SHIMADZU XRD-7000 X-RAY DIFFRACTOMETER

The Fridge

Operating
Instructions

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Table of Contents
Introduction

RADIA TION

SAFETY

Interactions of X-rays with Matter

Radiation Sources in the X-ray Diffraction

Laboratory

Working Safely with X-rays

BACKG ROUND

Background Information

X-ray Powder Diffraction

The Conventional Powder Diffractometer

References

SAMPL E

PREPA RATION

Preparation of Powder Samples

Preparation of Solid Samples

INSTR UMENT

O PERATIO N

Instrument Startup

Sample Loading

System Parameters Setup

10

Test Conditions Setup

11

Testing

13

Cleanup

14

Hardware Shutdown

14

DATA

ANALYSI S

Processing Data

15

Analyzing Data

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Introduction

he Shimadzu XRD-7000 Maxima is a state-of-the-art, multipurpose x-ray diffraction

system that is optimized for powder diffraction studies of crystalline materials. The
system is outfitted with a high-precision theta-theta goniometer (this is good) and a
large sample stage. The software system includes a powerful search/match tool and
the full International Center for Diffraction Data (ICDD) reference database of over 148,000
material phases. Many hardware upgrades environmental chambers, fiber analysis fixtures,
automatic sample loaders, etc. and software upgrades are available for the XRD-7000 system.
When some of you graduate, start companies, get rich, and throw some money back at Olin, we
may be able to afford a few of the cool upgrades.

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Radiation Safety1,2

-rays produced by the diffractometer pose a very real danger. Human tissue can be
severely damaged if exposed to the x-rays used in x-ray diffraction. Long-term,
chronic exposures at moderate levels can directly cause a variety of skin disorders, and
chronic relatively low- level exposures may be a factor resulting in increased cancer
risk in exposed personnel. Although modern XRD equipment includes safeguards designed to
minimize or eliminate radiation in the work environment, an awareness of the dangers of
radiation exposure and associated safety issues is required for anyone using the x-ray
diffractometer.

Interaction of X-Rays with Matter

X-rays are a type of electromagnetic radiation that interacts with matter. That interaction takes
place as either absorption (transfer of energy from the X-ray photon to the absorbing material) or
scattering (in which the X-ray photon is redirected by interaction with the scattering material).
The process of scattering is primary in producing diffraction data from test specimens, but both
processes result in the production of a variety of potentially damaging secondary radiation that
can produce significant short- and long-term health effects in the event of exposure of human
tissue.
The X-rays produced for diffraction analysis consist of characteristic radiation dependent on the
anode target plus the continuous spectrum. Recall that the energy of X-rays and their wavelength
are inversely proportional (higher energy = lower wavelength), and that
the continuous spectrum minimum wavelength decreases as the
accelerating voltage (kV) of the X-ray source increases. Also important to
understand is that an increase in filament current (ma) and kV (beyond the
minimum value required to produce characteristic radiation for the target)
will result in an increase in the intensity of the generated X-rays but will
not change their energy.

Radiation Sources in the X-Ray Diffraction Laboratory

The x-ray diffractometer is a source of very intense radiation, and exposure of any part of the
body to the primary beam can deliver hundreds of times the maximum permissible yearly dose in
a second, and an hour of exposure to the diffracted beam can result in a years worth of
permissible exposure. Whereas a primary beam exposure will produce noticeable skin damage
very quickly, a diffracted beam exposure might not be physically noticed at all.

http://epswww.unm.edu, University of New Mexico, Department of Earth and Planetary Sciences

R. Jenkins and D. J. Haas (Philips Electronic Instruments), Hazards in the Use of X-Ray Analytical Instrumentation, X-Ray Spectrometry, Vol. 2, No. 3, July 1973

