Shape Memory Polymer Research Articles

Prototyping sutureless shape-memory valve stent via integrated 3D printing

Abstract Transcatheter aortic valve replacement (TAVR) has increasingly emerged as a forefront option for treating aortic valve diseases. However, the currently prevalent valve prostheses used in TAVR typically involve stitching biologic leaflets onto metallic stents, which introduces challenges in the durability of leaflets and the biocompatibility of metallic stents. This work proposes an integrated additive manufacturing method for prototyping sutureless prosthetic aortic valves that combine shape memory polymer (SMP) stent and hydrogel valve leaflets. The SMP stent exhibits sufficient toughness to maintain structural integrity upon shape memory programming, while the Fe3+-treated hydrogel leaflets possess sufficient swelling resistance to ensure dimensional stability. Finally, the proof-of-concept valve stent is successfully fabricated by integrated 3D printing and validated via an in vitro hemodynamic experiment. Overall, our approach holds promise for prototyping sutureless polymeric valve stents for future generations.

A highly visible-transparent thermochromic smart window with broadband infrared modulation for all-season energy savings

Abstract Thermochromic smart windows effectively reduce the energy consumption for building through passive light modulation including the transmission of visible (TVis), near-infrared (TNIR), and the emissivity of mid-infrared (εMIR) in response to the ambient temperature change. However, thermochromic windows that maintain high TVis while modulating TNIR and εMIR simultaneously are highly desirable but still challenging. Here, we develop a thermochromic smart window based on a two-way shape memory polymer to enable reversible transformation and achieve TNIR modulation of 44.0% and εMIR modulation of 76.5% while maintaining high TVis (>50%). Compared to traditional windows based on silica glass, this device shows 4°C lower temperature in summer daytime, 2°C higher in winter daytime, and 1°C higher in spring nighttime. It is expected that our device can achieve greater annual energy savings in comparison with commercial glass anywhere in the world and promote the progress of thermochromic windows for energy-efficient buildings.

Regulation of Glass Transition Temperature in Thermo‐Responsive Epoxy Shape Memory Polymers: The Roles of Chemical Crosslinking Density and Chain Flexibility

ABSTRACTShape memory polymers (SMPs) are novel kinds of smart materials whose shape can be changed in external conditions such as heat stimulus. Due to their excellent structural versatility and high elastic strain, they have important applications in the field of biomaterials. Here, a series of amorphous shape memory polymer materials are prepared and their shape memory properties and glass transition temperature (Tg) are also investigated. A special kind of epoxy polymer, whose shape can be changed at around physiological temperature, is synthesized by regulating the crosslinking density and introducing flexible aliphatic epoxy chains. The shape memory function of this epoxy polymer is studied by deformation test. In addition, to explore their application in the field of biomedical materials, the biocompatibility of the materials are evaluated, including the effects on the erythrocyte hemolysis rate and cell activity. The experimental results show that this kind of epoxy polymer has good shape memory function and biocompatibility.

4D printing of smart scaffolds for bone regeneration: a systematic review.


As a novel emerging technology, four-dimensional (4D) printing allows 3D-printed materials to change over time. This systematic review is conducted to evaluate the purpose, materials, physiomechanical, and biological properties of 4D-printed scaffolds used for bone tissue engineering.
Method and materials:
An electronic search was conducted following the PRISMA 2020 guidelines in PubMed, Scopus, Web of Science, and Google Scholar online databases limited to English articles until April 2024. Studies in which scaffolds were fabricated through 3D printing methods responding to external stimulation were included. The quality of in vitro and in vivo studies was evaluated through the modified CONSORT checklist and SYRCLE's risk of bias tool.
Results:
The full text of 57 studies were reviewed, and 15 studies met the inclusion criteria. According to the analyzed studies, most scaffolds responded to temperature changes showing shape memory effect. Polyurethane (PU) and poly(lactic acid) (PLA) were the most common shape memory polymers, and the most common fabrication method used was Fused Deposition Modeling (FDM).
Conclusion:
A comprehensive systematic review of the studies from the past 10 years demonstrated several findings: 1) Shape memory, drug delivery, and shape morphing are three general purposes of 4D printing for bone regeneration. 2) Smart materials used for 4D printing mostly consist of shape memory polymers. 3) Temperature changes account for the majority of stimulation used for 4D printing. 4) incorporating 4D printing principles does not have a negative impact on the physiomechanical properties of the designed scaffold. 5) The 4D-printed scaffolds show a higher osteogenic differentiation capacity than their identical 3D-printed structures in terms of bone regeneration.&#xD.

