Excellent Shape Recovery Research Articles

Biodegradable shape memory polymer foams with appropriate thermal properties for hemostatic applications.

Shape memory polymer (SMP) foams are a promising material for hemostatic dressings due to their biocompatibility, high surface area, excellent shape recovery, and ability to quickly initiate blood clotting. Biodegradable SMP foams could eliminate the need for a secondary removal procedure of hemostatic material from the patients' wound, further facilitating wound healing. In this study, we developed hydrolytically and oxidatively biodegradable SMP foams by reacting polyols (triethanolamine or glycerol) with 6-aminocaproic acid or glycine to generate foaming monomers with degradable ester bonds. These monomers were used in foam synthesis to provide highly crosslinked SMP foam structures. The ester-containing foams showed clinically relevant thermal properties that were comparable to controls and excellent shape recovery within eight min. Triethanolamine-based ester-containing foams showed interconnected porous structure along with increased mechanical strength. Faster hydrolytic and oxidative biodegradation rates were achieved in ester-containing foams in comparison to controls. These biodegradable SMP foams with clinically applicable thermal properties possess great potential as an effective hemostatic device for use in hospitals or on battlefields.

Robust shape-retaining nanocellulose-based aerogels decorated with silver nanoparticles for fast continuous catalytic discoloration of organic dyes

In this work we present a green method to prepare aerogel membranes based on cellulose nanofibers (CNFs) crossed-linked with poly (ethylene imine) (PEI) and further decorated with silver nanoparticles (Ag NPs). The nanosized Ag NPs were reduced and immobilized on the surface of the pore walls inside the aerogel. The as-prepared composite aerogel membrane showed excellent continuous catalytic discoloration of aqueous cationic and anionic dye solutions in batch and flow filtration tests. Moreover, the aerogel membrane exhibited very stable catalytic activity with discoloration efficiency at as high as 98% after 10 times reuse and the water permeance was high, up to 5 × 104 L·m−2 h−1. Interestingly, the aerogel membrane showed excellent shape recovery in water and no obvious deterioration of the structure was observed during long time testing. Therefore, the obtained aerogel membranes showed great potential in waste water treatment and catalytic applications.

Tunable dialdehyde/dicarboxylate nanocelluloses by stoichiometrically optimized sequential periodate-chlorite oxidation for tough and wet shape recoverable aerogels.

Sequential periodate–chlorite (PC) oxidation has been optimized stoichiometrically according to the non-crystalline content in cellulose to generate a variety of versatile C2,C3 dialdehyde/dicarboxylate nanocelluloses (NCs) while economizing chemical and shear force inputs. The robust primary sodium periodate (NaIO4) oxidation not only regioselectively cleaved the C2–C3 carbon bond to oxidize the vicinal hydroxyls to aldehydes, but also governed the lengths of NCs, i.e., cellulose nanofibrils (PC-CNFs) at near-equal NaIO4 to non-crystalline anhydroglucose unit (AGU) stoichiometry and cellulose nanocrystals (PC-CNCs) at a doubled ratio. Secondary sodium chlorite (NaClO2) oxidation facilely converted C2,C3 dialdehydes to dicarboxylates and, upon deprotonation, facilitated defibrillation to NCs, irrespective of extents of carboxylation or charges. The optimal 0.5 : 1 NaIO4/AGU and 1 : 1 NaClO2/AGU oxidation produced highly uniform 1.26 nm thick, 3.28 nm wide, and ca. 1 μm long PC-CNFs with tunable surface aldehyde (0.71–0.0 mmol g−1) and carboxylate (0.64–1.35 mmol g−1) content at 94–98% yields. The C2–C3 glucosidic ring opening and oxidation along the 110 or 11̄0 crystalline surfaces increased the heterogeneity of the hydrophilic surfaces and flexibility of PC-CNFs to influence their self-assembling into fibrils and amphiphilic superabsorbent aerogels. The ultra-light (ρ = 10.3 mg cm−3) aerogels showed an ultra-high dry specific compression modulus (50.2 kPa mg−1 cm−3) and specific stress (8.2 kPa mg−1 cm−3 at 0.8 strain), cyclic wet compressive behavior, and excellent water-activated shape recovery following 0.8 strain dry compression.

