/a ratio,
ratio, are
are separated
separated
by
by the
the same distance
distance on the
the scale
scale as
as the
the horizontal
horizontal separation, at
separation, at the
the same
cia ratio,
c/a ratio, of
of the
the two corresponding
corresponding curves
curves on
on the
the chart.
chart.
The chart
chart and scale scale are
are used
used for
for indexing
indexing in in the
the following
following manner.
manner. The
spacing
spacing d d of
of the
the reflecting planes corresponding
reflecting planes corresponding to to each
each line
line onon the
the diffrac-
diffrac-
tion pattern is
tion pattern is calculated.
calculated. SupposeSuppose that that thethe first
first seven
seven of of these
these values
values for for
aa particular pattern
particular pattern are
are 6.00, 4.00, 3.33, 3.00,
6.00, 4.00, 3.33, 3.00, 2.83, 2.55, 2.83, 2.55, and 2.40A.
2.40A. A
strip
strip of
of paper
paper is
is then
then laid
laid alongside
alongside the
the d scale
scale in
in position
position I
I of
of Fig. 10-3,
Fig. 10-3,
and the observed d
the observed d values
values are are marked off off on
on its
its edge
edge with
with a pencil. The
a pencil.
 I I ~

306
Rin2 8 sl'aie ------
10 8 6 4 2 .1 .08 0 ,.04 02 .01
I I I I I I I I I

d ~l'ai(' (anl!:~trollls)

U:
bC

s
3

THE DETERMINATION OF CRYSTAL STRUCTURE

:i!lzJ

e
;
t:I
110
111 102 101 002 100 (JOI
18

1.6
I
/
J /'
A L
/
I
!

~
1.5 f- - -- --
~
1.4 J
I !~ ~1 <2l
!CD paper
strip
J.II o
IOJI
I

/ Y / : V n

~
12
cia
/ A / /'
1/ ,/
I
I
iI
1.0

~V I
I
.08
-;::,V
v::
.......
/
/ V______ / ~
I I
1
I ~
Cl

.06
~ / / i I
1 I
i
I
~lzJ

V
.04 .."....,~:':'-~ ~ ~ ~ ------ - I I
--
109 8 7 6 a 4 3 2 O!IOS070(i 05 04 03 0.2"
~
0.1
g

[CHAP. 10
-l(h 2 + k2 ) + (r l~. ]
+

-
a)2
'"
o
I

-C

FIG. 10-3.
I

Partial Hull-Davey chart for simple tetragonal latti('es.

J,

03
I
68
10-4
10-4 NON CUBIC CRYSTALS
NONCUBIC CRYSTALS (GRAPHICAL
(GRAPHICAL METHODS)
METHODS) 307
307

paper strip
paper strip is then
is then placed
placed on on the
the chart
chart and and moved
moved about,about, both
both vertically
vertically
and horizontally,
and horizontally, until
until aa position
position is
is found
found where
where each
each mark
mark on
on the strip
the strip
coincides
coincides with
with a
a line
line on
on the
the chart.
chart. Vertical
Vertical and
and horizontal
horizontal movements
movements
correspond to
correspond to trying
trying various
various c/a cia andand aa values,
values, respectively,
respectively, and and thethe only
only
restriction on these
restriction on these movements movements is
is that
that the
the edge
edge of
of the
the strip
strip must
must always
always
horizontal. When
be horizontal.
be When aa correct
correct fit fit has
has beenbeen obtained,
obtained, as as shown
shown by by posi-
posi-
tion II
tion II of
of Fig.
Fig. 10-3,
10-3, the the indices
indices of of each
each lineline are
are simply
simply readread from
from thethe corre-
corre-
sponding curves,
sponding curves, and and thethe approximate
approximate value value of cia from
of c/a from thethe vertical
vertical
position of
position of the
the paper
paper strip.
strip. In In thethe present
present example,
example, the cia ratio
the c/a ratio is is 1.5
1.5
and the
and the first
first line
line on on the
the pattern
pattern (formed(formed by by planes
planes of of spacing
spacing 6.00A)
6.00A) is is aa
001 line,
001 line, the
the second
second aa 100 100 line,
line, the
the third
third aa 101 line, etc.
101 line, etc. After
After all
all the
the lines
lines
have been
have been indexed
indexed in in this
this way,
way, the the dd values
values of of the
the two highest-angle
highest-angle lines lines
are used
are used to to set
set upup twotwo equations
equations of of thethe form of of Eq.
Eq. (10-3),
(10-3), and these these are are
solved simultaneously
solved simultaneously to to yield
yield thethe values
values of of aa and c.c. From these these values,
values,
the axial
the axial ratio
ratio c/a cia maymay then
then be be calculated
calculated with with more precision
precision thanthan it it can
can
be found graphically.
be found graphically.
Figure 10-3
Figure 10-3 is is only
only aa partial
partial Hull-Davey
Hull-Davey chart. chart. A complete
complete one, one, show-
show-
ing curves of higher
ing curves of higher indices, indices, is
is reproduced
reproduced on a
a small
small scale
scale in
in Fig. 10-4,
Fig. 10-4,
which applies
which applies to to body-centered
body-centered tetragonaltetragonal lattices.
lattices. Note that the curves
that the curves
of high
of high indices
indices are often so
are often so crowded that that it is difficult
it is difficult toto assign
assign thethe proper
proper
indices to
indices to the
the observed
observed lines.lines. It then becomes necessary
It then necessary to to calculate
calculate the the
indices
indices of these high-angle
of these high-angle lines lines onon thethe basis
basis ofof a and cc values
values derived from from
the
the already
already indexed
indexed low-angle
low-angle lines.lines.

Some
Some Hull-Davey
Hull-Davey charts, charts, likelike thethe one shown in in Fig.
Fig. 10-4,
10-4, are designed
designed
for
for use
use with
with sin sin 2 8
2
6 values
values rather
rather than d values. values. No change change in in the chart
itself
itself is
is involved,
involved, only only a a change
change in in the
the accompanying
accompanying scale. scale. This is is possible
possible
because
because an an equation
equation similar
similar to
to Eq.
Eq. (10-4)
(10-4) can be set
set up
up in
in terms of
of sin 22 88
rather than d,
rather than d, byby combining
combining Eq. (10-3) with the
Eq. (10-3) the Bragg
Bragg law. law. This equa- equa-
tion
tion isis

log
log sin
= log
sin2 8 =
2 ~
log - 22 + log [ (h2 + k2 ) +
log [ (h
2 p2] .
+ --^T
-
2
) (10-6)
4a
4a L (cia)
(c/a

The sin2 8
The sin 2
6 scale
scale is
is therefore
therefore a a two-range
two-range logarithmic
logarithmic one one (from
(from 0.01
0.01 to
to 1.0),
1.0),

[(h + + k )) +
equal in
equal in length
length toto the two-range [(h
the two-range 2
2 2
2 2
+ l2/(cla)2]
I /(c/a)
fc
2
scale on the chart
scale on the
]
charl
and
and running
running in in the
the same
same direction.
direction. A scale scale ofof this
this kind appears
appears at thethe to}:
top
of
of Fig.
Fig. 10-3.
10-3.
When
When thethe cia
c/a ratio
ratio becomes
becomes equalequal to to unity,
unity, aa tetragonal
tetragonal cell
cell become!
becomes
cubic. It
cubic. It follows
follows that
that aa cubic
cubic pattern
pattern can can bebe indexed
indexed on on aa tetragonal
tetragonal Hull
Hull-
Davey
Davey chart
chart by keeping
by keeping the
the paper
paper strip
strip always
always on
on the
the horizontal
horizontal line
line corre
corre-

sponding to
sponding c/a == 1.
to cia 1. This
This isis seldom
seldom necessary
necessary because
because aa slide
slide rule
rule wil
wil
serve
serve just
just as
as well.
well. However,
However, it
it is
is instructive
instructive to
to consider
consider aa tetragonal
tetragonal eel
eel

as a departure
as a departure from
from a
a cubic
cubic one
one and
and to
to examine
examine aa Hull-Davey
Hull-Davey chart
chart iJii
 308
308 THE DETERMINATION
THE DETERMINATION OF CRYSTAL STRUCTURE
OF CRYSTAL STRUCTURE [CHAP, 10
[CHAP. 10

0.01
0.01 -- I
IM|immil|IIM|MM[IIM|IIM|IIM[llll|IMI[IIM[UII|Mll|IIMI|MII[llll|llll|llll|llll|

002
0.02 - r------------r----------~~----------}-------~~~110

0.03 ~

112
0.04 -: 200

-
0.05": 103
211
0.06- 202

0.07- Q().4

O.CB-
009-
0.1-

(]I
N
Z
iii

0.2-

0.3'::

0.4 ..::

0.5 .=

0.6-

0.7- ~~~------~----------~~----------+_----------4660
O.S-
0.9-
1.0- . ..I.. ..I I.. ..I.. ,,!..,. I ,,,!, ,,,!,,,, I,,,, I,,,, , ,,,l.i i.li ml. 1I.J

0.50 0.75 1.50

AXIAL
AXIAL RATIO
RATIO

FIG.
FIG. 10-4.
10-4. Complete
Complete Hull-Davey
Hull-Davey chart
chart for
for body-centered
body-centered tetragonaiiattices.
tetragonal lattices.
10-4]
10-4] NONCUBIC CRYSTALS (GRAPHICAL
(GRAPHICAL METHODS) 309
309

that
that light,
light, since
since the
the chart
chart shows at at a a glance
glance how the powder pattern
the powder pattern
changes
changes for
for any given change
any given change in
in the
the cia
c/a ratio.
ratio. It
It shows,
shows, for
for example,
example, how
certain
certain lines
lines split
split into
into two as
as soon as
as the
the cia
c/a ratio
ratio departs
departs from unity,
unity, and
how even
even thethe order
order of
of the
the lines
lines on the pattern can change
the pattern change with changes
changes
in cia.
in c/a.
Another graphical
graphical method of of indexing
indexing tetragonal patterns has
tetragonal patterns been de-
has been de-
vised
vised byby Bunn. Like Like the
the Hull-Davey
Hull-Davey chart, chart, a a Bunn chartchart consists
consists of
of a
a
network of
network of curves,
curves, oneone for
for each
each value
value of hkl, but the
of hkl, the curves
curves are based on
are based on
somewhat different
different functions
functions of hkl and cia
of hkl c/a than those
those used
used byby Hull
Hull and
Davey,
Davey, withwith the
the result
result that
that thethe curves
curves are
are less
less crowded in in certain
certain regions
regions
of
of the
the chart.
chart. The Bunn chart chart is is accompanied
accompanied by by aa logarithmic
logarithmic scale of d
scale of d
values,
values, and the the combination
combination of of chart
chart and scale
scale is
is used
used inin exactly
exactly the
the same
way
way asas aa Hull-Davey
Hull-Davey chartchart and scale.scale.

Patterns of
Patterns of hexagonal
hexagonal crystals can
crystals can also
also be
be indexed
indexed by by graphical
graphical methods,
methods,
since
since the
the hexagonal
hexagonal unit
unit cell,
cell, like
like the
the tetragonal,
tetragonal, is
is characterized
characterized by
by two
variable parameters, a
variable parameters, a and c. c. The plane-spacing equation
plane-spacing equation is
is

h2
11 _ 44 h
= -.
2
+
+ hk + + kk 22 l22
+-.
I

- = + 22 '

d*2
d 33 atf2 7c
After
After some manipulation,
manipulation, this
this becomes

221ogd log a -- log

log d == 221oga -4 (h
log [\- (h
22 2 P ]
+ hk + kk 2 ) + --4-
-2 '
)
L33 (cia)
(c/a

which
which isis of
of exactly
exactly thethe same formform as as Eq.
Eq. (10-4)
(10-4) for
for the
the tetragonal
tetragonal system.
system.
A Hull-Davey
Hull-Davey chart
chart for
for the
the hexagonal
hexagonal system system can
can therefore
therefore be
be constructed
constructed
log rt(h (h + hk hk + k k 2)) + l2/(c/a)2]
2 2
by
by plotting
plotting the variation of
the variation of log [
22 I/(c/a)
2
with cia.
] c/a.
A Bunn chartchart may
may also
also be
be constructed
constructed for
for this
this system.
system. Special Special charts
charts for
for
hexagonal close-packed
hexagonal close-packed lattices
lattices may
may also
also be
be prepared by omitting all
prepared by omitting all

curves
curves for
for which
which (h +
(h + 2k)2k) is
is an integral multiple
integral multiple of
of 3
3 ~nd
and l is
is
I odd.
odd.
Figure
Figure 3-13(c),
3-13(c), the powder pattern
the powder pattern of of zinc
zinc made with with eu Cu Ka radiation,
radiation,
will
will serve
serve to to illustrate
illustrate how the the pattern
pattern of of a
a hexagonal
hexagonal substance
substance is is indexed.
indexed.
2
Thirteen
Thirteen lines
lines were
were observed
observed on this pattern; their
this pattern ;
their sin
sin2 (J 6 values
values and rela-
rela-
tive
tive intensit.ies
intensities are are listed
listed inin Table
Table 10-2.
10-2, A fit fit was obtained
obtained on a a Hull-
Hull-
Davey
Davey chart
chart forfor hexagonal
hexagonal close-packed
close-packed lattices lattices at approximate cia
at an approximate c/a
ratio
ratio of
of 1.87.
1.87. The chart
chart lines
lines disclosed
disclosed the the indices
indices listed
listed in in the
the fourth
fourth
column of
column of the
the table.
table. In In the
the case
case of of line
line 5, 5, two chart
chart lines
lines (103
(10-3 and 110)
11-0)
almost intersect at
almost intersect at cia
c/a =
= 1.87,
1.87, so
so the
the observed
observed line
line is
is evidently
evidently the
the sum
of
of two
two lines,
lines, almost
almost overlapping,
overlapping, one
one from the
the (103) plmes
(10-3) planes and the
the other
other
from
from (11,0) planes. The same
(11 -0) planes. same is is true
true of of line
line 11.
11. FourFour lines
lines on the
the chart,
chart,
namely, 200, 104,210,
namely, 20-0, 10-4, 21-0, and 204,
20-4, do not
not appear
appear on the
the pattern,
pattern, and it it

must be
must be inferred
inferred thatthat these
these are
are tootoo weak to be observed.
to be observed. On the the other
other
hand,
hand, all
all the
the observed
observed lineslines are
are accounted
accounted for, so we may
for, so may conclude
conclude that
that
310
310 THE DETERMINATION
THE DETERMINATION OF CRYSTAL STRUCTURE
OF CRYSTAL STRUCTURE 10
[CHAP. 10
[CHAP.

TABLE 10-2
TABLE 10-2

Line Intensity sin 2 9 hk I

I s 0.097 002
2 s 0.112 100
3 vs 0.136 101
4 m 0.209 102
5 s 0.332 103, 110
6 vw 0.390 004
7 m 0.434 112
8 m 0.472 201
9 vw 0.547 202
10 w 0.668 20'3
11 m 0.722 114, 10'5
12 m 0.806 211
13 w 0.879 212

the lattice
the lattice of
of zinc
zinc
is actually
actually hexagonal
is hexagonal close-packed.
close-packed. The next
next step
step is
is to
to
calculate the
calculate the lattice
lattice parameters.
parameters. of the
Combination of the Bragg
Bragg law
law and the
the
plane-spacing equation
plane-spacing equation gives
gives
(h 2+ + kk2) + l2].
~

0 = ")..2 [~ . (h
2
2
+ hk + 2

sm"20 = _ -
sin2 hk ) 1

-1-
2
4 3 a2 C2 \c
where X /4 has
where ")..214
2
has aa value
value of 0.595A22 for
of 0.595A for Cu Ka radiation.
radiation. Writing
Writing this
this
equation out
equation out for
for the two highest-angle
the two highest-angle lines, namely, 12 and 13,
lines, namely, 12 13, we obtain:
obtain:

0.595 (~
r .~ + ~).
, 7
+ -
.

0.806 = 0.595
0.806 =
3 i
(
a2 c2

0.879 0.595 (~
= 0.595
0.879 = .~
{--= + ~).
+ -;
3 a2 c2

Simultaneous
Simultaneous solution
solution of of these
these two equations
equations gives
= 2.66A, cc =
gives a = 2.66A,
= 4.95A,
4.95A,
and cia
c/a =
= 1.86.
1.86.
Rhombohedral
Rhombohedral crystals crystals areare also
also characterized
characterized by by unit
unit cells
cells having
having two
parameters,
parameters, in in this case a
this case a and a.a. No new chart is needed,
chart is needed, however,
however, to to
index
index the
the patterns
patterns of of rhombohedral
rhombohedral substances,
substances, since,
since, asas mentioned in in
Sec.
Sec. 2-4,
2-4, any
any rhombohedral
rhombohedral crystal crystal may
may be referred
referred to
to hexagonal
hexagonal axes.
axes. A
hexagonal
hexagonal Hull-Davey
Hull-Davey or or Bunn chart therefore be used to index the
chart may therefore
pattern of
pattern of a
a rhombohedral
rhombohedral crystal.crystal. The indicesindices so found
found will,
will, of
of course,
course,
refer to
refer to aa hexagonal
hexagonal cell, cell, and the
the method of
of converting
converting them to
to rhombo-
hedral indices is
hedral indices is described
described in in Appendix
Appendix 2. 2.

We can
can conclude
conclude that that thethe pattern
pattern of
of any
any two-parameter
two-parameter crystal
crystal (tetrag-
(tetrag-
onal, hexagonal,
onal, hexagonal, or
or rhombohedral)
rhombohedral) can
can be indexed
indexed on the
the appropriate
appropriate Hull-
Davey
Davey or chart. If
or Bunn chart. If the
the structure
structure is is known,
known, thethe procedure
procedure is is quite
quite
straightforward.
straightforward. The best best method is is to
to calculate the cia
calculate the c/a ratio
ratio from
from the
the
10-5)
10-5] NONCUBIC CRYSTALS (ANALYTICAL
(ANALYTICAL METHODS) 311
311

known parameters,
parameters, lay lay a a straightedge
straightedge on the the chart
chart toto discover
discover the proper
the proper
line
line sequence
sequence for
for this
this value
value of
of cia,
c/a, calculate
calculate the
the value
value of
of sin
sin
2
2 fJ
6 for
for each line
line
from the the indices
indices found on the the chart,
chart, and then
then determine the
the indices
indices of
of
2
the
the observed
observed lines lines byby a
a comparison
comparison of
of calculated
calculated and observed
observed sin
sin 2 fJ6
values.
values.
If the
If the structure
structure is is unknown,
unknown, the problem of
the problem of indexing
indexing is is not
not always
always so so
easy
easy as as it it seems in in theory.
theory. The most common source source of of trouble
trouble is is the
the
presence of
presence of extraneous
extraneous lines,lines, asas defined
defined in in Sec.
Sec. 10-2,
10-2, in in the
the observed
observed pat- pat-
tern.
tern. Such lines can be
lines can be very
very confusing
confusing and, and, if if any
any difficulty
difficulty in in indexing
indexing
is
is encountered,
encountered, every every effort
effort should
should be be made to to eliminate
eliminate them from the the
pattern,
pattern, eithereither experimentally
experimentally or or by by calculation.
calculation. In
In addition,
addition, the the ob-ob-
2
served
served sin sin 2 fJ6 values
values usually
usually contain
contain systematic
systematic errors errors which make a a simul-
simul-
taneous
taneous fit fit of
of all
all the
the pencil
pencil marks on the the paper
paper stripstrip to
to curves
curves on the the chart
chart
impossible,
impossible, even
even when the
the paper strip
paper strip is
is at
at the
the correct
correct cia
c/a position. Be-
position.
cause
cause of of these
these errors,
errors, the
the strip
strip has
has to
to be
be shifted
shifted slightly
slightly from line line toto line
line
in
in order
order to to make successive
successive pencil
pencil marks coincide
coincide with
with curves
curves on the
the chart.
chart.
Two important
important rules always be
rules must always be kept
kept in in mind when using using Hull-Davey
Hull-Davey
or
or Bunn charts:charts:
(1)
(1) Every
Every mark on the the paper
paper strip
strip must coincidecoincide with with a a curve
curve on the the
chart,
chart, except
except for for extraneous
extraneous lines.lines. A structure
structure which accounts accounts for for only
only a
portion of
portion of the
the observed
observed lineslines isis not
not correct:
correct all :all the
the lines
lines inin the
the pattern
pattern must
be
be accounted
accounted for, for, either
either as as due to to the
the structure
structure of of the
the substance
substance involved
involved
or
or as
as extraneous
extraneous lines. lines.

(2)
(2) There
There need need notnot bebe a a mark on on the paper strip
the paper strip for
for every
every curve
curve on the the
chart,
chart, because
because some lines
lines may
may have
have zero
zero intensity
intensity or
or be
be too
too weak to
to be
be
observed.
observed.
Orthorhombic,
Orthorhombic, monoclinic, monoclinic, and triclinic triclinic substances
substances yield yield powder
powder pat- pat-
terns
terns which
which are are almost
almost impossible
impossible to
to index
index by graphical methods,
by graphical methods, although although
the
the patterns
patterns of of some orthorhombic
orthorhombic crystals crystals have have beenbeen indexed
indexed by by aa com-
bination
bination o(
of graphical
graphical and analytical
analytical methods.
methods. The essential
essential difficulty
difficulty is is

the large
the large number of variable parameters
of variable parameters involved. involved. In
In the
the orthorhombic
orthorhombic
system
system therethere are are three
three such parameters (a,
such parameters (a, b,b, c),
c), in
in the
the monoclinic
monoclinic four four
(a, b,
(a, c, fl),
b, c, 0), and in in the
the triclinic
triclinic six b, c,
(a, b,
six (a, a, fl,
c, cr, 7). If
0, 'Y). If the
the structure
structure is is known,
known,
patterns of
patterns of substances
substances in in these
these crystal
crystal systems
systems can can be be indexed
indexed fiy 6y com-
2
parison
parison of of the
the observed
observed sin sin2 fJB values
values withwith those
those calculated
calculated for for all
all possible
possible
values
values of of hkl.
hkl.

10-15
10-5 Indexing
Indexing patterns
patterns of of noncubic
noncubic crystals (analytical methods).
crystals (analytical methods).
Analytical
Analytical methods of
of indexing
indexing involve
involve arithmetical
arithmetical manipulation
manipulation ofof the
the
2
observed
observed sin 6 values
sin2 fJ values in in an attempt
attempt to
to find
find certain
certain relationships
relationships between
between
them.
them. Since
Since each
each crystal
crystal system
system is
is characterized
characterized byby particular
particular relation-
relation-
2
ships
ships between
between sin
sin 2 fJ values, recognition
values, recognition of
of these
these relationships
relationships identifies
identifies
the
the crystal
crystal system
system and leads leads to
to a
a solution
solution of
of the
the line
line indices.
indices.
312
312 THE DETERMINATION OF CRYSTAL STRUCTURE [CHAP. 10
(CHA.P. 10

2
For example,
example, the
the sin 6 values
sin 2 fJ values in
in the
the tetragonal
tetragonal system
system must obey
obey the
the
relation:
relation:
sin
2 = A(h2 + k2 ) + Cl2 ,
(10-7)
(10-7)

where
where A (= = ).X 22 /4a
( j 4a22 )) and C (=(
= ).X 22 /4c 2
j 4.i?)) are
are constants
constants forfor anyone
any one pattern.
pattern.
The problem
problem isis to to find
find these
these constants,
constants, since, since, once found,
found, they
they will
will disclose
disclose
the cell
the cell parameters
parameters a
a and c
c and enable
enable the
the line
line indices
indices to
to be
be calculated.
calculated.
The value of A is
value of is obtained
obtained from the the hkO lines.
lines. When 1 == 0,
/ 0, Eq.
Eq. (10-7)
(10-7)
becomes
- A(hA(h2 +
2 2
sin
sin2 fJ = + k22 ).).
(h +
The permissible
permissible values
values ofof (h 22 + k22 ) are
) are 1,
1, 2,
2, 4,
4, 5,
5, 8,8, etc.
etc. Therefore the
2
hkO
hkO lines
lines must have sin 6 values
sin 2 (J values inin the
the ratio
ratio of
of these integers, and A will
these integers, will

be
be some number which is is 1, !, 1.
1, ^, f ^,t,
,
t, etc.,
etc.,
,
times
times the
the sin
sin
2
2 fJ
6 values
values of
of these
these
lines.
lines. C is
is obtained
obtained from the the other
other lines
lines on the
the pattern
pattern and the the use
use of
of
Eq. (10-7)
Eq. (10-7) in
in the
the form
sin2 fJ - A(h2 + k 22 )) == Cl 2
Cl 2 .

Differences
Differences represented
represented by
by the
the left-hand
left-hand side
side of
of the
the equation
equation are
are set
set up,
up,
for
for various
various assumed values
values of
of h and k,
k, in
in an attempt
attempt to
to find
find a consistent
consistent
2
set of
set Cl2 values,
of Cl values, which must be be in
in the
the ratio
ratio 1,
1, 4,
4, 9,
9, 16,
16, etc.
etc. Once these
these
values
values are found, C can be
are found, be calculated.
calculated.
For hexagonal
hexagonal crystals,
crystals, an exactly
exactly similar procedure is
similar procedure is used.
used. In
In this
this
2
case,
case, sin
sin2 fJ8 values
values are
are given
given by
by
sin2 (J = A(h2 + hk + k2 ) + Cl2 ,
(h +
where = X).2j3a
2
/3a 2 and C = = X).2j4c
2 2 22 + hk +
/4c2 . Permissible
Permissible values
values of
2
where A = . of (h + kk22 )
)

are
are tabulated
tabulated in in Appendix
Appendix 6; 6; they
they areare 1,3,4,7,9,
1, 3, 4, 7, 9, etc.
etc. The indexing
indexing pro-
pro-
cedure is
cedure is best
best illustrated
illustrated byby means of of aa specific
specific example,
example, namely,
namely, the the pow-
pow-
2
der pattern of
der pattern of zinc,
zinc, whose observed
observed sin 8 values
sin 2 fJ values are
are listed
listed inin Table
Table 10-2.
10-2.
2
We first
first divide
divide thethe sin 2 8 values
sin fJ values byby the
the integers
integers 1,1, 3,
3, 4,
4, etc.,
etc., and tabulate
tabulate
the
the results,
results, as
as shown by by Table
Table 10-3,
10-3, which applies
applies to
to the
the first
first six
six lines
lines of
of
the
the pattern.
pattern. We then then examine these these numbers,
numbers, looking
looking for
for quotients
quotients which
2
are
are equal
equal to
to one another
another or or equal
equal to to one
one ofof the
the observed
observed sin 8 values.
sin 2 (J values. InIn
TABLE 100a
10-3

.2 9 IIn 2 9 IIn 29 lin 29

Line hkl
11(1
-3- --r -7-
1 0.097 0.032 0.024 0.01"
2 0.112* 0.037 0.028 0.016 100
3 0.136 0.04.5 0.034 0.019
0.209
"
5
6
0.332
0.390
0.070.
0.111
0.130
0.052
0.(113
0.098
0.030
0.047
0.056
110
10-5]
10-5] NONCUBIC CRYSTALS (ANALYTICAL METHODS^
(ANALYTICAL METHODS) 313
313

TABLE 10-4
10-4

LIne IIn2 8 Iln2 8-A IIn2 8 -3A hkl

1 0.097 002
2 0.112 0.000. 100
3 0.136 0.024. 101
0.209 0.097. 102
"
5
6
0.332.
0.390
0.221
0.278 0.054
110, 103
004

this
this case,
case, the
the two starred
starred entries,
entries, 0.112
0.112 and 0.111,
0.111, are
are the
the most nearly
nearly
equal,
equal, so
so we assume that
that lines
lines 2
2 and 5
5 are
are hkO lines.
lines. We then
then tentatively
tentatively
put A ==0.112
put 0.112 which is is equivalent
equivalent toto saying
saying that
that line
line 22 is
is 100.
100. Since
Since the
the
2
sin2 8
sin 6 value
value of
of line
line 5
5 is
is very nearly
very nearly 3
3 times
times that
that of
of line
line 2,
2, line
line 5
5 should
should be
be
110.
1 10. To find
find the
the value
value ofof C,
C, we must use
use the
the equation
equation

0-
sin 2 8
sin 2
A(h22 + hk
- A(h +
+ k 2) =
= Cl2
2
)
2
.

2
We now subtractsubtract from each each sinsin 8 6 value
2 value thethe values
values of of A (= (= 0.112),
0.112),
22
3A
34 (= (= 0.336),
0.336), 4A (= (= 0.448),
0.448), etc.,
etc., and looklook forfor remainders
remainders (Cl (Cl )) which
are
are in
in the ratio of
the ratio of 1,
1, 4,
4, 9,
9, 16,
16, etc.
etc. These figures
figures areare given
given in in Table 10-4. 10-4.
Here thethe five
five starred
starred entries
entries are
are of
of interest, because these
interest, because these numbers (0.024, (0.024,
0.097,
0.097, 0.221,
0.221, and 0.390)
0.390) are
are very
very nearly
nearly in in the
the ratio
ratio 1,1, 4,
4, 9,
9, and 16. 16. We
therefore
therefore put 0.024 =
put 0.024 = C(I)2,
C(l)
2
0.097 =
0.097
,
= C(2)2,
C(2)
2
,
0.221 =
0.221 = C(3)2,
C(3)
2
and 0.390
,
0.390 = =
gives C = 0.024
C(4)2.
C(4)
2
. This
This gives = 0.024 and immediately
immediately identifies
identifies line
line 11 as
as 002002 and
2
line
line 6 as 004.
6 as 004. Since
Since line
line 3
3 has
has a a sin
sin 2 8 value
value equal
equal toto the
the sum of of A and C, C,
its
its indices
indices must be be 101.
101. Similarly,
Similarly, the the indices
indices of of lines
lines 44 and 5 5 are
are found
to
to be
be 102
102 and 103,103, respectively.
respectively. In
In this
this way,
way, indices
indices areare assigned
assigned to to all
all

the lines on the

the lines the pattern,
pattern, and a
a final
final check
check on their
their correctness
correctness is
is made in
in
the
the usual
usual manner, by aa comparison of
of observed
observed and calculated
calculated sin
sin 22 8 values.
values.
manner, by comparison
2
In
In the
the orthorhombic
orthorhombic system,
system, the the basic
basic equation
equation governing
governing the the sin sin 2 8
values
values is is
sin 6 =
sin 2 8
2 = AhAh22 + Bk 2 +
+ Bk2 Cl2.
+ Cl 2
.

