Shape memory behavior of carbon nanotube‐reinforced trans‐1,4‐polyisoprene and low‐density polyethylene composites

Shape memory composites of trans‐1,4‐polyisoprene (TPI) and low‐density polyethylene (LDPE) with easily achievable transition temperatures were prepared by a simple physical blending method. Carbon nanotubes (CNTs) were introduced to improve the mechanical properties of the TPI/LDPE composites. The mechanical, cure, thermal, and shape memory properties of the TPI/LDPE/CNTs composites were investigated in this study. In these composites, the cross‐linked network generated in both the TPI and LDPE portions acted as a fixed domain, while the crystalline regions of the TPI and LDPE portions acted as a domain of reversible shape memory behavior. We found that CNTs acted as not only reinforced fillers but also nucleation agents, which improved the crystalline degree of the TPI and LDPE portions of the composites. Compared with the properties at the other CNT doses, the mechanical properties of the TPI/LDPE composites when the CNT dose was 1 phr were improved significantly, showing excellent shape memory properties (R_f = 97.85%, R_r = 95.70%).     

Preparation of modified multi‐walled carbon nanotubes as a reinforcement for epoxy shape‐memory polymer composites

Effectively improving the mechanical properties and thermal resistance of epoxy shape‐memory polymers (ESMPs) without affecting their shape‐memory performance is necessary to expand these polymers in practical applications. In this article, modified multi‐walled carbon nanotubes (MWCNTs) were prepared and used as efficient reinforcement for enhancing the comprehensive properties of ESMPs. Increases of nearly 289% to 444% for impact strength and 112% to 184% for tensile force were obtained by adding only 0.1 to 1 wt% epoxy‐modified MWCNTs. The addition of unmodified and carboxyl‐modified MWCNTs was also investigated but showed less impact on the mechanical properties of the ESMPs than epoxy‐modified MWCNTs. Thermogravimetry analysis (TGA) and dynamic mechanical analyses (DMA) showed that less than 1 wt% modified MWCNTs can enhance the heat resistance of ESMPs greatly. Although the shape recovery time for composite materials increased upon adding the MWCNTs, the entire recovery time was still less than 1 minute, and the shape recovery rate was relatively high, nearly 100%.     

Effect of comonomer on thermal/mechanical and shape memory property of L‐lactide‐based shape‐memory copolymers

In this study, three kinds of L ‐lactide‐based copolymers, poly(lactide‐co‐glycolide) (PLGA), poly(lactide‐co‐p‐dioxanone) (PLDON) and poly(lactide‐co‐caprolactone) (PLC), were synthesized by the copolymerization of L ‐lactide (L) with glycolide (G), or p‐dioxanone (DON) or ε‐caprolactone (CL), respectively. The copolymers were easily soluble in common organic solvents. The compositions of the copolymers were determined by ¹H‐NMR. Thermal/mechanical and shape‐memory properties of the copolymers with different comonomers were compared. Moreover, the effect of the chain flexibility of the comonomers on thermal/mechanical and shape‐memory properties of the copolymers were investigated. The copolymers with appropriate lactyl content showed good shape‐memory properties where both the shape fixity rate (R_f)and the shape recovery rate (R_r) could exceed 95%. It was found that the comonomers with different flexible molecular chain have different effects on their thermal/mechanical and shape‐memory properties. Among them, PLGA has the highest mechanical strength and recovery rate while PLC copolymer has high recovery rate when the lactyl content exceeded 85% and the lowest transition temperature (T_trans). Copyright © 2007 John Wiley & Sons, Ltd.     

Novel interpenetrating networks with shape‐memory properties

Novel polyesterurethane/poly(ethylene glycol) dimethacrylate (PEGDMA) interpenetrating networks (IPNs) with good shape‐memory properties were synthesized using solvent casting method. The star‐shaped oligo[(rac‐lactide)‐co‐glycolide] was coupled with isophorone diisocyanate to form a polyesterurethane network (PULG), and PEGDMA was photopolymerized to form another polyetheracrylate network. IPNs were transparent and gel content exceeded 92%. The values of strain fixity rate and strain recovery rate were above 93%. PULG and PEGDMA networks in IPNs were amorphous and did not show any characteristic diffraction peaks in X‐ray diffraction spectra. Only one glass transition temperature (T_g) of the IPNs between T_g of PEGDMA and PULG was observed, which was proportional to PEGDMA content. PULG and PEGDMA networks were miscible when PEGDMA content was below 50 wt %. The hydrophilicity, transition temperatures, and mechanical properties of IPNs could be conveniently adjusted through variation of network compositions to match the promising potential clinical or medical applications. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 768–775, 2007     

