XRD

X-RAY PoWDER DIFFRACTOMETRY

INTRODUCTION
owder
small
x-ray diffractometry is a
technique that is used to identify
crystals of the analytes based on
the ways nat
analytes scatter
monochromatic x-rays. An important application of
ractometry is to identify minerals in ore
samples. The minerals often occur as
making them ideal for study. The micro-cysta
ror identification of minerals in technique
is also used in such diverse fields as art
paints to determine the authenticity of art objects), conservauon
and To00
Science (for determination of
crystal phases of fats in foods). Unlike x-ray fluorescence, X-ray
diffractometry can be used to identify compounds, not just elements.
In powder
x-ray diffraction, monochromatic x-rays are directed towards a
sample containing
randomly-onented micro crystals. The micro crystals are comprised of
atoms.he planes are spaced a distance d from their
paralle! planes Of orderea
neighbours. These planes act much like
partally-silvered mirrors, reflecting some of the intensity of the x-ray beam, while transmitting the
rest. The beams that are reflected from the
planes can interfere constructively, resulting in a
measurable intensity at a detector, or destructively, resulting in no intensity, depending on ne
angle at which they reflect. Consider the figure, below.

X-Rays

Atomic
Planes d sine

Base Ptachnert Corfg

Rtechmert Detector

X-Ray Generator

Recevng Cuics
Idet 0pic

MiniFlex300
MiniFlex600 L Goniometer

32
The x-rays impinge the sample at an angle
0 and are reflected at the same angle. In order for the
to interfere constructively, the difference in the path
beams reflected from the various planes
number of wavelengths. This is known as the Bragg
lengths of the rays must be an integral
diffraction condition and is stated: (1)
na-2dsin0

1.5406 A). Hence, if one knows the

Where is the wavelength of the x-rays (for this experiment,
and the wavelength of the radiation,
angles at which x-rays are difracted (constructively interfere),
one can determine the distances between the planes
of atoms in the crystal. A diffractogram is
a measure of the reflected intensity vs. twice the angle from the surface normal of the crystal.
The measured angle is 20 because experimentally it is only possible to measure the angle

between the incident and reflected beams, which (according to the figure) is 20.

We can expect many different angles for which the Bragg condition will hold because for any

given crystal there are many different arrangements of planes of atoms, and these planes will be
spaced different distances, d, apart. The distances are determined by the sizes of the atoms in
the crystal and their arrangements in space. Hence, each pure crystal will have a different
diffraction pattern.
The signal in XRD experiments is extremely low, so low, in fact, that single photons are detected
by the transducer. The unit of intensity in XRD experiments is the "count" (or "counts per
second"). One "count" is equal to one x-ray photon detected. Different diffractometers will
produce different absolute signals for the same analyte because of differences in detection
efficiencies, sample preparation, etc. For that reason, relative intensities of the peaks in a
diffractogram are reported in the literature. The relative intensity of a peak is
I Cpeakhg100 (2)
00 -Chg

Where Cpeak is the number of counts at the peak of interest, Cbg is the number of counts observed
for the background, and Cpcak is the number of counts at the
most intense peak in the
diffractogram. By this definition, the largest peak always has a relative intensity of 100.
The following experiment is meant as an introduction to some of the important aspects of XRD,
including sample identification and proper sample preparation

Part A: Collecting a Standard Quartz Diffractogram

Each student must bring a USB storage device to
store their data. DO NOT ATTEMPT ANY
PART OF THIS PROCEDURE UNTIL YOU
HAVE BEEN BRIEFED BY YOUR LAB
INSTRUCTOR. All instruments must be calibrated on a
The quartz standard used in this section regular basis to ensure quality of data.
produces peaks across the entire range of angles
Scanned by the diffractometer. By comparing the
positions of the peaks with literature
one can determine whether the scintillation
detector is properly values
in this experiment is a piece of natural sandstone that aligned. The quartz sample used
has been cut to fit into the
crystals of quartz in the sample are what create the diffractogram. instrument. Tiny

33
 XRD

1. e s s the Door Lock" button on the front of the MiniFlex 600 XRD. You will hear a Deeping
Sound, which lets you know that the shutter is closed and you can safely open the door.

Miniflex 600
CAUTION
&a Enabe

2. Pull the door open (it is stiff). Carefully in the quartz standard into the sample clips. Do not
use excessive force in doing this.
3. Once the quartz is inserted, close the door. The beeping should stop. MA
4. On the computer click the MiniFlex Guidance icon.
MiniFlex
5. The user name is Rigaku and there is no password. Guidance
6. Click on General Measurement in the pane on the right side of the screen.

