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A CRITICAL EVALUATION OF LINE OVERLAP CORRECTIONS IN X-RAY SPECTROMETRY

Larry E. Creasy Titanium Metals Corporation 900 Hemlock Road, Morgantown, PA 19543 ABSTRACT While it is generally recognized that line overlaps in wavelength X-ray spectrometry may be affected by factors such as variations in mass absorption, conventional line overlap correction models define the correction function as a constant and assume that it does not vary down to zero percent concentration of the interfering element. However, the overlap function is not a constant, even within the scope of a normal calibration set, and it becomes zero before the concentration of the interfering element reaches zero. By treating the overlap as a variable background and measuring the background using the Lorentz model, the need to establish an overlap function is removed and a more accurate calibration can be obtained. INTRODUCTION In X-ray spectrometry, the measured intensity (I) of the analyte peak is a composite of several factors and may be represented by the following equation: I = F[bkg] + F[conc.] + F[enh] F[abs] + F[ovr] Where: F[bkg] is a function of background F[conc.] is a function of concentration F[enh] is a function of enhancement F[abs] is a function of absorption, and F[ovr] is a function of line overlap In the calibration equation, the background is assumed to be a constant or the background is measured and subtracted from the measured peak intensity to give a net peak intensity. Intensity due to concentration is a linear function of concentration. The absorption and enhancement effects are not linear or constant. However, within narrow ranges, they may be approximated by a single factor for each affecting element using such models as LaChance-Traill1, RasberryHeinrich2, etc. These may be determined by regression or calculated using fundamental alpha type equations3. In more complex calibrations, these factors may be calculated using Fundamental Parameter models4. The line overlap function is always assumed to be constant with a zero concentration/zero interference intercept. These constants are typically determined by one of a number of techniques. The three most common techniques are:3 1. Measure the intensity at the analyte position on a sample of pure interfering element and ratio that value to another peak of that element. For example, to determine the constant for the overlap of Cr-K on the Mn-K peak, measure the intensity at the Mn-K location on a sample of pure chromium and ratio this value to the intensity of the Cr-K or K peak. This requires the use of very pure chromium.

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2. Using the same technique as above, but use a specimen that contains chromium, but no manganese. It is not always easy to find such a specimen. 3. Determine the constant by regression in the calibration process. Procedures 1 and 2 assume that there are no major absorption edges between the analyte peak and peak of the overlapping element that is used to make the correction. Even if there were no major absorption edges present, significant variations in the mass absorption coefficient could affect this correction factor. However, in dealing with the most common line overlaps where the analyte peak lies on the edge of another overlapping peak, such as the overlap of the Cr-K on the Mn-K, the Ni-K on CuK, or Fe-K on Co-K, etc., it will be shown that both of the assumptions, a zero/zero intercept and constancy, are not true. In an effort to increase the accuracy of the line overlap correction, it proposed that the overlap be treated as a variable background and measured for each sample, instead of assigning a single constant that would be applied to all samples. The model for this measurement is the Lorentz model that is available in some software packages for background correction. With properly selected locations around the analyte peak, the Lorentz equation models the shape of the shoulder of the overlapping peak very well. The equation for this model is as follows5:
Ib = a1 +a +a x (xi + a2 )2 + a3 4 5 i

Where: Ib = Intensity of the background, xi = 2-Theta angle, and a1.a5 are coefficients.

