Thermoplastic polyvinyl alcohol/multiwalled carbon nanotube composites: Preparation,mechanical properties,thermal properties,and electromagnetic shielding effectiveness

This study uses the solution mixing method to combine plasticized polyvinyl alcohol (PVA) as a matrix, and multiwalled carbon nanotubes (MWCNTs) as reinforcement to form PVA/MWCNTs films. The films are then laminated and hot pressed to create PVA/MWCNTs composites. The control group of PVA/MWCNTs composites is made by incorporating the melt compounding method. Diverse properties of PVA/MWCNTs composites are then evaluated. For the experimental group, the incorporation of MWCNTs improves the glass transition temperature (T_g), crystallization temperature, T_c), and thermal stability of the composites. In addition, the test results indicate that composites containing 1.5 wt % of MWCNTs have the maximum tensile strength of 51.1 MPa, whereas composites containing 2 wt % MWCNTs have the optimal electrical conductivity of 2.4 S/cm, and electromagnetic shielding effectiveness (EMI SE) of ?31.41 dB. This study proves that the solution mixing method outperforms the melt compounding method in terms of mechanical properties, dispersion, melting and crystallization behaviors, thermal stability, and EMI SE. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43474.     

Mechanical properties of carbon fiber reinforced bisphenol A dicyanate ester composites modified with multiwalled carbon nanotubes

A novel electrophoretic deposition (EPD) method was employed for grafting multiwalled carbon nanotubes (MWCNTs) on carbon fibers, which, after impregnation with bisphenol A dicyanate ester (BADCy), synergistically reinforced BADCy matrix composites (CNT‐C/BADCy). The effect of MWCNT presence on the mechanical properties of the composites was investigated. Composite tensile strength increased by 45.2% for an EPD duration of 2 min, while flexural strength exhibited a decreasing trend with EPD duration. Optical microscopy revealed that the existence of MWCNTs enhanced the fiber‐matrix interface while a large number of CNTs were observed to have pulled‐out from the matrix, a finding which explained the observed tensile strength increase in terms of energy dissipation by the specific toughening mechanism. The flexural strength decrease of the composites with CNTs as compared to specimens without nanotubes was found linked to the increased stress concentration in the BADCy matrix due to tube presence which weakens the adhesion between carbon fabrics. In a word, carbon nanotubes will enhance the micro interface and weaken the macro interface of the composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45100.     

Novel method of dispersion of multiwalled carbon nanotubes in a flexible epoxy matrix

We describe a simple and novel method for dispersing multiwalled carbon nanotubes (MWCNTs) in a flexible epoxy matrix. The MWCNTs were modified with half‐neutralized dicarboxylic acids having different numbers of carbon atoms. The modified MWCNTs were prereacted with epoxy in the presence of triphenylphosphine. The dispersion of the MWCNTs and the enhancement in the tensile properties were found to be better for composites prepared with a solvent. Among the half‐neutralized dicarboxylic acids used, half‐neutralized adipic acid (HNAA) exhibited the best performance. Scanning electron microscopy and transmission electron microscopy studies clearly indicated an improvement in the level of dispersion of the MWCNTs with the addition of the modifier. The good dispersion of the MWCNTs and the resulting improvement in their properties were attributed to the cation–π interactions (the cation of HNAA and the π‐electron clouds of the MWCNTs) between the HNAA and MWCNTs and the chemical bonding of ? COOH groups of HNAA and the epoxy resin. The cation–π interaction and chemical bonding was assessed with Fourier transform infrared spectroscopy and Raman spectroscopy. This approach did not destroy the π–electron clouds of the MWCNTs in contrast to a chemical functionalization strategy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2610–2618, 2013     

Fabrication of high mechanical performance UHMWPE nanocomposites with high-loading multiwalled carbon nanotubes