The indexing
indexing problem
problem is is considerably
considerably more difficult
difficult here,
here, in
in that
that three
three
unknown constants,
constants, A, A, B,
B, and C, C, have to to be determined.
determined. The general general
procedure, which is
procedure, is too
too lengthy
lengthy to to illustrate
illustrate here,
here, is
is to
to search
search for
for signifi-
signifi-
2
cant
cant differences
differences between
between various pairs of
various pairs of sin
sin 2 8
6 values.
values. For example,
example, con-con-
sider
sider any
any two lines
lines having
having indices hkO and hkl,
indices hkO hkl, with
with hk the the same forfor each,
each,
2
such
such as
as 120
120 and 121;
121 thethe difference
;
difference between
between theirtheir sin
sin 2 8 values
values isis C.
C. Sim-
2
ilarly,
ilarly, the
the difference
difference between
between the
the sin
sin 2 8 values
values of
of two lines
lines such
such as
as 310
310 and
312
312 is
is 4C,
4C, and so
so on.
on. If
If the
the structure
structure is
is such
such that
that there
there are
are many
many lines
lines
missing
missing from
from the
the pattern,
pattern, because
because of
of a
a zero
zero structure
structure factor
factor for
for the
the corre-
corre-
sponding planes, then
sponding planes, then the difficulties of
the difficulties of indexing
indexing are
are considerably
considerably increased,
increased,
inasmuch as the missing lines
inasmuch as the missing lines may be may be the
the very
very ones
ones which would supplysupply
314
314 DETERMINATION OF
THE DETERMINATION
THE CRYSTAL STRUCTURE
OF CRYSTAL STRUCTURE 10
[CHAP. 10
[CHAP.

the most
the most easily
easily recognized
recognized clues
clues if they
if they were
were present.
present. Despite
Despite suchsuch diffi-
diffi-
culties,
culties, this
this analytical
analytical method
method has
has been
been applied
applied successfully
successfully to
to a
a number
number
of orthorhombic
of orthorhombic patterns. patterns. One One requisite
requisite for for its
its success
success is is fairly
fairly high
high accu-
accu-
22
racy
racy in
in the
the sin
sin 9
6 values
values (at
(at least
least 0.OO(5),
0.0005), and the
the investigator
investigator should
should
therefore correct
therefore correct his his observations
observations for for systematic
systematic errors errors before
before attempting
attempting
to index
to index the the pattern.
pattern.
Monoclinic and
Monoclinic and triclinic
triclinic substances
substances yieldyield powder
powder patterns
patterns of of great
great com-
com-
plexity because
plexity because the
the number of
of independent
independent constants
constants involved
involved is
is now four
four
and six,
and six, respectively.
respectively. No generally generally successful method,
successful method, either analytical
either analytical
or graphical,
or graphical, of of indexing
indexing such
such patterns
patterns has has yetyet been
been devised.
devised.
We can can therefore
therefore conclude
conclude thatthat thethe powder
powder pattern
pattern of of aa substance
sUbstance hav- hav-
ing more
ing more than than two two independently
independently variablevariable cell cell parameters
parameters is is extremely
extremely
difficult, if
difficult, if not
not impossible,
impossible, to to solve.
solve. The structures
structures of of such
such materials
materials are are
almost always
almost always determined
determined by by the
the examination
examination of of aa single
single crystal,
crystal, by by either
either
the rotating-crystal
the rotating-crystal method or or one
one ofof its
its variations.
variations. With these these methods
it is aa relatively
it is relatively easy easy matter
matter to to determine
determine the the shape
shape and size size ofof an un-un-
known unit
known unit cell,
cell, no no matter
matter how low low its
its symmetry.
symmetry. Many substances, substances, of of
course,
course, are
are very
very difficult
difficult to
to prepare
prepare in
in single-crystal form,
single-crystal form, but, but, on the
the
other hand,
other hand, if if the
the substance involved is
substance involved is one
one of of low
low symmetry,
symmetry, the the time
time
spent in trying
spent in trying to
to obtain
obtain a
a single crystal
single crystal is
is usually
usually more fruitful
fruitful than the
the
time spent
time spent in in trying
trying to to solve
solve the
the powder
powder pattern.
pattern. The single-crystal speci-
single-crystal speci-
men need
need not not bebe large:
large: a crystal as
a crystal as small
small as as 0.1
0.1 mm in in any
any dimension can can
be successfully
be successfully handledhandled and will will give
give aa satisfactory diffraction pattern.
satisfactory diffraction pattern.
Readers
Readers interested
interested in in these
these single-crystal
single-crystal methods will will find
find them described
described
in some of
in some of the
the books
books listed
listed in
in Chap.
Chap. 18. 18.

10-6
10-6 The effecteffect of
of cell
cell distortion
distortion on the the powder
powder pattern.
pattern. At this
this point
point
we
we might digress slightly
might digress slightly from
from the
the main subject
subject of
of this
this chapter,
chapter, and exam-
ine
ine some
some of
of the
the changes
changes produced
produced in in a
a powder
powder pattern
pattern when the the unit
unit cell
cell

of
of the
the substance
substance involved
involved is is diRtorted
distorted in in various
various ways.
ways. As we have already
already
seen,
seen, there
there are
are many
many more lines lines on thethe pattern
pattern of of a substance
substance of of low sym-
sym-
metry,
metry, such
such as as triclinic,
triclinic, than
than on the pattern of
the pattern of a a substance
substance of of high
high sym-
sym-
metry,
metry, such
such asas cubic,
cubic, and we may may take
take it
it as
as aa general
general rule
rule that
that any
any distor-
distor-
tion of
tion of the
the unit
unit cell
cell which decreases
decreases itsits symmetry,
symmetry, in in the
the sense
sense of of intro-
intro-
ducing
ducing additional
additional variable
variable parameters,
parameters, will will increase
increase the the number of of lines
lines on
the
the powder
powder pattern.
pattern.
Figure
Figure 10-5
10-5 graphically
graphically illustrates
illustrates this
this point.
point. On the the left
left is
is the
the calcu-
calcu-
lated
lated diffraction
diffraction pattern
pattern of
of the
the body-centered
body-centered cubic
cubic substance
substance whose unit
unit
cell
cell is
is shown at at the
the top.
top. The line
line positions
positions are
are computed
computed for
for a
a =
= 4.00A
and Cr Kcx radiation. If
Ka radiation. If this
this cell
cell is
is expanded
expanded or or contracted
contracted uniformly
uniformly but
still
still remains
remains cubic,
cubic, the
the diffraction
diffraction lines
lines merely
merely shift
shift their
their positions
positions but but do
not
not increase
increase in in number,
number, since
since no change
change in
in cell
cell symmetry
symmetry is
is involved.
involved.
However,
However, if if the
the cubic
cubic cell
cell is
is distorted
distorted along
along only
only oneone axis,
axis, then
then itit becomes
10-6]
10-6] THE EFFECT OF CELL DISTORTION ON THE POWDER PATTERN 315
315

1
)..-_!!
4.16A
-
a/
/4.!X)A
1100J
CUBIC TETRAGONAL ORTHORHOMBIC
28 = 0- ~r-----'

01 1

Eo-<
IH I
I
11 0
H11 }
~
<:
::.:::,., 02 0
~ 200 i - - - - + _ - - - -
002
Z(i"o
- - --002
- - - '200 }
-"'"
C

~
~ 211
112
12 1
II 2
21 1 }
21 I
Z
0 02 2
""7-;,., 220 f---+- ____ ~Q2
220
- - - 202 }
<: 220 031
Eo-< 130\
'l1
is
310 i - - - - f _ - - - -
103
.?<!1
3](I
013
- - -103
___ 310
301
;-
}
22 2 }
222
222 t-----i

211
26 = 180 _ ' - - - - - '

FIG. 10-5.
10-5. Effects
Effects of
of cell
cell distortion
distortion on powder patterns. Lines
powder patterns, Lines unchanged
unchanged in
in
position
position are connected by
are connected by dashed
dashed lines.
lines.

tetragonal,
tetragonal, its
its symmetry
symmetry decreases,
decreases, and more diffraction
diffraction lines
lines are
are formed.
formed.
The center pattern shows the
center pattern the effect
effect of
of stretching
stretching the
the cubic
cubic cell
cell by 4
4 percent
by percent
along
along its
its [001] axis,
[001] axis, so
so that
that c
c is
is now 4.16A.
4.16A. Some lines
lines are
are unchanged
unchanged in
in
position,
position, some are shifted,
are shifted, and new lines have appeared.
lines have appeared. If
If the tetragonal
the tetragonal
316
316 THE DETERMINATION OF CRYSTAL STRUCTURE [CHAP. 10
[CHAP. 10

cell
cell is
is now stretched
stretched by by 8 percent
percent along along its its [OlO]
[010] axis,
axis, itit becomes ortho- ortho-
rhombic,
rhombic, with aa =
= 4.ooA,
4.00A, b
b =
= 4.32A,
4.32A, and c
c =
= 4.16A,
4.16A, as
as shown on the
the
right.
right. The result
result of
of this
this last
last distortion
distortion is
is to
to add still
still more lines
lines to
to the
the pat-
pat-
tern.
tern. increase in
The increase in the
the number of of lines
lines is is due essentially
essentially to to the
the intro-
intro-
duction of
duction of new plane plane spacings,
spacings, caused caused by by nonuniform distortion. distortion. Thus,
Thus,
in
in the cubic cell, the (200),
the cubic cell, the (200), (020), (020), and (002) planes
(002) planes all
all have the
the same spac-
spac-
ing
ing and onlyonly one one line
line isis formed,
formed, calledcalled thethe 200 line, line, but this
but this line
line splits
splits into
into
two when the the cell
cell becomes
becomes tetragonal,
tetragonal, since since now the (002) plane
the (002) plane spacing
spacing
differs
differs from
from the the other
other two.
two. When the the cell
cell becomes orthorhombic,
orthorhombic, all all three
three
spacings
spacings are are different
different and three three lines
lines are
are formed.
formed. '
Changes
Changes of of this
this nature
nature are are notnot uncommon among among phase phase transformations
transformations
and ordering
ordering reactions.
reactions. For example, example, the the powder
powder pattern
pattern of of slowly
slowly cooledcooled
plain
plain carbon
carbon steel steel shows lines lines due to to ferrite
ferrite (body-centered
(body-centered cubic) cubic) and
cementite
cementite (FeaC,(FeaC, orthorhombic).
orthorhombic). When the the same steel steel isis quenched
quenched from
the
the austenite
austenite region,region, the
the phases
phases present
present are
are martensite
martensite (body-centered
(body-centered
tetragonal) and,
tetragonal) and, possibly, possibly, some un transformed
untransformed austenite
austenite (face-centered
(face-centered
cubic).
cubic). The a
a and c
c parameters
parameters of
of the
the martensite
martensite cell
cell do not differ
differ greatly
greatly
from
from thethe a parameter
parameter of
of the
the ferrite
ferrite cell
cell (see Fig.
(see Fig. 12-5).12-5). The result
result is
is that
that
the
the diffraction
diffraction pattern
pattern of
of a quenched
quenched steel
steel shows pairs
pairs of
of martensite
martensite lines
lines
occurring
occurring at at about
about the the same 28 20 positions
positions as as thethe individual
individual lines lines of of ferrite
ferrite
in
in the
the previous pattern. If
previous pattern. If the
the quenched
quenched steel steel is is now tempered,
tempered, the the mar-
tensite
tensite wi1l
will ultimately
ultimately decompose
decompose into into ferrite
ferrite and cementite,
cementite, and each each pairpair
of
of martensite
martensite lines lines will
will coalesce
coalesce into into a a single
single ferrite
ferrite line.
line. Somewhat similar similar
effects
effects can
can be be produced
produced in in aa copper-gold
copper-gold alloy alloy having
having the the composition
composition repre- repre-
sented
sented by by the
the formula
formula AuCu. This alloy is
This alloy is cubic
cubic in in the
the disordered
disordered state state
but
but becomes
becomes either either tetragonal
tetragonal or
or orthorhombic
orthorhombic when ordered, depending
ordered, depending
on
on the
the ordering
ordering temperature
temperature (see (see Sec.
Sec. 13-3).
13-3).
The changes produced in
changes produced in aa powder
powder pattern
pattern by by cell
cell distortion
distortion depend,depend, in in
degree,
degree, on the
the amount of
of distortion.
distortion. If
If the
the latter
latter is
is small,
small, the
the pattern
pattern re-
re-
tains
tains the
the main features
features of of the pattern of
the pattern of the
the original
original undistorted
undistorted cell. cell. Thus,
Thus,
in
in Fig. 10-5,
Fig. 10-5, the
the nineteen
nineteen lines
lines of
of the
the orthorhombic
orthorhombic pattern
pattern fall
fall into
into the
the six
six
bracketed
bracketed groups shown, each group
groups shown, each group corresponding corresponding to
to one
one of
of the
the single
single
lines
lines on the the cubic
cubic pattern.
pattern. In
In fact,
fact, an experienced
experienced crystallographer,
crystallographer, if if

confronted
confronted with with this
this orthorhombic
orthorhombic pattern, pattern, might might recognize
recognize this this grouping
grouping
and guess
guess thatthat thethe unit
unit cell
cell ofof the
the substance
substance involvedinvolved was not not farfar from
cubic
cubic in shape, and that
in shape, that the the Bravais
Bravais lattice
lattice was either either simple
simple or body-
or body-
centered,
centered, sincesince the groups of
the groups of lines
lines areare spaced
spaced in in aa fairly
fairly regular
regular manner.manner.
But if if the
the distortion
distortion of the cubic
of the cubic cell cell had been been much larger, larger, each each line line of
of
the original
original pattern
pattern would split split into
into such
such widely separated
widely separated lines
lines that
that no
no
features
features of of the
the original pattern would
original pattern would remain.
remain.

10-7 Determination
Determination ofof the
the number ofof atoms in a
atoms in a unit
unit cell.
cell. To return
return
to the subject
subject of
of structure
structure determination,
determination, the
the next
next step
step after
after establishing
establishing
10-8]
10-8] DETERMINATION OF ATOM
DETERMINATION OF ATOM POSITIONS
POSITIONS 317
317

the shape
the shape and
and size
size of
of the
the unit
unit cell
cell isis to
to find
find the
the number
number of of atoms
atoms in
in that
that
cell,
cell, because
because the
the number
number of
of atoms
atoms must
must be
be known
known before
before their
their positions
positions
can be
can be determined.
determined. To To find
find this
this number
number we we use
use the
the fact
fact that
that the
the volume
volume
of the unit
of the unit cell, calculated
calculated from
cell, from thethe lattice
lattice parameters
parameters byby means
means of
of the
the
equations given
equations given inin Appendix
Appendix 1,1, multiplied
mUltiplied byby the measured density
the measured density of the
of the
substance equals
substance equals the
the weight
weight of
of all
all the
the atoms
atoms in
in the
the cell.
cell. From
From Eq.
Eq. (3-9),
(3-9),
we have
we have
pV
V
~A =
SA =
1.66020
1.66020

where SA
where ~A isis the
the sum of
of the
the atomic
atomic weights
weights of
of the
the atoms inin the
the unit
unit cell,
cell,
33 3
p is the density (gm/cm
p is the density (gm/cm ), ), and V is
is the
the volume of
of the
the unit
unit cell
cell (A 3
(A ).). If
If the
the
substance is
substance is an
an element
element ofof atomic
atomic weight
weight A, then
A then ,

SA =

where HI
where nl is the
is the number ofof atoms
atoms per
per unit
unit cell. If the
cell. If the substance
substance is
is aa chem-
ical compound, or an intermediate phase
ical compound, or an intermediate phase whose composition
composition can be repre-
be repre-
sented by
sented by aa simple
simple chemical
chemical formula,
formula, then
then

ZA = n 2 M,

where
where n n22 is
is the
the number of of "molecules"
"molecules" per per unit cell and M
unit cell M the molecular
weight.
weight. The number of of atoms perper cell
cell can then be calculated from n2
be calculated n 2 and
the
the composition
composition of of the
the phase.
phase.
When determined
determined in in this
this way,
way, the
the number of of atoms per
per cell
cell is
is always
always an
integer,
integer, within
within experimental
experimental error,
error, except
except for very few substances which
for a very
ha ve "defect
have "defect structures."
structures." In In these
these substances,
substances, atoms are simply
simply missing
missing
from
from aa certain
certain fraction
fraction ofof those
those lattice
lattice sites
sites which they
they would be expected
expected
to
to occupy,
occupy, andand the
the result
result is
is a
a nonintegral
nonintegral number of of atoms per
per cell.
cell. FeO
and the {3 phase
and the ft phase in
in the
the Ni-AI
Ni-Al system
system are
are well-known examples.
examples.

10-8
10-8 Determination
Determination of of atom positions.
positions. We now have to find find the posi-
posi-
tions of
tions of aa known number of
of atoms in
in a
a unit
unit cell
cell of
of known shape
shape and size.
size.

To
To solve
solve this problem, we must make use
this problem, use ofof the observed relative inten-
observed relative inten-

sities of
sities of the
the diffracted
diffracted beams,
beams, since
since these
these intensities
intensities are
are determined
determined by by
atom
atom positions.
positions. In In finding
finding the
the atom
atom positions,
positions, however,
however, wewe must
must again
again
proceed
proceed by by trial
trial and
and error,
error, because there is
because there is no
no known
known method
method of
of directly
directly
calculating
calculating atom
atom positions
positions from
from observed
observed intensities.
intensities.
To
To see
see why this is
why this is so,
so, we
we must
must consider
consider the
the two
two basic
basic equations
equations involved,
involved,
namely,
namely,

I = IFI p
2 (1 + cos2 , 20) (4-12)
sin 2 0 cos 8
318
318 DETERMINATION OF
THE DETERMINATION
THE CRYSTAL STRUCTURE
OF CRYSTAL STRUCTURE 10
(CHAP. 10
[CHAP.

which gives
which gives the
the relative
relative intensities
intensities of
of the
the reflected
reflected beams,
beams, and
and
NN
FF == ^f 2 l(hu *+ kv n+ lw
'L,fne2n(hun+kvn+lwn),
ne n\ (4-11)
(4-11)
11

which gives
which gives the
the value
value of
of the
the structure factor FF for
structure factor for the
the hkl reflection in
hkl reflection in terms
terms
of the
of the atom positions
atom uvw. Since
positions uvw. Since the
the relative
relative intensity I, the
intensity 7, the multiplicity
mUltiplicity
factor p,
factor and the
p, and the Bragg
Bragg angle
angle fJ are known for each line on the pattern, we
are known for each line on the pattern, we
can find
can find the
the value
value of
of \F\ for IFI
for each
each reflection
reflection from Eq.
from Eq. (4-12).
(4-12). But \F\ meas-
But meas- IFI
ures only
ures only the
the relative
relative amplitude
amplitude of
of each
each reflection,
reflection, whereas
whereas in
in order
order to
to use
use
Eq. (4-11)
Eq. for calculating
(4-11) for caleulating atom
atom positions,
positions, we must know the the value
value of F,
of F,
which measures
which measures both
both the
the amplitude
amplitude and phase of
and phase of one
one reflection relative
reflection relative to to
another.
another. This
This is the
is the crux
crux ofof thethe problem.
problem. The The intensities
intensities of of two reflected
reflected
beams are
beams are proportional
proportional to to the
the squares
squares of of their
their amplitudes
amplitudes but but independent
independent
of their
of their relative
relative phase.
phase. Since Since all all we cancan measure is is intensity,
intensity, we can can de-
de-
termine amplitude
termine amplitude but but not
not phase,
phase, which means that that we cannotcannot compute
compute
the structure
the structure factor
factor but but only
only its its absolute
absolute value.value. Any Any method of of avoiding
avoiding
this
this basic
basic difficulty
difficulty would
would constitute
constitute the
the much-sought-after
much-sought-after direct
direct method
method
of structure determination.
of structure determination. This
This difficulty appears
difficulty appears to
to be
be insurmountable,
insurmountable,
however, since
however, since nono direct
direct method,
method, generally
generally applicable
applicable to to all
all structures,
structures, has has
yet been
yet been devised,
devised, despite
despite the the large
large amount of effort devoted to the problem.
of effort devoted to the problem.
positions, therefore,
Atom positions, therefore, can can be be determined
determined only only by by trial
trial and error.error.
A set
set of
of atom positions
positions is is assumed,
assumed, the intensities corresponding
the intensities corresponding to to these
these
positions
positions are are calculated,
calculated, and the the calculated
calculated intensities
intensities are are compared
compared with
the
the observed
observed ones,ones, the the process
process being being repeated
repeated untiluntil satisfactory
satisfactory agreement
agreement
is
is reached.
reached. The problem problem of
of seleeting
selecting a
a structure
structure for
for trial
trial is
is not as hope-hope-
lessly
lessly broad
broad as
as it
it sounds,
sounds, since
since the
the investigator
investigator has many
many aids
aids to guide
guide
him.
him. Foremost
Foremost among among these
these is
is the
the accumulated knowledge
knowledge of
of previously
previously
solved
solved structures.
structures. From these these known structuresstructures he may be able to select select
aa few
few likely candidates,
likely candidates, and then
then proceed
proceed on the
the assumption
assumption that his
his un-
known structure
structure is
is the
the same as,
as, or
or very
very similar
similar to,
to, one of
of these known ones.
ones.
A great
great many
many known structures structures may may be be classified
classified into
into groups
groups according
according to
the kind of bonding (ionic, covalent,
the kind of bonding (ionic, covalent, metallic, metallic, or
or mixtures of
of these)
these) which
holds
holds the
the atoms
atoms together,
together, and a a selection
selection amongamong these
these groups
groups is aided
is aided by by aa
knowledge
knowledge of of the
the probable
probable kind kind of of atomic
atomic bonding
bonding in in the
the unknown phase, phase,
as
as judged
judged fromfrom the positions of
the positions of its
its constituent
constituent elements in in the periodic
periodic table.
table.
For
For example,
example, suppose
suppose the the phase
phase of of unknown structure structure has the chemical
formula
formula AB, AB, where
where A is is strongly
strongly electropositive
electropositive and and B B strongly
strongly electro-
electro-
negative,
negative, and
and that
that its
its powder
powder patternpattern is
is characteristic
characteristic of
of aa simple
simple cubic
cubic
lattice.
lattice. Then
Then the the bonding
bonding is
is likely
likely to
to be
be ionic,
ionic, oo.d
and the
the CsCI
CsCl structure
structure is
is

strongly suggested.
strongly suggested. But
But the
the FeSi
FeSi structure
structure shown
shown in
in Fig.
Fig. 2-19
2-19 is
is also
also aa
possibility.
possibility. In
In this
this particular
particular case, case, one
one or
or the
the other
other can
can be
be excluded
excluded by
by aa
density measurement,
density measurement, since
since the
the CsCI
CsCl cell
cell contains
contains one
one "molecule"
"molecule" and
and the
the
FeSi cell four.
FeSi cell four. If
If this were not
this were not possible, possible, diffracted
diffracted intensities
intensities would
would have
have
10-8)
10-8J OF ATOM
DETERMINATION OF
DETERMINATION ATOM POSITIONS
POSITIONS 319
319

to be
to be calculated
calculated on
on the
the basis
basis of
of each
each cell and
cell and compared
compared with with the the observed
observed
ones.
ones. It
It is this
is this simple
simple kind kind of of structure
structure determination,
determination, illustrated illustrated by by anan
example
example in
in the
the next
next section,
section, which
which the
the metallurgist
metallurgist should
should be
be able
able to
to carry
carry
out unaided.
out unaided.
Needless to
Needless to say,
say, many
many structures
structures are are too too complex
complex to to bebe solved
solved by by this
this
simple approach
simple approach and
and the
the crystallographer
crystallographer must
must turn
turn to
to more
more powerful
powerful
methods. Chief
methods. Chief amongamong these these are are space-group
space-group theory theory and and Fourier
Fourier series.
series.
Although any
Although any complete
complete description
description of of these
these subjects
subjects is beyond
is beyond the scope
the scope
of this
of this book,
book, aa few few general
general remarks
remarks may serve serve to to show
show their
their utility
utility in in struc-
struc-
ture determination.
ture determination. The The theory
theory of of space
space groups,
groups, one one of of the
the triumphs
triumphs of of
mathematical crystallography,
mathematical crystallography, relates relates crystal
crystal symmetry,
symmetry, on on thethe atomic
atomic
scale, to
scale, to the
the possible
possible atomic
atomic arrangements
arrangements which which possess
possess that that symmetry.
symmetry.
For example,
For example, if if aa given
given substance
substance is is known to to bebe hexagonal
hexagonal and to to have
have nn
atoms in
atoms in its
its unit
unit cell,
cell, then
then space-group
space-group theory theory lists lists all
all possible
possible arrange-
arrange-
ments of
ments of n atoms
atoms whichwhich will will have
have hexagonal
hexagonal symmetry. symmetry. This listing listing of of
possible arrangements
possible arrangements aids
aids tremendously
tremendously in
in the
the selection
selection of
of trial
trial struc-
struc-
tures. A further
tures. further reduction
reduction in in the
the number of of possibilities
possibilities can can then
then be be made
by noting
by noting the
the indices
indices of
of the
the reflections
reflections absent
absent from the
the diffraction
diffraction pattern.
pattern.
By such means
By such means alone, i.e., alone, i.e., before
before any
any detailed
detailed consideration
consideration is
is given
given to to
relative diffracted intensities, space-group
relative diffracted intensities, space-group theory theory can
can often
often exclude
exclude all
all but
but
two or
two or three
three possible
possible atomic
atomic arrangements.
arrangements.
Fourier series
A Fourier series isis a type of
a type infinite trigonometric
of infinite trigonometric series series hy by which any any
kind
kind ofof periodic
periodic function
function may may be expressed. ~ow
be expressed. Now the the one essential
essential prop-prop-
erty
erty of
of aa crystal
crystal is is that
that its
its atoms are are arranged
arranged in in space
space in in a periodic
periodic fashion.
But
But this
this means
means that that thethe density
density of of electrons
electrons is is also
also a a periodic
periodic function of
position
position in in the
the crystal,
crystal, rising
rising to to aa maximum at at the
the point
point where an atom is is

located
located and and dropping
dropping to
to a
a low
low value
value in
in the
the region
region between atoms. To re-
re-

gard
gard a a crystal
crystal in in this
this manner,
manner, as as aa positional
positional variation
variation of of electron
electron density
density
rather than
rather than as as anan arrangement
arrangement of
of atoms,
atoms, is
is particularly
particularly appropriate
appropriate where
diffraction
diffraction is is involved,
involved, in
in that
that x-rays
x-rays are
are scattered
scattered by
by electrons and not
by atoms
by atoms as
as such.
such. Since
Since the
the electron
electron density
density is
is a
a periodic
periodic function of posi-
posi-
tion,
tion, aa crystal
crystal may may be be described
described analytically
analytically by by means of of Fourier series. series.

This method of
This method of description description is
is very
very useful
useful in
in structure determination be-
be-
cause it can be shown that
cause it can be shown that the coefficientsthe coefficients of
of the various terms in
in the series
series

are
are related
related to the F values
to the values of of the
the various
various x-ray x-ray reflections.
reflections. But But suchsuch aa
series is
series is not
not of of immediate
immediate use, use, since
since thethe structure
structure factors factors are are not usually
not usually
known
known both both in in magnitude
magnitude and and phase.
phase. However,
However, another another kind kind of of series
series hashas
been
been devised
devised whose whose coefficients
coefficients are are related
related to to thethe experimentally
experimentally observ- observ-
IF!
able |F values
able values and and which
which gives,
gives, notnot electron
electron density,
density, but but information
information re- re-

garding
garding the
the various
various interatomic
interatomic vectors
vectors in
in the
the unit
unit cell.
cell. This
This information
information
is
is frequently
frequently enough enough to to determine
determine the the phase
phase of of the
the various
various structure
structure fac- fac-

tors;
tors; then
then the
the first
first kind
kind of
of series
series can
can be
be used
used to
to map
map out
out the
the actual
actual electron
electron
density
density throughout
throughout the the cell
cell andand thus
thus disclose
disclose the the atomatom positions.
positions.
320
320 THE DETERMINATION OF
OP CRYSTAL STRUCTURE [CHAP. 10
[CHA.P. 10

10-9
10-9 Eumple
Example of of structure
structure determination.
determination. As a simple simple example,
example, we
will
will consider
consider an intermediate
intermediate phasephase which occurs in in the cadmium-tellurium
system.
system. Chemical analysis analysis of of the specimen,
specimen, which appeared appeared essentially
essentially
one phase
phase under the
the microscope,
microscope, showed it
it to
to contain 46.6
46.6 weight percent
weight percent
Cd and 53.453.4 weight percent
weight percent Te.
Te. This is
is equivalent
equivalent to
to 49.8
49.8 atomic percent
percent
Cd and can be be represented
represented by by thethe formula CdTe. The specimen specimen was re- re-
duced toto powder
powder and a diffraction
diffraction pattern
pattern obtained with a Debye-Scherrer
Debye-Scherrer
camera and Cu Ka radiation.
radiation.
2
The observed
observed values
values ofof sin 6 for
sin 2 (J for the
the first
first 16 16 lines
lines are
are listed
listed in
in Table 10--5,
10-5,
together
together withwith the
the visually
visually estimated
estimated relative
relative line line intensities.
intensities. This pattern
pattern
can
can be
be indexed
indexed on the the basis
basis of
of a cubic
cubic unit
unit cell,
cell, and thethe indices
indices ofof the
the ob-
ob-
served
served lines
lines are
are given in the
given in table. The lattice
the table. lattice parameter,
parameter, calculated
calculated from
2
the sin 2 (J
the sin 6 value
value for
for the
the highest-angle
highest-angle line,line, isis 6.46A.
6.46A.
The density
density of of the
the specimen,
specimen, as as determined by by weighing
weighing a quantity
quantity ofof
the
the powder
powder in
in a
a pyknometer
pyknometer bottle,
bottle, was 5.82
5.82 gm/cm
gm/cm 3
3
. . We then find,
find, from
Eq.
Eq. (3-9),
(3-9), that
that
3
^ (5.82)(6.46)3
(5.82) (6.46)
j
~A = = 948.
948.
1.66020
Since the molecular weight
Since weight ofof CdTe is is 240.02,
240.02, the number of of "molecules"
per
per unit cell is 948/240.02 = 3.94,
unit cell is 948/240.02 = 3.94, or 4,
or 4, within experimental
within experimental error.
error.
At this point, we know that
this point, that the
the unit
unit cell
cell of
of CdTe is is cubic
cubic and thatthat it
it

contains
contains 4 "molecules" of of CdTe,
CdTe, i.e.,
i.e., 4 atoms of of cadmium and 4 4 atoms ofof
tellurium.
tellurium. We must now consider possible arrangements
consider possible arrangements of of these
these atoms
in
in the
the unit
unit cell.
cell. First
First we examine the the indices listed in
indices listed in Table
Table 10-5
10-5 for
for evi-
evi-
dence ofof the
the Bravais lattice.
lattice. Since
Since "he
die indices
indices of
of the
the observed
observed lines
lines are
are all
all

TABLE 10-5
10-5

Line Intemity sin2 e hkl

1 I 0.0462 111
2 VI 0.1198 220
3 VI 0.1615 311
4 vw 0.1790 222
5 m 0.234 400
6 m 0.275 331
7 s 0.346 422
8 m 0.391 511, 333
9 w 0.461 440
10 m 0.SQ.4 531
11 m 0.575 620
12 w 0.616 533
13 w 0.688
14
IS
m
VI
0.729
0.799
"""
71 I, 551
642
16 I 0.840 731,553
10-9)
10-9] EXAMPLE OF STRUCTURE DETERMINATION 321
321

unmixed, the
unmixed, the Bravais
Bravais lattice must be
lattice be face-centered.
face-centered. (Not (Not all
all possible
possible sets
sets
of
of indices are
unmixed indices are present,
present, however:
however: 200,
200, 420,
420, 600,
600, 442,
442, 622,
622, and 640
640
are missing
are missing from
from the
the pattern.
pattern. But these these reflections
reflections may be be too
too weak to be
to be
observed,
observed, and the
the fact
fact that
that they
they are
are missing
missing does
does not
not invalidate
invalidate our
our con-
con-
clusion that the
clusion that the lattice
lattice is face-centered.) Now there
is face-centered.) there are
are two common face-face-
centered
centered cubic
cubic structures
structures of
of the
the AB type, i.e., containing
type, i.e., containing two different
different
atoms inin equal
equal proportions,
proportions, and both both contain
contain four
four "molecules"
"molecules" per per unit
unit
cell: these
cell: these are
are the
the NaCl
NaCI structure
structure [Fig. 2-18(b)] and the
[Fig. 2-18(b)] the zinc-blende
zinc-blende form
form
of ZnS [Fig.
of [Fig. 2-19(b)].
2-19(b)]. Both of of these
these are
are logical
logical possibilities
possibilities even
even though
though
the bonding
the bonding inin NaCl isis ionic
ionic and
and in
in ZnS covalent,
covalent, since
since both
both kinds
kinds of
of bond-
bond-
ing have
ing have been
been observed
observed inin telluride
telluride structures.
structures.
next step
The next step is to calculate
is to calculate relative
relative diffracted
diffracted intensities
intensities for
for each
each struc-
struc-
ture and
ture and compare
compare them with
with experiment,
experiment, inin order
order to
to determine
determine whether
whether
or not
or not one of these
one of these structures
structures is
is the
the correct one. If
correct one. has the
If CdTe has the NaCl
NaCI
structure, then its
structure, then its structure
structure factor
factor for indices [see
for unmixed indices Example (e)
[see Example (e)
of Sec.
of Sec. 4-6]
4-6] is
is given
given by
by
16(/cd + h,Y,
= 16(fcd
F22 = 2
F /Te) if (h + k + I)
if (h,
is even,
l) is even,
(10-8)
F2 = 16(fcd
F 2 = -
16(/cd - /Te)
2
if (h
h,,)2, if ,
k + l)
(h + k is odd.
I) is odd.

