Multiple shape memory effects of trans‐1,4‐polyisoprene and low‐density polyethylene blends

A novel series of shape memory blends of trans‐1,4‐polyisoprene (TPI) and low‐density polyethylene (LDPE) were prepared using a simple physical blending method. The mechanical, thermal and shape memory properties of the blends were studied and schemes proposed to explain their dual and triple shape memory behaviors. It was found that the microstructures played an important role in the shape memory process. In TPI/LDPE blends, both the TPI crosslinking network and LDPE crystalline regions could work as fixed domains, while crystalline regions of LDPE or TPI could act as reversible domains. The shape memory behaviors were determined by the components of the fixed and reversible domains. When the blend ratio of TPI/LDPE was 50/50, the blends showed excellent dual and triple shape memory properties with both high shape fixity ratio and shape recovery ratio. © 2017 Society of Chemical Industry     

Reinforcement in the mechanical properties of shape memory liquid crystalline epoxy composites

In this work, novel thermoresponsive shape memory composites based on glass fiber and nanosilica‐modified liquid crystalline epoxies (LCEs) with lateral substituent were prepared and characterized. According to the comprehensive analysis of polarized optical microscopy, wide‐angle X‐ray diffraction measurements, and tan δ data, the orientation of mesogen units were hindered by the introduction of nanosilica and lateral substituents of liquid crystalline epoxies, so that additional physical cross‐links except for similar chemical cross‐links emerged with the introduction of surface‐treated nanosilica. And the increased cross‐links could enhance the shape memory properties of the composites which could recover to their original state quickly in a time shorter than 30 s with high shape fixing ratios (>96%) and high shape recovery ratios (>98%), which indicated the composites could be applied into self‐deployable structural materials. Moreover, the reinforcement in the dynamic storage moduli, tensile modulus, and the tensile strength and shape memory properties indicated that glass fiber and nanosilica‐modified shape memory liquid crystalline epoxy composites could be high‐performance composites and could be used as new candidates for aerospace smart materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42616.     

Facile fabrication of shape memory composites from natural Eucommia rubber and high density polyethylene

Shape memory materials are a type of smart material with potential applications in sensors, textiles, aerospace engineering and medical devices. In this study, we prepared Eucommia rubber and high density polyethylene (HDPE) composites with co‐continuous architecture by a simple physical blending method. The shape memory composites memorized two temporary shapes using different melting points of natural Eucommia rubber and HDPE with the addition of dicumyl peroxide (DCP). The architecture of Eucommia rubber/HDPE composites is critical to the materials' properties: each component forms a three‐dimensional percolating network and good properties of the two components may be synergically combined. Our results showed that the memory behavior of the composites was dependent on the degree of crystallinity in the composites. When the DCP was 1 phr, the physical and mechanical properties of the Eucommia rubber/HDPE composites improved and exhibited excellent shape memory behavior, with better values of the shape fixity ratio than of the shape recovery ratio. When DCP was 6 phr, the crystalline phase of Eucommia rubber in the composites was almost completely destroyed, which resulted in one temporary shape memory behavior of the composites. © 2016 Society of Chemical Industry     

Supramolecular semicrystalline polyolefin elastomer blends with triple‐shape memory effects

Supramolecular polyolefin elastomer blends possessing triple‐shape memory effects were prepared by melt blending of two semicrystalline maleated elastomers (maleated ethylene‐propylene‐diene rubber (mEPDM) and maleated polyethylene‐octene elastomer (mPOE)) in the presence of a small amount of 3‐amino‐1,2,4‐triazole (ATA). The amino group of ATA reacted with the maleic anhydride groups of both elastomers during melt blending to form supramolecular hydrogen‐bonded networks. Dynamic mechanical analysis of the blends showed drops in the storage modulus at two different transition temperatures (T_trans) belonging to the crystalline melting temperatures of each phase as well as a plateau above these two T_trans. This is an essential property for triple‐shape memory behavior. Dual‐shape memory properties of the blends were determined using one‐step programming under three different temperature ranges. When an individual crystalline phase is used for the fixing process, the switching temperature (T_sw) relates to the melting temperature of a particular phase during the recovery process. However, if both crystalline phases are used simultaneously for the fixing process, then the T_sw relates to the higher melting temperature. Cyclic two‐step programming revealed that two different shapes can be fixed, one by EPDM crystallization and the other by POE crystallization, and both programmed shapes can be recovered upon heating above a specific T_sw. © 2016 Society of Chemical Industry     

