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.     

Doped polyaniline/multi-walled carbon nanotube composites: Preparation, characterization and properties

This study reports the synthesis of doped polyaniline in its emeraldine salt form (PANI-ES) with carboxylic acid and acylchloride groups contained multi-walled carbon nanotubes (designated as c-MWNTs and a-MWNTs) by in situ polymerization. Both Raman spectra and HRTEM images indicate that carboxylic acid and acylchloride groups formed at both ends and on the sidewalls of the MWNTs. Based on the π-π* electron interaction between aniline monomers and functionalized MWNT and hydrogen bonding interaction between the amino groups of aniline monomers and the carboxylic acid/acylchloride groups of functionalized MWNT, aniline molecules were adsorbed and polymerized on the surface of MWNTs. Structural analysis by FESEM and HRTEM showed that PANI-ES/c-MWNT and PANI-ES/a-MWNT composites are core (c-MWNT or a-MWNT)- shell (doped-PANI-ES) tubular structures with diameters of several tens to hundreds of nanometers, depending on the PANI content. The conductivities of 0.5 wt% functionalized MWNT containing PANI-ES/c-MWNT and PANI-ES/a-MWNT composites are 60-70% higher than that of PANI without MWNT.     

Doped polyaniline/multiwalled carbon nanotube composites: Preparation and characterization

Polyaniline (PANI)/multiwalled carbon nanotube (MWNT) composites with a uniform tubular structure were prepared from in situ polymerization by dissolving amino‐functionalized MWNT (a‐MWNT) in aniline monomer. For this the oxidized multiwalled nanotube was functionalized with ethylenediamine, which provided ethylenediamine functional group on the MWNT surface confirmed by Fourier‐transform infrared spectra (FT‐IR). The a‐MWNT was dissolved in aniline monomer, and the in situ polymerization of aniline in the presence of these well dispersed nanotubes yielded a novel tubular composite of carbon nanotube having an ordered uniform encapsulation of doped polyaniline. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the nanotubes were coated with a PANI layer. The thermal stability and electrical conductivity of the PANI /MWNTs composites were characterized by thermogravimetric analysis (TGA) and conventional four‐probe method respectively. Compared with pure PANI, the electrical conductivity and the decomposition temperature of the MWNTs/PANI composites increased with the enhancement of MWNT content in PANI matrix. POLYM. COMPOS., 34:1119–1125, 2013. © 2013 Society of Plastics Engineers     

High thermal conductive m‐xylylenediamine functionalized multiwall carbon nanotubes/epoxy resin composites

In this study, multiwall carbon nanotubes (MWNTs) functionalized by m‐xylylenediamine is used as thermal conductive fillers to improve their dispersibility in epoxy resin and the thermal conductivity of the MWNTs/bisphenol‐A glycidol ether epoxy resin composites. Functionalization with amine groups of MWNTs is achieved after such steps as carboxylation, acylation and amidation. The thermal conductivity, impact strength, flexural strength, and fracture surfaces of MWNTs/epoxy composites are investigated with different MWNTs. The results show that m‐xylylenediamine is successfully grafted onto the surface of the MWNTs and the mass fraction of the organic molecules grafted onto MWNTs is about 20 wt %. The thermal conductivity of MWNTs/epoxy composites is further enhanced to 1.236 W/mK with 2 wt % m‐MWNTs. When the content of m‐MWNTs is 1.5 wt %, the impact strength and flexural strength of the composites are 25.85 KJ/m², 128.1 MPa, respectively. Scanning electron microscope (SEM) results show that the fracture pattern of composites is changed from brittle fracture to ductile fracture. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41255.     

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     

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     

Preparation of antibacterial PDMAEMA‐functionalized multiwalled carbon nanotube via atom transfer radical polymerization

Poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) was grafted onto the bromine‐functionalized multiwalled carbon nanotubes (MWNTs) by applying an atom transfer radical polymerization (ATRP). The PDMAEMA‐functionalized MWNT was characterized by Fourier transform infrared, transmission electron microscopy, Raman spectroscopy, thermal gravimetric analysis, and four‐probe resistivity meter. The wt % of PDMAEMA present in the PDMAEMA‐functionalized MWNT was estimated by applying the thermogram results for thermal gravimetric analysis. Variations of PDMAEMA content in the PDMAEMA‐functionalized MWNT were tried by changing the ATRP process conditions such as the type of ligand and copper complex, the amount of DMAEMA based on the weight of bromine‐functionalized MWNT, and the polymerization temperature. The phase behavior of PDMAEMA‐functionalized MWNT in water depending on temperature and pH value was analyzed, and the PDMAEMA‐functionalized MWNT showed the amphipathic nature. The PDMAEMA‐functionalized MWNT clearly showed an antibacterial effect against E. coli as well as S. aureus. The highest viability loss of E. coli achieved in this study was ～ 42% with the PDMAEMA‐functionalized MWNT containing 53.9 wt % of PDMAEMA. The PDMAEMA‐functionalized MWNT showed sheet resistance less than ～ 9.68 × 10³ Ω/sq. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci., 2013     

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.     

Functionalizing carbon nanotubes by grafting cyclotriphosphazene derivative to improve both mechanical strength and flame retardancy

An intumescent flame‐retardant, hex(4‐carboxylphenoxy) cyclotriphosphazene (HCPCP) was synthesized and covalently grafted on to the surface of multiwalled carbon nanotubes (MWNTs) to obtain MWNT‐HCPCP. MWNT/epoxy resin (EP) and MWNT‐HCPCP/ EP nanocomposites were prepared via thermal curing. Transmission electron microscopy results showed that a core–shell structure with MWNTs as the hard core and HCPCP as the soft shell were formed after HCPCP (10 wt%) were attached to the MWNTs. The results of flammability tests showed an increased limited oxygen index value for MWNT‐HCPCP/EP nanocomposites. The mechanical properties including tensile strength and elongation were both dramatically improved due to the better dispersion of MWNT‐HCPCP in the EP matrix. The grafting of HCPCP can improve both the dispersion of nanotubes in polymer matrix and flame retardancy of the nanocomposites. POLYM. COMPOS., 35:2187–2193, 2014. © 2014 Society of Plastics Engineers     

Grafting polyamide 6 onto multi‐walled carbon nanotubes using microwave irradiation

Chemical reactions under microwave irradiation can be very efficient, with a significant shortening of reaction time. Few studies have reported the use of microwaves to functionalize carbon nanotubes. In the work reported, a new method of formulating functionalized multi‐walled carbon nanotubes (MWNTs) was developed by covalent grafting of polyamide 6 (PA6) chains onto the carbon nanotubes assisted by microwave irradiation. PA6 chains were grafted onto acidified MWNTs through condensation reaction between the carboxylic groups of the MWNTs and the terminal amine groups of PA6 using microwave radiation heating. The functionalized carbon nanotubes (MWNT‐g‐PA6) were characterized systematically using infrared and Raman spectroscopy, transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). TEM showed that the surface of the MWNTs was covered with a layer of PA6. TGA results indicated that the MWNT‐g‐PA6 contained about 47 wt% of polymer. A novel, convenient and efficient functionalization approach is reported, involving covalently grafting PA6 chains onto MWNTs assisted by microwave irradiation. Copyright © 2010 Society of Chemical Industry     

Preparation and characterization of alkylated carbon nanotube/polyimide nanocomposites

BACKGROUND: The development of carbon nanotube‐reinforced composites has been impeded by the difficult dispersion of the nanotubes in polymers and the weak interaction between the nanofiller and matrices. Efficient dispersion of carbon nanotubes is essential for the formation of a functional nanotube network in a composite matrix. RESULTS: Multiwalled carbon nanotubes (MWNTs) were incorporated into a polyimide matrix to produce MWNT/polyimide nanocomposites. To disperse well the MWNTs in the matrix and thus improve the interfacial adhesion between the nanotubes and the polymer, ‘branches’ were grafted onto the surface of the nanotubes by reacting octadecyl isocyanate with carboxylated MWNTs. The functionalized MWNTs were suspended in a precursor solution, and the dispersion was cast, followed by drying and imidization to obtain MWNT/polyimide nanocomposites. CONCLUSION: The functionalized MWNTs appear as a homogeneous dispersion in the polymer matrix. The thermal stability and the mechanical properties are greatly improved, which is attributed to the strong interactions between the functionalized MWNTs and the polyimide matrix. Copyright © 2009 Society of Chemical Industry     

