Direct functionalization with 3,5‐substituted benzoic acids of multiwalled carbon nanotube/epoxy composites

Directly functionalized multiwalled carbon nanotubes (MWCNTs) with benzene‐1,3,5‐tricarboxylic acid (BTC) and 3,5‐diaminobenzoic acid (DAB) were successfully accomplished with less structural damage as confirmed by XPS and FT‐Raman results. Their dispersibility and thermal stability were achieved after the functionalization. The functional groups on MWCNT surfaces can accelerate the curing reaction of epoxy composites remarkable inducing rather low exothermic peak temperature (T_p) and exothermic heat of reaction (ΔH). The values of activation energy (E_a) obtained from Kissinger and Ozawa methods obviously decreased with the introduction of MWCNTs, especially DAB‐MWCNTs. The dynamic mechanical properties notably enhanced with the incorporation of unmodified and functionalized MWCNTs. The crosslink density (ρ) increased and free volume fraction (f_g) decreased, resulting in dramatic increase of glass transition temperatures (T_g) and decrease of coefficient of thermal expansion. Additionally, epoxy composites exhibited low dielectric constant close to that of neat epoxy resin. From these remarkable properties, MWCNT/epoxy composites can be considered as a good candidate for high performance insulation materials. POLYM. ENG. SCI., 53:2194–2204, 2013. © 2013 Society of Plastics Engineers     

Preparation and thermal properties of bio‐based gallic acid epoxy/carbon nanotubes composites by cationic ring‐opening reaction

In order to prepare the bio‐based polymeric materials, a gallic acid epoxy resin (GA‐ER) is synthesized by using biodegradable gallic acid, and the nanocomposites of GA‐ER/glycidyl methacrylate (GMA)/multiwalled carbon nanotubes (MWCNTs) were prepared by dual hybrid cationic ring‐opening reaction. Differential scanning calorimetry (DSC) results show that the curing reaction temperature of the nanocomposites is between 150 and 225°C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results suggest that MWCNTs are homodispersing in the GA‐ER/GMA matrix when the MWCNTs content is not more than 1.0 wt%. The glass transition temperature of the nanocomposite with 0.5 wt% MWCNTs is 9.3°C higher than that of pure resin system. The initial thermal degradation temperature and degradation activation energies E_a of the nanocomposite with 1.0 wt% MWCNTs is 10°C and 68.6 kJ/mol higher than that the pure resin system, respectively. POLYM. COMPOS., 37:3093–3102, 2016. © 2015 Society of Plastics Engineers     

Simultaneous enhancements in the mechanical,thermal, and electrical performances of glass‐fiber‐reinforced cyanate ester/epoxy composites with plasma‐functionalized carbon nanotubes at different temperatures

Woven glass‐fiber‐reinforced cyanate ester/epoxy composites modified with plasma‐functionalized multiwalled carbon nanotubes (MWCNTs) were prepared. The mechanical, thermal, and electrical properties of the composites were investigated at different temperatures. The results show that the interlaminar shear strength, thermal conductivity, and electrical conductivity of the composites at room temperature and the cryogenic temperatures were enhanced simultaneously by the incorporation of MWCNTs, whereas the nonconductive behavior of the composites as electrical insulating materials was not changed. Meanwhile, the reinforcing mechanism was also examined on the basis of the microstructure of the composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41418.     

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     

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.     

Effect of functionalized carbon nanotubes on the thermal conductivity of epoxy composites

Direct functionalized carbon nanotubes (CNTs) were utilized to form the heat flow network for epoxy composites through covalent integration. A method of preparing a fully heat flow network between benzenetricarboxylic acid grafted multi-walled carbon nanotubes (BTC-MWCNTs) and epoxy matrix is described. A Friedel-Crafts modification was used to functionalize MWCNTs effectively and without damaging the MWCNT surface. Raman spectra, X-ray photoelectron spectra and thermogravimetric analysis reveal the characteristics of functionalized MWCNTs. The scanning electron microscope images of the fracture surfaces of the epoxy matrix showed BTC-MWCNTs exhibited higher solubility and compatibility than pristine-MWCNTs. The MWCNTs/epoxy composites were prepared by mixing BTC-MWCNTs and epoxy resin in tetrahydrofuran, followed by a cross-linking reaction with a curing agent. The BTC was grafted onto the MWCNTs, creating a rigid covalent bond between MWCNTs and epoxy resin and forming an effective network for heat flow. The effect of functionalized MWCNTs on the formation of the heat flow network and thermal conductivity was also investigated. The thermal conductivity of composites exhibits a significant improvement from 0.13 to 0.96 W/m K (an increase of 684%) with the addition of a small quantity (1-5 vol%) of BTC-MWCNTs.     

