MSE 104: Materials Characterization

Laboratory 2: Powder Diffraction

Instructor: Lane W. Martin

Laboratory 2:
Powder Diffraction

Objectives
To understand and apply the methods of diffraction analysis appropriate for powder samples.
Equipment
Commercial X-ray diffractometer (Rigaku MiniFlexTM II)
Materials
Powdered specimens of various crystals, presented as unknowns.

The Experiment
Background. The most popular powder method of X-ray diffraction was devised independently in 1916 by
Debye and Scherrer, working in Germany, and in 1917 by Hull, working in the U.S. The method exploits
the fact that the specimen, as a powder, offers a guaranteed opportunity to observe diffraction. The
randomly-oriented crystallites comprising the powder present all possible orientations of crystal lattice
planes to the incident monochromatic radiation, maximizing the chance for constructive interference among
the scattered beams. In essence, all possible d-spacings from families of lattice planes in all possible
orientations within the specimen are sampled by the incident monochromatic radiation.

MSE 104: Materials Characterization

Laboratory 2: Powder Diffraction

Instructor: Lane W. Martin

For any of the powder methods, the beams resulting from constructive interference lie on the surfaces of
cones with axes parallel to the incident beam direction. The Hull/Debye-Scherrer method uses a thin strip
of film wrapped around the interior of a cylindrical camera to intercept these conical rays, exposing short,
arc-shaped lines on the film. Each arc represents one family of diffracting planes, and the full set enables
the experimentalist to identify the specimen by comparison with tabulated values of d-spacings.

(Left) A photograph of the original Debye-Scherrer camera and (right) a schematic illustration of
the setup and how the conical rays expose the film.
A diffractometer enables all of the same diffracted beam to be monitored, but it does so in serial, rather
than parallel fashion. This is, the powder sample is scanned by an incident beam, and the diffracted beams
are collected at the same angle, in the 2 geometry associated with all X-ray diffractometers. The
diffractometer that you are using in this laboratory is marketed as having special capabilities to optimize it
for powder diffraction analysis.
The tabulation of the powder diffraction file (PDF) began at Dow Chemical Company in 1938, and was
taken over by the American Society for Testing and Materials (ASTM) in 1941. The legendary ASTM Card
File was published by ASTM for the next 30 years, a single 3 inch x 5 inch index card (as they were
known back then, a very popular for inventory control in many different applications) for each pattern. In
1969, the activity was coordinated by the Joint Committee on Powder Diffraction Standards (JCPDS), a
group of ten professional societies from the U.S., France, England and Canada. Today, the PDF is
accessible in digital format, and there are hundreds of thousands of entries, maintained by the International
Center for Diffraction Data (ICDD), in Newtown Square, Pennsylvania, online at http://www.icdd.com/.
With so many data files to search, the identification of an unknown can be a formidable task; however, there
are established procedures for making this an easier job. Most of the PDF listings can be searched by a
subset grouping of the strongest (highest intensity) diffraction lines from the full spectrum.
The Hanawalt Search Manual1 keys the strongest line first, followed by the next strongest line, to eventually
match a total of eight (8) lines. The Fink Method2 uses the four (4) strongest lines, in descending order, to
obtain a match with at least eight (8) lines total. Modern digital data files can be searched rapidly enough
with just the three (3) strongest peaks coupled to a specified range of acceptable error, to obtain a match
in reasonable time. And there are other methods, including one that you may devise yourself.

MSE 104: Materials Characterization

Laboratory 2: Powder Diffraction

1
2

Instructor: Lane W. Martin

Hanawalt, J. D. and Rinn, H. W. Ind. Eng. Chem. Anal. 8, 244 (1976); Hanawalt, J. D. Adv. X-Ray Anal. 20, 63-73 (1976).
Bigelow, W. and Smith, J. V. ASTM Spec. Tech. Publ. STP 372, 54-89 (1965).

Procedures. The following outlines the specific procedures to be used for this section of the laboratory:
1. Load your first unknown powdered specimen into the holder, ensuring that there is enough powder
to create a measurable diffraction pattern. The best powder has a fine grain size and no preferred
orientation. If the powdered fragments are needle shaped, for example, it would be best to agitate
them so that they are not closely packed with the same alignment, to increase the range of
orientations seen by the X-ray beam.
2. Recall the standard (fixed) operating conditions for the MiniFlex II, namely, a voltage of 30 kV and
a current of 15 mA.
3. Start up the computer and engage the measurement software.
4. Record the spectrum from your first sample over a minimum angular range between +3 to +90.
5. Repeat for a second sample, another unknown powder.
6. Repeat for a third sample, another unknown powder.

