Crystalline state Avrami equation

The process of formation of the crystalline state is controlled by the kinetics of nucleation and this may arise in a number of ways. Primary nucleation in a quiescent state must be associated with foreign bodies such as deliberately added nucleating agents, such as fine talc particles, or residual impurities such as heterogeneous catalyst particles followed by spherulite growth. The plot of extent of crystallinity, (p, as a function of time is sigmoidal in nature and follows an Avrami equation of the form... 

The crystallisation behaviour of blow moulded PETP bottles, which helps determine the product s transparency, was investigated by DSC dynamic cooling experiments that simulated the cooling that occurs in the injection blow moulding manufacturing process. DSC measurements were used to obtain information on related aspects, such as the ease of crystallisation from glassy and molten states and crystallinity in the products. An Avrami equation was used for calculation of the crystallisation kinetic parameters. 40 refs. 

When applying this concept to the Avrami formulation the phantom nuclei have to be taken into account. They will now be located in both the untransformable as well as the transformed regions. The analysis proceeds as previously with either Eq. (9.26) or (9.27). Neither the fraction transformed nor untransformable appear explicity in either of these equations. Hence, in order to introduce the influence of the untransformable fraction on the extent of the transformation a decrease in N(r) with the level of crystallinity, or time, needs to be postulated. Several efforts have been made to resolve the problem in this manner.(63-66) However, they all involve postulating an arbitrary retardation in either the nucleation rate, the hneal growth rate, or in both. There is no physical or molecular basis for the functions that have been proposed. The normalization procedure that led to Eq. (9.42) was an effort to account for the fractions of untransformable material in the kinetics. The formalism of nucleation and growth has also been applied to the development of the stable crystalline state from a metastable one, rather than from the pure melt.(66a) Formally, the analysis is qualitatively similar to the two-stage series process that was discussed previously.(54,55)... 

The Avrami model (19,20) states that in a given system under isothermal conditions at a temperature lower than V. the degree of crystallinity or fractional crystallization (70 as a liinction of time (t) (Fig. 11) is described by Equation 5. Although the theory behind this model was developed for perfect crystalline bodies like most polymers, the Avrami model has been used to describe TAG crystallization in simple and complex models (5,9,13,21,22). Thus, the classical Avrami sigmoidal behavior from an F and crystallization time plot is also observed in TAG crystallization in vegetable oils. This crystallization behavior consists of an induction period for crystallization, followed by an increase of the F value associated with the acceleration in the rate of volume or mass production of crystals, and finally a metastable crystallization plateau is reached (Fig. 11). 

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