Department of Materials Science & Engineering

Undergraduate program
Sophomore class
Lab report

Experiment 3
X-Ray Diffraction of a Nickel and
Unknown Sample

Michael Ong
MSE The Ohio State University

MSE 2331
2041 College Road, 477 Watts Hall
Columbus OH 43210-1178
USA
http://www.mse.eng.ohio-state.edu
3/24/2015

Lee Casalena
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Abstract
This report examines the X-ray diffraction process on a given sample and the
experimental procedures required to analyze its data. X-ray diffraction is important as it
is used to identify the atomic and molecular structure of a crystal. In this experiment, two
samples were provided, one being a nickel sample and the other which is an unknown
sample. The purpose of this experiment is to perform X-ray diffraction on both the nickel
and unknown sample and to identify the unknown sample by analyzing the data extracted
using Bragg’s Law, the structure factor, and software such as the MiniFlex and PDXL
program. Both the nickel and unknown sample was found to have a FCC crystal
structure. The unknown sample was identified to be a Magnesium Oxide compound with
a lattice constant of 4.212 Angstroms.

1 Introduction and objectives

The objectives of this experiment were to perform X-ray diffraction on a nickel sample
and identify an unknown sample using the same method. The data of the X-ray
diffraction for both samples will be analyzed, compared and tabulated. In this
experiment, both the nickel and unknown samples were a loose crystalline powder held
together by a petroleum-based grease in an acrylic sample holder. The samples
underwent X-ray diffraction using the Rigaku Miniflex 600 which is a compact benchtop
theta:2-theta diffractometer. It is computer controlled and fully capable of providing
qualitative and quantitative analyses for unknown powder crystalline materials. [1]

1.1 Background of X-ray Diffraction

X-rays are a form of electromagnetic radiation that have high energies and short
wavelengths, which have properties that allow the occurrence of diffraction. Diffraction
occurs when a wave encounters a series of regularly spaced obstacles that are capable of
scattering the wave, and have spacings that are comparable in magnitude to the
wavelength. Furthermore, diffraction is a consequence of specific phase relationships that
are established between two or more waves that have been scattered by the obstacles. The
discovery of X-rays in 1895 enabled scientists to probe crystalline structure at the atomic
level. X-ray diffraction has been in use in two main areas, for the fingerprint
characterization of crystalline materials and the determination of their structure. Each
crystalline solid has its unique characteristic X-ray powder pattern which may be used as
a "fingerprint" for its identification. Once the material has been identified, X-ray
crystallography may be used to determine its structure, i.e. how the atoms pack together
in the crystalline state and what the interatomic distance and angle are etc. X-ray
diffraction is one of the most important characterization tools used in materials science.
[2]
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2 Approach and experimental procedures

The goal was to perform an X-ray diffraction on a nickel sample and an unknown sample
that was provided. The first step of this experiment was performing the X-ray diffraction
on the samples and acquiring the data. The software used to obtain the data was the
MiniFlex Guidance program. The diffractometer was started and the nickel sample placed
on a platform inside the diffractometer. The door of the diffractometer was shut close to
prevent harmful radiation rays from leaking out of the device during the diffraction
process. The scan parameters used during the X-ray diffraction were changed to fit the
requirements of this experiment. The nickel sample had to undergo both a fast and slow
scan, whereas the unknown sample only underwent a fast scan.

Both nickel and the unknown sample were a loose crystalline powder consisting of many
fine and randomly oriented particles that are exposed to monochromatic x-radiation. Each
powder particle is a crystal, and having a large number of them with random orientations
ensured that the particles were properly oriented such that every possible set of
crystallographic planes were available for diffraction. X-ray diffractometers consist of
three basic elements: an X-ray source, a sample holder, and an X-ray detector. X-rays
were generated by heating a filament to produce electrons, accelerating the electrons
toward the sample target by applying a voltage, and bombarding the sample with
electrons. When electrons have sufficient energy to dislodge inner shell electrons of the
target material, characteristic X-ray spectra are produced. These spectra consist of several
components, the most common being Kα and Kβ. These X-rays were collimated and
directed onto the sample. As the sample and detector were rotated, the intensity of the
reflected X-rays and the detector position (2-theta angle) were recorded. When the
geometry of the incident X-rays impinging the sample satisfied the Bragg Equation,
constructive interference occurs and a peak in intensity occurs. A detector recorded and
processed this X-ray signal and converted the signal to a count rate which is then output
to the computer as a plot of intensity vs. 2-theta diffraction angle. [3]

