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.     

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     

Modeling of effective elastic properties for polymer based carbon nanotube composites

Effective elastic properties of the nanocomposites filled with carbon nanotubes (CNTs) are investigated by the asymptotic expansion homogenization (AEH) method. In order to implement the homogenization method, a control volume finite element method (CVFEM) is employed in contrast to the previous studies. It is assumed that the nanocomposites have geometric periodicity with respect to local length scale and the elastic properties of nanocomposites can be represented by those of the representative volume element (RVE). Random orientation of the CNTs embedded in the nanocomposites is considered by using the orientation tensor. The effective elasticity tensor predicted by the homogenization method is compared with analytical and experimental results. In the experiment, the CNT surface is treated by oxygen plasma to improve interfacial bonding between the CNT and the matrix and to disperse the CNTs homogeneously in epoxy resin because the perfect interfacial bonding is presumed in the homogenization method. Homogeneous CNT dispersion is experimentally identified by the field emission scanning electronic microscope (FESEM). It is found that the numerically calculated elastic modulus is in good agreement with that obtained by analytic model.     

Reinforcement of epoxy resins with multi-walled carbon nanotubes for enhancing cryogenic mechanical properties

Epoxy resins are widely applied in cryogenic engineering and their cryogenic mechanical properties as important parameters have to be improved to meet the high requirements by cryogenic engineering applications. Carbon nanotubes (CNTs) are regarded as exceptional reinforcements for polymers. However, poor carbon nanotube (CNT)–polymer interfacial bonding leads to the unexpected low reinforcing efficiency. This paper presents a study on the cryogenic mechanical properties of multi-walled carbon nanotube reinforced epoxy nanocomposites, which are prepared by adding multi-walled carbon nanotubes (MWCNTs) to diglycidyl ether of bisphenol-F epoxy via the ultrasonic technique. When the temperature decreases from room temperature to liquid nitrogen temperature (77 K), a strong CNT–epoxy interfacial bonding is observed due to the thermal contraction of epoxy matrix because of the big differences in thermal expansion coefficients of epoxy and MWCNTs, resulting in a higher reinforcing efficiency. Moreover, synthetic sequence leads to selective dispersion of MWCNTs in the brittle primary phase but not in the soft second phase in the two phase epoxy matrix. Consequently, the cryogenic tensile strength, Young's modulus, failure strain and impact strength at 77 K are all enhanced by the addition of MWCNTs at appropriate contents. The results suggest that CNTs are promising reinforcements for enhancing the cryogenic mechanical properties of epoxy resins that have potential applications in cryogenic engineering areas.     

The reduction of carbon nanotube (CNT) length during the manufacture of CNT/polymer composites and a method to simultaneously determine the resulting CNT and interfacial strengths

Carbon nanotube/epoxy composites with an excellent dispersion of carbon nanotubes (CNTs) were prepared using a three-roll calandering technique. CNT length after processing of composites is measured and then characterized using a two-parameter Weibull distribution function. Significant reduction of the CNT length is observed as a result of the processing and it is thus suggested that great attention should be paid to the retention of CNT length after processing in order to obtain good mechanical properties. Because of the difficulties in manipulating nanometer sized CNTs during measurement of CNT strength and CNT-polymer interfacial strength, CNT strength and CNT-polymer interfacial strength have previously been determined using complicated methods with expensive or specially designed equipments. In this work a simple methodology based on the modified rule of mixtures is proposed to simultaneously determine the CNT strength and CNT-polymer interfacial strength.     

Interfacial improvement of carbon fiber/epoxy composites using a simple process for depositing commercially functionalized carbon nanotubes on the fibers

