bluuebunny/crossref_metadata_2025 huggingface dataset:
High Productivity Geochemical XRF Analysis
Authors: Ingham Mark N. , Vrebos Bruno A.R.
Published: March 2019

XRF has become over the years a method of choice when dealing with elemental analysis of large quantities of samples. Geochemical analysis pushes the technique to its limits because of the large number of samples to be analysed as well as the lower limits of detection required for many trace elements of geochemical and economic importance. The Analytical Geochemistry Group at the British Geological Survey (BGS) has access to a wide variety of methods for instrumental analysis. Instrumental methods for inorganic analysis include x-ray fluorescence as well as DC arc emission spectrometry, atomic absorption spectrometry, inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). X-ray fluorescence, however, is the technique of choice when it comes to the routine analysis of large numbers of solid samples. The XRF section at BGS currently runs three sequential spectrometers (one PW1480 and two PW2400s made by Philips Analytical X-Ray). In this paper, some aspects of the method of sample preparation and the calibration of the spectrometers for the analysis of the trace elements are discussed.
Quantitative Xrf Analysis of Coal After Successive Leachings
Authors: O'Keefe Catherine A. , Eriekson Thomas A.
Published: March 2019

Many of the operational problems encountered in the utilization of coal can be attributed to the inorganic constituents in coal. These problems depend upon the quantity and association of the inorganic components in the coal, the combustion conditions, and the combustion or gasification system, geometry. Thus the mineral concentrations and organie associations within a coal must be determined to predict the properties and behavior of the inorganic constituents of coal during combustion and utilization.
Special Handling Problems in X-Ray Diffractometry
Authors: Smith D. K. , Barrett C. S.
Published: March 2019

The success of a diffraction experiment often depends on the proper preparation of the sample under study. Many different methods of sample preparation have been devised for many different purposes. A survey was conducted to collect together many of these methods, and the results are reported in this paper.
Characterization of Thin by X-Ray Fluorescence and Diffraction Analysis
Authors: Huang T. C. , Parrish W.
Published: March 2019

This paper presents a comprehensive study of various applications of x-ray fluorescence and diffraction techniques for the characterization of thin films. With the proper use of x-ray instruments and techniques, a fairly complete understanding of the chemical and physical structure of thin films was obtained. The x-ray fluorescence (XRF) method was used for the determination of composition, mass-thickness, and density. The x-ray diffraction (XRD) method was used for structural characterization, including: local atomic arrangements of amorphous materials; phase identification, preferred orientation, crystallite size, stacking faults, microstrain, the annealing behaviors of polycrystalline films; and lattice mismatch between the epitaxial film and its single-crystal substrate.

In order to obtain a clear picture of the capabilities of the x-ray method and the properties of thin films, a series of carefully selected specimens representing a wide range of compositions and thicknesses was used. A number of practical x-ray techniques, which are valuable for this type of analysis, are also introduced.
Minimization of Preferred Orientation in Powders by Spray Drying
Authors: Smith Steven T. , Snyder Robert L. , Brownell W. E.
Published: March 2019

The spray drying of powders is a method of forming spherical or torroidal shaped agglomerates. A relatively simple method is given for preparing spray dried samples of the quantities used in x-ray diffraction analysis. This technique is shown to minimize preferred orientation effects on diffraction intensities from materials of widely differing symmetry and crystallite habit.
Low Temperature X-Ray Diffractometer with Closed Cycle Refrigeration System
Authors: Benedict U. , Cornay Y. , Dufour C.
Published: March 2019

An assembly consisting of an X-ray tube, a quartz crystal monochromator, and a vertical X-ray goniometer with proportional counter was mounted in a glove box for work with actinide metals and compounds. An evacuated camera containing the expander tube of a closed-cycle cryogenic system was fitted onto the goniometer. A thin layer of the powdered sample was fixed on the end-plate of the expander tube. Beryllium windows were provided in the camera wall for the incident and for the diffracted beam.

The cooling camera is suitable for use with thin powder layers or metallic foils. Thicker layers can be studied, but a strong thermal gradient perpendicular to the specimen surface is expected. The camera has been applied to the study of lattice contraction and phase transformation at low temperature In actinide metals and compounds .
X-Ray Powder Diffraction of Einsteinium Compounds
Authors: Haire R. G. , Peterson J. R.
Published: March 2019

X-ray powder diffraction (XRPD) analysis has proven to be extremely valuable in the study of the transplutonium elements. The high specific activity and the thermal energy associated with the radioactive decay of einsteinium isotopes make XRPD analysis of einsteinium samples very difficult. The major problems are destruction of the samples crystallinity and alteration of their chemical composition. Blackening of the X-ray film also compromises the analyses. By applying certain guidelines given here, a limited amount of success has been achieved in obtaining diffraction data on einsteinium and some of its compounds.
A Microcomputer Controlled Diffractometer
Authors: Goehner R. P. , Hatfield W. T.
Published: March 2019