Figure1: A schematic of the sample undergoing X-ray diffraction

in a Rigaku Miniflex 600 drawn using Paint software
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The second step of this experiment was analyzing the data from the X-ray diffraction of
both samples. This was done with the help of the PDXL software. The software was used
to input data from the X-ray diffraction, and analyzed the given information with its
database to output the most matching element or compound that fit the characteristics and
structural properties of the sample.

3 Results, analysis and discussion

For this experiment, the nickel underwent both a fast and slow scan, whereas the
unknown sample only underwent a fast scan. Exact values of the scan parameters of
nickel and unknown sample are shown in the table below.

Table 1: Scan parameters for nickel sample

Nickel (slow) Nickel (fast) Unknown (fast)
Start (deg) 40 40 30
Stop (deg) 100 100 100
Step 0.02 0.02 0.02
Speed (deg/min) 2 12 15.5

The plots of the X-ray scans for nickel and unknown sample with its {hkl} identities,
intensity peaks and 2-theta angles are shown in the figures below.
(1 1 1), 2.0367, 44.4464
Intensity (cps)

2e+004
(2 0 0), 1.7638, 51.7903

(2 2 0), 1.2472, 76.2856

(3 1 1), 1.0636, 92.8093

1e+004
(2 2 2), 1.0183, 98.3011

0e+000
40 50 60 70 80 90 100
Nickel, Ni, 03-065-2865

2-theta (deg)

Figure 2: Plot of Intensity vs. 2-theta for fast scan of nickel sample.
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Figure 3: Plot of Intensity vs. 2-theta for slow scan of nickel Sample.

1.5e+004
(2 0 0), 2.1069, 42.8905
Intensity (cps)

1.0e+004
(2 2 0), 1.4898, 62.2696

(4 0 0), 1.0521, 94.14

(1 1 1), 2.4328, 36.9184

(2 2 2), 1.2164, 78.5818

(3 1 1), 1.2705, 74.6447

5.0e+003

0.0e+000
40 60 80 100
Magnesium Copper Oxide, Mg.90 Cu.10 O, 01-077-2181

2-theta (deg)

Figure 4: Plot of Intensity vs. 2-theta for fast scan of unknown sample.
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In all three figures above, the intensity signal have waveforms that deviate from the
actual signal, this phenomenon is known as the noise of a signal. The noise of a signal is
usually unavoidable, therefore the signal to noise ratio is used to judge how much useful
data is present in the accompanying signal. Comparing the graphs of the fast and slow
scans of nickel, it can be seen that the fast scan of nickel has lower signal to noise ratio
than the fast scan. A faster scan is usually accompanied by higher background noise,
which reduces the signal to noise ratio. A high signal to noise ratio is usually desired,
which results in a higher accuracy of the signal readings.

The data from the X-ray scans were input into the PDXL software to identify the element
or compound that was tested on. The program gathered the results and information from
its own database, and short-listed the element or compound that fits its properties.
Erroneous suggestions were eliminated by having the filter settings properly set,
changing the tolerance of lattice constants to 3% and maximum figure of merit to 1, and
ensuring that the peaks lined up correctly to verify that the suggestion is correct. The
result of the analysis by the PDXL software determined that the unknown material is a
MgO compound.

