Improving the flexural and thermomechanical properties of amino-functionalized carbon nanotube/epoxy composites by using a pre-curing treatment

A prior thermal (pre-curing) treatment of mixtures of epoxy monomer and amino-functionalized carbon nanotubes (CNTs) was used to promote a chemical reaction between the matrix and the reinforcement, favouring the formation of a strong interface. Samples of epoxy resin and different weight percentages of amino-functionalized multi-walled CNTs were prepared with and without the pre-curing treatment (150 °C, 1 h). The degree of dispersion of the nanofiller was better when this pre-curing treatment was used. This allowed a higher CNT content while keeping a high sample homogeneity. Without the pre-curing step, the addition of CNTs increases both the flexural strength and strain to failure by 45%. Moreover, with the pre-curing step, the nanocomposite with 0.25 wt.% CNTs presents an increase of flexural strength by 58% and strain to failure by 68% regard to neat epoxy resin.     

Interfacial evaluation of carbon fiber/epoxy composites using electrical resistance measurements at room and a cryogenic temperature

Interfacial properties between fiber and matrix were evaluated using an electrical resistance (ER) fragmentation method. The single carbon fiber (CF) tensile test was performed in conjunction with electrical resistance measurements. The relationship between tensile properties of single carbon fiber specimens and the electrical resistance ratio (ERR) was investigated. The data showed a linear relationship between these properties. Fragmentation specimens were tested under tensile loading, and it was observed that, due to stress transfer from the matrix to the reinforcing fiber, the single carbon fiber broke first. The stress distribution along the carbon fiber was monitored via electrical resistance changes. ER fragmentation measurements were performed to predict CF fractured strength embedded in epoxy by an empirical formula of CF tensile results. These interfacial properties of CF epoxy composites were measured at room and a cryogenic temperature. Work of adhesion between the carbon fiber and the matrix was measured to verify the results of the ER fragmentation method, and the two procedures yielded consistent results and conclusions.     

Strain sensing in polymer/carbon nanotube composites by electrical resistance measurement

In this work multiwall carbon nanotubes (MWCNTs) dispersed in a polymer matrix have been used for strain sensing of the resulting nanocomposite under tensile loading. This was achieved by measuring the relative electrical resistance change (ΔR/R₀) in conductive polyvinylidenefluoride (PVDF)/MWCNTs nanocomposites prepared by melt-mixing with varying filler content from 0.5 wt.% to 8 wt.%. Two main parameters were systematically studied. The PVDF/MWCNTs mixing procedure that results in a successful MWCNTs dispersion, and the effect of MWCNTs content on material’s sensing behaviour. The samples were subjected to tensile loading and the longitudinal strain was monitored together with the longitudinal electrical resistance. The results showed that MWCNTs dispersed in insulating PVDF matrix have the potential to be used as a sensitive network to monitor the strain levels in polymer/carbon nanotube nanocomposites as the deformation level of each sample was being reflected by the resistance changes.     

RTM processing and electrical performance of carbon nanotube modified epoxy/fibre composites

This investigation focuses on nanoparticle filtration in the processing of multiscale carbon and glass fibre composites via resin transfer moulding. Surface modified and unmodified carbon nanotubes (CNTs) were incorporated into a commercial epoxy resin. The dispersion quality was evaluated using electrical measurements of the liquid suspensions. The manufacturing process was adapted to the challenges posed by the modified rheological behaviour of the CNT loaded resin. Nanoparticle filtration was observed; with some of the unmodified systems following so called ‘cake filtration’ behaviour. This resulted in nonlinear flow behaviour that deviated from the ideal response observed in RTM filling in conventional composites. The electrical conductivity of relatively high fibre volume fraction multiscale carbon and glass laminates increased by less than an order of magnitude with the addition of the nanotubes.     