On the
the other hand, if
other hand, if the
the ZnS structure
structure is
is correct, then the
correct, then the structure
structure factor
factor
for
for unmixed indices
indices (see
(see Sec.
Sec. 4-13)
4-13) is
is given
given byby
IFI2 ==
\F\
2
16(fci
16(/cd
2
+ hp2),
/Te
2
if
if(h(h + kk + l) is odd,
), l) is
odd,

IFI2 ==
\F\
2 - /Te) if (h
16(/cd - hp)2,
16(/Cd 2
(h + k
,
k + 1) is an odd multiple
if I) ismultiple of
of 2,
2, (10-9)
(10-9)

IFI2 ==
\F\
2
16(/cd + he)2,
16(/cd /Te)
2
(h + k + 1) is an even multiple
if (h,
kif I) is multiple of
of 2.
2.

Even before
before making
making aa detailed
detailed calculation
calculation of of relative
relative diffracted
diffracted inten-
inten-
sities
sities by
by means of
of Eq. (4-12),
Eq. (4-12), we can
can almost
almost rule
rule out
out the
the NaCI
NaCl structure
structure
as
as aa possibility
possibility simply
simply by inspection of
by inspection of Eqs.
Eqs. (10-8).
(10-8). The atomic
atomic numbers
of
of cadmium and tellurium tellurium areare 48 48 and 52, 52, respectively, so the
respectively, so the value
value ofof
(fCd + hp)2
(fed + /Te)
2
is
is several
several hundred
hundred times
times greater
greater than
than the
the value
value of
of (fcd
(/cd - /Te)
2
h,,)2,
,

for
for all
all values
values of of sin 0/X. Then,
sin fJ/X. Then, if if CdTe has has the
the NaCI
NaCl structure,
structure, thethe 111
111
reflection
reflection should
should be be very
very weak and the the 200
200 reflection
reflection very
very strong.
strong. Actu-
ally, III
ally, 111 isis strong
strong and 200 200 isis not
not observed.
observed. Further
Further evidence
evidence thatthat the
the
NaCI structure is
NaCl structure is incorrect
incorrect is is given
given in in the
the fourth
fourth column of of Table
Table 10-6,
10-6,
where thethe calculated intensities of
calculated intensities of the
the first
first eight
eight possible
possible lines
lines are
are listed:
listed:

there is
there is no agreement
agreement whatever
whatever between
between these
these values
values and the
the observed
observed in-in-
tensities.
tensities.
On thethe other
other hand,
hand, if if the
the ZnS structure
structure is is assumed,
assumed, intensity
intensity calcula-
calcula-
tions lead to
tionslead to the
the values
values listed
listed in
in the
the fifth
fifth column.
column. The agreement
agreement between
these
these values
values and the the observed
observed intensities
intensities is is excellent,
excellent, except
except forfor a few
minor inconsistencies
inconsistencies amongamong the
the low-angle reflections,
low-angle reflections, and these
these are
are due
to neglect of the absorption factor.
to neglect of the absorption factor. In particular, In particular, we note
note that
that the
the ZnS
322
322 THE DETERMINATION OF CRYSTAL STRUCTURE [CHAP. 10
[CHAP.

TABLE 10-6

1 2 3 4 5
OblMlf"Ved Calculated intensity
Line hid
intensity NaCI structure Zn 5 struc ture

1 111 s 0.05 12.4

2
3
2()()
220
311
nil
VI
vs
13.2
10.0
0.02 - 0.03
f-- 10.0
6.2

4 222 vw 3.5 0.007

5 400 m 1.7 1.7
6 331 m 0.01 2.5
420 nil 4.6 0.01
7 422 s 3.4
8 511, 333 m 1.8
9 440 w 1.1
10 531 m 2.0

600,442 nil 0.005

II 620 m 1.8
12 533 w 0.9
622 nil 0.004
13 444 w 0.6
14 711,551 m 1.8
640 nil 0.005
15 642 VI 4.0
16 731, 553 s 3.3

(N.B.
(N.B. Calculated
Calculated intensities
intensities have been
been adjusted
adjusted so
so that
that the
the 220
line
line has
has an intensity
intensity of
of 10.0
10.0 for
for both structures.)
structures.)

structure
structure satisfactorily
satisfactorily accounts
accounts for for all
all the
the missing
missing reflections
reflections (200,
(200, 420,
420,
etc.),
etc.), since
since the
the calculated
calculated intensities
intensities ofof these reflections are
these reflections are all
all extremely
extremely
low.
low. We can thereforetherefore conclude
conclude thatthat CdTe has has the
the structure
structure of of the
the zinc-
zinc-
blende
blende form of of ZnS.
ZnS.
After a given
given structure
structure has beenbeen shown to to be
be in
in accord
accord with
with thethe diffrac-
diffrac-
tion data, it is advisable to calculate
tion data, it is advisable to calculate thethe interatomic
interatomic distances
distances involved
involved in in
that
that structure.
structure. This calculation
calculation notnot only
only isis of
of interest
interest inin itself,
itself, but
but serves
serves
to
to disclose
disclose any
any gross
gross errors
errors that
that may
may have been been made,
made, since
since there
there is is obvi-
obvi-
ously
ously something
something wrong wrong with
with a proposed structure
a proposed structure if if it brings certain
it brings certain atoms
atoms
impossibly
impossibly close together. In
close together. In the present structure,
the present structure, the the nearest
nearest neighbor
neighbor
to the Cd atom at at 000 is is the
the Te atom at at 111.\ \. The Cd-Te interatomic
interatomic
distance is therefore Va
is therefore a/4 =
\/3 a/4: = 2.80A.
2.80A. For comparison,
comparison, we can can calcu-
calcu-
"
late
late a "theoretical"
theoretical" Cd-Te interatomic
interatomic distance
distance simply
simply by averaging the
by averaging the
distances of
distances of closest
closest approach
approach in
in the
the pure
pure elements.
elements. In
In doing this,
doing this, we re-
re-
gard
gard the atoms as
as rigid spheres
rigid spheres in
in contact, and ignore the effects
contact, and ignore the effects of coordi-of coordi-
 PROBLEMS 323
323

nation number and type type ofof bonding

bonding on atom size. size. These distances
distances of of
closest
closest approach
approach are 2.98A in
in pure
pure cadmium and 2.87
2.87AA in
in pure tellurium,
pure tellurium,
the average
average being
being 2.93A. The observed Cd-Te interatomic interatomic distance
distance is is

2.80A,
2.80A, oror some 4.5 percent smaller than the
4.5 percent the calculated
calculated value;
value; this
this differ-
differ-
is not unreasonable and can be largely
ence is largely ascribed
ascribed to to the
the covalent
covalent bond-
ing
ing which characterizes
characterizes this structure. In fact,
this structure. fact, it
it is
is a
a general
general rulerule that
that the
the
A-B interatomic distance
distance in
in an intermediate
intermediate phase
phase A
AzBII
x Bj, is
is always
always some-
what smaller than the average
average distance
distance of
of closest
closest approach
approach in in pure
pure A and
pure
pure B,
B, because the
because the mere existence
existence of the phase
of the phase shows that
that the
the attractive
attractive
forces unlike atoms is
forces between unlike is greater
greater than that
that between like atoms. If
like atoms. If
this
this were not true,
true, the
the phase
phase would not form. form.

PROBLEMS

10-1.
10-1. The powderpowder pattern
pattern of of aluminum,
aluminum, made with Cu Ka radiation,
with eu radiation, contains
contains
ten
ten lines,
lines, whose sin
sin
2
2 (J
6 values
values are
are 0.l11S, 0.1487, 0.294, 0.403, 0.439,0.583,0.691,
0.1118, 0.1487, 0.294, 0.403, 0.439, 0.583, 0.691,
0.727,
0.727, 0.872,
0.872, and 0.981.
0.981 . Index these
these lines
lines and calculate
calculate the
the lattice
lattice parameter.
parameter.
10-2.
10-2. A pattern
pattern is
is made of
of a
a cubic
cubic substance
substance with
with unfiltered
unfiltered chromium radia-
radia-
tion.
tion. The observed
observed sin 2
sin2 (J6 values
values and intensities
intensities are
are 0.265(m), 0.321(vs), 0.528(w),
0.265(m), 0.321(vs), 0.528(w),
0.638(s),
0.638(8) 0.793(s),
f 0.793(s), and 0.958(vs).
0.958(vs). Index thesethese lines
lines and state
state which are are due to to
Ka and which
which to to KfJ
K0 radiation.
radiation. Determine
Determine the
the Bravais
Bravais lattice
lattice and
and lattice
lattice param-
param-
eter.
eter. Identify
Identify thethe substance
substance by reference to
by reference to Appendix
Appendix 13. 13.

1D-3.
10-3. Construct
Construct a a Hull-Davey
Huil-Davey chart,
chart, and accompanying
accompanying sin
2
6 scale,
sin 2 (J scale, for
for hex-
hex-
agonal
agonal close-packed
close-packed lattices.
lattices. Use two-range
two-range semilog
semilog graph
graph paper,
paper, 8! 8j X 1111 in.
in.

Cover aa cia
c/a range
range of
of 0.50.5 to
to 2.0,
2.0, and plot
plot only
only the
the curves
curves 002,100,101,102,
00-2, 10-0, 10-1, 10-2,
and 110.
11-0.
1~ Use the
10-4. chart constructed
the chart constructed in in Prob. 10-3 to
Prob. 10-3 to index the first
index the first five lines on
five lines on the
the
powder pattern
powder pattern of a-titanium.
of a-titanium. With Cu Ka radiation, these lines
radiation, these have the
lines have the fol-
fol-

lowing sin
lowing
2
sin 2 (J values: 0.091,0.106,0.117,0.200,
B values: 0.091, 0.106, 0.117, 0.200, and and 0.268.
0.268.

In each
In each of
of the following problems
the following problems the pattern of
powder pattern
the powder of an element is
an element is represented
represented byby
the observed Bin2 (J values
the observed &in 2 values of
of the
the first
first seven
severt or eight lines
or eight lines on pattern, made with
the pattern,
on the with
Cu Ka radiation.
radiation. InIn each
each case,
case, index
index the lines, find
the lines, find the
the crystal
crystal system,
system, Bravais
Bravais lattice,
lattice,
and approximate
and approximate lattice
lattice parameter
parameter (or parameters), and
(or parameters), and identify
identify the
the ekment
element from
from the
the
tabulation given
tabulation given in Appendix 13.
in Appendix 18.

10-6
10-5 10-6 10-7
10-7 10-8
10-8
0.0806
0.0806 0.0603
0.0603 0.1202
0.1202 0.0768
0.0768
0.0975
0.0975 0.1610
0.1610 0.238
0.238 0.0876
0.0876
0.1122
0.1122 0.221
0.221 0.357
0.357 0.0913
0.0913
0.210
0.210 0.322
0.322 0.475
0.475 0.1645
0.1645
0.226
0.226 0.383
0.383 0.593
0.593 0.231
0.231
0.274
0.274 0.484
0.484 0.711
0.711 0.274
0.274
0.305
0.305 0.545
0.545 0.830
0.830 0.308
0.308
0.321
0.321 0.645
0.645 0.319
0.319
 CHAPTER 11
11

PRECISE PARAMETER MEASUREMENTS

11-1
11-1 Introduction.
Introduction. Many
Many applications
applications of of x-ray
x-ray diffraction
diffraction require
require pre-pre-
cise knowledge
cise knowledge of the of the lattice
lattice parameter (or parameters)
parameter (or parameters) of
of the
the material
material
under
under study.
study. In In the
the main,
main, these
these applications
applications involveinvolve solidsolid solutions;
solutions; since
since
the
the lattice
lattice parameter
parameter of of a a solid
solid solution
solution varies
varies with the the concentration
concentration of of
the
the solute,
solute, the the composition
composition of of aa given
given solution
solution can be determined from a
measurement of of its
its lattice
lattice parameter.
parameter. Thermal expansionexpansion coefficients
coefficients
can
can also
also be be determined,
determined, without a a dilatometer,
dilatometer, by by measurements of of lattice
lattice
parameter
parameter as as aa function
function of of temperature
temperature in in aa high-temperature
high-temperature camera. Or
the
the stress
stress in in aa material
material may may be be determined by by measuring
measuring the expansion or
the expansion or
contraction
contraction of of its
its lattice
lattice as as a result of
a result of that
that stress.
stress. Since,
Since, inin general,
general, a
change
change in in solute
solute concentration
concentration (or (or temperature,
temperature, or or stress) producf's only
stress) produces only
aa small
small change
change in in lattice
lattice parameter,
parameter, rather precise parameter
rather precise parameter measure-
measure-
ments must be made in in order
order to to measure these these quantities
quantities with with any
any accu-
accu-
racy.
racy. In
In this
this chapter
chapter we shall
shall consider
consider the
the methods that
that are
are used
used to
to obtain
obtain
high
high precision,
precision, leaving
leaving the the various applications to
various applications to bebe discussed
discussed at at a a later
later
time.
time. Cubic substances substances will will be dealt
dealt with first,first, because
because they
they are
are the
the sim-
sim-
plest,
plest, but
but our
our general
general conclusions
conclusions will
will also
also be
be valid
valid for
for noncubic
noncubic materials,
materials,
which will will be be discussed
discussed in in detail
detail later.
later.

The process
process of of measuring
measuring a a lattice parameter is
lattice parameter is aa very
very indirect
indirect one,
one, and
is
is fortunately
fortunately of
of such a
a nature
nature that
that high precision
high precision is
is fairly easily
fairly easily obtainable.
obtainable.
parameter a of
The parameter of a
a cubic
cubic substance
substance
is
is directly proportional to
directly proportional to the
the spacing
spacing
d of of anyany particular
particular set set of of lattice
lattice
I
panes. f
planes. IIf we measure tthe
he Bragg
Bragg 0 !j
j.sm(J

angle
angle 8 6 for
for this
this setset of planes, we can
of planes, can
j.(J- -
use
use thethe Bragg
Bragg law to determine d
to determine and, ~ () 6
d and,
knowing d,
knowing d, we can calculates. But ~
can calculate.a.
it
it isis sin
sin 8,0, not
not 8, 0, which appears
appears in in the
the 04
Bragg
Bragg law. law. Precision
Precision in or a,
d, or
in d, a, there-
there-
fore
fore depends
depends on precision in
on precision sin 8,
in sin 0, aa 02
derived
derived quantity,
quantity, and not not on precision
precision
in
in 8,0, the
the measured
measured quantity.
quantity. This This isis 20 40 60 ~o
80 90
fortunate
fortunate because because the the value
value of of sin
sin0 8 6 (degrees)

changes
changes very very slowly
slowly with with 8 in in the
the
FIG.
FIG. 11-1.
11-1. The variation
variation ofof sin
sin 8
neighborhood of
neighborhood of 90,
90, as
as inspection
inspection of of
with
with 8. The error
error in
in sin
sin 8 caused
0. caused byby a a
Fig.
Fig. II-lor
11-1 or a a table
table of of sines
sines will
will show.
show. given
given error
error in in 8 decreases
decreases asas 8 increases
increases
For thisthis reason,
reason, a a very
very accurate
accurate value value (A0 exaggerated).
(A8 exaggerated).
324
 11-1)
H_l] INTRODUCTION
INTRODUCTION 326
326

ofsin
of sin 8can beobtained
canbe obtainedfrom
fromaameasurement
measurementofof68which whichisisitself not itself
notparticu-
particu-
larly precise, provided that
that 68 i8
is near near
90.
90. AtAt 8 = 85,
85, for
for =
example,
example, aa 11
larly precise, provided
percenterror
percent errorin
in 8leads
leads to an error
to an error inin sin
sinB8ofof only
only0.1 percent. Stated
0.1 percent. Statedinin
anotherway,
another way, the
the angular
angularposition
position of
ofaa diffracted beamisis much
diffracted beam much more
moresensi-sensi-
tive to a given change
tive to a given change in
in plane spacing
plane spacing when
when 68 is
is large
large than
than when
when it
it is
is small.
small.

We can
We can obtain
obtain the
the same
same result
result directly
directly by
by differentiating
differentiating the Bragg law
the Bragg law
with respect to
with respect to B. 8. We
We obtain
obtain

D.-d
- == ~- cot0A0.
cot 8D..f). (11-1)
(H-1)
dd
In the
In the cubic
cubic system,
system,
= d
aa=dv'h 2 Vh +
+kk2 +
2 2
+12 I
2
.

Therefore
Therefore
D.-a D.-d
- == _
_
Aa Arf -

- == -- cot Ot:.O.
,
rts
cot0A0. (11-2)
(11-2)
a
a d
d

Since cot
Since cot 68 approaches
approaches zero
zero as
as 8 approaches
approaches 90,
90, Aa/a, the fractional
t:.a/a, the fractional error
error
in caused by
in aa caused by aa given
given error
error in
in 0, also approaches
0, also approaches zero
zero as
as 8 approaches
approaches 90,
90,
or as
or as 20 approaches 180.
20 approaches 180. key to
The key to precision
precision in
in parameter
parameter measurements
measurements
therefore lies
therefore lies in
in the
the use of backward-reflected
use of backward-reflected beams having
having 20
28 values
values as
as
near
near to 180 as
to 180 as possible.
possible.
Although the
the parameter
parameter errorerror disappears
disappears as as 20 approaches
approaches 180, 180, wewe can
can-
Although
not observe
not observe a
a reflected
reflected beam at
at this
this angle.
angle. But since the
the values
values of a calcu
of a calcu-

lated
lated forfor the
the various
various lines
lines on the pattern
on the pattern approach
approach the true true value
value moremore
closely
closely as
as 20
20 increases,
increases, we
we should
should be
be able
able to
to find
find the true value
value of
of a
a simply
by 20 == 180.
180.
by plotting the measured values against 28 20 and extrapolating
extrapolating to to 20
plotting the measured values against
Unfortunately,
Unfortunately, this this curve
curve is
is not
not linear
linear and
and the
the extrapolation
extrapolation of
of a
a nonlinear
nonlinear
curve
curve is is not
not accurate. However, it
accurate. However, it may
may be be shown
shown that that ifif the
the measured
measured
values of a are plotted
values of a are plotted against against certain
certain functions
functions of
of 0,
0, rather
rather than
than against
against
ooror 2020 directly, the resulting
directly, the resulting
curve
curve is
is aa straight
straight line
line which
which may
may be
be extrapa.
extrapo-
lated
lated with
with confidence.
confidence. The The bulk
bulk of of this
this chapter
chapter is is devoted
devoted to to showing
showing how how
these functions can
these functions can be derived be derived and
and used.
used. Because
Because the
the exact
exact form
form of
of the
the
function depends on the kind of
function depends on the kind of camera employed, camera employed, we
we shall
shall have
have to
to con-
con-
sider
sider successively
successively the the various cameras that
various cameras that are
are normally
normally used used for
for parameter
parameter
measurements.
measurements.
But
But firstfirst we
we might
might ask:
ask: what
what sortsort of of precision
precision is is possible
possible withwith suchsuch
methods?
methods? Without Without any any extrapolation
extrapolation or or any particular attention to good
any particular attention to good
experimental
experimental
technique,
technique, simply
simply byby selection of
selection of the
the parameter
parameter calculated
calculated
for
forthe
thehighest-angle
highest-angleline line on
onthe pattern, we
thepattern, wecancanusually
usually obtain
obtainan anaccuracy
accuracy
0.01A. Since
ofof0.01A. Since the the lattice
lattice parameters
parametersof of most
most substances
substances of metallurgical
of metallurgical
interest
interestare are in
in the
the neighborhood
neighborhood of of33 to 4A, this
to 4A, this represents
represents an anaccuracy
accuracy of of

about
about 0.3 0.3 percent. With good experimental technique and
percent. With good experimental technique
and thethe use of the
use of the
proper extrapolation function, this
this accuracy
accuracy can
can be
be increased
increased to to O.OOlA,
0.001A,
proper extrapolation function,
326
326 PRECISE PARAMETER MEASUREMENTS
PRECISE PARAMETER MEASUREMENTS 11
[CHAP. 11
[CHAP.

or 0.03
or 0.03 percent,
percent, without
without much
much difficulty.
difficulty. Finally,
Finally, about
about the
the best
best accuracy
accuracy
that can
that can bebe expected
expected is
is 0.0001A,
O.OOOIA, or
or 0.003
0.003 percent,
percent, but
but this
this can
can be
be obtained
obtained
only
only by
by the
the expenditure
expenditure of
of considerable
considerable effort,
effort, both
both experimental
experimental and
and com-
com-
putational.
putational.
In work
In work of
of high
high precision
precision it
it is
is imperative that
imperative that the
the units
units in
in which
which the
the
measured parameter
measured parameter is
is expressed,
expressed, kX or
or A,
A, be
be correctly
correctly stated.
stated. In
In order
order
to avoid
to avoid confusion
confusion on
on this
this point,
point, the reader
the reader is advised
is advised to
to review
review the
the dis-
dis-
cussion of
cussion of these units given
these units given in
in Sec.
Sec. 3-4.
3-4.

11-2 Debye-Scherrer
11-2 Debye-Scherrer cameras.
cameras. general approach
The general approach in
in finding
finding an
extrapolation function
extrapolation function is
is to
to consider
consider the
the various
various effects
effects which can
can lead
lead to
to
errors in
errors in the
the measured
measured values
values of
of 6,
(), and to
to find
find out how these
these. errors
errors in
in 6() t

vary with
vary with the
the angle
angle () itself. For aa Debye-Scherrer
Debye-Scherrer camera,
6 itself. camera, the
the chief
chief
sources of
sources of error
error in
in 6() are
are the
the following:
following:
(I)
(1) Film shrinkage.
Film shrinkage.
(2)
(2) Incorrect camera
Incorrect camera radius.
radius.
(3)
(3) Off-centering of
Off-centering of specimen.
specimen.
(4)
(4) Absorption in
Absorption in specimen.
specimen.
Since only
Since only the
the back-reflection
back-reflection region
region is
is suitable
suitable for
for precise
precise measurements,
measurements,
we shall consider these various
shall consider these various errors
errors in
in terms of
of the
the quantities S' and 0,
quantities S' tP,
defined
defined in Fig. 11-2.
in Fig. 11-2. S is the
S' is the distance
distance on the
f
the film between
film two correspond-
correspond-
ing back-reflection
ing lines; 2tP
back-reflection lines; is the
2<f> is the supplement
supplement of of 2(},
26, i.e.,
= 90 - n.
i.e., tP = 90 6.
</>

These
These quantities
quantities are
are related
related to to the radius R by
the camera radius by the equation
equation

S'
S f

tP = 4R' (11-3)
(H-3)
4R
Shrinkage of
Shrinkage of the
the film,
film, caused
caused by
by processing
processing and drying,
drying, causes an error
AS' in
dS' in the
the quantity
quantity S'.
S'. The camera radius may also
also be in
in error by
by an
amount llR.
Afl. The effects
effects of
of these
these two errors
errors on the of tP may be found
the value of <t>

by
by writing
writing Eq.
Eq. (11-3)
(11-3) inin logarithmic
logarithmic
form:
form:

In <f>
= In
In <I> = S' -- In
In S' 4 -- In
In 4 In R.
R.

Differentiation
Differentiation then
then gives
gives

lltP
A< llS'
AS' t:..R
Aft
= ---.
-= (11-4)
(11-4)
tP
4> S'
S' R
The error
error in
in <I> due toto shrinkage
<j> shrinkage and
the
the radius
radius error
error is
is therefore
therefore given
given by
by

t:..S'^AS' llR)
&R\
ll<l>S.R = ( s;- - Ii
R
U.
tP ' (11-5)
(11-5)
FIGURE 11-2
FIGURE 11-2
11-21
11-2] DEBYE-SCHERRER CAMERAS 327

(a)
(a) (h)
v,,,

FIG.
FIG. 11-3.
11-3. Effect
Effect of
of specimen
specimen displacement
displacement on line
line positions.
positions.

The shrinkage
shrinkage error
error can
can be
be minimized
minimized by by loading
loading the
the film
film so
so that
that the
the inci-
inci-
dent
dent beam entersenters through
through a a hole
hole inin the
the film,
film, since
since corresponding
corresponding back- back-
reflection
reflection lines
lines are
are then
then only
only a a short
short distance
distance apart
apart on the the film,
film, and their
their
separation
separation S' S' is
is little
little affected
affected by by film
film shrinkage.
shrinkage. The method of of film
film load-
load-
ing
ing shown in in Fig.
Fig. 6-5(a)
6-5 (a) isis not
not atat all
all suitable
suitable for precise measurements.
for precise measurements.
Instead, methods (b)
Instead, (b) or
or (c)
(c) ofof Fig.
Fig. 6-5 should
should bebe used.
used. Method (c), (c), the
the
unsymmetrical
unsymmetrical or or Straumanis method of of film
film loading,
loading, is is particularly
particularly recom-
recom-
mended since
since no knowledge
knowledge of of the
the camera radius
radius isis required.
required.
An off-center specimen also
off-center specimen also leads
leads toto an error
error inin cPo
0. Whatever the the dis-
dis-
placement
placement of
of the
the specimen
specimen from the
the camera center,
center, this
this displacement
displacement can can
always
always be
be broken
broken up
up into
into two components,
components, one
one (~) parallel
(Ax) parallel to
to the
the incident
incident
beam and the the other (Ay) at
other (dy) at right
right angles
angles to to the
the incident
incident beam.
beam. The effect effect
of
of the parallel displacement
the parallel displacement is is illustrated
illustrated in in Fig.
Fig. 11-3
11-3 (a).
(a). Instead
Instead of being
of being
at
at the
the camera center
center C',C", the
the specimen
specimen is is displaced
displaced a distance ~
a distance Ax to to the
the
point O.
point 0. The diffraction
diffraction lines
lines are
are registered
registered at at D and C instead instead ofof atat A
and B,B, the
the line positions for
line positions for a properly centered
a properly centered specimen.
specimen. The error error in in
S' is
S' is then (AC +
then (AC DB) == 2DB,
+ DB) 2DB, whichwhich is is approximately
approximately equal equal to 20 AT, or
to 20N, or

dS'
AS' = 20N = = 2.1x.sin
2Aaxsin 2cP.
2<t>. (11-6)
(11-6)

The effect
effect of
of aa specimen
specimen displacement
displacement at at right
right angles
angles toto the
the incident
incident beam
[Fig. 11-3(b)]
[Fig. ll-3(b)] is
is to
to shift
shift the
the lines
lines from
from A to
to C and from
from B to D. When
to D.
dy is small,
Ay small,
is AC is
is very nearly equal
very nearly equal to
to BD and so,
so, to
to a
a good approximation,
good approximation,
no error
error in S' is
in S' is introduced
introduced byby a a right-angle
right-angle displacement.
displacement.
The total
total error
error in S' due to
in S' to specimen
specimen displacement
displacement in in some direction
direction in-
in-
clined to
clined to the
the incident
incident beam is is therefore
therefore given
given byby Eq.
Eq. (11-6).
(11-6). This error
error
in S causes
in S' causes an error
error in
in the
the computed
computed value of q,.. Inasmuch as
value of as we are
are con-
f
. con-
sidering
sidering the
the various
various errors
errors one
one atat aa time,
time, we can
can now put put the
the radius
radius error
error
!Ul
A# equal
equal to
to zero,
zero, soso that
that Eq.
Eq. (11-4)
(11-4) becomes
becomes
dcP dS'
--- = ---, (11-7)
(H-7)
cP
* S'
S'
328
328 PRECISE PARAMETER MEASUREMENTS [CHAP. 11
(CRAP. 11

which shows how an error in S'

error in S' alone
alone affects
affects the
the value of 1/1. By
value of By combining
combining <t>.

Eqs.
Eqs. (11-3),
(11-3), (11-6), (11-7), we find
(ll-), and (11-7), find that
that the
the error in 1/1 due to
error in to the
the fact
fact <t>

that
that the
the specimen
specimen is
is off
off center
center is
is given by
given by

I/I~' I/I(2.1x sin

sin 21/1)
2^>) ax.
Ax
.11/1c = - - = =- SID
sin 1/1 cos 1/1.
</> </>. (11-8)
(11-8)
S'
o 4RI/I
4/i0 R
it

It
It should
should notnot bebe assumed that that thethe centering
centering error
error is
is removed when the the
specimen
specimen is is so
so adjusted,
adjusted, relative
relative to to the
the rotating
rotating shaft
shaft ofof the
the camera,
camera, thatthat
no perceptible
perceptible wobble can can bebe detected
detected when the the shaft
shaft is
is rotated.
rotated. ThisThis sort
sort
of
of adjustment
adjustment is
is taken
taken for
for granted
granted in
in this
this discussion.
discussion. The off-center
off-center error
error
refers to
refers to the possibility that
the possibility that thethe axis
axis of of rotation
rotation of the shaft
of the shaft is
is not located
located
at
at the
the center
center of of the
the camera,
camera, due to
to improper
improper construction
construction of
of the
the camera.
camera.
Absorption
Absorption in in the
the specimen
specimen also also causes
causes an error in 1/1.
error in <. This
This effect,
effect, often
often
the
the largest single
largest single cause
cause of
of error
error in
in parameter measurements,
parameter measurements, is
is unfortu-
unfortu-
nately
nately very
very difficult
difficult toto calculate
calculate with with any any accuracy.
accuracy. But we have seen, seen, in
in
Fig. 4-18(b), that
Fig. 4-18(b), that back-reflected
back-reflected rays rays come almostalmost entirely
entirely from tha.t that side
side
of
of the
the specimen
specimen which faces faces thethe collimator.
collimator. Therefore,
Therefore, to to a
a rough
rough approx-
approx-
imation,
imation, thethe effect
effect of
of aa centered,
centered, highlyhighly absorbing
absorbing specimen
specimen is is the
the same as as
that
that of
of aa nonabsorbing
nonabsorbing specimenspecimen displaced
displaced from the the camera center center inin the
the
manner shown in in Fig.
Fig. 11-3(a).
11 -3 (a). Consequently we can
Consequently can assume that that the
the
error in 1/1 due to
error in <t> to absorption,
absorption, .11/1.1,
A<fo is
is included
included
,
in
in the
the centering
centering error
error given
given
by Eq. (11-8).
byEq. (11-8).
Thus,
Thus, the
the over-all
over-all error
error inin 1/1 due to
</> to film
film shrinkage,
shrinkage, radius
radius error,
error, centering
centering
error,
error, and absorption,
absorption, is
is given
given by by the
the sum of
of Eqs. (11-5)
Eqs. (11-5) and (11-8):
(11-8):

= ~'
(/AS' A#\
.1R) Ax
ax
.1"-8 RCA = -S' - - R'".I. +
+ -R sin
sm cos 1/1.
.I. cos (11-9)
~, , ,
A<te,/2,c,A I ) <t>
."
</> </>. (1 1-9)
\ O K / 1

But
= 90
1/1 = 90 - 9,
0, A0 =
.11/1 = - .19,
A0,
= cos
sin 1/1 =
sin <t>cos 9,
0, and cos = sin
cos 1/1 = sin 9.
0. <f>

Therefore
Therefore Eq. (11-2) becomes
Eq. (11-2)

ad
Ad cos
cos 9 sin 1/1
sin
- = 9 ==
= - - . 1 A0 :
--.11/1 A</>
d sin
sin 9 cos 1/1
cos <t>

and
Ad
ad
- == sin
-- 1/1 [(~'
sin^r/AS' A#\
- - -.1R).1X
- )<H
Ax
I/I+-sinl/lcosl/l
sin cos
]1 . (11-10)
( (11-10)
d cos 1/1 L \ S'
cos < S' RI R J

In
In the
the back-reflection region, tP is
back-reflection region, is small
small and may
<
may bebe replaced,
replaced, in
in the
the second
second
term of
of Eq.
Eq. (11-10),
(11-10), by sin<tP cos
by sin 1/1, since
cos<, sin<1/1 "'" tP and cos
since sin tP "'" 1,
cos</> 1, for
for <f>
11-21
11-2] DE BYE-SCHERRER CAMERAS
DEBYE-SCHERRER CAMERAS 329
329

small values
small values of cpo
of <t>. We then
We then have
have
Ad
!ld /AS' Aft Ax\
dd == ((!lS'
s;- - !lR
R +
!lX).
h Ii sm 1 sin
22
cpo
<t>.

