Reinforcing brittle and ductile epoxy matrices using carbon nanotubes masterbatch

In this study, the mechanical and thermal properties of epoxy composites using two different forms of carbon nanotubes (powder and masterbatch) were investigated. Composites were prepared by loading the surface-modified CNT powder and/or CNT masterbatch into either ductile or brittle epoxy matrices. The results show that 3 wt.% CNT masterbatch enhances Young’s modulus by 20%, tensile strength by 30%, flexural strength by 15%, and 21.1 °C increment in the glass transition temperature (by 34%) of ductile epoxy matrix. From scanning electron microscopy images, it was observed that the CNT masterbatch was uniformly distributed indicating the pre-dispersed CNTs in the masterbatch allow an easier path for preparation of CNT-epoxy composites with reduced agglomeration of CNTs. These results demonstrate a good CNT dispersion and ductility of epoxy matrix play a key role to achieve high performance CNT-epoxy composites.     

Mechanical properties of high density polyethylene/carbon nanotube composites

Carbon-nanotubes (CNTs) have been used with polymers from the date of their inception to make composites having remarkable properties. An attempt has been made in this direction, in order to enhance mechanical and tribological properties of the composite materials. The latter, were achieved through the injection molding of high density polyethylene (HDPE) reinforced with specific volume fraction of CNTs. A considerable improvement on mechanical properties of the material can be observed when the volume fraction of CNT is increased. The composite reinforcement shows a good load transfer effect and interface link between CNT and HDPE. The volumetric wear rate is calculated from the Wang’s model, Ratner’s correlation and reciprocal of toughness. The results obtained clearly show the linear relationship with CNT loading which supports the microscopic wear model. It is concluded that both Halpin–Tsai and modified series model can be used to predict Young’s modulus of CNT–HDPE composites. From thermal analysis study, it is found that melting point and oxidation temperature of the composites are not affected by the addition of CNTs, however its crystallinity seems to increase.     

Effect of surfactant treatment on thermal stability and mechanical properties of CNT/polybenzoxazine nanocomposites

The mechanical and thermo-mechanical properties of polybenzoxazine nanocomposites containing multi-walled carbon nanotubes (MWCNTs) functionalized with surfactant are studied. The results are specifically compared with the corresponding properties of epoxy-based nanocomposites. The CNTs bring about significant improvements in flexural strength, flexural modulus, storage modulus and glass transition temperature, T_g, of CNT/polybenzoxazine nanocomposites at the expense of impact fracture toughness. The surfactant treatment has a beneficial effect on the improvement of these properties, except the impact toughness, through enhanced CNT dispersion and interfacial interaction. The former four properties are in general higher for the CNT/polybenzoxazine nanocomposites than the epoxy counterparts, and vice versa for the impact toughness. The addition of CNTs has an ameliorating effect of lowering the coefficient of thermal expansion (CTE) of polybenzoxazine nanocomposites in both the regions below and above T_g, whereas the reverse is true for the epoxy nanocomposites. This observation has a particular implication of exploiting the CNT/polybenzoxazine nanocomposites in applications requiring low shrinkage and accurate dimensional control.     

In situ polymerized nanocomposites: Polystyrene/CNT and Poly(methyl methacrylate)/CNT composites

Carbon nanotubes (CNTs) were incorporated into polystyrene (PS) and poly(methyl methacrylate) (PMMA) matrices via in situ emulsion and emulsion/suspension polymerization methods. The polymerizations were carried out using various initiators, surfactants, and carbon nanotubes to determine their influence on polymerization and on the properties of the composites. The loading of CNTs in the composites varied from 0 to 15 wt.%, depending on the CNTs used. Morphology and dispersion of the CNTs were analyzed by transmission and scanning electron microscopy techniques. The dispersion of multi-walled carbon nanotubes (MWCNT) in the composites was excellent, even at high CNT loading. The mechanical properties, and electrical and thermal conductivities, of the composites were also analyzed. Both electrical and thermal conductivities were improved.     

