Effect of carbon nanofiber functionalization on the in-plane mechanical properties of carbon/epoxy multiscale composites

In this work, vapor-grown carbon nanofibers (CNFs) were functionalized using an optimized route and dispersed in the matrix of carbon fabric-reinforced epoxy composites to develop multiscale carbon/epoxy composites. Functionalization was carried out through an oxidative treatment with a mixture of HNO₃/H₂SO₄ (1 : 3) using a combination of ultrasonication and magnetic stirring. Functionalized CNFs (F-CNFs) were characterized for their morphology, length, functional groups, and degradation due to oxidative treatment. The results showed that it was possible to efficiently functionalize CNFs without any degradation through proper selection of treatment duration. F-CNFs were dispersed homogeneously into the epoxy matrix using ultrasonication in combination with high-speed mechanical stirring. The incorporation of 0.1 wt % F-CNFs led to a 65% increase in Young's modulus and a 36% in tensile strength of neat carbon/epoxy composites. The fracture surfaces were studied using scanning electron microscopy to understand the property enhancement due to F-CNFs. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of solvent nature in casting-based carbon nanofiber/poly(methyl-methacrylate) nanocomposites

Eight different solvents, of different polarities, were used to prepare carbon nanofiber (CNF)/poly(methyl methacrylate nanocomposites by solvent casting. Selected solvents ranged from organic acetone to nonpolar toluene, passing through N-containing solvents. In addition, pristine and oxygen and nitrogen-functionalized CNFs were used. Two objectives were pursued: (1) the role of the solvent in the dispersion of the CNFs and (2) the benefit of the functionalization on the dispersion through the stability in the solvent and compatibility with the matrix. The dispersion analysis of the materials leads to the conclusion that solvents containing oxygen groups work better with the oxidized CNFs, similarly solvents containing nitrogen groups with the nitrogen-functionalized CNFs. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

多壁碳纳米管／环氧树脂复合材料性能研究

采用物理机械方法与化学方法相结合的手段,制备了多壁碳纳米管（MWNTS）／环氧树脂（Epoxy）复合材料。通过力学拉伸试验测试了MWNTs/Epoxy复合材料拉伸强度和拉伸模量与MWNTS添加量的关系,利用扫描电镜（SEM）分析了MWNTS／Epoxy复合材料的拉伸断面,并用表面电阻测试仪对所制备的碳纳米管复合材料进行了电学性能测试。结果表明：经过化学酸化的方法处理后的MWNTS在复合材料中的分散得到了改善,力学性能也得到了明显的提高,但酸处理后的复合材料的电学性能明显低于未处理的复合材料。     

Thermal and mechanical behavior of poly(vinyl butyral)‐modified novolac epoxy/multiwalled carbon nanotube nanocomposites

The effects of poly(vinyl butyral) (PVB) and acid‐functionalized multiwalled carbon nanotube modification on the thermal and mechanical properties of novolac epoxy nanocomposites were investigated. The nanocomposite containing 1.5 wt % PVB and 0.1 wt % functionalized carbon nanotubes showed an increment of about 15°C in the peak degradation temperature compared to the neat novolac epoxy. The glass‐transition temperature of the novolac epoxy decreased with increasing PVB content but increased with an increase in the functionalized carbon nanotube concentration. The nanocomposites showed a lower tensile strength compared to the neat novolac epoxy; however, the elongation at break improved gradually with increasing PVB content. Maximum elongation and impact strength values of 7.4% and 17.0 kJ/m² were achieved in the nanocomposite containing 1.5 wt % PVB and 0.25 wt % functionalized carbon nanotubes. The fractured surface morphology was examined with field emission scanning electron microscopy, and correlated with the mechanical properties. The functionalized carbon nanotubes showed preferential accumulation in the PVB phase beyond 0.25 wt % loading. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43333.     

