The molecules of block and graft copolymers are molecules of a higher order; they consist of homopolymer subchains which are interconnected by chemical valence bonds. This structural com plexity is manifested in the unusual behavior of block and graft copolymers both in solution and in bulk. Many types of interac tions are possible in block and graft copolymers in the solid state. Polymer subchains of one molecule can interact with other polymer subchains which may belong to the same molecule or to different molecules. Since polymer chains of chemically different composition are usually incompatible, thermodynamically unfavorable as well as thermodynamically favorable interactions exist in the solid state. In solutions of block and graft copolymers, the sit uation becomes even more complex, because interactions between the solvent molecules and the various subchains of the copolymer mole cules occur in addition to the interactions between the polymer chains. This multitude of interactions gives rise to a wide spec trum of colloidal and morphological properties which have no paral lel in less complex polymer systems such as homopolymers or random copolymers. Research on the colloidal and morphological behavior of block and graft copolymers is a relatively new field of endeavor. It started in 1954, when F. M. Merrett fractionated mixtures of grafted na tural rubber with the corresponding homopolymers and observed that colloidal sols were formed at certain points during his fractional precipitations.

The molecules of block and graft copolymers are molecules of a higher order; they consist of homopolymer subchains which are interconnected by chemical valence bonds. This structural com plexity is manifested in the unusual behavior of block and graft copolymers both in solution and in bulk. Many types of interac tions are possible in block and graft copolymers in the solid state. Polymer subchains of one molecule can interact with other polymer subchains which may belong to the same molecule or to different molecules. Since polymer chains of chemically different composition are usually incompatible, thermodynamically unfavorable as well as thermodynamically favorable interactions exist in the solid state. In solutions of block and graft copolymers, the sit uation becomes even more complex, because interactions between the solvent molecules and the various subchains of the copolymer mole cules occur in addition to the interactions between the polymer chains. This multitude of interactions gives rise to a wide spec trum of colloidal and morphological properties which have no paral lel in less complex polymer systems such as homopolymers or random copolymers. Research on the colloidal and morphological behavior of block and graft copolymers is a relatively new field of endeavor. It started in 1954, when F. M. Merrett fractionated mixtures of grafted na tural rubber with the corresponding homopolymers and observed that colloidal sols were formed at certain points during his fractional precipitations.

Block copolymers represent an important class of multi-phase material, which have received very widespread attention, particularly since their successful commercial development in the mid-1960s. Much of the interest in these polymers has arisen because of their rather remarkable micro phase morphology and, hence, they have been the subject of extensive microstructural examination. In many respects, the quest for a comprehensive interpretation of their structure, both theoretically and experimentally, has not been generally matched by a corresponding enthusiasm for developing structure/property relationships in the context of their commercial application. Indeed, it has been left largely to the industrial companies involved in the development and utilization of these materials to fulfil this latter role. While it is generally disappointing that a much greater synergism does not exist between science and technology, it is especially sad in the case of block copolymers. Thus these materials offer an almost unique opportunity for the application of fundamental structural and property data to the interpretation of the properties of generally processed artefacts. Accordingly, in this book, the editor has drawn together an eminent group of research workers, with the specific intention of highlighting some of those aspects of the science and technology of block copolymers that are potentially important if further advances are to be made either in material formulation or utilization. For example, special consideration is given to the relationship between the flow properties of block copo lymers and their microstructure.

A summary of block copolymer chemical structures and synthesis. It discusses physical methods of characterization such as computer simulation, microhardness, dielectric spectroscopy, thermal mechanical relaxation, ultrasonic characterization, transmission electron microscopy, X-ray scattering, and NMR, among others. It also outlines rheological and processing parameters in the multiphase polymer systems with stable microstructures.

Polymers may be classified as either homopolymers, consisting of one single repeating unit, or copolymers, consisting of two or more distinct repeating units. Block copolymers contain long contiguous blocks of two or more repeating units in the same polymer chain. Covering one of the hottest topics in polymer chemistry, Block Copolymers provides a coherent overview of the synthetic routes, physical properties, and applications of block copolymers. This pioneering text provides not only a guideline for developing synthetic strategies for creating block copolymers with defined characteristics, but also a key to the relationship between the physical properties of block copolymers and the structure and dynamics of materials. Covering features of the chemistry and physics of block copolymers that are not found in comparable texts, Block Copolymers illustrates the structure-activity relationship of block copolymers and offers suggestions for the design of specific applications. Divided into five sections-Block Copolymers includes chapters on: * Block Copolymers by Chemical Modification of Precursor Polymers * Nonlinear Block Copolymers * Adsorption of Block Copolymers at Solid-Liquid Interfaces * Theory of Block Copolymer Segregation * Phase Transformation Kinetics * Block Copolymer Morphology * Block Copolymer Dynamics Polymer chemists, physicists, chemical engineers, and materials scientists, as well as graduate students in polymer science, will find Block Copolymers to be an invaluable text.

This dissertation is focused on the characterization of elastomeric block copolymers confined via multilayer co-extrusion technology. In this work, we utilized both self-assembly and forced assembly to achieve hierarchical design within films for mechanical enhancement. When block copolymers are forced to self-assemble in restricted geometries, their physical properties tend to deviate from the bulk behavior. An understanding of their physical properties under confinement has become imperative as technology pushes polymeric applications toward thinner geometries. This work utilizes multilayer co-extrusion as a continuous, confining mechanism to exploit the effect of confining layer and layer thickness on commercially available block copolymers. It was discovered that the morphology and orientation of the block copolymer while under confinement drastically affects the mechanical response of the multilayer films. A thorough understanding of these key factors allows for a methodology to tune the mechanical response of multilayer films via a continuous methodology.