Thermosetting polyurethane multiwalled carbon nanotube composites

Thermosetting polyurethane (PU) multi‐walled carbon nanotube (MWCNT) nanocomposites at loadings up to 1 wt % were prepared via an addition polymerization reaction. The morphology of the nanocomposites and degree of dispersion of the MWCNTs was studied using a combination of scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and wide angle X‐ray diffraction (WAXD), and revealed the nanotubes to be highly dispersed in the PU matrix. Addition of just 0.1 wt % MWCNTs resulted in significant enhancements in stiffness, strength and toughness. Increases in Young's modulus, % elongation at break and ultimate tensile strength of 561, 302 and 397% were measured for the nanocomposites compared to the unfilled PU. The effect of the MWCNTs on the modulus of the PU was evaluated using the Rule of Mixtures, Krenchel and Halpin‐Tsai models. Only the Halpin‐Tsai model applied to high aspect ratio nanotubes was in good agreement with the modulus values determined experimentally. Strong interfacial shear stress was found between PU chains and nanotubes, up to 439 MPa, calculated using a modified Kelly‐Tyson model. Evidence for strong interfacial interactions was obtained from the Raman spectra of both the precursor materials and nanocomposites. When the MWCNTs were added to the isophorone diisocyanate an up‐shift of 14 cm^?1 and on average 40 cm^?1 was obtained for the position of the carbon‐hydrogen (C? H) out‐of plane bending (766 cm^?1) and isocyanate symmetric stretch (1420 cm^?1) modes respectively. Moreover, an up‐shift of 24 cm^?1 was recorded for the nanotube tangential mode (G‐band) for the 1.0 wt % nanocomposite because of the compressive forces of the PU matrix acting on the MWCNTs. The dynamic mechanical (DMA) properties of the PU thermoset and the nanocomposites were measured as a function of temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanical and thermal transmission properties of carbon nanofiber‐dispersed carbon/phenolic multiscale composites

The present article reports the development and characterization of carbon nanofiber (CNF)‐incorporated carbon/phenolic multiscale composites. Vapor‐grown CNFs were dispersed homogeneously in to phenolic resin using an effective dispersion route, and carbon fabrics were subsequently impregnated with the CNF‐dispersed resin to develop carbon fiber/CNF/phenolic resin multiscale composites. Mechanical and thermal transmission properties of multiscale composites were characterized. Elastic modulus and thermal conductivity of neat carbon/phenolic and multiscale composites were predicted and compared with the experimental results. It was observed that incorporation of only 1.5 wt % CNF resulted in 10% improvement in Young's modulus, 12% increase in tensile strength, and 36% increase in thermal conductivity of carbon/phenolic composites. Fracture surface of composite samples revealed the formation of stronger fiber/matrix interface in case of multiscale composites than neat carbon/phenolic composites. Enhancement of above properties through CNF addition has been explained, and the difference between the predicted values and experimental results has been discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of the nanotube aspect ratio and surface functionalization on the morphology and properties of multiwalled carbon nanotube polyamide‐based fibers

In this study, the effect of the carbon nanotube (CNT) aspect ratio and surface functionalization on the mechanical behavior and morphological changes of polyamide (PA)‐based fibers was investigated. Composites were prepared by the melt blending of CNTs with PA, and at a later time, the fibers were prepared by melt spinning and cold drawing. A reinforcement effect was noticed for all of the CNTs samples, and the increase in the mechanical properties and dimensional stability was more pronounced for highly oriented filaments. When the elongational flow was increased, the orientation of CNTs along the fiber direction was observed, but the nanotube alignment was much more difficult for CNTs with ultrathin outer diameters because of nanotube waviness and folding. Moreover, the presence of functional groups on the CNT surface hindered their orientation along the fiber direction because some interaction between the functional groups could occur. The morphological variations of the oriented, anisotropic fibers, as studied with transmission electron microscopy, scanning electron microscopy, small‐angle X‐ray scattering, and differential scanning calorimetry analysis, were correlated with changes in the mechanical behavior. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrical,mechanical, and crystallization properties of ethylene‐tetrafluoroethylene copolymer/multiwalled carbon nanotube composites

