Thermal,mechanical, and shape‐memory properties of nanorubber‐toughened,epoxy‐based shape‐memory nanocomposites

Epoxy‐based shape‐memory polymers (ESMPs) are a type of the most promising engineering smart polymers. However, their inherent brittleness limits their applications. Existing modification approaches are either based on complicated chemical reactions or done at the cost of the thermal properties of the ESMPs. In this study, a simple approach was used to fabricate ESMPs with the aim of improving their overall properties by introducing crosslinked carboxylic nitrile–butadiene nanorubber (CNBNR) into the ESMP network. The results show that the toughness of the CNBNR–ESMP nanocomposites greatly improved at both room temperature and the glass‐transition temperature (T_g) over that of the pure ESMP. Meanwhile, the increase in the toughness did not negatively affect other macroscopic properties. The CNBNR–ESMP nanocomposites presented improved thermal properties with a T_g in a stable range around 100 °C, enhanced thermal stabilities, and superior shape‐memory performance in terms of the shape‐fixing ratio, shape‐recovery ratio, shape‐recovery time, and repeatability of shape‐memory cycles. The combined property improvements and the simplicity of the manufacturing process demonstrated that the CNBNR–ESMP nanocomposites are desirable candidates for large‐scale applications in the engineering field as smart structural materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45780.     

The role of the interphase on the shear induced failure of multiwall carbon nanotubes reinforced epoxy nanocomposites

Multiwall Carbon Nanotubes (MWCNT) with an elevated aspect ratio were chemically functionalized with amines and two types of epoxide groups. Thermogravimetric analysis and Fourier Transform‐Infrared Spectroscopy (FTIR) analysis corroborated that the functionalization degree was substantial (up to 30 wt %) and the presence of a covalent bond with the MWCNT. The functionalized MWCNT (f‐CNT) were incorporated into an epoxy matrix after its dispersion in the diglycidyl ether of bisphenol A (DGEBA) precursor. To induce a shear failure mode, a short‐beam (SB) experimental setup was implemented. The SB shear strength (SBSS) proved that the functionalization had a strong influence on its value. For the case of pristine CNT, a neutral effect was obtained. A strong detrimental effect (?17.2% ± 9.5) was measured for the amine type f‐CNT and a positive effect (up to 10.9% ± 8.9) was measured of the epoxide type f‐CNT. Fractographic analysis of each formulation was correlated with SBSS performance, proving that the surface texture of the fractured samples was strongly correlated to its value. Furthermore, dynamic mechanical analysis proved that the damping factor and the crosslink molecular weight were correlated with the SBSS performance. A lower full width at half maximum of the damping factor was associated to an improvement of SBSS. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41364.     

Hyperbranched‐modified epoxy thermosets: Enhancement of thermomechanical and shape‐memory performances

In this study a complete characterization of the thermomechanical and shape‐memory properties of epoxy shape‐memory polymers modified with hyperbranched polymer and aliphatic diamine was performed. Focusing on the mechanical properties that are highly desirable for shape‐memory polymers, tensile behavior until break was analyzed at different temperatures and microhardness and impact strength were determined at room temperature. As regards shape memory performance, the materials were fully characterized at different programming temperatures to study how this influenced the recovery ratio, fixity ratio, shape‐recovery velocity, and switching temperature. Tensile testing revealed a peak in deformability and in the stored energy density at the onset of the glass transition temperature, demonstrating that this is the best programming temperature for obtaining the best shape‐memory performances. The Young's moduli revealed more rigid structures in formulations with higher hyperbranched polymer content, while microhardness showed higher values with increasing hyperbranched polymer content due to the increased crosslinking density. Impact strength was greatly improved as the aliphatic diamine content increases due to the energy dissipation capability of its flexible structure. As regards the shape‐memory properties, increasing the programming temperature has a minor effect on formulations with a lower hyperbranched polymer content and worsens these properties when the hyperbranched polymer content is increased. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44623.     

