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.

Shape Memory Effect of Four-Dimensional Printed Polylactic Acid-Based Scaffold with Nature-Inspired Structure.

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.

Rapid Volumetric Additive Manufacturing in Solid State: A Demonstration to Produce Water-Content-Dependent Cooling/Heating/Water-Responsive Shape Memory Hydrogels.

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.

Shape Memory Alloy-Based Reactive Tubular (SMART) Brake for Compact and Energy-Efficient Wearable Robot Design.

Soft wearable robots have been gaining increasing popularity for enhancing human physical abilities and assisting people who have physical limitations. These robots typically use tendon-driven mechanisms (TDMs) to enable remote actuation to provide better usability with compact design. TDMs comprise an actuator, an end-effector, and a transmission system by using cables or tendons to transfer forces from the actuator to the end-effector. Tendons are typically routed by frictionless guiding tubes to minimize force losses, variations in the force direction, and the volume. To make soft wearable robots even smaller, brakes need to be compacted because brakes are irreplaceable to ensure safety and energy efficiency. This study presents a shape memory alloy-based reactive tubular (SMART) brake for designing a compact and portable TDM-based device. The SMART brake actively adjusts the friction force between the brake and tendon, making it easy to achieve the desired friction state, ranging from low-friction states for free movement to high-friction states for effective braking. The brake is designed in a tubular shape, serving multifunctions as both a brake and a guiding tube. The brake's performance and theoretical model were validated through experiments and demonstrated by two wearable devices. The brake could hold a significant brake force of 19.37 N/11 mm while weighing only 0.3 g. These findings have major implications for the future development of TDM-based devices and soft wearable robots, paving the way for enhanced system portability, safety, and energy efficiency.

Additive manufacturing of Ni-free Ti-based shape memory alloys: A review.

Ni-free Ti-based Shape Memory Alloys composed of non-toxic elements have been studied as promising candidates for biomedical applications. However, high tool wear makes them complex to manufacture with conventional techniques. In this way, Additive Manufacturing technologies allow to fabricate complex three-dimensional structures overcoming their poor workability. Control of composition, porosity, microstructure, texture and processing are the key challenges for developing Ni-free Ti-based Shape Memory Alloys. This article reviews various studies conducted on the Additive Manufacturing of Ni-free Ti-based shape memory alloys, including their processing, microstructures and properties.

Advanced Soft Porous Organic Crystal with Multiple Gas-Induced Single-Crystal-to-Single-Crystal Transformations for Highly Selective Separation of Propylene and Propane.

Soft porous organic crystals with stimuli-responsive single-crystal-to-single-crystal (SCSC) transformations are important tools for unraveling their structural transformations at the molecular level, which is of crucial importance for the rapid development of stimuli-responsive systems. Carefully balancing the crystallinity and flexibility of materials is the prerequisite to construct advanced organic crystals with SCSC, which remains challenging. Herein, a squaraine-based soft porous organic crystal (SPOC-SQ) with multiple gas-induced SCSC transformations and temperature-regulated gate-opening adsorption of various C1-C3 hydrocarbons is reported. SPOC-SQ is featured with both crystallinity and flexibility, which enable pertaining the single crystallinity of the purely organic framework during accommodating gas molecules and directly unveiling gas-framework interplays by SCXRD technique. Thanks to the excellent softness of SPOC-SQ crystals, multiple metastable single crystals are obtained after gas removals, which demonstrates a molecular-scale shape-memory effect. Benefiting from the single crystallinity, the molecule-level structural evolutions of the SPOC-SQ crystal framework during gas departure are uncovered. With the unique temperature-dependent gate-opening structural transformations, SPOC-SQ exhibits distinctly different absorption behaviors towards C3 H6 and C3 H8 , and highly efficient and selective separation of C3 H6 /C3 H8 (v/v, 50/50) is achieved at 273 K. Such advanced soft porous organic crystals are of both theoretical values and practical implications.

Recent Developments in Ultrafine Shape Memory Alloys Using Amorphous Precursors.

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.

Electrospun Poly(carbonate-urea-urethane)s Nonwovens with Shape-Memory Properties as a Potential Biomaterial.

