X-RAY FLUORESCENCE

INSTRUMENT CALIBRATION
Theory and Application

by

Brian Lee Francom

A senior thesis submitted to the faculty of

Brigham Young University-Idaho

in partial fulfillment of the requirements for the degree of

Bachelor of Science

Department of Physics

Brigham Young University-Idaho

December 2008
Copyright © 2008 Brian Lee Francom

All Rights Reserved

ii
 BRIGHAM YOUNG UNIVERSITY-IDAHO

DEPARTMENT APPROVAL

of a senior thesis submitted by

Brian Lee Francom

This thesis has been reviewed by the research committee, senior thesis coordinator, and
department chair and has been found to be satisfactory.

___________________ __________________________________________
Date David Oliphant, Advisor/Senior Thesis Coordinator

___________________ __________________________________________
Date Ryan Nielson, Committee Member

___________________ __________________________________________
Date Ryan Dabell, Committee Member

___________________ __________________________________________
Date Stephen Turcotte, Chair

iii
 ABSTRACT

X-RAY FLUORESCENCE
INSTRUMENT CALIBRATION
Theory and Application

Brian Lee Francom

Department of Physics

Bachelor of Science

This report unveils all the measures taken to fully implement and calibrate the newly
installed x-ray fluorescence (XRF) detector in the Brigham Young University-Idaho x-
ray diffraction (XRD) instrument. X-ray and XRF theories are discussed. Different
calibration methods discussed include linear and quadratic approximations, linear and
cubis spline interpolations, and optimization. LabVIEW 7.1 programming code is
explained. Resulting XRF measurements are compared with accepted values and show
a calibration with a mean error of ±0.03 keV.

iv
 ACKNOWLEDGEMENTS

To my loving and patient wife, Danielle,

and to David Oliphant, who has guided me in this project.

v
Contents

ABSTRACT ................................................................................................................. iv
ACKNOWLEDGEMENTS ......................................................................................... v
List of Figures ............................................................................................................. vii
List of Tables ..............................................................................................................viii
Chapter 1 Introduction ................................................................................................ 1
1.1 History of XRF ............................................................................................... 1
1.2 Basic XRF Setup ............................................................................................ 1
Chapter 2 Review of Theory ........................................................................................ 5
2.1 XRF Theory .................................................................................................... 5
2.1.1 Elastic and Inelastic X-ray Scattering ...................................................... 5
2.1.2 Characteristic Radiation and its Measurement ......................................... 6
2.1.3 Continuous Radiation ............................................................................... 7
2.2 Calibration Theory ........................................................................................ 8
2.2.1 Linear and Quadratic Approximations ..................................................... 9
2.2.2 Linear and Cubic Spline Interpolation ................................................... 10
2.2.3 Optimization Method.............................................................................. 11
2.2.4 Calibration Sample ................................................................................. 11
Chapter 3 BYU-Idaho XRF Instrumentation .......................................................... 13
3.1 Previous Work.............................................................................................. 13
3.2 Specifications ................................................................................................ 13
Chapter 4 Study .......................................................................................................... 15
4.1 The Best Calibration Method ..................................................................... 15
4.2 Code Development ....................................................................................... 15
4.2.1 LabVIEW 7.1 Basics .............................................................................. 15
4.2.2 Creating the Calibration Program ........................................................... 15
4.3 Calibration Sample Development............................................................... 17
4.3.1 Sample Preparation ................................................................................. 17
4.4 Implementing the Calibration Program .................................................... 19
Chapter 5 Conclusion ................................................................................................. 21
Bibliography ................................................................................................................ 23
Appendix A: Various X-Ray Spectra ....................................................................... 24
Appendix B: A Typical Spectrum Data File ........................................................... 27
Appendix C: X-ray Energy Tables .......................................................................... 28

vi
List of Figures

Figure 1 The components of basic XRF instrumentation setup. A picture of the

setup is shown in Figure 12. ......................................................................... 2
Figure 2 A simplistic spectrum. Each pair of peaks typically represents one
element in the sample. .................................................................................. 2
Figure 3 The BYU-Idaho XRF/XRD instrument. ......................................................... 3
Figure 4 A simplistic model of the XRF process. (a) An incident x-ray ejects the
K-shell electron. (b) The atom returns to ground state by transitioning
an L-shell electron to the K-shell. ................................................................ 6
Figure 5 Four common electron transitions used in XRF measurements. ..................... 7
Figure 6 A simplistic spectrum with peaks from two elements. Typically, each
element in the sample will have pronounced Kα and Kβ peaks. The
continuous radiation of noise in the spectrum is called bremsstrahlung...... 8
Figure 7 A detailed view of the multi-channel analyzer (MCA). The small boxes
represent channels. The numbers represent a count of x-rays for a
specific energy. ............................................................................................. 8
Figure 8 The linear approximation method. ................................................................ 10
Figure 9 The linear interpolation method. ................................................................... 11
Figure 10 The cubic spline interpolation method. ....................................................... 11
Figure 11 The XRF detector. ....................................................................................... 14
Figure 12 An inside look of the XRF instrument. At top middle is the x-ray tube.
At right is the sample for testing. At bottom left is the XRF detector ...... 14
Figure 13 The block diagram view of the LabVIEW 7.1 calibration program. .......... 16
Figure 14 The sample used for calibration. ................................................................. 18
Figure 15 The front panel view of the LabVIEW 7.1 calibration program. ................ 20

vii
List of Tables

Table 1 Characteristic x-ray energies for select elements. .......................................... 17

