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Kinetics and mechanism of plasticized poly(vinyl chloride) films autohesion. Interface effect

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Kinetics of bis(2-diethylhexyl)phthalate plasticized poly(vinyl chloride) (PVC) autohesion development was monitored at 373 K, 393 K, 413 K. Three regions of bonding kinetics were observed (first time) at all temperatures: adhesion increase after initial contact, constant adhesion plateau, long contact time adhesion increase. Initial adhesion increase resulted from plasticizer diffusion into interface and capillary attraction, activation energy, Ea = 66 kJ mol−1. Plateau in adhesion kinetics is consistent with polymer segments diffusion across interface; duration decreased with temperature increase, yielding Ea = 113 kJ mol−1. Adhesion at plateau increased linearly with temperature increase, indicating Van der Waals attraction between the PVC macromolecules in interface. Final adhesion increase was stipulated by macromolecular segments diffusion into and entanglement within interface, Ea = 109 kJ mol−1. Scanning electron and optical microscopy confirmed plasticizer and polymer diffusion into interface (width up to 3.5 µm). PVC segments diffusivities in plasticized PVC were derived: 1.8 × 10−13 cm2 s−1 at 373 K, 1.1 × 10−12 cm2 s−1 at 393 K, 6.3 × 10−12 cm2 s−1 at 413 K.

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Acknowledgement

The support of this work by ICU Medical, Inc. Company, Austin, USA and particularly by Dr. Peter Kramer and Dr. Akanksha Nagpal is gratefully acknowledged. Discussions of surface interactions and capillary adhesion with Danielle M. Krongauz, The Weitzman Institute of Science were particularly helpful.

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Krongauz, V.V. Kinetics and mechanism of plasticized poly(vinyl chloride) films autohesion. Interface effect. J Therm Anal Calorim 147, 4177–4195 (2022). https://doi.org/10.1007/s10973-021-10832-0

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