Microstructural Characterization, Functional Behavior and Deformation Mechanism of Ni>sub>54Mn <sub>25</sub>Ga <sub>21-x</sub>Dy <sub>x</sub> High Temperature Shape Memory Alloys with Low Thermal Hysteresis

Potential applications at elevated temperatures require shape memory alloys (SMAs) to possess high transformation temperature, excellent shape recovery ability and thermal/functional stability. The present study investigated the influences of Dy addition on the microstructural characterization, functional behavior and possible deformation mechanisms in high temperature Ni54Mn25Ga21 SMAs. The results indicated that adequate Dy addition contributed to a desirable tradeoff among compressive strength, ductility and functional performance. Ni54Mn25Ga20.9Dy0.1 alloy showed the highest shape memory recoverable strain due to the improvement of mechanical properties and formation of small Dy-rich precipitates. Simultaneously, an obvious pseudoelasticity was observed over a wide temperature range with a maximum recoverable strain of 3.74% at 320°C in this alloy. All the Dy-containing alloys exhibited high thermal cyclic stability and quite low thermal hysteresis. However, it was revealed that a complicated and abnormal relationship between thermal hysteresis and the middle eigenvalue λ2 existed for the investigated alloys with a lattice transition from cubic to tetragonal. Calculated results based on energy minimization theory revealed that both the transformation strain and critical stress for inducing martensitic transformation varied with crystallographic orientations. The detwinning of pre-existing (112) compound twins and formation of (112) deformation twins were the dominant deformation mechanisms of martensite, which were highly compatible with the macroscopical recoverable strain. The present study provided valuable insights for developing high-performance multifunctional shape memory alloys for high temperature applications.

Influence of selective distribution of SiO2 nanoparticles on shape memory behavior of co-continuous PLA/NR/SiO2 TPVs

As a kind of commercial thermoplastic elastomers, thermoplastic vulcanizates (TPVs) have been widely used in many fields. In this work, a shape memory polymer (SMP) was fabricated based on co-continuous polylactide (PLA)/natural rubber (NR)/silica (SiO2) TPVs. Selective distribution of SiO2 nanoparticles was achieved with the impact of thermodynamic factor and different processing methods, and the influence on shape memory behavior was investigated as well. The results demonstrated that the co-continuous structure functioned actively in both shape fixity and recovery. The PLA phase played the role of “switch” to control the shape memory behavior, while the deformation of continuous rubber network stored sufficient resilience and successfully drove the shape recovery process. Excellent shape fixing ratio (~100%) and shape recovery ratio (>90%) were obtained when SiO2 nanoparticles were distributed in NR phase. The addition of SiO2 nanoparticles reinforced the rubber phase and the recovery ratio was effectively improved.

Highly compressible lignin hydrogel electrolytes via double-crosslinked strategy for superior foldable supercapacitors

Employing renewable, earth-abundant, low-cost natural materials to fabricate highly compressible, foldable and high-performance energy storage devices can greatly promote the sustainable development and wide applications of compression-resistant electronics. Herein, a hybrid double-crosslinked (DC) lignin hydrogel electrolyte with superior compressibility is firstly developed by postformation of lignin hydrophobic aggregation via simple treatment of single chemical crosslinked (SC) lignin hydrogel using H2SO4 solution. This synthetic DC lignin hydrogel exhibits significant improvement of mechanical strength, excellent shape recovery property and high ionic conductivity (0.08 S cm−1). The compression stress at fracture is 4.74 MPa, which is 40 times compared to that of SC lignin hydrogel. Exploiting this DC lignin hydrogel as electrolyte and PANI deposited carbon cloth as electrode, a flexible supercapacitor is constructed, which possesses high specific capacitance of 190 F g−1 and excellent energy density. Remarkably, this supercapacitor retains high specific capacitance after 500 cycle numbers of 180° bending, or 80% compression strain. Thus, this presented work opens a new avenue of lignin as a prominent candidate for potential application in compression-resistant and foldable energy storage devices.