Table 2 Compounds used in the calibration sample. ................................................... 18
Table 3 Trace amounts in the compounds listed in Table 2. ....................................... 18
Table 4 Experimental values and accepted values along with the corresponding
errors. .............................................................................................................. 21

viii
ix
 Chapter 1

Chapter 1 Introduction

1.1 History of XRF

X-ray fluorescence (XRF) has been proven to be a very useful technique for elemental
analysis of materials. Since its early beginnings, the field of XRF has blossomed into
one of the most important tools in materials analysis. The benefits of using XRF
rather than a traditional analysis method are that it is quick, non-destructive, and all-
inclusive (multiple tests are not required).

The power of XRF analysis was first realized by Henry Moseley in 1912,
seventeen years after Wilhelm Röntgen had discovered the x-ray. Moseley found that
it was possible to excite a sample and gather information from the x-rays being
emitted. Although Moseley was using electrons to excite the sample, it was realized
years later that x-rays could be used instead. The use of x-rays had a great advantage
over the use of electrons; when electrons were used, it was only possible to analyze
materials with a very high melting point, because of the inefficient energy conversion
by electrons [1]. After this discovery, a greater variety of materials were enabled to be
analyzed, making XRF an even more versatile analysis method.

1.2 Basic XRF Setup

The setup of XRF instrumentation is really quite simple; it generally consists of four
basic components [1]:

1. An excitation source
2. A sample
3. A detector
4. A data collection and analyzing system

The excitation source is typically an x-ray tube, but a radioactive isotope may
also be used; the BYU-Idaho XRF instrument uses an x-ray tube. The x-ray tube
sends a beam of x-rays with various energies to the sample, and the sample absorbs
and emits the x-rays to the detector. The detector senses each impinging x-ray and

1
Chapter 1

sends electrical pulses to the data collection and analyzing system. The analyzing
system categorizes each x-ray by its energy. Then, the data is collected and stored;
this is typically done with a computer (Figure 1).

An XRF measurement essentially gives two pieces of information: The energy

of an x-ray, and how many x-rays were received (count number or intensity for that
energy). When graphed in a spectrum, the energy of the x-rays is the independent
variable, and the count number is the dependent variable. A typical spectrum of such
data will show one or more peaks for each element present in the sample (Figure 2).

X-ray Tube

X-rays

Computer (Data
collection and storage)

Sample

Detector Analyzer

Figure 1 The components of basic XRF instrumentation setup. A picture of the setup is shown in Figure 12.

Intensity

Energy
Figure 2 A simplistic spectrum. Each pair of peaks typically represents one element in the sample.

2
 Chapter 1

While the XRF method is very quick and efficient, it can also give very
inaccurate results if the instrument is not calibrated correctly. This is a result of two
particular systematic errors: First, the instrument is not perfect and tends to drift from
previous calibrations, and second, characteristic x-ray energies are not totally unique
to an element and often overlap with other characteristic x-rays, as illustrated in
Section 2.1.2. These two errors can be resolved by implementing a good calibration
program and using it as often as necessary. BYU-Idaho has an x-ray diffraction
(XRD) instrument which is located in the Geology Department laboratory (Figure 3).
Since it was recently adapted to also perform XRF with a newly installed Amptek x-
ray/gamma ray detector, a proper calibration needed to be implemented. This work
focuses on the measures taken to appropriately calibrate the BYU-Idaho XRF
instrument.

Figure 3 The BYU-Idaho XRF/XRD instrument.

After calibration methods were researched, and a better calibration program

was created and implemented, the XRF measurements increased in accuracy. Because
of this calibration, users are now enabled to collect reproducible data with a mean
error of ±0.03 keV and a minimum error of ±0.01 keV.

3
Chapter 1

4
 Chapter 2

Chapter 2 Review of Theory

2.1 XRF Theory

2.1.1 Elastic and Inelastic X-ray Scattering

X-rays can interact with matter in several different ways; this section will focus on
only the two most common interactions which are elastic and inelastic scattering.
Scattering refers to the dispersed radiation that comes as a result of these interactions
[1].

Elastic scattering, also referred to as coherent or Rayleigh scattering, occurs

when an x-ray collides with an electron in an atom and no energy is lost in the
collision. In this case, the x-ray is best thought of as an electromagnetic wave. An
electron in the atom is oscillated in this wave, and the oscillating electron will radiate
an electromagnetic wave of the exact same energy as the incident x-ray. This re-
radiated x-ray generally leaves the atom in a random direction.

Inelastic scattering, also referred to as incoherent or Compton scattering,

occurs when an x-ray collides with an electron in an atom and its energy is transferred,
in whole or in part, to the electron. In this case, the x-ray is best thought of as a
photon. This photon can either bump the electron into higher orbital energies or eject
the electron completely from the atom. The incident x-ray photon will then deflect
away from the atom with a corresponding loss of energy (Figure 4).

The case in which the incident x-ray has sufficient energy to eject the electron
from the atom is called the photoelectric effect. As a result of this effect, the atom has
an electron vacancy and is considered to be in an unstable energy state. Since XRF
involves the study of x-rays emitted from unstable atoms (see Section 2.1.2), the
photoelectric effect is instrumental to XRF in providing these unstable energy states.
Electrons which are ejected due to the photoelectron effect can be studied using x-ray
photoelectron spectroscopy (XPS).

