Melt crystallization process concepts

Investigations at Cornell University are based on process concepts in which an ice slurry is produced from saline water by evaporation of a suitable immiscible refrigerant. After washing, the ice crystals are melted by direct condensation on the ice of the compressed refrigerant vapors. Potable water is the product, and the immiscible refrigerant recycles to the process. 

The many technological innovations in melt crystal growth of semiconductor materials all build on the two basic concepts of confined and meniscus-defined crystal growth. Examples of these two systems are shown schematically in Figure 1. Typical semiconductor materials grown by these and other methods are listed in Table I. The discussion in this section focuses on some of the design variables for each of these methods that affect the quality of the product crystal. The remainder of the chapter addresses the relationship between these issues and the transport processes in crystal growth systems. 

The mechanisms of crystal phase formation are a key problem in materials science that has not clear comprehension still now. At present, the study of this problem is especially important in connection with the development of nanostructured materials. There are two different approaches to consideration of crystal nucleation/growth as well as crystal melting/dissolution processes [1,2], In accordance with the first approach based on the atomic-molecular theory, the individual atoms or molecules take the leading part in these processes (the role of clusters is ignored). In accordance with the second approach based on the cluster theory, these processes are carried out mainly by means of clusters. Till recently the atomic-molecular theory was generally accepted. However, today many scientific data vote for the cluster theory. The aim of this paper is to analyze the main statements of the cluster conception of crystal phase formation and as a result to consider the nature of nanocrystal. 

In the context of the above-listed topics, there are several questions still open and often controversially debated. They concern nucleation - Which conditions are necessary to nucleate the polymer crystallization process . The applicability of thermodynamic concepts - Do concepts of equilibrium thermodynamics such as melting and crystallization describe correctly the nonequilibrium metastable nature of polymer crystals Morphological... 

The concept is illustrated by the processing of ultrahigh molecular weight polyethylene. The outer sheath was a melt crystallized billet of nylon 11 that could be extruded to draw ratio 5 at 120°C and 0.16 GPa using a silicone oil lubricant. Two samples of UHMWPE were prepared. The UHMWPE was melt crystallized in the rheometer at two different temperatures and pressures. 

Falling-film crystallization utilizes progressive freezing principles to purify melts and solutions. The technique established to practice the process is inherently cyclic. Figure 20-15 depicts the basic working concept. First a crystalline layer is formed by subcooling a liquid film on a vertical surface inside a tube. This coating is then... 

Union Carbide (34) and in particular Dow adopted the continuous mass polymerization process. Credit goes to Dow (35) for improving the old BASF process in such a way that good quality impact-resistant polystyrenes became accessible. The result was that impact-resistant polystyrene outstripped unmodified crystal polystyrene. Today, some 60% of polystyrene is of the impact-resistant type. The technical improvement involved numerous details it was necessary to learn how to handle highly viscous polymer melts, how to construct reactors for optimum removal of the reaction heat, how to remove residual monomer and solvents, and how to convey and meter melts and mix them with auxiliaries (antioxidants, antistatics, mold-release agents and colorants). All this was necessary to obtain not only an efficiently operating process but also uniform quality products differentiated to meet the requirements of various fields of application. In the meantime this process has attained technical maturity over the years it has been modified a number of times (Shell in 1966 (36), BASF in 1968 (37), Granada Plastics in 1970 (38) and Monsanto in 1975 (39)) but the basic concept has been retained. 

Let us start with an analogy. An ideal crystal, in which all the atoms are exactly located at the nodes of a geometrically perfect space lattice, can be conceived only on classical grounds and at absolute zero. However, it is impossible to accept this somewhat naive concept because of the uncertainty principle and thermal agitation at T 0°K. This does not, however, mean that the idea of crystallinity loses all definiteness or that, for instance, a crystal can melt in a continuous process, as Frenkel [1] seems to suggest. 

The concept of melting point may be put on a more quantitative basis. The process of melting is a thermal one and is characterized by the collapse of molecular units in a crystal to a disordered array. Energy is required to rupture the crystal lattice so that the heat of fusion, A/7fus, is positive. In addition, the solid-liquid transition involves an increase of randomness and the entropy of fusion, ASfts, is also positive. Melting point is the temperature of fusion (7 ) at which solid and liquid phases are in equilibrium. Therefore,... 

In the crystallization of melts, where relatively large degrees of supersaturation are attainable, nucleation and growth phenomena are more easily separated and studied experimentally than in crystallization from solution, which is characterized by rather narrow metastable regions. However, the basic concepts of nucleation are the same in both types of processes. In fact, much of the experimental verification of nucleation theory has come from studies of condensation and precipitation from the vapor phase. The highly publicized rainmaking experiments of several years ago made significant contributions (S6). 

In making models, we must respect the principles of equilibrium statistical mechanics, but cannot wholly rely on them, since we have every reason to believe that in polymer crystallization we have only a frustrated approach towards thermodynamic equilibrium. Most of the models are in some way or another founded on their authors conceptions of the nature of the process of high-polymer crystallization from the melt. That is a process on which direct detailed information is hard to get, and some imaginative extrapolation from what one knows about related problems is almost unavoidable. 

Closely allied with the concepts of metastable equilibrium and suspended transformations is Ostwald s rule (Ostwald s step rule or law of successive reactions). Essentially Ostwald s rule states that in all processes it is not the most stable state with the least amount of free energy that is initially obtained but the least stable state lying nearest to the original state in free energy (Ostwald 1897). It is easy to see how this rule and the concept of suspended transformations can explain the production of a metastable polymorph through crystallization from a melt or solution. 

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