Cr-K

Intensity

Mn-K

62

62.4

62.8 63.2 Degrees 2-Theta

63.6

64

Figure 1. Background Fit for Overlap Using Lorentz Equation

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An example of an overlap correction using the Lorentz equation to model the overlap interference under the analyte is shown in Figure 1. A minimum of five points are selected and the curve is generated, basically treating the overlap as a curved background. These five points are measured for every specimen and the overlap is subtracted, resulting in a net peak intensity. This study will deal only with the situations where the overlap is such that the analyte peak lies on the tail of the overlapping element, such as the overlap of Cr-K on the Mn-K peak. It will not address the situation where there is a complete overlap, such as the Mo-L1 on the P-K peak. EXPERIMENTAL Over 130 specimens were measured to determine overlap intensities. The measurements were made on a Rigaku RIX-2000 scanning x-ray spectrometer. The matrices included aluminum, iron, nickel, cobalt, copper (brasses), zirconium and titanium. The Mn-K, Cu-K, and Co-K lines were measured. The overlap intensities at the analyte locations were determined by direct measurement of samples that had no analyte in them or by using a Lorentz fit. The Lorentz fit was made using the standard software package for the instrument. In addition, a calibration scheme was set up to compare the conventional treatment of line overlap with a model that used the Lorentz equation to measure the overlap. In this test, about 25 iron-based reference materials were used, generally of the type that would be considered stainless steels. The accuracy of the Lorentz measured overlaps were compared to regression fits using both the K and the K lines of the overlapping element. RESULTS AND DISCUSSION Below are example scans of the region surrounding the K- lines of Co and Cu with concentrations of Fe and Ni at low levels. a b
5 3

Fe-K
4 2 3

Ni-K

Intensity (kcps)

Co-K
2 1 1

Cu-K

0 51.0

51.5

52.0

52.5

53.0

0 43.0

43.5

44.0

44.5

45.0

45.5

46.0

2-Theta

2-Theta

Figure 2. Zero Overlap from Interfering Elements In Figure 2, the overlap is shown to reach zero before the concentration or the intensity of the overlapping element reaches zero. The intensity level at which the overlap reaches zero will depend on the resolution of the spectrometer and the difference between the location of the two peaks. The concentration level at which this occurs will also depend on the matrix, since mass

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absorption affects the sensitivity of the peaks. In Figure 2a, the material is Ti with about 4.4% Fe. In Figure 2b, the material is cast iron with about 2.3% Ni. Having shown that the intercept of the overlap function is not zero-zero, the next question is Is the overlap function a constant?. Over 130 specimens were measured as previously described. The overlap ratios are shown plotted and described below. a
0.12

b
0.010 0.008

0.10

0.08

0.006

Overlap Ratio

0.06

0.004
0.04

0.02

0.002

0.00 0 200 400 600 800 1000

0.000 1200 0

200

400

600

800

1000

1200

Intensity of Cr-K (kcps)

Figure 3. Overlap Ratio - Cr-K on the Mn-K peak

Intensity of Cr-K (kcps)

In the plot of all the data, Figure 3a, the ratios are fairly consistent as the intensity of the Cr-K peak decreases until the intensity reaches about 100 kcps, at which point, the ratio increases significantly. Most of this rise is because the overlap values are at or near background and are fairly constant, and these numbers are divided by increasingly smaller Cr-K peak intensities. When the plot of ratio values less than 0.01 are examined (Figure 3b where more detail is seen), there is much scatter. Even in the region where the data is relatively flat, there is a range of ratios from less than 0.001 to 0.004. If pure Cr were used to determine the overlap ratio, the ratio would be found to be 0.0012, a value at the extreme low end. a
2.0 0.020

b
0.016

1.6

Overlap Ratio

1.2

0.012

0.8

0.008

0.4

0.004

0.0 0 4 8 12 16 20

0.000 0 50 100 150 200 250

Figure 4. Overlap Ratio - Fe-K on the Co-K - Fe intensity less than 20 kcps (a) and ratios less than 0.02 (b)

Intensity of Fe-K (kcps)

Intensity of Fe-K (kcps)

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The patterns for Fe-Co are similar to those for Cr-Mn. The range of the ratio values for Fe intensities greater than 30kcps is 0.006 to 0.014. The values increase dramatically at the low intensity levels. Again, the value for pure Fe is 0.0064, near the minimum. a
0.020 0.016

2.5

2.0

Overlap Ratio

1.5

0.012

1.0

0.008

0.5

0.004

0.0 0 4 8 12 16 20

0.000 0 100 200 300 400

Intensity of Ni-K (kcps)

Intensity of Ni-K (kcps)

