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.     

Hydrogen bonding and mechanical properties of thin films of polyether-based polyurethane-silica nanocomposites

Two series of thin films of polyether-based polyurethane-silica nanocomposites having hard segment content of 51% and 34% and different concentrations of SiO₂ nanoparticles (0, 0.5, 1.0 and 3.0 vol.%) have been prepared. Infrared linear dichroic (LDIR) ratio, mechanical and differential scanning calorimetry (DSC) measurements were performed in order to determine the influence of hydrogen bonding on their mechanical and thermal properties. The degree of phase separation (DPS) and orientational functions in dependence on strain were calculated from the polarized IR spectra. The presence of silica nanoparticles gives rise to significant differences in the mechanical (stress-strain) properties of the nanocomposites with regard to the pure polymer. The nanocomposite thin films with lower hard segment content (HSC) displayed decreased stiffness and tensile and increased elongation at break in comparison to the nanocomposites with higher HSC. There was no distinctive influence of nanoparticles on the glass transition temperatures of soft segments. Nanosilica significantly affected the melting behavior of the hard phase only in samples with higher HSC.     

Mechanical and shape memory performance of shape memory polyurethane-based aligned nanofibers

In recent years, shape memory polyurethane (SMPU) as a smart material has been used in various applications owing to its desirable shape memory effect and biocompatibility. In this study, unidirectional SMPU nanofibers are innovated by electrospinning to clarify the mechanical and shape memory properties with nanofiber directions. The results showed that when the nanofiber alignment degree is 0° (parallel to the tensile direction), the aligned SMPU nanofibers achieved the obvious improvement of tensile strength (increased to 135%) and elastic modulus (increased to 313%), compared with the random SMPU nanofiber. Moreover, the developed aligned nanofibers exhibited good ability against stress relaxation and creep under constant strain or constant stress conditions in cyclic loading. The aligned SMPU nanofibers with a 0° alignment degree exhibited excellent shape memory properties with shape recovery rates larger than 93% and shape fixity rates larger than 90%, and a dramatic increase of shape recovery stress.     

Thermomechanical and shape memory properties of SCF/SBS/LLDPE composites

A thermally triggered shape memory polymer composite was prepared by blending short carbon fiber (SCF) into a blend of poly(styrene-b-butadiene-b-styrene) triblock copolymer (SBS)/linear low density polyethylene (LLDPE) prior to curing. These composites have excellent processability compared with other thermosets. The dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) were investigated to assess the thermomechanical properties of the SCF/SBS/LLDPE composite. Scanning electron microscope (SEM) imaging of the samples was performed to show the distribution of the SCF in the composite. The study specifically focused on the effect of SCF on the shape memory behavior of the SCF/SBS/LLDPE composite. The results indicated that the large amount of SCF significantly improved the mechanical property of the polymer composites while not damaging the shape memory performance. The SCF/SBS/LLDPE composites exhibited excellent shape memory behavior when the SCF content was less than 15.0 wt%. Moreover, the shape fixity ratio and shape recovery time of the SCF/SBS/LLDPE composites increased with the SCF content.     

Biodegradable shape memory polyurethanes with controllable trigger temperature

A series of random copolymers(PCLAs) were synthesized by ring-opening polymerization of D,L-lactide(LA)and ε-caprolactone(CL) with different molar ratios. PCLA based polyurethanes(PCLAUs) were obtained by chain-extending of PCLA and polytetramethylene ether(PTMEG) with hexamethylene diisocyanate(HDI). All the PCLAUs exhibit good shape memory properties with high shape fixity ratios above 98% and shape recovery ratios above 82% in the first cycle and 91% in the second cycle. PCLAUs with less CL content show faster recovery speed and PCLAUs with more CL content show higher shape recovery ratio. The trigger temperature can be tuned or controlled around body temperature by adjusting the molar ratio of LA to CL. The PCLAUs have potential applications in implant biomedical devices, especially for minimally invasive deployable devices.     