Impedance characteristics and electrical modelling of multi-walled carbon nanotube/silicone rubber composites

Multi-walled carbon nanotube (MWCNT)-filled silicone rubber (SR) composites were prepared by solvent evaporation method, with different MWCNT concentrations from 0.5 wt% to 6.5 wt%. Alternating current (AC) electrical properties of samples with interdigital electrodes were measured in the frequency range from 20 Hz to 1 MHz. Impedance spectroscopy analysis reveals a frequency-independent percolation transition between 2.0 wt% and 2.9 wt%. Samples above the percolation threshold exhibit more regular variations: the magnitude of impedance decreases gradually with frequency in the low-frequency range, and then decreases as a power law beyond a critical frequency, with the exponent in a limited range indicating the AC universality of disordered solids; the plots of real and imaginary parts of impedance fit semicircles well in the complex plane, implying semiconductive behaviours. Over the concentration range tested, a multi-stage circuit model consisting of resistor–capacitor (RC) networks is proposed to simulate the electrical responses of samples. The validity of the modelling approach is verified by comparing simulation results to experimental results, and is further supported by the analysis of the characteristic frequency. The use of equivalent circuits in modelling provides a further insight into the conducting network inside nanocomposites and more valuable guidance for the design of correlative devices.     

Specific rheological and electrical features of carbon nanotube dispersions in an epoxy matrix

The rheological analysis of epoxy pre-polymer/MWCNT dispersions indicates that a physical network is formed. This is destroyed with an imposed shear, giving a viscoplastic and shear thinning behavior. Such destruction is not reflected in dynamic viscoelastic experiments, due to the very rapid recovery of the MWCNT network in the pre-polymer matrix. This responds to the observed lower electrical than rheological percolation threshold. Electrical conductivity results fulfill electron hopping/tunnelling mechanism, which implies a tube–tube distance close to 5 nm. However, rheological percolation requires nanotubes should touch each other, since no polymer chains are implied in the network.     

Experiments and micromechanical modeling of electrical conductivity of carbon nanotube/cement composites with moisture

Carbon nanotube (CNT)/cement composites have been proposed as a multifunctional material for self-sensing and traffic monitoring due to their unique electric conductivity which changes with the application of mechanical load. However, material constituent and environmental factors may significantly affect the potential application of these materials. Therefore, it is necessary to understand an influence of material constituent such as porosity and dispersion of CNT and environmental factor such as moisture on the electrical conductivity of CNT/cement composite. This paper investigates the effect of moisture on the effective electrical conductivity of CNT/cement composites. To prepare the specimens, multi-walled carbon nanotubes (MWCNTs) are well dispersed in cement paste, which is then molded and cured into cubic test specimens. By drying the specimens from the fully saturated state to the fully dry state, the effective electrical conductivity is measured at different moisture contents. As the water in the specimen is replaced by air voids, the electrical conductivity significantly decreases. Different ratios of MWCNTs to cement have been used in this study. Micromechanical models have been used to predict the effective electrical conductivities. A comprehensive model is proposed to take into account the effects of individual material phases on the effective electrical conductivity of CNT/cement composites with moisture effect.     

Viscoelastic and mechanical properties of multi walled carbon nanotube/epoxy composites with different nanotube content

The viscoelastic and mechanical properties of composites multi walled carbon nanotube (MWNT)/epoxy at different weight fractions (0.1, 0.5, 1 and 2 wt.%) were evaluated by performing tensile and dynamic-mechanical thermal analysis (DMTA) tests. The MWNT/epoxy composite were fabricated by sonication and a cast molding process. The results showed that addition of nanotubes to epoxy had significant effect on the viscoelastic and mechanical properties. However, the use of 0.5 wt.% increased the viscoelastic properties more significantly. Concerning viscoelastic modeling, the COLE–COLE diagram has been plotted by the results of DMTA test. These results show a good agreement between the Perez model and the viscoelastic behavior of the composite.     

