Nucleation, Development and Healing of Micro-Cracks in Shape Memory Polyurethane Subjected to Subsequent Tension Cycles.

Thermoresponsive shape memory polymers (SMPs) have garnered increasing interest for their exceptional ability to retain a temporary shape and recover the original configuration through temperature changes, making them promising in various applications. The SMP shape change and recovery that happen due to a combination of mechanical loading and appropriate temperatures are related to its particular microstructure. The deformation process leads to the formation and growth of micro-cracks in the SMP structure, whereas the subsequent heating over its glass transition temperature Tg leads to the recovery of its original shape and properties. These processes also affect the SMP microstructure. In addition to the observed macroscopic shape recovery, the healing of micro-crazes and micro-cracks that have nucleated and developed during the loading occurs. Therefore, our study delves into the microscopic aspect, specifically addressing the healing of micro-cracks in the cyclic loading process. The proposed research concerns a thermoplastic polyurethane shape memory polymer (PU-SMP) MM4520 with a Tg of 45 °C. The objective of the study is to investigate the effect of the number of tensile loading-unloading cycles and thermal shape recovery on the evolution of the PU-SMP microstructure. To this end, comprehensive research starting from structural characterization of the initial state and at various stages of the PU-SMP mechanical loading was conducted. Dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS) and scanning electron microscopy (SEM) were used. Moreover, the shape memory behavior in the thermomechanical loading program was investigated. The obtained average shape fixity value was 99%, while the shape recovery was 92%, which confirmed good shape memory properties of the PU-SMP. Our findings reveal that even during a single loading-unloading tension cycle, crazes and cracks nucleate on the surface of the PU-SMP specimen, whereas the subsequent temperature-induced shape recovery process carried out at the temperature above Tg enables the healing of micro-cracks. Interestingly, the surface of the specimen after three and five loading-unloading cycles did not exhibit crazes and cracks, although some traces of cracks were visible. The traces disappeared after exposing the material to heating at Tg + 20 °C (65 °C) for 30 min. The crack closure phenomenon during deformation, even without heating over Tg, occurred within three and five subsequent cycles of loading-unloading. Notably, in the case of eight loading-unloading cycles, cracks appeared on the surface of the PU-SMP and were healed only after thermal recovery at the particular temperature over Tg. Upon reaching a critical number of cycles, the proper amount of energy required for crack propagation was attained, resulting in wide-open cracks on the material's surface. It is worth noting that WAXS analysis did not indicate strong signs of typical highly ordered structures in the PU-SMP specimens in their initial state and after the loading history; however, some orientation after the cyclic deformation was observed.

Enhancing Tensile Modulus of Polyurethane-Based Shape Memory Polymers for Wound Closure Applications through the Addition of Palm Oil.

Thermo-responsive, biocompatible polyurethane (PU) with shape memory properties is highly desirable for biomedical applications. An innovative approach to producing wound closure strips using shape memory polymers (SMPs) is of significant interest. In this work, PU composed of polycaprolactone (PCL) and 1,4-butanediol (BDO) was synthesized using two-step polymerization. Palm oil (PO) was added to PU for enhancing the Young's modulus of the PU beyond the set criterion of 130 MPa. It was found that PU had the ability to crystallize at room temperature and the segments of individual PCL and BDO polyurethanes crystallized separately. The crystalline domains and hard segment of PU greatly affected the tensile properties. The reduction of crystalline domains by the addition of PO and deformation at the higher melting temperature of the crystalline PCL polyurethane phase improved the shape fixity and shape recovery ratios. The new irreversible phase, raised from the permanent deformation upon stretching at the between melting temperature of the crystalline PCL and BDO polyurethanes of 70 °C, resulted in a decrease in shape fixity ratio after the first thermomechanical stretching-recovering cycles. The demonstration of PU as a wound closure strip showed its efficiency and potential until the surgical wound healed.

Catalyst-Free Dynamic Covalent C=C/C=N Metathesis Reaction for Associative Covalent Adaptable Networks.

Covalent adaptable networks (CANs), leveraging the dynamic exchange of covalent bonds, emerge as a promising material to address the challenge of irreversible cross-linking in thermosetting polymers. In this work, we explore the introduction of a catalyst-free and associative C=C/C=N metathesis reaction into thermosetting polyurethanes, creating CANs with superior stability, solvent resistance, and thermal/mechanical properties. By incorporating this dynamic exchange reaction, stress-relaxation is significantly accelerated compared to imine-bond-only networks, with the rate adjustable by modifying substituents in the ortho position of the dynamic double bonds. The obtained plasticity enables recycle without altering the chemical structure or mechanical properties, and is also found to be vital for achieving shape memory functions with complex spatial structures. This metathesis reaction as a new dynamic crosslinker of polymer networks has the potential to accelerate the ongoing exploration of malleable and functional thermoset polymers.

