Toughening of cycloaliphatic epoxy resin by multiwalled carbon nanotubes

The toughness of cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexane carboxylate (ERL‐4221) has been improved by using multiwalled carbon nanotubes (MWCNTs) treated by mixed acids. The MWCNT/ERL‐4221 composites were characterized by Raman spectroscopy and their mechanical properties were investigated. A significant increase in the tensile strength of the composite from 31.9 to 55.9 MPa was obtained by adding only 0.05 wt % of MWCNTs. And a loading of 0.5 wt % MWCNTs resulted in an optimum tensile strength and cracking energy, 62.0 MPa and 490 N cm, respectively. Investigation on the morphology of fracture surface of the composites by field emission scanning electron microscopy demonstrated the crack pinning‐front bowing and bridging mechanisms of toughening. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fabrication of polystyrene/multiwalled carbon nanotube composite films synthesized by in situ microemulsion polymerization

A microemulsion polymerization method was used to achieve better compatibility between polystyrene (PS)/multiwalled carbon nanotubes (MWCNTs) nanocomposites and the host PS matrix to form films with excellent electrical and thermal properties. The films were prepared by embedding the PS/MWCNTs nanocomposite into the PS matrix. The MWCNTs were functionalized with PS nanoparticles to avoid the phase separation problem between the filler and host matrix and to enhance the good dispersibility of MWCNTs in the PS host matrix. The confirmation of the synthesis was analyzed by Fourier transform infrared spectroscopy, nuclear magnetic resonance, and Raman spectroscopy. The variation effect of the PS‐linking density on the MWCNT was revealed by scanning electron microscopy and transmission electron microscopy. An enhancement of the thermal and mechanical properties was revealed by thermal gravimetric analysis, differential scanning colorimetric analysis, and dynamic mechanical analysis. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Preparation and characterization of multi‐walled carbon nanotube/poly(ethylene terephthalate) nanoweb

Multi‐walled carbon nanotube (MWCNT)/Poly(ethylene terephthalate) (PET) nanowebs were obtained by electrospinning. For uniform dispersion of MWCNTs in PET solution, MWCNTs were functionalized by acid treatment. Introduction of carboxyl groups onto the surface of MWCNTs was examined by Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD) analysis. MWCNTs were added into 22 wt % PET solution in the ratio of 1, 2, 3 wt % to PET. The morphology of MWCNT/PET nanoweb was observed using field emission‐scanning electron microscopy (FE‐SEM) and transmission electron microscopy (TEM). The nanofiber diameter decreased with increasing MWCNT concentration. The distribution of the nanofiber diameters showed a bi‐modal shape when MWCNTs were added. Thermal and tensile properties of electrospun MWCNT/PET nanowebs were examined using a differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA), dynamic mechanical analyzer (DMA) and etc. Tensile strength, tensile modulus, thermal stability, and the degree of crystallinity increased with increasing MWCNT concentration. In contrast, elongation at break and cold crystallization temperature showed a contrary tendency. Electric conductivities of the MWCNT/PET nanowebs were in the electrostatic dissipation range. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Functionalization of multi-walled carbon nanotubes with non-reactive polymers through an ozone-mediated process for the preparation of a wide range of high performance polymer/carbon nanotube composites

Polymer chains are chemically bonded to multi-walled carbon nanotubes (MWCNTs) through an ozone-mediated process. Four polymers, poly(vinylidene fluoride) (PVDF), polysulfone (PSF), poly(2,6-dimethylphenylene oxide), and poly(phthalazinone ether ketone) are used to demonstrate this MWCNT functionalization. MWCNT-polymer hybrids are characterized by Fourier transform infrared spectroscopy, Raman spectrometry, X-ray photoelectron spectrometry, and high-resolution transmission electron microscopy. This approach provides a general method of preparation of matrix-polymer-modified MWCNTs to be used in the preparation of polymer/MWCNT composites. Compared to pristine MWCNTs and PSF-modified MWCNTs, PVDF-modified MWCNTs are more efficient additives to enhance the mechanical strength and electrical conductivity of PVDF. Therefore, matrix-polymer-modified MWCNTs are relatively attractive in the preparation of high performance polymer/MWCNT composites.     