To visualize how an electron reacts to inelastic collisions, the atom’s electronic

structure is modeled with various electron shells surrounding the nucleus. The
innermost shell is called the K-shell, the second innermost shell is called the L-shell,

5
Chapter 2

and so forth. These shells represent different energies for orbitals having differing
quantum number n. Other discrete energies exist within each shell which are due to
different subshells (orbitals of identical n but differing l) within each shell. However,
the energy differences between subshells are typically less than 0.50 keV. The easiest
unstable energy state to visualize is one in which the electron from the K-shell is
ejected, which is also the most commonly occurring state in XRF; this is called a K-
shell vacancy, as shown in Figure 4(a). Because of conservation of energy, the
unstable atom will adjust its electron configuration to compensate for the lost energy.
This phenomenon is discussed in the next section.

2.1.2 Characteristic Radiation and its Measurement

Every element has a set of characteristic x-rays. A characteristic x-ray has a very
specific energy that is unique to an element. For example, if an x-ray is measured to
have energy of 6.40 keV, it is very likely that x-ray was emitted from an iron atom.
Therefore, a characteristic x-ray can be thought of as an element’s “thumbprint.”

In the previous section, it was mentioned that an incident x-ray of sufficient

energy will eject an electron from an atom, leaving a vacancy. The atom will then
adjust its electron configuration to be in the lowest energy state; in other words, an
electron in a higher shell will drop down to fill the vacancy. The process of an
electron filling the vacancy creates an x-ray which is characteristic of a specific
electron transition for that element (Figure 4(b)).

M M

L Incident L

x-ray
K K

Ejected
electron Characteristic
x-ray
(a) (b)
Figure 4 A simplistic model of the XRF process. (a) An incident x-ray ejects the K-shell electron. (b) The atom
returns to ground state by transitioning an L-shell electron to the K-shell.

Typically, most electron transitions occur from the L-shell to the K-shell,
which is classified as a Kα transition. The second most common electron transition
occurs from the M-shell to the K-shell, which is classified as a Kβ transition. Two

6
 Chapter 2

other common transitions are the Lα and Lβ transitions (a transition from the M-shell
to the L-shell, and from the N-shell to the L-shell, respectively). When an atom
returns to its ground state, it typically does so using more than one electron transition.
As shown in Figure 5, XRF measurements are mainly concerned with these four
transitions because they are the most common and they are the most easily seen, while
other transitions have characteristic energies that are out of the detectable range of the
BYU-Idaho XRF instrument (Figure 5).

N
Lβ

M Kβ Lα

L Kα

Nucleus

Figure 5 Four common electron transitions used in XRF measurements.

One can notice by looking at a table of characteristic x-ray energies that the Kα
and Lα energies for many elements are very similar (see Appendix C), [7], [8]. For
example, the Kα energy of titanium (4.510 keV) is very close to the Lα energy of
barium (4.467 keV); this introduces a difference of only 0.043 keV [9]. Thus, a need
arises for better calibration in order to resolve overlapping energies.

2.1.3 Continuous Radiation

In every XRF measurement where an x-ray tube is used for the excitation source, a
broad range of energies is observed, producing a non-linear background noise in the
spectrum. The radiation that causes this is called continuous radiation or
bremsstrahlung (German for “braking radiation”). In the x-ray tube, electrons are
accelerated over a large potential difference, followed by rapid deceleration at the
anode. From this, a continuous range of x-rays are produced that may provide for
excitation of many different atoms [6]. The noise created from continuous radiation
does not impede measurements, providing the peaks of interest are relatively more
intense than the noise (Figure 6).

7
Chapter 2

Intensity Kα peaks

Kβ peaks

bremsstrahlung

Energy
Figure 6 A simplistic spectrum with peaks from two elements. Typically, each element in the sample will have
pronounced Kα and Kβ peaks. The continuous radiation of noise in the spectrum is called bremsstrahlung.

2.2 Calibration Theory

Since characteristic x-rays are the main factor in making an XRF measurement, it is
essential to be able to accurately measure their energies; this can only be done after a
calibration is performed. In this case, the equipment needing calibration is the
detector and multi-channel analyzer (MCA) system.

Once an x-ray impinges on the detector, the detector sends an electrical pulse
to the MCA. One can think of the MCA as a desktop coin sorter. Just as the coin
sorter will place each coin in its appropriate bin depending on the coin’s size, the
MCA will “place” each x-ray in its appropriate channel depending on the x-ray’s
energy. The data recorded is an array of numbers, each number representing the total
count of x-rays for that energy (intensity). The number placement in the array
represents the channel number, in ascending order (Figure 7).

Detector

0 1 2 1 1 3 6 8 9 7 3 2 1 1 4 3 1 1 0 0
1 keV 5 keV 10 keV 15 keV 20 keV

Multi-Channel Analyzer

Figure 7 A detailed view of the multi-channel analyzer (MCA). The small boxes represent channels. The numbers
represent a count of x-rays for a specific energy.

