Mechanical and shape‐memory behavior of shape‐memory polymer composites with hybrid fillers

Shape‐memory polymer (SMP) materials have several drawbacks such as low strength, low stiffness and natural insulating tendencies, which seriously limit their development and applications. Much effort has been made to improve their mechanical properties by adding particle or fiber fillers to reinforce the polymer matrix. However, this often leads to the mechanical properties being enhanced slightly, but the shape‐memory effect of reinforced SMP composites being drastically reduced. The experimental results reported here suggested that the mechanical resistive loading and thermal conductivity of a composite (with hybrid filler content of 7.0 wt%) were improved by 160 and 200%, respectively, in comparison with those of pure bulk SMP. Also, the glass transition temperature of the composite was enhanced to 57.28 °C from the 46.38 °C of a composite filled with 5.5 wt% hybrid filler, as determined from differential scanning calorimetry measurements. Finally, the temperature distribution and recovery behavior of specimens were recorded with infrared video in a recovery test, where a 28 V direct current circuit was applied. The effectiveness of carbon black and short carbon fibers being incorporated into a SMP with shape recovery activated by electricity has been demonstrated. These hybrid fillers were explored to improve the mechanical and conductive properties of bulk SMP. Copyright © 2010 Society of Chemical Industry     

Study on the Mechanical and Thermal Properties of Jute-Reinforced Methyl Acrylate Grafted PET Composites

Polyethylene terephthalate (PET) granules were grafted with methyl acrylate (MA) from the solution containing 10% MA in methanol (86%) solvent and photo initiator (4%) for 10 min and then cured under UV radiation. MA-grafted PET films were prepared at 260°C and 5 ton pressure using heat press. Jute fabric-reinforced, MA-grafted, PET-based composites (25% fiber by weight) were fabricated by compression molding. Mechanical, thermal and soil degradation tests of the composites were performed. It was found that the MA grafted PET composites showed higher mechanical properties over the ungrafted PET/jute composite.     

Catalytic grafting: A new technique for polymer/fiber composites. II. Plasma treated UHMPE fibers/polyethylene composites

In this paper, the catalytic grafting technique for preparation of polymer/fiber composites is extended to plasma treated ultra-high modulus polyethylene (UHMPE) fiber/high density polyethylene (HDPE) system. The OH groups introduced on the UHMPE fiber surface by oxygen plasma treatment were used to chemically anchor Ziegler-Natta catalyst which then was followed by ethylene polymerization on the fiber surface. The morphology and interfacial behavior, as well as the mechanical properties, of the HDPE composites reinforced by catalytic grafted or ungrafted UHMPE fibers were investigated by SEM, DSC, polarized light optical microscopy, and tensile testing. The experimental results show that the polyethylene grafted on the fibers acted as a transition layer between the reinforcing UHMPE fibers and a commercial HDPE matrix. The interfacial adhesion was also significantly improved. Compared with the composite reinforced by ungrafted UHMPE fibers, the composite reinforced by catalytic grafted UHMPE fibers exhibits much better mechanical properties.     

Study on the biocomposites with poly(ethylene glycol) dimethacrylate and surfaced‐grafted hydroxyapatite nanoparticles

In composites of hydroxyapatite (HA) nanoparticles with a polymer matrix, the aggregation of nanoparticles would induce structural defects. In order to improve the dispersibility of HA nanoparticles in poly(ethylene glycol) dimethacrylate (PEGDMA) matrix and enhance mechanical properties of the HA/PEGDMA composite as potential bone substitute material, surface‐grafted HA nanoparticles with poly(ethylene glycol) monomethacrylate (PEGMA) were prepared, and crosslinked with PEGDMA under UV light to form a composite. The structure of HA‐g‐PEGMA was characterized by X‐ray diffraction (XRD) and thermal gravimetric analysis (TGA). The dispersibility of HA‐g‐PEGMA nanoparticles in poly(PEGDMA) was evaluated by SEM. The mechanical properties of the composites were investigated by compressive test. The dispersibility of HA‐g‐PEGMA nanoparticles in poly(PEGDMA) matrix was better than the bare HA. At a 1 wt % content of loading, the strength of composites increased by 14%, and the modulus increased by 9%. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Processing and properties of nano‐ and macro‐hydroxyapatite/poly(ethylene‐co‐acrylic acid) composites

