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  • Analytical Chemistry and Spectroscopy  (350)
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  • 1980-1984  (350)
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  • 1983  (164)
  • 1982  (186)
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  • Physics  (350)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 11 (1982) 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 2
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    X-Ray Spectrometry 11 (1982), S. 2-7 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A simple scheme is described whereby x-ray absorption spectra, including the very strong rapidly varying structure near an absorption edge, may be calculated using only a short program and small amounts of computer time. The analysis also provides general rules for the existence of strong structures at the edge. The scheme can describe any neutral absorbing atom (or, with a little modification, ion) and includes the effect of the core hole when necessary. Fits to experiment show good agreement near absorption edges, with somewhat poorer agreement far from the edge. The method is of use in obtaining absorption spectra for use in crystal spectrometers for x-ray mirror calculations where a knowledge of the fine detail of the absorption is not necessary, but an accurate reproduction of the major structure near the edge is.
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  • 3
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    X-Ray Spectrometry 11 (1982), S. 19-24 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Phase transformation studies as well as the determination of linear expansion coefficients are used to show characteristics, accuracy and methods of data evaluation in energy dispersive x-ray diffractometry. A high temperature chamber was modified to withstand temperatures up to 2300°C with fixed angle geometry. Observation of phase transformations in time frames of 10s was possible. In addition, error analyses are made and a method of comparing intensities from angular dispersion to energy dispersive lines is presented.
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  • 4
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    X-Ray Spectrometry 11 (1982), S. 41-41 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 5
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    X-Ray Spectrometry 11 (1982), S. 46-50 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: In the X-ray fluorescence analysis of steels, a correction method is usually used so as to eliminate interfering spectrum overlap and absorption-enhancement effects. In correcting the former, the intensity correction method, by which measured x-ray intensity is corrected, is widely used. In the JIS method of x-ray fluorescence analysis of steels, however, the measured x-ray intensity is first converted into a tentative analytical value, and this value is then corrected for absorption-enhancement effects and finally for interfering spectrum overlap. In this report, a detailed comparison of both methods is made, and the characteristics of the JIS method are discussed.
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  • 6
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    X-Ray Spectrometry 11 (1982), S. 79-82 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Description / Table of Contents: The L x-ray spectrum of Np following α-decay of 241Am was carefully reinvestigated by using HPGe detectors. Energy values of major lines are in good agreement with data deduced from Bearden's work, except for Lα1 and Lβ2,15 which exceed theoretical values by 8 and 22 eV, respectively. Intensities of different components agree well with previous experimental work, and β9, β10, γ11, γ13, t and s lines were found for the first time for Np (Z = 93). L subshell probability ratios are consistent with the Hartree-Fock-Slater calculations of Scofield.
    Notes: Le spectre xL du Np accompagnant la désintégration de 241Am a été soigneusement examiné avec des détecteurs HPGe. Les valeurs des énergies des raies principales sont en bon accord avec les résultats déduits du travail de Bearden, sauf pour les raies Lα1 et Lβ2,15 qui dépassent les valeurs théoriques de 8 et 22 eV respectivement. Les intensités des différentes raies s'accordent bien avec les résultats antérieurs; les raies β9, β10, γ11, γ13, t et s sont caractérisées pour la première fois dans le Np (Z = 93). Les rapports de probabilité dans les sous-couches L sont cohérents avec les calculs Hartree-Fock-Slater de Scofield.
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  • 7
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    X-Ray Spectrometry 11 (1982), S. ix 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 8
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    X-Ray Spectrometry 11 (1982), S. ix 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 9
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method of correction for the particle-size effect in the x-ray fluorescence analysis of thin and monolayer samples is proposed. The method consists of the measurement of characteristic x-rays excited by x or γ radiation of two different energies. A concept of a substitute radiometric particle diameter instead of the particle-size distribution has been introduced in order introduced in order to enable a practical application of the proposed method. The particle-size correction factors have been obtained theoretically and experimentally for iron oxide (Fe3O4), calcium sulphate (CaSO4) and copper sulphide (Cu2S) with various particle-size distributions. The application limits of the proposed method have been discussed.
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  • 10
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    X-Ray Spectrometry 11 (1982), S. 144-148 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A simple semi-empirical procedure for the determination of elemental concentration in light element matrices is proposed. The method consists of taking x-ray fluorescence spectral measurements at several orientations of the thick planar samples with a standard x-ray fluorescence set-up consisting of a low power x-ray tube and a Si(Li) x-ray spectrometer. The measured intensities are then extrapolated to zero effective thickness for the fluorescent x-rays. In the following we have carried out the extrapolation procedure for the ratios of the Compton scattered Mo Kα x-rays to the fluorescent x-rays which provides the direct determination of the elements in p.p.m. units with respect to the light matrix.
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  • 11
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    X-Ray Spectrometry 11 (1982), S. viii 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 12
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    X-Ray Spectrometry 11 (1982), S. 154-155 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The Compton scattering technique for rapid determination of ash content in coal has been extended to coke samples. Some improvements in respect of the sample preparation and possible line overlap and background have been incorporated. A modified regression equation used in this work to compute the x-ray data is found to yield good results.
