Impurities nucleation

Since the PA-6 crystallization at its usual temperature of about 180°C is suppressed, and since almost all PA-6 droplets crystallize in a low temperature step together with the PVDF, Equation 8 must be fullfilled with M as the number density o,f nucleating impurities should be less than... 

Effect of gas phase nucleated impurities on deposited structure of pyrolytic graphite. Source Reprinted with permission from Campbell J, Sherwood EM, High Temperature Materials and Technology, John Wiley, New York, 1967. Copyright 1967, The Electrochemical Society, Inc. 

Figure 7.6. Effect of gas-phase nucleated impurities on deposited structure of pyrolytic graphite.l ...

An important approach to the study of nucleation of solids is the investigation of small droplets of large molecular clusters. Years ago, Turnbull showed that by studying small droplets one could eliminate impurities in all except a few droplets and study homogeneous nucleation at significant undercoolings [13]. 

The visible crystals that develop during a crystallization procedure are built up as a result of growth either on nuclei of the material itself or surfaces of foreign material serving the same purpose. Neglecting for the moment the matter of impurities, nucleation theory provides an explanation for certain qualitative observations in the case of solutions. 

Crystal Morphology. Size, shape, color, and impurities are dependent on the conditions of synthesis (14—17). Lower temperatures favor dark colored, less pure crystals higher temperatures promote paler, purer crystals. Low pressures (5 GPa) and temperatures favor the development of cube faces, whereas higher pressures and temperatures produce octahedral faces. Nucleation and growth rates increase rapidly as the process pressure is raised above the diamond—graphite equiUbrium pressure. 

In other cases, the inherent flaws or perturbations responsible for fracture are less easily recognized. The internal spalling of glass or the cavitation of a rapidly expanding liquid are examples although even here, some form of imperfection such as impurities, dislocations, or thermal fluctuations are expected to play an important role in nucleating the fracture process. 

The size of crystals produced in the gas-liquid system varied from 10 to 100 pm by controlling the level of supersaturation, while the liquid-liquid system produced crystals of 5—30 pm. The wide variation of crystal size is due to the marked sensitivity of the nucleation rate on the level of supersaturation, while the impurity content is another variable that can affect the crystal formation. 

Boiling in the bulk of the fluid generally takes place at submicron nucleation sites as impurities, crystals, or ions. When there is a shortage of nucleation sites in the bulk of the liquid, its boiling point can be exceeded without boiling then the liquid is superheated. There is, however, a limit at a given pressure above which a liquid cannot be superheated, and when this limit is reached, microscopic vapor bubbles develop spontaneously in the pure liquid (without nucleation sites). 

The carbonyl process developed in 1899 by L. Mond is still used, though it is mainly of historic interest. In this the heated oxide is first reduced by the hydrogen in water gas (H2 + CO). At atmospheric pressure and a temperature around 50°C, the impure nickel is then reacted with the residual CO to give the volatile Ni(CO)4. This is passed over nucleating pellets of pure nickel at a temperature of 230°C when it decomposes, depositing nickel of 99.95% purity and leaving CO to be recycled. 

Characteristic features of a—time curves for reactions of solids are discussed with reference to Fig. 1, a generalized reduced-time plot in which time values have been scaled to t0.s = 1.00 when a = 0.5. A is an initial reaction, sometimes associated with the decomposition of impurities or unstable superficial material. B is the induction period, usually regarded as being terminated by the development of stable nuclei (often completed at a low value of a). C is the acceleratory period of growth of such nuclei, perhaps accompanied by further nucleation, and which extends to the... 

The kinetic observations reported by Young [721] for the same reaction show points of difference, though the mechanistic implications of these are not developed. The initial limited ( 2%) deceleratory process, which fitted the first-order equation with E = 121 kJ mole-1, is (again) attributed to the breakdown of superficial impurities and this precedes, indeed defers, the onset of the main reaction. The subsequent acceleratory process is well described by the cubic law [eqn. (2), n = 3], with E = 233 kJ mole-1, attributed to the initial formation of a constant number of lead nuclei (i.e. instantaneous nucleation) followed by three-dimensional growth (P = 0, X = 3). Deviations from strict obedience to the power law (n = 3) are attributed to an increase in the effective number of nuclei with reaction temperature, so that the magnitude of E for the interface process was 209 kJ mole-1. 

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