Hydroxyapatite (HAp)/poly(ethylene‐co‐acrylic acid) composites have been synthesized by a solution‐based method, using nanosized (n‐HAp) and coarse hydroxyapatite (c‐HAp) particles, respectively. X‐ray diffraction study has indicated the development of compressive and tensile stresses in composites because of the thermal expansion mismatch between the particles and polymer matrix. Fourier transform infrared absorption spectra and thermal analysis have showed the presence of strong interfacial bonding between the particles and polymer. The surface roughness and the homogeneous dispersion of HAp particles in the polymer matrix have been observed by scanning electron microscopy. A comparison in mechanical properties between composites prepared with n‐HAp and c‐HAp particles, respectively, has been studied. Nanosized particles contribute excellent improvement of mechanical properties of the composites rather than the coarse particles. The uniform dispersion of HAp particles, followed by the improvement in mechanical properties of the composite, provides a means of preparing HAp/polymer composites for low load‐bearing implant applications. POLYM. COMPOS., 27:633–641, 2006. © 2006 Society of Plastics Engineers     

LDPE/SEBS/CB电致形状记忆复合材料的结构与性能

通过熔融共混法将热塑性弹性体氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)和低密度聚乙烯(LDPE)制成形状记忆聚合物(SMP)材料;在SMP材料中填充导电炭黑(CB),制成具有电致形状记忆特性的LDPE/SEBS/CB复合材料。通过SEM、DSC分析和力学性能、电性能、记忆性能测试,研究了CB含量对电致SMP材料结构与性能的影响。结果表明:当CB含量达到20%时,LDPE/SEBS/CB复合形状记忆材料的体积电阻率降至103Ω·cm左右,CB的导电网络趋于稳定;并且LDPE/SEBS/CB(2:2:1)复合形状记忆材料的形状固定率约90%,常温拉伸和高温拉伸时均表现出较高的形状回复率(约90%),拉伸模量约170MPa,拉伸强度约9.5MPa,断裂伸长率约400%。     

Synthesis of hydroxyapatite/poly(vinyl alcohol phosphate) nanocomposite and its characterization

Hydroxyapatite (HAp)/poly(vinyl alcohol phosphate) (PVAP) nanocomposite has been prepared using a solution‐based method varying HAp from 10 to 60% (w/w). X‐ray diffraction, Fourier transform infrared absorption spectra (FTIR), and thermal analysis have indicated the presence of bonding between HAp particles and PVAP matrix. Transmission electron microscope analysis shows the needle‐like crystals of HAp powder having a diameter of 6–10 nm and a length of 26–38 nm. The surface roughness and the homogeneous dispersion of HAp particles in the polymer matrix have been observed by scanning electron microscopy. Particle size distribution analysis shows the narrow distribution of hydrodynamic particles in the polymer matrix. The tensile stress–strain curves show the improvement in mechanical properties of the composites with increase in amount of HAp particles loading. The composites along with polymer are highly hemocompatible. The use of PVAP promotes the homogeneous distribution of particles on the polymer matrix along with strong particle–polymer interfacial bonding, which has supported the improvement in mechanical properties of the composites. The prepared HAp/PVAP composite with uniform microstructure would be effective to act as a potential biomaterial. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Modeling the effective properties and thermomechanical behavior of SMA‐SMP multifunctional composite laminates

