Control crosslink network and chain connectivity are essential to develop shape memory polymers(SMPs)with high shape memory capabilities,adjustable response temperature,and satisfying mechanistical properties.In this ...Control crosslink network and chain connectivity are essential to develop shape memory polymers(SMPs)with high shape memory capabilities,adjustable response temperature,and satisfying mechanistical properties.In this study,novel poly(ε-caprolactone)(PCL)-poly(2-vinyl)ethylene glycol(PVEG)copolymers bearing multi-pendant vinyl groups is synthesized by branched-selective allylic etherification polymerization of vinylethylene carbonate(VEC)with linear and tetra-arm PCLs under a synergistic catalysis of palladium complex and boron reagent.Facile thiol-ene photo-click reaction of PCL-PVEG copolymers with multifunctional thiols can rapidly access a serious crosslinked SMPs with high shape memory performance.The thermal properties,mechanical properties and response temperature of the obtained SMPs are tunable by the variation of PCL prepolymers,vinyl contents and functionality of thiols.Moreover,high elastic modulus in the rubbery plateau region can be maintained effectively owing to high-density topological networks of the PCL materials.In addition,the utility of the present SMPs is further demonstrated by the post-functionalization via thiol-ene photo-click chemistry.展开更多
4D-printable shape memory polymers(SMPs)hold great promise for fabricating shape morphing biomedical devices,but most existing printed polymers either require harsh activation conditions or lack sufficient mechanical ...4D-printable shape memory polymers(SMPs)hold great promise for fabricating shape morphing biomedical devices,but most existing printed polymers either require harsh activation conditions or lack sufficient mechanical strength for vascular implantation.Here,we report a dual-stimuli-responsive shape memory polymer system enhanced by acrylated Pluronic F127(PF127-DA)micelles,which can be fabricated using digital light processing(DLP)based 3D printing.The PF127-DA based nanoscale micelles,which are formed via self-assembly in the hydrogel ink for 3D printing,act as crosslinkers to improve mechanical strength,fatigue resistance and elastic recovery.After drying the printed hydrogel,the obtained SMPs exhibit excellent shape recovery behaviour under mild physiological conditions—specifically body temperature(37℃)and aqueous swelling—resulting in recovery stress up to about 150?k Pa.This swelling-assisted actuation enables effective radial support,making the printed constructs suitable for vascular use.In vitro cytocompatibility assays with NIH/3T3 fibroblasts confirmed the suitable biocompatibility.Furthermore,the self-expanding behavior of the printed stents was validated in an occluded vessel model under physiological conditions.These results demonstrate the feasibility of 4D printed micelle-enhanced SMP for patient-specific,minimally invasive vascular stents and other soft implantable devices requiring high recovery force under physiological stimulation.展开更多
Programmable/reprogrammable magneto-responsive composites(MRCs)are highly desirable for applications in soft robotics,morphable actuators,and biomedical devices due to their capabilities of undergoing reversible,compl...Programmable/reprogrammable magneto-responsive composites(MRCs)are highly desirable for applications in soft robotics,morphable actuators,and biomedical devices due to their capabilities of undergoing reversible,complex,untethered,and rapid deformations.However,current MRC-based devices primarily rely on soft matrices,which revert to their original shapes and cease functioning when external magnetic fields are removed.Moreover,their magnetization programming,deformations,and functioning need to alternate between encoding and actuation platforms,limiting the adaptability and efficiency.Here,we present a reprogrammable magnetic shape-memory composite(RM-SMC)integrating a shape-memory polymer(SMP)skeleton with phase-transition magnetic microcapsules.High-intensity laser melts microcapsules for magnetic realignment under programmed fields,while low-intensity laser softens SMP for structural reconfiguration without compromising integrity.This dual-laser strategy facilitates in situ magnetization programming,shape morphing,and function execution within a single material system.Our innovative approach enables unique applications,including omnidirectional multi-degree-of-freedom actuators that can activate light switches,solar trackers that optimize energy capture,and adaptive impellers that modulate fluid pumping.By eliminating platform alternation and enabling shape/function retention post-actuation,the RM-SMC platform overcomes critical limitations in conventional MRCs,establishing a paradigm for multifunctional devices requiring persistent configuration control and field-independent operation.展开更多
Shape memory polymers （SMPs） as one type of the most important smart materials have attracted increasing attention due to their promising application in the field of biomedicine, textiles, aerospace et al. Following...Shape memory polymers （SMPs） as one type of the most important smart materials have attracted increasing attention due to their promising application in the field of biomedicine, textiles, aerospace et al. Following a brief intoduction of the conception and classification of SMPs, this review is focused on the progress of shape memory polymers for biomedical applications. The progress includes the early researches based on thermo-induced SMPs, the improvement of the stimulus, the development of shape recovery ways and the expansion of the applications in biomedical field. In addition, future perspectives of SMPs in the field of biomedicine are also discussed.展开更多
Transfer printing based on switchable adhesive is essential for developing unconventional systems,including flexible electronics,stretchable electronics,and micro light-emitting diode(LED)displays.Here we report a des...Transfer printing based on switchable adhesive is essential for developing unconventional systems,including flexible electronics,stretchable electronics,and micro light-emitting diode(LED)displays.Here we report a design of switchable dry adhesive based on shape memory polymer(SMP)with hemispherical indenters,which offers a continuously tunable and reversible adhesion through the combination of the preloading effect and the thermal actuation of SMP.Experimental and numerical studies reveal the fundamental aspects of design,fabrication,and operation of the switchable dry adhesive.Demonstrations of this adhesive concept in transfer printing of flat objects(e.g.,silicon wafers),three-dimensional(3D)objects(e.g.,stainless steel balls),and rough objects(e.g.,frosted glasses)in two-dimensional(2D)or 3D layouts illustrate its unusual manipulation capabilities in heterogeneous material integration applications.展开更多