Automated powder diffractometers are beginning to come into general use. The principal reason for automating or purchasing an automated powder diffractometer is to increase the speed and accuracy of the analysis. Three principal methods are used. The first is that a multisample changer increases the through-put on the instrument since the unit can be operated unattended during the evening. The second is the diffractometer can be scanned at faster rates when digital data are collected, as opposed to the analog method of using a strip chart recorder. The third is the elimination of reading the peak positions and intensities from the strip charts. These readings would typically have to be tabulated manually for later interpretation. Another reason for having an automated powder diffractometer is for experiments where digital data are necessary to make the analysis practical. These experiments include routine quantitative analysis, radial distribution functions, Fourier profile analysis, and signal averaging to bring out very weak diffraction peaks.
Investigation of Detection Threshold Variation and Microcrystallite Nucleation in Nuclear Track Detectors Using Small Angle X-Ray Analysis
Authors: Aframian A.
Published: March 2019

The variations in the threshold registration of a number of plastic dielectric nuclear track detectors, DNTD's, have been investigated in terms of range energy relationships and the changes in structure affecting electron density distributions studied, using small angle X-ray diffraction. A similar mechanism has been employed to investigate the presence and formation of microcrystallite nucleation sites in lunar and terrestrial minerals, following proton and charged particle bombardments of 10-18 particles/cm2.
X-Ray Fluorescence Analysis of Stainless Steels and Low Alloy Steels Using Secondary Targets and the Exact Program
Authors: Harmon J. C. , Wyld G.E.A. , Yao T. C. , Otvos J. W.
Published: March 2019

Exact is a mini-computer based fundamental parameters program which is utilized for matrix corrections in energy-dispersive X-ray analyses. We have previously shown this technique to work well with radioactive sources. However, due to the limited selection of isotopic sources available and their inherent low X-ray flux, we have investigated the use of Fe, Sn, and Dy secondary-targets as sources of monochromatic X-rays. Results to date indicate that the secondary-targets provide X-ray radiation which has sufficient monochromaticity for our technique to remain valid.
'Pareds'-An Interactive On-Line System for the Interpretation of EDXRF Data
Authors: Wegscheider Wolfhard , Leyden Donald E.
Published: March 2019

Multielement data as they are obtained from energy-dispersive x-ray spectrometry can only be interpreted efficiently if multivariate statistical techniques are employed. It is shown that these and pattern recognition techniques can easily be implemented on the dedicated mini-computer system that is usually supplied with the spectrometer. These algorithms are helpful in interpreting multielement data and in gaining insight in and understanding of those aspects of the data structure that are inherent to the data. Such a program was tested using ground water data. Further extensions of the concept of integrated data interpretation are discussed.
Use of a New Versatile Interactive Regression Analysis Program for X-Ray Fluorescence Analysis
Authors: Schreiner W. N. , Jenkins R.
Published: March 2019

XRF can be a powerful tool for quantitative elemental analysis-it can also be a big headache. The problem is, of course, that to perform a proper quantitative analysis one needs to first develop a good matrix correction model to convert the measured line intensities to concentrations. For empirical models, aside from the inherent difficulties in optimizing a set of interelement correction coefficients, the commercially available computer controlled spectrometers have in the past either provided rather poor regression analysis programs with their software or none at all. The reason for this has been the rather limited core size of the online computer and the lack of fast efficient mass storage facilities such as floppy disks.
Energy-Dispersive X-Ray Analysis for Carbon on and in Steels
Authors: Musket R. G.
Published: March 2019

Alpha-particle induced X-ray emission studies of steel samples have provided quantitative, non-destructive determinations of the carbon content in surface layers and in the bulk. The analyses were performed using the ALPHA-X™ technique of alpha-induced X-ray emission. Absolute carbon surface densities were determined directly from the ratio of the carbon X-ray count-rate for the unknown layers to that for standard free-standing carbon films. Assessment of the bulk detection limit was made using a steel standard with 0.5 weight-percent carbon. The threesigma minimum detection limits for twenty minute analyses were 0.1μg carbon/cm2 (equivalent to≃5 Å) in the layers and 1000 ppm carbon in the bulk.
Using DEC Operating System for X-Ray Diffraction and X-Ray Fluorescence Analysis
Authors: Artz B. E. , Kao E. C. , Short M. A.
Published: March 2019

The Digital Equipment Corporation (DEC) operating system RSX-11M has recently been installed on a DEC PDP 11/34 computer which is used for the control of, and to acquire and process data from, three X-ray diffractometers, one X-ray fluorescence analysis unit and an electron microprobe. The RSX-11M system replaced the modified DEC 1 - 8 User BASIC previously employed, thus replacing an operating system which was known in detail only to its writer by a system which is supported by the computer manufacturer. There are three major advantages in the use of RSX-11M over 1 - 8 User BASIC: an improved handling of program scheduling, the integration of the software driver for the computer - X-ray electronics interface into the operating system without a major modification of the latter, and the ability of RSX-11M to undertake concurrent execution of instrument control, data acquisition, and data reduction. The 11/34 - RSX-11M system has been implemented to use FORTRAN; a BASIC interpreter has, however, been added which allows users to interact on-line with the computer. A command interpreter which can accept a command line from a terminal has been included.
A New X-Ray Spectroscopy Concept-Room Temperature Mercuric Iodide with Peltier-Cooled Preamplification
Authors: Huth G.C. , Dabrowski A.J. , Singh M. , Economou T.E. , Turkevich A. L.
Published: March 2019

