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.

This paper reports for the first time the fabrication and investigation of wetting properties of structured surfaces formed by lamellae with an exceptionally high aspect ratio of up to 57:1 and more. The lamellar surfaces were fabricated using a polymer with tunable mechanical properties and shape-memory behavior. It was found that wetting properties of such structured surfaces depend on temperature, and thermal treatment history-structured surfaces are wetted easier at elevated temperature or after cooling to room temperature when the polymer is soft because of the easier deformability of lamellae. The shape of lamellae deformed by droplets can be temporarily fixed at low temperature and remains fixed upon heating to room temperature. Heating above the transition temperature of the shape-memory polymer restores the original shape. The high aspect ratio allows tuning of geometry not only manually, as it is done in most works reported previously but can also be made by a liquid droplet and is controlled by temperature. This behavior opens new opportunities for the design of novel smart elements for microfluidic devices such as smart valves, whose state and behavior can be switched by thermal stimuli: valves that can or cannot be opened that are able to close or can be fixed in an open or closed states.

Amphiphilic copolymers with poly (alkyl acrylate) as hydrophobic and poly (acrylic acid) (AA) as hydrophilic block have been synthesised. The alkyl chain was varied from butyl to dodecyl, thereby varying systematically the polarity of the hydrophobic block whose length was between 35 and 70, while the PAA block had ~ 100 units. Such relatively short amphiphiles should equilibrate quickly in aqueous solution, and their corresponding self-assembly properties were characterised by means of critical micelle concentration (cmc) determination. Detailed information regarding the aggregate structures was obtained by static light scattering (SLS) and small angle neutron scattering (SANS). This could be correlated with the molecular architecture of the copolymers and the degree of ionisation of the PAA block. Generally, it is found that the aggregation numbers become smaller upon fully charging the PAA head group and only for dodecyl acrylate really well-defined micellar aggregates are formed. This means that the extent of hydrophobicity of the alkyl acrylate block and its length determine in a clear fashion the propensity for micelle formation and the mass and aggregation number of the formed micelles.

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.

Development of fiber‐spinning technologies and materials with proper mechanical properties is highly important for the manufacturing of aligned fibrous scaffolds mimicking structure of the muscle tissues. Here, the authors report touch spinning of a thermoplastic poly(1,4‐butylene adipate)‐based polyurethane elastomer, obtained via solvent‐free polymerization. This polymer possesses a combination of important advantages such as 1) low elastic modulus in the range of a few MPa, 2) good recovery ratio and 3) resilience, 4) processability, 5) nontoxicity, 6) biocompatibility, and 7) biodegradability that makes it suitable for fabrication of structures mimicking extracellular matrix of muscle tissue. Touch spinning allows fast and precise deposition of highly aligned micro‐ and nano‐fibers without use of high voltage. C2C12 myoblasts readily align along soft polymer fibers and demonstrate high viability as well as proliferation that make proposed combination of polymer and fabrication method highly suitable for engineering skeletal muscles.

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.

Herein, the fabrication of light‐sensitive high‐aspect ratio surfaces with switchable topography using melt‐electrowriting of shape‐memory polymers and deposition of light‐to‐heat converting black ink on it by dip coating is reported on. The lamellae exposed to low temperatures are hard and cannot be deformed by water droplets. The temperature reached upon illumination of surfaces is close to the melting point of the soft segment of the polyurethane that leads to softening of the polymer. Due to this, it is possible to locally deform and recover the light‐softened surface structures by water droplets deposited on lamellae. The deformed state can be fixed by cooling down resulting in the crystallization of the polymer. Thus, the reversibility of local deformation can be achieved. Finally, the application of the developed approach and materials for the fabrication of smart light‐controlled valves is demonstrated, which can be used for the controlled mixing of fluids in microfluidic devices.

The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adem.202201022.