Structural Metallurgy (MTN 104)

Books:
Reed-Hill, R.E., Physical Metallurgy, 2nd Ed., East-West Press. 2008

Raghavan, V., Materials Science and Engineering: A First Course, 5th

Ed., Prentice Hall. 2009

Balasubramaniam,
B l b i R C
R., Callisters
lli t Materials
M t i l S
Science
i and
dEEngineering,
i i
8th Ed., Wiley. 2010

Credits: 4 Relative Weightage:

Lectures 3/week CWS: 25, MTE: 25, ETE: 50
Tutorial 1/week

Objective:
To impart knowledge on the arrangement of atoms in materials, defect
structures and their characterization techniques
 Structural Metallurgy (MTN 104)

Tutorial instruction
1. Discussion on selected tropics
2. Test on numerical problems on regular intervals,
at the semester end averaging out marks out of 20 20.
3. Overall attendance will carry 5 marks
4 Separate copy for tutorials,
4. tutorials loose sheets will not
checked by TA.
5. Certain tutorial problems will be repeated in mid and
end term examination.
6. Individual calculator is mandatory in tutorial class. Sharing
will not be permitted
permitted.
 Structural Metallurgy: Syllabus content

Chapter 1: Atomic structure of Solids

Atomic Bonding; Crystal systems and space lattice; Crystal structure of metals,
ceramics, polymers; Indexing crystallographic planes and directions, Diffraction
methods, Braggs law, Stereographic projections.

Chapter 2: Crystal imperfections

Point defects
defects, thermodynamics of defects
defects, Schottky and Frenkel imperfection,
imperfection
Krger-Vink notation, vacancy motion; Line defects Burgers vector; Frank-Reed
source, slip systems, climb and cross-slip, critical resolved shear stress,
dislocation interactions; Surface imperfections stacking faults, antiphase
b
boundary,
d grain
i b boundary,
d grain
i bboundaries
d i iin bl
blockk copolymers,
l magnetici d
domain
i
walls, walls in liquid crystals

Chapter 3: Microstructure
Structural hierarchy in metal forging, semicrystalline polymer; Deformation
microstructure and crystallographic texture, X-ray pole figure; Solidification
microstructure; Solid-solid transformation; Ni base superalloy
 Structural Metallurgy: Syllabus content

Chapter 4: Binary phase diagrams

Isomorphous system, lever rule, eutectic system, zone refining, peritectic
transformation,, monotectics,, intermediate phases,
p , Cu-Zn,, Fe-Fe3C,, etc

Chapter 5: Diffusion
Diffusion in ideal solution; Kirkendall effect; Darkens Equation; Ficks second law;
Mantano method; Determination of intrinsic diffusivities; Temperature dependence
of diffusion coefficient; Chemical diffusion; Grain boundary and surface diffusion

Chapter 6: Characterization technique

Imaging Optical microscopy, scanning electron microscopy, transmission electron
microscopy, scanning probe (STM, AFM); Structure X-ray diffraction, Low energy
electron diffraction (LEED); Composition X-ray photoelectron spectroscopy (XPS),
X-ray energy dispersive spectroscopy (EDS)
(EDS), Auger electron spectroscopy (AES)
(AES),
secondary ion mass spectroscopy (SIMS), Rutherford backscattering (RB); Thermal
and gravimetric analysis
 Atomic structure of Solids

An atom is the smallest constituent unit of ordinary

Matter that has the properties of a chemical element.
Every solid, liquid, gas and plasma is composed of
neutral or ionized atoms. Atoms are very small; typical
sizes are in .

Atoms lack a well-defined outer boundary, so their

dimensions are usually described in terms of an atomic
radius.

Atomic arrangement
On the
O th periodic
i di ttable
bl off the
th elements:
l t
atom size tends to increase when moving down columns, but
decrease when moving across rows (left to right).

