Interpretation of X-ray Powder Diffraction Patterns . By H. Lipson and H. Steeple. Pp. viii + 335 + 3 plates. (Mac-millan: London; St Martins Press: New York, May 1970.) £4.

X-Ray Diffraction

A set of general guidelines for structure refinement using the Rietveld (whole-profile) method has been formulated by the International Union of Crystallography Commission on Powder Diffraction. The practical rather than the theoretical aspects of each step in a typical Rietveld refinement are discussed with a view to guiding newcomers in the field. The focus is on X-ray powder diffraction data collected on a laboratory instrument, but features specific to data from neutron (both constant-wavelength and time-of-flight) and synchrotron radiation sources are also addressed. The topics covered include (i) data collection, (ii) background contribution, (iii) peak-shape function, (iv) refinement of profile parameters, (v) Fourier analysis with powder diffraction data, (vi) refinement of structural parameters, (vii) use of geometric restraints, (viii) calculation of e.s.d.'s, (ix) interpretation of R values and (x) some common problems and possible solutions.

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Rietveld refinement guidelines

I. Introduction. Background. Focus of the review. Review procedure and results. The NEA-TDB data base system. Presentation of the selected data. II. Standards and Conventions. Symbols, terminology and nomenclature. Units and conversion factors. Standard and reference conditions. Fundamental physical constants. III. Selected Uranium Data. IV. Selected Auxiliary Data. V. Discussion of Data Selection. Elemental uranium. Aqua ions. Oxide, hydride and hydroxide species. VI. Discussion of Auxiliary Data Selection. Reference list. Authors list. Formula list. Discussion of selected references. Ionic strength corrections. Assigned uncertainties. The estimation of entropies.

Chemical thermodynamics of uranium

This is the first targeted review of the synthesis – microstructure – electrochemical performance relations of MoS2 – based anodes and cathodes for secondary lithium ion batteries (LIBs). Molybdenum disulfide is a highly promising material for LIBs that compensates for its intermediate insertion voltage (∼2 V vs. Li/Li+) with a high reversible capacity (up to 1290 mA h g−1) and an excellent rate capability (e.g. 554 mA h g−1 after 20 cycles at 50 C). Several themes emerge when surveying the scientific literature on the subject: first, we argue that there is excellent data to show that truly nanoscale structures, which often contain a nanodispersed carbon phase, consistently possess superior charge storage capacity and cycling performance. We provide several hypotheses regarding why the measured capacities in such architectures are well above the theoretical predictions of the known MoS2 intercalation and conversion reactions. Second, we highlight the growing microstructural and electrochemical evidence that the layered MoS2 structure does not survive past the initial lithiation cycle, and that subsequently the electrochemically active material is actually elemental sulfur. Third, we show that certain synthesis techniques are consistently demonstrated to be the most promising for battery applications, and describe these in detail. Fourth, we present our selection of synthesis methods that we believe to have a high potential for creating improved MoS2 LIB electrodes, but are yet to be tried.

Lithium ion battery applications of molybdenum disulfide (MoS2) nanocomposites

The elements occurring in high-level nuclear reactor wastes can be safely immobilised by incorporating them within the crystal lattices of the constituent minerals of a synthetic rock (SYNROC). The preferred form of SYNROC can accept up to 20% of high level waste calcine to form dilute solid solutions. The constituent minerals, or close structural analogues, have survived in a wide range of geochemical environments for periods of 20–2,000 Myr whilst immobilising the same elements present in nuclear wastes. SYNROC is unaffected by leaching for 24 h in pure water or 10 wt % NaCl solution at high temperatures and pressure whereas borosilicate glasses completely decompose in a few hours in much less severe hydrothermal conditions. The combination of these leaching results with the geological evidence of long-term stability indicates that SYNROC would be vastly superior to glass in its capacity to safely immobilise nuclear wastes, when buried in a suitable geological repository. A dense, compact, mechanically strong form of SYNROC suitable for geological disposal can be produced by a process as economical as that which incorporates radwaste in borosilicate glasses.