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  • 13
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    X-Ray Spectrometry 11 (1982), S. vi 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 14
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    X-Ray Spectrometry 12 (1983), S. 50-50 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 15
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A dependence of the observed Kβ2/Kβ1,3 intensity ratios of As, Se and Br on their concentrations in measured samples was found in a study of the use of these ratios in chemical state analysis. This paper includes the experiments and discussion on this concentration effect, which is caused by the large difference between the self-absorption coefficients of each element for its Kβ2 and Kβ1,3 radiations. An x-ray spectrometer was used for the measurements of the intensity ratios and absorption coefficients. Since the Kβ2 radiation of each element has a wavelength shorter than the Kβ1,3 radiation and longer than the K absorption edge, the self-adsorption coefficient of the Kβ2 radiation was presupposed to be smaller than that of the Kβ1,3 radiation. The results of experiments, however, were contrary to the supposition. The observed self-absorption coefficients of these elements for their Kβ2 radiations were 1.4-2.2 times those of their Kβ1,3 radiations, depending on the chemical states of the elements as absorbers or x-ray emitters. These values gave a solution to the concentration effect. The correction of the effect allows the inherent intensity ratios to be determined which may then be used for chemical state analysis.
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  • 16
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    X-Ray Spectrometry 11 (1982) 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 17
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    X-Ray Spectrometry 12 (1983), S. vii 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 18
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The linear relationship between the reciprocal of analyte-line intensity, and the reciprocal of concentration has been applied to the determination of ten major and minor elements in silicate rocks and minerals. The analyses were carried out on fused specimens of 11 rock standards, with and without added La2O3, and with and without added NaNO3. The method requires no absorption matrix effect corrections, and is ideally suited to the analysis of geological materials with a wide range of chemical composition. It clearly has the advantage of simplicity and speed, and can be applied to the analysis of samples when suitable standards are not available. The results obtained in all cases are in excellent agreement with the literature. However, the discs with La2O3 added yield results with better precision and accuracy than do those without La2O3. Na2O is normally determined on separately prepared rock powder pellets, but can be satisfactorily analysed by this method, using the La2O3 added discs, together with all of the other major and minor elements. Na2O analyses are more readily obtained using discs without added NaNO3. We, therefore, recommend that the analysis of geological materials be carried out on fused glass discs with La2O3 added and without NaNO3.
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  • 19
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    X-Ray Spectrometry 12 (1983), S. viii 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 20
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    X-Ray Spectrometry 12 (1983), S. 97-105 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The exponential equation R0 = R · eR0τdescribes the counting losses in wavelength-dispersive x-ray spectroscopic (WDF) detectors up to very high counting rates. The correction error can be considerably lower than 1% for a true counting rate of 7 · 105s-1. The dead time constant τ has however to be determined very accurately for this. Methods of determining τ with the desired accuracy are also described. And finally, a formula for correcting for dead time losses for two detectors in series, where each detector has a different dead time, is deduced and verified by experiment. Here again, one can calculate the true counting rate with an accuracy of 1% at a true counting rate of about 7 · 105 s-1.
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  • 21
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    X-Ray Spectrometry 12 (1983), S. 118-120 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The analysis of various elements in coal has become important as coal utilization increases. The application of x-ray fluorescence (XRF) to this type of analysis is complicated by matrix-correction needs and lack of matrix-matched standards. The application of fundamental parameter mathematical corrections using easily obtainable doped graphite standards is evaluated.
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  • 22
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    X-Ray Spectrometry 12 (1983), S. 132-132 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 23
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    X-Ray Spectrometry 12 (1983), S. 153-162 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Cross-sections for bremsstrahlung production in thin films may be derived theoretically only if certain approximations are made or if there is recourse to numerical techniques. In this paper, two approximate equations, one based on the Sommerfeld theory and the other on the Bethe-Heitler theory, are assessed for their accuracy in predicting cross-sections differential in photon energy and emergence angle when a thin foil target is bombarded with electrons with energies between 40 and 100 keV. Experimental data are presented from eight different target materials and these are processed initially to make comparisons between experimental and theoretical spectral shapes and subsequently to compare observed and predicted absolute cross-section values. Except for the heaviest target material (Au), the Bethe-Heitler theory provided a satisfactory description of all experimental observations. In contrast, the Sommerfeld theory provided a significantly inferior description of spectral shapes and consistently overestimated absolute cross-sections by 15-20%.
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  • 24
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    X-Ray Spectrometry 12 (1983), S. v 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 25
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    X-Ray Spectrometry 11 (1982), S. viii 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 26
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    X-Ray Spectrometry 12 (1983), S. 11-18 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: It is shown that when a narrow x-ray beam is used in energy dispersive fluorescence analysis of thick, low-Z samples large deviations from the predictions of the commonly used fundamental parameter model occur. A simple method by which the effects can be studied empirically is described. An approximate model allowing a direct calculation of the effécts is introduced. The validity of the model has been confirmed experimentally.
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  • 27
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The stoichiometry and thickness of TiNxOy films has been determined by electron microprobe and nuclear microanalysis. The difficulty arising in the electron microprobe from the interference between NKα and TiLI lines has been overcome by using a suitable Monte Carlo computing scheme. This procedure takes into account the SiKα intensity which was found to be sensitive to composition and thickness of the overlying TiNxOy film. The good agreement between electron microprobe and nuclear microanalysis results indicate the validity of the method.