pH and thermo‐responsive poly(N‐isopropylacrylamide) copolymer grafted to poly(ethylene glycol)

pH and thermo‐responsive graft copolymers are reported where thermo‐responsive poly(N‐isopropylacrylamide) [poly(NIPAAm), poly A ], poly(N‐isopropylacrylamide‐co‐2‐(diethylamino) ethyl methacrylate) [poly(NIPAAm‐co‐DEA), poly B ], and poly(N‐isopropylacrylamide‐co‐methacrylic acid) [poly(NIPAAm‐co‐MAA), poly C ] have been installed to benzaldehyde grafted polyethylene glycol (PEG) back bone following introducing a pH responsive benzoic‐imine bond. All the prepared graft copolymers for PEG‐g‐poly(NIPAAm) [ P‐N1 ], PEG‐g‐poly(NIPAAm‐co‐DEA) [ P‐N2 ], and PEG‐g‐poly(NIPAAm‐co‐MAA) [ P‐N3 ] were characterized by ¹H‐NMR to assure the successful synthesis of the expected polymers. Molecular weight of all synthesized polymers was evaluated following gel permeation chromatography. The lower critical solution temperature of graft copolymers varied significantly when grafted to benzaldehyde containing PEG and after further functionalization of copolymer based poly(NIPAAm). The contact angle experiment showed the changes in hydrophilic/hydrophobic behavior when the polymers were exposed to different pH and temperature. Particle size measurement investigation by dynamic light scattering was performed to rectify thermo and pH responsiveness of all prepared polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Microstructure and shape memory effect of acidic carbon nanotubes reinforced polyvinyl alcohol nanocomposites

Specimens of acidic multi‐walled carbon nanotubes (AMWNTs) reinforced polyvinyl alcohol (PVA) nanocomposites (AMWNTs‐PVA) were prepared using different amounts of AMWNTs by the traditional solution casting, involving ultrasonic wave agitation. The microstructures and tensile properties of AMWNTs‐PVA were investigated by scanning electron microscopy, dynamic mechanical analysis, and quasi‐static tensile testing. AMWNTs had good compatibility with PVA and dispersed evenly in the PVA matrix. The incorporation of AMWNTs improved the tensile modulus and strength of the PVA. The shape recovery testing revealed the shape recovery capacity of AMWNTs‐PVA. It was observed that the recovery ratio increased, and the shape recovery rate slightly decrease with the increase of AMWNTs content. The results showed that the AMWNTs had strong interaction with the segments of the PVA and hence affected the shape recovery behavior of PVA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Sustained release behavior of pH‐responsive poly(vinyl alcohol)/poly(acrylic acid) hydrogels containing activated carbon fibers

The composites of pH‐responsive poly(vinyl alcohol)/poly(acrylic acid) hydrogel and activated carbon fibers (ACFs) were prepared as sustained drug release system with excellent mechanical properties. The mechanical properties of hydrogels were improved greatly by addition of ACFs. The thinner ACFs were more effective in increasing the mechanical properties of composite hydrogels. The cumulative amount of release and the release period were dependent on the surface area and the pore volume of ACFs. The drug release was maximized at basic condition due to the pH‐sensitive hydrogel matrices and the initial bust phenomenon was alleviated by incorporating ACFs in the hydrogels. The drug release was sustained about four times longer and the mechanical property was increased about 2.6 times higher because ACFs worked as drug reservoir and reinforcement. Cytotoxicity evaluation confirmed the biocompatible characteristics of the ACFs‐containing hydrogels. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dual pH‐ and temperature‐responsive hydrogels with extraordinary swelling/deswelling behavior and enhanced mechanical performances

pH‐ and temperature‐responsive semi‐interpenetrating nanocomposite hydrogels (NC hydrogels) were prepared with surface‐functionalized graphene oxide (GO) as the crosslinker, N‐isopropylacrylamide (NIPAM) as the monomer, and chitosan (CS) as an additive. The effects of 3‐(trimethoxysilyl)propylmethacrylate‐modified GO sheets and CS content on various physical properties were investigated. Results show that PNIPAM/CS/GO hydrogels undergo a large volumetric change in response to temperature. Swelling ratios of PNIPAM/CS/GO hydrogels are much larger than those of the conventional organically crosslinked PNIPAM hydrogels. The deswelling test indicates that the deswelling rate was greatly enhanced by incorporating CS into the hydrogel network and using the surface‐functionalized GO as the crosslinker. The pH‐sensitivity of PNIPAM/CS/GO hydrogels is evident below their volume phase transition temperature. Moreover, the PNIPAM/CS/GO hydrogels have a much better mechanical property compared with traditional hydrogels even in a high water content of 90%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41530.     

