Shape Memory Polymer Nanocomposites Research Articles

Correction: Namathoti, S.; Vakkalagadda, M.R.K. Development of Multiwalled Carbon Nanotubes/Halloysite Nanotubes Reinforced Thermal Responsive Shape Memory Polymer Nanocomposites for Enhanced Mechanical and Shape Recovery Characteristics in 4D Printing Applications. Polymers 2023, 15, 1371

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Photo Switchable 4D Printing Remotely Controlled Responsive and Mimetic Deformation Shape Memory Polymer Nanocomposites

AbstractPhoto‐triggered shape morphing structures can be found in myriads of areas. Utilizing light as a switch can effectively control and regulate the precise deformation of structures. However, the integration of photo‐switching functions in shape‐morphing structures with complex geometries remains a challenge. Here, photoswitchable digital light processing based 4D printing high‐resolution and highly complex geometries, based on UV curable WO2.9 nanoparticle doped shape memory polymer nanocomposites is reported, which are highly deformable (stretchability up to ≈1000% at rubbery state) and fatigue resistant (repeatedly loaded >1200 times at ambient temperature). The presence of just trace WO2.9 nanoparticles (<0.20 wt.‰) contributes to the controlled photothermal property of nanocomposite via selective absorption of light, which enables reversibly photoswitchable (>50 times), spatial and remote control of 4D printing shape morphing structures. These findings offer a promising approach to expanding the applications of photo‐triggered shape‐morphing structures.

Thermal-mechanical enhancement investigation of shape memory polymer nanocomposite for anti-/deicing

The oriented arrangement of graphene oxide (GO) and magnetic graphene oxide (MGO) in shape memory epoxy resin (EP) by employing the coupling effect of electric and magnetic fields were investigated. The heat transfer experiments showed that the thermal conductivity of the aligned shape memory MGO/GO/EP composites was 90.29% higher than that of the random doped composites. Through the two-dimensional aligned of MGO, the tensile strength of the shape memory MGO/GO/EP composite was significantly improved. The tensile strength reaches 24.52 and 22.67 MPa along the X and Y direction respectively, which increased of 53.92% and 42.31%. The shape recovery experiments showed that the shape recovery and shape fixity of the two-dimensional aligned composites were 95.55% and 91.49%, which increased by 4.44% and 7.82%. The results demonstrated that the two-dimensional directional arrangements of MGO layers significantly enhance the heat transfer and mechanical properties of shape memory polymer. The improvement of thermal conductivity and mechanical properties directly affected the anti-deicing performance of the composites. Hence, the deicing time of the shape memory MGO/GO/EP composite was 324 s, which represented an 18.2% improvement of the deicing efficiency.

Recent Advances in Polymer Nanocomposites: Unveiling the Frontier of Shape Memory and Self-Healing Properties-A Comprehensive Review.

Shape memory and self-healing polymer nanocomposites have attracted considerable attention due to their modifiable properties and promising applications. The incorporation of nanomaterials (polypyrrole, carboxyl methyl cellulose, carbon nanotubes, titania nanotubes, graphene, graphene oxide, mesoporous silica) into these polymers has significantly enhanced their performance, opening up new avenues for diverse applications. The self-healing capability in polymer nanocomposites depends on several factors, including heat, quadruple hydrogen bonding, π-π stacking, Diels-Alder reactions, and metal-ligand coordination, which collectively govern the interactions within the composite materials. Among possible interactions, only quadruple hydrogen bonding between composite constituents has been shown to be effective in facilitating self-healing at approximately room temperature. Conversely, thermo-responsive self-healing and shape memory polymer nanocomposites require elevated temperatures to initiate the healing and recovery processes. Thermo-responsive (TRSMPs), light-actuated, magnetically actuated, and Electrically actuated Shape Memory Polymer Nanocomposite are discussed. This paper provides a comprehensive overview of the different types of interactions involved in SMP and SHP nanocomposites and examines their behavior at both room temperature and elevated temperature conditions, along with their biomedical applications. Among many applications of SMPs, special attention has been given to biomedical (drug delivery, orthodontics, tissue engineering, orthopedics, endovascular surgery), aerospace (hinges, space deployable structures, morphing aircrafts), textile (breathable fabrics, reinforced fabrics, self-healing electromagnetic interference shielding fabrics), sensor, electrical (triboelectric nanogenerators, information energy storage devices), electronic, paint and self-healing coating, and construction material (polymer cement composites) applications.