Effect of amino‐functionalization of multi‐walled carbon nanotubes on the dispersion with epoxy resin matrix

Amino‐functionalization of multiwalled carbon nanotubes (MWCNTs) was carried out by grafting triethylenetetramine (TETA) on the surfaces of MWCNTs through the acid–thionyl chloride way. The amino‐functionalized MWCNTs show improved compatibility with epoxy resin and, as a result, more homogenous dispersion in the matrix. The mechanical, optical, and thermal properties of the amino‐functionalized MWCNT/epoxy composites were also investigated. It was found that introducing the amino‐functionalized MWCNTs into epoxy resin greatly increased the charpy impact strength, glass transition temperature, and initial decomposing temperature of cured epoxy resin. In addition, introducing unfunctionalized MWCNTs into epoxy resin was found greatly depressing the light transmission properties, which would affirmatively confine the application of the MWCNTs/epoxy composites in the future, while much higher light transmittance than that of unfunctionalized MWCNTs/epoxy composites was found for amino‐functionalized MWCNTs/epoxy composites. SEM of the impact cross section and TEM of ultrathin film of the amino‐functionalized MWCNTs/epoxy composites showed that the amino‐functionalized MWCNTs were wetted well by epoxy matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 97–104, 2006     

Cure reaction of multi‐walled carbon nanotubes/diglycidyl ether of bisphenol A/2‐ethyl‐4‐methylimidazole (MWCNTs/DGEBA/EMI‐2,4) nanocomposites: effect of carboxylic functionalization of MWCNTs

BACKGROUND: The aim of this work was to study, using differential scanning calorimetry, the effect of carboxylic functionalization of multi‐walled carbon nanotubes (MWCNTs) on the cure reaction of MWCNTs/diglycidyl ether of bisphenol A/2‐ethyl‐4‐methylimidazole (MWCNTs/DGEBA/EMI‐2,4) nanocomposites. This is important for the practical design, analysis and optimization of novel materials processing. RESULTS: Comparing the influence of non‐functionalized MWCNTs and carboxyl‐functionalized MWCNTs, it was found that, at the initial curing stage, both MWCNTs act as catalyst and COOH functionalization of MWCNTs has a catalytic effect on the curing process. Then, at the later curing stage, non‐functionalized MWCNTs prevent the occurrence of vitrification, whereas COOH functionalization of MWCNTs promotes vitrification. Non‐functionalized MWCNTs decrease the degree of curing, as evidenced by lower total heat of reaction and lower glass transition temperatures of nanocomposites compared to neat epoxy; however, COOH functionalization of MWCNTs increases the degree of curing. CONCLUSION: For the development of composites, COOH functionalization of MWCNTs could bring a positive influence to the composite process. Its acceleration of cure could help shorten pre‐cure time or lower pre‐treatment temperature, and its effect of promoting vitrification could help shorten post‐cure time or lower post‐treatment temperature. Copyright © 2009 Society of Chemical Industry     

Mild functionalization of carbon nanotubes filled epoxy composites: Effect on electromagnetic interferences shielding effectiveness

The effect of nitric acid mild functionalized multiwalled carbon nanotubes (MWCNTs) on electromagnetic interference (EMI) shielding effectiveness (SE) of epoxy composites was examined. MWCNTs were oxidized by concentrated nitric acid under reflux conditions, with different reaction times. The dispersion of MWCNTs after functionalization was improved due to the presence of oxygen functional groups on the nanotubes surface. Functionalization at 2 h exhibits the highest EMI SE and electrical conductivity of MWCNTs filled epoxy composites. However, EMI shielding performance of MWCNTs filled epoxy composite declined when the functionalization reaction time was prolonged. This was due to extensive damage on the MWCNT structure, as verified by a Raman spectroscope. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42557.     

