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.     

Effect of the nanotube aspect ratio and surface functionalization on the morphology and properties of multiwalled carbon nanotube polyamide‐based fibers

In this study, the effect of the carbon nanotube (CNT) aspect ratio and surface functionalization on the mechanical behavior and morphological changes of polyamide (PA)‐based fibers was investigated. Composites were prepared by the melt blending of CNTs with PA, and at a later time, the fibers were prepared by melt spinning and cold drawing. A reinforcement effect was noticed for all of the CNTs samples, and the increase in the mechanical properties and dimensional stability was more pronounced for highly oriented filaments. When the elongational flow was increased, the orientation of CNTs along the fiber direction was observed, but the nanotube alignment was much more difficult for CNTs with ultrathin outer diameters because of nanotube waviness and folding. Moreover, the presence of functional groups on the CNT surface hindered their orientation along the fiber direction because some interaction between the functional groups could occur. The morphological variations of the oriented, anisotropic fibers, as studied with transmission electron microscopy, scanning electron microscopy, small‐angle X‐ray scattering, and differential scanning calorimetry analysis, were correlated with changes in the mechanical behavior. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Synergistic effects of hybrid carbon nanomaterials in room‐temperature‐vulcanized silicone rubber

This work examines nanocomposites based on nanofillers and room‐temperature‐vulcanized silicone rubber. The carbon nanofillers used were conductive carbon black (CB), carbon nanotubes (CNTs) and graphene (GE). Vulcanizates for CB, GE, CNTs as the only filler and hybrid fillers using CNTs, CB and GE were prepared by solution mixing. The elastic modulus for CNT hybrid with CB at 15 phr (4.65 MPa) was higher than for CB hybrid with GE (3.13 MPa) and CNTs/CB/GE as the only filler. Similarly, the resistance for CNT hybrid with CB at 10 phr (0.41 kΩ) was lower than for CB (0.84 kΩ) at 20 phr and CNTs as the only filler. These improvements result from efficient filler networking, a synergistic effect among the carbon nanomaterials, the high aspect ratio of CNTs and the improved filler dispersion in the rubber matrix. © 2016 Society of Chemical Industry     

Production of a cellular structure in carbon nanotube/natural rubber composites revealed by nanomechanical mapping

Composites based on an elastomer, natural rubber (NR), and pristine multiwalled carbon nanotubes (MWCNTs) were prepared using a two-roll mill mixer. The high shear stress produced a homogeneous dispersion of CNTs in the NR matrix. Using an atomic force microscopy nanomechanical mapping technique, the structure and nanoscale mechanical properties of the resulting composites were investigated in term of CNT loading. Topography, elastic modulus, and adhesive energy distribution maps of the materials were obtained at the same point and at the same time in a single scan. Such maps were used to identify and characterize the CNT, NR, and mechanical interfacial regions formed around the CNTs. The mechanical interfacial regions together with the CNTs divide the elastomer matrix into small “cells”. We claim that the cellular structure is produced in the CNTs/NR composites.     

Lignin-based carbon fibers: Carbon nanotube decoration and superior thermal stability

Lignin-based carbon fibers (CFs) decorated with carbon nanotubes (CNTs) were synthesized and their structure, thermal stability and wettability were systematically studied. The carbon fiber precursors were produced by electrospinning lignin/polyacrylonitrile solutions. CFs were obtained by pyrolyzing the precursors and CNTs were subsequently grown on the CFs to eventually achieve a CF–CNT hybrid structure. The processes of pyrolysis and CNT growth were conducted in a tube furnace using different conditions and the properties of the resultant products were studied and compared. The CF–CNT hybrid structure produced at 850 °C using a palladium catalyst showed the highest thermal stability, i.e., 98.3% residual weight at 950 °C. A mechanism for such superior thermal stability was postulated based on the results from X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, and electron energy loss spectroscopy analyses. The dense CNT decoration was found to increase the hydrophobicity of the CFs.     