With appropriate stimuli,such as heat,humidity,or magnetic field,shape memory polymers(SMPs)can recover to their original shapes from temporary,programmed states.Using thermal responsive SMPs as substrates,we demonstr...With appropriate stimuli,such as heat,humidity,or magnetic field,shape memory polymers(SMPs)can recover to their original shapes from temporary,programmed states.Using thermal responsive SMPs as substrates,we demonstrate a simple method to realize hybrid surface morphologies through confined thin film wrinkling in localized areas.The bilayer system was fabricated by depositing a layer of aluminum thin?lm on top of a SMP substrate programmed with a tensile strain.After the system was heated by a heating wire,hybrid wrinkling patterns were formed in a confined circular area around the heat source,with an inner spoke pattern and an outer ring pattern.Wrinkling patterns showed good symmetry,and the size of the wrinkling area can be tuned by controlling the heat input.This study o?ers a simple but effective approach to fabricate hybrid morphological features in micro-scale.With appropriate stimuli,such as heat,humidity,or magnetic field,shape memory polymers(SMPs)can recover to their original shapes from temporary,programmed states.Using thermal responsive SMPs as substrates,we demonstrate a simple method to realize hybrid surface morphologies through confined thin film wrinkling in localized areas.The bilayer system was fabricated by depositing a layer of aluminum thin?lm on top of a SMP substrate programmed with a tensile strain.After the system was heated by a heating wire,hybrid wrinkling patterns were formed in a confined circular area around the heat source,with an inner spoke pattern and an outer ring pattern.Wrinkling patterns showed good symmetry,and the size of the wrinkling area can be tuned by controlling the heat input.This study offers a simple but effective approach to fabricate hybrid morphological features in micro-scale.展开更多
Controlled and switchable adhesion is commonly observed in biological systems.In recent years,many scholars have focused on making switchable bio-inspired adhesives.However,making a bio-inspired adhesive with high adh...Controlled and switchable adhesion is commonly observed in biological systems.In recent years,many scholars have focused on making switchable bio-inspired adhesives.However,making a bio-inspired adhesive with high adhesion performance and excellent dynamic switching properties is still a challenge.A Shape Memory Polymer Bio-inspired Adhesive(SMPBA)was successfully developed,well realizing high adhesion(about 337 kPa),relatively low preload(about90 kPa),high adhesion-to-preload ratio(about 3.74),high switching ratio(about 6.74),and easy detachment,which are attributed to the controlled modulus and contact area by regulating temperature and the Shape Memory Effect(SME).Furthermore,SMPBA exhibits adhesion strength of80–337 kPa on various surfaces(silicon,iron,and aluminum)with different roughness(Ra=0.021–10.280)because of the conformal contact,reflecting outstanding surface adaptability.The finite element analysis verifies the bending ability under different temperatures,while the adhesion model analyzes the influence of preload on contact area and adhesion.Furthermore,an Unmanned Aerial Vehicle(UAV)landing device with SMPBA was designed and manufactured to achieve UAV landing on and detaching from various surfaces.This study provides a novel switchable bio-inspired adhesive and UAV landing method.展开更多
Solar arrays are the primary energy source for spacecraft.Although traditional rigid solar arrays improve power supply,the quality increases proportionally.Hence,it is difficult to satisfy the requirements of high-pow...Solar arrays are the primary energy source for spacecraft.Although traditional rigid solar arrays improve power supply,the quality increases proportionally.Hence,it is difficult to satisfy the requirements of high-power and low-cost space applications.In this study,a shape-memory polymer composite(SMPC)boom was designed,fabricated,and characterized for flexible reel-type solar arrays.The SMPC boom was fabricated from a smart material,a shape-memory polymer composite,whose mechanical properties were tested.Additionally,a mathematical model of the bending stiffness of the SMPC boom was developed,and the bending and buckling behaviors of the boom were further analyzed using the ABAQUS software.An SMPC boom was fabricated to demonstrate its shape memory characteristics,and the driving force of the booms with varying geometric parameters was investigated.We also designed and manufactured a reel-type solar array based on an SMPC boom and verified its self-deployment capability.The results indicated that the SMPC boom can be used as a deployable unit to roll out flexible solar arrays.展开更多
“Life”represents a distinctive attribute inherent to organisms in nature,evident in their capacity to actively adapt to changes in their environment.In contrast to the static and intricate constructs of additive man...“Life”represents a distinctive attribute inherent to organisms in nature,evident in their capacity to actively adapt to changes in their environment.In contrast to the static and intricate constructs of additive manufacturing(AM),the dynamic structure of 4D printing(4DP)adeptly integrates AM technology,responsive mechanisms,and external stimuli,imbuing it with a semblance of“life.”This fusion significantly broadens its functional applica-tions across biomedicine,actuators,and metamaterials.The escalating demand across diverse fields necessitates heightened criteria for 4DP,encompassing rapid response,multi-stimulus response,large shape change,and specific mechanical properties(e.g.,high strength,high modulus)capable of accommodating varying environ-mental conditions.In recent years,shape memory polymers(SMPs)have garnered increasing attention among 4DP researchers due to their ease of design and preprogramming at the molecular level,facilitating controlled transformations along predictable pathways.However,4DP of high-strength SMPs,as an indispensable part of the high-performance field,is full of challenges because the intrinsic properties of the raw materials are not well compatible with the printing principle and the printed configuration is not flexible enough.Consequently,this paper provides a concise overview of the response mechanisms and applications of five prominent high-strength SMPs utilized in 4DP:epoxy resin,poly(ether-ether-ketone),polyimide,polylactic acid,and polyurethane.Ad-ditionally,it delves into the associated challenges and prospects,offering researchers valuable insights into the potential value of high-strength SMPs within the domain of 4DP.展开更多
This study presents a semi-analytical solution to describe the behavior of shape memory polymers(SMPs) based on the nonlinear thermo-visco-hyperelasticity which originates from the concepts of internal state variables...This study presents a semi-analytical solution to describe the behavior of shape memory polymers(SMPs) based on the nonlinear thermo-visco-hyperelasticity which originates from the concepts of internal state variables and rational thermodynamics.This method is developed for the finite bending of multilayers in a dual-shape memory effect(SME) cycle.The layer number and layering order are investigated for two different SMPs and a hyperelastic material.In addition to the semi-analytical solution,the finite element simulation is performed to verify the predicted results,where the outcomes demonstrate the excellent accuracy of the proposed solution for predicting the behavior of the multilayer SMPs.Since this method has a much lower computational cost than the finite element method(FEM),it can be used as an effective tool to analyze the SMP behavior under different conditions,including different materials,different geometries,different layer numbers,and different layer arrangements.展开更多