\S' R R
The bracketed
The bracketed terms
terms are
are constant
constant for
for any
anyone film, so
one film, so that
that
!ld
-d == K sin A. =
sin22 4~ = K cos
cos22 6,
8, (11-11)
(11-11)
d

where
where K isis aa constant.
constant. Accordingly,
Accordingly, we have
have the
the important
important result
result that
that
2
the fractional errors
the fractional errors in
in d
d are directly proportional
are directly proportional to
to cos
cos 2 8,
0, and
and therefore
therefore
approach zero
approach zero as cos22 68 approaches
as cos approaches zero
zero or
or as
as 60 approaches
approaches 90. 90. InIn the
the
cuhic system,
cubic system,
!ld!la 2
-- ==- = K cos2 0.
= tfcos O. (11-12)
(11-12)
d
d a
a

Hence, for
Hence, for cubic
cubic substances,
substances, if the
if the value
value of of a computed
computed for for each
each line
line on
on the
the
2
pattern
pattern irs
is plotted against
plotted against cos
cos 2 0, a
6, a straight
straight line
line should
should result,
result, and ao,
a, the
the
true value
true value of of a, can be
a, can be found
found by by extrapolating
extrapolating this this line
line to cos22 60 =
to cos = 0. (Or,
O. (Or,
since sin
since sin 0=1
2
2 0 = 1 - cos 2
cos 0,
2 0, the
the various
various valuesvalues of a may be plotted
of a be plotted against
against
sin 0, and
sin 2 0,
2
and thethe line
line extrapolated
extrapolated to to sin 0 = 1.)
sin22 0=1.)
From the the various
various approximations
approximations involved involved in in the
the derivation
derivation of of Eq.
Eq.
(1 1-12), it is clear
clear that
that this
this equation is true only for large values
values of
(11-12), true only for large 6 (small
of 0 (small
it is equation is
values of
values of cp).
#). Therefore,
Therefore, only only lines
lines having
having 0 6 values
values greater
greater than about 60 60
should
should be be ursed
used in in the
the extrapolation,
extrapolation, and the the more lines lines there are with with 0
greater
greater thanthan 80,80, the the more precise
precise is is the
the value
value of a obtained.
of ao obtained. To increase
()
increase
the number of
the of lines
lines in in the
the hack-reflection
back-reflection region, region, it it is
is common practice practice to to
employ
employ unfiltered
unfiltered radiation
radiation ISO
so that
that K/3
K/3 as
as well
well as
as Ka can be reflected.
reflected. If
If

the
the x-ray
x-ray tube
tube is
is demountable, special
demountable, special alloy targets alloy targets can also
also be used to in-
in-

crease
crease the the number of of lines;
lines; or or two exposures
exposures can be made on the same film film
with different
with different characteristic
characteristic radiations.
radiations. In
In any case,
any case, it
it must never be
be
assumed that the
assumed that the process process of
of extrapolation
extrapolation can automatically
automatically produce a produce a
precise value of ao
precise value of a from careless from careless measurements made on a film
film of
of poor
poor
quality. For
quality. For high
high precision,
precision, the the lines
lines must be be sharp
sharp and the the Ka doublets
doublets
well
well resolved
resolved at at high
high angles,
angles, which means in in turn that the individualindividual par-par-
ticles of
ticles of the
the specimen
specimen must be be strain-free
strain-free and not too fine. fine. The line line posi-
posi-
tions
tions must
must be be determined
determined carefullycarefully and it it is
is best
best toto measure each each oneone two
two
or
or three
three times
times and and average
average the results. In
the results. In computing
computing aa for for each
each line,
line, the
the
proper wavelength
proper wavelength must
must be
be assigned
assigned to
to each
each component
component of
of the
the Ka
Ka doublet
doublet
when that
when that line
line isis resolved
resolved and, and, when when it it is
is not
not resolved,
resolved, the the weighted
weighted meanmean
wavelength
wavelength should
should be
be used.
used.
To
To illustrate
illustrate this this extrapolation
extrapolation method, method, we we shall
shall consider
consider aa powderpowder pat-pat-
tern
tern of of tungsten
tungsten made
made in
in a
a Debye-Scherrer
Debye-Scherrer camera
camera 5.73
5.73 cm
cm in
in diameter
diameter
with
with unfiltered
unfiltered copper radiation. The
copper radiation. The datadata for
for all
all lines
lines having
having 0 values
values
330
330 PRECISE PARAM:ETER MEASUREMENTS
PRECISE PARAMETER MEASUREIrIENTS 11
[CHAP. 11
[CHAP.

11-1
TABLE 11-1

Line 11M Radiation 9 IIn 2 9 a(A)

6 400 K~ 61.71 0 0.7754 3.162

5 321 Ka 65.91 0.8334 3.160
4 411,330 K~ 69.05 0.8722 3.162

3 400 Ka) 76.73 0.9473 3.166
2 400 Ka~ 77.48 0.9530 3.164
1 420 K~ 79.67 0.9678 3.164

greater than
greater than 60
60 are
are given
given in
in Table
Table 11-1.
11-1. drift in
The drift in the computed aa
the computed
values is
values is obvious:
obvious: in
in general
general they
they increase
increase with
with 86 and tend
tend to
to approach
approach the
the
true value
true value aau atat high
high angles.
angles. InIn Fig.
Fig. 11-4, these values
11-4, these values ofof a are
are plotted
plotted
2
against sin
against 6, and ao
sin 2 8, ao is
is found by
by ext.rapolation
extrapolation to be 3.165A.
to be 3.16.1A.
2
Other
Other fun('tions
functions of of 8, besides sin
0, besides sin 2 8 or cos 22 8,
or cos 0, may
may bebe used
used as
as a basis
basis for
for
extrapolation.
extrapolation. For example,
example, if
if we replac'e sin q, cos
replace sin cos < q, in
<f> Eq. (11-10)
in Eq. by
(11-10) by
instead of
q" instead
<t>, replacing q, by
of repla('ing sin q,
by sin cos q"
4> cos <, we obtain
</> obtain

tld
- =
= K<t>
Kq, tan
tan q,.
0.
d
Therefore,
Therefore, a a plot
plot of against q, tan
of a against tan q, will
will also be linear
also be
</> linear and wiII
< will extrapolate
extrapolate
to ao
to a at tan q, =
at q, tan
<t>
= O.
0. In practice,
pra(tice, there
there is is not
not much difference between an
difference between

against q, tan
tan q, and one
2 2
extrapolation
extrapolation against < one against
against ('os
<f>
cos 2 8 (or
(or sin
sin 2 8),
0), and either
either
will
will give
give satisfactory
satisfactory results.
results. If
If the
the various
various sources
sources of
of error,
error, particularly
particularly
absorption,
absorption, are
are analyzed
analyzed more rigorously
rigorously thanthan we have done hl're, here, it
it can
can
be
be shown that
that the
the relation
relation ~-
cos 2 d

o
~~
2 2 01 O.:l
0.2 0.3
0.3
/cos2
8 + cos
cos2 6\ 1
Arf
K 8)
Td
= (COS
K(\ sin
sin08 8
=
tf i 3165
a.170
3.170
.
. - - I/o = a IIi:iA

holds
holds quite accurately down to
quite a('curately to very
very
low
low values
values of
of 8 6 and notnot just
W |3
just at at high
high
angles. The value
angles. value of of au
ao can be be found 3 155
08 07
by plotting a
a against (cos
by plotting against (cos 0/sin + 22 8/sin 8 6 + J.O 0.9
n <2

cos2 8/8),
0/6), whic'h
which approaches
approaches zero zero as as 8
2
(,08 6
approaches 90.
90. Although it
it is
is doubt-
doubt- FIG.
FIG. 11-4.
11-4. Extrapolation
Extrapolation ofof meas-
approaches Although
ured lattice
lattice parameters
parameters against sin 2 8
against sin
2
6
ful
ful whether any any advantage
advantage resultsresults
(or cos
cos 2
2 8).
6 +
2 2 (or 0).
from using (cos 8/sin
using (cos
2
0/sin 8 + coscos2 8/8)
6/6)
2
instead
instead of of cos
cos2 8 6 in
in the
the back-reflection
back-reflection region,
region, the
the greater
greater range
range ofof linearity
linearity
of
of the
the former
former function
function is is an advantage
advantage in
in certain
certain cases.
cases.
N oncubic crystals
Noncubic crystals present
present additional
additional difficulties,
difficulties, regardless
regardless of of the
the par-
par-
ticular
ticular extrapolation function
extrapolation function chosen. chosen. (In
(In the following discussion, we
the following discussion,
 11-2J
11-2] DEBYE-SCHERRER CAMERAS 331
331

shall confine
shall confine our attention
our attention to to hexagonal
hexagonal and tetragonal
tetragonal crystals,
crystals, but but the
the
methods to
methods to be
be described
described can can bebe generalized
generalized to to apply
apply to to crystals
crystals of of still
still
lower symmetry.)
lower symmetry.) The difficulty
difficulty isis simply
simply this:
this: the
the position
position of of aa line
line which
has indices
has hkl is
indices hkl is determined
determined by parameters, aa and c,
by two parameters, c, and it it is
is impos-
impos-
sible to
sible to calculate
calculate both
both of of them from
from thethe observed
observed sinsin22 6 value
value of of that
that line
line
alone. One way
alone. way ofof avoiding
avoiding thisthis difficulty
difficulty is
is to
to ignore
ignore the hkllines
the hkl lines and
divide the
divide the remainder
remainder intointo two groups,
groups, those
those with
with indices
indices hkO hkO and those those
with
with indices
indices OOl.
001. A value
value of
of a is
is calculated
calculated for
for each
each hkO
hkO line
line and a
a value
value
of cc from each
of each 001
OOlline; separate extrapolations
line; two separate extrapolations are are then
then made to to find
find
ao and
a and cco. Since
. Since there
there are
are usually
usually veryvery few hkO and 001
few hkO OOllines in the
lines in the back-
back-
reflection region,
reflection region, some low-angle
low-angle lineslines have
have toto be
be included,
included, which means
that the
that the extrapolations
extrapolations must be
2
be made against
against (cos
2
0/sin 6 + cos
(cos 6/sin
2 +cos22 0/0)
6/6)
and notnot against cos 0.
against cos
2 6. And if if there
there are
are no lines of
no lines of the
the type
type hkOhkO and 001 OOl
with 6 greater
with greater than
than 80,
80, even
even the
the former
former function
function will
will not
not assure
assure an accu-accu-
rate extrapolation.
rate extrapolation.
better but
A better but more laborious
laborious method,
method, and one
one which utilizes
utilizes all
all the
the data,
data,
is
is that
that of
of successive
successive approximations.
approximations. In
In the
the tetragonal system,
tetragonal system, for
for exam-
ple, the
ple, the value
value of a for
of a for any line is
any line is given by
given by

+ k2) + _l2_]I~.
2
x r
a =
a = _>.._ [(h2
(
I

(11-13)
(11-13)
2 sin 6
2sm0L (c/a)2
The first
first step
step is
is to
to calculate
calculate approximate values, at,
approximate values, a\, and Ct, Ci, of
of the lattice
lattice
parameters
parameters from the
the positions
positions of
of the
the two highest-angle
highest-angle lines,lines, as
as was done
in
in Sec.
Sec. 10-4.
10-4. The approximate
approximate axial
axial ratio
ratio ct/at
Ci/a\ is
is then calculated
calculated and
used
used in
in Eq. (11-13)
Eq. (11-13) to
to determine
determine an a value
value for
for each
each high-angle
high-angle line
line on the
2
. pattern.
pattern. These values of
values of a
a are then extrapolated against
are then extrapolated against cos
cos 2 6 to
to find
find a
more accurate
accurate value of a,
value of namely a2.
a, namely a2 The value
value of
. of C2c 2 is
is found in similar
in similar
fashion
fashion by
by use
use of
of the
the relation
relation

c = _~_ [(:)2 (h2 + k2) + l2]~ (11-14)

2sm6
2sm0 a
2
and another
another extrapolation
extrapolation against
against cos cos2 6. 6. The process
process is is repeated
repeated with
the
the new value
value of
of the
the axial ratio C2/
axial ratio c 2 /aa22 to
to yield
yield still
still more accurate values of of
the
the parameters,
parameters, namely
namely C3 c3 and a3.
a3 Three extrapolations
.
extrapolations are are usually
usually suffi-
suffi-

to fix
cient to
cient fix the
the parameters
parameters with with high
high accuracy.
accuracy. In addition,addition, thethe accuracy
accuracy
of
of each
each extrapolation
extrapolation can can be
be improved
improved by by aa suitable
suitable choice
choice ofof lines.
lines. For
example,
example, the
the value
value of
of a
a calculated
calculated from Eq.
Eq. (11-13)
(11-13) is
is only
only ~lightly
slightly affected
affected

(h +
22 + k 2 2
by
by inaccuracies
inaccuracies in c/a when (h
in c/a k2 )) is
is large
large compared
compared to to l2,
Z,
since
since the
term
term involving c/a
involving c/a is
is itself
itself small.
small. Therefore,
Therefore, lines
lines with large
large h
h and k in-
in-

dices and a
dices small l index
a small Iindex should
should be be chosen
chosen for for each
each determination
determination of of a.
a.

Just the reverse

Just the reverse is
is true
true in
in the
the determination
determination of
of c,
c, as
as inspection
inspection of
of Eq.
Eq.
(11-14) will
(11-14) will show.
show.
332
332 PRECISE PARAMETER MEASUREMENTS
PRECISE PARAMETER MEASUREMENTS 11
[CHAP. 11
[CHAP.

() ()
2 e
(,OS20
cos
(]
cos 2 e

(a)
(a) (b)

FIG. 11-5.
FIG. Extreme forms
11-5. Extreme forms of
of extrapolation
extrapolation curves
curves (schematic):
(schematic): (a)
(a) large
large sys-
RYfI-
tematir errors,
tematic errors, small
small random
random errors;
errorR; (b)
(b) small
small systematic
sYRtematic errors,
errorR, large
large random
errors.
errors.

conclude this
To conclude this section,
section, aa few few general
general remarks on the the nature
nature of of errors
errors
may
may not
not be
be amiss.
amiss. In
In the
the measurement of
of a
a lattice
lattice parameter,
parameter, as
as in
in many
other physical
other physical observations,
observations, two kinds kinds of of error
error areare involved,
involved, systematic^
systematic
and random. A systematic
and random. systematic error error isis one which varies varies in regula~~
in aa regular manner
with ~
with particular parameter.
some particular parameter. Thus the the fractional
fractional errors errors in in aa due to to
the various
the various effects considered above (film
effects considered (film shrinkage, incorrect radius,
shrinkage, incorrect radius, off-
off-
center specimen,
center absorption) are
specimen, absorption) are all
all systematic
systematic errors errors because
hecaus(' they they vary
vary inin
aa regular
regular way way withwith B, (), decreasing
decreasing as as B() increases.
increases. Further,Further, a systemati('
systematic
error
error is is always
always of the same sign:
of the sign: for
for example,
example, the effe(t of
the effect of absorption
absorption in in a

Debye-Scherrer
Debye-Scherrer camera is
is always
always to
to make the
the computed
computed value of
of a less
less than
the
the true
true value.
value. Random errors, errors, on the the other
other hand,
hand, are are thethe ordinary
ordinary chance
errors
errors involved
involved in in any
any direct
direct observation.
observation. For example,
example, the
the errors
errors involved
in
in measuring
measuring the
the positions
positions of
of the
the various
various lines
lines on a film
film are
arc random errors;
errors;
they
they maymay be
be positive
positive or
or negative
negative and do not
not vary
vary in
in any
any regular
regular manner
with
with thethe position
position of of the
the lineline on thethe film.
film.
As we have already already seen, seen, the
the systematic
systematic errorserrors in in a approaeh
approach zero as ()B
approaches
approaches 90, 90 0 , and may be eliminated by use
may be eliminated by use of
of th('
the proper
proper extrapolation
extrapolation
function.
function. The magnitude magnitude of
of these
these errors
errors is
is proportional
proportional to
to the
the slope
slope of of
the
the extrapolation
extrapolation line
line and,
and, if
if these
these errors
errors are
are small,
small, the
the line
line will
will be quite
quite
flat.
flat. In
In fact,
fact, if
if we purposely
purposely increaseincrease the the systematie
systematic errors, errors, say,
say, by by using
using
aa slightly
slightly incorrect
incorrect value value of of the
the eamera
camera radiusradius in in ollr calculations, the
our calculations,
slope
slope of
of the
the line
line will
will increase
increase but
but the
the extrapolated
extrapolated value of
of a will
ao will remain
the
the same.
same. The random errors errors involved
involved in in measuring
measuring line
line positions
positions show
up
up as
as random errors
errors in
in a,
a, and are
are responsible
responsible for
for the deviation of
of the var-
ious
ious points
points from
from the
the extrapolatioh
extrapolation line.
line. The random errors
errors in
in a also
also de-
de-
crease
crease in in magnitude
magnitude as
as ()
B inereases,
increases, due essentially
essentially to
to the
the slow
slow variation
variation of
of
sin "with
sin at lar~
with fJ at angles.
large angles.
These
These various
various effects
effects are are summarized
summarized gl'aphieally
graphically in Fig. II-5.
in Fig. 1 1-5. In (a)
(a)
the
the calculated
calculated points
points conform
conform quite closely
quite closely to
to the
the line,
line, indicating small
indicating small
random errors,errors, but the the lineline itself
itself is
is quite
quite steep
steep because of of large
large systematic
systematic
11-41
11-4] PINHOLE CAMERAS 333
333

errors.
errors. The opposite
opposite situation
situation isis shown inin (b):
(b) here
here the
the systematic
:
systematic error
error
is small, but the wide scatter
is small, scatter of
of the
the points
points shows that large
large random errors
errors
have been made. Inasmuch as as the
the difficulty
difficulty of
of drawing
drawing the
the line
line increases
increases
with the
the degree
degree of scatter, it
of scatter, it is
is obvious that
that every
every possible
possible effort
effort should
should
be made toto minimize random errors
errors atat the
the start.
start.

11-3
11-3 Back-reflection focusing cameras. A camera of
Back-reflection focusing of this
this kind is is pre-
pre-
ferred
ferred forfor work of of the
the highest
highest precision,
precision, since
since the
the position
position of of a diffraction
diffraction
line
line on thethe film
film is
is twice
twice asas sensitive
sensitive toto small
small changes
changes in plane spacing
in plane spacing with
with
this
this camera as as it
it is
is with a Debye-Scherrer
Debye-Scherrer camera of of the
the same diameter.
diameter.
It
It is,
is, of
of course,
course, notnot free
free from sources
sources ofof systematic
systematic error.
error. The most im-
portant
portant of of these
these areare the
the following:
following:

(1)
(1) Film shrinkage.
shrinkage.
(2)
(2) Incorrect
Incorrect camera radius.radius.
(3) Displacement
(3) Displacement of
of specimen
specimen from camera circumference.
circumference.
(4) Absorption
(4) Absorption in
in specimen.
specimen. (If (If the
the specimen
specimen has very low
has very low absorption,
absorption,
many
many of
of the
the diffracted
diffracted rays
rays will
will originate
originate at
at points
points outside
outside the
the camera cir-cir-

cumference
cumference even even though
though the
the specimen
specimen surface
surface coincides
coincides with
with the circum-
circum-
ference.)
ference.)
A detailed
detailed analysis
analysis ofof these
these various
various sources
sources of
of error
error shows thatthat they pro-
they pro-
duce
duce fractional
fractional errors
errors inin dd which are
are very
very closely proportional to
closely proportional to q, tan
< tan q"
0,
where q, is
where </> is again equal
again equal to
to (90
(90
0 - 8).
8). This
This function
function is
is therefore
therefore the
the one to
to
use
use inin extrapolating
extrapolating lattice parameters measured with
lattice parameters with this
this camera.
camera.

11-4
11-4 Pinhole
Pinhole cameras.
cameras. The pinholepinhole camera,
camera, used
used inin back reflection,
reflection,
is
is not
not really
really an instrument
instrument of
of high precision
high precision in
in the
the measurement of
of lattice
lattice
parameters,
parameters, but
but it
it is
is mentioned here
here because
because of
of its
its very great
very great utility
utility in
in met-
allurgical
allurgical work.
work. Since
Since both
both the
the film
film and the
the specimen
specimen surface
surface are
are Bat,
flat, no
focusing
focusing of
of the
the diffracted
diffracted rays occurs,
rays occurs, and the
the result
result is
is that
that the
the diffraction
diffraction
lines
lines are broader than
are much broader than isis normally
normally desirable
desirable for precise measurement
for precise
of
of their
their positions.
positions. The chief
chief sources
sources of
of systematic
systematic error
error are
are the
the following:
following:

(1) Film shrinkage.

(1) shrinkage.
(2)
(2) Incorrect
Incorrect specimen-to-film
specimen-to-film distance.
distance.
(3) Absorption
(3) Absorption in
in the
the specimen.
specimen.
In
In this
this case
case itit may
may bebe shown that
that the
the fractional
fractional error
error in in d is proportional
is proportional

to sin 4q,
to sin tan or to the equivalent expression cos 22 8(2 cos 22 8 - 1),
40 tan q"
<, or to the equivalent expression cos 8(2 cos 6 1), where
q, =
= (90
(90
0 - 8).
6). With either
either of
of these
these extrapolation
extrapolation functions
functions a
a fairly
fairly pre-
pre-
cise
cise value
value of of the
the lattice
lattice parameter
parameter can
can be
be obtained;
obtained in
in
;
addition,
addition, the back-
the back-
reflection
reflection pinhole
pinhole camera has has the
the particular advantage that
particular advantage that mounted metal- metal-
lographic specimens
lographic specimens may may be
be examined directly.
directly. This
This means that
that a
a param-
param-
eter
eter determination
determination can can be made on the part of
the same part of a a specimen
specimen as as that
that ex-
ex-
amined under
amined under the
the microscope.
microscope. A dual
dual examination
examination of
of this
this kind is
is quite
quite val-
val-
uable
uable inin many problems, especially
many problems, in the
especially in the determination
determination of phase diagrams.
of phase diagrams.
334
334 PRECISE PARAMETER MEASUREMENTS
PRECISE PARAMETER MEASUREMENTS 11
[CHAP. 11
[CHAP.

11-5 Diffractometers.
11-6 Diffractometers. The commercial
The commercial diffractometer
diffractometer isis aa rather
rather new
new
instrument and
instrument and relatively
relatively little use
little use has
has been
been made
made of
of itit for
for the
the precise
precise
measurement
measurement of lattice
of lattice parameters.
parameters. For For that
that reason,
reason, no no generally
generally validvalid
procedure
procedure for
for use
use in
in such
such measurements
measurements has
has yet
yet been
been devised,
devised, and
and until
until
this isis done
this done the the back-reflection
back-reflection focusing focusing cameracamera must must be be recognized
recognized as as the
the
most accurate
most accurate instrument
instrument for for parameter
parameter measurements.
measurements.
One reason
One reason for for thethe inferiority
inferiority of of the
the diffractometer
diffractometer in in this
this respect
respect isis the
the
impossibility of
impossibility of observing observing the
the same
same back-reflected
back-reflected cone
cone of
of radiation
radiation on
on both
both
sides of
sides of the
the incident
incident beam. beam. Thus, Thus, the the experimenter
experimenter has has no no automatic
automatic
check on
check on thethe accuracy
accuracy of of the
the angular
angular scale of the instrument or the
scale of the instrument or the pre-
pre-
cision of
cision of its
its alignment.
alignment.
When aa diffractometer
diffractometer is is used
used to to measure
measure plane plane spacings,
spacings, the the more im- im-
portant sources
portant sources of of systematic
systematic error error in in dd are
are the
the following
following: :

Misalignment of
(i) Misalignment
(1) of the
the instrument.
instrument. In In particular,
particular, the the center
center of of the
the
incident beam must
incident must intersect
intersect the the diffractometer
diffractometer axis axis and the the 0 position
position
of the
of the receiving
receiving slit. slit.
(2)
(2) Use
Use of
of a
a flat
flat specimen instead
specimen instead of of aa specimen
specimen curvedcurved to to conform
conform to to
the focusing
the focusing circle.circle.
(3) Absorption
(3) Absorption in in the
the specimen.
specimen.
(4) Displacement
(4) Displacement of
of the
the specimen
specimen from the the diffractometer
diffractometer axis. axis. (This
(This
is usually the largest
is usually the largest single single source
source of
of error.)
error.)
(5)
(5) Vertical divergence of
Vertical divergence the incident
of the incident beam.beam.
These sources of
These sources of error
error cause
cause thethe fractional
fractional errorerror inin d to to vary
vary in in a
a compli-
compli-
cated
cated way way with with e, 0, soso that
that no simplesimple extrapolation
extrapolation function can be used to to
obtain
obtain high high accuracy.
accuracy. Because Because some, some, but not all, all, of
of these sources of of error
2
cause t:::.djd
cause Ad/d to to bebe approximately
approximately proportional
proportional to to cos
cos2 9, 0, a fairly
fairly accurate
value
value of of the
the lattice
lattice parameter
parameter can can be be obtained
obtained by by simple
simple extrapolation
extrapolation
against
against cos
cos 22 9, just as
0, just as with
with the
the Debye-Scherrer
Debye-Scherrer camera.
camera. Therefore,
Therefore, in
in the
light
light of
of our
our present knowledge,
present knowledge, the
the suggested
suggested procedure
procedure is:
is:

(a)
(a) Carefuliy
Carefully align align the the component
component parts parts of of the
the instrument in in accordance
with
with the the manufacturer's
manufacturer's instructions.
instructions.
(b)
(b) Adjust
Adjust the the specimen
specimen surfacesurface to to coincide
coincide as as closely
closely as as possible
possible with
the diffractometer
the diffractometer axis. axis.
2
(c)
(c) Extrapolate
Extrapolate the the calculated
calculated parameters
parameters againstagainst cos cos2 9. 8.

This
This procedure
procedure will will undoubtedly
undoubtedly be be improved
improved as as additional
additional experience
experience
with
with thisthis instrument
instrument is is accumulated.
accumulated. In In fact,
fact, some
some investigators
investigators feel feel that

lattice
lattice parameters
parameters will will oneone day
day be be measurable
measurable with the the diffractometer
diffractometer with with
greater accuracy than
greater accuracy than withwith anyany kind
kind of of powder
powder camera,
camera, but but whether
whether this this

isis true
true or or not
not remains
remains to to be
be seen.
seen. There There is, is, however,
however, one one circumstance
circumstance in in
which
which the diffractometer is
the diffractometer is superior
superior to
to aa camera
camera for
for parameter
parameter measure-
measure-
ments
ments and and that that is is wheJ;l
wheij the the diffraction
diffraction lines lines areare abnormally
abnormally broad; broad; this this
pal'ticular application
particular application arises
arises in
in stress
stress measurement
measurement and
and will
will be
be described
described
in
in Chap.
Chap. 17. 17.
11-6)
11-6] METHOD
METHOD OF
OF LEAST
LEAST SQUARES
SQUARES 335
335

11-6 Method
11-6 Method of squares. All
least squares.
of least All the
the previously
previously described
described methods
methods of of
accurately measuring
accurately measuring lattice
lattice parameters
parameters depend
depend in
in part
part on
on graphical
graphical ex-
ex-
trapolation. Their
trapolation. Their accuracy
accuracy therefore
therefore depends
depends on on the
the accuracy
accuracy with with which
which
aa straight
straight line line can
can bebe drawn
drawn through
through aa set set of
of experimental
experimental points,points, each
each of of
which
which is
is subject
subject to
to random
random errors.
errors. However,
However, different
different persons
persons will
will in
in gen-
gen-
eral draw
eral draw slightly
slightly different
different lines
lines through
through the the same
same setset of of points,
points, so so that
that itit isis
desirable to
desirable to have
have an an objective,
objective, analytical
analytical method
method of of finding
finding the the line
line which
which
best fits
best fits the
the data.
data. This
This cancan bebe done
done by by the
the method of least squares.
method of least squares. Since Since
this method
this method can be used
can be used inin aa variety
variety of of problems,
problems, it it will be described
will be described here here
in aa quite
in quite general
general way;
way; in in the
the next
next section,
section, its its application
application to to parameter
parameter
measurements will
measurements will be
be taken
taken up up in in detail.
detail.
If aa number
If number of of measurements
measurements are are made
made of of the
the same
same physical
physical quantity
quantity
and ifif these
and these measurements
measurements are are subject
subject onlyonly to to random
random errors,
errors, then
then thethe
theory
theory of
of least
least squares
squares states
states that
that the
the most
most probable
probable value
value of
of the
the measured
measured
quantity is
quantity is that
that which
which makes
makes the the sum of of the
the squares
squares of of the
the errors
errors aa mini-
mini-
mum. The The proof
proof ofof this
this theorem
theorem is is too
too long
long toto reproduce
reproduce here here butbut we can can
at least demonstrate
at least demonstrate its
its reasonableness
reasonableness by
by the
the following simple
following simple example. example.
Suppose five
Suppose five separate
separate measurements
measurements are are made of of the
the same physical
physical quan-quan-
tity, say
tity, say thethe time
time required
required forfor a a falling body to
falling body to drop
drop a given
a given distance,
distance, and and
that these
that these measurements
measurements yield yield thethe following
following values:
values: 1.70,
1.70, 1.78,
1.78, 1.74,
1.74, 1.79,
1.79,
and
and 1.74
1.74 sec.
sec. Let
Let x x equal the most probable
equal the probable valuevalue of the time.
of the time. Then Then thethe
error
error inin the
the first
first measurement
measurement is is el = (x -- 1.70),
ei = (x 1.70), thethe error
error in in the second

is
is e2
e2 == (x - 1.78), and
(x - 1.78), and so so on.
on. The sum of of the
the squares
squares of of the errors
errors isis given
given
by
by

Z(e )) =
2;(e 22 = (x -- 1.70)22
(x 1.70) +
+ (x - 1.78) 2
(x - 1.78)2

+ (x 1.74) +
+ (x -- 1.74)2 2
1.79) +
+ (x -- 1.79)2
(x+ (x -- 1.74)2.
1.74)
2
(x
2
.

We can
can minimize
minimize the
the sum ofof the
the squared
squared errors
errors by
by differentiating
differentiating this
this

expression
expression with
with respect
respect to
to x
x and
and equating
equating the
the result
result to
to zero:
zero:

d2;(e 2 )
^-t = 2(x
~ - 1.70) +
2(x - 1.70)
- 1.78) .+
2(x - 1.78)
+ 2(x - 1.74) + 2(x
2(x - 1.74)
,+ 2(x
- 1.79)
2(x - 1.79)
dx
++ 2(x - 1.74) =- 0
2(x - 1.74)
whence
whence
xx =
= 1.75
1.75 sec.
sec.

On
On the
the other
other hand,
hand, the
the arithmetic
arithmetic average
average of of the
the measurements
measurements is is also
also
1.75
1.75 sec.
sec. This
This should
should not
not surprise
surprise us
us asas we
we know,
know, almost
almost intuitively,
intuitively, that
that
the
the arithmetic
arithmetic average
average of
of a
a set
set of
of measurements
measurements gives
gives the
the most
most probable
probable
value.
value. This
This example
example maymay appear
appear trivial,
trivial, inin that
that no
no one
one would
would take
take the
the
trouble to
trouble to use
use the
the method
method of of least
least squares
squares when
when the
the same
same result
result can
can be
be
obtained by simple averaging,
obtained by simple averaging, but
but at
at least
least it
it illustrates
illustrates the
the basic
basic principle
principle
involved
involved inin the
the least-squares
least-squares method.
method.
336
336 PRECISE PARAMETER MEASUREMENTS
PRECISE PARAMETER MEASUREMENTS 11
[CHAP. 11
[CHAP.

Naturally, there
Naturally, there are
are many
many problems
problems in in which
which thethe method
method of of simple
simple
averaging
averaging cannot
cannot be
be applied
applied and
and then
then the
the method
method of
of least
least squares
squares becomes
becomes
particularly valuable.
particularly valuable. Consider,
Consider, forfor example,
example, the the problem
problem referred
referred toto
above,
above, that
that of
of finding
finding the
the straight
straight line
line which
which best
best fits
fits aa set
set of
of experimen-
experimen-
tally determined
tally determined points.
points. If there are
If there are only
only two
two points,
points, there
there is
is no
no problem,
problem,
because the two
because the two constants
constants which
which define
define aa straight
straight line
line can
can bebe unequivocally
unequivocally
determined from
determined from these
these two
two points.
points. But,But, in in general,
general, there will be
there will be more
more
points available
points available thanthan constants
constants to
to be
be determined.
determined. Suppose
Suppose that
that the
the vari-
vari-

ous points
ous points have
have coordinates
coordinates x\y\,
XIY}, X2Y2,
X 2 y 2 #32/3, and ,
that it is known
X3Y3, '" and that it is known that that
xx and
and yY are
are related
related by by an
an equation
equation of of the
the form
yy - + bx.
= aa + bx. (11-15)
(11-15)

Our problem
Our problem is
is to
to find
find the
the values
values of
of the
the constants
constants aa and 6, since these
b, since these de-
de-
fine the straight line. In
fine the straight line. In general,
general, thethe line will not
line will not pass
pass exactly
exactly through
through
any
any of
of the
the points
points since
since each
each is
is subject
subject to
to a
a random error.
error. Therefore
Therefore each
each
point
point is
is in
in error
error by
by an
an amount given by
given by its
its deviation
deviation from the
the straight
straight line.
line.