Overall behavior and microstructural deformation of R-CNT/polymer composites

Carbon nanotubes (CNTs) are an excellent candidate for the reinforcement of composite materials owing to their distinctive mechanical and electrical properties. Reticulate carbon nanotubes (R-CNTs) with a 2D or 3D configuration have been manufactured in which nonwoven connected CNTs are homogeneously distributed and connected with each other. A composite reinforced by R-CNTs can be fabricated by infiltrating a polymer into the R-CNT structure, which overcomes the inherent disadvantages of the lack of weaving of the CNTs and the low strength of the interface between CNTs and the polymer. In this paper, a 2D plane strain model of a R-CNT composite is presented to investigate its micro-deformation and effective stiffness. Using the two-scale expansion method, the effective stiffness coefficients and Young’s modulus are determined. The influences of microstructural parameters on the micro-deformation and effective stiffness of the R-CNT composite are studied to aid the design of new composites with optimal properties. It is shown that R-CNT composites have a strong microstructure-dependence and better effective mechanical properties than other CNT composites.     

Elevated temperature tensile properties and thermal expansion of CNT/2009Al composites

1.5 vol.% and 4.5 vol.% carbon nanotubes reinforced 2009Al (CNT/2009Al) composites with homogeneously dispersed CNTs and refined matrix grains, were fabricated using powder metallurgy (PM) followed by 4-pass friction stir processing (FSP). Tensile properties of the composites between 293 and 573 K and the coefficient of thermal expansion (CTE) from 293 to 473 K were tested. It was indicated that load transfer mechanism still takes effect at temperatures elevated up to 573 K, thus the yield strength of the 1.5 vol.% CNT/2009Al composite at 423–573 K, was enhanced compared with the 2009Al matrix. However, for the 4.5 vol.% CNT/2009Al composite, the yield strength at 573 K was even lower than that for the matrix, due to the quicker softening of ultrafine-grained matrix. Compared with the 2009Al matrix, the CTEs of the composites were greatly reduced for the zero thermal expansion and high modulus of the CNTs and could be well predicted by the Schapery’s model.     

Influence of dry grinding in a ball mill on the length of multiwalled carbon nanotubes and their dispersion and percolation behaviour in melt mixed polycarbonate composites

Ball milling of carbon nanotubes (CNTs) in the dry state is a common way to produce tailored CNT materials for composite applications, especially to adjust nanotube lengths. For Nanocyl^TM NC7000 nanotube material before and after milling for 5 and 10 h the length distributions were quantified using TEM analysis, showing decreases of the mean length to 54% and 35%, respectively. With increasing ball milling time in addition a decrease of agglomerate size and an increase of packing density took place resulting in a worse dispersability in aqueous surfactant solutions. In melt mixed CNT/polycarbonate composites produced using masterbatch dilution step, the electrical properties, the nanotube length distribution after processing, and the nano- and macrodispersion of the nanotubes were studied. The slight increase in the electrical percolation threshold in the melt mixed composites with ball milling time of CNTs can be assigned to lower nanotube lengths as well as the worse dispersability of the ball milled nanotubes. After melt compounding, the mean CNT lengths were shortened to 31%, 50%, and 66% of the initial lengths of NC7000, NC7000-5 h, and NC7000-10 h, respectively.     

Sugarcane bagasse cellulose/HDPE composites obtained by extrusion

Natural fibers used in this study were both pre-treated and modified residues from sugarcane bagasse. Polymer of high density polyethylene (HDPE) was employed as matrix in to composites, which were produced by mixing high density polyethylene with cellulose (10%) and Cell/ZrO₂·nH₂O (10%), using an extruder and hydraulic press. Tensile tests showed that the Cell/ZrO₂·nH₂O (10%)/HDPE composites present better tensile strength than cellulose (10%)/HDPE composites. Cellulose agglomerations were responsible for poor adhesion between fiber and matrix in cellulose (10%)/HDPE composites. HDPE/natural fibers composites showed also lower tensile strength in comparison to the polymer. The increase in Young’s modulus is associated to fibers reinforcement. SEM analysis showed that the cellulose fibers insertion in the matrix caused an increase of defects, which were reduced when modified cellulose fibers were used.     

