Crystalline morphology and properties of multi-walled carbon nanotube filled isotactic polypropylene nanocomposites: Influence of filler size and loading

Isotactic polypropylene (PP) nanocomposites with multi-walled carbon nanotubes (MWCNTs) of various diameters (10–50 nm) were fabricated by extrusion and compression-molding techniques and characterized by X-ray diffraction measurements, differential scanning calorimetry, scanning electron microscopy, mechanical test and differential thermal analyses. The pure PP exhibits both the a- and b-axes oriented α-crystal, whereas the MWCNTs induce the b-axis orientation of the α-crystal along with the formation of minor γ-phase crystal in nanocomposites. Crystallinity, long period of lamellae, tensile strength, tensile modulus (TM) and microhardness (H) of PP considerably change by different loading and sizes of MWCNTs. The estimated values H/TM = 0.09–0.10 for all samples approach the predicted value of 0.10 for polymers. The increase in crystallinity has been demonstrated by both XRD and DSC studies. Mathematical models have been invoked to explain the changes in mechanical properties. An increase in thermal stability of polymer matrix occurs with increasing MWCNTs size and loading.     

Influence of multi-walled carbon nanotubes on electrochemical performance of transparent graphene electrodes

In this work, carbon-carbon nanocomposites as transparent electrodes were prepared by a chemical reduction of graphite oxide (GO) and multi-walled carbon nanotubes (MWNTs). The electric, optical, and electrochemical properties of graphene-MWNT nanocomposites (G-MCs) were investigated as a function of the MWNT content. It was found that chemically bonded G-MCs were successfully formed with a reduction of the functional groups of the GO and acid-treated MWNTs, resulting in the conjugation of 1D MWNTs onto a 2D graphene surface. The electrical conductivity of the graphene was significantly enhanced by introducing the MWNTs. In addition, the G-MCs showed improved current density and high efficiency compared with graphene alone. This indicated that the improved electrochemical performance of the G-MCs can be attributed to the increase in the activity and electrical conductivity enhanced by π-π interaction between graphene and MWNTs.     

Rheological and mechanical properties of surface modified multi-walled carbon nanotube-filled PET composite

Poly(ethylene terephthalate) (PET)/multi-walled carbon nanotube (MWCNT) composites were prepared by in situ polymerization. To improve the dispersion of MWCNTs in PET matrix, the surface modified MWCNTs having acid groups (acid-MWCNT) and diamine groups (diamine-MWCNT) were used. The functional groups on the surface of modified MWCNTs were confirmed by infrared (IR) spectrometry. SEM analysis showed better dispersion of diamine-MWCNTs as compared to pristine-MWCNTs and acid-MWCNTs in the PET. The reaction between PET and diamine-MWCNTs was evidenced by the shifting of the G band to a higher frequency in Raman spectroscopy and an increase of the complex viscosity in rheological properties. The composites containing functionalized MWCNTs showed a large increase in the tensile strength and modulus. The PET/diamine-MWCNT composites showed maximum tensile strength and modulus increases by 350% and 290% at 0.5 and 2.0 wt%, respectively, as compared to pure PET.     

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.     

Thermoelectric behavior of aerogels based on graphene and multi-walled carbon nanotube nanocomposites

In this work, we presented that the Seebeck coefficient and electrical conductivity can be increased simultaneously in aerogels based on graphene and multi-walled carbon nanotube (graphene-MWCNT) nanocomposites, and at the same time the thermal conductivity is depressed due to 3D porous skeleton structure. As a result, graphene-MWCNT aerogels possess ultra-low thermal conductivities (∼0.056 W m⁻¹ K⁻¹) and apparent density (∼24 kg m⁻³), thereafter the figure of merit (ZT) of ∼0.001 is achieved. Although the ZT value is too low for practical application as a thermoelectric (TE) material, the unique structure in this project provides a potential way to overcome the challenge in bulk semiconductors that increasing electrical conductivity generally leads to decreased Seebeck coefficient and enhanced thermal conductivity.     