An aqueous suspension deposition method was used to coat the sized carbon fibers T700SC and T300B with commercially carboxylic acid-functionalized and hydroxyl-functionalized carbon nanotubes (CNTs). The CNTs on the fiber surfaces were expected to improve the interfacial strength between the fibers and the epoxy. The factors affecting the deposition, especially the fiber sizing, were studied. According to single fiber-composite fragmentation tests, the deposition process results in improved fiber/matrix interfacial adhesion. Using carboxylic acid-functionalized CNTs, the interfacial shear strength was increased 43% for the T700SC composite and 12% for the T300B composite. The relationship between surface functional groups of the CNTs and the interfacial improvement was discussed. The interfacial reinforcing mechanism was explored by analyzing the surface morphology of the carbon fibers, the wettability between the carbon fibers and the epoxy resin, the chemical bonding between the fiber sizing and the CNTs, and fractographic observation of cross-sections of the composites. Results indicate that interfacial friction, chemical bonding and resin toughening are responsible for the interfacial improvement of nanostructured carbon fiber/epoxy composites. The mechanical properties of the CNT-deposited composite laminate were further measured to confirm the effectiveness of this strategy.     

The role of multi‐walled carbon nanotubes in epoxy nanocomposites and resin transfer molded glass fiber hybrid composites: Dispersion,local distribution,thermal, and fracture/mechanical properties

Hybrid composites containing endless glass fiber reinforcement and surface‐functionalized carbon nanotubes (CNTs) dispersed in the matrix phase were produced by resin transfer molding (RTM). An efficient surface modification of the nanotubes enhances the compatibility with the matrix system and the dispersion quality, enabling the impregnation process via liquid composite molding. We assessed the quality of the RTM process by newly developed methodologies for the quantification of the filtering of CNTs. First, we established a method to analyze the CNT length distribution before and after injection for thermosetting composites to characterize length‐dependent withholding respectively the size distribution of nanotubes in the hybrid composites. Second, the resulting test laminates were locally examined by Raman spectroscopy and compared to reference (nanocomposite) samples of known CNT content to non‐destructively quantify the local CNT concentration along the resin flow path. Moreover, the thermal and mechanical properties of the modified composites were investigated. The nanocomposites containing 0.5 wt% surface‐functionalized CNTs exhibited superior ductility and increased fracture toughness. Glass fiber hybrid composites containing 0.5 wt% functionalized CNTs in the resin phase exhibited increased fracture toughness in mode I and a slight deterioration in mode II due to the constrained formation of hackles. POLYM. COMPOS., 38:1849–1863, 2017. © 2015 Society of Plastics Engineers     

Mapping local microstructure and mechanical performance around carbon nanotube grafted silica fibres: methodologies for hierarchical composites

The introduction of carbon nanotubes (CNTs) modifies bulk polymer properties, depending on intrinsic quality, dispersion, alignment, interfacial chemistry and mechanical properties of the nanofiller. These effects can be exploited to enhance the matrices of conventional microscale fibre-reinforced polymer composites, by using primary reinforcing fibres grafted with CNTs. This paper presents a methodology that combines atomic force microscopy, polarised Raman spectroscopy, and nanoindentation techniques, to study the distribution, alignment and orientation of CNTs in the vicinity of epoxy-embedded micrometre-scale silica fibres, as well as, the resulting local mechanical properties of the matrix. Raman maps of key features in the CNT spectra clearly show the CNT distribution and orientation, including a 'parted' morphology associated with long grafted CNTs. The hardness and indentation modulus of the epoxy matrix were improved locally by 28% and 24%, respectively, due to the reinforcing effects of CNTs. Moreover, a slower stress relaxation was observed in the epoxy region containing CNTs, which may be due to restricted molecular mobility of the matrix. The proposed methodology is likely to be relevant to further studies of nanocomposites and hierarchical composites.     

Surface functionalities of multi-wall carbon nanotubes after UV/Ozone and TETA treatments

A carbon nanotube (CNT) surface was successfully modified using the UV/Ozone treatment and a triethylenetetramine (TETA) solution for use as the reinforcement for polymer matrix composites. These treatments along with ultra-sonication are aimed to disperse the CNTs uniformly in the resin matrix, as well as to provide the CNT surface with chemical functionalities for adhesion with epoxy resin. Fourier transform infra-red spectroscopy and X-ray photoelectron spectroscopy are performed to evaluate the changes in chemical structure and surface functional groups arising from the UV/O₃ and TETA treatments, confirming the efficiency of the processes. The practical implications of the surface functional groups for improving the interfacial adhesion in CNT-epoxy composites are discussed.     