Experimental study of mechanical and electrical properties of carbon nanofiber/epoxy composites

Epoxy nanocomposites of different content of carbon nanofibers up to 1 wt.% have been fabricated under room temperature and refrigerated curing conditions. The composites were studied in terms of mechanical and electrical properties. Flexural modulus and hardness were found to increase significantly in refrigerated samples due to prevention of aggregates of nanofibers during cure condition. Increase and shifting in G-band by Raman spectra of these samples confirmed stress transfer and reinforcement between epoxy matrix and carbon nanofiber. Electrical conductivity improved by 3–6 orders after infusing carbon nanofibers in insulating epoxy. Room temperature samples acquired higher conductivity that was attributed to network formation by aggregates of nanofibers along the fiber alignment direction as revealed by electron microscopic studies.     

In-situ damage sensing of woven composites using carbon nanotube conductive networks

We report an in situ analysis of the microstructure of woven composites using carbon nanotube (CNT)-based conductive networks. Two types of specimens with stacking sequences of (0/90)_s (on-axis) and (22/85/−85/−22) (off-axis) were manufactured using ultra-high-molecular-weight polyethylene fibers and a CNT-dispersed epoxy matrix via vacuum-assisted resin transfer molding. The changes in the electrical resistance of the woven composites in response to uniaxial loading corresponded to the changes in the gradient of the stress–strain curves, which is indicative of the initiation and accumulation of microscopic cracking and delamination. The electrical resistance of the woven composites increased due to both elongation and microscopic damage; interestingly, however, it decreased beyond a certain strain level. In situ X-ray computed tomography and biaxial loading tests reveal that this transition is due to yarn compaction and Poisson’s contraction, which are manifest in textile composites.     

In situ assessment of carbon nanotube flow and filtration monitoring through glass fabric using electrical resistance measurement

Filtration of nanofillers into porous fabric media is still an issue during the preparation of advanced fiber-reinforced composites. The assessment of resin/multiwall carbon nanotube (MWCNT) flow, MWCNT filtration, and the cure monitoring of glass fiber/carbon nanotube-polyester composites by means of the measurement of the electrical resistance was introduced. The vacuum-assisted resin transfer molding technique was used. The electrical resistances measured over the span of a composite were qualitatively correlated with MWCNT flow and the degree of MWCNT filtration. It was found that while the complexity of the fabrics could likely introduce preferential deposition of MWCNTs, their filtration is mainly affected by their dispersion state in the resin suspension. Relationships among critical parameters such as the lengths and diameters of MWCNTs, the inter- and intra-tow dimensions of glass fabrics, the dispersion level of MWCNTs, and the viscosity of nanocomposite samples are discussed and correlated to the filtration, cure, and flow phenomena. We showed that our method can also serve as an early warning to obviate defects in the resulting composite.     

High electrical performance of carbon nanotubes/rubber composites with low percolation threshold prepared with a rotation-revolution mixing technique

The present study demonstrates a novel mixing approach for achieving a good dispersion of carbon nanotubes (CNTs) in a styrene-butadiene rubber (SBR), which leads to a significant improvement in electrical properties. Our mixing technique consists of (1) pretreatment by ultrasonication to disentangle the bundles of CNTs in organic solvent and (2) “rotation-revolution” mixing of the CNTs with SBR without mechanical shear, which prevents CNTs from collapsing during the mixing process. The present mixing method does not require the addition of any dispersing agents (amphiphilic molecules) or chemical modification of the CNTs to obtain a good dispersion. Compared with a conventional Banbury mixing technique, our method leads to a significant decrease in the percolation threshold (less than 1 phr), where the electrical conductivity suddenly increases due to the formation of percolation networks of CNTs in SBR. This is because the aspect ratio of the CNTs was maintained even after the mixing process, whereas CNTs were broken during the conventional Banbury mixing. The effect of using different types of CNTs on electrical conductivity was also investigated. The results show that the percolation threshold is largely related to the structural quality (graphitization) of the CNTs as well as their aspect ratio.     

