Synthesis of glass fiber‐multiwall carbon nanotube hybrid structures for high‐performance conductive composites

The conductive polyamide 66 (PA66)/carbon nanotube (CNT) composites reinforced with glass fiber‐multiwall CNT (GF‐MWCNT) hybrids were prepared by melt mixing. Electrostactic adsorption was utilized for the deposition of MWCNTs on the surfaces of glass fibers (GFs) to construct hybrid reinforcement with high‐electrical conductivity. The fabricated PA66/CNT composites reinforced with GF‐MWCNT hybrids showed enhanced electrical conductivity and mechanical properties as compared to those of PA66/CNT or PA66/GF/CNT composites. A significant reduction in percolation threshold was found for PA66/GF‐MWCNT/CNT composite (only 0.70 vol%). The morphological investigation demonstrated that MWCNT coating on the surfaces of the GFs improved load transfer between the GFs and the matrix. The presence of MWCNTs in the matrix‐rich interfacial regions enhanced the tensile modulus of the composite by about 10% than that of PA66/GF/CNT composite at the same CNT loading, which shows a promising route to build up high‐performance conductive composites. POLYM. COMPOS. 34:1313–1320, 2013. © 2013 Society of Plastics Engineers     

Effects of carbon nanofiller functionalization and distribution on interlaminar fracture toughness of multi-scale reinforced polymer composites

Carbon nanofillers with different surface functional groups and aspect ratios, including carboxyl carbon nanotubes, un-functionalized carbon nanofibers (CNFs), glycidyloxypropyl-trimethoxysilane carbon nanotubes (GPS-CNTs) and nanofibers were evaluated for their potential for increasing the interlaminar fracture toughness of an S2-glass fiber/epoxy composite. The fillers were added in the matrix of the fiber reinforced plies, in the resin interlayer between plies, or in both regions. Comparisons were made based on mode I and mode II interlaminar fracture toughness. For composites made with CNTs dispersed in the matrix, fracture toughness was largely unaffected except for a slight increase seen with long GPS-CNTs. However, adding a CNF or CNT modified resin interlayer significantly increased the fracture toughness, with the highest improvement over the baseline material achieved by adding long GPS-CNTs in the interlayer (79% and 91% for mode I and mode II onset toughness, respectively). Important material parameters identified for improving interlaminar fracture toughness are the nanofiller aspect ratio and concentration at the fracture plane. Based on microscopic evaluations of the fracture surfaces, a high density of high aspect ratio nanofillers causes the best entanglement between the filler and glass fibers and effectively obstructs interlaminar crack propagation.     

Effect of dispersion conditions on the mechanical properties of multi-walled carbon nanotubes based epoxy resin composites

A suitable dispersion technique and quantitative evaluation of degree of dispersion of carbon nanotubes (CNT) in any solvent and matrix system has been one of the key issues for achieving enhanced performance of CNT reinforced composites. We report the use of UV–vis spectroscopy as a useful technique to ascertain the degree of dispersion of multiwalled carbon nanotubes (MWCNT) in the epoxy resin. The study has enabled to maximize dispersion of MWCNT in the epoxy resin using two different routes. As a result the composite samples prepared with only 0.3 wt.% amine functionalized MWCNT showed flexural strength of 140 MPa over the neat resin value of 55 MPa, an improvement of ~155% which is maximum reported so far for CNT-epoxy isotropic composites.     

Mechanical properties and electrical conductivity in a carbon nanotube reinforced silicon nitride composite

The influence of carbon nanotubes (CNTs) addition on basic mechanical, thermal and electrical properties of the multiwall carbon nanotube (MWCNT) reinforced silicon nitride composites has been investigated. Silicon nitride based composites with different amounts (1 or 3 wt%) of carbon nanotubes have been prepared by hot isostatic pressing. The fracture toughness was measured by indentation fracture and indentation strength methods and the thermal shock resistance by indentation method. The hardness values decreased from 16.2 to 10.1 GPa and the fracture toughness slightly decreased by CNTs addition from 6.3 to 5.9 MPa m^1/2. The addition of 1 wt% CNTs enhanced the thermal shock resistance of the composite, however by the increased CNTs addition to 3 wt% the thermal shock resistance decreased. The electrical conductivity was significantly improved by CNTs addition (2 S/m in 3% Si₃N₄/CNT nanocomposite).     