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  • 28
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    X-Ray Spectrometry 12 (1983), S. v 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 29
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    X-Ray Spectrometry 12 (1983), S. 23-29 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: In the Japanese Industrial Standard for the x-ray fluorescence analysis of steels, the ‘estimated binary calibration curve’ method has been adopted. In this method, the calibration curve for the binary system, consisting of an analyte and the principal constituent elements is estimated and derived by using multicomponent standard samples. The measured x-ray intensity is first converted into a tentative analytical value from this calibration curve, and then the analytical result is derived from this tentative value using the correction procedure. In this paper, some methods and standard samples of making the estimated binary calibration curve are compared and discussed, also, the characteristics of the JIS method are described.
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  • 30
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    X-Ray Spectrometry 12 (1983), S. 121-127 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The Rasberry-Heinrich method and its three modifications (delta method, expanded square intensity method and double constant method) together with the Tertian and a strictly empirical method were used for the analysis of copper mattes and slags. The expanded square intensity method, which represents a combination of theory and empiricism, gave the most accurate results.
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  • 31
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    X-Ray Spectrometry 12 (1983) 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 32
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    X-Ray Spectrometry 12 (1983), S. 138-147 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: PIXE (particle induced x-ray emission) analysis of aerosols has been applied to four different samplers to determine sample thickness corrections, detection limits and required sampling times in different environments. The samplers (two total filter samplers, a two stage filter sampler and a cascade impactor) were used with filters made by Ghia, Millipore, Nucleopore and backings of polystyrene film, respectively. The calculations were based on the accumulation mode aerosol (particles in the 0.05-2μm diameter range) composition. Sampling times (resulting in detection limits 10 times lower than assumed aerosol concentrations) ranged from a quarter of an hour in urban, to a quarter of a day in rural and to two weeks in remote environments. These sampling times are calculated with the requirement that at least one element representing each of the following sources was detected: fossil fuel combustion (S, V and Ni), leaded petrol combustion (Br and Pb) and general industrial activities (Cr, Cu and Zn). Generally the two stage filter sampler employed with Nuclepore filters yielded the highest time resolution when specific flow rate, thickness and substrate impurities were taken into consideration. Thickness corrections based on a proton energy of 2.55 MeV and typical ambient urban and rural aerosol matrices show that elements of low atomic number such as P, S and Cl, where the x-ray self absorption effect is most important, require a 10-20% correction with a uniform deposit thickness of about 0.5 mg cm-2 and a non-nuniform (conical) deposit thickness of about 1 mg cm-2. For elements of higher atomic number than vanadium (K x-rays) the proton energy loss correction dominates. Sampling times resulting in the above mentioned deposit thicknesses were shortest for the cascade impactor while the Millipore and Nuclepore filter samplers were least critical in this respect.
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  • 33
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Two approximate theories are considered for the production of characteristic x-rays when thin foil targets are bombarded with electrons with energies between 40 and 100 keV. One, due to Kolbenstvedt, is semi-classical in nature whilst the other, due to Bethe, contains two parameters which are normally adjusted empirically. Data from six different target materials are presented, but because errors in experimentally derived absolute cross-sections are large, a comparison is made between theoretical and observed ratios of characteristic Kα photons to bremsstrahlung photons in a 20 eV channel directly beneath the peak. By adjusting the Bethe parameters and using a modified Bethe-Heitler theory to predict the bremsstrahlung, agreement between experiment and theory of typically 10% is recorded. Finally, a means of simplifying the equations used to enable rapid calculation of x-ray spectra with a pocket calculator is indicated.
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  • 34
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    X-Ray Spectrometry 12 (1983), S. 175-181 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The construction of a mobile XRF unit is described. It consists of a radionuclide source (109Cd), shielding, a sample exchanger for powdered samples, a semiconductor detector and an electronic measuring and evaluation system. The disadvantage of the supply of liquid nitrogen or liquid air for the semiconductor detector is avoided by use of a mobile unit for the production of liquid air constructed for this purpose. Numerous measurements were carried out at several location within the Federal Republic of Germany.
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  • 35
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    X-Ray Spectrometry 12 (1983), S. 148-149 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method has been investigated which allows calculations of the absorption correction factors in the energy range 1.0-5.0 keV using 55Fe excitation source. From the experimentally-measured absorption factors between 6.0 and 20.0 keV using 109Cd excitation source, the coefficients at lower energies with the associated absorption jumps are generated through an iterative procedure.
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  • 36
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    X-Ray Spectrometry 12 (1983), S. 134-137 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The application limits of a correction method for the particle-size effect in x-ray fluorescence (XRF) analysis are estimated theoretically in the presented paper. This correction method requires the use of two sources of exciting γ-or x-radiation of different energies.1 The influence of the different values of the parameter t′ (which is a function of the linear absorption coefficients for primary and fluorescent radiation) and the influence of the relative standard deviation, Sr (resulting from counting statistics) have been taken into account in evaluating the efficiency of the method. In addition, the criteria for the selection of the optimum energies of the exciting radiation, the proper times of measurement and the activities of the sources of primary radiation are proposed. An example of the application of the proposed criteria to the determination of iron (as Fe3O4) is presented.
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  • 37
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    X-Ray Spectrometry 12 (1983), S. 170-172 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method for measuring the surface density of pure element thin films using x-ray fluorescence and coherent scattering of primary radiation has been developed. The accuracy is greatly improved by intensity ratio measurements where the dependence on the accuracy of the fundamental parameters is eliminated.