Poly(methacrylic acid)‐grafted clay–thermoplastic elastomer composites with water‐induced shape‐memory effects

Composites with excellent water‐induced shape‐memory effects (SMEs) were successfully synthesized by first using clay as the SME‐activating phase and thermoplastic polyurethane (TPU) as the matrix. Naturally abundant clay was grafted with poly(methacrylic acid) (PMAA) to improve particle interactions, which allowed for the formation of strong percolation networks in the composites, determined by swelling tests and dynamic mechanical analysis in combination with theoretical modeling. This led to significant improvements of the polymer modulus and high water absorptions, causing reversible modulus changes of up to 30 times from the wet to the dry condition. The results from cyclic wetting‐drying‐stretching tests showed the TPU–clay composite containing 10.4 vol % PMAA‐grafted clay exhibited the best SMEs among the composites investigated, with the shape fixity and shape recovery ratios being 82% and 91%, respectively. Besides SMEs, these new polymer–clay composites were also pH‐sensitive and mechanically adaptive upon exposure to water. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1513–1522     

Synthesis and characterization of biodegradable,amorphous, soft IPNs with shape‐memory effect

Star‐shaped oligo[(D ,L ‐lactide)‐co‐ε‐caprolactone]s (PCLA) with various number average molecular weights were synthesized via ring‐opening polymerization of D ,L ‐lactide (DLLA) and ε‐caprolactone (CL) with organic Sn as catalyst and pentaerythritol as an initiator. The elastic amorphous interpenetrating polymer networks (IPNs) of polyesterurethane/poly(ethylene glycol) dimethacrylate (PEGDMA) were synthesized in situ by UV‐photopolymerization of PEGDMA and thermal polymerization of PCLA with isophorone diisocyanate (IPDI). IPNs are transparent soft materials and the gel content of the IPNs is exceeding 87%. They are rubbery when PEGDMA content is above 10% at room temperature. IPNs show good shape‐memory properties. IPNs recover quickly its permanent form in 10 sec when the environment temperature is above its glass transition temperature (T_g). IPNs have only one single T_g between the T_g of PEGDMA and polyesterurethane. The strain recovery rate (R_r) and the strain fixity rate (R_f) are above 90%. No characteristic peaks of PEG crystallites in X‐ray diffraction pattern (XRD) demonstrate that they are amorphous polymer networks. The wettability, degradation rate, mechanical properties, and T_g of the IPNs could be conveniently adjusted by changing PEGDMA content in IPNs. The soft IPNs are promising suitable as potential soft substrates with tailored mechanical properties for potential clinical or medical use. Copyright © 2011 John Wiley & Sons, Ltd.     

Biodegradable shape‐memory polymer—polylactide‐co‐poly(glycolide‐co‐caprolactone) multiblock copolymer

In this study, biodegradable shape‐memory polymers—polylactide‐co‐poly(glycolide‐co‐caprolactone) multiblock (PLAGC) copolymers—were synthesized by the coupling reaction of both macrodiols of polylactide (PLLA‐diol) and poly(glycolide‐co‐caprolactone) (PGC‐diol) in the presence of 1,6‐hexanediisocyanate as coupling agent. The copolymers formed were found to be thermoplastic and easily soluble in common solvents. The compositions of the copolymers were determined by ¹H‐NMR and the influences of segment lengths and contents of both macrodiols on the properties of the PLAGC copolymers were investigated. It was found that the copolymers had adjustable mechanical properties which depended on contents and segment lengths of both macrodiols. The copolymers showed such good shape‐memory properties that the strain fixity rate (R_f) and the strain recovery rate (R_r) exceed 90%. By means of adjusting the compositions of the copolymers, PLAGC copolymers with transition temperatures around 45°C could be obtained. The degradation rate determination showed that the PLAGC copolymers have fast degradation rates, the mechanical strengths of the PLAGC copolymers would be completely lost within 1–2 months depending on molecular weights and contents of the both segments of PLLA and PGC. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis and characterization of hydrophilic polyester‐PEO networks with shape‐memory properties

Shape‐memory polyester‐polyethylene oxide networks are synthesized through photopolymerization of hydrophobic poly[(D,L‐lactide)‐co‐glycolide]tetraacrylate (PLGATA) and hydrophilic poly(ethylene glycol) dimethacrylate (PEGDMA). The materials can recover their original shape either quickly by heating stimulus or slowly upon immersion in water. The wettability, mechanical properties, and transition temperature of the polymer networks could be conveniently adjusted by variation of the compositions of PLGATA and PEGDMA. The hydrophilicity of PEGDMA could prospectively improve blood compatibility of polymer networks. They offer a high potential for biomedical applications such as smart implants, drug delivery systems, or medical devices. Copyright © 2010 John Wiley & Sons, Ltd.     

