Cure behavior of epoxy/MWCNT nanocomposites: The effect of nanotube surface modification

The effect of carboxyl and fluorine modified multi-wall carbon nanotubes (MWCNTs) on the curing behavior of diglycidyl ether of bisphenol A (DGEBA) epoxy resin was studied using differential scanning calorimetry (DSC), rheology and infrared spectroscopy (IR). Activation energy (E_a) and rate constants (k) obtained from isothermal DSC were the same for the neat resin and fluorinated MWCNT system (47.7 and 47.5 kJ/mol, respectively) whereas samples containing carboxylated MWCNTs exhibited a higher activation energy (61.7 kJ/mol) and lower rate constant. Comparison of the activation energies, rate constants, gelation behavior and vitrification times for all of the samples suggests that the cure mechanisms of the neat resin and fluorinated sample are similar but different from the carboxylated sample. This can be explained by the difference in how the fluorinated nanotubes react with the epoxy resin compared to the carboxylated nanotubes. Although the two systems have different reaction mechanisms, both systems have similar degrees of conversion as calculated from the infrared spectroscopic data, glass transition temperature (T_g), and predictions based on DSC data. This difference in reaction mechanism may be attributed to differences in nanotube dispersion; the fluorinated MWCNT system is more uniformly dispersed in the matrix whereas the more heterogeneously dispersed carboxylated MWCNTs can hinder mobility of the reactive species and disrupt the reaction stoichiometry on the local scale.     

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     

Surfactant-Assisted Dispersion of MWCNTs in Epoxy Resin Used in CFRP Strengthening Systems

The epoxy resin used as the bonding agent in carbon fiber-reinforced polymer (CFRP) strengthening systems was modified by the infusion of multiwalled carbon nanotubes (MWCNTs). Two types of surfactants, Triton X-100 and C₁₂E₈, were used to disperse the nanotubes in the epoxy resin employing ultrasonic mixing. Dynamic mechanical analysis and tensile tests were conducted to study the effect of the surfactant-assisted dispersion of nanotubes on the thermal and mechanical properties of epoxy composites. The morphology of the epoxy composites was interpreted using scanning electron microscopy (SEM). Moreover, the effect of surfactant treatment on the structure of nanotubes was investigated by Fourier transform infrared (FT-IR). Based on the experimental results, the tensile strength and the storage modulus of the epoxy resin were increased by 32% and 26%, respectively, by the addition of MWCNTs. This was attributed to the homogeneous dispersion of nanotubes in the epoxy resin according to the SEM images. Another reason for the enhancement in the tensile properties was the reinforced nanotube/epoxy interaction as a result of the surfactant anchoring effect which was proved by FT-IR. A moderate improvement in the glass transition temperature (T _g) was recorded for the composite fabricated using Triton X-100, which was due to the restricted molecular motions in the epoxy matrix. To characterize the temperature-dependent tensile behavior of the modified epoxy composites, tensile tests were conducted at elevated temperatures. It was revealed that the MWCNT modification using surfactant substantially improves the tensile performance of the epoxy adhesive at temperatures above the T _g of the neat epoxy.     

Effect of functionalization on the thermo-mechanical and electrical behavior of multi-wall carbon nanotube/epoxy composites

The effect of the functionalization of multi-wall carbon nanotubes (MWCNTs) on the structure, the mechanical and electrical properties of composites was investigated. Samples based on epoxy resin with different weight percentage of MWCNTs or COOH-functionalized carbon nanotubes (MWCNT–COOH) were prepared and characterized. Dynamic-mechanical thermal analysis shows that the storage modulus increases with the addition of MWCNTs, whereas a constant value or even a weak reduction was observed for functionalized nanotubes. Two phases were suggested in the composites with MWCNT–COOH, both by dynamic-mechanical properties and by water transport. Chemical functionalization of MWCNTs increases the compatibility with the epoxy matrix due to the formation of an interface with stronger interconnections. This, in turn, causes a significant decrease in the electrical conductivity of this type of composite with respect to the untreated MWCNTs which can be explained in terms of tunnelling resistance between interacting nanotubes.     