Using conventional mixing techniques, the mechanical properties of prepared carbon nanotube (CNT)/polymer composites are not impressive enough, because of their aggregation problem at a high loading of CNTs. In this article, high mechanical performance ultrahigh molecular weight polyethylene (UHMWPE) nanocomposites with high loading of multiwalled CNTs were successfully fabricated by a new manufacturing technique. Specifically, the tensile strength and storage modulus at 25 °C of UHMWPE nanocomposites with 32 wt % of nanotubes prepared by the novel technique reaches 107.6 MPa and 6.0 GPa, respectively, about 4.7 times and 5.0 times of that of pure UHMWPE resin, which are also very high experimental results compared with polyethylene nanocomposite prepared by traditional hot-compression techniques. These attractive results suggest that the high-loading CNTs without sacrificing their dispersion and the impregnation quality of polymer-impregnated buckypapers are essential for fabricating CNTs/polymer composites with superior mechanical properties. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48667.     

Influence of preparation methods on the electrical and nanomechanical properties of poly(methyl methacrylate)/multiwalled carbon nanotubes composites

Poly(methyl methacrylate)/multiwalled carbon nanotubes (PMMA/MWCNT) composites were prepared by two different methods: melt mixing and solution casting. For solution casting, two different solvents, toluene and chloroform, were used to prepare PMMA solutions with different concentrations of MWCNT. The dispersion of the CNT in the composite samples was verified by scanning electron microscopy. For the nanocomposites prepared by both methods, the electrical conductivity increased with increasing filler content, showing typical percolation behavior. In addition, an increase of 11 orders of magnitude in the electrical conductivity relative to the matrix conductivity was determined by broadband dielectric spectroscopy and four probe conductivity measurements. A maximum value of σ_DC ～ 1.6 S/cm was found for the highest filler loaded sample (3.67 vol %), which was prepared by solution casting from toluene. Nanoindentation analysis was used to characterize the surface mechanical properties of the composite samples prepared by the different methods. Indentation tests were performed at various penetration depths, and it was revealed that the melt mixing process resulted in stiffer neat PMMA samples compared to the solution casted PMMA samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41721.     

Effect of processing parameters on the surface resistivity of ethylene propylene diene terpolymer/multiwalled carbon nanotube nanocomposites

In this study, ethylene propylene diene terpolymer (EPDM) is melt‐mixed with multiwalled carbon nanotube (MWCNT). To realize full‐scale application of MWCNT to the rubber industries, the effect of melt‐processing parameters on the surface resistivity in the rubber/MWCNT nanocomposites should be well understood. The effect of rotor speed, mixing temperature, and annealing time on the surface resistivity of the EPDM/MWCNT nanocomposites has been investigated. The surface resistivity of EPDM/MWCNT nanocomposites with 3 phr MWCNT increases with increasing the rotor speed and decreasing the mixing temperature. Tensile strength and tensile modulus of EPDM/MWCNT (3 phr) nanocomposites are higher than those of EPDM, respectively. For the nanocomposite with 3 phr MWCNT loadings, surface resistivity increases as the annealing time at room temperature increases. This is the first report that surface resistivity of rubber/MWCNT nanocomposites increases significantly on annealing at room temperature. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40129.     

Thermal and mechanical properties of homogeneous ternary nanocomposites of regioregular poly(3‐hexylthiophene)‐wrapped multiwalled carbon nanotube dispersed in thermoplastic polyurethane: Dynamic‐ and thermomechanical analysis

An interesting correlation between initial loading and nature of wrapping of regioregular poly(3‐hexylthiophene) (rrP3HT) on multiwalled carbon nanotube and their combined effect on dynamic‐ and thermomechanical properties in ternary system (thermoplastic polyurethane as matrix) is highlighted. Wrapping of rrP3HT on carbon nanotube (CNT) makes the hexyl side chains thermally nonequivalent and composites more stable. Dynamic‐ and thermomechanical analysis ascertained the miscibility (single T_g = ?40°C), large mechanical reinforcement, and improved storage modulus of nanocomposites in the presence of CNT compared to its blends. Two breaks at ～ ?100 and ～ ?40°C for TPU‐P3HT composites (PHs) and TPU‐P3HT‐MWCNT composites (PHCs) in the loss modulus vs. temperature plot indicates two different types of transitions in P3HT chains. Dimensional stability by expansion probe technique measures low coefficient of thermal expansion of PHCs compared to its blends. Softening property by penetration probe technique suggests that 2.5 wt % loading of P3HT exhibits lowest degree of penetration compared to other nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