Experimental investigation into mechanical, thermal, and shape memory behavior of thermoresponsive PU/MXene shape memory polymer nanocomposite

This research presents an experimental investigation into the mechanical, thermal, and shape memory behavior of a thermos-responsive polyurethane (PU) reinforced with 0–1.0 wt % of MXene (Ti3C2Tx) nanofiller. The PU/MXene nanocomposites were fabricated using sonication and injection molding route. The 0.5 wt % PU/MXene nanocomposite showed the optimum mechanical properties i.e. tensile modulus, tensile strength, and hardness value, which are improved by 22, 281, and 19 %, respectively, compared to pure PU. The improvement is observed in melting temperature (Tm), the heat of melting (hm), crystallization temperature (Tc), and the heat of crystallization (hc) results. The percentage of crystallinity revealed enhancements of 6 %, 18 %, 24 %, and 34 % for 0.1, 0.2, 0.3, and 0.5 wt % PU/MXene samples respectively compared to pure PU. The findings from the shape recovery experiments demonstrated that the inclusion of MXene has no impact on both the shape fixity and shape recovery performance. The PU/MXene nanocomposite with improved mechanical and thermal properties can find potential applications in robotics actuators, medical devices, sensors, etc.

4D printed and multi-stimulus responsive shape memory polymer nanocomposites developed on hydrogen bonding–metal-phenolic sacrificial network: Application for hazardous chemical operations soft robots

Designing 4D printed shape memory polymers (SMPs) with mechanical robust and multi-stimulus responses applied in soft robot holds vast promise. While significant progress has been made in this area, implementing SMP composites with multi-stimulus response capabilities for fused filament fabrication (FFF) 4D printing typically sacrifices the inherent mechanical properties of the materials, limiting the requirements for robust and tough applications of SMP in soft robotics. In this work, Fe3O4 nanoparticles are employed as functional particles, and the "hydrogen bonding–metal-phenolic" sacrificial network in the nanoparticles and polymer is designed to achieve NIR light and magnetic stimulation response without sacrificing the maximum strength and toughness of the 4D printable SMP. The SMP nanocomposite developed from the sacrificial network has a tensile strength of 18.98 MPa and an elongation at break of 897 %, a 40 % increase in strength and 196 % increase in elongation at break compared to SMP nanocomposites with direct Fe3O4 addition. In addition, the shape-programmable soft robot with NIR light and magnetic stimulation response is developed based on 4D printing. The remote precision control and drugs release demonstrates the potential application of 4D printed soft robots in hazardous chemical operations.

4D printing of shape memory polymer nanocomposites for enhanced performances and tunable response behavior

The emergence of four-dimensional (4D) printing introduces a novel approach to the design and manufacturing of high-performance multifunctional shape memory polymers (SMPs). Herein, two types of nanomaterials were blended or embedded into SMPs matrix to enable 4D printing of shape memory polymer composites (SMPCs) via photocuring. The incorporation of hexagonal boron nitride (HBN) nanoparticles enhanced the thermal stability and mechanical properties of SMPs, and accelerated their thermally responsive shape recovery speed. HBN nanoparticles also significantly improved the performance stability of SMPs, even after undergoing multiple shape memory cycles. Electrically responsive shape memory behavior in SMPCs was achieved by embedding a spray-coated polyaniline: polystyrene sulfonate /graphene (PANI: PSS/GR) electrothermal layer (ETL). The applied voltage, ETL resistance, HBN blend content, and sample thickness had a significant regulation effect on electrically responsive shape recovery behavior and shape recovery force. PANI: PSS improved adhesion between ETL and SMPCs matrix, filled the gaps between graphene platelets, which resulted in rapid, uniform, and stable heating upon energization. The presented electrically responsive gripper was capable of grasping objects of various shapes and sizes. This strategy broadens the potential applications of 4D printed SMPCs in challenging environments while propelling the advancement of 4D printing.

A novel green synthesis approach for shape memory polymer nanocomposites decorated with silver nanoparticles

