Kinetics amorphization

To confirm that the matrix is amorphous following primary solidification, isothermal dsc experiments can be performed. The character of the isothermal transformation kinetics makes it possible to distinguish a microcrystalline stmcture from an amorphous stmcture assuming that the rate of heat released, dH/dt in an exothermic transformation is proportional to the transformation rate, dxjdt where H is the enthalpy and x(t) is the transformed volume fraction at time t. If microcrystals do exist in a grain growth process, the isothermal calorimetric signal dUldt s proportional to, where ris... 

The following mechanisms in corrosion behavior have been affected by implantation and have been reviewed (119) (/) expansion of the passive range of potential, (2) enhancement of resistance to localized breakdown of passive film, (J) formation of amorphous surface alloy to eliminate grain boundaries and stabilize an amorphous passive film, (4) shift open circuit (corrosion) potential into passive range of potential, (5) reduce/eliminate attack at second-phase particles, and (6) inhibit cathodic kinetics. 

Hydrated amorphous silica dissolves more rapidly than does the anhydrous amorphous silica. The solubility in neutral dilute aqueous salt solutions is only slighdy less than in pure water. The presence of dissolved salts increases the rate of dissolution in neutral solution. Trace amounts of impurities, especially aluminum or iron (24,25), cause a decrease in solubility. Acid cleaning of impure silica to remove metal ions increases its solubility. The dissolution of amorphous silica is significantly accelerated by hydroxyl ion at high pH values and by hydrofluoric acid at low pH values (1). Dissolution follows first-order kinetic behavior and is dependent on the equilibria shown in equations 2 and 3. Below a pH value of 9, the solubility of amorphous silica is independent of pH. Above pH 9, the solubility of amorphous silica increases because of increased ionization of monosilicic acid. 

Crystallization kinetics have been studied by differential thermal analysis (92,94,95). The heat of fusion of the crystalline phase is approximately 96 kj/kg (23 kcal/mol), and the activation energy for crystallization is 104 kj/mol (25 kcal/mol). The extent of crystallinity may be calculated from the density of amorphous polymer (d = 1.23), and the crystalline density (d = 1.35). Using this method, polymer prepared at —40° C melts at 73°C and is 38% crystalline. Polymer made at +40° C melts at 45°C and is about 12% crystalline. 

We now apply the thermodynamic and kinetic theory of Chapters 5-8 to four problems making rain getting fine-grained castings growing crystals for semiconductors and making amorphous metals. 

More recently, simulation studies focused on surface melting [198] and on the molecular-scale growth kinetics and its anisotropy at ice-water interfaces [199-204]. Essmann and Geiger [202] compared the simulated structure of vapor-deposited amorphous ice with neutron scattering data and found that the simulated structure is between the structures of high and low density amorphous ice. Nada and Furukawa [204] observed different growth mechanisms for different surfaces, namely layer-by-layer growth kinetics for the basal face and what the authors call a collected-molecule process for the prismatic system. 

Since interactions at the molecular level between polymer components in the blends occur only in the amorphous phase, it is reasonable to assume that these effects are due to kinetic factors and, in particular, to the influence of a polymer component on the nucleation or crystallization kinetics of the other one. 

Another interesting case is the much higher solvent resistance of the P crystalline form of s-PS, with respect to the other ones. In fact, it has been found that the sorption of solvents (which are suitable to produce transformations from the a or the y form toward clathrate structures) occurs only in the amorphous phase, for the case of P form samples [122-124]. Sorption kinetic curves of liquid methylene chloride in s-PS samples in the a and p form are, for instance, compared in Fig. 21 [124]. 

The kinetics and mechanisms of dehydration of crystalline hydrates are considered in Chaps. 4 and 5. It is, however, relevant to mention here that the conditions during dehydration can influence the reactivity of the anhydrous salt (or lower hydrate) formed. Thus, anhydrous solids produced under high vacuum are often amorphous, while those prepared in the presence of appreciable amounts of water vapour may be crystalline [281-283,374],... 

Hydrated metal sulphates have long been used to study water removal processes, and characteristic kinetic behaviour is conveniently illustrated by reference to these substances. Frost and co-workers [602,603] have investigated the structures, stabilities and adsorption properties of various intermediate amorphous phases, the immediate reaction products which can later undergo reorganization to yield crystalline phase. 

Ni3C decomposition is included in this class on the basis of Doremieux s conclusion [669] that the slow step is the combination of carbon atoms on reactant surfaces. The reaction (543—613 K) obeyed first-order [eqn. (15)] kinetics. The rate was not significantly different in nitrogen and, unlike the hydrides and nitrides, the mobile lattice constituent was not volatilized but deposited as amorphous carbon. The mechanism suggested is that carbon diffuses from within the structure to a surface where combination occurs. When carbon concentration within the crystal has been decreased sufficiently, nuclei of nickel metal are formed and thereafter reaction proceeds through boundary displacement. 

Catherine, U., and Couderc, C., "Electrical Characteristics and Growth Kinetics in Discharges Used for Plasma Deposition of Amorphous Carbon, Thin Solid Films, Vol. 144, 1986, pp. 265-280. 

Tyndall, G. W. and Waltman, R. J., Thermodynamics of Confined Perfluoropolyether Film on Amorphous Carbon Surface Determined from the Time-Dependent Evaporation Kinetics," J. Phys. Chem. B, Vol. 104,2000, pp. 7085-7095. 

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