MatS 3801 XRD 1 Lab

Version: 10/01/2018

XRD 1 Lab: Introduction to X-ray Diffraction (XRD)

1. Objectives
 Operate an x-ray diffractometer (Rigaku MiniFlex diffractometer).
 Learn how to properly mount foil and powdered samples for XRD analysis.
 Understand, interpret, and analyze XRD patterns.
 Determine the chemical composition in a binary alloy utilizing XRD peak shifting from
Vegard’s law.
 Determine the volume percent of a two-phase powder mixture by performing a
quantitative analysis of XRD peak heights.

2. Pre-lab activities
Submit a pre-lab report containing solutions to the pre-lab questions, an overview of the
procedure, and a summary of important safety considerations for the lab. See the course’s Lab
Notebook Guidelines document for details on what needs to be submit and grading policy. Pre-lab
questions can be typed or neatly hand written. The procedure and safety considerations should be
typed. A physical copy of the pre-lab report must be turned in at the start of your lab session
and a digital copy must be submitted to Canvas by that same time. See Section 6 for pre-lab
questions.

3. Activities to complete during lab

Work as a group to collect XRD patterns of a Ni foil, a Cu0.70Ni0.30 foil, and a powder
mixture of Cu and Fe. While the instrument is collecting data, your group will learn how to use
MDI’s JADE software package to analyze each XRD pattern. Your group will also be provided
with XRD patterns from a Cu foil and a Cu1-xNix of unknown composition.

4. Post-lab assignment
See Section 10 of the post-lab questions associated with this experiment. While data will
gathered as a group, you will ultimately submit an individually written “formal” style report. See
the course’s Formal Lab Report Guidelines for the requirements for a formal style lab report. To
assist with the writing process, three “stages” of the report will be turned in throughout the
semester. See your group’s Weekly Schedule for relevant due dates.

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5. Additional resources (found on Canvas)

 Rigaku MiniFlex 600 X-ray Diffractometer Standard Operating Procedures (SOP).
 Rigaku MiniFlex 600 Quick Reference Guide.
 Table of atomic scattering factors and graph of the Debye-Waller temperature factor from
Elements of X-ray Diffraction Second Edition by B. D. Cullity.

6. Pre-lab Questions
1. In a couple of sentences describe Vegard’s Law. Write down this equation and define all
your variables. You will need to look up Vegard’s Law in an external reference and make
sure to provide a properly formatted reference.
2. What is the difference between a substitutional solid solution alloy and a mixture? Based
on your response, how would the x-ray diffraction pattern of a substitutional solid solution
alloy made of Cu and Ni be different from the x-ray diffraction pattern of a mixture of Cu
and Ni powders that were simply mixed together?
3. Read Section 2.4.5 in Brandon and Kaplan in regards to measurement errors associated
with XRD measurements. Specifically focus on the discussion related to Equations 2.21 –
2.23 which explain how to correct for what is commonly referred to as a “sample height
displacement error”. In a couple of sentences explain the origin of a sample height
displacement error, how it affects a measured diffraction pattern, and how you can correct
for it using the “extrapolation method” assuming the material you are measuring has a
cubic crystal structure.
4. What are the “reflection rules” (a.k.a. “systematic absences”) for simple cubic, body
centered cubic, and face centered cubic systems? Your MatS 3011 textbook Materials
Science and Engineering An Introduction by W. D. Callister and D. G. Rethwisch (Section
3.16 in 9th edition) is a good section to review about this.

7. Lab Schedule
This experiment occurs during a two week window. Groups 1 and 2 will complete the
experiment during the week of 10/1/2018 and lab Groups 3 and 4 will complete the experiment
during the week of 10/8/2018. Each three hour long lab session will be divided into two intervals
that are 90 minutes long. Groups 2 (first week) and 4 (second week) will perform the lab during
the first 90 minute interval and then Groups 1 (first week) and 3 (second week) will perform the
lab during the second 90 minute interval. Please arrive to the lab when you are scheduled to start
the lab.

