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  • Analytical Chemistry and Spectroscopy  (862)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 9 (1980), S. 13-18 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The theoretical relationships between fluorescence intensity and concentration have been used for the calculation of correction constants of the Lachance--Traill and Rasberry--Heinrich equation for systems of solutions. The constants have also been calculated by means of the multivariate least--squares method. Those two alternatives have been tested on systems of Cu--Fe--Zn and Cu--Fe--Zn--Pb in 3.5% aqueous nitric acid and compared with the simple two-variable linear relationship between fluorescence intensity and concentration. The multivariate least--squares alternative gives for the Lachance--Traill method very accurate results (average relative deviation does not exceed 0.18%). In a theoretical discussion, the relationship between optimum sample concentration and solvent correction (enhancement) constant is shown. The optimum conditions for a background reading are also calculated.
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  • 2
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 9 (1980), S. 25-27 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A non-linear rise in intensity of copper Kα1 and Kα2 X-ray lines has been observed from certain areas of the polycrystalline copper target of a microfocus tube operated at tube currents between 0.1 and 0.5 mA and a tube potential of 13 kV. Under the same conditions the intensity rise of the bremsstrahlung is found to be linear. A functional relationship between total count and tube current has been obtained.
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  • 3
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 9 (1980), S. 39-39 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 4
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 9 (1980), S. 48-51 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The operation of a computer system for producing on-line chemical analyses from a three-spectrometer JEOL JXA-5A electron microprobe is briefly discussed. A new method for acquiring the X-ray data by integrating the area under the peak is discussed in greater detail. The increased reliability of the results from this new method are illustrated by considering the effect of focus error on the measured count rates.
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  • 5
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 9 (1980), S. 60-65 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Methods are considered for optimizing a conventional Bragg--Brentano X-ray powder diffractometer for the identification of crystalline phases in airborne particulates deposited on membrane filters. The instrumental parameters investigated include detector stepping increment and scan range, Kβ filtration, and the incident beam divergence slit width. Sample-related factors such as substrate material (cellulose ester, polycarbonate and polytetrafluoroethylene), off-axis displacement of the sample and X-ray induced specimen degradation were also studied. Scan times for sample deposits of several hundred μcm-2 are in the vicinity of 24 h with an 800 W tube. These times may be reduced substantially by one or more of the following modifications: rotating anode or synchrotron radiation source, energy-dispersive diffractometry, and Bragg--Brentano diffractometry with a position-sensitive gas detector.
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  • 6
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 9 (1980), S. 28-31 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A non-destructive method for the determination of platinum in reforming catalysts and doped Venezuelan laterites employing a radionuclide, 8mCi of 109Cd, and a PDP-11/05 processor is presented. The total variation for 100s of fluorescent time is about 3% for a 10% Pt-reforming catalyst. The total variation can be reduced to less than 1% by increasing the fluorescent time so that about 80 000 counts or greater are accumulated. The platinum was determined using the Lα and Lβ lines of platinum, as well as their sum. The different types of variation for each of these measuring parameters is given. Finally, both the calculated and measured values for the prepared calibration standards and the doped Venezuelan laterites were in excellent agreement.
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  • 7
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 9 (1980), S. 90-94 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: In charged particle induced X-ray emission studies, the characteristic X-rays are superimposed on a continuous background of electromagnetic radiation. This background is a significant source of uncertainty when charged particle induced X-ray emission is used for analytical purposes. It is demonstrated that the angular distribution of secondary electron bremsstrahlung exhibits significant structure and may be exploited to improve the detection limits attainable with this method. For low-energy continuum X-rays, good agreement is obtained with predictions of the relativistic retardation model. Deviations at higher photon energies are attributed to Compton scattered γ-rays. Finally, suggestions are made regarding optimum energy and angle selections for direct application of particle induced X-ray emission as an analytical technique, especially when biological samples are investigated.
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  • 8
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 9 (1980), S. 101-109 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A computer control system for an electron probe microanalyser has been designed using CORAL-66, a high level compiler language, for the control program and CAMAC modules for the instrument interface. The consequences of the choices made in the design are discussed. The performance of the system was measured by comparing the results from carrying out typical operations by hand and by computer control. The results showed an improvement in precision for general operation and analysis, a reduction in the time for analysis and an improvement in operator performance from using the control system.
