In order to develop an optimum system for flash x-ray diffraction, consideration must be given to both optimum x-ray generation and optimum x-ray detection in the correct wavelength regime suitable for diffraction. Historically, most workers have concentrated their efforts in either the generation area or detection area, but not both. As early as 1942, experimental recording of Laue diffraction patterns was reported using a pulsed x-ray generator and exposure times of milliseconds. Recently, successful x-ray diffraction experiments have been reported with exposure times less than 100 nanoseconds.

The purpose of the present paper is to trace the development of generation and detection systems for flash x-ray diffraction and to summarize the present state-of-the-art for such systems. A comparative evaluation is presented for flash x-ray diffraction systems using generators which rely on increased electron beam current and those which rely on higher potential difference. Comparison is also made between detection systems incorporating film recording, scintillators fiber-optically coupled to photomultiplier tubes, and image-intensifier systems both lens and fiber-optically coupled to fluorescent screens.

A detailed description of the most rapid flash x-ray diffraction system developed to date is given. This system uses a Field Emission Fexitron single channel 300 kilovolt pulsed x-ray generator incorporating an x-ray tube with a beryllium output window. A fluorescent screen converts the x-ray diffraction image into a visible one and this visible image is focused on the first stage photocathode of an image intensifier tube either by direct fiber-optic coupling or by using a coupling lens. The image intensifier tube used is a cascaded three-stage electrostatic focus type with fiber-optic input and output faceplates and inter-stage couplers. Using this system Laue transmission diffraction patterns of single crystals and powder patterns of polycrystalline aggregates have been obtained with exposure times of 30 nanoseconds.

Various industries throughout the world require Standard methods for trade of products and referee analysis. Over the past 20-30 years, a number of wet-chemical Standard methods have been developed and are in use. Due to the large number of elements required for analysis in most products, XRF methods have become attractive as techniques to handle many elements simultaneously with a simple single sample preparation. Despite XRF being in daily use in many industries as an ‘in-house’ method, there are relatively few National or International Standard XRF methods.

This paper reports and discusses the results of a computer modeling study on powder diffraction profile analysis for crystallite size and strain of polycrystalline materials. The results of this computer modeling show that if the spans of diffraction profiles in reciprocal space (1/d) are not carefully chosen, an overestimation on size and an underestimation on strain may result in analysis by both the Warren-Averbach and the Hall-Williamson methods. A general way to eliminate such errors based on profile fitting and regeneration is presented and discussed in this paper.

A prolonged study has been roade of the unusual X-ray powder patterns generated by certain pyrolytically formed boron compounds, consisting of two to four moderately broad diffraction lines in the 1-4 Å range. These broad lines are unexpectedly made to disappear by a singie sharp blow with a hammer on the specimen in a Plattner diamond mortar, the disappearance being accompanied by the spontaneous generation of the standard diffraction lines expected for normally crystalline materials. The same diffraction pattern changes also may be brought about by regular grinding methods, fracture, or thermal annealing. Transmission electron diffraction yields results identical with those obtained by X-ray. Orientation studies demonstrate that the phenomenon is not orientation dependent. Controlled fracture has been applied in an attempt to develop a hypothesis. It appears from the constancy of the width and position of the diffraction lines among samples that the phenomenon being studied has a definite potential energy, well located somewhere between amorphous and crystalline states. Demonstration of this phenomenon of line broadening has been obtained with boron, boron carbide, and in part with silicon, carbide. These materials have been formed by various methods: pyrolytic decomposition of carborane, low pressure electrical discharge in diborane, chemical reaction between boron halide and hydrogen.

Different geometries are considered for source excited energy-dispersive X-ray fluorescence (EDXRF) analysis Systems, including the recessed source geometry introduced in the present work. The calculated physical excitation-detection efficiencies, for the side (or annular), central, receded and recessed source geometries are presented as a function of the target to source distance, for Ca, K, S and Si targets excited with a Fe-55 XBF-3 X-ray source and xenon filled gas proportional scintillation counters. The last two geometries present in gênerai the highest efficiencies. The recessed source geometry présent the best performance with peak efficiencies a factor of 3.3 better than those for the standard side or annular source geometries.

The P-L2,3 emission spectra of the phosphorus compounds were obtained using a secondary excitation. We found that the spectra depended upon the chemical state, the main peak of L2,3 emission spectra shifts to a higher energy, and the peak of intensity of higher energy increases with an increase of oxidation number. It should be noted that the phosphorous spectra of the phosphate anions scarcely reveal influences of the phosphate compounds, except that of H3PO4. We concluded that the spectral feature for the phosphorus compounds is influenced by the condition of surrounding atoms but is not influenced by the bond condition.