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Working Safely with X-rays

It is imperative that anyone working with the x-ray diffractometer be properly trained and
knowledgeable of its use in order to prevent injuries. If you do not feel you are properly trained
to use the diffractometer, seek appropriate assistance from a competent and experienced user.
To minimize (and hopefully eliminate) the likelihood of exposed to radiation in the laboratory,
our x-ray diffractometer includes many safety-related features, including
Complete shielding of the X-ray source and diffracted beam such that all radiation is
contained within an enclosed area.
Fail-safe safety interlocks installed on the x-ray chamber that prevent accidental opening of
the chamber door. If the door is forced open, the X-ray source is turned off. The x-ray
source will not operate if the door is open.
A fail-safe indicator light should be present which is illuminated when the x-ray source is
turned on.
Sealed openings of the chamber to eliminate any possible leakage.
Under no circumstances should anyone attempt to override any of the safety features of the x-ray
diffractometer.
The system should be checked for leakage periodically with the system at operating conditions
using properly calibrated survey equipment. The system should also be checked if any of the
following conditions exist:
Any change in the components of the system (with the exception of minor components such
as scattering and receiving slits).
Prior to and after any maintenance requiring the disassembly or removal of a component in
the system
Anytime a visual inspection of the system reveals an abnormal condition.
For routine operations of modern X-ray powder diffractometers, the radiation exposure in
routine operations should be virtually nonexistent.

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Background Information

NOTE: The following background text is taken directly or adapted from the Diffraction Methods section of ASM
Handbook, Volume 10 Materials Characterization.

X-ray diffraction techniques are some of the most useful in the characterization of crystalline
materials, such as metals, intermetallics, ceramics, minerals, polymers, plastics, or other inorganic
or organic compounds. X-ray diffraction techniques can be used to identify the phases present in
samples from raw starting materials to finished product and to provide information on the
physical state of the sample, such as grain size, texture, and crystal perfection. Most x-ray
diffraction techniques are rapid and nondestructive; some instruments are portable and can be
transported to the sample. The sample may be as small as an airborne dust particle or as large as
an airplane wing. In general, x-ray analysis is restricted to crystalline materials, although some
information may be obtained on amorphous solids and liquids. XRD samples are acceptable in
many forms, depending on the availability of the material and the type of analysis to be
performed. Single crystals from a few microns to a few inches in diameter or loose or
consolidated aggregate of many small crystals can be used. Although the overall size of the
sample may be large, the actual area of the sample examined in a given experiment rarely exceeds
1 cm2.
The type of information obtained from x-ray diffraction studies ranges from sample composition
to details of the crystal structure or the state of orientation of the crystallites. Phase identification
can be conducted on virtually all single crystal or powder samples. Also useful are measurements
of the physical state of a sample that detect differences from the ideal crystal (presence of defects,
strain, etc.).

X-ray Powder Diffraction

X-ray powder diffraction techniques are used to characterize samples in the form of loose
powders or aggregates of finely divided material. These techniques cover various investigations,
including qualitative and quantitative phase identification and analysis, determination of
crystallinity, microidentification, lattice-parameter determinations, high-temperature studies, thin
film characterization, and, in some cases, crystal structure analysis. The powder method is
perhaps best known for its use as a phase characterization tool partly because it can routinely
differentiate between phases having the same chemical composition but different crystal
structures (polymorphs). Although chemical analysis can indicate that the empirical formula for a
given sample is FeTiO3, it cannot determine whether the sample is a mixture of two phases (FeO
and one of the three polymorphic forms of TiO2) or whether the sample is the single-phase
mineral FeTiO3 or ilmenite. The ability of x-ray powder diffraction to perform such
identifications more simply, conveniently, and routinely than any other analytical method explains
its importance in many industrial applications as well as its wide availability and prevalence.

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In general, an x-ray powder diffraction characterization of a substance consists of placing a

powder sample of a crystalline material in a collimated monochromatic beam of x-radiation.
Chapter 3 of your textbook describes the process of x-ray diffraction, and how the XRD finds the diffraction pattern
for your material. The diffraction pattern is recorded on film or using detector techniques, then
analyzed to provide x-ray powder data.
In x-ray powder diffraction analysis, samples usually exist as finely divided powder (usually less
than 44 m in size) or can be reduced to powder form. The particles in a sample comprise one or
more independently diffracting regions that coherently diffract the x-ray beam. These small
crystalline regions are termed crystallites. Consolidated samples, such as ceramic bodies or asreceived metal samples, will likely have crystallites small enough to be useful for powder
diffraction analysis. The size limitation is important in x-ray powder diffraction because most
applications of powder diffraction rely on x-ray signals from a statistical sample of crystallites.
Braggs Law (Equation 1) states that the angular position, , of the diffracted x-ray beam depends
on the spacing, d, between planes of atoms in a crystalline phase and on the wavelength, , of the
x-ray.
n = 2d sin