Fabrication of poly(ε‐caprolactone) (PCL)/poly(propylene carbonate) (PPC)/ethylene‐α‐octene block copolymer (OBC) triple shape memory blends with cycling performance by constructing a co‐continuous phase morphology

In this paper, a triple shape memory material was prepared by ultra‐simple melt blending from poly(ε‐caprolactone) (PCL), poly(propylene carbonate) (PPC) and ethylene‐α‐octene block copolymer (OBC). The obtained material possessed a co‐continuous phase morphology and presented an excellent triple shape memory effect (triple‐SME). Theoretical prediction demonstrated that a special continuous phase morphology could be constructed by adjusting the proportions of the blend. Moreover, the results indicated that a close relationship existed between the phase morphology and the triple‐SME of PCL/PPC/OBC. The sample with 35 vol% PPC content contributed to the formation of a continuous phase morphology and exhibited the optimal triple‐SME. Additionally, the sample PCL/PPC/OBC (32.5/35/32.5) showed outstanding structure and performance stability during cycle loading–unloading tests, which evidenced the prominent cycling shape memory property (nearly 100% shape fixing and recovery of temporary shape). Overall, this work could provide an efficient, convenient and recyclable method to obtain high‐performance shape memory materials. © 2020 Society of Chemical Industry     

Morphology and properties of shape memory thermoplastic polyurethane composites incorporating graphene‐montmorillonite hybrids

A novel hybrid containing graphene oxide (GO) and montmorillonite (MMT) was first synthesized by solution reaction. Then shape memory thermoplastic polyurethane (TPU) composites incorporating MMT–GO hybrid was fabricated via melt blending. Infrared spectra indicated that GO and MMT have been combined together through chemical hydrogen bonding. Tensile tests showed that MMT‐GO hybrids provided substantially greater mechanical property enhancement than using MMT or GO as filler alone. With only 0.25 wt % loading of MMT–GO hybrid (the mass ratio of MMT:GO is 1:1), there was a relatively high improvement in tensile properties of TPU composites, compared with those of TPU/GO and TPU/MMT composites at the same filler content. Thermal analysis indicated that MMT‐GO hybrids enhanced the thermal decomposition temperatures of TPU composites. Shape memory property tests showed that the shape fixing rate of TPU composites was effectively enhanced by incorporating MMT–GO hybrid. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46149.     

Triple‐shape memory properties of polyurethane/polylactide–polytetramethylene ether blends

A facile method to prepare triple‐shape memory polymers was developed by blending polyurethane and polylactide–polytetramethylene with well‐separated glass transition temperatures. The thermal properties of the blends were characterized using modulated differential scanning calorimetry and differential scanning calorimetry. Field emission scanning electron microscopy, Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction were used to characterize the microstructures and crystal structures of the blends. The mechanical properties were also evaluated. The versatile triple‐shape memory effect and quantitative shape memory response were evaluated by consecutive thermal mechanical experiments based on a two‐step programming process and subsequent progressive thermal recovery. The results show that the blends have phase‐separated microstructures resulting in an ability to fix two temporary shapes independently and can recover to their original shapes sequentially. The blends have excellent triple‐shape memory properties and may have some applications in multi‐shape coatings, adhesives, films and temperature sensing or actuating elements. © 2015 Society of Chemical Industry     

Effect of the crosslinking density and programming temperature on the shape fixity and shape recovery in epoxy–anhydride shape‐memory polymers

In addition to the fabrication of thermoset epoxy–anhydride shape‐memory polymers (SMPs), a systematic experimental investigation was conducted to characterize the crosslinking density, micromorphology, thermal properties, mechanical properties, and shape‐memory effects in the epoxy SMP system, with a focus on the influence of the crosslinking density and programming temperature on the shape‐fixity and shape‐recovery behaviors of the polymers. On the basis of the crosslinking density information determined by NMR technology, we concluded that the effect of the crosslinking density on the shape‐fixity behaviors was dependent on the programming temperature. The advantage of a nice combination of crosslinking density and programming temperature provided an effective approach to tailor the actual shape recovery within a wide range. The increasing crosslinking density significantly improved the shape‐recovery ratio, which could be further improved through a decrease in the programming, whereas the crosslinking density was more fundamental. This exploration should play an important role in the fabrication and applications of SMP materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40559.     