Multiwalled carbon nanotubes (MWCNTs) were melt‐mixed in a conical twin‐screw extruder with a random copolymer of ethylene and tetrafluoroethylene. Surprisingly, the electrical percolation threshold of the resultant composites was quite low; ～0.9 wt %. In fact, this value is as low or lower than the value for most MWCNT/semicrystalline polymer composites made with roughly equivalent aspect ratio tubes mixed in a similar manner, for example, melt mixing. This low percolation threshold, suggestive of good dispersion, occurred even though the polymer surface energy is quite low which should make tubes more difficult to disperse. Dynamic mechanical measurements confirmed the rather low percolation threshold. The effect of nanotubes on crystallization kinetics was quite small; suggesting perhaps that a lack of nucleation which in turn reduces/eliminates an insulating crystalline polymer layer around the nanotubes might explain the low percolation threshold. Finally, the modulus increased with the addition of nanotubes and the strain at break decreased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41052.     

A liquid‐like multiwalled carbon nanotube derivative and its epoxy nanocomposites

Multiwall carbon nanotubes (MWCNTs) with liquid‐like behavior at room temperature were prepared with sulfonic acid terminated organosilanes as corona and tertiary amine as canopy. The liquid‐like MWCNT derivative had low viscosity at room temperature (3.89 Pa s at 20°C) and exhibited non‐Newtonian shear‐thinning behavior. The weight fraction of MWCNT in the derivative was 16.72%. The MWCNT derivative showed very good dispersion in organic solvents, such as ethanol and acetone. The liquid‐like MWCNT derivative was incorporated into epoxy matrix to investigate the mechanical performance of the nanocomposites and the distribution of MWCNTs in the matrix. When the liquid‐like MWCNT derivative content was up to 1 wt %, the flexural strength and impact toughness of composites were 12.1 and 124% higher than the pure epoxy matrix, respectively. Transmission electron microscope (TEM) confirmed the very good dispersion of the liquid‐like MWCNT derivative in epoxy matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2217–2224, 2013     

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.     

Thermal and electrical conductivity of melt mixed polycarbonate hybrid composites co‐filled with multi‐walled carbon nanotubes and graphene nanoplatelets

In this work, we present thermoplastic nanocomposites of polycarbonate (PC) matrix with hybrid nanofillers system formed by a melt‐mixing approach. Various concentrations of multi‐walled carbon nanotubes (MWCNT) and graphene nanoplatelets (GnP) were mixed in to PC and the melt was homogenized. The nanocomposites were compression molded and characterized by different techniques. Torque dependence on the nanofiller composition increased with the presence of carbon nanotubes. The synergy of carbon nanotubes and GnP showed exponential increase of thermal conductivity, which was compared to logarithmic increase for nanocomposite with no MWCNT. Decrease of Shore A hardness at elevated loads present for all investigated nanocomposites was correlated with the expected low homogeneity caused by a low shear during melt‐mixing. Mathematical model was used to calculate elastic modulus from Shore A tests results. Vicat softening temperature (VST) showed opposite pattern for hybrid nanocomposites and for PC‐MWCNT increasing in the latter case. Electrical conductivity boost was explained by the collective effect of high nanofiller loads and synergy of MWCNT and GnP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42536.     

