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Determination of Crystal Structure by

X-Ray Powder Diffractometry


Raina N. Smith
PHY 450, Senior Physics Lab
March 11, 1998

Abstract: Diffraction occurs when electromagnetic radiation is scattered off of a regular periodic
system of objects (atoms, in our case) and the distance between the centers of these objects is
approximately the same as the wavelength of the radiation. X-Rays are useful in identifying
crystal structures since x-ray radiation represents the spectrum of radiation around 0.1
nanometers, which is an acceptable approximation of the size of atoms and ions. X-ray diffraction
provides angle values for the maximum intensity of scattering (in 2 ), which in turn can be used
to calculate the distance between lattice planes. These distances are then used in conjunction with
the Miller indices to calculate the lattice parameters for that particular compound.
Raina N. Smith
PHY450
February 2, 1998

Introduction
After Wilhelm Roentgen discovered x-rays in 1895, many people worked diligently to determine
their characteristics. It was the determination that x-rays were a form of electromagnetic
radiation, but with wavelengths much shorter than visible light, that caused Max von Laue to
propose that crystal lattices could be used as three-dimensional gratings.1 He said that the waves
scattered through such a grating should be the right wavelength to produce observable
interference. Von Laue designed the experiment which was consequentially performed by Walter
Friedrich and Paul Knipping. The results convincingly showed both the wave-nature of x-rays,
and the proposed lattice structure of crystals. William Lawrence Bragg then determined the
equation known as Bragg's law:
nλ = 2d sin θ

where n = 1, 2 ,3 , ... and d is the distance between lattice planes, as well as developing an
apparatus with William Henry Bragg (his father) known as a Bragg Spectrometer which rotated
the crystal and detector around a fixed x-ray beam to determine the intensity of the diffracted
beam as a function of the scattering angle. It is this same principle which is used in modern x-ray
diffraction techniques.

My experiment consists of using an x-ray diffractometer and Bragg's law to determine the
distance between lattice planes corresponding to the angle of each peak of intensity for several
samples, and to then determine the Miller indices of the crystal plane responsible for each
intensity. I will then calculate the lattice parameters (length of unit cell edges) to determine the
crystal structure of the samples.

Experimental Method
The apparatus used will be the Rigaku Geigerflex X-Ray Diffractometer as shown below in
Figure 1. It consists of an x-ray tube to which is applied a high voltage, a goniometer which
measures the angle between the x-ray beam incident to the sample and the diffracted beam (see
Figure 2), and a scintillation-type counter. Electric signals sent by the counter are counted to get
a rate-per-second, which is then converted to the corresponding voltages by the ratemeter, and
recorded on the chart recorder.2

Figure 1: Rigaku Geigerflex Diffractometer

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Raina N. Smith
PHY450
February 2, 1998

Scintillation
X-Ray Tube Counter

Bragg angle 
   diffraction angle

Sample

Figure 2: Goniometer angle relations (a top-down view)


Powdered samples of known cubic systems are ground to a uniform fine consistency using a
mortar and pestle and placed in the hole on the sample plate. A glass slide is then used to smooth
the sample and pack it in tightly into the plate for vertical mounting. The sample is then placed in
the sample holder inside the goniometer, and the following steps are taken to start the
diffractometer system:3
1) circuit breaker is switched on,
2) cooling water is turned on,
3) water supply unit is switched on,
4) power to x-ray generator is switched on,
5) x-ray switch is turned on,
6) x-ray voltage is slowly turned up to 40 kV,
7) x-ray current is slowly turned up to 20mA,
8) electric circuit panel (ECP) switch is turned on,
9) chart recorder is turned on,
10) press START button of ECP,
11) confirm settings of the following:
-MODE switch: DIFF x1
-BASE LINE: As set previously
-INDOW: As set previously
-MODE: RM
-RM-DA: RM
12) press POWER switch of goniometer controller (GC),
13) verify that SCAN switch of GC is off,
14) set INDIC switch to 2 ,
15) set AXIS switch to 2 / ,

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Raina N. Smith
PHY450
February 2, 1998

16) press DATUM button of GC


17) confirm settings of the following on the GC:
-AM switch: 1
-RECYCLE switch: OFF
-STEP WIDTH switch: CONT
-MODE switch: MANU
18) set digital switches of GC to the desired 2 range,
19) set SCAN SPEED switch to 2 per minute,
20) set RANGE to 10K x1 CPS,
21) set TIME CONST of ECP ratemeter to 20 mm per minute,
22) set switch of shutter unit to OPEN,
23) set MODE switch of GC to AUTO,
24) set Auto switch of GC to START

