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  • Articles  (6,161)
  • Electronic structure and strongly correlated systems  (5,491)
  • Analytical Chemistry and Spectroscopy
  • 2015-2019  (5,491)
  • 1975-1979  (670)
  • Physics  (6,161)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 7 (1978), S. 195-197 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An equation has been derived for the computaion of the standard deviation of the results of X-ray micro analysis. The contributions of partial standard deviations of all magnitudes are included. The equation is gernerally applicable to multiple measurements and various methods of measurements.
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  • 2
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 7 (1978), S. 190-194 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: It is demonstrated that an evalution procedure for conversion X-ray intensity to element concentration used on an existing spectrometer can be used in reverse to provide intensity data for calibrating another spectrometer. Extensive remeasurement o standards is therby eliminated. Intensities are calulated for postulated changes in compostion and these form the input data for the spectrometer computer regression program. Such data are free from measurement error. Calibration and α coefficents from claulated intensities are found to give analytical results of an accuracy comparable with those derived from experimentally produced calibration. The intensity calculations can be extended to include the determination of calibration and α coefficents without using the sepctrometyer regression programs. Considedrable expense and effort can be saved.
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  • 3
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 7 (1978), S. 217-224 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: For application for the fundamental parameter approach to quantitative chemical analysis of mixtures by X-ray fluorescence, accrate knowledge is required of fluroescence yields and ralative intensities of X-ray lines of the various elements involved. The spread in published data suggests, however, that these parameters are not known with as much accuracy as could be used profitably. In this paper we describe a method by which K-shell flurescence yield and Kα/Kβ intensity ratio can both be measured in the same experiment to within approximately 0.5% for pure elements available as thin polcrystalline foil. Results are given for the particular case of nickel (Z=28) for which we find ωK = 0.452 ± 0.002 and Kα/Kβ=6.91 ± 0.335, but the method is readily applicable to anty element whose atomic number falls in the approximate range 20 ≲ Z ≲ 50 and which can be obtained in suitable physical form. A key factor in the experimental design is use of a non-dispersive (intrinsic germanium) X-ray analyzer; this makes it possible to employ a very simple transmission geometry which can be characterized quite precisely. Experimental conditions, and precautions needed to obtain accurate and consistant results, are described in some detail. Among other corrections applied, allowance is made for scattering of both exciting statistics and residual uncertaintes incalculating corrections for scattering. Among these residual uncertainties are errors in correcting scattering coefficients for anomalous dispersion. Such errors are significant only when evaluating fK, the K-shell excitation efficienvcy; the important product fK ωK can, however, be determined (fKωK = 0.398 ± 0.002) with greater reliability than ωK itself.
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  • 4
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 7 (1978), S. 241-248 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The Properties of diffracting crystals a Bragg and of near 45° are studied for use as an X-ray polarizer. Such crystals have many advantages over the Barkla type polarizer when used in an energy-dispersive X-ray analyzer. The study shows that many matching λ-d combinations are available, but the present work was done with LiF (200). With this crystal, the second order diffraction of Cu Kβ radiation occurs at 43.67° and an improvement of peak to background ratio by a factor 45 was obtained. The study revealed that a substantial improvement of peak to minimum detection limit can be obtained with a larger deviation of the polarization angle, as long as this deviation is accompanied by a higher X-ray output.
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  • 5
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 7 (1978), S. vii 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 6
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979), S. v 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 7
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979), S. 1-1 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 8
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979), S. 2-6 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A procedure has been developed for extracting net peak intensities from electron-beam-induced energy-dispersive X-ray spectra. The procedure has been implemented in a computer program which requires very modest storage capacity of a minicomputer, yet can be executed in a few seconds to yield net intensities. The program structure is simple. Provided the peak to background ratio is better than ∼5 to 1 the intensities are adequate for correction to quantitative analysis with accuracies comparable with more sophisticated and time-consuming methods. The procedure has been used extensively on a computer-controlled scanning electron microscope to give rapid information from complicated spectra.
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  • 9
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979), S. 33-41 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An off-line non-linear least squares fitting procedure is described as part of a program package ‘RUNFIT’. This program supports most of the intensity/correction algorithms currently employed in X-ray fluorescence spectrometry. The program runs under the Data General DOS operating system and requires a minimum hardware configuration of 32K 16 bit words and two floppy disks. The minimization technique is based on the Marquardt scheme which has the main advantage that the step direction taken in the minimization process always lies in the direction of steepest descent. The RUNFIT program includes various statistical tests on the fitted data which enable the user to make accurate judgements as to the quality of the fitted data. Several examples are given of the use of this approach to typical analytical situations.
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  • 10
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979), S. vi 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 11
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979), S. vii 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 12
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979), S. 51-51 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 13
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979), S. 68-72 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: X-ray fluorescence analysis under high vacuum (∼10-6 torr) was applied to the determination of fluorine in slags. Slag samples are converted into glass beads using a fusion method and the fluorescent X-ray intensity of characteristic X-ray F Kα (1.83 nm) is measured to determine fluorine. The calibration curve has excellent linearity and accuracy; σd is 0.18% for 11 kinds of samples involving fluorine of 0.10% to 16.78% (mean: 6.96%).