Poly(vinyl alcohol) reinforced with large-diameter carbon nanotubes via spray winding

For practical application of carbon nanotube (CNT)/polymer composites, it is critical to produce the composites at high speed and large scale. In this study, multi-walled carbon nanotubes (MWNTs) with large diameter (∼45 nm) and polyvinyl alcohol (PVA) were used to increase the processing speed of a recently developed spraying winding technique. The effect of the different winding speed and sprayed solution concentration to the performance of the composite films were investigated. The CNT/PVA composites exhibit tensile strength of up to 1 GPa, and modulus of up to 70 GPa, with a CNT weight fraction of 53%. In addition, an electrical conductivity of 747 S/cm was obtained for the CNT/PVA composites. The good mechanical and electrical properties are attributed to the uniform CNTs and PVA matrix integration and the high degree of tube alignment.     

Effect of carbon nanotube (CNT) content on the mechanical properties of CNT-reinforced aluminium composites

The interest in carbon nanotubes (CNTs) as reinforcements for aluminium (Al) has been growing considerably. Efforts have been largely focused on investigating their contribution to the enhancement of the mechanical performance of the composites. The uniform dispersion of CNTs in the Al matrix has been identified as being critical to the pursuit of enhanced properties. Ball milling as a mechanical dispersion technique has proved its potential. In this work, we use ball milling to disperse up to 5 wt.% CNT in an Al matrix. The effect of CNT content on the mechanical properties of the composites was investigated. Cold compaction and hot extrusion were used to consolidate the ball-milled Al–CNT mixtures. Enhancements of up to 50% in tensile strength and 23% in stiffness compared to pure aluminium were observed. Some carbide formation was observed in the composite containing 5 wt.% CNT. In spite of the observed overall reinforcing effect, the large aspect ratio CNTs used in the present study were difficult to disperse at CNT wt.% greater than 2, and thus the expected improvements in mechanical properties with increase in CNT weight content were not fully realized.     

The influence of carbon nanotubes on the PVC glass transition temperature

The suspension poly(vinyl chloride) with the K number 70 (PVC S-70) compound was applied as a matrix of the nanocomposite, and the multi-wall carbon nanotubes (MWCNT) in the concentration range between 0.01 wt.% and 0.05 wt.% as a nanofiller. The T_g determination was realized by means of DMTA, dielectric losses measurements and DSC measurements. In all cases the PVC matrix revealed lower T_g comparing with corresponding composites with CNTs, and a clear relationship between the frequency, CNT contain and the T_g was found. With an increase of the charging frequency an increase of T_g of about 3 °C by DMTA measurements, realized by frequencies f = 1 Hz and f = 10 Hz, and of 9 °C by f = 1000 Hz, was noted. Independent on the frequency a maximum of the T_g increase was observed by the CNT concentration of about 0.01–0.02 wt.%.     

Interlaminar and intralaminar reinforcement of composite laminates with aligned carbon nanotubes

Three-dimensional reinforcement of woven advanced polymer–matrix composites using aligned carbon nanotubes (CNTs) is explored experimentally and theoretically. Radially-aligned CNTs grown in situ on the surface of fibers in a woven cloth provide significant three-dimensional reinforcement, as measured by Mode I interlaminar fracture testing and tension-bearing experiments. Aligned CNTs bridge the ply interfaces giving enhancement in both initiation and steady-state toughness, improving the already tough system by 76% in steady state (more than 1.5 kJ/m² increase). CNT pull-out on the crack faces is the observed toughening mechanism, and an analytical model is correlated to the experimental fracture data. In the plane of the laminate, aligned CNTs enhance the tension-bearing response with increases of: 19% in bearing stiffness, 9% in critical strength, and 5% in ultimate strength accompanied by a clear change in failure mode from shear-out failure (matrix dominated) without CNTs to tensile fracture (fiber dominated) with CNTs.     

Percolation model of reinforcement efficiency for carbon nanotubes dispersed in thermoplastics

Considerable experimental work on carbon nanotube-reinforced composites has shown that the reinforcement efficiency of carbon nanotubes (CNTs) becomes lower than the theoretical expectation when CNT content reaches a critical value. This critical volume fraction (percolation threshold) is considered related to the formation of percolating network. In this work, a percolation model is proposed to describe the observed sharp decrease in the reinforcement efficiency of multiwalled CNTs (MWCNTs) dispersed in thermoplastics when the CNT content exceeds the percolation threshold. The percolation threshold is estimated via a numerical simulation of randomly curved CNTs according to the statistics on geometrical features of real CNTs. The percolation model, integrated into the Halpin–Tsai equations, is verified using the experimental data of various thermoplastic composites reinforced with MWCNTs. The developed mechanical model achieves a good agreement with the measured moduli of nanocomposites, and demonstrates an excellent prediction capability over a wide range of CNT content.     

