Quantitative multicomponent analysis of phases by x-ray diffraction still remains one of the most difficult applications of any element or phase spectroscopic method. The level of quality of XRD quantitative analysis is largely in the hands of the operator, but several relatively new methods for processing basic diffraction data are becoming known and more frequently used, including fulltrace (observed and calculated) subtraction methods (Smith et al, 1988), Rietveld procedures (Bish and Howard, 1988; Taylor and Aldridge, 1993), and chemical “apportionment” target-transformation methods (Starks, et al, 1984). In spite of these new advances, the single or multiple peak reference intensity ratio (RIR, or kj) procedure remains a simple and attractive technique for routine quantitative XRD analysis (Schreiner, 1995; Snyder, 1992; Davis, 1992).

Double bending fatigue tests were performed on cold worked 1100 aluminum, with a maximum bending stress varying from 100 to 50% of the yield stress. Variation of residual macrostress from the cold worked state during the fatigue tests was measured by the photographic x-ray diffraction method. A general decrease of this macrostress was observed. Line profile analysis was used to study the change in the mean effective domain size and microstrain. A rate dependence of the increase in the effective domain size with respect to the maximum bending stress was observed. Microhardness and tensile tests were also made on the specimens during the fatigue testing and the results are correlated with the x-ray Parameters.

Since first introduced by Claisse, twenty-five years ago, borate fusions have been used in XRF analysis of a wide variety of materials because fusion eliminates many of the problems associated with particle size and matrix effects encountered in the analysis of powders. Geological and environmental materials such as rocks, ores, sediments, slags, air-borne particulates, etc., lend themselves nicely to lithium or sodium tetraborate or lithium metaborate fusion because the inherent presence of silica in these materials stabilizes the resultant glass from crystallization.

Aluminum, is determined within the range 2-16% in iron. Repeatability of X-ray determinations is within a standard deviation of 0.07 % aluminum for a sample containing 10.2% aluminum. The standard deviation of the chemical values from the straight line calibration curve is 0.3% aluminum. X-ray analytical time is approximately 5% of the time required for chemical analysis. Peak-to-background ratio is improved by using a chromium-target thin-window X-ray tube instead of a tungsten tube.

An interchangeable Bragg-Brentano:Seeman-Bohlin diffractometer, with variable specimen setting, has been constructed. A study of the influence of the geometry on the resolution, angular displacement and intensity of diffraction profiles clearly demonstrates that the standard Bragg-Brentano method is to be preferred when recording Bragg reflections below 40°,2θ. At higher Bragg angles, which permit the specimen to be set further away from the X-ray source, it is demonstrated that the diffracted intensity of the Seeman-Bohlin method can be increased above that of the Bragg- Brentano because the use of an increased divergent angle does not reduce the resolution. A study of the effect of specimen setting on the systematic errors associated with the Seeman- Bohlin geometry indicates that a setting of 60° (half-angle from the X-ray source) gives optimum resolution with minimum displacement error.

It is important to establish precision and accuracy of an X-ray diffraction (XRD) residual stress measurement procedure in order to compare capabilities of instrumentation and techniques, as well as to provide confidence limits for experimental data. There is no broadly acceptable method for establishment of precision and accuracy. This paper describes a proposed approach and one which is used at The Pennsylvania State University.

One impediment to the measurement of precision and accuracy is that no standard specimen with a known residual stress level is available. Proposed standard specimens have been abandoned for various reasons, including the concern for stability of the original stress condition and the existence of stress gradients, i.e., stress inhomogeneity, in the specimens. However, there is one type of specimen which has been accepted by ASTM as an alignment and zero residual stress confirmation standard. That type of specimen is a powdered sample of metal or ceramic which provides XRD peaks in the vicinity of the Bragg angle in which residual stress measurements are to be performed.

Some researchers tend to report detector counting statistics as the uncertainty of stress measurement but such statistical scatter accounts for only one part of uncertainty in precision and accuracy. The total uncertainty is best determined directly through repeated residual stress measurements performed by removal and readdressing the test specimen or through a repetition of measurements under predictably changing conditions.