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  • 14
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979), S. 92-94 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method of elimination of absorption matrix effects in samples of ‘intermediate’ thickness, based on the use of measurements of the intensities of fluorescent X-rays of all determined elements and the intensity of Compton back-scattered radiation, is described. An empirical correction equation proposed in this paper has been checked experimentally using the samples obtained by precipitation of several elements from water solution by sodium diethyldithiocarbamate (NaDDTC). The accuracy of determinations of Cr, Fe, Zn and Pb varies from 1 to 18% (1 s.d.) for mass per unit area from 2000 to 60 μg cm-2, respectively.
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  • 15
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979) 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 16
    Electronic Resource
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    X-Ray Spectrometry 8 (1979), S. 96-101 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: X-ray fluorescence spectrum excitation theory is now well developed and uses the assumption that the primary X-ray radiation beam is parallel. At the same time, in order to increase intensity it is necessary to keep the radiation source and fluorescence object as close as possible. In so doing the primary radiation divergence is found to be significant, and to ensure high accuracy of the intensity calculations it is necessary to evaluate the influence of this factor.Considerations are carried out for the cases of point, circular and line sources of primary radiation, selective effects being absent.The concept of the effective incidence angle is introduced which makes it possible to calculate X-ray fluorescence intensities by formulae without correction for the primary radiation divergence. Values of the correction coefficients are given which correct for the dependence of the effective angle on chemical composition of the fluorescence material. The value of the effective incidence angle of primary radiation for a circular source is determined and compared with its theoretical value. Statistical treatment of the results shows insignificant differences between the experimental intensities and those calculated with correction for the primary radiation divergence when chemical composition variation of the material analysed is quite large.
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  • 17
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979), S. 149-158 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Physical surface analysis methods using charged particles on the excitation side can easily be applied to elemental distribution mapping. One common feature of all known methods is that they work on a micron scale, with respect to spatial resolution and investigated sample area. This paper deals with a new approach to the problem of element mapping using X-ray fluorescence radiation. In contrast to the well-known scanning procedures, this method allows the investigation of larger areas (several square centimetres) at lower spatial resolutions (≳ 100 μ). The method applies a mechanical scanning device, a modern energy-dispersive detector and a computer. The scanning unit allows translation and rotation movements of the sample. By generating a line-shaped X-ray beam and translating the sample across the fixed X-ray strip while measuring the intensity of the fluorescence radiation in a specified energy window, one obtains a strip resolution of the species investigated. If many translation measurements are made under different angular orientations of the sample, a computer converts the strip resolutions of the scanning profiles into a point resolution of the specified element. The mathematical background is known in the literature as ‘representation of a function by its line integrals’ or ‘image reconstruction from projections’. Computer simulation studies and experimental results will be discussed.
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  • 18
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979), S. 200-202 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 19
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 8 (1979), S. 190-195 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The demand for comprehensive analysis of materials by XRF using automated instrumentation has led to increasing use of the coefficient approach for dealing with the ever-present interelement effect. A survey of the literature shows that this has often led to a multiplicity of families of calibration curves being replaced by a multiplicity of tables of correction coefficients. A practical approach is outlined which facilitates the recognition of (a) the alpha subset of influence coefficients, and (b) three related subsets of alpha coefficients - basic, modified and hybrid. This mobility of alpha coefficients (alloys, oxides, fusions, solutions) coupled to their adaptability (geometry, primary radiation) and accessibility (theoretical, experimental) has wide implications. It permits a consolidated view of the influence coefficients, and comparison of the sign, magnitude and pattern of basic alphas so as to establish if and when there is consensus. The confirmed alpha coefficients thus obtained can then be transferred with confidence to suit specific operating conditions and methods. Examples are given using data that have appeared in XRF literature.
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  • 20
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    X-Ray Spectrometry 8 (1979), S. viii 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 21
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    X-Ray Spectrometry 4 (1975) 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 22
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    X-Ray Spectrometry 4 (1975), S. 1-1 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 23
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    X-Ray Spectrometry 4 (1975), S. 85-89 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The zinc concentration in an epitaxial layer of InSb was measured by proton excited X-rays. For the determination of zinc concentration, the X-ray yield was compared to that from known zinc concentrations. As layer thickness, stopping power and X-ray absorption must be taken into account, a general mathematical evaluation was developed. In an appendix, the derived equations are shown to allow a layer thickness determination. The calculated values agree quite well with the experimental results.
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  • 24
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The use of Nickel-59 as an excitation source for the X-ray fluorescence analysis of carbon and low alloy steels has been investigated. Nickel-59 has a half life of 80 000 y and is essentially a pure source of cobalt K X-rays. It is ideal as an X-ray source for field systems because the encapsulated source is small, rugged and requires no external power or maintenance. The prototype system require ∼2½ minutes to obtain a manganese analysis, and 15 minutes to determine vanadium, chromium and manganese concentrations. These times could be shortened about a factor of 40 with a more intense excitation source and a larger area detector. The feasibility of portable field systems is discussed.
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  • 25
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    X-Ray Spectrometry 4 (1975), S. 74-76 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A single crystal of indium antimonide (zinc blende type InSb) was evaluated as an X-ray monochromator. The long 2d spacing of 7.481 Å makes it possible to diffract Si K α in an ordinary X-ray emission spectrometer. The indium antimonide data were compared with crystals of EDDT, Ge and LiF. Indium antimonide shows seven times higher Si Kα intensity than EDDT. It also has very low second order reflection. A low coefficient of thermal expansion (4.9 × 10-6 °C-1), together with its very stable chemical nature will facilitate high precision measurement ranging from 14Si to 46Pd(Kα), 38Sr to 92U(Lα) and 74W to 92U(Mα).
