Interest in renewable polymers increased exponentially in the last decade and in this context poly(lactic acid) (PLA) became the leader mainly for practical reasons. Nevertheless, it is outstanding also from a scientific point of view, because its thermal and morphological properties are offering challenging new insights. With regard to dynamic mechanical analysis (DMA), PLA does not have the classical behavior of a thermoplastic polymer. Often, overlapping events (enthalpic relaxation, glass transition and crystallization) that occur as the temperature increases make the DMA result of a PLA look inexplicable even for polymer scientists. This review offers a perspective of the main phenomena that can be revealed in a DMA experiment and systematizes the information that can be obtained for every region (glassy, glass transition, rubbery, cold-crystallization and melting). Also, some unusual patterns registered in some cases will be commented upon. The review intends to offer indices that one should pay attention to in the interpretation of a DMA experiment, even if the investigator has only basic skills with DMA investigations.
This paper presents the course of synthesis and the properties of biodegradable terpolymers obtained by ROP of L-lactide with glycolide, catalysed with zirconium(IV) acetylacetonate and conducted in the presence of a macroinitiator – trimethylene carbonate oligomers terminated with hydroxyl groups. The oligomers were also prepared by ROP reaction of TMC catalysed by zinc(II) acetylacetonate monohydrate in the presence of polyols as initiators. Depending on the type of initiator used, the oligomers had a linear or branched structure of the chain with different hydroxyl end-groups. Some of the obtained oligomers formed a network. The effect of the terpolymer chain structure on mechanical and thermomechanical properties as well as shape-memory behaviour was shown. The ability to control the speed of return from a temporary to a permanent shape, the value of stress of return triggered by this phenomenon, and the magnitude of the temperature range in which the phenomenon took place through appropriate selection of conditions for programming the temporary shape or/and terpolymer chain microstructure has been shown. The possibility of adjusting these parameters as presented in this paper is vital in the process of designing a bioresorbable material, which can be used for forming self-expanding stents or self-clamping surgical staples.
This paper presents experimental and modeling results of the effects of thermomechanical couplings occurring in a polyurethane shape memory polymer (SMP) subjected to tension at various strain rates within large strains. The SMP mechanical curves, recorded using a testing machine, and the related temperature changes, measured in a contactless manner using an IR camera, were used to investigate the polymer deformation process at various loading stages. The effects of thermomechanical couplings allowed the determination of the material yield point in the initial loading stage, the investigation of nucleation and development of the strain localization at larger strains and the estimation of the effects of thermoelastic behavior during the unloading process. The obtained stress–strain and thermal characteristics, the results of the dynamic mechanical analysis and estimated values of the shape fixity and shape recovery parameters confirmed that the shape memory polymer ( Tg = 45 °C) is characterized by good mechanical and shape memory properties, as well as high sensitivity to the strain rate. The mechanical response of the SMP subjected to tension was simulated using the finite element method and applying the large strain, two-phase model. Strain localization observed in the experiment was well reproduced in simulations and the temperature spots were correlated with the accumulated viscoplastic deformation of the SMP glassy phase.
15 February 1999 in Journal of Polymer Science Part A: Polymer Chemistry