Nanostructured thermosetting epoxy systems modified with poly(isoprene‐b‐methyl metacrylate) diblock copolymer and polyisoprene‐grafted carbon nanotubes

Nanostructured thermosetting composites based on an epoxy matrix modified with poly(isoprene‐b‐methyl methacrylate) (PI‐b‐PMMA) block copolymer were prepared through PI block segregation. Morphological structures were examined by means of atomic microscopy force microscopy. As epoxy/pristine multi‐walled carbon nanotubes (MWCNT) systems were found to present big agglomerations, with a very poor dispersion of the nanofiller, epoxy/PI‐b‐PMMA/MWCNT systems were prepared by using polyisoprene‐grafted carbon nanotubes (PI‐g‐CNT) to enhance compatibility with the matrix and improve dispersion. It was found that the functionalization of MWCNT with grafted polyisoprene was not enough to totally disperse them into the epoxy matrix but an improvement of the dispersion of carbon nanotubes was achieved by nanostructuring epoxy matrix with PI‐b‐PMMA when compared with epoxy/MWCNT composites without nanostructuring. Nevertheless, some agglomerates were still present and the complete dispersion or confinement of nanotubes into desired domains was not achieved. Thermomechanical properties slightly increase with PI‐g‐CNT content for nanostructured samples, whereas for nonnanostructured epoxy/PI‐g‐CNT composites they appeared almost constant and even decreased for the highest nanofiller amount due to the presence of agglomerates. Compression properties slightly decreased with block copolymer content, while remained almost constant with nanofiller amount. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of carbon nanotube dispersion on the mechanical properties of phenolic resin composites

Despite the much touted mechanical properties of carbon nanotubes, composites reinforced with nanotubes have failed to achieve mechanical properties which rival those present in conventional fiber reinforced polymer composites. This article describes an attempt to bridge this gap. Multi‐walled carbon nanotubes (MWCNT) were synthesized using a chemical vapor deposition method and were dispersed in phenolic resin by both the wet and dry dispersion techniques before molding into composite bars (50 × 5 × 3 mm³). Although no improvement in the mechanical properties of the MWCNT/phenolic composites was observed over the neat resin value when wet mixing dispersion was employed, an improvement of nearly 158% (160 MPa as compared with 62 MPa for neat resin) was achieved in 5 vol% MWCNT containing phenolic resin prepared by the dry mixing. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Synthesis,morphology and physical properties of multi-walled carbon nanotube/biphenyl liquid crystalline epoxy composites

We have developed multi-walled carbon nanotube/liquid crystalline epoxy composites and studied the effects of incorporation carbon nanotubes (CNTs) on the morphology, thermal and mechanical properties of the composites. The CNTs are functionalized by liquid crystalline (LC) 4,4′-bis(2,3-epoxypropoxy) biphenyl (BP) epoxy resin for the ease of dispersion and the formation of long range ordered structure. The epoxy functionalized CNT (ef-CNT) were dispersed in the LC BP epoxy resin that can be thermal cured with an equivalent of 4,4′-diamino-diphenylsulfone to form composite. The curing process was monitored by polarized optical microscopy. The results indicate the LC resin was aligned along the CNTs to form fiber with dendritic structure initially then further on to obtain micro-sized spherical crystalline along with fibrous crystalline. With homogeneous dispersion and strong interaction between nanotubes and matrix, the composite containing 2.00 wt.% ef-CNT exhibits excellent thermal and mechanical properties. When the amount of ef-CNT exceeds 2.00 wt.%, vitrification stage of curing is fast reached, which lowers the degree of conversion. As compared with the neat resin, the composite containing 2.00 wt.% ef-CNT increases the glass transition temperature by 70.0 °C, the decomposition temperature by 13.8 °C, the storage modulus by 40.9%, and the microhardness by 63.3%.     

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.     

Simultaneous dispersion and alignment of carbon nanotubes in epoxy resin through chronoamperometry

A novel technique of dispersion, stretching and alignment of carbon nanotubes (CNTs) in an epoxy resin has been developed based on chronoamperometry. The procedure is to apply an electrical field in non-cured CNT/epoxy mixtures, using an electrode of large surface. CNT movements can be promoted by their intrinsic polarisation or by the introduction of electrical charges over their surfaces. The efficiency of the process can be monitored through the electrical current passing through the system as a function of time. Different experimental conditions, such as the applied voltage, have been analysed. The composites have been characterised through their thermal, mechanical and electrical behaviour. They show high dispersion degree of nanotubes, which are found to be stretched and untangled. CNTs show alignment along a preferred direction in the epoxy matrix, which affects to their electrical conductivity.     