The research work presents the modeling of effective properties and thermo‐mechanical behavior of shape memory fiber (SMF) and shape memory polymer (SMP) composite laminates using micromechanical approaches based on the method of mixtures (MOM) and method of cells (MOC). The fiber is made of a nickel‐titanium (Ni‐Ti) shape memory alloy (SMA), while the matrix consists of a shape memory thermoset epoxy polymer (SMP). The use of an SMP matrix provides large strain compatibility with the SMA fiber, while being active at high temperatures without losing its elastic properties. Additionally, the SMP matrix is also able to produce similar pseudoelastic and shape memory effects, which are noticed in SMAs. In the analysis, a two step homogenization scheme is followed. In the first step the effective properties of each layer are determined via a micromechanics approach with iso‐strain conditions. In the second step the effective properties of the SMF‐SMP composite are computed making a thin plate theory assumption, which takes into account the transverse shear deformations. The possible elastic couplings for SMF‐SMP laminates are discussed, and the laminate force and moment resultants are computed for various laminate configurations. The analysis takes into account the effects of phase transformations and the resulting change in the fiber–matrix modulus. The results have been compared by considering different fiber volume fractions, temperatures, fiber orientations, and lamina stacking sequences. The results show that adaptive SMA‐SMP composites laminates can be developed that provide shape controllability via tunable laminate stiffnesses leading to optimal response. Furthermore, the work presents the necessary framework for a reliable and efficient analysis of SMA‐SMP laminates for practical applications. The theory can be directly used in established plate and shell formulations of finite element analysis. Finally, the variations in force and moment resultants with respect to fiber orientations and stacking sequences are presented, which are useful to study the bending and buckling characteristics of active composites for shape control of adaptive structures. The work concludes that efficient adaptive laminate development for high performance composite applications, exhibiting large shape adaptivity, high stresses, and increased stiffness, are feasible as compared to SMA composites without active matrix. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Effects of stretch induced softening to the free recovery behavior of shape memory polymer composites

During a cyclic tension test, many elastomeric materials exhibit an appreciable softening in their mechanical properties resulting from the previous stretch, known as the Mullins effect. This paper explores the influence of the stretch induced softening effect to the free recovery behavior of an acrylate shape memory polymer (SMP) composite by incorporating carbon black (CB) as filler materials. The observed softening effect in this SMP composite is considered to be a consequence of stretch induced alternation of filler–polymer interactions inside the composite. Further experiments find that a larger prior stretch gives a larger increase in material softening, which in turn decreases the shape recovery speed. To capture the experimental observations, a multi-branch one dimensional (1D) model is applied, where the modulus in the equilibrium branch is modeled to decrease with stretching deformation following a damage-like softening function. It is found that the loss in modulus due to softening consequently reduces the driving force for recovery and thus results in a slow recovery. Parametric studies further demonstrate that the discounted shape recovery speed will finally reach a saturated level when gradually increasing the programmed strain level in a shape memory cycle.     

Short glass fiber reinforced radiation crosslinked shape memory SBS/LLDPE blends

The poly(styrene‐b‐butadiene‐b‐styrene) triblock copolymer (SBS) and linear low density polyethylene(LLDPE) were blended and irradiated by γ‐rays to prepare shape memory polymer(SMP). Various amounts of short glass fiber (SGF) were filled into SMP to form a novel shape memory SGF/SBS/LLDPE composite. The effect of SGF on the shape memory SGF/SBS/LLDPE composite was studied in terms of mechanical, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC) and shape memory effects. It is found that the SGF act as reinforcing fillers and significantly augment the glassy and rubbery stated moduli, tensile strength and shape memory properties. When SGF content is <2.0 wt %, full recovery can be observed after only several minutes at different temperatures and shape recovery speed reduces as the SGF content increases. The shape recovery time decreases as the temperature of the shape memory test increases and the shape recovery rate decreases with increment of cycle times. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40691.     

Highly filled poly(l-lactic acid)/hydroxyapatite composite for 3D printing of personalized bone tissue engineering scaffolds

The designing of new biodegradable polymer composites is one of the most promising areas of modern orthopedics and regenerative surgery. At present, a number of methods have been proposed for designing and processing biodegradable polymer composites via various 3D printing technologies; however, the homogeneity of filler distribution together with mechanical properties of scaffolds made of such composites are far from those required for clinical use. In this study, the method for producing biodegradable composite material based on poly(l -lactic acid) (PLLA) solution in organic solvent and hydroxyapatite (HAp) powder was proposed. The influence of HAp weight fraction and additional annealing on PLLA matrix crystallinity was investigated. It was shown that crystallinity of PLLA decreases from 58.84 ± 1.21 to 17.33 ± 1.69 as HAp weight fraction increased from 0 to 50 wt%. However, HAp filler promoted PLLA crystallites growth according to the X-ray powder diffraction analysis. The results of nanoindentation showed Young's modulus values of the 3D-printed scaffolds with 50 wt% of HAp at the level of human femur and tibia.     