Strain and damage monitoring in carbon-nanotube-based composite under cyclic strain

The resistive behavior of multi-walled carbon nanotube (MWCNT)/epoxy resins, tested under mechanical cycles and different levels of applied strain, was investigated for specimens loaded in axial tension. The surface normalized resistivity is linear with the strain for volume fraction of MWCNTs between 2.96 × 10⁻⁴ and 2.97 × 10⁻³ (0.05 and 0.5% wt/wt). For values lower than 0.05% wt/wt, close to the electrical percolation threshold (EPT) a non-linear behavior was observed. The strain sensitivity, in the range between 0.67 and 4.45, may be specifically modified by controlling the nanotube loading, in fact the sensor sensitivity decreases with increasing the carbon nanotubes amount. Microscale damages resulted directly related to the resistance changes and hence easily detectable in a non-destructive way by means of electrical measurements. In the fatigue tests, the damage is expressed through the presence of a residual resistivity, which increases with the amount of plastic strain accumulated in the matrix.     

Synergistic flame retardancy effect of graphene nanosheets and traditional retardants on epoxy resin

Novel non-toxic halogen-free flame retardants are replacing traditional flame retardants in polymer and polymer matrix composite structures. In this study, graphene nanosheet (GNS) is investigated in combination with traditional layered double hydroxide (LDH), layered rare-earth hydroxide (LRH), and phosphorus-based flame retardant (DOPO) to enhance the flame retardancy of epoxy resin. A synergistic flame retardancy effect is achieved in GNS/LDH and GNS/DOPO systems where combined GNS and LDH increased the viscosity of the epoxy melt, and limited the flame propagation through inhibition of dripping. The limiting oxygen index of epoxy increased from 15.9 to 23.6 with addition of 0.5 wt.% each of GNS and LDH. With the addition of 2.5 wt.% of both GNS and LDH, the total heat release of epoxy resin also reduced from 33.4 MJ/m² to 24.6 MJ/m². The synergistic effect of GNS and DOPO adopted a different mechanism. The addition of 2.5 wt.% of GNS and DOPO reduced the peak heat release rate from 1194 kW/m² to 396 kW/m², and the total heat release rate from 72.5 MJ/m² to 48.1 MJ/m². The synergistic mechanisms of the flame retardants were closely analyzed and correlated with the flame retardant properties.     

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.     

Characterization of epoxy functionalized graphite nanoparticles and the physical properties of epoxy matrix nanocomposites

This work presents a novel approach to the functionalization of graphite nanoparticles. The technique provides a mechanism for covalent bonding between the filler and matrix, with minimal disruption to the sp² hybridization of the pristine graphene sheet. Functionalization proceeded by covalently bonding an epoxy monomer to the surface of expanded graphite, via a coupling agent, such that the epoxy concentration was measured as approximately 4 wt.%. The impact of dispersing this material into an epoxy resin was evaluated with respect to the mechanical properties and electrical conductivity of the graphite–epoxy nanocomposite. At a loading as low as 0.5 wt.%, the electrical conductivity was increased by five orders of magnitude relative to the base resin. The material yield strength was increased by 30% and Young’s modulus by 50%. These results were realized without compromise to the resin toughness.     

Micro-infiltration of three-dimensional porous networks with carbon nanotube-based nanocomposite for material design

Epoxy composite beams reinforced with a complex three-dimensional (3D) skeleton structure of nanocomposite microfibers were fabricated via micro-infiltration of 3D porous microfluidic networks with carbon nanotube nanocomposites. The effectiveness of this manufacturing approach to design composites microstructures was systematically studied by using different epoxy resins. The temperature-dependent mechanical properties of these multifunctional beams showed different features which cannot be obtained for those of their individual components bulks. The microfibers 3D pattern was adapted to offer better performance under flexural solicitation by the positioning most of the reinforcing microfibers at higher stress regions. This led to an increase of 49% in flexural modulus of a reinforced-epoxy beam in comparison to that of the epoxy bulk. The flexibility of this method enables the utilization of different thermosetting materials and nanofillers in order to design multifunctional composites for a wide variety of applications such as structural composites and components for micro-electromechanical systems.     

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.     