High performance polyurethane composites with isocyanate‐functionalized carbon nanotubes: Improvements in tear strength and scratch hardness

A microwave‐assisted functionalization of carbon nanotubes (CNTs) with isocyanate groups allowed a reduction of functionalization time from 24 h to 30 min with no change in the degree of functionalization or in the nanotube characteristics. Polymer nanocomposites with enhanced mechanical properties were obtained because of the tailored interface by the covalent linkage between the surface‐modified multiwalled‐carbon nanotubes (MWCNTs) and an elastomeric polyurethane (PUE) matrix. The mechanical data revealed that the composite containing 0.25 wt % of MWCNT‐NCO showed an increase of 31% in tear strength and 28% in static toughness. A good adhesion between the matrix and individually dispersed nanotubes was observed in the scanning electron microscopy and transmission electron microscopy images. Nanoindentation and nanoscratch experiments were conducted to investigate the properties on the sub‐surface. An increase by a factor of 3 in the scratch hardness was observed for the composite with 0.50 wt % of MWCNT‐NCO with respect to the neat PUE. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44394.     

Investigation of cure kinetics in epoxy/multiwalled carbon nanotube nanocomposites

With the increased interest in thermoset resin nanocomposites, it is important to understand the effects of the material on nanoscale characteristics. In this study, a curing reaction of an epoxy resin, which contained 0.25, 0.50, or 1.00 wt % of multiwalled carbon nanotubes (MWCNTs), at different heating rates was monitored by differential scanning calorimetry; cure kinetics were also evaluated to establish a relationship between crosslinking (network formation) and mechanical properties. MWCNT concentrations above 0.25 wt % favored crosslinking formation and decreased the activation energy (E_a) in the curing reaction. Examination of the kinetic mechanism suggests that the MWCNT locally restricted the spatial volume and favored the formation of nodular morphology in the resin, especially for high MWCNT concentrations. The MWCNT exhibited some entanglement in the matrix, which hindered a more pronounced effect on the mechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39857.     

Development of hydroxyapatite nanoparticles reinforced chlorinated acrylonitrile butadiene rubber/chlorinated ethylene propylene diene monomer rubber blends

Hydroxyapatite nanoparticles (HA) reinforced polymer blend based on chlorinated nitrile rubber (Cl-NBR) and chlorinated ethylene propylene diene monomer rubber (Cl-EPDM) were prepared. Resulting blend composites were analyzed with regard to their rheometric processing, crystallinity, glass transition temperature (T_g), mechanical properties, oil resistance, AC conductivity, and transport behavior. The decrease in optimum cure time with the addition of HA is more advantageous for the development of products from these blend nanocomposites. The XRD, FTIR, and SEM confirmed the attachment and uniform dispersion of HA nanoparticles in the Cl-NBR/Cl-EPDM blend. The good compatibility between polymer blend and nanoparticles was also deduced by the formation of spherically shaped HA particles in the blend matrix determined by TEM analysis. DSC analysis showed an increase in T_g of the blend with the filler loading. The addition of HA particles to the blend produced a remarkable increase in tensile and tear strength, hardness, AC conductivity, abrasion, and oil resistance. The diffusion of blend composites was decreased with an increase in penetrant size. The diffusion mechanism was found to follow an anomalous trend. Among the blend composites, the sample with 7 phr of HA not only showed good oil and solvent resistance but also a remarkable increase in AC conductivity and mechanical properties.     