This paper describes results from the use of powder specimens to establish the repeatability of measurements with a portable instrument after removal and readdressing of the specimens. Also, results showing the uncertainty of the measured stress change in specimens subjected to known loads are discussed.

Previous work on modification of the collagen lattice, presented at these meetings, has served to confirm the Ramachandran proposal for the structure of this important protein, together with information on the lengths and tensile strengths of these bonds, including hydrogen bonds, hydrophobe bonds, and Vander Waals attractions. Rat tail tendons were suspended in 2 M aqueous solutions of dimethylsulfoxide, acetone, trimethylamineoxide and 1,4-cyclohexanedione, all of which showed evidence of ligation by expansion of the collagen lattice and refinement of the 100 spot in the x-ray diffraction pattern run by rotation on the collagen fiber axis. In the case of trimethylamineoxide and cyclohexanedione, oriented crystallization also occurred, with the long direction of the molecule in the plane perpendicular to the fiber axis of collagen. With the monofunctional ligands, the -C=0 group forms a hydrogen bond to the N-H group in the Ramachandran standard revised model, leaving the methyl groups to form the hydrophobe bond.

Total Reflection X-Ray Fluorescence Analysis (TXRF) has become a powerful analytical tool for trace element analysis. Because of its advantages in excitation and background reduction TXRF has been applied for the analysis of light elements (C,O,F,Na,...). A special Ge(HP) detector offering an ultra thin window in combination with a spectrometer specially designed for the requirements of light element analysis was used. Also a new windowless X-ray tube for efficient excitation of the light elements was tested. The system was checked with standard aqueous solutions; detection limits in the ng range (7 ng for O) are obtained.

Oxygen K-V (Kα) X-ray fluorescence spectra of MgO, Cu2O, CuO, La2CuO4, La2-xSrxCuO4, YBa2Cu3O7-x , and GdBa2Cu3O7-x are measured. The local (oxygen) and partial (2p) electron density of states (DOS) of these compounds are calculated by the cluster approximation with the discrete variational (DV) Hartree-Fock-Slater (Xα) method. The calculated O 2p DOS are compared with the measured X-ray fluorescence spectra. It is found that the measured 0 K-V X-ray fluorescence line shapes are well reproduced by the O 2p DOS calculated by a cluster including the second nearest neighbor atoms (oxygen atoms) in the solids. This indicates that the oxygen K-V X-ray emission spectra reflect the oxygen-oxygen orbital hybridization in the solid as well as the oxygen-metal orbital hybridization.

Metallic impurities present in crude oils lead to the rapid deactivation of catalysts used in refineries and a drop in the yield of oil products. The determination of these impurities is therefore of primary importance. The conventional and most widely used methods to determine trace metals in oils and petroleum products are chemical analysis methods such as atomic absorption spectrometry (AAS) and inductively coupled plasmaoptical emission spectrometry (ICP-OES). Sample preparation for these methods includes decomposition of the crude sample by dry ashing and combustion of the oil sample followed by chemical treatment of the dry ash residue (ASTM, 1983; Fassel et al., 1976). Major drawbacks of chemical analysis methods are the length of time required to prepare the sample and the possibility of losing trace metallorganic compounds in the form of volatile compounds.

During the course of catalytic experiments on bulk copper single crystals, several crystals were intentionally oxidized to form thick (6000 Å) Cu2O films on the copper substrates. These oxidized crystals were investigated by means of a high temperature chamber installed on a General Electric XRD-5 X-ray diffractometer. It was discovered subsequently that the lattice spacings of the Cu2O decreased upon heating and increased upon cooling. Bulk single crystals and polycrystals of copper were oxidized at 3 Torr of air for several hours. All of the oxidized crystals were examined with copper and chromium radiation and both showed similar results. Typical of the results was an oxidized (110) copper disc which showed a net contraction upon heating of 1% for the (110) Cu2O planes. This slightly oriented Cu2O film was distinguished because -it contracted on heating to 440°C from room temperature, then expanded from 440°-540°C, and then expanded again when cooled from 540°C to room temperature. CuO also was detected in the diffraction pattern and the CuO and copper spacings were behaving normally with the temperature changes. A polycrystal of Cu2O was'examined and that, of course, also acted normally as its temperature was varied. Borie and co-workers have reported and explained very nicely similar anomalous behavior for thinner (500 Å) (110) oriented Cu2O films grown on (110) copper substrates. They showed that the epitaxial forces would cause an oxide film grown at high temperatures to contract parallel to the metal interface and expand normal to the interface as the copper cools and contracts. The oxide would expand normal to the surface in. order to keep its unit cell volume constant.

