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     

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     

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.     

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     

Polymer nanocomposites reinforced with multi‐walled carbon nanotubes for semiconducting layers of high‐voltage power cables

Polymer nanocomposites reinforced with multi‐walled carbon nanotubes (MWCNTs) have been newly introduced for semiconducting layers of high‐voltage electrical power cables. Homogeneity of the MWCNT‐reinforced polymer nanocomposites was achieved by solution mixing, and their mechanical, thermal and electrical properties were investigated depending on the type of polymer. By changing the polymer matrix, the volume resistance of the MWCNT‐reinforced polymer nanocomposites could be varied by more than four orders of magnitude. Through systematic experiments and analysis, two possible factors affecting the volume resistance were found. One is the degree of crystallinity of the polymer used and the other is the change of MWCNT morphology under strain. By increasing the degree of crystallinity above a certain level, the volume resistance linearly increased. The MWCNTs embedded in the nanocomposites gradually protruded through the surface on stretching the sample and reversibly returned back to the original positions at a relatively small strain (below 20%). Based on the criteria of tensile properties and volume resistance, a poly[ethylene‐co‐(ethyl acrylate)]/MWCNT nanocomposite was selected as the best candidate for the semiconducting layers of high‐voltage electrical power cables. Copyright © 2009 Society of Chemical Industry     

Rheological properties and fracture toughness of epoxy resin/multi‐walled carbon nanotube composites

Multi‐walled carbon nanotubes (MWCNTs), surface‐treated via chemical functionalization, i.e., oxidation and amidation, were used to reinforce diglycidylether of bisphenol F (DGEBF) epoxy resin. The effects of the functionalization on the dispersion stability, rheological properties, and fracture toughness of DGEBF/MWCNT composites were investigated. The dispersion homogeneity of the MWCNTs in the epoxy matrix improved after functionalization. In addition, isothermal rheology measurements revealed that the DGEBF/dodecyl amine‐functionalized MWCNT (D‐MWCNT) composite had a longer gel time and higher activation energy of cross‐linking than the DGEBF/acid‐treated MWCNT (A‐MWCNT) composite. The fracture toughness of the former was also significantly higher than that of the latter; this resulted from the relatively high dispersion stability of the D‐MWCNTs in the epoxy matrix, owing to the presence of alkyl groups on the D‐MWCNT surface. POLYM. ENG. SCI., 55:2676–2682, 2015. © 2015 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     

Electrical and mechanical properties of multi‐walled carbon nanotubes reinforced PMMA and PS composites

The use of multi‐walled carbon nanotubes (MWCNT) as reinforcing material for thermoplastic polymer matrices, polymethyl methacrylate (PMMA), and polystyrene (PS) has been studied. MWCNT were synthesized by chemical vapor deposition (CVD) technique using ferrocene‐toluene mixture. As‐prepared nanotubes were ultrasonically dispersed in toluene and subsequently dispersed in PMMA and PS. Thin polymer composite films were fabricated by solvent casting. The effect of nanotube content on the electrical and mechanical properties of the nanocomposites was investigated. An improvement in electrical conductivity from insulating to conducting with increasing MWCNT content was observed. The carbon nanotube network showed a classical percolating network behavior with a low percolation threshold. Electromagnetic interference (EMI) shielding effectiveness value of about 18 dB was obtained in the frequency range 8.0–12 GHz (X‐band), for a 10 vol% CNT loading. An improved composite fabrication process using casting followed by compression molding and use of functionalized MWCNT resulted in increased composites strength. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Electrically conductive multi‐walled carbon nanotube‐reinforced amorphous polyamide nanocomposites

Nanocomposites (NCs) based on an amorphous polyamide (aPA) and multi‐walled carbon nanotubes (MWCNTs) were obtained by melt‐mixing. As individual nanotubes were mostly observed, dispersion of the carbon nanotubes was deemed good. The electrical percolation threshold (p_c) occurred at 2.97 wt% MWCNTs and as a result, electrical conductivity improved by nine orders of magnitude upon addition of 6 wt% MWCNTs. The 6 wt% MWCNTs also led to an increase in both thermal stability (measured by the degradation temperature) and Young's modulus (19%) for the NCs, and ductility remained the same. POLYM. COMPOS., 35:587–595, 2014. © 2013 Society of Plastics Engineers     