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  • 9
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 9 (1980), S. 123-125 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A simple equation relating the intensity of characteristic X-ray lines to their respective weight fractions has been obtained for a thick sample excited by an isotopic source. It follows from the equation that a single intense line in a standard sample suffices to generate calibration constants over a wide range of elements. Validity of this aproach has been demonstrated by the analysis of a standard soil sample using only the Fe Kα line for calibration. A procedure for correction of peak overlaps has been given using the Kβ/Kα ratios, modified by the matrix effects. The method is very useful for the analysis of soil samples and can be conveniently applied to other matrices.
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  • 10
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    X-Ray Spectrometry 9 (1980), S. 146-149 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Theory and experimental results from X-ray fluorescence analysis without standards are presented. The composition of an unknown specimen is calculated from its count rates without the use of standard specimens. A fast algorithm employing linear approximation techniques uses these normalized count rates as start values for the concentrations and delivers final results usually after the second or third iteration. Accuracy is typically around 10% relative and can be improved by system calibration with standards of arbitrary composition.
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  • 11
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 10 (1981), S. 85-90 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A systematic investigation of the chemical effects on the calcium X-ray K emission spectra from 32 chemical compounds was carried out using a two-crystal X-ray spectrometer. The observed chemical shifts of the Ca Kα1,2, Kα3,4, Kβ1,3 and Kβ5 lines relative to the respective lines from CaF2 varied in the range +0.06 to +0.30, +0.09 to +0.32, -0.06 and +1.1 to +3.2eV, respectively. A certain dependence on the nature of surrounding groups was found in these shifts. The profile changes in the Ca Kβ5 and Kβ5′ bands from all compounds were discussed by subdividing them roughly into three types, depending upon their characteristic features.
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  • 12
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 10 (1981), S. 103-108 
    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 to eliminate absorption-enhancement effects. It is a desirable that the correction factors should be common to all experimental conditions and therefore the fluorescent X-ray intensity should be specified in a common unit. For this purpose, the JIS method converts the fluorescent X-ray intensity into a tentative analytical value from the calibration curve of binary alloys, while the α-correction methods employs the ratio of the intensity of an analytical sample to that of a pure substance for the fluorescent X-ray intensity. In this report a detailed comparison of these methods is made, and the good and bad points of the JIS method discussed.
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  • 13
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    X-Ray Spectrometry 10 (1981), S. 126-127 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The evaluation of the true chemical composition of multicomponent alloys by electron probe microanalyser requires the application of several correction factors, viz. atomic number, absorption and fluorescence corrections. Calculation of these factors is dependent upon a set of empirical correlations and needs the use of a computer. An alternative simple procedure of converting raw data into true composition using constants A is presented here. The paper describes the evaluation of these A constants, by rewriting the Ziebold-Ogilivie relation in the form: k/C = A + (1- A)k, and their use in computing true compositions.
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  • 14
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An X-ray flourescence method is described for the direct determination, without pretreatment, of up to 55 trace elements in coal and coal-derived materials. A single assay specimen is prepared by blending finely crushed sample with a binder and briquetting. Calibration is effected by a suite of synthetic calibration standards prepared from spectrographically pure materials blended into graphite. Variations in ash and sulphur content required matrix absorption corrections to analyte and background intensities, which were achieved by use of relationships with the measured Compton scattered radiation. Prior knowledge of or assumptions concerning the composition of the coal are not required. Accurate results are presented for three NBS coal standard reference materials. Certain elements (including TI, Hg, Te, In, Cd, Ag and most rare earths) are normally present in coal at levels below the detection capability of the described method and require quantification by alternative techniques.
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  • 15
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    X-Ray Spectrometry 10 (1981), S. 153-153 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 16
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    X-Ray Spectrometry 10 (1981), S. 168-170 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Si(Li) detector efficieneres are measured up to 100 keV photon energy in typical X-ray fluorescence geometries using 55Fe, 109Cd, 57Co and 241Am annular sources. The targets are common chemical compounds. The photopeak yield is normalized by the use of a bare CaF2(Eu) scintillator which is free of dead layer. The scintillator response is corrected for escape peak losses. The presented method permits the detection of long term changes in detector response. Discrepancies are found in published nominal detector thicknesses.