Effect of graphene and CNT reinforcement on mechanical and thermomechanical behavior of epoxy—A comparative study

Graphene‐nanoplateles (Gr) and multiwalled carbon nanotubes (CNTs) reinforced epoxy based composites were fabricated using ultrasonication, a strong tool for effective dispersion of Gr/CNTs in epoxy. The effect of individual addition of two different nanofillers (Gr and CNT) in epoxy matrix, for a range of nanofiller content (0.1–1 wt %), has been investigated in this study. This study compares mechanical and thermomechanical behavior of Gr and CNT reinforced epoxy. Gr reinforcement offers higher improvement in strength, Young's modulus, and hardness than CNT, at ≤0.2 wt %. However, mode‐I fracture toughness shows different trend. The maximum improvement in fracture toughness observed for epoxy‐Gr composite was 102% (with 0.3 wt % loading of Gr) and the same for epoxy‐CNT composite was 152% (with 0.5 wt % loading of CNT). Thorough microstructural studies are performed to evaluate dispersion, strengthening, and toughening mechanisms, active with different nanofillers. The results obtained from all the studies are thoroughly analyzed to comprehend the effect of nanofillers, individually, on the performance of the composites in structural applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46101.     

碳纤维补强氧化铝陶瓷的研究

采用热压的方法制备了碳纤维／氧化铝复合陶瓷，与未加碳纤维的氧化铝陶瓷相比，其抗弯强度有明显提高，但断裂韧性提高不大。为了改善碳纤维与氧化铝基体的结合状态，利用化学气相沉积的方法分别在碳纤维表面沉积了ＳｉＣ，ＴｉＣ和ＳｉＯ２＋ＳｉＣ。研究结果表明，当采用有沉积层的碳纤维补强氧化铝陶瓷时，抗弯强度和断裂韧性都有明显提高。     

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     

短切碳纤维含量对Csf/SiC复合材料力学性能的影响

以Si作为主要烧结助剂,采用热压烧结法制备了短切碳纤维-碳化硅(short carbon fiber reinforced SiC composite,Csf/SiC)复合材料.采用X射线衍射仪、扫描电镜、硬度仪以及力学性能试验机等,研究了Csf含量对所制备材料的结构、组成、形貌及复合材料的弯曲强度、Vickers硬度和断裂韧性的影响.结果表明:采用热压法能制备出致密且Csf分布均匀的Csf/SiC复合材料.Csf/SiC复合材料的弯曲强度随Csf含量增加先增大后减小,含15%(体积分数,下同)Csf的Csf/SiC样品强度最高,达到466MPa,并且Csf含量小于30%的Csf/SiC样品强度高于无纤维SiC材料.材料的Vickers硬度随Csf含量增加而降低.Csf/SiC样品的断裂韧性随Csf含量增加而逐渐增大,Csf含量为53%时,达到最大为5.5MPa·m1/2,与无纤维SiC样品相比,增加近2倍.     

Failure investigation of carbon nanotube/3Y-TZP nanocomposites

3Y-TZP matrix composites containing 0.1–1 wt.% of multi-wall (MWCNT) and single-wall (SWCNT) carbon nanotubes were fabricated by spark plasma sintering technique. The sintered composites reached full density. Hardness and fracture toughness were measured using Vickers indention method. The hardness of the composite decreased with increasing weight content of the MWNT. The fracture toughness was 5.52 MPa m^0.5 when the amount of MWCNTs was 0.5 wt.%, however it decreased to 4.5 MPa m^0.5 when the content was raised to 1.0 wt.%. The composite containing 0.5 wt.% SWCNTs showed similar fracture toughness as that of matrix. The incorporation of CNTs into 3Y-TZP matrix led to no prominent improvement on the mechanical properties. The failure mechanism was analyzed finally.     

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     

Physical interactions at carbon nanotube-polymer interface

Mechanical properties of carbon nanotube (CNT) reinforced polystyrene rod and CNT reinforced epoxy thin film were studied and the CNT-polymer interface in these composites was examined. Transmission and scanning electron microscopy examinations of CNT/polystyrene (PS) and CNT/epoxy composite showed that these polymers adhered well to CNT at the nanometer scale. Molecular mechanics simulations and elasticity calculations were used to quantify some of the important interfacial characteristics that critically control the performance of a composite material. In the absence of chemical bonding between CNT and the matrix, it is found that the non-bond interactions, consist of electrostatic and van der Waals forces, result in CNT-polymer interfacial shear stress (at 0 K) of about 138 and 186 MPa, respectively, for CNT/epoxy and CNT/PS. The high interfacial shear stress calculated, about an order of magnitude higher than micro fiber reinforced composites, is believed attributed to intimate contact between the two solid phases at the molecular scale. Simulations and calculations also showed that local non-uniformity of CNT and mismatch of the coefficients of thermal expansions between CNT and polymer matrix also promote the stress transfer ability between the two.     