Thermo-Mechanical Behavior and Strain Rate Sensitivity of 3D-Printed Polylactic Acid (PLA) below Glass Transition Temperature (Tg).

This study investigated the thermomechanical behavior of 4D-printed polylactic acid (PLA), focusing on its response to varying temperatures and strain rates in a wide range below the glass transition temperature (Tg). The material was characterized using tension, compression, and dynamic mechanical thermal analysis (DMTA), confirming PLA's strong dependency on strain rate and temperature. The glass transition temperature of 4D-printed PLA was determined to be 65 °C using a thermal analysis (DMTA). The elastic modulus changed from 1045.7 MPa in the glassy phase to 1.2 MPa in the rubber phase, showing the great shape memory potential of 4D-printed PLA. The filament tension tests revealed that the material's yield stress strongly depended on the strain rate at room temperature, with values ranging from 56 MPa to 43 MPA as the strain rate decreased. Using a commercial FDM Ultimaker printer, cylindrical compression samples were 3D-printed and then characterized under thermo-mechanical conditions. Thermo-mechanical compression tests were conducted at strain rates ranging from 0.0001 s-1 to 0.1 s-1 and at temperatures below the glass transition temperature (Tg) at 25, 37, and 50 °C. The conducted experimental tests showed that the material had distinct yield stress, strain softening, and strain hardening at very large deformations. Clear strain rate dependence was observed, particularly at quasi-static rates, with the temperature and strain rate significantly influencing PLA's mechanical properties, including yield stress. Yield stress values varied from 110 MPa at room temperature with a strain rate of 0.1 s-1 to 42 MPa at 50 °C with a strain rate of 0.0001 s-1. This study also included thermo-mechanical adiabatic tests, which revealed that higher strain rates of 0.01 s-1 and 0.1 s-1 led to self-heating due to non-dissipated generated heat. This internal heating caused additional softening at higher strain rates and lower stress values. Thermal imaging revealed temperature increases of 15 °C and 18 °C for strain rates of 0.01 s-1 and 0.1 s-1, respectively.

Constitutive model for shape memory polymer and its thermodynamic responses in finite element analysis.

BACKGROUND: As a new intelligent polymer material, shape memory polymer (SMP) was a potential orthodontic appliance material. OBJECTIVE: This study aimed to investigate the thermodynamic responses of SMP under different loads via finite element analysis (FEA). METHODS: FEA specimens with a specification of 0.1 × 0.1 × 1 mm were designed. One end of the specimen was fixed, and the other was subjected to displacement load. Different loading, cooling, and heating rates were separately exerted on the specimen in its shape recovery process and used to observe the responses of the SMP constitutive model. Furthermore, specimens with various tensile elongation and sectional areas were simulated and used to elucidate their effect on shape recovering force. RESULTS: The specimens obtained a similar stress of 0.5, 0.44, and 1.07 Mpa for different loading, cooling, and heating rates after a long time. The shape recovering force of specimen increased from 0.0102 to 0.0315 N when the elongation improved from 10% to 40% and to 0.0408 N when the sectional areas were expanded to 0.2 × 0.2 mm. CONCLUSION: The stiffness of SMP was small at a high temperature but large at a low temperature. The effects of the loading, cooling, and heating rates on SMP can be eliminated after a long time. Furthermore, it was possible to increase the recovering force by increasing the elongation or expanding the sectional area of the specimen. The force was quadratically dependent on the elongation ratio.

Strengthening-Durable Trade-Off and Self-Healing, Recyclable Shape Memory Polyurethanes Enabled by Dynamic Boron-Urethane Bonds.