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  • 26
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: For the case where the power method fails to give a non-negative eigenvector for system (1) a program has been set up to calculate all the eigenvalues and eigenvectors of system (1).
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  • 27
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    X-Ray Spectrometry 4 (1975), S. 93-93 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 28
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    X-Ray Spectrometry 4 (1975), S. A16 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 29
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    X-Ray Spectrometry 4 (1975), S. 138-148 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A Monte Carlo model is derived for the simulation X-ray fluorescence from homogeneous samples including primary, secondary and tertiary fluorescence events. The model is designed specifically for an annular radioisotope source mounted coaxially with a circular detector. It is verified with analytical relationships for the limited case of fixed sample entrance and exit angles. The results indicate accuracies (2% or better) that are well within our knowledge of X-ray fluorescence parameters (such as fluorescence yields), yet can be calculated with very modest (15 seconds) digital computer calculation time.
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  • 30
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    X-Ray Spectrometry 4 (1975), S. 157-157 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
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  • 31
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    X-Ray Spectrometry 4 (1975), S. 159-160 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method is presented discussing the determination of gadolinium in Gd2O3 + UO2 pellets. The relative accuracy ranges between 1 and 2%.
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  • 32
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    X-Ray Spectrometry 4 (1975), S. 166-170 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The theoretical relationship between relative intensity and concentration is used for the estimation of influence coefficients for the Rasberry-Heinrich, Claisse-Quintin and Lachance-Traill method. Those coefficients are used to evaluate Rasberry-Heinrich, Beattie-Brissey and Shiraiva-Fujino measurements in the system of iron + nickel + chromium. An improved program, printing the average error of calculation per element had containing safeguards to avoid the divergence of iteration, is used for computation. The Rasberry-Heinrich method gives the best results. Theoretical reasons are given in explanation.
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  • 33
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    X-Ray Spectrometry 4 (1975), S. 178-185 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The application of a simple, empirical inter-element correction procedure to the analysis of nickel-base alloys is described. The correction factors are considered in relation to the effects predicted from a study of the mass absorption coefficients.
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  • 34
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    X-Ray Spectrometry 4 (1975), S. 186-189 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Using a commercially available flat crystal spectrometer in a slightly modified form, an investigation was made of the peak intensity ratios (Kβ5/Kβ1) and the relative intensities of Kβ″ to Kβ5 in different oxidation states of 3d-transition metal atoms existing in forms of oxidic compounds. The peak intensity ratios (Kβ5/Kβ1) for V, Cr, Mn, Fe, Co, Ni and Cu, as well as the peak profiles of Kβ″ and Kβ5 for V, Cr and Mn, were investigated. Results suggest that changes in the intensities of the Kβ5 and Kβ″ bands can be applied to determining the oxidation number of a metal atom in its oxide.
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  • 35
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    X-Ray Spectrometry 4 (1975), S. 190-195 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Techniques have been developed for analysing the heavy element content of atmospheric particulate fractions by means of X-ray fluorescence spectrometry. Special attention is devoted to the nondestructive analysis of particulates collected on the cellulose and fibreglass filters used in high volume air samplers. It is shown that the X-ray fluorescence data must be corrected for absorption of radiation by the filter medium in the case of cellulose due to penetration of the particulates into the body of the filter. Fibreglass is shown to be superior to cellulose in that most of the particulates are trapped near the surface of the paper. A novel feature of the analytical method described is that a comparison of X-ray fluorescence intensities from the front and back of the filter leads to a determination of filter collection efficiency. A second method for determining collection efficiency, using a tandem arrangement of filter papers, is also described.
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  • 36
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    X-Ray Spectrometry 4 (1975), S. 196-201 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A Comprehensive study of the interfacing of an X-ray energy dispersive spectrometer to a transmission electron microscope is presented. Optimum detector location, sample tilt, collimation and accelerating voltage are discussed. Quantitative elemental analysis is obtained for thin film specimens using corrections for spectrometer response, absorption and background. Peak spectra are sorted using a method of profile fitting based on nonlinear simplex minimization. Using a simple analysis scheme, the peak data is reduced to elemental composition with an accuracy and precision on the order of 1%. Examples from Fe-Ni and Ho-Co alloys are given.
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  • 37
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    X-Ray Spectrometry 4 (1975), S. A17 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 5 (1976), S. 2-6 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The position, shape and the extended fine structure of the cobalt K absorption discontinuity have been studied in the pure metal and in its four chalcogenides, CoO, CoS, CoSe and CoTe, using a forty centimetre diameter bent crystal X-ray spectrograph. It has been found that the discontinuity shifts towards the high energy side in the chalcogenides and that the chemical shift ΔE depends upon the effective ionic charge on the absorbing atom. The fine structure within the main discontinuity is discussed on the basis of band structure and molecular orbital diagram, while the extended fine structure is interpreted on Lytle's theory. The results obtained throw light on the chemical bonding prevalent in these compounds.