Nanotube fracture during the failure of carbon nanotube/alumina composites

Multi-walled carbon nanotubes (MWCNTs) underwent failure during crack opening in a MWCNT/alumina composite. Transmission electron microscope observations and single nanotube pullout tests revealed that the MWCNTs, rather than pulling out from the alumina matrix, broke in the outer shells and then the inner core was pulled away, leaving fragments of the outer shells in the matrix (i.e., they underwent failure in a “sword-in-sheath” fracture mode, as observed for MWCNTs under tensile loading). Some MWCNTs failed leaving either a very short sword-in-sheath failure or a clean break. Theoretical predictions based on the MWCNT failure and pullout models suggested that the use of MWCNTs having a much higher load carrying capacity may lead to composites with a higher fracture toughness. These results may provide new insight into the fracture mechanisms and suggest a new design methodology for MWCNT-based ceramic composites, leading to improved fracture toughness.     

Improved fracture toughness of carbon fiber composite functionalized with multi walled carbon nanotubes

Woven carbon fiber (CF) laminae are functionalized in situ with carbon nanotubes (CNTs) to test the hypothesis that growing CNTs on CF (i.e., carbon fiber bundles or tow) would enhance the properties of polymeric carbon composites, specifically epoxy–carbon composites that are used in aerospace applications. The CNT as-grown on the woven CF were shown to substantially improve the fracture toughness of the cured composite on the order of 50%. This was accompanied by no loss in structural stiffness of the final composite structure. In fact, the flexural modulus increased approximately 5%. The significant increase in the fracture toughness as tested under the ASTM D 5528 standard indicates that the damage tolerance of a composite structure would benefit from the CNT material applied in this way. Our approach has allowed for significantly larger samples to be uniformly functionalized with CNTs than is reported elsewhere in the open literature. In addition, this work demonstrated CNT functionalization on flexible substrates that remains flexible after functionalization, whereas most CNT growth substrates are rigid in order to withstand the high (>800 °C) growth temperatures often encountered in CNT synthesis.     

Characterization and compression properties of injection molded carbon nanotube composites

Since the development of carbon nanotubes (CNTs) in 1991, they have received much attention with improved mechanical, thermal, and electrical properties of their composites compared to common polymer composites. The CNTs are currently used to increase the modulus of common thermoplastics and thermosets, including urethanes and epoxies. The CNTs are difficult to disperse within any media because of limited chemical reactivity and potential agglomeration in their “as grown” state. This study evaluated the effect of incorporating bundled and unbundled CNTs at different concentrations into Polyurethane/CNT/woven fiber reinforced composites. Optical microscopy and atomic force microscopy (AFM) characterized the dispersion of CNTs within the polymer matrix in injection molded CNT/polyurethane composites. Polyurethane/CNT/woven fiber reinforced composite plaques were prepared and then characterized by mechanical compression testing. Optical microscopy and AFM qualitatively determined a decreased agglomerate size resulting in improved mechanical properties. Results of this study show significant differences in yield stress, stress at failure, and modulus of elasticity within the various treatments. No significant differences were found for yield strain, strain at failure, and toughness. However, the conservativeness of the statistical model warrants further investigation for strain at failure and toughness with possible interaction effects of CNT concentration for each composite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Characterizing elastic properties of carbon nanotube‐based composites by using an equivalent fiber

Effective elastic properties for carbon nanotube (CNT)‐reinforced composites are obtained through a variety of micromechanics techniques. An embedded CNT in a polymer matrix and its surrounding interphase is replaced with an equivalent fiber for predicting the mechanical properties of the CNT/polymer composite. Formulas to extract the effective material constants from solutions for the representative volume element under three loading cases are derived based on the elasticity theory. The effects of an interphase layer between the nanotubes and the polymer matrix as result of effective interphase layer are also investigated. Furthermore, this research is aimed at characterizing the elastic properties of CNTs‐reinforced composites using Eshelby–Mori–Tanaka approach based on an equivalent fiber. The variations of mechanical properties with tube radius, interphase thickness, and degree of aggregation are investigated. It is shown that the presence of aggregates has stronger impact than the interphase thickness on the effective modulus of the composite. This is because aggregates have significantly lower modulus than individual CNTs. POLYM. COMPOS., 2013 © 2013 Society of Plastics Engineers     

