X-ray fractography is a new method utilizing the X-ray diffraction technique to observe the fracture surface for the analysis of the micromechanisms and mechanics of fracture. The X-ray residual stress has been confirmed to be a particularly useful parameter when studying the fracture surfaces of high strength steels. The method has been applied to the fracture surface of fracture toughness and fatigue specimens.

The salts of hydrazine or methyl derivatives of hydrazine were prepared by neutralization of the base with inorganic acids, for instance, HBF4, HClO4, H SO4, and HCl. Upon recrystallization of the product from a suitable solvent, X-ray diffraction patterns were obtained. Hydrazine tetrafluoborate H2N-NH2·HBF4 was found to crystallize in the monoclinic system. Cell dimensions and possible space groups were determined. The corresponding perchlorate salt crystallizes in two forms, one of which is isomorphous with hydrazine tetrafluoborate. The second form seems to be stabilized by small amounts of water.

The tetrafluoborate salt was prepared from the 1,1-dimethyl hydrazine. It was found to crystallize in the tetragonal system with a primitive unit cell. The perchlorate salt of this base is isomorphous with the fluoborate but with a slightly larger unit cell. Both materials undergo plastic-like deformation. The general appearance and mechanical properties are similar to those of a hydrocarbon wax. The 1,1-dimethyl hydrazine sulfate and the 1,1-dimethyl hydrazine hydrochloride have a lower symmetry than the HBF4 salt and do not show the wax-like properties of the latter. Based on the study of these chemically related compounds an explanation is offered for the properties of 1,1-dimethyl hydrazine tetrafluoborate in terms of crystalline structure.

Slow data acquisition rates have, in the past, limited the use of X-ray diffraction for characterization of polymeric materials. Photon counting techniques yield quantitative data in digital form for computer analysis. However, a great deal of data acquisition time is required when data is taken sequentially; i.e., when each intensity determination (at a particular goniometer setting) requires a separate time interval, during which intensity at other angle values is ignored. The problem is particularly acute for oriented polymers since two or more diffraction angles are involved: The Bragg angle along with at least one orientation angle. For this reason, an area-imaging (two-dimensional) proportional counter has been developed for use with a four-circle X-ray diffraction system. Although basically a single-crystal unit, this goniometer has been used in this laboratory and others for studies of oriented polymers. The receiving pinhole collimator and aperture have been removed, and the area-imaging counter has been mounted on the detector arm track. The original receiving aperture is still used for alignment, and the area detector Is positioned with its center at the receiving aperture center position.

A minicomputer program system for phase Identifications in x-ray powder diffraction is described. The routines written in FORTRAN comprise the users’ special purpose standard-file management (creation of microfiles from the complete JCPDS-data base or own standards, as well as utility routines for corrections, supplements and bookkeeping) and the measured data processing, including raw data acceptance, data reduction by two selectable peak-search routines (trendoriented or 2nd derivative) and an exhaustive search/match procedure through selected microfiles. The data reduction and analysis programs have manifold graphical displays allowing manual interference. In one run up to five phases can be matched. The weight portion of every phase is estimated, using I/I (corundum)- values, Hie whole analysis (in automatic operation) consumes about 1 or 2 minutes of the processor time on a pdp 11/34 minicomputer. This matches well to the data collection times accessible for fast powder diffraction systems /I/.

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.

Errors pertinent in dual beam absorptiometry have been studied. Five areas are given in detail: 1. Scattering, in which a computer analysis of multiple scattering shows little error. 2. Geometrical configuration effects, in which the shape of the sample influences accuracy. 3. Poisson variations, in which dosage and statistical error are minimized. 4. Absorption coefficients, in which variations in compilations are examined. 5. Filtering, wherein is shown the need for Kβ filtering. A zero filter system is outlined.

The statistical fluctuations of photon counts arediscussedas a factor limiting the precision of the analytical result. Assuming a Poisson distribution, the theoretical standard deviation of the result can be calculated. While this prediction does not consider causes of variation other than the count statistics, it is useful in developing methods and checking instrument reliability. Practical examples using experimental results are given.

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.

A technique is described for the study of the early stages of precipitation hardening in single-crystalline and poly crystalline copperberyllium alloys. Since no trace of the equilibrium precipitate responsible for hardening can be detected by ordinary X-ray or metallographic techniques prior to the onset of overaging, the described method is based on the changes produced in the matrix as the result of the formation of aggregates along preferred lattice planes. Such formations produce accommodation strains in the matrix lattice which, can be detected as a change in the intensity and angular range of matrix reflection.