Preparation and properties of polyurethane/multiwalled carbon nanotube nanocomposites by a spray drying process

A spray drying approach has been used to prepare polyurethane/multiwalled carbon nanotube (PU/MWCNT) composites. By using this method, the MWCNTs can be dispersed homogeneously in the PU matrix in an attempt to improve the mechanical properties of the nanocomposites. The morphology of the resulting PU/MWCNT composites was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SEM and TEM observations illustrate that the MWCNTs are dispersed finely and uniformly in the PU matrix. X‐ray diffraction results indicate that the microphase separation structure of the PU is slightly affected by the presence of the MWCNTs. The mechanical properties such as tensile strength, tensile modulus, elongation at break, and hardness of the nanocomposites were studied. The electrical and the thermal conductivity of the nanocomposites were also evaluated. The results show that both the electrical and the thermal conductivity increase with the increase of MWCNT loading. In addition, the percolation threshold value of the PU composites is significantly reduced to about 5 wt % because of the high aspect ratio of carbon nanotubes and exclusive effect of latex particles of PU emulsion in dispersion. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of water‐soluble polypyrrole/multi‐walled carbon nanotube composites

Water‐soluble polypyrrole (PPy)/multi‐walled carbon nanotube (MWCNT) composites were prepared by mixing chemically modified MWCNTs carrying carboxylic groups (c‐MWCNTs) and sulfonated PPy (SPPy) aqueous colloids in solution. Fourier transform infrared spectroscopy, Raman spectroscopy, X‐ray photoelectron spectroscopy, X‐ray diffraction, field‐emission scanning electron microscopy and high‐resolution transmission electron microscopy were used to characterize the structure and morphology of the resulting composites. Raman and X‐ray photoelectron spectra demonstrate the presence of electrostatic interactions between the radical species of the SPPy and the carboxylic acid species of the c‐MWCNTs. The addition of c‐MWCNTs into SPPy efficiently enhances its thermal stability and electrical conductivity. Owing to the doping effect and one‐dimensional linear structure of the c‐MWCNTs, the conductivity of SPPy/c‐MWCNT composites at room temperature is increased by two orders of magnitude by the introduction of 5 wt% c‐MWCNTs into the SPPy matrix. Copyright © 2010 Society of Chemical Industry     

Improvement in properties of multiwalled carbon nanotube/polypropylene nanocomposites through homogeneous dispersion with the aid of surfactants

The effects of different surfactants on the properties of multiwalled carbon nanotubes/polypropylene (MWCNT/PP) nanocomposites prepared by a melt mixing method have been investigated. Sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (NaDDBS) were used as a means of noncovalent functionalization of MWCNTs to help them to be dispersed uniformly into the PP matrix. The effects of these surfactant‐treated MWCNTs on morphological, rheological, thermal, crystalline, mechanical, and electrical properties of MWCNT/PP composites were studied using field emission scanning electron microscopy, optical microscopy, rheometry, tensile, and electrical conductivity tests. It was found that the surfactant‐treatment and micromixing resulted in a great improvement in the state of dispersion of MWCNTs in the polymer matrix, leading to a significant enhancement of Young's modulus and tensile strength of the composites. For example, with the addition of only 2 wt % of SDS‐treated and NaDDBS‐treated MWCNTs, the Young's modulus of PP increased by 61.1 and 86.1%, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Aminofunctionalization effect on the microtribological behavior of carbon nanotube/bismaleimide nanocomposites

