This issue of the MRS BULLETIN is devoted to a class of materials undergoing a transition from a period in which they were viewed primarily as cheap substitutes for other materials into a new period where polymers are seen as high tech, value-added materials in their own right. The six articles included here focus on a portion of the wide range of topical areas concurrently at the frontiers of polymer materials science.

Polymers are molecules consisting of a large number of units (mers) covalently connected to form macromolecules of very high molar mass (upwards of 106). Polymer chemists have learned how to make an almost endless variety of highly complex yet well- defined macromolecules utilizing a wide variety of monomers. Once polymer physicists and materials scientists depended on industry to provide samples (which were far from model materials to work on). Today, significant improvements in chemical synthesis and a growing collaborative effort between polymer chemists and materials scientists have resulted in the availability of extremely well-defined materials (molecular weight distribution, composition, sequence of monomer types along the chain backbone, stereochemistry of these units and overall molecular architecture, e.g., branching vs. linear) for the attainment of novel properties and the investigation of structure-property relationships. Given the sophistication of current polymer synthesis, it is now possible to test structure-property hypotheses systematically and to rationally design macromolecules to form specified microstructures and provide desirable physical properties.

The typical mental image conjured by the word polymer is an entangled mass of cooked spaghetti. This is in fact very appropriate for the class of flexible chain polymers in the noncrystalline state. The pioneering work of P.J. Flory in elucidating the nature of such materials, e.g., polymer melts and amorphous polymers above their glass transition temperature, made crucial use of the essentially Gaussian behavior of the end-to-end distance vector of a flexible chain polymer in the condensed state.

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.