Mercuric iodide (HgI2) with high atomic numbers of 80 and 53 for the components, and wide bandgap (2.1 eV) has been considered a potentially useful material for gamma ray spectroscopy for the last number of years. Considerable effort by numerous groups has been directed toward purification and growth of large single crystals of this material. Even with continuing improvement, however, the material is still characterized by good electron transport properties and only modest to poor hole transport behavior. Interesting results nevertheless have been reported in mid-range gamma ray spectroscopy using “up to millimeter thick sections of HgI2. One question always asked is: has the fundamental of lattice scattering etc. been reached in increasing hole transport behavior in this material? There is interesting speculation at this time that this may not be so.
J. D. Hanawalt Powder Diffraction Award Lecture
Authors: Frevel L. K.
Published: March 2019

A condensed chronology of computer SEARCH/MATCH programs for the analysis of multiphase crystalline powders is presented covering the years 1965 to 1981. For this period the various algorithms for searching a data base of standard powder diffraction patterns, {ds, (I/I1)s}, are predicated on empirical “fingerprint” matching of the experimental powder data, {dν,Iν}, with one or more of the standard patterns. Within the past year an interactive computer SEARCH/MATCH program has been developed based on a structure-sensitive SEARCH procedure.

The evolution of computer SEARCH/MATCH procedures undoubtedly will continue and will be influenced by marked improvements in the quality of digitized, machine-readable, powder diffraction data. Three conjectures are offered on future developments in x-ray diffractometry.
Fuzzy Sets and Inverted Search - Two Concepts for Compound Identification in Spectra
Authors: Blaffert Thomas
Published: March 2019

This paper describes a new approach to the interpretation of spectra with ‘fuzzy sets’ and a fast search algorithm for spectrum libraries, using a combination of this theory and the inverse search method. The concepts are applied in a computer program named CIF (Compound identification with Inverted search and Fuzzy sets) which is used in the current application for the interpretation of X-ray powder diffraction signals. The methods are readily applicable to other kinds of spectra such as IR, UV, chromatrography etc.
Recent Applications of XSA in Heat Treatment and Fatigue of Steels
Authors: Macherauch E. , Scholtes B.
Published: March 2019

This paper is intended to give an exemplary review of recent investigations performed in the X-ray laboratory of the Institut für Werkstoffkunde I of the Universität Karlsruhe, FRG, concerning particular problems of residual stresses of heat-treated and fatigued steels. The experimental work was mainly performed with computer-controlled Karlsruhe type ψ-diffractometers. If linear distributions of residual lattice strains occurred the sin2ψ-method was applied to determine residual stresses. The experiments were performed with plain carbon steels of 0.22 and 0.45 wt.-% carbon (German grade Ck 22 and Ck 45) and some low alloyed steels.
Determination of Residual Stresses in Transformation-Toughened Ceramics
Authors: James M. R. , Green D. J. , Lange F. F.
Published: March 2019

The strength of ceramics or glasses can be increased by placing their surfaces into compression. Techniques include ion exchange, temperature glazing, surface chemical reactions and stress-induced phase transformations. Although most of these techniques are well recognized, little effort has been expended In experimentally determining the magnitude of the compressive stress, and in particular, to use experimental evidence to identify important material and process parameters that need to be controlled. The goal of this investigation was to determine some of the factors that effect the magnitude, profile and depth of the compressive layer introduced by a structural phase transformation. X-ray residual stress measurements were used to directly determine the state of the surface residual stress.
Suppression of X-Ray Fluorescence Background in X-Ray Powder Diffraction by a Mercuric Iodide Spectrometer
Authors: Nissenbaum J. , Levi A. , Burger A. , Schieber M. , Burshtein Z.
Published: March 2019

We have explored the merits of using a Hgl2 spectrometer as a detector in x-ray diffraction systems instead of a proportional gas counter, or a scintillation counter. The full width at half maximum energy resolution of the HgI2 spectrometer used was about 1.1 keV for the CuKα line (8.1 keV), and about 1.5 keV for the MoKα line (17.4 keV), The energy resolution was utilised to eliminate x-ray fluorescence background from powder diffraction spectra. We demonstrate the suppression of Fe x-ray fluorescence in diffraction patterns of ErFe03 obtained with a Cu x-ray tube, and of Y x-ray fluorescence in diffraction patterns of Y2O3 obtained with a Mo x-ray tube. The peak height to background ratios were improved by about an order of magnitude in both cases.
Multiphase Quantitative Analysis of Colorado Oil Shales Involving Overlap of the Diffraction Peaks
Authors: Smith D. K. , Sterner S. M. , Kerrick D. M. , Meddaugh W. S.
Published: March 2019