Consequently, the smallest atom is helium with a radius of 0.32 , while one of the
largest is caesium at 2.25 .
 Atomic structure of Solids

Atomic
At i bbonding:
di B di fforces d
Bonding develop
l as atoms
t are b
brought
ht iinto
t proximity
i it tto each
h
other. The nature of the bonding forces has a direct effect upon the type of solid
structure which develops and therefore upon the physical properties of the material.

Melting point provides a useful indication of the amount of thermal energy needed to
sever these interatomic (or interionic) bonds.
some solids melt at relatively low temperatures (m.p. of tin = 232C)
ceramics melt at extremely high temperatures (m (m.p.
p of alumina exceeds 2000C)
2000 C).

Customarily we identify four principal types of bonding in materials, namely:

metallic bonding,
ionic bonding,
covalent bonding

However, in many solid materials it is possible for bonding to be mixed, or even

intermediate, in character.
 Atomic structure of Solids
Metallic bonding: the elements with the most pronounced metallic characteristics
are grouped on the left-hand side of the Periodic Table
Table. In general
general, they have a few
valence electrons in the outermost orbital, which are relatively easy to detach.

Each atom in a metal donates one or more valence electrons forming a common pool
of electron cloud/gas
cloud/gas. The 'free'
free valence electron in this way is shared among all atoms
(or more specifically among the regular array of positively-charged cations), rather than
associated with an individual atom. The bond results because the metal atoms become
somewhat positively charged due to loss of their electrons while the electron cloud
remains surrounded to them.
Metallic bonding may be seen as an
extreme example of delocalization of
electrons over a large system of
covalent bonds, in which every atom
participates. Therefore, metallic
bonding is more collective in nature
in terms of sharing of the electrons
and non-directional.
 Atomic structure of Solids
Ionic bonding: For ionic bond to take place one element is usually electropositive and
other
th iis electronegative,
l t ti th
thus existing
i ti a llarge electronegativity
l t ti it difference.
diff
There is no precise value that distinguishes ionic from covalent bonding, but a difference
of electronegativity of over 1.7 is likely to be ionic, and a difference of less than 1.7 is
likelyy to be covalent.

The ionic bond develops when electron(s) are transferred from atoms of active metallic
elements (electropositive) to atoms of active non-metallic elements (electronegative),
thereby enabling each of the resultant ions to attain a stable closed shell
shell.

For example, the ionic structure of magnesia (MgO),

a ceramic oxide, forms when each magnesium atom
(Z = 12) loses two electrons from its L-shell (n = 2)
and these electrons are acquired by an oxygen atom
(Z = 8), producing a stable octet configuration in its
L-shell Overall
L-shell. Overall, the ionic charges balance and the
structure is electrically neutral.

Ionic bonding is non-directional, essentially electrostatic in character

and can be extremely strong; for instance, magnesia
is a very useful refractory oxide (m.p. = 2930C).
 Atomic structure of Solids
Covalent bonding: The prefix co- means jointly thus a "co-valent bond", in essence,
means that the atoms share valence. The covalent bonding g thus occurs by y the sharingg
of electrons between neighbouring atoms. This is in contrast to the transfer of electrons
from one atom to another in the ionic bonding.
It occurs when valence electrons of
opposite spin from adjacent atoms
are able to pair within overlapping
spatially-directed orbitals, thereby
enabling each atom to attain a
stable electronic configuration

Covalencyy is g
greatest between atoms of similar electronegativities.
g
Consider first the formation of a hydrogen molecule. When two hydrogen atoms are very
far apart, they do not interact, and the lone electrons of the atoms stay in their respective
1s gground states. When the atoms come closer , the electron p probablity
y cloud of the 1s
states overlaps. As the 1s orbitals can have two electrons of opposite spin, the sharing
of electrons between two atoms takes place.
Furthermore, the electrons pparticipating
p g in the bonds are tightly
g y bound so that covalent
solids, in general, have low electrical conductivity and act as insulators, sometimes
as semiconductors (e.g. silicon). Carbon in the form of diamond is an interesting
prototype for covalent bonding.
 Atomic structure of Solids
Sharing of electrons and the formation of covalent bonds readily occurs between atoms
which have unfilled p orbitals. The p orbitals are directional in nature and hence permit
efficient ovrlapping of the orbitals in the direction of the maximum electron probablity
density.
This process by which s-orbitals and p-orbitals combine to form projecting hybrid sp-
orbitals is known as hybridization. In general, a large degree of overlap of sp-orbitals
and/or a high electron density within the overlap 'cloud' will lead to an increase in the
strength of the covalent bond
bond.