Electrospun PCL-based polyurethane/HA microfibers as drug carrier of dexamethasone with enhanced biodegradability and shape memory performances

Shape memory polymers (SMP) with better biodegradability and better stability have great potential applications in biomedical fields, such as the drug carriers or the tissue engineering scaffolds. In this study, poly(e-caprolactone)(PCL)-based polyurethane(PU) microfibers were fabricated with the containing of hydroxyapatite(HA) to enhance the biodegradability and to exhibit excellent shape memory performance. The composition, the morphology, the thermal stability, and the mechanical properties of the microfibers were characterized and detected using Fourier transform infrared spectroscopy (FTIR), 1H nuclear magnetic resonance (1HNMR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC). and dynamic mechanical analysis (DMA), etc. And dexamethasone was selected as drug model to investigate the delivery and release behaviors of the carrier of the microfibers. It was revealed that HA enhanced the degradation rate of the shape memory polyurethane (SMPU) fibers, and the fibers could guarantee a sustained long time drug release. The detection on the shape memory performance found that, with the different addition amounts of HA, the composite microfibers of (SMPU) and HA exhibited the different shape memory transition temperature (Ttrans) values. And with the addition of 3 wt% of HA, the excellent shape recovery ratios of Rr (> 97%) and the shortest recovery time of ~ 6 s could be obtained. With further increase of the amounts of HA, the recovery force and the recovery time were reduced and prolonged, respectively. The obtained results proved that the biodegradable SMPU/HA composite microfibers have more valuable application prospects in biomedical fields.

Shape Memory Behavior of Emulsion-Templated Poly(ε-Caprolactone) Synthesized by Organocatalyzed Ring-Opening Polymerization

Organocatalyzed ring-opening polymerization (ROP) of e-caprolactone (CL) and 4,4′-bioxepanyl-7,7′-dione as a bis-lactone cross-linker was performed within the oil-in-oil high internal phase emulsions (HIPEs) at 50 °C. In this way, the cross-linked poly(e-caprolactone) (PCL) polyHIPE foams of ∼85% porosity were synthesized. Thermomechanical properties of the prepared polyHIPEs were studied and proved to greatly depend on a degree of PCL cross-linking. The melting and crystallization temperatures as well as the degree of crystallinity of PCL polyHIPE foams decrease with an increasing cross-linking degree. Semi-crystalline polyHIPEs demonstrate shape memory behavior with excellent shape fixity and shape recovery. At an appropriate degree of PCL cross-linking, the polyHIPE temporary shape can be fixed at room temperature, while a transition to the permanent shape occurs upon heating at 40 °C. Moreover, a two-way shape memory behavior of the PCL polyHIPEs under constant stress was observed.

Shape memory properties of polyethylene/ethylene vinyl acetate /carbon nanotube composites

The safe operation of electrical equipment relies on advanced polymer insulation to contain electrical pathways. Polymer sheath materials should be mechanically robust and chemically stable in order to protect the internal metal wiring from environmental attack. Polyethylene (PE) and ethylene vinyl acetate (EVA) have often been used as electrical cable jacket materials for electrical power industry. Partially crosslinked PE is able to shrink and wrap tightly around the metal wires upon stimulated by external heat, exhibiting shape memory behaviour. In this work, multiwalled carbon nanotubes (MWCNTs) were introduced to partially crosslinked linear medium density polyethylene (LMDPE) and EVA blend in order to enhance the shape memory performance at lower temperature by promoting the thermal transfer and antistatic properties of the polymer nanocomposite. The morphologies of the partially crosslinked and non-crosslinked composites are analysed. The MWCNTs preferentially resided in the EVA phase while the peroxide crosslinking process drastically altered the morphology and electrical properties. The addition of 3 wt% of MWCNTs resulted in a percolation transition and enhanced the alternating current (AC) conductivity by 10 orders of magnitude for non-crosslinked LMDPE/EVA and by 3 orders of magnitude for crosslinked LMDPE/EVA composites. LMDPE/EVA (80/20) containing 3 wt% MWCNTs possessed excellent shape recovery of 100% and shape fixing of 82%. The addition of MWCNTs can not only promote the shape memory efficiency of the polymer sheath material, but also introduce antistatic properties to avoid electrical shocking or sparking.

