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     

Nanoscale characterization of interphase properties in maleated polypropylene‐treated natural fiber‐reinforced polymer composites

Contact resonance force microscopy has been used to evaluate the effect of maleated polypropylene (MAPP) concentration on interphase thickness as well as the spatial distribution of mechanical properties within the interphase of cellulose fiber‐reinforced polypropylene composites. The average interphase thickness values ranged from 25 nm to 104 nm for different concentrations of MAPP. The interphase region showed a gradient in the elastic modulus, with a gradual decrease in modulus from fiber to matrix. The interphase region in the specimen containing 0% MAPP showed a narrow interphase with steep gradient in modulus from fiber to matrix, whereas the use of MAPP significantly increased the interphase thickness which resulted in a more gradual change in modulus from fiber to matrix. POLYM. ENG. SCI., 2013. © Society of Plastics Engineers     

Alignment and properties of carbon nanotube buckypaper/liquid crystalline polymer composites

Carbon nanotubes (CNTs) have been recognized as a potential superior reinforcement for high‐performance, multifunctional composites. However, non‐uniform CNT dispersion within the polymer matrix, the lack of adequate adhesion between the constituents of the composites, and lack of nanotube alignment have hindered significant improvements in composite performance. In this study, we present the development of a layer‐by‐layer assembly method to produce high mechanical performance and electrical conductivity CNT‐reinforced liquid crystalline polymer (LCP) composites using CNT sheets or buckypaper (BP) and self‐reinforcing polyphenylene resin, Parmax. The Parmax/BP composite morphology, X‐ray diffraction, mechanical, thermal, and electrical properties have been investigated. SEM observations and X‐ray diffraction demonstrate alignment of the CNTs due to flow‐induced orientational ordering of LCP chains. The tensile strength and Young's modulus of the Parmax/BP nanocomposites with 6.23 wt % multi‐walled carbon nanotube content were 390 MPa and 33 GPa, respectively, which were substantially improved when compared to the neat LCP. Noticeable improvements in the thermal stability and glass transition temperature with increasing CNT content due to the restriction in chain mobility imposed by the CNTs was demonstrated. Moreover, the electrical conductivity of the composites increased sharply to 100.23 S/cm (from approximately 10^?13 S/cm) with the addition of CNT BP. These results suggest that the developed approach would be an effective method to fabricate high‐performance, multifunctional CNT/LCP nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Investigation of the nanoscale mechanical properties of carbon fiber/epoxy resin interphase. I. analysis of fiber‐stiffening effect during the nanoindentation process based on numerical simulation

The interphase in fiber reinforced polymer composites is a narrow region around the fiber with the thickness in nanoscale, and its properties have a significant effect on the composite mechanical properties. Nanoindentation method was widely accepted for the measurement of the interphase properites. Different from the homogenous material, the modulus diffence between fiber and matrix is very obvious, it is difficult to get the intrinsic properties of the interphase just depending on the experimental data due to the fiber‐stiffening effect. A numerical method is developed to simulate the nanoindentation process, to understand the fiber‐stiffening effect during the nanoindentation process in the carbon fiber/epoxy composites. The predicted results reveal that the fiber impacts the indentation response in the vicinity region of the fiber. When the indent contacts the fiber, there will be a mutation in the load–displacement curve, and the fiber‐stiffening effect is obvious, which is less affected by the thickness and modulus of the interphase and the resin matrix modulus. If the interphase thickness is smaller than the distance of indent contacting the fiber, it is nearly impossible to get the intrinsic modulus of the interphase due to the effect of fiber. On the other hand, if the interphase thickness is larger than that, in the near region about 100 nm away the indent contacting the fiber, the indentation response can reflect the difference of the interphase modulus. The gradient of the curve, that is, the indentation force varying with the distance from the fiber surface, decreases with the increase in the interphase modulus. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Molecular dynamics simulation of mechanical properties and interaction energy of polythiophene/polyethylene/poly(p‐phenylenevinylene) and CNTs composites