Figure 5. Overlap Ratio - Ni-K on Cu-K - Ni intensity less than 20 kcps (a) and ratios less than 0.02 (b)

Exhibiting the same pattern as previously observed, the range of ratio values for Ni intensities greater than 50 kcps is 0.002 to 0.009 and increases at the low intensity levels. In this case, the value for pure Ni is near the average at 0.0049. It is apparent that the overlap ratio is not a precise constant and the function does not have a zero-zero intercept. Having shown that the single factor function for line overlap is inadequate, the question arises What is the practical implication? To determine this, a calibration was set up for Mn, Co, and Cu in stainless steels. The Fe concentrations varied from 51 to 88%, the Cr from 2 to 22% and the Ni from 0.2 to 28%. The three elements in question were calibrated using regression to determine an overlap factor for the K line and the K line of the overlapping elements and using the Lorentz function to subtract the overlap. The sigma values for each fit were examined. The data for each calibration is shown in the Appendix. A summary of the sigma values is shown in Table 1. Table 1. Summary of Calibration Sigma Values K 0.036 Mn K 0.041 K 0.024 Co K 0.032 K 0.012 Cu K 0.014

Sigma

Lorentz 0.021

Lorentz 0.011

Lorentz 0.012

Using the Lorentz model, there was significant improvement over the conventional regression fits for Co and Mn. The sigma value of the calibration using the Lorentz model to subtract the overlap for Co improved to 0.011, as compared to 0.024 using the regression fit against the Fe-

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K and 0.032 against the Fe-K. The improvements for Mn were 0.021 for the Lorentz model as compared to 0.036 and 0.041 for the regression fits. There was no significant improvement in the Cu calibrations, probably because the separation of Cu- K from the Ni- K is greater than for the other two pairs. Therefore, the overlap interference is less. CONCLUSION It has been shown that the line overlap for the situation where the analyte peak lies on the tail of another element is not best described by single factor function. The overlap does become zero before the concentration of the overlapping element becomes zero. There is considerable scatter in the overlap ratios and the function is non-linear, especially near the low end. It was not the intent to resolve the line overlap function, that is, to determine the best model to define the line overlap, but rather, to show that there is a better way to handle the overlap in these situations. The Lorentz model, commonly used for curved background correction, is a very effective tool to subtract this overlap and to calibrate using a net analyte intensity. This results in a more accurate calibration, in some cases by a factor of more than two. REFERENCES 1. LaChance, G.R. and Traill, R.J., A Practical Solution to the Matrix Problem in X-ray Analysis, Can. Spectry., Vol. 11, 1966, p43. 2. Rasberry, S.D. and Heinrich, K.F.J., Calibration for Interelement Effects in X-Ray Fluorescence Analysis, Analytical Chemistry, Vol. 46, 1974, p81. 3. Standard Guide for Correction of Interelement Effects in X-ray Spectrometric Analysis (E1361), Annual Book of ASTM Standards Vol. 0306. 4. A number of these are described in Jenkins, R, et al. Quantitative Spectrometry, Second Edition, Marcel Dekker, Inc., NY 1995, Ch. 10. 5. Private discussion with Katsu Toda, Rigaku/USA

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APPENDIX CALIBRATION DATA FOR STAINLESS STEELS Calibration Calculations for Mn