8
 Chapter 2

A calibration is a process in which specific energy values are assigned to the

correct channel in the MCA. This is done by sending x-rays of known energy values
to the MCA; once the user identifies the channels where the x-rays were sorted, he or
she can assign the known energy values to those channels. Since it is not practical to
assign energy values to each channel manually, the calibration process consists of
identifying six to eight channels with known energy values and then applying a curve
fitting technique to those data points. Through this method, all the channels in the
MCA can be calibrated indirectly.

Many calibration methods exist. For this work, it suffices to review three
methods. Each method assumes that the calibration data has at least six data points.

2.2.1 Linear and Quadratic Approximations

A linear or quadratic approximation is one of the most general curve-fitting

techniques. In cases where the data appear to be linear, a linear approximation can be
sufficient. To do this, one would apply the least-squares regression equations to find
the slope and intercept of the fitted line. These equations are

y  mx  b (1)

sy
mr (2)
sx

b  y  mx (3)

Equation (1) represents the linear fit where x represents the channel number
(independent variable), and y represents the energy (dependent variable). The symbols
s x and s y are the sample standard deviations of the channel data and the energy data,
respectively; m is the slope of the line, b is the y-intercept of the line, r is the
correlation coefficient, and x , y are the mean x and y values [2].

A linear approximation is the easiest calibration to perform, but it also

introduces the most error (about ±0.1 keV); this results because the MCA does not
have a perfect linear correlation between energy and channel number. Therefore, it
does not result in the desired accuracy (Figure 8). A slightly better approximation is
done with a quadratic least-squares regression, yet this still results in a higher error
than what is desired, with an error of about ±0.05 keV. This results because these two
approximation methods fit a single curve to the whole data set.

9
Chapter 2

.
Energy
.
.
. .
Channel Number

Figure 8 The linear approximation method.

2.2.2 Linear and Cubic Spline Interpolation

The spline interpolation method is used to interpolate between every data point for a
more accurate calibration (it is also used for extrapolation near the end points of the
graph). This method has the advantage of uniquely fitting a line between pairs of data
points; hence, it is not a general fit like the approximation method. A linear
interpolation involves taking two data points and fitting a line between those points
(Figure 9). This is done for every gap between two adjacent data points. The
equations for the linear interpolation are the same as equations (1), (2), and (3), only
using two data points at a time.

The cubic spline interpolation method involves the same design as the linear
interpolation, only creating polynomials for the curve fitting [3]. This requires that
three or more points are used for each calculation (Figure 10). For a cubic spline
interpolation

y  Ay 0  By1  Cy0  Dy1 (4)

where
x1  x
A B  1 A (5)
x1  x0

C
6
 
A  A x1  x0 
1 3 2
D 
1 3
6

B  B x1  x0 
2

Similar to the linear interpolation, x is the independent variable (channel

number), and y is the dependent variable (energy). The functions A, B, C, and D are

10
 Chapter 2

used as substitutions to the main equation (4) and are all functions of x. Using the
cubic spline interpolation method, the error is reduced to about ±0.02 keV.

.
Energy Energy
.
.
. . .
Channel Number Channel Number

Figure 9 The linear interpolation method. Figure 10 The cubic spline interpolation method.

2.2.3 Optimization Method

In principle, the optimization method would provide the most accurate calibration by
using the whole data set taken from the calibration sample rather than six to eight data
points as used in the approximation and spline interpolation methods. In the
optimization method, the calibration spectrum is compared point by point with a
predicted spectrum which simulates what the calibration spectrum should look like.
As the two spectra are compared, the calibration spectrum is adjusted to achieve
minimum error with respect to the predicted spectrum. The goal is to provide a
calibration spectrum that has a very high correlation coefficient with the predicted
spectrum.

In order to create a predicted spectrum, a correct set of all the peaks would
need to be modeled; this would include the proper modeling of the peak intensities.
Also, a proper bremsstrahlung would need to be modeled and included in the
spectrum. There exists a detailed article which describes the appropriate methods for
peak simulation by E. D. Greaves, et al [4]. While the optimization method could
reduce the error to ±0.01 keV or better, simulating a predicted spectrum is difficult
and time consuming. Therefore, the optimization method is not practical in this case.

2.2.4 Calibration Sample

The calibration sample preferably contains an adequate number of elements to provide

sufficient peaks for calibration; typically, there are at least six to eight peaks in the

11
Chapter 2

spectrum. These peaks should be separated from other peaks by at least 3 to 4 keV to
avoid confusion in assigning peaks to their corresponding elements. The
concentration of each element should be adjusted such that all peak intensities are
approximately equal.

A calibration sample made from a variety of compounds should be

homogeneous. To ensure this is done, all compounds to be included are crushed into a
fine powder using a mortar and pestle. The mixture is then made into a slurry using
acetone, set into a sample plate, and smoothed out to dry; the sample plate allows for
easy insertion into the XRF instrument. A well prepared and easily accessible
calibration sample will improve the calibration procedure.

12
 Chapter 3

Chapter 3 BYU-Idaho XRF Instrumentation

3.1 Previous Work

This work mainly follows that of Lance Nelson and David Oliphant. Lance Nelson
worked to install a new XRD detector which was donated to BYU-Idaho. His study
was focused on the anatomy of x-ray detectors and their application [5]. David
Oliphant has spent much time installing and implementing an Amptek XRF detector in
the XRF/XRD instrument, and it is ready for calibration and measurements (Figure
11).