It is felt that epitaxial forces are not causing the anomalous behavior in the present work mainly because the 6000 Å of Cu2O is too thick for epitaxy to exert a meaningful force. The oxide film on the (110) copper was slightly (110) oriented but all of the Cu2O reflections behaved similarly. An additional reason to discount epitaxy is that this Cu2O film expanded upon heating from 440°-540°C. For these thick oxide films epitaxial forces do not seem to be the controlling factor; therefore, a point defect mechanism must be the cause. Changing oxidation and diffusion rates with temperature would produce various vacancy concentrations in the oxide layer and cause the spacings to vary.

The mass absorption coefficient is a useful parameter for quantitative characterization of materials. If the chemical composition of a sample is known, the mass absorption coefficient can be calculated directly. However, the mass absorption coefficient must be determined empirically if the chemical composition is unknown. Traditional methods for determining the mass absorption coefficient involve measuring the transmission of monochromatic X-rays through a sample of known thickness and density. Reynolds (1963,1967), however, proposed a method for determining the mass absorption coefficient by measuring the Compton or inelastic X-ray scattering from a sample using Mo radiation on an X-ray fluorescence spectrometer (XRF). With the recent advances in solid-state detectors/electronics for use with conventional powder diffractometers, it is now possible to readily determine mass absorption coefficients during routine X-ray diffraction (XRD) analyses.

Using Cu Kα radiation and Reynolds’ method on a Siemens D-500 diffractometer fitted with a Kevex Si(Li) solid-state detector, we have measured the mass absorption coefficients of a suite of minerals and pure chemical compounds ranging in μ/ρ from graphite to Fe-metal (μ/ρ = 4.6-308 using Cu Kα radiation) to ±4.0% (lσ). The relationship between the known mass absorption coefficient and the inverse count rate is linear with a correlation coefficient of 0.997. Using mass absorption coefficients, phase abundances can be determined during quantitative XRD analysis without requiring the use of an internal standard, even when an amorphous component is present.

Quantitative phase analysis by X-ray diffraction (QTXRD) has been an established tool of analytical chemistry for more than four decades. Despite its age, this tool remains ascendant as the only universally applicable method for determining the manner in which elements are combined into crystalline phases in multiphase solids. QTXRD is entering its second renaissance. The first came with the introduction of the counter diffractometer in the late 1940's. The specimen preparation and data collection processes were exacting and tedious, but reasonably accurate analyses could be obtained. The second came with the introduction of computer controlled diffractometers, whose software packages include QTXRD routines, in the late 1970's. With the tedium of data collection and analysis greatly reduced, we can expect even more widespread adoption of this tool in the general analytical laboratory.

The development of linear position-sensitive detectors (PSD) has resulted in a large reduction of data acquisition times in the field of x-ray stress analysis. However, we also require two-dimensional (2-D) diffraction patterns for material evaluation. Especially, the microbeam x-ray diffraction technique gives valuable information on the structure of crystalline materials and this technique has been applied to fracture analysis by x-rays. Many kinds of 2-D PSD have been developed that have insufficient spatial resolution. So x-ray film has still been used as a 2-D detector, but it requires relatively long exposure times and then the process after exposure is very troublesome.

This paper presents the theoretical and practical aspects of measuring residual stresses by X-ray diffraction with emphasis on the analysis of aluminum alloys. The theoretical considerations of radiation) beam geometry, and peak location will be discussed in regard to establishing optimum analysis techniques. The precision and reproducibility of this technique have been investigated so that results can be applied accurately. The approach, however, is basically a practical one, with the intent of studying residual stress systems as they affect engineering applications. Residual stress systems produced by thermal and mechanical treatments have been determined and the effect of treatment modifications and variations on the resultant stress system have been analyzed. The effect of operational variables such as time and temperature on the developed stress system are shown. From this, the merits of a particular treatment can be determined with respect to its intended application.