A 1D micromechanics-based constitutive model for the thermoviscoelastic behavior of crosslinked semicrystalline shape memory polymers: numerical simulation and experimental validation

Abstract The paper develops a 1D thermoviscoelastic constitutive model for the crystallization- and melting-induced one-way and two-way shape memory effects, as well as isothermal yielding behaviors, of crosslinked semi-crystalline polymers. A micromolecular chain model is proposed to characterize the transition between the amorphous and crystalline phases. Structural equations including a modified Eying model that combine phase transition and viscoelasticity equations are employed to predict the shape memory effects. An extensive experimental campaign has been carried out on poly (ethylene-co-vinyl acetate) based semi-crystalline elastomers to characterize the thermoviscoelastic temperature-stress-strain relations of the material under different loading and rate conditions. Some results guide the determination of the model parameters, while the rest validate the model capabilities. Comparisons with the experimental results show that the model can well reproduce the stress-strain-temperature responses, providing valuable insights for application development.

Integrating Photothermal-Responsive Shape Memory and Self-Healing Polymers in 4D-Printed Thermally Comfortable Smart Wearables

Integrating Photothermal-Responsive Shape Memory and Self-Healing Polymers in 4D-Printed Thermally Comfortable Smart Wearables

Harnessing nanostructures and fiber architecture: A synergistic leap in shape memory polymer composites

This research investigates the synergistic effects of carbon fiber orientation and nanostructure reinforcement across 21 configurations of shape memory polymer composites. It examines uni-directional (UD), bi-directional Twill (BDT), and bi-directional Plain (BDP) fiber architectures, along with varying concentrations of MWCNT and GnP at 0.4%, 0.6%, and 0.8%. The fabrication process involves initially preparing nanostructure-modified epoxy nanocomposites through ultrasonication followed by hand layup techniques to fabricate three-phase shape memory polymer composites. Optimal tensile performance is observed in GnP-modified UD composites at a 0.6 wt% concentration, achieving a tensile strength of 728.32 MPa and a modulus of 71.29 GPa. Furthermore, enhancements in thermomechanical and shape memory properties are noted in GnP-modified BDT composites and are further improved in GnP-modified BDP composite configurations. GnP-modified composites outperform MWCNT ones due to GnP’s sheet structure aligning parallel to the load and its larger surface area, which facilitate enhanced interaction with the matrix. These improvements, supported by FESEM analysis, highlight enhanced interfacial bonding and result in high shape recovery ratios, with all configurations exceeding 90%, despite polymer modification.

Programable shape recovery properties and snap-through instabilities of viscoelastic and shape-memory NS metamaterials

The combination of smart material and mechanical metamaterial has the potential to bring novel properties and additional functionalities, which, however, has been ignored for a long time. This work numerically, experimentally, and analytically examines the negative stiffness (NS) metamaterials based on shape memory polymers (SMPs) with a focus on the tunable and temperature-dependent properties induced by the interaction of material and geometry nonlinearity. A universal discrete model of a series of shape-memory NS metamaterial is developed by separating the bending effect and stretching effect, where the viscoelastic material is described by the generalized Maxwell-Wiechert model, and an SMP constitutive model is proposed based on multiplicative decomposition of the deformation gradient. The mechanical and shape-memory properties influenced by temperature, geometry, material and loading rate are experimentally observed through relaxation tests and cyclic compression tests. Then the discrete model and finite element analysis (FEA) is adopted to examine the novel mechanical responses in a wide range of parameters. Results show that viscoelasticity and loading rate play a significant role in mechanical responses, and tunable load-capacity and stability can be achieved for shape-memory metamaterial. A phase diagram of different stabilities is constructed showing strictly monotonic, S-shaped, and snapping responses. Additionally, repeated compression and recovery performance proves the possibility of reusable applications. This work provides new opportunities for functional metamaterial to obtain programmable shape recovery and mechanical responses.

