4D Fabrication of Two-Way Shape Memory Polymeric Composites by Electrospinning and Melt Electrowriting.

This work presents a new method for 4D fabrication of two-way shape memory materials that are capable of reversible shapeshifting right after manufacturing, upon application of proper heating and cooling cycles. The innovative solution presented here consists in the combination of highly stretched electrospun shape memory polymer (SMP) nanofibers with a melt electrowritten elastomer. More specifically, the stretched nanofibers are made of a biocompatible thermoplastic polyurethane (TPU) with crystallizable soft segments, undergoing melt-induced contraction and crystallization-induced elongation upon heating and cooling, respectively. Reversible actuation during crystallization becomes possible due to the elastic recovery of the elastomer component, obtained by melt electrowriting of a commercial TPU filament. Thanks to the design freedom offered by additive manufacturing, the elastomer structure also has the role of guiding the shape transformation. Electrospinning and melt electrowriting process parameters are set up so to obtain smart 4D objects capable of two-way shape memory effect (SME), and the possibility of reversible and repeatable actuation is demonstrated. The two components are then combined in different proportions with the aim of tailoring the two-way SME, taking into account the effect of design parameters such as the SMP content, the elastomer pattern, and the composite thickness.

A Comparison of Interpolyelectrolyte Complexes (IPECs) Made from Anionic Block Copolymer Micelles and PDADMAC or q-Chitosan as Polycation.

Block copolymers synthesized via Atom Transfer Radical Polymerization from alkyl acrylate and t-butyl acrylate and the subsequent hydrolysis of the t-butyl acrylate to acrylic acid were systematically varied with respect to their hydrophobic part by the variation in the alkyl chain length and the degree of polymerisation in this block. Depending on the architecture of the hydrophobic part, they had a more or less pronounced tendency to form copolymer micelles in an aqueous solution. They were employed for the preparation of IPECs by mixing the copolymer aggregates with the polycations polydiallyldimethylammonium chloride (PDADMAC) or q-chit. The IPEC structure as a function of the composition was investigated by Static Light and Small Angle Neutron Scattering. For weakly-associated block copolymers (short alkyl chain), complexation with polycation led to the formation of globular complexes, while already existing micelles (long alkyl chain) grew further in mass. In general, aggregates became larger upon the addition of further polycation, but this growth was much more pronounced for PDADMAC compared to q-chit, thereby leading to the formation of clusters of aggregates. Accordingly, the structure of such IPECs with a hydrophobic block depended largely on the type of complexing polyelectrolyte, which allowed for controlling the structural organisation via the molecular architecture of the two oppositely charged polyelectrolytes.

Dual Stimuli-Responsive Orthodontic Aligners: An In Vitro Study.

Aligner therapy for orthodontic tooth movement is gaining importance in orthodontics. The aim of this contribution is to introduce a thermo- and water-responsive shape memory polymer (SMP), which could lay the foundation for a new type of aligner therapy. The thermal, thermo-mechanical, and shape memory properties of thermoplastic polyurethane were studied by means of differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and various practical experiments. The glass transition temperature of the SMP relevant for later switching was determined to be 50 °C in the DSC, while the tan δ peak was detected at 60 °C in the DMA. A biological evaluation was carried out using mouse fibroblast cells, which showed that the SMP is not cytotoxic in vitro. On a digitally designed and additively manufactured dental model, four aligners were fabricated from an injection-molded foil using a thermoforming process. The aligners were then heated and placed on a second denture model which had a malocclusion. After cooling, the aligners were in a programmed shape. The movement of a loose, artificial tooth and thus the correction of the malocclusion could be realized by thermal triggering the shape memory effect, at which the aligner corrected a displacement with an arc length of approximately 3.5 mm. The developed maximum force was separately determined to be about 1 N. Moreover, shape recovery of another aligner was realized within 20 h in 37 °C water. In perspective, the present approach can help to reduce the number of orthodontic aligners in therapy and thus avoid excessive material waste.

Smart Mechanically Tunable Surfaces with Shape Memory Behavior and Wetting-Programmable Topography.

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.

Fibrous Scaffolds for Muscle Tissue Engineering Based on Touch-Spun Poly(Ester-Urethane) Elastomer.

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.

Actuating Shape Memory Polymer for Thermoresponsive Soft Robotic Gripper and Programmable Materials.

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 M n 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.