Enhanced thermal and tensile behaviour of MWCNT reinforced palm oil polyol based shape memory polyurethane

Shape memory polyurethane (SMPU) has received tremendous interest because of its low cost, low density, as well as easy processing. However, its inferior mechanical properties compared to shape memory alloys have constrained its application in a broad range of engineering areas. Nanofillers are commonly added to polymers to overcome the problem associated with low mechanical characteristics. This study aims to examine the effect of various loadings of multiwalled carbon nanotubes (MWCNT) on the thermal stability, soft segment crystallinity, tensile and shape memory behaviour of palm oil polyol based SMPU nanocomposites. The SMPU nanocomposites were synthesised using a two-step polymerisation process. Microphase-separated SMPU nanocomposites obtained as the differential scanning calorimetric analysis showed two melting transitions, which belonged to the soft and hard phase domains. Furthermore, it was found that MWCNT had acted as a nucleating agent, which promoted the crystallisation process of SMPU nanocomposites. The thermal stability and tensile properties of SMPU/MWCNT nanocomposites were enhanced significantly as the MWCNT was added to the SMPU matrix. A considerable enhancement in the shape fixity (SF) value was revealed for PU-30 and PU-40 samples with the addition of MWCNT. The shape recovery (SR) time of SMPU was faster for samples reinforced with MWCNT, whereas SF increased while SR decreased upon increasing the shape memory cycle. The SMPU nanocomposites produced demonstrated enhanced thermal and tensile properties, which has the potential as smart material in many industrial applications.     

Bio-based ethylene-co-vinyl acetate/poly (lactic acid) thermoplastic vulcanizates with enhanced mechanical strength and shape memory behavior

With the increasing attention to the shortage of petroleum resources and environmental pollution, it is more urgent to develop new type biomass-derived and bio-degradability polymer materials. In this study, a various of bio-based ethylene-co-vinyl acetate (EVA)/poly (lactic acid) (PLA) thermoplastic vulcanizates (TPVs) with enhanced mechanical strength and shape memory behavior were prepared. The Fourier transform infrared spectroscopy (FTIR), torque rheometer, swelling equilibrium experiments, and thermal gravimetric analysis (TGA) indicate that the EVA component is more aggressive to the active radicals than PLA component, and the improvement of gel content for EVA component is more than that of PLA component. The scanning electronic microscope (SEM) and transmission electron microscopy (TEM) show that the co-continuous structure of EVA/PLA/AD TPV could be well maintained when the TMPTA was introduced into the multicomponent system. Obviously, the results also exhibit that the improvement of mechanical strength and shape memory behavior for EVA/PLA/AD TPV could be attributed to the increased gel content, especially the gel content of EVA component, without changing the crystallization behavior of EVA/PLA/AD TPV.     

Enhanced mechanical and shape memory properties of polyurethane block copolymers chain-extended by ethylene diamine

Effect on shape memory and mechanical properties of polyurethane (PU) copolymers by changing the chain extender from 1,4-butanediol (BD) to ethylenediamine (ED) was investigated. PU copolymers composed of the different ratio of hard and soft segment were prepared and characterized by IR, DSC, XRD, and UTM. Glass transition temperature of PU increased to room temperature range by adopting ED as a chain extender. The XRD peak pattern changed with hard segment content. ED type PU achieved the high mechanical properties at lower hard segment content than BD type PU. Especially, strain at break of ED type significantly improved compared to BD type. Shape recovery rates were similar for both types of PU, but ED type showed better shape retention rate than BD type. The reason for the differences between two types of PU is discussed in this paper.     