Bremsstrahlung emission from four x-ray tubes operating at 12 to 300 kV was measured. Spectral distributions are given in terms of absolute-photon and energy fluxes. Silicon and germanium semiconductors, sodium iodide scintillators, and a xenon proportional counter were used to measure the spectra. Detector distortions were corrected by assuming an undistorted spectrum, distorting the spectrum with a Monte Carlo computer program, and comparing the results with measurement. The assumed undistorted spectrum was revised until the Monte Carlo calculation gave satisfactory agreement with spectral measurements from all four types of detectors. The effects on the spectra of varying the tube potential, tube current, target aperture, and detector aperture were investigated. Corrections for the intervening material and the solid angle subtended by the detector were applied to obtain the absolute-photon and energy flux from the target. Total fluxes in the L lines, K lines, and continuum are given. X-ray-production efficiencies varied from 0.026% at 12 kV to 1% at 300 kV. The constant of proportionality varied in the range (0.23 to 0.73) x 10-6 kV-1.

An adapter for a standard Norelco spectrographte attachment will be described which permits the examination of a selected area of the specimen by X-ray fluorescence analysis. The size of the area can be varied depending upon the choice of pinholes with sizes available dovwi to 0.010 in. or 250μ. The sample is placed into a specially modified sample holder so that it can be moved at orthogonal directions under the beam from outside the spectrograph while the sample is under X-ray irradiation. Dam on applications will also be given.

Improvements in x-ray tube technology for the low-power tubes used in energy-dispersive XRF systems can provide better performance. These improvements are occurring in six areas: thin-window tubes, lower kV capability, higher kV and mA capability, pulsed tubes, smaller focal spots, and miniaturization. These improvements will lead to better excitation of the light elements, analysis of low-mass samples, higher count rates, small spot analysis, and smaller systems.

Machined parts made of fine ceramics are usually finished by grinding (Yajima et al.,1990, Mishima et al.,1987). The residual stress introduced by grinding will influence the fracture strength and the function of ceramics, and needs further consideration. Over the past few years, a considerable number of studies have evaluated ground ceramics by means of the X-ray method. However, it is well known that X-ray stress measuring data, 2 θ φ φ-sin2 φ curves of the surface layer of the unidirectionally machined ceramics are showing non-linear behavior (Kishimoto et al.,1987) . In this case, the sin2 φ method is inadequate for the evaluation of the stress (Sasaki et al.,1989).

Machine parts made of ceramics are usually finished by grinding. Residual stresses as well as defects introduced by grinding will influence the fracture strength and the function of the ceramic parts. Although several investigators measured the grinding residual stresses by the X-ray diffraction method, their grinding conditions were rather limited.

The necessary first step in using an x-ray fluorescence spectrometer for quantitative analysis is to obtain the intensities for the various elements. With a wavelength dispersive system this usually requires simply setting the crystal to the proper angle (and possibly adjusting the pulse height selector) and making a dead-time correction. With the energy dispersive x-ray fluorescence analyzer it is necessary to take into account the presence of erroneous peaks in the spectrum, to obtain true intensity values.

False peaks due to diffraction of white tube radiation from the sample can usually be shifted to portions of the energy spectrum where they do not interfere with emission lines of interest by selection of the proper tube-sample-detector geometry. Modern amplifier design provides a built – in dead time correction and greatly reduces the effects of pulse-pile-up, although the latter phenomenon will still produce small peaks at exact multiples of major peaks.

A low-temperature X-ray diffraction apparatus has been constructed to study structure and structural changes of electrolytes in the frozen state. This apparatus, which is inexpensive and easy to construct, is an attachment to a standard wide-angle diffractometer. Diffraction patterns may be obtained of various types of materials at any temperature from room temperature to −196°C with a control of ±1°C. The diffraction patterns are recorded on a strip-chart recorder as they are being obtained. Thus, this diffractometer method has several advantages over the camera methods usually employed for low-temperature X-ray diffraction work. A unique sample-introduction method is described which ensures a polycrystalline material suitable for obtaining diffraction patterns. Such patterns are shown for various concentrations of salts in water at several low temperatures, phase transformations being in evidence.

A protocol for semi-quantitative XRD analysis of fly ash has been applied to 178 ashes in studies of the typical mineralogy of high-calcium and iow-calcium fly ash, the consistency of fly ash mineralogy from a typical power station, the partitioning of chemical constituents into crystalline phases, and the crystalline phases relevant to the use of fly ash in concrete.

