The thermal expansion behavior of pure, Ge-doped and Li-doped hexagonal cordierites with respective compositions: 2MgO 2Al2O3 5Si02 2Mg0 2Al2O3 4Si02 Ge02) and 2MgO (2+x)AL203 (5-2x)Si02 xLi20 with x = .174, was investigated using time-of-flight neutron powder diffraction at temperatures from 22 to 750°C in vacuum. The data were refined in space group P6/mcc using the Rietveld method. The lattice thermal expansion curves of all 3 samples were quite similar. The negative axis expansion is associated with (1)displacement of the T2 cations generally toward the axis channels and (2) changes in the distortion of the coupled T1/M tetrahedra/octahedra in the structure. Both contributions were present in all 3 samples but the first was more dominant in the Ge doped sample. The nature and origin of the distortions in T1 and M are discussed.

A series of computer programs have been written (collectively called XRDQUAL) for automated identification of XRD patterns. The algorithms used in XRDQUAI, have been selected for maximum compatibility with computerbased calculations and decisions, XRDQUAI relies heavily on probabilistic logic and calculations. The overall sequence used can be divided into three general steps.

High precision composition-depth profiles can be determined quickly using a recent development. This method requires that noncompositional broadening arising from the instrument, crystal defects, and the radiation source be removed from the diffraction pattern before calculating the composition-depth profile. Effective deconvolution techniques, profiling theory, methodology of profiling, and the effect of residual noncompositional broadening on the profile are discussed. Examples include statistical analyses of error in the profile due to random counting errors and variance in the lattice parameter calibration.

For phase analysis of small amounts of material in an x-ray powder diffractometer the sample is often spread on a sample mounting plate or support plate. Different types of plates on which thin samples can be mounted are:

• - silver membrane filters

• - metal or other polycrystalline plates

• - polymer membrane filters, for example PVC, polycarbonate, cellulose nitrate

• - glass slides

• - single crystals; cut so that no diffraction lines occur.

Filters are often used to collect environmental dust; these samples can be analysed “as received,” Glass slides are inexpensive, flat, and readily available. Polycrystalline filters and plates have the disadvantage of possible line overlap with lines of the sample material (refer to figure 1), Glass plates or polymer filters have the high and curved background due to amorphous scatter as shown in figure 2.

A quantitative X-ray diffraction method has been developed for rapid determination of the crystalline phases present in by-product filter cakes from wet-process phosphoric acid manufacture. A new technique to reduce preferred orientation of the crystallites by removing the top layer of the X-ray samples with adhesive tape is described, statistical analysis of synthetic sample mixtures of CaS04.2H2O, CaSO4 · 0.5H20, CaSo4, and α-Si02 indicates that the calcium sulfate phases present in typical filter cakes can be determined with an accuracy of about 3% at the 95% confidence level; quartz can be determined at about 14%. The method has been applied to the analysis of 10 filter-cake samples from an experimental hemihydrate plant. The results are in good agreement with data from X-ray fluorescence and chemical analyses

Clay minerals are one of the most difficult classes of materials to analyze by x-ray powder diffraction, yet powder diffraction is the only technique which can yield the important crystallographic information necessary to identify and classify the minerals. The importance of clay minerals in industry and in the studies of rocks, due to their chemical properties and sensitivity to geological changes, often requires the analyses of large numbers of samples in short periods of time. Such sample throughput requires computerized analysis* Because definitive, meaningful d-I data are difficult to obtain from the broad diffraction peaks obtained from most clay samples, this problem has been approached by using the whole diffraction, trace as the basis of a computerized analytical scheme.

As part of a continuing project dealing with evaluation, testing, and preparation of new high quality X-ray powder diffraction standards for phosphate and arsenate minerals, new X-ray and supporting data for minyulite, KAl2(PO4)2(0H,F).4H20, have been obtained and Interpreted with the aid of a calculated powder pattern.

