For more than a decade the Institute of Geological Sciences has carried out large-scale geochemical analysis in pursuit of mineral exploration and regional geochemical reconnaissance programmes for the Department of Industry. Over this period an XRF analytical system has been developed to meet part of this requirement for multielement data. The elements of interest range from the fourth period to uranium, and have become more numerous as exploration and analytical techniques have expanded. In particular, additions have been made of those elements such as arsenic, molybdenum and tungsten which are more difficult of determination by conventional methods.

The use of coal, as either a primary energy source or as a source of feedstock chemicals, has been complicated by the noxious and toxic chemical species formed in its gaseous effluents and also by the huge quantities of ash vhich result from its processing. Both the noxious gases and the ash have been the subjects of Federal legislations.

X-ray powder patterns (XRPP), composed of atom-pair and self x~ray scattering and the diffraction produced by crystalline phases, have long been used to investigate coals and particularly their combustion ashes (1-3). Over twenty different crystalline phases have recently been reported to exist in certain lignite fly ash (3). Analysis of the crystalline phases has typically been emphasized in previous papers involving coals and ashes, but the amorphous scattering has been given little treatment.

A compact, high-intensity pulsed soft X-ray system has been used to study the response characteristics of a plastic scintillation phosphor (NE-102). In particular, the decay characteristics of this phosphor plated on one surface with a thin (<1000 Å) layer of aluminum were investigated. Although, absolute calibration of the X-ray source had not been performed, estimates of X-ray scintillation efficiency were obtained, using two separate methods, which were in agreement to within a factor of two.

The primary purpose of this cursory program was to establish the validity of transferring calibration data from plated to unplated NE-102 scintillators employed in a photometric recording system. The results of the ensuing investigation indicated the equivalence of the two, but revealed several interesting and unsuspected phenomena. These were (1) an apparent scintillation light reflectance component of zero from the plated aluminum “mirror” surface, (2) a change in pulse waveform from electron beam input to scintillation light output, and (3) a 90-nsec delay between electron beam and photomultiplier signals. The methods employed in obtaining and verifying these data are subject to errors from uncertainty in the characteristics of several components employed in the experimental setup. These uncertainties and other measurement errors caused independent estimates of the external scintillation light efficiency to range from 0.1 to 0.2 %.

Other potential applications of a pulsed soft X-ray system to measurement problems in industry and research include dynamic studies in the fields of X-ray crystallography, instrumental methods of materials analysis, and radiography of low-density subjects.

Two kinds of improved techniques are described for precise measurement of lattice parameters with an accuracy of 1 ∼7x10-5, in both of which a differenoe of Bragg angles between two X-ray beams such as K α1 and K β1 is measured.

In the first technique, which was applied to relatively imperfect crystals such as gallium arsenide, gallium arsenide phosphide, and gallium phosphide, two different diffraction planes were utilized for two radiations such as CuK α1 and CuK β1 in order to reduce the difference of the Bragg angles to the order of several minutes of arc.

In the second technique, which was applied to a nearly perfect crystal such as silicon, a double crystal arrangement of parallel setting was used, where lattice parameter of the specimen was relatively measured in comparison with the one of the first crystal which was known beforehand.

The problem of background radiation in X-ray fluorescence trace element analysis of fused-glass iron ore samples is addressed. A first-order model of coherent and Comptcn scattering with primary absorption is presented and used to correct measurements. Overlap coefficients for elements in iron ores are presented. The importance of these corrections is demonstrated. The accuracy achieved with X-ray measurements after background corrections compares well with the accuracy of chemical analysis.

A flow proportional counter for ultrasoft x-ray applications has been constructed and used to measure proportional counter parameters in the ultrasoft x-ray region at atmospheric and subatmospheric pressures for counting gases of P-10 and methane. We find that at atmospheric pressures the parametrization given by Zastawny for describing gas amplification in proportional counters applies and have measured values for the parameters for P-10 and methane. For subatmospheric pressures the Zastawny parameters are inadequate. A new parametrizatlon is required. In addition, the linearity of the detector for x-rays of energies of 15 KeV to 0.5 KeV was measured for pressures ranging from 750 Torr to 150 Torr and found to be excellent in all pressure regions.

The efficiency of the recessed source geometry for the analysis of the content of wear metals in engine lubricant oils by Energy Dispersive X-Ray Fluorescence (EDXRF) methods is calculated by a Monte Carlo simulation considering X-ray detectors of the Gas Proportional Scintillation Counter type and excitation by Cd-109, Cm-244 and Fe-55 radioactive sources. Calculated spectra for the case of a typical aircraft oil with Cu, Fe, Cr, Ti, Sn and Ag impurities in the p.p.m. range were obtained and results are presented that allow the prediction of the counting rate per mCi and p.p.m. of the impurity content. The performance of the system is discussed concerning its potential applications to in-line monitoring of the wear metals.