Amptek, the company that produced the XRF detector and the MCA, provides
software to run both of these components. This software has been installed on the
computer in the XRF laboratory. The software enables the user to easily run an
experiment and record the data. The software also includes a built-in linear and
quadratic approximation calibration feature. After some use of this calibration feature,
we concluded that it could not provide an accuracy of ±0.01 keV.

3.2 Specifications

The x-ray tube in the instrument produces x-rays with energies up to about 30 keV.
The XRF detector is not very sensitive in the range between 0 keV and 3 keV, and
measurements in this range tend to be quite problematic; consequently, data in this
range do not serve for accurate XRF measurements and are typically ignored.

The MCA has a total of 16,000 channels; this allows a maximum resolution of
about 0.003 keV per channel. The resolution can be adjusted using the Amptek
software; the maximum resolution can be obtained when the 16,000 channel option is
selected. We have chosen to use the 8,000 channel option because minimum errors of
±0.01 keV can still be obtained with this resolution, and the XRF measurements take
about half the amount of time on this setting compared to using the 16,000 channel
option.

13
Chapter 3

Figure 11 The XRF detector.

Figure 12 An inside look of the XRF instrument. At top middle

is the x-ray tube. At right is the sample for testing. At bottom
left is the XRF detector

14
 Chapter 4

Chapter 4 Study

4.1 The Best Calibration Method

Observation indicated that the most efficient calibration would result from using a
cubic spline interpolation; this method gives the desired accuracy, and LabVIEW 7.1
has a built-in spline interpolation function which is easy to use. We concluded that the
linear and quadratic approximations and the linear interpolation do not give the
desired accuracy. Using the optimization method can give an equally or more
accurate calibration than a spline interpolation, but the underlying mathematics and
code necessary for this method were impractical. Therefore, for sakes of accuracy and
time, a cubic spline interpolation method was used and implemented.

4.2 Code Development

4.2.1 LabVIEW 7.1 Basics

LabVIEW 7.1 was the programming language of choice for its visual ease. It is
relatively easy to debug, and console input/output is simple to implement. LabVIEW
7.1 employs small icons to represent functions and wires to represent data transfers.
For and while loops can be easily performed; these looping structures appear as boxes
in the block diagram. There are also sub-programs called virtual instruments (VI’s)
that can be called to perform more complex functions. Specifically, some of the VI’s
that were used in this calibration program were the Peak Detection VI, Spline
Interpolant VI, Spline Interpolation VI, and xy-Graph VI.

4.2.2 Creating the Calibration Program

The goal of the calibration program was twofold: First, to read a calibration file and
calculate the cubic spline interpolation calibration, and second, to read a file
containing data from an unidentified sample and determine the elements in that
sample.

15
Chapter 4

The first objective in creating the calibration program was to enable reading of
the XRF calibration spectrum file. This is done by using the “read file” icon. These
spectrum data files always have header information which is easily skipped by
instructing the program to start reading after “<<DATA>>.” An example of a typical
spectrum data file displaying the header information is shown in Appendix B.

After reading the data and organizing it into a one dimensional array, the next
step consisted of using the Peak Detection VI. This VI searches through the data for
peak locations. Its sensitivity can be controlled using the threshold and width values.
Specifically, the threshold is the intensity value below which peaks are neglected, and
the width is the number of data points used in determining a peak, similar to a width
value used in a smoothing function. The threshold and width values should be
carefully chosen; visually evaluating the spectrum in advance is helpful in determining
these values, especially the threshold value. The width value, in practice, is between 8
and 16 but should be no higher than 20; width values higher than 20 result in
inaccurate peak locations.

Having obtained the peak locations, the program pairs them with their
corresponding energy values. These energy values are input by the user and
correspond to the known elements and their characteristic x-rays. The program then
runs these values through a while loop to calculate the spline interpolation for
calibration. After the spline interpolation routine, the while loop yields a one
dimensional array containing the calibrated energies, the number representing the
calibrated energy, and the number placement in the array representing the
corresponding channel (Figure 13 shows the block diagram view). The calibrated
energies array is then ready to be used as a calibrated x-axis for an XRF measurement.
The program graphs the calibration spectrum and the spectrum to be identified in the
same plot, using the calibrated x-axis.

Figure 13 The block diagram view of the LabVIEW 7.1 calibration program.
16
 Chapter 4

4.3 Calibration Sample Development

For the calibration sample, elements were chosen from the periodic table based on the
energy differences between each element, ensuring a difference of at least 3 to 4 keV.
These elements, along with their corresponding characteristic x-ray energies [9], are
shown in Table 1.

Table 1 Characteristic x-ray energies for select elements.

Element Name Kα Energy (keV)a Kβ Energy (keV)a
Manganese 5.899 6.490
(Copper) 8.048 8.905
Bromine 11.924 13.292
Strontium 14.165 15.836
Molybdenum 17.479 19.607
Cadmium 23.174 26.095
a
Reference [9].

Because the anode in the x-ray tube is composed of copper, many of the
characteristic x-rays of copper are reflected off the sample to the detector. As a result,
copper peaks are present in every XRF measurement. It is a difficult process to
eliminate the copper peaks from the spectrum, and seeing that the copper peaks did not
affect the measurement, we determined that copper can be used as one of the
calibration elements.