The mismatch in thermal expansion coefficients between the fiber-rich and resin-rich regions of a shape memory polymer composite(SMPC)laminate,along with the residual strain during SMPC fabrication,results in buckling...The mismatch in thermal expansion coefficients between the fiber-rich and resin-rich regions of a shape memory polymer composite(SMPC)laminate,along with the residual strain during SMPC fabrication,results in buckling deformation of the inhomogeneous laminate.This paper presents a macroscopic model for buckling of an inhomogeneous SMPC laminate under initial biaxial prestrains.Both linear and nonlinear buckling analyses are carried out using the energy method.The influences of prestrain biaxiality,temperature,and ply angle on the buckling wavelength,critical buckling prestrain,and buckling amplitude are calculated.The results demonstrate that the critical buckling wavelength of the SMPC laminate is independent of the prestrain,while the amplitude is almost independent of temperature.In addition,the optimal fiber stacking configuration with the maximum critical buckling prestrains of inhomogeneous SMPC laminates is determined by a genetic algorithm.展开更多
As a kind of popular smart materials, shape memory polymers （SMPs） have a great potential for applications in deployable aerospace structures and other engineering struc- tures. However, the vibration analysis of sh...As a kind of popular smart materials, shape memory polymers （SMPs） have a great potential for applications in deployable aerospace structures and other engineering struc- tures. However, the vibration analysis of shape memory polymer structures, which would play an important role in engineering, has not gained much attention. In this study, we propose a dynamic model and establish the governing equations for characterizing the dynamic behavior of a shape memory polymer membrane subjected to time-dependent forces. The derivation of governing equations is based on a well-developed constitutive model of SMPs combined with the Euler-Lagrange equation. With the proposed model, two different loading cases are stud- ied： the equal-biaxial sinusoidal force and the uniaxial sinusoidal force. To analyze the dynamic response of a shape memory polymer membrane and find some effective ways to control vibra- tion, the isothermal amplitude-frequency response, the time-dependent behavior of vibration and the vibration in a variable temperature process are investigated in the numerical simulation. It is observed that temperature, mechanical force and heating rate have significant effects on the dynamic performances of a shape memory polymer membrane. We also investigate the shape memory behavior of SMP membrane involving the dynamic response. The influence of dynamics on shape fixation and shape recovery is discussed. These results and discussion may provide guidance for exploring the vibration and dynamic performances of shape memory polymer in deployable aerospace structures.展开更多
Submicron-sized peanut-shaped poly（methyl methacrylate）/polystyrene （PMMA/PS） particles were successfully synthesized by seeded soap-free emulsion polymerization of styrene on the spherical crosslinked PMMA seed p...Submicron-sized peanut-shaped poly（methyl methacrylate）/polystyrene （PMMA/PS） particles were successfully synthesized by seeded soap-free emulsion polymerization of styrene on the spherical crosslinked PMMA seed particles. The obtained peanut- shaped particles showed a novel internal morphology： PS phase formed one domain which linked to the other domain having PMMA core encased by PS shell.展开更多
Heteroarm star-shaped polymers were synthesized by conventional free radical polymerization in two steps by the use of polyfunctional chain transfer agent.In the first step,free radical polymerization of methyl methac...Heteroarm star-shaped polymers were synthesized by conventional free radical polymerization in two steps by the use of polyfunctional chain transfer agent.In the first step,free radical polymerization of methyl methacrylate was carried out in the presence of a polyfunctional chain transfer agent,pentaerythritol tetrakis(3-mercaptopropinate).At appropriate monomer conversions,two-arm PMMA having two residual thiol groups at the chain center or three-arm PMMA having one residual thiol group at the core were o...展开更多
This paper presents the development of a thermoplastic shape memory rubber that can be programmed at human body temperature for comfortable fitting applications.We hybridized commercially available thermoplastic rubbe...This paper presents the development of a thermoplastic shape memory rubber that can be programmed at human body temperature for comfortable fitting applications.We hybridized commercially available thermoplastic rubber(TPR)used in the footwear industry with un-crosslinked polycaprolactone(PCL)to create two samples,namely TP6040 and TP7030.The shape memory behavior,elasticity,and thermo-mechanical response of these rubbers were systematically investigated.The experimental results demonstrated outstanding shape memory performance,with both samples achieving shape fixity ratios(Rf)and shape recovery ratios(R_(r))exceeding 94%.TP6040 exhibited a fitting time of 80 s at body temperature(37℃),indicating a rapid response for shape fixing.The materials also showed good elasticity before and after programming,which is crucial for comfort fitting.These findings suggest that the developed shape memory thermoplastic rubber has potential applications in personalized comfort fitting products,offering advantages over traditional customization techniques in terms of efficiency and cost-effectiveness.展开更多
A Shape Memory Polymer Composite(SMPC)is developed by reinforcing an epoxy-based polymer with randomly oriented short glass fibers.Diverging from previous research,which primarily focused on the hot programming of sho...A Shape Memory Polymer Composite(SMPC)is developed by reinforcing an epoxy-based polymer with randomly oriented short glass fibers.Diverging from previous research,which primarily focused on the hot programming of short glass fiber-based SMPCs,this work explores the potential for programming below the glass transition temperature(Tg)for epoxy-based SMPCs.To mitigate the inherent brittleness of the SMPC during deformation,a linear polymer is incorporated,and a temperature between room temperature and Tg is chosen as the deformation temperature to study the shape memory properties.The findings demonstrate an enhancement in shape fixity and recovery stress,alongside a reduction in shape recovery,with the incorporation of short glass fibers.In addition to tensile properties,thermal properties such as thermal conductivity,specific heat capacity,and glass transition temperature are investigated for their dependence on fiber content.Microscopic properties,such as fiber-matrix adhesion and the dispersion of glass fibers,are examined through Scanning Electron Microscope imaging.The fiber length distribution and mean fiber lengths are also measured for different fiber fractions.展开更多