An end-to end overlap of p orbitals giving rise to (sigma) bond. When there is a lateral
overlap of p orbitals, (pi) bonds are said to form.
 Atomic structure of Solids
Conductivity: The thermal and electrical conductivities of a solid are, to a large extent,
depend on the presence of free electrons in the solid.
In ionic solids, the electron transfer produces the stable inert gas configuration around
both the cations and the anions. Hence, there are no free electrons in ionic solids.
Likewise, covalent bonding produces the inert gas configuration around atoms sharing
the electrons, with the result that there are no free electrons here either.
Hence, typical ionic and covalent materials are good thermal and electrical insulators.
In contrast, metals have free
f electrons and are therefore
f good conductors off heat and
electricity.

Mechanical properties of solids are dependent on the strength of the bonds as well as
the directional nature of bonding. Solids with strong and directional bonds tend to be
brittle. For example, covalently bonded diamond is very hard and brittle.
As metallic bonds are relatively weak and nondirectional, metals are soft, ductile and
malleable. They can change their shape permanently without breaking.
Ionic solids fall in between covalent and metallic solids in that theyy mayy exhibit a veryy
limited amount of ductility.
 Atomic structure of Solids
Crystalline: Periodic arrangement of atoms in 3D
Ex.- Metals, Ceramics etc.
There exists a long range ordering of atoms
Densed,
Densed ordered packing of atoms
The free energy of the crystalline state is always
lower than that of the noncrystalline state.

Noncrystalline/amorphous: Atoms without periodic arrangement, ex, Glass

Slow cooling rates allow enough time for crystallization, while fast cooling rates may
prevent crystallization altogether
altogether.
The rate of cooling which is considered as slow or fast will vary widely for different
materials, depending on the magnitude of the kinetic barrier.
Metal cooling rate required to prevent crystallization may be as high as 106 K s-11.
silicate cooling at the rate of a fraction of K per hour may be sufficient to prevent
crystallization.
There exists a short range ordering of atoms
Non densed, random packing of atoms
 Atomic structure of Solids
single
C
Crystalline
t lli

Single Crystal Poly Crystal

A crystalline solid can be either a single crystal or polycrystal.

Single crystal: entire solid consists of only one crystal. No grain boundaries.
Difficult
Diffi lt tto achieve
hi and
d costly
tl tto synthesize.
th i
thermodynamically more stable due to lack of defects, like grain boundaries,
triple junction, dislocations etc.

Polycrystalline: an aggregate of many crystals separated by well-defined boundaries.

natural product and thus relative less costly to synthesize.
thermodynamically less stable due to lack of defects, like grain boundaries,
triple junction
junction, dislocations etc
etc.

free energy (G) comparison: Gamorphous>Gpolycrystalline> Gsingle crystalline

 Introduction to crystallography and crystal system
Space Lattice: Space lattice is defined as an array of points in three dimensions in
which every point has identical to that every other points in the array.

Unit cell: It is a subdivision of a lattice that still retains

the overall characteristic of the entire lattice. More
precisely, a unit cell is the smallest unit which, when
repeated in space indefinitely, will generate the
space lattice.

Lattice point: If each atom in lattice is replaced by a

point, then each point is called lattice point.
A three-dimensional space lattice is generated by repeated translation of three
noncoplanar vectors, a , b and c.

There are only 14 distinct arrangement of lattice points possible in three

three-dimensional
dimensional
space lattice. These unique arrangement of lattice points are known as Bravais lattices.