4.3.1 Sample Preparation

To create the sample, compounds were obtained from the BYU-Idaho chemistry
department. The manganese, bromine, strontium, and cadmium compounds were
available, but the molybdenum compound was not. The compounds were available in
salt, hydrated salt, and hydrated nitrate forms.

Before mixing the compounds, a thorough study was performed to calculate

the proportionalities of the elements in each compound. The goal was to make a
calibration sample that had equal amounts of the elements of interest; this way, it was
believed the intensities of each peak in the spectrum would be equal. Using
molarities, the mole per compound mass was formulated for each compound and was
used to calculate the correct proportions for the calibration sample. After the sample
was constructed and measured, observation showed that the manganese and strontium
peaks were five to six times the intensity of the other peaks, and the cadmium peak
was 1/20 to 1/30 times the intensity of the other peaks. Three more samples were
made in an effort to improve the intensity levels, but all three still had disproportionate
intensity levels.

The ratios of the intensity levels of the first four samples served as a means to
re-calculate the proportionalities and create a better sample. A final sample was made
and measured, and observation showed that the peak intensities were within two to

17
 Chapter 4

three times the intensities of the surrounding peaks. The copper peak intensity was
disproportionately large; however, this intensity cannot be controlled because these
copper characteristic x-rays are emitted from the x-ray tube. The actual amounts of
compounds used in the calibration sample and the trace amounts in the compounds are
shown in Table 2 and Table 3.

Table 2 Compounds used in the calibration sample.

Compound Amount Used (grams) ±0.0003 grams
MnCl2 ·4H2O 0.0117
KBr 0.0224
SrCl2 ·6H2O 0.0706
Cd(NO3)2 ·4H2O 4.0357

Table 3 Trace amounts in the compounds listed in Table 2.

Compound Cl Cu Fe Pb Zn Ba Other
MnCl2 ·4H2O - - .0005 .0005 .01 - .210
KBr .20 - .0005 .0005 - .002 .04
SrCl2 ·6H2O - - .5 ppm .5 ppm - .002 .0521
Cd(NO3)2 ·4H2O .001 .002 .001 .005 .05 - .1135

When creating the first four samples, no acetone was necessary to combine
them since three of the compounds were hydrates. The water in the compounds was
released when the mixture was crushed and combined, providing a homogeneous
solution which was easily set into the sample plate. The fifth and last sample did not
release as much water as the first four, so a small amount of acetone was used to help
combine the mixture (Figure 14).

Figure 14 The sample used for calibration.

18
 Chapter 4

4.4 Implementing the Calibration Program

Once the program was constructed, the next step consisted of implementing the
program. Initially, we thought that one could simply upload the calibration file onto
the computer connected to the XRF instrument and use it in the Amptek software.
Unfortunately, this was not the case; the software only allows its own calibrations to
be used. This meant that another solution not involving the Amptek software had to
be employed.

After some inspection, it became apparent that a spectrum file from the XRF
instrument could be easily uploaded into the calibration program itself. The
calibration program was modified to enable the spectrum file to be imported and then
plotted on the calibrated energy axis.

The front panel of the program (Figure 15) was made so that the user could
input and adjust the known calibration energy values. In the “Calibration” box, the
user can adjust the peak detection sensitivity values (threshold and width). Displayed
in this box is the calibration fit graph, the number of calibration peaks detected, and
the locations of the detected peaks. The adjacent “Materials Identification” box
enables the user to adjust the peak detection sensitivity values for the unidentified
spectrum. Displayed in this box are the number of peaks detected and the
corresponding element energies of those peaks. The main graph displays both the
calibration spectrum (dashed line) and the spectrum for identification (solid line).

Upon running the program, a dialog box opens which asks for a spectrum file
(typically from an unidentified sample) to be uploaded. After the file is uploaded, the
program runs the calibration process and plots the spectra. The main graph in Figure
15 shows a spectrum taken from a silver ring. To see spectra of the calibration and
other samples, see Appendix A.

By comparing two calibration spectra which were taken two and a half months
apart, it is seen that the maximum drift in any energy value is approximately 0.03 keV.
Since the MCA has this tendency to drift in accuracy over a two and a half month
period, it is recommended that the calibration sample be tested and implemented at
least once a month to ensure accuracy.

19
Chapter 4

Figure 15 The front panel view of the LabVIEW 7.1 calibration program.

20
 Chapter 5

Chapter 5 Conclusion
After calibration methods were researched and a better calibration program was
created and implemented, several different samples were measured and compared to
the accepted values [9]. These measurements, along with their corresponding
accepted values, are shown in Table 4.

Table 4 Experimental values and accepted values along with the corresponding errors.
Element Name Transition Measured Accepted Absolute
Energy (keV) Energy (keV)b Error (keV)
Iron Kα 6.388 6.404 .016
Iron Kβ 7.052 7.058 .006
Silver Kα 22.085 22.163 .078
Gold Lβ 11.453 11.442 .011
Nickel Kα 7.492 7.478 .014
Zinc Kα 8.671 8.639 .032
b
Reference [9].

Mean Error Maximum Error Minimum Error

.026 .078 .006

Measurements in the lower range of energies (3 to 15 keV) tend to have a

lower error amount, and measurements in the higher range of energies (15 to 28 keV)
tend to have a higher error amount. However, as a result of the calibration, the XRF
measurements have in general increased in accuracy. Users are now able to collect
reliable sample data, down to a mean error of about ±0.03 keV and a minimum error
of ±0.01 keV.

