Solid state transformations

Driving forces for solid-state phase transformations are about one-third of those for solidification. This is just what we would expect the difference in order between two crystalline phases will be less than the difference in order between a liquid and a crystal the entropy change in the solid-state transformation will be less than in solidification and AH/T will be less than AH/T . 

Most metals in commercial use contain quite large quantities of impurity (e.g. as alloying elements, or in contaminated scrap). Solid-state transformations in impure metals are usually limited by the diffusion of these impurities through the bulk of the material. 

In the case of selective oxidation catalysis, the use of spectroscopy has provided critical Information about surface and solid state mechanisms. As Is well known( ), some of the most effective catalysts for selective oxidation of olefins are those based on bismuth molybdates. The Industrial significance of these catalysts stems from their unique ability to oxidize propylene and ammonia to acrylonitrile at high selectivity. Several key features of the surface mechanism of this catalytic process have recently been descrlbed(3-A). However, an understanding of the solid state transformations which occur on the catalyst surface or within the catalyst bulk under reaction conditions can only be deduced Indirectly by traditional probe molecule approaches. Direct Insights Into catalyst dynamics require the use of techniques which can probe the solid directly, preferably under reaction conditions. We have, therefore, examined several catalytlcally Important surface and solid state processes of bismuth molybdate based catalysts using multiple spectroscopic techniques Including Raman and Infrared spectroscopies, x-ray and neutron diffraction, and photoelectron spectroscopy. 

Redox Processes and Solid State Transformations In Bismuth Molybdates... 

Even when complete miscibility is possible in the solid state, ordered structures will be favored at suitable compositions if the atoms have different sizes. For example copper atoms are smaller than gold atoms (radii 127.8 and 144.2 pm) copper and gold form mixed crystals of any composition, but ordered alloys are formed with the compositions AuCu and AuCu3 (Fig. 15.1). The degree of order is temperature dependent with increasing temperatures the order decreases continuously. Therefore, there is no phase transition with a well-defined transition temperature. This can be seen in the temperature dependence of the specific heat (Fig. 15.2). Because of the form of the curve, this kind of order-disorder transformation is also called a A type transformation it is observed in many solid-state transformations. 

Balema, V.P., K.W. Dennis, and V.K. Pecharsky, Rapid solid-state transformation of tetrahedral [A1H4] into octahedral [A1H6]j in lithium aluminohydride, Chem. Commun., 17, 1665, 2000. 

Balema, V.P., J.W. Wiench, K.W.M. Dennis, M. Pruski, and V.K. Pecharsky, Titanium catalyzed solid-state transformations in LiAlH4 during high-energy ball-milling, /. Alloys Compd., 329, 108, 2001. 

Further examples of how HREM portrays at near atomic scale the mode of solid-state transformation that takes place in solids... 

The diagrams that will be mainly considered are those concerning the behaviour of the alloys in the liquid and solid states that is, melting and solid-state transformation diagrams. A number of different diagram types can be defined and classified on the basis of the different mutual solubility of the components (in the liquid and in the solid state with the formation of more or less extended liquid and/or solid solutions) and of their reactivity, resulting in the formation of various, so-called intermediate phases . 

Figure 2.11. The Au-Si diagram is an example of a simple eutectic system with complete mutual solubility in the liquid state and no (or negligible) solubility in the solid state at a temperature of 363°C the liquid having the composition of 18.6 at.% Si solidifies with the simultaneous crystallization of the practically pure gold and silicon mechanically mixed. In the Cr-U system a slightly more complex situation due to the solid-state transformations of uranium is shown.

A solid-state transformation that involves an electrocyclic ring opening is described by Bellus and his co-workers (78). They found that when 1,2,5,6-tetracyano-anri-tricyclo-[4.2.0. O Joctane (33) is heated in the crystal, only 1,2,5,6,-tetracyano-(Z,E)-cycloocta-l, 5-diene (34a) is formed, as expected on... 

As described above, most solid-state reactions are heterogeneous, in the sense that reactant and product are in different solid phases. In many of these, product crystals first appear as nuclei that grow at the expense of the parent crystal. On the other hand, there are some solid-state reactions that are not accompanied by a phase change and for which, therefore, analogy with a solid-state transformation is not plausible. Such reactions are of particular interest in several respects They make possible conversion of a single crystal of reactant to a single crystal of product they enable study, for example by X-ray diffraction, of the structures of the parent and product molecules as functions of the degree of conversion in more or less constant environments and one can elucidate from them the constraints that the parent crystal imposes both on the reaction pathway and on the conformation of the product. It is in connection with the latter that this subject is of particular interest in the present context. This class of processes has been discussed by Thomas (183). 

The solvent-mediated transformation of o -L-glutamic acid to the S-form was quantitatively monitored over time at a series of temperatures [248]. The calibration model was built using dry physical mixtures of the forms, but still successfully predicted composition in suspension samples. Cornel et al. monitored the solute concentration and the solvent-mediated solid-state transformation of L-glutamic acid simultaneously [249]. However, the authors note that multivariate analysis was required to achieve this. Additionally, they caution that it was necessary to experimentally evaluate the effect of solid composition, suspension density, solute concentration, particle size and distribution, particle shape, and temperature on the Raman spectra during calibration in order to have confidence in the quantitative results. This can be a substantial experi-... 

We now distinguish solid state transformations as first-order transitions or lambda transitions. The latter class groups all high-order solid state transformations (second-, third-, and fourth-order transformations see Denbigh, 1971 for exhaustive treatment). We define first-order transitions as all solid state transformations that involve discontinuities in enthalpy, entropy, volume, heat capacity, compressibility, and thermal expansion at the transition point. These transitions require substantial modifications in atomic bonding. An example of first-order transition is the solid state transformation (see also figure 2.6)... 

Here we are concerned with changes in the solid structure of the waste form, such as devitrification and phase separation in waste-containing glasses. Thus we need to understand the mechanisms and kinetics of the solid-state transformations and the effect of these changes on the solubility of the wastes. Besides the transformations that might occur in the dry state, we also need to know what hydrothermal changes might occur. 

Waste-Form Stability. If they occur at all, solid state transformations in dry glass and UO2 matrices will be too slow under the temperature conditions of service to be observable in the laboratory at the same temperature. Here we need to extrapolate from high temperature laboratory conditions to low temperature service conditions. It will be desirable to develop an intimate knowledge of the processes of phase separation and devitrification of sodium borosilicate glasses at temperatures below the softening point by meticulous application of electron microscopic. X-ray crystallographic and other techniques. The glasses will contain inactive elements representative of the fission product... 

In terms of practical use, one of the most important features of phase equilibria can often be the effect of composition on some critical temperature. This can be a liquidus or solidus or a solid-state transformation temperature, such as the /3-transus temperature, (T ), in a Ti alloy. The solidus value can be critical, as solution heat-treatment windows may be limited by incipient melting. In some materials a solid-state transformation temperature may be of prime importance. For example, in Ti alloys it may be specified that thermomechanical processing is performed at some well-defined temperature below the / -transus temperature. The CALPHAD route provides a method where such temperatures can be quickly and reliably calculated. 

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