Microstructure and properties of polyurethane nanocomposites reinforced with methylene-bis-ortho-chloroanilline-grafted multi-walled carbon nanotubes

Methylene-bis-ortho-chloroanilline (MOCA), an excellent cross-linker widely used to prepare cured polyurethane (PU) elastomers with high performance, was used to modify a multi-walled carbon nanotube. PU/carbon nanotube (CNT) nanocomposites were prepared by incorporation of the MOCA-grafted CNT into PU matrix. Fourier transform infrared spectra have shown that the modified CNTs have been linked with PU matrix. The microstructure of composites was investigated by Field-Emission Scanning Electron Microscopy. The results of Dynamic Mechanical Thermal Analysis and Differential Scanning Calorimetry have investigated the grafted CNTs as cross-linker in the cured composites. The studies on the thermal and mechanical properties of the composites have indicated that the storage modulus and tensile strength, as well as glass transition temperature and thermal stability are significantly increased with increasing CNT content.     

Comparative study on repeated impact response of E-glass fiber reinforced polypropylene & epoxy matrix composites

In this study, E-glass fiber reinforced composites have been manufactured with two types of resin, polypropylene and epoxy (Thermoplastic and Thermoset) and they have been subjected to the low velocity single and repeated impacts and effect of resin type on the impact response of composites are investigated. Impact energies were chosen as 20 J, 50 J, 80 J and 110 J for single impact tests while 50 J was chosen for repeated impact tests. Comparisons between the results of 110 J single and 50 J repeated impacted specimens were performed. As a result of the study it is concluded that the resin type is a crucial parameter for the repeated impact response of the composites.     

Effect of the addition of milled carbon fiber as a secondary filler on the electrical conductivity of graphite/epoxy composites for electrical conductive material

In this work, carbon composite bipolar plates consisting of synthetic graphite and milled carbon fibers as a conductive filler and epoxy as a polymer matrix developed using compression molding is described. The highest electrical conductivity obtained from the described material is 69.8 S/cm for the in-plane conductivity and 50.34 S/cm for the through-plane conductivity for the composite containing 2 wt.% carbon fiber (CF) with 80 wt.% filler loading. This value is 30% greater than the electrical conductivity of a typical graphite/epoxy composite with 80 wt.% filler loading, which is 53 S/cm for the in-plane conductivity and 40 S/cm for the through-plane conductivity. The flexural strength is increased to 36.28 MPa compared to a single filler system, which is approximately 25.22 MPa. This study also found that the General Effective Media (GEM) model was able to predict the in-plane and through-plane electrical conductivities for single filler and multiple filler composites.     

Interlaminar reinforcement of glass fiber/epoxy composites with graphene nanoplatelets

This work investigated the ability of graphene nanoplatelets (GnPs) to improve the interlaminar mechanical properties of glass-reinforced multilayer composites. A novel method was developed for the inclusion of GnPs into the interlaminar regions of plain-weave, glass fabric fiber-reinforced/epoxy polymer composites processed with vacuum assisted resin transfer molding. Flexural tests showed a 29% improvement in flexural strength with the addition of only 0.25 wt% GnP. At the same concentration, mode-I fracture toughness testing revealed a 25% improvement. Additionally, low-velocity drop weight impact testing showed improved energy absorption capability with increasing concentration of GnPs. Ultrasonic C-scans and dye penetration inspection of the impact- and back-sides of the specimens qualitatively support these results. Finally, the impact damage area was quantified from the C-scan data. These results showed that the impact-side damage area decreased with increasing concentration of GnP, while the back-side damage area increased.     

The mechanics of graphene nanocomposites: A review

The preparation and characterisation of the different forms of graphene are reviewed first of all. The different techniques that have been employed to prepare graphene such as mechanical and solution exfoliation, and chemical vapour deposition are discussed briefly. Methods of production of graphene oxide by the chemical oxidation of graphite are then described. The structure and mechanical properties of both graphene and graphene oxide are reviewed and it is shown that although graphene possesses superior mechanical properties, they both have high levels of stiffness and strength. It is demonstrated how Raman spectroscopy can be used to characterise the different forms of graphene and also follow the deformation of exfoliated graphene, with different numbers of layers, in model composite systems. It is shown that continuum mechanics can be employed to analyse the behaviour of these model composites and used to predict the minimum flake dimensions and optimum number of layers for good reinforcement. The preparation of bulk nanocomposites based upon graphene and graphene oxide is described finally and the properties of these materials reviewed. It is shown that good reinforcement is only found at relatively low levels of graphene loading and that, due to difficulties with obtaining good dispersions, challenges still remain in obtaining good mechanical properties for high volume fractions of reinforcement.     