Throughout the course of this project, a variety of future supplementary

projects have been uncovered. Prospective students will find this project helpful as
they consider the following possibilities:

1. A study of the XRF detector sensitivities at low x-ray energies

There are many instances when an XRF measurement has detected excessive
noise in the lower range of the spectrum. Often, there tend to be large peaks

21
Chapter 5

around one or two keV. A detailed study about this anomaly would be useful
since many elements have characteristic x-rays in this region.

2. The development of a program that automatically qualifies elements in the

sample
The program written in this project is currently capable of detecting peaks in
an unidentified spectrum, and the characteristic x-ray energies are listed.
However, extra effort is required on behalf of the user to look up the energies in a
list to identify which elements are present in the sample. Furthermore, the user
might need to identify two or more peaks for one element to be certain that it is
present in the sample. With some alteration of the calibration program, this
process could be automated.

3. The development of a program that quantifies elements in the sample

Some quantifying work was performed in this project to determine correct
proportionalities for the calibration sample. A deeper study of quantification can
be done using ratios of intensities of different peaks in the spectrum. The
calibration program can be altered to make these calculations. A program that
quantifies elements in the sample is useful in a variety of applications.

4. The development of a calibration sample that has a larger energy range

The calibration sample in this project has eight useful peaks ranging from 6
keV to 23 keV. A calibration sample can be made to have more than eight useful
peaks in a broader range of energies. In the current calibration, there was growing
error as energy increased in the 18 to 28 keV range. A calibration sample with
more peaks in this range can substantially reduce this error.

These different areas were lightly examined in this project, but due to limited time,
they were not studied in depth. It is hopeful that a prospective student will choose to
further develop the BYU-Idaho XRF instrument.

22
Bibliography

[1] R. Jenkins, X-Ray Fluorescence Spectrometry (John Wiley & Sons, Inc., New
York, 1999), 2nd ed., p. 5-12, 75-76.

[2] M. Sullivan, Fundamentals of Statistics (Prentice Hall, 2006), 2nd ed., tables.

[3] W. H. Press, S. A. Teukolsky, W. T. Vetterling, B. P. Flannery, Numerical

Recipes in C (Press Syndicate of the University of Cambridge, New York,
1992) 2nd ed., p. 105-116.

[4] E. D. Greaves, L. Bennum, F. Palacios, and J. A. Alfonso, X-Ray Spectrom. 34,

196-199 (2005).

[5] L. J. Nelson, Senior Thesis, BYU-Idaho (2007).

[6] P. V. Espen, in Handbook of X-Ray Spectrometry, edited by R. E. V. Grieken

and A. A. Markowicz (Marcel Dekker, Inc., New York, 2002), Chap. 4, p. 239-
242.

[7] HoribaJobin Yvon, Table of X-Ray Emission Lines,

www.jobinyvon.com/xray, accessed 12/07/2008.

[8] HoribaJobin Yvon, Table of X-Ray Emission Lines,

www.jobinyvon.com/xray, accessed 12/07/2008 (modified).

[9] Lawrence Berkeley National Laboratory, Table of Radioactive Isotopes,

http://ie.lbl.gov/toi/, accessed 11/21/2008.

23
Appendix A: Various X-Ray Spectra

Cu

Sr
Br

Mn Cd

This spectrum shows the peaks measured from the calibration sample.

24
A spectrum of a metal car key likely containing Ni and Zn

A spectrum of an unknown sample likely containing Fe

25
 A spectrum of a U.S. dollar coin likely containing Ni

A spectrum of an unknown rock sample likely containing Fe

26
Appendix B: A Typical Spectrum Data File
<<PMCA SPECTRUM>>
TAG - live_data
DESCRIPTION -
GAIN - 5
THRESHOLD - 50
LIVE_MODE - 0
PRESET_TIME - 0
LIVE_TIME - 4113.826667
REAL_TIME - 4132.213333
START_TIME - 11/07/2008 13:57:30
SERIAL_NUMBER - 2542
<<CALIBRATION>>
LABEL - Channel
00
1058 8.05
<<ROI>>
706 821
979 1104
1501 1621
1784 1918
2933 3091
<<DATA>>
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0