Tough reinforced open porous polymer foams via concentrated emulsion templating

Low-density but very resilient and robust polymer foams possessing an interconnected open porous network have been synthesised by the polymerisation of the continuous phase of concentrated or high internal phase emulsions containing polyethylene glycol dimethacrylate (PEGDMA) as main crosslinker. The synthesised polymer foams did not display the undesirable properties, such as brittleness and chalkiness, which are commonly observed for highly crosslinked porous polymer monoliths synthesised by the polymerisation of high internal phase emulsions. An effective way to improve the mechanical performance of open porous polymer foams is to raise the apparent foam density. Therefore, the continuous phase of the emulsions was increased up to 40 vol.%. The mechanical properties can be further increased by the incorporation of silica particles into the polymer. Methacryloxypropyltrimethoxysilane was added to the continuous phase to ensure that the silica particles were covalently bonded into the inorganic polymer network formed by the hydrolytic condensation of the silane groups. The addition of reinforcement increased the mechanical properties. The Young's modulus and the crush strength of the polymer foams increased by up to 360% and by up to 300%, respectively, in comparison to non-reinforced samples.     

Electrical,rheological, and mechanical properties copolymer/carbon black composites

This work aims to evaluate the electrical conductivity and the rheological and mechanical properties of copolymer/carbon black (CB) conductive polymer composites (CPCs). The copolymers, containing ethylene groups in their structure, used as matrix were polyethylene grafted with maleic anhydride (PEgMA), ethylene-methyl acrylate–glycidyl methacrylate (EMA-GMA), and ethylene-vinyl acetate (EVA). For comparison purposes, bio-based polyethylene (BioPE)/CB composites were also studied. The electrical conductivity results showed that the electrical percolation threshold of BioPE/CB composite was 0.36 volume fraction of CB, whereas the rheological percolation threshold was 0.25 volume fraction of CB. The most conductive CPC was BioPE/CB. Among the copolymer/CB CPCs, PEgMA/CB showed the highest conductivity, which can be attributed to the fact that the PEgMA copolymer had higher crystallinity. It also has a higher amount of ethylene groups in its structure. Torque rheometry analysis indicated that EMA-GMA copolymer may have reacted with CB. Rheological measurements under oscillatory shear flow indicated the formation of a percolated network in BioPE/CB and copolymer/CB composites. Morphology analysis by scanning electron microscopy (SEM) indicated the formation of a percolated network structure in BioPE/CB composite and finely dispersed CB particles within the PEgMA copolymer. Wetting of CB particles/agglomerates by the copolymer matrix was observed in EVA/CB and EMA-GMA/CB composites. Conductive CB acted as reinforcing filler as it increased the elastic modulus and tensile strength of BioPE and the copolymers.     

Influence of uniaxial compression on the shape memory behavior of vitrimer composite embedded with tension-programmed unidirectional shape memory polymer fibers

Tension programmed shape memory polymer (SMP) fibers have been used as sutures for closing wide-opened cracks per the close-then-heal strategy. However, the composite may be subjected to compression loading during service. These compression loads can reduce the amount of recoverable strain in these pre-tensioned fibers, limiting their ability to close cracks. The purpose of this study is to investigate the effect of in-service compression loading on the shape memory effect (SME) of composites consisting of SMP fiber and SMP matrix. To this end, pre-stretched shape memory Polyethylene Terephthalate (PET) fibers were embedded into a shape memory vitrimer to obtain composite samples with different fiber volume fractions. The SME of both the PET fiber and the vitrimer was investigated. The effect of compression load on the SME of the composite was studied. It is found that, uniaxial compression on the composite along the fiber direction significantly reduced the shrinking ability of the embedded pre-tensioned SMP fibers. Hence, this is a factor that needs to be considered when designing such types of self-healing composites.     

