Polymer, orientation process

Introduction Fundamental Aspects of Orientational Processes in Crystallizable Polymers... 

These two different approaches for attaining an oriented state in flexible-chain and rigid-chain polymers indicate that the fundamental property of macromolecules - their flexibility - is of great importance to the orientation processes. However, the mechanism of the transition into the oriented state and the properties of highly oriented systems exhibit many features characteristic of both rigid- and flexible-chain polymers. 

The processes of ordering in polymer systems consisting of linear polymers are related, at least on one level of supermolecular organization, to the development of a predominant localization of macromolecules (or their parts) along some directions the orientation axes, i.e. to the transition of the system into the oriented state. The most simple and most widely spread type of polymer orientation is the uniaxial orientation, i.e. the one-dimensional orientation in the direction of the axes of macromolecules. 

Usually, the transition of polymer systems into the oriented state occurs as a result of deformation e.g. upon exposure to external stress. When the polymers undergo deformation both the macromolecule as a whole and its parts (segments) can undergo orientation. The rates of these orientation processes are very different and, hence, the orienting forces affect first of all the orientation of chain segments and subsequently that of a chain molecule as a whole. However, by varying the extension velocity and the temperature, only the overall orientation process may predominate, thus extension of all chains occurs in a single act. 

Polymer Flexibility as a Decisive Parameter of the Thermodynamic and Kinetic Features of Orientation Processes... 

Hence, the main aim of the technological process in obtaining fibres from flexible-chain polymers is to extend flexible-chain molecules and to fix their oriented state by subsequent crystallization. The filaments obtained by this method exhibit a fibrillar structure and high tenacity, because the structure of the filament is similar to that of fibres prepared from rigid-chain polymers (for a detailed thermodynamic treatment of orientation processes in polymer solutions and the thermokinetic analysis of jet-fibre transition in longitudinal solution flow see monograph3. ... 

The SD is a phase separation process usually occurring in systems consisting of more than two components such as in solutions or blends. However, in the present case the system employed is composed of one component of pure PET. In this case, what triggers such an SD type phase separation Doi et al. [24, 25] proposed a dynamic theory for the isotropic-nematic phase transition for liquid crystalline polymers in which they showed that the orientation process... 

In summary, therefore, processing, and in particular injection moulding, can introduce limited chemical degradation, local polymer orientation, orientation of short fibre reinforcements, internal stresses, warpage, shrinkage and defects such as weld lines and voids. 

Mechanical properties of polymers are improved by orientation processes [22, 24, 29]. Because of the biaxial orientation, films from blown film lines exhibit, e.g., a high puncture and tear propagation resistance. Blown film lines can be designed to produce flexible PE-LD or PE-HD films of 5-200 pm. 

This indicates that kinetic parameters of orientational process are defined mostly by the macroscopic viscosity of a polymer. The substantial difference in mesophase... 

The discovered dependence of kinetic parameters of orientation processes on the degree of polymerization 44) is a consequence of the duplex nature of LC polymers — that is the presence of the main chain and of mesogenic side groups. This is why a correct juxtaposition of the kinetic characteristics of orientational processes of low-molecular and polymeric liquid crystals requires an explicit knowledge of the degree of polymerization of a corresponding polymer. 

Up to now we have considered the CP film as an amorphous, homogeneous and isotropic medium. However, CPs are intrinsically anisotropic since the 7r-electrons are delocalized along the macromolecule backbone. An anisotropic optical response, typical of oriented samples, is extremely important both for fundamental science (e.g., comparison with theoretical predictions) and for technological reasons (polarized emission is recommended in displays [55,56]). The orientation process for conjugated polymers is very difficult and several approaches have been used to remove the typical random-coil conformation of CP and to induce the extended aligned conformation. It is not the aim of this article to review all orientational techniques used with CPs. However, it should be mentioned that very high degrees of orientation have been achieved... 

If the orientation process in semi-crystalline fibres is carried out well below the melting point (Tm), the thread does not become thinner gradually, but rather suddenly, over a short distance the neck. The so-called draw ratio (A) is the ratio of the length of the drawn to that of the undrawn filament it is about 4-5 for many polymers, but may be as high as 40 for linear polyolefins and as low as 2 in the case of regenerated cellulose. 

Because of the profound influence that the overall shape of a polymer chain undoubtedly has on any orientation process, which involves rotation of the whole molecule, it is worthwhile digressing on the subject of equilibrium conformation. Flexible, linear polymers tend to be somewhat coiled-up in the liquid phase or in a solution. In a good solvent, polymer-solvent contacts are preferred energetically to polymer-polymer contacts and so the coils... 

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