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    X-Ray Spectrometry 5 (1976), S. 7-12 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Description / Table of Contents: It is shown that the well known hyperbolic equation of a binary system is still operable in the range of grain size effects. In this paper, the evaluating, as well as the handling of grain size parameters, will be greatly simplified, as demonstrated by reduction of published experimental data. A possibility results to differentiate the effects treated here from other sample effects.
    Notes: Bei geeigneter Wahl der Koeffizienten ist es Möglich, die bekannte hyperbolische Gleichung für die Röntegenspektral-analyse des Zweistoffsystems auch im Gebiet des Korngrößen-einflusses beizubehalten. Damit wird die experimentelle Bestimmung und Handhabung der Korngrößenparameter wesentlich vereinfacht, wie an Hand von Literaturdaten belegt wird; insbesondere ergibt sich ein Weg, den Korngrößeneinfluß von anderen Einflußfaktoren abzutrennen.
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    X-Ray Spectrometry 5 (1976), S. 13-15 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Thin windows for X-ray spectrometer flow counters can be produced by stretching unorientated polypropylene film. A piece of the stretched film is clamped into a holder and pressed onto a copper ring made from thin copper sheeting. The mounted window is then suspended in a high vacuum coating unit and flashed with aluminium to a thickness of approximately 20 nm.
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    X-Ray Spectrometry 5 (1976), S. 88-91 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The simple, Wegstein and hyperbolic procedures of iteration are compared and shown to differ only in the ways in which the derivative of the correction factor with respect to concentration are calculated. The simple and hyperbolic methods are demonstrated either to provide slow convergence in certain cases or to lead to wrong values, or even to show divergence. The Wegstein procedure is recommended as being, in general, the fastest and most reliable method.
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    X-Ray Spectrometry 5 (1976), S. A14 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 5 (1976), S. A17 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 5 (1976), S. A16 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 5 (1976), S. A15 
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    X-Ray Spectrometry 5 (1976), S. A15 
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    X-Ray Spectrometry 5 (1976) 
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    X-Ray Spectrometry 5 (1976), S. 117-117 
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    X-Ray Spectrometry 5 (1976), S. 123-128 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The background beneath the fluorescence lines of energy dispersive X-ray spectra obtained with a molybdenam secondary target tube-excited system can be obtained from the intensities of the coherently and incoherently scattered radiation. The background intensity at a particular energy is equal to the product of a proportionality factor multiplied by the incoherently scattered radiation intensity, plus another proportionality factor multiplied by the coherently scattered radiation intensity. The proportionality factors are determined from measurements of a number of molybdenum-loaded cellulose filters.The proposed procedure provides accurate results for the analysis of complex X-ray spectra of thin samples of varying composition.
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    X-Ray Spectrometry 5 (1976), S. 118-122 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Experiments and a literature survey both show that energy dispersive microprobe analysis of Ni in steel generally gives substantial negative errors. This situation has been related to significantly lower X-ray intensity ratios, k values, from an energy dispersive spectrometer system compared with a conventional wavelength dispersive spectrometer. Lower Fe contents in the specimens have been shown to give decreasing errors, which appear to be independent of the ZAF correction calculations.It is suggested that the systematic error for Ni is caused by the method of background subtraction, which seems to reduce the Ni Kα area. The error can be minimized if peak-height intensities are used and if the background level is measured and subtracted manually.
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    X-Ray Spectrometry 5 (1976), S. 129-133 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An X-ray fluorescence method has been developed to determine the metal concentration in the aqueous and organic phases from solvent extraction processes. The method has been specifically applied to the determination of copper, but can be extended to include other elements which form soluble organic complexes. Accuracy and precision are comparable with that obtainable by the electrogravimetric technique for the analysis of copper in aqueous solution, but are superior to the atomic absorption analysis of copper in organic solution. Rapid analysis is achieved by presenting a diluted sample directly to the spectrometer. Inter-element absorption enhancement effects are corrected by the selection of a suitable internal standard which is added to the diluent.
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    X-Ray Spectrometry 5 (1976), S. A14 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 5 (1976), S. A16 
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    X-Ray Spectrometry 5 (1976), S. 179-179 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 5 (1976) 
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    X-Ray Spectrometry 5 (1976), S. 188-193 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Correction for the absorption of the X-rays in aerosol loaded filters can be based on the measurement of the front-to-back intensity ratio. Experimental verification that an accurate and precise absorption correction can be obtained is given. The ‘two-lines’ method based on the accurate measurement of the lead Mα to Lβ intensity ratio in actual samples is used. The distribution of the aerosol in the filter is exponential with a variable gradient.
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    X-Ray Spectrometry 8 (1979), S. 52-56 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: During fusion of uncalcined oxide samples there may be a loss of a variable mass of volatile constituents, corresponding with the loss on ignition (LOI). On the other hand, partially reduced samples, such as sinters of iron ores, may contain one or more elements in various states of oxidation related to the gain on ignition in air (GOI). Both phenomena influence the analyte X-ray fluorescence intensities obtained from the fused sample.Full explanations are given along with a rigorous mathematical treatment for a proposed method that has demonstrated its practical value in the past decade. It is based on the de Jongh-Norrish equations in which the mass difference LOI-GOI is treated as one element with the assigned atomic number zero. References are made to practical results.
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    X-Ray Spectrometry 8 (1979), S. 65-67 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Escape peak losses in Si(Li) detectors for X-rays in the energy range 2.3-14.2 keV are measured and compared with calculations for normal incidence geometry. The importance of the results for multi-elemental X-ray emission analysis is pointed out.