Phosphorite is a sedimentary rock with a high enough content of phosphate minerals to bo of economic Interest. Most phosphorites are composed predominantly of m1crocrystall1no to cryptocrystalline carbonate fluorapatlte thenceforth In this report referred to simply by the mineral group name apatite). Florida produces roughly 1/3 of the world's supply of phosphate rock, most of which is used 1n the fe rtiliz e r Industry.

Long term continuation of phosphorite mining In Florida will require exploitation of the extensive hlgh-magneslum phosphorite deposits south of the present mining d istrict 1n central Florida, and this will require new technology In order to produce beneficlated concentrates with less than 1% MgO, a limit Imposed by fe r tiliz e r processing technology. In order to develop benefication methods applicable to these ores, it is essential to know how Mg occurs in phosphorites. Dolomite, CaMg(C03)2, is the chief host of Mg In phosphorites from Florida. Magnesium may also be present, however, as a substituent In apatite (the chief phosphate.mineral in these deposits), as a minor substituent 1n calcite (CaCO3), in certain clay minerals (particularly palygorskite and to a lesser extent in some smectites), and/or in organic matter within the apatite particles.

The instrumentation developed for poly crystalline diffractometry using the storage ring at the Stanford Synchrotron Radiation Laboratory is described. A pair of automated vertical scan diffractometers was used for a Si (111) channel monochromator and the powder specimens. The parallel beam powder diffraction was defined by horizontal parallel slits which had several times higher intensity than a receiving slit at the same resolution. The patterns were obtained with 2:1 scanning with’ a selected monochromatic beam, and an energy dispersive diffraction method in which the monochromator is step-scanned, and the specimen and scintillation counter are fixed. Both methods use the same instrumentation.

The Debye microdiffractometer, a recently developed instrument, enables diffraction patterns to be obtained from very small samples or from selected areas of samples. The instrument discussed here, a Rigaku Model 2870E1 microdiffractometer, features an annular sealed proportional counter which is moved along the primary beam axis for two theta scanning, as seen in Figure 1, This configuration allows most of a Debye cone to be detected, making the use of a primary bean typically less than 100 microns in diameter practical. An integral microscope facilitates sample positioning for diffraction from selected areas of a specimen. The capability of the Instrument is apparent from the diffractometer traces of Figure 2, in which intermetallie compounds in a braze joint are identified.

The adsorption of liquids in 2eolites has been a widely studied phenomenon, and with the development of ZSM-5, considerable work has been carried out on this zeolite, However, few articles have been published dealing with changes in the X-ray diffraction patterns when the zeolite pores contain adsorbed molecules. The purpose of this paper is to report changes in the X-ray diffraction pattern of ZSM-5 after mixing it with various organic solvents.

This work began after studies of both deactivated and partially deactivated ZSM-5 catalysts showed that their X-ray diffraction patterns changed in intensities and peak positions after use in microreactor studies. If coke or hydrocarbons were causing the above changes, as postulated, would hydrocarbons adsorbed in ZSM-5 produce the same changes? Simpson and Steinfink showed that the low-angle lines of faujasite decreased in intensity after the adsorption of m-dichlorobenzene.

The residual stress left on the fracture surface is one of the important parameters in X-ray fractography and has been used to analyse fracture mechanisms in fracture toughness, stress corrosion cracking and fatigue tests especially of high strength steels.

In this study, the distribution of residual stress near fatigue fracture surfaces made in air and in 3.5% NaCl solution was measured by the X-ray diffraction method. The effect of aqueous environment on the plastic deformation near fatigue fracture surfaces was discussed on the basis of the residual stress distribution.

Superplastic deformation involves the controlled processing of materials in order to produce extensive deformation, the longest recorded elongation being nearly 5000%. Components of very complex shape can be formed in this way, thus offering substantial savings over the use of conventional manufacturing routes. Typically, these savings can be 50% in cost (through reduced man-hours required for component manufacture, from improved structural efficiency and from reduced material costs) and 25% in weight (through more efficient use of materials and the reduced requirement for joints and fasteners).

The success of the superplastic process will depend, in large part, on achieving an adequate balance between the deformation input and the relief of work hardening by thermally activated relaxation processes. An attempt has therefore been made to establish whether the residual strain in superplastically deformed materials is related to deformation, parameters, and if so, to interpret this strain data in terms of the mechanisms of superplasticity.