Theyy belong
g to seven crystal
y systems.
y

Lattice points are located at the corner of the unit cells and, in some cases, at either
faces or the center of the unit cell.
 The Bravais Lattices
Crystal Spacelattice Unitcell Number ofnearest
System neighbours, i.e.
neighbours,i.e.
Coordinationno
I.Cubic (1) Simple (Lattice
points at the eight
p g
a=b=c corners of the unit
===90 cell)

Si l cubic=6
Simple bi 6

(2) Body centered CN=8

(Points at the eight
corners and at the
body center)

(3) Face centered CN=12

(Points at the eight
corners and at the
six face centres)
 The Bravais Lattices

Crystal System Space lattice Unit cell

II Tetragonal
II.Tetragonal (4) Simple (points at the
eight corners of the
a=bc unit cell)
===90

(5) Body centered

(Points at the eight
corners
co esa and d at tthe
e
body center)
 The Bravais Lattices
Crystal
y System
y Space
p lattice Unit cell
III.Orthorhombic (6) Simple (Lattice
points at the eight
abc corners of the unit
===90 cell)

(7) Base centered

(Points at the eight
corners and at two
face centres
opposite to each
other)
th )
(8) Body centered
(Points at the eight
corners and d att th
the
body center)
(9) Face centered
(P i t att the
(Points th eight
i ht
corners and at the
six face centres)
 The Bravais Lattices
C t lS t
CrystalSystem S
Spacelattice
l tti U it ll
Unitcell

IV.Rhombohedral (10) Simple (points at the

eight corners of the unit
a=b=c cell)
==90

V.Hexagonal (11) Simple [(i)points at

the eight corners of the
a=bc unit cell outlined by thick
==90
==90 lines
=120
or (ii) points at the twelve
corners of the hexagonal
prism and at the centres
of the two hexagonal
faces]
 The Bravais Lattices

C
CrystalSystem
lS S
Spacelattice
l i U i ll
Unitcell

IV.Monoclinic (12) Simple (points at

the eight corners of the
abc unit cell)
==90

(13) b
base-centred
t d
(Points at the eight
corners and at two face
centres opposite
pp to
each other)

V.Triclinic (14) Simple (points at

the eight corners of the
abc unit cell)
90
 Crystallographic planes-indexing
Algorithm
1. Read off intercepts of plane with axes in terms of a, b, c
2. Take reciprocals of intercepts
3. Cleared of fractions and reduce to smallest integer values
4. Enclose in parentheses, no commas i.e. (hkl)
Crystallographic planes-indexing

All parallel
ll l planes
l h
have
same Miller indices.
Crystallographic planes-indexing

Shift origin for inverse plane

 Lattice/intrplanar Spacing

-The
The distance between two adjacent parallel planes
of atoms with the same Miller indices is called the
interplanar spacing, dhkl.
a
- for cubic materials : d hkl
h2 k 2 l 2

Lines of lowest indices have the greatest spacing and the greatest
density of lattice points
Angle
A l between
b t two
t planes
l
(h1k1l1) and (h2k2l2)
h1h2 k1k 2 l1l2
cos
h12 k12 l12 h22 k 22 l22
 Crystallographic Direction-significance

Metals deform more easily, for example, in directions along which atoms are in
closest contact.

Another real-world example is the dependence of the magnetic properties of iron

and other magnetic materials on the crystallographic directions.

It is much easier to magnetize iron in the [100] direction compared to [111] or [110]
directions. This is why the grains in Fe-Si steels used in magnetic applications are
oriented in the [100] or equivalent directions.
In the case of magnetic materials used for recording media, we have to make sure
the grains are aligned in a particular crystallographic direction such that the stored
information is not erased easily.