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    X-Ray Spectrometry 8 (1979), S. 57-62 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Description / Table of Contents: X-ray fluorescence analysis using an energy dispersive spectrometer system (Ge(Li) or Si(Li) and multichannel analyser) enables quick and simultaneous determination of different elements in a sample. The improvement of the detection limits to nanogram amounts of medium Z elements is achieved by reducing the unwanted background from scattered radiation. This is performed by X-ray total reflection on the plane, polished surface of the sample substrate at angles below the critical angle of total reflection, which is in the region of some milliradians and is measured between incident X-ray beam and surface of the substrate. In the case of X-ray total reflection the effective thickness of the substrate which is equivalent to the penetration depth of the X-rays lies between 40 and 70 nm. Therefore the substrate combines its good mechanical strength, chemical resistance and choice of dimensions with the low background properties of ultrathin foils as sample carrier. A counting interval of 120 s and a required sample volume of 5 μl are standard measuring conditions. Concentrations in the ppm region and absolute nanogram amounts can be detected.
    Notes: Energiedispersive Röntgenfluoreszenzanalyse ermöglicht die rasche und gleichzeitige Bestimmung verschiedener Elemente in einer Probe. Die bei Winkeln von einigen Minuten auftretende Totalreflexion von Röntgenstrahlen an der polierten Oberfläche eines Probenträgers, z.B. Quarzglas, und eine spezielle Geometrie-Primärstrahl-Probe-Detektor wird dazu verwendet, um den durch klassische und Compton-Streuung hervorgerufenen Hintergrund zu senken. Dadurch konnten Nachweisgrenzen für Elemente mittlerer Ordnungszahl im Nanogrammbereich erzielt werden. Tritt Totalreflexion von Röntgenstrahlen auf, so dringen diese nur in einer Tiefe von etwa 40-70 nm in den Probenträger ein und bestimmen dadurch die effektive Dicke. Man verbindet daher mechanische Festigkeit, chemische Widerstandsfähigkeit und beliebige Dimensionierung des Probenträgers mit den für geringen Hintergrund günstigen Eigenschaften extrem dünner Folien. Standardmeßzeiten von 120s und ein Probenvolumen von 5 μl sind ausreichend, um Konzentrationen im ppm Bereich, d.h. Absolutmengen von Nanogramm mit RFA nachzuweisen.
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    X-Ray Spectrometry 8 (1979), S. 76-78 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The extracted minor phases in superalloys are analyzed by X-ray fluorescence spectrometry without the use of standards. The calculation in the analysis is simplified by using a monochromatic X-ray source and the fundamental parameter method. The extracts on the microfilter are approximated by thin film on the filter substrate, though the extracts were not homogeneous. This source permits a simple calculation using the thin film model to transform the measured X-ray intensity to mass thickness and mass fraction, since the mass absorption coefficient for the primary beam is easily found in a commercially available table. A great advantage of this method is that the calculations are possible by using a small programmable calculator.
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    Notes: This paper describes a new approach for deriving a simple relation between mass attenuation coefficient and X-ray energy or wavelength. Parameters of the latter have been adjusted to fit all up-to-date experimental, interpolated and extrapolated data thus providing means for computing a set of tables covering all values of coefficients usually encountered in applied X-ray spectroscopy. The accuracy is generally much better than ±5% with respect to the average of well-established data.
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    X-Ray Spectrometry 8 (1979), S. 73-75 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A new fundamental parameter method applied to energy dispersive X-ray spectrometry is presented. Am-241 and I-125 radioisotope sources were used for excitation. The method is applied to copper-zinc-lead ternary and copper-zinc-lead-tin quaternary alloys and to high-alloy steel specimens. It is also tested using data given in the literature. The measurements and calculations were performed on-line by a program running in a 16K, 12 bit minicomputer interfaced to a multichannel analyser. The results were compared with wet chemical analysis.
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    X-Ray Spectrometry 8 (1979), S. 79-84 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: A disability of energy-dispersive X-ray (EDX) analyzers is the relatively poor resolution of available detectors. Much work has been done in efforts to separate overlapping peaks. It is recognized that the distribution of signals registered in the several channels around a peak is essentially Poisson, but most efforts at deconvolution have been based on Gaussian statistics, probably because of difficulties encountered in the use of the Poisson formula. These difficulties have been overcome, and a simple method for deconvoluting two, three or more overlapping peaks in an EDX spectrum has been developed.
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    X-Ray Spectrometry 8 (1979), S. v 
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    X-Ray Spectrometry 8 (1979), S. vi 
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    X-Ray Spectrometry 4 (1975), S. 62-64 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: One way carrying out quantitative X-ray fluorescence analysis with fundamental parameters is the method of variable take-off angle. At angles nearly parallel to the sample surface, the equations can be solved more easily and no knowledge of the white spectrum and μ(λ) is needed. For practical application, in order to get a well defined geometry, we used a diffraction goniometer, an X-ray tube with Mo target and an energy dispersive detector, followed by a multichannel analyser. After calibrating the system, all information essential for a quantitative analysis was obtained from a single measurement. The validity of the final equations was verified by experiments with different alloys, consisting of two, three and four components.