For example,
For example, Eq.Eq. (11-15) states that
(11-15) states that the
the value
value of
of yY corresponding
corresponding to to xx =
= x\
Xl
is (a + bXl)'
is (a + tei). Yet the
the first
first experimental
experimental point point has
has a
a "alue
value of
of y
y =
= Yl.
y\.

Therefore e^
Therefore the error
e}, the error in
in the
the first
first point,
point, isis given
given by
by
el =
ei = (a
(a + bXl) -- Yl.
+ 6x0 yi.

We can
can calculate
calculate the
the errors
errors in
in the other points
the other points in
in similar
similar fashion, and then
fashion, and then
write
write down
down the
the expression
expression for
for the
the sum of
of the
the squares
squares of
of these
these errors:
errors :

2(e
2
)
= (a + bx l - yi)
2
+ (a + bx 2 - y2 )
2
+ .
(1 1-16)
(I 1-16)

According
According toto the
the theory
theory ofof least
least squares,
squares, the
the "best"
"best" straight
straight line
line is
is that
that
which
which makes
makes the
the sum of of the
the squared
squared errors
errors a minimum. Therefore,
Therefore, the
the
best of a
value of
best value a is
is found
found byby differentiating
differentiating Eq. respect to a
(11-16) with respect
Eq. (11-16)
and
and equating
equating the
the result
result to
to zero:
zero:

d~(e2)
=
-- =
da
2(a
2(a +
+ bXl
bx l -- Yl)
yi ) + 2(a +
+ 2(a + bX2 y +
bx -- Y2) + ... 2 2)
- - - = 0,
= 0,
da
or
or
~a
Sa + fcSz -- ~y
+ b~x = O.
Zy = 0. (11-17)
(11-17)

The
The best
best value of b
value of b is
is found
found in
in a
a similar
similar way:
way:

= 2xi(a + bx -l yi) + 2x2 (a + 6a*

- 2) + = 0>
d&
or
or
a~x ++ b~X2
&Ss -- ~xY
2x2
== O.
0. (11-18)
(11-18)

Equations (11-17) and

Equations (11-17) (11-18) are
and (11-18) are the
the normal equations. Simultaneous
normal equations. Simultaneous
solution
solution of
of these
these two
two equations yields
equations yields the
the best
best values
values of
of aa and
and 6, which
b, which
can then be substituted into Eq. (11-15)
can then be substituted into Eq. (11-15) to
to give
give the
the equation
equation of
of the
the line.
line.
11-6]
11-6] METHOD OF LEAST SQUARES 337
337

normal equations
The normal equations as
as written
written above can be rearranged
can be rearranged as
as follows:
follows:
'1:.y =
Zt/ '1:.a
= Sa + 62x
+ b'1:.x
and
and (11-19)
(11-19)
'1:.xy = a'1:.x + b'1:.x2
A comparison
comparison of
of these
these equations
equations and Eq.
Eq. (11-15) that the
(11-15) shows that the following
following
rules can
rules can be
be laid
laid for the
down for the formation
formation of
of the
the normal
normal equations
equations: :

(a) Substitute
(a) Substitute the
the experimental
experimental values
values of x into Eq.
of and yy into (11-15). If
Eq. (11-15). If
there are
there are n experimental
experimental points,
points, n equations
equations in
in a and bb will
will result.
result.
(b) obtain the
(b) To obtain the first
first normal
normal equation,
equation, multiply
multiply each
each ofof these
these equa-
n equa-
tions
tions by the
by the coefficient
coefficient of
of a in
in each
each equation,
equation, and add.
add.
(c)
(c) To obtain the second
obtain the second normal
normal equation, multiply each
equation, multiply each equation
equation byby
the coefficient
the coefficient of
of b, and add.
b, add.
As an illustration, suppose
an illustration, suppose that
that we determine
determine the
the best
best straight line
straight line
through
through the
the following
following four
four points:
points :

x 10 18 30 42
- - - - - - - -- -
y 15 11 11 8

The normal
normal equations
equations are
are obtained
obtained in three steps:
in three steps :

(a)
(a) Substitution
Substitution of
of the
the given
given values:
values:

= a
15 = +
+ lOb
106
= a
11 =
11 + 18b
186
= a
11 =
11 + 30b
306
= a
8 = + 42b
426

(b)
(b) Multiplication
Multiplication by
by the
the coefficient
coefficient of
of a:
a:

15 = a+
15 = lOb
106
11 = a
11 = + 18b
186
11 = a+
11 = 30b
306
8 = a+
8= 42b
426

45 = 4a
45 = +
+ IOOb
1006 (first
(first normal equation)
equation)

(c)
(c) Multiplication
Multiplication by
by the
the coefficient
coefficient of
of b:
6 :

150
150 = 10a +
= lOa 100b
1006
198 =
198 18a +
= 18a + 324b
3246
30a +
330 == 30a 900b
9006
336 == 42a ++ 1764b
17646

1014 =
1014 = l00a
lOOa +
+ 3088b
30886 (second
(second normal equation)
equation)
338
338 PRECISE PARAMETER MEASUREMENTS
PRECISE PARAMETER MEASUREMENTS 11
[CHAP. 11
[CHAP.

Simultaneous solution
Simultaneous solution ofof the
the two
two
normal equations
normal gives aa == 16.0
equations gives 16.0 and
and 20
20
6b== -0.189.
-0.189. The
The required
required straight
straight
line isis therefore
line therefore 15
15

yy = 16.0 -
= 16.0 - 0.189*.
0.189x.
10
This line
This line is shown
is shown in in Fig.
Fig. 11-6,
11-6, to-
to- y 10
gether with the four given
gether with the four given points.points.
.)
The least-squares
The least-squares method
method is is not
not
confined to
confined to finding
finding the
the constants
constants ofof aa
straight line;
line; it
it can
can be
be applied
applied toto any
any o L - _ - ' - _ - ' - _ - - - '_ _ _..L1_ _
straight () 10
10 20
20 30
30 40
40 50
50
kind of
kind of curve.
curve. Suppose,
Suppose, for
for example,
example, x
that xx and
that and yyare
are known to to be
be related
related
by aa parabolic
by parabolic equation
equation FIG. 11-6.
FIG. 11-6. Best
Best straight
straight line,
line, de-
de-
termined by
termined least-squares method.
by least-squares method.
y
y = aa + bx
= bx + ex
cx
22

.

Since there
Since there are
are three
three constants here,
unknown constants here, we need three
three normal
normal equa-
equa-
tions. These
tions. These are
are
"1:,y
Si/
= "1:,a
= Sa + b2x
+ + cSx
b"1:,x + c"1:,x 2 ,
2
,

"1:,xy = a"1:,x + b~X2 + c"1:,x3 , (11-20)

(11-20)

- aZz
2x 22 yy =
"1:,x a"1:,x 22 + b"1:,x 3 +
+ blx* + c"1:,x
cSx 4
4
,

These
These normal
normal equations
equations can can be
be found by by the
the same methods as as were used
were used
for
for the
the straight-line
straight-line case,
case, i.e.,
i.e., successive
successive multiplication
multiplication of of the n observa-
n
tional equations by
tional equations by the
the coefficients
coefficients of a, b,
of a, 6, and c,c, followed byby addition of of

the
the equations
equations in
in each
each set.
set.
It
It should
should bebe noted
noted that
that the
the least-squares
least-squares method is is not a way
way of
of finding
finding
the
the best curve to
best curve to fit
fit a a given
given set
set of
of observations.
observations. The investigator
investigator must
know
know at at the
the outset,
outset, from
from his
his understanding
understanding of
of the phenomenon
phenomenon involved,
involved,
the kind of
the kind of relation
relation (linear,
(linear, parabolic,
parabolic, exponential,
exponential, etc.)
etc.) the two quantities
quantities
xx and
and yare
y are supposed
supposed to to obey.
obey. All All the
the least-squares
least-squares method can do is is give
give
him the best values of the constants
him the best values of the constants in
in the
the equation
equation he selects,
selects, but it
it does
this
this in
in a
a quite
quite objective
objective and unbiased manner.

11-7
11-7 Cohen's
Cohen's method.
method. In In preceding
preceding sections
sections we have seen that that the
most
most accurate
accurate value
value of
of the
the lattice
lattice parameter
parameter of of a
a cubic
cubic substance
substance is is found
found
by plotting
by plotting the
the value
value of
of aa calculated
calculated for
for each
each reflection
reflection against
against aa particular
particular
function,
function, which
which depends
depends on on the
the kind
kind of
of camera
camera used,
used, and
and extrapolating
extrapolating to to
aa value
value aoa atat 86 =
= goo.
90. TwoTwo different
different things
things are
are accomplished
accomplished by
by this
this pro-
pro-
cedure:
cedure: (a)(a) systematic
systematic errors
errors are eliminated by
are eliminated by selection
selection of
of the
the proper
proper
extrapolation function,
extrapolation function, and
and (b)
(b) random
random errors
errors are
are reduced
reduced in
in proportion
proportion
to
to the
the skill
skill of
of the
the investigator
investigator inin drawing
drawing the
the best
best straight
straight line
line through
through thethe
11-7)
11-7] COHEN'S METHOD 339
339

experimental points. M. U. Cohen proposed,

experimental points. proposed, in
in effect,
effect, that
that the
the least-squares
least-squares
method be used toto find
find the
the best
best straight
straight line
line so
so that
that the
the random errors
errors
would be minimized inin a reproducible
reproducible and objective
objective manner.
Suppose
Suppose a cubic
cubic substance isis being
being examined inin a Debye-Scherrer
Debye-Scherrer camera.
camera.
Then Eq. (11-12), namely,
Eq. (11-12), namely,

Ad
t:.d Aa
t:.a 2
=
-=-=Kcos= #cos 2 (J0, (11-12)
(11-12)
dd aa '
defines
defines the
the extrapolation
extrapolation function.
function. But instead
instead of
of using
using the
the least-squares
least-squares
2
method toto find
find the
the best
best straight
straight line
line on a of a
plot of
a plot a against
against 00S2 0, Cohen
cos (J,
2
applied
applied the
the method to to the
the observed
observed sin 2
sin (J6 values
values directly.
directly. By
By squaring
squaring
the
the Bragg
Bragg law and taking logarithms
taking logarithms of
of each side,
side, we obtain
obtain

(~)
2
\
In sin 2 (J = In - -- 21n
2 d. In d.
(X J
Differentiation
Differentiation then gives
gives
2
A sin
t:. sin 2 (J
6 2t:.d
2Ad
---= --. (11-21)
sin
sm 2 (J d
d
2
By
By substituting
substituting this
this into
into Eq.
Eq. (11-12)
(11-12) we findfind how the
the error
error in
in sin 6 varies
sin 2 (J varies
with
with (J:
6:

6 == --2K = D sin
2 2 2 2
A sin
t:. sin 2 (J 2K sin 6 cos
sin 2 (J 6 =
cos 2 (J sin 2 2(J,
26, (11-22)
(11-22)

where D is is a
a new constant.
constant. [This
[This equation
equation is
is valid
valid only
only when the
the cos
2
cos 2 (J
extrapolation
extrapolation function
function is
is valid.
valid. If
If some other
other extrapolation
extrapolation function
function is is

used,
used, Eq.Eq. (11-22)
(11-22) must bebe modified
modified accordingly.]
accordingly.] Now the the true
true value
value ofof
2
sin 6 for
sin 2 (J for any
any diffraction
diffraction line
line is
is given
given by
by
')..2
X
2
2
sin 2 (J
sin 9 (true)
(true)
= 40.0 2- (h
= 22 +
+ k 22 + 2
+ l2), I
2 (h ),
4a

where ao,
a the
the true
,
true value
value of
of the
the lattice parameter, is
lattice parameter, is the
the quantity
quantity we are
are
seeking.
seeking. Hut
But
sin 2
6 (observed)
sin 2 (J (observed) - sin
2
6 (true)
sin 2 (J = A sin
(true) = t:.
2
sin 2 (J,
6,

sin 2
sin 2 8
e - --- X
2
')..2
2
- (h 2
2 (h
+
+ k2 +
+ l2)
fc
2
I
2
)
= D sin
= 2
sin 2 29
20,
40.0
4oo 2 '
sin2
sin2 8=
= Ca +
+ Ad,
A6, (11-23)
(11-23)
where
C = X /4a 2,
= ')..2/40.0
2 2
,
a =
= (h
(ft
22 +
+ k2 +
2
+ 7,2),I
2
), A == D/I0,
D/10, and 6 = 10
6 =
2
sin2 29.
10 sin 20.

(The
(The factor
factor 10
10 is
is introduced
introduced into
into the
the definitions
definitions of
of the quantities A and 6
the quantities d

solely
solely to
to make the
the coefficients
coefficients of
of the
the various
various terms
terms in
in the
the normal equations
equations
of the
of the same order
order ofof magnitude.)
magnitude.)
340
340 PRECISE PARAMETER MEASUREMENTS [CHAP. 11
[CHAP. 11

a, and a
2
The experimental
experimental values of of sin
sin2 9,0, a, d are
are now substituted
substituted into
into
Eq. (11-23)
Eq. (11-23) for
for each of
of the
the n back-reflection
back-reflection lines
lines used in
in the determina-
determina-
tion. gives n equations
tion. This gives equations inin the
the unknown constants C and A, A, and these
these
equations
equations can be solved for
for the
the most probable
probable values of
of C and A by
by the
the
method of of least
least squares.
squares. Once C is
is found, ao
found, OQ can be
be calculated
calculated directly
directly
from the
the relation
relation given
given above;
above; the constant A is
the constant is related
related to
to the
the amount ofof
systematic
systematic error
error involved
involved and is
is constant
constant for
for anyone
any one film,
film, but varies
varies
slightly from one film
slightly from film to
to another.
another. The two normal normal equations
equations we need
need to
to
find
find C and A are are found from Eq. (11-23) and the
Eq. (11-23) the rules
rules previously
previously given.
given.
They
They are
are
2:a sin22 9 == C2:a2 + A 2:a6,
Sasin

2:6
26 sin 2
sin 2 9 = C2:a6
6 = C2a5 +
+ A28
A2:a2 2
.

To illustrate
illustrate the
the way
way in
in which such calculations
calculations are
are carried
carried out,
out, we will
will
apply
apply Cohen's
Cohen's method to to a
a determination
determination ofof the
the lattice
lattice parameter
parameter ofof tung-
tung-
sten from measurements made on the
sten the pattern
pattern shown in in Fig. 6-10. Since
Fig. 6-10. Since
this
this pattern
pattern was made with a a symmetrical
symmetrical back-reflection
back-reflection focusing
focusing camera,
camera,
the
the correct
correct extrapolation
extrapolation function
function is
is

Ild
Ad
- =
= Kq, tan q,.
K<t> tan <t>.

d
Substituting
Substituting this
this into
into Eq. (11-21), we have
Eq. (11-21),

Il 2 = --2K<t>
sin 2 8 =
A sin 2Kq, sin 2
sin 2 8 tan q,
6 tan

= - 2K
= q, cos22 q,^ tan
2K0cos tan q,
=
= Dq, sin
D<t>sin 2q"
20,

where D is
is a
a new constant.
constant. We can therefore
therefore write,
write, for
for each
each line
line on the
the
pattern,
pattern,
2

sin
2
B = cos
2 --
4a
X
-
2 (h?
+ k2 + I
2
) + D<t> sin 20, (11-24)
(11-24)

cos = Ca
C0 s 2 q, =
2
+ A5,
A6, (11-25)
(11-25)
where
C = 2
X /4a 2
,
a = (h
2
+ k
2
+ I
2
), A = D/10, and 8 = 100 sin 20.

Equation 11-24 cannot

Equation 11-24 cannot be
be applied
applied directly
directly because
because lines
lines due toto three
three
different
different wavelengths (Cu Kal,
wavelengths (Cu Kai, Cu Ka2,
Ka%, and Cu KfJ)
K/3) are
are present
present on the
the
pattern,
pattern, which means that
that A
X varies
varies from line
line to
to line,
line, whereas
whereas in
in Eq. (11-24)
Eq. (11-24)
it
it is
is treated
treated as
as a
a constant.
constant. But thethe data can be
data can be "normalized"
"normalized" to to anyone
any one
wavelength
wavelength by by use
use of
of the
the proper multiplying
proper multiplying factor.
factor. For
For example,
example, sup-
sup-
pose
pose we decide
decide to
to normalize
normalize all
all lines
lines to
to the Kfi wavelength.
the KfJ wavelength. Then for for a
a
11-7)
11-7] COHEN'S METHOD 341
341

11-2
TABLE 11-2

Observed Normalized to K ~
Line ilkl A tP
2
COI'r/J 6 2
COI'r/J 6

1 321 Ko) 14 24.518 0 0.82779 3.2 0.67606 2.6

2 321 K0 2 14 24.193 0.83205 3.2 0.67617 2.6
3 411,330 K~ 18 21.167 0.86961 2.5 0.86961 2.5

4 400 Ko) 16 13.302 0.94706 1.0 0.n346 0.8

5 400 K0 2 16 12.667 0.95191 1.0 0.n3S7 0.8
6 420 K~ 20 10.454 0.96708 0.7 0.96708 0.7

particular line
particular line formed
formed by Kai
by radiation, for
Kat radiation, instance, we have
for instance, have

COS
2
<t>Kai
= Ot + A8xai,

2
cos
J
4>A- ai
= + /X
(
A AS
2 )
,
Kai .

\X -
/ VA/JCai /

From the
the Bragg
Bragg law,
law,

( -XKi) cos22 q,KUl

- 2 COS
_
Ka -= cos
22
q,K{J,
COS <t>Ktl,<t> ,

XKUl

2
cos q,K{J = (XKi) ( XK{J 2)
- - 2 a + A - - 2 OKulI (11-26)
4aO XKuI
where (XKi 2 22 )OKuI is
is a
a normalized 0. Equation
jX KuI
(\K0 /^K ai )f>Ka }
5. (11-26) now refers
Equation (11-26) refers
only
only to
to the
the K{3 wavelength.
K/3 wavelength. Lines
Lines due to
to Ka2
Ka^ radiation
radiation can be normalized
normalized
in
in a
a similar
similar manner.
manner. When this this has
has been
been done forfor all
all lines, the quantity
lines, the quantity
2 2
C in
in Eq. (11-25) is
Eq. (11-25) is then
then a
a true
true constant,
constant, equal
equal to
to XKfl
XA /4aj4ao2. The values
values r
j3
.

of
of the
the two normalizing
normalizing factors,
factors, for
for copper
copper radiation,
radiation, are
are

XKi jXKuI 2 =
= 0.816699 and XKi jX Ku2 2 == 0.81265l.
0.812651.
2
Table
Table 11-2 shows the the observed
observed and normalized
normalized values
values of
of cos
cos2 q, and 06 <t>

for
for each
each line
line on the
the tungsten pattern. The values
tungsten pattern. values of
of 0
6 need not
not be calcu-
calcu-
lated to
lated to more thanthan two significant
significant figures,
figures, since
since 0
6 occurs
occurs in
in Eq.
Eq. (11-25)
(11-25)
only
only in
in the
the last
last term
term which
which is
is very
very small
small compared
compared to
to the
the other
other two.
two. From
the
the data
data inin Table
Table 11-2,
11-2, we obtain
obtain

Sa22
2;a = 1628,
= 1628, 2522
2;0 = 21.6,
= 21.6, 2;ao
2a5 = 157.4,
= 157.4,

= 78.6783, cos2 q, =
= 7.6044.
2
2;a
Sa cos 2
cos2 q, = 78.6783,
<t>
2;0
25 cos 7.6044.
<f>
342
342 PRECISE PARAMETER MEASUREMENTS
PRECISE PARAMETER MEASUREMENTS 11
[CHAP. 11
[CHAP.

The normal
The normal equations
equations are
are
78.6783 =
78.6783 1628C
= 1628C ++ 157.4A,
157.4A,

7.6044 == 157.4C
7.6044 157.4C ++ 21.
21.6A.
6A.
Solving these,
Solving these, we find
we find
C = X*0
C 2
'AK//4ao2
/4a = 0.0483654
2 =
and
0.0483654 and ao == 3.3.1651A,
a 1651 A,

AA == -0.000384.
-0.000384.
The constant
The A, called
constant A, called the
the drift
drift constant,
constant, is
is aa measure
measure ofof the
the total
total sys-
sys-
tematic error
tematic error involved
involved in
in the
the determination.
determination.
Cohen's method
Cohen's method ofof determining
determining lattice
lattice parameters
parameters isis even
even more
more valuable
valuable
when applied
when applied to noncubic substances,
to noncubic substances, since,
since, as
as we saw
saw in
in Sec.
Sec. 111-2, straight-
1-2, straight-
forward graphical
forward graphical extrapolation
extrapolation cannot
cannot be
be used when there
there is
is more than
than one
one
lattice parameter
lattice parameter involved.
involved. Cohen's
Cohen's method,
method, however,
however, provides
provides aa direct
direct
means
means of
of determining
determining these
these parameters, although
parameters, although the
the equations
equations are
are natu-
natu-
rally
rally more
more complex
complex than
than those
those needed
needed for
for cubic
cubic substances.
substances. For example,
example,
suppose that
suppose that the
the substance
substance involved
involved is
is hexagonal.
hexagonal. Then
'A22
X 4
4 h22
h + hk
+ hk +
+ kk2 2
\ 2
}.2 12
2

=- +-
I

sin 2 6(J (true)

sin
2
(true) = - .- . - . - ^2
4 3 ao 2 4 co
and
and
2 2
2 X
}.2 2 2}.2 2 X2
sin
sin (J
2
6 - - (h 2
2 (h
+ hk
hk + kk 2 ) - --- (1 ) =
) = D sin
sin 28,
26, 2 (I
2
)
2

3a 2
3ao 4co2
4c

if
if the pattern is
the pattern is made in
in a
a Debye-Scherrer
Debye-Scherrer camera. By rearranging
rearranging this
this
equation
equation and
and introducing
introducing new symbols,
symbols, we obtain
obtain

sin 2
6 =
sin 2 (J = Ca + By +
+ B,,), + A 0, ,46, (11-27)
(11-27)
where
where
(h + +
C = }.2/3ao2,
2
X /3a
2
,
= (h
a = 22 + hk + k 2),
/c
2
), B X /4c 2,
B == }.2/4co
2 2
,
= 122 ,
")'7 = I ,

A == D/I0,
D/10, and = 10 sin 2(J.
6 = 10 sin2
2
26.

The
The values of C,
values of C, B,
#, and A,A, of
of which only
only the first
first two are
are really
really needed,
needed,
are
are found
found from
from the
the three
three normal equations:
equations:

Za sin
2:a 2 = C2:a
sin2 (J6 = CZa22 + B2:a")'
B2ay + A2:ao,
AZat,
sin2 (J6 = CZay +
= C2:a,,), BZy +
2
2:")'
S 7 sin 2
+ B2:")'2 + AAZyd,
2:,,),0,
2:6sin CSaS +
S6 sin22 (J6 == C2:ao fiZfry +
+ B2:o,,), A2822
+ A2:o .

11-8
11-8 Calibration
Calibration method.
method. One One other
other procedure
procedure forfor obtaining
obtaining accurate
accurate
lattice
lattice parameters
parameters is
is worth
worth mentioning,
mentioning, if
if only
only for
for its
its relative
relative simplicity,
simplicity,
and
and that
that is
is the
the calibration
calibration method
method already
already alluded
alluded to
to in
in Sec. 6-7. It
Sec. 6--7. It is
is

based
based onon aa calibration
calibration of
of the
the camera
camera film
film (or
(or diffractometer
diffractometer angular scale)
angular scale)
by
by means
means of of aa substance
substance ofof known
known lattice
lattice parameter.
parameter.
 PROBLEMS
PROBLEMS 343

If the
If the specimen
specimen whose parameter isis to
whose parameter to bebe determined
determined isis in in the
the form
form of of aa
powder,
powder, it
it is
is simply
simply mixed
mixed with
with the
the powdered
powdered standard
standard substance
substance and
and aa
pattern
pattern made
made of
of the
the composite
composite powder. powder. If
If the
the specimen
specimen is
is aa polycrysta1-
polycrystal-
line piece
line piece of of metal,
metal, the the standard
standard powder powder may may be be mixed
mixed withwith petroleum
petroleum
jelly
jelly and
and smeared
smeared over
over the
the surface
surface of
of the
the specimen
specimen in
in a
a thin
thin film.
film. The
The
amount of
amount of the
the standard
standard substance
substance used used should
should be be adjusted
adjusted so so that
that the the in-in-
tensities of
tensities of the
the diffraction
diffraction lineslines from
from the the standard
standard and and those
those from
from the the speci-
speci-
men are
men not too
are not too unequal.
unequal. InasmuchInasmuch as as the
the true
true angle
angle 8 can can be be calculated
calculated
for any diffraction
for any diffraction line line from
from the the standard
standard substance,
substance, aa calibration
calibration curve curve
can be
can be prepared
prepared relating
relating the the true
true angle
angle 68 to to distance
distance alongalong thethe camera
camera film film
(or angular position
(or angular position on
on the
the diffractometer
diffractometer scale).
scale). This
This curve
curve is
is then
then used
used
to find
to find the
the true
true angle
angle 68 forfor any
any diffraction
diffraction line line from the the specimen,
specimen, since since
it may
it may be be assumed
assumed that that anyany systematic
systematic errors errors involved
involved in in the
the determina-
determina-
tion will
tion will affect
affect the the diffraction
diffraction lineslines of of both
both substances
substances in in the
the same way. way.
This method
This method works works best best when there there is is aa diffraction
diffraction line line from the the stand-
stand-
ard substance
ard substance very very close
close to to aa line
line from
from the the specimen
specimen and both both lines
lines areare in in
the back-reflection
the back-reflection region. region. Practically
Practically all all systematic
systematic errors errors are thus elim-
are thus elim-
inated. To achieve
inated. achieve this this condition
condition requiresrequires an intelligent
intelligent choicechoice of of thethe
standard
standard substance
substance and/or
and/or the
the incident
incident wavelength.
wavelength. The most popular
popular
standard substances are
standard substances are probably
probably quartz quartz and sodium chloride, chloride, although
although
pure metals
pure metals such
such as
as gold
gold and silver
silver are
are also
also useful.
useful.
One disadvantage of
One disadvantage of the
the calibration
calibration method is is that the accuracy
accuracy of of the
the
parameter
parameter determination
determination depends
depends on
on the
the accuracy
accuracy with which the param-
param-
eter
eter of of the
the standard
standard substance
substance is is known. If
If the absolute value of of thethe
parameter
parameter of
of the
the standard
standard is
is known,
known, then
then the
the calibration
calibration method gives
gives the
the
absolute value
absolute value of of the
the parameter
parameter of
of the
the specimen
specimen quite quite accurately.
accurately. If
If not,
not,
then
then onlyonly a a relative
relative valuevalue of of the
the parameter
parameter of of the specimen
specimen can be be ob-ob-
tained, but
tained, but it
it is
is an
an accurate
accurate relative
relative value.
value. And frequently
frequently this
this is
is no dis-
dis-

advantage in the differences

advantage at at all,
all, since
since we are are often
often interested
interested only only in differences in in the
the
parameters of
parameters of a number a number of
of specimens
specimens and not in
in the absolute values
values of
of

these parameters.
these parameters.
If
If absolute
absolute values
values are are required,
required, the the only
only safesafe procedure
procedure is is to
to measure
measure the the
absolute value of the
absolute value of the parameter parameter of
of the
the standard
standard substance
substance by
by one
one of
of the
the
methods described
methods described in
in the
the preceding
preceding sections.
sections. It
It should
should not
not be
be assumed
assumed
that
that aa particular
particular samplesample of of quartz,
quartz, for for example,
example, has has the
the exact
exact lattice
lattice param-
param-
eters tabulated under
eters tabulated under "quartz" "quartz" in
in some
some reference
reference book,
book, because
because this
this par-
par-
ticular sample may contain
ticular sample may contain enough impurities enough impurities in
in solid
solid solution
solution to
to make
make
its
its lattice
lattice parameters
parameters differ differ appreciably
appreciably from from the the tabulated
tabulated values.
values.

PROBLEMS
PROBLEMS

11-1. The
11-1. The lattice
lattice parameter
parameter of
of copper
copper is to be
is to be determined to an
determined to an accuracy
accuracy of
of

dbO.OOOlA at
O.OOOlA at 20C.
20C. Within
Within what
what limits
limits must
must thethe temperature
temperature of
of the
the specimen
specimen
be
be controlled
controlled if
if errors
errors due to thermal
due to thermal expansion
expansion are to be
are to be avoided?
avoided? The
The linear
linear
coefficient of thermal expansion
coefficient of thermal expansion of
of copper
copper is
is 16.6
16.6 X
X to-
10~86
in.jin.jOC.
in./in./C.
344
344 PRECISE PARAMETER MEASUREMENTS [CHAP.
[CHAP. 11 11
11-2.
11-2. The following
following data
data were obtained
obtained from a a Debye-Scherrer pattern of
Debye-Scherrer pattern of a
a
simple
simple cubic
cubic substance,
substance, made with copper
copper radiation.
radiation. The given
given sin
2
6 values
sin 2 (} values are
are
for
for the Kat lines
the KOLI lines only.
only.

hh*2 +
+ k2 +
A: + l2P
2
sin 2
sin 2 (J

38
38 0.9114
0.9114
40
40 0.9563
0.9563
41
41 0.9761
0.9761
42
42 0.9980
0.9980

Determine
Determine the the lattice
lattice parameter
parameter a, a, accurate
accurate toto four
four significant
significant figures. by graphi-
figures, by graphi-
cal
cal extrapolation
extrapolation of
of a against
against cos
cos 2
2 (J.
6.

11-3.
11-3. From the the data
data given
given in Prob. 11-2,
in Prob. 11-2, determine
determine thethe lattice parameter to
lattice parameter to
four
four significant
significant figures
figures by by Cohen's
Cohen's method.
11-4.
11-4. From the the data
data given
given in in Table 11-2, 11-2, determine
determine thethe lattice parameter of
lattice parameter of

tungsten to
tungsten to five
five significant
significant figures
figures by by graphical
graphical extrapolation
extrapolation of against q, tan
of a against <j> tan q,.
<t>.