AbstractA new, low‐cost, and direct green synthesis strategy was developed for the preparation of polymer composites composed of silver nanoparticles (AgNPs) decorated on a shape memory polymer blend using Rubus caesius L. leaves. X‐ray powder diffraction, ultraviolet‐visible spectroscopy (UV–vis), scanning electron microscopy, and energy dispersive X‐ray spectroscopy (EDS) elemental composition were applied to characterize the crystal size, morphology, and elemental composition of Ag‐NPs. UV–vis spectra detected the characteristic absorbance signal of AgNPs at about 430 nm, and the average crystal size of nanoparticles was calculated as about 12.60 nm. When nanocomposite films were characterized by attenuated total reflectance infrared spectroscopy, characteristic polylactic acid, and poly ethylene glycol (PEG) signals were determined. From the thermogravimetric analysis curves, it was determined that the amount of residue of nanocomposites increased as the amount of AgNP increased. It was seen that AgNPs did not affect the Tg temperature of the nanocomposite films, while it was also a proof that the polymer blend was immiscible. It was observed that the shape recovery properties of nanocomposite films were better with increasing AgNPs content. Finally, both green synthesized AgNPs and nanocomposites prepared with shape memory polymers showed very good antibacterial activity against Gram‐positive and Gram‐negative bacteria.Highlights Green synthesis of silver nanoparticles (AgNPs) was carried out with Rubus caesius L. leaves. The synthesized AgNPs were characterized by ultraviolet visible spectroscopy and x‐ray powder diffraction. Composite films were prepared with poly lactic acid/poly ɛ‐caprolactone blend by solvent casting method. The amount of residue of nanocomposites increased with increasing AgNPs percentage. The nanocomposite film containing 10% AgNPs has good activity.

Influence of nanofiller addition on the mechanical, thermal, and shape recovery behavior of shape memory polymer nanocomposite: A brief review

Shape memory polymers (SMPs) are macromolecules that exhibit a shape memory effect due to linear chains and crosslinking sites. SMPs may alter structure, size, stiffness, and form in response to external stimuli. The neat SMP has low mechanical and thermal properties, which may be improved by adding nanofillers called shape memory polymer nanocomposite (SMPNC). The current review study performs an in-depth investigation of the mechanical, thermal, and shape recovery behavior of SMPNC. The significance of the research highlights that the addition of nanofiller has a positive impact on safe fixity, but it has little impact on the shape recovery behavior of the SMPNC. It was observed that the addition of nanofiller and their concentration improves the mechanical and thermal properties.. The SMPNC has potential uses in a variety of industries, including aerospace, automotive, biomedical engineering, smart textiles, tactile devices, and robotics.

Recent trends in thermo‐responsive elastomeric shape memory polymer nanocomposites

AbstractShape memory polymers (SMPs) are polymeric smart materials, a class of stimuli‐responsive polymers that can return to their initial shape from a programmed temporary shape under the application of external stimuli, such as light, heat, magnetism, and electricity. Because of these unique features, SMPs can find applications in many fields, like aerospace, biomedical devices, flexible electronics, soft robotics, shape memory arrays, and 4D printing. The comparatively low density, low cost, easy biodegradability, and biocompatibility make SMPs a better candidate for shape memory applications. Among them, thermo‐responsive SMPs can revert to their permanent shape depending on a temperature greater than their polymer transition temperature. Thermo‐responsive SMPs combine semi‐crystalline or elastomeric polymers with improved mechanical and electrical properties. Integrating nanofillers into the polymer elastomer matrices can further enhance these properties, forming shape‐memory polymer nanocomposites (SMPNCs). This review focuses on the basics, design, and classifications of thermo‐responsive SMPs and the characteristics of elastomers and blends of polymers used. Incorporating various nanofillers to get SMPNCs to have improved properties over SMPs is also presented. The importance of Tg (glass transition temperature) and Tm (melting temperature) based SMPs and SMPNCs, various elastomers used, and the methods for preparation like solution casting, melt compounding, in situ polymerization, and their possible future applications are also discussed.

Development of Multiwalled Carbon Nanotubes/Halloysite Nanotubes Reinforced Thermal Responsive Shape Memory Polymer Nanocomposites for Enhanced Mechanical and Shape Recovery Characteristics in 4D Printing Applications

The mechanical and shape-recovery characteristics of 4D-printed thermally responsive shape-memory polyurethane (SMPU) reinforced with two types of reinforcements, multiwalled carbon nanotubes (MWCNTs) and Halloysite nanotubes (HNTs), are investigated in the present study. Three weight percentages of reinforcements (0, 0.5, and 1) in the SMPU matrix are considered, and the required composite specimens are obtained with 3D printing. Further, for the first time, the present study investigates the flexural test for multiple cycles to understand the 4D-printed specimens' flexural behavior variation after shape recovery. The 1 wt% HNTS-reinforced specimen yielded higher tensile, flexural, and impact strengths. On the other hand, 1 wt% MWCNT-reinforced specimens exhibited quick shape recovery. Overall, enhanced mechanical properties were observed with HNT reinforcements, and a faster shape recovery was observed with MWCNT reinforcements. Further, the results are promising for the use of 4D-printed shape-memory polymer nanocomposites for repeated cycles even after a large bending deformation.

