Polymer crystallization behaviors

In what follows, we use simple mean-field theories to predict polymer phase diagrams and then use numerical simulations to study the kinetics of polymer crystallization behaviors and the morphologies of the resulting polymer crystals. More specifically, in the molecular driving forces for the crystallization of statistical copolymers, the distinction of comonomer sequences from monomer sequences can be represented by the absence (presence) of parallel attractions. We also devote considerable attention to the study of the free-energy landscape of single-chain homopolymer crystallites. For readers interested in the computational techniques that we used, we provide a detailed description in the Appendix. ... 

The consequences of the computed defect properties for polymer crystal behavior have been discussed in the literature cited and will not be gone into here. We suffice to conclude that it is possible to devise a computational strategy that allows the energy minimization of chain assemblies large enought to permit realistic and practical simulation of the energies and packings of defects in polymer crystals. 

Polymer crystallization behavior near an inorganic surface has been the focus of extensive study. In most cases the inorganic surface is shown to produce a nucleating or epitaxial effect,which often stabilizes the bulk crystal phase or, in some cases, promotes growth of a different crystal phase. The polymer mechanical and thermal properties can be enhanced through this mechanism, where the surface-nucleated crystalline phase has better mechanical and thermal characteristics than the bulk crystal phases. Fillers with large surface area maximize these filler-induced enhancements of the material properties a dramatic manifestation of such a response is found in nylon-6/montmorillonite... 

Whenever a phase is characterized by at least one linear dimension which is small, the properties of the surface begin to make significant contributions to the observed behavior. We shall examine the structure of polymer crystals in more detail in Sec. 4.7, but for now the following summary of generalizations about these crystals will be helpful ... 

This is a highly polar polymer and crystalline due to the presence of amide linkages. To achieve effective intercalation and exfoliation, the nanoclay has to be modified with some functional polar group. Most commonly, amino acid treatment is done for the nanoclays. Nanocomposites have been prepared using in situ polymerization [85] and melt-intercalation methods [113-117]. Crystallization behavior [118-122], mechanical [123,124], thermal, and barrier properties, and kinetic study [125,126] have been carried out. Nylon-based nanocomposites are now being produced commercially. 

The preparation and study of metal nanoparticles constitutes an important area of current research. Such materials display fascinating chemical and physical properties due to their size [62, 63]. In order to prevent aggregation, metal nanoparticles are often synthesized in the presence of ligands, functionalized polymers and surfactants. In this regard, much effort has focused on the properties of nanoparticles dispersed into LCs. In contrast, the number of nanoparticles reported that display liquid crystal behavior themselves is low. Most of them are based on alkanethiolate stabilized gold nanoparticles. 

The previous sections in this chapter have tried to stress upon the significance of distribution of sequence lengths in polyethylene-based copolymers. The sequence length of interest in a system of ethylene-octene copolymers would be the number of methylene units before a hexyl branch point. As was discussed, this parameter has a greater impact on the crystallization behavior of these polymers than any other structural feature like branch content, or the comonomer fraction. The importance of sequence length distributions is not just limited to crystallization behavior, but also determines the conformational,... 

Within the present model, we have many unsolved problems. Most of the present studies on 3D crystallization from the melt deal with the relatively short Cioo chain. The study of the much longer Ciooo chain is still preliminary we want to clarify more polymer-like behavior such as the reeling-in process of the chains. Since the polymers in the ideal melt are the ideal Gaussian and highly entangled, we need a much larger MD cell to accommodate such large polymers. 

Fig. 3 Difference in crystallization behavior between an atomic or short chain molecular system and a polymer system, a Atoms or short chain molecules can be independently rearranged on each lattice point, while b the order of the repeating units within a polymer chain is maintained during the rearranging process. Therefore, a chain should slide along its chain axis and disentangle for rearrangement onto the lattice points...

But the topological nature has not been confirmed more directly to date. It is expected that the topological restriction increases with an increase in molecular weight (M) and the number density of entanglement (ve). Therefore, the studies of the M or ve dependence of crystallization behavior should be important in confirming directly the important role of topological nature in polymer crystallization. 

The polybutadienes prepared with these barium t-butoxide-hydroxide/BuLi catalysts are sufficiently stereoregular to undergo crystallization, as measured by DTA ( 8). Since these polymers have a low vinyl content (7%), they also have a low gl ass transition temperature. At a trans-1,4 content of 79%, the Tg is -91°C and multiple endothermic transitions occur at 4°, 20°, and 35°C. However, in copolymers of butadiene (equivalent trans content) and styrene (9 wt.7. styrene), the endothermic transitions are decreased to -4° and 25°C. Relative to the polybutadiene, the glass transition temperature for the copolymer is increased to -82°C. The strain induced crystallization behavior for a SBR of similar structure will be discussed after the introduction of the following new and advanced synthetic rubber. 

Rheo-optical Studies. One of the most useful techniques for studying the crystallization behavior of stereoregular polymers is rheo-optical measurements (11). 

With the details associated with ADMET chemistry reasonably well understood, we have embarked on a study of the synthesis of well-controlled polymer structures via metathesis polycondensation chemistry [37]. A series of well-defined polyolefins have been designed to model the crystallization behavior of polyethylene and its related copolymers, including new materials synthesized by metallocene-based catalysts. This synthesis concept has been reduced to practice, and polymers that will aid in the understanding of branching within polyethylene itself have been produced. 

Due to the symmetry of 19a, which possesses a methyl group on each and every ninth carbon, the carbon NMR spectrum displays only six resonances. This conclusively demonstrates that these techniques are able to prepare polymers whose regularity can be controlled with ease. The polymers themselves are sufficiently high in molecular weight to mimic crystallization behavior of polyethylene in its substituted forms. 

The critical state of stress-induced crystallization at high spinning speeds is governed by the viscoelasticity of the polymer in combination with its crystallization behavior. Any kind of coarse particle obviously disturbs the structure and affects the resistance against deformation. The development of stress is controlled by the rheological properties of the polymer. Shimizu et al. [4] found that increasing the molecular weight drastically promotes the crystallinity under stress conditions. 

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