Metamaterials,owing to their exceptional physical characteristics that are absent in natural materials,have emerged as a crucial constituent of intelligent devices and systems.However,there are still significant chall...Metamaterials,owing to their exceptional physical characteristics that are absent in natural materials,have emerged as a crucial constituent of intelligent devices and systems.However,there are still significant challenges that necessitate immediate attention,as they have considerably constrained the applicability of metamaterials,including fixed mechanical properties post-fabrication and restricted design freedom.Here,thermo-responsive,photo-responsive,electro-responsive,and magneto-responsive shape memory polymer nano-composites were developed,and shape memory gradient metamaterials were fabricated using multi-material 4D printing technology.The correlation mechanism between the design parameters and the mechanical properties of multi-responsive gradient metamaterials was systematically analyzed,and the highly designable and programmable configuration and mechanical properties of the gradient metamaterials were realized.More importantly,4D printed multi-responsive shape memory polymer gradient metamaterials can be programmed in situ without additional infrastructure for multi-functional mechanical functions,paving the way for the realization of multiple functions of a single structure.Based on the multi-responsive gradient metamaterials,4D printed digital pixel metamaterial intelligent information carriers were fabricated,featuring customizable encryption and decryption protocols,exceptional scalability,and reusability.Additionally,4D printed gradient metamaterial logic gate electronic devices were developed,which were anticipated to contribute to the development of smart,adaptable robotic systems that combine sensing,actuation,and decision-making capabilities.展开更多
The continuous improvement in patient care and recovery is driving the development of innovative materials for medical applications.Medical sutures,essential for securing implants and closing deep wounds,have evolved ...The continuous improvement in patient care and recovery is driving the development of innovative materials for medical applications.Medical sutures,essential for securing implants and closing deep wounds,have evolved to incorporate smart materials capable of responding to various stimuli.This study explores the potential of thermoresponsive sutures,made from shape memory materials,that contract upon heating to bring loose stitches closer together,promoting optimal wound closure.We developed nanocomposites based on a blend of poly(lactic acid)(PLA)and thermoplastic polyurethane(TPU)—biopolymers that inherently exhibit shape memory—enhanced with carbon nanotubes(CNT)and graphene nanoplatelets(GN)to improve mechanical performance.PLA/TPU(50/50)nanocomposites were prepared with 1 and 2 wt%GN,as well as hybrid formulations combining 1 wt%CNT with 1 or 2 wt%GN,using a twin-screw extrusion process to form filaments.These filaments were characterized through differential scanning calorimetry(DSC),field emission gun scanning electron microscopy(FEG-SEM),tensile testing,and shape memory assessments.While the PLA/TPU blend is immiscible,TPU enhances the crystallinity(X_(c))of the PLA phase,further increased by the addition of CNT and GN.FEG-SEM images indicate CNTs primarily in the PLA phase and GN in the TPU phase.PLA/TPU with 1 or 2 wt%GN showed the highest potential for suture applications,with a high elastic modulus(~1000 MPa),significant strain at break(~10%),and effective shape recovery(~20%at 55℃ for 30 min).These findings suggest that these nanocomposites can enhance suture performance with controlled shape recovery that is suitable for medical use.展开更多
A cup shape is a dynamic morphology of cells and organelles. With the aim of elucidating the formation of the biotic cup-shaped morphology, this study investigated cup-shaped vesicles consisting of an amphiphilic dibl...A cup shape is a dynamic morphology of cells and organelles. With the aim of elucidating the formation of the biotic cup-shaped morphology, this study investigated cup-shaped vesicles consisting of an amphiphilic diblock copolymer from the aspect of synthetic polymer chemistry. Cup-shaped vesicles were obtained by the polymerization-induced self-assembly of poly(methacrylic acid)-block-poly(n-butyl methacrylate-random-methacrylic acid), PMAA-b-P(BMA-r-MAA), in an aqueous methanol solution using the photo nitroxide-mediated controlled/living radical polymerization technique. Field emission scanning electron microscopic observations demonstrated that the cup-shaped vesicles were suddenly formed during the late stage of the polymerization due to the extension of the hydrophobic P(BMA-r-MAA) block chain. During the early stage, the polymerization produced spherical vesicles rather than a cup shape. As the hydrophobic block chain was extended by the polymerization progress, the spherical vesicles reduced the size and were accompanied by the generation of small particles that were attached to the vesicles. The vesicles continued to reduce the size due to further extension of the hydrophobic chain;however, they suddenly grew into cup-shaped vesicles. This growth was accounted for by a change in the critical packing shape of the copolymer due to the hydrophobic chain extension. These findings are helpful for a better understanding of the biotic cup-shaped vesicle formation.展开更多
The rapid development of additive manufacturing and advances in shape memory materials have fueled the progress of four-dimensional （4D） printing. With the right external stimulus, the need for human interaction, se...The rapid development of additive manufacturing and advances in shape memory materials have fueled the progress of four-dimensional （4D） printing. With the right external stimulus, the need for human interaction, sensors, and batteries will be eliminated, and by using additive manufacturing, more complex devices and parts can be produced. With the current understanding of shape memory mechanisms and with improved design for additive manufacturing, reversibility in 4D printing has recently been proven to be feasible. Conventional one-way 4D printing requires human interaction in the programming （or shapesetting） phase, but reversible 4D printing, or two-way 4D printing, will fully eliminate the need for human interference, as the programming stage is replaced with another stimulus. This allows reversible 4D printed parts to be fully dependent on external stimuli; parts can also be potentially reused after every recovery, or even used in continuous cycles-an aspect that carries industrial appeal. This paper presents a review on the mechanisms of shape memory materials that have led to 4D printing, current findings regarding 4D printing in alloys and polymers, and their respective limitations. The reversibility of shape memory materials and their feasibility to be fabricated using three-dimensional （3D） printing are summarized and critically analyzed. For reversible 4D printing, the methods of 3D printing, mechanisms used for actuation, and strategies to achieve reversibility are also highlighted. Finally, prospective future research directions in reversible 4D printing are suggested.展开更多
基金financially supported by the National Natural Science Foundation of China(No.22171182)Sichuan Tianfu Emei Plan.