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  • 17
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    X-Ray Spectrometry 10 (1981), S. 177-179 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Early model wavelength-dispersive X-ray fluorescence spectrometers can be inexpensively fitted with computer capability through the use of a microcomputer. The principal advantage of the microcomputer over a minicomputer is low cost and the principal disadvantage is relatively slow computational speed. We have found that an Apple II plus microcomputer can perform all of the tasks previously assigned to a larger (and more expensive) minicomputer. Ready availability, ease of service and program flexibility make the microcomputer an attractive choice for a laboratory computer. A matrix effect correction program, XRF-4, has been run in the microcomputer with excellent results.
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  • 18
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    X-Ray Spectrometry 10 (1981), S. 196-197 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method of identifying small samples of fibres by X-ray powder diffraction is described, which is ideally suited to forensic analysis. Being non-destructive it can be used to indicate the most suitable solvent for further more complete analytical methods.
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  • 19
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    X-Ray Spectrometry 10 (1981), S. viii 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 20
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    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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  • 21
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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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  • 22
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    X-Ray Spectrometry 11 (1982), S. 35-35 
    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 11 (1982), S. 36-39 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 24
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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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  • 25
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    X-Ray Spectrometry 11 (1982), S. 66-69 
    ISSN: 0049-8246
    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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  • 26
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    X-Ray Spectrometry 11 (1982), S. vii 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 27
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    X-Ray Spectrometry 11 (1982), S. ix 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 28
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    X-Ray Spectrometry 11 (1982), S. ix 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 29
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    X-Ray Spectrometry 11 (1982), S. 99-99 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 30
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    X-Ray Spectrometry 11 (1982), S. 64-65 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    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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  • 31
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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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  • 32
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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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  • 33
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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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  • 34
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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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  • 35
    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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  • 36
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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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    X-Ray Spectrometry 12 (1983), S. 50-50 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 38
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    X-Ray Spectrometry 12 (1983), S. 47-49 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    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. 121-127 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    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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    X-Ray Spectrometry 12 (1983) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 41
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    X-Ray Spectrometry 12 (1983), S. 138-147 
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    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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  • 42
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    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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    X-Ray Spectrometry 12 (1983), S. 175-181 
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    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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    X-Ray Spectrometry 12 (1983), S. 132-132 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 45
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    X-Ray Spectrometry 12 (1983), S. 153-162 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    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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    X-Ray Spectrometry 12 (1983), S. v 
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    X-Ray Spectrometry 13 (1984), S. 16-22 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: In connection with progress in the creation of differential and so-called differential methods of concentration correction, work has been carried out on the ordering of equations. It has been shown that it is possible to create three principal, complete systems of so-called differential concentration correction equations by (1) using the Claisse method, (2) using the method of function expansion in a Taylor series and (3) using a special method discussed in this paper. These equations can be used instead of the classical concentration correction methods. Moreover, it has been proved that the respective procedures can be used in the creation of expressions which are the analogues of classical intensity correction equations.
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    X-Ray Spectrometry 13 (1984), S. 27-32 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: The methodology of direct hair analysis by energy-dispersive x-ray fluorescence was studied. The effect on the XRF result of having a non-homogeneous radial distribution of the analyte in a single hair strand and the macroscopic effects in a bundle of hairs were calculated to evaluate possible systematic errors. The detection limits were mapped as a function of the target thickness and surface fraction. It appeared that a 10 mg cm-2 sample thickness, i. e. a target with about four layers of hair strands, is recommended. The standard deviation of this simple direct analytical method is 6-19% for some important elements. Discrepancies with neutron activation analysis had a mean value of around 15%. About twelve elements can be determined simultaneously on a routine basis.
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    X-Ray Spectrometry 13 (1984), S. vii 
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    X-Ray Spectrometry 13 (1984), S. 110-114 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: A method for spectral background evaluation in x-ray energy analysis is proposed, based on a simple model of background generation in the detector. This model assumes that photons, of a given energy, interacting with the detector have probabilities of generating background counts within lower energy windows. The usefulness of the method resides in the fact that it allows a background evaluation with different levels of complexity and accuracy. The method also permits accurate background calculation with samples of variable mass and composition, such as biological and environmental materials.