An interpretation of the age hardening sequence in a copper - beryllium, alloy after isothermal annealing is presented in terms of fundamental transformations.

Residual strains and stresses were measured in hot-pressed α-Al2O3 composites containing 25 wt% β (cubic) SiC whiskers with and without a 50-100Å thick carbon coating. X-ray diffraction methods were used including the separation of macrostresses from the microstresses in the -Al2O3 and SiC phases by the method of Noyan and Cohen. The presence of the carbon coating on the whiskers reduced the magnitude of the residual microstresses in the whiskers by ˜13% and in the matrix by ˜10%. The measured residual stresses in the whiskers and the reduction due to the carbon film were in good agreement with calculations from recent models proposed by Hsueh, Becher and Angelini, and by Li and Bradt.

X-ray emission spectra have been obtained with a single crystal spectrometer having a resolution λ/dλ of 6,640 for iron Kβ5 spectra. The spectrometer consisted of a Jarrel-Ash Microfocus unit in conjunction with a Picker diffractometer which was operated as a rocking crystal spectrometer with a stepping angle of 1/400th of a degree. Kβ5 and Kβ1,3 spectra have been obtained from iron, Fe0.9Mn0.9Ge, Fe1.60Ge, FeGe, FeGe2 and germanium. Because the K05 spectra are due to 4p - Is transitions from the 3d bands, the Kβ5 intensities are a direct measure of the overlap or hybridization of the 3d - 4s - 4p bands. The experimental results can be correlated either with orbitals derived on the basis of coordination, or more roughly with possible band distributions.

The x-ray spectroscopy of laser-generated plasmas can be applied to photon energies of less than 1 keV, provided calibrations of the response of energy discriminators and detectors are performed in the sub-kilovolt region. In our application we use photographic film to monitor the intensity of radiation dispersed by a curved lead stearate crystal. We have determined the response to sub-kilovolt x-rays of two types of film, Kodak No-Screen and the special vacuum ultra-violet Kodak type 101-01. This calibration was obtained by exposing samples of film to continuous beams of nearly monochromatic characteristic radiation from an array of targets. The fluorescent radiations were the K series of carbon and magnesium and the L series of titanium, nickel, cobalt and copper. The response data are presented as a series of characteristic curves, plotting for each film type and photon energy the net diffuse photographic density as a function of the photon flux incident on the film. The processing of all film was in accordance with the manufacturer's suggestions. We attempt to characterize the accuracy and reproducibility of these data. The data demonstrate the greater sensitivity of the type 101-01 to sub-kilovolt x-rays.

The intensity and spectral purity of the incident fluorescent beams were monitored by a thin-window gas proportional counter that used flowing propane gas at sub-atmospheric pressures. We describe the procedures and results of a determination of the quantum efficiency of this counter as a function of photon energy.

Spectrographic analysis for carbon and boron using fluorescent x-rays has been studied over the past few years; principles and applications for using those ultra-soft x-rays were described, based on the combination of total reflection and filtering rather than on the wavelength dispersive method of Bragg reflection (1, 2). However, oxygen and nitrogen, with x-ray wavelengths of 23.7lÅ and 31.60Å, respectively, cannot be detected as easily because of their high absorption by the detector window materials such as polypropylene, polyester or formvar films.

A feasibility test at the Naval Research Laboratory has shown that a miniature X-ray Fluorescence (XRF) sensor can be constructed for the cone penetrometer. Such a sensor would have detection limits for heavy metal contaminants in soils of a few parts per million. The next step is to demonstrate the capabilities of such a sensor in the cone penetrometer. A sensor for this purpose is being constructed and will be tested both in the laboratory and in the field. The XRF sensor will be capable of evaluating the in-situ detection limits and field screening (semi-quantitative) capabilities of x-ray fluorescence and can be transitioned to field activities for further evaluation and feedback. The sensor will consist of a miniature x-ray tube and an x-ray detector, together with appropriate apertures and x-ray filters, in a custom fabricated section of penetrometer pipe. The sensor will use commercially available components. High voltage and signal cables will couple the sensor to electronics in the truck. Boron carbide will be used for the x-ray windows which protect the sensor components from soil abrasion.