11-5. If
11-5. If the
the fractional
fractional error error in
in thethe plane
plane spacing
spacing dd is
is accurately proportional to
accurately proportional to
the function (cos
the function 2
2
(Jlsin
(cos 0/sin (J
6 +
+ cos
cos 2
2
(JI(J)
6/6) over
over the
the whole range
range of 0, show that
of (J, that a
a plot
plot
of a
of A sin 6 against
against sin 6 has
has aa maximum,
maximum, as as illustrated
illustrated for
for a
a particular
particular ease by
2
sin 2 (J sin 2 (}
2
case by
Fig.
Fig. 10-1.
10-1. At approximately
approximately what value
value of
of (J
6 does
does the
the maximum occur?
occur?
 CHAPTER 12

PHASE-DIAGRAM DETERMINATION

12-1 Introduction.
Introduction. An alloy alloy is is a combination of of two or or more metals,metals,
or of metals and nonmetals.
or of nonmetals. IItt may consist consist of of a single
single phase or
phase or of of a
a mix-
mix-
ture of phases,
ture of phases, and these
these phases
phases may be of be of different
different types,
types, depending
depending only only
on the
the composition
composition of of the
the alloy
alloy and the the temperature,
temperature,* * provided
provided the the alloy
alloy
is at
is at equilibrium.
equilibrium. The changes changes in in the
the constitution
constitution of of the
the alloy
alloy produced
produced
by
by given
given changes
changes in in composition
composition or or temperature
temperature may may be be convenieQ.tly
convenieptly shown
by
by means of of a phase diagram, also
phase diagram, also called
called an equilibrium
equilibrium diagram
diagram or or consti-
consti-
diagram. It
tution diagram. It is
is a plot
plot of of temperature
temperature vs. vs. composition,
composition, divided
divided into into
areas wherein a particular
particular phasephase or or mixture
mixture of of phases
phases is is stable.
stable. As such such itit

forms a sort sort of

of map of of the alloyalloy system
system involved.
involved. Phase diagrams diagrams are are
therefore
therefore of of great
great importanee
importance in in metallurgy,
metallurgy, and much time time and efforteffort have
been devoted to to their
their determination.
determination. In In this
this chapter
chapter we willwill consider
consider how
x-ray
x-ray methods can be used in in the
the study
study of of phase
phase diagrams,
diagrams, particularly
particularly of of
binary systems. Ternary
binary systems. Ternary systems
systems will will be discussed
discussed separately
separately in in Sec.
Sec. 12-6.
12-6.
X-ray
X-ray methods are, are, of
of course,
course, not the the only
only ones
ones which can can be be used
used inin
investigations
investigations of of this kind. The two classical
this kind. classical methods are are thermal
thermal analysis
analysis
and microscopic
microscopic examination,
examination, and many many diagrams
diagrams have been been determined
determined
by
by these means alone. alone. X-ray
X-ray diffraction,
diffraction, however,
however, supplements
supplements these these older
older
techniques
techniques in in many
many useful
useful waysways and provides,
provides, in in addition,
addition, thethe only
only means
of determining the crystal
of determining crystal struct.ures
structures of of the
the various
various phases
phases involved.
involved. Most
phase
phase diagrams
diagrams today today are are therefore
therefore determined by by aa combination
combination of of all
all

three methods. In addition,

three addition, measurements
measurements of of other
other physical
physical properties
properties
may be used to to advantage
advantage in in some alloy alloy systems:
systems: the the most
most important
important of of
these subsidiary
these subsidiary techniques
techniques are
are measurements of
of the
the change
change in
in length
length and
of the change
of change in electric resistance
in electric resistance as as a a function
function of of temperature.
temperature.
In general,
In general, thethe various
various experimental
experimental techniques
techniques differ in sensitivity,
differ in sensitivity, and
therefore in
therefore in usefulness,
usefulness, from from one one portion
portion of of the
the phase
phase diagram
diagram to to another.
another.
Thus,
Thus, thermal analysis
analysis is
is the
the best
best method for
for determining
determining the
the liquidus
liquidus and
solidus, including
solidus, including eutectic
eutectic and peritectic horizontals,
peritectic horizontals, but
but it
it may fail
may fail to
to
reveal the
reveal the existence
existence of of eutectoid
eutectoid and peritectoid
peritectoid horizontals
horizontals because
because of of the
the
sluggishness
sluggishness of of some solid-state
solid-state reactions
reactions or or the
the small heat effects
small heat effects involved.
involved.
Such features
features of the diagram
of the diagram are are best
best determined
determined by by microscopic
microscopic examina-
examina-
tion or
tion or x-ray
x-ray diffraction,
diffraction, and the the same applies
applies to to the
the determination
determination of of solvus
solvus
(solid solubility)
(solid solubility) curves.
curves. It
It is
is a
a mistake
mistake to
to rely entirely
rely entirely on
on any one
any one method,method,
the wise
and the wise investigator
investigator will will useuse whichever
whichever technique
technique is is most
most appropriate
...pprqpriate
to .the
to problem at
the problem at hand.
hand.
* The
pressure on
pressure the alloy
on the alloy is
is another eft'ecth"e variable,
Mother effective but
variable, but it is llsoally held
it is usually
consta.nt at
constant that of
at that of the
the atmosphere
atmosphere and
and may
may be be neglected.
neglected. ' .
,
-

345
345
346
346 PHASE-DIAGRAM DETERMINATION [CHAP. 12
[CHAP. 12

12-2 General principles.

12-2 General principles. The key key toto the
the interpretation
interpretation of of the powder
powder
patterns
patterns of
of alloys
alloys is
is the
the fact
fact that
that each
each phase
phase produces
produces its
its own pattern
pattern in-
in-

dependently
dependently of
of the
the presence
presence or
or absence
absence of
of any
any other phase.
phase. Thus a single-
single-
phase
phase alloy
alloy produces
produces a a single
single pattern
pattern whilewhile the pattern
pattern of of a two-phase
two-phase alloyalloy
consists
consists of of two
two superimposed
superimposed patterns, patterns, one due to
to each phase.
phase.
Assume,
Assume, for for example,
example, that that two metals A and B are completely completely soluble
soluble in in

the
the solid
solid state,
state, as
as illustrated
illustrated by
by the
the phase diagram
phase diagram of
of Fig.
Fig. 12-1.
12-1. The
solid
solid phase
phase a, a, called
called a a continuous
continuous solid solid solution,
solution, is is of
of the substitutional
substitutional type; type;
it
it varies
varies in in composition,
composition, but but notnot in in crystal
crystal structure,
structure, from
from purepure A to to pure
pure
B,
B, which
which must must necessarily
necessarily have have the the same structure.
structure. The lattice lattice parameter
parameter
of
of a a also
also varies
varies continuously
continuously from that that ofof pure
pure A to to that
that ofof pure
pure B. Since
all
all alloys
alloys in in a a system
system of of this
this kindkind consist
consist of of the
the same single
single phase,
phase, theirtheir
powder
powder patterns
patterns appear appear quitequite similar,
similar, the the only
only effect
effect of
of a change
change in in composi-

I
composi-
tion
tion being
being to to shift
shift the the diffraction-
diffraction-

line
line positions
positions in
in accordance with
with the the hqllld
liquid

change
change in
in lattice
lattice parameter.
parameter.
More commonly,
commonly, the the two metals A r..::
and B are only partially soluble
are only partially soluble in in the ~

solid
solid state.
state. The first first additions
additions of of B ~
to
to A go go into
into solid
solid solution
solution in
in the
the A Q..~ a
lattice,
lattice, which may may expandexpand or contract ;::::
or contract
as
as a a result,
:..
result, depending
depending on the the relative
relative Eo-
sizes
sizes of of the
the A and B atoms and the the
type
type of of solid
solid solution
solution formed (substi- (substi-
tutional
tutional or or interstitial).
interstitial). Ultimately
Ultimately
the
the solubility of B in in A
A B
solubility limit
limit of A isis reached,
reached, PERCENT B B -
and further
further additions
additions of of B causecause the the
FIG. 12-1.
FIG. 12-1. Phase
Phase diagram
diagram of of two
precipitation of
precipitation of aa second
second phase.phase. This metals, sho\\<ing complete solid
solid solu-
solu-
metals, showing complete
second
second phasephase may may be be aa B-rich
B-rich solid solid bility.
bility.
solution
solution with the the same structure
structure as as B,B,
as in
as in the
the alloy system
alloy system illustrated
illustrated by Fig. 12-2(a).
by Fig. 12-2(a). Here the the solid
solid solutions
solutions
a and (3 are
/3 are called primary solid
called primary solid solutions
solutions or terminal solid
or terminal solid solutions.
solutions. Or Or the
the
second phasephase which
which appearsappears may may have
have no connection with
connection with the the B-rich
B-rich solid
solid
solution, as
solution, in the
as in the system
system shown shown in in Fig.
Fig. 12-2(b).
12-2(b). Here Here the
the effect
effect of
of super-
super-
saturating a.a with
saturating with metalmetal B is is to
to precipitate
precipitate the the phase
phase designated
designated "Y. 7. This
This
phase is
phase is called intermediate solid
called an intermediate solid solution
solution or intermediate phase.
or intermediate phase. It It usu-
usu-
ally has
ally has aa crystal
crystal structure
structure entirely
entirely different
different from that of
from that of either
either aa oror 0, and
{J, and
it is
it is separated
separated from from each each of of these
these terminal
terminal solid solid solutions,
solutions, on on the
the phase
phase di- di-
agram, by
agram, by at at least
least one one two-phase
two-phase region. region.
diagrams much more
Phase diagrams more complex
complex than than those
those just
just mentioned
mentioned are are often
often
encountered in
encountered in practice,
practice, but but they
they are are always
always reducible
reducible to to aa combination
combination of of
fairly simple
fairly simple types.types. When an an unknown phase phase diagram
diagram is is being
being investi-
investi-
gated, it
gated, it is
is best
best to to make aa preliminary
preliminary survey survey of of the
the whole
whole system
system by by pre-
pre-
12-2J
12-2] GENERAL PRINCIPLES
GENERAL PRINCIPLES 347
347

liquid

f
>il
~
~
E-
..:
~
>il
e::.--:
~
E-<

A B A B
PERCENT B
PER('E~TB - PERCENT B
PERt'EXT B -
(al
(a) II.)
(b)

FIG. 12-2. Phase diagrams

diagrams showing
showing (a)
(a) partial
partial solid
solid solubility,
solubility, and
and (b)
(b) partial
partial
solid
solid soluhility
solubility together
together with the formation of
of an intermediate
intermediate phase.
phase.

paring
paring a series
series of alloys
alloys at at definite
definite composition
composition intervals,
intervals, saysay 5 5 or
or 10 10 atomic
atomic
percent,
percent, from pun>
pure A to
to pure
pure B. The powder pattern
powder pattern of
of each
each alloy
alloy and each
each
pure
pure metal is
is then prepared.
prepared. These patterns may appear
patterns may appear quite complex quite complex
but, no matter what the
but, the complexities,
complexities, the patterns may
the patterns may bebe unraveled
unraveled and and
the proper
the proper sequence
sequence of of phases
phases across
across the diagram may
the diagram may be be established,
established, if if

proper attention is
proper is paid
paid to to the
the following prineiples:
following principles :

(1) Equilibrium. Each alloy

(1) Equilibrium. alloy must be be atat equilibrium
equilibrium at the temperature
at the temperature
where the the phase
phase relations
relations are are being
being studied.
studied.
sequence. A horizontal
(2) Phase sequence.
(2) horizontal (constant
(constant temperature)
temperature) line line drawn
drawn
across the
across the diagram
diagram must must passpass through
through single-phase
single-phase and and two-phase
two-phase regions regions
alternately.
alternately.
(3) Single-phase
(3) Single-phase regions.
regions. In In aa single-phase
single-phase region,region, aa change
change in in composi-
composi-
tion generally
tion generally produces
produces aa change change in in lattice
lattice parameter
parameter and thereforetherefore aa shift
shift
in the
in the positions
positions of of the
the diffraction
diffraction lines
lines ofof that
that phase.
phase.
(4) Two-phase
(4) Two-phase regions.
regions. In In aa two-phase
two-phase region,region, aa change
change in in composition
composition
of the alloy
of the alloy produces
produces a change
a change in in the
the relative
relative amounts of of the
the twotwo phases
phases
but no change
but change in in their
their compositions.
compositions. These These compositions
compositions are are fixed
fixed atat the
the
intersections of
intersections of aa horizontal
horizontal "tie "tie line"
line" with
with the
the boundaries
boundaries of of the
the two-phase
two-phase
field. Thus,
field. Thus, in in the
the system
system illustrated
illustrated in in Fig.
Fig. 12-2(a),
12-2(a), the the tie
tie line
line drawn
drawn at at
temperature TI
temperature TJ shows that that the
the compositions
compositions of of a and ft{3 at at equilibrium
equilibrium at at
this temperature
this temperature are are xx and yy respectively.
respectively. The powder po".-der pattern
pattern of of aa two-
two-
phase
phase alloy
alloy brought
brought to
to equilibrium
equilibrium at
at temperature
temperature TI TJ will
will therefore
therefore consist
consist
of the
of the superimposed
superimposed patterns patterns of of a ofof composition
composition xx and ft{3 of of composition
composition y. y.
The patterns
The patterns of of aa series
series of of alloys
alloys in in the
the xy range will
xy range all contain
will all contain the the same
same
diffraction lines
diffraction lines at at the
the same
same positions,
positions, but but thethe intensity
intensity of of the
the lines
lines ofof the
the
phase relative
aa phase relative to to the
the intensity
intensity of of the
the lines
lines ofof the
the ft{3 phase will decrease
phase will decrease in in
348
348 PHASE-DIAGRAM DETERMINATION [CHAP. 12
[CRAP. 12

aa regular
regular manner 88 as the
the concentration
concentration of of B in in the alloy
alloy changes
changes from x x to
to y,y,
since
since this
this change
change in
in total
total composition
composition decreases
decreases the amount of
of a relative
relative
to
to the
the amount of of fl.
ft.

These principles are

These principles are illustrated
illustrated with with reference
reference to to the
the hypothetical
hypothetical alloy alloy
system
system shown in in Fig.
Fig. 12-3.
12-3. This This system
system contains
contains two substitutional
substitutional ter- ter-

minal solid
minal solid solutions
solutions a and and fl,p, both
both assumed to to be face-centered
face-centered cubic, cubic, and
an
an intermediate
intermediate phase phase '7, Y, which
which is is body-centered
body-centered cubic. cubic. The solubility
solubility of of
either
either A or or B in in '7
Y is
is assumed
assumed to to be
be negligibly
negligibly small:
small: the
the lattice
lattice parameter
parameter
of'Y
of 7 isis therefore
therefore constant
constant in in all
all alloys
alloys in in which this this phase
phase appears.
appears. On the the
other hand,
other hand, the
the parameters
parameters of
of a and fl vary
vary
ft with composition
composition in
in the
the manner
shown
shown by by the
the lower part of
lower part of Fig. 12-3. Since
Fig. 12-3. Since the the B atom is is assumed to to bebe
larger
larger than
than thethe A atom,atom, the the addition
addition of of B expands
expands the the A lattice,
lattice, and the the

parameter of
parameter of a
a increases
increases from from al ai for pure A to
for pure a 3 for
to a3 for aa solution
solution of of composi-
composi-
tion
tion x,x, which
which represents
represents the
the limit
limit of
of solubility
solubility of
of B in
in A at
at room tempera-
tempera-
ture.
ture. In In two-phase
two-phase (a (a + + '7) Y) alloys
alloys containing
containing more than x percent percent B, B, the
the
parameter
parameter of
of a remains
remains constant
constant at
at its
its saturated
saturated value
value a3.
a 3. Similarly,
Similarly, the the
addition of
addition of A to
to B causes the parameter of {3 to decrease from a2
causes the parameter of ft to decrease from to a.
a 2 to a4 atat
the
the solubility
solubility limit,
limit, and then then remain constant constant in in the
the two-phase
two-phase ('(7 Y+ + (3)ft)

field.
field.

Calculated
Calculated powder patterns are
powder patterns are shown in in Fig.
Fig. 12-412-4 forfor the
the eight
eight alloys
alloys
designated
designated by
by number in
in the
the phase
phase diagram
diagram of
of Fig.
Fig. 12-3.
12-3. It
It is
is assumed
assumed that
that
the
the alloys
alloys have been
been brought
brought to
to equilibrium
equilibrium at
at room temperature
temperature by by slow
slow
cooling.
cooling. Examination of of these
these patterns
patterns reveals
reveals the the following:
following :

(1) Pattern
(1) Pattern of of pure
pure A (face-centered
(face-centered cubic). cubic).
(2)
(2) Pattern
Pattern of of a almost
almost saturated
saturated with with B. B. The expansion
expansion of of the
the lattice
lattice
causes
causes the the lines
lines toto shift
shift toto smaller
smaller anglesangles 20. 20.

(3)
(3) Superimposed
Superimposed patterns patterns of of a and '7. Y. The aa phase phase is is now saturated
saturated
and hashas itsits maximum parameterparameter 3 a3.
a .

(4)
(4) Same as as pattern
pattern 3, 3, except
except for for a a change
change in in the
the relative
relative intensities
intensities of of
the
the two patterns
patterns which
which is
is not
not indicated
indicated on
on the
the drawing.
drawing.
(5)
(5) Pattern
Pattern of pure '7Y (body-centered
of pure (body-centered cubic). cubic).
(6)
(6) Superimposed
Superimposed patterns patterns of'Y of 7 and of of saturated
saturated {3 with
ft with a parameter of
a parameter a4
of a4'.

(7)
(7) Pattern
Pattern of pure {3 with
of pure ft with a a parameter
parameter somewhat greater greater than than a a.
4.

(8)
(8) Pattern
Pattern of of pure
pure B (face-centered
(face-centered cubic). cubic).
When an unknown phase phase diagram
diagram is is being
being determined,
determined, the the investigator
investigator
must,
must, of
of course,
course, work in
in the
the reverse
reverse direction
direction and deduce
deduce the the sequence
sequence of of
phases
phases across the
across the diagram
diagram from from the the observed
observed powder patterns. This
powder patterns. This is is

done by by visual
visual comparison
comparison of patterns prepared
of patterns prepared from from alloys
alloys ranging
ranging in in

composition from pure

composition pure A to pure B,
to pure B, andand thethe previous
previous example
example illustrates
illustrates
the nature of of the
the changes
changes which can can be be expected
expected from
from one
one pattern to
pattern to an-
an-
other.
other. Corresponding
Corresponding lines
lines in
in different
different patterns
patterns are
are identified
identified by placing
by placing
the films
films side
side by
by side
side asas inin Fig. 12-4 and
Fig. 12-4 and noting
noting which
which lineslines are
are common to to
 12-2]
12-2] GENERAL PRINCIPLES 349
349

t liquid
'Y (BCC)
r.1
~
~
E-<
~
-,~...
~
<D
room A'-----'---'--L--'------+--,---'--~,--=B
PERCENT , B-;

I
{j 1
114
a 1

,'a3
I

:r 11 B
PERCENT B
B -
*-

FIG.
FIG. 12-3.
12-3. Phase diagram
diagram and lattice
lattice constants
constants of
of a
a hypothetical
hypothetical alloy
alloy system.
system.

28 =
26 = (J0 26 = 180

(2)

FIG.
FIG. 12-4.
12-4. Calculated
Calculated powder patterns of
powder patterns of alloys
alloys 1
1 to
to 8
8 in
in the
the alloy
alloy system
system shown
shown
in
in Fig.
Fig. 12-3.
12-3.
350
350 PHASE-DIAGRAM DETERMINATION [CHAP. 12
[CHAP. 12

the patterns. ** This may

the two patterns. may be be difficult
difficult in in some alloy
alloy systems
systems where the
phases
phases involved
involved have complex complex diffraction
diffraction patterns,
patterns, or where it
it is
is suspected
suspected
that
that lines
lines due to to KfJ
K$ radiation
radiation may be present present in patterns and not in
in some patterns in
others.
others. IIt t is
is important
important to
to remember that a diffraction
diffraction pattern
pattern of
of a given
given
phase
phase is characterized not
is characterized not only
only by by line positions but also
line positions also byby line
line intensities.
intensities.
This means that
This that the
the presence
presence of of phase
phase X X inin a mixture of of phases
phases cannot be
proved merely
proved merely by by coincidence
coincidence of
of the
the lines
lines of
of phase
phase X with a set
set ofof lines
lines inin
the pattern
the pattern of
of the
the mixture;
mixture; the
the lines
lines in
in the pattern
pattern of
of the mixture which
coincide
coincide with
with thethe lines
lines of phase X must also
of phase also have the the same
same relative
relative intensities
intensities

as
as the
the lines
lines ofof phase
phase X. The addition addition of of one oror more phases
phases to to a particular
a particular
phase
phase weakens the the diffraction lines of
diffraction lines of that phase, simply
that phase, simply by by dilution,
dilution, but it it

cannot
cannot change
change the the intensities
intensities of of those
those lines
lines relative
relative toto one another.
another. Finally,
Finally,
it
it should
should be be noted
noted that
that the
the crystal
crystal structure
structure of of a phase
phase need not not be known
for the
for presence of
the presence of that
that phase
phase to to be detected
detected in in aa mixture:
mixture it : it is
is enough
enough to to
know the positions and intensities
the positions intensities of of the
the diffraction
diffraction lines
lines ofof that
that phase.
phase.
Phase diagram
diagram determination
determination by by x-ray
x-ray methods usually begins with
usually begins with a a
determination
determination of of the
the room-temperature
room-temperature equilibria. equilibria. The first
first step
step is
is to
to
prepare
prepare a a series
series ofof alloys
alloys by by melting
melting and casting,
casting, or or by
by melting
melting and solidifi-
solidifi-

cation
cation in in the
the melting
melting crucible.
crucible. The resulting ingots
resulting ingots are
are homogenized
homogenized at at a a
temperature
temperature just just below the
the solidus
solidus to
to remove segregation,
segregation, and very slowly
very slowly
cooled to
cooled temperature, tt Powder specimens
to room temperature. specimens are are then prepared by
then prepared by
grinding
grinding or or filing,
filing, depending
depending on on whether
whether the the alloy
alloy is brittle or
is brittle not. If
or not. If the
the
alloy
alloy isis brittle
brittle enough
enough to to be
be ground
ground into powder, the
into powder, the resulting powder is
resulting powder is

usually
usually sufficiently
sufficiently stress-free
stress-free to to give
give sharp
sharp diffraction
diffraction lines.
lines. Filed
Filed pow-
pow-
ders,
ders, howeyer,
however, must be re-annealed re-annealed to to remove the the stresses
stresses produced
produced by by
plastic deformation during
plastic during filing before they
filing before they areare ready
ready forfor x-ray
x-ray examina-
examina-
tion.
tion. Only
Only relatively
relatively low temperatures
temperatures are are needed
needed to to relieve
relieve stresses,
stresses, but but
the filings
filings should
should again
again be be slowly cooled,
slowly cooled, after
after the
the stress-relief
stress-relief anneal,
anneal, to to
ensure equilibrium
equilibrium at
at room temperature.
temperature. Screening Screening is
is usually necessary
usually necessary
to obtain finefine enough
enough particles
particles forfor x-ray
x-ray examination,
examination, and when two-phase two-phase
alloys
alloys are
are being
being screened,
screened, the the precautions
precautions mentioned
mentioned in in Sec.
Sec. 6-3
6-3 should
should be be
observed.
observed.
After the room-temperature
room-temperature equilibria equilibria are are known,
known, a a determination
determination of of
the phases
the present at high
phases present at high temperatures
temperatures can can be be undertaken.
undertaken. Powder

* Superposition
Superposition of of the
the two films
films is
is generally
generally confusing
confusing andand may
may make some some ofof
the
the weaker lineslines almost
almost invisible.
invisible. A better
better method
method of of comparison
comparison consists
consists in
in slit-
slit-
ting
ting each
each Debye-Scherrer
Debye-Scherrer filmfilm lengthwise
lengthwise down its its center
center and placing the
and placing the center
center
of
of oneone film
film adjacent
adjacent toto the
the center
center ofof another.
another. TheThe curvature
curvature ofof the
the diffraction
diffraction
lines
lines then does
does not
not interfere
interfere with
with the
the comparison
comparison of of line positions.
line positions.

tt Slow cooling
Slow cooling alone
alone may
may notnot suffice
suffice to produce room-temperature
to produce room-temperature equilibrium,
equilibrium,
which
which is is often
often very
very difficult to achieve.
difficult to achieve. It It may be promoted
may be promoted by by cold
cold working
working and
and
recrystallizing
recrystallizing thethe cast
cast alloy,
alloy, in
in order
order to
to decrease
decrease its
its grain
grain size
size and
and thus
thus accelerate
accelerate
diffusion, prior to
diffusion, prior to homogenizing
homogenizing and and slow
slow cooling.
cooling.
12-3)
12-3] SOLID SOLUTIONS 35]
351

specimens
specimens areare sealed
sealed in
in small
small evacuated silica silica tubes,
tubes, heated
heated to to the
the desired
desired
temperature
temperature long long enough
enough for for equilibrium
equilibrium to to bebe attained,
attained, and rapidly
rapidly
quenched.
quenched. Diffraction patterns of
Diffraction patterns of the
the quenched
quenched powders
powders are are then made at at
room temperature.
temperature. This method works very very well
well inin many
many alloy
alloy systems,
systems,
in
in that
that the
the quenched
quenched powder
powder retains
retains thethe structure
structure it it had at at the
the elevated
elevated
temperature.
temperature. In some alloys, however,
alloys, however, phasesphases stable
stable at
at high-temperature
high-temperature
will
will decompose
decompose on cooling
cooling to to room temperature,
temperature, no matter matter how rapidrapid the
the
quench,
quench, and such
such phases
phases can
can only
only be
be studied
studied by
by means of
of a
a high-tempera-
high-tempera-
ture
ture camera or or diffractometer.
diffractometer.
The latter
latter instrument
instrument is is of
of particular
particular value
value inin work of of this
this kind because
kind because
it
it allows
allows continuous
continuous observation
observation of of aa diffraction
diffraction line.
line. For example,
example, the
the
temperature below
temperature below which a a high-temperature
high-temperature phase phase is is unstable,
unstable, such
such as
as a
eutectoid
eutectoid temperature,
temperature, can can bebe determined by by setting
setting the the diffractometer
diffractometer
counter to
counter to receive
receive a a prominent
prominent diffracted
diffracted beam of of the
the high-temperature
high-temperature
phase,
phase, and then
then measuring
measuring the the intensity
intensity of of this
this beam as as aa function
function of
of tem-
perature
perature asas the specimen is
the specimen is slowly
slowly cooled.
cooled. The temperature
temperature at at which the
the
intensity
intensity falls
falls to
to that
that of
of the
the general background
general background is
is the
the temperature
temperature re-re-
quired,
quired, and any hysteresis
any hysteresis in
in the
the transformation
transformation can
can be
be detected
detected by
by a
a simi-
simi-
lar
lar measurement on heating.
heating.

12-3
12-3 Solid
Solid solutions.
solutions. Inasmuch as as solid solubility, to
solid solubility, to a a greater
greater or or
lesser extent, is
lesser extent, is soso common between metals,
between metals, we might digress a little
might digress a little at at
this point to
this point to consider
consider how thethe various
various kinds
kinds of
of solid
solid solutions
solutions may
may be be dis-
dis-
tinguished
tinguished experimentally. Irrespective of
experimentally. Irrespective of its
its extent
extent or
or its position on
its position on the
the
phase
phase diagram,
diagram, anyany solid
solid solution
solution may
may bebe classified
classified as
as one
one ofof the
the following
following
types, solely on the
types, solely the basis
basis of
of its
its crystallography:
crystallography :

(1) Intersitial.
(1) Intersitial.
(2)
(2) .substitutional.
JSubstitutional.
(a)
(a) Random.
(b)
(b) Ordered.
Ordered. (Because
(Because of
of its
its special
special interest,
interest, this
this type
type is
is described
described
separately
separately in
in Chap.
Chap. 13.)
13.)
(c)
(c) Defect.
Defect. (A(A very
very rare
rare type.)
type.)

An interstitial
interstitial solid
solid solution
solution of of B inin A isis to be expected
to be expected only
only when the the
B atom isis so
so small
small compared
compared to to the
the A atom that that it
it can
can enter
enter the
the interstices
interstices
of
of the
the A lattice
lattice without
without causing
causing much distortion.
distortion. As a a consequence,
consequence, about
the
the only
only interstitial
interstitial solid
solid solutions
solutions of of any
any importance
importance in in metallurgy
metallurgy are are
those
those formed between
between a a metal
metal and one one ofof the
the elements,
elements, carbon,
carbon, nitrogen,
nitrogen,
hydrogen, boron, all
hydrogen, and boron, all of
of which havehave atoms less than 2A in
less than in diameter.
diameter.
The interstitial
interstitial addition
addition ofof B to
to A isis always accompanied
always accompanied by by an
an increase
increase in
in
the
the volume of of the
the unit
unit cell.
cell. If
If A is
is cubic,
cubic, then
then the
the single
single lattice
lattice parameter
parameter
increase. If
a must increase. If A is
is not
not cubic,
cubic, then
then one
one parameter
parameter may may increase
increase and
the
the other
other decrease,
decrease, as
as long
long asas these
these changes
changes result
result inin an
an increase
increase inin cell
cell
352
352 PHASE-DIAGRAM DETERMINATION
PHASE-DIAGRAM DETERMINATION [CHAP. 12
[CHAP. 12

3.10
3.10 3.65 Brile::
3.65 ~ril 3
a (austenite)
-~
ZrilR
305
305 3.60 ril~-"l
3.60
gR
rilO
E-~
"fJe::
too
w
me::
j
3.00
3.00 3.55
3.55 ~<
<&l..
Zril
rilE-< 2.95
H 2.95
E-<ril
i

p::-
<.-: 3 290
290
-<!