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    X-Ray Spectrometry 13 (1984), S. 126-133 
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    Topics: Physics
    Notes: Qualitative microprobe analysis of sodian potassian hydroxonian meta-autunite failed to reveal any sodium, although nearly 3% was present. Potassium, magnesium and calcium were underestimated to a smaller extent in related natural and synthetic structures. The effect is due to the migration of these interlayer cations from the analysed region - almost instantaneously in the case of sodium - and a consequent decrease in count rates, under the influence of the space-charge resulting from the incident electron beam. Experiments with the autunites and with a soda-glass subjected to various coating treatments showed that the effect of charging can be dramatic. Such charging also occurs when alkali metals are not present, a fact which has important implications for all microprobe analyses.
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    X-Ray Spectrometry 13 (1984), S. 142-145 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Description / Table of Contents: In a geochemical exploration project, about 25 000 stream-sediment samples have been analysed. In a new multi-element technique, 36 elements have been determined by a combination of various methods. Optical spectroscopy with are and ICP excitation and wavelength- and energy-dispersive XRFS were used. An XRFS method is presented which allows the analysis of the fraction with particle diameter 〈 0. 18 mm for up to 30 elements with high precision over a large matrix range. The basic idea is to use a large number of reference samples with very different compositions for the calculation of the calibration line.
    Notes: Im Rahmen des österreichischen Rohstoff-Forschungsprojektes Geochemische Basisuntersuchung von Bach- und Flußsedimenten wurden mehr als 25 000 Proben einer Multielementanalytik auf 36 Elemente unterzogen. Neben optischer Spektroskopie mit Kohlebogen- und induktiv gekoppelter Plasmaanregung gelgangten wellenlangen- und energie-dispersive XRFS zum Einsatz. Es wird ein Verfahren beschrieben, das es ermoglicht, die Analyse der Fraktion mit einem Korndurchmesser 〈0.18 mm auf bis zu 30 Elemente rnit hoher Genauigkeit bei einer breiten Streuung des Matrixbereiches durchzufiihren. Der Grundgedanke dabei ist, eine große Zahl von gut analysierten Referenzproben verschiedenster Zusammensetzung fiir die Eichung heranzuziehen.
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    X-Ray Spectrometry 13 (1984), S. 151-152 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method for determining the ash content of coal by measuring the x-ray fluorescence of Si, Al, Ca and Fe using a diffraction spectrometer is presented. The experiments were carried out on 72 samples of coal from different deposits. A mean standard deviation of the ash content of about 1. 65% was achieved.
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    X-Ray Spectrometry 13 (1984), S. vi 
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    X-Ray Spectrometry 13 (1984), S. vii 
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    X-Ray Spectrometry 13 (1984) 
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    X-Ray Spectrometry 13 (1984), S. 153-155 
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    Topics: Physics
    Notes: The fine structure in the vicinity of the K absorption edge of cobalt in some cobalt biomolecular complexes has been studied using a bent crystal x-ray spectrograph of the Cauchois type. The average metal - ligand bond length in these complexes has been determined by applying Levy's theory.
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    X-Ray Spectrometry 13 (1984), S. 121-125 
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    Topics: Physics
    Notes: In Part 1, a new formalism was proposed to correct with accuracy the matrix effects in XRF analysis. In this paper it is shown how to adapt this new formalism to practical situations. From an estimate of composition calculated by the Claisse-Quintin algorithm and an appropriate calibration, the new algorithm is used to refine the estimated composition for greater accuracy. This last approach is equivalent to the ‘fundamental parameters’ method but is presented in a simpler version adaptable to any mini-computer.
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    Notes: The Philips PW 1450/00 or /10 automatic hardware-programmed X-ray spectrometer, when used in conjunction with the PW 1466 60 position sample loader, permits measurement of both standard and unknown using the same channel only when the ratio mode is selected. Further, a standard must be measured for every unknown. An electronic modification is described which overcomes both of these restrictions.
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    X-Ray Spectrometry 9 (1980), S. 52-56 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: In X-ray fluorescence analysis the concept of radiometric diameter, d, is often introduced in considerations of the fluorescent intensity from a particulate sample. It represents the mean geometric path of the X-rays through one particle and is usually simply taken to be equal to the volume-to-area ratio of the particle. The effective radiometric path is, however, itself dependent on geometry and absorption effects. Rigorous calculations of the fluorescent intensity from a particle in the π and π/2 geometries were carried out to evaluate the errors involved. It appears that, for π geometry, the discrepancy between these exact results and the intensity calculated via the use of d does not exceed 5.2%. For the π/2 geometry, the errors are much larger and can amount to 50% in realistic cases of X-ray fluorescence analysis. These conclusions are also applicable to monolayers. The effective radiometric diameter approaches d only when absorption effects become negligible, but is smaller in other cases.