Cure behavior and thermal stability analysis of multiwalled carbon nanotube/epoxy resin nanocomposites

As‐received multiwalled carbon nanotubes (MWCNTs) were first treated by a 3 : 1 (v/v) mixture of concentrated H₂SO₄/HNO₃ and further functionalized by ethylenediamine/dicyclohexylcarbodiimide/tetrahydrofuran solution. MWCNT/epoxy nanocomposites were prepared. Their cure behaviors were investigated by dynamic differential scanning calorimetry. Quantitative analysis of the activation energy as a function of the degree of curing was carried out by the Flynn‐Wall‐Ozawa method. The fitted multiple regression equations for values of the activation energy of different systems were obtained. MWCNTs have the retardation effect on the cure reaction of epoxy resin, while the functional groups on the surface of amine‐modified MWCNTs could accelerate the cure reactions. Thermal stability was studied by thermogravimetric analysis. The filling of amine‐modified MWCNTs is beneficial to lower the cure activation energy and improve thermal stability of the nanocomposite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Noncovalent functionalization of carbon nanotube using poly(vinylcarbazole)‐based compatibilizer for reinforcement and conductivity improvement in epoxy composite

A new compatibilizer [P(GMA‐co‐VCz) copolymer] containing carbazole moiety and reactive epoxide group, which can functionalize multiwalled carbon nanotubes (MWCNTs) for making superior epoxy composites, was prepared by a simple one‐pot free radical polymerization. The designed compatibilizer could noncovalently functionalize multiwalled carbon nanotube (MWCNTs) via π‐π interaction as evidenced from fluorescence, Raman, and FTIR spectra analysis, and efficiently disperse MWCNTs in organic solvents. TEM images suggest a good wrapping of P(GMA‐co‐VCz) on MWCNTs surface. P(GMA‐co‐VCz) functionalized MWCNTs were more homogeneously dispersed in epoxy matrix than the case without compatibilizer, indicating that the compatibilizer improves the compatibility between MWCNTs and epoxy resin. In addition, the presence of epoxide groups in compatibilizer could generate covalent bonds with the epoxy matrix and improve the interface interaction between MWCNTs and epoxy matrix. As a result, mechanical and electrical properties of the epoxy composites with compatibilizer were largely improved as compared with those of composites without compatibilizer. The addition of as little as 0.15 wt % of MWCNTs to epoxy matrix affords a great increase of 40% in storage modulus and 52.5% in elongation at break. Furthermore, a sharp decrease of almost 9 orders of magnitude in volume resistivity of epoxy composite is observed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45022.     

Fabrication and characterization of homogeneous composites of polypropylene and multiwalled carbon nanotubes

The polypropylene‐grafted multiwalled carbon nanotubes (PP‐MWCNTs) were produced from the reaction of PP containing the hydroxyl groups and MWCNTs having 2‐bromoisobutyryl groups. The PP‐MWCNTs had a significantly rougher surface than the original MWCNTs. PP‐MWCNTs had PP layers of thickness 10–15 nm on the outer walls of the MWCNTs. PP/PP‐MWCNT composites and PP/MWCNT composites were prepared by solution mixing in o‐xylene. Unlike PP/MWCNT composites, PP‐MWCNTs were homogeneously dispersed in the PP matrix. As a consequence, the thermal stability and conductivity of PP/PP‐MWCNT composites were dramatically improved even if only 1 wt % of PP‐MWNTs was added to the PP matrix. The good miscibility of PP and PP‐MWCNTs plays a critical role in the formation of the homogeneous composites and leads the high thermal stability and conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Pseudoreinforcement effect of multiwalled carbon nanotubes in epoxy matrix composites