Addressing the demand for integrating strength and durability reinforcement in shape memory polyurethane (SMPU) for diverse applications remains a significant challenge. Here a series of SMPUs with ultra-high strength, self-healing and recyclability, and excellent shape memory properties through introducing dynamic boron-urethane bonds are synthesized. The introducing of boric acid (BA) to polyurethane leading to the formation of dynamic covalent bonds (DCB) boron-urethane, that confer a robust cross-linking structure on the SMPUs led to the formation of ordered stable hydrogen-bonding network within the SMPUs. The flexible crosslinking with DCB represents a novel strategy for balancing the trade-off between strength and durability, with their strengths reaching up to 82.2 MPa while also addressing the issue of durability in prolonged usage through the provision of self-healing and recyclability. The self-healing and recyclability of SMPU are demonstrated through rapid dynamic exchange reaction of boron-urethane bonds, systematically investigated by dynamic mechanical analysis (DMA). This study sheds light on the essential role of such PU with self-healing and recyclability, contributing to the extension of the PU's service life. The findings of this work provide a general strategy for overcoming traditional trade-offs in preparing SMPUs with both high strength and good durability.

Fabrication of Shape Memory Polymer Endovascular Thrombectomy Device for Treating Ischemic Stroke.

Stroke is the second result for death and ischemic stroke constitutes most of all stroke cases. Ischemic stroke takes place when blood clot or embolus blocks cerebral vessel and interrupts blood flow, which often leads to brain damage, permanent disability, or death. There is a 4.5-h (golden hour) treatment window to restore blood flow prior to permanent neurological impairment results. Current stroke treatments consist mechanical system or thrombolytic drug therapy to disrupt or dissolve thrombus. Promising method for stroke treatment is mechanical retrieving of thrombi employing device deployed endovascularly. Advent of smart materials has led to research fabrication of several minimally invasive endovascular devices that take advantage of new materials capabilities. One of these capabilities is shape memory, is capability of material to store temporary form, then activate to primary shape as subjected to stimuli. Shape memory polymers (SMPs) are employed as good materials for thrombectomy device fabrication. Therefore, current review presents thrombectomy device development and fabrication with SMPs. Design, performance, limitations, and in vitro or in vivo clinical results of SMP-based thrombectomy devices are identified. Review also sheds light on SMP's future outlook and recommendations for thrombectomy device application, opening a new era for advanced materials in materials science.

Multiscale Transfer Printing via Shape Memory Polymer with High Adhesion and Modulus Switchability.

Flexible electronics have gained significant attention as an innovative solution to meet the growing need for information collection from the human body and the environment. However, a critical challenge lies in the need for a transfer printing technique that can fabricate rigid and brittle devices on flexible organic substrates. Here, we develop a multiscale transfer printing technique using an ultraviolet-curable shape memory polymer (SMP) that serves as both the stamp and the receiver substrate. The SMP demonstrates exceptional mechanical performance with toughness at room temperature and remarkable flexibility near its glass transition temperature. The SMP material exhibits an impressive shape recovery ratio and remarkable adhesion switchability. We demonstrate robust transfer printing of diverse objects with different materials and morphologies and in situ transfer of multiscale metallic structures. In addition, the in situ fabricated transparent hyperthermia patches with embedded metal grids are demonstrated, offering potential application in the field of sensors, wearable devices, and electronic skin.

A Solvent-Templated Porous Liquid Crystal Elastomer with Tactile Sensation beyond Reversible Actuation toward Versatile Artificial Muscles.

Liquid crystal elastomers (LCEs), as a classical two-way shape-memory material, are good candidates for developing artificial muscles that mimic the contraction, expansion, or rotational behavior of natural muscles. However, biomimicry is currently focused more on the actuation functions of natural muscles dominated by muscle fibers, whereas the tactile sensing functions that are dominated by neuronal receptors and synapses have not been well captured. Very few studies have reported the sensing concept for LCEs, but the signals were still donated by macroscopic actuation, that is, variations in angle or length. Herein, we develop a conductive porous LCE (CPLCE) using a solvent (dimethyl sulfoxide (DMSO))-templated photo-cross-linking strategy, followed by carbon nanotube (CNT) incorporation. The CPLCE has excellent reversible contraction/elongation behavior in a manner similar to the actuation functions of skeletal muscles. Moreover, the CPLCE shows excellent pressure-sensing performance by providing real-time electrical signals and is capable of microtouch sensing, which is very similar to natural tactile sensing. Furthermore, macroscopic actuation and tactile sensation can be integrated into a single system. Proof-of-concept studies reveal that the CPLCE-based artificial muscle is sensitive to external touch while maintaining its excellent actuation performance. The CPLCE with tactile sensation beyond reversible actuation is expected to benefit the development of versatile artificial muscles and intelligent robots.

4D-Printed Tool for Compressing a Shape Memory Polyurethane Foam during Programming.