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8. Safety Considerations
 Make sure to wear all standard personal protective equipment required for the Valspar –
CEMS Materials Science and Engineering Teaching Lab. This includes impact resistant
safety goggles, long pants, and closed toe shoes.
 The x-ray diffractometer produces ionizing radiation in the form of x-rays. X-rays are being
generated by the x-ray tube source whenever the x-ray generator is powered on. You will
know when the x-ray generator is on when the light on the top of the diffractometer is
illuminated (yellow color).
 Make sure to wear the thermoluminescent dosimeter (TLD) ring when loading and
removing samples.
 Wear gloves when handling samples.

9. Experimental Procedure

Part 1 – Safety and Start Up

The instructor will first go over the various safety features of a modern x-ray
diffractometer. Listen carefully to these features and how to operate the instrument safely. After
the safety training you will then learn how to start up and prepare the diffractometer for
measurement. Using the Standard Operating Procedures guide for the diffractometer, complete
the following steps:
1. Instrument Start-up
2. Initializing the Goniometer
3. Powering up the X-ray Generator
4. Checking Instrument Status Before Measurement
When these steps are completed, the TA will demonstrate how to mount a sample onto a
sample holder.

Part 2 - Vegard’s Law analysis of Cu1-xNix foils

There are four samples for this part: a Cu foil, a Ni foil, a known Cu0.70Ni0.30 foil, and an
unknown Cu1-xNix sample. Vegard's Law will be used to determine the composition of the
unknown sample by considering the shift in the lattice parameter. You will scan only two samples
during your lab session (the Ni foil and the Cu0.70Ni0.30 foil); the Cu foil and the unknown Cu1-xNix
foil XRD patterns will be provided to you.

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Following the Sample Measurement section of the Standard Operating Procedures guide,
load a foil sample into the diffractometer and measure its x-ray diffraction pattern. For each scan
measure from 30 – 130o with a step size of 0.05o/step and duration time of 0.5 s. All of the other
parameters should follow their default values described in the Standard Operating Procedures
guide. Make sure to save your data in the folder: C:\Windmax\Data\MatS_3801\2XXX\<GROUP
NAME> where 2XXX is the year <GROUP NAME> is your group name.

1. Each measurement will take about 15 minutes to complete. While you are waiting, sketch
the main parts of the MiniFlex. Show the arrangement of the source, sample, diffracted
beam monochromator, and detector. Discuss with the instructor about what the
monochromator does, how it works, and what type of detector the diffractometer has.
2. Once the first sample is complete, continue with next sample. The General Measurements
function will automatically save the parameters that you entered, but make sure to check
the scan parameters before each run to make sure that everything is what it is supposed to
be.
3. While this scan is going, begin to analyze your first sample’s data. Your instructor will
assist you in learning how to operate JADE 2010, an X-ray diffraction data analysis
software. To open your data, select the small teal folder on the lower left hand side of the
screen, then select the Open Other Folder option. Double click on your data file (select the
.raw data).
4. In the upper left hand corner, save the raw file by selecting Save Current Data. This is so
you can access the raw data again once you have analyzed it. Save as a .xy file so that it
can be uploaded into Excel later.
5. Select the Database tab at the top and then Retrievals. There are a variety of libraries that
you can search; Inorganics is the largest library, and is the one that we will use. From here
double click on Ni (whichever you ran first; select it such that is highlighted purple) to
display known references for the element. The instructor will show you how to overlay the
library diffraction pattern onto your data.
6. Once you have overlain the diffraction pattern on your data, you can assign the hkl’s of the
references peaks. The instructor will show you how to do this. This will assign the peaks
that the library has assigned to the reference peaks.
7. Select the Save Current Plot as a .bmp file of your data. This shows the image of your
peaks and the overlaid hkl references. This will be useful to have when you start analyzing
your data later.
8. Use the Profiles | Paints tab at the bottom to fit each diffraction peak. The instructor will
assist you when fitting these peaks. You can copy your fitted profile data by right clicking
on the Profiles | Paints tab and selecting the Copy List option. It is best to paste this list
into Microsoft Excel.

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9. The instructor will provide you with the data for the Cu foil and the Cu0.70Ni0.30 foil during
this time. To manage your time, make sure that you are aware when scans are complete so
you can load in the next sample. You can go back to analyzing data after your next sample
is loaded.

