Relationship between phase transformation

Transmission electron microscopes (TEM) with their variants (scanning transmission microscopes, analytical microscopes, high-resolution microscopes, high-voltage microscopes) are now crucial tools in the study of materials crystal defects of all kinds, radiation damage, ofif-stoichiometric compounds, features of atomic order, polyphase microstructures, stages in phase transformations, orientation relationships between phases, recrystallisation, local textures, compositions of phases... there is no end to the features that are today studied by TEM. Newbury and Williams (2000) have surveyed the place of the electron microscope as the materials characterisation tool of the millennium . 

Elucidation of the phase relationships between the different forms of carbon is a difficult field of study because of the very high temperatures and pressures that must be applied. However, the subject is one of great technical importance because of the need to understand methods for transforming graphite and disordered forms of carbon into diamond. The diagram has been revised and reviewed at regular intervals [59-61] and a simplified form of the most recent diagram for carbon [62] is in Fig. 5. 

The thermal decomposition of a solid, which necessarily (on the above definition) incorporates a chemical step, is sometimes associated with the physical transformations to which passing reference was made above melting, sublimation, and recrystallization. Aspects of the relationships between physical transitions and decomposition reactions of solids are discussed in a book by Budnikov and Ginstling [1]. Since, in general, phase changes exert significant influence upon concurrent or subsequent chemical processes, it is appropriate to preface the main survey of the latter phenomena with a brief account of those features of melting, sublimation, and recrystallization which are relevant to the consideration of thermal decomposition reactions. 

X-Ray and electron diffraction measurements have been most usually used to characterize the phases present in any reactant mixture, and provide a means of identification of solid reactants, intermediates and products. In addition to such qualitative analyses, the method can also be used quantitatively, with suitable systems, to determine the amounts of particular solids present [111], changes in lattice parameters during reaction, topotactical relationships between reactants and products, the presence of finely divided or strained material, crystallographic transformations, etc. 

The phase relationship between the most commonly known tetragonal phase CaC2-I and phase(s) II (or III) is still in question. CaC2-I transforms reversibly into the cubic phase IV, as does the phase (II -r) III. It is interesting to note that the cubic phase IV seems to have a memory for its respective precursor phase (III or I) that is regained after cooling down phase IV. The synthesis of... 

Figure 5.6. Relationship between Co and Mn contents extracted from solid-phase of six Israeli arid-zone soils with sequential dissolution procedures (after Han et al., 2002b. Reprinted from J Environ Sci Health, Part A, 137, Han F.X., Banin A., Kingery W.L., Li Z.P., Pathways and kinetics of transformation of cobalt among solid-phase components in arid-zone soils, p 184, Copyright (2002), with permission from Taylor Francis)...

Another example of pressure-induced polymorphism is seen in the case of amiloride hydrochloride, where ball-milling Form-B causes a solid-state phase transformation into Form-A [43]. These workers deduced the phase relationship between two different pressure-induced polymorphs of the dihydrate, as well as the alternative route to one of those dihydrate forms that used the anhydrous form as the source material and effected the phase transformation through storage at high degrees of relative humidity storage. 

Contradictory opinions have been referred to in the literature particularly on the nature of the iron-tarmate and its interaction with the rusted steel due to the diversity of the material used in different studies. Studies have included the use of tannic acid [7-10], gallic acid [11], oak tannin [12, 13], pine tannin [14] and mimosa tannin [15]. In order to establish the correlation between the ferric-taimate formation and the low inhibition efficiency observed at high pH from the electrochemical studies, phase transformations of pre-rusted steels in the presence of tannins were evaluated. In this work the quantum chemical calculations are conducted to analyse the relationship between the molecular stracture and properties of ferric-taimate complex and its inhibitory mechanism. 

It was demonstrated by Sundman (1985) and later by Ansara et al. (1988) that an order-disorder transformation could be modelled by setting specific restrictions on the parameters of a two>sublattice phase. One of the first phases to be considered was an A B-ordered compoimd. In such circumstances the sublattice formula A, B)j(A, B) can be applied and the possible relationships between site fiactions and mole fiactions are given in Figure 5.6. The dashed lines denoted xb = 0.25, 0.5 and 0.75 show variations in order of the phase while the composition is maintained constant. When these lines cross the diagonal joining AjA and B3B the phase has disordered completely as Vb Vb As the lines go toward the boundary edge the phase orders and, at the side and comers of the composition square, there is complete ordering of A and B on the sublattices. 

The second type of transformation, the reconstructive transformation involves dis-solution/reprecipitation the initial phase breaks down completely (dissolves) and the new phase precipitates from solution (for a review see Blesa Matijevic, 1989). There is, therefore, no structural relationship between the precursor and the product. In contrast to the solid-state transformation, the reconstructive process is... 

The transformation of ferrihydrite to hematite by dry heating involves a combination of dehydration/dehydroxylation and rearrangement processes leading to a gradual structural ordering within the ferrihydrite particles in the direction of the hematite structure. This transformation may or may not be facilitated by the postulated structural relationship between the two phases. EXAFS studies have shown, for example, that some face sharing between FeOg octahedra, characteristic of hematite, also exists in 6-line ferrihydrite (see chap. 2). 

Many crystalline solids can undergo chemical transformations induced, for example, by incident radiation or by heat. An important aspect of such solid-state reactions is to understand the structural properties of the product phase obtained directly from the reaction, and in particular to rationalize the relationships between the structural properties of the product and reactant phases. In many cases, however, the product phase is amorphous, but for cases in which the product phase is crystalline, it is usually obtained as a microcrystalline powder that does not contain single crystals of suitable size and quality to allow structure determination by single-crystal XRD. In such cases, there is a clear opportunity to apply structure determination from powder XRD data in order to characterize the structural properties of product phases. 

Conventional routes to ceramics involve precipitation from solution, drying, size reduction by milling, and fusion. The availability of well-defined mono-dispersed particles in desired sizes is an essential requirement for the formation of advanced ceramics. The relationship between the density of ceramic materials and the sizes and packing of their parent particles has been examined theoretically and modeled experimentally [810]. Colloid and surface chemical methodologies have been developed for the reproducible formation of ceramic particles [809-812]. These methodologies have included (i) controlled precipitation from homogeneous solutions (ii) phase transformation (iii) evaporative deposition and decomposition and (iv) plasma- and laser-induced reactions. 

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