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     

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.     

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.     

Preparation and characterization of poly[(butylene succinate)‐co‐(butylene adipate)]/carbon nanotube‐coated silk fiber composites

Biodegradable composites consisting of aliphatic polyesters (poly[(butylenes succinate)‐co‐(butylenes adipate)] (PBSA)) and Bombyx mori silk fibers coated with carbon nanotubes (CNTs) were prepared by melt compression molding. The mechanical properties of PBSA were enhanced by the incorporation of a small amount (3 wt%) of CNT‐coated silk fibers, while allowing its potential biodegradability to be retained, which could make these composites good candidates for commodity materials such as general‐purpose plastics. This improvement is attributed to the interactions between PBSA and CNT‐coated silk fibers in the composites. The average interfacial shear strength of the composites consisting of CNT‐coated silk fibers and PBSA matrix was 1.7 MPa, as measured by the microbond droplet test, while that of composites consisting of pure silk fibers and PBSA was only 1.1 MPa. The morphology of the CNT‐coated silk fiber‐reinforced composites was observed using scanning electron microscopy. Copyright © 2007 Society of Chemical Industry     

Ultradrawing properties of ultra‐high molecular weight polyethylene/functionalized carbon nanotube fibers

Systemic investigation of the influence of the plain and functionalized carbon nanotube (CNT) contents on the ultradrawing properties of ultrahigh molecular weight polyethylene/carbon nanotubes (UHMWPE/CNTs, FC_y) and UHMWPE/functionalized CNTs (FC_fx‐y) as‐prepared fibers are reported. In a way similar to those found for the orientation factor values, the achievable draw ratios (D_ra) of the FC_y and FC_fx‐y as‐prepared fibers approached a maximum value as their CNT and/or functionalized CNT contents reached their corresponding optimum values. The maximum D_ra values obtained for FC_fx‐0.001 as‐prepared fiber specimens prepared at varying maleic anhydride grafted polyethylene (PE_‐g‐MAH)/modified CNTs weight ratios were significantly higher that of the FC_0.0015 as‐prepared fiber specimen prepared at the optimum plain CNT content. Tensile property analysis further suggested that excellent orientation and tensile properties of the drawn FC_y and FC_fx‐y fibers can be obtained by ultradrawing the fibers prepared at their optimum plain CNT and/or functionalized CNT contents. To understand the interesting orientation, ultradrawing and tensile properties of FC_y and FC_fx‐y fiber specimens, FTIR, specific surface area, and SEM morphology analysis of the plain and functionalized CNTs were performed in this study. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Enhanced compatibilization and orientation of polyvinyl alcohol/gelatin composite fibers using carbon nanotubes

Polyvinyl alcohol (PVA)/gelatin composite fibers containing carbon nanotubes (CNTs) had been prepared by wet‐spinning method. A remarkable increase of tensile strength of the PVA/gelatin fibers was achieved by adding small amount of CNT. The mechanism of reinforcement has been studied using a combination of differential scanning calorimetry (DSC), 2D wide‐angle X‐ray diffraction (2D‐WAXD) and scanning electron microscopy (SEM). SEM showed a decreased gelatin domain size by adding CNTs, suggesting a possible compatibilization effect between PVA and gelatin. On the other hand, an increased crystallinity and degree of orientation of PVA/gelatin fibers has been observed by adding CNTs. Thus, the increased compatibilization, crystallinity and degree of orientation in PVA/gelatin/CNTs composite fibers should be the reasons for the observed increase of mechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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.     

Using supercritical carbon dioxide in preparing carbon nanotube nanocomposite: Improved dispersion and mechanical properties