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     

Electrically conductive polycarbonate/ethylene‐propylene copolymer/multi‐walled carbon nanotubes nanocomposites with improved mechanical properties

In this article, the effect of Multi‐walled carbon nanotubes (MWCNTs) on the electrical conductivity and mechanical properties of polycarbonate (PC) toughened with cross‐linked ethylene‐propylene copolymer (EPC) was investigated. The solubility parameters of the PC and EPC were calculated using Hoy methods to clarify the miscibility of the polymer blends. It could be concluded that in the cooled state, the blends form a heterogeneous structure with two separate phases. The tensile, flexural, impact toughness properties of the PC/EPC blend and PC/EPC/MWCNT nanocomposites were carried out to illuminate the optimum concentration of polymer blends and MWCNTs. The 335% increment for the impact strength results appeared with combination of 10% EPC in the PC matrix. The flexural modulus and strength of PC/EPC blend increased by 75.1% and 59.1%, respectively. The Nielsen model was performed to fit the best curve of theoretical simulation to experimental results for elastomeric dispersed in the plastic matrix. Halpin‐Tsai model was applied to estimate the stiffness of nanocomposites blends with different volume fraction and aspect ratio of MWCNTs in the PC/EPC blends. Finally, in the presence of MWCNTs, all nanocomposite samples were semi‐conducting and the percolation threshold of the PC/EPC (10%) blends was between 0.5% and 1.0% MWCNTs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44661.     

Effect of the addition of multi‐walled carbon nanotubes on the thermomechanical properties of epoxy resin

The influence of multi‐walled carbon nanotubes (MWCNTs) on thermosetting epoxy is examined using dynamic mechanical analysis, thermogravimetric analysis, and differential scanning calorimetry (DSC). Specimens are prepared with loadings of 0.1 and 1 wt% MWCNTs which are dispersed in the resin using two different dispersion methods. While the storage modulus of the specimens is improved, both the glass transition temperature and the thermal stability are reduced by the addition of MWCNTs with both effects being greater for the higher MWCNT loading, for both dispersion systems. The DSC results additionally indicate that the level of residual unreacted epoxy increases progressively with the addition of the nanotubes. This finding is considered as confirmation that the MWCNTs obstruct crosslinking of the epoxy resin. POLYM. COMPOS., 38:1873–1880, 2017. © 2015 Society of Plastics Engineers     

Mechanical,thermal and electrical properties of multi‐walled carbon nanotube/aluminium nitride/polyetherimide nanocomposites

A series of polyimide‐based nanocomposites containing polyimide‐grafted multi‐walled carbon nanotubes (PI‐g MWCNTs) and silane‐modified ceramic (aluminium nitride (AlN)) were prepared. The mechanical, thermal and electrical properties of hybrid PI‐g MWCNT/AlN/polyetherimide nanocomposites were investigated. After polyimide grafting modification, the PI‐g MWCNTs showed good dispersion and wettability in the polyetherimide matrix and imparted excellent mechanical, electrical and thermal properties. The utilization of the hybrid filler was found to be effective in increasing the thermal conductivity of the composites due to the enhanced connectivity due to the high‐aspect‐ratio MWCNT filler. The use of spherical AlN filler and PI‐g MWCNT filler resulted in composite materials with enhanced thermal conductivity and low coefficient of thermal expansion. Results indicated that the hybrid PI‐g MWCNT and AlN fillers incorporated into the polyetherimide matrix enhanced significantly the thermal stability, thermal conductivity and mechanical properties of the matrix. Copyright © 2012 Society of Chemical Industry     

Thermo-physical and impact properties of epoxy nanocomposites reinforced by single-wall carbon nanotubes

