Sensitivity factor analysis

Chapter 10 provides an exhaustive description of how these techniques can be applied to a large number of industrial alloys and other materials. This includes a discussion of solution and substance databases and step-by-step examples of multi-component calculations. Validation of calculated equilibria in multi-component alloys is given by a detailed comparison with experimental results for a variety of steels, titanium- and nickel-base alloys. Further selected examples include the formation of deleterious phases, complex precipitation sequences, sensitivity factor analysis, intermetallic alloys, alloy design, slag, slag-metal and other complex chemical equilibria and nuclear applications. 

Thus, as for XP S, the average surface concentration Na can, in principle, be calculated by measurement of the Auger current, according to Eq. (2.13). Again, as in XPS, relative sensitivity factors are generally used. The Auger current for the same transition XYZ in a standard of pure A is measured under the same experimental conditions as in the analysis of A in M, whereupon the ratio of the atomic concentrations is... 

In principle GD-MS is very well suited for analysis of layers, also, and all concepts developed for SNMS (Sect. 3.3) can be used to calculate the concentration-depth profile from the measured intensity-time profile by use of relative or absolute sensitivity factors [3.199]. So far, however, acceptance of this technique is hesitant compared with GD-OES. The main factors limiting wider acceptance are the greater cost of the instrument and the fact that no commercial ion source has yet been optimized for this purpose. The literature therefore contains only preliminary results from analysis of layers obtained with either modified sources of the commercial instrument [3.200, 3.201] or with homebuilt sources coupled to quadrupole [3.199], sector field [3.202], or time-of-flight instruments [3.203]. To summarize, the future success of GD-MS in this field of application strongly depends on the availability of commercial sources with adequate depth resolution comparable with that of GD-OES. 

However, the spatial resolution of AES is mueh greater than that of XPS and ean approaeh approximately 25 nm. This makes AES a powerful technique for constructing high-resolution maps showing the distribution of chemical species across a surface. Because of the small analysis area, it is an easy matter to combine AES with inert gas sputtering to construct depth profiles showing the distribution of chemical species as a function of distance away from the surface and into the bulk of the solid. Quantitative analysis can be done using sensitivity factors and an equation similar to Eq. 17. 

Saddle point. 170 Salt effects. 206-214 Scavenging (see Reactions, trapping) Second-order kinetics. 18-22, 24 in one component, 18-19 in two components (mixed), 19-22 Selectivity. 112 Sensitivity analysis. 118 Sensitivity factor, 239-240 Sequential reactions (see Consecutive reactions)... 

From Table IV the relative magnitudes of the reactant state "sensitivity factor" (N) are 4>1>2=3= zero. From this analysis the decomposition rates of traiw-phenyl, alkyl diazenes (2) and iert-butyl peresters (3) can be predicted by assuming a dependence only on transition state effects, with no need to incorporate the back strain of the reactants into the equation. 

Mass Spectrometry. The mass spectra were obtained on a CEC 21-llOB mass spectrometer with the batch inlet system maintained at 250°C to assure complete vaporization of the samples. Sensitivity factors for quantitative analysis were obtained from standards of di-, tetra-, hexa-, and octa-chlorodibenzo-p-dioxin. The factors for the intermediate chlorinated species were estimated by interpolation. The analyses were based... 

As XRF is not an absolute but a comparative method, sensitivity factors are needed, which differ for each spectrometer geometry. For quantification, matrix-matched standards or matrix-correction calculations are necessary. Quantitative XRF makes ample use of calibration standards (now available with the calibrating power of some 200 international reference materials). Table 8.41 shows the quantitative procedures commonly employed in XRF analysis. Quantitation is more difficult for the determination of a single element in an unknown than in a known matrix, and is most complex for all elements in an unknown matrix. In the latter case, full qualitative analysis is required before any attempt is made to quantitate the matrix elements. 

XRF nowadays provides accurate concentration data at major and low trace levels for nearly all the elements in a wide variety of materials. Hardware and software advances enable on-line application of the fundamental approach in either classical or influence coefficient algorithms for the correction of absorption and enhancement effects. Vendors software packages, such as QuantAS (ARL), SSQ (Siemens), X40, IQ+ and SuperQ (Philips), are precalibrated analytical programs, allowing semiquantitative to quantitative analysis for elements in any type of (unknown) material measured on a specific X-ray spectrometer without standards or specific calibrations. The basis is the fundamental parameter method for calculation of correction coefficients for matrix elements (inter-element influences) from fundamental physical values such as absorption and secondary fluorescence. UniQuant (ODS) calibrates instrumental sensitivity factors (k values) for 79 elements with a set of standards of the pure element. In this approach to inter-element effects, it is not necessary to determine a calibration curve for each element in a matrix. Calibration of k values with pure standards may still lead to systematic errors for unknown polymer samples. UniQuant provides semiquantitative XRF analysis [242]. 

Houben [256] has compared the determination of flame-retardant elements Br, P, S, K, Cl and F in polycarbonate using commercial (X40 and UniQuant ) software. For the X40 method, a calibration line for each element in PC or PC/ABS blends was mapped for the conversion of intensities to concentrations. With the universal UniQuant method, sensitivity factors (ks) were calibrated with pure standards. The X40 method turned out to be more reliable than UniQuant for the determination of FRs in PC and PC/ABS blends, even in the case of calibration of k values with PC standards. Standard errors of 5 % were achieved for Br, P, S and K, and 20% for Cl and F the latter element could not be determined by means of UniQuant (Table 8.44). GFR PC cannot be quantified with these two methods, because of the heterogeneous nature of the composites. Other difficult matrices for XRF analysis are PBT, PS and PP compounds containing both BFRs and Sb203 (10-30wt %) due to self-absorption of Sb and interelement effects. 