Original multiwalled carbon nanotubes (O‐MWCNTs) and aminofunctionalized ethylenediamine‐treated multiwalled carbon nanotubes (MWCNTs‐EDA) were mixed with bismaleimide (BMI) resin to prepare O‐MWCNT/BMI and MWCNT‐EDA/BMI composites, respectively. Raman spectroscopy, thermogravimetric analysis, and infrared spectroscopy were used to investigate the influence of aminofunctionalization on the multiwalled carbon nanotube (MWCNT) framework. Dynamic mechanical analysis, scanning electron microscopy images of the fractured surface, and field emission scanning electron microscopy of the worn surface were used to determine the possible friction and wear mechanisms of the system. The MWCNT‐EDA/BMI composite exhibited a higher friction coefficient value and a lower wear loss rate value than the O‐MWCNT/BMI composite, which was attributed to the larger number of defects caused by the aminofunctionalization of the MWCNTs, the stronger interfacial adhesion formed between the MWCNTs‐EDA and the BMI resin, and the better dispersive state of the MWCNTs‐EDA in the BMI matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesizing multi‐walled carbon nanotube‐polymethyl methacrylate conductive composites and poly(lactic acid) based composites

Multi‐walled carbon nanotube was modified with polymethyl methacrylate (MWCNT‐PMMA) by in situ solution radical polymerization in the presence of 2,2′‐Azobis (isobutyronitrile) as an initiator. The products with different addition of methyl methacrylate (MMA) were pressed into slices to prepare specimens for electrical conductivity testing. It was found that the MWCNT‐PMMA nanocomposites demonstrate excellent electrical conductivity. To investigate the microsphere morphology and the colloidal surfactant of MWCNTs in MWCNT‐PMMA composites, samples were submitted to scanning electron microscopy and transmission electron microscopy. The thermogravimetric analysis of the prepared composites confirmed that MWCNTs as a thermal stabilizer for PMMA, which could have a wide range of potential applications, such as in catalysts, sensors, environmental remediation, and energy storage. Two series of poly(lactic acid) (PLA) based biocomposites with different MMA additions and MWCNT‐PMMA composites contents were prepared with twin‐screw extruding and injection molding. The results show the mechanical properties changed a little with the MMA and MWCNT‐PMMA composites contents increasing, which suggested the well compatibility between MWCNT‐PMMA composites and PLA. POLYM. COMPOS., 37:503–511, 2016. © 2014 Society of Plastics Engineers     

Characterization of conductive multiwall carbon nanotube/polystyrene composites prepared by latex technology

Conductive multiwall carbon nanotube/polystyrene (MWCNT/PS) composites are prepared based on latex technology. MWCNTs are first dispersed in aqueous solution of sodium dodecyl sulfate (SDS) driven by sonication and then mixed with different amounts of PS latex. From these mixtures MWCNT/PS composites were prepared by freeze-drying and compression molding. The dispersion of MWCNTs in aqueous SDS solution and in the PS matrix is monitored by UV–vis, transmission electron microscopy, electron tomography and scanning electron microscopy. When applying adequate preparation conditions, MWCNTs are well dispersed and homogeneously incorporated in the PS matrix. The percolation threshold for conduction is about 1.5 wt% of MWCNTs in the composites, and a maximum conductivity of about 1 S m⁻¹ can be achieved. The approach presented can be adapted to other MWCNT/polymer latex systems.     

The role of a biobased epoxy monomer in the preparation of diglycidyl ether of bisphenol A/MWCNT composites

A biobased epoxy monomer (GA‐II) derived from gallic acid for multiwalls carbon nanotubes’ (MWCNTs) dispersion improvement is reported in this article. The aromatic group in its molecular structure made it to be absorbed onto the surface of MWCNTs via π‐π interactions and the GA‐II anchored MWCNT could be homogeneously dispersed in DGEBA matrix via sonication. That was proved by Raman and UV spectroscopy as well as scanning electron microscope. After curing reaction, the epoxy/MWCNT composites demonstrated enhanced mechanical properties, excellent thermal conductivity, and high electrical conductivity. With the addition of only 0.5 wt% GA‐II modified MWCNT, the tensile strength, tensile modulus, flexural strength, and flexural modulus of the composites were improved by 28%, 40%, 22%, and 16%, respectively. The thermal and electrical conductivities were also improved from 0.15 to 0.25 W/m K (67% increased) and from 0.7 × 10⁻¹⁴ to 0.24 × 10⁻⁴ S cm⁻¹ (10 orders increased). POLYM. COMPOS., 38:1640–1645, 2017. © 2015 Society of Plastics Engineers     