Multi-functional polyurethane composites with self-healing and shape memory properties enhanced by graphene oxide

Development of shape memory polymer materials with integrated self-healing ability, shape memory property, and outstanding mechanical properties is a challenge. Herein, isophorone diisocyanate, polytetramethylene ether glycol, dimethylglyoxime, and glycerol have been used to preparation polyurethane by reacting at 80°C for 6 h. Then, graphene oxide (GO) was added and the reaction keep at 80°C for 4 h to obtain polyurethane/GO composite with self-healing and shape memory properties. Scanning electron microscopy shows that the GO sheets were dispersed uniformly in the polyurethane matrix. The thermal stability was characterized by thermogravimetric analyses. The tensile test shows that the Young's modulus of the composites increases from 38.57 ± 4.35 MPa for pure polyurethane to 95.36 ± 10.35 MPa for the polyurethane composite with a GO content of 0.5 wt%, and the tensile strength increases from 6.28 ± 0.67 to 15.65 ± 1.54 MPa. The oxime carbamate bond and hydrogen bond endow the composite good self-healing property. The healing efficiency can reach 98.84%. In addition, the composite has excellent shape memory property, with a shape recovery ratio of 88.6% and a shape fixation ratio of 55.2%. This work provides a promising way to fabricate stimulus-responsive composite with versatile functions.     

Shape memory CTBN/epoxy resin/cyanate ester ternary resin and their carbon fiber reinforced composites

Carboxylated-terminated liquid acrylonitrile rubber (CTBN) and epoxy resin (JEF-0211) were coreacted with cyanate ester (CE) to form CTBN/EP/CE ternary resin systems. Further, the ternary resin system was applied as prepreg for carbon fiber composites with vacuum bag degassing molding process. CTBN/EP/CE ternary shape memory polymer (SMP) exhibited relatively high tensile strength, Young's modulus, impact strength, and excellent shape memory properties. Compared with CTBN/EP/CE ternary SMP, CTBN/EP/CE carbon fiber composites showed much higher mechanical properties, such as their tensile strength and Young's modulus were high to 570 MPa and 36.7 GPa, respectively. Furthermore, CTBN/EP/CE carbon fiber composites exhibited good shape memory properties, their shape fixity ratio and shape recovery ratio were more than 95% after 30 times repeating shape memory tests. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48756.     

Surface grafting of carbon fibers with artificial silver‐nanoparticle‐decorated graphene oxide for high‐speed electrical actuation of shape‐memory polymers

Poor heat conduction in the interface between the carbon fiber and polymer matrix is a problem in the actuation of shape‐memory polymer (SMP) composites by Joule heating. In this study, we investigated the effectiveness of grafting silver‐nanoparticle‐decorated graphene oxide (GO) onto carbon fibers to improve the electrothermal properties and Joule‐heating‐activated shape recovery of SMP composites. Self‐assembled GO was grafted onto carbon fibers to enhance the bonding of the carbon fibers with the polymeric matrix via van der Waal's forces and covalent crosslinking, respectively. Silver nanoparticles were further self‐assembled and deposited to decorate the GO assembly, which was used to decrease the thermal dissimilarity and facilitate heat transfer from the carbon fiber to the polymer matrix. The carbon fiber was incorporated with SMP to achieve the shape recovery induced by Joule heating. We found that the silver‐nanoparticle‐decorated GO helped us achieve a more uniform temperature distribution in the SMP composites compared to those without decoration. Furthermore, the shape‐recovery behavior and temperature profile during the Joule heating of the SMP composites were characterized and compared. A unique synergistic effect of the carbon fibers and silver‐nanoparticle‐decorated GO was achieved to enhance the heat transfer and a higher speed of actuation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41673.     

