A novel approach to fabricate high volume fraction nanocomposites with long aligned carbon nanotubes

Conventional micro-fiber-reinforced composites provide insight into critical structural features needed for obtaining maximum composite strength and stiffness: the reinforcements should be long, well aligned in a unidirectional orientation, and should have a high reinforcement volume fraction. It has long been a challenge for researchers to process CNT composites with such structural features. Here we report a method to quickly produce macroscopic CNT composites with a high volume fraction of millimeter long, well aligned CNTs. Specifically, we use the novel method, shear pressing, to process tall, vertically aligned CNT arrays into dense aligned CNT preforms, which are subsequently processed into composites. Alignment was confirmed through SEM analysis while a CNT volume fraction in the composites was calculated to be 27%, based on thermogravimetric analysis data. Tensile testing of the preforms and composites showed promising mechanical properties with tensile strengths reaching 400 MPa.     

Effects of CNT diameter on mechanical properties of aligned CNT sheets and composites

Drawing, winding, and pressing techniques were used to produce horizontally aligned carbon nanotube (CNT) sheets from free-standing vertically aligned CNT arrays. The aligned CNT sheets were used to develop aligned CNT/epoxy composites through hot-melt prepreg processing with a vacuum-assisted system. Effects of CNT diameter change on the mechanical properties of aligned CNT sheets and their composites were examined. The reduction of the CNT diameter considerably increased the mechanical properties of the aligned CNT sheets and their composites. The decrease of the CNT diameter along with pressing CNT sheets drastically enhanced the mechanical properties of the CNT sheets and CNT/epoxy composites. Raman spectra measurements showed improvement of the CNT alignment in the pressed CNT/epoxy composites. Research results suggest that aligned CNT/epoxy composites with high strength and stiffness are producible using aligned CNT sheets with smaller-diameter CNTs.     

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.     

Magnetic alignment of nickel-coated carbon fibers

Magnetic composites of nickel-coated carbon nanofibers have been successfully fabricated by employing a simple microwave-assisted procedure. The scanning electron microscopy images show that a complete and uniform nickel coating with mean size of 25 nm could be deposited on carbon fibers. Magnetization curves demonstrate that the prepared composites are ferromagnetic and that the coercivity is 96 Oe. The magnetic carbon nanofibers can be aligned as a long-chain structure in an external magnetic field.     

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.     

Multifunctional properties of high volume fraction aligned carbon nanotube polymer composites with controlled morphology

Advanced composites, such as those used in aerospace applications, employ a high volume fraction of aligned stiff fibers embedded in high-performance polymers. Unlike advanced composites, polymer nanocomposites (PNCs) employ low volume fraction filler-like concepts with randomly-oriented and poorly controlled morphologies due to difficult issues such as dispersion and alignment of the nanostructures. Here, novel fabrication techniques yield controlled-morphology aligned carbon nanotube (CNT) composites with measured non-isotropic properties and trends consistent with standard composites theories. Modulus and electrical conductivity are maximal along the CNT axis, and are the highest reported in the literature due to the continuous aligned-CNTs and use of an unmodified aerospace-grade structural epoxy. Rule-of-mixtures predictions are brought into agreement with the measured moduli when CNT waviness is incorporated. Waviness yields a large (10×) reduction in modulus, and therefore control of CNT collimation is seen as the primary limiting factor in CNT reinforcement of composites for stiffness. Anisotropic electron transport (conductivity and current-carrying capacity) follows expected trends, with enhanced conductivity and Joule heating observed at high current densities.     

Highly aligned flax/polypropylene nonwoven preforms for thermoplastic composites

A major challenge for natural fibre composites is to achieve high mechanical performance at a competitive price. Composites constructed from unidirectional yarns and woven fabrics are known to perform significantly better than composites made from random nonwoven mats, but unidirectional yarns and fabrics are much more expensive to manufacture than random nonwoven mats. Here, we report on highly aligned natural fibre nonwoven mats that can be used as a replacement for unidirectional woven fabrics. A drawing operation is added to the conventional nonwoven process to improve fibre alignment in the nonwoven preforms and the final composites. The modified nonwoven manufacturing process is much simpler and cheaper than the unidirectional woven fabric process because of the elimination of expensive spinning and weaving operations. The composites fabricated from the highly aligned nonwoven mats showed similar mechanical strength as the composites made from unidirectional woven fabrics.     