Formation of a carbon fiber/polyhedral oligomeric silsesquioxane/carbon nanotube hybrid reinforcement and its effect on the interfacial properties of carbon fiber/epoxy composites

A carbon fiber/polyhedral oligomeric silsesquioxane/carbon nanotube (CF–POSS–CNT) hybrid reinforcement was prepared by grafting CNTs onto the carbon fiber surface using octaglycidyldimethylsilyl POSS as the linkage in an attempt to improve the interfacial properties between carbon fibers and an epoxy matrix. X-ray photoelectron spectroscopy, scanning electron microscopy, dynamic contact angle analysis and single fiber tensile testing were performed to characterize the hybrid reinforcements. Interlaminar shear strength (ILSS), impact toughness, dynamic mechanical analysis and force modulation atomic force microscopy were carried out to investigate the interfacial properties of the composites. Experimental results show that POSS and CNTs are grafted uniformly on the fiber surface and significantly increase the fiber surface roughness. The polar functional groups and surface energy of carbon fibers are obviously increased after the modification. Single fiber tensile testing results demonstrate that the functionalization does not lead to any discernable decrease in the fiber tensile strength. Mechanical property test results indicate the ILSS and impact toughness are enhanced. The storage modulus and service temperature increase by 11 GPa and 17 °C, respectively. POSS and CNTs effectively enhance the interfacial adhesion of the composites by improving resin wettability, increasing chemical bonding and mechanical interlocking.     

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%.     

Influence of carbon nanotube reinforcement on the processing and the mechanical behaviour of carbon fiber/epoxy composites

Carbon nanotubes (CNTs) were incorporated in an epoxy matrix that was then reinforced with carbon fibers. A fixed amount (0.5 wt.%) of different types of CNTs (functionalized and non-functionalized) were dispersed in the epoxy matrix, and unidirectional prepregs are produced. The key issues like CNT dispersion and its stability during the processing steps and the final mechanical properties of composites are discussed in detail. The temperature-viscosity profile of the epoxy matrix reinforced with different types of CNTs indicated a strong dependency on the type of CNTs. The pronounced effect of the presence of CNTs in the matrix is reflected by the decrease of the coefficient of thermal expansion by ∼32% for the double-walled CNTs epoxy system. There is also a substantial increase in fracture toughness Mode-1 by over 80% for the pristine multi-walled CNTs in combination with the epoxy resin modified by using a compatibilizer. The influence of such CNT-resin modification also induced overall positive trends in all the mechanical properties that were evaluated.     

Multiscale fiber‐reinforced composites prepared by vacuum‐assisted resin transfer molding

Carbon nanotube (CNT)/aramid fiber epoxy composites were produced using a new manufacturing method proposed in this study. The rheological and morphological experiments of the CNT/PEO nanocomposites indicates that the PEO nanocomposites have a good dispersion state of the CNTs. The flexural mechanical properties of the aramid fiber/CNT epoxy composites were measured. The CNTs dispersed in the epoxy resin between the aramid fibers were observed using field emission scanning electron miscroscope (FESEM). It was found that the flexural properties of the multiscale fiber‐reinforced composites were higher than those of aramid fiber/epoxy composites. POLYM. COMPOS., 28:458–461, 2007. © 2007 Society of Plastics Engineers.     

The effect of carbon nanotube orientation on erosive wear resistance of CNT-epoxy based composites

Aligned carbon nanotube (CNT) polymer composites are envisioned as the next-generation composite materials for a wide range of applications. In this work, we investigate the erosive wear behavior of epoxy matrix composites reinforced with both randomly dispersed and aligned carbon nanotube (CNT) arrays. The aligned CNT composites are prepared in two different configurations, where the sidewalls and ends of nanotubes are exposed to the composite surface. Results have shown that the composite with vertically aligned CNT-arrays exhibits superior erosive wear resistance compared to any of the other types of composites, and the erosion rate reaches a similar performance level to that of carbon steel at 20° impingement angle. The erosive wear mechanism of this type of composite, at various impingement angles, is studied by Scanning Electron Microscopy (SEM). We report that the erosive wear performance shows strong dependence on the alignment geometries of CNTs within the epoxy matrix under identical nanotube loading fractions. Correlations between the eroded surface roughness and the erosion rates of the CNT composites are studied by surface profilometry. This work demonstrates methods to fabricate CNT based polymer composites with high loading fractions of the filler, alignment control of nanotubes and optimized erosive wear properties.     

