Physics 366 Lab Report 2

Michael Dobbs, Sonoma State University

November 11, 2014
Abstract
X-Ray Diractometry was used to analyze multiple samples to
identify their chemical composition and determine their structure.
Compiled data was used to calculate the extent of the sample.

Introduction

X-Ray Diractometry (XRD) is a powerful tool used to identify the structure

of a solid by sending X-Rays into the sample and detecting the constructive
interference of the waves that are reflected o of dierent planes within the
sample. The Bragg Law is used to calculate the lattice spacing from the angles where constructive interference occurs. The Jade program calculates the
orientation of the planes and uses a database of known diraction patterns to
help identify the sample used in the experiment. Tools within the program
can identify the full width at half maximum of the peaks which determines
the extent of the sample.

Background

Samples that are loaded into the XRD have various properties such as defining crystal structures, oriented planes, and varying amounts of dierent elements and structures. Samples must be crushed into a fine powder in order
for the XRD to properly assess these properties because the angle between
the detector and the x-ray source must be kept constant, thus needing a
seemingly smooth surface.
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2.1

Crystal Structure

Elements or compounds in the solid phase align their atoms in crystal structures with varying patterns, some complex and some simple. Single crystals
have all atoms linearly aligned in x, y, and z directions, creating cubes or
boxes. Polycrystalline structures are multi-domain, meaning their structure
and orientations change at domain boundaries throughout the sample. These
domains are on the long-range order, where transitions occur every couple
micrometers or so. Amorphous crystal structures are disordered and on the
short-range order, having domain boundaries every couple of nanometers.
These transitions are very random because the usual distance between atoms
is on the scale of .2nm or 2 angstroms.
When a repeating pattern of atoms occurs, called a basis, space lattices
are used to represent these bases as a single lattice point. This makes illustrating the structure of an atom much easier.
Crystal structures may be defined by repeating patterns called unit cells.
Each unit cell can be moved in the x, y, or z direction to create a repeating
pattern in the sample. Primitive cells are a type of unit cell where only a
total of one atom is encompassed in the cell. A simple cubic contains a cell
at every corner of the cube with an eighth of the atom occupying each cell.
Body-centered cubics look like a simple cubic, but with a lattice in the center
of cube, giving the unit cell a total of two atoms. Face-centered cubes have
the corners of a simple cubic and an atom on each of the six faces of the
cube, giving the unit cell a total of 4 atoms. Some structures are illustrated
in Figure 1. Knowing that a crystal is of a certain structure and having a
certain lattice spacing, one can calculate the density of atoms, or the number
of atoms per volume by dividing the number of atoms in a unit or primitive
cell by the area of that cell.

2.2

Miller Indices

Miller indices are used to describe the orientations of planes within a sample.
A vector connecting one side of the plane with another can be written as a
sum of scalar multiples of vectors in the x, y, and z directions:
~r = h
x + k y + l
z

(1)

where h, k, and l are scalar multiples. Using hkl notation, one may describe
a vector [h k l] that is perpendicular to the plane (h k l) where the plane is
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described by the the reciprocals of the x, y, and z intercepts of h, k, and l

respectively. Meaning if z is the intercept in the z direction, h = z1 . Some
illustrated planes and their respective Miller indices are shown in Figure 2.

2.3

Bragg Law

X-rays diracting o of dierent planes travel dierent distances. Constructive interference of these waves only occurs at certain angles due to the
periodicity of the waves. When constructive interference between the x-rays
diracting o of these planes occurs, a signal is received by the detector.
Otherwise, the destructive nature of these waves causes the signal to be diminished. The Bragg Diraction Law defines the periodicity of the detected
signal by equating the extra distance an adjacent x-ray must travel to the
wavelength of the incident beam. The Bragg Law is defined by:
2d sin() = m

(2)

where d is the lattice constant (distance between planes), is the angle of

incidence (between the incoming x-ray and the outermost plane of the crystal
structure), m is a positive integer, and is the wavelength of the incident
x-ray. An illustration is represented in Figure 3.

2.4

The X-Ray Diractometer

Utilizing the Bragg Diraction Law, the XRD emits x-rays onto a sample
and detects the constructive interference of the waves. By applying voltage
to a tungsten filament, electrons are emitted and accelerated toward a copper
target, where the electron bombards the copper target at high speed and its
kinetic energy is transferred to an emitted x-ray, using the equation:
eV =

hc

(3)

min

where e is the elementary charge, V is the accelerating voltage, h is the planck

constant, c is the speed of light, and is the wavelength of the emitted xray. This assumes that all of the energy of the electron is transferred to
the x-ray, which doesnt always occur. These x-rays are sent toward the
sample. Divergent slits are used to spread the x-rays across the sample,
and machinery guides the x-ray source and the detector along the sample
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at dierent angles ranging from 4-80 degrees. The detector catches signals
of constructive interference and counts how many it gets. Since x-rays are
very energetic, the detector can get very hot, so it is imperative that a cooler
be used so that the detector does not melt. Figure 4 depicts an X-Ray
Diractometer schematic. While scanning, the Jade program compiles the
data and creates the spectra.

Procedure and Safety

X-rays are low wavelength, high energy light waves that can easily damage
the skin. Precautions must be taken for the safety of the XRD user, and
procedures must be followed word for word to ensure the longevity of the
equipment.