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    X-Ray Spectrometry 9 (1980), S. 77-80 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The X-ray K absorption edges of Co in some 1,10 phenanthroline-based complexes of cobalt have been recorded. The results have been discussed qualitatively in terms of the effective nuclear charge on the central metal atom and the nature of the ligand.
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    X-Ray Spectrometry 9 (1980), S. 95-95 
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    X-Ray Spectrometry 9 (1980), S. 96-100 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The use of the multiple linear regression program for the derivation of influence coefficients destroys the data bank in the Philips PW 1450/10 spectrometer computer and interrupts analysis. Consideration of the basis of α-coefficients as applied to relatively dilute solutions leads to methods of avoiding the use of this program. Linear regression involving a single independent variable and simple algebraic expressions can be used to derive the coefficients. The requirements for converting α-coefficients applicable to one solvent for use in a different solvent are described.
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    Notes: Fifty pairs of window/non-window glasses, the samples in each pair being matched in refractive index to the fourth decimal place, have been analysed using energy-dispersive X-ray fluorescence spectrometry. The spectra, from 200μg fragments, were compared using a computer based multi-dimensional data processing system. Forty-three pairs of glasses were readily discriminated and forty-nine pairs showed significant differences at about the 5% level. The spectral data for the 100 glass samples were then examined graphically for trends in the elemental levels between the window and non-window glasses. This led to the construction of two linear combinations, namely the peak area ratio (to calcium) of iron with that of magnesium and the peak area of arsenic with refractive index. When plotted against each other these linear combinations and a selection rule allowed 95% of the glasses to be correctly classified.
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    X-Ray Spectrometry 9 (1980), S. 57-59 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: To obtain intense linear polarized monochromatic X-rays a single crystal where Bragg reflection occurs at an angle 2θ=90° is used. A number of suitable crystal materials is listed which fulfil the requirements of the Bragg equation for the wavelengths of standard X-ray tubes and the angular condition. As the first result of a new construction a detection limit of 1 ng Ca was determined using a Cr anode and a Ta single crystal (002) plane as polarizer.
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    X-Ray Spectrometry 9 (1980), S. 66-69 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: This paper shows the employment of five X-ray methods for the investigation of a thickness range of 1 Å to 0.1 mm. The well known techniques (X-ray fluorescence and scanning electron microscopy) are treated, a new method (energy-dispersive X-ray diffraction) is discussed and X-ray photoelectron spectroscopy measurements are essentially improved by a new evaluation method. Low energy electron induced X-ray spectrometry is mentioned. As far as significance of the measured thicknesses is concerned, the range of 10--50 nm deserves special attention.
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    X-Ray Spectrometry 9 (1980) 
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    X-Ray Spectrometry 9 (1980), S. 81-89 
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    Topics: Physics
    Notes: Optimized multilayer X-ray spectrometry, using lead myristate and lead stearate analyzers (2d values of 80 and 100 Å) has been applied to the measurement of the O--Kα and the C--Kα spectral bands from CO and CO2 in the gas and solid phases. The LII, III spectra were also measured for argon in the gas and solid states under similar conditions in order to identify and to minimize any non-molecular components in the CO and CO2 spectra. These molecular orbital data have been related to those obtained with X-ray and ultraviolet photoelectron spectroscopy and grating X-ray spectroscopy. The consistency of the results of these complementary measurements is excellent. The ionization energies for the C and O 1s levels have been determined to be 295.4 and 542.0 eV for CO and 296.8 and 540.3 eV for CO2. The MO data have also been compared with that predicted from the symmetry, strength and binding energy of the molecular orbital spectral components as calculated using the currently available computational models, CNDO/2, MINDO/3, MNDO, extended Hückel and ab initio. The molecular orbital calculated results for these organic compounds, CO and CO2, are not in as good agreement with the experimental data as previously demonstrated for molecular orbital spectra measured for C--Kα and the LII, III bands of Cl, S and P for both organic and inorganic compounds.