.....
:Se:: a (martensite)
<
&l..
Si 2.85
2.85

280
280 _l L_

0 05 1.0
1.0 15
15 20
20
WEIGHT PERCENT CARBON
WEIGHT CARBO:\'"

FIG. 12-5.
FIG. 12-5. Variation of
Variation of martensite
martensite and austenite
austenite lattice
lattice parameters
parameters with
with
carbon content.
carbon content. (After
(After C.
C. S.
S. Roberts,
Roberts, Trans.
Trans. A.I.M.E.
A.I.M.E. 197,
197, 203,
203, 1953.)
1953.)

volume.
volume. Thus,
in austenite, which is
Thus, in austenite,is an interstitial
interstitial solid
solid solution
solution of
of car-
car-
bon in
bon in face-centered
face-centered cubic
cubic -y-iron,
'Y-iron, the
the addition of
addition of carbon increases the cell
increases the cell
edge a. But
edge a. But in
in martensite,
martensite, aa supersaturated
supersaturated interstitial
interstitial solid
solid solution
solution ofof
carbon in
carbon in a-iron,
a-iron, the
the cc parameter
parameter of of the
the body-centered
body-centered tetragonal
tetragonal cell
cell in-
in-
creases while
creases while the
the a parameter
parameter decreases,
decreases, when carbon is is added.
added. These
These
effects are illustrated
effects are illustrated in
in Fig.
Fig. 12-5.
12-5.
The
The density of an
density of an interstitial
interstitial solid
solid solution is given
solution is by the
given by the basic
basic density
density
equation
equation
1.66020~A
1.660202^1 , ^
p=
p . (3-9)
(3-9)
V
where
where
~A = n.A. + n,A,;
nA l l ]
(12-1)
(12-1)

n. and n,
n 8 and n are
l are numbers of of solvent
solvent and interstitial
interstitial atoms,
atoms, respectively,
respectively, per per
unit
unit cell;
cell; and A.
A 8 and A,
A are
aret atomic
atomic weights
weights of
of solvent
solvent and interstitial
interstitial

atoms,
atoms, respectively.
respectively. Note that that the
the value
value of of n.
n 8 is
is constant and independent
independent
of
of the
the concentration
concentration of of the
the interstitial element, and that n,
interstitial element, n is
is normally
normally a
t

small
small fraction
fraction of
of unity.
unity.
The formation
formation of of aa random substitutional
substitutional solid solid solution
solution of B and A
may
may be
be accompanied
accompanied either
either by
by an
an increase
increase or
or decrease
decrease in
in cell
cell volume,
volume, de-de-
pending
pending on
on whether
whether the
the B atom
atom is
is larger
larger or
or smaller
smaller than the A atom.
atom. In
In
continuous
continuous solidsolid solutions
solutions of of ionic
ionic salts,
salts, the
the lattice
lattice parameter
parameter of
of the
the solu-
solu-
tion
tion isis directly
directly proportional
proportional to to the
the atomic
atomic percent
percent solute
solute present.
present. ThisThis
relationship,
relationship, known
known as
as Vegard's law,
Vegard's law, is
is not
not strictly obeyed
strictly obeyed by by metallic
metallic
solid
solid solutions
solutions and,
and, inin fact,
fact, there
there is
is no
no reason
reason why why it it should
should be.
be. However,
However,
it
it is
is often
often used
used as
as aa sort
sort of
of yardstick
yardstick by by which
which one
one solution
solution may
may be be com-
com-
pared
pared with
with another.
another. Figure 12--6 shows examples
Figure 12-6 shows examples of of both
both positive
positive and
and
negative
negative deviations
deviations from
from Vegard's law among
Vegard's law among solutions solutions of
of face-centered
face-centered
cubic
cubic metals,
metals, and
and even
even larger
larger deviations
deviations have
have been
been found
found in in hexagonal
hexagonal close-
close-
12-3)
12-3] SOLID SOLUTIONS 353
353
4.10 ,.-----,,----,.----r--"""T----,
Ag

Pd
~ I'd'
E 3 ~o 1---I--AfL--_t~~_+----l
~;;
<: a 701--7'5ih~~--_t--_+-

a ;,0'--_ _'--_---''--_----'_ _---'-_ _---':\NiI

o 211 -t1I
40 fill
(>() XO
80 lOO
l(H)

"\To\ll<'
ATOMIC PEH('El'IT
PERCENT
FIG.
FIG. 12-6.
12-6. Lattire
Lattice parameters
parameters of
of some continuous
continuous 80lid
solid solutions.
solutions. Dot-dash
Dot-dash
lines
lines indirate
indicate Yegard's
Vegard's law.
law. (From
(From Structure
Structure of by C.
Metals, by
of Metals, S. Barrett,
C. S. Barrett, 1952,
1952,
McGraw-Hill Book Company,
Company, Inr.)
Inc.)

packed solutions.
packed solutions. In terminal
terminal and intermediate
intermediate solid
solid solutions,
solutions, the
the lattice
lattice
parameter mayor
parameter may or maymay not
not vary
vary linearly
linearly with
with the
the atomic
atomic percent
percent solute
solute
and,
and, when the variation is
the variation is linear,
linear, the
the parameter
parameter found by by extrapolating
extrapolating toto
100
100 percent
percent solute
solute does
does not
not usually
usually correspond
correspond toto the
the atom sizesize deduced
deduced
from the
the parameter
parameter of of the pure solutE',
the pure solute, even when allowance
allowance is is made for
for a
possible
possible change
change inin coordination
coordination number.
The density
density of
of aa random substitutional
substitutional solid
solid solution
solution is
is found
found from Eq.Eq.
(3-9)
(3-9) with the ~A
with the 2A factor
factor being
being given
given by
by
^solvent^solvent I
(12-2)
(12-2)

where n again
again refers
refers to
to the
the number of of atoms per per cell
cell and A to to the
the atomic
atomic
weight.
weight. Whether a a given
given solution
solution is
is interstitial
interstitial or
or substitutional
substitutional may
may be
decided by
decided determining
by determining whether
whether the
the x-ray density
x-ray density calculated
calculated according
according to to
Eq. (12-1)
Eq. (12-1) or
or that
that calculated
calculated according
according to
to Eq. (l2-2) agrees
Eq. (12-2) agrees with
with the
the di-
di-
rectly
rectly measured density.
density.
Defect substitutional
substitutional solid
solid solutions
solutions are are ones
ones in in which some lattice lattice
sites, normally occupied
sites, normally occupied by by atoms at
at certain
certain compositions,
compositions, are
are simply
simply
vacant at
vacant at other
other compositions.
compositions. Solutions
Solutions of of this
this type
type areare rare
rare among
among metals;
metals ;

the
the best-known example
example is is the intermediate fJ solution
the intermediate solution in
ft in the
the nickel-alu-
nickel-alu-
minum system.
system. A defect
defect solution
solution is
is disclosed
disclosed by
by anomalies
anomalies in
in the
the curves
curves
of
of density
density and lattice
lattice parameter
parameter V8.
vs. composition. Suppose,
composition. Suppose, for
for example,
example,
that
that the
the solid
solid solution
solution ofof B and A is is perfectly
perfectly normal up up to
to xx percent
percent B, B,
354
354 PHASE-DIAGRAM DETERMINATION
PHASE-DIAGRAM DETERMINATION 12
[CHAP. 12
[CHAP.

but beyond
but beyond that
that point
point aa defect
defect lattice
lattice isis formed;
formed; i.e.,
i.e., further
further increases
increases in
in
BB content
content are
are obtained,
obtained, notnot by
by further
further substitution
substitution of of B
B for
for A,
A, but
but by
by
dropping A
dropping atoms from
A atoms from the
the lattice
lattice to
to leave
leave vacant
vacant sites.
sites. Under
Under these
these cir-
cir-
cumstances,
cumstances, the
the density
density and
and parameter
parameter curves
curves will
will show
show sudden
sudden changes
changes
in slope,
in slope, or
or even maxima
even maxima or or minima,
minima, at at the
the composition
composition x. x. Furthermore,
Furthermore,
the x-ray density calculated according
the x-ray density calculated according to
to Eq. (12-2)
Eq. (12-2) will
will no
no longer agree
longer agree
with the direct density simply because
with the direct density simply because Eq. (12-2),Eq. (12-2), as
as usually used,
usually used, appliesapplies
only to
only to normal
normal solutions
solutions where
where all
all lattice
lattice sites
sites are
are occupied;
occupied; i.e.,
i.e., it
it is
is tacitly
tacitly
assumed there
assumed there that
that (n
(nsolvent + nnsolute)
80 vent + i
equals the
so ute ) equals
i the total
total number oflattice sites
number of lattice sites
in the
in the structure
structure involved.
involved. The The actual
actual structure
structure of of aa defect
defect solid
solid solution,
solution,
including the proportion
including the proportion of of vacant
vacant lattice
lattice sites
sites at
at any
any given
given composition,
composition,
can be
can be determined
determined by by aa comparison
comparison of of the
the direct
direct density
density withwith the the x-ray
x-ray
density,
density, calculated
calculated according
according to
to Eq.
Eq. (12-2),
(12-2), and an analysis
analysis of
of the
the dif-
dif-

fracted intensities.
fracted intensities.

12-4 Determination
12-4 Determination of of solvus
solvus curves
curves (disappearing-phase method). To
(disappearing-phase method). To
return
return to
to the
the main
main subject
subject of
of this
this chapter,
chapter, we might
might now consider
consider the
the
methods used
methods used for
for determining
determining the the position
position of
of aa solvus
solvus curve on aa phase
phase
diagram. Such
diagram. Such aa curve
curve forms
forms thethe boundary
boundary between a single-phase
a single-phase solid
solid
region and
region and aa two-phase
two-phase solid
solid region,
region, and thethe single-phase
single-phase solid
solid may bebe aa
primary or
primary or intermediate
intermediate solid solution.
solid solution.
One method
method of locating such
of locating curves is
such curves the "lever law."
is based on the law." This
This
law,
law, with
with reference
reference toto Fig.
Fig. 12-7
12-7 for
for example,
example, states
states that
that the relative propor-
relative propor-
tions
tions of a. and
of a ft in
and {3 in an
an alloy
alloy of
of composition
composition ^z in in equilibrium
equilibrium atat temperature
temperature
TJ
TI is
is given
given byby the
the relative
relative lengths
lengths of of the
the lines
lines zy
zy and zx,
zx, or
or that

Wa (z -- x)
W,,(z =
x) = W~(y - z), (12-3)
(12-3)

where W" Wa and W W&~ denote

denote the the relative
relative
weights
weights of
of a
a and {3
ft if
if x, y,
x, y, and zz are
are
expressed
expressed in
in weight percent.
weight percent. It
It fol-
fol-

lows
lows from
from Eq. Eq. (12-3)
(12-3) thatthat thethe weight
weight
fraction
fraction of of {3
ft in
in the
the alloy
alloy varies
varies line-
line-
PS
arly
arly with
with composition from
composition from at point 0 at point w
xx to
to 1 1 at
at point
point y. y. The intensity
intensity of of
any
any diffraction
diffraction line line from
from thethe {3ft phase
phase
also
also varies
varies from
from zero zero atat xx to
to aa maxi-
maxi-
mum at at y,y, but
but the the variation
variation with with
weight
weight percent
percent B B isis not
not generally WEIGHT PERCENT
WEIGHT PERCENT BB - *>
generally
linear. * Nevertheless,
*
linear. Nevertheless, this this variation
variation
FIG.
FIG. 12-7.
12-7. Lever-law
Lever-law construction
construction
may
may be
be used
used to
to locate
locate the
the point
point x. x. A A for
for finding
finding the
the relative
relative amounts
amounts of of two
two
series
series of
of alloys
alloys in
in the
the two-phase region
two-phase region phases
phases in
in aa two-phase
two-phase field.
field.

* The
The reasons
reasons for
for nonlinearity
nonlinearity are
are discussed
discussed in
in Sec.
Sec. 14-9.
14-9.
12-4]
12-4] SOLVUS CURVES (DISAPPEARING-PHASE
(DISAPPEARING-PHASE METHOD) 355
355

is
is brought
brought to to equilibrium
equilibrium at at temperature
temperature Tl T\ and quenched.
quenched. From diffrac- diffrac-

tion
tion patterns
patterns made at
at room temperature,
temperature, the ratio
ratio of
of the
the intensity
intensity I/#{j of
of aa
prominent
prominent line
line of
of the
the {jftphase
phase to
to the
the intensity
intensity I
I a
a of
of a
a prominent
prominent line
line of
of the
a phase
phase is plotted as
is plotted as a a function
function of of weight percent B.
weight percent B. The composition
composition at at
which the ratio I/0//
the ratio {j/ I a extrapolates
a extrapolates to
to zero
zero is
is taken
taken as
as the
the point
point x.
x. (Use
(Use of of
the ratio II$/I
the ratio {3/I aa rather
rather than I/#(3 alone alone eliminates
eliminates the the effect
effect of of any change
any change
which maymay occuroccur in in the
the intensity
intensity of of the
the incident
incident beam from one diffraction diffraction
pattern
pattern to
to another.
another. However,
However, this
this ratio
ratio also
also varies
varies nonlinearly
nonlinearly with
with weight
weight
percent B.)
percent B.) Other Other points
points on on thethe solvus
solvus curve curve areare located
located by by similar
similar experi-
experi-
ments on alloys
alloys quenched
quenched from other other temperatures.
temperatures. This method is is known,
known,
for
for obvious
obvious reasons,
reasons, as as the
the disappearing-phase
disappearing-phase method.
Since
Since the curve of
the curve of IfJ/l vs. weight
Ip/I a vs. weight percentpercent B is is not linear,
linear, high
high accuracy
accuracy
in
in the
the extrapolation
extrapolation depends depends on having having severalseveral experimental
experimental points points close close
to
to the phase boundary
the phase boundary which is is being
being determined.
determined. The accuracy accuracy of of the
disappearing-phase
disappearing-phase method is is therefore
therefore governed
governed by by the
the sensitivity
sensitivity of of the
x-ray
x-ray method in
in detecting
detecting small
small amounts of
of a
a second
second phase
phase in
in a
a mixture,
mixture,
and this
this sensitivity
sensitivity varies varies widely
widely from one alloy alloy system
system to to another.
another. The
intensity
intensity of
of a
a diffraction
diffraction line
line depends on,
depends on, among among other
other things, the
things, the atomic
scattering
scattering factor
factor j,
/, which in
in turn
turn is
is almost
almost directly
directly proportional to
proportional to the
atomic number Z.
atomic Z. Therefore,
Therefore, if
if A and B have nearly
nearly the
the same atomic
number,
number, the the a a. and {j phases will
ft phases will consist consist of of atoms having having almost
almost the the same
scattering powers, and the
scattering powers, the intensities
intensities of the a and fJ diffraction
of the ft patterns
diffraction patterns
will
will also
also bebe roughly
roughly equal equal when the the two phasesphases are are present
present in in equal
equal amounts.
Under favorable
favorable circumstances
circumstances such such as as these,
these, an x-ray pattern
an x-ray pattern can reveal reveal
the
the presence
presence of less than
of less than 1 1 percent
percent of of a a second
second phase.
phase. On the the other
other hand,hand,
if
if the
the atomic
atomic number of of B isis considerably
considerably less less than
than thatthat of of A,
A, the
the intensity
intensity
of the fJ pattern
of the ftpattern may may be be soso much lower lower than than that
that of of the
the a pattern
pattern that a
relatively large
relatively large amount of
of fJ
ft in
in a
a two-phase
two-phase mixture
mixture will
will go
go completely un-
completely
detected.
detected. This amount may may exceed
exceed 50
50 percent
percent in
in extreme cases,
cases, where the
'

atomic numbers of
atomic of A and B differ differ by by some 70
70 or
or 80
80 units.'
units. Under such cir- cir-

cumstances,
cumstances, the
the disappearing-phase
disappearing-phase x-ray x-ray method is
is practically
practically worthless.
worthless.
On the
the whole,
whole, the the microscope
microscope is is superior
superior to to x-rays
x-rays when the the disappearing-
disappearing-
phase method is
phase is used,
used, inasmuch as as the
the sensitivity
sensitivity of of the
the microscope
microscope in in de-
de-
tecting
tecting the presence of
the presence of aa second
second phase phase is is generally
generally very very highhigh and independ-
independ-
ent
ent of
of the
the atomic
atomic numbers of of the
the elements
elements involved.
involved. However,However, this this sensi-
sensi-
tivity
tivity does
does depend
depend on on thethe particle
particle size size of of the
the second phase, and if
second phase, if this
this is is

very
very small,
small, as as it
it often
often is is at
at low temperatures,
temperatures, the the second phase phase may not be
detectable
detectable under under the the microscope.
microscope. Hence the the method of of microscopic
microscopic ex- ex-
amination is
amination is not
not particularly
particularly accurate
accurate for
for the
the determination
determination of
of solvus
solvus
curves
curves at at low temperatures.
temperatures.
Whichever techniquetechnique is is used
used to to detect
detect the the second
second phase,phase, the the accuracy
accuracy of of
the
the disappearing-phase
disappearing-phase method increases
increases as
as the
the width of
of the
the two-phase
two-phase re-
re-
gion decreases. If
gion decreases. the (a
If the +
(a + fJ) ft) region
region is is only
only a a few
few percent
percent wide,wide, then the
 356
356 PHASE-DIAGRAM DETERMINATION [CHAP. 12
[CHAP. 12

relative
relative amounts of of a and fJ will vary rapidly
will vary
ft rapidly with slight
slight changes
changes in in the

total
total composition
composition of of the
the alloy,
alloy, and thisthis rapid
rapid variation
variation of Wa /Ws will
of Wa/WS will

enable
enable the
the phase
phase boundary
boundary to to be
be fixed
fixed quite precisely. This is
quite precisely. is true,
true, for
for the
the
x-ray method,
x-ray method, even
even if
if the
the atomic
atomic numbers of
of A and B are
are widely
widely different,
different,
because,
because, if
if the (a +
the (a + fJ)
ft) region
region is
is narrow,
narrow, the compositions
compositions of of a and fJ
ft do not

differ
differ very
very much and neither
neither do their
their x-ray scattering powers.
x-ray scattering powers.

12-1
12-6 Determination
Determination of of solvus
solvus curves
curves (parametric
(parametric method).
method). As we have
just seen, the disappearing-phase
just seen, the disappearing-phase method of
of locating
locating the boundary of
the boundary of the
the
aa field
field is
is based
based on on a a determination
determination of the composition
of the composition at at which the fJ
which the ft phase
phase
just disappears
just disappears from a series of
a series (a +
of (a + fJ)
ft) alloys.
alloys. The parametric
parametric method,
method, on
the
the other
other hand,
hand, is is based
based on on observations
observations of of the
the a solid
solid solution
solution itself.
itself. This
method depends
depends on on the
the fact,
fact, previously
previously mentioned,
mentioned, that that thethe lattice
lattice pa-pa-
rameter of
rameter of a a solid
solid solution
solution generally
generally changes
changes with composition
composition up up toto the
the
saturation
saturation limit,limit, and then then remains constant beyond that
constant beyond that point.
point.
Suppose
Suppose the
the exact
exact location
location of
of the
the solvus
solvus curve
curve shown in
in Fig.
Fig. 12-8(a)
12-8(a) is is

to
to bebe determined.
determined. A series series of
of alloys,
alloys, 1
1 to
to 7,
7, is
is brought
brought to
to equilibrium
equilibrium at
at
temperature
temperature T t , where the
T\, the a field
field is
is thought
thought to to have almost
almost its its maximum

width,
width, and quenched
quenched to
to room temperature.
temperature. The lattice
lattice parameter of
parameter of a isis

measured for for each

each alloy
alloy and plotted against alloy composition,
plotted against alloy composition, resulting resulting in
in
aa curve
curve such
such as as that
that shown in in Fig.
Fig. 12-8(b).
12-8(b). This This curve
curve has
has two branches:
branches:
an inclined
inclined branch
branch be, 6c, which shows how the parameter of
the parameter of aa varies
varies with
with the
the
composition
composition of of a,
a, and a a horizontal branch de,
horizontal branch de, which shows that that thethe a phase
a phase
in
in alloys
alloys 6 6 and 7 7 is
is saturated,
saturated, because
because its its lattice
lattice parameter
parameter doesdoes notnot change
change
change in
with change in alloy
alloy composition.
composition. In In fact,
fact, alloys
alloys 6 6 and 7 7 are
are inin aa two-
two-
phase region at
phase region at temperature
temperature Tt, T\, and thethe only
only difference
difference between
between them is is in
in
the
the amounts of of saturated
saturated a they they contain.
contain. The limit
limit of
of the
the aa field
field at
at tem-
tem-
perature
perature T TIt is
is therefore
therefore given
given by by the
the intersection
intersection of of the
the two branches
branches of of

t
~Tl
Il:l
~
ID
12345'
2 6 77
H
E-<
a+tI r
<:
Il:l ...".o--o--e

-
~T2
.....
~
E-<
6
7

A y
y x
x A y x
B -*
WEIGHT PERCENT B - WEIGHT PERCENT B -
(a)
(a) (b)
(b)

FIG.
FIG. 12-8.
12-8. Parametric method tor
tor determmmg
determining a
a Holvus
solvus c'UI've.
curve.
12-5]
12-5] SOLVUS CURVES (PARAMETRIC
(PARAMETRIC METHOD)
METHOD) 357
357

the parameter
parameter curve. curve. In this this way,
way, we have located located one point point on on the
the solvus
solvus
curve, namely x percent
curve, namely percent B at at T T\.1.
Other points
points could
could be found in in a a similar
similar manner. For example, example, if if the
the
same series
series of of alloys
alloys were equilibrated
equilibrated at
at temperature
temperature TT22 ,
,
a
a parameter
parameter
similar to
curve similar to Fig.
Fig. 12-8(b)
12-8(b) would be obtained, obtained, but but itsits inclined
inclined branch branch
would be shortershorter and its its horizontal
horizontal branch lower. lower. But heat heat treatments
treatments
and parameter
parameter measurements on all all these
these alloys
alloys are are unnecessary,
unnecessary, once once thethe
parameter-composition
parameter-composition curve of the solid
curve of the solid solution
solution has has been
been established.
established.
Only
Only one one two-phase
two-phase alloy alloy is is needed to to determine
determine the the rest
rest of of thethe solvus.
solvus.
Thus,
Thus, if alloy 6 is
if alloy is equilibrated
equilibrated at at T2 T2 and then then quenched,
quenched, itwillit 'will contain
contain Qa
saturated
saturated at at that
that temperature.
temperature. Suppose Suppose the the measured parameter parameter of of Qa inin
this
this alloy
alloy is a y Then,
is all. .
Then, from the the parameter-romposition
parameter-composition curve, curve, we find find that
that
a of
of parameter
parameter all a y contains
contains y percent B.
y percent B. This
This fixes
fixes a a point
point on the the solvus
solvus at at
temperature
temperature T 22 Points on the
. the solvus
solvus at at other
other temperatures
temperatures may may be be found
found
by
by equilibrating
equilibrating the the same alloy, alloy 6,
alloy, alloy 6, at
at various
various temperatures,
temperatures, quench- quench-
ing,
ing, and mea!mring
measuring the
the lattice
lattice parameter
parameter of
of the
the contained
contained a.
Q.

The parameter-composition
parameter-composition rurve, curve, branch
branch be be of
of Fig.
Fig. 12-8(b),
12-8(b), thus thus serves
serves
as
as aa sort
sort ofof mast.er
master curve for for thethe determination
determination of of the
the whole
whole solvus.
solvus. For For a a
given aecuraey
given accuracy of
of lattice
lattice parameter measurement,
parameter measurement, the
the accuracy
accuracy with
with which
which
t.he
the solvus
solvus can can be be located
located depends
depends markedlymarkedly on on the
the slope
slope ofof the
the parameter-
parameter-
composition
composition rurve. curve. If If this
this curve
curve is is nearly
nearly flat,
flat, i.e.,
i.e., if
if changes
changes in in the
the com-
com-
position of
position of the
the solid
solid solution produce very
solution produce very small
small changes
changes in in parameter,
parameter, then then
the romposition,
composition, as as determined from the parameter, will
the parameter, will bebe subject
subject to to con-
con-
siderable
siderable error
error and so so will
will the
the location
location of of the
the solvus.
solvus. However,
However, if if the
the curve
curve
is
is steep, just the
steep, just the opposit.e
opposite is is true,
true, and relatively
relatively erudecrude parameter
parameter measure- measure-
ments may suffice to
may suffice to fix
fix the
the location
location of of the
the solvus
solvus quitequite accurately. In
accurately. In
either case, relative
either case, relative parameter
paramet.er measurements are are just
just asas good
good as
as absolute
absolute
parameter measurements of
parameter of the
the same accuracy.
accuracy.
Figure
Figure 12-9 illustrates the
12-9 illustrates the use use ofof the
the parametric
parametric method in in determining
determining
the solid
solid solubility
solubility of
of antimony
antimony in
in copper
copper as
as a
a function
function of
of temperature.
temperature.
The sloping curve in
sloping curve in (a)
(a) was found found from parameter measurements
from parameter measurements made
on a series
series ofof alloys, containing from 0 to
alloys, containing to about
about 12 weight percent
12 weight percent Sb, Sb, equi-
equi-
librated at 630C.
librated at 630C. The horizontal horizontal lines lines represent
represent the the parameters
parameters of of two-
two-
phase alloys,
phase containing about
alloys, containing about 12 weight percent
12 weight percent Sb, Sb, equilibrated
equilibrated at the
at the
temperatures indicated.
temperatures indicated. The solvus solvus curvecurve constructed
constructed from from thesethese datadata is is
given in
given in (b), together with
(b), together with adjoining
adjoining portions
portions of of the
the phase
phase diagram.
diagram.
In most cases,
In cases, the the parametric
parametric method is is more
more accurate
accurate than than the the disap-
disap-
pearing-phase method,
pearing-phase method, whetherwhether based based on on x-ray
x-ray measurements
measurements or or micro-
micro-
scopic examination,
scopic examination, in in the
the determination
determination of of solvus
solvus curves
curves at at lowlow tempera-
tempera-
tures. mentioned earlier,
tures. As mentioned earlier, bothboth x-rayx-ray diffraction
diffraction and and microscopic
microscopic ex- ex-
amination may
amination may fail fail toto disclose
disclose the the presence
presence of of small
small amounts
amounts of of aa second
second
phase, although
phase, although for for different
different reasons.
reasons. When this this occurs,
occurs, thethe disappearing-
disappearing-
phase
phase method always
always results
results in
in aa measured extent of solubility
extent of solubility higher higher thanthan
 358
358 PHASE-DIAGRAM DETERMINATION
PHASE-DIAGRAM DETERMINATION [CHAP. 12
[CHAP. 12

1100
\ r-- r--- r--- L

3.6800
1000

900
\ - r---
6300
;;t:~000
'\ a+L
"" 3.6700
L:. -500 0 "" 800
t
X~
MC
=: 3.66(K) l'
/ - .... 450 0
I ~7()()
W
400 0 ~
"" .....
r--
~
/ ~600 1
afZ 36500
H
/ a
%~ ~ Ja+(J
~ 3.6400 g: .')(X)
tf

V I
V
a.
$ .....
~
..-;
2 300 0 ~4(K)
../'
8
U
~ 3.6300
!/ I0 V
V a+'Y.'
3(x)
~
14
211
&
3
..:l
3.6200

3.6100
/ 200
/
3.6000 100
o 2 4 6
G !'
8 HI
10 12
12 14 () 2 4 6 ~ 10 12 14
ANTnWNY
WEIGHT PERCENT ANTIMONY WEIGHT PERCENT ANTIMONY
^yEIGHT
(a)
(a) (h)
(h)

FIG.
FIG. 12-9.
12-9. &lvus
Solvus rurve
curve determination
determination inin the
the copper-antimouy
copper-antimony system
system byby the
the
parametric
parametric method:
method: (a)
(a) parameter vs. composition
parameter VB. composition cun'e;
curve; (b)
(b) solubility vs. tempera-
solubility VB. tempera-
ture curve. (J.
ture curve. Mathevvson, Trans.
C. Mertz and C. H. Mathewson,
(J. C. Mertz and C.
A.l.M.E. 124,
Trans. A.I.M.E. 124, 59,
59, ]937.)
1937.)

the
the actual
actual extent.
extent. But But thethe parametric
parametric method,
method, since
since it it is
is based onon measure-
measure-
ments made on
ments made on thethe phase
phase whose
whose range
range ofof solubility
solubility is is being
being determined
(the
(the a
a phase),
phase), is
is not
not influenced
influenced by
by any
any property
property of
of the second phase
phase (the (the
fJ phase).
phase). The
The fJ phase
phase
ft
may
may have
have an x-ray
x-ray scattering
scattering power
power much higher
higher
or
or lower than that
lower than that of of the
the a a phase,
phase, and the the fJ phase
phase may precipitate
precipitate in in the
the

form of
form of large particles
large particles or
or small
small ones,
ones, without affecting
affecting the parameter
parameter
measurements made on
measurements on the
the aa phase.
phase.
Note that
Note that thethe parametric
parametric methodmethod is is not
not confined
confined to to determining
determining the the
extent of primary solid
extent of primary solid solutions,solutions. as
as in
in the
the examples
examples given given above.
above. It
It may
may
also
also be
be used
used to to determine
determine the the solvus curves which
solvus curves which bound
bound an an intermediate
intermediate
solid solution on
solid solution on thethe phase
phase diagram.
diagram. NoteNote also
also that
that the
the parametric
parametric method
method
may be
may be employed
employed even even when
when thethe crystal
crystal structure
structure of of the
the aa phase
phase is so com-
is so com-
plex that
plex that itsits diffraction
diffraction lineslines cannot
cannot be be indexed.
indexed. In In this
this case,
case, the
the plane
plane
spacing
spacing dd corresponding
corresponding to
to some
some high-angle
high-angle line,
line, or,
or, even
even more
more directly,
directly,

the 28
the 28 value
value of of the
the line,
line, isis plotted
plotted against
against composition
composition and and the
the resulting
resulting
curve
curve used
used in in exactly
exactly the
the same
same way
way as
as aa parameter-composition
parameter-composition curve.
curve. In
In
fact, the "parametric"
fact, the "parametric"
method
method could
could be
be based
based on
on the
the measurement
measurement of
of any
any
property of
property of the
the solid
solid solution
solution which
which changes
changes withwith thethe composition
composition of of the
the
solid solution, e.g.,
solid solution, e.g., its
its electric resistivity.
electric resistivity.
12-6)
12-6] TERNARY SYSTEMS 359
359

12-6
12-6 Ternary
Ternary systems.
systems. The determinationdetermination of of aa ternary
ternary phase phase diagram
diagram
is
is naturally
naturally more complicated
complicated than that that ofof a binary
binary diagram,
diagram, because because of of
the
the extra
extra composition
composition variable variable involved,
involved, but the the same general principles
general principles
can be applied.
applied. The x-ray x-ray methods described described above,
above, based on either either thethe
disappearing-phase
disappearing-phase or
or the
the parametric technique,
parametric technique, can be
be used
used with very
very
little
little modification
modification and have proved proved to to be very
very helpful
helpful in in the
the study
study of of ter-
ter-
nary systems.
nary systems.
Phase
Phase equilibria
equilibria in in aa ternary
ternary system
system can can only
only bebe represented
represented completely
completely
in three
in three dimensions,
dimensions, since there are three independent
since there are three independent variablesvariables (two (two com-
positions
positions and the the temperature).
temperature). The composition composition is plotted in
is plotted in an equi-
equi-
lateral
lateral triangle
triangle whose comers corners represent
represent the the three
three pure components, A,
pure components, A, B,B,
and C, C, and the the temperature
temperature is plotted at
is plotted at right
right angles
angles to to the plane of
the plane of the
the
composition
composition triangle.
triangle. Any
Any isothermal
isothermal sectionsection of of the
the three-dimensional
three-dimensional
model is is thus
thus an equilateral
equilateral triangle
triangle on which the phase equilibria
the phase equilibria at at that
that
temperature
temperature can be depicted depicted in in two dimensions.
dimensions. For this this reason
reason we usuallyusually
prefer to
prefer to study
study ternary
ternary systems
systems by by determining
determining the the phase equilibria at
phase equilibria at a a
number of of selected
selected temperatures.
temperatures. B
The study o one phase
phase
study of of aa ternary
ternary systemsystem of of
ct two phases
phases
components A,
components A, B,
B, and C begins begins with three
three phases
phases
aa determination
determination of of the
the three
three binary
binary
phase diagrams AB,
phase diagrams AB, Be, BC, and CA, CA, if if

these
these are
are not already known. We then
not already
make up up a a number of of ternary
ternary alloys,
alloys,
choosing
choosing their their compositions
compositions almost
at
at random but but with some regard regard for for
what
what the the binary
binary diagrams
diagrams may may sug-sug-
gest
gest the
the ternary
ternary equilibria
equilibria to be. The
to be.
diffraction patterns of
diffraction patterns of these
these explora-
explora- A c
tory alloys will
tory alloys will disclose
disclose the number
the number FIG.
FIG. 12-10.
12-10. Isothermal
Isothermal sectionsection ofof
and kind of of phases
phases at equilibrium
equilibrium in in hypothetiral
hypothetical ternary
ternary diagram.
diagram.
each
each alloyat
alloy at the
the temperature
temperature selected.selected.
These preliminary
These preliminary data
data will
will roughly
roughly delineate
delineate the the various
various phase phase fields
fields on

the isothermal section, and

the isothermal section, and will suggest will suggest what other
other alloys
alloys need be prepared
prepared
in
in order
order toto fix
fix the
the phase
phase boundaries
boundaries more exactly. exactly.
Suppose
Suppose these preliminary results
these preliminary results suggest
suggest an isothermal
isothermal section section of of the
the
kind
kind shown
shown in in Fig. 12-10, where
Fig. 12-10, where the phase boundaries
the phase boundaries have been drawn to
conform
conform to to the
the diffraction
diffraction resultsresults represented
represented by by the
the small
small circles.
circles. This
section
section shows
shows three
three terminal
terminal ternaryternary solidsolid solutions,
solutions, a, a, {j, and 'Y,
/3, joined in
7, joined in
pairs
pairs by by three
three two-phase
two-phase regions,regions, (a
(a ++ {J),
0), ({J
(ft++ 'Y),
7), and (a
(a +
+ 'Y),
7), and in
in
the
the center
center a a single region
single region where
where the
the three
three phases, a,
phases, a, 0, {J, and 'Y,
7, are in
in equi-
equi-
librium.
librium.
In
In aa single-phase
single-phase region region the the composition
composition of of the phase involved,
the phase involved, say say a,a, is
is

continuously variable.
continuously variable. In
In a
a two-phase
two-phase region region tie
tie line~
lines exist,
exist, justjust as
as in
in
360 PHASE-DIAGRAM DETERMINATION [CHAP. 12
[CHAP. 12

binary
binary diagrams,
diagrams, along
along which the
the relative
relative amounts of of the
the two phases
phases change
change
but not their
their compositions.
compositions. Thus in in the (a(a +
+ 1')
7) field
field of
of Fig.
Fig. 12-10,
12-10, tie
tie

lines
lines have been drawn to to connect the
the single-phase
single-phase compositions
compositions which are are
in
in equilibrium
equilibrium in in the
the tw(}-phase
two-phase field.
field. Along
Along the line
line de,
de, for
for example,
example, a of of
composition
composition d is
is in
in equilibrium
equilibrium with 'Y
y of
of composition
composition e, e, and the relative
relative
amounts of of these
these two phases
phases can be
be found by by the lever
lever law.
law. Thus the the con-
con-
stitution
stitution of
of alloy
alloy X is
is given by
given by the
the relation
relation

W..a (Xd)
W (Xd) = Wy (Xe).
= Woy(Xe).
Both thethe relative
relative amounts and the the compositions
compositions ofof the
the two phases
phases will
will vary
vary
along
along anyany line
line which is
is not
not a
a tie
tie line.
line.