The carbon nanotube possesses outstanding physical properties. Theoretically, adding carbon nanotubes into a polymer matrix can remarkably improve the mechanical properties of the polymer matrix. In the present work, a series of composites was prepared by incorporating multiwalled carbon nanotubes (MWNTs) into an epoxy resin. The influences of MWNT content and curing temperature on the flexural properties of the epoxy resin were investigated. The results showed that a very low MWNT content should be used to ensure homogeneous dispersion of MWNTs in the epoxy matrix. A higher MWNT content may lead to deteriorated mechanical properties of the composites because of the aggregation of MWNTs. A decline in the flexural properties of the neat epoxy resin with increasing curing temperature was found. However, under the same curing conditions, improvement in flexural properties was observed for the composite with the low MWNT content and a mild curing temperature. The improvement was far beyond the predictions of the traditional short‐fiber composite theory. In fact, this improvement should be attributed to the retarding effect of MWNTs on the curing reaction of epoxy matrix. Therefore, the improvement in the flexural properties was only a pseudoreinforcement effect, not a nano‐reinforcement effect of the MWNTs on the epoxy resin. Perhaps, it is better for MWNTs to be used as functional fillers, such as electrical or thermal conductive fillers, than as reinforcements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3664–3672, 2006     

Morphology,thermal expansion,and electrical conductivity of multiwalled carbon nanotube/epoxy composites

Multiwalled carbon nanotube/epoxy composites loaded with up to 0.5 wt % multiwalled carbon nanotubes were prepared and characterized. Infrared microscopy, scanning electron microscopy, thermogravimetry, differential scanning calorimetry, thermomechanical analysis, and electrical conductivity measurements of the composites were performed. Infrared microscopy and scanning electron microscopy images showed that the debundled nanotubes were well dispersed. The thermal expansion coefficients, before and after the glass transition, remained approximately constant with the addition of nanotubes, whereas the electrical conductivity at room temperature increased approximately 5 orders of magnitude. This result was attributed to the thermal expansion coefficients of the intertube gap on the carbon nanotube bundles, which were in the same range as that of the epoxy resin. Therefore, nanocomposites capable of electrostatic dissipation can be processed as neat epoxy materials with respect to the volume changes with temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of multi‐walled carbon nanotubes/carbon fiber/epoxy composites

Multi‐walled carbon nanotubes/carbon fiber (MWCNTs/CF) hybrid fillers are employed to prepare MWCNTs/CF/epoxy composites. Results reveal that a great improvement of the thermal conductivities of the epoxy composites with the addition of MWCNTs/CF hybrid fillers, and the thermal conductivity of the MWCNTs/CF/epoxy composites is 1.426 W/mK with 8 vol% treated MWCNTs/CF hybrid fillers (5 vol% MWCNTs + 3 vol% CF). Both the flexural and impact strength of the MWCNTs/CF/epoxy composites are increased firstly, but decreased with the excessive addition of MWCNTs. The flexural and impact strength of the MWCNTs/epoxy composites are optimal with 2 vol% MWCNTs. For a given MWCNTs/CF hybrid fillers loading, the surface treatment of MWCNTs/CF hybrid fillers can further increase the thermal conductivities and mechanical properties of the MWCNTs/CF/epoxy composites. POLYM. COMPOS., 35:2150–2153, 2014. © 2014 Society of Plastics Engineers     

Water‐Processable Multiwalled Nanotube: Phenol‐Induced Reversible Oxidation Process and Ambipolar Charge Transport Property

Due to the fascinating electronic, thermal, and mechanical properties of single‐walled carbon nanotubes (SWCNTs), extensive efforts have been devoted to the development of SWCNT‐based materials. These materials' semiconducting properties and related applications, such as field‐effect transistors (FETs), have been investigated by researchers for many years. However, despite the significant progress achieved, it remains challenging to separate semiconducting and metallic nanotubes from the mixtures of as‐grown SWCNTs. In a few studies, composites of water‐processable phenol formaldehyde resin/multiwalled carbon nanotubes (MWCNTs) have been found to exhibit a quasireversible oxidation process and to behave as semiconductors or field‐effect transistors. This finding has rarely been reported for MWCNTs, and it differs greatly from findings regarding intrinsic semiconductive SWCNTs. Significantly, field‐effect transistors fabricated with MWCNT composites as their semiconductor active layers have shown ambipolar charge transport characteristics. The results provide a high value‐added application pathway for the application of polymer/MWCNTs as the FET materials for electronic devices that offer higher performance at a lower cost.     