The physical and mechanical properties of many industrially important polymers are profoundly influenced by their degree of crystallinity; such properties include flex modulus, tensile strength, percent elongation, and impact strength. Commonly used polymers influenced by their crystallinity level include polyethlene, polypropylene, polyesters, and nylons. Many of these materials are above their glass transition temperature at room temperature and would be useless were it not for their crystalline phase which typically has a melting point far above room temperature. The crystalline ‘ regions (domains) in these materials are frequently very small, typically in the nanometer range in diameter. These crystalline domains act as reinforcing fillers (in somewhat the same manner as carbon black In rubber) and give strength to the polymer.

Interest in advanced thermoplastic composites for use in high performance structures stems from their order of magnitude improvement in fracture toughness and delamination resistance over epoxy based composites, their strong solvent resistance, and the possibility of dramatically lower fabrication costs through processing flexibility. The chemical and mechanical properties of semicrystalline thermoplastics depend on the morphology of the material, such as the crystallinity content and spherulite size. We describe here the use of x-ray diffraction to characterize the degree of crystallinity of the polyetheretherketone-graphite composite system, a leading thermoplastic candidate for use in aerospace vehicles. In reflection, diffraction from the microcrystalline graphite fibers dominates the scattered signal and must be adequately accounted for. The technique is useful on large samples and for quality control. In transmission, the graphite signal is weak, thus simplifying data analysis; however, sample thickness must be limited.

The transition temperatures of solid-solid phase changes in selected polyalcohols, “plastic crystals,” can be adjusted by using interstitial and substitutional dopants. An investigation is under way of the structural changes in these during heating and cooling, and of the thermodynamic properties such as the transition, temperatures and enthalpy changes, as a function of the percent of dopant. The purpose of the investigation is to find and evaluate materials having potential value In thermal storage applications. Dopants for pentaerythritol discussed in this report are trimethylolpropane (TMP), ammonia, boron trifluoride, pentaglycerine (PG) and neopentylglycol (NPG).

Over the past 25 years, numerous studies of polymers utilizing both X-ray diffraction (XRD) and differential scanning calorimetry (DSC) have been reported in the literature. These studies have suffered because the two techniques must be performed on separate samples and under conditions that are often dissimilar. By combining the two techniques into one instrument, typical problems encountered with variations in sample preparation and thermal and atmospheric environment are eliminated. This is quite important in the study of polymers since one must match not only temperatures between the two techniques, but also heating rates as well. Matched thermal conditions are necessary because polymer properties such as crystallinity and crystallite size depend on both the temperature and thermal history of the sample under study.

The analysis of multi-phase pharmaceuticals, particularly when similar structures are involved (i.e. polymorphs, salts or hydrates), can often be a difficult task. Historically, x-ray powder diffraction (XRD) and differential scanning calorimetry (DSC) have been utilized to study pharmaceutical samples. Relative to other materials, diffraction data for pharmaceuticals are often complex due to the large number of diffraction maxima caused by the size of the molecule and/or the molecular symmetry. Multi-phase mixtures tend to have a large number of overlapping peaks which can hinder the difftactionist's ability to identify phases and interpret the data. When similar structures are analyzed calorimetrically, their thermal events may severely overlap (as will be shown), preventing accurate interpretation of the data. In addition there are several types of thermal events which may not be related to structural transitions. A common one in pharmaceuticals is the loss of solvent or absorbed (versus molecular) water.

A high-temperature crystal growth experiment produced discrete singlecrystal products of Allr and IrSi. The preparation, and examination of these phases is described within. This project is part of a materials compatibility study relating to radioisotopic heat sources. These heat sources are comprised of a PuO2 fuel pellet encapsulated in an Ir alloy containment shell. Thorium is introduced as an additive within the Ir to maintain ductility. Si and P are picked up inadvertently in the fuel processing. The compatibility of the heat sources with Al is of interest because of potential interactions with the Al alloy hardware associated with the heat source environment.