Metals phase stability

In a pure metal, phase stability is determined by the comparative band-forming energies for various symmetries and by the repulsive forces from closed inner shells. The various metallic phases found in the first three long periods are given in Table XVIII. 

To build up a theory of metallic phase stability the conventional arguments for the discussion of crystal structures have to be completed by the concept of spatial correlation of electrons. The parameters of the spatial correlations may be analyzed from the ample empirical material of determined crystal structures by means of several evident rules. The surprising result is that for many crystal structures two correlations are essential for understanding the special features of the crystal structures. This two-correlations model makes possible an easy survey of metallic structures. Two examples of crystal structure-type families are considered, the Cu-family and the W-family. 

Catalytic Properties. In zeoHtes, catalysis takes place preferentially within the intracrystaUine voids. Catalytic reactions are affected by aperture size and type of channel system, through which reactants and products must diffuse. Modification techniques include ion exchange, variation of Si/A1 ratio, hydrothermal dealumination or stabilization, which produces Lewis acidity, introduction of acidic groups such as bridging Si(OH)Al, which impart Briimsted acidity, and introducing dispersed metal phases such as noble metals. In addition, the zeoHte framework stmcture determines shape-selective effects. Several types have been demonstrated including reactant selectivity, product selectivity, and restricted transition-state selectivity (28). Nonshape-selective surface activity is observed on very small crystals, and it may be desirable to poison these sites selectively, eg, with bulky heterocycHc compounds unable to penetrate the channel apertures, or by surface sdation. 

Pure metallic cobalt has a soHd-state transition from cph (lower temperatures) to fee (higher temperatures) at approximately 417°C. However, when certain elements such as Ni, Mn, or Ti are added, the fee phase is stabilized. On the other hand, adding Cr, Mo, Si, or W stabilizes the cph phase. Upon fcc-phase stabilization, the energy of crystallographic stacking faults, ie, single-unit cph inclusions that impede mechanical sHp within the fee matrix, is high. 

Processes in which solids play a rate-determining role have as their principal kinetic factors the existence of chemical potential gradients, and diffusive mass and heat transfer in materials with rigid structures. The atomic structures of the phases involved in any process and their thermodynamic stabilities have important effects on drese properties, since they result from tire distribution of electrons and ions during tire process. In metallic phases it is the diffusive and thermal capacities of the ion cores which are prevalent, the electrons determining the thermal conduction, whereas it is the ionic charge and the valencies of tire species involved in iron-metallic systems which are important in the diffusive and the electronic behaviour of these solids, especially in the case of variable valency ions, while the ions determine the rate of heat conduction. 

G. Foumet, Order-disorder phenomena in solid solutions, in. Phase Stability in Metals and Alloys", P S. 

The thermodynamic phase stability diagrams appear to be preferred by corrosion scientists and technologists for the evaluation of gas-metal systems where the chemical composition of the gaseous phase consisting of a single gas or mixture of gases has a critical influence on the formation of surface reaction products which, in turn, may either stifle or accelerate the rate of corrosion. Also, they are used to analyse or predict the reason for the sequence of formation of the phases in a multi-layered surface reaction product on a metal or alloy. 

A detailed explanation of the construction of thermodynamic phase stability diagrams may be found in References 22-25. In this section the basic principles of construction and interpretation for the specific situation of gas-metal equilibria will be addressed using a hypothetical system. 

Fig. 7.67 Phase stability diagram for a metal-sulphur-oxygen (M-S-O) system at I 000 K. (For the thermodynamic data AC 000 for the various across-boundary reactions, see Table 7.37)...

These isothermal diagrams can be used to consider the phase stability areas for more than one metal in contact with a common atmosphere and thus to assess the condensed phases which can be stable under the prevailing conditions. Figure 7.75 shows a stability diagram having phase areas for Co-S-O solid lines) and for Cu-S-O system broken lines). From this diagram it can be seen clearly that at 950 K at certain gas mixtures, pure metals Co and... 

There have been numerous studies with the objective of gaining an understanding of the factors that influence the stability, stoichiometry, and H-site occupation in hydride phases. Stability has been correlated with cell volume [7] or the size of the interstitial hole in the metal lattice [8] and the free energy of the a p phase conversion. This has been widely exploited to modulate hydride phase stability, as discussed in Sec. 7.2.2.1. 

The thermodynamics treatment followed in this volume strongly reflects our backgrounds as experimental research chemists who have used chemical thermodynamics as a base from which to study phase stabilities and thermodynamic properties of nonelectrolytic mixtures and phase properties and chemical reactivities in metals, minerals, and biological systems. As much as possible, we have attempted to use actual examples in our presentation. In some instances they are not as pretty as generic examples, but real-life is often not pretty. However, understanding it and its complexities is beautiful, and thermodynamics provides a powerful probe for helping with this understanding. 

Heine, V. In Phase Stability in Metals and Alloys Rudman, P.S. Stringer, J.S. ... 

Exploratory solid state synthesis seems to be the only workable route to new phases because of a general inability to predict relative phase stabilities and thence structures or compositions , published in K4La6li40s A new Structure Type for Rare-Earth-Metal Cluster Compounds that Contain Discrete Tetrahedral K4l Units. S. Uma, J.D. Corbett, Inorg. Chem. 1999, 38, 3831-3835. 

Katsuyama S, Tanaka Y, Hashimoto H, Majima K, Nagai H (1997) Effect of substitution of La by alkaline earth metal on the thermoelectric properties and the phase stability of y-La3S4.1 Appl Phys 82 5513-5519... 

It is shown that the stabilities of solids can be related to Parr s physical hardness parameter for solids, and that this is proportional to Pearson s chemical hardness parameter for molecules. For sp-bonded metals, the bulk moduli correlate with the chemical hardness density (CffD), and for covalently bonded crystals, the octahedral shear moduli correlate with CHD. By analogy with molecules, the chemical hardness is related to the gap in the spectrum of bonding energies. This is verified for the Group IV elements and the isoelec-tronic III-V compounds. Since polarization requires excitation of the valence electrons, polarizability is related to band-gaps, and thence to chemical hardness and elastic moduli. Another measure of stability is indentation hardness, and it is shown that this correlates linearly with reciprocal polarizability. Finally, it is shown that theoretical values of critical transformation pressures correlate linearly with indentation hardness numbers, so the latter are a good measure of phase stability. 

Electronic transitions like insulator-metal transitions, magnetic order-disorder transitions, spin transitions and Schottky-type transitions (due to crystal field splitting in the ground state in/element-containing compounds) profoundly influence the phase stability of compounds. A short description of the main characteristics of these transitions will be given below, together with references to more thorough treatments. 

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