Thermal and shape memory properties of cyanate/polybutadiene epoxy/polysebacic polyanhydride copolymer

A novel thermal‐induced shape memory polymer was synthesized by copolymerization of a new kind of epoxy resin‐polybutadiene epoxy (PBEP), bisphenol A‐type cyanate ester (BACE), and polysebacic polyanhydride (PSPA) with different mass ratios. Fourier transform infrared spectroscopy (FTIR), bending test, dynamic mechanical analysis (DMA), and shape memory property were investigated systematically. It was found that the PSPA significantly enhanced the bending strength and flexural modulus. The DMA results showed that the glass transition temperature reduced with increasing content of PSPA. Furthermore, the shape memory tests proved that the copolymer possessed excellent shape memory properties. The shape recovery time decreased with increasing content of PSPA and temperature. The shape memory rate increased as the PSPA content increased. The shape recovery ratio decreased with increasing cycle times. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42045.     

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.     

Poly(vinyl alcohol)/chitosan/honey/clay responsive nanocomposite hydrogel wound dressing

Many efforts have been made to develop modern wound dressings to overcome limitations of traditional ones. Smart nanocomposite hydrogels are appropriate candidates. In this work, a novel responsive nanocomposite hydrogel based on poly(vinyl alcohol)/chitosan/honey/clay was developed and evaluated as a novel wound dressing. The morphology and properties of synthesized nanocomposite hydrogels loaded with honey as a drug model were investigated. The exfoliated morphology of nanocomposite was confirmed by X‐ray diffractometry. Swelling studies were performed at 20 and 37 °C at various pH. The results showed that swelling increased as a result of temperature rise and maximum swelling occurred at a pH of 2. In vitro release of honey was also studied at the same conditions. Corresponding results indicated faster honey release rate at higher pH values. MTT results exhibited no cytotoxicity in nanocomposite hydrogel system. Investigation of antibacterial activity revealed more than 99% antibacterial activity for proposed system. In vivo results confirmed the wound healing ability of developed system. Generally, appropriate properties of proposed system made it ideal in wound dressing applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46311.     

Estimation of the mechanical properties of urea–formaldehyde microcapsules by compression tests and finite element analysis

Information on the mechanical properties of microcapsules is essential to understanding their performance during manufacturing, processing, and applications. The mechanical properties of urea–formaldehyde (UF) microcapsules filled with ethyl phenyl acetate (EPA) were determined by applying single‐microcapsule compression and a finite element model. Microcapsules were prepared by in situ polymerization, and the average wall thickness of microcapsules was 192 ± 12 nm as determined using scanning electron microscopy. The deformation behavior of the microcapsule was measured by a single‐microcapsule compression experiment between two parallel plates. The results show that both burst deformation and burst force were linearly related to microcapsule size. A model for an elastic shell filled with incompressible fluid was used to simulate compression of the microcapsule in ABAQUS. Dimensionless parameters were introduced to the model. The relationship between dimensionless force and dimensionless displacement depended on the ratio of wall thickness to diameter (ε). However, the relationship remained the same when ε was less than 1% and can be fitted well by the mathematical equation. An estimation of Young's modulus can be obtained from the compression data for the dimensionless deformation from 10% to 15%. The average Young's modulus of a UF/EPA microcapsule is estimated to be 2.12 ± 0.45 GPa. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43414.     

Stress memory of a thermoset shape memory polymer

The performance of stress recovery and shape recovery are equally important for high performance shape memory polymers (SMPs) in emerging applications. However, unlike shape recovery, stress recovery does not always follow a monotonic behavior, i.e., “stress plateau,” “stress overshoot,” and “stress undershoot” can be observed. In order to reveal the complicated stress memorization and recovery behavior, this study employs a phenomenological model which considers the recovery stress as the sum of residual programming stress, memorized stress, thermal stress, and relaxed stress for amorphous crosslinked SMPs. This model is demonstrated by a stress recovery experiment in which a polystyrene based SMP was programmed at two prestrain levels above the glass transition temperature, i.e., 20% (neo‐Hookean hyperelastic region) and 50% (strain‐hardening region), and two fixation temperatures, i.e., 20°C (below T_g) and 45°C (within the T_g region), respectively. In addition, a clear distinction between the memorized stress and recovery stress is presented. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42112.     