Carbon nanotubes (CNTs) have very important applications in ultrastrong lightweight materials. CNTs can improve mechanical properties of polymer matrix such as breaking stress and Young's modulus. In this article, we studied the interaction between polythiophene (PT)/polyethylene (PE)/poly(p‐phenylenevinylene) (PPV) and CNTs by molecular dynamics (MD) simulation based on a reactive force field (ReaxFF). We studied the influence of CNT diameter, polymer type, and temperature on interaction energy. We found that a large radius CNT at low temperature shows the strongest interaction energy with PT. In addition, we computed the mechanical properties of CNTs‐polymer composites such as the breaking stress, breaking strain, and Young's modulus. Our results show that there is a direct relation between mechanical properties and interaction energy. We found that the mechanical properties of CNTs‐PT composite are better than CNTs‐PPV and CNTs‐PE and it is a good candidate for ultrastrong lightweight materials. We studied the influence of temperature on the mechanical properties. Our results show that CNTs‐polymer composites show stronger mechanical properties at low temperature. We found that ReaxFF can reproduce the other force fields results and it is a very powerful force field to study the various properties of CNTs‐polymer composites. POLYM. COMPOS., 35:2261–2268, 2014. © 2014 Society of Plastics Engineers     

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.     

Effect of deposited carbon nanotubes on interlaminar properties of carbon fiber‐reinforced epoxy composites using a developed spraying processing

Carbon fiber‐reinforced epoxy composites, with incorporated carboxylic multiwall carbon nanotubes (CNTs), were prepared using vacuum‐assisted resin infusion (VARI) molding, and the in‐plane and out‐of‐plane properties, including mode‐I (G_Ic) and mode‐II (G_IIc) interlaminar fracture toughness, interlaminar shear strength (ILSS), tensile, and flexural properties were measured. A novel spraying technique, which sprays a kind of epoxy resin E20 with high viscosity after spraying the CNTs, was adopted to deposit the CNTs on the surface of carbon fiber fabric. The E20 was used to anchor CNTs on the fabric surface, avoiding that the deposited CNTs were removed by the infusing resin during VARI process. The spraying processing, including spraying amount and spraying sequence, was optimized based on the distribution of CNTs on the fibers. After that, three composite specimen groups were fabricated using different carbon fiber fabrics, including as‐received, CNT‐deposited with E20, and CNT‐deposited without E20. The effects of CNTs on the processing quality and mechanical properties of carbon fiber‐reinforced polymer composites were studied. The experimental results show that all studied laminates have uniform thickness with designed values and no obvious defects form inside the laminates. Compared with the composite without CNTs, depositing CNTs with E20 increases by 24% in the average propagation G_Ic, by 11% in the propagation G_IIc and by 12% in the ILSS, while it preserves the in‐plane mechanical properties, However, depositing CNTs without E20 reduces interlaminar fracture toughness. These phenomena are attributed to the differences in the distribution of CNTs and the fiber/matrix interfacial bonding for different spraying processing. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Effect of processing technique on the dispersion of carbon nanotubes within polypropylene carbon nanotube‐composites and its effect on their mechanical properties

Carbon nanotube‐reinforced polymer composites are being investigated as promising new materials having enhanced physical and mechanical properties. With regards to mechanical behavior, the enhancements reported thus far by researchers are lower than the theoretical predictions. One of the key requirements to attaining enhanced behavior is a uniform dispersion of the nanotubes within the polymer matrix. Although solvent mixing has been used extensively, there are concerns that any remaining solvent within the composite may degrade its mechanical properties. In this work, a comparison is carried out between solvent and “solvent‐free” dry mixing for dispersing multiwall carbon nanotubes in polypropylene before further melt mixing by extrusion. Various weight fractions of carbon nanotubes (CNTs) are added to the polymer and their effect on the mechanical properties of the resulting composites is investigated. Enhancements in yield strength, hardness, and Young's modulus when compared with the neat polymer, processed under similar conditions, are observed. Differences in mechanical properties and strain as a function of the processing technique (solvent or dry) are also clearly noted. In addition, different trends of enhancement of mechanical properties for the solvent and dry‐mixed extrudates are observed. Dry mixing produces composites with the highest yield strength, hardness, and modulus at 0.5 wt% CNT, whereas solvent mixing produces the highest mechanical properties at CNT contents of 1 wt%. It is believed that this difference is primarily dependent on the dispersion of CNTs within the polymer matrix which is influenced by the processing technique. Field emission scanning electron microscopy analysis shows the presence of clusters in large wt% CNT samples produced by dry mixing. Samples produced by solvent mixing are found to contain homogeneously distributed CNTs at all CNT wt fractions. CNT pull‐out is observed and may explain the limited enhancement in mechanical properties. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