Deformation in polycrystalline materials is highly inhomogeneous on a micro scale. This inhomogeneity arises from the anisotropy of the constituent grains, coupled with local configurational parameters such as texture, gram size or proximity to a free surface. In a recent paper, we had outlined a new method that extended the traditional x-ray stress analysis to yield quantitative measures of such inhomogeneous deformation. In this paper, this method is used to study the partitioning of inhomogeneous deformation between the phases of 60-40 brass tensile specimens subjected to applied loads.

This paper describes the imaging of fossils using elemental x-ray area mapping (EXAM). The technique utilizes a commercially available instrument originally designed for the silicon chip industry. The EXAM data are processed digitally with imaging software to remove surface irregularities and enhance specimen details. Applications of this technique to specimens with irregular surfaces are described.

Stresses in polymeric materials can be measured by diffracting X-rays from embedded crystallites that yield suitable powder diffraction lines. An appropriate technique for this has been, reported by C. S. Barrett and Paul Predecki elsewhere and is reviewed here with additional details. It is based on a diffractometer modified so as to operate at very high 26 angles, with specimens prepared in various ways. Results show that adequate precision is reached by scanning Ka doublet in a few minutes and simply noting any displacement of peaks compared with peaks from an unstressed specimen; higher precision can be reached with slower scans or more detailed analysis of the peaks. Tests with embedded metallic particles were successful when the particles were (A) distributed throughout a moulded polymethyl methacrylate (Lucite) sheet of the order of a millimeter thick, alone or sandwiched between layers of particle-free material, or (B) embedded in polyester resin applied to a surface of Plexiglas bars, or (C) embedded in graphite-fiber epoxy composites in a layer at a chosen position within a specimen.

For many years the International Centre for Diffraction Data has sponsored round robins covering various aspects of X-ray powder Diffraction with the objective of illuminating and understanding current practices and problems associated with, the analysis of diffraction data. As computer analysis of diffraction data becomes ever more sophisticated, analytic capabilities are extended and the performance, not only of the instrumentation must be checked, but also that of the software which converts the measured data into useful results. In recent years, therefore, we have personally participated in a cell parameter round-robin, a d-spacing round-robin, a peak hunting round-robin, and, most recently, the present intensity round-robin and a line profile round-robin. Still others are in progress or being planned.

As the Environmental Protection Agency adds ever more sites to the National Priorities List for Superfund clean-up, there is a tremendous need for a fast method of screening for contaminants. In the case of inorganics, we can apply field-portable X-ray fluorescence technology.

With commercially available field-portable X-ray fluorescence equipment using in-situ measurements we can quickly screen a site (hundreds of measurements), input the data to a portable computer, process it, and print a colored concentration isopleth map of the contaminant of interest, all in realtime.

The in-situ measurement approach pioneered by Lockheed is the key to rapid screening capability. Problems arising from particle size distribution, soil heterogeneity, and bulk density are minimized by employing site-specific standards in the construction of our calibration curves. Inherent in these site-specific standards are all the matrix problems which occur in the routine samples.

The strength of field-portable X-ray fluorescence technology is the accuracy of analysis above the quantitation limits. The difficulty in measuring low concentrations near the detection limit is the weak point of field-portable units.

NOTICE: Although this research was funded in part by the U.S. EPA through Contract 68-03-3249 to Lockheed Engineering & Sciences Company, it has not undergone Agency review and does not necessarily reflect Agency policy.

The use of a field portable XRF analyzer incorporating a semiconductor, mercuric iodide, energy dispersive spectrometer is described with emphasis on the benefits of high resolution x-ray detection for rapid screening of hazardous metallic wastes. Results are presented of “in-situ” and “prepared sample” soil measurement for different sites to show the potential of Fundamental Parameter analysis to obtain acceptable quality data with minimum calibration effort, obviating the need for site-specific standards.

We describe a new and reliable experimental technique for the measurement of mass absorption coefficients in the 0.1 to 1 keV energy range. In this technique, the absorbing film is supported directly on a substrate which under proton bombardment will generate the x-rays whose absorption will be measured. Results are given for thirteen different metals at the C Kα (277 eV) line.

Total reflection X-ray fluorescence (TXRF) analysis of “low Z” elements, Ti, Fe, Ni, Cu, Zn and “high Z” elements, Zr, W, Au, Pb, are required for micro scale semiconductor device production processes. In the past, the W–Lβ X-rays have been used for the analysis of S to Zn.