K Correction Sample Cert. Calc Diff. Value 160 1.65 1.586 -0.064 1151 2.17 2.167 -0.003 1152 1.19 1.208 0.018 1154 1.74 1.731 -0.009 1155 1.63 1.625 -0.005 1171 1.80 1.788 -0.012 1172 1.76 1.776 0.016 1173 0.174 0.179 0.005 1184 1.04 0.997 -0.043 1185 1.22 1.243 0.023 1193 0.65 0.615 -0.035 1194 0.667 0.665 -0.002 1223 1.08 1.170 0.090 1230 0.64 0.624 -0.016 1287 1.66 1.712 0.052 B474 1.70 1.660 -0.041 C1154 1.42 1.450 0.030 D845 0.77 0.782 0.012 D846 0.53 0.511 -0.019 D848 2.13 2.083 -0.047 D849 1.63 1.672 0.042 D850 N.C. ------- ------Sigma 0.036 N.C. = Not Certified K Correction Calc Diff. 1.647 2.141 1.212 1.715 1.607 1.875 1.759 0.145 1.023 1.224 0.630 0.652 1.153 0.639 1.675 1.620 1.499 0.762 0.529 2.061 1.664 -------0.003 -0.030 0.022 -0.025 -0.023 0.075 -0.001 -0.029 -0.017 0.004 -0.020 -0.015 0.073 -0.001 0.015 -0.080 0.079 -0.008 -0.001 -0.069 0.034 ------0.041 Lorentz Calc 1.633 2.179 1.160 1.748 1.651 1.795 1.764 0.175 1.022 1.236 0.653 0.656 1.140 0.635 1.663 1.702 1.433 0.779 0.505 2.096 1.650 ------Diff. -0.017 0.009 -0.030 0.008 0.021 -0.005 0.004 0.001 -0.018 0.016 0.003 -0.011 0.060 -0.005 0.003 0.002 0.013 0.009 -0.026 -0.034 0.020 ------0.021

Calibration Calculations for Cu

K K Correction Correction Cert. Calc. Diff. Calc. Diff. Value 0.172 0.168 -0.004 0.177 0.005 0.25 0.253 0.003 0.245 -0.005 0.50 0.516 0.016 0.504 0.004 0.56 0.560 0.000 0.544 -0.016 0.169 0.170 0.001 0.173 0.004 0.121 0.115 -0.006 0.121 0.000 0.105 0.111 0.006 0.110 0.005 0.204 0.204 0.000 0.199 -0.005 N.C. ------- ------- ------- ------0.067 0.063 -0.004 0.065 -0.002 0.103 0.139 0.036 0.153 0.050 0.047 0.061 0.014 0.064 0.017 0.081 0.067 -0.014 0.067 -0.014 0.14 0.138 -0.002 0.147 0.007 0.58 0.585 0.005 0.575 -0.005 0.35 0.355 0.005 0.340 -0.010 0.40 0.394 -0.006 0.399 -0.002 0.065 0.055 -0.010 0.056 -0.009 0.19 0.191 0.001 0.198 0.008 0.16 0.154 -0.006 0.148 -0.012 0.21 0.210 0.000 0.203 -0.007 0.36 0.336 -0.024 0.353 -0.007 0.012 0.014 Lorentz Calc. Diff. 0.169 0.250 0.490 0.544 0.168 0.121 0.114 0.204 ------0.065 0.141 0.052 0.083 0.134 0.571 0.337 0.388 0.070 0.195 0.177 0.213 0.359 -0.003 0.000 -0.010 -0.016 -0.001 0.000 0.009 0.000 -------0.002 0.038 0.005 0.002 -0.006 -0.009 -0.013 -0.012 0.005 0.005 0.017 0.003 -0.001 0.012

Calibration Calculations for Co

Sample B474 1173 1171 160 1155 1154 1172 1230 1287 C1154 1194 Sigma Cert. Value 0.019 0.064 0.10 0.101 0.101 0.12 0.12 0.15 0.31 0.38 2.77 K Correction Calc. Diff. 0.017 0.085 0.084 0.092 0.096 0.102 0.111 0.147 0.274 0.326 2.780 -0.002 0.021 -0.016 -0.009 -0.005 -0.018 -0.009 -0.003 -0.036 -0.054 0.010 0.024 K Correction Calc. Diff. 0.020 0.072 0.092 0.098 0.098 0.100 0.108 0.158 0.227 0.329 2.779 0.001 0.008 -0.008 -0.003 -0.003 -0.020 -0.012 0.008 -0.083 -0.051 0.009 0.032 Lorentz Calc. 0.002 0.065 0.088 0.097 0.099 0.113 0.117 0.134 0.295 0.382 2.778 Diff. -0.017 0.001 -0.012 -0.004 -0.002 -0.007 -0.003 -0.016 -0.015 0.002 0.008 0.011