Flexible and durable shape memory EVA/MXene/EVA fiber membrane for programmable EMI shielding

Flexible and lightweight electromagnetic interference (EMI) shielding materials are currently the focus of electromagnetic protection material research. By applying shape memory polymers to the field of electromagnetic shielding, intelligent electromagnetic shielding composites with programmable shielding performance can be prepared. In this study, a flexible EVA/MXene/EVA electromagnetic shielding composite membrane with programmable shielding effectiveness was prepared using electrospinning, vacuum filtration, and hot pressing techniques. Even with a low MXene content, the EMI shielding effectiveness in the X-band still achieved 40.5 dB, and the specific EMI shielding effectiveness was as high as 6.23 × 103 dB cm2 g−1. The composite membrane exhibited excellent shape memory performance, with a shape fixation rate (Rf) of 93.8 % and a shape recovery rate (Rr) of 92.1 %, achieving a programmable shielding effectiveness of 14.1–40.5 dB under 0–30 % tensile strain. Additionally, the composite membrane could serve as a switch for electromagnetic shielding, controlling the reception and shielding of electromagnetic waves. Simultaneously, the composite membrane exhibits excellent hydrophobicity, electrothermal conversion capability, and durability. Importantly, it retains almost the same shielding effectiveness even after undergoing 500 cycles of bending and folding, as well as prolonged exposure to strong acids and alkalis. This work not only offers new insights into the development of multifunctional and intelligent electromagnetic shielding composites suitable for harsh environments but also expands the application scope of shape memory smart materials.

Rubber-assisted and modulated epoxy topological network for developing fatigue-resistant, high-strain-cycle high performance shape memory polymer composites

High performance shape memory polymer (HPSMP) has a wide range of application such as smart device, smart mold. In this study, we designed a rigid-flexible shape memory epoxy with flexible chain segment as the main chain and rigid benzene ring as the side group. Meanwhile, carboxyl-terminated nitrile butadiene rubber (CTBN) was accessed into the epoxy main chain as a fatigue-resistant functional filler. The results showed that the flexible backbone plays a major role in improving the ductility. The superior fatigue-resistant shape memory cycling performance was synergistically achieved by modulating the epoxy topological network through altering the disulfide cross-linker prompted by CTBN, and the materials exhibited good high and low-temperature resistant mechanical properties. Comparatively, it is found that disulfide bonding can significantly improve the tensile property and thermal stability for epoxy. The synergistic effect between the elastic chain segments in CTBN and the flexible backbone achieves excellent shape recovery ratio. Therefore, the rational structural design provides an effective way to develop HPSMP, which can expand the application areas for HPSMP.

Tendon‐Driven Stiffness‐Tunable Soft Actuator via Thermoelectric‐based Bidirectional Temperature Control

AbstractSoft robots have excellent spatial adaptability and high flexibility, but they are limited by the low stiffness of their constituent materials when faced with high‐load tasks. In recent years, there have been many works on the development of stiffness‐tunable soft actuators by introducing variable stiffness materials into soft actuators, but the existing solutions usually suffer from the problems of slow response, complex structure, and the need of many auxiliary devices to support the completion of the stiffness tuning cycle. This paper proposes a tendon‐driven stiffness‐tunable soft actuator that addresses these issues. Benefiting from the bidirectional temperature control of thermoelectric modules and the excellent in‐plane thermal conductivity of graphene, the actuator is capable of achieving the heating and cooling process by transferring the heat flow through the graphene structure into and out of the shape‐memory polymer (SMP) layer of the tendon‐driven actuator. This enables stiffness tuning via a single device, reducing the dependence on complex external cooling systems. The use of tendon‐driven actuators further eliminates the complex bellow structure of conventional pneumatic actuators and dramatically reduces the size and manufacturing difficulty of individual actuators. Finally, the high load capacity and shape adaptability of the actuator are demonstrated by a gripper equipped with three actuators, which successfully grips objects of various shapes and weights, ranging from less than 10 g to up to 1.6 kg.