The thermal properties of a carbon nanotube‐enriched epoxy: Thermal conductivity,curing, and degradation kinetics

Multiwalled carbon nanotube‐enriched epoxy polymers were prepared by solvent evaporation based on a commercially available epoxy system and functionalized multiwalled carbon nanotubes (COOH–MWCNTs). Three weight ratio configurations (0.05, 0.5, and 1.0 wt %) of COOH–MWCNTs were considered and compared with neat epoxy and ethanol‐treated epoxy to investigate the effects of nano enrichment and processing. Here, the thermal properties of the epoxy polymers, including curing kinetics, thermal conductivity, and degradation kinetics were studied. Introducing the MWCNTs increased the curing activation energy as revealed by differential scanning calorimetry. The final thermal conductivity of the 0.5 and 1.0 wt % MWCNT‐enriched epoxy samples measured by laser flash technique increased by up to 15% compared with the neat material. The activation energy of the degradation process, investigated by thermogravimetric analysis, was found to increase with increasing CNT content, suggesting that the addition of MWCNTs improved the thermal stability of the epoxy polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2722–2733, 2013     

Controlled dispersion of multiwalled carbon nanotubes modified by hyperbranched polylysine

Hyperbranched polymers have been found effective in controlling the dispersibility of carbon nanotubes in aqueous solutions. In this study, hyperbranched polylysine (HBPL) was synthesized using lysine and N,N′‐methylenebisacrylamide as precursors via Michael addition. The HBPL then was used to noncovalently modify multiwalled carbon nanotubes (MWCNTs) to prepare MWCNTs‐HBPL. The obtained MWCNTs‐HBPL composites were characterized using FTIR spectroscopy, Raman spectroscopy, thermogravimetric analysis, and scanning electron microscopy. The results showed that the HBPL was successfully attached to the surface of MWCNTs via noncovalent interactions. The dispersibility of the MWCNTs‐HBPL composites in aqueous solutions was investigated using digital photographs, ultraviolet–visible absorption spectroscopy, and zeta potential measurements. The results demonstrated that both the mass ratio of MWCNT to HBPL and the pH of the solution had a significant impact on the dispersibility of the MWCNTs/HBPL solution, suggesting that HBPL treatment is an effective method of controlling the dispersibility of MWCNTs in aqueous solutions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46249.     

The partial replacement of silica or calcium carbonate by halloysite nanotubes as fillers in ethylene propylene diene monomer composites

The effect of partial replacement of silica or calcium carbonate (CaCO₃) by halloysite nanotubes (HNTs) on the curing behavior, tensile properties, dynamic mechanical properties, and morphological characteristics of ethylene propylene diene monomer (EPDM) composites was studied. Five different compositions of EPDM/Silica/HNT and EPDM/CaCO₃/HNT compounds (i.e. 100/30/0, 100/25/5, 100/15/15, 100/5/25, and 100/0/30 parts per hundred rubber (phr)) were prepared on a two‐roll mill. The results indicated that the replacement of CaCO₃ by HNTs increased the tensile strength, elongation at break (E_b), and tensile modulus of composites from 0 to 30 phr of HNTs whereas for silica, the maximum tensile strength and E_b occurred at 5 phr loading of HNTs with an enhanced stress at 300% elongation (M300). The curing results show that, with replacement of silica or CaCO₃ by HNTs, the cure time (t₉₀) and cure rate (CRI) were decreased and increased, respectively. Scanning electron microscopy investigation confirmed that co‐incorporation of 5 phr of HNTs with silica would improve the dispersion of silica and enhanced the interactions between fillers and EPDM matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of fiber surface grafting by functionalized carbon nanotubes on the interfacial durability during cryogenic testing and conditioning of CFRP composites

