Subject crystal phase transformation

In Chapter 3 we described the structure of interfaces and in the previous section we described their thermodynamic properties. In the following, we will discuss the kinetics of interfaces. However, kinetic effects due to interface energies (eg., Ostwald ripening) are treated in Chapter 12 on phase transformations, whereas Chapter 14 is devoted to the influence of elasticity on the kinetics. As such, we will concentrate here on the basic kinetics of interface reactions. Stationary, immobile phase boundaries in solids (e.g., A/B, A/AX, AX/AY, etc.) may be compared to two-phase heterogeneous systems of which one phase is a liquid. Their kinetics have been extensively studied in electrochemistry and we shall make use of the concepts developed in that subject. For electrodes in dynamic equilibrium, we know that charged atomic particles are continuously crossing the boundary in both directions. This transfer is thermally activated. At the stationary equilibrium boundary, the opposite fluxes of both electrons and ions are necessarily equal. Figure 10-7 shows this situation schematically for two different crystals bounded by the (b) interface. This was already presented in Section 4.5 and we continue that preliminary discussion now in more detail. 

Diffuse crystal/crystal interfaces often appear in systems subject to incipient chemical or structural instabilities associated with phase separation, long-range ordering, or displacive phase transformations [2], Examples of interfaces associated with the first two types are shown in Fig. 18.7. 

While in volumes 180 and 181 of this series several basic aspects of morphology, inter-phase structure and disorder were addressed, in the present volume, molecular interactions, modeling, phase transformation and crystallization kinetics are considered (see the subject index including keywords from volumes 180 and 181 at the end of the book). Needless to say, in spite of substantial success over 60 years or more we are still far from having a complete and unambiguous picture of polymer crystallization. We firmly believe that a fruitful approach to such a complex problem requires one to give way to many different and sometimes conflicting viewpoints, as we have attempted to do in these volumes. We do hope that they are not only a time-capsule left for... 

Photoswitchable materials could be important components in molecular-scale electronic devices and several new systems have been reported. There have been other investigations of phototropic systems in which light is used to drive a reversible conformational change " or, in the case of liquid crystals, a phase transformation. Such photosystems are of interest for the engineering of microscopic photoactive devices but the subject is still in its infancy and practical devices remain elusive. Much more subtle is the use of light to trigger a change in... 

The solubility of the most stable crystal form in a polymorphic system is termed the equilibrium solubility. While the measurement of equilibrium solubility at a given temperature is a routine practice in pharmaceutical research (Grant and Brittain, 1995), evaluation of the solubility of a metastable polymorph is frequently more complicated owing to the tendency of metastable forms to undergo a phase transformation to the more stable polymorph in the medium of measurement. It is therefore prudent to include a determination of the phase at the completion of any solubility measurement to verify exactly which polymorphic form has been the subject of the measurement. 

Phase relations in the C-Fe-W system are of great interest above all because of the importance of tungsten as alloying element in steels. Therefore constitution of this system has been studied quite intensively. Other important aspects of this subject, in particular the dissolution of iron carbides during austenitization of tungsten steels, phase transformations of carbides as well as diffusion interaction of carbides with iron and steels also attract attention of investigators widely. Details of experimental studies of phase relations, crystal strac-tures and thermodynamics as well as applied techniques are presented in Table 1. 

In this context, literature [90] states that at room temperature, acetoxypropyl cellulose exhibits both chiral nematic phases—the lyotropic and the termotropic one. When subjected to specific conditions of shear flow, the cellulose derivative cholesteric liquid crystal suffers transformations, such as cholesteric helix and cholesteric-to-nematic transition. The films prepared from anisotropic solutions of termotropic acetoxypropyl cellulose in an isotropic solvent exhibit anisotropic mechanical properties, generated by the molecular orientation of the solution under shear stress. Thus, liquid crystalline solutions give rise to films with anisotropic mechanical properties the films are brittle when stretched parallel to the shear direction and ductile when stretched perpendicular to it. 

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). 

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