Poly(carbonate-urea-urethane) (PCUU)-based scaffolds exhibit various desirable properties for tissue engineering applications. This study thus aimed to investigate the suitability of PCUU as polymers for the manufacturing of nonwoven mats by electrospinning, able to closely mimic the fibrous structure of the extracellular matrix. PCUU nonwovens of fiber diameters ranging from 0.28 ± 0.07 to 0.82 ± 0.12 µm were obtained with an average surface porosity of around 50-60%. Depending on the collector type and solution concentration, a broad range of tensile strengths (in the range of 0.3-9.6 MPa), elongation at break (90-290%), and Young's modulus (5.7-26.7 MPa) at room temperature of the nonwovens could be obtained. Furthermore, samples collected on the plate collector showed a shape-memory effect with a shape-recovery ratio (Rr) of around 99% and a shape-fixity ratio (Rf) of around 96%. Biological evaluation validated the inertness, stability, and lack of cytotoxicity of PCUU nonwovens obtained on the plate collector. The ability of mesenchymal stem cells (MSCs) and endothelial cells (HUVECs) to attach, elongate, and grow on the surface of the nonwovens suggests that the manufactured nonwovens are suitable scaffolds for tissue engineering applications.

Martensitic Phase-Transforming Metamaterial: Concept and Model.

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.

Effect of Heat Treatment Time and Temperature on the Microstructure and Shape Memory Properties of Nitinol Wires.

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.

Shape-Memory Three-Dimensional Evaporators with High Portability for Efficient Solar-Driven Freshwater Production.

Solar-driven water evaporation can alleviate the severe water scarcity situation in a nonpolluting and sustainable manner. Although the design of integrated three-dimensional (3D) solar evaporators has been proven to be effective in achieving ultrahigh evaporation rates and energy efficiency, their scalable application is still hindered by complex manufacturing processes and poor portability. Herein, we report a highly portable shape-memory 3D solar evaporator by depositing MXene on low-cost lignin-cellulosic sponges for freshwater production. When not in use, the 3D evaporator can be compressed into a thin film with up to 89.3% volume reduction, ensuring minimal space occupation and high portability. When needed, due to the shape-memory effect, the 3D structure can be rapidly restored by swelling the compressed film in water, resulting in an efficient 3D solar evaporator. This 3D evaporator exhibits not only a high evaporation rate of 2.48 kg m-2 h-1 under 1 sun illumination but also excellent long-term stability and recyclability. In addition, the 3D evaporator itself can serve as a water reservoir without requiring a continuous water supply during evaporation, showing remarkable application flexibility. This work opens a new perspective for manufacturing highly portable and efficient 3D solar evaporators and may facilitate their progress from the laboratory to commercial applications.

Cyclic Stability of Two-Way Shape Memory Effect in Aged Ni50.3Ti32.2Hf17.5 Polycrystals after Various Thermomechanical Treatments.

In the present paper, the cyclic stability of the high-temperature two-way shape memory effect was studied in high-strength Ni50.3Ti32.2Hf17.5 polycrystals after various thermomechanical treatments-training (thermocycling under stress) and stress-induced martensite aging. The effect of training and stress-induced martensite aging on the microstructure, the two-way shape memory effect, and its cyclic stability was determined. It was found out that both thermomechanical treatments induce the high-temperature two-way shape memory effect at T > 373 K, with a strain of 1.5% in tension. The influence of cyclic tests (up to 100 stress-free cycles of cooling/heating) on the two-way shape memory effect strain, the transformation temperatures, and the microstructure was established. Different degradation mechanisms of the two-way shape memory effect were established after thermocycling and stress-induced martensite aging.

4D Printing of Biocompatible Scaffolds via In Situ Photo-crosslinking from Shape Memory Copolyesters.

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.

Three-Dimensional Printed Shape Memory Gels Based on a Structured Disperse System with Hydrophobic Cellulose Nanofibers.

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.

A shape memory alloy implant can be an effective surgical treatment in the atlantoaxial joint stabilization using rabbits as substitutes for toy-breed dogs.