Improving thermal conductivity and shear strength of carbon nanotubes/epoxy composites via thiol‐ene click reaction

This study investigates the effect of the thiol‐ene click reaction on thermal conductivity and shear strength of the epoxy composites reinforced by various silane‐functionalized hybrids of sulfhydryl‐grafted multi‐walled carbon nanotubes (SH‐MWCNTs) and vinyl‐grafted MWCNTs (CC‐MWCNTs). The results of Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, thermal gravimetric analysis (TGA), and transmission electron microscopy (TEM) show that the sulfhydryl groups and vinyl groups are successfully grafted onto the surface of MWCNTs, after treatment of MWCNT with triethoxyvinylsilane and 3‐mercaptopropyltrimethoxysilane, respectively. Scanning electron microscopy (SEM), HotDisk thermal constant analyzer (HotDisk), optical microscope, and differential scanning calorimetry (DSC) are used to characterize the resultant composites. It is demonstrated that the hybrid of 75 wt % SH‐MWCNTs and 25 wt % CC‐MWCNTs has better dispersion and stability in epoxy matrix, and shows a stronger synergistic effect in improving the thermal conductivity of epoxy composite via the thiol‐ene click reaction with 2,2′‐azobis(2‐methylpropionitrile) as thermal initiator. Furthermore, the tensile shear strength results of MWCNT/epoxy composites and the optical microscopy photographs of shear failure section indicate that the composite with the hybrid MWCNTs has higher shear strength than that with raw MWCNTs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44579.     

Properties of surface‐modified multiwalled carbon nanotube filled poly(ethylene terephthalate) composite films

Poly(ethylene terephthalate) (PET)/multiwalled carbon nanotube (MWCNT) composites were prepared by in situ polymerization. To improve the dispersion of MWCNTs in the PET matrix, functionalized MWCNTs having acid groups (acid‐MWCNTs) and acetic groups (acetic‐MWCNTs) on their surfaces were used. The functional groups were confirmed by infrared spectrometry. Scanning electron microscopy showed that acetic‐MWCNTs had a better dispersion in the PET matrix than pristine MWCNTs and acid‐MWCNTs. A reaction between PET and acetic‐MWCNTs was confirmed by a shift of the Raman G band to a higher frequency and an increase of the complex viscosity in the rheological properties. The composites containing functionalized MWCNTs showed a large increase in their tensile strengths and moduli. The values of the strengths and moduli of the PET/acetic‐MWCNT composites were higher than those of the PET/acid‐MWCNT composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Microstructural characterization of corn starch‐based porous thermoplastic composites filled with multiwalled carbon nanotubes

Microstructural characterization of corn starch‐based porous thermoplastic (TPS) composites containing various contents (0.1, 0.5, and 1 wt %) of multiwalled carbon nanotubes (MWCNTs) was performed. Corn starch was plasticized with a proper combination of glycerol and stearic acid. TPS composites with MWCNT were prepared conducting melt extrusion followed by injection molding. TPS containing 1 wt % of MWCNTs exhibited higher tensile strength and elastic modulus values than neat TPS. Moreover, TPS electrical conductivity was determined to increase with increasing content of MWCNTs. X‐ray diffraction measurements revealed that incorporation of MWCNTs increased the degree of TPS crsystallinity to some extent. Scanning electron microscopy examination revealed that MWCNT altered TPS surface morphology and tensile failure modes, significantly. Transmission electron microscopy investigation showed that dispersion characteristics of MWCNTs within TPS were in the form of tiny clusters around micro pores of TPS, which is considered influential on electrical conductivity of the resulting composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Reinforcement of styrene-butadiene-styrene tri-block copolymer by multi-walled carbon nanotubes via melt mixing