A comparative study on dispersion of carbon nanotubes in (styrene‐butadiene rubber)‐based nanocomposites

The efficient dispersion of carbon nanotubes (CNTs) is a challenging task in reaching the usable nanocomposites. In this study, a comparative analysis on dispersion of multiwalled CNTs multiwalled carbon nanotubes (MWNTs) in styrene‐butadiene rubber (SBR) latex was carried out by using two anionic surfactants, sodium dodecyl benzene sulfonate and sodium lauryl sulfate. The MWNTs were first predispersed in distilled water using two surfactants individually followed by gentle mixing the MWNT predispersion into SBR latex. By using the technique of ultraviolet‐visible spectroscopy, the study on MWNT dispersion in aqueous media was focused on surfactant concentration, MWNT functionality, and ultrasonication time. The ultraviolet‐visible absorptions showed the positive effect of MWNT functionality in addition to surfactant concentration with no great effect of ultrasonication time over 15 min. In comparison with sodium lauryl sulfate, the existing benzene ring in the sodium dodecyl benzene sulfonate structure seems to result in higher adsorption of surfactant onto the MWNTs surface and, hence, better MWNT dispersion. The MWNT dispersion was further improved by using hydroxyl functionalized MWNTs mainly because of the formation of hydrogen bonding between the hydrophilic head of surfactant and the existing hydroxyl group of the functionalized MWNTs. After mixing the MWNT predispersion into SBR latex, the dispersion of MWNTs was further characterized by using electrical volume conductivity, microscopy technique, and rheological measurements. In rheometry tests of the lattices, the storage modulus at terminal zone was utilized for tracking the degree of MWNT dispersion in the nanocomposite. The pictures of scanning electron microscopy showed the efficiency of MWNT functionality in enhancing the degree of dispersion. In conductivity tests, the percolation threshold was obtained at about 1 part by weight per hundred parts of resin of the functionalized MWNT in dried film. J. VINYL ADDIT. TECHNOL., 23:28–34, 2017. © 2015 Society of Plastics Engineers     

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     

环氧树脂/多壁碳纳米管导电复合材料研究

采用不同氧化性的酸对多壁碳纳米管(MWNTs)进行处理,制备了环氧树脂(EP)/MWNTs导电复合材料.研究表明,少量的MWNTs就能使EP的导电性能有很大的提高;HNO3>酸化处理不仅可在MWNTs表面引入活性基团并将MWNTs截短到合适的长度,改善其在树脂中的分散性,而且能有效去除非晶碳杂质,提高MWNTs的导电性,使EP/MWNTs复合材料的导电性能最好,渗流阈值只有0.5%左右;未处理的MWNTs在EP中的分散性较差,复合材料的渗流阈值为1.3%左右;而经混酸酸化处理的MWNTs中存在许多缺陷,且MWNTs的长度变得太短,复合材料的导电性能最差,渗流阈值为1.6%左右.     

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     

Synthesis and characterization of polyimide/multi‐walled carbon nanotube nanocomposites

Polyimide/multi‐walled carbon nanotube (PI‐MWNT) nanocomposites were fabricated by an in situ polymerization process. Chemical compatibility between the PI matrix and MWNTs is achieved by pretreatment of the carbon nanotubes in a mixture of sulfuric acid and nitric acid. The dispersion of MWNTs in the PI matrix was found to be enhanced significantly after acid modification. The glass transition (T_g) and decomposition (T_d) temperature of PI‐MWNT nanocomposites were improved as the MWNT content increased from 0.5 to 15 wt%. The storage modulus of the PI/MWNT nanocomposites is nine times higher than that of pristine PI at room temperature. The tensile strength of PI doubles when 7 wt% MWNTs is added. The dielectric constant of the PI‐MWNT nanocomposites increased from 3.5 to 80 (1 kHz) as the MWNT content increased to 15 wt%. The present study demonstrates that enhanced mechanical properties can be obtained through a simple in‐situ polymerization process. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Poly(ethylene terephthalate) nanocomposite fibers with functionalized multiwalled carbon nanotubes via in-situ polymerization