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    X-Ray Spectrometry 4 (1975), S. 52-61 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: A fast, efficient calibration procedure is proposed based on the accurate analysis of multicomponent systems by means of the influence coefficient method. It relies on a series of well designed additions made to a suitable standard composition, the latter also being used as a reference sample. We show that, for an n element composition, using the hypothesis of constant coefficients, (n + 1) preparations - allowing n(n + 1) intensity measurements - are in principle sufficient to calculate the n2 calibration parameters [i.e. n(n - 1) influence coefficients and n referenc relative intensities] which are necessary for a complete analysis. Actual analyses are carried out by measuring the fluorescent intensities using the ratio (i.e. unknown/standard) method, and then calculating the concentrations from the usual relationships through an iterative calculation, preferably executed by a computer program. A detailed description of a typical application is given, which involved the study of fused specimens (borax fusion) of bauxite and resulted in the very accurate analysis of calcined samples, as well as the direct analysis of raw bauxites following an adequate treatment of the ignition loss problem. While the method is immediately applicable to every system studied in either solid or liquid solution, it clearly extends to compact systems over a suitable compositional range, provided that carefully controlled additions can be achieved and that all prepared samples are homogeneous.
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    X-Ray Spectrometry 4 (1975), S. 71-73 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Direct X-ray fluorescence analysis of pieces of cloth cut from clothing on which there is a suspected paint smear has been found to be a useful forensic technique for comparing a reference paint sample with the smeared substance. Even though the X-ray method does not compare all the constituents of the paint, it may often be sufficient to distinguish rapidly between two suspect paint sources, and can therefore be a valuable method in paint transfer cases such as hit and run accidents. A feature of the method is that elements present in the cloth, such as sulphur in wool and titanium in some synthetic fibres, can be used as internal standards.
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    X-Ray Spectrometry 4 (1975), S. 90-91 
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    Notes: A table is presented summarizing recently available data of experimentally determined K shell X-ray fluorescence yields.
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    X-Ray Spectrometry 4 (1975), S. 92-92 
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    X-Ray Spectrometry 4 (1975), S. 95-98 
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    Notes: An X-ray method for the analysis of thin oxide films on steels has been developed. The oxide layer is first stripped off by the action of bromine in methanol in an inert atmosphere. It is then dissolved and a small amount of the solution is allowd to evaporate on a filter paper impregnated with disodium carbonate. The matrix effects are thus negligible, which can be seen from the standard curves obtained from synthetic oxides in this way. From the standard curves the precision has been estimated to be about ± 5%. The method has been used to analyse oxide layers formed on four different steels oxidized at high temperatures.
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    X-Ray Spectrometry 4 (1975), S. 114-116 
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    Topics: Physics
    Notes: Measurements on several Ge(111) crystals have shown a variation of a factor of two in their reflectivity for p Kα radiation. High background readings for phosphorous using the Ge(111) crystal are shown to be due to germanium L spectra fluorescence from the crystal. The background can be reduced by almost a factor of four without appreciably diminishing the net P Kα count rate by selecting the optimum setting of the pulse height analyser.
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    X-Ray Spectrometry 4 (1975), S. A18 
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    X-Ray Spectrometry 4 (1975), S. A19 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 5 (1976) 
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    X-Ray Spectrometry 4 (1975), S. A18 
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    X-Ray Spectrometry 5 (1976), S. 1-1 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 5 (1976), S. 16-28 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: With the appropriate excitation, a specimen will emit an X-ray spectrum where the characteristic line intensities are strongly dependent on the elemental composition. The measurement of these intensities thus affords a method of accurate quantitative elemental analysis. A digitized record of the spectrum may be obtained using a lithium drifted silicon detector, associated electronics and some storage medium. The recorded data is the original spectrum convoluted by the appropriate instrumental function. This paper describes several procedures which may be applied to this data to obtain accurate estimates of the individual X-ray line intensities, mainly with reference to the spectra obtained by electron excitation of thick specimens. The choice of a particular procedure depends on the quality of the data acquistion system, and the likely systematic errors which have been calculated for illustrative examples with special reference to the effects of drift and resolution changes in the electronics. Background subtraction techniques involving interpolation, extrapolation and filtering are discussed, together with methods for deconvolution of overlapping peaks, in particular least squares regression. A versatile new procedure, iterative stripping, is presented which simultaneously accomplishes background subtraction and peak deconvolution.
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    X-Ray Spectrometry 5 (1976), S. 29-30 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Eleven international standards [U.S.G.S. Standards. G-2, GSP-1, AGV-1 and BCR-1; C.R.P.G. standards: GA, GH, BR and Mica-Fe; A.N.R.T. standard: DR-N; G.S.J. standards: JG-1 and JB-1] have been analysed by X-ray fluorescence for niobium and yttrium. Coefficients for full matrix effect correction are reported.
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    X-Ray Spectrometry 5 (1976), S. 31-35 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method for the conversion of X-ray intensities to composition is given. The method is based on the Lachance-Traill equation which uses empirical inter-element correction coefficients. The coefficients are treated as ‘sliding constants’ the values of which depend on the relative concentrations of the analyte and the interfering elements. Values for the coefficients are calculated over wide concentration ranges using the theoretical equations of Sherman. The calculated coefficients are adjusted empirically to achieve high accuracy.Only the measured X-ray intensities from the sample and a single standard are required for an analysis. Final results are obtained by solving a set of simultaneous linear equations. Results of analyses of high alloy steels containing Cr, Ni, Mn, Mo, Cu, Si, Ti, Cb and Fe are given to illustrate the accuracy of the method.