This paper describes a new three crystal monochromator coupled with a gold direct-drive rotating anode target. This development has produced significant improvements in the sensitivities and LLD's for all measured elements. The monochromator makes the Au Lα (9.71 keV), Au Lβ (11.44 keV) and Au Lγ (13.33 keV) available for routine use in TXRF analyses. The Au Lα X-ray is best used for the lower Z elements, Na to Cu. The best result for W, Cu and Zn are obtained with the Au Lβ X-ray. This is the result of both increased peak intensity and lower background. For the heavier elements, such as Au and Pb, the Au L X-ray yields intensities 100 times higher than what has been achieved in the past.

52 elements of the periodic system are considered as potentially usable by living organisms. Most of them, as some heavy metals, are required only in trace amounts. If a certain concentration of a given trace element is exceeded in an organism it becomes toxic. Plant analyses are considered in agronomy as a diagnostic tool and as a guide to fertilizer practice as the plant uptake is the best criterion of nutrient and micronutrient availability. But nowadays also toxic metals may be assimilated by plants due to the increasing contamination by inorganic compounds containing these toxic elements. In geosciences plant analyses may be of importance because indicator plants are employed for the geochemical prospection of certain heavy metals.

X-ray fluorescence spectroscopy is new becoming a tool in research and. industry. Semiconductor detectors are proving valuable in measuring fluorescent X rays, and so are providing a versatile tool for rapid multielement analysis of many types of samples. This paper will mainly be concerned with, different types of copper ore. An experimental setup has been designed to determine Cu, Fe and Pb of concentration ranging from 0.1 to 20, to 5, and to 4 percent, respectively, with analytical precision of 20% relative at 0.1% Cu, and 3% relative at 20% Cu. For excitation a 100 mCi Pu-238 source and/or a low power air-cooled X-ray tube were used. Data acquisition and “on-line” evaluation for each sample takes about 100 seconds. Electronics blocks and sub-systems used In the set-up are available commercially. The most important benefit to be obtained from the setup is the ability to provide precise, reproducible determinations of large numbers of samples day after day.

Recent advances in semiconductor particle detector resolutions along with new electronic circuitry associated with these detectors make possible their application in nondispersive elemental analysis. The use of radioactive sources for exciting the characteristic X-rays provides highly stable systems which can be used to accumulate data for prolonged periods. Due to the inherent stability of the detector and the excitation source, the only limitation in sensitivity is the ability to accumulate statistics above the background of scattered counts. Since this method of analysis is nondispersive, it has the capacity to determine many elements simultaneously. Solutions composed of mixtures of three or four elements were studied. The elements selected were bromine, rubidium, and strontium. These elements exhibit wide variations in mass absorption coefficients for the various characteristic X-rays emitted. The concentrations of the elements in solution varied from 10 ppm to 5% by weight. The relative intensities of the characteristic X-ray lines were compared with the concentration of the solutions to establish sensitivity curves and to study linearity of response as well. The interelemental interference was studied and the effect was evaluated for the particular elements under study. Means were developed for predicting and correcting for matrix effects.

Moderate counting rates, in excess of 400 cps at a signal/noise ratio of 18 on 3.5% NaaO in rocks, permit high-precision quantitative analysis for light elements in silicates. Special advantages of fluorescence analysis in the 10 A region, with adequate excitation provided by an aluminum target tube, will be described. These advantages include an ease of discrimination by excitation potential and by high dispersion using large 2d space crystals. Minor and simple modifications of the optic path combined with electronic discrimination make the method ideal for sodium and magnesium. Routine runs over periods of days have been made possible by a new technique of calibration involving computer corrections for systematic drift from any source. Repeated tests show that the total analytical error, including specimen preparation, closely approaches that of the counting statistics used, and that the drift corrections are complete. In granitic rod; analyses resulting precisions (standard deviation/mean) are 1% for 2-5% Na2O and 2% for 0.25-1.0% MgO.

X-ray stress analysis in austenltic stainless steel is generally carried out on the ϒFe(311) diffraction line produced by Cr- Kβ X-rays. However, it is often pointed out that not much reliance can be placed on the precision of the stress because the contrast between a diffraction peak and its background is poor. In addition, to measure the stress is sometimes impossible on a specimen which has martensite structure produced by thes train induced transformation, because the ϒFe(211) line appears in the neighborhood of the desired ϒFe(311) line, since Cr-K6 X-rays accompany Cr-Ka from a conventional X-ray source. If Cr-Ka X-rays can be eliminated and only Cr-KB X-rays directed on the specimen, only the λe(311) line with high contrast will be obtained and one can expect to measure the residual stress with high precision.