文摘Control crosslink network and chain connectivity are essential to develop shape memory polymers(SMPs)with high shape memory capabilities,adjustable response temperature,and satisfying mechanistical properties.In this study,novel poly(ε-caprolactone)(PCL)-poly(2-vinyl)ethylene glycol(PVEG)copolymers bearing multi-pendant vinyl groups is synthesized by branched-selective allylic etherification polymerization of vinylethylene carbonate(VEC)with linear and tetra-arm PCLs under a synergistic catalysis of palladium complex and boron reagent.Facile thiol-ene photo-click reaction of PCL-PVEG copolymers with multifunctional thiols can rapidly access a serious crosslinked SMPs with high shape memory performance.The thermal properties,mechanical properties and response temperature of the obtained SMPs are tunable by the variation of PCL prepolymers,vinyl contents and functionality of thiols.Moreover,high elastic modulus in the rubbery plateau region can be maintained effectively owing to high-density topological networks of the PCL materials.In addition,the utility of the present SMPs is further demonstrated by the post-functionalization via thiol-ene photo-click chemistry.
基金Natural Science Basic Research Program of Shaanxi(No.2025JC-YBMS-358)the Fundamental Research Funds for the Central Universities(No.D5000250307)。
文摘4D-printable shape memory polymers(SMPs)hold great promise for fabricating shape morphing biomedical devices,but most existing printed polymers either require harsh activation conditions or lack sufficient mechanical strength for vascular implantation.Here,we report a dual-stimuli-responsive shape memory polymer system enhanced by acrylated Pluronic F127(PF127-DA)micelles,which can be fabricated using digital light processing(DLP)based 3D printing.The PF127-DA based nanoscale micelles,which are formed via self-assembly in the hydrogel ink for 3D printing,act as crosslinkers to improve mechanical strength,fatigue resistance and elastic recovery.After drying the printed hydrogel,the obtained SMPs exhibit excellent shape recovery behaviour under mild physiological conditions—specifically body temperature(37℃)and aqueous swelling—resulting in recovery stress up to about 150?k Pa.This swelling-assisted actuation enables effective radial support,making the printed constructs suitable for vascular use.In vitro cytocompatibility assays with NIH/3T3 fibroblasts confirmed the suitable biocompatibility.Furthermore,the self-expanding behavior of the printed stents was validated in an occluded vessel model under physiological conditions.These results demonstrate the feasibility of 4D printed micelle-enhanced SMP for patient-specific,minimally invasive vascular stents and other soft implantable devices requiring high recovery force under physiological stimulation.
基金supported by the National Natural Science Foundation of China(Nos.52075516,61927814,62325507,and 52122511)the National Key Research and Development Program of China(No.2021YFF0502700)+2 种基金the Major Scientific and Technological Projects in Anhui Province(202103a05020005,202203a05020014)the Students’Innovation and Entrepreneurship Foundation of USTC(CY2022G09)the Hefei Municipal Natural Science Foundation(No.HZR2450)。
文摘Programmable/reprogrammable magneto-responsive composites(MRCs)are highly desirable for applications in soft robotics,morphable actuators,and biomedical devices due to their capabilities of undergoing reversible,complex,untethered,and rapid deformations.However,current MRC-based devices primarily rely on soft matrices,which revert to their original shapes and cease functioning when external magnetic fields are removed.Moreover,their magnetization programming,deformations,and functioning need to alternate between encoding and actuation platforms,limiting the adaptability and efficiency.Here,we present a reprogrammable magnetic shape-memory composite(RM-SMC)integrating a shape-memory polymer(SMP)skeleton with phase-transition magnetic microcapsules.High-intensity laser melts microcapsules for magnetic realignment under programmed fields,while low-intensity laser softens SMP for structural reconfiguration without compromising integrity.This dual-laser strategy facilitates in situ magnetization programming,shape morphing,and function execution within a single material system.Our innovative approach enables unique applications,including omnidirectional multi-degree-of-freedom actuators that can activate light switches,solar trackers that optimize energy capture,and adaptive impellers that modulate fluid pumping.By eliminating platform alternation and enabling shape/function retention post-actuation,the RM-SMC platform overcomes critical limitations in conventional MRCs,establishing a paradigm for multifunctional devices requiring persistent configuration control and field-independent operation.
基金partially supported by the National Natural Science Foundation of China (Nos.21574105 and 51725303)the Sichuan Province Youth Science and Technology Innovation Team (No.2016TD0026)
文摘Shape memory polymers （SMPs） as one type of the most important smart materials have attracted increasing attention due to their promising application in the field of biomedicine, textiles, aerospace et al. Following a brief intoduction of the conception and classification of SMPs, this review is focused on the progress of shape memory polymers for biomedical applications. The progress includes the early researches based on thermo-induced SMPs, the improvement of the stimulus, the development of shape recovery ways and the expansion of the applications in biomedical field. In addition, future perspectives of SMPs in the field of biomedicine are also discussed.
基金The authors acknowledge the supports of the National Natural Science Foundation of China(Grant Nos.11872331 and U20A6001)Zhejiang University K.P.Chao’s High Technology Development Foundation.
文摘Transfer printing based on switchable adhesive is essential for developing unconventional systems,including flexible electronics,stretchable electronics,and micro light-emitting diode(LED)displays.Here we report a design of switchable dry adhesive based on shape memory polymer(SMP)with hemispherical indenters,which offers a continuously tunable and reversible adhesion through the combination of the preloading effect and the thermal actuation of SMP.Experimental and numerical studies reveal the fundamental aspects of design,fabrication,and operation of the switchable dry adhesive.Demonstrations of this adhesive concept in transfer printing of flat objects(e.g.,silicon wafers),three-dimensional(3D)objects(e.g.,stainless steel balls),and rough objects(e.g.,frosted glasses)in two-dimensional(2D)or 3D layouts illustrate its unusual manipulation capabilities in heterogeneous material integration applications.