[1]

The intensity of the diffracted beam depends on the arrangement of the atoms on these planes.
A powder pattern from a single-phase material will have maxima at positions dictated by the size
and shape of its unit cell and will increase in complexity as the symmetry of the material decreases,
as shown in Figure 1. For example, many metal patterns and those from simple compounds that
tend to be mostly of cubic symmetry and have small unit cell edges will produce powder patterns
having fewer lines or maxima than would be expected from a compound of lower symmetry or
one having a very large unit cell. A pattern of a mixture of phases in which all the individual
patterns are superimposed will produce a complex experimental pattern, especially when the
number of phases present in the mixture exceeds approximately three or when the phases
constituting the mixture are all of very low symmetry or have very large unit cell dimensions.

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Figure 1. Two superimposed XRD graphs. Note that the CH4 hydrate has distinctly more
peaks than Ice (Ih), since it has a much more complex crystalline structure.

Phase identification using x-ray powder diffraction is based on the unique pattern produced by
every crystalline phase. Much as a fingerprint is unique for each person, the diffraction pattern can
act as an empirical fingerprint for that phase, and qualitative identification of phases can be
accomplished by pattern-recognition methods that include established manual techniques and the
newer methods that use computers, most of which implement programs based on heuristic
algorithms. All of these methods make use of the database maintained by the JCPDS
International Centre for Diffraction Data.

The Conventional Powder Diffractometer

Although film techniques have been in use since the inception of x-ray diffraction, the advent of
powder diffractometer has been more recent. Powder diffractometers have been in use as a
laboratory tool since the late 1950s and early 1960s.
The Bragg-Brentano geometry is used most commonly for powder diffractometers. Figure 2
shows this geometry as used for vertical diffractometers. In the vertical geometry, the axis A is
horizontal.

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In the variation of the Bragg-Brentano geometry that the Olin XRD system uses, termed the -
diffractometer geometry, the sample is held stationary with its surface in a horizontal plane as the
x-ray tube and the detector move.

Figure 2. Geometry of the Bragg-Brentano diffractometer. F, line source of x-rays

from the anode of the x-ray tube; P, soller slits (collimator); D, divergent slit; A, axis
about which sample and detector rotate; S, sample; R, receiving slit; RP, receiving
soller slits; SS, scatter slit.

See the ASM Handbooks, Volume 8 Residual Stress Measurements Nondestructive Procedures for
additional information on XRD instrumentation.

References

Callister 3.16 (on the CD)

Askeland Section 3.9

ASM Handbooks Online, Volume 10 Materials Characterization, Diffraction Methods.

http://unit.aist.go.jp/eutech/euhydrate/image/X_ray.jpg - XRD Graph

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Sample Preparation

Preparation of Powder Samples

1. Use fine powder if possible. If your powder is coarse (>240 grit or xxx microns), grind it with

a mortar and pestle or a ball mill.

2. If only a small quantity of powder is available, skip to Step 3. If a large quantity of powder is

available, fill the recess of an aluminum sample holder with powder and use a flat object, e.g.,
a glass slide, to level the powder with the top face of the sample holder. Skip to step 4.
3. If you dont have enough powder to fill the recess of an aluminum sample holder, youll need
to deposit some of your powder onto a glass slide. Mix a few drops of amyl acetate, acetone,
or methanol with some of your powder to create a paste. Spread a thin, even layer of the
paste onto the middle of a glass slide. Its important to maintain a fairly flat sample surface, so
try to avoid bumps and chunks. When youre satisfied with the deposited layer, wait for the
solvent to dry.

Preparation of Solid Samples

1. Prepare a flat sample with approximate dimensions of 1 wide x 2 long x 3/16 (maximum)

thick.
2. Remove all dirt, grease, etc. from the surface of the solid.
3. Load your sample.

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Instrument Operation

This section will walk you through the basic operation of the x-ray diffractometer. Youll have to
follow a series of tasks that includes
Powering up the instrument,
Loading your sample,
Viewing system parameters and calibrating the instrument,
Setting your testing conditions,
Collecting x-ray diffraction data for your sample, and
Analyzing your results.
It may seem boring at times, but itll be worth it! Just think of yourself as a mad scientist armed
with the power to identify completely unknown samples. Is it mullite (kind of like a fossilized
mullet)? Is it diamond? Is it ice-nine? Only your analysis will tell.