The taking of data will begin, and will be recorded on chart paper as intensity versus 2 . These 2
values are used to calculate the value for d in Bragg's law, which can then be looked up in
reference tables to obtain the Miller indices associated with that peak. The lattice parameter a is
the unit cell edge width of the crystal. It is related to the distance d and the Miller indices hkl as
follows (for a cubic system)4:

a = d hkl h 2 + k 2 + l 2

Results and Analysis


The results of the experiment for the ten different samples are in the table on the next page. Some
samples seemed consistent with expected values, but most exhibited unusual behavior. There
were some samples which seemed to have the peak intensities switched for a pair of distances,
and most showed extraneous peaks indicating contamination of sample, or perhaps bad sample
preparation. The chart paper ran out after our first couple of attempts while we were getting used
to the apparatus, and the only refills we had did not fit properly, so the paper tended to slip and
catch alternately, making analysis of the data more guess-work than anything. I wanted to redo
the experiments carefully from start to finish and bought a mortar and pestle to aid me in sample
preparation, but due to a machine malfunction (large water leak), I was unable to operate the
equipment safely.

I have listed the calculated interplanar distances and peak intensities, and the proposed Miller
indices based on them. The peak intensities were calculated based on a peak-height/max. peak-
height ratio which was then normalized to 100. The distance between lattice planes was
calculated using Bragg's law with n=1.

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Raina N. Smith
PHY450
February 2, 1998

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Raina N. Smith
PHY450
February 2, 1998

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Raina N. Smith
PHY450
February 2, 1998

Accepted values for the data are as follows (please note that the Al sample was a foil, and not a
power—solid Al information was not available):

Data From Powder Diffraction File5


Sample Peak Accepted Inteplanar
Sample Type Intensity Spacings, d (in Angstroms) hkl
KCl powder 100 3.146 200
59 2.224 220
23 1.816 222
20 1.407 420
13 1.284 422
8 1.573 400
KBr powder 100 3.292 200
57 2.333 220
17 1.475 420
16 1.905 222
15 3.800 111
10 1.649 400
8 1.346 422
Al powder 100 2.338 111
47 2.024 200
24 1.221 311
22 1.431 220
CuO powder 100 2.523 (1bar)11
96 2.323 111
49 2.530 002
30 2.312 200
25 1.866 (2bar)02
20 1.505 (1bar)13
19 1.375 220113
ZnO powder 100 2.480 101
71 2.816 100
56 2.602 002
40 1.626 110
35 1.477 103
29 1.911 102
28 1.379 112
14 1.359 201
12 0.907 213
10 1.093 203
10 1.042 211

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Raina N. Smith
PHY450
February 2, 1998

Choosing the two acceptable samples, KCl sample number 4 and the KBr sample, calculated
values for the lattice parameters are as follows:

Sample Sample Calculated Inteplanar Proposed Calculated


Sample Type Number Spacings, d ( ) Miller Indices Lattice Parameters
KCl powder 4 3.151 200 6.302
KCl powder 4 2.252 220 6.370
KCl powder 4 1.823 222 6.314
KCl powder 4 1.409 420 6.299
KCl powder 4 1.574 400 6.296
KBr powder 1 3.229 200 6.458
KBr powder 1 2.296 220 6.495
KBr powder 1 1.458 420 6.519
KBr powder 1 1.630 400 6.520
KBr powder 1 1.875 222 6.496

As would be expected in cubic crystals, the calculated lattice parameters are approximately equal
for each of the samples irregardless of which plane (Miller Indices) caused the diffraction peak.

Conclusion
While most of the data taken contained extraneous peaks and switched intensities of peaks, two
of the samples (KCl sample number 4 and the KBr sample) produced data which resulted in
acceptable calculations of the lattice parameters for each, substantiating that both samples were
indeed cubic crystalline forms.

I believe that having the correct chart paper on hand would have helped tremendously in obtaining
more accurate results, as would having a mortar and pestle to assure uniformly pulvarized
samples. These steps should be taken before any more powder data is taken (as well as repairing
the leak in the system).

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Raina N. Smith
PHY450
February 2, 1998

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1
Thornton, Stephen T. and Andrew Rex, Modern Physics for Scientists and Engineers (Saunders College Publishing, Fort
Worth, TX, 1993), p. 176.
2
Rigaku Corporation, General Operating Procedure for Rigaku Geigerflex X-Ray Diffractometer System, Models #
CN2028 and #CN2038, Manual # ME200DM. pp. 3-4.
3
Rigaku Corporation, General Operating Procedure for Rigaku Geigerflex X-Ray Diffractometer System, Models #
CN2028 and #CN2038, Manual # ME200DM. pp. 5-7.
4
Shackelford, James F., Introduction to Materials Science for Engineers, Second Edition (MacMillan Publishing
Company, New York, 1988), p.110.
5
JCPDS—International Centre for Diffraction Data, Powder Diffraction File, Alphabetical Index, Inorganic Phases 1981.