Developing multifunctional polymers with excellent mechanical properties, outstanding shape memory characteristics, and good self-healing properties is a formidable challenge. Inspired by the woven cross-linking strategy, a series of supramolecular polyurethane (PU) with an interwoven network structure composed of covalent and supramolecular cross-linking nodes have been successfully synthesized by introducing the ureido-pyrimidinone (UPy) motifs into the PU skeleton. The best-performing sample exhibited ultrahigh strength (∼77.2 MPa) and toughness (∼312.7 MJ m-3), along with an ideal self-healing efficiency (up to 90.8% for 6 h) and satisfactory temperature-responsive shape memory effect (shape recovery rates up to 96.9%). Furthermore, it ensured recyclability. These favorable properties are mainly ascribed to the effective dissipation of strain energy due to the disassembly and reconfiguration of supramolecular nodes (i.e., quadruple hydrogen bonds (H-bonds) between UPy units), as well as the covalent cross-linking nodes that maintain the integrity of the polymer network structure. Thus, our work provides a universal strategy that breaks through the traditional contradictions and paves the way for the commercialization of high-performance multifunctional PU elastomers.

Miniature shape-morphing soft actuators driven by external stimuli and fluidic pressure hold great promise in morphing matter and small-scale soft robotics. However, it remains challenging to achieve both rich shape morphing and shape locking in a fast and controlled way due to the limitations of actuation reversibility and fabrication. Here, fully 3D-printed, sub-millimeter thin-plate-like miniature soft hydraulic actuators with shape memory effect (SME) for programable fast shape morphing and shape locking, are reported. It combines commercial high-resolution multi-material 3D printing of stiff shape memory polymers (SMPs) and soft elastomers and direct printing of microfluidic channels and 2D/3D channel networks embedded in elastomers in a single print run. Leveraging spatial patterning of hybrid compositions and expansion heterogeneity of microfluidic channel networks for versatile hydraulically actuated shape morphing, including circular, wavy, helical, saddle, and warping shapes with various curvatures, are demonstrated. The morphed shapes can be temporarily locked and recover to their original planar forms repeatedly by activating SME of the SMPs. Utilizing the fast shape morphing and locking in the miniature actuators, their potential applications in non-invasive manipulation of small-scale objects and fragile living organisms, multimodal entanglement grasping, and energy-saving manipulators, are demonstrated.

In this study, we demonstrate the feasibility of rapid volumetric additive manufacturing in the solid state. This additive manufacturing technology is particularly useful in outer space missions (microgravity) and/or for harsh environment (e.g., on ships and vehicles during maneuvering, or on airplanes during flight). A special thermal gel is applied here to demonstrate the concept, that is, ultraviolet crosslinking in the solid state. The produced hydrogels are characterized and the water-content-dependent heating/cooling/water-responsive shape memory effect is revealed. Here, the shape memory feature is required to eliminate the deformation induced in the process of removing the uncrosslinked part from the crosslinked part in the last step of this additive manufacturing process.

The four-dimensional (4D) printing is an evolving technology that has immense scope in various fields of science and technology owing to ever-challenging needs of human. It is an innovative upgradation of 3D printing procedure, which instills smart capabilities into materials such that they respond to external stimulus. This article aims to investigate the feasibility of 4D printing of polylactic acid (PLA)-based composite scaffolds fabricated by incorporating four different nature-inspired architectures (honeycomb, giant water lily, spiderweb, and nautilus shell). The composites were developed by adding 1, 3, and 5 wt.% of Calcium Phosphate (CaP) into PLA. Various thermomechanical tests were accomplished to evaluate the properties of developed material. Furthermore, the shape memory characteristics of these scaffolds were examined using thermally controlled conditions. The characterization tests displayed favorable outcomes in terms of thermal stability and hydrophilic nature of the PLA and PLA/CaP composite materials. It was found that the honeycomb structure showed the best shape memory and mechanical behavior among the four designs. Furthermore, the introduction of CaP was found to enhance mechanical strength and shape memory property, whereas the surface integrity was adversely affected. This study can play a vital role in developing self-fitting high-shape recovery biomedical scaffolds for bone-repair applications.

This article presents the results of studies of the features of the development of thermoelastic martensitic transformations during cooling/heating in the free state and under load of Ti50Ni49.7-XNbXMo0.3 alloys (X = 0.5, 1.0 and 1.5 at% Nb) with shape memory effects. Using X-ray diffraction analysis, it was found that all the alloys studied at room temperature contained a multiphase mixture consisting of intermetallic compounds with the TiNi (B2, B19\'), Ni56Ti29Nb15, and Ti2Ni compositions. Scanning electron microscopy was used to study the microstructure of TiNi (Nb,Mo) alloys and it was found that the distribution of fine Ni56Ti29Nb15 particles in the matrix depends significantly on the concentration of the alloying element. A correlation was established between changes in the structural-phase state in TiNi (Nb,Mo) alloys and the occurrence of the B2↔B19\' martensitic transition in the free state and under load. Based on physical and mechanical studies, the temperature ranges of the martensitic transformations (MT) in the free state and under load were established. Based on the thermodynamic description of the MT and the analysis of the characteristic temperatures of the MT, it was found that the MT mechanism is strongly dependent on the concentration of the alloying element.