Analysis of solution heat-treated and quenched 2014 aluminum has shown a significant effect of the quench temperature on the resultant residual stress system. The results obtained from shot-peening this alloy are presented, as well as the effect of time and temperature on the shot-peened stress gradient.

When X-ray residual stresses are determined taking into account the stress gradients within the penetration depth of X-rays, three assumptions have usually been made; 1) the stress gradient is linear in respect to the depth from the specimen surface, 2) the penetration depth of X-rays is a function of Sin2ψ and 3) the strain measured by X-rays corresponds to the average strain weighted on the intensity of the diffracted X-rays. However, the assumption of the penetration depth of X-rays is the reason we sometimes observed noticeable errors which depend on the combination of stress components in the stress tensor.

The development of materials with optimum fatigue characteristics hinges on a better understanding of the fatigue mechanism ( i .e ., fatigue crack nucleation and propagation) under specific loading conditions. A correlation was established between the residual macroscopic stress level--as measured by x-ray diffraction analysis, the fatigue damage in the form of slip-band formation and intensification, and the fatigue life at various applied stress levels of pure iron and low-carbon steel.

Residual stresses were measured by an automated diffractometer technique (Fe 211 Kα reflection, Cr radiation) and computer calculation of both macroscopic (line shift) and microscopic (line broadening) stresses . Surface fatigue damage was observed by optical microscopy.

The production of standard x-ray diffraction patterns at NBS imposes special requirements in the data processing of powder patterns. The patterns should be complete and have an overall accuracy of better than 0.01 degree two theta. To ensure completeness all the observable peaks should be indexed. To make certain that the sample is a pure phase, weak peaks have to be identified as well.

The indexing of all the peaks implies that the cell constants must be known and there should be a good agreement between all the calculated and observed peak positions. In practice this is achieved by a least-squares refinement of the unit cell parameters. This serves as a test of the assumed unit cell and also as an interpretation of the observed peaks. Finally, an attempt is made to identify the space group. This step also requires the identification of weak peaks. The agreement of a known space group with the observed reflections further confirms the purity of the sample.

We have studied a series of laminated thin films by x-ray diffraction to correlate their structural and magnetic properties. Previous works have shown that the signal-to-noise characteristics of laminated magnetic films with non-magnetic interlayers can exceed that of single layer magnetic films. In the case where the magnetic layer is known to have low signal-to-noise performance, the signal has been observed to increase as the number of layers whereas the noise increases as the square root of the number of layers. This yields a net improvement of the signal-to-noise ratio, making the overall film more attractive as a magnetic recording medium. In this paper, we investigate films which are laminated layers of magnetic CoPtCr and non-magnetic Cr. The films were deposited with sputtering parameters that generally give low noise characteristics in single layer films. Up to four layers of CoPtCr films were made with Cr spacer layers of 2 nm. We observe some improvement in signal-to-noise characteristics and reduction in coercivity. X-ray diffraction analysis shows that the crystallographic c-axis, which corresponds to the magnetic easy axis, becomes more preferentially oriented perpendicular to the film plane with each additional layer. This change in preferred orientation is consistent with the reduced in-plane coercivity of the film. In the double CoPtCr layer with one Cr spacer layer experiment, we see that as the Cr spacer layer is increased from 0.5 to 8 nm, the c-axis of the CoPtCr again becomes more preferentially oriented out of the film plane, resulting in decreased in-plane coercivity. The media signal-to-noise improves once the Cr spacer layer is beyond 2 nm, consistent with previous observations.

Chromium nitride hard coatings have been prepared by a plasma process by varying nitrogen partial pressure. The crystallographic structure of these samples has been investigated by XRD and their chemical composition and stoichiometry by Low Energy Electron Induced x-ray Spectrometry (LEEIXS).