Crystallinity polymer transport properties

The preceding structural characteristics dictate the state of polymer (rubbery vs. glassy vs. semicrystalline) which will strongly affect mechanical strength, thermal stability, chemical resistance and transport properties [6]. In most polymeric membranes, the polymer is in an amorphous state. However, some polymers, especially those with flexible chains of regular chemical structure (e.g., polyethylene/PE/, polypropylene/PP/or poly(vinylidene fluoride)/PVDF/), tend to form crystalline... 

In addition to the opportunities for new materials synthesis and characterization along these lines, transport properties, rheology, and processing techniques for liquid crystal polymers are essentially unexplored. Experiences with synthesis of polymer structure based on these liquid crystal templates may open up other creative avenues for template synthesis, for example, inside other crystalline structures, chlathrates, or zeolites, or on surfaces [4], Composites, alloys, or mixtures of liquid crystalline and flexible polymers may produce new materials. 

Mandelkern et al. (1968) have proved that the WLF formulation, which has had an outstanding success in explaining the segmental mobility and flow properties of completely amorphous polymers, is not applicable to the transport process involved in the growth of spherulites in melts of semi-crystalline polymers. Rather, a temperature-independent energy of activation, specific to a given polymer and dependent on its glass temperature, suffices to explain the experimental data now available. Mandelkern s equation reads ... 

Polymeric materials have advantages because of their stability and structureforming properties. Electron- and ion-active organic polymeric materials have attracted attention for new devices. In Chapter 5, Kato and co-workers focus on polymeric liquid crystalline materials that are used for the development of functional materials transporting ions and electrons. The nanostructures such as smectic and columnar phases exhibited by side-chain, main-chain, dendritic, and network polymers may exhibit one- and two-dimensional transportation properties. 

The unique molecular packing of rod-like chains in liquid crystalline polymers (LCP) closely resembles the extended chain structure of highly oriented flexible chain polymers, suggesting that these materials are good candidates for barrier applications. Thermotropic LCP s, first developed in the early 1970 s, have been the object of much interest because of their excellent mechanical properties and ease of product fabrication. Preliminary observations have shown that a commercially available wholly aromatic thermotropic copolyester has gas permeability coefficients that are lower than those of polyacrylonitrile (4.). These results raise some fundamental questions as to the nature of the mechanism for transport of small molecules through a matrix of ordered rigid rod-like chains. 

We first give a concise review of the effects of orientation and crystallinity on the barrier properties of polymeric materials, paying particular attention to their effects on the solubility and diffusion coefficients. This will provide useful background for considering the transport properties of liquid crystal polymers which, because of their unique properties, may have some role to play in the quest for improved barrier polymers. 

To date, reports of investigations on the gas transport properties of main chain liquid crystalline polymers appear to have been limited to the work conducted in our laboratory. Chiou and Paul (4.) have briefly described the transport parameters of an extruded film of an LCP having a similar structure to the commercial product Vectra. This copolyester belongs to the family of napthylene thermotropic polymers (NTP s) commercialized by Hoechst-Celanese Corp. whose synthesis and properties have been described previously (iLS.). Transient permeation experiments were conducted with a series of gases. The effective... 

Table 2. Comparison of Gas Transport Properties of a Wholly Aromatic Liquid Crystalline Polymer (Vectra type) with Polyacrylonitrile at 35 C...

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