Fingerprinting..

Advantages:
relatively quick and easy, can be non-destructive
Problems:
need reliable standards - new phases will not be in the
PDF
some things in the database are rubbish!
often need other (chemical) information to narrow down
searches
not very sensitive - can hide up to 10% impurities
(depending on relative weights see later)
problems from preferred orientation, etc.
not much good for organics, organometallics.

Preferred Orientation
Remember: we rely on a random orientation of crystallites.
When crystals are platey or needle-shaped (acicular) they
will pack in a non-random fashion, preferentially exposing
some planes to the incident radiation.

Thus some diffraction

peaks will be enhanced
relative to others.
This can also happen if a
sample is packed down,
or a thin film, etc.
Brushite plates, SEM by Anna Fotheringham

Preferred Orientation
Intensity mismatch due to using single crystal

So e.g. all (n00) peaks may be enhanced

Uses: different structures

Even if two structures are the
same (and they are chemically
similar) differences can be
observed:
Peak positions (unit cell changes)
and relative intensities (atoms)

5 38 1 6 -ICSD
Lamb d a: 1 .5 4 1 78 Mag n if: 1 .0 FW HM : 0. 20 0
Space g rp: F m -3 m Direct cell: 5. 64 0 0 5 .6 4 00

5 . 64 0 0 90 .0 0 9 0. 0 0 9 0 .0 0

NaCl

25038 2 5 -ICSD
30
40
Lamb d a: 1 .5 4 1 78 Mag n if: 1 .0 FW HM : 0. 20 0
Space g rp: F m -3 m Direct cell: 6. 28 0 0 6 .2 8 00

50

60

70

6 . 28 0 0 90 .0 0 9 0. 0 0 9 0 .0 0

KCl

There is another major point

here:
K+ and Cl- are isoelectronic

20

30

40

50

60

70

Uses: different structures

BUT, sometimes you cant
really see any changes on
visual inspection

This often happens in open

structures where there is space
for change of light atoms

Zeolite A

Uses: polymorphs
Different
polymorphs will
have different
powder patterns
e.g. Zn S

Uses: polymorphs
K3SO4F: tetragonal & cubic forms

Peak Broadening
In an X-ray diffraction pattern, peak width depends on
the instrument
radiation not pure monochromatic
Heisenberg uncertainty principle
focussing geometry
the sample
- a crystalline substance gives rise to sharp lines,
whereas a truly amorphous material gives a broad
hump.
What happens between the two?

Peak Broadening
If crystal size < 0.2 m, then peak broadening occurs
At <50nm, becomes significant.
Why?
Braggs law gives the condition for constructive
interference.
At slightly higher than the Bragg angle, each plane gives
a lag in the diffracted beam.
For many planes, these end up cancelling out and thus the
net diffraction is zero.
In small crystals, there are relatively fewer planes, so there
is a remanent diffraction

Peak Broadening
We can calculate the average size of the crystals
from the broadening:

0 .9
t
B cos B

Scherrer formula

t is the thickness of the crystal, the wavelength, B the

Bragg angle.
B is the line broadening, by reference to a standard, so
that
2
2
2

B B M BS

where BS is the halfwidth of the standard material in

radians. (A normal halfwidth is around 0.1o)

Peak Broadening
Halfwidth: Full width at half-maximum - FWHM

This can be different in different directions (anisotropic),

so by noting which peaks are broadened we can also infer
the shape of the crystals.

Uses: particle size determination

Here we see particle size increasing with temperature
200

150

1050oC
100

50

30oC
0
15

20

25

30

35
20 /

40
o

45

50

55

60

Particle size determination: Example

Peak at 28.2 2 with FWHM of 0.36 2
Standard material has FWHM of 0.16 2
2
2
2
= CuK = 1.540
B B M BS
0.36 = 0.36 x /180 = 0.0063 rad (Bm)
0 .9
t
0.16 = 0.16 x /180 = 0.0028 rad (Bs)
B cos B
B = 0.0056 rad

0.9 1.540
t
0.0056 cos14.1
t = 255 = 0.0255 m

Particle size determinaton

An estimate, rather than an absolute value - also will be
dominated by smallest particles.
Good for indication of trends.
A useful complement to other measurements
such
as surface area, electron microscopy etc.

Amorphous / micro-crystalline?
It can be difficult to distinguish between an
amorphous material and a crystalline sample
with very small particle size.
BUT the idea of such a small size crystal being
crystalline doesnt make sense!
5nm = 50 = e.g. 10 unit cells
Is this sufficient for long range order??

Unit cell refinement

As the peak positions reflect the unit cell
dimensions, it is an easy task to refine the
unit cell.

2d sin = and e.g.

1 h2 k 2 l2
d 2 a 2 b2 c2

Thus if we can assign hkl values to each peak, we can

gain accurate values for the unit cell
We minimise the difference, e.g.

d
obs calc

This is known as least squares refinement. We will

come back to this later.

Variable temperature/pressure
Need special apparatus

Here (see previous) we could follow a phase transition as

we heated the sample up following the change in unit cell
parameters.
J. M .S. Skakle, J. G. Fletcher, A. R. West, Dalton 1996 2497

BaTiO3 T/P
Variable pressure hard to do: neutron diffraction (later)
Much of these data actually from dielectric measurements.
T. Ishidate, PRL (1997) 78 2397

S. A. Hayward, S. A. T. Redfern, H. J. Stone, M. G. Tucker,

K. R. Whittle, W. G. Marshall, Z. Krist. (2005) 220 735.

Uses: more advanced

Structure refinement the Rietveld method
A refinement technique, not determination

Hugo Rietveld,
b1932

Whole-pattern fitting - not just the Bragg reflections

Needs a MODEL - pattern calculated from model, compared

point-by-point with observed pattern.
Originally developed (1967,1969) for use with neutron data
- good reproducible peak shapes
1977 - first report of application to X-ray data
http://home.wxs.nl/~rietv025/

Uses: Rietveld Refinement

Here there was a similarity
between the powder pattern
of this phase and an
existing one also chemical
composition similar.

Ca/Ce

0.3333

0.6667

-0.0038(18)

Ce

0.2337(4)

-0.0108

0.25

Si

0.403(3)

0.380(3)

0.25

O1

0.316(4)

0.467(4)

0.25

O2

0.597(5)

0.467(4)

0.25

O3

0.340(2)

0.252(3)

0.071(3)

O4

0.25

J. M. S. Skakle, C. L. Dickson, F. P. Glasser, Powder Diffraction (2000) 15, 234-238

Uses: more advanced

Quantitative phase analysis (how much of each)
Nave approach - relative intensity of peak maxima?
- Consider mixture of Ba,Si,O
- Ba component would scatter more than Si component
(e.g. Ba2SiO4 c.f. SiO2)
HA
80.18 %
b-TCP 19.82 %

1,600

Counts

Thus uses Rietveld

method and takes
into account relative
scattering from each
crystalline phase

1,400
1,200
1,000
800
600
400
200
0
-200
-400

10

20

30

40

2Th Degrees

50

60

Summary
Many different uses for powder X-ray diffraction!

Fingerprinting: identifying phases, distinguishing

similar materials, identifying polymorphs, (following
chemical reactions)
Indication of particle size from peak broadening
Unit cell refinement
Variable temperature/pressure measurements

Crystal structure refinement

Quantitative analysis