Part 3 – Quantitative Analysis of a Powder Mixture

For this section of the experiment, you will use the intensities of individual diffraction
peaks (taking intensity correction factors into account) from a powder mixture of Cu and Fe to
calculate the volume fraction of each material. The integrated intensity from a diffraction peak is
proportional to the volume fraction of that material in a sample. This means, for a material with
multiple crystalline phases, XRD can be used to determine the volume fraction of these phases, if
the structure factors for the different phases are known (see the Post-lab Questions section). For a
multi-phase metal mixture, this corresponds to a quantitative analysis of the phase composition.

1. Go to the General Measurement window, and change the Stop angle to 100°. If the scan
goes higher it will spill powder all over the diffractometer (and you will have to clean it
up!). All other parameters remaining the same, run a scan on the unknown powder mixture.
2. Once the powder scan is complete, open the scan file in Jade 2010, identify which peaks
belong to Cu and which peaks belong to Fe, and fit all peaks. Save a picture of your
workspace and fitted peak parameters for later analysis.
3. Now adjust the 2θ scan window to include only the (111) and (110) peaks of Cu and Fe,
respectively. Use a step size of 0.02o and a dwell time of 2 s.
4. When this scan complete, open the scan file in Jade 2010 and use the “Profiles” option to
fit each peak. Again save a picture of your workspace and the fitted peaks table for further
analysis.
a. The table is very important here as it has both peak position and the integrated peak
area!

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Part 4 - Instrument Shutdown
1. Use the Instrument Shutdown section in the Standard Operating Procedures guide to
properly shutdown and log off the instrument.
2. Final Lab Checklist: Before you leave make sure that you,
a. Share ALL data (.raw files, .xy files, analysis Excel files, any pictures) with all
group members. Make sure that everyone has the data either stored locally (via
removable drives) or in a shared Google Drive.
i. Do not leave the lab until you have confirmed that all group members
have access to all of the data!
b. Record the manufacturer and model of the x-ray diffractometer somewhere in your
running log.
c. Have an estimate of (or know where to find) the instrumental accuracy on 2θ and λ
for the diffractometer.
d. Discuss with your group where there are sources of instrumental and random
uncertainty (consider the post-lab questions in your discussions).
e. Clean up your work area.
f. Submit the carbon copy of your running log to the TA / instructor.

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10. Post-lab Questions

The following is a list of important questions that should be included in the Results and
Analysis section of your formal report. See the course’s Formal Lab Report Guidelines for the
requirements for a formal style lab report. Discussion of all topics should be written in a paragraph-
like prose using topic transitional phrases or sentences between each topic. Do not refer to each
question in the report directly as Question 1, 2, etc. These questions should be viewed as a
minimum level of effort required for this section, and you should create additional figures /
tables and provide additional analysis to further develop your Results and Analysis section.
All figures and tables should be professionally created and will be evaluated for impact,
clarity, captions / titles, and format. Samples calculations must be provided and properly
documented in appendices (use separate appendices for each calculation style). All calculations
must be typed out. All reported values must be reported with uncertainties. For each
measurement and calculation, think carefully on what uncertainty factors are present and are
relevant. All units must be in SI.

Cu-Ni alloy analysis (Determining alloy composition w/ Vegard’s Law)

1. Qualitatively compare and contrast the four Cu-Ni alloy x-ray diffraction patterns with
respect to each other and to reference x-ray diffraction patterns. How do the peak positions
and relative peak intensities vary between each sample? Are there any observed signs of
crystallographic texturing in any of the samples? How do you know, and if so, in which
direction and for what hkl plane?
2. Determine the lattice parameter for each of the Cu-Ni foil samples using the extrapolation
method discussed in Brandon and Kaplan. For the Cu and Ni foils, compare your calculated
lattice parameter to the known values for Cu and Ni.
3. Make a plot of lattice parameter versus mole fraction of Ni (i.e., x). Does the lattice
parameter you calculated for the Cu0.70Ni0.30 sample (i.e. 70 mol. % Cu) agree with the
predicted value according to Vegard’s Law? Note: Use mole fraction and not weight
fraction for the calculations.
4. For the unknown alloy sample, determine the lattice parameter (extrapolated value) from
the XRD data and then determine the composition of this sample using Vegard’s Law.
5. For the Cu sample use the extrapolated lattice parameter to calculate the relative error (i.e.
the % error) for lattice parameter calculated from each diffraction peak. Make a plot of the
absolute value of this error vs. θ. Is there a trend?
6. Repeat step 9 for the nickel, the Cu0.70Ni0.30 sample (70 mol. % copper), and the unknown
alloy. Combine all the data onto one graph. Comment on your major sources of error.