Mechanical properties of aligned multi-walled carbon nanotube/epoxy composites processed using a hot-melt prepreg method

This study examined the mechanical properties of aligned multi-walled carbon nanotube (CNT)/epoxy composites processed using a hot-melt prepreg method. Vertically aligned ultra-long CNT arrays (forest) were synthesized using chemical vapor deposition, and were converted to horizontally aligned CNT sheets by pulling them out. An aligned CNT/epoxy prepreg was fabricated using hot-melting with B-stage cured epoxy resin film. The resin content in prepreg was well controlled. The prepreg sheets showed good drapability and tackiness. Composite film specimens of 24-33 μm thickness were produced, and tensile tests were conducted to evaluate the mechanical properties. The resultant composites exhibit higher Young’s modulus and tensile strength than those of composites produced using conventional CNT/epoxy mixing methods. For example, the maximum elastic modulus and ultimate tensile strength (UTS) of a CNT (21.4 vol.%)/epoxy composite were 50.6 GPa and 183 MPa. These values were, respectively, 19 and 2.9 times those of the epoxy resin.     

Mechanical properties of multi-walled carbon nanotube/epoxy composites

Untreated and acid-treated multi-walled carbon nanotubes (MWNT) were used to fabricate MWNT/epoxy composite samples by sonication technique. The effect of MWNT addition and their surface modification on the mechanical properties were investigated. Modified Halpin–Tasi equation was used to evaluate the Young’s modulus and tensile strength of the MWNT/epoxy composite samples by the incorporation of an orientation as well as an exponential shape factor in the equation. There was a good correlation between the experimentally obtained Young’s modulus and tensile strength values and the modified Halpin–Tsai theory. The fracture surfaces of MWNT/epoxy composite samples were analyzed by scanning electron microscope.     

Stress-strain behavior of multi-walled carbon nanotube/PEEK composites

This study examined the effects of multi-walled carbon nanotube (CNT) dispersion on stress-strain behaviors of poly-ether-ether-ketone (PEEK) at room temperature. Tensile test specimens containing 9 wt.% and 15 wt.% of CNT were fabricated using injection molding. Results of focused ion beam (FIB) observations show that many CNTs in the CNT/PEEK composite are aligned longitudinally. Although the PEEK stress-strain behavior is almost linear up to 1.5% strain, the stress-strain curves of CNT/PEEK composites exhibit considerable nonlinear and hysteretic behaviors from extremely low strain (<0.1%) under both tensile and compressive loading. The experimental results suggest that the viscoelastic deformation effects on nonlinear and hysteresis behaviors are not strong below 1.5% strain. Presumably, the slippage at the CNT-PEEK interface occurs with increasing applied stress because of poor interfacial load-transfer capability.     

Computational and experimental study of interfacial bonding of single-walled nanotube reinforced composites

In the development of nanotube reinforced polymer composites, one of the fundamental issues that scientists and engineers are confronting is the nanotube/polymer interfacial bonding, which will determine load transfer capability from the polymer matrix to the nanotube. In this paper, the interfacial bonding of single-walled nanotube (SWNT) reinforced epoxy composites was investigated using a combination of computational and experimental methods. The interfacial bonding was predicted using molecular dynamics (MD) simulations based on a cured epoxy resin model, which was constructed by incorporating three-dimensional cross-links formed during curing reaction. Based on the pullout simulations, the interfacial shear strength between the nanotube and the cured epoxy resin was calculated to be up to 75 MPa, indicating that there could be an effective stress transfer from the epoxy resin to the nanotube. In the experiments, single-walled nanotube reinforced epoxy composites were fabricated, characterized and analyzed. The uniform dispersion and good interfacial bonding of the nanotubes in the epoxy resin resulted in a 250–300% increase in storage modulus with the addition of 20–30 wt% nanotubes. These experimental results provided evidence of stress transfer in agreement with the simulation results.     

