Chain-length dependent relaxation dynamics in glass-forming polymers

We present experimental and computational results on the effects of molecular size, monomer chemistry, and flexibility on the relaxation behaviour of glass-forming polymers. We show experimental data from broadband dielectric spectroscopy, calorimetry, and oscillatory rheology together with RIS computer simulation calculations. We discuss the length-dependence of molecular relaxation dynamics, chain conformation and shape; and relate these features to the glass transition temperature. We discuss the links between glass-formation in small molecules and oligomeric/polymeric glass-formers and the dependences on polymer chemistry and flexibility.