Charing polymer wrapped carbon nanotubes for simultaneously improving the flame retardancy and mechanical properties of epoxy resin

Molybdenum-phenolic resin (Mo-PR) was grafted onto the surface of multi-walled carbon nanotubes (MWCNTs) to obtain modified MWCNTs (CNT-PR). Compared to epoxy resin, epoxy resin/CNT-PR nanocomposites showed the improvements in flame retardancy and mechanical properties. Structural characterization showed that the grafted Mo-PR improved the dispersion of MWCNTs in epoxy resin and enhanced the interfacial interaction between CNT-PR and epoxy resin. On the other hand, the grafted Mo-PR could show high char yield during the process of combustion. Thus the flame retardancy of nanocomposites was improved, especially for the heat release rate and total smoke production. Furthermore, the combination of CNT-PR with melamine dramatically promoted the LOI value and the level of UL-94 rating.     

Rheological and thermal properties of epoxy nanocomposites reinforced with alkylated multi‐walled carbon nanotubes

The effects of functionalized multi‐walled carbon nanotubes (MWCNTs) on thermal and chemorheological behaviors of an epoxy‐based nanocomposite system were investigated. Chemical functionalization of MWCNTs by acid modification (A‐MWCNTs) and chemical amidation (D‐MWCNTs) was confirmed using Fourier transform infrared spectroscopy and thermogravimetric analysis. It was found that the D‐MWCNTs had a significant effect on the chemorheological behaviors of the epoxy‐based nanocomposite. Compared to the epoxy/A‐MWCNT nanocomposite, the epoxy/D‐MWCNTs nanocomposite showed a significant increase in gel time, as obtained from isothermal rheology measurements. Also, the storage modulus of the diglycidylether of bisphenol F (DGEBF)/D‐MWCNTs nanocomposite was higher than that of the DGEBF/D‐MWCNTs nanocomposite and gradually increased with an increase of frequency. This could be interpreted by the relatively strongly interconnected structure of the D‐MWCNTs in the DGEBF epoxy resin, which arises from the functionalized alkyl groups of the D‐MWCNTs in dispersion phases with the DGEBF epoxy resin. Copyright © 2012 Society of Chemical Industry     

Effect of non-ionic surfactants on thermomechanical properties of epoxy/multiwall carbon nanotubes composites

Epoxy/multiwall carbon nanotubes (MWCNTs) composites were investigated using three different non-ionic surfactants (BYK-110, Tween-80 and Nonidet-P40) separately as a modifier. The role of surfactants in dispersion of MWCNTs in the epoxy matrix was studied. Among three surfactants used, performance of Nonidet-P40 was found to be the best in improving the thermomechanical properties of the epoxy resin and achieving good dispersion of MWCNTs. The good dispersion of Nonidet-P40 modified MWCNT in the epoxy matrix is a result of the π–π interaction between π electrons of the Nonidet-P40 and π electron clouds of MWCNTs as well as H-bonding interaction between of Nonidet-P40 and the epoxy matrix. This type of interaction does not disturb the π electron clouds of MWCNTs as opposed to chemical functionalization strategy.     

Influence of the epoxy functionalization of multiwall carbon nanotubes on the nonisothermal cure kinetics and thermal properties of epoxy/multiwall carbon nanotube nanocomposites

Multiwall carbon nanotubes were functionalized with epoxy groups by chemical modification in four stages. At each stage, the compound was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy (SEM). Epoxy composite samples were prepared by mixing diglycidyl ether of bisphenol A‐based epoxy resin and synthetic epoxy‐functionalized multiwall carbon nanotube (E‐MWCNT) with different percentages (1, 3, 6, 9, 12, and 15%) in acetone. Ultrasonic dispersion was used to produce homogenous blends. The optimum ratio of the reacting components (9%) was investigated by total enthalpy of the curing reaction from differential scanning calorimetry (DSC) thermograms. The kinetics of the curing reaction for epoxy composites with 4,4′‐diaminodiphenylsolfon as a curing agent was studied by means of a DSC nonisothermal technique. The kinetic parameters such as activation energy, pre‐exponential factor, and rate constant were obtained from DSC data. The structure ofthe nanocomposites and dispersion of the E‐MWCNTs in the nanocomposites were observed using SEM, and the thermal properties were studied by thermogravimetric analysis. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

