Evaluation of Shape Recovery Performance of Shape Memory Polymers with Carbon-Based Fillers.

This study focuses on enhancing the thermal properties and shape recovery performance of shape memory polymers (SMPs) through the application of carbon-based fillers. Single and mixed fillers were used to investigate their effects on the glass transition temperature (Tg), thermal conductivity, and shape recovery performance. The interaction among the three-dimensional (3D) structures of mixed fillers played a crucial role in enhancing the properties of the SMP. These interactions facilitated efficient heat transfer pathways and conserved strain energy. The application of mixed fillers resulted in substantial improvements, demonstrating a remarkable 290.37% increase in thermal conductivity for SMPCs containing 60 µm carbon fiber (CF) 10 wt% + graphite 20 wt% and a 60.99% reduction in shape recovery time for SMPCs containing CF 2.5 wt% + graphite 2.5 wt%. At a content of 15 wt%, a higher graphite content compared to CF improved the thermal conductivity by 37.42% and reduced the shape recovery time by 6.98%. The findings demonstrate that the application of mixed fillers, especially those with high graphite content, is effective in improving the thermal properties and shape recovery performance of SMPs. By using mixed fillers with high graphite content, the performance of the SMP showed significant improvement in situations where fast response times were required.

Influence of Infill Patterns on the Shape Memory Effect of Cold-Programmed Additively Manufactured PLA.

In four-dimensional additive manufacturing (4DAM), specific external stimuli are applied in conjunction with additive manufacturing technologies. This combination allows the development of tailored stimuli-responsive properties in various materials, structures, or components. For shape-changing functionalities, the programming step plays a crucial role in recovery after exposure to a stimulus. Furthermore, precise tuning of the 4DAM process parameters is essential to achieve shape-change specifications. Within this context, this study investigated how the structural arrangement of infill patterns (criss-cross and concentric) affects the shape memory effect (SME) of compression cold-programmed PLA under a thermal stimulus. The stress-strain curves reveal a higher yield stress for the criss-cross infill pattern. Interestingly, the shape recovery ratio shows a similar trend across both patterns at different displacements with shallower slopes compared to a higher shape fixity ratio. This suggests that the infill pattern primarily affects the mechanical strength (yield stress) and not the recovery. Finally, the recovery force increases proportionally with displacement. These findings suggest a consistent SME under the explored interval (15-45% compression) despite the infill pattern; however, the variations in the mechanical properties shown by the stress-strain curves appear more pronounced, particularly the yield stress.

Mechanical and Fatigue Properties of Welded Fe-Mn-Si Shape Memory Alloys.

This paper presents the experimental results of a study evaluating the mechanical and fatigue performance of welded Fe-Mn-Si SMA. For the experimental study, welded and welded-and-heat-treated Fe-Mn-Si SMA specimens were fabricated, and fatigue tests were performed at various stress amplitudes. In addition, direct tensile tests and recovery stress tests were also performed to evaluate the material properties of Fe-Mn-Si SMAs. The elastic modulus, yield strength, and tensile strength of the welded specimens were reduced by 35.4%, 12.1%, and 8.6%, respectively, compared to the values of the non-welded specimens. On the other hand, the elastic modulus, yield strength, and tensile strength of the welded-and-heat-treated Fe-Mn-Si SMA specimens were increased by 18.6%, 4.9%, and 1.3%, respectively, compared to the values of the welded specimens. Both welded and welded-and-heat-treated Fe-Mn-Si SMAs failed at lower cycles than the conventional Fe-Mn-Si SMAs at the same stress amplitude. High-cycle fatigue failure, characterized by cycles exceeding 104, typically occurs at relatively low stress levels within the elastic region, whereas low-cycle fatigue failure, generally occurring within cycles below 104, involves high stress levels that encompass both elastic and plastic deformation. Regardless of the welding condition, the stress amplitude at which Fe-Mn-Si SMA transitions from high-cycle to low-cycle failure exceeded the yield strength.

Ultratough Supramolecular Polyurethane Featuring an Interwoven Network with Recyclability, Ideal Self-Healing and Editable Shape Memory Properties.