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     

Predicting mechanical properties of multiscale composites

Abstract

The effect of carbon nanotube (CNT) integration in polymer matrixes (two-phase) and fibre reinforced composites (three-phase) was studied. Simulations for CNT/polymer composites (nanocomposites) and CNT/fibre/polymer composites (multiscale) were carried out by combining micromechanical theories applied to nanoscale and woven fibre micromechanic theories. The mechanical properties (Young’s modulus, Poisson’s ratio and shear modulus) of a multiscale composite were predicted. The relationships between the mechanical properties of nano- and multiscale composite systems for various CNT aspect ratios were studied. A comparison was made between a multiscale system with CNTs infused throughout and one with nanotubes excluded from the fabric tows. The mechanical properties of the composites improved with increased CNT loading. The influence of CNT aspect ratio on the mechanical properties was more pronounced in the nanocomposites than in the multiscale composites. Composites with CNTs in the fibre strands generated more desirable mechanical properties than those with no CNTs in the fibre strands.     

High strength micron size carbon fibers from polyacrylonitrile–carbon nanotube precursors

An improved, high strength, carbon fiber derived from islands-in-a-sea bi-component gel spun polyacrylonitrile (PAN)–carbon nanotube (CNT) precursor fibers containing 1 wt% mixture of single, double, and few walled CNTs was developed. Microscale experiments with properly designed MEMS tools provided the mechanical properties of individual, 1-μm diameter carbon filaments, which were isolated from bundles of 407 fibers. The statistics of the mechanical strength were described well by the cumulative Weibull probability density function that resulted in characteristic strength of 6.2 GPa and a Weibull modulus of 4.5, while the highest tensile strength and Young’s modulus values were 7.3 GPa and 318 GPa, respectively. At the lower end of the spectrum, the strength values correlated well with predictions based on an effective flaw size obtained from fracture cross-sections. On the other hand, the failure cross-sections of the high strength carbon fibers contained a large number of long and oriented CNTs but no discernible flaws. The high interfacial strength between the CNTs and the surrounding carbon resulted in fracture and telescopic pull-out of the CNTs, which was corroborated by individual CNT pull-out experiments with MEMS tools inside an SEM, and in situ fiber failure observations of telescopic pull-out of CNTs inside a TEM.     

Enhanced electrical properties of polycarbonate/carbon nanotube nanocomposites prepared by a supercritical carbon dioxide aided melt blending method

Polycarbonate/carbon nanotube (CNT) nanocomposites were generated using a supercritical carbon dioxide (scCO₂) aided melt blending method, yielding nanocomposites with enhanced electrical properties and improved dispersion while maintaining the aspect ratio of the as-received CNTs. Baytubes^® C 150 P CNTs were benignly deagglomerated with scCO₂ resulting in 5 fold (5X), 10X and 15X decreases in bulk density from the as-received CNTs. This was followed by melt compounding with polycarbonate to generate the CNT nanocomposites. Electrical percolation thresholds were realized at CNT loading levels as low as 0.83 wt% for composites prepared with 15X CNT using the scCO₂ aided melt blending method. By comparison, a concentration of 1.5 wt% was required without scCO₂ processing. Optical microscopy, transmission electron microscopy, and rheology were used to investigate the dispersion and mechanical network of CNTs in the nanocomposites. The dispersion of CNTs generally improved with scCO₂ processing compared to direct melt blending, but was significantly worse than that of twin screw melt compounded nanocomposites reported in the literature. A rheologically percolated network was observed near the electrical percolation of the nanocomposites. The importance of maintaining longer carbon nanotubes during nanocomposite processing rather than focusing on dispersion alone is highlighted in the current efforts.     

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     

Carbon nanotube reinforced hydroxyapatite composite coatings produced through laser surface alloying

Carbon nanotube (CNT) reinforced hydroxyapatite composite coatings have been successfully fabricated by laser surface alloying. The phase compositions and the microstructure of the composite coatings were studied using X-ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). TEM observation showed that a large amount of CNTs can be found with their original tubular morphology in the composite coatings, even though some CNTs react with titanium element in the substrate during laser irradiation. Additionally, measurement on the elastic modulus, hardness of the composite coatings by nanoindentation tests indicated that the mechanical properties are affected by the amount of CNTs in the starting precursor materials. Therefore, CNT reinforced hydroxyapatite composite coating is a promising coating material for high-load-bearing metal implants.     