Model-based design of a mechanically intelligent shape-morphing structure

Soft robotics has significant interest within the industrial applications due to its advantages in flexibility and adaptability. Nevertheless, its potential is challenged by low stiffness and limited deformability, particularly in large-scale application scenarios such as underwater and offshore engineering. The integration of smart materials and morphing structures presents a promising avenue for enhancing the capabilities of soft robotic systems, especially in large deformation and variations in stiffness. In this study, we propose a multiple smart materials based mechanically intelligent structure devised through a model-based design framework. Specifically, the intelligent structure incorporates smart hydrogel and shape memory polymer (SMP). Employing the finite element method (FEM), we simulated the complex interactions among smart material to analyze the performance characteristics of the intelligent structure. The results demonstrate that, utilizing smart hydrogel and shape memory polymer (SMP) can effectively attain large deformation and exhibit variable stiffness due to the shape memory effect. Besides, the shape-morphing structures exhibit customized behaviours including bending, curling, and elongation, all while reducing reliance on external power sources. In conclusion, utilizing multiple smart materials within the model-based design framework offers an efficient approach for developing mechanically intelligent structure capable of complex deformations and variable stiffness, thereby providing support for underwater or offshore engineering applications.

Ethylene vinyl acetate/copper sulphide with near-infrared light active shape memory behavior

This thesis presents the preparation of ethylene vinyl acetate (EVA)-based shape memory polymer composites (SMPC) (EVA/CuS) with near-infrared light photo-thermal response. The composites were prepared using EVA as the matrix material and copper sulphide (CuS) particles as the functional phase. The designability of SMPs was considered in the preparation of these composites. The results demonstrated that the incorporation of CuS, as a functional phase, enhanced the cross-linking degree and augmented the shape memory properties of EVA. Additionally, it served as a photo-thermal functional filler, imparting its photo-thermal properties. It can be observed that as the quantity of CuS particles incorporated into the EVA/CuS composite film increases, the photothermal conversion performance of the composite film improves, the shape fixation rate rises, and the rate of recovery of light-responsive shape memory accelerates. The temperature of the composites increased to 116.7°C in 20 s when the CuS addition was 2 wt% and the NIR light intensity was 0.5 W/cm2. At a NIR light intensity of 0.6 W/cm2, the “U” shape of the sample was restored to a straight state in 30 s, and the shape recovery rate reached 100%. In this experiment, optical near-infrared photostimulation-responsive EVA/CuS composites have been successfully prepared. These composites demonstrate the ability to achieve remote control and fast response of EVA shape memory behavior, offering a new avenue for the preparation of photo-responsive EVA-based shape memory materials.

Shape Memory Polymer Foam Based on Nanofibrillar Composites of Polylactide/Polyamide.

This paper presents the novel development of a shape memory polymer foam based on polymer-polymer nanocomposites. Herein, polylactide (PLA)/biosourced polyamide (PA) foams are fabricated by in situ fibrillation of polymer blends and a subsequent supercritical CO2 foaming technique. In this system, PLA serves as a shape memory polymer to endow this foam with a shape memory effect (SME), and in situ generated PA nanofibers are employed to reinforce the PLA cell walls and provide an additional permanent phase. A concentration of PA, 5 wt.%, was chosen to form an entangled nanofibrillar network. Foams of PLA/PA nanoblends with the same content of constituents were fabricated to reveal the effect of minor phase morphology on the cell structure and shape memory behavior of polymer foams. Profiting from the reinforcing effect of PA nanofibers, the PLA/PA nanocomposite foam exhibits smaller foam cells, a narrower cell size distribution and a comparable cell concentration than the PLA/PA nanoblend foam. In addition, PA nanofibers, unlike PA nanodroplets, favor the shape fixation ratio and recovery ratio and shorten the shape recovery time.

