Structural transformations of illite-smectite samples of hydrothermal genesis with increasing contents of illite layers were studied by X-ray powder diffraction. The samples were K-saturated and subjected to wetting and drying cycles to increase three-dimensional structural ordering. Diffraction profiles were analyzed with the help of a specially devised computer program based on the approximation of individual diffraction reflections by “bell-shaped” functions, with minimization of the differences between experimental and simulated profiles. The data indicate that the transformations of these illite-smectite samples were accompanied not only by variations in the proportion of illite and smectite layers and in the pattern of their alternation, but also by a change in structure within 2:1 layers.

The study of the fundamentals of the α → ω and β → ω phase transformations induced by high-pressure torsion (HPT) in Ti–Nb-based alloys is presented in the current work. Prior to HPT, three alloys with 5, 10, and 20 wt% of Nb were annealed in the temperature range of 700–540°C in order to obtain the (α + β)-phase state with a different amount of the β-phase. The samples were annealed for a long time in order to reach equilibrium Nb content in the α-solid solution. Scanning electron microscope (SEM), transmission electron microscopy, and X-ray diffraction techniques were used for the characterization of the microstructure evolution and phase transformations. HPT results in a strong grain refinement of the microstructure, a partial transformation of the α-phase into the ω-phase, and a complete β → ω phase transformation. Two kinds of the ω-phase with different chemical compositions were observed after HPT. The first one was formed from the β-phase, enriched in Nb, and the second one from the almost Nb-pure α-phase. It was found that the α → ω phase transformation depends on the Nb content in the initial α-Ti phase. The less the amount of Nb in the α-phase, the more the amount of the α-phase is transformed into the ω-phase.

Homogeneous and heterogeneous phase relationships in the alkali feldspars are reviewed, and behaviour diagrams developed. Al,Si ordering is almost certainly continuous and higher order in both albite and potassium feldspar and has been established reversibly or nearly so down to below 500°C in albite and possibly to ∼ 200°C in potassium feldspar. The degree of order in intermediate albite changes strongly over a range of ∼ 75–150°C depending on pressure, low albite being stable up to about 620–650°C and high albite above about 725°C at low pressure. Symmetry is broken at ∼ 980°C mainly by a cooperative shearing of the whole framework and not by Al,Si ordering alone; there is a thermal crossover near 700°C shearing being dominant above (high albite) and ordering dominant below (intermediate albite).

In potassium feldspar symmetry is broken by Al,Si ordering at a temperature of about 500°C The change in degree of order with respect to temperature has been followed easily and reversibly in sanidine from ∼ 1075 to ∼ 550°C and to a lesser extent in microcline from 450 to 200°C. Ordering rates in sanidine down to 500°C and ordering rates in microcline between 450 and 200°C are almost as fast as in albite. Ordering in sanidine at 500°C and below slows and then stops with the development of the tweed orthoclase domain texture. The tweed texture acts as a barrier to further order because the strain energy associated with the (incipient) twin domain texture balances or nearly balances the free energy decrease resulting from ordering. Ordering stops not because of the kinetics of Al,Si diffusion, but because the total driving force is very small or nil. Ordering can readily proceed to completion, with the formation of low microcline, only if the domain-texture barrier is overcome by processes involving fluids or strong external stresses. There is no barrier in albite.

The symmetry-breaking process in alkali feldspar changes with composition from mainly shearing in albite to ordering in potassium feldspar. Symmetry is broken equally at a compositional crossover (metastable with respect to exsolution) near Ab80-75 at low pressure and progressively displaced towards Or at higher pressures. Ordering in pure albite occurs by a (nearly) one-step path which progressively becomes two-step with substitution of Or. Diagrams showing the near-equilibrium variation of the order parameters at low pressure with composition and T are given, as well as two extreme phase and behaviour diagrams for complete coherent and complete incoherent (strain-free) relationships. These diagrams can be used to understand feldspar relationships and microtextures in hypersolvus and subsolvus rocks, the occurrence of orthoclase, and of intermediate and low microcline.

Networks of interacting twin walls form hierarchical, mesoscopic structures in minerals. The typical thickness of transformation twins at T ≪ TC is ˜3 nm and increases at T → TC as . The internal structure of twin walls is derived to be chiral in systems with coupled order parameters. The effect of wall bending is discussed.

