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Herein, we report on how to teach a thermoplastic polyurethane elastomer completely stress-free, bidirectional motion. Briefly spoken, we applied training, consisting of extensive tensile deformation in the specimen's viscoelastic state, initiating deformation-induced crystallization. Once unloaded, thermo-reversible specimen expansion and contraction could be detected. Following the microstructural evolution of such a trained specimen by in situ wide-angle X-ray scattering gave evidence for progressive growth of oriented crystallites during cooling. Upon heating, crystallite melting resulted in structural disorder. Beyond this, modification of the training method was used to introduce a geometrically more complex crystalline order. Here, actuation in the form of a decrease and an increase in sample thickness and specimen twisting and untwisting were witnessed. The novel semi-crystalline polymer actuator highlights an enormous potential for realizing versatile reversible shape changes in elastomers.
Shape memory polymers (SMPs) can change their shape on application of a suitable stimulus. To enable such behavior, a ‘programming’ procedure fixes a deformation, yielding a stable temporary shape. In thermoresponsive SMPs, subsequent heating triggers entropy-elastic recovery of the initial shape. An additional shape change on cooling, i.e. thermoreversible two-way actuation, can be stimulated by a crystallization phenomenon. In this thesis, cyclic thermomechanical measurements systematically determined (1) the shape memory and (2) the actuation behavior under constant load as well as under stress-free conditions. Chemically cross-linked, star-shaped polyhedral oligomeric silsesquioxane polyurethane (SPOSS-PU) hybrid polymer networks and physically cross-linked poly(ester urethane) (PEU) block copolymers were investigated around the melting and crystallization temperatures of their polyester soft segments. (1) The SPOSS-PUs showed excellent shape fixities and recoverabilities of almost 100% at high cross-linking density, while PEUs exhibited pronounced shape memory properties at increased soft segment content. Furthermore, two-fold programmed SPOSS-PU specimens were able to recover their initial shape in two thermally separated events. Even a neck, which formed during deformation of SPOSS-PUs with high soft segment content, was reversed. (2) In PEUs, globally oriented crystallization on cooling drove expansion of the sample, in particular at high soft segment content and after application of a strong deformation. Melting reversed that orientation; the PEU sample contracted and thereby completed the thermoreversible actuation cycle. Under load, multiple polymorphic phase transitions enabled two successive expansion and contraction steps, while under stress-free conditions various geometric shape changes, including the increase and decrease of PEU sample length and thickness as well as twisting and untwisting could be experimentally witnessed. Such actuation technology allows for entirely new applications, enabling mimicry of reversible, bidirectional and repeated organic movements.