In the field of microelectronics, there is continuing research in developing new materials to be used in semiconductor fabrication. They must be formed as thin films in a controlled, reproducible and uniform manner to be useful in semiconductor manufacturing applications. Depth profiling by AES is used to assess the properties of such films. The samples are sputtered with an argon ion beam and analysis performed using standard sensitivity factors, and it is possible to demonstrate that such films are uniform throughout a depth of, say, 250 nm. 

Matrix of sensitivity factors in multicomponent analysis (e.g., absorbance factors)... 

In some diseases a simple ordinal scale or a VAS scale cannot describe the full spectrum of the disease. There are many examples of this including depression and erectile dysfunction. Measurement in such circumstances involves the use of multiple ordinal rating scales, often termed items. A patient is scored on each item and the summation of the scores on the individual items represents an overall assessment of the severity of the patient s disease status at the time of measurement. Considerable amoimts of work have to be done to ensure the vahdity of these complex scales, including investigations of their reprodu-cibihty and sensitivity to measuring treatment effects. It may also be important in international trials to assess to what extent there is cross-cultural imiformity in the use and imderstand-ing of the scales. Complex statistical techniques such as principal components analysis and factor analysis are used as part of this process and one of the issues that need to be addressed is whether the individual items should be given equal weighting. 

Figure 26 shows an analysis of the area ratios for the core and 02j levels which are also essentially core like (cf. Fig. 15). For polyacrylic acid the measured areas for the various structural features for the 0ls levels and Cts levels and the overall ratios for the Cis to 0ls levels (corrected for differing sensitivity factors) are 1.0, 2.0 and 1.6 respectively, in excellent agreement with the theoretical values of 1.0, 2.0 and 1.5 based on a statistical sampling of the polymer repeat unit. The area ratios for the individual components for the Cu levels show an excellent correlation with the number of carbon atoms in the alkyl groupsb. (Slope Experimental 0.99, Theoreti-...

Figure 2.31 Relative sensitivity factors of several elements for silicon analysis a) positive secondary ions were measured using Oj primary ion beam (R. C. Wilson, F. A. Stevie and C. W. Magee, Secondary Ion Mass Spectrometry 1989. Reproduced by permission of John Wiley Sons, Inc.)...

Semi-quantitative results obtained from XPS analyses after Ar+ sputtering (4 kV, 100 iA) and using the Scofield sensitivity factors see J.H. Scofield. J. Electron. Spectros. Rel. Phenom., 8,129 (1976). Overestimated values C recontamination of the surface due to the use of separate sputtering and analysis chambers. 

XPS analysis of y-APS applied to nickel and silicon substrates was also carried out using a Surface Science Instruments SSX-100-03 instrument equipped with a monochromatic A1 Ka source. The X-ray source had an energy of 1487 eV and the instrument operated at a spot size of 600 //m. Pass energies for survey and high resolution spectra were 150 and 52 eV, respectively. Atomic concentrations were once again obtained from the high resolution spectra using sensitivity factors provided with the software. 

Quantitative analysis depends upon the availability of various parameters such as cross sections, sensitivity factors, and penetration or escape depths. Tables of these quantities are useful although not always reliable or readily found. The ability of any technique to solve a particular problem will depend upon both the accessibility and accuracy of supporting data. 

Dissociated neuronal cultures provide a versatile system for analysis of mechanisms underlying neurotransmitter release. These cultures can be prepared from fetal or postnatal brain tissue. This preparation has been particularly instrumental in analysis of synapses deficient in key components of the release machinery. For instance, genetic deletion of synaptic SNARE (soluble N-ethylmaleimide-sensitive factor attachment protein receptors) proteins such as synaptobrevin-2 and SNAP-25... 

Auger electron spectroscopy (AES) is particularly suited for surface analysis (depth 0.5-1 nm). AES depth profile analysis was employed to determine the thickness and composition of surface reaction layers formed under test conditions in the Reichert wear apparatus in the presence of four different ZDDPs additives at different applied loads (Schumacher et al., 1980). Using elemental sensitivity factors the concentration of the four elements (S, P, O, C) was determined at three locations corresponding to a depth of 1.8, 4.3, and 17 nm. No significant correlation between wear behavior and carbon or oxygen content of the reaction layer was observed. A steady state sulfur concentration is reached after a very short friction path. Contrary to the behavior of sulfur, phosphorus concentration in the presence of ZDDPs increases steadily with friction path, and no plateau value is reached. 

CONTENTS 1. Chemometrics and the Analytical Process. 2. Precision and Accuracy. 3. Evaluation of Precision and Accuracy. Comparison of Two Procedures. 4. Evaluation of Sources of Variation in Data. Analysis of Variance. 5. Calibration. 6. Reliability and Drift. 7. Sensitivity and Limit of Detection. 8. Selectivity and Specificity. 9. Information. 10. Costs. 11. The Time Constant. 12. Signals and Data. 13. Regression Methods. 14. Correlation Methods. 15. Signal Processing. 16. Response Surfaces and Models. 17. Exploration of Response Surfaces. 18. Optimization of Analytical Chemical Methods. 19. Optimization of Chromatographic Methods. 20. The Multivariate Approach. 21. Principal Components and Factor Analysis. 22. Clustering Techniques. 23. Supervised Pattern Recognition. 24. Decisions in the Analytical Laboratory. 

Mass Spectrometry A Practical Handbook for Depth Pro ling and Bulk Impurity Analysis, by Wilson et al. [69]. This book is focused on profiling and quantitative analysis primarily in semiconductors and contains many tables of relative sensitivity factor (RSF) data, profile illustrations, and SIMS spectra. 

---