Degradable Poly(ether-ester-urethane)s Based on Well-Defined Aliphatic Diurethane Diisocyanate with Excellent Shape Recovery Properties at Body Temperature for Biomedical Application.

The aim of this study is to offer a new class of degradable shape-memory poly(ether-ester-urethane)s (SMPEEUs) based on poly(ether-ester) (PECL) and well-defined aliphatic diurethane diisocyanate (HBH) for further biomedical application. The prepolymers of PECLs were synthesized through bulk ring-opening polymerization using ε-caprolactone as the monomer and poly(ethylene glycol) as the initiator. By chain extension of PECL with HBH, SMPEEUs with varying PEG content were prepared. The chemical structures of the prepolymers and products were characterized by GPC, 1H NMR, and FT-IR, and the effect of PEG content on the physicochemical properties (especially the shape recovery properties) of SMPEEUs was studied. The microsphase-separated structures of the SMPEEUs were demonstrated by DSC and XRD. The SMPEEU films exhibited good tensile properties with the strain at a break of 483%–956% and an ultimate stress of 23.1–9.0 MPa. Hydrolytic degradation in vitro studies indicated that the time of the SMPEEU films becoming fragments was 4–12 weeks and the introduction of PEG facilitates the degradation rate of the films. The shape memory properties studies found that SMPEEU films with a PEG content of 23.4 wt % displayed excellent recovery properties with a recovery ratio of 99.8% and a recovery time of 3.9 s at body temperature. In addition, the relative growth rates of the SMPEEU films were greater than 75% after incubation for 72 h, indicating good cytocompatibility in vitro. The SMPEEUs, which possess not only satisfactory tensile properties, degradability, nontoxic degradation products, and cytocompatibility, but also excellent shape recovery properties at body temperature, promised to be an excellent candidate for medical device applications.

Robust and stretchable self-healing polyurethane based on polycarbonate diol with different soft-segment molecular weight for flexible devices

The self-healing polyurethane films have received significant attention due to their unique shape memory behaviors and the hydrogen bonding arising from the urethane linkages. However, it is still a challenge to develop self-healing polyurethane with transparent, high impact resistance, and excellent shape recovery and mechanical properties. In particular, polycarbonate-based polyurethane shows transparency, weatherability and excellent mechanical properties. In this work, transparent self-healing polyurethane film with robust mechanical properties (breaking stress of 26 MPa and elongation at break of 630%) was synthesized by controlling the different molecular weight of the polycarbonate diol and incorporating dynamic disulfide bonds for reversibility. As a result, the self-healing polyurethane film showed an excellent self-healing ability with 98% healing efficiency and excellent shape memory ability with a recovery efficiency of ˃92%. In addition, we have identified a potential application for the self-healing flexible substrate in flexible electronics because of their stable electrical resistance even upon mechanical deformation.

Effect of zirconium on the properties of polycrystalline Cu-Al-Be shape memory alloy

This paper presents an investigation of the effect of zirconium on the properties of polycrystalline Cu-Al-Be shape memory alloy. Mechanical and shape memory properties have been evaluated by varying the compositions of Zr to Cu88.13-Al11.42-Be0.45 alloy ranging from 0.05 to 0.4 wt% with step 0.1 wt%. The results unveil reduction in the grain size of 89.18% with the improved tensile strength of 667 ± 30 MPa and ductility of 23.95 ± 0.86% and excellent shape recovery ratio of 100% with the addition of Zr up to 0.3 wt%. Increase in transformation temperatures is observed with the addition of Zr.

