Abstract
This paper deals with the determination of the main characteristics and the assignment of the molecular motions leading to the solid-state transitions observed in amorphous polymers at temperatures lower than the glass--rubber transition. First, the specific features of these secondary transitions (β, γ, δ, ...) are briefly described. Then, the behaviour of various polymer systems is analysed: poly(cycloalkyl methacrylates) and their intracycle motions, poly(ethylene tere-phthalate) and bisphenol A polycarbonate β transition and the effect of small molecule antiplasticisers, aryl-alkyl polyamide transitions, the β transition of poly(methyl methacrylate) and its maleimide as well as glutarimide random copolymers. Additionally linear polymers, aryl-aliphatic epoxy systems, with or without antiplasticisers, illustrate the case of crosslinked amorphous polymers. Whereas all the systems considered were investigated by dynamic mechanical measurements and 13C solid-state nuclear magnetic resonance experiments, some systems were also studied by other techniques such as dielectric relaxation and molecular modelling. Poly(methyl methacrylate) and bisphenol A polycarbonate constitute the best examples of the level of description of the molecular motions involved in the β transition and, in particular, the nature and extent of the cooperativity which develops in the high-temperature part of the transition. This is achieved by combining all the experimental and modelling techniques presently available.
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Acknowledgments
The authors are greatly indebted to the Ph.D. students D. Bauchiere, F. Beaume, B. Bordes, B. Brule, S. Cukierman, L. Heux, B. Lousteau, L. Teze and P. Tordjeman; to the post-docs P.L. Lee and A.S. Maxwell who have been involved in many of these studies; and to their colleagues S. Choe, G. Davies, J. Schaefer, U. Suter, J. Virlet, I.M. Ward for their fruitful collaboration on various topics. They thank C. Gaillet-Sulpice for her help in producing the figures given in this paper.
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Monnerie, L., Lauprêtre, F., Halary, J.L. Investigation of Solid-State Transitions in Linear and Crosslinked Amorphous Polymers. In: Kausch, HH. (eds) Intrinsic Molecular Mobility and Toughness of Polymers I. Advances in Polymer Science, vol 187. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b136955
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DOI: https://doi.org/10.1007/b136955
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