In this review, we systematically reviewed the recent advances in the development of ultrafine shape memory alloys with unique shape memory effects and superelastic behavior using amorphous metallic materials. Its scientific contribution involves defining and expanding the range of fabrication methods for single-phase ultrafine/nanocrystalline alloys with multicomponent systems. In multicomponent amorphous alloys, the crystallization mechanism depends on the alloy composition and is a selectable factor in the alloy designing method, considering the thermodynamic and physical parameters of constituent elements. The crystallization kinetics can be controlled by modulating the annealing condition in a supercooled liquid state with consideration of the crystalline temperature of the amorphous alloys. The phase stability of austenite and martensite phases in ultrafine shape memory alloys developed from amorphous precursors is determined according to alloy composition and grain size, which strongly influence the shape memory effect and superelastic behavior. A methodological framework is subsequently suggested to develop the ultrafine shape memory alloys based on the systematic alloy designing method, which can be considered an important strategy for developing novel ultrafine/nanocrystalline shape memory alloys with excellent shape memory and superelastic effects.

We successfully developed a mechanical metamaterial that displays martensitic transformation for the first time. This metamaterial has a bistable structure capable of transitioning between two stable configurations through shear deformation. The outer shape of the unit cell of this structure is a parallelogram, with its upper and lower sides forming the bases of two solid triangles. The vertices from these triangles within the parallelogram are linked by short beams, while the remaining vertices are linked by long beams. The elastic energy of the essential model of the metamaterial was formulated analytically. The energy barrier between these two stable configurations consists of the elastic strain energy due to the tensile deformation of the short beams, the compressive deformation of the long beams, and the bending deformation of the connecting hinges. One example of a novel metamaterial was additively manufactured via the materials extrusion (MEX) process of thermoplastic polyurethane. The metamaterial exhibited deformation behaviors characteristic of martensitic transformations. This mechanical metamaterial has the potential to obtain properties caused by martensitic transformation in actual materials, such as the shape memory effect and superelasticity.

In this study, the effect of heat treatment parameters on the optimized performance of Ni-rich nickel-titanium wires (NiTi/Nitinol) were investigated that were intended for application as actuators across various industries. In this instance, the maximum recovery strain and actuation angle achievable by a nitinol wire were employed as indicators of optimal performance. Nitinol wires were heat treated at different temperatures, 400-500 °C, and times, 30-120 min, to study the effects of these heat treatment parameters on the actuation performance and properties of the nitinol wires. Assessment covered changes in density, hardness, phase transition temperatures, microstructure, and alloy composition resulting from these heat treatments. DSC analysis revealed a decrease in the austenite transformation temperature, which transitioned from 42.8 °C to 24.39 °C with an increase in heat treatment temperature from 400 °C to 500 °C and was attributed to the formation of Ni4Ti3 precipitates. Increasing the heat treatment time led to an increase in the austenite transformation temperature. A negative correlation between the hardness of the heat-treated samples and the heat treatment temperature was found. This trend can be attributed to the formation and growth of Ni4Ti3 precipitates, which in turn affect the matrix properties. A novel approach involving image analysis was utilized as a simple yet robust analysis method for measurement of recovery strain for the wires as they underwent actuation. It was found that increasing heat treatment temperature from 400 °C to 500 °C above 30 min raised recovery strain from 0.001 to 0.01, thereby maximizing the shape memory effect.

Inks for 3D printing were prepared by dispersing bacterial cellulose nanofibers (CNF) functionalized with methacrylate groups in a polymerizable deep eutectic solvent (DES) based on choline chloride and acrylic acid with water as a cosolvent. After 3D printing and UV-curing, the double-network composite gel consisting of chemically and physically crosslinked structures composed from sub-networks of modified CNF and polymerized DES, respectively, was formed. The rheological properties of inks, as well as mechanical and shape memory properties of the 3D-printed gels, were investigated in dynamic and static modes. It was shown that the optimal amount of water allows improvement of the mechanical properties of the composite gel due to the formation of closer contacts between the modified CNF. The addition of 12 wt% water results in an increase in strength and ultimate elongation to 11.9 MPa and 300%, respectively, in comparison with 5.5 MPa and 100% for an anhydrous system. At the same time, the best shape memory properties were found for an anhydrous system: shape fixation and recovery coefficients were 80.0 and 95.8%, respectively.

The complexity of surgical treatments for large-area soft tissue injuries makes placing large implants into injury sites challenging. Aliphatic polyesters are often used for scaffold preparation in tissue engineering owing to their excellent biodegradability and biocompatibility. Scaffolds with shape-memory effect (SME) can also avoid large-volume trauma during the implantation. However, the complexity and diversity of diseases require more adaptable and precise processing methods. Four-dimensional (4D) printing, a booming smart material additive manufacturing technology, provides a new opportunity for developing shape memory scaffolds. With the aim of personalized or patient-adaptable soft tissues such as blood vessels, we developed a feasible strategy for fabricating scaffolds with fine architectures using 4D printing crosslinkable shape memory linear copolyesters using fused deposition modeling (FDM). To overcome the weak bonding strength of each printed layer during FDM, a catalyst-free photo-crosslinkable functional group derived from biocompatible cinnamic acid was embedded into the linear copolyesters as in situ crosslinking points during FDM printing. Under ultraviolet-assisted irradiation, the resulting 4D scaffold models demonstrated excellent SME, desirable mechanical performance, and good stability in a water environment owing to the chemical bonding between each layer. Moreover, the excellent biocompatibility of the scaffold was evaluated in vitro and in vivo. The developed composite scaffolds could be used for minimally invasive soft tissue repair.