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     

Mechanical and thermal enhancements of benzoxazine‐based GF composite laminated by in situ reaction with carboxyl functionalized CNTs

An easy and efficient approach by using carboxyl functionalized CNTs (CNT‐COOH) as nano reinforcement was reported to develop advanced thermosetting composite laminates. Benzoxazine containing cyano groups (BA‐ph) grafted with CNTs (CNT‐g‐BA‐ph), obtained from the in situ reaction of BA‐ph and CNT‐COOH, was used as polymer matrix and processed into glass fiber (GF)‐reinforced laminates through hot‐pressed technology. FTIR study confirmed that CNT‐COOH was bonded to BA‐ph matrices. The flexural strength and modulus increased from 450 MPa and 26.4 GPa in BA‐ph laminate to 650 MPa and 28.4 GPa in CNT‐g‐BA‐ph/GF composite, leading to 44 and 7.5% increase, respectively. The SEM image observation indicated that the CNT‐COOH was distributed homogeneously in the matrix, and thus significantly eliminated the resin‐rich regions and free volumes. Besides, the obtained composite laminates showed excellent thermal and thermal‐oxidative stabilities with the onset degradation temperature up to 624°C in N₂ and 522°C in air. This study demonstrated that CNT‐COOH grafted on thermosetting matrices through in situ reaction can lead to obvious mechanical and thermal increments, which provided a new and effective way to design and improve the properties of composite laminates. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of high-performance carbon nanotube/polyamide composite materials by elastic high-shear kneading and improvement of properties by induction heating treatment

Polyamide 66 (PA66) nanocomposites were prepared by compounding carbon nanotubes (CNTs) using an elastic high-shear kneading method, and the mechanism to understand their excellent properties was verified. In addition, we developed a microwave heat treatment that increases toughness quickly and at low cost. By combining 6.6 vol% or more of CNTs, PA66 with improved mechanical properties, such as higher elastic modulus and yield strength, was achieved, making it possible to obtain a composite having excellent high-temperature characteristics that does not melt even at a temperature above the melting point. These effects appeared to be due to defibration of CNT aggregates and isolation and dispersion in PA66. A lamellar crystal of PA66 grows around the CNT, forming an interphase. The higher performance appeared to be attributable to a continuous three-dimensional structure in which CNTs are bound via the interphase, and the improvement of the elastic modulus of the composite material was tentatively ascribed to a Halpin-Tsai model in which the size of the unit cell of the three-dimensional structure is introduced. The resulting CNT/PA66 composite materials are superior not only in performance but also in price.     

Optimization of stress wave propagation in a multilayered elastic/viscoelastic hybrid composite based on carbon fibers/carbon nanotubes

The hypothesis of incorporating carbon nanotubes (CNTs) into the interfacial layers of fiber‐reinforced polymer composites fiber‐reinforced Polymers (FRPs) to enhance their mechanical properties and mitigate the stress wave propagation during a blast event is investigated. A numerical model is developed to simulate the stress wave propagation in a laminated elastic/viscoelastic FRP. Coupled with multiobjective optimization paradigms, the optimal CNTs contents in the interfacial layers are determined to minimize the stress‐to‐strength ratio in each layer. A case study demonstrating the design of a five‐layered FRP subjected to a blast event is presented. The simulation revealed that the viscoelastic properties of the matrix material contribute significantly to the energy dissipation during stress wave propagation. It is shown that addition of 0.69% CNTs by volume to the epoxy interface significantly enhances the ability of composite to resist blast loading. Results were compared with a standard model that assumes only elastic behavior. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Fabrication and properties of carbon nanotube/styrene–ethylene–butylene–styrene composites via a sequential process of (electrostatic adsorption aided dispersion)‐plus‐(melt mixing)