Mechanical and Shape Recovery Characterization of MWCNTs/HNTs-Reinforced Thermal-Responsive Shape-Memory Polymer Nanocomposites.

Mechanical and shape recovery characteristics of thermal-responsive shape-memory polyurethane (SMPU) reinforced with two types of reinforcements, multiwalled carbon nanotubes (MWCNTs) and halloysite nanotubes (HNTs), were studied in the present research work. Three weight percentages of reinforcement (0, 0.5 and 1%) in the SMPU matrix were considered, and the required composite specimens were obtained through injection moulding. Tensile, flexural, impact and shape recovery behaviours were studied experimentally. Further, flexural tests were performed for multiple cycles to understand the specimens' flexural strength variation after shape recovery. The concentration of both reinforcements (MWCNTs and HNTs) considered in the present study significantly improved mechanical properties and shape recovery.

Magnetic- and light-responsive shape memory polymer nanocomposites from bio-based benzoxazine resin and iron oxide nanoparticles

Shape memory polymers (SMPs) are a class of smart materials that can be programmed to recover from temporary shape to permanent shape by applying external stimuli (temperature, magnetic field, light, electric field, and moisture, etc.). This unique property of SMPs makes them an appealing candidate in application for soft robotics, such as smart actuators, artificial muscles, and biomedical devices. In this contribution, we have developed multi-stimuli-responsive SMPs from bio-based benzoxazine resin and iron oxide nanoparticles (Fe3O4 NPs) that could be actuated by magnetic field and light. The nanocomposites were characterized by infrared spectroscopy, in which molecular interaction between benzoxazine/epoxy copolymers and Fe3O4 NPs was observed. Effects of nanoparticle content (0–5 wt%) on magnetic, mechanical, thermal, and thermo-mechanical properties of nanocomposites were investigated. Shape memory performance of nanocomposites was significantly improved with incorporation of Fe3O4 NPs. Shape fixity increased from 85% of neat copolymers to 93% of copolymers filled with 3 wt% Fe3O4 NPs, while shape recovery increased from 94% to 98%. Moreover, shape fixity could be done without external force contact by 808 nm-light actuation and magnetic attraction, due to photothermal and magnetic properties of nanocomposites. Shape recovery was tested under actuation by magnetic field. The highest shape recovery ratio was 99% within 26 s for copolymers filled with 5 wt% Fe3O4 NPs. Lastly, preliminary application of nanocomposites was demonstrated as they could push a 1 g-object within 10 s of actuation by magnetic field. In overall, these nanocomposites with multi-stimuli-responsive shape memory property had a good potential to be applied for soft robotics.

Chemically Crosslinked Amphiphilic Degradable Shape Memory Polymer Nanocomposites with Readily Tuned Physical, Mechanical, and Biological Properties.

Facile surgical delivery and stable fixation of synthetic scaffolds play roles just as critically as degradability and bioactivity in ensuring successful scaffold-guided tissue regeneration. Properly engineered shape memory polymers (SMPs) may meet these challenges. Polyhedral oligomeric silsesquioxanes (POSSs) can be covalently integrated with urethane-crosslinked polylactide (PLA) to give high-strength, degradable SMPs around physiological temperatures. To explore their potential for guided bone regeneration, here we tune their hydrophilicity, degradability, cytocompatibility, and osteoconductivity/osteoinductivity by crosslinking star-branched POSS-PLA with hydrophilic polyethylene glycol diisocyanates of different lengths and up to 60 wt % hydroxyapatite (HA). The composites exhibit high compliance, toughness, up to gigapascal storage moduli, and excellent shape recovery (>95%) at safe triggering temperatures. Water swelling ratios and hydrolytic degradation rates positively correlated with the hydrophilic crosslinker lengths, while the negative impact of degradation on the proliferation and osteogenesis of bone marrow stromal cells was mitigated with HA incorporation. Macroporous composites tailored for a rat femoral segmental defect were fabricated, and their ability to stably retain and sustainedly release recombinant osteogenic bone morphogenetic protein-2 and support cell attachment and osteogenesis was demonstrated. These properties combined make these amphiphilic osteoconductive degradable SMPs promising candidates as next-generation synthetic bone grafts.

Effect of the amine and carboxyl functionalised graphene on the thermomechanical and interfacial properties of the shape memory polymer nanocomposites

Effect of the amine and carboxyl functionalised graphene on the thermomechanical and interfacial properties of the shape memory polymer nanocomposites

Review of Thermoresponsive Electroactive and Magnetoactive Shape Memory Polymer Nanocomposites.