In
In a three-phase
three-phase field,
field, the
the compositions
compositions of of the
the phases
phases are
are fixed
fixed and are
are
given by
given by the
the corners
corners of
of the
the three-phase
three-phase triangle.
triangle. Thus the
the compositions
compositions
of
of a, 0, and 'Y
a, {J, 7 which are
are at
at equilibrium
equilibrium in in any
any alloy
alloy within the three-phasf'
three-phase
field
field of
of Fig.
Fig. 12-10 are
are given by a,
given by a, b,
6, and c,
c, respectively.
respectively. To determine the the

~d / J
~-('
,",---o---o--~~v-- /
/
I
(,I a + "'t

A
(a)

8 /:l
fa :..
along all('
alou/!: nhc 0 alou/!: .I/ld
C>::
~
.....
""
;::\
-<
;x<
...::
Il..
fil
""
E=:
.....
< b ...::
...<
- PERCENT A A PERCENT A
- - PEHCENT
(h) (<')
(c)

FIG.
FIG. 12-11.
12-11. Parametric
Parametric method of
of locating
locating phase
phase boundaries
boundaries in
in tcmury
ternary diagrams.
diagrams.
 PROBLEMS 361
361

relative
relative amounts ofof these
these phases,
phases, say
say in
in alloy
alloy Y,
Y, we draw aa line through Y
line through
to
to any corner
any corner of
of the
the triangle,
triangle, say
say 6, apply the
b, and apply the lever
lever law:
law:
WI/(bY) = W"+'Y(Yg)
and
and
Wa.. (ag)
W (ag) = W y (ge).
= W'Y(ge).

These relations
These relations form
form the
the basis
basis of
of the
the disappearing-phase
disappearing-phase method ofof locat-
locat-
ing
ing the
the sides
sides and corners
corners of
of the
the three-phase triangle.
three-phase triangle.
Parametric methods are
Parametric are very
very useful
useful in
in locating
locating phase
phase boundaries
boundaries on all
all
portions of the
portions of the isothermal
isothermal section.
section. Suppose,
Suppose, for
for example,
example, that
that we wish
wish to
to
determine the
determine the aa/(a
/(a. +
+boundary of
'Y) boundary
7) of the
the phase
phase diagram
diagram in
in Fig.
Fig. 12-11 (a).
(a).
might prepare
Then we might prepare aa series of alloys
series of alloys along the line
along the line abc, where be
abc, where is aa
be is
tie line in the
tie line in the (a
(a +
+ 7)
'Y) field, and measure
field, measure the
the parameter
parameter of
of a in
in each
each one.
one.
resulting parameter-composition
The resulting parameter-composition curve
curve would then
then look
look like
like Fig.
Fig.
12-11(b), since the
12-ll(b), since the composition
composition and parameter
parameter of
of a in
in alloys
alloys along
along be is
be is
constant. However,
constant. However, we do
do not
not generally
generally know the
the direction
direction of
of the
the line
line be
be
at this stage,
at this because tie
stage, because tie lines
lines cannot be be located
located byby any
any geometrical
geometrical con- con-
struction but must be determined by
struction but by experiment.
experiment. But suppose
suppose we measure
the parameter of
the parameter of a along
along some arbitrary line, say
arbitrary line, the line
say the line Abd.
Abd. Then we
can
can expect
expect the
the parameter-composition
parameter-composition curve
curve to
to resemble
resemble Fig.
Fig. 12-11 (c).
12-1 l(c).
parameter of
The parameter a along
of a along thethe line
line bd is
bd is not
not constant,
constant, since bd is not a tie
since bd is not a tie

line,
line, but
but in
in general
general itit will
will change
change at at a
a different
different rate
rate than along
along the
the line
line Ab
in
in the
the one-phase
one-phase field.
field. This
This allows
allows us
us toto locate
locate the
the point
point b b on the
the phase
phase
boundary
boundary by by the point of
the point of inflection
inflection on the parameter curve.
the parameter curve.
point f/ on the
The point the (a (a + 'Y)/(a
7) /(a + tJ& + 'Y) 7) boundary
boundary can be be located
located in in
similar
similar fashion,
fashion, along
along a a line
line such
such as efg chosen
as efg chosen at at random. Along Along ef ef the
parameter
parameter of of a will
will change
change continuously,
continuously, because
because ef ef crosses
crosses over
over a a series
series ofof
tie
tie lines,
lines, but along
along fg fg in
in the
the three-phase
three-phase field
field the
the parameter
parameter of
of a will
will be
constant
constant and equal
equal toto the
the parameter
parameter of of saturated
saturated a a of
of composition
composition h. h. The
parameter-composition
parameter-composition curve
curve will
will therefore
therefore have the
the form of
of Fig. 12-1l(b).
Fig. 12-ll(b).

PROBLEMS

12-1. Metals
12-1. Metals A and and B form
form a a terminal
terminal solid
solid solution a, cubic
solution a, cubic in
in structure.
structure. The
variation
variation of of the
the lattice
lattice parameter
parameter of of a with
with composition,
composition, determined
determined by by quench-
quench-
ing
ing single-phase
single-phase alloys
alloys from
from anan elevated
elevated temperature,
temperature, is is found
found toto be
be linear,
linear, the
the
parameter
parameter varying
varying from
from 3.6060A
3.6060A for for pure
pure A to to 3.6140A
3.6140A in a containing
in a containing 4.04.0 weight
weight
percent
percent B. B. The solvus
solvus curve
curve is to be
is to be determined
determined by by quenching
quenching a a two-phase
two-phase alloy
alloy
containing
containing 5.0
5.0 weight percent
weight percent B from
from a
a series
series of
of temperatures
temperatures and measuring
measuring thethe
parameter
parameter of
of the
the contained
contained a.
a. How accurately
accurately must
must the
the parameter
parameter be
be measured
measured
ifif the
the solvus
solvus curve
curve is to be
is to be located
located within
within 0.1 0.1 weight
weight percent
percent B at at any
any tempera-
tempera-
ture?
ture?
12-2. The
12-2. The two-phase
two-phase alloy mentioned in
alloy mentioned in Prob.
Prob. 12-1,
12-1, after
after being
being quenched
quenched from
from
aa series of temperatures, contains
series of temperatures, contains a
a having
having the
the following
following measured
measured parameters:
parameters:
362
362 PHASE-D1AGRAM
PHASE-DIAGRAM DETERMINATION [CHAP. 12
[CHAP.

Temperature
Temperature Parameter
100C
100C 3.6082A
200 3.6086
3.6086
300 3.6091
3.6091
400 3.6098
3.6098
500
500 3.6106
3.6106
600
600 3.6118
3.6118

Plot
Plot the
the solvus
solvus curve
curve over
over this
this temperature
temperature range.
range. What is
is the
the solubility
solubility of
of B in
in
A at
at 440C?
440C?
 CHAPTER 13
13

ORDER-DISORDER TRANSFORMATIONS

13-1
13-1 Introduction.
Introduction. In most substitutional
substitutional solid solid solutions,
solutions, the the two
kinds of
kinds of atoms A and B are are arranged
arranged more or or less
less at
at random on the the atomic
sites
sites of
of the
the lattice.
lattice. In
In solutions
solutions of of this
this kind
kind the
the only
only major
major effect
effect of of a
change
change in in temperature
temperature is is to
to increase
increase oror decrease
decrease the
the amplitude
amplitude of of thermal
thermal
vibration.
vibration. But, But, as as noted inin Sec.
Sec. 2-7,
2-7, there
there are
are some solutioqs
solutions which have
this
this random structure only at
structure only at elevated
elevated temperatures.
temperatures. When these these solu-
solu-
tions
tions are
are cooled
cooled below a a certain
certain critical
critical temperature
temperature T r , the
TV, the A atoms
arrange
arrange themselves
themselves in in an orderly,
orderly, periodic
periodic manner on one set set of
of atomic
sites,
sites, and the
the B atoms do likewise
likewise on another
another set.
set. The solution
solution is
is then

said to
said to be ordered
ordered or or to possess aa superlaUice.
to possess superlattice. When this
this periodic arrange-
periodic arrange-
ment of of A and B atoms persistspersists over
over very
very large
large distances
distances in in the crystal, it
the crystal, it

is
is known as as long-range
long-range order.
order. If
If the
the ordered
ordered solution
solution is
is heated above T e,
c,

the
the atomic arrangement
arrangement becomes random again
again and the
the solution
solution is
is said
said to
to
be disordered.
disordered.
The change
change in in atom arrangement
arrangement which occurs occurs on ordering
ordering produces
produces
changes
changes in
in a
a large
large number of
of physical
physical and chemical
chemical properties
properties,f and the the
existence
existence of of ordering
ordering may may be inferred
inferred from some of
of these
these changes.
changes. How-
ever, the
ever, the only
only conclusive
conclusive evidence
evidence forfor aa disorder-order
disorder-order transformation
transformation is is a

particular
particular kind
kind of
of change
change in
in the
the x-ray
x-ray diffraction
diffraction pattern
pattern of
of the
the substance.
substance.
Evidence of of this
this kind was first
first obtained
obtained by by the
the American metallurgist
metallurgist Bain
in 1923,
in 1923, for a gold-copper solid solution having the composition AuCu
for a gold-copper solid solution having the composition AuCua. a.
Since that time,
Since that time, the
the same phenomenon
phenomenon has has been discovered
discovered in many
in many other
other
alloy
alloy systems.
systems.

13-2 Long-range
Long-range order order in in Aueua.
AuCua. The gold gold and copper
copper atoms of of
AuCua,
AuCu 3 above aa critical
,
critical temperature
temperature of of about
about 395C,
395C, are are arranged
arranged more or or
less at
less at random on the the atomic sites
sites of
of aa face-centered
face-centered cubic cubic lattice,
lattice, as
as illus-
illus-

trated
trated inin Fig. 13-1 (a). If
Fig. 13-1(a). If the
the disorder
disorder is is complete,
complete, the probability that
the probability that a
particular site is
particular site is occupied
occupied by by aa gold
gold atom is simply 1,
is simply f the
,
the atomic fraction
fraction
of
of gold
gold in
in the alloy, and the
the alloy, probability that
the probability that itit is
is occupied
occupied byby a copper
copper atom
is I,
is f the
,
the atomic fraction
fraction ofof copper.
copper. t!hese
/ These probabilities
probabilities areare the
the same forfor
every
every site
site and,
and, considering
considering the the structure
structure as whole, we can regard
as a whole, regard each
site
site as
as being occupied by
being occupied by aa statistically
statistically "average"
"average" gold-copper
gold-copper atom.
atom. Be-
low the
the critical
critical temperature,
temperature, the the gold
gold atoms in in a perfectly ordered
a perfectly ordered alloy
alloy
occupy only
occupy only the
the comer
corner positions
positions of
of the
the unit
unit cube
cube and the
the copper
copper atoms the
face-centered
face-centered positions,
positions, as
as illustrated
illustrated in
in Fig.
Fig. 13-1
13-1 (b).
(b). Both structures
structures are
are
cubic
cubic and have
have practically
practically the
the same lattice
lattice parameters.
parameters. FigureFigure 13-2
13-2 shows
363
364 ORDER-DISORDER TRANSFORMATIONS
ORDER-DISORDER TRANSFORMATIONS 13
[CHAP. 13
[CHAP.

o gold
gold atom
atom

0: I

o
copper atom
copper atom

0--.---- V_y "average"

'

'average"
gold-copper atom
gold-copper atom

(a)
(a) Disordered
Disordered (b)
(b) Ordered
Ordered

FIG. 13-1.
FIG. 13-1. Unit
Unit cells of the
cells of the disordered
disordered and
and ordered
ordered forms
forms of
of AuCu
AuCua.3 .

the two
how the two atomic
atomic arrangements
arrangements differ
differ on a particular
particular lattice
lattice plane.
plane. The
same kind
same kind of
of ordering
ordering has
has been
been observed
observed inin PtCu
PtCu3,3 FeNi 3a, MnNi 33, and , , ,

(MnFe)Ni3a.
(MnFe)Ni .

What differences
differences will
will exist
exist between
between the the diffraction
diffraction patterns
patterns of of ordered
ordered
and disordered
and disordered AuCu
AuCu3? 3 ? Since
Since there
there is
is only a
a very slight
only very slight changechange in
in the size
the size
of the unit cell on ordering,
of the unit cell on ordering, and none in
in its
its shape,
shape, there
there will
will be practically
practically
no change
no in the
change in the positions
positions ofof the
the diffraction
diffraction lines.
lines. But thethe change
change inin the
the
positions of
positions the atoms
of the atoms must necessarily
necessarily cause
cause aa change
change in line intensities.
in line intensities.
can determine
We can determine thethe nature
nature of
of these
these changes
changes by by calculating
calculating the
the structure
structure
factor F for
factor for each
each atom arrangement:
arrangement:
(a)
(a) Complete
Complete disorder.
disorder. The atomic
atomic scattering
scattering factor
factor ofof the "average"
"average"
gold-copper
gold-copper atom is
is given
given by
by
fay
/av =
= (atomic
(atomic fraction
fraction Au) Au +
Au) /fAu (atomic
(atomic fraction
fraction Cu) feu,
Cu) /c u ,

4/Au +
fay
/av
= l!Au
= + !ieu.
f/Cu-

There
There are
are four
four "average"
"average" atoms per
per unit cell,
cell, at 0 0, !
0, f !\ 0,
0, !
\0 !,
\, and
o !!.
\ \. Therefore
Therefore the
the structure
structure factor
factor is
is given
given byby
F =
F = "'1;f * (k u + kv +i w
2f eQ22 ,n(hu-Hv+lw),
i )

F == Av[l
fav[l +
+ ee T1 (hH) + eri(h+ll + eri(k+l)j.

Disordered Ordered

o e
Disordered

(
j gold
gold ^B copper
copper

FIG. 13-2. Atom arrangements

FIG. 13-2. arrangements on
on aa 11001
(100) plane,
plane, disordered
disordered and
and ordered
ordered AuCua.
AuCu 3.
13-21
13-2] LONG-RANGE ORDER IN AuCua
AuCu 3 365
By
By example
example (d)
(d) of
of Sec.
Sec. 4-6,
4-6, this
this becomes

= 4fav
F = = (fAu
4/av = (/Au +
+ 3fcu),
3/cu), for hkl unmixed,
for hkl unmixed,

F == 0,
0, for hkl mixed.
for hkl mixed.

We therefore
therefore find,
find, as
as might be expected,
might be expected, that
that the
the disordered
disordered alloy
alloy produces
produces
aa diffraction
diffraction pattern
pattern similar
similar to
to that
that of
of any
any face-centered
face-centered cubic
cubic metal,
metal, say
say
pure
pure gold
gold or
or pure
pure copper.
copper. No reflections
reflections of
of mixed indices
indices are present.
are present.
(b) Complete
(b) Complete order.
order. Each unit
unit cell
cell now contains
contains one gold
gold atom, at 000,
atom, at 0,
and three
three copper
copper atoms, at ,^ ,0,
atoms, at ^ 0, ,0"
^ f and 0 ,^ ,.
, f .

F
F == fAu
/A + fcu[e1l"i(hHl + e1l"i(h+ll + e1l"i(k+ll];
F == (/AU +
(fAu + 3fcu), for
3/cu), hkl unmixed,
for hkl unmixed,
(13-1)
(13-1)
= (fAu
F = -
(/AU - /Cu),
fcu), for hkl mixed.
for hkl

The ordered
ordered alloy
alloy thus produces diffraction
thus produces diffraction lines
lines for
for all
all values
values of hkl, and
of hkl,
its
its diffraction pattern therefore
diffraction pattern therefore resembles
resembles that that of of a
a simple
simple cubic
cubic substance.
substance.
In other
other words,
words, there
there has been a change change of of Bravais
Bravais lattice
lattice on ordering;
ordering; the the
Bravais lattice of
Bravais lattice of the
the disordered
disordered alloy
alloy is
is face-centered
face-centered cubic
cubic and that
that of
of the
the
ordered
ordered alloy simple
alloy simple cubic.cubic.
The diffraction
diffraction lines
lines from planes
planes of of unmixed indicesindices are
are called fundamen-
called fundamen-
tal lines,
tal lines, since
since they
they occur
occur at
at the
the same positions
positions and with with the
the same intensi-
intensi-
ties
ties in
in the
the patterns
patterns of of both
both ordered
ordered and disordered
disordered alloys.
alloys. The extra extra lines
lines
which appear
appear in in the
the pattern
pattern of of an ordered
ordered alloy,
alloy, arising
arising from planes planes of of
mixed indices,
indices, are called superlattice
are called superlattice lines,
lines, and their presence is
their presence is direct
direct evi-
evi-
dence that
dence that ordering
ordering has has taken
taken place.
place. The physical
physical reason
reason forfor the
the forma-
forma-
tion
tion ofof superlattice
superlattice lines
lines may
may be
be deduced from an examination
examination of
of Fig.
Fig. 13-1.
13-1.
Consider
Consider reflection
reflection from the the (100) planes
(100) planes of
of the
the disordered
disordered structure,
structure, and
let
let an incident
incident beam of of wavelength
wavelength X
X make such
such an angle
angle of of incidence
incidence 9 B
that
that the
the path
path difference
difference between
between rays
rays scattered
scattered by adjacent (100)
by adjacent (100) planes planes is
is

wavelength. But there

one whole wavelength. there isis another
another planeplane halfway
halfway between
between these these
two, containing,
two, containing, on the average, exactly
the average, exactly the the same distribution
distribution of of gold
gold and
copper
copper atoms.
atoms. This This plane
plane scatters
scatters a a wave whichwhich is is therefore
therefore X/2 X/2 outout ofof
phase
phase with the scattered by
the wave scattered by eIther
either adjacent
adjacent (100) plane and of
(100) plane of ex-
ex-
actly
actly the
the same amplitude.
amplitude. Complete
Complete cancellation
cancellation results
results and there there is is no

100 reflection.
reflection. In
In the
the ordered
ordered alloy,
alloy, on the the other
other hand,
hand, adjacent
adjacent (100) (100)
planes
planes contain
contain both gold gold and copper
copper atoms,
atoms, but but the plane halfway
the plane halfway between
contains
contains onlyonly copper
copper atoms.
atoms. The rays
rays scattered
scattered by
by the
the (100) plimes and
(100) planes
those
those scattered
scattered by by the
the midplanes
midplanes are
are still
still exactly
exactly out
out of
of phase,
phase, but
but they
they now
differ
differ in
in amplitude
amplitude because
because of
of the
the difference
difference in
in scattering power
scattering power of
of the
the gold
gold
and copper
copper atoms.
atoms. The ordered
ordered structure
structure therefore
therefore produces
produces a
a weak 100
100
reflection.
reflection. And as as Eqs. (13-1) show, all the superlattice
Eqs. (13-1) show, all the superlattice lines are lines are much
weaker thanthan thethe fundamental
fundamental lines, lines, since
since their
their structure
structure factors
factors involve
involve
366 ORDER-DISORDER TRANSFORMATIONS [CHAP. 13
[CHAP. 13

<a)

// I I

111
111 200 220
f/ f/ f/

(b) "

(c)

// 110
I 210//\\211
100
KM)
8
no
I

8
210 211
8 8

FIG. 13-3.
FIG. 13-3. Powder patterns
patterns of
of AuCua
AuCiis (very
(very coarse-grained)
coarse-grained) made with
with filtered
filtered
copper
copper radiation:
radiation: (a)
(a) quenched
quenched from 440C
440C (disordered);
(disordered); (b)
(b) held
held 30
30 min at
at 360C
360C
and quenched
quenched (partially
(partially ordered);
ordered) (c)
(c) slowly
slowly cooled
;
cooled from 360C
360C toto room tempera-
tempera-
ture
ture (completely
(completely ordered).
ordered).

the
the difference,
difference, rather
rather than the
the sum,
sum, of
of the
the atomic
atomic scattering
scattering factors
factors of
of each
each
atom.
atom. This effect is
This effect is shown quite
quite clearly
clearly in Fig.
in 13-3, where f/ and ss are
Fig. 13-3, are
used to
to designate
designate thethe fundamental and superlattice
superlattice lines,
lines, respeetively.
respectively.
At low temperatures,
temperatures, the the long-range
long-range order
order inin AuCua
AuCua is is virtually perfect
virtually perfect
but, as Tc
but, as T isis approached,
c approached, some randomness sets sets in.
in. This departure
departure from
perfect
perfect order
order can
can be
be described
described by
by means ofof the
the long-range
long-range order
order parameter
parameter
S,
S, defined
defined as
as follows:
follows:

S = (13-2)
(13-2)
i -F
where rTAA == fraction
fraction ofof A sites
sites occupied
occupied by by the
the "right"
"right" atoms,
atoms, i.e.,
i.e., A atoms,
atoms,
and FA = = fraction
fraction ofof A atoms in in the
the alloy.
alloy. When the
the long-range
long-range order
order isis

perfect,
perfect, fA
r A =
= 11 by definition,
by definition, and therefore
therefore S
$ =
= 1.
1. When the
the atomic
atomic
arrangement
arrangement is is completely
completely random,
random, fA rA = FA and S =
= FA = O.
0. For example,
example,
consider
consider 100 atoms of of AuCua, i.e.,
AuCus, i.e., 25
25 gold
gold atoms and 75
75 copper
copper atoms.
atoms.
Suppose
Suppose the
the ordering
ordering is
is not
not perfect
perfect and only
only 22
22 of
of these
these gold
gold atoms are
are on
on
"gold sites," i.e.,
"gold sites," i.e., cube comer
corner positions,
positions, the
the other
other 3
3 being
being on "copper
"copper sites."
sites."
Then,
Then, considering
considering the the gold
gold atom as as the
the A atom in in Eq.
Eq. (13-2),
(13-2), we find
find that
that
= it
rr A = f| =
= 0.88
0.88 and F
FA A =
= llJ o
-fifc =
= 0.25.
0.25. Therefore,
Therefore,
0.88 -- 0.25
0.88 0.25
S = =
= 0.84
0.84
1.00 -- 0.25
1.00 0.25

describes
describes the
the degree
degree of
of long-range
long-range order
order present.
present. The same result
result is
is ob-
ob-
tained if we consider
tained if consider the
the distribution
distribution of
of copper
copper atoms.
atoms.
13-21
13-2] LONG-RANGE ORDER IN
IN AuCu
Auera3 367
367

Any departure
Any departure from
from perfect
perfect long-range
long-range order
order in
in aa superlattice
superlattice causes
causes the
the
superlattice lines
superlattice lines to
to become weaker. It may
weaker. It may be
be that the
shown that the structure
structure
factors of
factors of partially
partially ordered
ordered AuCua
AuCua are
are given
given by
by
F =
= (/AU + 3/cu),
(JAu + for hkl
3fcu), for unmixed,
hkl unmixed,
(13-3)
(13-3)
F = S(fAu -
= S(/Au for hkl
feu), for
- /cu), mixed.
hkl mixed.
Comparing these
Comparing these equations
equations with with Eqs.
Eqs. (13-1),
(13-1), we note note that
that only
only the
the super-
super-
lattice lines are affected. But the
lattice lines are affected. the effect
effect isis aa strong
strong one,one, because
because the
the inten-
inten-
sity
sity of
of a
a superlattice
superlattice line
line is
is proportional
proportional to
to 1F12
\F\
2
and therefore
therefore to
to S2.
S.
2
For
example,
example, a
a decrease
decrease in
in order
order from
from S
K =
= 1.00
1 .00 to
to S =
= 0.84
0.84 decreases
decreases the
the in-
in-

tensity
tensity of
of a
a superlattice
superlattice line
line hy
by about
about 30
30 percent.
percent. The weakening
weakening of
of super-
super-
lattice lines
lattice lines by by partial
partial disorder
disorder is is illustrated
illustrated in in Fig.
Fig. 13-3.
13-3. By By comparing
comparing
the integrated
the integrated intensity
intensity ratio ratio of of aa superlattice
superlattice and fundamentalfundamental line, line, we
can determine
determine S experimentally.
experimentally.
can
Values of
Values of S obtained
obtained in in this
this wayway are are
i 1 o(l
t------~ __ s AuOus
shown in Fig. 13-4
in Fig. 13-4 as as a a function
function of of
08
the
the absolute temperature T,
absolute temperature T, expressed
expressed
as
as aa frartion
fraction of of the
the critical
critical tempera-
tempera- () 6
Of)
ture Te.
ture T e For
. For AuCu
AuCua3 the the value
value of of S ,<;
decreases
decreases gradually,
gradually, with increasing increasing 04
04
temperature,
temperature, to
to about
about 0.8
0.8 at
at Tc
T c and
then
then drops abruptly to
drops abruptly to zero.
zero. Above 02
Tc
T c the
the atomir
atomic distribution
distribution is is random
and
and there
there are are no no superlattice
superlattice lines. lines. o L---"'------'_--'_--'-_---L_---'--
()
044 0.5
0.5 06G 07 08 09 1.0
1.0
Recalling
Recalling the
the approximate
approximate law
law of
of con-
con-
TIT,
T/T
C
servation
servation of of diffracted
diffracted energy,
energy, already
already FIG.
FIG. \3-4.
13-4. Variation
Variation ofof the
the long-
long-
alluded to
alluded to in
in Ser.
Sec. 4-12,
4-12, Wl' we might
might ex- ex- range
range order parameter S with
order parameter with temper-
temper-
pert
pect that
that thethe energy
energy lostlost from the the su-su- ature, for
ature, for AuCu3
AuCu 3 and CuZn. (AuCua (AuCu 3

perlattice data
data from from D. D. T. Keating and B.
T. Keating B. E.
perlattice lines
lines should
should appear
appear in in some E.

form
form in in the
the pattern
Warren, J.
J. Appl. Phys.
P%s. 22, 286,1951;
pattern of of a a completely
completely Warren, Appl. 22, 286, 1951;
CuZn data from D.
data from D. Chipman
Chipman and
disordered
disordered alloy.alloy. As a a matter
matter of of fart
fact
B.
B. E. E. Warren, J.
Warren, J. Appl.
Appl. Phys. 21, 696,
Phys. 21, 696,
it
it does,
does, inin the
the form
form of of aa weak diffuse diffuse 1950.)
1950.)
background
background extending
extending over over the the whole
range
range of
of 28.
26. This
This diffuse
diffuse scattering
scattering is is due to to randomness,
randomness, and is is another

illustration
illustration of of the
the general
general law
law that
that any departure
any departure from perfect
perfect periodicity
periodicity
of
of atom
atom arrangement
arrangement results results in in some diffuse scattering at
diffuse scattering at non-Bragg
non-Bragg angles.
angles.
Von Laue showed
Laue showed that
that if
if two kinds
kinds of
of atoms A and B are
are distributed
distributed

completely at
completely at random
random in in a a solid
solid solution,
solution, then then thethe intensity
intensity of of the diffuse
diffuse

scattering
scattering produced
produced is is given
given by by
I D = k(fA - fB)2, (13-4)
where k
where k is
is aa constant for anyone
constant for any one composition,
composition, and /AfA and fB /B are atomic
scattering factors.
scattering factors. Both fA
/A and fB
/B decrease
decrease as
as (sin
(sin 0)/\ increases, and so
9)/>.. increases,
 368
368 ORDER-DISORDER TRANSFORMATIONS
ORDER-DISORDER TRANSFORMATIONS [CHAP. 13
[CHAP. 13

llOO~----------------------------------------------------~
1100

1000
1000

900
900

800
800

~
W~ 700
700
:::>
t>
a
Eo<
<
A::

~~~r
600
g
I
500
500 -

400
400 l-I
I
I
I
300i
300
I
I ,-J~
200 1
20U I I I I
AuCu
AuOu
I
j
-
() 10 20 30 40
40 50
50 {)(J
60 70
70 tlO 90
90 KK)
IOO
10 20 30
eu Au
Au
Ou ATOMIC PERC KNT Au
ATOMIC PERCENT
1
Au
1

FIG. not
FIG. 13-5.
3-5. Phase
Phase diagram
diagram of
of the
the gold-copper
gold-copper system.
system. Two-phase
Two-phase fields
fields not
1

labeled
labeled for lack of
for lack of room.
room. (Compiled from Metals
(Compiled from Metals Handbook,
Handbook, American
American Soeiety
Society
for A.I.M.E. 197,
1948; J. B. Newkirk, Trans. A.I.M.E. 197, S2:3, N. Rhines,
for Metals, 823, 1953;
1953; F.
F. N. Rhines,
Metals, 1948; J. B. Newkirk, Trans.
W.W. E.
E. Bond, and
and R.
R. A.
A. Rummel,
Rummel, Trans.
Trans, A.S.il-f.
A.S.M, 47,
47, 1955;
1955; R.
R. A.
A. Oriani. Ada Metal-
Onani, Acta Metal-
Bond,
lurgica 2,608,1954; and G. C. Kuczynski, unpublished
lurgica 2, 608, 1954; and G. C. Kuczynski, unpublished
result~.)
results.)

does
does their
their difference; therefore IIDD is maximum atat 2(J = 0 and
20 =
difference; therefore is aa maximum and decreases
decreases
as
as 28
20 increases.
increases. This This diffuse
diffuse scattering
scattering isis very
very difficult
difficult toto measure
measure experi-
experi-
mentally.
mentally. ItIt is
is weak
weak toto begin
begin with
with and
and is
issuperimposed
superimposed on
on other
otherforms
forms of
of

diffuse scattering
diffuse scattering that
that may
may also
also be
be present,
present, namely,
namely, Compton
Compton modified
modified
scattering, temperature-diffuse scattering, ete. etc. ItIt isis worth
worth noting, how-
noting, how-
scattering, temperature-diffuse scattering,
ever, that Eq. (13-4)
ever, that Eq. (13-4)
is
is quite general
quite general and
and applies
applies to
toany
any random
random solid
solidsolu-
solu-

tion, whether or not it is

tion, whether or not it is capable
capable of
of undergoing ordering
undergoing ordering at
at low
low tempera-
tempera-
tures.
tures. We WewiIIwillreturn
returnto tothis
thispoint
pointininSec.
Sec. 13-5.
13-5.
13-3]
13-3] OTHER EXAMPLES OF LONG-RANGE ORDER 369
369

Another aspect
aspect of of long-range
long-range order that requiresrequires some mention is is the
the
effect
effect ofof change
change in in composition.
composition. SinceSince the ratioratio of
of corner sites
sites toto face-
face-
centered
centered sites in the
sites in the AuCua
AuCu 3 lattice
lattice is
is 1 :3, it
1:3, it follows
follows that perfect
perfect order
order can
can
only be attained when the
only the ratio
ratio of
of gold
gold to to copper
copper atoms is is also
also exactly
exactly
1 :3.
1 :3. But ordering
ordering can alsoalso take place in
take place in alloys
alloys containing
containing somewhat more, more,
or
or somewhat less, less, than 25 atomic percent
percent gold,
gold, asas shown byby the phase dia-
the phase dia-
gram
gram of
of Fig.
Fig. 13-5.
13-5. (Here
(Here the
the ordered phase
phase is
is designated
designated a' to
'
to distinguish
distinguish
it
it from the disordered phase a stable
disordered phase stable atat high
high temperatures.)
temperatures.) In an ordered ordered
alloy containing
alloy containing somewhat more than 25 atomic percent gold,
percent gold, all
all the
the corner
corner
sites
sites are
are occupied by gold
occupied by gold atoms, atoms, and the
the remainder of
of the
the gold
gold atoms
occupy
occupy some of the face-centered sites normally
of the face-centered sites normally occupied
occupied byby copper
copper atoms.
atoms.
Just
Just the
the reverse
reverse isis true
true for
for an alloy
alloy containing
containing less less than 25
25 atomic percent
percent
gold. But,
gold. But, as as the
the phase
phase diagram
diagram shows,
shows, there
there are
are limits
limits to
to the
the variation
variation in in

composition which the ordered lattiee

composition lattice will
will accept
accept without becoming
becoming un- un-
stable.
stable. In fact,
fact, if
if the gold
gold content is is increased
increased to to about 50 atomic per- per-
cent, an entirely
cent, entirely different
different ordered alloy,
alloy, AuCu,
AuCu, can be formed.
formed.

13-3
13-3 Other examples
examples of of long-range
long-range order.
order. Before
Before considering
considering thethe or-
or-
dering
dering transformation in
in AuCu,
AuCu, which is
is rather
rather complex,
complex, we might
might examine
the
the behayiour
behaviour of of {3-brass.
/3-brass. This alloy
alloy isis stable
stable at
at room temperature
temperature overover a a
composition range
composition range of
of ahout
about 46 to
to almost 50 atomic percent zinc,
percent zinc, and so
so
may
may hebe represented
represented fairly
fairly eIosely
closely byby the
the formula CuZn. At high high tempera-
tempera-
tures its structure
tures its structure is, statistically, hody-centered
is, statistically, body-centered cubic, cubic, with
with the
the copper
copper and
zinc
zinc atoms distributed
distributed at at random. Below a a critical
critical temperature
temperature of of about
about
465C,
465C, ordering
ordering oeGurs;
occurs; thethe cell
cell corners
corners areare then