Effects of surface modification on rheological and mechanical properties of CNT/epoxy composites

Despite superior properties of carbon nanotubes (CNTs), physical properties of the CNT/epoxy composites are not improved significantly because interfacial bonding between the CNTs and the polymer matrix is weak. CNTs were treated by an acidic solution to remove impurities and modified subsequently by amine treatment or plasma oxidation to improve interfacial bonding and dispersion of nanotubes in the epoxy matrix. The functional groups on the surface of treated CNTs were investigated by X-ray photoelectron spectroscopy. The surface modified CNTs were embedded in the epoxy resin by ultra-sonication and the cured nanotube containing composites were characterized by field emission scanning electron microscopy. Rheological properties of nanotube containing epoxy resin and mechanical properties of the modified CNT/epoxy composites were improved because the modification of CNTs improved dispersion and interaction between the CNT and the epoxy resin.     

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     

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.     

Investigation of CNT modification of epoxy resin in CFRP strengthening systems

The use of carbon fiber‐reinforced polymers (CFRPs) to reinforce old structures has become popular in recent years. In this study, the chemical structure of the epoxy resin used as the bonding agent in the CFRP strengthening system was modified by dispersing multi‐walled carbon nanotubes (MWCNTs) in order to improve the performance of the strengthening system. Composites were fabricated with different mixing orders employing the solvent‐assisted dispersion method and ultrasonic mixing. Thermogravimetric analysis, dynamic mechanical analysis, and tensile tests were conducted to investigate the effect of CNT dispersion and fabrication method on the thermal and mechanical properties of epoxy composite. In addition, the temperature‐dependent tensile behavior of fabricated composites was studied by performing tensile tests at elevated temperatures. The morphology of CNT/epoxy composites was characterized using scanning electron microscopy (SEM). Fourier transform infrared (FTIR) was also used to show the influence of solvent on the molecular structure of composites. Based on the experimental results, the decomposition temperature of the epoxy resin was heightened by 15°C as a result of solvent‐assisted dispersion of nanotubes. However, the glass transition temperature (T_g) was slightly reduced due to the solvent effect. FTIR analysis revealed that the solvent negatively affects the curing process of epoxy composite. A considerable enhancement was recorded in the tensile properties as a result of CNT infusion. This was attributed to the homogeneous dispersion of nanotubes which was shown by SEM images. Using solvent to disperse nanotubes led to the reduction of tensile strength of the epoxy composite at elevated temperature due to the lower T_g. POLYM. COMPOS. 37:1021–1033, 2016. © 2014 Society of Plastics Engineers     

Grafting of Amine-Functionalized Multiwall Carbon Nanotubes with Free Acid Anhydride in Carboxylic Acid Modified Epoxy

The novel approach was developed for grafting of amine-functionalized multiwall carbon nanotubes with carboxylic acid, modified epoxy resin containing free acid anhydride group, which gives enhanced grafting. The amine-functionalized multiwall carbon nanotubes was dispersed in benzyl alcohol by sonication at 60°C and incorporated with modified epoxy. The amine functioned Multiwall carbon nanotubes were controlled loading of carboxylic acid, modified epoxy resin-grafted with amine-functionalized multiwalll carbon nanotube polymer composites. These were characterized by FTIR, SEM. TEM and NMR analysis. The improved mechanical properties observed for low amounts of MWCNT loading due to uniform dispersion.     

Electrical and mechanical properties of acrylonitrile‐butadiene‐styrene/multiwall carbon nanotube nanocomposites prepared by melt‐blending

The electrical properties in polymer/carbon nanotube (CNT) nanocomposites are governed not only by the degree of dispersion but also to a greater extent on the aspect ratio of the CNTs in the final composites. Melt‐mixing of polymer and CNTs at high shear rate usually breaks the CNTS that lowers the aspect ratio of the nanotubes. Thus, homogeneous dispersion of CNTs while retaining the aspect ratio is a major challenge in melt‐mixing. Here, we demonstrate a novel method that involves melt‐blending of acrylonitrile‐butadiene‐styrene (ABS) and in situ polymerized polystyrene (PS)/multiwalled CNT (MWCNT) nanocomposites, to prepare electrically conducting ABS/MWCNT nanocomposites with very low CNT loading than reported. The rationale behind choosing PS/MWCNT as blending component was that ABS is reported to form miscible blend with the PS. Thus, (80/20 w/w) ABS/(PS/MWCNT) nanocomposites obtained by melt‐blending showed electrical conductivity value ≈1.27 × 10^?6 S cm^?1 at MWCNT loading close to 0.64 wt %, which is quite lower than previously reported value for ABS/MWCNT system prepared via solution blending. Scanning electron microscopy and differential scanning calorimetry analysis indicated the formation of homogenous and miscible blend of ABS and PS. The high temperature (100°C) storage modulus of ABS (1298 MPa) in the nanocomposites was increased to 1696 MPa in presence of 0.64 wt % of the MWCNT. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of carbon nanotube/epoxy composite films with a high nanotube loading by a mixed-curing-agent assisted layer-by-layer method and their electrical conductivity

A mixed-curing-agent assisted layer-by-layer method is reported to synthesize carbon nanotube (CNT)/epoxy composite films with a high CNT loading from ∼15 to ∼36 wt.%. The mixed-curing-agent consists of two types of agents, one of which is responsible for the partial initial curing at room temperature to avoid agglomeration of the CNTs, and the other for complete curing of epoxy resin at high temperature to synthesize epoxy composite films with good CNT dispersion. The electrical conductivity of the composites shows a value up to ∼12 S/m, which is much higher than that for CNT/epoxy composites with a low CNT loading prepared using conventional methods.     