Improvements in carbon nanotube (CNT) dispersion and subsequent mechanical properties of CNT/poly(phenylsulfone) (PPSF) composites were obtained by applying the supercritical CO₂ (scCO₂)‐aided melt‐blending technique that has been used in our laboratory for nanoclay/polymer composite preparation. The preparation process relied on rapid expansion of the CNTs followed by melt blending using a single‐screw extruder. Scanning electronic microscopy results revealed that the CNTs exposed to scCO₂ at certain pressures, temperatures, exposure time, and depressurization rates have a more dispersed structure. Microscopy results showed improved CNT dispersion in the polymer matrix and more uniform networks formed with the use of scCO₂, which indicated that CO₂‐expanded CNTs are easier to disperse into the polymer matrix during the blending procedure. The CNT/PPSF composites prepared with scCO₂‐aided melt blending and conventional melt blending showed similar tensile strength and elongation at break. The Young's modulus of the composite prepared by means of conventional direct melt blending failed to increase beyond the addition of 1 wt% CNT, but the scCO₂‐aided melt‐blending method provided continuous improvements in Young's modulus up to the addition of 7 wt% CNT. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

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     

Strain rate-dependent tensile properties and dynamic electromechanical response of carbon nanotube fibers

This investigation into the rate-dependent tensile behavior of carbon nanotube (CNT) fibers provides insight into the role of strain rate and specimen gage length on tensile strength. Chemical vapor produced CNT continuous fibers made of single and dual wall CNTs are evaluated and the potential for fiber improvement by post-process stretching to improve alignment is explored. Post-processed CNT fibers exhibit significantly higher strengths (3–5 GPa) and moduli (80–200 GPa) than untreated fibers. During dynamic tension evaluation, real-time electrical measurements provide correlations between high rate deformation/damage mechanical behavior and electrical resistance of the fiber specimens. Furthermore, this first look into the dynamic tensile behavior of CNT fibers demonstrates their potential to serve as sensors in high rate applications.     

Combination of hot extrusion and spark plasma sintering for producing carbon nanotube reinforced aluminum matrix composites

Aluminum (Al)/carbon nanotube (CNT) composites with nanoscale dispersion and regular orientation of the CNTs were fabricated by a combination of some advanced powder processes. The CNTs were well dispersed onto the Al particles by a nanoscale dispersion method. Moreover, the highly densified CNT composites were prepared by spark plasma sintering and subsequent hot extrusion. Microstructural observations by optical, field-emission scanning electron, and high-resolution transmission electron microscopies confirmed that the sintered Al/CNT compact and extruded bulk material had a good dispersion of oriented CNTs. Raman spectroscopy showed that the processing did little damage to the CNTs. As a result, the composites exhibited tensile strengths that were thrice larger than pure aluminum because of the CNT reinforcement.     

The effect of carbon nanotube aspect ratio and loading on the elastic modulus of electrospun poly(vinyl alcohol)-carbon nanotube hybrid fibers

The reinforcement effect of carbon nanotubes (CNTs) has been examined as a function of their loading and aspect ratio in poly(vinyl alcohol) (PVA) based hybird fibers. Lignosulfonic acid sodium salt (LSA) was used to disperse CNTs to produce consistently high CNT loaded PVA-LSA-CNT hybrid fibers using an electrospinning process. The elastic modulus of individual fibers was measured using atomic force microscopy. The presence of CNTs significantly increased the average elastic modulus of PVA-LSA-CNT fibers compared to PVA-LSA fibers. The elastic modulus, however, exhibited no fiber diameter dependency. Transmission electron microscopy (TEM) was used to determine the loading and the aspect ratio of CNTs in each hybrid fiber. The CNT loading in PVA-LSA-CNT fibers varied widely due to non-uniform CNT dispersion and displayed no relationship with the elastic modulus. Our results also demonstrated that the average value of CNT aspect ratio significantly affected the elastic modulus of the hybrid fibers. Such a result was in agreement with theoretical prediction in which the stress transfer efficiency in a composite matrix is strongly dependent on the CNT aspect ratio.     

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.     

Enhanced foamability of isotactic polypropylene composites by polypropylene‐graft‐carbon nanotube

In this article, utilizing a nucleophilic substitution reaction between epoxy group in polypropylene‐graft‐glycidyl methacrylate (PP‐g‐GMA) and carboxyl groups in oxidized carbon nanotubes (O‐CNTs), PP‐g‐CNT was fabricated for reinforcing the interfacial adhesion between CNTs and polypropylene (PP) matrix, favoring the enhancement of melt strength and elastic modulus, i.e., enhancing the foaming ability of PP composites. Cellular structure and thermo‐mechanical properties of PP foams were characterized by scanning electron microscopy and dynamic mechanical analysis, respectively. The average cell diameter of PP foams decreased from 289.2 (PP‐g‐GMA) to 96.7 μm (PP‐g‐CNT foams with 2.0 wt % O‐CNT) and the distribution of cell size also became more uniform. The storage modulus of PP‐g‐CNT foams increased by nearly 62.5% at ?40°C, compared with that of PP‐g‐GMA foams. This work also provided a new procedure for improving the foam ability and thermo‐mechanical property of PP composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 961‐968, 2013     