Electroactive and magnetoactive shape memory polymer nanocomposites (SMCs) are multistimuli-responsive smart materials that are of great interest in many research and industrial fields. In addition to thermoresponsive shape memory polymers, SMCs include nanofillers with suitable electric and/or magnetic properties that allow for alternative and remote methods of shape memory activation. This review discusses the state of the art on these electro- and magnetoactive SMCs and summarizes recently published investigations, together with relevant applications in several fields. Special attention is paid to the shape memory characteristics (shape fixity and shape recovery or recovery force) of these materials, as well as to the magnitude of the electric and magnetic fields required to trigger the shape memory characteristics.

Investigation of the Mechanical Properties for Polymer Reinforced by Nanoparticles with Considering Viscoelasticity of the Matrix

Investigation of the Mechanical Properties for Polymer Reinforced by Nanoparticles with Considering Viscoelasticity of the Matrix

Simple models for tensile modulus of shape memory polymer nanocomposites at ambient temperature

Abstract This article analyzes the tensile modulus of shape memory polymer nanocomposites (SMPNs) at ambient temperature. Several conventional models, such as rule of mixtures, Halpin–Tsai and Kerner–Nielsen, cannot practically estimate the modulus due to the absence of some main parameters for nanocomposites. Additionally, some parameters in Kerner–Nielsen and Sato–Furukawa models are useless and ineffective, due to the small concentration and high modulus of nanofillers in SMPNs. Therefore, Kerner–Nielsen and Sato–Furukawa models are simplified and modified to deliver the simple models for calculation of modulus in SMPNs. Various nanocomposite samples are provided to prove the validity of the suggested models. The results demonstrate that the predictions of the suggested models have a good match with the experimental results. The models also demonstrate high simplicity and good accuracy for the calculation of modulus in SMPNs at ambient temperature. Generally, the calculated results disclose that the modified Kerner–Nielsen model is preferable for approximation of modulus in SMPNs.

Efficient inductively heated shape memory polyurethane acrylate network with silane modified nanodiamond@Fe3O4 superparamagnetic nanohybrid

Multifunctional magnetic shape memory polymer (SMP) nanocomposites with high sensitivity was synthesized through inclusion of silane functionalized [email protected]3O4 (S-NDF) hybrid nanoparticle into polycaprolactone (PCL) based polyurethane acrylate (PUA) matrix followed by in situ crosslinking of the matrix. Highly biocompatible and superparamagnetic nanodiamond(ND)@Fe3O4 nanohybrids were synthesized through in situ co-precipitation method. The morphological analysis suggested that S-NDFs filled PUAs (2 to 9 wt% loadings) well interacted with both soft and hard domains of the matrix. The base polymer and the nanocomposites presented excellent shape fixity ratio (above 97%) and shape recovery ratio (above 99.5%) in hot water. Furthermore, PUA/S-NDF nanocomposites with nanohybrid loading of 9 wt% exhibited excellent shape recovery rate (above 96%) in a very small magnetic field (H = 0.76 kA.m−1) as well as faster magnetic responsiveness compared to Fe3O4 loaded nanocomposites. Moreover, PrestoBlue cell viability assay suggested biocompatibility of the base polymers and the nanocomposites.

DLP 4D‐Printing of Remotely, Modularly, and Selectively Controllable Shape Memory Polymer Nanocomposites Embedding Carbon Nanotubes

AbstractAn in‐depth investigation on novel electro‐activated shape memory polymer composites (SMPCs) for digital light processing 3D‐Printing, consisting of a poly(ethylene glycol) diacrylate/poly(hydroxyethyl methacrylate) matrix embedding multi‐walled carbon nanotubes (CNTs), is reported here. The composition of the photocurable (meth)acrylate system is finely tuned to tailor the thermomechanical properties of the matrix, whereas the effect of CNTs on the photoreactivity and rheological properties of the formulations is investigated to assess the printability. Electrical measurements confirmed that the incorporation of CNT into the polymeric matrix enables the electrical conductivity and thus the possibility to remotely heat the nanocomposite using the Joule effect. The feasibility to drive a shape memory cycle via Joule heating is proved, given that the high shape fixity (Rf) and shape recovery (Rr) ratios achieved (Rf ≈ 100%,Rr > 95%) confirmed the significant electrically‐triggered responsiveness of such CNT/SMPCs. Finally, it is shown how to activate a modular and selective electro‐activated shape recovery, which may ultimately envisage the 4D‐Printing of remotely and selectively controllable smart devices.