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    X-Ray Spectrometry 5 (1976), S. 36-40 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Depth distributions of X-ray production by electrons in the energy range of six to fifteen key have been measured for Si and Cu characteristic X-rays in matrices of Al, Ni, Ag and Au. Corrections from these curves show that the modified Philibert absorption correction predicts the wrong dependence on matrix atomic number at these low electron energies, while the Duncomb and Reed atomic number correction shows too strong a dependence on atomic number. The curves should be valuable for comparison with both theoretical and empirical models for quantitative analysis at low energies.
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    X-Ray Spectrometry 5 (1976), S. 92-92 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Ammonium acid phthalate crystals are observed to deteriorate in a high vacuum environment and to decrease in reflectivity.
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    X-Ray Spectrometry 5 (1976), S. 115-115 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 5 (1976), S. 104-114 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Spectral distributions of X-rays generated by a General Electric EA 75 Cr/W dual target X-ray tube have been measured using exciting voltages of 20, 30, 40 45 and 50 kV c.p. A carefully characterized and previously described lithium-drifted silicon detector was used and corrections were applied for second order effects in the detection system and for detector efficiency. Relative errors are believed to be of the order of 1% over most of the range covered (4-50 ke V), increasing to about 10% over the lower range of photon energies (2.5-4 ke V). Although the resolution of the detector is limited, it was nevertheless possible by computation to separate groups of characteristic spectral lines from continua and to determine self-absorption jump ratios in these continua. Spectral distributions obtained using chromium and tungsten targets are compared with earlier data of Birks and his collaborators and with the forms of continua predicted by Kulenkampff's equation. Agreement is only fair. The experimental method employed for studying spectral distributions is believed to be the most accurate and reliable now available and is particularly convenient in terms of the rapidity with which distributions can be measured. Further work is required to remove remaining uncertainties concerning the generation of X-rays at thick targets.
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    X-Ray Spectrometry 5 (1976), S. 93-103 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A detailed study of the performance of a silicon detector system is reported, with emphasis on the feasibility of using such a system for accurate quantitative analysis of X-ray spectra covering a wide range of photon energies (2.5-50 ke V). Calibration of efficiency, with an accuracy of ± 0.1% over most of this range, is described. Second order effects in the detection system have been characterized quantitatively, including escape peaks, pulses due to Compton recoil electrons, pulses whose energies are reduced because of incomplete charge collection and sum pulses. This information has been used to devise programs that permit accurate correction of spectra as recorded in a multi-channel analyzer. Corrections are made for the following factors in turn; sum pulses, the second order effects enumerated above and detector efficiency. An analysis of the formation and distribution of sum pulses that represent close coincidences not resolved and eliminated by the pulse pile-up rejector is given in an Appendix. Methods are described for removing sum counts, including ‘mixed’ sum counts, from spectra. The removal of these counts reduces the overall count but results in essentially undistorted representations of spectra as they would be recorded in a system having infinitesimal dead-time. Some recommendations are made for improving the design of silicon detectors for quantitative spectral analysis.
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    X-Ray Spectrometry 5 (1976), S. A13 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 5 (1976), S. 142-148 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The empirical determination of the correction coefficients makes it possible to include into their values all actual changes in the measuring technique which affect the correction. It is neither necessary nor favourable to use all matrix elements for the correction. Therefore, selection criteria are given which allow arrangement of the matrix elements according to their importance to the correction.The correction strategy is described with the aid of two practical examples: a good agreement is found between theory and practice.
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    X-Ray Spectrometry 5 (1976), S. 169-171 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Optimum energy window widths are derived using random counting statistics for use in quantitative energy dispersive analysis over a wide range of peak-to-background ratios. It is shown that a peak energy window width equal to the full width as half maximum gives good results for most practical cases.
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    X-Ray Spectrometry 5 (1976), S. 172-174 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Analysis of dissolved elements in fresh water at concentrations from parts per billion to the high parts per million range can be carried out using 200-500 ml sampling volumes. Preconcentration using ion-exchange resin-loaded filter papers is automatically and quickly carried out and the prepared and dried filters analyzed by energy dispersive X-ray fluorescence analysis. Excitation by a filtered low power tube, subtraction of a blank filter paper spectrum, automatic computer stripping of peak overlaps and removal of spectrum background gives net elemental counts that can be used with linear calibration curves to directly obtain concentration values. The system and approach readily lend themselves to laboratory use as well as unattended operation.
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    X-Ray Spectrometry 5 (1976), S. 154-168 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The bremsstrahlung spectrum from a thick specimen bombarded with 20 ke V electrons is studied with emphasis on the shape rather than the absolute intensity in the energy range 1-10 keV. Monte Carlo calculations are described in detail and used to compare the absorption corrections for characteristic and continuous (bremsstrahlung) radiation from a thick specimen and to determine the extent to which anisotropy modifies the intensity distribution of the continuum. The absorption corrections are found to differ by roughly 5% for f(χ) = 0.5 and 10% for f(χ) = 0.2, but it is shown that the ratio of the corrections can be predicted by using the ratio of two Philibert-type formulae. Anisotropy has little influence on the absorption correction but changes in atomic number or geometry may result in the intensity distribution being altered by typically 5-10% across the energy range 1-10keV. Numerical integration gives values for the generated brems-strahlung intensity which are used in constructing an expression to represent the functional form of the background. Although experimental spectra confirm this to be superior to the combination of Kramers' law and a characteristic absorption expression, several sources of error at low energies, including bremsstrahlung from the Be window, are pointed out and improvements suggested. In order to eliminate the principal uncertainty, that of the overall efficiency curve for a Si(Li) detector and pulse-processor, it is recommended that a stored spectrum be used as a ‘background standard’ for explicit background corrections. Errors are then reduced to the 0.1% absolute concentration level, which is suitable for quantitative analysis.