High modulus ratio shape‐memory polymers achieved by combining hydrogen bonding with controlled crosslinking

A new type of poly(methyl acrylate)‐co‐(acrylic acid) (PMA‐AA) networks obtained by combining hydrogen bonding with controlled crosslinking exhibit full and rapid shape‐memory recovery. The structure, thermal properties, dynamical mechanical properties and shape‐memory effects of these networks were presented. High modulus ratios were achieved for the series of PMA‐AA networks based on intense self‐complementary hydrogen bonding in poly(acrylic acid) (PAA) segments. This lead to excellent shape‐memory effects with strain‐recovery ratio above 99%. Meanwhile, faster recovery speed was achieved by the synergistic effect of hydrogen bonding and controlled crosslinking compared to the linear PMA‐AA copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1241–1245, 2011     

Oxidative Degradation of trans‐1,4‐Polyisoprene Cast Films and Single Crystals by Enzyme‐Mediator Systems

Depolymerization and morphological changes of cast films and single crystals of trans‐1,4‐polyisoprene with three enzyme‐mediator systems, lipoxygenase/linoleic acid (LPO/LH), horseradish peroxidase/1‐hydroxybenzotriazole (HRP/1‐HBT) and laccase/1‐hydroxybenzotriazole/linoleic acid (laccase/1‐HBT/LH), were investigated by scanning electron microscopy and gel permeation chromatography. Treatment of cast film with a LPO/LH system involving radical generation via lipid peroxidation led to a marked decrease in the molecular weight of polymers. LPO/LH system resulted in the morphological damage of single crystals of trans‐1,4‐polyisoprene. Laccase/1‐HBT/LH also destroyed the single crystals and depolymerized emulsified trans‐1,4‐polyisoprene. On the contrary, spherulites appeared on the surface of cast films and the molecular weight slightly decreased after treatment with HRP/1‐HBT, indicating that the amorphous region was predominantly degraded and the crystal region remained unchanged. The morphology of single crystals remained unchanged during the treatment of HRP/1‐HBT system for 6 d. In addition, Fenton reagent/linoleic acid was used as a chemical initiator of lipid peroxidation for degradation of trans‐1,4‐polyisoprene cast films. This system reduced molecular weight of the cast films, as well as LPO/LH system.

Scanning electron micrographs of trans‐1,4‐polyisoprene single crystals before (A) and after (B) treatment with the lipoxygenase/linoleic acid system.     

Thermo‐/moisture‐responsive shape‐memory effect of poly(2‐ethyl‐2‐oxazoline) networks

In this work, poly(2‐ethyl‐2‐oxazoline) (PEtOx) is crosslinked to realize a moisture‐ and thermo‐responsive shape‐memory polymer. The obtained PEtOx networks exhibit excellent shape‐memory properties with storable strains of up to 650% and recovery values of 100% over at least 10 shape‐memory cycles. The trigger temperature (T_trig) of 68 °C of a PEtOx network at a relative humidity (RH) of 0% decreases with increasing moisture and equals room temperature at an RH of 40%. Thus, programmed PEtOx networks trigger sensitively on a certain temperature/moisture combination and, further, can be programmed as well as triggered at room temperature exclusively by varying humidity. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1053–1061     

Synthesis and characterization of photocrosslinked poly(ε‐caprolactone)s showing shape‐memory properties

Poly(ε‐caprolactone) (PCL) with a pendent coumarin group was prepared by solution polycondensation from 7‐(3,5‐dicarboxyphenyl) carbonylmethoxycoumarin dichloride and α, ω‐dihydroxy terminated poly(ε‐caprolactone) with molecular weights of 1250, 3000, and 10,000 g/mol. These photosensitive polymers underwent a rapid reversible photocrosslinking upon exposure to irradiation with alternating wavelengths (>280/254 nm) without a photoinitiator. The thermal and mechanical properties of the photocrosslinked films were examined by means of differential scanning calorimetry and stress–strain measurements. The crosslinked films exhibited elastic properties above the melting temperature of the PCL segment along with significant decrease in the ultimate tensile strength and Young's modulus. Shape‐memory properties such as strain fixity ratio (R_f) and strain recovery ratio (R_r) were determined by means of a cyclic thermomechanical tensile experiments under varying maximum strains (ε_m = 100, 300, and 500%). The crosslinked ICM/PCL‐3000 and ‐10,000 films exhibited the excellent shape‐memory properties in which both R_f and R_r values were 88–100% for tensile strain of 100–500%; after the deformation, the films recovered their permanent shapes instantaneously. In vitro degradation was performed in a phosphate buffer saline (pH 7.2) at 37 °C with or without the presence of Pseudomonas cepacia lipase. The presence of the pendent coumarin group and the crosslinking of the polymers pronouncedly decreased the degradation rate. The crosslinked biodegradable PCL showing a good shape‐memory property is promising as a new material for biomedical applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2422–2433, 2009     

