I. INTRODUCTION

Early structural characterization of polymers focused on solution properties and their relationship to molecular weight [1 4]. Subsequently spectroscopic and chromatographic techniques were developed, and reviews are widely available [5 10]. In this chapter, various characterization techniques are described. The two prior editions discussed in some detail procedures for the analysis of elastomers. Much of this information is not otherwise available in the open literature, at least not in self-contained fashion. Thus, in preparing the third edition, a significant amount of the previous text was retained, especially that specific to elastomers. Discussion of the classical methods of analysis is largely unchanged, although the text and references have been updated. The coverage of NMR, SANS, and secondary relaxations has been expanded, and several new topics, including orientation, defects, and blends, have been added.

Knowledge of chemical composition, compositional and sequence distribution, molecular weight and its distribution, and the degree and type of branching allows inferences to be drawn concerning the mechanical properties (Chapters 4, 10), the rheology (Chapters 5, 6), curing behavior (Chapter 7), filler reinforcement (Chapter 8), and chemical reactivity (Chapter 11) of rubber. However, relationships between fundamental molecular variables and the properties of condensed matter are semiquantitative at best, and correlation never guarantees causation. Following the earlier editions, methods for molecular weight determination are discussed at greater length than spectroscopic methods.This bias is based on the idea that areas in which common problems might arise,...