Instrument Startup
1. Turn on the water chiller. The switch is on the right side of the front panel.
2. Turn on the XRD main power supply. The switch is on the left side of the instrument.
3. Turn on the computer and login as guest to the this computer domain (not

MILKYWAY). You dont need a password.

Sample Loading
Load your sample, as follows:
1. Open the XRD chamber door. Inside the chamber, you will see a complex hardware system
with a large sample area (in the middle) and two arms that rotate around the sample stage
area. The x-ray source is mounted on the left arm, and the x-ray detector is mounted on the
right arm. Unless you know what youre doing, you shouldnt touch anything connected to
the rotating arms.
2. Locate the sample mounting fixture in the center of the stage assembly. The mounting
fixture is a half cylinder with two spring clips (on the underside) that protrudes from the top
center of the stage assembly.
3. With the sample facing up and toward you, slide your sample holder between the half-cylinder
and the spring clips. If you are using an aluminum sample holder, you should center the
holder (left and right edges flush with the half cylinder) and slide the holder all the way back.
4. Be careful not to get any of your powder on the XRD hardware. If you do, please wipe it off
with a soft tissue or paper towel.

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System Parameters Setup

1. To open the XRD hardware status software, double click the 1-Display System Parameters

icon on the desktop.

a. When asked to open and close the XRD chamber door, do it. This step checks the safety
interlocks on the XRD chamber.
b. When asked to calibrate, answer yes. This step calibrates the goniometer position. When
this step is complete, you should see some numbers appear next to the Theta (deg) and
2Theta items under the Right System heading.
2. Minimize the Display or XRD System Parameter Setup Program window or move the

box to the bottom right of the screen (its sometimes nice to leave the window visible while
youre testing).

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Test Conditions Setup

1. Double click on the 2-Set Test Conditions icon on the desktop to open the Untitled-Right

Gonio System: Analysis Condition Edit Program window. This will open a box like this:

2. To open a new test parameters window, double click on the highlighted (blue) box under Edit

Analysis Condition. This will open a large dialog box with lots of adjustable test parameters.
The default parameters (shown below) are fine for a typical scan (35 min.), but if youd like to
speed things up a bit, try changing the Scan Speed to 4 deg. per minute.

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3. When you hit OK, the following dialog box opens. Type in a filename, sample name, etc.,

and hit New to create a new folder for your data.

4. Hit Close to close the Standard Condition Edit dialog box. This will send you back to the

Untitled-Right Gonio System: Analysis Condition Edit Program window. Dont close
the window.

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Testing
1. Now you need to do something weird to satisfy the quirky (or should I say lousy) software.

You need to minimize all your windows and double click on the 3-Run Test icon on the
desktop. This will open the Right Gonio System: Analysis and Spooler Program testing
window, and for some mysterious reason, opening this window is required at this point.
Minimize the new window that appears.
2. Return to your Untitled-Right Gonio System: Analysis Condition Edit Program
window, which should still be open from the previous steps.
3. Click on your test method (in blue below) and hit the Append button.

4. Click the Start button. This may or may not start your test (depending on whether its the

first test to be run since the machine was turned on). You can tell that the test has started if
the x-ray source clicks on and the goniometer parts start moving.
5. Click on the Right Gonio System: Analysis and Spooler Program window to see a live
view of the data collection. If the test started in Step 4, youll see some action. If the test did
not start in Step 4, hit the Start button now, and the test should begin.
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6. Once the test has started, sit back and enjoy the show. The entertainment value of live x-ray

diffraction data collection lies somewhere between Star Wars: Episode I and Star Wars:
Return of the Jedi. For those who arent Star Wars fans, the live data collection lies
somewhere between watching paint dry and watching lead oxide-laden rain water fall from
our buildings.

Cleanup
1. If you were testing one of the powders used in the materials science courses, return the

powder to the vial. Otherwise, dispose of your powder in an appropriate manner.

2. Rinse the sample holder with DI water. You may need to use a cleaning brush to remove all

the powder from the aluminum sample holders. Return the aluminum sample holders to the
XRD desk.

Hardware Shutdown
1. Turn off the main XRD power (left side of the instrument).
2. Wait approximately 20 minutes to allow cooling of the x-ray source, then turn off the

water chiller.