基金The financial supports from NSF(CMMI-1405355)and ACS Petroleum Research Fund(53780-DNI7)are gratefully acknowledged.
文摘With appropriate stimuli,such as heat,humidity,or magnetic field,shape memory polymers(SMPs)can recover to their original shapes from temporary,programmed states.Using thermal responsive SMPs as substrates,we demonstrate a simple method to realize hybrid surface morphologies through confined thin film wrinkling in localized areas.The bilayer system was fabricated by depositing a layer of aluminum thin?lm on top of a SMP substrate programmed with a tensile strain.After the system was heated by a heating wire,hybrid wrinkling patterns were formed in a confined circular area around the heat source,with an inner spoke pattern and an outer ring pattern.Wrinkling patterns showed good symmetry,and the size of the wrinkling area can be tuned by controlling the heat input.This study o?ers a simple but effective approach to fabricate hybrid morphological features in micro-scale.With appropriate stimuli,such as heat,humidity,or magnetic field,shape memory polymers(SMPs)can recover to their original shapes from temporary,programmed states.Using thermal responsive SMPs as substrates,we demonstrate a simple method to realize hybrid surface morphologies through confined thin film wrinkling in localized areas.The bilayer system was fabricated by depositing a layer of aluminum thin?lm on top of a SMP substrate programmed with a tensile strain.After the system was heated by a heating wire,hybrid wrinkling patterns were formed in a confined circular area around the heat source,with an inner spoke pattern and an outer ring pattern.Wrinkling patterns showed good symmetry,and the size of the wrinkling area can be tuned by controlling the heat input.This study offers a simple but effective approach to fabricate hybrid morphological features in micro-scale.
基金financial support from the National Natural Science Foundation of China(No.51605220)the Jiangsu Province Natural Science Foundation,China(No.BK20160793)+1 种基金the Postgraduate Research and Practice Innovation Program of Nanjing University of Aeronautics and Astronautics,China(No.xcxjh20210514)the Fundamental Research Funds for the Central Universities,China(No.XCA2205406)。
文摘Controlled and switchable adhesion is commonly observed in biological systems.In recent years,many scholars have focused on making switchable bio-inspired adhesives.However,making a bio-inspired adhesive with high adhesion performance and excellent dynamic switching properties is still a challenge.A Shape Memory Polymer Bio-inspired Adhesive(SMPBA)was successfully developed,well realizing high adhesion(about 337 kPa),relatively low preload(about90 kPa),high adhesion-to-preload ratio(about 3.74),high switching ratio(about 6.74),and easy detachment,which are attributed to the controlled modulus and contact area by regulating temperature and the Shape Memory Effect(SME).Furthermore,SMPBA exhibits adhesion strength of80–337 kPa on various surfaces(silicon,iron,and aluminum)with different roughness(Ra=0.021–10.280)because of the conformal contact,reflecting outstanding surface adaptability.The finite element analysis verifies the bending ability under different temperatures,while the adhesion model analyzes the influence of preload on contact area and adhesion.Furthermore,an Unmanned Aerial Vehicle(UAV)landing device with SMPBA was designed and manufactured to achieve UAV landing on and detaching from various surfaces.This study provides a novel switchable bio-inspired adhesive and UAV landing method.
基金Supported by National Natural Science Foundation of China(Grant Nos.52105013 and 51835002)Self-Planned Task of State Key Laboratory of Robotics and System(HIT)of China(Grant No.SKLRS202202C)China Postdoctoral Science Foundation(Grant No.2020M681087).
文摘Solar arrays are the primary energy source for spacecraft.Although traditional rigid solar arrays improve power supply,the quality increases proportionally.Hence,it is difficult to satisfy the requirements of high-power and low-cost space applications.In this study,a shape-memory polymer composite(SMPC)boom was designed,fabricated,and characterized for flexible reel-type solar arrays.The SMPC boom was fabricated from a smart material,a shape-memory polymer composite,whose mechanical properties were tested.Additionally,a mathematical model of the bending stiffness of the SMPC boom was developed,and the bending and buckling behaviors of the boom were further analyzed using the ABAQUS software.An SMPC boom was fabricated to demonstrate its shape memory characteristics,and the driving force of the booms with varying geometric parameters was investigated.We also designed and manufactured a reel-type solar array based on an SMPC boom and verified its self-deployment capability.The results indicated that the SMPC boom can be used as a deployable unit to roll out flexible solar arrays.
基金supported by National Natural Science Foundation of China(Grant Nos.51935012,52005481)LICP Cooperation Foundation for Young Scholars(Grant No.HZJJ22-11)+1 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB0470303)Major Program of the Lanzhou Institute of Chemical Physics,CAS(Grant No.ZYFZFX-7).
文摘“Life”represents a distinctive attribute inherent to organisms in nature,evident in their capacity to actively adapt to changes in their environment.In contrast to the static and intricate constructs of additive manufacturing(AM),the dynamic structure of 4D printing(4DP)adeptly integrates AM technology,responsive mechanisms,and external stimuli,imbuing it with a semblance of“life.”This fusion significantly broadens its functional applica-tions across biomedicine,actuators,and metamaterials.The escalating demand across diverse fields necessitates heightened criteria for 4DP,encompassing rapid response,multi-stimulus response,large shape change,and specific mechanical properties(e.g.,high strength,high modulus)capable of accommodating varying environ-mental conditions.In recent years,shape memory polymers(SMPs)have garnered increasing attention among 4DP researchers due to their ease of design and preprogramming at the molecular level,facilitating controlled transformations along predictable pathways.However,4DP of high-strength SMPs,as an indispensable part of the high-performance field,is full of challenges because the intrinsic properties of the raw materials are not well compatible with the printing principle and the printed configuration is not flexible enough.Consequently,this paper provides a concise overview of the response mechanisms and applications of five prominent high-strength SMPs utilized in 4DP:epoxy resin,poly(ether-ether-ketone),polyimide,polylactic acid,and polyurethane.Ad-ditionally,it delves into the associated challenges and prospects,offering researchers valuable insights into the potential value of high-strength SMPs within the domain of 4DP.