Quick water-responsive shape memory hybrids with cellulose nanofibers

A type of quick water-responsive shape memory hybrids is fabricated by introducing cellulose nanofibrous mats as the filler in a polymeric matrix. Cellulose nanofibrous mats are obtained through hydrolyzing electrospun cellulose acetate (CA) nanofibers, then casted in thermoplastic polyurethane (TPU) solution to form the hybrids. The quick shape memory behavior of the formed hybrids is demonstrated using dynamic mechanical analysis (DMA) and stress–strain cyclic test. According to a predetermined protocol, the hybrids present desirable shape fixation and recovery, and the elastic modulus (E′) is shown to be responsive promptly and reversibly against drying and wetting cycle. Shape memory mechanism of the hybrids involves the reversible and competitive hydrogen bonds within cellulose before and after water immersion as well as the entropy elasticity of the TPU matrix. This study can pave a way to design novel smart materials by facile methods through incorporating natural nanomaterials as water sensitive fillers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 767–775     

Poly(urethane-oxazolidone): Synthesis, characterisation and shape memory properties

Poly(urethane-oxazolidone) were synthesized by reacting isocyanate-terminated oxazolidone with hydroxy-telechelic poly(tetramethylene oxide) (PTMO). The molar ratios of the reactants were varied to get polymers of varying oxazolidone and urethane compositons. The polymers were characterized by DSC, FTIR, XRD, dynamic mechanical thermal analysis and chemical analyses. An increase in the concentration of urethane and oxazolidone groups caused a decrease in tensile strength and elongation of the poly(urethane-oxazolidone). The polymers possessed crystallites of PTMO whose melting transition temperature decreased on enhancing the oxazolidone concentration. The polymers exhibited thermo-responsive shape memory properties, which was confirmed and quantified by cyclic tensile tests. The influence of oxazolidone modification and the consequent soft/hard segment variation on the thermal, mechanical, dynamic-mechanical and shape recovery properties of the resultant polymers was investigated. The oxazolidone moities conferred enhanced shape recovery and shape fixity to the polyurethane.     

Temperature memory effect in CuAlNi single crystalline and CuZnAl polycrystalline shape memory alloys

Temperature memory effect (TME) induced by incomplete cycling in CuAlNi single crystalline and CuZnAl polycrystalline shape memory alloys were investigated by differential scanning calorimeter. Results showed that the TME is a common phenomenon in shape memory alloys, caused by a partial martensite to parent phase transformation.     

Competing and decisive roles of 1D/2D/3D sp2-carbons in controlling the shape switching,contact sliding,and functional properties of polymers

Stimuli-controllable shape-shifting polymers, such as shape memory polyurethane (SMPU), are promising for robotics, aerospace, sensing, automobiles, and many other applications. However, slow actuation or high shape recovery time, low recovery stress, and inadequate understanding of friction and wear characteristics of SMPU limit its widespread practical uses. Further, SMPU has been engineered with diverse foreign materials but inconsistent results and ambiguous underlying mechanisms, especially when SMPU is modified with sp²-carbon materials, are also major concerns. Here we determine and simultaneously cross-compare the role of 1D/2D/3D graphitic carbons, namely carbon nanotubes, multilayer graphene and graphite, in controlling the properties of SMPU. The designed SMPU-composites display 8–15-folds faster shape recovery in different mediums, higher recoverable stress, faster healing of the dents, 2–3-folds lower friction, better wear resistance, and improved thermal, wettability, and dielectric properties than pristine SMPU. Further, while the introduction of 2D/3D graphitic carbons massively degrade the elongation, 1D carbon nanotubes maintains the stretchability of SMPU. Eventually, we develop a novel heat alarm device employing SMPU-composite as a major component that acts as a heat sensor, an actuator, and enables the closure of the circuit. Our results uncover many unknown phenomena of engineered SMPU and pave the way for the development of smart-technologies.     

