Crystalline phases solid solution

Mixed crystals Te2,oBri, U with x < 0.75 are easily prepared by annealing the respective vitreous form which can be recovered from the melt in a reversible process. The reversibility indicates the close relationship between the glassy and the crystalline state. Crystallized samples were investigated by the X-ray powder technique and were shown to consist of single-phase solid solutions The cell volume versiK composition plot is given in Fig. 25 and obeys to Vegard s rule. 

In order to widen the nematic range of the monomers and to decrease their melting temperatures, we have made binary mixtures of compounds n = 0 and n = 1 (Table l). We observed that the experimental diagram did not exhibit an eutectic, as is generally observed with other liquid crystals. The two compounds are probably miscible in all proportions in their crystalline state (solid solution). The phase diagrams, experimental and calculated, are plotted on Figure 1. 

Similarly, there is high mutual solid solubility between U, Np, and Pu when they occur in their complex crystalline forms at low temperatures. Solid miscibility gaps of only a few atomic percent separate a-Np and /J-Np from a-Pu and /3-Pu, although the terminal solid solutions have different crystal structures. The same may be said of the extent of solid solubility between the low-temperature forms in the systems U-Np and U-Pu, provided that the broadly stable intermediate phases that occur are considered to be transitional extensions of the terminal solid solution phases. Fig. 19.S shows schematically that regions of single-phase solid solution exist over virtually the entire compositional region at low temperatures in the ndghboring binary systems U-Np and Np-Pu [31]. ... 

If we look at the mechanistic and crystallographic aspects of the operation of polycomponent electrodes, we see that the incorporation of electroactive species such as lithium into a crystalline electrode can occur in two basic ways. In the examples discussed above, and in which complete equilibrium is assumed, the introduction of the guest species can either involve a simple change in the composition of an existing phase by solid solution, or it can result in the formation of new phases with different crystal structures from that of the initial host material. When the identity and/or amounts of phases present in the electrode change, the process is described as a reconstitution reaction. That is, the microstructure is reconstituted. 

Reactions of the general type A + B -> AB may proceed by a nucleation and diffusion-controlled growth process. Welch [111] discusses one possible mechanism whereby A is accepted as solid solution into crystalline B and reacts to precipitate AB product preferentially in the vicinity of the interface with A, since the concentration is expected to be greatest here. There may be an initial induction period during solid solution formation prior to the onset of product phase precipitation. Nuclei of AB are subsequently produced at surfaces of particles of B and growth may occur with or without maintained nucleation. 

The structure of CaB contains bonding bands typical of the boron sublattice and capable of accommodating 20 electrons per CaB formula, and separated from antibonding bands by a relatively narrow gap (from 1.5 to 4.4 eV) . The B atoms of the B(, octahedron yield only 18 electrons thus a transfer of two electrons from the metal to the boron sublattice is necessary to stabilize the crystalline framework. The semiconducting properties of M B phases (M = Ca, Sr ", Ba, Eu, Yb ) and the metallic ones of M B or M B5 phases (Y, La, Ce, Pr, Nd ", Gd , Tb , Dy and Th ) are directly explained by this model . The validity of these models may be questionable because of the existence and stability of Na,Ba, Bft solid solutions and of KB, since they prove that the CaB -type structure is still stable when the electron contribution of the inserted atom is less than two . A detailed description of physical properties of hexaborides involves not only the bonding and antibonding B bands, but also bonds originating in the atomic orbitals of the inserted metal . ... 

The irradiation (or ion bombardment) of solid solutions, where a scavenger can be present, should also be explored further. Here it will be important to ensure that the solids are indeed solutions before conclusions can be safely drawn. It is curious to note that the yields observed in frozen solutions are in several cases very similar to the yields in the pure crystalline solutes. This suggests the possibility that the frozen targets had segregated, and that the solute was in fact present as micro crystals. (If this is the case, it may well be that a new method can be developed on this basis for making phase studies at high dilution.)... 

Fig. 4 Oxygen Is XPS spectra including curve-fitted components for (a) Catalyst I, (b) Catalyst I after reduction In Fig. 2, a marble-like pattern was observed, which is attributable to solid solution phase of CoO and MgO, because XRD measurement on Catalyst II showed the existence of CoO-MgO solid solution phase [7, 8]. On the other hand, for Catalyst I, no solid solution phase of CoO-MgO was observed. In addition, XRD pattern of Catalyst I indicated the existence of CoO or C03O4. These results suggest that in the case of Catalyst I, Co is loaded on the surface of MgO as CoO or C03O4 phase. Magnified TEM image of Catalyst I after reduction is shown in Fig. 3. In this figure, crystalline lattice image was observed. It is likely that the observed lattice corresponds to the metal phase of Co, because XRD measurement on Catalyst I after reduction showed the existence of Co metal phase [7, 8].

Solid solutions are very common in crystalline solids. A solid solution may be defined as a single crystalline phase with variable composition. In general, these... 

The ability of XB to control recognition, self-organization, and self-assembly processes in the different phases of matter is clearly emerging in the literature. This chapter focusses on self-assembly in the solid phase, while the chapters of B. Duncan and A. Legon (in this volume) deal with the liquid crystalline phase and gas phase, respectively. Relatively few papers are reported in the literature on self-assembly processes in solution [66-68,207,208]. Several analytical techniques have been used to detect XB formation, to define its nature, to establish its energetic and geometric characteristics, and to reveal... 

As was discussed earlier in Section 1.2.8 a complication arises in that two of these properties (solubility and vapor pressure) are dependent on whether the solute is in the liquid or solid state. Solid solutes have lower solubilities and vapor pressures than they would have if they had been liquids. The ratio of the (actual) solid to the (hypothetical supercooled) liquid solubility or vapor pressure is termed the fugacity ratio F and can be estimated from the melting point and the entropy of fusion. This correction eliminates the effect of melting point, which depends on the stability of the solid crystalline phase, which in turn is a function of molecular symmetry and other factors. For solid solutes, the correct property to plot is the calculated or extrapolated supercooled liquid solubility. This is calculated in this handbook using where possible a measured entropy of fusion, or in the absence of such data the Walden s Rule relationship suggested by Yalkowsky (1979) which implies an entropy of fusion of 56 J/mol-K or 13.5 cal/mol-K (e.u.)... 

The solids occurring in nature are seldom pure solid phases. Isomorphous replacement by a foreign constituent in the crystalline lattice is an important factor by which the activity of the solid phase may be decreased. If the solids are homogeneous, that is, contain no concentration gradient, one speaks of homogeneous solid solutions. The thermodynamics of solid solution formation has been discussed by Vaslow and Boyd (1952) for solid solutions formed by AgCI(s) and AgBr(s). 

To understand the dissolution of ionic solids in water, lattice energies must be considered. The lattice enthalpy, A Hh of a crystalline ionic solid is defined as the energy released when one mole of solid is formed from its constituent ions in the gas phase. The hydration enthalpy, A Hh, of an ion is the energy released when one mole of the gas phase ion is dissolved in water. Comparison of the two values allows one to determine the enthalpy of solution, AHs, and whether an ionic solid will dissolve endothermically or exothermically. Figure 1.4 shows a comparison of AH and A//h, demonstrating that AgF dissolves exothermically. 

A general presentation and discussion of the origin of structure of crystalline solids and of the structural stability of compounds and solid solutions was given by Villars (1995) and Pettifor (1995). For an introduction to the electronic structure of extended systems, see Hoffmann (1987, 1988). In this chapter a brief sampling of some useful semi-empirical correlations and, respectively, of methods of classifying (predicting) phase and structure formation will be summarized. 

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