Formation and mechanical characterisation of SU8 composite films reinforced with horizontally aligned and high volume fraction CNTs

Carbon nanotube (CNT) reinforced composites have been identified as promising structural materials for the mechanical components of microelectromechanical systems (MEMS), potentially leading to advanced performance. High alignment and volume fraction of CNTs in the composites are the prerequisites to achieve such desirable mechanical characteristics. In particular, horizontal CNT alignment in composite films is necessary to enable high longitudinal moduli of the composites which is crucial for the performance of microactuators. A practical process has been developed to transfer CNT arrays from vertical to horizontal alignment which is followed by in situ wetting, realign and pressurized consolidation processes, which lead to a high CNT volume fraction in the range of 46-63%. As a result, SU8 epoxy composite films reinforced with horizontally aligned CNTs and a high volume faction of CNTs have been achieved with outstanding mechanical characteristics. The transverse modulus of the composite films has been characterised through nanoindentation and the longitudinal elastic modulus has been investigated. An experimental transverse modulus of 9.6 GPa and an inferred longitudinal modulus in the range of 460-630 GPa have been achieved, which demonstrate effective CNT reinforcement in the SU8 matrix.     

The influence of nano/micro hybrid structure on the mechanical and self-sensing properties of carbon nanotube-microparticle reinforced epoxy matrix composite

Nano/micrometer hybrids are prepared by chemical vapor deposition growth of carbon nanotubes (CNTs) on SiC, Al₂O₃ and graphene nanoplatelet (GNP). The mechanical and self-sensing behaviors of the hybrids reinforced epoxy composites are found to be highly dependent on CNT aspect ratio (AR), organization and substrates. The CNT–GNP hybrids exhibit the most significant reinforcing effectiveness, among the three hybrids with AR1200. During tensile loading, the in situ electrical resistance of the CNT–GNP/epoxy and the CNT–SiC/epoxy composites gradually increases to a maximum value and then decreases, which is remarkably different from the monotonic increase in the CNT–Al₂O₃/epoxy composites. However, the CNT–Al₂O₃ with increased AR ⩾ 2000 endows the similar resistance change as the other two hybrids. Besides, when AR < 3200, the tensile modulus and strength of the CNT–Al₂O₃/epoxy composites gradually increase with AR. The interrelationship between the hybrid structure and the mechanical and self-sensing behaviors of the composites are analyzed.     

Properties of composites of carbon nanotube fibres

Composites have set the standard for high strength materials for several decades. With the discovery of nanotubes, new possibilities for reinforced composites have arisen, with potential mechanical properties superior to those of currently available materials. This paper reports the properties of epoxy matrix reinforced with fibres of carbon nanotubes (CNTs) which, in many ways, are similar to standard composites reinforced with commercial fibres. The composites were formed by the back diffusion of the uncured epoxy into an array of aligned fibres of CNTs. The fibre density and volume fraction were measured from thermogravimetric analysis (TGA). Properties in tension and compression were measured, and the level of fibre–matrix interaction analysed fractographically. The results show the significant potential for this route to CNT reinforcement.     

Processing and mechanical properties of carbon nanotube-alumina hybrid reinforced high density polyethylene composites

Carbon nanotube-alumina hybrid reinforced high density polyethylene (HDPE) matrix composites were prepared by melt processing technique. Microstructure studies verified that the nanotubes consisting of well-crystallized graphite formed a network structure with Al₂O₃ in the hybrid, which was homogeneously dispersed in the HDPE matrix composites. Mechanical measurements revealed that 5% addition of nanotube-alumina hybrid results in 100.8% and 65.7% simultaneous increases in Young's modulus and tensile strength, respectively. Fracture surface showed homogenous dispersion of nanotubes and Al₂O₃ in the HDPE matrix and presence of interlocking like phenomena between hybrid and HDPE matrix, which might contribute to the effective reinforcement of the HDPE composites.     