Tough and tunable shape memory PLA/PAE melt-blends actuated by temperature

Development of shape memory materials are very important due to their scientific and technological values. Typically, poly(lactic acid) (PLA) has received increasing attentions because of shape memory properties and biodegradability, however, its semi-crystalline structure restricts its shape recovery ratio and toughness both. Herein, we report a reinforced PLA-based elastomer material prepared by physical blending with different weight ratios of polyamide elastomer (PAE). After the modification, PLA/PAE elastomers show excellent shape recovery (> 99%) from ~ 25 to ~ 70 °C and toughness (impact strength ~ 50 kJ/m2). By regulating the weight ratio of PAE at 10 wt%, the resulting PLA/PAE elastomers showed relative low glass transition temperature (Tg) at ~ 61 °C versus pure PLA (~ 65 °C). Besides, the storage modulus (E′) decreased to ~ 8000 MPa (at 10 wt% PAE) indicated that PAE weakened the PLA crystallinity and promoted its toughness. Comparing with pure PLA, PLA/PAE elastomers showed almost 45% decrease on loss modulus (E″), which indicated that elasticity and shape recovery behavior have been promoted. With the increase of PAE ratio in PLA/PAE elastomers, the initial recovery temperature of blends showed decreasing trend, which indicated that blends are more helpful for shape recovery actuated by temperature. This work provided a new PLA/PAE elastomer with stronger toughness and faster thermo-induced shape recovery that may show great potential for fundamental research and biomedical applications.

Electrically-responsive graphene-based shape-memory composites

Shape memory materials can open new design opportunities in fields as diverse as healthcare, transportation or energy generation. In this respect, shape memory polymers (SMPs) have attracted much attention due to their advantages over metals in terms of weight and reliability. However, they are still marred by slow reaction times and poor mechanical performance. In this work we show how, by integrating a graphene network in a SMP matrix, it is possible to create composites with very low carbon contents (below 1wt%) able to change shapes in short times (10s of seconds) in response to low electric voltages (<10V). This is possible because the conductive network is highly interconnected at the microscopic scale, acting as a very efficient Joule heater. The composites exhibit excellent shape fixity (>0.95±0.03) and shape recovery ratios (>0.98±0.03). Due to the 2D nature of graphene, this network directs crack propagation during fracture resulting in materials that retain bending strengths close to 100MPa and exhibit significant extrinsic toughening (with toughness that reach values up to 3 times the initiation value). Furthermore, changes in conductivity can be used to follow the formation and growth of damage in the material before catastrophic failure, allowing the use of this material as a damage sensor. These results provide practical guidelines for the design of reliable shape memory composites for structural and sensing applications.

A novel heat-triggered shape-memory polymer based on ethylene–vinyl acetate copolymer/nitrile–butadiene rubber thermoplastic vulcanizates

Achieving considerable shape-memory effects is a challenge for typical sea-island structured polymer blends. In this article, we successfully fabricated a novel heat-triggered shape-memory polymer (HSMP) based on ethylene–vinyl acetate copolymer/nitrile–butadiene rubber (EVA/NBR) thermoplastic vulcanizates (TPVs) via dynamic vulcanization. The influence of deformation temperature ( Td), recovery temperature ( Tr), and recovery time on the shape-memory behavior of the EVA/NBR (weight ratio = 80/20) TPV was investigated systematically. The shape-memory result of the EVA/NBR (weight ratio = 80/20) TPV demonstrated that when the Td was close to the melting temperature ( Tm) of the EVA phase (76°C), the TPV could obtain a good shape fixity ratio (&gt;95%) and an excellent shape recovery ratio (&gt;95%) at 100% stretch ratio. A shape-memory mechanism was proposed for this HSMP. The dynamic mechanical analysis results under temperature sweep mode showed that with increasing EVA content in TPVs, the tan δ decreased, while the storage modulus increased. The morphology observation showed that the cross-linked NBR particles were dispersed evenly in the etched surface of EVA/NBR TPV with an average diameter of approximately 2–6 μm. The longitudinal stretching surface of the EVA/NBR TPV exhibited the banding-like texture microstructure during the stretching process.

Thermal- and salt-activated shape memory hydrogels based on a gelatin/polyacrylamide double network.

Shape memory hydrogels have been extensively studied in the past decades owing to their exceptionally promising potential in a wide range of applications. Here, we present a gelatin/polyacrylamide double network hydrogel with thermal- and salt-activated shape memory effect. The thermally activated behavior is attributed to the reversible triple helix transformation of gelatin, and the salt-activated performance can be ascribed to the formation of hydrophobic interaction domains under the Hofmeister effect. The hydrogel can memorize a temporary shape successfully through soaking with (NH4)2SO4 solution or decreasing temperature, and recovers its permanent shape by extracting ions with deionized water or increasing temperature. In particular, the hydrogel exhibits excellent shape fixity and recovery ratio. The presented strategy may enrich the construction as well as application of biopolymer based shape memory hydrogels.