Improving delamination resistance of carbon fiber reinforced polymeric composite by interface engineering using carbonaceous nanofillers through electrophoretic deposition: An assessment at different in-service temperatures

In this article, modification of carbon fiber surface by carbon based nanofillers (multi-walled carbon nanotubes [CNT], carbon nanofibers, and multi-layered graphene) has been achieved by electrophoretic deposition technique to improve its interfacial bonding with epoxy matrix, with a target to improve the mechanical performance of carbon fiber reinforced polymer composites. Flexural and short beam shear properties of the composites were studied at extreme temperature conditions; in-situ cryo, room and elevated temperature (−196, 30, and 120°C respectively). Laminate reinforced with CNT grafted carbon fibers exhibited highest delamination resistance with maximum improvement in flexural strength as well as in inter-laminar shear strength (ILSS) among all the carbon fiber reinforced epoxy (CE) composites at all in-situ temperatures. CNT modified CE composite showed increment of 9% in flexural strength and 17.43% in ILSS when compared to that of unmodified CE composite at room temperature (30°C). Thermomechanical properties were investigated using dynamic mechanical analysis. Fractography was also carried out to study different modes of failure of the composites.     

The role of grafting force and surface wettability in interfacial enhancement of carbon nanotube/carbon fiber hierarchical composites

The grafting force of carbon nanotube (CNT) on carbon fiber (CF) and the wettability of CF surface were experimentally studied, where hierarchical CNT/CF reinforcement was prepared using chemical vapor deposition (CVD). Then, their effects on interfacial improvement were experimentally and theoretically investigated. The results show that the CNT/CF grafting force is so strong, more than 5 μN, and CNT/CF attachment can sustain the fracture of the CNTs. This is expected to be contributed to the improvement of interfacial properties. However, the deposited catalyst deteriorates the wettability, which could seriously degrade the interfacial properties. As a result, experimental results from the micro-droplet test show that there is only a 30% increase in the interfacial shear strength of hierarchical CNT/CF reinforced composite comparing with that of as-received CF reinforced composite. An analytical model was developed to predict the effects of CNT/CF grafting force on interfacial improvement, and the predicted results are in agreement with the experimental one.     

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.     

Synergistic strengthening effect of graphene-carbon nanotube hybrid structure in aluminum matrix composites

High-performance reinforcement and tailored architecture are currently explored to develop advanced metal matrix composites. In this work, aluminum (Al) matrix composite reinforced by hybrid carbon nanofillers was fabricated by a composite flake assembly process. It was found that for various carbon nanofiller volume fractions, a striking synergistic strengthening effect was achieved by employing graphene (reduced graphene oxide, RGO) and carbon nanotube (CNT) hybrid structure as reinforcement in the Al matrix. Particularly, a tensile strength of 415 MPa was achieved with the addition of 1.5 vol.% of RGO-CNT hybrid, which is significantly higher than those reinforced by individual CNT or RGO (326 and 331 MPa, respectively). The synergistic strengthening effect was attributed to the formation of a planar network of RGO and CNT, which improves the load transfer efficiency between the matrix and the reinforcement in composites. Our study highlights the importance of reinforcement architecture for enhancing the strengthening ability in composites, and provides an effective route to fully take the advantage of the superior properties of various reinforcements.     

Effect of carbon nanotube length on thermal,electrical and mechanical properties of CNT/bismaleimide composites

Multi-wall carbon nanotubes (MWCNTs) with lengths of 0.65–1.3 mm were used to fabricate aligned and continuous MWCNT/bismaleimide composites. We found that longer CNTs resulted in higher thermal and electrical conductivities of the composites. The tensile strength and Young’s modulus, however, exhibited no CNT length dependency. Investigation of the CNT morphology by transmission electron microscopy revealed that the average nanotube diameter and wall number also increased with the CNT length, while the aspect ratio remained nearly unchanged. The structural changes significantly affected the phonon and electron transport in the composite structure, but the interplay of increased CNT length and diameter led to no appreciable change in the mechanical properties of the composites.