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    X-Ray Spectrometry 11 (1982), S. 13-18 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: The shape of energy dispersive diffraction lines from flat powder samples is determined by the Bragg angle, beam divergences, absorption of the radiation, specimen misalignment and detector performance. Due to asymmetric line broadening, the lines appear to be shifted, usually to lower energies. Two ‘specimen transparency models’ are presented, based upon the accurate determination of line positions and line intensities that are possible.
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    X-Ray Spectrometry 11 (1982), S. 35-35 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 11 (1982), S. 36-39 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 11 (1982), S. 55-63 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A rapid method of routine whole rock analyses of major and trace elements, using low dilution fusions, is described. The method is particularly suited to use with automated x-ray fluorescence equipment, and is effective for rocks which range widely in composition. Corrections for matrix effects based on a matrix of influence coefficients, the calculation of a mass absorption coefficient from major component data and Compton scatter methods are discussed; data are presented which demonstrate that all three procedures can be used with low dilution fusions. Spectral impurities (principally of Cu, Ni and Zn) which cause problems in some trace element analyses using low dilution fusions and may also affect pressed rock powder studies are investigated and a simplified correction procedure is proposed. Lower limits of detection, accuracy and precision for determinations of 20 elements, carried out using low dilution fusions, indicate that the low dilution fusion procedure is well suited to routine whole rock analyses of major and trace elements.
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    X-Ray Spectrometry 11 (1982), S. 66-69 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: It is well known that calibration curves in x-ray fluorescence spectrometry offer to the analyst different alternatives to fit measured data. We have set out to compare two well-known algorithms, those of Rasberry and Heinrich (R-H) and Lachance and Traill modified by Claisse and Quintin (LTCQ), with computer generated data using the fundamental parameter method. It is seen that both work reasonable well for binary samples, but in ternary samples deviations from reference points are larger for R-H than for LTCQ. We conclude from this study that ternary effects in R-H are not accounted for adequately, since only binary coefficients are needed to determine a calibration curve for any ternary as well as any multicomponent sample. In LTCQ, inclusion of an additional coefficient determined from a ternary standard suffices to improve considerably the degree of fitting to reference.
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    X-Ray Spectrometry 11 (1982), S. vii 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 11 (1982), S. 99-99 
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    X-Ray Spectrometry 11 (1982), S. 112-116 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: Certain concentration correction equations are considered as a consequence of the Shiraiwa and Fujino equation. Particular correction equations are related to special physical cases. A set of differential equations, derived on the ground of Claisse's considerations, co-exist with the set of classic correction equations. The mutual relations between the classic correction equations are presented.
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    X-Ray Spectrometry 11 (1982), S. 128-134 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The effects of particles size, sample-to-flux ratio, fusion temperature and fusion period on the speed of lattice decomposition of three different iron ores were tested. Russian Krivoj Rog (hematite), Jugok concentrate (magnetite) and Polish siderite were used for structural investigations. In order to estimate the degree of crystallographic destruction of the material, x-ray diffractometry was used. Contrary to the usual large dilution associated with fusion, experiments with minimum flux contribution were carried out. The heat treatment (fusion) of samples was performed in graphite crucibles. The minimum flux technique was compared with dilution fusion (Pt-Au crucibles) on 32 iron ore standards.
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    X-Ray Spectrometry 11 (1982), S. 149-152 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An experimental study of the fine structure of the electron excited Cu Kα1,2 doublet in the energy range 20-40 ke V is presented. The spectra are different from earlier published ones in the sense that both the intensity and the resolution are high. A convex-crystal setting of the spectrometer is discussed. It is pointed out that when using a point source in association with a convex crystal the broadening due to the curvature of the planes vanishes. The high intensity enables one to unambigiously introduce two Lorentzians. The characteristic profile and location of the difference between the experimental data points and the fits show that the asymmetry of the Cu Ka1 and Kα2 lines most probably is due to the radiative Auger mechanism K-LM.
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    X-Ray Spectrometry 11 (1982), S. 153-153 
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    X-Ray Spectrometry 11 (1982), S. 159-163 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A new type of a formed filter paper is proposed as a sample medium for a microdroplet analysis by x-ray fluorescence spectrometry. It has a circular center part, separated by a narrow circular groove from its edge, and four, paraffined, supporting bridges. It can thus keep a spot area constant when a liquid sample drops at the center part. After dropping the liquid sample, the paper is dried and used for the x-ray measurement. It can be stored for years without any chemical change. This formed filter paper is effective in improving the linearity range of a calibration curve and the precision of a fluorescent x-ray measurement as compared with a non-formed filter paper. The sample volume required is only 20 to 100 μ1 and therefore microscale analysis of the liquid sample is allowable.
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    X-Ray Spectrometry 11 (1982), S. 181-186 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The Monte Carlo model for predicting the complete spectral response from homogeneous samples has been extended to heterogeneous samples which may be considered to be spherical particles suspended in a homogeneous matrix. The spherical particles may have any distribution of size and spatial position as specified input. The particle compositions are either: Model 1-a homogeneous mixture of all the sample elements present or Model 2-a single pure element appropriately chosen at random from those present. These two sample compositions should represent extremes of the matrix interferences encountered in practice and should, therefore, bound the x-ray and source scattering spectral responses observed. The sample Monte Carlo results reported here for both heterogeneous models approach the limiting values predicted by the homogeneous model when used for decreasingly small particle sizes and generally exhibit a smooth relationship with particle size. Although comparisons with two sets of experimental results are not entirely satisfactory, the general trends are properly predicted. It is concluded that the models are accurate within our present capability of testing them (at present we only have available two particle spatial distributions for packing fractions of 0.4 and 0.6, both for particles of uniform size).