Effect of carbon black silanization on isothermal curing kinetics of epoxy nanocomposites

The present study was carried out to determine the effect of carbon black (CB) nanofiller silanization and loading on isothermal curing kinetics of epoxy nanocomposites. The epoxy resin specimens incorporated with 2, 4, and 8 wt% pristine CB and silanized CB were cured at isothermal temperatures of 43, 60, and 104°C. Differential scanning calorimetry was used to characterize the curing kinetics, Fourier transform infrared spectroscopy was employed to confirm silanization of CB nanofillers, and scanning electron microscopy was utilized to study the morphology of nanocomposite specimens. It was also observed that the silanization did not change the curing kinetics of CB nanocomposites significantly as compared to the neat epoxy resin. However, the curing reactions of the pristine CB nanocomposites were slower than the neat epoxy resin marked by an average 10 and 4% decrease in the final degree of cure for the nanocomposite specimens cured at 43 and 60°C, respectively. The morphological studies revealed that the silanized CB particles exhibited a more stable and homogeneous dispersion in the epoxy resin than the pristine CB particles. Potential applications for the fabricated nanocomposites include sensors, actuators, and conductive coatings for electrostatic dissipation control in plastic parts.     

Poly dimethylsiloxane/carbon nanofiber nanocomposites: fabrication and characterization of electrical and thermal properties

This article presents the fabrication and characterization of poly dimethylsiloxane/carbon nanofiber (CNF)-based nanocomposites. Although silica and carbon nanoparticles have been traditionally used to reinforce mechanical properties in PDMS matrix nanocomposites, this article focuses on understanding their impacts on electrical and thermal properties. By adjusting both the silica and CNF concentrations, 12 different nanocomposite formulations were studied, and the thermal and electrical properties of these materials were experimentally characterized. The developed nanocomposites were prepared using a solvent-assisted method providing uniform dispersion of the CNFs in the polymer matrix. Scanning electron microscopy was employed to determine the dispersion of the CNFs at different length scales. The thermal properties, such as thermal stability and thermal diffusivity, of the developed nanocomposites were studied using thermogravimetirc and laser flash techniques. Furthermore, the electrical volume conductivity of each type of nanocomposite was tested using the four-probe method to eliminate the effects of contact electrical resistance during measurement. Experimental results showed that both CNFs and silica were able to impact on the overall properties of the synthesized PDMS/CNF nanocomposites. The developed nanocomposites have the potential to be applied to the development of new load sensors in the future.     

Electrical and mechanical properties of carbon nanotube‐epoxy nanocomposites

In this work, electrical conductivity and thermo‐mechanical properties have been measured for carbon nanotube reinforced epoxy matrix composites. These nanocomposites consisted of two types of nanofillers, single walled carbon nanotubes (SW‐CNT) and electrical grade carbon nanotubes (XD‐CNT). The influence of the type of nanotubes and their corresponding loading weight fraction on the microstructure and the resulting electrical and mechanical properties of the nanocomposites have been investigated. The electrical conductivity of the nanocomposites showed a significantly high, about seven orders of magnitude, improvement at very low loading weight fractions of nanotubes in both types of nanocomposites. The percolation threshold in nanocomposites with SW‐CNT fillers was found to be around 0.015 wt % and that with XD‐CNT fillers around 0.0225 wt %. Transmission optical microscopy of the nanocomposites revealed some differences in the microstructure of the two types of nanocomposites which can be related to the variation in the percolation thresholds of these nanocomposites. The mechanical properties (storage modulus and loss modulus) and the glass transition temperature have not been compromised with the addition of fillers compared with significant enhancement of electrical properties. The main significance of these results is that XD‐CNTs can be used as a cost effective nanofiller for electrical applications of epoxy based nanocomposites at a fraction of SW‐CNT cost. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical and thermal performances of epoxy resin/graphitic carbon nitride composites

In this paper, a series of graphitic carbon nitride (g-C₃N₄) was synthesized under different thermal oxidation etching temperatures and epoxy/g-C₃N₄ composites were prepared via solution blending. The morphology and structure of g-C₃N₄ were investigated by transmission electron microscope, X-ray diffraction (XRD), Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The tensile fracture morphology and structure of epoxy resin (EP) composites were demonstrated by scanning electron microscopy and XRD, respectively. Mechanical properties of EP composites were characterized by tensile testing, and the thermal performances were investigated by dynamic mechanical thermal analysis and thermal gravimetric analysis. The results revealed that the active groups on g-C₃N₄ sheets increased under thermal oxidation etching and the C to N ratio of g-C₃N₄ decreased from 0.94 to 0.76 with the increasing etching temperature. Noticeably, the tensile strength of EP composites was enhanced by 58% with the addition of C₃N₄-NS-500 and the thermal properties were also improved significantly, including T_0.5 (the decomposition temperature at the mass loss of 50%) increased by 21.5 °C and glass transition temperature improved by 8 °C. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48598.     