A dual‐induced self‐expandable stent based on biodegradable shape memory polyurethane nanocomposites (PCLAU/Fe3O4) triggered around body temperature

Concerning the occurrence of in‐stent restenosis and stent thrombosis of stent implantation with balloon angioplasty, a dual‐induced self‐expandable stent based on biodegradable shape memory polyurethane nanocomposites (PCLAU/Fe₃O₄) was developed. The stent could maintain its temporary shape at body temperature for a certain period of time while it was able to recover to its permanent shape at the temperature a little above body temperature (around 40 °C) in both a water bath and an alternating magnetic field. The trigger temperature and remote local heating ensured enough operation time and harmless activation without heating the body tissue. The nanocomposites had high fixing ratios above 99% and recovery ratios above 82% at both 37 and 40 °C. Cytotoxicity and in vitro degradation showed the nanocomposites had good biocompatibility and biodegradability. The PCLAU/Fe₃O₄ nanocomposites with dual‐responsive shape memory effects, desirable mechanical properties, biocompatibility, and biodegradability show great potential for vascular stents. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45686.     

Effect of the addition of silane coupling agents on the properties of wollastonite‐reinforced poly(ether ether ketone) composites

The wollastonite was grafted with different silane coupling agents, which could improve interface adhesion. Wollastonite and modified wollastonite‐reinforced poly(ether ether ketone) (PEEK) composites were prepared by melt blending. The mechanical properties, rheology behavior, and thermal properties of the composites were investigated. The modified wollastonite‐reinforced PEEK composites exhibited better mechanical properties than the unmodified wollastonite‐reinforced PEEK composites based on good interfacial adhesion. The composites had lower activation volume and complex shear viscosity. Furthermore, the modified wollastonite‐reinforced PEEK composites had higher crystallization peak temperature (T_c) and crystalline fraction (χ_c) compared with the unmodified wollastonite‐reinforced PEEK composites. This study shows that the traditional silane coupling agents could effectively improve the performance of PEEK composites. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Enzymatic Interesterification of High Oleic Sunflower Oil and Tripalmitin or Tristearin

The objective of this study was to produce low saturated, zero‐trans, interesterified fats with 20 or 30 % saturated fatty acids (SFA) such as C16:0 or C18:0. Tripalmitin (TP) or tristearin (TS) was blended with high oleic sunflower oil (HOSO) at different ratios (0.1:1, 0.3:1, and 0.5:1 [w/w]). Total C16:0 and C18:0 compositions of the resulting TP/HOSO and TS/HOSO blends, respectively, were plotted against blending ratios. Linear interpolation was used to estimate blending ratios that would yield physical blends (PB) with 20 or 30 % SFA. Interesterified blends (IB) were then synthesized from the customized PB using Lipozyme TL IM as the biocatalyst. Total and sn‐2 fatty acid compositions, triacylglycerol (TAG) molecular species, thermal behavior, and oxidative stability of PB and IB were compared. The total fatty acid compositions of PB and IB were similar but fatty acid positional distributions and TAG molecular species composition differed. IB contained 5–10 % more SFA at the sn‐2 position than corresponding PB. Furthermore, interesterification generated mono‐ and disaturated TAG species which resulted in broader melting profiles for IB. However, IB had lower oxidative stability than PB. The reformulation of food products with zero‐trans interesterified fats may be advantageous to the reduction of cardiovascular disease burden in the population.     