OBJECTIVE: To investigate the feasibility of using shape memory alloy (SMA) implants for atlantoaxial joint stabilization using a rabbit model as a substitute for canines. ANIMALS: 20 rabbit cadavers. METHODS: We prepared rabbit cadavers from the middle of the skull to the third cervical vertebra. The vertebral body and canal sizes of the atlas and axis were compared using CT data from rabbits, normal dogs, and dogs with atlantoaxial instability (AAI) to assess the feasibility of using rabbits as substitutes for toy-breed dogs. The shape memory alloy (SMA) implants were designed to stabilize the atlantoaxial joint without compromising the spinal canal passage for safety and were classified into SMA-1 and SMA-2 based on their design. To evaluate the strength, the ventrodorsal force was measured with atlantoaxial ligaments intact, after removing the ligaments, and after applying conventional wire or SMA implants to stabilize the atlantoaxial joint. The time taken for implant application was measured. RESULTS: No significant difference in vertebral body size of the atlas and axis was observed. A significant difference in vertebral canal size was observed between the animals. In biomechanical testing, the SMA-2 implant provided more stabilization, while the SMA-1 implant had lower strength than the conventional method using wires. The application time of wire was the longest, while that of SMA-1 was the shortest. CLINICAL RELEVANCE: SMA implants provide comparable strength and demonstrate superior efficacy compared to conventional dorsal wire fixation of atlantoaxial stabilization. Therefore, SMA implants can be an effective surgical option for AAI.

On the Thermomechanical Behavior of 3D-Printed Specimens of Shape Memory R-PETG.

From commercial pellets of recycled polyethylene terephthalate glycol (R-PETG), 1.75 mm diameter filaments for 3D printing were produced. By varying the filament's deposition direction between 10° and 40° to the transversal axis, parallelepiped specimens were fabricated by additive manufacturing. When bent at room temperature (RT), both the filaments and the 3D-printed specimens recovered their shape during heating, either without any constraint or while lifting a load over a certain distance. In this way, free-recovery and work-generating shape memory effects (SMEs) were developed. The former could be repeated without any visible fatigue marks for as much as 20 heating (to 90 °C)-RT cooling-bending cycles, while the latter enabled the lifting of loads over 50 times heavier than the active specimens. Tensile static failure tests revealed the superiority of the specimens printed at larger angles over those printed at 10°, since the specimens printed at 40° had tensile failure stresses and strains over 35 MPa and 8.5%, respectively. Scanning electron microscopy (SEM) fractographs displayed the structure of the successively deposited layers and a shredding tendency enhanced by the increase in the deposition angle. Differential scanning calorimetry (DSC) analysis enabled the identification of the glass transition between 67.5 and 77.3 °C, which might explain the occurrence of SMEs in both the filament and 3D-printed specimens. Dynamic mechanical analysis (DMA) emphasized a local increase in storage modulus of 0.87-1.66 GPa that occurred during heating, which might explain the development of work-generating SME in both filament and 3D-printed specimens. These properties recommend 3D-printed parts made of R-PETG as active elements in low-price lightweight actuators operating between RT and 63 °C.

Soft Mechanical Metamaterials with Transformable Topology Protected by Stress Caching.

Maxwell lattices possess distinct topological states that feature mechanically polarized edge behaviors and asymmetric dynamic responses protected by the topology of their phonon bands. Until now, demonstrations of non-trivial topological behaviors from Maxwell lattices have been limited to fixed configurations or have achieved reconfigurability using mechanical linkages. Here, a monolithic transformable topological mechanical metamaterial is introduced in the form of a generalized kagome lattice made from a shape memory polymer (SMP). It is capable of reversibly exploring topologically distinct phases of the non-trivial phase space via a kinematic strategy that converts sparse mechanical inputs at free edge pairs into a biaxial, global transformation that switches its topological state. All configurations are stable in the absence of confinement or a continuous mechanical input. Its topologically-protected, polarized mechanical edge stiffness is robust against broken hinges or conformational defects. More importantly, it shows that the phase transition of SMPs that modulate chain mobility, can effectively shield a dynamic metamaterial's topological response from its own kinematic stress history, referred to as "stress caching". This work provides a blueprint for monolithic transformable mechanical metamaterials with topological mechanical behavior that is robust against defects and disorder while circumventing their vulnerability to stored elastic energy, which will find applications in switchable acoustic diodes and tunable vibration dampers or isolators.