Kinetic models and rate equations for polymorphic reconstructive phase transformations in polycrystalline aggregates are usually based on the assumptions that (a) the product phase nucleates on grain boundaries in the reactant phase and (b) growth rates of the product phase remain constant with time at fixed P-T. Recent observations of experimentally-induced transformations between (Mg,Fe)2SiO4 olivine (α) and its high pressure polymorphs, wadsleyite (β) and ringwoodite (γ), demonstrate that both these assumptions can be invalid, thus complicating the extrapolation of experimental kinetic data. Incoherent grain boundary nucleation appears to have dominated in most previous experimental studies of the α–β–γ transformations because of the use of starting materials with small (<10–20 µm) grain sizes. In contrast, when large (0.6 mm) olivine single crystals are reacted, intracrystalline nucleation of both β and γ becomes the dominant mechanism, particularly when the P-T conditions significantly overstep the equilibrium boundary. At pressures of 18–20 GPa intracrystalline nucleation involves (i) the formation of stacking faults in the olivine, (ii) coherent nucleation of γ-lamellae on these faults and (iii) nucleation of β on γ. In other experiments, intracrystalline nucleation is also observed during the β-γ transformation. In this case coherent nucleation of γ appears to occur at the intersections of dislocations with (010) stacking faults in β, which suggests that the nucleation rate is stress dependent. Reaction rims of β/γ form at the margins of the olivine single crystals by grain boundary nucleation. Measurements of growth distance as a function of time indicate that the growth rate of these rims decreases towards zero as transformation progresses. The growth rate slows because of the decrease in the magnitude of the Gibbs free energy (stored elastic strain energy) that develops as a consequence of the large volume change of transformation. On a longer time scale, growth kinetics may be controlled by viscoelastic relaxation.

Feldspar of composition Ca0.2Pb0.8Al2Si2O8 (PbF80An20) was synthesized from melt and subsequently isothermally annealed at T = 960°C for 4 days. In situ HT X-ray powder spectra of PbF80An20 feldspar, triclinic I1̄ at room temperature, were collected in the temperature range 20–800°C, and a displacive continuous ferroelastic transition to a I2/c monoclinic phase was observed. An analysis of the symmetry-required components of the spontaneous strain tensor reveals the second order character (β = 0.46 ± 0.02) of the transition with TC = 680 ± 15°C. A linear coupling was observed between the e4 and e6 components of the spontaneous strain. The transition is analogous to those observed, with increasing temperature, along the join An–SrF and in disordered Na-rich alkali feldspars. A comparison with Ca0.2Sr0.8Al2Si2O8 feldspar (TC = 680°C, McGuinn and Redfern, 1997) shows that PbF80An20 has a higher spontaneous strain (εs = 0.028 in PbF80An20vs 0.020 in Ca0.2Sr0.8Al2Si2O8) and a higher e4 component, possibly related to the higher distortion of the non-tetrahedral polyhedron in lead feldspar.

Materials chemistry was in its infancy when I started my independent research efforts in India after returning from the United States in the late 1950s. I have investigated phase transformations of TiO2 and CsCl, and also carried out defect calculations. While working on rare-earth oxides, I made TbO2 and PrO2 by a simple solution route; this is probably an early example of chimie douce (soft chemistry). I started working on transition-metal oxides by building simple instruments, including a thermobalance and furnaces. In 1987, we were able to fully characterize the first liquid N2 superconductor (YBa2Cu3O7) using a home-built AC susceptometer. Oxides have been of great interest to me because of the variety of phenomena exhibited by them. I have studied various aspects of transition-metal oxides, including metal-insulator transitions, colossal magnetoresistance, and multiferroics. The last two decades have included research on synthesis, characterization, and properties of various nanomaterials, and in particular, two-dimensional nanosheets (graphene and its inorganic analogues). Two-dimensional sheets and other nanomaterials have been covalently cross-linked to derive new materials with novel properties. Work on water splitting and reduction of CO2, besides using aliovalent anion substitution to generate novel inorganics (Zn2NF in place of ZnO), has also been conducted.

High-pressure research, whether static or dynamic, provides “windows” to novel states, transformations, and properties of highly compressed extended states of light elemental solids that may comprise the internal structures of giant planets and stars. These low-Z extended solids are extremely hard, have high energy density, and exhibit novel electronic and nonlinear optical properties—superior to other known materials at ambient conditions. These materials are often formed at formidably high pressures and are highly metastable at ambient conditions; only a few systems have been recovered at ambient conditions, limiting the materials to the realm of fundamental scientific discovery. An exciting new research area has recently emerged that aims to understand and ultimately allow for control of the stability, bonding, structure, and properties of low-Z extended solids. This article presents an overview of the basic principles that govern and control the pressure-induced chemistry in dense solids. This is aimed at identifying high energy density, low-Z extended solids that are amenable to up-scaled synthesis and stabilization at ambient conditions.

An attachment for commercial X-ray powder diffractometers is described. The device is made of four different parts that are largely independent of each other, and can be freely interchanged or replaced, and aligned independently. It can be home-built, or modified, with high flexibility according to user requirements, and has been tested on different problems concerning high-temperature phase transitions and solid-state reactions up to 1200 °C under vacuum, under inert gas or under various oxygen partial pressures. Examples are given of possible designs of the various parts.

Effects of Ti and Si particle sizes on phase transformations of Ti–Si–Cu system were explored through differential thermal analysis (DTA), x-ray diffraction (XRD), and field emission scanning electron microscope (FESEM). For Ti[15]Si[15]Cu[45] system, fine Ti easily dissolves into Si–Cu liquid to form Ti–Si–Cu liquid at ∼795 °C, which further participates into the reaction of β-Ti and Si to yield abundant quantity of Ti5Si3 at ∼917 °C. For Ti[150]Si[15]Cu[45] system, nonetheless, the reaction of coarse Ti with Si–Cu liquid involves more difficulty in forming the ternary liquid , which is the causal factor for the delay in the formation of Ti5Si3 to ∼948 °C. For Ti[15]Si[150]Cu[45] system, coarse Si results in the formation of insufficient Si–Cu liquid initially, whereas Ti–Cu liquid forms at ∼960 °C instead, which further reacts with coarse Si to form Ti–Si–Cu liquid, and then Ti5Si3is precipitated from the liquid.

The effects of austenitizing temperature and cooling rate on the microstructures and textures produced by phase transformations in high strength hot rolled Fe-C-Mn steel plates are investigated using orientation imagining microscopy. Samples machined from the plates are austenitized at temperatures between 820-950°C during 30 minutes and quenched in either iced-water, water or oil. Finally, the quenched samples are tempered at 450°C during 30 minutes. Characterization of microstructure and textures produced by these heat treatments was performed by conventional metallography using a reflected light microscope and orientation imaging microscopy using backscattered-electron diffraction patterns in a scanning electron microscope with thermo-ionic electron source.

The results show that the microstructure and texture produced under a given combination of austenitizing temperature and cooling rate are strongly dependent on the mechanism involved in the phase transformation of the austenite (γ). High austenitizing temperatures and cooling rates promote martensitic transformation and development of textures containing significant volume fractions of Br, Cu, transformed-Cu and transformed-Br orientation components. In this case, the austenite and martensite phases are clearly related through the Kurdjumov-Sachs orientation relationship. In contrast, low temperatures and low cooling rates result in a complex mixture of transformation products, such as polygonal ferrite, Widmanstäten ferrite, martensite, bainite and pearlite. The textures formed under these conditions are quite different and contain significant volume fractions of cube, rotated-cube, Goss and rotated-Goss components, following the Bain orientation relationship.

This work concerns the use of parallel electron energy loss spectroscopy (PEELS) to investigate the detection, distribution, and quantification of carbon in various steel microstructures generated by rapid cooling rates or by isothermal transformation. The feasibility of detecting C in steels containing very small amounts of carbon was first examined by calculating the minimum detectable mass fraction for a variety of binary Fe-C alloy specimen thicknesses and microscope conditions. These theoretical studies indicated that the detection of carbon in steel microconstituents containing about 0.01 wt.% (or even less) was easily possible with an analytical transmission electron microscope equipped with a LaB6 emitter and a PEEL spectrometer. These theoretical calculations seemed to be reasonable, as it proved possible to make a quantitative PEELS study of the partitioning between the microconstituents ferrite, retained austenite, and martensite found in an ultralow carbon (0.03 wt.%) steel weld metal provided care was taken to avoid hydrocarbon contamination. Studies of both carbon and molybdenum segregation to ferrite/martensite interfaces in an isothermally transformed Fe-C-Mo alloy were also carried out in order to investigate the nature of the “solute drag” effect in this alloy system.

The objective of the present work is the in-situ study of the transformation of small oxide precipitates in a metal matrix by conventional and high-resolution transmission electron microscopy (HRTEM). As an example the reduction of Mn3O4 into MnO for nano-sized oxide precipitates in a silver matrix was studied in detail. A convenient method for monitoring the reduction process is shown for a large number of precipitates simultaneously. It is based on two-beam dark-field images showing distinct Moiré patterns for the MnO and the various types of Mn3O4 precipitates embedded within an Ag matrix. A controlling factor of the transformation kinetics appeared to be the rate in which the system can relax the strains due to the accompanying volume reduction of the precipitates. Other interesting aspects of the Mn3O4 to MnO transformation scrutinized and explained were the shape change of the precipitates upon reduction and the fact that mixed Mn3O4/MnO precipitates were only detected within a small temperature/time interval. Ostwald ripening of the MnO precipitates was observed as well.

This study discusses the use of in situ high-resolution transmission electron microscropy (HRTEM) techniques to determine the structure, composition, and interphase boundary dynamics during phase transformations at the atomic level. Three main in situ HRTEM techniques are described: (1) in situ HRTEM dynamic studies that are performed on the same precipitate plates from different viewing directions to determine the three-dimensional structure of the interfaces; (2) in situ compositional mapping of precipitate interfaces obtained by energy-filtering TEM experiments at temperature in a HRTEM, and (3) real-time HRTEM image simulations that are being created for comparison with and interpretation of experimental in situ HRTEM dynamic observations. The results from these studies demonstrate that it is possible to understand the mechanisms and kinetics of interphase boundary motion at the atomic level.