A comparative study on the properties of the different amino‐functionalized multiwall carbon nanotubes reinforced epoxy resin composites

Multiwall carbon nanotubes (MWCNTs) were amino‐functionalized by 1,2‐ethylenediamine (EDA)' triethylenetetramine (TETA), and dodecylamine (DDA), and investigated by fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and thermogravimetric analysis (TGA). The dispersion of the DDA functionalized MWCNT in DMF is better than that of the MWCNT functionalized by the EDA and the TETA. Carbon nanotubes reinforced epoxy resin composites were prepared, and the effect of the amino‐functionalization on the properties of the composites was investigated by differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA), and TGA. The composites reinforced by the MWCNTs demonstrate improvement in various mechanical properties. The increase of T_g of the composites with the addition of amino‐functionalized MWCNT compared to the T_g of the composites with the addition of unfunctionalized MWCNT was due to the chemical combination and the physical entanglements between amino group from modified MWNTs and epoxy group from the epoxy resin. The interfacial bonding between the epoxy and the amino group of the EDA and the TETA‐modified MWCNT is more important than the well dispersion of DDA‐modified MWCNT in the composites for the improvement of the mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of multi‐walled carbon nanotubes dispersity on the light transmittancy of multi‐walled carbon nanotubes/epoxy composites

Two types of multi‐walled carbon nanotubes (MWCNTs), chemically modified and unmodified, were dispersed in epoxy resin with ultrasonication. The light transmittance characteristics of epoxy composites with different ratios of MWCNTs to epoxy resin were measured at wavelengths ranging from 200 to 1100 nm. Results showed that composites with modified MWCNTs had a much higher light transmittance than those with unmodified MWCNTs. This was presumably due to a more uniform dispersion of modified MWCNTs in the epoxy matrix, as indicated by both transmission electron microscopy and optic microscopy. The wavelength dependency of light transmittance of the composites was expressed empirically as a function of weight fraction (f_w) of MWCNTs and the light wavelength (λ). POLYM. ENG. SCI. 46:635–642, 2006. © 2006 Society of Plastics Engineers.     

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.     

Preparation and properties of multiwalled carbon nanotube/epoxy‐amine composites

Different amounts of multiwalled carbon tubes (MWCNTs) were incorporated into an epoxy resin based on diglycidyl ether of bisphenol A and both epoxy precursor and composite were cured with 4,4′‐diamino diphenyl sulfone. Transmission and scanning electron microscopy demonstrated that the carbon nanotubes are dispersed well in the epoxy matrix. Differential scanning calorimetry measurements confirmed the decrease in overall cure by the addition of MWCNTs. A decrease in volume shrinkage of the epoxy matrix caused by the addition of MWCNTs was observed by pressure–volume–temperature measurements. Thermomechanical and dynamic mechanical analysis were performed for the MWCNT/epoxy composites, showing that the T_g was slightly affected, whereas the dimensional stability and stiffness are improved by the addition of MWCNTs. Electrical conductivity measurements of the composite samples showed that an insulator to conductor transition takes place between 0.019 and 0.037 wt % MWCNTs. The addition of MWCNTs induces an increase in both impact strength (18%) and fracture toughness (38%) of the epoxy matrix with very low filler content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improving rheological properties of covalently MWCNT/epoxy nanocomposites via surface re-modification