Package
Preinstalled User defined

Packages ist:
7. Enter in the location that you wish to store the data, and the file
Maintenance
name as shown below. Detector Adjustment (SC)
Detector Adjustment D/teX)
General Measurement Create Angle Correcton Data

General Measurement
Automalic generalion of data fle names General Measurement
BasicParts
Dondition
Analysis
condtion Spin Sample
No. Exec. Folder Fle name Sample name Memo Set. 1
1 cdata quartz std quartz Nol
2
Nol Set
Not Se
3
4
No1 Set
Nol
5 0
6
No1
No1
7
Nol
8

9
Nol Set
10
Nol Set

Opbcal devioes confimaion message

XG lernination condition
Set Meas. Conditions
OStop theXRoy Show ODon't show
The stalus quo

Run OK Cancel

34
 XRD
11. Once the scan is
name is complete,
Rigaku and there is noyou can open t alysis software PDXL2. The user
password.
PDXL2
12. Under the file
option near
the top left corner, select load
quartz file that you just created. measurement datd al
Select temsto Display
13. Select the tems
Graph properties icon to adjust labelling. Click ] No.
Select and the one box that
should be selected is for"d value". d value
14. To export this file 2-theta value
into a format File EdtView Analysis Graph Help Height
that you can Rell. Height
import into Excel (or Daf Copy Data Measurement/Ptocessed Data

similar program), under Copy Image Salculated Data

Edit Print Resolution Phase Profile Data

Copy Data select Measurement

- Bactground Data
genaiue Data
/ Processed Data. Open Notepad Sir Datieuten Profie via

and paste the information. Save as a .txt file. There are several OK Cancel
different methods of exporting data, but with this method is one
that is used with a number of different instruments. Quartz Notepad
Notepad File Edit Format View Help
can be found from the
start menu. After you paste the
information to Notepad, make sure that you save this file to your quartz
2-theta (deg) Intensity (cps)
USB (it does not autosave).
20.000000 340.000000
20.050000 336.666667
15. At home, this file can be opened by first opening Excel, selecting 20.100000 353.333333
20.1500e0 393.333333
File Open Going to the USB where you have the file and
20.200000 430.000000
change the viewed files from "Excel files" to "All files". This will 20.250000 436.666667
open the Text Import Wizard. Clicking Next will bring you to
Step 2, ensure that the "Space box is checked. Click Next, and then
Finish. This will give you two columns, the first is your two theta TextImport Wizard- Step 2 of 3
values, and the second is the intensity. This can be used to
This screen lets you set the delim
reproduce your diffractogram in Excel if you highlight the values and preview below.
choose the (X,Y) Scatter Chart, which can be found on the Insert tab.
Delimiters

Tab
1? . Semicolon Treat
Recommended PivotChart Line Column UComma Text quali
Charts Space **********

Charts Sparkilines other

Insert Scatter 0X. Y) or Bubble Chart
Use this chart type to show the
relationship between sets of values
H
You can then take time to
Click the arrow to see the different properly label
types of scatter and bubble charts your axis, ensure that the scale is
available and pause the pointer on
the icons to see a preview in your
correct, make a proper title, and then
document. change your graph so that it is an entire
page.
 XRD

Effect of Grinding
Part B: The of unknown, you may see differences in
crystal structure your
size and
Depending on the particle and those that are coarsely around
are finely ground
samples that
between grinding.
orientation on Larger
the diffractogram randomisation of the crystallite

The changes
result from
increased
orientations. This changes the of ratios
in preferred
chance of aligning
diminished. Good sample
particles have a greater a c c e n t u a t e d and others
certain peaks are
the peak
intensities so that
because the peak intensities must to relate
quantitative work
therefore, critical for
preparation is,
concentration of analyte
in a reproducible way.
the

from your instructor and divide it into two

equal
of sodium chloride (NaCl)
1. Obtain a sample
parts. minutes until a fine powder is
pestle for about 5
or
a mortar and
2 Grind half the sample with
Leave the other half of the sample
unground.
obtained.

