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.
Shape memory polymers (SMPs) are stimuli-responsive materials, which are able to retain an imposed, temporary shape and recover the initial, permanent shape through an external stimulus like heat. In this work, a novel manufacturing method is introduced for thermoresponsive quick response (QR) code carriers, which originally were developed as anticounterfeiting technology. Motivated by the fact that earlier manufacturing processes were sometimes too time-consuming for production, filaments of a polyester urethane (PEU) with and without dye were extruded and processed into QR code carriers using fused filament fabrication (FFF). Once programmed, the distinct shape memory properties enabled a heating-initiated switching from non-decodable to machine-readable QR codes. The results demonstrate that FFF constitutes a promising additive manufacturing technology to create complex, filigree structures with adjustable horizontal and vertical print resolution and, thus, an excellent basis to realize further technically demanding application concepts for shape memory polymers.
4D printing of shape memory polymers enables the production of thermoresponsive objects. In this contribution, a facile printing strategy is followed for an in-house synthesized thermoplastic poly(ether urethane). Processing by means of fused filament fabrication, in which the difference between nozzle temperature and material-specific glass transition temperature of the polymer is kept as low as possible, allows to obtain highly shrinkable objects whose shape and thermoresponsiveness can be precisely controlled. The effectiveness of the method also applies to the printing material polylactic acid. One possible application lies in highly shrinkable objects for assembly purposes. As proof-of-concept, lightweight hands-free door openers for healthcare applications are functionally simulated and developed. Once printed, such devices shrink when heated to fit on door handles, allowing an easy assembly. At the end-of-use, a heating-initiated disassembling and mechanical recycling are proposed. In perspective, a reuse of the materials in 4D printing can contribute to the emergence of a circular economy for such highly functional materials.
Thermoresponsive objects can be manufactured from shape memory polymers (SMPs) via fused filament fabrication (FFF). Here a new technological approach to obtain thermally actuating objects using an in-house synthesized, phase segregated poly(ester urethane) (PEU) is introduced. Under almost stress-free conditions of a dynamic mechanical analysis, cuboid objects obtained from FFF shrank when heated to 62 °C and expanded when cooled to 15 °C with a maximum thermoreversible strain of 7.2%. Actuation can be traced back to the phenomena of melting-induced contraction and crystallization-induced elongation of the PEU's soft segment, supported by internal stresses as implemented in course of FFF. To translate small changes in shape to a next larger scale, an artificial butterfly is developed in which the movements of two actuator elements are transferred to the wings with the aid of a lever concept. Following a different approach, additive manufacturing of cylindrical samples implied application potential as a self-sufficient gripper, enabling a programmable material behavior in the sense of temperature-controlled gripping, transport, and release of exemplarily selected smooth surfaced objects in the form of vials.
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