Thermodynamic and shape memory properties of TPI/HDPE hybrid shape memory polymer

The traditional processing technology of shape memory polymer composites is complex and the cost of high performance filler is high. Therefore, low-cost high density polyethylene (HDPE) was introduced into trans-1,4-polyisoprene (TPI) matrix as reinforcing phase, and a novel shape memory polymer was prepared by mechanical melt blending, which fully exerted the excellent properties of plastic and rubber. Because of the difference in molecular chain distribution between different blend ratios of TPI/HDPE hybrid SMPCs specimens, the change of the blend ratio of the two components affects the thermodynamic and shape memory properties of the SMPCs. A series experimental results show that the TPI/HDPE hybrid SMPCs with the blend ratio of 80/20 has excellent thermodynamic and shape memory properties. And we believe that the relevant conclusions of this study can provide valuable design reference for the development of high-performance TPI SMPCs.     

Triple shape memory effect of foamed natural Eucommia ulmoides gum/high‐density polyethylene composites

This paper proposes a new technique for the preparation of foamed Eucommia ulmoides gum (EUG)/high‐density polyethylene (HDPE) shape memory composites and establishes the relationship between structures and properties in foamed shape memory composites. Eucommia ulmoides gum/HDPE shape memory composites are designed to memorize 2 temporary shapes by exploiting the different melting points of the 2 phases; the triple shape memory effect in the composites is investigated via mechanical measurements, thermal analysis, and shape memory behavior analysis. The results show that HDPE phase enables the composites to effectively memorize the first temporary shape and EUG phase contributes the second temporary shape. When the ratios of EUG and HDPE were 80/20 and 70/ 30, the composite exhibited satisfactory shape memory behavior with favorable shape fixity ratio and shape recovery ratio, in addition to excellent mechanical properties (tensile strength of 15 MPa, tear strength above 51 KN/m, and foam porosity of about 11%).     

Influence of programming strain rates on the shape‐memory performance of semicrystalline multiblock copolymers

Multiblock copolymers named PCL‐PIBMD consisting of crystallizable poly(ε‐caprolactone) segments and crystallizable poly[oligo(3S‐iso‐butylmorpholine‐2,5‐dione)] segments coupled by trimethyl hexamethylene diisocyanate provide a versatile molecular architecture for achieving shape‐memory effects (SMEs) in polymers. The mechanical properties as well as the SME performance of PCL‐PIBMD can be tailored by the variation of physical parameters during programming such as deformation strain or applied temperature protocols. In this study, we explored the influence of applying different strain rates during programming on the resulting nanostructure of PCL‐PIBMD. Programming was conducted at 50 °C by elongation to ε_m = 50% with strain rates of 1 or 10 or 50 mm min^?1. The nanostructural changes were visualized by atomic force microscopy (AFM) measurements and investigated by in situ wide and small angle X‐ray scattering experiments. With increasing the strain rate, a higher degree of orientation was observed in the amorphous domains. Simultaneously the strain‐induced formation of new PIBMD crystals as well as the fragmentation of existing large PIBMD crystals occurred. The observed differences in shape fixity ratio and recovery stress of samples deformed with various strain rates can be attributed to their different nanostructures. The achieved findings can be relevant parameters for programming the shape‐memory polymers with designed recovery forces. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1935–1943     

Recovery stress and work output in hyperbranched poly(ethyleneimine)‐modified shape‐memory epoxy polymers

In this study a series of hyperbranched modified shape‐memory polymers were subjected to constrained shape recoveries in order to determine their potential use as thermomechanical actuators. Materials were synthesized from a diglycidyl ether of bisphenol A as base epoxy and a polyetheramine and a commercial hyperbranched poly(ethyleneimine) as crosslinker agents. Hyperbranched polymers within the structure of the shape‐memory epoxy polymers led to a more heterogeneous network that can substantially modify mechanical properties. Thermomechanical and mechanical properties were analyzed and discussed in terms of the content of hyperbranched polymer. Shape‐memory effect was analyzed under fully and partially constrained conditions. When shape recovery was carried out with fixed strain a recovery stress was obtained whereas when it was carried out with a constraining stress the material performs mechanical work. Tensile tests at Tg^E′ showed excellent values of stress and strain at break (up to 15 MPa and almost 60%, respectively). Constrained recovery performances revealed rapid recovery stress generation and unusually high recovery stresses (up to 7 MPa) and extremely high work densities (up to 750 kJ/m³). The network structure of shape‐memory polymers was found to be a key factor for actuator‐like applications. Results confirm that hyperbranched modified‐epoxy shape memory polymers are good candidates for actuator‐like shape‐memory applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1002–1013     