Effect of crosslink density on thermal conductivity of epoxy/carbon nanotube nanocomposites

The effect of the polymeric crosslink density on the thermal conductivity of an epoxy nanocomposite was investigated by adding two different diamine‐functionalized multiwalled carbon nanotubes (diamine‐MWNTs) to the epoxy resin as co‐curing agents and conducting fillers. Tetramethylenediamine (TMDA)‐MWNTs resulted in an epoxy nanocomposite with a higher crosslink density than octamethylenediamine (OMDA)‐MWNTs. Interestingly, epoxy/TMDA‐MWNT nanocomposites under 1.5 wt % nanotube concentration, showed a higher thermal conductivity than an epoxy/OMDA‐MWNT nanocomposite with the same concentration of nanotubes. In contrast, for higher diamine‐MWNT concentrations (over 2.0 wt %), the thermal conductivity of the epoxy/OMDA‐MWNT nanocomposite was higher than that with TMDA‐MWNTs. We observed that for low MWNT concentrations, where a percolating network was not formed, a high crosslink density enhanced the thermal conductivity via phonon transport. However, for high MWNT concentrations, a high crosslink density hinders the formation of a percolating network and lowers the thermal conductivity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44253.     

Effect of amine-terminated butadiene-acrylonitrile/clay combinations on the structure and properties of epoxy nanocomposites

The effect of the clay content and the method of its combination with amine-terminated butadiene-acrylonitrile (ATBN) on the structure and behavior of epoxy was studied. In the case of the simultaneous addition of both components, the increasing clay content had a very small effect on the size of the reaction-induced phase separation-formed particles at 5% rubber content due to predominant elimination of two major clay effects, i.e., the nucleation due to phase separation and the kinetics. As a result, both the time window between the onset of phase separation and vitrification and the viscosity at the cloud point did not change significantly. The minor change in the particle size/clay content dependences with different curing temperatures indicates that the balance between the two clay effects shifted. The corresponding study of the mechanical behavior indicated that the best balanced mechanical properties were obtained at certain clay/ATBN ratios, and thus, there was synergy between the components. Similar mechanical parameters were obtained for the application of both components in the form of ATBN/montmorillonite intercalate. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of nanosized carbon black on the morphology,transport, and mechanical properties of rubbery epoxy and silicone composites

Three different types of nanosized carbon black (CB), Printex XE2 (CBP), Vulcan XC72, and Printex 140 U (CBU), were dispersed by mechanical mixing in rubbery epoxy (RE) and silicone to produce composites. It was found that the maximum possible loading of CB in the polymers depended on the surface area of CB. For a given loading, all three CBs produced similar improvements in the thermal conductivity of the resulting composites, but their effects on the electrical conductivity varied and ranged from insulating composites with CBU to conducting composites with CBP. CBP produced a greater improvement in the electrical conductivity than the thermal conductivity of the polymers compared to the other CBs. This was attributed to the high structure of CBP, which led to the formation of a concatenated structure within the matrix. The CB/silicone composites had a similar thermal conductivity to that of the CB/RE composites, but only the CBP/silicone composite produced at 8 wt % loading was electrically conducting. The compression and hardness properties of RE were also significantly improved with the addition of CB. However, in the case of silicone, only CBP had a considerable effect on the compression properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Response surface predictions of the viscoelastic properties of vapor‐grown carbon nanofiber/vinyl ester nanocomposites

