Thermodynamics melt growth

Figure 10-10. Plot of the natural logarithm of the reduced growth rate of spherulites of different polymers as a function of a reduced temperature. Tch is the characteristic temperature, about 50 K below the glass transition temperature, at which all molecular motion ceases. Tm is the thermodynamic melting point (after A. Gandica and J. H. Magill).

Melt growth is the formation of a crystalline solid from a liquid phase that has essentially the same composition as the solid. If the composition of the liquid shows a larger deviation from that of the solid one deals with solution growth. Fundamentals of thermodynamics of melt growth can be found, e.g. in (15). 

In the next section we describe a very simple model, which we shall term the crystalline model , which is taken to represent the real, complicated crystal. Some additional, more physical, properties are included in the later calculations of the well-established theories (see Sect. 3.6 and 3.7.2), however, they are treated as perturbations about this basic model, and depend upon its being a good first approximation. Then, Sect. 2.1 deals with the information which one would hope to obtain from equilibrium crystals — this includes bulk and surface properties and their relationship to a crystal s melting temperature. Even here, using only thermodynamic arguments, there is no common line of approach to the interpretation of the data, yet this fundamental problem does not appear to have received the attention it warrants. The concluding section of this chapter summarizes and contrasts some further assumptions made about the model, which then lead to the various growth theories. The details of the way in which these assumptions are applied will be dealt with in Sects. 3 and 4. 

Primary crystallization occurs when chain segments from a molten polymer that is below its equilibrium melting temperature deposit themselves on the growing face of a crystallite or a nucleus. Primary crystal growth takes place in the "a and b directions, relative to the unit cell, as shown schematically in Fig. 7.8. Inevitably, either the a or b direction of growth is thermodynamically favored and lamellae tend to grow faster in one direction than the other. The crystallite thickness, i.e., the c dimension of the crystallite, remains constant for a given crystallization temperature. Crystallite thickness is proportional to the crystallization temperature. 

Behavior of trace element that can be treated as effective binary diffusion The above discussion is for the behavior of the principal equilibrium-determining component. For minor and trace elements, there are at least two complexities. One is the multicomponent effect, which often results in uphill diffusion. This is because the cross-terms may dominate the diffusion behavior of such components. The second complexity is that the interface-melt concentration is not fixed by thermodynamic equilibrium. For example, for zircon growth, Zr concentration in the interface-melt is roughly the equilibrium concentration (or zircon saturation concentration). However, for Pb, the concentration would not be fixed. 

Shortly afterwards Frank (F3) derived the same results and extended the discussion to include the case where both heat and mass diffusion control the phase growth. In this case the melting point depression is related by thermodynamic considerations to the interface concentration, which can be determined either iteratively or by means of a convenient graphical aid. Frank also considers several related problems, such as the growth of a compound, where two dissolved substances which diffuse independently unite to form the new phase. 

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