Effect of carbon nanotube type and functionalization on the electrical,thermal, mechanical and electromechanical properties of carbon nanotube/styrene–butadiene–styrene composites for large strain sensor applications

Thermoplastic elastomer tri-block copolymer, namely styrene–butadiene–styrene (SBS) composites filled with carbon nanotubes (CNT) are characterized with the main goal of obtaining electro-mechanical composites suitable for large deformation sensor applications. CNT/SBS composites with different filler contents and filler functionalizations are studied by morphological, thermal, mechanical and electrical analyses. It is shown that the different dispersion levels of CNT in the SBS matrix are achieved for pristine or functionalized CNT with strong influence in the electrical properties of the composites. In particular covalently functionalized CNTs show percolation thresholds higher than 8 weight percentage (wt%) whereas pristine CNT show percolation threshold smaller than 1 wt%. On the other hand, CNT functionalization does not alter the conduction mechanism which is related to hopping between the CNT for concentrations higher than the percolation threshold.Pristine single and multiwall CNT within the SBS matrix allow the preparation of composites with electro-mechanical properties appropriate for strain sensors for deformations up to 5% of strain, the gauge factor varying between 2 and 8. Composites close to the percolation threshold show larger values of the gauge factor.     

Cryogenic mechanical behaviors of carbon nanotube reinforced composites based on modified epoxy by poly(ethersulfone)

Cryogenic mechanical properties are important parameters for epoxy resins used in cryogenic engineering areas. In this study, multi-walled carbon nanotubes (MWCNTs) were employed to reinforce diglycidyl ether of bisphenol F (DGBEF)/diethyl toluene diamine (DETD) epoxy system modified by poly(ethersulfone) (PES) for enhancing the cryogenic mechanical properties. The epoxy system was properly modified by PES in our previous work and the optimized formulation of the epoxy system was reinforced by MWCNTs in the present work. The results show that the tensile strength and Young’s modulus at 77 K were enhanced by 57.9% and 10.1%, respectively. The reported decrease in the previous work of the Young’s modulus of the modified epoxy system due to the introduction of flexible PES is offset by the increase of the modulus due to the introduction of MWCNTs. Meanwhile, the fracture toughness (K_IC) at 77 K was improved by about 13.5% compared to that of the PES modified epoxy matrix when the 0.5 wt.% MWCNT content was introduced. These interesting results imply that the simultaneous usage of PES and MWCNTs in a brittle epoxy resin is a promising approach for efficiently modifying and reinforcing epoxy resins for cryogenic engineering applications.     

Structure-property relationship of SELF-sustained homogeneous ternary nanocomposites: Key issues to evaluate properties of rrP3HT wrapped MWNT dispersed in TPU

An interesting correlation between nature of wrapping, wrapping thickness and crystallinity of regioregular poly(3-hexyl thiophene) (rrP3HT) wrapped multi-walled nanotube (MWNT) arises due to different loading of rrP3HT and their combined effect on the properties of a ternary system prepared by uniform dispersion of wrapped CNT into thermoplastic polyurethane (TPU) are highlighted in the article. Data accumulated through different techniques demonstrate that 2.5 wt.% of rrP3HT with 0.5 wt.% of MWNT can be the ideal ratio of filler to achieve highest properties in these stable self-sustained homogeneous composites. Wrapping of rrP3HT on the wall of CNT through π-π and/or CH-π interaction is ascertained from shifting in peak position and I_asym/I_sym ratio of CC bond of rrP3HT in FTIR spectroscopy. Strong quenching of fluorescence intensity of rrP3HT in composite further support π-π interaction between rrP3HT and CNTs. SEM micrograph of rrP3HT/TPU blends suggest uniform globular dispersion of polythiophene into TPU matrix without any separate phase domain and addition of CNTs considerably reduce globule size. Single Tg(∼−40 °C, DMA, DSC, TMA) clearly ascertain the miscibility of composite. An ‘order to order transition’ through coil to rod transformation leads to strong, sharp red shifting (∼150 nm shift compared to pristine rrP3HT) in emission peaks of rr-poly (3-hexylthiophene) in blends. Further red shifting and highest quenching is observed in case of 2.5% rrP3HT loaded ternary system whereas blue shifting and quenching in case of 0.5 wt.% (non-uniform wrapping) and 5 wt.% (agglomerates) rrP3HT loading.