Temperature‐responsive alginate‐g‐poly(N,N‐diethylacrylamide) copolymer: Synthesis,characterization, and swelling behavior

Temperature‐responsive polymers have recently gained importance due to their applications in drug delivery. Herein, temperature‐responsive graft copolymer (Alg‐g‐PDEAAm) of alginate and N,N‐diethylacrylamide was synthesized by microwave‐assisted copolymerization using potassium persulfate/N,N,N′,N′‐tetramethylethylenediamine initiator system. The reaction conditions for the best grafting (331%) have been optimized by changing microwave irradiation time, temperature, N,N‐diethylacrylamide, and alginate concentrations. The spectroscopic characteristic, thermal properties, and surface morphology of the copolymers were investigated by FTIR, ¹H‐NMR, DSC/TGA, XRD, gel permeation chromatography, and SEM. Furthermore, low critical solution temperatures of Alg‐g‐PDEAAm copolymers were detected by UV spectroscopy. Swelling ratio of graft microspheres was carried out at 25, 32, and 37 °C, and microspheres were found exhibiting temperature‐responsive property. Cytotoxicity test indicated the Alg‐g‐PDEAAm copolymer and its microsphere were biocompatible. Therefore, based on the results the synthesized temperature‐responsive copolymer could be considered as a promising biomaterial. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46688.     

Microwave curing of epoxy polymers reinforced with carbon nanotubes

The driver for this study is the observation that heating of carbon nanotubes (CNTs) with electromagnetic field can offer a more efficient and cost‐effective alternative in heat transfer for the production of composites. The idea of this study is twofold; CNT can work as microwave (MW) radiation susceptors and they can act as nanoreinforcements in the final system. To test these assumptions, a household oven was modified to control the curing schedule. Polymers with different CNT concentrations were prepared (0.5 and 1.0 wt %). The dispersion of the CNTs in the epoxy was achieved using shear‐mixing dissolver technique. MW and conventionally cured specimens were also produced in a convection oven for reference. Thermal and mechanical tests were used as control point. A curing schedule investigation was further performed to quantify the energy and time‐saving capabilities using CNT and MWs. The presence of CNTs into epoxy matrix has been proven beneficial for the shortening of the curing time. MW‐cured composites showed the same degree of polymerization with the conventionally cured composites in a shorter time period and this time was reduced as the CNT concentration was increased. A good distribution of the CNT is required to avoid hot spot effects and local degradation. Mechanical performance was, in some cases, favored by the use of CNT. The benefit from the use of MWs and CNT could reach at least 40% in terms of energy needed and time without sacrificing mechanical performance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of carbon nanofiber reinforced thermoplastic polyurethane nanocomposites

The effect of CNFs on hard and soft segments of TPU matrix was evaluated using Fourier transform infrared (FTIR) spectroscope. The dispersion and distribution of the CNFs in the TPU matrix were investigated through wide angle X‐ray diffraction (WAXD), field emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HRTEM), polarizing optical microscope (POM), and atomic force microscope (AFM). The thermogravimetric analysis (TGA) showed that the inclusion of CNF improved the thermal stability of virgin TPU. The glass transition temperature (T_g), crystallization, and melting behaviors of the TPU matrix in the presence of dispersed CNF were observed by differential scanning calorimetry (DSC). The dynamic viscoelastic behavior of the nanocomposites was studied by dynamical mechanical thermal analysis (DMTA) and substantial improvement in storage modulus (E') was achieved with the addition of CNF to TPU matrix. The rheological behavior of TPU nanocomposites were tested by rubber processing analyzer (RPA) in dynamic frequency sweep and the storage modulus (G') of the nanocomposites was enhanced with increase in CNF loading. The dielectric properties of the nanocomposites exhibited significant improvement with incorporation of CNF. The TPU matrix exhibits remarkable improvement of mechanical properties with addition of CNF. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermomechanical and shape memory properties of thermosetting shape memory polymer under compressive loadings