A full factorial design of experiments and response surface methodology were used to investigate the effects of formulation, processing, and operating temperature on the viscoelastic properties of vapor‐grown carbon nanofiber (VGCNF)/vinyl ester (VE) nanocomposites. Factors included VGCNF type (pristine, oxidized), use of a dispersing agent (DA) (no, yes), mixing method (ultrasonication, high‐shear mixing, and a combination of both), VGCNF weight fraction (0.00, 0.25, 0.50, 0.75, and 1.00 parts per hundred parts resin (phr)), and temperature (30, 60, 90, and 120°C). Response surface models (RSMs) for predicting storage and loss moduli were developed, which explicitly account for the effect of complex interactions between nanocomposite design factors and operating temperature on resultant composite properties; such influences would be impossible to assess using traditional single‐factor experiments. Nanocomposite storage moduli were maximized over the entire temperature range (～20% increase over neat VE) by using high‐shear mixing and oxidized VGCNFs with DA or equivalently by employing pristine VGCNFs without DA at ～0.40 phr of VGCNFs. Ultrasonication yielded the highest loss modulus at ～0.25 phr of VGCNFs. The RSMs developed in this investigation may be used to design VGCNF‐enhanced VE matrices with optimal storage and loss moduli for automotive structural applications. Moreover, a similar approach may be used to tailor the mechanical, thermal, and electrical properties of nanomaterials over a range of anticipated operating environments. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

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     

碳纳米管增强天然橡胶复合材料的制备与性能研究

碳纳米管以其特殊的结构与优异的性能成为橡胶的理想填料。本文分别采用四种不同牌号(分别为Flotube7000 9000 9011 9400)的碳纳米管为实验原料,制备了碳纳米管/天然橡胶复合材料,并对其性能进行了研究探讨。结果发现,碳纳米管的加入能显著提高复合材料的力学性能和热导率,具有一维取向排列且长径比较大的Flotube7000(以下简称7000)对力学性能的提高程度最大,Flotube7000以及经过酸处理的表面具有-OH、–COOH官能团的Flotube9011(以下简称9011)对导热性能提高程度最为明显。     

Functionalised multi‐walled carbon nanotubes for epoxy nanocomposites with improved performance

BACKGROUND: Carbon nanotubes (CNTs) are fast becoming key components in the production of high‐strength composite materials. Two methods to prepare nanocomposites by covalent bonding between an epoxy matrix and functionalised CNTs that acted as cross‐linkers during polymerisation were investigated. RESULTS: In the standard method, 1 wt% functionalised CNTs was dispersed in epoxy, hardener was added and the composite was cured. In the masterbatch approach, 1 wt% functionalised CNTs was mixed with epoxy in the presence of triethylamine accelerator, then cured. This yielded partially cured epoxy; additional hardener was required to achieve complete curing. Improvements were observed in storage modulus (E′), flexural modulus (E_B), wear resistance and hardness. Thermal stability did not change appreciably for samples prepared by either the standard or masterbatch methods. Variations in the results obtained as a function of preparation method, functionalised CNTs and hardener used are discussed. CONCLUSION: Epoxy nanocomposites having improved mechanical properties were obtained by incorporating functionalised CNTs. Better interaction between the epoxy and CNT was achieved using the masterbatch method; this was attributed to covalent bonding between the CNTs and epoxy. However, optimisation of the CNTs, accelerator and hardener used in composite preparation is required to obtain improved physical properties. Copyright © 2009 Society of Chemical Industry     

Effects of mineral fillers addition and preparation method on the morphology and electrical conductivity of epoxy/multiwalled carbon nanotube nanocomposites

This study investigated the correlation between the electrical conductivity and the micro and nanomorphology of multiwalled carbon nanotubes (MWCNTs)/epoxy nanocomposites with and without the inorganic fillers montmorillonite (MMT), sepiolite and calcium carbonate (CaCO₃). The nanocomposites were prepared by dispersing the MWCNT and fillers through ultrasonication directly in the resin or solvent. For nanocomposites without fillers, the compositions prepared with solvent demonstrated higher electrical conductivities, which correlate with a microscale morphology formed by networks of highly interconnected MWCNT agglomerates. The addition of MMT induced a deleterious effect on the electrical conductivity of the nanocomposites since this filler hinders the formation of MWCNT agglomerate networks. The effect of sepiolite on electrical conductivity is also negative, but in this case, nonmorphological effects are likely of greater importance. The addition of CaCO₃ improved the electrical conductivity of the binary nanocomposites under specific conditions. For this filler, a synergic effect was achieved for the composition prepared with solvent, which resulted in an approximately sixfold increase in electrical conductivity relative to the nanocomposite without filler.     

