Beruflich Dokumente
Kultur Dokumente
INSTRUMENT CALIBRATION
Theory and Application
by
Brian Lee Francom
Bachelor of Science
Department of Physics
Brigham Young University-Idaho
December 2008
ii
DEPARTMENT APPROVAL
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
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 xray 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
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 K and K 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 allinclusive (multiple tests are not required).
The power of XRF analysis was first realized by Henry Moseley in 1912,
seventeen years after Wilhelm Rntgen 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.
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.
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 xray/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.
Chapter 1
Chapter 2
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 Kshell 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.
Incident
x-ray
Ejected
electron
(a)
Characteristic
x-ray
(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 K transition. The second most common electron transition
occurs from the M-shell to the K-shell, which is classified as a K transition. Two
6
Chapter 2
other common transitions are the L and L 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
M
L
L
K
Nucleus
One can notice by looking at a table of characteristic x-ray energies that the K
and L energies for many elements are very similar (see Appendix C), [7], [8]. For
example, the K energy of titanium (4.510 keV) is very close to the L 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.
Chapter 2
Intensity
K peaks
K peaks
bremsstrahlung
Energy
Figure 6 A simplistic spectrum with peaks from two elements. Typically, each element in the sample will have
pronounced K and K peaks. The continuous radiation of noise in the spectrum is called bremsstrahlung.
Detector
0
1 keV
1
5 keV
10 keV
4
15 keV
0
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.
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.
mr
sy
sx
b y mx
(1)
(2)
(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.
Chapter 2
Energy
.
.
Channel Number
Figure 8 The linear approximation method.
(4)
where
x1 x
x1 x0
B 1 A
1 3
2
A A x1 x0
6
(5)
1 3
2
B B x1 x0
6
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
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
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
14
Chapter 4
Chapter 4 Study
4.1
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
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
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
Manganese
(Copper)
Bromine
Strontium
Molybdenum
Cadmium
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.
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.
Compound
MnCl2 4H2O
KBr
SrCl2 6H2O
Cd(NO3)2 4H2O
Compound
MnCl2 4H2O
KBr
SrCl2 6H2O
Cd(NO3)2 4H2O
Cl
.20
.001
Cu
.002
Fe
.0005
.0005
.5 ppm
.001
Pb
.0005
.0005
.5 ppm
.005
Zn
.01
.05
Ba
.002
.002
-
Other
.210
.04
.0521
.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).
18
Chapter 4
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
Iron
Iron
Silver
Gold
Nickel
Zinc
K
K
K
L
K
K
Measured
Energy (keV)
6.388
7.052
22.085
11.453
7.492
8.671
Accepted
Energy (keV)b
6.404
7.058
22.163
11.442
7.478
8.639
Absolute
Error (keV)
.016
.006
.078
.011
.014
.032
Reference [9].
Mean Error
.026
Maximum Error
.078
Minimum Error
.006
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]
[3]
[5]
[6]
and
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]
23
Cu
Br
Mn
Sr
Cd
This spectrum shows the peaks measured from the calibration sample.