The method of intensity ratios can be used for quantitative x-ray diffraction analysis even when none of the diffraction peaks of any phase can be individually resolved. The method uses intensity values from a finite number of discrete integration intervals and appropriate reference-intensity-ratios measured on a set of reference samples to yield a best fit composite pattern that is matched to the unknown by least-squares refinement. Solid-solution phases are analyzed by using multiple reference patterns and determining the best choice during the pattern matching procedure. The method may be extended easily to employ whole diffraction traces by using a large number of small intervals.
Continuing Development of Mercuric Iodide X-Ray Spectrometry
Authors: Iwanczyk J.S. , Dabrowski A.J. , Huth G.C. , Drummond W.
Published: March 2019

The continuing development in recent years of mercuric iodide room temperature x-ray spectrometers has led to steady improvment in the spectral energy resolution capability of these systems. This has been due largely to the continuing reduction in the electronic noise level of the associated preamplification electronics. It has been demonstrated that a system consisting of a mercuric iodide detector in combination with a pulsed-optical feedback preamplifier provides superior energy resolution performance in x-ray spectrometry in comparison to the other types of preamplification. Previously, results have been reported by us of the energy resolution of such systems with both the detector and input FET of the preamplifier at room temperature and with the input FET cooled by liquid nitrogen and the mercuric iodide x-ray detectors lightly cooled.
Comparison of Experimental and Theoretical Intensities for a New X-Ray Tube for Light Element Analysis
Authors: Kikkert John , Hendry Graham
Published: March 2019

While x-ray fluorescence spectrometry is a highly sensitive and highly repoducible method of analysing samples, its one weakness is its relatively low sensitivity for light elements. This is mainly due to two problems: firstly the low fluorescent yield of the low atomic number elements, and secondly to the inherent inefficiency of exciting these elements. While it is not possible to improve the fluorescent yield, considerable improvements in light element sensitivity can be achieved by improvements in x-ray tubes.
Comparison of X-Ray Backscatter Parameters for Complete Sample Matrix Definition
Authors: Niels K.K. , Rogers V.C.
Published: March 2019

Equations for computing sample absorption coefficients and matrix corrections from fundamental parameters require measurement or prior knowledge of all bulk element concentrations for samples of finite thickness. Uses of these equations in commercial software have thus required either 1) “similar” standards, 2) limited applications to metal alloys, oxides or specially-prepared matrices of known composition, or 3) user supplied definitions of bulk light element concentrations. A fourth option, which provides superior analytical flexibility, is the use of backscattered x-ray intensities with element scatter cross-sections to define the unmeasured light-element component of the sample matrix. Backscatter intensities constitute the only spectral basis for routinely characterizing the light-element component of geological, biological and other materials which contain significant H, C, N, O, etc. They thus offer a unique basis for utilizing fundamental-parameter matrix corrections in the general case of unknown samples without standards.
XRF Analysis of Low Level Cation Concentration of Sodium Silicate Solutions
Authors: Sabino E. H. , Derolf M. R. , Bass J. L.
Published: March 2019

Sodium silicate solutions have been manufactured commercially for over one hundred years. Such solutions have been used in the past as major constituents in waxes, polishes and adhesives, and in detergents. A current additional use is their application in enhanced oil recovery. In many uses of sodium silicate solutions trace metal levels adversely effect performance. Depending on the source of the raw materials used in the silicate production and on processing conditions iron and vanadium in particular may be found at the 50-200 ppm level. X-ray fluorescence is used as a rapid method for analysis of iron in sand, one of the raw materials used in silicate manufacture. In order to use an instrument already at the plant site, we decided to develop an XRF method for metals analysis in the silicate solutions as well.
Wall Effect and Detection Limit of the Proportional Counter Spectrometer
Authors: Järviner Marja-Leena , Sipilä Heikki
Published: March 2019

The detection limit of the proportional counter spectrometer is determined by the low-energy background caused by the wall effect. The choice of the filling gas of the proportional counter has been studied to minimize the background. Detection limits (3σ) for different elements have been calculated. Theoretical results have been compared with the experimental value obtained with Cd-109 and Am-24l excitation. The results are applied to the analysis of metal concentrations in oil samples and mapping the contents of zinc in the bark of living trees with a portable XRF-analyzer.
Research in the Quantitative Analysis of Individual Particles by X-Ray Fluorescence Spectrometry
Authors: Lankosz M. , Holynska B. , Pella P.A. , Blackburn D.H.
Published: March 2019

In a previous publication, we compared measurements of the x-ray microfluorescence of calcium and iron from homogeneous spherical glass particles with the results of Monte Carlo simulation. That work was performed to verify a Monte Carlo model developed for the characterization of particle size effects using a polished flat sample of the same composition as a reference standard. The present work extends our comparison to synthetic glass particles containing elements of higher atomic number. We also modified our Monte Carlo model to include simulation of x-ray fluorescence from elements in irregular shaped synthetic particles. In addition, the Compton scattering from spherical and irregular shaped particles was simulated using Monte Carlo and compared with experimental measurements.
XRFA of Carbon in Steels
Authors: Weber F. , Mantler M. , Wariwoda L.
Published: March 2019

A set of standard samples consisting of low alloy steels, tool steels and a graphite standard was prepared carefully for measurements by polishing (down to 0.3μm alumina powder) and cleaning of the surfaces. Photographs from optical and scanning electron microscopical images were taken in order to provide information about the microstructure. The measured carbon fluorescent intensities are interpreted in view of this information as well as compared to calculated data based on fundamental parameter models. Thereby excitation by iron and carbon photoelectrons as well as secondary enhancement effects by iron K and L lines and other matrix elements were taken into account.

