Physical ageing in poly(vinyl acetate) 1. Enthalpy relaxation

✍ Scribed by J. M. G. Cowie; S. Harris; I. J. McEwen

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 216 KB
• Volume: 35
• Category: Article
• ISSN: 0887-6266
• DOI: 10.1002/(sici)1099-0488(199705)35:7<1107::aid-polb9>3.0.co;2-s

✦ Synopsis

The enthalpy changes DH ϱ between a poly(vinyl acetate) glass formed by rapid cooling and the corresponding fully relaxed glass have been estimated at four temperatures below the glass transition. The values obtained were different to those expected by extrapolating liquid behavior below the glass transition and were found to agree well with the predictions of a simple expression for the combined main chain conformational and free volume contributions to enthalpy. Conformational contributions from the side chain alone were also considered but were not required to obtain agreement with experiment. It can be concluded that the side chains remained mobile below the glass transition and do not contribute to the heat capacity discontinuity at T g .