Influence of electrolessly silver-plated multi-walled carbon nanotubes on thermal conductivity of epoxy matrix nanocomposites

In this work, multi-walled carbon nanotubes (MWCNTs) were electrolessly Ag-plated in order to investigate the effect of plating time on the thermal conductivity of Ag-plated MWCNTs-reinforced epoxy matrix composites. MWCNT surfaces were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS). The thermal conductivity of Ag-plated MWCNT-reinforced epoxy nanocomposites was measured using the thermal equilibrium method with ASTM D5470. From the results, it was found that the thermal conductivity of the composites enhanced with increasing plating time. In particular the Ag-10/EP sample showed more than 150% enhancement of the thermal conductivity compared to the as-received CNTs/EP sample. These results were attributed to the high contents of Ag particles and the increase of the interfacial adhesion between the Ag-CNTs and EP matrix in the composites.     

Improving the through-thickness thermal and electrical conductivity of carbon fibre/epoxy laminates by exploiting synergy between graphene and silver nano-inclusions

Fibre-reinforced polymer composites typically feature low functional (e.g., electric and thermal conductivity) and structural (e.g. mechanical strength and fracture toughness) properties in the laminate’s thickness direction. In the event of lightning strikes, overheating, and impact by foreign objects, composite laminates may suffer wide spread structural damage. This research explores the synergistic physical interaction between two-dimensional nanostructured (graphene nano-platelets) and, zero- or one-dimensional conductive fillers (silver nanoparticles or silver nanowires, respectively) when both are dispersed in fibre–polymer laminates. The results reveal a synergistic improvement in the through-thickness thermal conductivity that is more than the additive improvements by each constituent. Specifically, the simultaneous inclusion of graphene nano-platelets and silver nanoparticles/nanowires at a combined loading of 1 vol% resulted in approximately 40% enhancement in the through-thickness thermal conductivity while the inclusion of graphene nano-platelets alone at the same loading resulted only in 9% improvement. Similarly, the through-thickness electrical conductivity of carbon fibre/epoxy laminates incorporating graphene nano-platelets together with silver nanoparticles/nanowires was notably higher (⩾70%) than can be achieved by graphene nano-platelets alone (∼55%). These results demonstrate that the presence of nano-reinforcements exhibiting varied phonon transport and electron transfer pathways, and geometric aspect ratios promote synergistic physical interactions. Small improvements were found in the mechanical properties, including tensile, flexural or compressive properties of the carbon fibre-reinforced laminates, due to the relatively low concentrations of the nano-fillers.     

Mechanical property characterization of carbon nanofiber/epoxy nanocomposites reinforced by GMA-grafted UHMWPE fibers

Carbon nanofibers (CNFs) dispersed epoxy resin was reinforced with unidirectional glycidyl methacrylate (GMA) grafted ultra-high molecular weight polyethylene (UHMWPE) fibers. Tensile tests were performed on unfilled, and CNF filled epoxy to identify the effect of adding CNFs on the mechanical properties of epoxy. The highest improvement in strength was obtained with 1 wt% of CNF. Tensile and flexural properties improvements in three-component nanocomposites were confirmed by obtained results. The combined use of CNFs and GMA-grafted UHMWPE fibers leads to a significant synergy in the mechanical properties of nanocomposites. The mechanisms of such synergism were analyzed by fracture studies using scanning electron microscopy.     

Experimental study to assess the effect of carbon nanotube addition on the through-thickness electrical conductivity of CFRP laminates for aircraft applications

The present paper tests experimentally the through-thickness electrical conductivity of carbon fiber-reinforced polymer (CFRP) composites laminates for aircraft applications. Two types of samples were prepared: Type A samples with carbon nanotubes (CNTs) and Type B samples without CNTs. During the electrical experiments, electrical currents of several mA were injected through the specimens. Electrical resistance was monitored simultaneously in order to deduce the changes in the through-the-thickness electrical conductivity caused by the addition of CNTs. Improvement of electrical conduction by two orders of magnitude was achieved through the addition of 1 wt% carbon nanotubes as compared to classic CFRP without CNTs. For moisture saturated samples, the influence of moisture absorption on such measures was found to be negligible.