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     

Electrical and thermal conductivity and tensile and flexural properties of carbon nanotube/polycarbonate resins

Adding conductive carbon fillers to insulating thermoplastic polymers increases the resulting composite's electrical conductivity. Carbon nanotubes (CNTs) are very effective at increasing composite electrical conductivity at low loading levels without compromising composite tensile and flexural properties. In this study, varying amounts (2–8 wt %) of CNTs were added to polycarbonate (PC) by melt compounding, and the resulting composites were tested for electrical conductivity (1/electrical resistivity), thermal conductivity, and tensile and flexural properties. The percolation threshold was less than 1.4 vol % CNT, likely because of CNTs high aspect ratio (1000). The addition of CNT to PC increased the composite electrical and thermal conductivity and tensile and flexural modulus. The 6 wt % (4.2 vol %) CNT in PC resin had a good combination of properties for electrical conductivity applications. The electrical resistivity and thermal conductivity were 18 Ω‐cm and 0.28 W/m · K, respectively. The tensile modulus, ultimate tensile strength (UTS), and strain at UTS were 2.7 GPa, 56 MPa, and 2.8%, respectively. The flexural modulus, ultimate flexural strength, and strain at ultimate flexural strength were 3.6 GPa, 125 MPa, and 5.5%, respectively. Ductile tensile behavior is noted in pure PC and in samples containing up to 6 wt % CNT. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Stress transfer in polyacrylonitrile/carbon nanotube composite fibers

Gel spun polyacrylonitrile/carbon nanotube (PAN/CNT) composite fibers have been produced, and the stress-induced G′ Raman band shifts in the CNTs have been monitored to observe stress transfer during fiber strain. Improvements in CNT quality, CNT dispersion, and post-processing fiber drawing are shown to increase the stress transfer from the matrix to the CNT. Radial breathing mode (RBM) intensity of specific CNT chiralities confirms CNT debundling during fiber processing. During PAN/CNT fiber straining, there reaches a plateau in the CNT G′ downshift, signifying that the stress on the CNT is maintained despite continued straining of the PAN/CNT fiber. Correlating CNT strain with CNT modulus and volume fraction allows for the interfacial shear strength (τ_i) of the PAN-CNT interface to be determined. The as-spun and fully drawn PAN/CNT-A (99/1) nano composite fibers exhibit τ_i of 13.1 and 30.9 MPa, respectively, while an improved CNT dispersion (PAN/CNT-A (99.9/0.1)) results in τ_i equal to 44.3 MPa.     

Role of multi-wall carbon nanotube network in composites to crystallization of isotactic polypropylene matrix

The composites (iPP/CNTs) made of isotactic polypropylene (iPP) and multi-wall carbon nanotubes (CNTs) were prepared by solution blending. To improve compatibility between CNTs and iPP and to enhance dispersion of CNTs in iPP matrix, CNTs were chemically modified by grafting alkyl chains. The chemically modified CNTs had about 6 wt% grafted alkyl chains. Rheological measurements indicated that CNTs caused gelation in iPP/CNTs due to CNT network formation and the critical gelation CNT concentration was about 7.4 wt%, which was considered to be high due to the low CNT aspect ratio in this study. Crystallization behaviors of iPP/CNTs were studied by using optical microscopy (OM) and differential scanning calorimetry (DSC). Radial growth rates of spherulites during isothermal crystallization of iPP/CNTs with CNT concentrations less than 2.0 wt% measured by using OM showed decreasing trends with increasing CNT concentration. Avrami analysis of the exothermic heat flow curves during isothermal crystallization of iPP/CNTs measured by DSC indicated that crystallization rates were accelerated when CNT concentrations were lower than the critical gelation concentration, because CNTs mainly functioned as nucleating agents for crystallization, while crystallization rates did not change obviously when CNT concentrations were higher than the critical gelation concentration, because CNT network could form and mainly functioned to provide restriction to mobility and diffusion of iPP chains to crystal growth fronts.     