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    X-Ray Spectrometry 9 (1980), S. 206-211 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: Multielement thin film standards are made by mixing a solution of different elements and a radioactive tracer (24Na) with the water soluble polymer mehtylcellulose. A film is produced by spreading the liquid mixture evenly on glass plates and letting it dry. Standards of the desired size and shape are punched out. The concentrations of the elements are calculated from the tracer activity. Ten sets of standards containing the elements Na, Mg, Al, Si, P, S, Cl, K, Cs, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Ag, Cd, Sn, Sb, Ba and Pb in different groupings have been prepared. Homogeneity and accuracy oof the standards are extensively discussed. The accuracy is also estimated by the alalysis of the standards using several techniques. The precision of the analysis factors derived from the standards is better than 1-2%, while the accuracy for the elements Al, Cl, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Br, Sb, Ba and Pb is found to be better than 5%.
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    X-Ray Spectrometry 10 (1981), S. 2-7 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Description / Table of Contents: It is shown that the simple models described in literature concerning X-ray analysis are not sufficient to correct the influence of the particle size especially for elements of low atomic numbers (≤ 20) in pressed powder samples. On the basis of proposals for an empirical correction it is possible to analyse single-phase systems with high precision independent of a model and without knowing the average particle size of the examined materials. The considerations necessary for the determination of element concentrations are used to explain the experimental results for a glass powder.
    Notes: Es wird gezeigt, daß die in der Literatur beschriebenen einfachen Modellezur Korrektur des Korngrößeneinflusses für die quantitative Röntgenfluoreszenzanalyse von Elementen mit niedriger Ordnungszahl (≤ 20) in gepreßten Pulverproben nicht ausreichen. Auf der Basis eines empirischen Korrekturvorschlages ist es jedoch möglich, ein mit einem Bindemittel verpreßtes Pulver ohne Kenntnis seiner mittleren Korngröße mit einer für die Praxis ausreichenden Genauigkeit zu analysieren. Es werden die zur Analysenberechnung notwendigen Voraussetzungen beschrieben und die verwendeten mathematischen Formeln am Beispiel eines Glaspulvers erläutert.
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    X-Ray Spectrometry 10 (1981), S. 25-27 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The X-ray K absorption edges of cobalt in some complexes with nitrogen based ligands [α-Co(py)2Cl2, Co(py)2Br2, Co(bipy)Br2 and Co(phen)Br2] have been recorded using a 40 cm bent crystal spectrogrph. The absorption edge shift and edge width have been discussed in terms of effective nuclear charge, molecular symmetry and the nature of the ligand. The radii of the first coordination sphere have been calculated using Levy's method and a correlation suggested.
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    X-Ray Spectrometry 10 (1981), S. 28-30 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An improved version of the LAMA program for the quantitative analysis of composition and mass thickness of thin film materials by X-ray fluorescence (XRF) has been developed. The divergence and slow convergence problems occasionally experienced with the LAMA-1 program have been eliminated by using the linear approximation method and the algorithm of simultaneous refinement of composition and thickness to greatly increase its capability and performance. A study of over a hundred simulated thin films showed that the LAMA-2 program converged much faster than LAMA-1 and gave better accuracy. The efficiency of the program has been improved to the point where it is feasible to operate on a minicomputer.
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    X-Ray Spectrometry 10 (1981), S. iv 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 10 (1981), S. v 
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    X-Ray Spectrometry 10 (1981), S. v 
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    X-Ray Spectrometry 10 (1981), S. 57-60 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method of absorption correction in X-ray diffraction (XRD) phase analysis, based on measurements of Compton scattering, is described. Compton scattering of Mo Kα was measured and Cu Kα was used for XRD analysis. Under these conditions, the method is valid for phase analysis of silicate and carbonate rocks. Quartz content was determined in 13 samples by the proposed method and the conventional method of internal standard. The two sets of results are in a good agreement.
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    X-Ray Spectrometry 10 (1981), S. 61-63 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The experimental evaluation of the Rhodes-Hunuer model of the particle size effect in X-ray fluorescence analysis of ‘thin’ and monolayer samples is reported. The calculations and experiments were carried out for samples of iron oxide(Fe3O4) and copper sulphide (Cu2S) having particles of one size and a histog am distribution of particle sizes. For iron oxide particles, it was found that sticking causes a significant systematic discrepancy between the experimental results and the Rhodes-Hunter model prediction. For copper sulphide particles the model was applicable.