Similarly crystals used for making turbine blades are aligned along certain directions
f better
for b tt mechanical
h i l properties.
ti
 Crystallographic direction-indexing

Algorithm:
1. Vector repositioned (if necessary) to pass through origin.
2. Read off projections in terms of unit cell dimensions a, b, and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas [uvw]
ex: 1, 0, => 2, 0, 1 => [201]
5. Family of [110] directions is designated as <110>

Some directions in cubic crystals:

 Atomic packing fraction-FCC
Each unit cell has:
eight 1/8 atom at corners
six atoms at the center of six faces
Therefore,
Th f each
h unitit cellll
has (8x1/8)+(6x1/2)=4 atoms

volume of atoms in unit cell

APF
Volume of unit cell
4r 3
But ; Vatoms 4 16.746r 3 Atoms contact each other across cube diagonal,
3
3
therefore,
4r a 2 a 2 ( 4r ) 2
Vunit cell a 3 22.64r
3

2
16.746r 3
a 2 2
( 4r ) 2
Therefore; APF 3
0.74 4r
22.64r a
2
That is,
is 74% of the volume of the FCC unit cell
is occupied by atoms and the remaining 26% is
empty space.
 Atomic packing fraction-BCC
b
Each unit cell has:
eight 1/8 atom at corners
1 full atom at the center
Therefore,
Th f each
h unitit cellll
has (8x1/8)+1=2 atoms

volume of atoms in unit cell

APF
Volume of unit cell
Atoms contact each other at cube diagonal,
4r
3
Therefore,
But ; Vatoms 2 8.373r 3
3
b 2 a 2 a 2 2a 2
4r 2 b 2 a 2 2a 2 a 2
3
4r
Vunit cell a
3
12.32r 3
3 4r
a
8.723r 3 3
Therefore; APF 3
0.68
12.32r

That is,
is 68% of the volume of the BCC
unit cell is occupied by atoms and the
remaining 32% is empty space.
Atomic packing fraction-BCC
 Planar atomic density

Planar atomic density :

Equivalent number of atoms whose centers are insected by selected area
p
Selected area

Example:
p In Iron ((BCC, a=0.287 nm), ) the (110)
( ) plane
p intersects center of 5 atoms
(four and 1 full atom). Calculate the planar atomic density.

Solution :
1
- Equivalent number of atoms 4 1 2 atoms
4
- Area of (110) plane a 2 a a 2 2
2
Planar density, p
(0.287) 2 2
17.2 atoms

nm 2
1.72 1019 atoms/m 2
 Linear atomic density

Linear atomic density :

Number of atom intersecting direction vector
L
unit length of direction vector

Example: For a FCC copper crystal(a=0.361 nm), the [110] direction intersects 2 half
diameters and 1 full diameter.

Solution :
- The number of atomic diameters intersected by this length
1 1
of line are : 1 2 atomic daimeters
2 2
- The length of the line a 2 0.361 2 nm

2 atoms
i.e. L
0.361 2
3.92
3 92 atoms/
t / nm
3.92 109 atoms/ m
 XRaydiffraction
X-rays are usually used as medium to perform diffraction in crystals. It helps in
Identifying the crystal structure
Calculate lattice parameter
(The wave length (0.5 2.5 ) of X-Ray is same as distance between crystal lattice planes).
Measure stresses in the material
Measure crystallographic texture

Generation: When electrons moving at high speeds are directed to a metal target
target,
a small percentage of their kinetic energy is converted into X-Rays.
 SomeaspectofXrays
x-rays are electromagnetic radiation of exactly the same nature as light but of very
much shorter wavelength.

x-rays used in diffraction have wavelengths lying approximately in the range 0.5-2.5A,
whereas the wavelength of visible light is of the order of 6000A.

X-ray is much more penetrating than light and could easily pass through the human
body, wood, quite thick pieces of metal, and other "opaque" objects.

By placing a source of x-rays on one side of the object and photographic film on the
other, a shadow picture, or radiograph, could be made, the less dense portions of the
object
j allowing
gaggreater p
proportion
p of the x-radiation to p
pass through
g than the more
dense. In this way the point of fracture in a broken bone or the position of a crack in a
metal casting could be located.
 XRayproduction
1 2
KE eV mv
2
e charge of electron 4.8 10 10 esu
V voltage across electrode 30 kV
m mass of electron 9.1 10 28 gm
v velocity just before impact

c
eV h h [ignoring loss of energy]

1
V

Electrons are usually used for this purpose, the radiation being produced in an x-ray
tube which contains a source of electrons and two metal electrodes.