The thermo-physical properties and the impact strength of diglycidyl ether of bisphenol F (DGEBF) epoxy nanocomposites reinforced with fluorinated single-wall carbon nanotubes (FSWCNT) are reported. A sonication technique was used to disperse FSWCNT in the glassy epoxy network resulting in nanocomposites having large improvement in modulus with extremely small amount of FSWCNT. The glass transition temperature decreased approximately 30 °C with an addition of 0.2 wt% (0.14 vol%) FSWCNT, without adjusting the amount of the anhydride curing agent. This was because of non-stoichiometry of the epoxy matrix that was caused by the fluorine on the single-wall carbon nanotubes. The correct amount of the anhydride curing agent needed to achieve stoichiometry was experimentally examined by dynamic mechanical analysis (DMA). The storage modulus of the epoxy at room temperature (which is below the glass transition temperature of the nanocomposites) increased up to 0.63 GPa with the addition of only 0.30 wt% (0.21 vol%) of FSWCNT, representing an up to 20% improvement compared with the neat epoxy. The Izod impact strength slightly decreased when the amount of FSWCNT was increased to 0.3 wt%. The excellent improvement in the storage modulus was achieved without sacrificing impact strength.     

Enhanced dielectric properties of polyamide 11/multi‐walled carbon nanotubes composites

Composites with multi‐walled carbon nanotubes (MWNTs) involved in polyamide 11 (PA11) were prepared via a conventional melt blending method. The structure, morphology, crystallization behavior, electrical, and dielectric properties of composites were investigated. The results demonstrated that the dispersed uniformly MWNTs favored the formation of α crystal of PA11 when the composites were quenched from melt. The dielectric constant of composites was dependent on the electric field frequency and MWNTs content, and the highest value of dielectric constant was as high as 350 for the composite with 1.21 vol % MWNTs at 10³ Hz, accompanied by a low dielectric loss. The enhanced dielectric properties could be interpreted by the formation of abundant nanocapacitors within the composites and the interfacial polarization effect resulting from accumulation of charge carriers at the internal interfaces between MWNTs and PA11. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42642.     

Epoxy resin nanocomposites reinforced with ionized liquid stabilized carbon nanotubes

Epoxy resin nanocomposites reinforced with three different ionic liquid functionalized carbon nanotubes (f-CNTs) were fabricated by an in situpolymerization method. The influence of the anions on the curing process was studied through differential scanning calorimetry (DSC) and normalized Fourier transform infrared (FTIR) spectroscopy. The composition of the nanocomposites was analyzed by X-ray photoelectron spectroscopy. Two different mechanisms are proposed to explain the curing process of the neat epoxy and its composites. The electric conductivity and mechanical properties of the nanocomposites are also reported. The tensile strength was increased dramatically due to the insertion of f-CNTs. Scanning electron microsopy fracture surface analysis indicates a strong interfacial bonding between the carbon nanotubes and the polymer matrix.     

Mechanical and surface properties of polyurethane/fluorinated multi‐walled carbon nanotubes composites

To improve the mechanical and surface properties of poly(etherurethane) (PEU), multi‐walled carbon nanotubes (MWCNTs) were surface grafted by 3,3,4,4, 5,5,6,6,7,7,8,8,8‐tridecafluoro‐1‐octanol (TDFOL) (MWCNT‐TDFOL) and used as reinforcing agent for PEU. Fourier‐transform infrared spectroscopy revealed the successful grafting of MWCNTs. PEU filled with MWCNT‐TDFOL could be well dispersed in tetrahydrofuran solution, and tensile stress–strain results and dynamic mechanical analysis showed a remarkable increase in mechanical properties of PEU by adding a small amount of MWCNT‐TDFOL. Contact angle testing displayed a limited improvement (just 9°) in the hydrophobicity of PEU surface by solution blending with MWCNT‐TDFOL. However, a large improvement of surface hydrophobicity was observed by directly depositing MWCNT‐TDFOL powder on PEU surface, and the water contact angle was increased from 80° to 138°. Our work demonstrated a new way for the modification of carbon nanotubes and for the property improvement of PEU. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal degradation behaviour of multi‐walled carbon nanotube‐reinforced poly(L‐lactide) nanocomposites