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    X-Ray Spectrometry 5 (1976), S. 180-187 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Control systems for a Geoscan microprobe based on a minicomputer with a core of 4 K of 16-bit words and for a Japan Electron Optics Laboratory JEOL JXA-50 with a minicomputer having 16 K words are described in general terms. Similar analysis strategies are used in both systems, but the Geoscan software operates on a ‘stand-alone basis’ while that for the JXA-50 is based on a modified version of an Interdata operating system, supporting an interactive program for flexible operator control of the probe. Lower initial cost and less programming effort were involved in the Geoscan control system, but this is balanced in the larger JXA-50 installation by greater flexibility and ease of operation.The integration of non-dispersive X-ray detector systems with microprobe control systems, the suitability of the software operating system for incorporation of such devices and for extension to digital beam scanning and particle area analysis are also briefly considered.
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    X-Ray Spectrometry 5 (1976), S. 197-199 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Two different methods were used to determine the amount of glass phase in mullite refractory grog. Quantitative X-ray diffractometry with calcium fluoride as an internal standard, was used to determine the amount of the crystalline phases, mullite and α-corundum. The amount of glass phase was calculated as the difference from 100%. The other method used the scanning electron microscope, equipped with an energy-dispersive detector. Samples consisting of polished sections were analysed both in the scanning mode and with the spot situated in the glass phase. The bulk chemical composition and the chemical composition of the glass phase thus found, was used to calculate the amount of glass phase in the samples. Agreement within the estimated uncertainties of the two methods was achieved with three different samples.
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    X-Ray Spectrometry 5 (1976), S. 194-196 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The dead time (t) of an X-ray counting system may be readily determined to the nearest 0.4 μs by accurately measuring the counting rate per second (R) for any selected wavelength on two specimens, whose R values differ by a factor of approximately 10, at several tube or specimen currents. The R of the most intense specimen should cover the range up to 6 × 104 counts per second. \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm{t =}}\frac{{{\rm{a}}_{\rm{1}} {\rm{b - ab}}_{\rm{1}}}}{{{\rm{ab (a}}_{\rm{1}} {\rm{- b}}_{\rm{1}} {\rm{) - a}}_{\rm{1}} {\rm{b}}_{\rm{1}} {\rm{(a - b)}}}}, $$\end{document} where a and b are the R values of the two specimens at one current, and a1 and b1 the R values of the same specimens at another. The average t is determined from as many current pairs as possible. All counting rates (R) are thereafter corrected by the equation \documentclass{article}\pagestyle{empty}\begin{document}$$ R_ \circ = \frac{R}{{1.0 - tR}}, $$\end{document} where R0 is the true and R the measured rates per second. R should not exceed about 6 × 104.For energy-dispersive detectors, the R values of Kα and Kβ peaks may be used from a single specimen and substituted for a and b in the above equation to obtain t.
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    X-Ray Spectrometry 5 (1976), S. 200-203 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The calculation and use of spectrometer-dependent variables for use in calibration equations converting X-ray intensities to concentrations are described. The variables correct for changes in both sensitivity and background, allow common calibration equations to be used for two spectrometers and obviate the need for recalibration.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Notes: A computer program, used to ‘curve-fit’ complex spectra of overlapping peaks in other spectral applications, has been used with X-ray fluorescence data. Compensation is made for analytical error introduced through peak overlap. A typical case of this ‘inter-element interference’, that of titanium upon vanadium, is taken to demonstrate the method. A comparison between the computer-generated results and those determined by the conventional inter-element correction method favours the curve-fitting procedure.
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    Notes: An empirical model that includes the effect of incidence and exit angles and non-random packing effects is proposed for describing the effect of particle size on the measured X-ray fluorescence (XRF) response from thick heterogeneous samples. An exact model is derived that illustrates these effects for the ideal case of reglarly oriented cubes, and the previous models at high concentrations of a single homogeneous particale the proposed model and the previous models at high concentrations of a single homogeneous particle type where the largest difference between the previous models is observed. It is shown that at specific angles of incidence and exit the proposed model agrees closely with each of the earlier models. Experimental data taken at different incidence angles show that the proposed model provides the best least-squares fit to the observed data on the basis of the minimum reduced chi-square value.
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    X-Ray Spectrometry 7 (1978), S. vii 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Notes: Over recent years, some confusion has arisen regarding the transmission properties of commercially available frame-mounted polypropylen flow counter windows compared to those of the loose sheet polyethylene teraphthalate (Mylar) material previously available. Experimental results obtained for Ca to F Kα characteristic radiations inclusive enable the transmissions of 6 μm Mylar 1 μm polypropylene to be calculated which in turn are compared to earlier published data.
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