4D Printing of Ultra‐High Performance Shape Memory Polymer for Space Applications

Developing thermoplastic polyimide (TPI), capable of handling space conditions, through 4D printing is challenging due to its high melting temperature and inherent viscosity. This study presents 4D printing of TPI for shape memory investigation under repetitive cycles for the first time, exploring its potential for self‐deployable hinges in space devices. 4D‐printed TPI exhibits outstanding shape memory effect (SME) with shape fixity (Rf) up to 100% and shape recovery (Rr) of 100% in first cycle. Rf is noted to be increasing up to third cycle and then fixed to 100% up to tenth cycle, while Rr shows a decreasing trend in subsequent cycle with a drop of 37% in tenth cycle. Moreover, it exhibits extremely high glass‐transition temperature, Tg = 263.10 °C, degradation temperature, Td = 520 °C, and storage modulus of 1600 MPa. Among existing high‐performance (HP) and conventional shape memory polymers (SMPs), 3D‐printed TPI exhibits superior performance. Tg of the TPI is found to be 66.52%, 107.16%, and 62.41%, higher than existing HP‐SMPs, polyether ether ketone (Tg = 158 °C), polyamide (Tg = 127 °C), and polyether ketone ketone (Tg = 162 °C), respectively. This investigation reveals a novel characteristic, the SME, of 4D‐printed TPI with ultra‐high Tg and Td, demonstrating suitability for self‐deployable hinges, contributing to materials engineering and 4D printing.

4D Printing: Research Focuses and Prospects

As an emerging technology in the field of additive manufacturing, 4D printing is highly disruptive to traditional manufacturing processes. Therefore, it is necessary to systematically summarize the research on 4D printing to promote the development of related industries and academic research. However, there is still an obvious gap in the visual connection between 4D printing theory and application research. We collected 2070 studies from 2013 on 4D printing from the core collection of Web of Science. We used VOSviewer 1.6.20 and CiteSpace software 6.3.3 to visualize the references and keywords to explore focuses and trends in 4D printing using scientometrics. In addition, real-world applications of 4D printing were analyzed based on the literature. The results showed that “tissue engineering applications” is the most prominent focus. In addition, “shape recovery”, “liquid crystal elastomer”, “future trends”, “bone tissue engineering”, “laser powder bed fusion”, “cervical spine”, “4D food printing”, “aesthetic planning” are also major focuses. From 2013 to 2015, focuses such as “shape memory polymers” and “composites” evolved into “fabrication”. From 2015 to 2018, the focus was on “technology” and “tissue engineering”. After 2018, “polylactic acid”, “cellulose”, and “regenerative medicine” became emerging focuses. Second, emerging focuses, such as polylactic acid and smart polymers, have begun to erupt and have become key research trends since 2022. “5D printing”, “stability” and “implants” may become emerging trends in the future. “4D + Food”, “4D + Cultural and Creative”, “4D + Life” and “4D + Clothing” may become future research trends. Third, 4D printing has been widely used in engineering manufacturing, biomedicine, food printing, cultural and creative life, and other fields. Strengthening basic research will greatly expand its applications in these fields and continuously increase the number of applicable fields.

Pyramid-like magnetic carbon composites device toward tunable and adaptive radar-visible compatible properties

Equipped with intelligent adjustable electromagnetic-visible light compatibility characteristics is of significant importance in military stealth fields. In this work, a tunable microwave absorption and visible light change metamaterial based on polylactic acid (PLA) thermal stimulation was fabricated using 4D printing technology with hydroxylated carbon nanotubes (CNTOH) and carbonyl iron powder (CIP) as active ingredients. The printing filament was synthesized, which exhibited excellent absorption performance with a bandwidth of 5.83 GHz and sufficient shape recovery ability. On this basis, a temperature-dominated shape memory variation cone device was also manufactured and the visible light color-changing coating was sprayed. The microwave absorption performance is adjusted according to the petal angle, achieving a bandwidth variation of 5.9–9.8 GHz. This work confirms the potential exploratory value of the designed shape memory polymer in the field of microwave absorption, and provides unlimited possibilities for designing intelligent controlled stealth materials.

