Polyphenylene sulfide for high-rate composite manufacturing: Impacts of processing parameters on chain architecture, rheology, and crystallinity

Abstract

High performance semi-crystalline thermoplastics necessitate high temperature processing to form useful structures, but the effects of repeated exposure to these extreme environments on key polymer properties are not well understood. This work investigates the influence of degradation-driven structural changes resulting from exposure to standard melt processing conditions in oxygen rich environments on the rheological properties, crystallization behavior, and crystal structure of polyphenylene sulfide (PPS). Melt processing temperatures (300°C, 320°C, and 340°C) and hold times (up to 60 min) are varied to probe the effects of thermal exposure on polymer properties. Extended melt-state exposure causes an increase in PPS melt viscosity due to the formation of complex branched/crosslinked structures where increasing temperature causes this process to occur more rapidly. Dynamic isothermal rheology of PPS displays a 70x increase in the complex viscosity at 10 rad/s after 60 minutes at 340°C. Frequency sweep rheological experiments reveal a notable deviation from linearity (terminal slope = 2) with slopes as low as 0.14 after thermal exposure. Stress recovery experiments indicate thermally processed PPS requires more time to relax stress under an applied strain. Imperfections along the polymer backbone in the form of branches/crosslinks decrease overall crystallinity and reduce lamellar thickness, with no changes to the unit cell structure. For semi-crystalline high performance thermoplastic matrix composites relying on high degrees of crystallinity to provide solvent resistance and strength, these results have serious implications for the need to tightly control melt processing steps and understand the final material state. Furthermore, viscoelastic properties of post-processed PPS polymers should be considered for recycling and reuse strategies.