Damping characteristics and mechanical properties of silica filled PUR/PEMA simultaneous interpenetrating polymer networks

Simultaneous polyurethane/poly(ethyl methacrylate) interpenetrating polymer network was synthesised by the one-shot route at the 70PUR/30PEMA composition ratio. This semi-miscible IPN exhibited its potential as a material for damping application by a broad loss factor (tan δ) ? 0.3 spanning a temperature range of 132 °C. The TEM micrographs revealed a multiphase morphology where the mixing between the two polymers was extensive. Incorporation of silica was made in order to study the effects of filler on the IPN properties in terms of glass transition temperature, dynamic mechanical properties, and mechanical and thermal properties. Dynamic mechanical thermal analysis indicated that the filler enhanced the damping ability of the IPN at certain temperature range. Furthermore, the addition of filler resulted in improved material strength.     

Shape memory hybrid based on polyvinyl alcohol and 0D silver nanoparticles

Shape memory hybrids (SMH) have drawn significant attention because they allow an easy alternative for the design of shape memory materials with tailored properties or features. In this work, a shape memory hybrid was made, based on polyvinyl alcohol (PVA) as the elastic domain and 0D silver nanoparticles (Agnps) as the transition domain, a dissolution method of mixing both components, and evaporation of water afterward allowed the formation of films of the hybrid material. Two different size distributions of silver nanoparticles were used (13.7 ± 2.6 and 67.9 ± 14.1 nm), in order to study the effect of the size on the shape memory effect (SME) of the final SMH, under temperature stimuli. The materials obtained were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy, infrared spectroscopy (IR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) techniques. The crystallinity of PVA was slightly altered with the addition of Agnps. Finally, the shape memory effect was tested on both hybrid materials, resulting in a better response to temperature for the SMH prepared with Agnps of 68 nm, also the shape recovery time can be tuned varying both the increase of temperature and the size distribution of Agnps used.     

Phase transition behavior of a poly(oxyethylene-b-butylene adipate) ionomer with shape memory properties

A series of biodegradable poly(oxyethylene-b-butylene adipate) ionomers (POBAi) were prepared by two-step in situ polymerization using adipic acid, 1,4-butanediol and mixed monomers of bis(poly(oxyethylene)) sulfonated dimethyl fumarate. The chemical composition of these POBAi was ascertained by ¹H NMR spectroscopy. The objective of this study was to investigate the shape memory effect of POBAi containing ionomer compared to non ionic POBA. It was observed that POBA5.0i showed a good shape memory effect than that of POBA 2.5 mol% or none of ionic group due to much physical cross-linking point by rich ionic group. Stress-induced phase transition was investigated during the shape deformation and recovery process using a wide-angle X-ray diffractometer (WAXD). The POBA crystal phase transition from β- to α-form was observed in all POBA samples by either thermal treatment or physical drawing. The α-form crystal did not recover to the initial β-form during the recovery process because the monoclinic α-form crystal is structurally more stable than the orthorhombic β-form crystal.     

Effects of surface modification of fumed silica on interfacial structures and mechanical properties of poly(vinyl chloride) composites

Poly(vinyl chloride) (PVC)-based composites were prepared by blending PVC with nano-SiO₂ particles, which were treated with dimethyl dichlorosilane (DMCS), γ-methylacryloxypropyl trimethoxy silane (KH570). The dispersion and interfacial compatibility of nano-SiO₂ particles in PVC matrix was characterized by SEM, which indicated that DDS had a better dispersion and compatibility than UTS but worse than KHS. The mechanical properties, processability and effective interfacial interaction of nano-SiO₂/PVC composites were studied. The nano-SiO₂ particles treated with KH570 or DMCS significantly reinforced and toughened the PVC composites. The maximum impact strength of PVC composites was achieved at a weight ratio of nano-SiO₂/PVC:4/100. The tensile yield stress increased with increasing the content of treated inorganic particles. The incorporation of untreated nano-SiO₂ particles adversely affected the tensile strength of the composite. Although the equilibrium torques of all nano-SiO₂/PVC composites were higher than that of pure PVC, the surface treatments did reduce the equilibrium torque. The interfacial interaction parameter, B, and interfacial immobility parameter, b, calculated respectively from tensile yield stress and loss module of nano-SiO₂/PVC composites, were employed to quantitatively characterize the effective interfacial interaction between the nano-SiO₂ particles and PVC matrix. It was demonstrated that the nano-SiO₂ particles treated with KH570 had stronger effective interface interaction with PVC matrix than those treated with DMCS, which also had stronger effective interface interaction than the untreated nano-SiO₂ particles.     

