Copolymer theory, solid solution

Our understanding of the physics of block copolymers is increasing rapidly. It therefore seemed to me to be timely to summarize developments in this burgeoning field. Furthermore, there have been no previous monographs on the subject, and some aspects have not even been reviewed. The present volume is the result of my efforts to capture the Zeitgeist of the subject and is concerned with experiments and theory on the thermodynamics and dynamics of block copolymers in melt, solution, and solid states and in polymer blends. The synthesis and applications of these fascinating materials are not considered here. 

Three limiting theories are outlined next. The first is an equilibrium theory of the eutectic phase diagram of copolymers as developed by Hory which has been widely used, even for systems not in equilibrium. The second is the corresponding theory for the formation of solid solutions. The third is the application of cold crystallization to copolymers as a limiting, nonequilibrium theory of melting and crystallization. 

Fig. 7 A typical force-distance profile obtained for mica surfaces precoated with a 10% charged CMA/AM copolymer across a solution containing SDS at a concentration of 0.02 cmc. ( ) and ( ) represent the first approach and separation respectively, ( ) and (o) the following ones. The solid line corresponds to the theoretical decay length at the present ionic strength (based on the surfactant concentration) according to the Poisson-Boltzmann theory...

This name covers all polymer chains (diblocks and others) attached by one end (or end-block) at ( external ) solid/liquid, liquid/air or ( internal ) liquid/liq-uid interfaces [226-228]. Usually this is achieved by the modified chain end, which adsorbs to the surface or is chemically bound to it. Double brushes may be also formed, e.g., by the copolymers A-N, when the joints of two blocks are located at a liquid/liquid interface and each of the blocks is immersed in different liquid. A number of theoretical models have dealt specifically with the case of brush layers immersed in polymer melts (and in solutions of homopolymers). These models include scaling approaches [229, 230], simple Flory-type mean field models [230-233], theories solving self-consistent mean field (SCMF) equations analytically [234,235] or numerically [236-238]. Also first computer simulations have recently been reported for brushes immersed in a melt [239]. 

FIGURE 1.16 Determination of the chain overlap concentration c, the entanglement concentration Cg, the electrostatic hlob overlap concentration c from the concentration dependence of specific viscosity for a 17%-quaternized P2VP copolymer (17PMVP-C1) in solution in ethylene glycol at 25°C. Symbols are experimental data and solid lines represent the power laws predicted from scaling theory. (Adapted from Don and Colby [2006].)... 

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