Carbon nanotube (CNT)/styrene–ethylene–butylene–styrene (SEBS) composites were prepared via a sequential process of (electrostatic adsorption assisted dispersion)‐plus‐(melt mixing). It was found that CNTs were uniformly embedded in SEBS matrix and a low percolation threshold was achieved at the CNT concentration of 0.186 vol %. According to thermal gravimetric analysis, the temperatures of 20% and 50% weight loss were improved from 316°C and 352°C of pure SEBS to 439°C and 463°C of the 3 wt % CNT/SEBS composites, respectively. Meanwhile, the tensile strength and elastic modulus were improved by about 75% and 181.2% from 24 and 1.6 MPa of pure SEBS to 42 and 4.5 MPa of the 3 wt % CNT/SEBS composite based on the tensile tests, respectively. Importantly, this simple and low‐cost method shows the potential for the preparation of CNT/polymer composite materials with enhanced electrical, mechanical properties, and thermal stability for industrial applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40227.     

The transverse elastic modulus of fiber-reinforced composites as defined by the concept of interphase

A theoretical expression for the prediction of the transverse elastic modulus in fiber-reinforced composites was developed. The concept of interphase between fibers and matrix was used for the development of the model. This model considers that the composite material consists of three phases, that is, the fiber, the matrix, and the interphase. The latter is the part of the polymer matrix lying at the close vicinity of the fiber surface. In the present investigation it was assumed that the interphase is inhomogeneous in nature with continuously varying mechanical properties. Different laws of variation of its elastic modulus and Poisson ratio were taken into account in order to define the overall modulus of the composite. Thermal analysis method was used for the estimation of the thickness of the interphase. The results obtained were compared with the respective values of other models as well as with experimental data. © 1993 John Wiley & Sons, Inc.     

Influence of Thrower–Stone–Wales defects on the interfacial properties of carbon nanotube/polypropylene composites by a molecular dynamics approach

A molecular dynamics (MD) simulations study is performed on Thrower–Stone–Wales (TSW) defected carbon nanotube (CNT)/polypropylene (PP) composites. We identify the degradation of the CNT and the improvement of the interfacial adhesion between the defected CNTs and PP molecules considering different CNTs with different numbers of TSW defects. By embedding the CNTs into a PP matrix, the effect of the TSW defects on the transversely isotropic elastic stiffness of polymer composites is calculated by MD simulations. Even if the TSW defects degrade the elastic properties of the CNTs, the transverse Young’s modulus and the transverse and longitudinal shear moduli of the composites increase due to the stronger interfacial adhesion between the defected CNTs and matrix, whereas the longitudinal Young’s modulus of the composites decreases. To elucidate the improved interfacial load transfer between the CNTs and the matrix, random polymer chain crystallization onto the surface of CNTs is simulated. The simulation shows that PP chains are wrapped more uniformly onto the surfaces of defected CNTs than onto the pristine CNT. The non-bond adhesion energy between the PP chains and the defected CNTs is greater than that between the PP chains and the pristine CNT.     