Carbon fiber reinforced epoxy (CE) composite is ideal for a cryogenic fuel storage tank in space applications due to its unmatched specific strength and modulus. In this article, inter-laminar shear strength (ILSS) of carbon fiber/epoxy (CE) composite is shown to be considerably improved by engineering the interface with carboxyl functionalized multi-walled carbon nanotube (FCNT) using electrophoretic deposition technique. FCNT deposited fibers from different bath concentrations (0.3, 0.5, and 1.0 g/L) were used to fabricate the laminates, which were then tested at room (30°C) and in-situ liquid nitrogen (LN) (−196°C) temperature as well as conditioning for different time durations (0.25, 0.5, 1, 6, and 12 h) followed by immediate RT testing to study the applicability of these engineered materials at the cryogenic environment. A maximum increment in ILSS was noticed at bath concentration of 0.5 g/L, which was ~21% and ~ 17% higher than neat composite at 30°C and − 196°C, respectively. Short-term LN conditioning was found to be detrimental due to developed cryogenic shock, which was further found to be compensated by cryogenic interfacial clamping upon long-term exposure.     

Effect of tungsten disulfide nanotubes on the thermomechanical properties of polypropylene‐graft‐maleic anhydride nanocomposites

In this work, the influence of tungsten disulfide nanotubes (INT‐WS₂) on the mechanical, thermal, structural, and morphological characteristics of Polypropylene‐graft‐maleic anhydride (PPGMA) nanocomposites is investigated. The addition of 5% INT‐WS₂ increases the Young's Modulus by 28.5% and the storage modulus by 196.5% (in the rubbery state). Furthermore, the nanocomposites' thermal stability increases (up to 10 °C) with the addition of INT‐WS₂. Transmission electron microscopy observations of the nanocomposites revealed that nanotubes' length is significantly reduced during processing and that nanotubes are well‐dispersed inside the PPGMA matrix. DSC results indicated that INT‐WS₂ serve as nucleating agents in PPGMA. Moreover, AFM observations (coupled with DSC results) suggested the formation of fibrillar crystallites in the nanocomposites. This interfacial crystalline structure seems to interpose between the PPGMA and INT‐WS₂. Thus, it plays a crucial role in the load transfer from the amorphous part of the polymer to the rather stiff INT‐WS₂. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43887.     

Enhancement of physical and mechanical properties of polyamide 66 fibers using polysiloxane-functionalized multi-walled carbon nanotubes

A polyamide 66/3-aminopropyl-terminated poly(dimethylsiloxane) (PA66/APDMS)-carboxylate multiwalled carbon nanotubes (CMWNTs) nanocomposite (PA66/APDMS-CMWNTs) was synthesized using a one-pot method, and the product was melt-spun into fibers. The glass transition temperature (T_g) of the PA66/APDMS-CMWNTs nanocomposite fiber is 68.0°C, which is 22% higher than that of the pure PA66 fiber. This result indicates that there is a strong interfacial interaction between APDMS-CMWNTs and the PA66. Furthermore, the crystallinity of PA66/APDMS-CMWNTs nanocomposite fiber reaches a maximum due to the addition of APDMS-CMWNTs. Additionally, the tensile strength and Young's modulus of PA66/APDMS-CMWNTs nanocomposite fiber are 167% and 631% higher, respectively, than that of the pure PA66 fiber. The strengthening mechanism was discussed using force balance-based expression, which demonstrates that the stress on the PA66 is more efficiently transferred to the APDMS-CMWNTs. These results argue that using APDMS-CMWNTs as a filler can enhance the physical-mechanical properties of PA66 with an elevated degree never being reported.     

