IntroductiontoPolymerPhysics.ppt

Introduction to Polymer Physics Prof. Dr. Yiwang Chen School of Materials Science and Engineering, Nanchang University, Nanchang 330047 Chapter 4 Molecular weight For a discrete distribution of molecular weights, an average molecular weight, M, may be defined as Where Ni indicates the number of moles of molecules with a molecular weight of Mi and the parameter ? is a weighting factor that defines a particular average of the molecular-weight distribution. The weight, Wi, of molecules with molecular weight Mi is then Molecular weights that are important in determining polymer properties are the number-average, Mn (?=1), the weight-average, Mw (?=2), and the z-average, Mz (?=3), molecular weights. Since the molecular-weight distribution of commercial polymers is normally a continuous function, molecular-weight averages can be determined by integration if the proper mathematical form of the molecular-weight distribution (i.e., N as a function of M) is known or can be estimated. Such mathematical forms include theoretical distribution functions derived on the basis of a statistical consideration of an idealized polymerization, such as the Flory, Schultz, Tung, and Pearson distributions, and standard probability functions, such as the Poisson and logarithmic-normal distributions. Polydispersity index A measure of the breadth of the molecular-weight distribution is given by the ratios of molecular-weight averages For this purpose, the most commonly used ratio is Mw/Mn, which is called the polydispersity index or PDI. The PDIs of commercial polymers vary widely. For example, commercial grades of polystyrene with a Mn of over 100,000 have polydispersities indices between 2 and 5, while polyethylene synthesized in the presence of a stereospecific catalyst may have a PDI as high as 30. In contrast, the PDI of some vinyl polymers prepared by “living” polymerization can be as low as 1.06. Example Problem A polydisperse sample of polystyrene is prepared by mixing three mono