From Melt Processing to Composting: Solvent-Free Thermoplastic Starch/Polyvinyl Alcohol Blends with Tailored Structure and Performance

Thermoplastic starch (TPS) and polyvinyl alcohol (PVA) blends were prepared over the full compositional range (0–100 wt% PVA) by solvent-free twin-screw extrusion and injection molding. This enabled a systematic evaluation of structure–performance–disintegration relationships under industrially relevant conditions. The blends exhibited clear composition-dependent trends in thermal and mechanical behavior. Increasing PVA content from 0 to 100 wt% raised the onset degradation temperature (T5%) from 160.5 °C to 290.5 °C and increased crystallinity from near zero to 12.24%. Mechanically, the response evolved from a rigid TPS-rich state to a ductile PVA-rich one. FTIR and SEM analyses indicated partial compatibility, with limited molecular-level interactions leading to morphologically homogeneous but only partially miscible blends. Under simulated composting conditions, all formulations showed substantial physical disintegration. PVA-rich blends (≥60 wt%) disintegrated rapidly (>80% mass loss within two days), primarily by dissolution rather than microbial degradation. Overall, this work provides a comprehensive, scalable assessment of solvent-free TPS/PVA blends, clarifies their limited compatibility under melt processing, and demonstrates how composition can be used to tailor structure, performance, and disintegration behavior across the full compositional range.