Immobilisation of high level nuclear reactor wastes in SYNROC

Calculated X-ray Powder Patterns for Silicate Minerals

Cristobalite and tridymite are distinct forms of crystalline silica which, along with quartz, are encountered in industrial operations and industrial products. Because the International Agency for Research on Cancer has designated “crystalline silica” as an IARC Group 2A (probable carcinogen) and quartz and cristobalite as a Group 1 (carcinogen), it is important to properly identify and quantify the silica phase in all materials used in production and encountered in products. Opal is a form of hydrated silica which is also encountered in industry. Although some forms of opal mimic cristobalite and tridymite, they are not truly crystalline. The term “silica” in the industrial sense is used to mean any material whose composition is SiO2 whether it is crystalline or noncrystalline. Some people also consider silica to include hydrated SiO2. There are many forms of SiO2 which have both long-range and short-range order and are recognized as crystalline phases among which are quartz, cristobalite, and tridymite. The hydrated silicas, on the other hand, pose an enigma. Only a few forms show sufficient long-range and short-range order to be considered crystalline. The mineral silhydrite is an example. Opal in all its forms lacks sufficient order to be considered crystalline. Even opal-C, which produces a X-ray pattern similar to the diffraction pattern of cristobalite, lacks not only sufficient order to be considered crystalline but also contains water in the structural make-up. This paper discusses a classification and nomenclature for these forms which is critical to proper regulation. It also reviews the recent literature on tridymite, cristobalite, and opal, and provides an extensive bibliography. Modern studies have shown that opal-A is disordered, but opal-CT and opal-C contain ordered domains that mimic stacked sequences of cristobalite and tridymite sheets such that X-ray patterns show features similar to the crystalline cristobalite and tridymite. There is debate on whether the ordered regions have lost the water that characterizes the opals. In fact, heating studies have shown that all opals show changes on heating characteristic of materials that lose water in the process. The TEM evidence showing domains in the range 10–30 nm in a matrix of disordered opal suggest that the proper term for this system is paracrystalline analogous to inorganic and organic polymers.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0885715600009696

Opal, cristobalite, and tridymite: Noncrystallinity versus crystallinity, nomenclature of the silica minerals and bibliography

The aim of any diffraction experiment is to obtain reproducible data of high accuracy and precision so that the data can be correctly interpreted and analyzed. Various methods of sample preparation have been devised so that reproducibility, precision and accuracy can be obtained. The success of a diffraction experiment will often depend on the correct choice of preparation method for the sample being analyzed and for the instrument being used in the analysis.A diffraction pattern contains three types of useful information: the positions of the diffraction maxima, the peak intensities, and the intensity distribution as a function of diffraction angle. This information can be used to identify and quantify the contents of the sample, as well as to calculate the material's crystallite size and distribution, crystallinity, and stress and strain. The ideal preparation for a given experiment depends largely on information desired.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/E959F6D80796DB1D5DFFEA55C7C8E844/S0885715600011581a.pdf/div-class-title-jcpds-international-centre-for-diffraction-data-sample-preparation-methods-in-x-ray-powder-diffraction-div.pdf

JCPDS — International Centre for Diffraction Data Sample Preparation Methods in X-Ray Powder Diffraction

A new quantitative X-ray powder diffraction (QXRPD) method has been developed to analyze polyphase crystalline mixtures. The unique approach employed in this method is the utilization of the full diffraction pattern of a mixture and its reconstruction as a weighted sum of diffraction patterns of the component phases. To facilitate the use of the new method, menu-driven interactive computer programs with graphics have been developed for the VAX series of computers. The analyst builds a reference database of component diffraction patterns, corrects the patterns for background effects, and determines the appropriate reference intensity ratios. This database is used to calculate the weight fraction of each phase in a mixture by fitting its diffraction pattern with a least-squares best-fit weighted sum of selected database reference patterns.The new QXRPD method was evaluated using oxides found in ceramics, corrosion products, and other materials encountered in the laboratory. Experimental procedures have been developed for sample preparation and data collection for reference samples and unknowns. Prepared mixtures have been used to demonstrate the very good results that can be obtained with this method.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0885715600012409

Quantitative X-Ray Powder Diffraction Method Using the Full Diffraction Pattern

DISSOLUTION and transport of radionuclides by ground-water are the main threats to the effective isolation of radioactive wastes by burial in deep geological formations. Calcine and glass are two solid forms which have been studied in this way for radioactive waste disposal. Long term release rates, based on extractions of radionuclides by simulated groundwater at 25 °C and atmospheric pressure, are projected to be very low from borosilicate glass, the most favourable candidate waste form. We present here evidence that contact with pressurised water at the 200–400 °C temperatures that could occur near the waste in the early years of storage rapidly alters the borosilicate glass and promotes interactions between waste and both shale and basalt repository wall rocks. The specific examples are the formation of a uranyl silicate (weeksite) directly from hydrothermal alteration of the glass and the reaction of caesium and sodium from calcine with aluminosilicates in basalt and shale to form the caesium sodium aluminosilicate, pollucite.

Deane K. Smith

Papers

Calculated X-ray Powder Patterns for Silicate Minerals

Opal, cristobalite, and tridymite: Noncrystallinity versus crystallinity, nomenclature of the silica minerals and bibliography

JCPDS — International Centre for Diffraction Data Sample Preparation Methods in X-Ray Powder Diffraction

Quantitative X-Ray Powder Diffraction Method Using the Full Diffraction Pattern

Interactions between nuclear waste and surrounding rock