24
25
26
27
28
29
30
L
K
L
L
L
K
L
M
M
L
L
M
K
L
K
L
L
L
K
L
L
K
L
L
L
K
L
K
L
L
L
K
L
K
L
L
L
L
K
K
L
L
L
L
K
L
K
L
L
L
L
K
2.7
2.81
2.83
2.84
2.9
2.96
2.98
3
3.08
3.13
3.15
3.17
3.19
3.29
3.31
3.32
3.4
3.49
3.59
3.6
3.6
3.69
3.7
3.84
3.94
4.01
4.03
4.09
4.1
4.2
4.29
4.46
4.47
4.51
4.62
4.65
4.83
4.84
4.93
4.95
5.03
5.04
5.23
5.26
5.41
5.43
5.43
5.49
5.64
5.72
5.85
5.9
45Rh
17Cl
45Rh
46Pd
46Pd
18Ar
47Ag
90Th
91Pa
48Cd
47Ag
92U
18Ar
49In
19K
48Cd
50Sn
49In
19K
50Sn
51Sb
20Ca
52Te
51Sb
53I
20Ca
52Te
21Sc
54Xe
53I
55Cs
21Sc
56Ba
22Ti
55Cs
57La
56Ba
58Ce
22Ti
23V
59Pr
57La
60Nd
58Ce
24Cr
61Pm
23V
59Pr
62Sm
60Nd
63Eu
25Mn
K
L
L
L
L
K
L
K
L
L
L
K
L
L
K
L
L
L
K
L
L
K
L
L
K
L
L
K
L
L
K
L
L
L
K
L
L
K
L
L
K
L
L
K
L
L
K
L
L
K
L
L
5.95
5.96
6.06
6.21
6.27
6.4
6.46
6.49
6.5
6.71
6.72
6.93
6.95
6.98
7.06
7.18
7.25
7.42
7.48
7.53
7.6
7.65
7.81
7.9
8.05
8.1
8.15
8.26
8.4
8.4
8.64
8.65
8.71
8.91
8.91
9.02
9.18
9.25
9.34
9.4
9.57
9.67
9.71
9.89
9.9
10.01
10.26
10.27
10.36
10.54
10.55
10.71
24Cr
L
K
L
L
K
L
L
K
L
L
K
L
L
L
K
L
L
K
L
L
L
K
K
L
L
L
K
K
L
L
K
K
L
L
K
K
L
K
L
K
L
K
K
K
K
K
K
K
K
K
K
K
61Pm
64Gd
62Sm
65Tb
26Fe
63Eu
25Mn
66Dy
64Gd
67Ho
26Co
68Er
65Tb
26Fe
69Tm
66Dy
70Yb
28Ni
67Ho
71Lu
26Co
68Er
72Hf
29Cu
69Tm
73Ta
28Ni
70Yb
74W
30Zn
75Re
71Lu
76Os
29Cu
72Hf
77Ir
31Ga
73Ta
78Pt
30Zn
74W
79Au
32Ge
80Hg
75Re
31Ga
81Tl
76Os
33As
82Pb
77Ir
31
10.84
10.98
11.07
11.13
11.22
11.43
11.44
11.73
11.73
11.82
11.92
12.03
12.21
12.34
12.5
12.61
12.65
12.65
12.97
13.02
13.29
13.29
13.4
13.45
13.61
13.88
14.11
14.17
14.32
14.77
14.96
14.96
15.24
15.71
15.78
15.84
16.2
16.62
16.7
16.74
17.22
17.48
17.67
18.37
18.62
19.28
19.61
20.22
20.62
21.18
21.66
22.16
83Bi
32Ge
78Pt
84Po
34Se
85At
79Au
33As
86Rn
80Hg
35Br
87Fr
81Tl
88Ra
34Se
82Pb
89Ac
36Kr
90Th
83Bi
91Pa
35Br
37Rb
84Po
92U
85At
36Kr
38Sr
86Rn
87Fr
39Y
37Rb
88Ra
89Ac
40Zr
38Sr
90Th
41Nb
91Pa
39Y
92U
42Mo
40Zr
43Tc
41Nb
44Ru
42Mo
45Rh
43Tc
46Pd
44Ru
47Ag
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
22.72
23.17
23.82
24.21
24.94
25.27
26.1
26.36
27.28
27.47
28.49
28.61
29.73
29.78
30.97
31
32.19
32.29
33.44
33.62
34.72
34.99
36.03
36.38
37.36
37.8
38.72
39.28
40.12
40.75
41.54
42.27
43
43.83
44.48
45.41
46
47.04
47.55
48.7
49.13
50.38
50.74
52.11
52.39
53.88
54.07
55.68
55.79
57.52
57.53
59.32
45Rh
48Cd
46Pd
49In
47Ag
50Sn
48Cd
51Sb
49In
52Te
50Sn
53I
51Sb
54Xe
55Cs
52Te
56Ba
53I
57La
54Xe
58Ce
55Cs
59Pr
56Ba
60Nd
57La
61Pm
58Ce
62Sm
59Pr
63Eu
60Nd
64Gd
61Pm
65Tb
62Sm
66Dy
63Eu
67Ho
64Gd
68Er
65Tb
69Tm
66Dy
70Yb
67Ho
71Lu
68Er
72Hf
69Tm
73Ta
74W