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Data Analysis

This section will walk you through basic data processing and x-ray pattern analysis. It should be
noted that analysis of x-ray diffraction data is not always easy or straightforward, particularly when
dealing with samples that contain multiple crystalline phases. This section presents a simplified
look at data processing and analysis; there are a lot of little analytical tricks that are not presented
here. You should seek help from experienced users if you have trouble analyzing a pattern.

Processing Data
1. Double click on the 4-Process Data icon on the desktop to open the XRD: Basic Process

window (shown below).

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2. Open Windows Explorer and find your raw data file in the c:/xddata/Standard xxx, where

xxx are some numbers. The last Standard xxx directory should contain a folder with your
sample name followed by some numbers. Open the folder with your sample name.
3. Drag and drop the *.raw data file into the background of the XRD: Basic Process window.
An XRD pattern should appear, as shown below.

4. Click on the Go button on the toolbar to process your data with the standard parameters.

This step will smooth your pattern, subtract background noise, separate overlapping peaks,
and search for peaks.
5. You should end up with a series of XRD patterns like those shown in the following image. If
everything looks ok, hit the save button on the toolbar to save the processed data.

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Analyzing Data
1. Double click on the 5-Analyze-Search-Match icon on the desktop to open the Untitled:

XRD Qualitative Analysis window.

2. Open your processed data file with the pkr extension.

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Your pattern with marked peaks should appear in the window, as follows:

3. Go to SearchPre-Search in the pull-down menus. Click the search button to accept the

default background parameters. You may want to increase the Background Intensity value if
your pattern is very noisy and full of low intensity false peaks. The Background Intensity
number is a percentage of the maximum peak intensity.

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You should now see a number of blue peaks in the Peak Data and Residual Peak boxes, as
shown below.

4. Now the fun begins. Go to SearchSearch in the pull-down menus to open the search

Conditions dialog box.

5. Unless you know something about your sample (whether it is a mineral, organic, inorganic,
metal, etc.), select the MAX search option to search all 148,000+ files in our diffraction
databases. The other default parameters are usually fine, but you may want to consider
changing the following:
a. Matching Peaks: Value could be lowered if you only have a couple of peaks, or raised if
you arent having much success with the automatic search/match.
b. B.G. Intensity: Value should match what you entered for step 3.
c. Window Width: Value could be lowered if you have a relatively pure sample and a
pattern with high intensity, narrow peaks.
d. Exist Atom, Major Atom, and Absent Atom: These buttons open a periodic
table dialog box that will allow you to select atoms that you know are present or absent in
your sample. You may want to use this feature if you already have chemical data from
another analysis, e.g., EDS or ICP.

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6. Hit the Search button and wait for the computer to search through the tens of thousands of

database entries. The result of the search is a list of possible matching materials, as shown in
the example figure on the next page. The software places the matching hits in order,
starting with the best match. Scroll through the matching hits, and you should see the
diffraction peaks from the hit appear in the <Card Data> graph.
In the example shown below, the first hit (SiO2) clearly matches the collected and processed
data. Take a look at the peak locations (d value) and intensities it couldnt be much better!
Your sample may correspond to one of the first few hits, or it may not.. If it does not seem
to match any of the suggested compounds, dont lose hope. Try entering some different
search parameters and running the search again. Also, keep in mind that many real x-ray
diffraction samples contain multiple crystalline phases, so look for compounds that match a
few but not necessarily all of the diffraction peaks.

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NOTE: If you do start to lose hope with the search/match program, call someone with a lot
of x-ray diffraction experience.
7. Entering Database Cards. Once you have found a database card that seems to match your

x-ray diffraction pattern, you may enter the card as a hit by clicking on the Entry button on
the toolbar (the 6th button from the left) and clicking OK. The entry action will tag your card
with a specific color, and the card peaks will appear in the <Entry Data> graph. You may
enter as many matching peaks as you like. Each entry will be tagged with a different color.
To erase entered cards, click on the Erase button on the toolbar (the 7th button from the left).
8. Subtracting Found Peaks. You may wish to re-run the search without the peaks from the

matching database entries. To do so, click on the SearchSubtract option from the pulldown menu and click on OK. This will mark matching peaks in red on the <Residual
Peaks> graph and leave un-matching peaks in blue. Run the search as before (see Step 6
above), and you will receive search results for just the un-matching residual peaks.

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