Hydrolytic aging of crystallizable shape memory poly(ester urethane): Effects on the thermo-mechanical properties and visco-elastic modeling

The shape memory functionality of a segmented poly(ester urethane) and its hydrolytically aged specimens has been studied by cyclic thermo-mechanical measurements with an imposed strain of 100%. The shape memory effect was triggered by a melting transition in the soft segment phase. Aging was enforced by immersion in hot de-ionized water. In the course of the immersion the tensile properties (secant moduli, stress and strain at yield and break) were impaired by hydrolysis. Advanced specimen embrittlement finally led to rupture during the first thermo-mechanical cycle. This happened after 68 days of aging at 55 °C and correspondingly after 8 days at 80 °C. The residual strain after the first cycle, which was about 25%, increased significantly with aging time. Therefore, the total strain recoverability became ever smaller: aged specimens needed conditioning by at least two cycles for a full development of shape recoverability. Likewise the recovery force decreased continuously. Despite these degradation effects, it was observed that the shape fixity and the cycle-related shape recovery of appropriately conditioned specimens (number of cycles N > 2) remained on a constant high level (at round 100% and between 90% and 100%, respectively) throughout the whole aging period. These observations are discussed within the framework of a simplified model of the behavior of crystallizable shape memory polymers. The amorphous state of the polymer is described by the equation of the linear visco-elastic solid. As for the semi-crystalline state the material is assumed to react elastically with respect to deviations from the configuration, which was frozen up under constraint conditions. The curves of the dependence of the material behavior on aging time at 55 °C match perfectly those at 80 °C when the time axis is adjusted by a factor of 8.5, from which the apparent activation energy for hydrolytic aging in the amorphous state of 82 kJ mol⁻¹ could be deduced.     

Influence of shape and surface properties of microstructured reaction areas on the deposition of silica

Differently shaped reaction areas for silica deposition were created by photochemical grafting of hydrophobic poly(acrylic acid 2-ethyl-hexylester) as barrier and a hydrophilic polymer employing a mask having hexagons, pentagons, squares and stripes. Poly(ethylene glycol), poly(acrylic acid), branched and linear poly(ethylene imine) and linear poly(methylpropylene imine) have been applied as hydrophilic polymer in the reaction area. These patterned films have been used in silica mineralization experiments by dipping them into a silica precursor solution. Investigations of the polymer films and silica depositions have been done by contact angle measurements, ellipsometry and scanning electron microscopy (SEM). Silica deposition occurs only in the hydrophilically coated areas, resulting in regular arrays of lens-like silica particles. There are only minor differences due to the shape of the reaction area. The influence of the different hydrophilic polymers can be explained by their wetting behaviour.     

The role of microstructure on the mechanical properties of polyurethane foams containing thermoregulating microcapsules

Rigid polyurethane foams with up to 50 wt% of microcapsules from LDPE-EVA containing Rubitherm^®RT27 were synthesized. The influence of microcapsules on the foams density, microstructure and mechanical resistance was studied. Cell size and strut and wall thicknesses were analyzed by SEM. The relationships between densities and foam microstructures with their Young's moduli and collapse stress were found by the Gibson and Ashby formulations and the Kerner equation for mechanical properties of composites. It was found a cell structure change from polyhedral closed-cells to spherical or amorphous open-cells. A good agreement between the experimental and theoretical data was observed but requiring a cell form factor. Thus, Fitting parameters confirmed the high trend of these microcapsules to be incorporated into the foam cell walls and the form factors depicted the abrupt change of cell morphology. Thus, these equations are suitable for predicting the mechanical properties of foams containing fillers of low mechanical resistance.