Styrene-butadiene-styrene tri-block copolymer (SBS) was reinforced with multi-walled carbon nanotubes (MWCNTs) by the interaction through melt mixing. The tensile strength of SBS/MWCNT composites increased with increasing MWCNT content. The interactions between SBS and MWCNTs were characterized by solubility of MWCNTs in tetrahydrofuran, dynamic mechanical analysis, X-ray photoelectron microscope, ultraviolet spectra and transmission electron microscopy. The results showed that there were interactions between MWCNTs and SBS occurred during melt mixing, leading to an improvement of the mechanical properties of SBS/MWCNT composites, as well as the homogeneous dispersion of MWCNTs in SBS. The interactions between MWCNTs and SBS were supposed to consist of the π-π interaction between MWCNTs and the phenyl groups of SBS, as well as the chemical bonding of polybutadiene segments with MWCNTs.     

Lignin‐based polyurethane doped with carbon nanotubes for sensor applications

Modified eucalyptus kraft lignin doped with multiwall carbon nanotubes (MWCNTs) was used as a macromonomer in step‐growth polymerization with tolylene 2,4‐diisocyanate terminated poly(propylene glycol) with the aim of producing a conductive copolymer for all‐solid‐state potentiometric chemical sensor applications. The crosslinked elastomeric polyurethane obtained was characterized by Fourier transform infrared attenuated total reflection spectroscopy, scanning electron microscopy, tunnelling electron microscopy and atomic force microscopy. Doping of lignin‐based polyurethane with MWCNTs produced a significant enhancement of its electrical conductivity without deterioration of thermal and viscoelastic properties. The polymer composite displayed a low percolation threshold at an MWCNT concentration of 0.18% (w/w), which was explained by the oriented distribution of MWCNTs along lignin clusters. All lignin‐based polyurethanes doped with MWCNTs at concentrations above the percolation threshold are suitable for sensor applications. Copyright © 2012 Society of Chemical Industry     

Polyester and multiwalled carbon nanotube composites: characterization,electrical conductivity and antibacterial activity

Poly(butylene terephthalate) (PBT) composites containing multiwalled carbon nanotubes (MWCNTs) were prepared using a melt‐blending process and used to examine the effects on the composite structure and properties of replacing PBT with acrylic acid‐grafted PBT (PBT‐g‐AA). PBT‐g‐AA and multihydroxyl‐functionalized MWCNTs (MWCNTs‐OH) were used to improve the compatibility and dispersibility of the MWCNTs within the PBT matrix. The composites were characterized morphologically using transmission electron microscopy, and chemically using Fourier transform infrared, solid‐state ¹³C NMR and UV‐visible absorption spectroscopy. The antibacterial and electrical conductivity properties of the composites were also evaluated. MWCNTs or MWCNTs‐OH enhanced the antibacterial activity and electrical conductivity of the PBT/MWCNT or PBT‐g‐AA/MWCNTs‐OH composites. The functionalized PBT‐g‐AA/MWCNTs‐OH composites showed markedly enhanced antibacterial properties and electrical conductivity due to the formation of ester bonds from the condensation of the carboxylic acid groups of PBT‐g‐AA with the hydroxyl groups of MWCNTs‐OH. The optimal proportion of MWCNTs‐OH in the composites was 1 wt%; in excess of this amount, the compatibility between the organic and inorganic phases was compromised. Copyright © 2011 Society of Chemical Industry     