mount by covering the one side of the hole with cellophane

3 Prepare an aluminium sample
tape
4 Load the ground NaCl into the sample mount and pack it with a spatula. Carefully smooth the
top of the sample so that it is flush with the top of the aluminium mount. This is critical for
good resuts because the angle measurement is referenced to the top of the mount.
5 Pace a piece of yellow film on top of your sample, and tape around the edges to ensure your
ample does not fall out during a scan. Do not tape over the
top where the X-rays pass
Collect the diffractogram as described previously. Save the file to disk when
omplete, Repeat with the unground NaCl. Ensure that you collection is
have exported
allow for use in Excel each file to .txt to
Part C: Collection of a
Diffractogram of an Unknown Sample
Prepare your unknown sample by placing about
for about 5 minutes or until a fine 1g in a dean mortar
powder is obtained. and
1. Load your sample into the grinding it with a pestle
sample mount.
2 Scan your sample as
before, again
Part D:
Identification of the Unknownexporting to .txt.
ThePDXL2 software has
search the differer a
rather
is.
Performing a ases of each comprehensive
is often compound, andlibrary within it.
techniques in order tearch You
o
narrow the done in concert can identify what are able to
many options with other your sample a0e g
that are elemental
. To
panelperfom
a available. analysis
click the search of your
Auto Unknown, first open O
37 Search button. Dats Pro

the file
in
PDXL2, On the
left
 You are then given options to limit the scope Auhe Search
of the
search. For now click Execute to search the entire O Specdy nb
database. Irogr
Fgerds
Popm
Onge Supcondutrg ma
Mired elfed
CSD palm
peodct t d e paten
HOgc emert ard yaion
Lut Paulrgpaiten
Comon phate Pinary
3. On the right Conoei
panel you will see the various options with Edonal palien
the most probable
showing in the Candidate phase. erc
CGart magrelorent.arce
You can move elercsds
compounds up or down but usually the r d t o n

software gives the most probable candidates correctly. DPharmacecd

This is where you need to use some sense. We

are not
giving you radioactive unknowns, so you could
eliminate anything with uranium in it. This is where you
SuDAile Elementsfiter Other
would use information from other tests to
help narrov Cose

the options and

eventually identify your unknown.

4. You can look at the quality of the match by first selecting the Phase data view tab
Phase data view
from the center window, and then click the candidate
phase that you wish to compare to your Canddete ptes
diffractogram Phae name Chemical fomda OM FOM RIR DBcardn
(your unknown is not quartz). You can then use the Ovetz low S02 C 0150 306 41412

wheel on the mouse to move the intensity of the library match up and down. Look for
differences in intensity, and (more importantly) differences in peak position.
5. Once you are confident in the match
(your unknown is a single phase of a compound) click
the Set button in the bottom right corner of the screen. The table in the
bottom of the screen
will be updated to include the peaks that match from the library to your sample. The software
often picks up "peaks" that are actually noise.
Any "unknown" peaks should be looked at. If
they are noise, then they can be removed by clicking delete. If you think that they are a
it is possible that your sample has some contamination in it. Please
peak,
consult with your
6. Print your results for your unknown (please print
to.pdf). There are a number of report options
that appear when you click print. Please ensure that the "Profiles
with header and "Analysis
results: Peak list" are selected.

Print
X
tems toprint
Profles Oaystal sructure Analysis results: General
Profles with header Peak list Analysis resuts: Peak list
For empty vaue:
General phase informationAnalysis results: Profle parameters
OPhase data Data set
Analysis resuts: Structure parameters
3D profiles Data set management

tems Margin Range Header Footer

Print Setup. Preview.. Print dose

 Print all three graphs (on 3 separate sheets of 8.5°x11" paper). You may have to
Daper orientation from Portrait' to 'Landscape. This is done in
change the
Page Setup, under the File
menu.

11"
e 0 OkMa iarsadea)

8.5"

Inciude the report

that was made for your unknown from
Use the report sheets that are PDXL2
available on D2L
Answer the following questions on a
1. According to your separate sheet of paper in
quartz diffractogram, is the 12-point font.
2 What
might account for the difractometer properly
your quartz differences between the aligned? Explain.
3 Which NaCl
díffractogram and the standard
values?
relative intensities
that you
sample, ground or unground, behaves obtained from
4. The
xray intensities for more like the
this
represents the number of experiment are very low. standard?
energy of a photons that struck the The
the speed ofsingle photon is given by the detector y-axis on your
light, and . is the
Dower (in watts) of
the wavelength
equation E hc/), during the collection
of the
=

where his
diffractogram
diffractogramm
interval. The
5. largest peak your ground x-radiation Planck' s
Compari ng
what are the the report
that
in
NaCl (1.56x1010 constant,
cis
was made m).
benefits (or using PDXL2 diffractogram. Determine
the
6. 1f
you are disadvantages)
your unsure of the identity of of using Excelversus the one
compound and
compound more suggest other your
to
present your
that you
made in Excel,
identification.) precisely. propertieunknown,
s or explain why. data over
(This question doestechniques List all the PDXL2
that
not
apply to those be used possi
could
to
bilities tor
who made identify the
a positive
positive