Crystallization of elastic polymers

A central result of the discussion in the last chapter was the strong influence of finite-size effects on the freezing behavior of flexible polymers constrained to regular lattices. Thus, (unphysical) lattice effects interfere with (physical) finite-size effects and the question remains what polymer crystals of small size could look like. Since all effects in the freezing regime are sensitive to system or model details, this question cannot be answered in general. Nonetheless, it is obvious that the surface exposed to a different environment, e.g., a solvent, is relevant for the formation of the whole crystalhne or amorphous stmcture. This is true for any physical system. If a system tries to avoid contact with the environment (a polymer in bad solvent or a set of mutually attracting particles in vacuum), it will form a shape with a minimal surface. A system that can be considered as a continuum object in an isotropic environment, like a water droplet in the air, will preferably form a spherical shape. 

But what if the system is small and discrete Small crystals consisting of a few hundred cold atoms, e g., argon [154], but also as different systems as spherical virus hulls enclosing the coaxially wound genetic material [155,156] exhibit an icosahedral or icosahedral-like shape. But why is just the icosahedral assembly naturally favored  

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In a semicrystalline polymer, the crystals are embedded in a matrix of amorphous polymer whose properties depend on the ambient temperature relative to its glass transition temperature. Thus, the overall elastic properties of the semicrystalline polymer can be predicted by treating the polymer as a composite material... 

Usually, crystallization of flexible-chain polymers from undeformed solutions and melts involves chain folding. Spherulite structures without a preferred orientation are generally formed. The structure of the sample as a whole is isotropic it is a system with a large number of folded-chain crystals distributed in an amorphous matrix and connected by a small number of tie chains (and an even smaller number of strained chains called loaded chains). In this case, the mechanical properties of polymer materials are determined by the small number of these ties and, hence, the tensile strength and elastic moduli of these polymers are not high. 

Both stress-induced crystallization and orientational crystallization can be used for the preparation of polymer materials with mechanical property values (e.g. tenacities and elastic moduli) much higher than those for polymer films and fibers obtained by conventional processing. We believe that the advantage of orientational crystallization over more complex methods consists in the possibility of obtaining samples of elastic moduli and tenacities in a one-step continuous process. 

Since the increase of the elastic modulus of oriented polymers with draw ratio is, to a large extent, the consequence of the tie molecules or intercrystalline bridges interconnecting crystal blocks within the fibrils 72) one may anticipate a correlation to exist between indentation anisotropy and modulus. Recent data 23) illustrating the... 

Chain flexibility also effects the ability of a polymer to crystallize. Excessive flexibility in a polymer chain as in polysiloxanes and natural rubber leads to an inability of the chains to pack. The chain conformations required for packing cannot be maintained because of the high flexibility of the chains. The flexibility in the cases of the polysiloxanes and natural rubber is due to the bulky Si—O and rxv-olelin groups, respectively. Such polymers remain as almost completely amorphous materials, which, however, show the important property of elastic behavior. 

From a practical point of view the purpose of this study was to increase the crystallizability of the polycarbonate by incorporating in it well-defined amounts of plasticizer. With this modification, crystalline polycarbonate films could be made with a higher modulus of elasticity, and these would extend the usefulness of the polymers as photographic film bases. When this study was completed an article was published by Sears and Darby (16), who made an extensive study of the plasticization of polycarbonate using 50 plasticizers of widely differing types. The crystallization tendency in the presence of plasticizers was recognized by these authors as a problem and was circumvented by quench cooling. 

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