Effects of in-situ reactive phenolic resin on shape memory performance of polynorbornene

In this paper, resorcinol prepolymer (HT1005) in-situ reacted with hexamethoxymethyl melamine (HMMM, formaldehyde donor) to produce cured phenolic resin to modify polynorbornene (PNB) as a shape memory polymer (SMP). A moving die rheometer (MDR) was used to characterize the crosslinking degree of phenolic resin. Fourier transform infrared spectroscopy, differential scanning calorimeter, universal electronic tensile testing machine, dynamic mechanical analysis and X-ray diffraction was used to investigated the mechanical properties and shape memory performance of PNB composites. Infrared results showed that HT1005 reacted with HMMM forming a chemical cross-linking network in PNB. With the increase of HT1005 and HMMM, the phenolic resin network was gradually improved. When stress was applied to the composite, the phenolic resin rigid network first beared part of the external force, which improved the mechanical properties of the composite. When the content of HT1005 was too much, its dispersibility will become poor, and the rigid phenolic resin network will be too dense, which limited the recovery of PNB molecular chains. A small amount of HT1005 will be more uniformly dispersed in the PNB, the strength of the phenolic resin network was moderate, and the composite material had excellent shape memory and mechanical properties.     

The effect of grafted caged silica (polyhedral oligomeric silesquioxanes) on the properties of dental composites and adhesives

With the emergence of commercial grafted caged silica (Polyhedral Oligomeric Silesquioxanes, POSS) having a three-dimensional (3D) morphology with peripheral functionality, new opportunities have been created for formulating dental adhesives and composites with enhanced mechanical and physical properties. The objective of the present study was to investigate the properties obtained by incorporating grafted caged silica into acrylate based dental composite and adhesive systems. Two commercial POSS materials (methacrylated and octaphenyl grafted) were added to dental restorative-glass-filled pre-polymers, based on BisGMA (bis-phenol A-glycidyldimethacrylate), HEMA (2-hydroxyethylmethacrylate) and TEGDMA (tetraethylglycidylmethacrylate). The nanostructured organic/inorganic hybrid compounds exhibited enhanced mechanical and thermal properties in cases where the POSS added was in concentrations up to 2 wt%. Beyond this threshold concentration, properties decreased due to agglomeration. In the case of the acrylated POSS, the T _g increased by 5°C, the composite compressive strength by 7%, and the bond shear strength by 36% and the shrinkage was reduced by 28% compared with neat dental composites and adhesives. Furthermore, in the case of octaphenyl grafted POSS, the compressive strength was reduced by 20%, the adhesive shear bond strength decreased by 49% and the shrinkage was reduced by 67%. It was concluded that the type of the grafted functional group of the caged silica was the dominant factor in nano-tailoring of improved dental composites and adhesives.     

Surface modification of ultra-high molecular weight polyethylene fibers by γ-radiation-induced grafting

A technique for grafting acrylic polymers on the surface of ultra-high molecular weight polyethylene (UHMWPE) fibers utilizing ⁶⁰Co gamma radiation at low dose rates and low total dose has been developed. Unlike some of the more prevalent surface modification schemes, this technique achieves surface grafting with complete retention of the exceptional UHMWPE fiber mechanical properties. In particular, poly(butyl acrylate) and poly(cyclohexyl methacrylate) were successfully grafted onto UHMWPE fibers with no loss in tensile properties. The surface and tensile properties of the fibers were evaluated using Fourier transform infrared/photoacoustic spectroscopy (FTIR/PAS), X-ray photoelectron spectroscopy (XPS), and tensile tests. The reinforcement efficiency of untreated, polymer-grafted, and plasma-treated UHMWPE fibers in polystyrene and a poly(styrene-co-butyl acrylate-co-cyclohexyl methacrylate) statistical terpolymer was characterized using mechanical tensile tests. The thermoplastic matrix composites were prepared with 4 wt% discontinuous (10 mm), randomly distributed UHMWPE fibers. An approximate 30% increase in composite strength and modulus was observed for poly(cyclohexyl methacrylate)-grafted fibers in the terpolymer and polystyrene matrices. A comparable improvement was realized with the plasma-treated fibers. On the other hand, poly(butyl acrylate) grafts induced void formation, i.e. energy dissipation through plastic deformation and volume expansion at the fiber/matrix interface in terpolymer composites. The latter resulted in a 75% increase in the elongation to failure. The effect of polymer grafts on fiber/matrix adhesion is discussed in terms of the graft and matrix chain interactions and solubility, graft chain mobility, and fracture surface characteristics as determined by scanning electron microscopy (SEM).