基金Project supported by the Iran National Science Foundation (INSF)(No.98027408)。
文摘This study presents a semi-analytical solution to describe the behavior of shape memory polymers(SMPs) based on the nonlinear thermo-visco-hyperelasticity which originates from the concepts of internal state variables and rational thermodynamics.This method is developed for the finite bending of multilayers in a dual-shape memory effect(SME) cycle.The layer number and layering order are investigated for two different SMPs and a hyperelastic material.In addition to the semi-analytical solution,the finite element simulation is performed to verify the predicted results,where the outcomes demonstrate the excellent accuracy of the proposed solution for predicting the behavior of the multilayer SMPs.Since this method has a much lower computational cost than the finite element method(FEM),it can be used as an effective tool to analyze the SMP behavior under different conditions,including different materials,different geometries,different layer numbers,and different layer arrangements.
基金supported by the National Natural Science Foundation of China(Grant Nos.12102107 and 12272113)China National Postdoctoral Program for Innovative Talents(No.BX2021090).
文摘The mismatch in thermal expansion coefficients between the fiber-rich and resin-rich regions of a shape memory polymer composite(SMPC)laminate,along with the residual strain during SMPC fabrication,results in buckling deformation of the inhomogeneous laminate.This paper presents a macroscopic model for buckling of an inhomogeneous SMPC laminate under initial biaxial prestrains.Both linear and nonlinear buckling analyses are carried out using the energy method.The influences of prestrain biaxiality,temperature,and ply angle on the buckling wavelength,critical buckling prestrain,and buckling amplitude are calculated.The results demonstrate that the critical buckling wavelength of the SMPC laminate is independent of the prestrain,while the amplitude is almost independent of temperature.In addition,the optimal fiber stacking configuration with the maximum critical buckling prestrains of inhomogeneous SMPC laminates is determined by a genetic algorithm.
基金Authors are grateful for the support from the National Natural Science Foundation of China through Grant numbers 11572236, 11372236.
文摘As a kind of popular smart materials, shape memory polymers （SMPs） have a great potential for applications in deployable aerospace structures and other engineering struc- tures. However, the vibration analysis of shape memory polymer structures, which would play an important role in engineering, has not gained much attention. In this study, we propose a dynamic model and establish the governing equations for characterizing the dynamic behavior of a shape memory polymer membrane subjected to time-dependent forces. The derivation of governing equations is based on a well-developed constitutive model of SMPs combined with the Euler-Lagrange equation. With the proposed model, two different loading cases are stud- ied： the equal-biaxial sinusoidal force and the uniaxial sinusoidal force. To analyze the dynamic response of a shape memory polymer membrane and find some effective ways to control vibra- tion, the isothermal amplitude-frequency response, the time-dependent behavior of vibration and the vibration in a variable temperature process are investigated in the numerical simulation. It is observed that temperature, mechanical force and heating rate have significant effects on the dynamic performances of a shape memory polymer membrane. We also investigate the shape memory behavior of SMP membrane involving the dynamic response. The influence of dynamics on shape fixation and shape recovery is discussed. These results and discussion may provide guidance for exploring the vibration and dynamic performances of shape memory polymer in deployable aerospace structures.
基金supported by National Natural Science Foundation of China(No.50943028)Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry
文摘Submicron-sized peanut-shaped poly（methyl methacrylate）/polystyrene （PMMA/PS） particles were successfully synthesized by seeded soap-free emulsion polymerization of styrene on the spherical crosslinked PMMA seed particles. The obtained peanut- shaped particles showed a novel internal morphology： PS phase formed one domain which linked to the other domain having PMMA core encased by PS shell.
文摘Heteroarm star-shaped polymers were synthesized by conventional free radical polymerization in two steps by the use of polyfunctional chain transfer agent.In the first step,free radical polymerization of methyl methacrylate was carried out in the presence of a polyfunctional chain transfer agent,pentaerythritol tetrakis(3-mercaptopropinate).At appropriate monomer conversions,two-arm PMMA having two residual thiol groups at the chain center or three-arm PMMA having one residual thiol group at the core were o...
基金supported by the Aeronautical Science Foundation of China(Grant Nos.2024Z009052003,20230038052001 and 20230015052002)the Third Batch of Science and Technology Plan Projects in Changzhou City in 2023(Applied Basic Research,Grant No.CJ20230080).
文摘This paper presents the development of a thermoplastic shape memory rubber that can be programmed at human body temperature for comfortable fitting applications.We hybridized commercially available thermoplastic rubber(TPR)used in the footwear industry with un-crosslinked polycaprolactone(PCL)to create two samples,namely TP6040 and TP7030.The shape memory behavior,elasticity,and thermo-mechanical response of these rubbers were systematically investigated.The experimental results demonstrated outstanding shape memory performance,with both samples achieving shape fixity ratios(Rf)and shape recovery ratios(R_(r))exceeding 94%.TP6040 exhibited a fitting time of 80 s at body temperature(37℃),indicating a rapid response for shape fixing.The materials also showed good elasticity before and after programming,which is crucial for comfort fitting.These findings suggest that the developed shape memory thermoplastic rubber has potential applications in personalized comfort fitting products,offering advantages over traditional customization techniques in terms of efficiency and cost-effectiveness.
文摘A Shape Memory Polymer Composite(SMPC)is developed by reinforcing an epoxy-based polymer with randomly oriented short glass fibers.Diverging from previous research,which primarily focused on the hot programming of short glass fiber-based SMPCs,this work explores the potential for programming below the glass transition temperature(Tg)for epoxy-based SMPCs.To mitigate the inherent brittleness of the SMPC during deformation,a linear polymer is incorporated,and a temperature between room temperature and Tg is chosen as the deformation temperature to study the shape memory properties.The findings demonstrate an enhancement in shape fixity and recovery stress,alongside a reduction in shape recovery,with the incorporation of short glass fibers.In addition to tensile properties,thermal properties such as thermal conductivity,specific heat capacity,and glass transition temperature are investigated for their dependence on fiber content.Microscopic properties,such as fiber-matrix adhesion and the dispersion of glass fibers,are examined through Scanning Electron Microscope imaging.The fiber length distribution and mean fiber lengths are also measured for different fiber fractions.