Triple‐shape‐memory polymer films created by forced‐assembly multilayer coextrusion

Triple‐shape‐memory polymers are capable of memorizing two temporary shapes and sequentially recovering from the first temporary shape to the second temporary shape and eventually to the permanent shape upon exposure to a stimulus. In this study, unique three‐component, multilayered films with an ATBTA configuration [where A is polyurethane (PU), B is ethylene vinyl acetate (EVA), and T is poly(vinyl acetate) (PVAc)] were produced as a triple‐shape‐memory material via a forced‐assembly multilayer film coextrusion process from PU, EVA, and PVAc. The two well‐separated thermal transitions of the PU–EVA–PVAc film, the melting temperature of EVA and the glass‐transition temperature of PVAc, allow for the fixing of the two temporary shapes. The cyclic thermomechanical testing results confirm that the 257‐layered PU–EVA–PVAc films possessed outstanding triple‐shape‐memory performance in terms of the shape fixity and shape‐recovery ratios. This approach allowed greater design flexibility and simultaneous adjustment of the mechanical and shape‐memory properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44405.     

Multi‐stimuli responsive shape memory polymers synthesized by using reaction‐induced phase separation

Thermo‐induced multishape memory polymers are a growing focus of smart materials because of its promising applications. Multishape memory effect is generally attained by using polymers with broad phase transition and multiphase polymers. The latter is of particular interest for copolymerization and polymer compositing. One requirement has to be fulfilled to achieve multishape memory effect, which is to have two reversible phase transitions. In this study, we report synthesis of polymer composite composed of strong segregated polymers by using reaction‐induced phase separation. We demonstrate the method by using polyurethane (PU) and poly(methacrylic acid) (PMAA). With adjusting the weight ratio, the polymer composites exhibit a phase spectrum from phase separation to miscible composite. The composite with PU/PMAA =3:1 demonstrated triple‐shape memory effect. Based on the results, we argued the effect of segregation on the shape memory effect for polymer composites. With the addition of PMAA, the polymer composite also exhibits pH/water‐induced shape memory effect. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43534.     

Synthesis,characterization, and properties of flexible magnetic nanocomposites of cobalt ferrite–polybenzoxazine–linear low‐density polyethylene

A simple method for the preparation of magnetic nanocomposites consisting of cobalt ferrite (CF; CoFe₂O₄) nanoparticles, polybenzoxazine (PB), linear low‐density polyethylene (LLDPE), and linear low‐density polyethylene‐g‐maleic anhydride (LgM) is described. The composites were prepared by the formation of benzoxazine (BA)–CF nanopowders followed by melt blending with LLDPE and the thermal curing of BA. The composites were characterized by X‐ray diffraction, thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy, universal testing machine measurement, and vibrating sample magnetometry. The composites consisting of LLDPE, PB, and LgM (47.5L–47.5PB–5LgM) exhibited a higher tensile strength (23.82 MPa) than pure LLDPE and a greater elongation at break (6.11%) than pure PB. The tensile strength of the composites decreased from 19.92 to 18.55 MPa with increasing CF loading (from 14.25 to 33.25 wt %). The saturation magnetization of the composites containing 33.25 wt % CF was 18.28 emu/g, and it decreased with decreasing amount of CF in the composite. The composite films exhibited mechanical flexibility and magnetic properties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Biodegradable magnetic‐sensitive shape memory poly(ɛ‐caprolactone)/Fe3O4 nanocomposites

A novel biodegradable magnetic‐sensitive shape memory poly(?‐caprolactone) nanocomposites, which were crosslinked with functionalized Fe₃O₄ magnetic nanoparticles (MNPs), were synthesized via in situ polymerization method. Fe₃O₄ MNPs pretreated with γ‐(methacryloyloxy) propyl trimethoxy silane (KH570) were used as crosslinking agents. Because of the crosslinking of functionalized Fe₃O₄ MNPs with poly(?‐caprolactone) prepolymer, the properties of the nanocomposites with different content of functionalized Fe₃O₄ MNPs, especially the mechanical properties, were significantly improved. The nanocomposites also showed excellent shape memory properties in both 60 °C hot water and alternating magnetic field (f = 60, 90 kHz, H = 38.7, 59.8 kA m^?1). In hot water bath, all the samples had shape recovery rate (R_r) higher than 98% and shape fixed rate (R_f) nearly 100%. In alternating magnetic field, the R_r of composites was over 85% with the highest at 95.3%. In addition, the nanocomposites also have good biodegradability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45652.     