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    X-Ray Spectrometry 11 (1982), S. vii 
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    X-Ray Spectrometry 12 (1983), S. 2-7 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: Two common methods of applying dead-time corrections in EDS systems, both of which are carried out internally in the electronics, are examined. The Barnhart method shows serious discrepancies when making dead-time corrections and in certain cases no correction is made at all. The problem is associated with the reliance on the fast amplifier to count all x-rays collected by the detector. In practice, however, the fast amplifier does not always succeed in carrying out this function since x-rays with energies 〈 1500 eV may fall below its threshold level. The problems become worse when a formvar window is substituted for beryllium since a greater proportion of low energy x-rays can now reach the detector. The magnitude of the discrepancy is shown also to be a function of specimen and electron accelerating voltage. Similar experiments with an EDS system using the Covell method show that no such discrepancies arise.
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    X-Ray Spectrometry 12 (1983), S. vi 
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    X-Ray Spectrometry 12 (1983), S. 67-71 
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    Topics: Physics
    Notes: A new geometry for a radioactive source was developed for the XRF determination of trace elements in the range 0.1-50 μg in samples with diameters from 2-5 mm. The new set-up was constructed with five 241Am (45mCi each) point sources. The shielding and configuration of the source, as well as the choice of appropriate collimators in the optimal shapes and dimensions, were investigated in detail. The study was carried out to establish the conditions for obtaining maximum sensitivity. The count rates and signal-to-background ratios were compared with those obtained with an annular source and showed an improvement of a factor of ∼2 in the signal-to-background ratio and of a factor of 2-9 in the peak intensity for the elements studied (29≤ Z ≤ 47).
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    X-Ray Spectrometry 12 (1983), S. 72-78 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: Improvements of the detection limits in photon induced x-ray fluorescence analysis are obtained by the reduction of the radiation background using linear polarized x-rays for excitation. A single crystal where Bragg reflection takes place at an angle 20 = 90° produces linear polarized and monochromatic x-rays. The use of a single crystal instead of amorphous scattering materials increases the intensity of the polarized beam in some cases up to a factor 104. The use of curved crystals instead of standard flat crystal geometries shows a further increase in the intensity of the exciting beam in the focus line. The crystals in use for both geometries are described. Samples can be investigated in either form, liquid or solid, no special preparation technique is required. Detection limits are given for some elements, absolute amounts of 150 picogram can be detected in some cases.
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    X-Ray Spectrometry 12 (1983), S. vii 
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    X-Ray Spectrometry 12 (1983) 
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    X-Ray Spectrometry 12 (1983), S. 106-110 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: Energy dispersive x-ray fluorescence is shown to be an effective analytical method for determination of calcium, sulfur and phosphorous concentrations in wet process phosphoric acid. Periodic monitoring of these quantities is essential to plant operation, and is presently carried out using separate wet chemical analyses. The XRF method described here has the advantages of increased speed, of multi-element determinations from a single measurement, and of having the potential for on-line use in an automatic plant control loop.
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    X-Ray Spectrometry 12 (1983), S. 82-86 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The study of the energy resolution and linearity of germanium, x-ray detectors at very low energies is difficult due to the degradation of the spectral line shapes resulting from incomplete charge collection in the detectors's surface dead layer. The use of low-energy, K escapes peaks obviates this difficulty as they are absorbed at depths characteristic of their full-energy parent photons. Measurements have been performed using particle-induced x-ray emission analysis of targets having characteristic K and L x-ray energies just above the Ge K-edge. The escape peaks retain pure Gaussian shapes down to the noise level of the detector and open up the possibility of a selective field of high-resolution escape-peak spectroscopy.
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    X-Ray Spectrometry 12 (1983), S. 92-96 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The results of investigations into the effect of geometrical surface structure in x-ray fluorescence analysis of Cu-Ni alloy are presented. The experimental materials were samples of spectrometric standard quality, in which surfaces were especially prepared by grinding and polishing. The surface state was estimated qualitatively, using a scanning electron microscope, and quantitatively, using a profilograph, by the determination of the roughness parameters Ra and Rz. The relationships between the roughness parameters and Cu, Ni and Si fluorescent radiation intensities, as well as the scattered radiation from the x-ray tube anode element were established. The optimum range of the surface state for a given alloy has been defined.
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    X-Ray Spectrometry 12 (1983), S. 115-117 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: Epoxy adhesive and aluminium powder have been used as binders to make permanent standards for x-ray fluorescence and diffraction. These standards are easy and cheap to fabricate and are very durable. They can be used as internal standards or calibration standards. Three methods of fabrication are proposed and compared.