Strain sensing in composites using aligned carbon nanotube sheets embedded in the interlaminar region

This paper introduces a novel technique for embedding aligned sheets of two millimeters long, interconnected CNTs into the interlaminar region of composite structures. The potential of these embedded CNT sheets to function as damage detecting and strain sensing elements was demonstrated via various mechanical tests that were accompanied by real time electrical resistance change data acquisition. The experimental results suggested that the CNT sheet sensitivity could be further enhanced by an oxygen plasma treatment and also by pre-straining the CNT sheets before embedding them. The samples containing two CNT sheets layers exhibited long term stability, sensitivity and repeatability which are vital features for health monitoring.     

Viscoelastic properties of multi-walled carbon nanotube/epoxy composites using two different curing cycles

Along with carbon nanotubes (CNT) morphology, impurity, and functionalization, polymer curing cycle is another important factor in determining the mechanical properties of the CNT/polymer composite samples. This work investigates the effect of two different curing cycles on mechanical and thermo-mechanical properties of the nanotube in the composite in order to optimize the curing condition in term of time and temperature. Nanocomposite samples were prepared by mixing multi-wall carbon nanotubes with epoxy resin using sonication method. The mechanical and viscoelastic properties of the resulting composite samples were evaluated by performing tensile and dynamic mechanical thermal analyses (DMTA) test. The results indicate that the mechanical and viscoelastic properties of pure epoxy and composite samples have been affected by the condition curing process. Concerning viscoelastic modeling, the COLE–COLE diagram has been plotted by the result of DMTA tests. These results show a good agreement between the Perez model and the viscoelastic behavior of the composite.     

Self-sensing and dispersive evaluation of single carbon fiber/carbon nanotube (CNT)-epoxy composites using electro-micromechanical technique and nondestructive acoustic emission

Self-sensing and interfacial evaluation were investigated with different dispersion solvents for single carbon fiber/carbon nanotube (CNT)-epoxy composites by electro-micromechanical technique and acoustic emission (AE) under loading/subsequent unloading. The optimized dispersion procedure was set up to obtain improved mechanical and electrical properties. Apparent modulus and electrical contact resistivity for CNT-epoxy composites were correlated with different dispersion solvents for CNT. CNT-epoxy composites using good dispersion solvents exhibited a higher apparent modulus because of better stress transferring effects due to the relatively uniform dispersion of CNT in epoxy and enhanced interfacial adhesion between CNT and the epoxy matrix. However, good solvents exhibited a higher apparent modulus but lower thermodynamic work of adhesion, W_a for single carbon microfiber/CNT-epoxy composite. It is attributed to the fact that hydrophobic behavior with high advanced contact angle was observed for CNT-epoxy in the good solvent, which might not be compatible well with the carbon microfiber. Damage sensing was also detected simultaneously using AE combined with electrical resistance measurement. Electrical resistivity increased stepwise with progressing fiber fracture due to the decrease in electrical contact by the CNT.     

Reinforcement efficiency of multi-walled carbon nanotube/epoxy nano composites

Mechanical reinforcement of polymer matrices loaded by carbon nanotubes is expected to benefit by both the high aspect ratio and the very high modulus of such nanofillers and, consequently, it depends not only by their content within the hosting system but also by the state of dispersion. This work analyses the effect on the bending modulus of dispersed multi-walled carbon nanotube (MWCNT) into an epoxy system. Results indicate that reinforcement efficiency is characterised by two limiting behaviours whose transition region coincides with the development of a percolative network of nanotubes. Well below the percolation threshold, the carbon nanotubes, contribute to the composite modulus with their exceptional modulus (in this case a value of 1.780 TPa was found), whereas it dramatically decreases above this limit due to the reduction of the effective aspect ratio and the micron sized cluster formation. An estimate of the maximum reinforcement induced by carbon nanotubes has been proposed based on percolation and stress transfer theory for large aspect ratio fillers.