Results suggest that the count rates are not only a function of the total carbon content, but also of graphite segregations and to some extent of the specimen preparation procedure. Graphite particles are easily washed out and the little remaining holes may remain partially covered with carbon or filled with polishing residuals, which leads to reduced count rates.
On-Line Paint Coating Weight Gauge Using Compton Scattered X-Rays
Authors: Matsuura Naoki , Kurozumi Shigetoshi , Fukuzaki Tatsuo , Arai Tomoya
Published: March 2019

Coating weight measurements by X-ray fluorescence analysis have been well established technology in industrial applications. The coating film measurements such as tin-plated steel and galvanized steel are carried out with an on-line gauge which is based on laboratory experiments. The approximate sample speed is 200m/min for a tin plate gauge, 150m/min for galvanized steel and 100m/min for electrolytic zinc coating steel.
X-Ray Fluorescence Critical Sample Thickness and Volume of Material Excited in Catalysts
Authors: Kunz Frank , Belitz Ronald
Published: March 2019

During the past fifteen years wavelength dispersive x-ray fluorescence (WDXRF) spectrometry has been the primary analytical technique for quantitative elemental analysis of automotive catalyst precious metals, contaminants, and substrate materials. While extensive work has been devoted to improving the accuracy of WDXRF quantitative procedures, minimal attention has been given to the calculation of critical sample thickness (primary x-ray beam depth of penetration) and total volume of material excited for each element in the catalyst. However, with the increasing use of WDXRF for measuring and comparing elemental concentrations at the inlet, middle, and outlet surfaces of catalysts, critical sample thickness and volume of material excited becomes very important for accurate interpretation of results.
An Automated On-Stream XRD Analyser for Process Control in the Phosphate Industry
Authors: Engelbrecht Johann P. , de Bruyn S. W. , de Villiers Johan P.R.
Published: March 2019

A dedicated on-stream X-ray diffraction (XRD) system for the analysis of rock phosphate-bearing slurries was configured to the requirements of industry for process control. The slurry-handling system includes a multiplexer, header tank, de-aerator, sample splitters and two windowless sample presenters. The x-ray system is comprises a line-focus molybdenum anode X-ray tube, two pyrolytic graphite primary-beam monochromators, two vertical fixed-geometry goniometers, and a simultaneous four scintillation-detector system. The X-ray beam is transmitted through the slurry curtains so that the forward diffracted X-ray intensities of apatite (francolite) and quartz are measured simultaneously. Data obtained by the on-stream XRD analyses of apatite and quartz in rock phosphate from the Florida area in the USA are presented. Lower limits of detection in the order of 0.1 per cent can be achieved for both the apatite and quartz in slurries containing 30 per cent solids. The solids content is a variable that must be known if feeds, tailings, and concentrates are to be measured using a universal algorithm. It can be calculated from the total mineral content of the slurry or from density measurements.
Mirror Heaters for High Temperature X-Ray Diffraction
Authors: Schneider Julius
Published: March 2019

For the generation of high temperatures in X-ray and neutron diffraction experiments various techniques such as resistance heating, radiation heating, induction heating and gas flame heating have been applied (Aldebert, 1984). Mirror heaters usually employ some kind of focussing geometry to concentrate the radiation emanating from the heating element onto the sample: Two large parabolic mirrors focussing heat radiation from a carbon arc were used by Stecura (1968) to reach sample temperatures up to 1700°C. Hubert et al. (1974) used radiation from a short arc xenon lamp focussed by two parabolical mirrors to reach sample temperatures of 3200°C.
The X-Ray Study on Fatigue Crack Growth Behavior of ZAS Alloy
Authors: Yajima Zenjiro , Kishi Yoichi , Hirose Yukio
Published: March 2019

X-ray fractography was applied to the fatigue fracture surface of ZAS (Zinc Alloy for Stamping) alloy, which has composite microstructures: Zn-phase, Al-phase and Zn-Cu phase. The fatigue test was conducted by using compact tension specimens. Residual stresses were measured on and beneath fatigue fracture surfaces. The plastic zone size was determined from residual stress distributions beneath the fatigue fracture surfaces. The results are discussed in connection with fracture mechanics and fracture processes.
Separation of Kα Doublet for Profile Analysis by Use of FFT
Authors: Yoshioka Yasuo , Ohya Shinichi
Published: March 2019

Line-profile analysis is important for material evaluation as well as x-ray stress analysis. In the general case, the half-value breadth of the Kα doublet is used as the line-profile parameter, but it is preferable to use the half-value breadth of the Kα1 diffraction profile because of high resolution.
Study of Thin Films and Multilayers using Energy-Dispersive Diffraction of Synchrotron Radiation
Authors: Cernik R. J. , Clark S. M. , Pattison P.
Published: March 2019