Motion-Adaptive Tessellated Skin Patches With Switchable Adhesion for Wearable Electronics.

Skin-interfaced electronics have emerged as a promising frontier in personalized healthcare. However, existing skin-interfaced patches often struggle to simultaneously achieve robust skin adhesion, adaptability to dynamic body motions, seamless integration of bulky devices, and on-demand, damage-free detachment. Here, a hybrid strategy that synergistically combines these critical features within a thin, flexible patch platform is introduced. This design leverages shape memory polymers (SMPs) arranged in a tessellated array, comprising both rigid and compliant SMPs. This configuration enables exceptional deformability, motion adaptability, and ultra-strong, repeatable skin adhesion while offering on-demand adhesion control. Furthermore, the design facilitates the seamless integration of bulky electronics without compromising skin adhesion. By incorporating sizeable electronics including signal acquisition circuits, sensors, and a battery, it is demonstrated that the proposed tessellated patch can be securely mounted on the skin, accommodate dynamic body motions, precisely detect physiological signals with an outstanding signal-to-noise ratio (SNR), wirelessly transmit data, and be effortlessly released from the skin.

Dynamically customizable 4D printed shape memory polymer biomedical devices: a review

Abstract There is an increased risk of complications and even surgical failures for various types of medical devices due to difficult to control configurations and performances, incomplete deployments, etc. Shape memory polymers (SMPs)-based 4D printing technology offers the opportunity to create dynamic, personalized, and accurately controllable biomedical devices with complex configurations. SMPs, typical representatives of intelligent materials, are capable of programmable deformation in response to stimuli and dynamic remodeling on demand. 4D printed SMP medical devices not only enable active control of configuration, performance and functionality, but also open the way for minimally invasive treatments and remote controllable deployment. Here, the shape memory mechanism, actuation methods, and printing strategies of active programmable SMPs are reviewed, and cutting-edge advances of 4D printed SMPs in the fields such as bone scaffolds, tracheal stents, cardiovascular stents, cell morphological regulation, and drug delivery are highlighted. In addition, promising and meaningful future research directions for 4D printed SMP biomedical devices are discussed. The development of 4D printed SMP medical devices is inseparable from the in-depth cooperation between doctors and engineers. The application of 4D printed SMP medical devices will facilitate the rapid realization of "smart medical care" and accelerate the process of "intelligentization" of medical devices.

CFD investigations of a shape-memory polymer foam-based endovascular embolization device for the treatment of intracranial aneurysms.

The hemodynamic and convective heat transfer effects of a patient-specific endovascular therapeutic agent based on shape memory polymer foam (SMPf) are evaluated using computational fluid dynamics studies for six patient-specific aneurysm geometries. The SMPf device is modeled as a continuous porous medium with full expansion for the flow studies and with various degrees of expansion for the heat transfer studies. The flow simulation parameters were qualitatively validated based on the existing literature. Further, a mesh independence study was conducted to verify an optimal cell size and reduce the computational costs. For convective heat transfer, a worst-case scenario is evaluated where the minimum volumetric flow rate is applied alongside the zero-flux boundary conditions. In the flow simulations, we found a reduction of the average intra-aneurysmal flow of > 85% and a reduction of the maximum intra-aneurysmal flow of > 45% for all presented geometries. These findings were compared with the literature on numerical simulations of hemodynamic and heat transfer of SMPf devices. The results obtained from this study can serve as a guide for optimizing the design and development of patient-specific SMPf devices aimed at personalized endovascular embolization of intracranial aneurysms.