基金supported by the National Key R&D Program of China(2022YFB3805700)the National Natural Science Foundation of China(Grant No.12302198)+2 种基金China Postdoctoral Science Foundation(2022M720042)Heilongjiang Postdoctoral Science Foundation(LBH-Z22016)Key Project of Heilongjiang Provincial Department of Science and Technology(2022ZX02C25).
文摘Metamaterials,owing to their exceptional physical characteristics that are absent in natural materials,have emerged as a crucial constituent of intelligent devices and systems.However,there are still significant challenges that necessitate immediate attention,as they have considerably constrained the applicability of metamaterials,including fixed mechanical properties post-fabrication and restricted design freedom.Here,thermo-responsive,photo-responsive,electro-responsive,and magneto-responsive shape memory polymer nano-composites were developed,and shape memory gradient metamaterials were fabricated using multi-material 4D printing technology.The correlation mechanism between the design parameters and the mechanical properties of multi-responsive gradient metamaterials was systematically analyzed,and the highly designable and programmable configuration and mechanical properties of the gradient metamaterials were realized.More importantly,4D printed multi-responsive shape memory polymer gradient metamaterials can be programmed in situ without additional infrastructure for multi-functional mechanical functions,paving the way for the realization of multiple functions of a single structure.Based on the multi-responsive gradient metamaterials,4D printed digital pixel metamaterial intelligent information carriers were fabricated,featuring customizable encryption and decryption protocols,exceptional scalability,and reusability.Additionally,4D printed gradient metamaterial logic gate electronic devices were developed,which were anticipated to contribute to the development of smart,adaptable robotic systems that combine sensing,actuation,and decision-making capabilities.
基金This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoalde Nível Superior-Brasil(CAPES)-Finance Code 001.
文摘The continuous improvement in patient care and recovery is driving the development of innovative materials for medical applications.Medical sutures,essential for securing implants and closing deep wounds,have evolved to incorporate smart materials capable of responding to various stimuli.This study explores the potential of thermoresponsive sutures,made from shape memory materials,that contract upon heating to bring loose stitches closer together,promoting optimal wound closure.We developed nanocomposites based on a blend of poly(lactic acid)(PLA)and thermoplastic polyurethane(TPU)—biopolymers that inherently exhibit shape memory—enhanced with carbon nanotubes(CNT)and graphene nanoplatelets(GN)to improve mechanical performance.PLA/TPU(50/50)nanocomposites were prepared with 1 and 2 wt%GN,as well as hybrid formulations combining 1 wt%CNT with 1 or 2 wt%GN,using a twin-screw extrusion process to form filaments.These filaments were characterized through differential scanning calorimetry(DSC),field emission gun scanning electron microscopy(FEG-SEM),tensile testing,and shape memory assessments.While the PLA/TPU blend is immiscible,TPU enhances the crystallinity(X_(c))of the PLA phase,further increased by the addition of CNT and GN.FEG-SEM images indicate CNTs primarily in the PLA phase and GN in the TPU phase.PLA/TPU with 1 or 2 wt%GN showed the highest potential for suture applications,with a high elastic modulus(~1000 MPa),significant strain at break(~10%),and effective shape recovery(~20%at 55℃ for 30 min).These findings suggest that these nanocomposites can enhance suture performance with controlled shape recovery that is suitable for medical use.
文摘A cup shape is a dynamic morphology of cells and organelles. With the aim of elucidating the formation of the biotic cup-shaped morphology, this study investigated cup-shaped vesicles consisting of an amphiphilic diblock copolymer from the aspect of synthetic polymer chemistry. Cup-shaped vesicles were obtained by the polymerization-induced self-assembly of poly(methacrylic acid)-block-poly(n-butyl methacrylate-random-methacrylic acid), PMAA-b-P(BMA-r-MAA), in an aqueous methanol solution using the photo nitroxide-mediated controlled/living radical polymerization technique. Field emission scanning electron microscopic observations demonstrated that the cup-shaped vesicles were suddenly formed during the late stage of the polymerization due to the extension of the hydrophobic P(BMA-r-MAA) block chain. During the early stage, the polymerization produced spherical vesicles rather than a cup shape. As the hydrophobic block chain was extended by the polymerization progress, the spherical vesicles reduced the size and were accompanied by the generation of small particles that were attached to the vesicles. The vesicles continued to reduce the size due to further extension of the hydrophobic chain;however, they suddenly grew into cup-shaped vesicles. This growth was accounted for by a change in the critical packing shape of the copolymer due to the hydrophobic chain extension. These findings are helpful for a better understanding of the biotic cup-shaped vesicle formation.
基金supported by the Singapore Centre for 3D Printing which is funded by the Singapore National Research Foundation.
文摘The rapid development of additive manufacturing and advances in shape memory materials have fueled the progress of four-dimensional （4D） printing. With the right external stimulus, the need for human interaction, sensors, and batteries will be eliminated, and by using additive manufacturing, more complex devices and parts can be produced. With the current understanding of shape memory mechanisms and with improved design for additive manufacturing, reversibility in 4D printing has recently been proven to be feasible. Conventional one-way 4D printing requires human interaction in the programming （or shapesetting） phase, but reversible 4D printing, or two-way 4D printing, will fully eliminate the need for human interference, as the programming stage is replaced with another stimulus. This allows reversible 4D printed parts to be fully dependent on external stimuli; parts can also be potentially reused after every recovery, or even used in continuous cycles-an aspect that carries industrial appeal. This paper presents a review on the mechanisms of shape memory materials that have led to 4D printing, current findings regarding 4D printing in alloys and polymers, and their respective limitations. The reversibility of shape memory materials and their feasibility to be fabricated using three-dimensional （3D） printing are summarized and critically analyzed. For reversible 4D printing, the methods of 3D printing, mechanisms used for actuation, and strategies to achieve reversibility are also highlighted. Finally, prospective future research directions in reversible 4D printing are suggested.