We present the results of a preliminary study of the use of polychromatic synchrotron radiation in energy-dispersive mode for the rapid characterization of thin film and multilayer materials. This technique takes advantage of the high intensity and excellent collimation properties of white beam synchrotron radiation. The glancing angle diffraction geometry allows structural depth probing as well as enhanced signal-to-noise by suppressing substrate contributions. The technique was successfully applied to metallic films a few hundred Angstroms thick, and to W-C multilayers.
Enhanced Range of Measurable Thickness of Thin Crystalline Layers Using θ/2θ Decoupled Powder X-ray Diffraction
Authors: Kimmel G. , Kaplan W.
Published: March 2019

X-ray diffraction is one of the most useful methods for the characterisation of thin crystalline layers or coatings. The most interesting techniques are: the identification of phases and their relative quantities, texture analysis, and residual stress measurements.

Thin layers which are transparent to the x-ray beam (in the diffracted wavelength) yield different intensities as compared with a bulk sample.
X-ray Residual Stress Analysis of Zn-Ni Alloy Electroplating Layers
Authors: Sasaki Toshihiko , Kuramoto Makoto , Yoshioka Yasuo
Published: March 2019

Zn-Ni-alloy electroplated steels are one of the surface-treated materials with a high corrosion resistance and are mostly used for automobiles. It is said that the corrosion resistance is more than four times as great as that of Zn-plated steels. Concerning x-ray stress measurement, Kyono et al reported the result of measurement on y (552) planes and showed that the sin2φ diagram was severely curved.

X-ray stress analysis in surface-treated materials will become more important. Some problems, however, remain to be studied when we apply the x-ray method to thin layers. For example, the effective x-ray penetration depth may be different from that in ordinary materials. And complex gradients of stresses and compositions may exist.
The Determination of Elemental Composition, Thickness and Crystalline Phases in Single and Multi-Layer Thin Films
Authors: Brown R. A. , Toda K. , Wilson R. L.
Published: March 2019

The purpose of this paper is to show how XRD and XRF can be used as complimentary tools to determine multi-layer thin film composition, both elemental and crystalline, as well as film thickness.
Near-Surface Chemical Characterization Using Grazing Incidence X-ray Fluorescence
Authors: Sakurai Kenji , lida Atsuo
Published: March 2019

External X-ray total reflection occurs when collimated X-ray beams impinge on a smooth, flat surface of matter at a small glancing angle, typically a few mrad. With respect to the X-ray fluorescence technique, total reflection experiments have allowed the trace determination of solution samples using an X-ray mirror as a sample support. The grazing incidence X-ray fluorescence technique (GIF) is also suitable for near-surface element analysis of the material, because the penetration depth of X-rays is 10-1000 Å around the critical angle.
Structure Refinements in Chemistry and Physics. A Comparative Study Using the Rietveld and the Two- Step Method
Authors: Will G. , Jansen E. , Schäfer W.
Published: March 2019

Two strategies are at present commonly used in studying and refining crystal structures from powder diffraction data: the total pattern refinement proposed by Rietveid (1969) and the two-step method originally proposed and applied by Will (Will et al., 1965). The latter one works by separating-the intensity determination of the individual peaks from the actual structure refinement, structure analysis or any structural calculation (tor example based on line broadening). Both methods have their merits, and their drawbacks.
X-ray Powder Diffraction QPA by Rietveid Pattern- Fitting - Scope and Limitations
Authors: O'Cannar B.H. , Deyu Li , Jordan B. , Raven M. D. , Fazey P. G.
Published: March 2019

The X-ray Analytical Science Group at Curtin university of Technology has been developing and evaluating Rietveld pattern-fitting for materials analysis since 1985. The results are reviewed with particular reference to preferred orientation, crystallinity and phase abundance.
Problems in the Derivation of d-Values from Experimental Digital XRD Patterns
Authors: Jenkins Ron , Nichols Monte
Published: March 2019

Most commercially available, automated powder diffractometers include software packages for the determination of d-values from experimentally recorded digitized patterns. While many of these patterns offer great flexibility to the user, indications from a recent Round-Robin Study [1] are that many users are confused as to the correct use of such parameters as choice of step size and counting time, the degree of data smoothing, peak-hunting parameters, setting of background level, and the consequences of background subtraction and α2 stripping. This paper will reviews these various factors and give some guidelines as to the establishment of optimum conditions.
XRD Acquisition Parameters for Detection of Weak Peaks
Authors: Seabaugh P. W. , Sullenger D. B. , Hudgens C. R. , Nichols M, C. , Boehme D. R.
Published: March 2019