A study on rheological behavior of MWCNTs/epoxy composites

Rheological behaviors of multiwalled carbon nanotubes (MWCNTs)/epoxy composites with various MWCNT contents were investigated by using a time sweep and frequency sweep experiment with oscillatory rheometry. The functional groups on the acid-treated MWCNTs were investigated by fourier transfer-infrared spectroscopy (FT-IR). The composites containing acid-treated MWCNTs exhibited faster gel time than pure epoxy resins. The storage (G′) and loss (G″) moduli of the composites showed solid-like behavior owing to interaction between the MWCNTs and the epoxy resins. The 1.0 wt% MWCNT composites had the highest crosslinking activation energy (E_c) due to good dispersion and strong interfacial bonding. These results imply that three-dimensional crosslinking might take place among the hydroxyl group in epoxy resins and the carbonyl or hydroxyl group in acid-treated MWCNTs.     

Thermal stability and kinetics analysis of epoxy composites modified with reactive polyol diluent and multiwalled carbon nanotubes

The effect of polyether polyol and amino‐functionalized multiwalled carbon nanotubes (NH₂‐MWCNTs) on the thermal stability of three‐phase (epoxy/polyol/NH₂‐MWCNTs) epoxy composites was investigated. Thermal stability and degradation characteristics of polyol/MWCNTs modified epoxy composites was evaluated using thermogravimetric analysis. The kinetics of thermal degradation was assessed from data scanned at 5, 10, and 20°C/min. Activation energy for degradation of epoxy nanocomposites was calculated using different differential and integral methods, that is, Kissinger's, Flynn–Wall–Ozawa, Coats–Redfern, and Horowitz–Metzger methods. In addition, the integral procedure decomposition temperature was determined to evaluate the inherent thermal stability of the modified composite system. Rate of thermal degradation in MWCNT/Polyol samples was found to be reduced significantly while activation energy of degradation was increased compared to unmodified epoxy composite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41558.     

Improvement of dispersion of carbon nanotubes in epoxy resin through pyrogallol functionalization

Multiwalled carbon nanotubes (MWNTs) were functionalized with pyrogallol. The functionalized MWNTs were well‐dispersed in the epoxy/curing agent/ethanol solution, as demonstrated by UV‐vis spectra and optical micrographs. Epoxy resin/MWNTs composites were prepared via solution mixing method. The cure behavior was characterized using differential scanning calorimetry. Pyrogallol‐functionalized carbon nanotubes (CNTs) reacted with the epoxy through the mediation reaction of pyrogallol with the curing agent, leading to the interfacial bonding between the functionalized carbon nanotubes (CNTs) and the resin matrix. Due to the excellent dispersion and interfacial bonding, the mechanical strength and electrical conductivity of the epoxy resin/CNTs composites have been improved. POLYM. ENG. SCI. 56:1079–1085, 2016. © 2016 Society of Plastics Engineers     

Thermal conductivity and dynamic mechanical property of glycidyl methacrylate‐grafted multiwalled carbon nanotube/epoxy composites

The well dispersed multiwalled carbon nanotube (MWCNT)/epoxy composites were prepared by functionalization of the MWCNT surfaces with glycidyl methacrylate (GMA). The morphology and thermal properties of the epoxy nanocomposites were investigated and compared with the surface characteristics of MWCNTs. GMA‐grafted MWCNTs improved the dispersion and interfacial adhesion in epoxy resin, and enhanced the network structure. The storage modulus of 3 phr GMA‐MWCNTs/epoxy composites at 50°C increased from 0.32 GPa to 2.87 GPa (enhanced by 799%) and the increased tanδ from 50.5°C to 61.7°C (increased by 11.2°C) comparing with neat epoxy resin, respectively. Furthermore, the thermal conductivity of 3 phr GMA‐MWCNTs/epoxy composite is increased by 183%, from 0.2042 W/mK (neat epoxy) to 0.5781 W/mK. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011