Although several force application concepts are known that can be used to deform shape memory polymers (SMPs) within the scope of programming, controlled deformation is challenging in the case of samples with a cylinder-like shape, which need to be homogeneously compressed starting from the lateral surface. To solve this problem, this contribution follows a material approach that takes advantage of four-dimensional (4D) printing. Fused filament fabrication (FFF) was used as an additive manufacturing (AM) technique to produce a thermoresponsive tool in a cylindrical shape from a polyether urethane (PEU) having a glass transition temperature (Tg) close to 55 °C, as determined by differential scanning calorimetry (DSC). Once it was 4D-printed, a sample of laser cut polyester urethane urea (PEUU) foam with a cylindrical wall was placed inside of it. Subsequent heating to 75 °C and keeping that temperature constant for 15 min resulted in the compression of the foam, because the internal stresses of the PEU were transferred to the PEUU, whose soft segments were completely molten at 65 °C as verified by DSC. Upon cooling to -15 °C and thus below the offset temperature of the soft segment crystallization transition of the PEUU, the foam was fixed in its new shape. After 900 days of storage at temperatures close to 23 °C, the foam recovered its original shape upon reheating to 75 °C. In another experiment, a 4D-printed cylinder was put into hibernation for 900 days before its thermoresponsiveness was investigated. In the future, 4D-printed tools may be produced in many geometries, which fit well to the shapes of the SMPs to be programmed. Beyond programming SMP foams, transferring the forces released by 4D-printed tools to other programmable materials can further expand technical possibilities.

Restoration Temperature Control through Glass Transition Temperature Modulation of Shape Memory Polymer for Thermally Switchable Adhesive.

Shape memory polymers (SMPs) undergo changes between arbitrary shapes and programmed shapes upon exposure to specific stimulus, allowing them to restore their original shape. All kinds of external stimuli have a threshold to change the shape of the SMP. Especially, for the thermal type SMP, the critical temperature for shape restoration is typically near the glass transition temperature (Tg). In this study, the controllability of the restoration temperature is analyzed by adjusting the Tg of the polymer using Norland Optical Adhesive 63, which can be cured with UV irradiation. By varying the ambient temperature from 20 to 120 °C during UV exposure, Tg changes ranging from 35.84 to 50.50 °C are obtained, with corresponding changes in restoration temperature. As a practical application, a thermal-activated SMP dry adhesive is developed with programmable Tg and switchable adhesion. The fabricated SMP dry adhesive exhibited strong adhesion to substrates with various surface roughness. Additionally, the shape memory effect allowed for easy detachment through shape recovery, and different adhesive performances at different temperatures are achieved by programming various Tg values. Moreover, the simple manufacturing process of the SMP dry adhesive is confirmed to be suitable for continuous fabrication processes based on roll-to-roll methods.

Aortic Valve Engineering Advancements: Precision Tuning with Laser Sintering Additive Manufacturing of TPU/TPE Submillimeter Membranes.

Synthetic biomaterials play a crucial role in developing tissue-engineered heart valves (TEHVs) due to their versatile mechanical properties. Achieving the right balance between mechanical strength and manufacturability is essential. Thermoplastic polyurethanes (TPUs) and elastomers (TPEs) garner significant attention for TEHV applications due to their notable stability, fatigue resistance, and customizable properties such as shear strength and elasticity. This study explores the additive manufacturing technique of selective laser sintering (SLS) for TPUs and TPEs to optimize process parameters to balance flexibility and strength, mimicking aortic valve tissue properties. Additionally, it aims to assess the feasibility of printing aortic valve models with submillimeter membranes. The results demonstrate that the SLS-TPU/TPE technique can produce micrometric valve structures with soft shape memory properties, resembling aortic tissue in strength, flexibility, and fineness. These models show promise for surgical training and manipulation, display intriguing echogenicity properties, and can potentially be personalized to shape biocompatible valve substitutes.

Ultra-Large Stress and Strain Polymer Nanocomposite Actuators Incorporating a Mutually-Interpenetrated, Collective-Deformation Carbon Nanotube Network.