The use of high-intensity, 8Kw, x-ray sources (Rigaku rotating-anode generator and wide - angle goniometer for this study) provides both opportunities and challenges. With high - intensity x-ray sources, detection limits can be lowered significantly while still offering count times of practical duration. On the other hand, the availability of high intensity x-ray sources puts greater demands on information extraction procedures and on the mechanical preciseness of sample containment and support. In particular we addressed the use of a cylindrical aluminum sample cell with a 0.010’’ polycrystalline (cold rolled) beryllium window electron –beam welded to an aluminum frame. See Figure 1. This cell permitted analysis of various air-sensitive specimens. The sample was pressed against the back of the beryllium window by a spring-loaded backing plate.
Correction of X-ray Diffraction Profiles Measured by PSPC System
Authors: Ohya Shin'ichi , Yoshioka Yasuo
Published: March 2019

When an x-ray diffraction profile Is measured for stress analysis or profile analysis by the use of a linear (straight line) position sensitive proportional counter (PSPC) , a convex-type background line is obtained because of the geometrical problem and the absorption of x-rays. Such phenomenon is remarkable when a wide angular range is set on a linear PSPC and it is, in particular, necessary to correct with a straight background for accurate measurement of diffraction angle or half-value breadth of the broadened diffraction profile.
X-ray Analysis of the Structure of Wholly Aromatic Copolyamides and Copolyester Carbonates
Authors: Schneider A.-I. , Blackwell J.
Published: March 2019

This paper summarizes our work on the structures of two wholly aromatic copolymers: the copolyamide prepared from terephthalic acid, phenylene diamine, and 3,4'-diaminodiphenyl ether (mole ratio 50/25/25) and the copolyester carbonate prepared from p-hydroxy benzoic acid and hydroquinone, with the introduction of carbonate units (mole ratio 60/20/20). X-ray fiber diagrams of both copolymers exhibit a number of aperiodic meridional maxima that are similar to those reported for a series of wholly aromatic copolyesters. The latter systems have been shown to consist of arrays of parallel chains of completely random comonomer sequence: the aperiodic maxima arise due to structural correlations along the extended random sequences. The structures studied in the present paper are more complex due to the presence of kinked units, i.e. the 1,3 phenylenes and ether linkages of the copolyamide, and the carbonate groups of the copolyester carbonate. The results obtained show that the x-ray data can be explained by completely random monomer sequences. However, the chains are significantly distorted in order to produce more extended conformations than might be expected for isolated chains. These distortions minimize the effects of the kinked units and lead to better chain packing.
Polymorphism in Syndiotactic Polystyrene
Authors: Landes B. G. , Malanga M.T. , Thill B.P.
Published: March 2019

Polystyrene has been commercially manufactured for over fifty years. Today it enjoys widespread application in appliances, food containers, packaging, toys and thermal insulation. Generally, the term polystyrene is used as a generic descriptor for “he atactic configuration of the polymer chain. In this context the term configuration refers to structural regularity with respect to the substituted carbon atom within the polymer chain. In atactic polystyrene (PS) the phenyl groups are distributed randomly along either side of the polymer backbone. (Figure 1). Since there is no significant degree of long range order along this chain the polymer will not crystallize to any appreciable level.
Phase Diagram Studies on Neopentylglycol and Pentaerythritol-Thermal Energy Storage Materials
Authors: Chandra Dhanesh , Lynch Renee A. , Ding Wei , Tomlinson John J.
Published: March 2019

Pentaerythritol (PE) and neopentylglycol (NPG) are organic molecular crystals which have hydrogen-bonded lattices with layered- and chain-type structures, respectively. The PE undergoes solid-state phase transitions at 416K, from tetragonal to a cubic (γ’) structure and NPG also undergoes this transition at 317K from a monoclinic to a cubic (γ) structure. The phase transitions in binary PE-NPG solid solutions show more than one solid-solid transition in which the NPG-rich β transforms to γ at a constant temperature but the transition of the PE-rich a phase to γ’ passes through a two-phase field at a temperature that varies as a function of composition. Structural analyses by high-temperature x-ray diffractometry have revealed some new, interesting transitions. A phase diagram has been constructed for 0-30 mol% NPG in the PE-NPG system, using x-ray diffraction and differential scanning calorimetry results, and work is in progress to complete this diagram. The variation of lattice parameters as a function of temperature in the α, γ and γ’ phases for PE+20 mol% NPG are presented here, together with a discussion of phase transitions for certain compositions.
X-Ray Mass Absorption Coefficients: Measurements and Uses in the Quantitative Diffraction Analysis of Pyrite in Coals
Authors: Wertz David L. , Smithhart Charles B. , Wertz Stacey L.
Published: March 2019

The mass absorption coefficient (μ) of a weakly absorbing solid material may be measured by either the transmission or the reflection method. The latter typically employs a crystalline substrate and the diffraction method, measuring the transmission of the diffraction peak(s) of the substrate through the analyte. Compressing or compacting a powdered sample is not required when the reflection method is used.
The Concept of Pathlength Distributions Applied to Fundamental Parameter Approach
Authors: Ebel H. , Pöhn C. , Svagera S. , Mantler M. , Wernle M. , Ebel M. F.
Published: March 2019