Data Reduction and Analysis

Observations
1. Observe the spacings of the diffraction peak sin your output files. Powder patterns of cubic
substances can usually be distinguished by inspection: simple cubic structures generate a large
number of regularly spaced peaks; body-centered cubic structures generate about half as many
regularly-spaced peaks; face-centered cubic structures generate a pattern of peaks in a pair, single,
pair, single...sequence. Non-cubic crystals sometimes have distinctive patterns, too, like the
doublets seen in tetragonal crystals with c/a ratio close to one.
2. Note discrepancies. If the pattern of peaks is not the anticipated one, be suspicious of
contaminants. Remember that a fine powder has large surface area and is therefore susceptible to
reacting with the atmosphere, forming oxides, nitrides, and hydroxides.
3. Develop a hypothesis for the structure of your unknown specimens (including possible
contaminants) to guide your additional experiments and data analysis. For example, you might
begin with the assumption that the sample is cubic, and prepare to find one of three possibilities,
simple, body-centered, or face-centered.
Measurements
Take measurements of the locations of all Bragg peaks, expressed as 2B in degrees for each one,
noting locations of possible peak overlaps.
Tabulations
Tabulate in a spreadsheet the measured values of 2B and the corresponding d-spacings (from Braggs
Law) for each peak, labeling an additional column to mark the relative intensities of each peak. That
third column is used during your search of the PDF listings.
Analysis
1. Using the three strongest peaks as a search index and some common sense regarding feasibility
(your powders would not be radioactive for example), consult the powder diffraction file (PDF) to
determine their identities.

MSE 104: Materials Characterization

Laboratory 2: Powder Diffraction

Instructor: Lane W. Martin

2. When you are reasonably confident of the identity of each unknown, return to your spreadsheet
and enter the indices of each peak with their corresponding values in another column of your
table. In your write-up, describe the meaning of these indices, how you chose your assignments
(why 021 and not 210?), and the associated accuracy of those assignments.
3. Add another column to your table and enter the lattice parameters (a, b, and c) calculated for each
of the lines measured above, based on your assumption of the structure. If you assume a cubic
structure, remember that the interplanar spacing ( ) of the family of planes in that cubic
crystal is given by3
1
2 + 2 + 2
2 =
2

where is the lattice parameter. If your sample is not cubic, refer to reference [3] for the proper
equations relating d-spacings to lattice parameters.
4. Note variations in lattice parameters that are calculated from each peak. Is there a trend? Do these
variations arise from random error? systematic error? Explain.
5. If your diffraction pattern comes from a sample with cubic symmetry, plot the lattice parameter ()
values against the Nelson-Riley function4
=

cos 2 cos 2
+
sin

to obtain the cubic lattice constant 0 for your unknown.

6. If you can identify any suspected contaminants or mixing of powders, report those results, too,
using the same methodologies and spreadsheet entries as above.
3

B.D. Cullity and S.R. Stock, Elements of X-Ray Diffraction, 3rd Edition, Prentice-Hall, New York, (2001), Appendix 3, p.
619.
B.D. Cullity and S.R. Stock, Elements of X-Ray Diffraction, 3rd Edition, Prentice-Hall, New York, (2001), p. 366.

Laboratory Report
In analyses of the type performed in this lab, you may be plagued by potential sources of systematic error,
for example an offset of the angular scale on which your 2B values are found. These can arise from
misalignment of the diffractometer, the divergence of the incident X-ray beam, and absorption of X-rays by
the specimen, for example. Other sources of error are highlighted in your textbook and technical articles on
diffractometers.
In your lab write-up, identify any potential sources of systematic error that occur to you. Comment on how
you know (or might confirm) that they are systematic, and the magnitude of the error in your particular
case. Distinguish these from any sources of random error, identifying what might be the most likely
candidates for random errors, and specify the magnitude of any random errors you may have encountered
in your data collection and analysis. Comment on what might be done to increase precision in your
experiments. Comment on what might be done to increase accuracy, explaining the differences in the case
of your personal data sets. Your report should answer all questions posed in this manual, and follow the
Lab Guide.

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Copper

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Iron

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Zinc

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Calcite

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Appendix I: Data from the Powder Diffraction File

Sylvite

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Potassium Iodide

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Periclase

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Halite

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Nahcolite

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Rutile

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Zinc Oxide (cubic)

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Zinc Oxide (hexagonal)

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Zinc Sulfide (hexagonal)

MSE 104 Lab 02

Appendix I: Data from the Powder Diffraction File

Zinc Sulfate