Multiscale modeling of interface debonding effect on mechanical properties of nanocomposites

Mechanical behavior of SiO₂ nanoparticle‐epoxy matrix composites was investigated via finite element analysis with an emphasis on the nanofiller‐interphase debonding effect using a three‐dimensional nanoscale representative volume element (RVE). The new model, in which a cohesive zone material (CZM) layer is considered as an inclusion‐interphase bonding, can be applied to polymer nanocomposites reinforced by inclusions of different forms, including spherical, cylindrical, and platelet shapes. Upon validation by experimental data, the model was used to study the effects of interphase properties, nanoparticle size, and inclusion volume fraction on the mechanical properties of nanocomposites. According to the results, taking into account the inclusion‐interphase debonding provides more precise results compared with perfect bonding, especially in nanocomposites with nanoparticles of smaller size. Moreover, the outcomes disclosed that the amount of changes in the elastic modulus by particle size variation is higher when the relative thickness (the interphase thickness to the particle diameter ratio) increases. For relative thicknesses lower than a critical value, the particle size and the interphase properties have negligible effect on the elastic modulus of the nanocomposite, and the elastic modulus of nanocomposite mostly depends on nanofiller content. POLYM. COMPOS., 38:789–796, 2017. © 2015 Society of Plastics Engineers     

Improved tensile properties of carbon nanotube modified epoxy and its continuous carbon fiber reinforced composites

Carbon nanotubes (CNTs) were used to improve the tensile properties of an epoxy resin and its continuous carbon fiber (CF) reinforced composites. Micrography picture showed that CNTs has been well incorporated into the composites, and made the fracture cross section more rougher through sharing the stress. For the CNT/epoxy composite, the tensile strength and modulus both increased upon the CNT addition, and at a CNT volume concentration of 2.0%, the maximum enhancements in the tensile strength and modulus were achieved as 26.7% and 21.5%, respectively. For the CNT‐CF/epoxy composite, the maximum enhancement in tensile strength was achieved as 11.6% at a CNT volume concentration of 1.0% and then decreased with the further increase of the CNT addition, but the tensile modulus increased monotonically upon the CNT addition. POLYM. COMPOS., 36:1664–1668, 2015. © 2014 Society of Plastics Engineers     

Influence of multiwalled carbon nanotubes on the processing behavior of epoxy powder compositions and on the mechanical properties of their fiber reinforced composites

This study reports the preparation of advanced carbon fiber composites with a nanocomposite matrix prepared by dispersing multiwall carbon nanotubes (CNTs) in a powder type epoxy oligomer with two different processing techniques (1) master batch dilution technique and (2) direct mixing (with the help of twin‐screw extruder in both cases). The master batch technique shows a better efficiency for the dispersion of the CNTs aggregates. The rheological results demonstrate that the incorporation of the CNTs into the epoxy oligomer leads, as expected, to a marked increase in the viscosity and of the presence of a yield stress point that also depends on the processing technique adopted. Carbon fiber (CFRP) and glass fiber (GFRP) composite materials were produced by electrostatic spraying of the epoxy matrix formulations on the carbon and glass fabric, respectively, followed by calendering and mold pressing. The mechanical properties of the obtained epoxy/CNT‐matrix composite materials, such as interlaminar fracture toughness, flexural strength, shear storage and loss moduli are discussed in terms of the processing techniques and fabric material. The incorporation of 1 wt% CNTs in the epoxy matrix results in a relevant increase of the fracture toughness, flexural strength and modulus of both CFRP and GFRP. POLYM. COMPOS., 37:2377–2383, 2016. © 2015 Society of Plastics Engineers     

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     

Synergistic strengthening by load transfer mechanism and grain refinement of CNT/Al–Cu composites

CNT/Al–Cu composites were fabricated by mixing of Al powders and CNT/Cu composite powders which were prepared by molecular level mixing process. The CNT/Al–Cu–Cu composites show a microstructure with a homogeneous dispersion of CNTs in the Al–Cu matrix and had a 3.8 times increase of yield strength and 30% increase of elastic modulus compared to Al–Cu matrix. The strengthening mechanism of CNT/Al–Cu composites was discussed by controlling the aspect ratio of CNTs and it was thought that the CNT/Al–Cu composites were strengthened by both load transfer from the Al matrix to the CNTs and dispersion strengthening of damaged short CNTs. At the same time, the addition of CNTs increases the grain refinement effect of the Al–Cu matrix which results in a grain size strengthening mechanism of the CNT/Al–Cu composites.