From figure 2, the three most intense reflections have the (1 1 1), (2 0 0), and (2 2 0)
planes. The schematic of these three crystal planes can be found in the Appendix. Using
Bragg’s Law equation:

nλ = 2dsinθ (Equation 1)
the d-spacings of the sample can be found, and subsequently its lattice parameter
calculated by the equation:
dhkl = a / √(h2+k2+l2) (Equation 2)

An example of the simulation of powder diffraction of a BCC and FCC metal, in this case
iron, were done in CrystalMaker using the CrystalDiffract tool as shown in the figures
below.
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Figure 5: Powder diffraction simulation of BCC Fe in CrystalMaker

Figure 6: Powder diffraction simulation of FCC Fe in CrystalMaker

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Figure 7: Powder diffraction simulation of MgO in CrystalMaker

From figures 5-6, a noticeable trend can be seen where the sum of the {hkl} values of the
intensity peaks of the BCC crystal structure are all even, whereas the {hkl} values of the
intensity peaks of the FCC crystal structure are all even or all odd. Shown below are the
tables of the simulated XRD data for both BCC and FCC iron, and MgO compound.

Table 2: Simulated XRD Data for BCC Fe

h k l dhkl 2-Theta
0 1 1 2.029 44.611
0 0 2 1.435 64.927
1 1 2 1.172 82.203
1 -1 2 1.172 82.203
0 2 2 1.015 98.769
0 3 1 0.908 116.139
0 1 3 0.908 116.139
2 -2 2 0.829 136.775
2 2 2 0.829 136.775
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Table 3: Simulated XRD Data for FCC Fe

h k l dhkl 2-Theta
1 1 1 2.032 44.545
0 0 2 1.760 51.907
0 2 2 1.244 76.475
1 1 3 1.061 93.062
2 2 2 1.016 98.580
0 0 4 0.880 122.157
1 3 3 0.808 145.039
0 2 4 0.787 156.249

Table 4: Simulated XRD Data for MgO Compound

h k l dhkl 2-Theta
1 1 1 2.43180 36.9319
0 0 2 2.10600 42.9064
0 2 2 1.48917 62.2940
1 1 3 1.26997 74.6755
2 2 2 1.21590 78.6149
0 0 4 1.05300 94.0215
1 3 3 0.96630 105.7107
0 2 4 0.94183 109.7346
2 2 4 0.85977 127.2429
1 1 5 0.81060 143.6919
3 3 3 0.81060 143.6919

As seen in the tables 2-3, both the BCC and FCC crystal structure share certain {hkl}
planes that results in a intensity peak such as the (0 0 2), (0 2 2), and (2 2 2), while most
of the other planes in BCC are absent in FCC and vice-versa. For an intensity peak to be
obtained, constructive interference has to occur. The difference in lattice sites of both
crystal structures has different results of diffraction. Constructive interference in a BCC
crystal does not necessarily occur in a FCC crystal when diffracted on the same plane and
incident angle. A more accurate method of determining which planes are allowed and
forbidden for crystal structures is using the structure factor as shown in the equation
below.
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2π (hu+kv+lw)
F(θ) = i fie (Equation 3)

In a BCC crystal, the two atoms in the basis are at (0,0,0) and (1/2,1/2,1/2).
F = fat exp(2πi*0) + fat exp[2πi(h/2+k/2+l/2)]
When the sum of h,k, and l are odd, F = fat (1) + fat (-1) = 0, so no diffraction occurs.
However when the sum of h,k, and l are even, F = fat + fat = 2fat, thus diffraction occurs.
The same can be done for a FCC crystal, with the four basis atoms located at (0,0,0),
(1/2,1/2,0), (1/2,0,1/2), and (0,1/2,1/2). Using equation 3, the structure factor FCC shows
that strong diffraction occurs when the {hkl} planes are all odd or all even, and no
diffraction when {hkl} planes are mixed.

To determine the crystal structure of the nickel sample, the structure factor can be applied
to see if it follows the BCC or FCC allowed planes. Another method would be to make a
comparison between the nickel’s XRD data and the simulated XRD data. Shown below
are the tables of the XRD data for the fast and slow scan of nickel, and the unknown
sample.