Synergistic effects of carbon nanotubes and carbon black on the fracture and fatigue resistance of natural rubber composites

The quasi‐static fracture and dynamic fatigue behaviors of natural rubber composites reinforced with hybrid carbon nanotube bundles (CNTBs) and carbon black (CB) at similar hardness values were investigated on the basis of fracture mechanical methods. Mechanical measurement and J‐integral tests were carried out to characterize the quasi‐static fracture resistance. Dynamic fatigue tests were performed under cyclic constant strain conditions with single‐edged notched test pieces. The results indicate that synergistic effects between CNTBs and CB on the mechanical properties, fracture, and fatigue resistance were obtained. The composite reinforced with 3‐phr CNTBs displayed the strongest fatigue resistance. The synergistic mechanisms and dominating factors of quasi‐static and dynamic failure, such as the dispersion state of nanotubes, hybrid filler network structure, strain‐induced crystallization, tearing energy input, and viscoelastic hysteresis loss, were examined. The weakest fatigue resistance of the composite filled with 5‐phr CNTBs was ascribed to its strikingly high hysteresis, which resulted in marked heat generation under dynamic fatigue conditions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42075.     

Thermal conductivity and dielectric properties of polypropylene‐based hybrid compounds containing multiwalled carbon nanotubes

In this article, we explore the possibility to develop composites with improved thermal conductivity and electrically insulating properties. The strategy adopted is to combine a thermal and electrical conductive filler (multiwalled carbon nanotubes) with secondary dielectric (but thermally conductive) fillers. To this end, particles with different compositions, sizes, and shape were used as secondary fillers and the composites, prepared by melt compounding, are characterized in terms of thermal and dielectric properties. Results show that, in ternary formulations, an increase of thermal conductivity is always verified for all kind of secondary particles. Analogously, increments in electrical conductivity are observed for ternary compounds containing larger size secondary fillers, while a significant reduction is achieved with the addition of smaller ones. This behavior is explained in terms of mutual distribution of the fillers and is consistent with direct (scanning electron microscopy) and indirect (rheological) observations. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46470.     

Thermosetting polyurethane‐multiwalled carbon nanotube composites: Thermomechanical properties and nanoindentation

In this study, composites based on a thermoset polyurethane elastomer (PU) and multiwalled carbon nanotubes (MWCNT) in the case of a PU of high elastic modulus (>200 MPa) are analyzed for the first time. As‐grown and modified nanotubes with 4 wt % of oxygenated functions (MWCNT‐ox) were employed to compare their effect on composite properties and maxima mechanical properties (elastic modulus and tensile strength) were reached at 0.5 wt % of MWCNT‐ox. Furthermore, by examining the morphology using optical and electron microscopies better dispersion and interaction of the nanotube‐matrix was observed for this material. DMTA data supports the observation of an increase in the glass transition temperature of ～20°C in the nanocomposites compared with the thermoset PU, which is an important result because it shows extended reliability in extreme environments. Finally, nanoindentation tests allowed a comparison with the conventional mechanical tests by measuring the elastic modulus and hardness at the subsurface of PU and the nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41207.     

Cryogenic mechanical properties and failure mechanism of epoxy nanocomposites modified by multiwalled carbon nanotubes with tunable oxygen-containing groups on surface

The surface chemistry and structure of multiwalled carbon nanotube (MWCNT) plays an important role in MWCNT/epoxy nanocomposites. In this contribution, oxidized multiwalled carbon nanotube (OMCNT) with tunable oxygen-containing groups is prepared by finely controlling oxidation time and centrifugal speeds. Effects of oxygen-containing group content on mechanical properties of the OMCNT/E51 epoxy nanocomposites at 77 K are investigated in detail. It reveals that oxygen-containing groups on the OMCNT surface contribute to significant increases in tensile strength and impact resistance of the OMCNT/E51 epoxy nanocomposites compared with those of the pristine MWCNT/E51 nanocomposites. A positive correlation between the oxygen-containing group content and interfacial properties of OMCNT and epoxy matrix is demonstrated by thermogravimetric analysis and fracture morphology, and homogeneous dispersion of the OMCNT in epoxy matrix is obtained with the increase of oxygen-containing groups on surface of the OMCNT. However, proper content of oxygen-containing groups is essential to OMCNT/E51 nanocomposites because excessive oxidation tends to make sever structural defects on the OMCNT and has a side effect on cryogenic mechanical properties of OMCNT/E51 nanocomposites.