BACKGROUND: Polymer/multi‐walled carbon nanotube (MWCNT) composites are one of the most promising alternatives to conventional polymer composites filled with micrometre‐sized fillers. This approach can also be applied for the improvement of mechanical properties and thermal stability of biodegradable aliphatic polyesters, such as poly(L ‐lactide) (PLLA), which have been receiving increasing attention due to environmental concerns. Thermal degradation behaviour provides useful information for the determination of the optimum processing conditions and for identification of potential applications of final products. RESULTS: The PLLA/MWCNT composites investigated showed a higher thermal degradation peak temperature and onset temperature of degradation along with a higher amount of residue at the completion of degradation than neat PLLA. Moreover, PLLA/MWCNT composites with a greater MWCNT content showed higher activation energy of thermal degradation than those with a lower MWCNT loading, which confirmed the positive effect of MWCNT incorporation on the enhancement of PLLA thermal stability. CONCLUSION: This study explored the thermal degradation behaviour of PLLA/MWCNT composites by observing the weight loss, molecular weight and mechanical properties during non‐isothermal and isothermal degradation. The incorporation of MWCNTs into the PLLA matrix enhanced considerably the mechanical properties and thermal stability. Copyright © 2009 Society of Chemical Industry     

Morphology,thermal, and electrical properties of polypropylene hybrid composites co‐filled with multi‐walled carbon nanotubes and graphene nanoplatelets

In this study, nanocomposites of polypropylene (PP) with various loadings of multi‐wall carbon nanotubes (MWCNT) and graphene nanoplatelets (GnP) were formed by masterbatch dilution/mixing approach from individual masterbatches PP‐MWCNT and PP‐GnP. Melt mixing on a twin‐screw extruder at two different processing temperatures was followed by characterization of morphology by transmitted‐light microscopy including the statistical analysis of agglomeration behavior. The influence of processing temperature and weight fractions of both nanofillers on the dispersion quality is reported. Thermal properties of the nanocomposites investigated by DSC and TGA show sensitivity to the nanofillers weight fraction ratio and to processing conditions. Electrical conductivity is observed to increase up to an order of magnitude with the concentration of each nanofiller increasing from 0.5 wt % to 1.0 wt %. This is related with a decrease of electrical conductivity observed for unequal concentration of both nanofillers. This particular behavior shows the increase of electrical properties for higher MWCNT loadings and the increase of thermo‐mechanical properties for higher GnP loadings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42793.     

Thermo‐mechanical and tribological properties of multi‐walled carbon nanotubes filled friction composite materials

Multi‐walled carbon nanotubes (MWCNTs) filled graphite lubricated phenolic‐based friction composites reinforced with combination of lapinus/Kevlar fibers have been fabricated and subsequently evaluated for their dynamic‐mechanical and tribological properties. The experimental results indicated that the higher MWCNT content enhances the thermal stability, whereas, lower MWCNT content enhances the thermo‐mechanical properties of the friction composites. The tribo‐performance evaluation has revealed that with the increase in MWCNT content, the friction‐fade and friction‐recovery performances are enhanced. The friction‐stability and friction‐variability coefficients are influenced by the combination of MWCNT, graphite, lapinus, and Kevlar constituents. The wear performance decreases with the increase in lapinus and MWCNT, whereas, it increases when the amount of Kevlar or graphite is increased in the composites. Wear surface morphological studies have led to the qualitative characterization of the topographical attributes and the nature of the frictional contact patches which is crucial in understanding the role of MWCNT on friction and wear mechanisms of the investigated automotive brake friction materials. POLYM. COMPOS., 38:1183–1193, 2017. © 2015 Society of Plastics Engineers