Mechanical,rheological, and electrical properties of multiwalled carbon nanotube reinforced ASA/Na‐ionomer blend

Varying amounts of multiwalled carbon nanotubes (MWCNTs) was melt‐extruded with the acrylonitrile‐styrene‐acrylate (ASA)/Na‐ionomer blend, and mechanical, rheological, and electrical properties were studied Optical micrographs show good dispersion level at low MWCNT content and network formation at higher nanotubes percentage. DC conductivity model data shows percolation threshold reached at 1% MWCNT content and after percolation, two‐dimensional network structure was formed. The “peak and valley” type surface topology of matrix may be responsible for low percolation threshold limit. The polymer/nanotubes interactions at low MWCNT content increased the mechanical strengths, which were reduced by the network structure and agglomerates of nanotubes at higher nanotubes content. The MWCNTs interacted differently with the architecturally complex polymer chains and controlled chain dynamics accordingly. The Carreau‐Yasuda model was found fit to viscosity data and the model parameters data suggest the zero shear viscosity is function of MWCNTs content but the infinite shear viscosity is independent of nanoparticles content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42516.     

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.     

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     

Influence of processing condition and carbon nanotube on mechanical properties of injection molded multi‐walled carbon nanotube/poly(methyl methacrylate) nanocomposites

In this work, multi‐walled carbon nanotubes (MWCNT) and poly(methyl methacrylate) (PMMA) pellets were compounded via corotating twin‐screw extruder. The produced MWCNT/PMMA nanocomposite pellets were injection molded. The effect of MWCNT concentration, injection melt temperature and holding pressure on mechanical properties of the nanocomposites were investigated. To examine the mechanical properties of the MWCNT/PMMA nanocomposites, tensile test, charpy impact test, and Rockwell hardness are considered as the outputs. Design of experiments (DoE) is done by full factorial method. The morphology of the nanocomposites was performed using scanning electron microscopy (SEM). The results revealed when MWCNT concentration are increased from 0 to 1.5 wt %, tensile strength and elongation at break were reduced about 30 and 40%, respectively, but a slight increase in hardness was observed. In addition, highest impact strength belongs to the nanocomposite with 1 wt % MWCNT. This study also shows that processing condition significantly influence on mechanical behavior of the injection molded nanocomposite. In maximum holding pressure (100 bar), the nanocomposites show highest tensile strength, elongation, impact strength and hardness. According to findings, melt temperature has a trifle effect on elongation, but it has a remarkable influence on tensile strength. In the case of impact strength, higher melt temperature is favorable. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43738.     

Mechanical and fracture properties of halloysite nanotube reinforced vinyl‐ester nanocomposites

The mechanical and fracture properties of vinyl‐ester composites reinforced with halloysite nanotubes have been investigated. Enhancements in toughness are attributed to crack bridging, deflection, and localized plastic deformation, while strength improvements can be attributed to the large aspect ratio of fillers, favorable interfacial adhesion and dispersion, and inter‐tubular interaction. Comparisons of experimental data on elastic modulus and mathematical models for predicting particulate polymer composites have verified the models of Paul and Guth. The aspect ratio of fillers and the degree of interfacial adhesion are crucial factors in the prediction of elastic modulus in these polymer nanocomposites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1716–1725, 2013     

Electrical conductivity and tensile properties of block‐copolymer‐wrapped single‐walled carbon nanotube/poly(methyl methacrylate) composites

Poly(methyl methacrylate) (PMMA) composites containing raw or purified single‐walled carbon nanotubes (SWCNTs) are prepared by in situ polymerization and solution processing. The SWCNTs are purified by centrifugation in a Pluronic surfactant, which consists of polyethyleneoxide and polypropyleneoxide blocks. Both the effects of SWCNT purity and non‐covalent functionalization with Pluronic are evaluated. Electrical conductivity of PMMA increases by 7 orders of magnitude upon the integration of raw or purified SWCNTs. The best electrical properties are measured for composites made of purified SWCNTs and prepared by in situ polymerization. Strains at fracture of the SWCNT/PMMA composites are nearly identical to those of the neat matrix. A certain decrease in the work to fracture is measured, particularly for composites containing purified SWCNTs (?31.6%). Fractography and Raman maps indicate that SWCNT dispersion in the PMMA matrix improves upon the direct addition of Pluronic, while dispersion becomes more difficult in the case of purified SWCNTs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41547.     