Gel-spun carbon nanotubes/polyacrylonitrile composite fibers. Part I: Effect of carbon nanotubes on stabilization

Addition of carbon nanotubes (CNTs) in polyacrylonitrile (PAN) fibers significantly improves the mechanical properties of the resulting carbon fibers. This study focuses on the effect of different types of CNTs on chemical, mechanical and structural changes during the stabilization of gel-spun CNT/PAN composite fibers. Among the different types of CNTs, it was observed that CNTs containing more walls had lower reinforcement efficiency than CNTs containing fewer walls. Similarly CNTs containing fewer walls exhibited higher orientation of the ladder polymer and greater effect on the formation of β-amino nitrile in the stabilized fibers. Wide angle X-ray diffraction, infrared spectroscopy, and scanning electron microscopy were used to determine the optimum stabilization time. Additionally, it was found that the higher tension applied during stabilization improved the properties of the stabilized fibers, and the addition of CNTs increased the maximum tension that the fiber can bear.     

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.     

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     

Polypropylene/carbon nanotube nanocomposite fibers: Process–morphology–property relationships

This study is focused on aligning carbon nanotubes in polypropylene matrix by melt spinning. Two different weight percentages (0.5% and 1.0%) of nanotubes were used for the synthesis of the nanocomposite fibers. The effect of the nanotubes on the crystallization and mechanical behavior of polypropylene as well as the effect of draw ratio on the nanocomposite morphology and properties is also discussed. Correlation of fiber morphology and nanotube alignment was done using differential scanning calorimetry, wide‐angle X‐ray diffraction, and transmission electron microscopy. Significant improvement in tensile modulus and tensile strength were observed, which is characteristic of a highly aligned nanotube system. A substantial vincrease in the onset of decomposition was observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3844–3850, 2007     

An improved method for functionalisation of carbon nanotube spun yarns with aryldiazonium compounds

We report a method for modifying carbon nanotube (CNT) spun yarns with aryldiazonium salts that involves the pH controlled application of the diazonium salts to CNTs both during and after the yarn formation process. This largely facilitates the chemical accessibility to CNTs within the yarn, potentially enabling a more extensive and uniform modification. The modified CNT yarns were characterised by X-ray photoelectron spectroscopy, Raman spectroscopy and scanning electron microscopy, and also examined for their mechanical properties. The results demonstrated that a CNT spun yarn was effectively modified by this method without impairing the yarn integrity. The formation of oligomerised polyene structures on the CNT surfaces was observed. This modification resulted in an increase in tensile strength and Young’s modulus of the CNT yarn. The functional groups grafted on CNTs also provide opportunities to form crosslinks in the yarn to further improve mechanical properties.     

Comparative study on the electrical,thermal, and mechanical properties of multiwalled carbon nanotubes filled polypropylene and polyamide 6 micromoldings

In this work, a series of carbon nanotubes filled polypropylene (PP/CNT) and polyamide 6 (PA6/CNT) composites were prepared by melt blending and subsequently molded by compression molding and microinjection molding (μIM), respectively. Electrical conductivity results indicate that the percolation threshold of corresponding microparts shifted to higher filler concentrations when compared with that of compression molded counterparts, suggesting the prevailing shearing conditions in μIM is unfavorable for the construction of conductive pathways. In addition, Raman spectral analysis shows that there is a preferential alignment of CNTs along the flow direction of microparts. Thermal properties of both melt blended samples and subsequent microparts were evaluated using differential scanning calorimetry and thermogravimetric analysis. The mechanical properties of subsequent microparts are greatly affected by filler concentration, which might be related to the structural change that induced by the state of dispersion of CNTs.