The high voltage maintained across these electrodes

electrodes, some tens of thousands of volts
volts,
rapidly draws the electrons to the anode, or target, which they strike with very high velocity

X-rays
y are p
produced at the p
point of impact
p and radiate in all directions.

Most of the kinetic energy of the electrons striking the target is converted into heat, less
than 1 percent being transformed into x-rays.
 XRayproduction
Target: The spectrum is caused by the rapid declaration of electrons by the target,
the origin of the characteristic spectrum lies in the atoms of the target metal itself
itself.

If one of the electrons bombarding the target has sufficient kinetic energy, it can knock
an electron out of the K shell, leaving the atom in an excited, high-energy state.
O off the
One th outer
t electrons
l t immediately
i di t l falls
f ll iinto
t th
the vacancy iin th
the K shell,
h ll emitting
itti
energy in the process, and the atom is once again in its normal energy state.

The
eeenergy
e gy e
emitted
ed iss in the
e form
o o of radiation
ad a o o of a de
definite
e
wavelength and is, in fact, characteristic K radiation.

The K-shell vacancy may be

filled by an electron from any
one of the outer shells, thus
giving rise to a series of K
Lines; K and K lines.

it is more probable that a K-shell

vacancy will be filled by an L electron
than by an M electron,
electron and the result
is that the K line is stronger than the
K line.
 Diffractionbyatoms
Similarity - from prior knowledge
Diffraction of visible light by a ruled grating
Wave encounter set of regularly spaced scattering objects
Wavelength of wave in question has same order of magnitude as of spacing
between scattering centers

German physicist von Laue reasoned

If crystals
l are composed
d off regularly
l l spaced
d atoms - can act as scattering
i
centers for x-rays.
If x-rays have wavelength about equal to interatomic distance in crystal

It should be possible to diffract x-rays by means of crystals

 XRaydiffraction
Crystal planes of target metal act as mirror reflecting X-Ray beam.
If rays leaving a set of planes are out of phase (as in case of arbitrary angle of incidence
no reinforced beam is produced.
If rays leaving are in phase, reinforced beams are produced.

Wave 1 Resultantwave

A
Constructive A A 2A
A+A=2A
(inphase)
Wave 2
A

Wave 3 Destructive
Outofphase AA=0
A
 XRaydiffraction
A beam of X-Rays of wave length , impinging at an angle can be real only if the rays
from each successive plane reinforce each other.
For this to be the case, the extra distance a ray, scattered from each successive plane,
has to travel, i.e., the path difference (PNQ), must be equal to an integral number of
wave length
length, n 1
1

2
n= PN+NQ 2
=2ONsin O
=2dsin
d = interplanar spacing P Q Crystal planes
N

For constructive interference the distance PNQ travelled by 2

2-2
2 should be equal to n

Bragg
gg law n 2d sin Essential condition for diffraction

Diffraction can occur whenever the Bragg law is satisfied.

 XRayfordiffraction
The angle between the diffracted beam and the transmitted beam is always 2 2.
This is known as the diffraction angle, and it is this angle, rather than

y, we mayy write: n sin 1

Since sin cannot exceed unity,
2d

Therefore, n must be less than 2d.

For diffraction, the smallest value of n is 1. (n =0; corresponds to the beam diffracted in
the same direction as the transmitted beam. It cannot be observed.)

Therefore the condition for diffraction at any observable angle 2 is < 2d.
2d
For most sets of crystal planes d is of the order of 3A or less, which means that
cannot exceed about 6A.

A crystal could not possibly diffract ultraviolet radiation, for example, of

wavelength about 500A. On the other hand, if is very small (gama rays), the
diffraction angles are too small to be conveniently measured.
 X-Ray for diffraction
Diffraction is essentiallyy a scattering
gpphenomenon in which a large
g number of atoms
cooperate. Since the atoms are arranged periodically on a lattice, the rays scattered
by them have definite phase relations between them; these phase relations are such

that destructive interference occurs in most directions of scattering,

scattering but in a few
directions constructive interference takes place and diffracted beams are formed.

