Uses of X-Ray Powder Diffraction

Identification of single-phase materials minerals,

chemical compounds, ceramics or other engineered
materials.
Identification of multiple phases in microcrystalline mixtures
(i.e., rocks)
Determination of the crystal structure of identified materials
Identification and structural analysis of clay minerals
Recognition of amorphous materials in partially crystalline
mixtures

Bragg diffraction

Bragg diffraction a deeper look!

When x-rays are incident on an atom, they
make the electronic cloud move as does any
electromagnetic wave. The movt of these
charges re-radiates waves with the same
frequency (blurred slightly due to a variety of
effects); this phenomenon is known as
Rayleigh scattering (or elastic scattering).
The scattered waves can themselves be scattered but this secondary scattering is assumed to be
negligible.
These re-emitted waves interfere with each
other either constructively or destructively
(overlapping waves either add together to
produce stronger peaks or subtract from each
other to some degree), producing a diffraction
pattern on a detector or film.

The resulting wave interference pattern is the basis of diffraction analysis.

Bragg diffraction or reflection?

This incoming photon interacts with the electrons in the crystal and scatters
in a coherent manner (Thompson scattering). Incoherent scattering
(Compton scattering) will not result in diffraction. The scatter is a very small
amplitude event and happens in all directions.
In select directions (due to the regular lattice of atoms) the coherently
scattered photons are in-phase and constructively interact. In these
directions you observe a large intensity of scattered photons. in the other
directions there are still photons being scattered, but they are at a much
lower intensity.
You can call it whatever you want, but fundamentally this is an electronphoton interaction and the coherently scattered photons can
constructively interact.

constructive and destructive interference

The 14 Bravais Lattices

Miller Indices (1)

A set of three integers that designate

crystallographic planes, as determined
from reciprocals of fractional axial
intercepts.

Miller Indices (2) assigning Miller Indices (hkl) for a cubic system
Step 1 : Identify the intercepts on the x, y and z axes. a , ,
Step 2 : Specify the intercepts in fractional co-ordinates a/a, /a, /a

i.e. 1, ,

Step 3 : Take the reciprocals of the fractional intercepts

Miller Indices: (100)

Intercepts : a , a , a
Fractional intercepts : 1 , 1 , 1
Miller Indices : (111)
Intercepts : a , a ,
Fractional intercepts : 1 , 1 ,
Miller Indices : (110)

Intercepts : a , a ,
Fractional intercepts : , 1 ,
Miller Indices : (210)

Miller Indices (3)

Further notes :
(i) in some instances the Miller indices are best multiplied or divided through by a
common number in order to simplify them by, for example, removing a common
factor. This operation of multiplication simply generates a parallel plane which is at a
different distance from the origin of the particular unit cell being considered.
e.g. (200) is transformed to (100) by dividing through by 2 .
(ii) if any of the intercepts are at negative values on the axes then the negative sign
will carry through into the Miller indices; in such cases the negative sign is denoted
by overstriking the relevant number.
e.g. (00 -1) is instead denoted by
(iii) in the hcp crystal system there are four principal axes; this leads to four Miller
Indices e.g. you may see articles referring to an hcp (0001) surface. It is worth
noting, however, that the intercepts on the first three axes are necessarily related
and not completely independent; consequently the values of the first three Miller
indices are also linked by a simple mathematical relationship.

Unit
cells

Bragg reflection from a set of parallel planes

Fig 2.1 A three-dimensional point
lattice and some examples of a set
of parallel planes of points

Fig 2.2 Bragg refln from

a set of parallel planes
wa
v es

d=
are

dis
t be
tw

in p

has
e

pla
nes

at B

JL

(IIA
DG
)

path length diff JE EK

nl JE EK
JE EK
sin

BE BE
JE EK
2 sin
d
n 2d sin

(a) Bragg refln from a set

of lattice planes

Collecting the data

(c) The form of a powder pattern

(asymmetric film mounting).

(b) The cone of

diffraction X-rays from
a powder specimen.
The cone contains
all X-rays reflected
from one particular family
of lattice planes in all
crystals which are
correctly oriented.

(d) Plot of 2 vs
X-ray intensity

X-Ray Diffraction: Single Crystal vs Powder

x-rays

Single Crystal

single
crystal

refinement

diffraction
pattern
phases

electron
density map
fitting

ORTEP: Oak Ridge

thermal ellipsoid plot

sample: large no
of crystallites in
every possible
orientation to the
X-ray beam

unit cell

Powder X-Ray Diffraction

atomic
model

X-Ray production (1)

braking radiation

X-Ray production (2)

b) characteristic photon

high speed
electrons

a) B
rem
s

stra
h

l u ng

ph o

t on

X-Ray production (3)

a) Bremsstrahlung (braking radiation)

X-Ray production (4)

b) characteristic radiation

The complete crystal structure

The solution of the complete crystal structure
involves determining the position of all the atoms in
the unit cell relative to an axial system
The solution of the complete requires the d-spacings
of all the diffraction peaks in the powder pattern.

not complete

Why 32 crystallographic point groups?

Crystals have smooth faces and sharp edges that enclose space;
To fulfill space filling reqt, the symmetry of the faces requires tt
the crystal shape be limited to a small no of symmetry elements.
These are 1-, 2-, 3-, 4-, 6-fold rotatn axes, mirror planes and a
centre of symmetry. All of these elements must pass through the
centre of the crystal so that the collection (just 32 arrangements
possible) of symmetry elements forms a pt gp.
As a result, only the followg crystal axis systems are possible:
system
Triclinic
Monoclinic
Orthorhombic
Tetragonal
Cubic
Hexagonal
(a) rhomobohedral
(b) hexagonal

minimal symmetry Axial conditions

1 or
2 or 1
222 2
4 or
4 or s
four 3s
3 or 6 ( or3 )
3
6
3
6

abc,
abc,
abc,
a=bc,
a=b=c,

==90
===90
===90
===90

a=b=c, ==90
a=bc, ==90, = 120

Why 14 Bravais lattices?

How many point lattices are possible in the derivation of the Laue
eqns? Consider only the allowed symmetry elements and their
combinatns, AND that every lattice pt has identical surroundings.

The Bragg condition

Each plane can satisfy the Bragg condition and give a bright
spot due to constructive interference. For a cubic system,
Braggs Law is usually written as
2 2
2
2

sin
(
h

l
)
2
4a
2