In the measurement of residual stresses in hardened carbon steels by X-ray diffraction the principal difficulty encountered is determining the precise location of the broad diffraction lines. Christenson and RowlandM have proposed a workable technique, but it entails a complicated correction calculation. A simplified correction procedure, based on theoretical considerations, will be described which shortens the time required to obtain accurate data and cuts the time required for calculation to a fraction of that required for the previous method.

It can be shown that the asymmetry of the broad diffraction lines in the back reflection region is largely due to 6 dependent intensity factors. Thus, the proposed correction procedure uses a multiplicative correction to peak intensity which includes all significant geometrical and absorption factors. The line position is then determined accurately as the axis of a parabola fitted to the corrected data. Since the data is taken in the vicinity of the peak, the time required to obtain accurate data is reduced and furthermore it is possible to determine residual stresses in as-quenched steel even though the structure is tetragonal.

Examples of the type of stresses measured and the correlation between this new method and that of Christenson and Rowland will be presented.

The location of x-ray diffractometer line profiles is of fundamental importance in x-ray stress analysis. Objective estimates of the line profile position may be derived from diffractometer measurements at a number of equally-spaced points in the region of maximum intensity. These estimates are generally based upon the corresponding turning-point of a polynomial fitted to step-scanning data. Techniques are described which simplify the computation involved. A least-squares fitting of a quadratic is satisfactory for most routine applications provided that a reasonable number of points is involved. The three-point parabola method is less satisfactory. Expressions are presented, derived using the maximum-likelihood approach, for peak location and counting variance using both quadratic and cubic equations.

Computed tomography (CT), commonly known as CAT scanning (computerized axial tomography), is a technology that produces an image of the internaI structure of a cross sectional slice through an object via the reconstruction of a matrix of X-ray attenuation coefficients. This non-destructive method is fast (50 ms to 7 min per image depending on the technological generation of the instrument) and requires minimal sample preparation. Images are generated from digital computations, and instruments essentially have a linear response. This allows quantitative estimations of density variations, dimensions and areas directly from console displays.

A prototype of a new high temperature chamber has been developed at our institute. Like most of such chambers it has an evacuated housing which is watercooled, and in its center a tungsten heating strip is mounted on watercooled clamps (fig.1). A special way of clamping compensates for thermal expansion automatically and thus keeps the specimen in an aligned position. The specimen is mounted directly onto the heating strip's surface. Specimens are prepared using fine powders mixed with distilled water and acetone to give a thin slurry. This mixture is put onto the heating strip and carefully dried with a heatgun. This way of preparing a specimen makes it cling to the heating strip quite well even at temperatures above 3000K and therefore provides good thermal contact.

Spectrum analysis in the ultrasoft X-ray region is complicated by the fact that this radiation is almost totally absorbed in any medium. This has necessitated spectrometer components which minimize this effect. Nondispersive and total reflection techniques, though high in speed, lack good resolution and in the case of the latter, are usually restricted to analysis of elements differing by at least three atomic numbers.

Diffracting media which have proven successful are the long-chain organic crystals and gratings at grazing incidence. The grating is superior to the organic crystal concerning resolution and dispersion and has proven to be comparable arid in some cases better for peak intensity and line-to-background ratios.

Lightly-ruled gratings have been used for many years, but little attention has been given the blazed grating until recently. Since the critical angle of total reflection for a given material is wavelength-dependent, it may be utilized to discriminate against shorter wavelengths and thus improve line-to-background ratios. The optimum conditions for sensitivity, then, would be to relate the input angle to the blaze angle and vary the input angle as a function of wavelength, thereby maximizing the line intensity or the line-to-backgrourid ratio as required.

Several gratings with varying blaze angles and surface finishes are evaluated with O Kα (23.7Å) and C Kα (44Å) radiation.

The importance of groove profile is emphasized by comparing the profile as determined by the electron microscope with the experimental evidence. The variation of diffraction efficiency with wavelength and input angle is then considered theoretically and compared with experimental results.

An IBM 7090 computer program has been written to determine precise lattice parameters for cubic, tetragonal, orthorhombic, and hexagonal systems. Leastsquares analysis is made with data fitted to the equation

where E is the eccentricity and A. is the absorption-divergence error. The computer program will make the least-squares analysis with neither, either, or both of the error(s) included. Data can then be reprocessed for other combinations of errors. After having determined the lattice parameter(s), on request, the computer program will predict the interplanar spacings, including the errors, so that observed data in the high-angle region may be indexed by comparison. Use of the program indicates that the most consistently reproducible parameters are obtained using only A, the absorption—divergence error.