Stimulus-responsive polymer-based actuators are extensively studied, with the challenging goal of achieving comprehensive performance metrics that include large output stress and strain, fast response, and versatile actuation modes. The design and fabrication of nanocomposites offer a promising route to integrate the advantages of both polymers and nanoscale fillers, thus ensuring superior performance. Here, it is started from a three-dimensional (3D) porous sponge to fabricate a mutually interpenetrated nanocomposite, in which the embedded carbon nanotube (CNT) network undergoes collective deformation with the shape memory polymer (SMP) matrix during large-degree stretching and releasing, increases junction density with polymer chains and enhances molecular orientation. These features result in substantial improvement of the overall mechanical properties and during thermally actuated contraction, the bulk SMP/CNT composites exhibit output stresses up to 19.5 ± 0.97 MPa and strains up to 69%, accompanied by a rapid response and high energy density, exceeding the majority of recent reports. Furthermore, electrical actuation is also demonstrated via uniform Joule heating across the self-percolated CNT network. Applications such as low-temperature thermal actuated vascular stent and wound dressing are explored. These findings lay out a universal blueprint for developing robust and highly deformable SMP/CNT nanocomposite actuators with broad potential applications.

Electro-Mechanical Characterisation and Damage Monitoring by Acoustic Emission of 3D-Printed CB/PLA.

Even though the influence of the printing direction on the mechanical properties of 3D-printed samples by fused filament fabrication is established in the literature, very little is known about mechanical and electrical coupling. In this study, electrically conductive polylactic acid filled with carbon black particles undergoes monotonic and repeated progressive tensile loading to better understand the influence of the printing direction on the electro-mechanical properties of three-dimensional-printed samples. The objective is to analyse the electro-mechanical behaviour of this composite for its potential application as an actuator. The classical laminate theory is also applied to evaluate the relevance of this theory in predicting the mechanical characteristics of this material. In addition, a comprehensive damage analysis is performed using acoustic emission, infrared thermography, scanning electron microscopy, and X-ray microcomputed tomography imaging. Results show that the degradation of the mechanical and electrical properties is highly influenced by the printing direction. The appearance and development of crazes in 0° filaments are highlighted and quantified. The conclusions drawn by this study underline the interest in using longitudinal and unidirectional printing directions to improve the conductive path within the samples. Furthermore, the evolution of the resistance throughout the experiments emphasizes the need to control the implemented voltage in the design of future electro-thermally triggered actuators.

Patterned Manipulated Surface Based on Femtosecond Laser with Adjustable Wetting Speed and Directional Fluid Delivery.

Recently, due to the crucial roles of multifunctional liquid manipulation surfaces in biomedical transportation, microfluidics, and chemical engineering, the demand for controllable and functional aspects of directed liquid transportation has increased significantly. However, designing an intelligent manipulation surface that is easy to manufacture and fully functional remains an immense challenge. To address this challenge, a smart surface that can regulate the rate of liquid transport within a patterned channel by temperature is reported. A synergistically controlled approach of poly(N-isopropylacrylamide) and micropillar shape-memory polymers (SMPs) was used to modulate the wetting rate of liquids on surfaces. By femtosecond laser direct writing, temperature-responsive composite surfaces are embedded in the microstructure of shape-memory polymers (SMPs) in a patterned manner, resulting in the preparation of novel programmable liquid manipulation surfaces incorporating boundaries possessing asymmetric wettability. Since the smart surface is based on SMP, the superhydrophobic part in the superhydrophobic/controllable wettability patterning platform is also programmed for droplet directional transport, which takes advantage of the difference in wettability between the rewritable indentation track and the periphery to allow droplets to flow into the temperature-controlled velocity track, enriching the functionality of the surface. In addition, based on its excellent controllability and patterning, the surface has been shown to be used in microfluidic circuit chips with self-cleaning properties, which provides new ideas for circuit timing control. This study provides promising prospects for the effective development of multifunctional liquid steering surfaces, lab-on-a-chip, and microfluidic devices.

3D-Printed Shape Memory Poly(alkylene terephthalate) Scaffolds as Cardiovascular Stents Revealing Enhanced Endothelialization.

Cardiovascular diseases are the leading cause of death and current treatments such as stents still suffer from disadvantages. Balloon expansion causes damage to the arterial wall and limited and delayed endothelialization gives rise to restenosis and thrombosis. New more performing materials that circumvent these disadvantages are required to improve the success rate of interventions. To this end, the use of a novel polymer, poly(hexamethylene terephthalate), is investigated for this application. The synthesis to obtain polymers with high molar masses up to 126.5 kg mol-1 is optimized and a thorough chemical and thermal analysis is performed. The polymers are 3D-printed into personalized cardiovascular stents using the state-of-the-art solvent-cast direct-writing technique, the potential of these stents to expand using their shape memory behavior is established, and it is shown that the stents are more resistant to compression than the poly(l-lactide) benchmark. Furthermore, the polymer's hydrolytic stability is demonstrated in an accelerated degradation study of 6 months. Finally, the stents are subjected to an in vitro biological evaluation, revealing that the polymer is non-hemolytic and supports significant endothelialization after only 7 days, demonstrating the enormous potential of these polymers to serve cardiovascular applications.