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.

Variations in the Thermomechanical and Structural Properties during the Cooling of Shape-Memory R-PETG.

One of the useful features of 3D-printed specimens of recycled polyethylene terephthalate glycol (R-PETG) is the ability to repetitively develop free recovery as well as the work-generating, shape-memory effect. This behavior is enabled by the R-PETG's capacity to stiffen during cooling, thus allowing for a new temporary shape to be induced. Aiming to devise an explanation for the polymer's stiffening, in this study, the variation in some of the R-PETG's parameters during cooling are emphasized and discussed. The evolution of an R-PETG filament's shape was monitored during room-temperature-bending heating-cooling cycles. Straight-shape recovery and the complete loss of stiffness were observed at the start and the end of heating, respectively, followed by the forced straightening of the filament, performed by the operator, around 40 °C, during cooling. The tests performed by dynamic mechanical analysis disclosed the rise of the storage modulus (E') after 100 °C heating followed by either liquid-nitrogen- or air-cooling to room temperature, in such a way that E' was always larger after cooling than initially. Static tests emphasized a peculiar stress variation during a heating-cooling cycle applied in air, within the heating chamber of the tensile testing machine. Tensile-failure tests were performed at -10 °C at a rate of 100 mm/min, with specimens printed at various deposition directions between 10 and 40° to the transversal direction. The specimens printed at 40°, which had the largest ultimate strains, were broken with tensile rates between 100 and 500 mm/min. Deformation rate increase favored the shift from crazing to delamination failure modes. The correlation between the structural changes, the sharp E' increase on heating, and the stiffening induced by cooling represents a novel approach that enables the use of 3D-printed R-PETG for the fabrication of the active parts of low-priced lightweight resettable actuators.

The Utilization of Shape Memory Alloy as a Reinforcing Material in Building Structures: A Review.

Shape memory alloy (SMA), a type of smart material, is widely used in the design of reinforcement and repair, isolation, and shock absorption of building structures because of its outstanding characteristics, such as the shape memory effect (SME), superelasticity (SE), and high damping. It not only improves the bearing capacity, ductility, and mechanical properties of the structural components of buildings but can also effectively slow down the strong response of engineering structures under the effect of an earthquake. It plays a key role in energy dissipation and shock absorption as well as sustainable development. To promote the application of SMA in building structures, this paper summarizes the research on the use of SMA as a reinforcing material in building structures, including work related to SMA material characteristics and types, SMA-reinforced structural components, and SMA isolation devices. In addition, the shortcomings of SMA applications in building structures are analyzed, and valuable suggestions for future research methods are put forward. SMA has been applied to engineering practice in the form of embedded and external reinforcement, which shows that it has broad application prospects in future buildings.

Fully 3D-Printed Miniature Soft Hydraulic Actuators with Shape Memory Effect for Morphing and Manipulation.

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.

Design, Modeling, and Experimental Validation of an Active Microcatheter Driven by Shape Memory Effects.

Microcatheters capable of active guidance have been proven to be effective and efficient solutions to interventional surgeries for cardiovascular and cerebrovascular diseases. Herein, a novel microcatheter made of two biocompatible materials, shape memory alloy (SMA) and polyethylene (PE), is proposed. It consists of a reconfigurable distal actuator and a separate polyethylene catheter. The distal actuator is created via embedding U-shape SMA wires into the PE base, and its reconfigurability is mainly dominated by the shape memory effect (SME) of SMA wires, as well as the effect of thermal mismatch between the SMA and PE base. A mathematical model was established to predict the distal actuator's deformation, and the analytical solutions show great agreement with the finite element results. Structural optimization of such microcatheters was carried out using the verified analytical model, followed by fabrication of some typical prototypes. Experimental testing of their mechanical behaviors demonstrates the feasibility of the structural designs, and the reliability and accuracy of the mathematical model. The active microcatheter, together with the prediction model, will lay a solid foundation for rapid development and optimization of active navigation strategies for vascular interventions.

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 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.

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.

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.

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.

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.

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.

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.

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.