Resin film infusion: Toward structural composites with nanofillers

Resin Film Infusion (RFI) has been used to fabricate composites with continuous unidirectional E‐glass and epoxy with low weight fractions of carbon nanotubes (CNTs) in matrix. An ultrasound‐assisted dissolution‐evaporation method with thermoplastics or block copolymers as dispersing agents for nanoparticles enabled uniform dispersion of CNTs in the resin. Rheological characterization of CNT‐filled epoxy revealed that viscosity, and hence processing of the resin remains unaffected as compared to pristine resin at elevated temperatures of subsequent composite manufacturing. Local flow of the modified resin through the sandwiched fabric plies in RFI process as against the global flow in traditional liquid composite molding processes, made sure that uniform distribution of nanoparticles is accomplished throughout the composite. Compressive properties of hybrid composites improved considerably with CNTs at loading fractions as low as 0.2 wt %. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Carbon nanotube/epoxy composites fabricated by resin transfer molding

Carbon nanotube (CNT)/epoxy composites with controllable alignment of CNTs were fabricated by a resin transfer molding process. CNTs with loading up to 16.5 wt.% were homogenously dispersed and highly aligned in the epoxy matrix. Both mechanical and electrical properties of the CNT/epoxy composites were dramatically improved with the addition of the CNTs. The Young’s modulus and tensile strength of the composites reach 20.4 GPa and 231.5 MPa, corresponding to 716% and 160% improvement compared to pure epoxy. The electrical conductivity of the composites along the direction of the CNT alignment reaches over 1 × 10⁴ S/m.     

Modification of carbon nanotubes and its effect on properties of carbon nanotube/epoxy nanocomposites

We have studied an effect of three types of modifications of carbon nanotubes (CNTs) on dispersion and mechanical properties of final epoxy‐amine based nanocomposites. First approach includes end‐walled covalent chemical modification at the ends of nanotubes. The second one is side‐walled covalent chemical modification along the whole length of nanotubes. The third procedure is noncovalent, physical modification done by the CNT surface coating with polyaniline. The modification of nanotubes was determined by X‐ray photoelectron spectroscopy. The prepared epoxy‐amine nanocomposites were characterized by dynamic‐mechanical analysis, tensile testing, light microscopy, transmission electron microscopy, and thermogravimetry. We observed an improvement of the mechanical properties and the thermal stability by addition of the carbon nanotubes to the epoxy matrix. The strong interactions between the nanotube and the polymer matrix were discovered in the nanocomposites with physically modified nanotubes. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Dispersion and thermal conductivity of carbon nanotube composites

A mechanical method was used to shorten carbon nanotubes (CNTs) for improving dispersion without reducing their thermal conductivity. Single walled carbon nanotubes (SWCNTs) were mechanically cut to produce short and open-ended fullerene pipes. These shortened SWCNTs were then used in polymer composites. Both atomic force microscopy and scanning electron microscopy characterizations suggested that nanotube shortening significantly improved CNT dispersion. Thermal conductivity of composites containing short CNTs were found to be much better than those containing pristine CNTs.     

热固性树脂/碳纳米管复合材料的研究进展

介绍了碳纳米管(CNTs)在改性环氧树脂(EP)、酚醛树脂(PF)、双马来酰亚胺树脂(BMI)以及氰酸酯树脂(CE)等热固性树脂方面的应用,综述了EP/CNTs、PF/CNTs、BMI/CNTs、CE/CNTs复合材料的近期研究进展,详细叙述了CNTs对热固性树脂的力学性能、热性能、摩擦性能的改善情况,结合扫描电镜分析结果研究了CNTs在EP和BMI中的分散情况,并指出了热固性树脂/CNTs复合材料存在的问题和应用前景。     

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.