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     

Dispersion, interfacial interaction and re-agglomeration of functionalized carbon nanotubes in epoxy composites

The surface, interfacial and dispersion properties of carbon nanotubes (CNTs), and the mechanical properties of the CNT/epoxy composites affected by CNT functionalization are investigated. It is demonstrated that there exists strong correlations between amino-functionalization, dispersion, wettability, interfacial interaction and re-agglomeration behaviour of CNTs and the corresponding mechanical and thermo-mechanical properties of CNT/epoxy composites. The amino-functionalized CNTs exhibit higher surface energy and much better wettability with epoxy resin than the pristine CNTs, and the attached amine molecules arising from the functionalization effectively inhibit the re-agglomeration of CNTs during the curing of resin. These ameliorating effects along with improved interfacial adhesion between the matrix and functionalized CNTs through covalent bonds result in improved flexural and thermo-mechanical properties compared with those without functionalization.     

Evaluation of mechanical properties of untwisted carbon nanotube yarn for application to composite materials

Carbon nanotubes (CNTs) with superior mechanical properties have been of interest as reinforcement for polymer composites. However, the length of individual CNTs is limited. As a solution, yarns spun by twisting together multi-walled carbon nanotubes (MWCNTs) have been reported. In this study, untwisted CNT yarns were prepared by a non-conventional method drawing CNTs through a die. The MWCNTs in these yarns are held together by strong van der Waals forces that arise due to the interactions on the long and smooth surfaces of the MWCNTs. Here, mechanical properties of untwisted CNT yarn were studied by tensile tests. The strength of the CNT yarn was increased by increasing the apparent density of the yarn. The CNT yarns showed high tensile strength of 1 GPa and elastic modulus of 79 GPa at a yarn diameter of 35 μm. The interfacial shear strength between the CNT yarn and epoxy resin was studied by the microdroplet method, and it was very low. The wettability of the CNT yarn was affected by a type of curing agent. A unidirectional composite of epoxy resin and CNT yarn was prepared by the pultrusion molding method. Mechanical properties of the unidirectional composite were affected by the type of curing agent.     

Nano- and microstructural effects on thermal properties of poly (l-lactide)/multi-wall carbon nanotube composites

In this work the thermal properties of poly (l-lactide)/multi-wall carbon nanotube (PLLA/MWCNT) composites have been investigated. Thermal conductivity was determined after measuring specific heat capacity (C_p), thermal diffusivity (D) and bulk density (ρ) of composites. Thermal conductivity rises up to 0.345 W/m K at 5 wt.% after reaching a minimum value of about 0.12 W/m K at 0.75 wt.%. In order to understand the heat-conduction process, experimentally obtained thermal conductivities were fitted to an existing theoretical model. The much lower thermal conductivity of composites compared with the value estimated from the intrinsic thermal conductivity of the nanotubes and their volume fraction could be explained in terms of the obtained large thermal resistance (R_k) of 1.8 ± 0.3 × 10^?8 m² K/W at nanotube–matrix interface. The CNT dispersion in the composites was analyzed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Although the thermal resistance dramatically reduces the estimated bulk thermal conductivity of composites, the existence of an interconnected conductive nanotube network for thermal diffusion in PLLA/MWCNT composites demonstrates that the addition of carbon nanotubes represents an efficient strategy in order to successfully enhance the thermal conductivity of insulator polymers.     

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.     

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     

Delamination toughness of fiber-reinforced composites containing a carbon nanotube/polyamide-12 epoxy thin film interlayer

We present a simple, out-of-autoclave approach to improve the delamination toughness of fiber-reinforced composites using epoxy interlayers containing 20 wt.% polyamide-12 (PA) particles and 1 wt.% multi-walled carbon nanotubes (MWCNTs). Composites were prepared by integrating partially cured thin films at the laminate mid-plane using vacuum-assisted resin transfer molding. The introduction of epoxy/PA interlayers increased fracture toughness due to the ductile deformation and crack bridging of PA particles within an interlaminar damage zone with uniform thickness of about 20 μm. Composites interlayered with epoxy/PA/MWCNT exhibited nearly 2.5 and 1.5 times higher fracture toughness than composites containing neat epoxy and epoxy/PA interlayers, respectively, without an observable increase in interlaminar thickness. The fracture surface was analyzed to identify failure modes responsible for the fracture toughness improvement. The MWCNTs are proposed to inhibit critical loading of defects by minimizing stress concentration within the interlaminar region, thereby enabling greater deformation of the PA particles during fracture.     

A study on rheological behavior of MWCNTs/epoxy composites

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