Flammability of thermoplastic carbon nanofiber nanocomposites

Five commodity thermoplastics (polyethylene, polypropylene, thermoplastic polyurethane, poly(butylene terephthalate), and poly(amide 6)) were melt compounded with vapor grown carbon nanofibers via twin screw extrusion. These materials were then analyzed for flammability behavior by cone calorimeter to determine how the nanofibers would reduce flammability of the polymers. It was found by cone calorimeter that the nanofibers greatly reduced peak heat release rate and improved many other flammability parameters of the samples. However, smoke release was increased in all samples, which may be one drawback of using these materials. Interestingly, the amount of flammability reduction was not uniform across all samples, with nanofiber reducing flammability the most in the thermoplastic polyurethane sample. The mechanism of flammability reduction in the polymers tested in this paper is shown again to be a mass loss rate reduction induced by the formation of thick tangled networks of carbon nanofibers during polymer decomposition. This mechanism was confirmed by studying the mass loss rate curves and electron microscopy analysis of the final chars collected from the cone calorimeter experiments. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of epoxy based nanocomposites

Epoxy‐clay nanocomposites were synthesized to examine the effects of the content and type of different clays on the structure and mechanical properties of the nanocomposites. Diglycidyl ether of bisphenol‐A (epoxy) was reinforced by 0.5–11 wt % natural (Cloisite Na⁺) and organically modified (Cloisite 30B) types of montmorillonite. SEM results showed that as the clay content increased, larger agglomerates of clay were present. Nanocomposites with Cloisite 30B exhibited better dispersion and a lower degree of agglomeration than nanocomposites with Cloisite Na⁺. X‐ray results indicated that in nanocomposites with 3 wt % Cloisite 30B, d‐spacing expanded from 18.4 Å (the initial value of the pure clay) to 38.2 Å. The glass transition temperature increased from 73°C, in the unfilled epoxy resin, to 83.5°C in the nanocomposite with 9 wt % Cloisite 30B. The tensile strength exhibited a maximum at 1 wt % modified clay loading. Addition of 0.5 wt % organically modified clay improved the impact strength of the epoxy resin by 137%; in contrast, addition of 0.5 wt % unmodified clay improved the impact strength by 72%. Tensile modulus increased with increasing clay loading in both types of nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1081–1086, 2005     

Preparation and thermal,electrical, and morphological properties of multiwalled carbon nanotubeand epoxy composites

Multiwalled carbon nanotube (MWCNT)/epoxy composites are prepared, and the characteristics and morphological properties are studied. Scanning electron microscopy microphotographs show that MWCNTs are dispersed on the nanoscale in the epoxy resin. The glass‐transition temperature (T_g) of MWCNT/epoxy composites is dramatically increased with the addition of 0.5 wt % MWCNT. The T_g increases from 167°C for neat epoxy to 189°C for 0.5 wt % CNT/epoxy. The surface resistivity and bulk resistivity are decreased when MWCNT is added to the epoxy resins. The surface resistivity of CNT/epoxy composites decreases from 4.92 × 10¹² Ω for neat epoxy to 3.03 × 10⁹ Ω for 1 wt % MWCNT/epoxy. The bulk resistivity decreases from 8.21 × 10¹⁶ Ω cm for neat epoxy to 6.72 × 10⁸ Ω cm for 1 wt % MWCNT/epoxy. The dielectric constant increases from 3.5 for neat epoxy to 5.5 for 1 wt % MWCNT/epoxy. However, the coefficient of thermal expansion is not affected when the MWCNT content is less than 0.5 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1272–1278, 2007