This article describes the application of the chemical surface re-modification of carboxylated multi-walled carbon nanotubes (MWCNTs) through in-situ esterification of oligomeric unsaturated aliphatic hydroxyl terminated polyesters. The Fourier transform infrared spectroscopy and the thermogravimetric analysis proved covalent treatment of MWCNTs. Consequently, the acid–base titration method was employed to determine the population of the re-modified sites within the polyester chains. The dispersion state of the re-modified MWCNTs was investigated by the transmission electron microscopy relevant to the cured nanocomposite sample along with the Ultraviolet–Visible spectroscopy while using various solvents. The degree of dispersion was correlated to the Hansen solubility parameters. In summary, our study shows an appropriate dispersion of the re-modified MWCNTs into the solvents with a high dispersive fashion. In addition, the rheological properties of the re-modified MWCNTs/epoxy resin having various nanoinclusions were considerably studied and discussed. Also, an improved rheological response was observed in the case of the re-modified MWCNT nanocomposite samples.     

Acid‐Based Surfactant‐Aided Dispersion of Multi‐Walled Carbon Nanotubes in Epoxy‐Based Nanocomposites

In this study, the dispersion of multi‐walled carbon nanotubes (MWCNTs) in epoxy was facilitated by an anionic surfactant, linear alkyl benzene sulfonic acid. Different types of composites were prepared using a fixed amount of MWCNTs (0.5 wt%), in absence of solvent/surfactant, in presence of solvent and solvent/surfactant. The composites were characterized using Fourier transform infrared spectrophotometer, thermogravimetric analyzer (TGA), differential scanning calorimeter (DSC), universal testing machine, pendulum impact system, X‐ray diffraction, and scanning electron microscope. The epoxy/MWCNTs nanocomposite exhibited significantly higher mechanical properties due to the better dispersion in the presence of the surfactant. The tensile strength and flexural strength were increased by 75% and 108%, respectively. The thermal, structural, and morphological analyses were also excellent as a result of the better dispersion. In addition, the solvent‐surfactant behavior was hypothesized for the epoxy/MWCNTs system. POLYM. ENG. SCI., 59:E80–E87, 2019. © 2018 Society of Plastics Engineers     

The effect of a doubly modified carbon nanotube derivative on the microstructure of epoxy resin

The surface of multi wall carbon nanotubes (MWCNTs) was first covalently functionalized with oleyl amine and then non-covalently wrapped with polycarbosilane (PCS). The hybrid functional groups were chosen to introduce different features in the MWCNTs properties. For covalent functionalization a long chain unsaturated aliphatic amine was used to simultaneously achieve the dissociation of MWCNT bundles along with the dispersion and interaction with the host matrix using the amide functionality and double bond. On the other hand, a thermally stable polymer was selected which can interact with both resin and glass fabric to promote interfacial adhesion. This hybrid doubly modified MWCNT is thus possesses duel advantages in glass fiber based epoxy composite. The pristine, covalent, noncovalent and covalent-noncovalent doubly modified MWCNT systems were used to study the viscoelastic behavior and interactions of functionalized MWCNTs in the matrix above and below the glass transition temperature of the matrix. The PCS coating on the MWCNTs is amorphous and thermally insulating whereas the nanotube is highly graphitized and thermally conducting. This contrasting behavior provides us to insight into the temperature dependant resin microstructure and curing thermodynamics of epoxy resin in the presence of MWCNTs.     

The effects of triethylenetetramine grafting of multi‐walled carbon nanotubes on its dispersion,filler‐matrix interfacial interaction and the thermal properties of epoxy nanocomposites

This study describes the influence of triethylenetetramine (TETA) grafting of multi‐walled carbon nanotubes (MWCNTs) on the dispersion state, interfacial interaction, and thermal properties of epoxy nanocomposites. MWCNTs were first treated by a 3:1 (v/v) mixture of concentrated H₂SO₄/HNO₃, and then TETA grafting was performed. Chemically grafted MWCNT/bisphenol‐A glycidol ether epoxy resin/2‐ethyl‐4‐methylimidazole nanocomposites were prepared. TETA grafting could establish the connection of MWCNTs to the epoxy matrix and transform the smooth and nonreactive MWCNT surface into a hybrid material that possesses the characteristics of both MWCNTs and TETA, which facilitates homogeneous dispersion of MWCNTs and improves nanotube‐epoxy interfacial interaction. Therefore, the impact property, glass transition temperature, thermal stability, and thermal conductivity of epoxy nanocomposites are enhanced. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