Modified shape memory epoxy resin composites by blending activity polyurethane

A series of modified shape‐memory epoxy resin composites were prepared by blending activity polyurethane (APU). Fourier transform infrared spectroscopy (FTIR), tensile tests, scanning electron microscope (SEM), dynamic mechanical analysis (DMA), and fold‐deploy shape memory tests were used to characterize the structure, mechanical, morphology, thermodynamics, and shape memory performance of these materials. FTIR results suggest that APU has been introduced into the resin matrix resin. Tensile test results show that the addition of appropriate APU can increase the elongation at break significantly, compared with neat epoxy. SEM results indicate that the fracture mechanism has changed from brittle to ductile, suggesting that the brittleness of the material has been overcome. DMA results show that modified materials have lower glass transition temperature (T_g) and lower cross‐linking density for shape memory function. Furthermore, the fold‐deploy shape memory tests prove that the materials possess excellent shape memory properties. They can be deformed into different shapes and recover their original shapes fully within 2 min at T_g, while they are hardly affected by ninefold‐deploy cycles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A Dual‐Crosslinked Strategy to Construct Physical Hydrogels with High Strength,Toughness, Good Mechanical Recoverability,and Shape‐Memory Ability

A novel type of physical hydrogel based on dual‐crosslinked strategy is successfully synthesized by micellar copolymerization of stearyl methacrylate, acrylamide, and acrylic acid, and subsequent introduction of Fe³⁺. Strong hydrophobic associations among poly(stearyl methacrylate) blocks form the first crosslinking point and ionic coordination bonds between carboxyl groups and Fe³⁺ serve as the second crosslinking point. The mechanical properties of the hydrogel can be tuned in a wide range by controlling the densities of two crosslinks. The optimal hydrogel shows excellent mechanical properties (tensile strength of ≈6.8 MPa, elastic modulus of ≈8.0 MPa, elongation of ≈1000%, toughness of 53 MJ m^?3) and good self‐recovery property. Furthermore, owing to stimuli responsiveness of physical interaction, this hydrogel also shows a triple shape memory effect. The combination of two different physical interactions in a single network provides a general strategy for designing of high‐strength hydrogels with functionalities.     

Novel phase change materials based on fatty acid eutectics and triallyl isocyanurate composites for thermal energy storage

In this study, a series of dimension‐stabilized fatty acid eutectics and triallyl isocyanurate (TAIC) composite phase change materials were prepared via in situ reaction by blending the fatty acids and TAIC, in which the fatty acids were introduced as a phase change material (PCM), and TAIC performed as a supporting material by self‐crosslinking. Fourier transform infrared spectroscopy, X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy (SEM), and thermogravimetric analysis were applied to investigate the chemical structure, crystalline properties, phase transition behavior, microstructure, and thermal stability of the composites. The results indicated that the composite possessed excellent thermal reliability and heat storage durability even after 300 heating–cooling cycles. Moreover, the composites had applicable phase transition temperatures in the range of 26–40 °C and satisfying latent heat storage capacities of higher than 110 J/g. The SEM images showed that the particle size of the nanoparticles of the composites was about 200 nm after treatment. The dimensional measurement of the composites proved a high service temperature of 100 °C, indicating that the composites were promising for thermal energy storage materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44866.     

Flow behaviour and microstructure evolution in novel SiO2/PP/LCP ternary composites: effects of filler properties and mixing sequence

When silica (SiO₂) fillers were introduced into the polypropylene (PP) and liquid‐crystalline polymer (LCP) blend, it was found that the mixing sequence, the filler size, and the filler surface nature affected the rheology of the composites and the morphology of the LCP phase in the ternary composite. In particular, the compatibility between the filler and the PP matrix was found to exert a strong influence on the droplet‐fibril transition. The incorporation of the hydrophobic silica to the LCP/PP blend facilitated the fibrillation of LCP because the hydrophobic filler demonstrated affinity towards the hydrophobic PP matrix. The preferential residence of the hydrophobic silica in the PP phase would minimise the LCP domain disruption leading to the formation of LCP fibrils with high aspect ratios. The use of fine filler and in situ blending, which promoted the filler–LCP interaction, could prevent coalescence, inhibit deformation and hinder fibril development as well. © 2003 Society of Chemical Industry