3.1

Safety Measurements

To safely operate the XRD one must be familiar with the set-up and operating procedures. There are two sets of safety interlocks, one for the sample
cover and the other is the lucite doors. The sample cover must be correctly
harnessed, and the lucite doors must be closed. The lucite doors are made of
a heavy metal that reduces radiation. The reduction of radiation is proportional to the thickness of the doors, for example about .17mm of lead reduces
the radiation to ten percent of the original. When x-rays are being produced,
a red light turns on and can be observed outside the apparatus. Another way
to reduce radiation is distance. The farther you are away from the XRD, the
less radiation you will be exposed to, thus intensity is inversely proportional
to the square of the distance (inverse square law). Exposure time is the final
factor. The permissible limit of exposure is .24mrem/hr. An excellent way
to determine if there is an x-ray leak is use of the Geiger counter, which calculates the x-ray background. This device must be used before and during
the scan to ensure safety.

3.2

Operation of Machine

Before doing anything in the lab, one must sign in on the logbook detailing
the time, sample, and length of run. The sample can then be mounted with
all systems o, ensuring the cover is secured and the lucite doors are closed.
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A Geiger counter is used to check for leaks. The knife switch is then engaged
and the water circulation pump and chiller to cool the detector is turned
on. The XRD is then turned on and allowed to warm up. A check that the
shutters are closed is necessary. The emission of x-rays begins by pressing the
X-ray On button on the main console. To refrain from burning the tungsten
filament, the voltage and current must be tuned according to the directions
on the machine. The DMax is turned on and the computer is used to set-up
the scan using the Jade program.

3.3

The Jade Program

On the computer, MDI Jade 6.5 is used to operate the XRD. One may set
the range of angles to scan, how long the scan should commence for, and
collect data in the form of spectra. The spectra obtained come in the form of
a graph with 2 as the independent variable and Intensity as the dependent
variable. It contains diraction peaks at certain angles where the intensity
is high. Once the data is collected, the search/math feature of the Jade
program can be used to determine the identity of the sample. Jade uses a
database of known x-ray diraction peaks to match to the sample data, and
compiles a list that is organized in terms of how close the match is to your
data. Another factor that can be calculated from your data is the extent of
the sample, or how pure the sample is. This is determined by the full width
at half maximum of each peak, and the purest of samples will have a peak
mirroring that of the delta function. The Scherrer equation relates the size
of the domains in the sample to the broadening of the peak in the diraction
spectra following the formula:
=

K
cos()

(4)

where is the mean size of the domains, K is the shape factor, is the x-ray
wavelength, is the full width at half maximum, and is the Bragg angle
or angle of constructive interference. Not only can Jade calculate the angle
and extent, but also the lattice spacing and hkl indices. The Jade program
is a powerful tool for crystallography.

Data Analysis

Two samples were run in the course of the class periods. A Quartz sample was
determined to have very sharp and defined peaks. Under XRD analysis of the
sample, a spectra was obtained (Figure 5) and a search/match was done. The
search/match gave results of Quartz (SiO2 ) and SiO with a high percentage
of peak unity, telling us that the sample is most likely pure Quartz. The peaks
are well defined, meaning the sample does not have many imperfections. The
highest peak at around 2 = 26.62 was fit to a Gaussian curve in the form
of:
2
f (x) = e

(x
)
2 2

(5)

where the full width at half maximum is defined by:

F W HM = 2(2 ln(2))1/2

(6)

Table 1 displays each peak of the Quartz sample and its FWHM. The highlighted FWHM from table 1 coincides to the fit curve from Mathematica
(following Table 1). Jades calculation and the fitted curve calculation were
close (.22 and .204), therefore the fitting results agree with Jade. From interpreting the spectra of Quartz, one may infer that the sample is very well
defined because of the sharp peaks. This means that the data is very trustworthy, with a low standard deviation from the actual. Therefore the data
is accurate and the results are palpable.
In comparison, the Hoover Dam sample that was run had many peaks and
lots of noise. When a search/math was run on the sample, many compounds
had the possibility of being in the sample such as Magnesiohomblende, fluoroedenite, and Tremolite, to name a few. So many results were given that
matched many peaks in the spectra that the XRD Data cannot be the defining data of the sample. The spectra can be seen in Figures 6, 7, and 8 showing
the large amount of peaks and the small spacing between many peaks. When
peaks are this close, there is a big problem with dierentiating the two. There
also could be a peak hidden in the middle of the two, causing many problems
with identification. The sheer large number of peaks causes much overlap
between the XRD spectra of the suggestions that Jade gave, giving a large
number of results that could possible fit the data. Therefore the data is
inconclusive because there are too many possibilities for compound results.

Conclusion

When used safely, X-Ray Diractometry is a powerful tool used to determine

the identity of a sample, though the sample must be in powder form. XRD is
only conclusive when the relative number of search/match results is small or
when only a few of the suggested results have a high percentage of peak unity
or overlap, otherwise the data is inconclusive due to a high number of results
or much peak overlap. XRD can be used in unison with the EDX to better
conclude what is in the sample. By utilizing the Jade program, one may
calculate the lattice spacing and Miller Indices of the crystal structure from
the angle at which constructive interference occurs and therefore conclude
the structures within the sample.

Figures

Figure 1: Various Crystal Structures

Figure 2: Various Planes and Their Miller Indices in a Crystal

Figure 3: Illustration of Bragg Difraction and Lattice Spacing

Figure 4: An X-Ray Diractometer Schematic