4D Printing of Triple-Shape Memory Cyanate Composites Based on Interpenetrating Polymer Network Structures.

The triple-shape memory polymer (TSMP) can be programmed into two temporary shapes (S1 and S2) and shows an ordinal recovery from S2 to S1 and eventually to the permanent shape upon heating, which realizes more complex stimulus-response motions. We introduced a novel strategy for forming triple-shape memory cyanate ester (TSMCE) resins with high strength and fracture toughness via three-step curing, including four-dimensional (4D) printing, UV post-curing, and thermal curing. The obtained TSMCE resins presented two separated glass transition temperature (Tg) regions due to the formation of an interpenetrating polymer network (IPN), which successfully endowed the polymers with the triple-shape memory effect. The two Tg increased with the increasing cyanate ester (CE) prepolymer content; their ranges were 82.7-102.1 °C and 164.4-229.0 °C, respectively. The fracture strain of the IPN CE resin was up to 10.9%. Moreover, the cooperation of short carbon fibers (CFs) and glass fibers (GFs) with the polymer-accelerated phase separation resulted in two well-separated Tg peaks exhibiting better excellent triple-shape memory behaviors and fracture toughness. The strategy for combining the IPN structure and 4D printing provides insight into the preparation of shape memory polymers integrating high strength and toughness, multiple-shape memory effect, and multifunctionality.

Effects of Accelerated Aging on Thermal, Mechanical and Shape Memory Properties of Cyanate-Based Shape Memory Polymer: III Vacuum Thermal Cycling.

Shape memory polymers (SMPs) with intelligent deformability have shown great potential in the field of aerospace, and the research on their adaptability to space environments has far-reaching significance. Chemically cross-linked cyanate-based SMPs (SMCR) with excellent resistance to vacuum thermal cycling were obtained by adding polyethylene glycol (PEG) with linear polymer chains to the cyanate cross-linked network. The low reactivity of PEG overcame the shortcomings of high brittleness and poor deformability while endowing cyanate resin with excellent shape memory properties. The SMCR with a glass transition temperature of 205.8 °C exhibited good stability after vacuum thermal cycling. The SMCR maintained a stable morphology and chemical composition after repeated high-low temperature cycle treatments. The SMCR matrix was purified by vacuum thermal cycling, which resulted in an increase in its initial thermal decomposition temperature by 10-17 °C. The continuous vacuum high and low temperature relaxation of the vacuum thermal cycling increased the cross-linking degree of the SMCR, which improved the mechanical properties and thermodynamic properties of SMCR: the tensile strength of SMCR was increased by about 14.5%, the average elastic modulus was greater than 1.83 GPa, and the glass transition temperature increased by 5-10 °C. Furthermore, the shape memory properties of SMCR after vacuum thermal cycling treatment were well maintained due to the stable triazine ring formed by the cross-linking of cyanate resin. This revealed that our developed SMCR had good resistance to vacuum thermal cycling and thus may be a good candidate for aerospace engineering.

Effect of Material Change on Stirnol Engine: A Combination of NiTiNOL (Shape Memory Alloy) and Gamma Stirling Engine.

Population explosion, industrialization, and urbanization have accelerated energy requirements across the globe. This has led to the human quest to find simple and cost-effective energy solutions. A promising solution is the revival of the Stirling engine with the addition of Shape Memory Alloy NiTiNOL in it. The experimental results reveal that the addition of a NiTiNOL spring at the base plate of the Stirling engine enhances the overall efficiency of the engine, demonstrating some impact of the shape memory alloy toward the performance output of the Stirling engine. The newly modified engine has been named the STIRNOL ENGINE. The comparative study of Stirling and Stirnol engines reveals a minuscule efficiency improvement, yet there is a furtherance that opens a window for future researchers to get a lead and venture into this new field. We are confident that with more complex designs and better Stirling and NiTiNOL combinations, more efficient engines can be invented in the future. This research focuses on changing the material of the base plate of the Stirnol engine and ascertaining its performance differential through the integration of the NiTiNOL spring. A minimum of four types of materials are utilized for experimentation.