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    X-Ray Spectrometry 10 (1981), S. 74-77 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Relative X-ray fluorescent intensity data have been generated numerically for binary samples under mono-chromatic excitation in those cases of absorption plus enhancement that are dealt with in this work. These data were fitted to the empirical Rasberry-Heinrich equation, keeping both coefficients different from zero, since from our numerical calculations it is shown that in most cases the best fit is achieved when A ≠ 0. Furthermore, this approach shows that a third coefficient introduced into the empirical equation improves the fitting. The aforementioned results suggest that the empirical equation could be deduced from the theoretical equation of fundamental parameters under suitable approximation. The result is an equation similar to that of Rasberry and Heinrich, from which analytical approximated coefficients are obtained. It is then possible to calculate a calibration curve using fundamental parameters values.
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    X-Ray Spectrometry 10 (1981), S. 147-151 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An X-ray narrow band detector based upon a selective X-ray filter and selective secondary emitter is described. The detector transmission band makes up 0.3-1.5 Ke Vin the range 2-40 KeV. The detection efficiency of X-rays reaches 5%, the area of the detector entrance window being 10cm2.A high luminosity of the narrow band detector makes it possible to decrease the required power of an X-ray tube to a few watts in X-ray spectral quantitive analysis. optimal relations between the detector elements as well as optimal conditions of fluorescence excitation are discussed. The application of the narrow band detector to X-ray spectral quantitative analysis is illustrated.
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    X-Ray Spectrometry 10 (1981), S. 109-112 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Different sources of counting loss are described and the relation Rt = Rm exp (Rt τ) is considered valid for most commercial XRF counting devices. Based on a series of Kα/Kβ measurements and an initial estimate of the Rt (Kα)/Rt (Kβ) value, corresponding τ values can be computed. If the chosen Rt (Kα)/Rt (Kβ) value differs from the correct one, the τ values will not be identical. The computer program iterates the Rt (Kα)/Rt (Kβ) value until the τ values have reached a desired level of agreement. The program is given together with a worked example of the calculation.
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    X-Ray Spectrometry 10 (1981), S. 138-146 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: It is shown that the depth distribution of X-ray production in the electron microprobe can be accurately described by a Gaussian modified at the sample surface by a transient. Assuming that the Gaussian is a consequence of the electrons undergoing a random walk in the sample and that the transient corresponds with the change from collimated to random electron trajectories enables theoretical values for the amplitudes and coefficients of the two functions to be predicted. There is excellent agreement between the predicted and the observed values. The Lenard coefficient and the electron range can both be estimated from the coefficient in the Gaussian. It is suggested that for microprobe work, Lenard's law for electron absorption be replaced by this revised law. Both the absorption and atomic number corrections of the traditional ZAF approach are replaced by the new function.
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    X-Ray Spectrometry 10 (1981), S. viii 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 10 (1981), S. 171-176 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Escape peak and thick target yield formalisms are shown to be equivalent, although experimental results using a practical source-target-detector geometry favor the latter. A bare non-hygroscopic CaF2(Eu) scintillator is used to measure the K X-ray yield from thick targets of pure elements excited by monoenergetic photons. The scintillator is found free of dead layer up to the limit of 0.1 μm: it can thus detect photons above 2 keV energy with intrinsic efficiency approaching 100%.
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    X-Ray Spectrometry 10 (1981), S. 193-195 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: In order to empirically test five mathematical equations of matrix correction, the theoretical X-ray intensities of the ternary system Cr—Fe—Ni were used. The smallest analysis error was obtained from a complicated equation which was derived from theory. Simplification of this equation resulted in the equation developed by Rasberry and Heinrich which proved to be almost as effective and is thus to be preferred in practice because of its simpler structure. A further simplification, dispensing with a special correction for secondary fluorescence, led to a greatly increased analysis error. As expected, using the matrix element intensities instead of their concentrations resulted in larger analysis errors. Special consideration of the secondary fluorescence did not yield a better result. These results agree qualitatively well with the results obtained by Stankiewicz and Sanner which were obtained by means of the analysis of synthetic oxide standards.
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    X-Ray Spectrometry 11 (1982), S. 1-1 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    X-Ray Spectrometry 11 (1982), S. 25-28 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    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. 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. viii 
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    X-Ray Spectrometry 12 (1983), S. 11-18 
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    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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    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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    X-Ray Spectrometry 12 (1983), S. v 
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    X-Ray Spectrometry 12 (1983), S. vi 
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    X-Ray Spectrometry 11 (1982) 
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    X-Ray Spectrometry 12 (1983), S. 2-7 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    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. 51-51 
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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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