The fundamental parameter approach for quantitative x-ray fluorescence analysis is an application of the equations derived by Sherman and by Shiraiwa and Fujino. Both derivations assume plane and smooth specimen surfaces and defined entrance and take-off angles of x-rays. Our investigation is dedicated to a more general description of measured characteristic signals. Consequently we have to deal with equations that allow us to account for the parameters mentioned below.
Qualitative XRF Analysis with Pattern Recognition
Authors: Yin Lo. I. , Seltzer Stephen M.
Published: March 2019

In many applications of energy-dispersive XRF analysis, quantitative information concerning the chemical composition of the samples is not required. Rather, one is interested in whether a given sample is similar to some reference material or whether the chemical composition is changing from one sample to the next. We have investigated the use of pattern-recognition techniques in such applications. It will be demonstrated with experimental data that the pattern-recognition approach is extremely simple and fast. It uses only a single parameter, the normalized correlation coefficient, and can be applied directly to raw data. The efficacy of the method is illustrated with Si(Li) spectra of geological and pigment samples, and proportional counter spectra of geological samples. The pattern-recognition method should be ideally suited for field XRF applications, and the algorithm can be easily implemented on a personal computer.
Synchrotron Radiation X-Ray Fluorescence Analysis
Authors: Gilfrich John V.
Published: March 2019

The physical principles giving rise to synchrotron radiation(SR), the facilities necessary to make use of this source of radiation and the way in which it can be used for x-ray diffraction experiments have been described in other parts of this proceedings. The use of synchrotron radiation as an excitation source for x-ray fluorescence takes advantage of many of its unique properties to provide the potential for an improved analytical capability, beyond that which can be realized with more conventional laboratory x-ray sources. Workers around the world are studying this application (as well as a wide variety of others) , to establish the potential of this technique. Table 1 lists some of the facilities where significant XRF effort is being expended. This list is not intended to be complete, but just to convey some idea of the magnitude of the research which is being carried out.
On-Line X-Ray Fluorescence Spectrometer for Coating Thickness Measurements
Authors: Matsuura N. , Arai T.
Published: March 2019

The principles and techniques for performing coating thickness measurements in the laboratory and on-line using nuclear radiation have been established for tin or zinc coated steels. Recently, additional engineering efforts have been made toward the development of new coating substances consisting of complex layered materials. For example, zinc-iron alloy metal has higher corrosion resistance than pure zinc-coated steel sheets and evaluations have been made of beneficial characteristics in automobile production processes, such as easy welding, good paintability, high efficiency for press plastics forming, etc.
Process Control Applications of the Peltier Cooled SI (LI) Detector Based EDXRF Spectrometer
Authors: Harding Anthony R.
Published: March 2019

The demand for on-line analyzers capable of compositional determinations in petroleum and chemical process streams has increased dramatically in recent years. Total control of production plant processes and resources requires the analysis of feed, intermediate, and product materials. This paper will describe a rugged, on-stream energy dispersive X-ray fluorescence (EDXRF) analyzer configured for the continuous determination of composition in solid and liquid samples. The detector in the X-ray sensor is a lithium-drifted silicon crystal which is thermoelectrically cooled (Peltier effect) to achieve operational temperatures. This approach to detector cooling offers advantages over traditional cryogenic liquid cooling when EDXRF is used in the process control environment.

Three applications of the thermoelectrically-cooled detector-based EDXRF spectrometer will be presented here. The first is the analysis of a catalyst solution to monitor depletion of the active species. Second, two components of a plating bath solution will be determined simultaneously in a flowing sample stream. In the third application, the spectrometer will be oriented in a downward looking configuration to monitor inorganic constituents in absorbent samples as they are transported by conveyor belt to the X-ray measurement area.
Concepts of Influence Coefficients in XRF Analysis and Calibration
Authors: Rousseau Richard M.
Published: March 2019

It will be shown that there are different types of influence coefficients to correct for matrix effects in XRF analysis: the empirical coefficients calculated from regression analysis and valid for the standards on hand only; the theoretical binary coefficients that are essentially constant in a given concentration range; then the theoretical multi-element coefficients calculated from one given composition and valid for one specimen only.

With theoretical coefficients, however, a special calibration process is needed, because theory cannot take into account all the instrumental parameters. In the proposed calibration method it will be shown that the slope of the calibration curves is the link to correlate the theoretical formalism to the experimental reality; that the standards used do not have to be similar to the unknowns and that a few only are required; that the calibration curves can be extrapolated by a factor of two or three; that pure analytes are not required.
How to Use the Features of Total Reflection of X-Rays for Energy Dispersive XRF
Authors: Schwenke H. , Berneike W. , Knoth J. , Weisbrod U.
Published: March 2019

The total reflection of X-rays is mainly determined by three parameters , that is the orltical angle, the reflectivity and the penetration depth. For X-ray fluorescence analysis the respective characteristic features can be exploited in two rather different fields of application. In the analysis of trace elements in samples placed as thin films on optical flats, detection limits as low as 2 pg or 0.05 ppb, respectively, have been obtained. In addition, a penetration depth in the nanometer regime renders Total Reflection XRF an inherently sensitive method for the elemental analysis of surfaces. This paper outlines the main physical and constructional parameters for instrumental design and quantitation in both branches of TXRF.