The Effect of Polyol Types and Molecular Weight on the Shape Memory Properties of Palm Kernel Oil – based Polyurethane

Abstract The main objective of this study was to investigate the effect of different types and molecular weight (MW) of polyol on the shape memory properties of palm kernel oil–based shape memory polyurethane (SMPU) prepared by two step bulk polymerization procedure. Poly(ethylene glycol) (PEG) and poly(e-caprolactone) (PCL) with MW 2000 and MW 4000 were used as the main material for soft segment. The addition of palm kernel oil polyol (PKO-p) in the SMPU system is due to the concern of the renewable resources. Shape fixity and shape recovery properties were investigated using bending test to evaluate the shape memory effect. The results indicate that the shape fixity of SMPU depends primarily on the types of polyol whereas MW had a slight effect towards the shape fixity. SMPU synthesized from PEG with MW 2000 performed a good shape fixity, about 96% compared to that of PCL with MW 2000, about 29%. In the case of PCL – based SMPU, the increase of shape fixity is proportional to the increase of MW. All samples, except the one based on PEG4000, exhibited excellent shape recovery (100%).

Ultralight, hydrophobic, anisotropic bamboo-derived cellulose nanofibrils aerogels with excellent shape recovery via freeze-casting

Cellulose aerogels have shown outstanding potential as renewable functional materials; however, their practical applications are still limited by inherent hydrophilicity and weak mechanical properties. To overcome hydrophilicity and fragility issues of aerogels, in this study, silylated bamboo-derived cellulose nanofibrils (CNF) aerogels with aligned porous structures were achieved by directionally freeze-casting a mixture of CNF suspension and methyltrimethoxysilane sol. The silylated CNF aerogels exhibited distinct aligned lamellar structures and significantly anisotropic mechanical properties. They had improved strength and stiffness in the axial direction (along the freezing direction) and excellent rapid shape recovery ability in the radial direction (perpendicular to the freezing direction) with a significant high shape recovery ratio of 92% after 100 cycles at 80% compression. Owing to their ultra-low density, hydrophobicity, and high compressive recoverability, the silylated CNF aerogels can be potentially used in a wide range of industrial applications, such as hydrophobic polymer nanocomposites, absorbents, and biomedical scaffolds.

The Shape-Memory Effect of Hindered Phenol (AO-80)/Acrylic Rubber (ACM) Composites with Tunable Transition Temperature.

To broaden the types and scope of use of shape-memory polymers (SMPs), we added the hindered phenol 3,9-bis[1,1-dimethyl-2-{b-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro-[5,5]-undecane (AO-80), which comprises small organic molecules, to acrylic rubber (ACM) to form a series of AO-80/ACM rubber composites. The structural, thermal, mechanical property, and shape-memory properties of the AO-80/ACM rubber composites were investigated. We identified the formation of intra-molecular hydrogen bonding between –OH of AO-80 and the carbonyl groups and the ether groups of ACM molecules. The amount of AO-80 used can be adjusted to tailor the transition temperature. AO-80/ACM rubber composites showed excellent shape recovery and fixity. The approach for adjusting the transition temperature of AO-80/ACM rubber composites provides remarkable ideas for the design and preparation of new SMPs.

Development of supramolecular shape-memory polyurethanes based on Cu(II)–pyridine coordination interactions

Shape-memory polymers with supramolecular switch have received increasing attention. This study reports the synthesis and characterization of supramolecular shape-memory polyurethane based on Cu(II)–pyridine coordination, obtained by mixing pyridine containing polyurethane with CuCl2. The results show that there are strong metal–ligand coordination interactions formed between Cu(II) and the pyridine ring in a series of CuCl2-doped polyurethane samples. The Cu(II)–pyridine coordination plays a crucial role in the enhanced physical netpoints for outstanding shape-memory properties. Indeed, the so-synthesized CuCl2-doped polyurethane exhibits not only a rapid tensile shape recovery but also excellent crimp shape recovery. The CuCl2-doped polyurethane containing suitable metal–ligand coordination interactions shows more than 99% shape fixation and more than 95% shape recovery. Our findings promote further applications of shape-memory polymers in multiple engineering fields.