Hydrogen bond containing multiwalled carbon nanotubes in polyurethane composites

Introduction of hydrogen bonding sites onto multi‐walled carbon nanotubes (MWCNTs) included carboxylic acid, amide‐amine, and novel amide‐urea MWCNTs for the formation of homogenous polyurethane composites. Acid oxidation and subsequent derivatization introduced hydrogen bonding functionality onto MWCNTs to reveal the effect of surface functionalization on mechanical properties in a 45 wt% hard segment polyurethane matrix. Raman spectroscopy showed an increase in the D/G peak ratio, which indicated successful oxidation, and X‐ray photoelectron spectroscopy also revealed elemental compositions that supported each step of the functionalization strategy. Thermogravimetric analysis supported functionalization with an increase in percent weight loss for each functionalization, and the MWCNT surface functionalization determined pH‐dependent dispersibility. The nonfunctionalized MWCNT composites showed poor dispersion with transmission electron microscopy, and in sharp contrast, the functionalized composites displayed homogenous dispersions. Tensile testing revealed improved stress at break in the functionalized MWCNT composites at low loadings due to homogenous dispersion. POLYM. COMPOS., 37:1425–1434, 2016. © 2014 Society of Plastics Engineers     

Dispersion of multiwalled carbon nanotubes in polyacrylonitrile‐co‐starch copolymer matrix for enhancement of electrical,thermal, and gas barrier properties

Nanomaterials gained great importance on account of their wide range of applications in many areas. Carbon nanotubes (CNTs) exhibit exceptional electrical, thermal, gas barrier, and tensile properties and can therefore be used for the development of a new generation of composite materials. Functionalized multiwalled carbon nanotubes (MWCNTs) reinforced Polyacrylonitrile‐co‐starch nanocomposites were prepared by in situ polymerization technique. The structural property of PAN‐co‐starch/MWCNT nanocomposites was studied by X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The conductivity, tensile strength, and thermal properties of nanocomposites were measured as a function of MWCNT concentrations. The thermal stability, conductivity, and tensile strength of PAN‐co‐starch/MWCNT nanocomposites were improved with increasing concentration of MWCNTs. Oxygen barrier property of PAN‐co‐starch/MWCNT nanocomposites was calculated and it was found that, the property was reduced substantially with increase of MWCNTs proportion. The synthesized PAN‐co‐starch/MWCNT nanocomposites may used for electrostatically dissipative materials, aerospace or sporting goods, and electronic materials. © 2013 Society of Plastics Engineers     

Effects of multiwall carbon nanotubes on the thermal and mechanical properties of medium density polyethylene matrix nanocomposites produced by a mechanical milling method

Medium‐density polyethylene/multiwall carbon nanotube (MDPE/MWCNT) nanocomposites were produced by a mechanical milling method using a high‐energy ball mill. The MDPE and MWCNTs were added to the ball mill at a constant 20:1 weight ratio of ball/powders and milled for 10 h to obtain polyethylene matrix nanocomposites reinforced with 0.5, 1, 2.5, and 5 weight percent of MWCNTs. To clarify the role of both MWCNT content and milling time on the morphology of MDPE, some nanocomposite samples were investigated by using a scanning electron microscope. To evaluate the role of milling on the microstructure of the nanocomposites, very thin films of MDPE/MWCNTs were prepared and studied by transmission electron microscopy. Thermal behavior of these nanocomposites was investigated by using differential scanning calorimetry (DSC). Standard tensile samples were produced by compression molding. The dependence of the tensile properties of MDPE on both milling time and MWCNT content was studied by using a tensile test. The results of the microscopic evaluations showed that the milling process could be a suitable method for producing MDPE/MWCNT nanocomposites. The addition of carbon nanotubes to MDPE caused a change in its morphology at constant milling parameters. The results of the DSC tests showed that the crystallization temperature of MDPE increased as MWCNTs were added, although no dependency was observed as milling time increased. Crystallization index changed from 50 to 55% as MWCNT content increased from 0 to 5%. The results of the tensile tests showed that both the Young's modulus and the yield strength of MDPE increased as MWCNTs were added. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers