Phase transformations, types

Research. A significant impact on research at high pressure has come about with the use of gem quaHty diamonds as Bridgman-type anvils in a smaU compact high pressure device (40—42). With this type of apparatus, pressures greater than those at the center of the earth (360 GPa = 3.6 Mbars) have been reached, and phase transformations of many materials have been studied. Because of the x-ray transparency of diamond, it is possible to determine the stmcture of the phases under pressure. Because of the strenuous environment, crystals selected for this appHcation have to be of very high quaHty. 

Ca3(BN2)2 is readily formed when (distilled) calcium metal is melted in the presence of (layer-type) boron nitride. This reaction provides some insight on how alkaline-earth metals like calcium may act as a catalyst in the phase transformation of layered a-BN into its cubic modification. Instead of metals, nowadays alkaline-earth (Ca, Sr, Ba) nitridoborates can be used as a flux catalyst in high-pressure and high-temperature transformation reactions to produce cubic boron nitride [15]. 

The phase transformation relationships for the solvatomorphs of naproxen sodium have been reported [71], The dihydrate phase is obtained upon crystallization from water, and a monohydrate phase could be prepared by the dehydration of the dihydrate phase in a desiccator (RH = 0%) for two days. The anhydrate phase could be obtained from either the monohydrate or dihydrate by drying the substance in an oven at 120 °C for two hours. Thermal analysis data was used to demonstrate the existence of two types of water in the dihydrate phase, and that each could be removed at a characteristic temperature. 

Differential thermal analysis (DTA) consists of the monitoring of the differences in temperature existing between a solid sample and a reference as a function of temperature. Differences in temperature between the sample and reference are observed when a process takes place that requires a finite heat of reaction. Typical solid state changes of this type include phase transformations, structural conversions, decomposition reactions, and desolvation processes. These processes may require either the input or release of energy in the form of heat, which in turn translates into events that affect the temperature of the sample relative to a nonreactive reference. 

Notice, moreover, that one face-centred cubic cell of atoms X in which all the interstices are occupied (the octahedral by X and the tetrahedral by Z atoms) is equivalent to a block of 8 XZ, CsCl-type cells (see Fig. 3.31). This relationship (and others with other structures such as Li3Bi and MnCu2Al) should be kept in mind when considering, for instance, phase transformations occurring in ordering processes. 

Metastable crystalline phases frequently crystallise to a more stable phase in accordance with Ostwald s rule of stages, and the more common types of phase transformation that occur in crystallising and precipitating systems include those between polymorphs and solvates. Transformations can occur in the solid state, particularly at temperatures near the melting point of the crystalline solid, and because of the intervention of a solvent. A stable phase has a lower solubility than a metastable phase, as indicated by the solubility curves in Figures 15.7a and 15.7/ for enantiotropic and monotropic systems respectively and,... 

Mitrovic and Knezic (1979) also prepared ultrafiltration and reverse osmosis membranes by this technique. Their membranes were etched in 5% oxalic acid. The membranes had pores of the order of 100 nm, but only about 1.5 nm in the residual barrier layer (layer AB in Figure 2.15). The pores in the barrier layer were unstable in water and the permeability decreased during the experiments. Complete dehydration of alumina or phase transformation to a-alumina was necessary to stabilize the pore structure. The resulting membranes were found unsuitable for reverse osmosis but suitable for ultrafiltration after removing the barrier layer. Beside reverse osmosis and ultrafiltration measurements, some gas permeability data have also been reported on this type of membranes (Itaya et al. 1984). The water flux through a 50/im thick membrane is about 0.2mL/cm -h with a N2 flow about 6cmVcm -min-bar. The gas transport through the membrane was due to Knudsen diffusion mechanism, which is inversely proportional to the square root of molecular mass. 

Under normal conditions, matter can appear in three forms of aggregation solid, liquid, and gas. These forms or physical states are consequences of various interactions between the atomic or molecular species. The interactions are governed by internal chemical properties (various types of bonding) and external physical properties (temperature and pressure). Most small molecules can be transformed between these states (e.g., H2O into ice, water, and steam) by a moderate change of temperature and/or pressure. Between these physical states— or phases—there is a sharp boundary phase boundary), which makes it possible to separate the phases—for example, ice may be removed from water by filtration. The most fundamental of chemical properties is the ability to undergo such phase transformations, the use of which allows the simplest method for isolation of pure compounds from natural materials. 

It is commonplace to assume a form of the Gibbs energy function which excludes the pressure variable for solid-state phase transformations, as the magnitude of the PAV term is small at atmospheric pressures. This is of course not the case in geological systems, or if laboratory experiments are deliberately geared to high-pressure environments. Klement and Jayaraman (1966) provide a good review of the data available at the time when some of the earliest CALPHAD-type calculations were made (Kaufman and Bernstein 1970, Kaufman 1974). Much work was also carried out on specific alloy systems such as Fe-C (Hilliard 1963) and the Tl-In system (Meyerhoff and Smith 1963). 

Ideally, a phase transformation should be investigated using a combination of techniques which enable changes in composition, structure, surface area, morphology and porosity of the solid phases and in the composition of the solution to be monitored, together with the reaction kinetics. This type of comprehensive investigation is rare for iron oxide interconversions in most cases only one or two of the above aspects of the transformation have been considered. 

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