Table 5: XRD Data for Nickel Fast Scan

h k l dhkl 2-Theta
1 1 1 2.037 44.437
0 0 2 1.765 51.778
0 2 2 1.247 76.292
1 1 3 1.063 92.848
2 2 2 1.018 98.363

Table 6: XRD Data for Nickel Slow Scan

h k l dhkl 2-Theta
1 1 1 2.032 44.555
0 0 2 1.761 51.870
0 2 2 1.246 76.389
1 1 3 1.063 92.927
2 2 2 1.017 98.428
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Table 7: XRD Data for Unknown Sample

h k l dhkl 2-Theta
1 1 1 2.437 36.848
0 0 2 2.107 42.895
0 2 2 1.490 62.263
1 1 3 1.270 74.655
2 2 2 1.216 78.608
0 0 4 1.052 94.139

Since the slow scan of nickel has less noise than the fast scan, its data was used to make a
comparison with the simulated BCC and FCC Fe data. The nickel data has the same
{hkl} planes as the simulated FCC Fe data. Furthermore, comparing figure 3 with figures
5-6, it can be seen that the intensity peaks of figures 3 are similar to figure 6 but different
than figure 5. Thus, the nickel sample tested in this experiment has a FCC crystal
structure. For the unknown sample, it can be seen that figure 4 is similar to figure 7 with
the same intensity peaks and {hkl} planes, showing that it has FCC crystal structure. In
addition, the dhkl and 2-Theta values are also very similar as shown in Tables 4 and 7.
Using a combination of Bragg’s Law (equation 1) and the formula for d-spacing
(equation 2), the lattice constant of the unknown sample was calculated to be 4.212
Angstroms, which is also the lattice constant of MgO, thus verifying that the unknown
material is indeed MgO as suggested by the PDXL software. [4]

The X-ray diffractions on the nickel sample and unknown sample provided important
data, which was then analyzed to determine and verify that the unknown sample is a
MgO compound. The experiment went by smoothly with only slight errors during the
experimental procedures. The intensity peaks in figure 4 were not properly labeled in the
PDXL software and had to be manually labeled. Initially, the results of the analysis of the
unknown sample by the PDXL software suggested that it was a CsCl compound, after re-
analyzing the sample, it then suggested that it was a MgO compound and gave consistent
results upon further re-analyzes. There were also some minor deviations in the data for
the fast and slow scan of nickel.

4 Summary and conclusions

The objectives were to perform X-ray diffraction on a nickel and unknown sample and to
identify the unknown sample. The unknown sample was identified after the analyses of
the data were obtained. The unknown sample was found to be a MgO compound with a
FCC crystal structure by comparing its intensity peaks with Nickel sample and the
simulated XRD data for Fe and MgO.
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Although the experiment was relatively successful, it could be still be improved. The
scanning parameters of the samples can be changed so that it covers a wider range of
diffraction angle allowing more planes of the material to be analyzed. More data can be
obtained, thus getting a more accurate and consistent result. The experiment was
conducted safely with no safety incidents.

References
1. Notes on XRD Background and Objectives, distributed in MSE 2331
[MATSCEN/2331/matscen_2331_sp2015_/XRD Background Objective.pdf]
2. William Callister, “Materials Science and Engineering” in: X-Ray Diffraction:
Determination of Crystal Structures, Section 3.19, December 2009
3. Hanno Zur Loye, “X-Ray Diffraction, How It Works”; pp. 2
Retrieved from http://www.chem.sc.edu/faculty/zurloye/xrdtutorial_2013.pdf
4. SPI Supplies Brand® MgO Magnesium Oxide Single Crystal Substrates, Blocks,
and Optical Components. By Structure Probe, Inc.
Retrieved from http://www.2spi.com/catalog/submat/magnesium-oxide.shtml