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In this work, using supramolecular polyurethanes theories, two polycaprolactone-based polyurethanes with 2-ureido-4-[1H]-pyrimidinone (UPy) motifs capable of forming quadruple hydrogen bonds were synthetized and characterized, focusing our attention on their capability to show thermally activated shape-memory response. In particular, 1H NMR analyses confirmed the chemical structure of the supramolecular polyurethanes, while DSC showed their totally amorphous morphology. DMTA in tensile mode was used to study their thermally activated shape-memory properties. In our case, the UPy units are the switching domains while the network formed by the segregated hard segments is the permanent domain obtained materials with excellent shape-memory response at both 100 and 85 °C. These materials are promising for multi-responsive materials where bio-based and potentially recyclable polymers with excellent shape-memory properties are needed. [ABSTRACT FROM AUTHOR]

In this work the thermally-activated shape memory response of biodegradable nanocomposites based on PLA/PCL blend reinforced with different type of cellulose nanocrystals has been reported, and compared with those of the neat matrix, at the same transition temperature of 55 °C and at the same different deformations, 50%, 100% and 150%. In particular, cellulose nanocrystals have been synthesized and then functionalized by “grafting from” reaction by ring opening polymerization of both PLLA and PCL using the OH groups onto the cellulose nanocrystals surface as initiators for the reaction. The morphology, thermal and mechanical analysis have been performed in order to obtain the parameters for the thermo-mechanical shape memory cycles. Moreover, the addition of the CNC-based nanofillers on the compatibility of PLA-PCL blends in 70:30 proportion has been evaluated. All the biodegradable nanocomposite formulations showed excellent shape memory response, similar to those of the neat matrix, with strain recovery ratio and strain fixity ratio higher than 80% and 90%, respectively. This fact indicates that in this case, the shape memory response of the nanocomposites is mainly controlled by the response of the neat blend and they are slightly influenced by the increase of compatibility between the components of the blend. In addition, all nanocomposite films were fully disintegrated under composting conditions confirming their biodegradable nature, obtaining that the presence of CNC-based nanofillers speeds up the disintegration rate of the nanocomposites in comparison with the pure matrix. [ABSTRACT FROM AUTHOR]

Blending commercial homopolymers represents a low cost and an easy scalable process to extend the use of the pristine homopolymers to an industrial level. Actually, the processing of blends by extrusion is the usual solution followed in the industry. However, commonly polymer blends are immiscible, provoking phase separation, which can be in the macro, micro or nano scale, depending on the polymers as well as on the processing conditions, affecting the final properties of the blends. Therefore, this paper aims to study the shape memory behavior in biodegradable blends based on poly(lactic acid) (PLA) and poly(ε-caprolactone) (PCL) in different concentrations. A completely thermal and mechanical characterization of the blends was performed, correlating the results with the observed morphology. In addition, two different biodegradation studies were performed in order to correlate the effect of each homopolymer with the degradation behavior of the biodegradable blends. [ABSTRACT FROM AUTHOR]

For soft robotics and programmable metamaterials, novel approaches are required enabling the design of highly integrated thermoresponsive actuating systems. In the concept presented here, the necessary functional component was obtained by polymer syntheses. First, poly(1,10-decylene adipate) diol (PDA) with a number average molecular weight Mn of 3290 g·mol−1 was synthesized from 1,10-decanediol and adipic acid. Afterward, the PDA was brought to reaction with 4,4′-diphenylmethane diisocyanate and 1,4-butanediol. The resulting polyester urethane (PEU) was processed to the filament, and samples were additively manufactured by fused-filament fabrication. After thermomechanical treatment, the PEU reliably actuated under stress-free conditions by expanding on cooling and shrinking on heating with a maximum thermoreversible strain of 16.1%. Actuation stabilized at 12.2%, as verified in a measurement comprising 100 heating-cooling cycles. By adding an actuator element to a gripper system, a hen's egg could be picked up, safely transported and deposited. Finally, one actuator element each was built into two types of unit cells for programmable materials, thus enabling the design of temperature-dependent behavior. The approaches are expected to open up new opportunities, e.g., in the fields of soft robotics and shape morphing. [ABSTRACT FROM AUTHOR]

Epoxy/Polycaprolactone (PCL) blends cured with a conventional diamine (4,4′-diaminodiphenylmethane, DDM) and with different amounts of a disulfide containing diamine (4, 4´-dithioaniline, DSS) were prepared through melting. The curing process was studied by FTIR and differential scanning calorimetry (DSC) and the mechanical behavior of the networks was studied by DMA. The shape memory properties and the recyclability of the materials were also analyzed. All blends showed a very high curing degree and temperature activated shape memory effect, related to the glass transition of the epoxy resin. The PCL plasticized the mixture, allowing tailoring of the epoxy glass transition. In addition, in the blends cured with DSS, as a consequence of the disulfide exchange reaction, the permanent shape could be erased and a new shape could be reprogrammed. Using this strategy, reprogrammable permanent shape memory materials were obtained. [ABSTRACT FROM AUTHOR]

Liquid crystal polymers have attracted massive attention as stimuli-responsive shape memory materials due to their unique reversible large-scale and high-speed actuations. These materials can be utilized to fabricate artificial muscles, sensors, and actuators driven by thermal order–disorder phase transition or trans–cis photoisomerization. This review collects most commonly used liquid crystal monomers and techniques to macroscopically order and align liquid crystal materials (monodomain), highlighting the unique materials on the thermal and photo responsive reversible shape memory effects. Challenges and potential future applications are also discussed. [ABSTRACT FROM AUTHOR]