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Bernhard Wunderlich "Macromolecular Physics. Volume 3: Crystal Melting"

Macromolecular Physics, Volume 3 , provides an up-to-date summary and evaluation of theories, experiments, and extrapolations on equilibrium and irreversible melting of homopolymers, copolymers, and isomers. The book presents the reader with a review of the following topics:

• characterization of matter

• mechanism of melting

• the difference between small and large molecule melting

• heats, entropies, volume changes, and heat capacity changes on fusion

• molecular weight, pressure, deformation , and diIuent effects on melting

• experimental handling of irreversible melting

• size effects, superheating, reorganization , recrystallization, and strain effects

• surface and single-phase melting

The book is in three sections and goes from the topics of equilibrium to non-equilibrium and copolymer melting.

Section I deals with equilibrium melting and starts with the characterization of matter through its equilibrium melting behaviour. The equilibrium melting process is then presented in terms of general statements about melting and further discussed for the case of flexible linear macromolecules. The general problems of extrapolation to equilibrium data of flexible linear macromolecules are reviewed for volume and

heat-capacity changes on melting, melting temperature and heat of fusion. A review on available experimental data follows. Changes in the equilibrium melting temperature as a function of molecular-weight distribution, pressure effects and diluent effects are presented and analyzed. From this section it is clear that equilibrium melting of flexible linear macromolecules can give insight into the nature of molecules and phase structures.

Section II provides ways of recognizing irreversible melting. For the first time, experimental methods that can fix metastable structures long enough for investigation are reviewed. A selection of experimental information based on (a) crystals grown from solution, (b) crystals grown from the melt, (c) deformed crystals is presented. The final four chapters deal with some special topics: the melting at above zero-entropy production, melting temperatures occurring from superheating, the changes in the temperature of melting

due to the effects of diluent or solvent; the observation of a local melting equilibrium at the surface, and the possible description of melting in single-phase systems.

Perhaps the most challenging part of this book is reached with section III where copolymer and isomer melting is treated. The first part deals with a necessary presentation of the chain structure and conformation in semi-crystalline copolymers and isomers. Next, an effort is made to discuss approximations to equilibrium melting. This incorporates attempts to describe phase diagrams mathematically as well as a discussion on some experimental approximations. Then the non-equilibrium melting of copolymers and isomeric

macromolecular systems is presented following a classification in terms of random copolymers, regular copolymers and block copolymers. These sections incorporate the available experimental data. Finally, side-chain crystallization is treated as a special case of copolymer crystals.

The book is carefully produced, fully illustrated and carefully proof-read.

Researchers and graduate students in the polymer and materials fields will find this book useful as a basis for the development of further research.

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