Diffraction and reflection, however, differ fundamentally in at least three aspects:

(1) The diffracted beam from a crystal is built up of rays scattered by all the atoms of
the crystal which lie in the path of the incident beam.
The reflection of visible light takes place in a thin surface layer only
only.

(2) The diffraction of monochromatic x-rays takes place only at those particular angles
of incidence which satisfyy the Bragggg law.
The reflection of visible light takes place at any angle of incidence.

(3) The reflection of visible light by a good mirror is almost 100 percent efficient.
The intensity of a diffracted xx-ray
ray beam is extremely small compared to that of the
incident beam.
 Determination of crystal structure by structure factor rule
XRayfordiffraction
Intensityy as a function of atom p
position ((atomic arrangement)
g )

The resultant wave scattered by all the atoms of the unit cell is called the
structure factor and is designated by the symbol (F).

F f 1e 2 i ( hu1 kv1 lw1 )

f 2e 2 i ( hu 2 kv2 lw2 )
f 3e 2 i ( hu3 kv3 lw3 )

f atomic scattering factor; it is related to sum of the waves scattered by

electrons that is present in an atom. So f is related to atomic number Z.
uvw coordinates of the atoms in a unit cell
(hkL) plane

Adding together all the waves scattered by individual atoms

N
F f ne 2 i ( hu n kvn lwn )

Intensityy is proportional
p p to square
q of amplitude
p
2
IF
Determination of crystal structure by structure factor rule

Forexample,structurefactorofBCCcell

This cell has two atoms of the same kind located at 0 0 0 and

2 i ( h.0 k .0 l .0 ) 2 i ( h. 12 k . 12 l . 12 )
F fe fe
F f [1 e i ( h k l ) ]
F 2f h (h k l) is
when i even;
F2 4 f 2

F 0 when (h k l) is odd e i cos i sin

no diffractio
diff ti n Also e i e3 i e5 i 1
e 2 i e 4 i e 6 i 1
 Determination of crystal structure by structure factor rule

Forexample,structurefactoroffCC cell

This cell has four atoms of the same kind located

at 0 0 0 and 0 , 0 , 0

2 i ( h.0 k .0 l .0 ) 2 i ( h. 12 k . 12 l .0 ) 2 i ( h. 12 k .0 l . 12 ) 2 i ( h.0 k . 12 l . 12 )
F fe fe fe fe
F f [1 e i ( h k ) e i ( h l ) e i ( k l ) ]

generally, in fcc materials, diffraction occur from (111), (200), (220) etc
not from various other planes such as (100), (210), (112), etc.
e i cos i sin
Structure factor indentifies which plane to provide e i e3 i e5 i 1
diffraction and which are not.
e 2 i e 4 i e 6 i 1
 2d sin [Bragg's law]
2
sin 2
2

4d
2 2 1 h2 k 2 l 2
2 (h k 2 l 2 ) cubic : 2 2
4a d a
sin 2 (h 2 k 2 l 2 ) [ and a are constant]

Bravais lattice Reflection present Reflection absent

Simple all None
Base centered h and k unmixed h and k mixed
Body centered (h+k+l) even (h+k+l) odd
Face centered h k and l unmixed h k and l mixed (odd+even)
(either all odd/all even)
Allowedreflectionforcubiclattices
Primitiveh2 +k2 +l2 =1,2,3,4,5,6,8,9,10,11,12,13,14,16
Body centered h2 +k
Bodycenteredh + k2 +l
+ l2 =2,4,6,8,10,12,14,16
= 2 4 6 8 10 12 14 16
Facecenteredh2 +k2 +l2 =3,4,8,11,12,16,19,20,24,27,32
Diamondcubich2 +k2 +l2 =3,8,11,16,19,24,27,32
 Allowedreflectionforcubiclattices
B d t d h2 +kk2 +ll2 =2,4,6,8,10,12,14,16
Bodycenteredh 2 4 6 8 10 12 14 16

d spacing value :
a
d hkl
h2 k 2 l 2
a
d110 0.7 a
2
a
d 200 0.5a
4
a
d 211 0.4a
6