Shape memory polymers (SMPs) are an emerging class of active polymers that may be used for a range of reconfigurable structures. In this study, the thermomechanical and shape memory behavior of a thermosetting SMP was investigated using large‐scale compressive tests and small‐scale indentation tests. Results show that the SMP exhibits different deformation modes and mechanical properties in compression than in tension. In glassy state, the SMP displays significant plastic deformation and has a much higher modulus and yield strength in comparison to those obtained in tension. In rubbery state, the SMP behaves like a hyperelastic material and again has a much higher modulus than that obtained in tension. The SMPs were further conditioned separately in simulated service environments relevant to Air Force missions, namely, (1) exposure to UV radiation, (2) immersion in jet‐oil, and (3) immersion in water. The thermomechanical and shape recovery properties of the original and conditioned SMPs were examined under compression. Results show that all the conditioned SMPs exhibit a decrease in T_g as compared to the original SMP. Environmental conditionings generally result in higher moduli and yield strength of the SMPs in the glassy state but lower modulus in the rubbery state. In particular, the UV exposure and water immersion, also weaken the shape recovery abilities of the SMPs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Alkali‐responsive membrane prepared by grafting dimethylaminoethyl methacrylate onto ethylene vinyl alcohol copolymer membrane

An alkali‐responsive membrane was prepared by grafting dimethylaminoethyl methacrylate (DMAEMA) onto ethylene vinyl alcohol copolymer (EVAL) membrane using ultraviolet (UV) irradiation graft polymerization. A subtranslucent state of EVAL membrane swelling in the DMAEMA solution was observed, and such a state enabled the passage of UV light through all the pores, inducing graft polymerization inside the pores and on the back. Attenuated total reflectance Fourier‐transform infrared spectrometer (ATR‐FTIR), X‐ray photoelectron spectroscopy (XPS), field‐emission scanning electron microscopy (FESEM), and energy‐dispersive X‐ray spectroscope (EDX) confirmed that the poly(DMAEMA)‐grafted chains existed not only on the top surface, but also inside the pores and on the back. Atomic force microscopy (AFM) and nitrogen adsorption analysis confirmed that the grafted chains collapsed in air, and decreased the surface roughness, surface area, and pore size of the grafted membranes. Alkali‐responsive properties of the poly(DMAEMA)‐grafted EVAL membrane (i.e., contact angle, permeability, and selectivity) were observed in the pH range of 9–10. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41775.     

Electrical and mechanical properties of carbon nanotube‐epoxy nanocomposites

In this work, electrical conductivity and thermo‐mechanical properties have been measured for carbon nanotube reinforced epoxy matrix composites. These nanocomposites consisted of two types of nanofillers, single walled carbon nanotubes (SW‐CNT) and electrical grade carbon nanotubes (XD‐CNT). The influence of the type of nanotubes and their corresponding loading weight fraction on the microstructure and the resulting electrical and mechanical properties of the nanocomposites have been investigated. The electrical conductivity of the nanocomposites showed a significantly high, about seven orders of magnitude, improvement at very low loading weight fractions of nanotubes in both types of nanocomposites. The percolation threshold in nanocomposites with SW‐CNT fillers was found to be around 0.015 wt % and that with XD‐CNT fillers around 0.0225 wt %. Transmission optical microscopy of the nanocomposites revealed some differences in the microstructure of the two types of nanocomposites which can be related to the variation in the percolation thresholds of these nanocomposites. The mechanical properties (storage modulus and loss modulus) and the glass transition temperature have not been compromised with the addition of fillers compared with significant enhancement of electrical properties. The main significance of these results is that XD‐CNTs can be used as a cost effective nanofiller for electrical applications of epoxy based nanocomposites at a fraction of SW‐CNT cost. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and pH‐responsive performance of silane‐modified poly(methylacrylic acid)

The poly(methylacrylic acid) modified by silane [poly(methylacrylic acid‐co‐vinyl triethoxylsilane) (PMAA)] was prepared via free‐radical polymerization with different mass ratios of methylacrylic acid to vinyl triethoxylsilane (VTES). The swelling performance of the prepared PMAA in different solutions with various pH values, salt species (NaCl and CaCl₂), and concentrations was investigated in detail. The results indicated that the introduction of silane boosted the stability of the obtained PMAA in aqueous solutions in the presence of an increased quantity of VTES additive. Meanwhile, the different swelling ratios of PMAA in various pH solutions showed a high pH responsivity. In addition, we found that when the PMAA underwent a number of swelling–deswelling cycles, it demonstrated the good reversibility properties when the pH value of the swelling medium was changed from 9.0 to 1.4. Moreover, the swelling mechanism of PMAA in different solutions with different pH values was investigated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40403.