Enhancing the Thermal Performance of Shape Memory Polymers: Designing a Minichannel Structure.

This research proposes a numerical approach to improve the thermal performance of shape memory polymers (SMPs) while their mechanical properties remain intact. Sixteen different 3D minichannel structures were numerically designed to investigate the impact of embedded water flow in microchannel networks on the thermal response and shape recovery of SMPs. This work employs two approaches, each with different physics: approach A focuses on solid mechanics analysis and, accordingly, thermal analysis in solids without considering the fluid. approach B tackles solid and fluid mechanics analysis and thermal analysis in both solid and fluid subdomains, which inherently calls for fluid-structure coupling in a uniform procedure. Finally, the results of these two approaches are compared to predict the SMP's thermal and mechanical behavior. The structural designs are then analyzed in terms of their shape recovery speed, recovery ratio, and recovery parameters. The results indicate that isotropic structures thermally outperform their anisotropic counterparts, exhibiting improved thermal characteristics and faster shape recovery. Additionally, it was observed that polymeric structures with a low volume fraction of embedded branches thermally perform efficiently. The findings of this study predict that the geometrical angle between the main branch and sub-branches of SMP favorably impacts the enhancement of thermal characteristics of the structure, accelerating its shape recovery. Approach B accelerates the shape recovery rate in SMPs due to fluid flow and uniform heat transfer within the structures.

Reconfigurable Microlens Array Enables Tunable Imaging Based on Shape Memory Polymers.

Microlens arrays (MLAs) with a tunable imaging ability are core components of advanced micro-optical systems. Nevertheless, tunable MLAs generally suffer from high power consumption, an undeformable rigid body, large and complex systems, or limited focal length tunability. The combination of reconfigurable smart materials with MLAs may lead to distinct advantages including programmable deformation, remote manipulation, and multimodal tunability. However, unlike photopolymers that permit flexible structuring, the fabrication of tunable MLAs and compound eyes (CEs) based on transparent smart materials is still rare. In this work, we report reconfigurable MLAs that enable tunable imaging based on shape memory polymers (SMPs). The smart MLAs with closely packed 200 × 200 microlenses (40.0 µm in size) are fabricated via a combined technology that involves wet etching-assisted femtosecond laser direct writing of MLA templates on quartz, soft lithography for MLA duplication using SMPs, and the mechanical heat setting for programmable reconfiguration. By stretching or squeezing the shape memory MLAs at the transition temperature (80 °C), the size, profiles, and spatial distributions of the microlenses can be programmed. When the MLA is stretched from 0 to 120% (area ratio), the focal length is increased from 116 to 283 µm. As a proof of concept, reconfigurable MLAs and a 3D CE with a tunable field of view (FOV, 160-0°) have been demonstrated in which the thermally triggered shape memory deformation has been employed for tunable imaging. The reconfigurable MLAs and CEs with a tunable focal length and adjustable FOV may hold great promise for developing smart micro-optical systems.

Switchable Adhesive Based on Shape Memory Polymer with Micropillars of Different Heights for Laser-Driven Noncontact Transfer Printing.

Switchable adhesive is essential to develop transfer printing, which is an advanced heterogeneous material integration technique for developing electronic systems. Designing a switchable adhesive with strong adhesion strength that can also be easily eliminated to enable noncontact transfer printing still remains a challenge. Here, we report a simple yet robust design of switchable adhesive based on a thermally responsive shape memory polymer with micropillars of different heights. The adhesive takes advantage of the shape-fixing property of shape memory polymer to provide strong adhesion for a reliable pick-up and the various levels of shape recovery of micropillars under laser heating to eliminate the adhesion for robust printing in a noncontact way. Systematic experimental and numerical studies reveal the adhesion switch mechanism and provide insights into the design of switchable adhesives. This switchable adhesive design provides a good solution to develop laser-driven noncontact transfer printing with the capability of eliminating the influence of receivers on the performance of transfer printing. Demonstrations of transfer printing of silicon wafers, microscale Si platelets, and micro light emitting diode (µ-LED) chips onto various challenging nonadhesive receivers (e.g., sandpaper, stainless steel bead, leaf, or glass) to form desired two-dimensional or three-dimensional layouts illustrate its great potential in deterministic assembly.