Defects in Liquid-Crystalline Polymers

MRS Bulletin ◽  
1995 ◽  
Vol 20 (9) ◽  
pp. 23-28 ◽  
Author(s):  
M. Kléman

The properties of imperfections (or defects) of the atomic or molecular order in condensed matter can be conveniently described under two headings: (1) Topological properties—Defects break a specific symmetry of the ordered system at a local scale, that is, along a point defect, a line defect (a dislocation or a disclination), or a surface defect (a wall). (2) Elastic properties—Defects are sources of two types of distortions of the order: long-range distortions, which depend crucially on the broken symmetry but also on the material constants, and short-range distortions in the “core” region of the defect where the order parameter of the ordered phase is broken. These distortions are irreversible in the sense that defects appear during plastic deformation (in solids) or rheological flow (in liquid crystals).To illustrate this classification, let us recall the example of dislocation lines in solids. These defects break translational symmetries (henceforth a dislocation is defined topologically by the translation b it breaks, the so-called Burgers vector). They are at the origin of rather weak, long-range, internal distortions and stresses that depend on the elastic constants (in the region of the good crystal) and rather strong, short-range distortions and stresses in the “core” region, implying a complete rearrangement of the molecular order. These stresses are different in the static and dynamic states, and the shape of the dislocation line, as well as its size, etc., depend on the history of the sample.In this article, we will focus on defects in liquid-crystalline polymers. A synthetic polymer that displays mesomorphic order (intermediate between crystalline and liquid) is usually made of units that are themselves mesogenic and that align coherently when in contact.

MRS Bulletin ◽  
1987 ◽  
Vol 12 (8) ◽  
pp. 18-21 ◽  
Author(s):  
Alan Windle

Not much more than a decade ago, the plastics industry viewed itself as a mature branch of the heavy chemical industry. Its raison d'être was the mass production of four or five main-line polymers, and profits were equated to tonnage output, plant efficiency, and clever downstream processing such as film blowing. The chemistry was essentially simple and the monomer, of course, cheap. There was, however, a spark of new thinking. A trend was developing toward the design and manufacture of more complex, more expensive polymers, with special properties which could command a special price. Such products would sell advanced scientific know-how, not just engineering expertise which could all too easily be exported to the major oil producers in the form of a polymer plant.Designing particular molecules to achieve desired properties is now a major theme of polymer producers. There is a move toward increasing the aromatic content of polymer backbones to achieve greater levels of chemical and thermal stability, while the development of new cross-linking systems remains as chemically intensive as ever. It is, however, the introduction of liquid crystalline polymers which, above all, has exploited the principles of molecular design, while at the same time challenging our understanding in a new area of polymer science.A polymer is “liquid crystalline” where the chains are sufficiently rigid to remain mutually aligned in the liquid phase although the perfect positional periodicity of a crystal is no longer present. In other words there is a long-range orientational order without long-range positional order (Figure 1). Structurally, therefore, the phase is intermediate between a crystal and a liquid leading to the use of the term mesophase. Where the liquid crystalline phase forms on melting the polymer, it is known as thermotropic, but where it is achieved by solvent addition it is called Inotropic. Increasing temperature, or solvent concentration, will eventually lead to the reversion of the liquid crystal phase to the normal isotropic polymer melt.


Author(s):  
Linda C. Sawyer

Recent liquid crystalline polymer (LCP) research has sought to define structure-property relationships of these complex new materials. The two major types of LCPs, thermotropic and lyotropic LCPs, both exhibit effects of process history on the microstructure frozen into the solid state. The high mechanical anisotropy of the molecules favors formation of complex structures. Microscopy has been used to develop an understanding of these microstructures and to describe them in a fundamental structural model. Preparation methods used include microtomy, etching, fracture and sonication for study by optical and electron microscopy techniques, which have been described for polymers. The model accounts for the macrostructures and microstructures observed in highly oriented fibers and films.Rod-like liquid crystalline polymers produce oriented materials because they have extended chain structures in the solid state. These polymers have found application as high modulus fibers and films with unique properties due to the formation of ordered solutions (lyotropic) or melts (thermotropic) which transform easily into highly oriented, extended chain structures in the solid state.


Author(s):  
Christine M. Dannels ◽  
Christopher Viney

Processing polymers from the liquid crystalline state offers several advantages compared to processing from conventional fluids. These include: better axial strength and stiffness in fibers, better planar orientation in films, lower viscosity during processing, low solidification shrinkage of injection moldings (thermotropic processing), and low thermal expansion coefficients. However, the compressive strength of the solid is disappointing. Previous efforts to improve this property have focussed on synthesizing stiffer molecules. The effect of microstructural scale has been overlooked, even though its relevance to the mechanical and physical properties of more traditional materials is well established. By analogy with the behavior of metals and ceramics, one would expect a fine microstructure (i..e. a high density of orientational defects) to be desirable.Also, because much microstructural detail in liquid crystalline polymers occurs on a scale close to the wavelength of light, light is scattered on passing through these materials.


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