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    X-Ray Spectrometry 12 (1983), S. 128-131 
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    Notes: K-absorption edge-shifts of copper in CuCl2—2H2O CuSo4—5H2O, Cu(NO3)2—3H2O, Cu(en)3Cl2, Cu(en)3SO4 and Cu(en)3(NO3)2 in aqueous solutions as well as in polycrystalline form were measured using the x-ray absorption spectroscopic technique. Effective charge on copper ions are estimated using the method of Gianturco and Coulson. The results of the present study reveal interesting results regarding the nature of chemical bonding. An attempt is made to interpret the results in the light of the available data on these samples.
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    Mass Spectrometry Reviews 1 (1982), S. 349-393 
    ISSN: 0277-7037
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Mass Spectrometry Reviews 2 (1983) 
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    Mass Spectrometry Reviews 1 (1982), S. 309-348 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology , Physics
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    Mass Spectrometry Reviews 2 (1983), S. 1-45 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology , Physics
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    Mass Spectrometry Reviews 2 (1983), S. 47-76 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology , Physics
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    Mass Spectrometry Reviews 2 (1983) 
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    X-Ray Spectrometry 11 (1982), S. 1-1 
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    X-Ray Spectrometry 11 (1982), S. 25-28 
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    Notes: An improved x-ray fluorescence method has been developed for the analysis of chrome containing refractory materials (raw materials, in process and final products). It involves the fusion of the powdered samples with a mixture of sodium hexametaphosphate and lithium metaborate in the presence of lanthanum oxide into a glass disc followed by polishing of the disc before exposure to the x-rays. Three British standards, two South African Standards and one NBS Standard were used for standardizing the method. SiO2, Fe2O3, Al2O3, CaO MgO and Cr2O3 were used in the standardization because these compounds constitute the majority of the materials under analysis. Linear regression analysis of the data showed that all the lines were linear, the coefficient of determination being equal or close to 1.00 with a mean error of less than ±3.5%, excepting CaO which had a mean error of ±8.6% because of its low concentration and the larger variance in its standard value.
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    X-Ray Spectrometry 11 (1982), S. 29-31 
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    Notes: The binder is composed of nine parts (by mass) styrene copolymer and one part wax. Both ingredients are marketed under brand names and are available as 10 μm powders, which can be conveniently blended in bulk. Exceptionally robust briquettes containing 10% binder have been made from a great variety of sample types, including metal powders, ion exchange resins, coal, charcoal, graphite, ash, vegetable matter and geological materials. Normally the sample and binder are milled together in a swing mill and milling behaviour is not adversely affected. The briquettes are not affected by vacuum, radiation or age. Erratic milling efficiency of the six-vessel swing mills used and modifications to overcome the problem are described. For the most satisfactory ejection of a briquette, the cylinder wall of the die should taper slightly outwards near the ejecting end. A pressure of at least 0.04 MPa is recommended to ensure maximum x-ray fluorescence intensity, but higher pressures improve briquette strength. In the above-mentioned laboratory 0.23 MPa is normally used. The time the briquette is held under full load is not important. The simplicity of the method makes it possible to mill and press more than 1000 briquettes per day. Binder cost is approximately 3 cents per gram.
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    X-Ray Spectrometry 11 (1982), S. 42-45 
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    Topics: Physics
    Notes: Accurate values for x-ray relative intensity factors, which are the fraction of intensity measured, are important for quantitative calculation procedures used in scanning transmission electron microscope thin film x-ray microanalysis. We have developed equations for calculating these parameters for the K, L and M shells and have applied them to a thin film quantitative analysis procedure. The K shell values were obtained from experimental and theoretical data in the literature and show a constant region between atomic numbers 20 and 30. To obtain L shell values measurements were made with an electron probe and an energy dispersive system on a 200 kV scanning transmission electron microscope. These data were combined with values calculated from Coster-Kronig and fluorescence yield data in the literature. The result was two curves with a step at atom number 51 and a significantly different magnitude than values used in other thin film methods. The following equations for use in a computer program were developed from these curves; aLα1.2(Z=27-50)=1.617-0.0398Z+3.766 × 10-4Z2; aLα1,2(Z=51-92)=0.609-1.619 × 10-3Z-0.03248 sin [0.161(Z-51)].
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    X-Ray Spectrometry 11 (1982), S. 64-65 
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    Topics: Physics
    Notes: Finely divided metal particles, formed in the interlayer space of montmorillonite, have been identified by a x-ray microprobe technique and their dimensions measured by scanning electron microscopy. The dimensions of Ni0 and Cu0 obtained on reduction of the respective metal ions by H2 have been shown to be ∼ 100 Å.
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    X-Ray Spectrometry 11 (1982), S. 83-88 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A SRSO1 Siemens x-ray spectrometer equipped with a logical controller was controlled by a Tektronix 4051 computer to record step by step the x-ray fluorescence intensities. Ten samples can be analysed after the recording of 2 spectra (LiF (110) and PET) for each sample on a magnetic tape. On a host computer, a program first reduces the x-ray fluorescence spectra to find the peak parameters for each line and another program subsequently identifies the elements.
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    X-Ray Spectrometry 11 (1982), S. vii 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 11 (1982), S. 100-108 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A ‘single pass’ method of analysing silicate rocks for their major element composition has been developed using a Philips 1212 x-ray fluorescence spectrometer. Samples need only be submitted once to the spectrometer and all ten major elements (SiO2, TiO2, Al2O3, Fe2O3T, MnO, MgO, CaO, Na2O, K2O and P2O5) are determined using a Cr x-ray tube and three analysing crystals, i.e. TIAP, PET and LiF220. The method has been evaluated in terms of the quality of the calibration lines for each element, the precision of replicated analyses and by the analysis of rock standards as unknown samples. The single pass method is rapid, facilitates on-line data reduction and is capable of producing high quality analytical data.