Poly(ethylene terephthalate) (PET) hybrids with newly synthesized functionalized multiwalled carbon nanotubes (MWNTs) were obtained by carrying out the in situ polycondensation of ethylene glycol with dimethyl terephthalic acid. The PET hybrids were melt-spun to produce monofilaments with various functionalized MWNT contents and draw ratios (DRs). The thermomechanical properties and morphologies of the PET hybrid fibers were determined using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide angle X-ray diffraction (XRD), electron microscopy (SEM and TEM), and a universal tensile machine (UTM). The XRD analysis and TEM micrographs show that the levels of nanosize dispersion can be controlled by varying the MWNT content. It was found that the addition of only a small amount of functionalized MWNTs was sufficient to improve the properties of the PET hybrid fibers. The maximum enhancement in the ultimate tensile strength was found to arise at a functionalized MWNT content of 0.5 wt %. However, the initial modulus was found to increase linearly with increases in the functionalized MWNT loading from 0 to 1.5 wt %. The thermal properties and conductivities of the PET hybrid fibers were found to be better than those of pure PET fibers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of thermally conductive polystyrene/carbon nanotubes composites

Thermally conductive polystyrene (PS)/multi‐walled carbon nanotubes (MWNTs) nanocomposites was prepared through a simple solution‐evaporation method assisted by ultrasonic irradiation. To enhance the dispersion of MWNTs in PS, MWNTs were chemically functionalized with poly(styrene‐co‐maleic anhydride) (SMA) (MWNT‐g‐SMA), which had benzene group and exhibited strong affinity with PS. The thermal conductive properties of PS increased and the mechanical properties decreased in presence of MWNTs, while by addition of MWNT‐g‐SMA, the properties of the composites can be improved to some extent. The thermal conductivity can reach 0.89 W/m K for the composite with 33.3 vol % MWNT‐g‐SMA, which was four times higher than that of neat PS. A linear increase of the thermal conductivity was observed with increasing MWNTs‐g‐SMA content, and the Maxwell–Eucken model and the Agari model were used for theoretical evaluation. Compared with MWNT‐OH, MWNT‐g‐SMA with larger diameter exhibited diffused boundary with the PS matrix, resulting from the strong interfacial bonding of the two phases. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study on the performance of syntactic foam reinforced by hybrid functionalized carbon nanotubes

Hollow glass microspheres (HGMs)/epoxy syntactic foam were reinforced by hybrid functionalized carbon nanotubes that were synthesized by simultaneous covalent and noncovalent functionalization of carbon nanotubes. The effect of hybrid functionalized carbon nanotubes on density, mechanical properties, and water absorption of HGMs/epoxy syntactic foam was studied. The study indicated that the dispersion of carbon nanotubes in epoxy resin can be improved by hybrid functionalization. The compression strength of syntactic foam reinforced by hybrid functionalized carbon nanotubes was significantly enhanced. The maximum compressive strength of syntactic foam corresponding to chitosan modified carbon nanotubes approached 60 MPa. Hybrid functionalized carbon nanotubes had little effect on the water absorption ability of syntactic foam, and was less than 1%. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48586.     

Polymeric carbon nanocomposites from multiwalled carbon nanotubes functionalized with segmented polyurethane

Multiwalled carbon nanotubes (MWNT) were functionalized with segmented polyurethanes (PU) by the “grafting to” approach. Raman and X‐ray photoelectron spectroscopy (XPS) spectra show that the sidewalls of MWNTs have been functionalized with acid treatment, and the amount of COOH increases with increasing acid treatment time. FTIR and X‐ray diffraction (XRD) spectra confirm that PU is covalently attached to the sidewalls of MWNTs by esterification reaction. Similar to the parent PU, the functionalized carbon nanotube samples are soluble in highly polar solvents, such as dimethyl sulfoxide (DMSO) and N,N‐dimethylformamide (DMF). The functionalized acid amount and the grafted PU amount were determined by thermogravimetric analyses (TGA). Comparative studies, based on SEM images between the PU‐functionalized and chemically defunctionalized MWNT samples, also reveal the covalent coating character. Dynamic mechanical analysis (DMA) of nanocomposite films prepared from PU and PU‐functionalized MWNTs show enhanced mechanical properties and increased soft segment T_g. Tensile properties indicate that PU‐functionalized MWNTs are effective reinforcing fillers for the polyurethane matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007