Theoretical description of unconstrained thermally induced shape‐memory recovery in crosslinked polyethylenes

A new theoretical approach based on the modified three‐element Eyring‐Halsey model was developed for the derivation of an equation describing the thermally induced recovery of predeformed and crystallized crosslinked polymers. The proposed approach takes into account the influence of crystallizable covalent network and of entangled slipped molecular chains. Modeling of thermally induced shape‐memory (SM) recovery strain and SM recovery rate detected at constant heating rate has been successfully performed for nearly linear and two short‐chain branched polyethylenes, which were crosslinked by peroxide. The values of material constants determined by fitting agree with the estimations existing in literature. Fitting results have shown that increase of degree of branching and crosslink density accompanied with reducing crystallinity results in increasing contribution of the entangled slipped chains to the total stored SM strain. The physical sense of main fitting parameters and their dependences on the material constants such as crystallinity are discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 815–822     

Mechanical and shape‐memory properties of poly(mannitol sebacate)/cellulose nanocrystal nanocomposites

Polyesters based on polyols and sebacic acid, known as poly(polyol sebacate)s (PPS), are attracting considerable attention, as their properties are potentially useful in the context of soft‐tissue engineering applications. To overcome the drawback that PPSs generally display rather low strength and stiffness, we have pursued the preparation of nanocomposites based poly(mannitol sebacate) (PMS), a prominent example of this materials family, with cellulose nanocrystals (CNCs). Nanocomposites were achieved in a two‐step process. A soluble, low‐molecular‐weight PMS pre‐polymer was formed via the polycondensation reaction between sebacic acid and D‐mannitol. Nanocomposites with different CNC content were prepared by solution‐casting and curing under vacuum using two different profiles designed to prepare materials with low and high degree of crosslinking. The as‐prepared nanocomposites have higher stiffness and toughness than the neat PMS matrix while maintaining a high elongation at break. A highly crosslinked nanocomposite with a CNC content of 5 wt % displays a sixfold increase in Young's modulus and a fivefold improvement in toughness. Nanocomposites also exhibit a shape memory effect with a switch temperature in the range of 15 to 45 °C; in particular the materials with a thermal transition in the upper part of this range are potentially useful for biomedical applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3123–3133     

Biodegradable thermoset shape‐memory polymer developed from poly(β‐amino ester) networks

The purpose of this study was to develop a degradable thermoset shape‐memory polymer from poly(β‐amino ester) (PBAE) networks. PBAE was chosen to be the crosslinker as it is biodegradable and has been projected as a potential material for biomedical applications. The low glass transition temperature of PBAE was increased to a biomedically relevant range using methyl methacrylate and methyl acrylate as the linear chain builders. The thermo‐mechanical properties of the networks were tailored such that they exhibited onset of glass transition temperature in between the room temperature (22 °C) and the body temperature (37 °C). Free‐strain recovery tests under heating and isothermal conditions were performed to quantify shape‐memory behavior. Testing showed that sampled programmed at 10 °C initiated deformation recovery at a lower temperature and a faster rate as compared to programming at 60 °C. Higher thermal conductivity of water enabled the samples to recover faster in water than in air. Samples with higher PBAE crosslinking densities exhibited higher normalized mass loss under regular and accelerated conditions. The amount of water absorption in the networks also increased with the crosslinker concentration independent of the testing conditions. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Actuation design for high‐performance shape memory polyurethanes

A series of shape memory polyurethanes were synthesized from poly(tetramethylene glycol), 4,4‐methylene diphenyl diisocyanate, and 1,3‐butanediol. The prepolymers with different molecular weights (M_c) were capped with 2‐hydroxyl ethylacrylate or 3‐aminopropyltriethoxysilane (APTES) and crosslinked by UV curing or a sol–gel reaction. Variations of the crosslinker functionality (f), subchain density (N), and hard segment content (HSC) produced systematic variations of the glass transition temperature (6–45 °C), accompanied by changes in the mechanical, dynamic mechanical and shape memory properties. More than 95% of shape fixity and 98% of shape recovery up to the fourth cycles were obtained with APTES crosslinked 3000M_c with 30% of HSC. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1473–1479