The effect of silica nanoparticles and carbon nanotubes on the toughness of a thermosetting epoxy polymer

Silica nanoparticles and multiwalled carbon nanotubes (MWCNTs) have been incorporated into an anhydride‐cured epoxy resin to form “hybrid” nanocomposites. A good dispersion of the silica nanoparticles was found to occur, even at relatively high concentrations of the nanoparticles. However, in contrast, the MWCNTs were not so well dispersed but relatively agglomerated. The glass transition temperature of the epoxy polymer was 145°C and was not significantly affected by the addition of the silica nanoparticles or the MWCNTs. The Young's modulus was increased by the addition of the silica nanoparticles, but the addition of up to 0.18 wt % MWCNTs had no further significant effect. The addition of both MWCNTs and silica nanoparticles led to a significant improvement in the fracture toughness of these polymeric nanocomposites. For example, the fracture toughness was increased from 0.69 MPam^1/2 for the unmodified epoxy polymer to 1.03 MPam^1/2 for the hybrid nanocomposite containing both 0.18 wt % MWCNTs and 6.0 wt % silica nanoparticles; the fracture energy was also increased from 133 to 204 J/m². The mechanisms responsible for the enhancements in the measured toughness were identified by observing the fracture surfaces using field‐emission gun scanning electron microscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Mechanical and barrier properties of epoxy resin filled with multi-walled carbon nanotubes

Different multi-walled carbon nanotube (MWCNT) concentrations were incorporated in an epoxy resin and both the epoxy precursor and the composite were cured at 110 °C with a tertiary amine. Infrared spectroscopy was used to follow the curing progress by determining the decrease of the band due to the epoxy group. It was shown that the presence of MWCNTs accelerates the process, halving the time for the disappearance of the epoxy band. Atomic force microscopy demonstrated that the carbon nanotubes are well embedded in the epoxy matrix and singularly dispersed or in bundles, depending on their concentration. As a consequence of the good dispersion and interpenetration of the carbon nanotubes in the epoxy matrix, the glass transition temperature increased with increasing MWCNT concentration. Dynamic-mechanical analysis indicated a higher elastic modulus, particularly at high temperatures. The study of the transport properties, sorption and diffusion of water vapour at different activities, showed improved barrier properties on increasing the CNT concentration.     

Noncovalent functionalization of carbon nanotubes using branched random copolymer for improvement of thermal conductivity and mechanical properties of epoxy thermosets

A branched random copolymer, poly[(hydroxyethyl acrylate)‐r‐(N‐vinylcarbazole)] (BPHNV), was synthesized through a facile one‐pot free radical polymerization with hydroxyethyl acrylate and N‐vinylcarbazole monomers, using 4‐vinylmethylmercaptan as the chain transfer agent. BPHNV was employed to noncovalently modify multiwall carbon nanotubes (MWCNTs) by π–π interaction. The as‐modified MWCNTs were then incorporated into epoxy resin to improve the thermal conductivity and mechanical properties of epoxy thermosets. The results suggest that, due to both the conjugation structure and the epoxy‐philic component, BPHNV could form a polymer layer on the wall of MWCNTs and inhibit entanglement, helping the uniform dispersion of MWCNTs in epoxy matrix. Owing to the unprecedented thermal conductivity of MWCNTs and the enhancement in the interfacial interaction between fillers and matrix, the thermal conductivity of epoxy/MWCNTs/BPHNV composites increases by 78% at extremely low filler loadings, while the electrical resistivity is still maintained on account of the insulating polymer layer. Meanwhile, the mechanical properties and glass transition temperature (T_g) of the thermosets are elevated effectively, with no significant decrease occurring to the modulus. The addition of as little as 0.1 wt% of MWCNTs decorated with 1.0 wt% of BPHNV to an epoxy matrix affords a great increase of 130% in impact strength for the epoxy thermosets, as well as an increase of over 13 °C in T_g. © 2018 Society of Chemical Industry