N
Peak intensity depends structure factor
i.e. atomic number Z, and typical (hkl) giving finite F.
F f n e 2 i ( hu kv lw )
n n n

since (fixed) =2d sin ; smaller the d-spacing larger the

Allowedreflectionforcubiclattices
Facecenteredh2 +k2 +l2 =3,4,8,11,12,16,19,20,24,27,32
, , , , , , , , , ,

d spacing value :
a
d hkl
h2 k 2 l 2
a
d111 0.58a
3
a
d 200 0.5a
4
a
d 220 0.35a
8

Peak intensity (I) depends on structure factor F

since (fixed) =2d sin ; smaller the d-spacing larger the
XRD patterns taken from a series of the Al-based glassy alloys from the ternary
to the quinary system, for
f as-spun ribbons, wedge-casting samples and as-cast rods
1 mm in diameter.

no long range periodicity

no clear peak
 Stereographic projection
The stereographic projection is a convenient way to depict 3-D information
about crystallographic planes and directions on a 2-D drawing.
Angular relationships among faces, crystal edges, atomic planes, zones
and crystallographic symmetry elements can be displayed and solved
Angular relationships are preserved in this projection

Usedfor
Determiningcrystalorientation
Determining crystal orientation
Determiningthecrystallographicindicesofsurfacemarkings slip
lines twins deformation band
linestwins,deformationband
Crystallographicinformationofphasetransformation
Preferredorientationofpolycrystallinematerials(texture)
Preferred orientation of polycrystalline materials (texture)
 Concept and plotting

1. Assume crystal (or unit cell) to be very small so that all crystal planes
passes through center located exactly at the center of a sphere (reference)
2 Crystal planes and their normals extend them till they intersect the sphere
2.
3. The point where normal cut the sphere is called Pole of the plane
4. Plane cutting
g sphere
p trace of a plane
p (great
(g circle))
Poles of cubic crystal
Multiple figures are required to understand planes. Stereographic projections show
all planes in a single figure.
Standard (001) stereographic projection of cubic crystal
Sphere can be symmetrically
divided into four slice
take one quarter at a time.
Z-axis pointing straight
towards you.

Yaxis

xaxis
 Interstitial sites
Interstitial sites:
Interstitial atoms usually enter into the void (ex. octahedral/tetrahedral) sites in a
crystal forming solid solution.
The
Th extent
t t off solid
lid solubility
l bilit ddepends
d on th
the compatibility
tibilit b
between
t void
id size
i and d
diameter of the interstitial atoms (e.g. H,C,N,O,B).

Octahedral site: An interstitial p

position has a coordination number of six. An atom
or ion in the octahedral site touches six other atoms or ions.
Tetrahedral site: An interstitial position that has a coordination number of four.
An atom or ion in the tetrahedral site touches four other atoms or ions.

Octahedral voids tetrahedral voids

octa= eight; tetra=four
hedral= faces hedral= faces
 Carbon dissolves more in austenite (~2%) than in ferrite (0.025%) Why?
austenite
t it (fcc)
(f ) iis more closed-packed
l d k d th
than ferrite
f it (bcc),
(b ) still
till it di
dissolves
l more carbon.
b

fcc bcc

Carbon

Carbon atoms prefer octahedral voids over tetrahedral

((though
g larger
g in size)) in bcc for the ease of strain relaxation.

C (0.80 ) in ferrite (bcc) to occupy octahedral site (0.19).

size difference is large poor solid solubility
C (0.80 )
in austenite (fcc) to occupy octahedral site (0.51).

size difference is less better solid solubility.
Nevertheless, lattice strain is inevitable in both the cases to limit solid solubility up to 2%
Interstitial sites