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    X-Ray Spectrometry 11 (1982), S. 121-127 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Several mathematical models for correcting x-ray fluorescence intensities are proposed in the literature. However, it is not always easy for the analyst to choose the best one for a particular case. Therefore a modular program has been written to compare automatically mathematical models for quantitative x-ray spectrometry with the object of determining the best conditions of analysis (models, number and nature of interfering elements and matrix effects). The graphic display of the standard deviation of the standards as a function of the interfering elements used in the correction simplifies and accelerates the interpretation of the matrix effects.
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    X-Ray Spectrometry 12 (1983), S. 47-49 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A new crystal-type x-ray spectrometer is described, which employs a position-sensitive detector for simultaneous radiation detection in a certain energy range given by the spectrometer design. The main specifications are (a) better energy resolution and (b) longer data collection times compared with an energy-dispersive spectrometer.
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    X-Ray Spectrometry 12 (1983), S. vi 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 81
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    X-Ray Spectrometry 12 (1983), S. 59-66 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A serpentine mineral specimen used for a standard in a Materials Analysis Company Model 400 electron microprobe equipped with a Kevex Model 5000A energy dispersive sperctrometer and an on-line Hewlett-Packard 2100 computer, was repeatedly analysed during a study of serpentinization. The results of the repeated analyses were statistically analysed and show an acceptable level of accuracy and precision. The relative and absolute errors for the serpentine standard lie within the same ranges as the errors for the other standards (forsterite, enstatite, diopside, kyanite and kaersutite) used, although the standard deviations for the serpentine analyses are slightly greater. These results are within acceptable limits and indicate that serpentine can be routinely analysed by energy dispersed analysis, using a serpentine standard for magnesium and silicon determinations, with the same accuracy but with slightly lower precision than less hydrous silicates. Most elements were present in amounts between 2 to 63 wt% of the oxide in the standards used but 0.31 wt% Al2O3 present in the serpentine standard was routinely determined with acceptable results.
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    X-Ray Spectrometry 11 (1982), S. 164-166 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The L11 and L111 absorption discontinuities of Tb in various Tb compounds have been recorded using an automated and highly stable x-ray unit. The energy shifts have been discussed in terms of effective ionic charge. Applying Levy's method, the radii of the first coordination sphere have been calculated from the extended fine structure.
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    X-Ray Spectrometry 11 (1982), S. 173-180 
    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 and combined with an existing detector response function model to ptdict the entire pulse-height spectra for energy-dispersive, x-ray fluorescence systems that consist of an annular-ring, photon exciting source, a coaxially positioned right circular homogental sample, and a cirular si(Li) detector. A method is dervied and demonstrated for using the predicted and experimental pulse-height spectra on a chi-square basis to determine elemental amounts. This approach allows the use of all the information available in an entire energy-dispersive, x-ray fluorescence pulse-hight spectrum for analysis purposes.
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    X-Ray Spectrometry 12 (1983) 
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    X-Ray Spectrometry 12 (1983), S. 8-10 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A new procedure of powder sample preparation for x-ray emission analysis by melting has been worked out in detail. The mixture sample-flux was melted and cooled in graphite crucible. The resulting glass disk was ready for direct measurement. The re-fused graphite electrode of an electric arc furnace was used as the material for the graphite crucible. The dimension and shape of the crucible bottom were determined on the basis of sample holder dimension and sample behaviour during the cooling step. The reproducibility of Kα line measurement was below 1%. Resistance of the crucible to handling and the influence of graphite on Fe Kα, Ca Kα, SKα, Si Kα and Mg Kα line intensities also were investigated.
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    X-Ray Spectrometry 12 (1983), S. 30-37 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The rigorous relationship existing between effective fundamental coefficients, as expressed by Tertian's identities, and Sherman's basic equations for x-ray fluorescence intensities is recalled. The properties of these coefficients in the case of binary systems are described, for usual as well as for some anomalous situations, and a general, accurate hyperbolic equation is suggested to account for coefficient variation with composition. The properties of effective coefficients in the general case of multicomponent systems (alloys, etc.) are then examined, and illustrated on the typical Fe—Ni—Cr ternary system, confirming the essential exactness of this approach. As a consequence, the authors propose to make use of calculated effective coefficients to apply mathematical matrix corrections, and give a first outline of the analytical procedure.
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    X-Ray Spectrometry 12 (1983) 
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    X-Ray Spectrometry 12 (1983), S. 51-51 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 11 (1982), S. 8-12 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An accurate, rapid and relatively cheap method adapted for use in the phosphate industry for on-line simultaneous multielement analysis of phosphate ore and calcined phosphate, using x-ray fluorescence, is described. The method of analysis is sufficiently accurate for the phosphate industry, which demands great accuracy in P2O5 analysis. A statistical evaluation of precision and accuracy is given.