Residual stress measurements were made on a ground rail steel (0.75 %C) using the newly developed ϕ-integral method and the conventional ψ-differential method. The strains <εϕψ> were measured as a function of the azimuth angle ϕ, the angle of rotation about an axis perpendicular to the specimen surface, from 0° to 360° in steps of 15°, at fixed tilt angles ψ, the angle between the normals to the specimen surface and the reflecting planes (hkl), set between 0° and 45° in steps of 9°.

It was found that <εϕψ> plotted as a function of ϕ is not periodic with the period of 180° and consequently exhibits the so-called ψ-splitting when plotted as a function of sin2ψ at constant ϕ. The Fourier coefficients of the function <εϕψ> plotted versus ϕ were used to evaluate the strain tensor <εij> in the integral method. Assuming that isotropic elasticity theory is applicable, the stress tensor <σij> was calculated, and excellent agreement was found between the values determined with the ϕ integral and ψ-differential methods.

During recent years energy dispersive x-ray fluorescence (EDXRF) has been used to measure the elemental content of atmospheric aerosols. The code described here is used to reduce EDXRF data and determine the elemental composition of samples collected on membrane filters. The program has been specifically written for EDXRF analysis of size-fractionated aerosols collected by a dichotomous sampler.

The x-ray fluorescence spectrometer used in our laboratory employs a pulsed-mode x-ray tube and a lithium-drifted silicon detector. Pulse-height spectra are produced for elements ranging in atomic number from Z = 13 to Z = 82 (corresponding to an energy range from 1.4 to 32.1 keV). Approximately uniform x-ray production is attained by producing independent spectra from three secondary targets (Ti, Mo, Sm).

In X-ray fluorescence analysis, the specific secondary radiation intensities of the elements are generated and measured by a spectrometer. Usually, the measured intensities are corrected for instrument drift first, then converted into element concentrations. In routine analysis, the intensity is always affected by the instability of the instrument. Instrumental instability consists of two components: short and long term drift Short-term instability is caused by fluctuations in the ambient laboratory conditions and the instrument's components. Long-term drift is caused by aging of the instrument's components (mainly X-ray tube, crystals, detectors, electronic circuitry) and results in a gradual intensity decrease. For example, the X-ray tube output decreases due to pitting of the target and sublimation of metal on the inside of the window. The quantum efficiency of detectors gradually decreases due to drift in potential supply and changes in ambient pressure and temperature.

HFIT is a program for the analysis of diffraction diagrams containing overlapping peak clusters. Profile functions have been implemented to analyze synchrotron diffraction data. It is written un Turbo C++ for PC operations. The analysis is done by operator interaction. The analysis is done on sections of the diffractogram containing a maximum of 2048 data points or 100 diffraction maxima. Special care is taken for smoothing the data and for the subtraction of background.

The magnetic crystal disrortion of weakly ferromagnetic α-Fe2O3 was investigated by x-ray diffraction techniques. Here crystal distortion is taken as the temperature dependent changes of lattice constants and thermal expansion coefficients. Moreover, the oxygen position parameter and the carbon-oxygen distance of MnCO3 were determined.

The lattice constants and thermal expansion coefficients of α-Fe2O3 were measured from room temperature down to 243°K. The crystal distortion, as measured by the changes in lattice constants, thermal expansion coefficients and axial ratio, was found to be highly anisotropic. The co hexagonal lattice constant was influenced very slightly by magnetic distortion; it changed only by 0.01 percent between room temperature and the Morin temperature of 254°K. On the other hand, the ao lattice constant changes by 0.11 percent between room temperature and the Morin temperature. The thermal expansion coefficients of the lattice constants showed a similar contrast. The co coefficient was found to be independent of temperature from room temperature down to the Morin temperature. However, in the same temperature range, the ao coefficient showed an anomalous increase with decreasing temperature. In addition, the ao coefficient showed an infinite discontinuity at the Morin temperature.

The change in the axial ratio with temperature suggests that the net weak ferromagnetic moment of α-Fe2O3 reaches a maximum at 275°K.

The oxygen position parameter, x, in MnCO3 as determined from two reflections has a value of 0.2702 ± 0.001. The carbon-oxygen distance as calculated from the lattice constants and the oxygen position parameter is 1.29 ±0.002 Å. This value is another confirmation of the Pauling theory of the resonating carbonate structure.