In situ preparation of polyimide/amino‐functionalized carbon nanotube composites and their properties

In order to improve the dispersion of carbon nanotubes (CNTs) in polyimide (PI) matrix and the interfacial interaction between CNTs and PI, 4,4′‐diaminodiphenyl ether (ODA)‐functionalized carbon nanotubes (CNTs‐ODA) were synthesized by oxidation and amidation reactions. The structures and morphologies of CNTs‐ODA were characterized using Fourier transform infrared spectrometer, transmission electron microscopy, and thermal gravimetric analysis. Then a series of polyimide/amino‐functionalized carbon nanotube (PI/CNT‐ODA) nanocomposites were prepared by in situ polymerization. CNTs‐ODA were homogeneously dispersed in PI matrix. The influence of CNT‐ODA content on mechanical properties of PI/CNT‐ODA nanocomposites was investigated. It was found that the mechanical properties of nanocomposites were enhanced with the increase in CNT‐ODA loading. When the content of CNTs‐ODA was 3 wt%, the tensile strength of PI/CNT‐ODA nanocomposites was up to 169.07 MPa (87.11% higher than that of neat PI). The modulus of PI/CNTs‐ODA was increased by 62.64%, while elongation at break was increased by 66.05%. The improvement of the mechanical properties of PI/CNT‐ODA nanocomposites were due to the strong chemical bond and interfacial interaction between CNTs‐ODA and PI matrix. POLYM. COMPOS., 35:1952–1959, 2014. © 2014 Society of Plastics Engineers     

Electrospinning of polylactide and its composites with carbon nanotubes

Electrospinning of the biodegradable polylactide (PLA) and its composites containing carbon nanotubes (CNTs) was studied in terms of solution concentrations and solvents effects as well as CNT loadings. The results reveal that the PLA fibers obtained from the solutions using the mixed solvents of chloroform/assistant solvent (v/v 3/1) show better morphologies than those from the solutions using chloroform as the single solvent. This is due to the synergistic effect by the improved conductivity and altered viscosity with addition of assistant solvent. Moreover, the surface structure of fibers depends on the volatility of assistant solvents strongly. Using volatile acrylonitrile or acetone as the assistant solvents, the columned fibers with porous surface structure are obtained; while the flat fibers with fluted surface are formed using nonvolatile dimethyl sulfoxide as the assistant solvents. As for electrospinning of the PLA/CNT composites, the morphology of obtained fibers is closely related to the dispersion of CNTs in the fibers. At low loading levels, the CNTs can be well embedded in the PLA matrix and oriented along the fiber axis, forming nanowire structure. At high loading levels, the CNTs are mainly dispersed as entangled bundles along the fiber axis, and as a result, the obtained fibers show tortuous or misshaped morphologies. Compared with that of the neat PLA fibers, the overall morphologies of the composite fibers are more or less degraded because the presence of some small CNT aggregates in the solutions easily leads to the formation of beaded fiber structure during electrospinning. The conductivity of the obtained composite fiber mats was further studied in terms of CNT loadings. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Mechanical properties of carbon nanotube/carbon fiber reinforced thermoplastic polymer composite

Carbon nanotube (CNT)/carbon fiber (CF) hybrid fiber was fabricated by sizing unsized CF tow with a sizing agent containing CNT. The hybrid fiber was used to reinforce a thermoplastic polymer to prepare multiscale composite. The mechanical properties of the multiscale composite were characterized. Compared with the base composite (traditional commercial CF), the multiscale composite reinforced by the CNT/CF hybrid fiber shows increases in interlaminar shear strength (ILSS) and impact toughness. Laminate containing CNTs showed a 115.4% increase in ILSS and 27.0% increase in impact toughness. The reinforcing mechanism was also discussed by observing the impact fracture morphology. POLYM. COMPOS., 38:2001–2008, 2017. © 2015 Society of Plastics Engineers     

Characterisation of carbon nanotube films deposited by electrophoretic deposition

Electrophoretic deposition (EPD) was shown to be a convenient method to fabricate uniform coatings of carbon nanotubes (CNTs) with desired thickness and excellent macroscopic homogeneity. The CNT deposition kinetics are controlled by the applied electric field and deposition time which, in turn, prove to be linearly correlated with the deposition yield and thickness. The CNT films were characterised by using a range of techniques including high resolution scanning electron microscopy, nanoindentation and atomic force microscopy. Nanoindentation results revealed differences in the local microstructure of CNT deposits leading to variations of Young’s modulus and hardness, which were ascribed to differences in the packing density of CNTs, as observed also by AFM. A mathematical model for the kinetic of EPD of CNTs based on Hamaker’s law was proposed and the predictions of the model were shown to be in good agreement with experimental results.