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    X-Ray Spectrometry 11 (1982), S. 32-34 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method is described for the calibration of Ar Kα counting rates, measured using crystal spectrometers equipped with Ar-flow proportional counters. Linear extrapolation from overvoltage corrected x-ray yields of the elements with Kα x-ray energies lower than those of the ArK absorption edge gives an accurate description of the experimental Ar Kα intensity ratios from counters operated at different values of gas pressure. Results of all-element film analyses provided by a matrix correction procedure, ZAF, indicate an accuracy better than 5% relative for the determination of Ar concentrations ranging from 0.1 to 10 wt%.
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    X-Ray Spectrometry 11 (1982) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 11 (1982), S. 51-54 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An x-ray fluorescence technique was developed to analyze the thickness of Ag and Pd metallization layers on the back side contacts of Si solar cells. The technique employed a Sn secondary target x-ray source excited by a Cr target x-ray tube. Sn Kβ excited Ag Kα in the overlying Ag contact while Sn Kα and Kβ excited Pd Kα in the underlying Pd film. The emitted Ag and Pd Kα intensities were compared with corresponding intensities emitted from pure bulk Ag and Pd standards. Attenuation of Sn Kβ and Sn, Ag and Pd Kα in the Ag contact and in the standards was accounted for in the calculations. The results on 17 cells compared favorably with neutron activation analyses. An accuracy of ±10% was estimated for a 40 nm Pd film beneath a 7 μm Ag contact. Palladium films as thin as 1.5 nm were analyzed. The technique is nondestructive and can be applied to process control in a production environment as well as to laboratory testing of experimental cells.
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    X-Ray Spectrometry 11 (1982), S. 70-78 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: It has been shown that x-ray fluorescence calibration curve coefficients are closely related to matrix effects, such as absorption or absorption plus enhancement of the fluorescent radiation. In the classical paper of Rasberry and Heinrich,1 a single coefficient (named Aik) calibration curve was proposed when pure absorption is the predominant effect on the spectral line of interest. Similarly, and for practical purposes, a single coefficient (named Bik) was also considered when absorption and enhancement are present. We propose a new interpretation of calibration curve coefficients based on analytical expressions obtained recently for binary compounds under monochromatic excitation. Six distinct possible cases of calibration curves arise. Examples of binary compounds for each case are given. The data considered have been computed using the fundamental parameters method which allowed us to study a large number of possible mixtures for an arbitrary monochromatic excitation. Finally, through a different approach we discuss how this analysis could be extended to consider polychromatic excitation.
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    X-Ray Spectrometry 11 (1982), S. 89-98 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The isolated atom model of x-ray scatter has been used to develop a new analytical strategy for internal standardization in x-ray fluorescence spectrometry. The method defines quantitatively by how much and within what limitations various background-ratio calibration techniques can improve results for particular elements in specific materials. The analytical strategy is based on a modified peak to background ratio equation, where the background intensity is raised by an exponent T. The variable T combines as special cases all existing analytical strategies which use scattered x-rays, together with the basic linear calibration where T=0. Variation in T was evaluated using extensive computer processing of matrix data for typical soil and plant materials. It was found that T varied with analyte, scatter wavelength and the matrix component contributing to the mass absorption error. Most existing methods using a background-ratio technique are shown to be improved by using a value of T other than the previously assumed unity or zero.
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    X-Ray Spectrometry 11 (1982) 
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    X-Ray Spectrometry 11 (1982), S. 109-111 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An x-ray fluorescence method was developed for the determination of P and Ca in raw phosphates. A modified mathematical method suggested by Lucas-Tooth and Pyne was used to correct for matrix effects. The constants and influence coefficients in the algorithm were assessed using a set of 20 standard samples whose composition was determined by chemical analysis. The correspondence of P and Ca concentrations, as determined by the x-ray method in samples from different deposits all over the world, with the results of chemical analysis can be characterized by the coefficient of variation v of the differences between the two methods. The value of v was 1.2% and 1.8% for P and Ca, respectively. The effects of a preliminary treatment of phosphates by calcination and of reducing the number of phosphate rock deposits, the samples of which are analysed, on the value of v are discussed.
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    X-Ray Spectrometry 11 (1982), S. 135-139 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The matrix effects which exist in x-ray fluorescence analysis are considered, Shiraiwa and Fujino equations being the initial point of these considerations. Matrix effects are divided into two groups: simple and so-called unusual. Among the simple ones, absorption and enhancement effects are considered. New concepts of ‘absolute’ and ‘relative’ absorption effects are introduced. It is shown that the expressions of simple matrix effects can be easily separated in the Shiraiwa and Fujino equation. Additionally, the unusual matrix effects, including the Birks-Harris effect and some cases of the Mitchell-Kellam effects, were found to be well described by certain equations based on the Shiraiwa and Fujino equation, provided the appropriate assumptions were made.
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    X-Ray Spectrometry 11 (1982), S. 156-158 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: X-ray fluorescence analyses of briquetted rock samples for S, Cl and F were carried out utilizing experimental coefficients to correct matrix effects. Data on thirty-two international standards are reported.
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    X-Ray Spectrometry 11 (1982), S. 167-169 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Fundamental parameter interelement correction methods such as NRLXF are finding increased use in quantitative x-ray spectrometry. The purpose of this work was to compare the results obtained with each of the three options in NRLXRF, namely empirical, full, and theoretical, with a semiempirical model such as Rasberry-Heinrich and an NBS fundamental parameter method to check for consistency. Well characterized alloys were chosen for making the intercomparison.
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