27
Appendix C: X-ray Energy Tables

28
29
30
Lα 2.7 45Rh Kβ 5.95 24Cr Lα 10.84 83Bi Kβ 22.72 45Rh
Kβ 2.81 17Cl Lβ 5.96 61Pm Kβ 10.98 32Ge Kα 23.17 48Cd
Lβ 2.83 45Rh Lα 6.06 64Gd Lβ 11.07 78Pt Kβ 23.82 46Pd
Lα 2.84 46Pd Lβ 6.21 62Sm Lα 11.13 84Po Kα 24.21 49In
Lβ 2.9 46Pd Lα 6.27 65Tb Kα 11.22 34Se Kβ 24.94 47Ag
Kα 2.96 18Ar Kα 6.4 26Fe Lα 11.43 85At Kα 25.27 50Sn
Lα 2.98 47Ag Lβ 6.46 63Eu Lβ 11.44 79Au Kβ 26.1 48Cd
Mα 3 90Th Kβ 6.49 25Mn Kβ 11.73 33As Kα 26.36 51Sb
Mα 3.08 91Pa Lα 6.5 66Dy Lα 11.73 86Rn Kβ 27.28 49In
Lα 3.13 48Cd Lβ 6.71 64Gd Lβ 11.82 80Hg Kα 27.47 52Te
Lβ 3.15 47Ag Lα 6.72 67Ho Kα 11.92 35Br Kβ 28.49 50Sn
Mα 3.17 92U Kα 6.93 26Co Lα 12.03 87Fr Kα 28.61 53I
Kβ 3.19 18Ar Lα 6.95 68Er Lβ 12.21 81Tl Kβ 29.73 51Sb
Lα 3.29 49In Lβ 6.98 65Tb Lα 12.34 88Ra Kα 29.78 54Xe
Kα 3.31 19K Kβ 7.06 26Fe Kβ 12.5 34Se Kα 30.97 55Cs
Lβ 3.32 48Cd Lα 7.18 69Tm Lβ 12.61 82Pb Kβ 31 52Te
Lα 3.4 50Sn Lβ 7.25 66Dy Lα 12.65 89Ac Kα 32.19 56Ba
Lβ 3.49 49In Lα 7.42 70Yb Kα 12.65 36Kr Kβ 32.29 53I
Kβ 3.59 19K Kα 7.48 28Ni Lα 12.97 90Th Kα 33.44 57La
Lβ 3.6 50Sn Lβ 7.53 67Ho Lβ 13.02 83Bi Kβ 33.62 54Xe
Lα 3.6 51Sb Lα 7.6 71Lu Lα 13.29 91Pa Kα 34.72 58Ce
Kα 3.69 20Ca Kβ 7.65 26Co Kβ 13.29 35Br Kβ 34.99 55Cs
Lα 3.7 52Te Lβ 7.81 68Er Kα 13.4 37Rb Kα 36.03 59Pr
Lβ 3.84 51Sb Lα 7.9 72Hf Lβ 13.45 84Po Kβ 36.38 56Ba
Lα 3.94 53I Kα 8.05 29Cu Lα 13.61 92U Kα 37.36 60Nd
Kβ 4.01 20Ca Lβ 8.1 69Tm Lβ 13.88 85At Kβ 37.8 57La
Lβ 4.03 52Te Lα 8.15 73Ta Kβ 14.11 36Kr Kα 38.72 61Pm
Kα 4.09 21Sc Kβ 8.26 28Ni Kα 14.17 38Sr Kβ 39.28 58Ce
Lα 4.1 54Xe Lβ 8.4 70Yb Lβ 14.32 86Rn Kα 40.12 62Sm
Lβ 4.2 53I Lα 8.4 74W Lβ 14.77 87Fr Kβ 40.75 59Pr
Lα 4.29 55Cs Kα 8.64 30Zn Kα 14.96 39Y Kα 41.54 63Eu
Kβ 4.46 21Sc Lα 8.65 75Re Kβ 14.96 37Rb Kβ 42.27 60Nd
Lα 4.47 56Ba Lβ 8.71 71Lu Lβ 15.24 88Ra Kα 43 64Gd
Kα 4.51 22Ti Lα 8.91 76Os Lβ 15.71 89Ac Kβ 43.83 61Pm
Lβ 4.62 55Cs Kβ 8.91 29Cu Kα 15.78 40Zr Kα 44.48 65Tb
Lα 4.65 57La Lβ 9.02 72Hf Kβ 15.84 38Sr Kβ 45.41 62Sm
Lβ 4.83 56Ba Lα 9.18 77Ir Lβ 16.2 90Th Kα 46 66Dy
Lα 4.84 58Ce Kα 9.25 31Ga Kα 16.62 41Nb Kβ 47.04 63Eu
Kβ 4.93 22Ti Lβ 9.34 73Ta Lβ 16.7 91Pa Kα 47.55 67Ho
Kα 4.95 23V Lα 9.4 78Pt Kβ 16.74 39Y Kβ 48.7 64Gd
Lα 5.03 59Pr Kβ 9.57 30Zn Lβ 17.22 92U Kα 49.13 68Er
Lβ 5.04 57La Lβ 9.67 74W Kα 17.48 42Mo Kβ 50.38 65Tb
Lα 5.23 60Nd Lα 9.71 79Au Kβ 17.67 40Zr Kα 50.74 69Tm
Lβ 5.26 58Ce Kα 9.89 32Ge Kα 18.37 43Tc Kβ 52.11 66Dy
Kα 5.41 24Cr Lα 9.9 80Hg Kβ 18.62 41Nb Kα 52.39 70Yb
Lα 5.43 61Pm Lβ 10.01 75Re Kα 19.28 44Ru Kβ 53.88 67Ho
Kβ 5.43 23V Kβ 10.26 31Ga Kβ 19.61 42Mo Kα 54.07 71Lu
Lβ 5.49 59Pr Lα 10.27 81Tl Kα 20.22 45Rh Kβ 55.68 68Er
Lα 5.64 62Sm Lβ 10.36 76Os Kβ 20.62 43Tc Kα 55.79 72Hf
Lβ 5.72 60Nd Kα 10.54 33As Kα 21.18 46Pd Kβ 57.52 69Tm
Lα 5.85 63Eu Lα 10.55 82Pb Kβ 21.66 44Ru Kα 57.53 73Ta
Kα 5.9 25Mn Lβ 10.71 77Ir Kα 22.16 47Ag Kα 59.32 74W

31