High electrical conductivity of nylon 6 composites obtained with hybrid multiwalled carbon nanotube/carbon fiber fillers

The synergetic effect of multiwalled carbon nanotubes (MWNTs) and carbon fibers (CFs) in enhancing the electrical conductivity of nylon 6 (PA6) composites was investigated. To improve the compatibility between the fillers and the PA6 resin, we grafted γ‐aminopropyltriethoxy silane (KH‐550) onto the MWNTs and CFs after carboxyl groups were generated on their surface by chemical oxidation with nitric acid. Fourier transform infrared spectroscopy and thermogravimetric analysis proved that the KH‐550 molecules were successfully grafted onto the surface of the MWNTs and CFs. Scanning electron microscopy and optical microscopy showed that the obtained modified fillers reduced the aggregation of fillers and resulted in better dispersion and interfacial compatibility. We found that the electrical percolation threshold of the MWNT/PA6 and CF/PA6 composites occurred when the volume fraction of the fillers were 4 and 5%, respectively. The MWNT/CF hybrid‐filler system exhibited a remarkable synergetic effect on the electrically conductive networks. The MWNT/7% CF hybrid‐filler system appeared to show a second percolation when the MWNT volume fraction was above 4% and a volume resistivity reduction of two orders of magnitude compared with the MWNT/PA6 system. The mechanical properties of different types of PA6 composites with variation in the filler volume content were also studied. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40923.     

Effect of glass fiber on the electrical resistivities of polyoxymethylene/maleic anhydride‐grafted polyethylene/multiwalled carbon nanotube composites

The effect of glass fiber (GF) on the electrical resistivities of polyoxymethylene (POM)/maleic anhydride‐grafted polyethylene (MAPE)/multiwalled carbon nanotube (MWCNT) composites is investigated. The POM/MAPE/MWCNT composites at a MWCNT loading of 0.75% are nonconductive because most of MWCNTs are isolated in the MAPE islands, and their electrical resistivities decrease significantly after the addition of GF because of the formation of MAPE‐coated GF structure, which facilitates the formation of conductive paths and was confirmed by field emission scanning electron microscopy (FESEM). The formation of MAPE‐coated GF structure is attributed to the interaction between GF and MAPE during melt compounding, as contrasted by the uncoated GF using high‐density polyethylene (HDPE) instead of MAPE. Nonconductive POM/5–20% MAPE/0.75% MWCNT composites become conductive upon the addition of 20% GF. This preparation method for conductive materials can be generalized to POM/5–20% maleic anhydride‐grafted polypropylene (MAPP)/0.75% MWCNT composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41794.     

Electrical conductivity and mechanical performance of multiwalled CNT‐filled polyvinyl chloride composites subjected to tensile load

This article reports a study on the strain‐sensitive conductivity (tensoresistivity) and mechanical properties of polyvinyl chloride/multiwalled carbon nanotube (PVC/MWCNT) composites subjected to tensile loading at different strain rates for potential use in sensor‐enabled geosynthetics and other applications involving electrically conductive polymer composites. Results indicate that adding 0.5 wt % MWCNT to the composite results in 57% reduction in its ultimate (failure) strain and a fivefold increase in its tensile modulus while leaving its ultimate strength almost unchanged. Laser scanning confocal microscopy is used to investigate the microscopic failure mechanism of the composite and how it contributes to the strain‐sensitive conductivity of the composites. It is observed that tensile fractures are initiated from inside the largest bundles between 18% and 36% strain and continue through further fractal‐like fracturing in smaller bundles. Gauge factors (e.g., 3.17) comparable to or exceeding those of typical strain gauges are obtained for the composite, indicating its strong potential for structural performance monitoring and damage detection applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43665.     