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Powder Mixture Analysis (Determining Phase Composition) for Cu-Fe powder

As we will discuss more in lecture, it is possible to determine the volume percent of

individual crystalline phases present in a mixture by analyzing XRD peak intensities. As one would
guess, increasing the volume percent of one crystalline phase at the expense of other crystalline
phase(s) will increase the intensity of diffraction peaks of that crystalline phase relative to the other
phase(s) present in the sample. However one must also account for other factors that can affect
XRD peaks heights. These other factors include correcting for the angular dependence of the
absorption/beam profile, the angular dependence of the Lorentz Polarization factor, the
multiplicity of planes in a crystal, the variation in peak intensity with temperature (which is also
angular dependent).

When comparing two x-ray diffraction reflections corresponding to two different

crystalline phases (named phase “A” and phase “B” in this example), the integrated diffraction
peak intensity can be described as,

𝐾𝑅𝐴 𝑐𝐴
𝐼𝐴 = (1)
2µ𝑚

where K is a constant known as the Scale Factor (which accounts for the overall instrument
performance and will be canceled out later), cA is the volume fraction of phase A, RA is an angle-
dependent term related to phase A that depends on its Structure Factor and other factors (see
below), and µm is the absorption coefficient for the mixture at the x-ray wavelength λ that is used.
When comparing two diffraction peaks from phase A and B, the volume fraction of the two phases
can be determined by comparing the ratios of the above equation,

𝐼𝐴 𝑅𝐴 𝑐𝐴
= and 𝑐𝐴 + 𝑐𝐵 = 1 (2)
𝐼𝐵 𝑅𝐵 𝑐𝐵

For the Cu and Fe mixture, the diffraction patterns are indexed using FCC and BCC
structures respectively. The (111) peak of Cu can be compared with the (110) peak of Fe to
determine the relative contributions of the two components. As mentioned above, the term Ra is
angle dependent and is more appropriately described by uniquely to an hkl plane via the
relationship,

1 1+cos2(2𝜃)
𝑅 = [ 2] [|𝐹|2 𝑝 ( )] 𝑒 −2𝑀 (3)
𝑉 sin2 (𝜃)cos(2𝜃)

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where V is the volume of a unit cell, p is the planar multiplicity (how many planes contribute to a
reflection), and F is the Structure Factor for the specific hkl reflection under analysis. The Structure
Factor, F, depends on the Atomic Scattering Factor, f, of the elements in the phase and the crystal
structure of the phase. The weighted average of multiple components can be used for f. The
Structure Factors for cubic crystals can be summarized with the following relationships,

F = f for simple cubic for all reflections,

F = 2f for BCC when h + k + l is even,
F = 4f for FCC for unmixed hkl.

The f values for Cu and Fe as a function of the scattering angle are found in the hand out
from Cullity. The temperature factor, e-2M, can be read off the figure also given in the handout
from Cullity (assume Fe is similar to Cu in this respect).

In this analysis section, perform the following tasks:

1. Label all peaks in your XRD pattern of the Fe-Cu powder mixture.
2. Determine the lattice parameters of Fe and Cu using the same method described in the Cu-
Ni alloy analysis. You will need the lattice parameters to later calculate the unit cell
volumes.
3. Calculate the ratio of integrated X-ray diffraction peaks intensities between the Cu (111)
and Fe (110) peaks.
4. Find the multiplicity for the (111) FCC and (110) BCC planes.
5. Calculate R for each phase (Cu and Fe) using the provided formulas above. Do a detailed
calculation that shows all the values used and determine the volume fraction of the two
phases. Calculate the weight fractions as well.
6. When performing an uncertainty analysis for THIS PART ONLY, only account for
instrumental uncertainty on 2θ and λ and ignore random uncertainty.
7. Describe in general how you can use XRD to determine whether a sample is single phase
or multi-phase.

Grading: Since this experiment is the individual report for the course, the post-lab scoring for the
experiment will follow the scoring breakdown for the Lab Report described in the syllabus.
However the pre-lab and running log scores will be included in the Lab Notebook scoring for the
course and have the following point breakdown:

 Pre-lab assignment:10 points

 Lab notebook: 30 points

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