Preparation and properties of carbon nanotube/binary‐polymer composites with a double‐segregated structure

A carbon nanotube (CNT)/poly(methyl methacrylate) (PMMA)/ultrahigh molecular weight polyethylene (UHMWPE) composite containing a double‐segregated structure was formalized by means of a facile mechanical mixing technology. In the composite, the CNTs were decorated on the surfaces of PMMA granules, and the CNTs decorated granules formed the continuous segregated conducting layers at the interfaces between UHMWPE particles. Morphology observations confirmed the formation of a specific double‐segregated CNT conductive network, resulting in an ultralow percolation threshold of ～0.2 wt %. The double‐segregated composite containing only 0.8 wt % CNT loading exhibited a high electrical conductivity of ～0.2 S m^?1 and efficient electromagnetic shielding effectiveness of ～19.6 dB, respectively. The thermal conductivity, temperature‐resistivity behaviors, and mechanical properties of the double‐segregated composites were also studied. This work provided a novel conductive network structure to attain a high‐performance conducting polymer composite at low filler loadings. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39789.     

Graphene nanoplatelet‐polyetherimide composites: Revealed morphology and relation to properties

In this research, a novel sample preparation technique was applied to reveal the morphology exfoliated graphene nanoplatelets [GNP, ～10 nm thick and ～5 µm in diameter)] and Polyetherimide (PEId) nanocomposite and study the relationship between processing and properties. The morphology of nanoscale fillers used to be hard to capture through conventional sample preparation. The polish‐plasma etching approach presented in this article successfully created contrast between filler and matrix. As a result, distribution and orientation of the fillers were obtained to study the effect of injection molding, compression molding and annealing. It was found that the orientation was significantly different depending on processing routes. The information obtained from morphology study also led to the modification of Tandon–Weng model, resulting in improved prediction of elastic modulus of the composite. The SEM images also clearly revealed change of filler orientation after annealing. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4081–4089, 2013     

Influence of rubber content on mechanical,thermal, and morphological behavior of natural rubber toughened poly(lactic acid)–multiwalled carbon nanotube nanocomposites

The effects of natural rubber (NR) on the mechanical, thermal, and morphological properties of multiwalled carbon nanotube (CNT) reinforced poly(lactic acid) (PLA) nanocomposites prepared by melt blending were investigated. A PLA/NR blend and PLA/CNT nanocomposites were also produced for comparison. The tensile strength and Young's modulus of PLA/CNT nanocomposites improved significantly, whereas the impact strength decreased compared to neat PLA. The incorporation of NR into PLA/CNT significantly improved the impact strength and elongation at break of the nanocomposites, which showed approximately 200% and 850% increases at 20 wt % NR, respectively. However, the tensile strength and Young's modulus of PLA/NR/CNT nanocomposites decreased compared to PLA/CNT nanocomposites. The morphology analysis showed the homogeneous dispersion of NR particles in PLA/NR/CNT nanocomposites, while CNTs preferentially reside in the NR phase rather than the PLA matrix. In addition, the incorporation of NR into PLA/CNT lowered the thermal stability and glass‐transition temperature of the nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44344.     

Carbon nanotubes‐filled thermoplastic polyurethane–urea and carboxylated acrylonitrile butadiene rubber blend nanocomposites

This article reports the preparation and characterization of multiwalled carbon nanotubes (MWCNTs)‐filled thermoplastic polyurethane–urea (TPUU) and carboxylated acrylonitrile butadiene rubber (XNBR) blend nanocomposites. The dispersion of the MWCNTs was carried out using a laboratory two roll mill. Three different loadings, that is, 1, 3, and 5 wt % of the MWCNTs were used. The electron microscopy image analysis proves that the MWCNTs are evenly dispersed along the shear flow direction. Through incorporation of the nanotubes in the blend, the tensile modulus was increased from 9.90 ± 0.5 to 45.30 ± 0.3 MPa, and the tensile strength at break was increased from 25.4 ± 2.5 to 33.0 ± 1.5 MPa. The wide angle X‐ray scattering result showed that the TPUU:XNBR blends were arranged in layered structures. These structures are formed through chemical reactions of ? NH group from urethane and urea with the carboxylic group on XNBR. Furthermore, even at a very low loading, the high degree of nanotubes dispersion results in a significant increase in the electrical percolation threshold. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40341.