Electric field effects on CNTs/vinyl ester suspensions and the resulting electrical and thermal composite properties

In this study, electrical conductivity of a vinyl ester based composite containing low content (0.05, 0.1 and 0.3 wt.%) of double and multi-walled carbon nanotubes with and without amine functional groups (DWCNTs, MWCNTs, DWCNT-NH₂ and MWCNT-NH₂) was investigated. The composite with pristine MWCNTs was found to exhibit the highest electrical conductivity. Experiments aimed to induce an aligned conductive network with application of an alternating current (AC) electric field during cure were carried out on the resin suspensions with MWCNTs. Formation of electric anisotropy within the composite was verified. Light microscopy (LM), scanning electron (SEM) and transmission electron microscopy (TEM) were conducted to visualize dispersion state and the extent of alignment of MWCNTs within the polymer cured with and without application of the electric field. To gain a better understanding of electric field induced effects, glass transition temperature (T_g) of the composites was measured via Differential Scanning Calorimetry (DSC). It was determined that at 0.05 wt.% loading rate of MWCNTs, the composites, cured with application of the AC electric field, possessed a higher T_g than the composites cured without application of the AC electric field.     

Pseudo-ductility in intermingled carbon/glass hybrid composites with highly aligned discontinuous fibres

The aim of this research is to manufacture intermingled hybrid composites using aligned discontinuous fibres to achieve pseudo-ductility. Hybrid composites, made with different types of fibres that provide a balanced suite of modulus, strength and ductility, allow avoiding catastrophic failure that is a key limitation of composites. Two different material combinations of high strength carbon/E-glass and high modulus carbon/E-glass were selected. Several highly aligned and well dispersed short fibre hybrid composites with different carbon/glass ratios were manufactured and tested in tension in order to investigate the carbon ratio effect on the stress–strain curve. Good pseudo-ductile responses were obtained from the high modulus carbon/E-glass composites due to the fragmentation of the carbon fibres. The experimental results were also compared with an analytical solution. The intermingled hybrid composite with 0.25 relative carbon ratio gave the maximum pseudo-ductile strain, 1.1%, with a 110 GPa tensile modulus. Moreover, the initial modulus of the intermingled hybrids with 0.4 relative carbon ratio is 134 GPa, 3.5 times higher than that of E-glass/epoxy composites. The stress–strain curve shows a clear “yield point” at 441 MPa and a well dispersed and gradual damage process.     

Fibre orientation of novel dynamically sheet formed discontinuous natural fibre PLA composites

This paper describes work carried out to fabricate and to assess the fibre orientation in PLA reinforced by aligned discontinuous harakeke and hemp fibre mats produced using a dynamic sheet former (DSF). These mats were combined with PLA sheets to make composites with fibre contents of 5–40 wt% using a hot press. It was found that the fibre orientation factors (K_θ) for both harakeke and hemp fibre composites were higher than those values seen in the literature for composites prepared using injection moulding and hot pressed using randomly oriented fibre mats, but slightly lower than the highest values obtained with aligned fibre nonwoven preform composites utilising more processing stages. The highest K_θ values for harakeke and hemp fibres in this work were found to be 0.58 and 0.44 respectively. K_θ decreased, reflecting increased fibre misalignment as fibre content increased, believed to be due to fibre agglomeration and the higher pressure required during processing.     

Electrical and thermal property enhancement of fiber-reinforced polymer laminate composites through controlled implementation of multi-walled carbon nanotubes

Aligned carbon nanotubes (CNTs) are implemented into alumina-fiber reinforced laminates, and enhanced mass-specific thermal and electrical conductivities are observed. Electrical conductivity enhancement is useful for electrostatic discharge and sensing applications, and is used here for both electromagnetic interference (EMI) shielding and deicing. CNTs were grown directly on individual fibers in woven cloth plies, and maintained their alignment during the polymer (epoxy) infiltration used to create laminates. Using multiple complementary methods, non-isotropic electrical and thermal conductivities of these hybrid composites were thoroughly characterized as a function of CNT volume/mass fraction. DC and AC electrical conductivity measurements demonstrate high electrical conductivity of >100 S/m (at 3% volume fraction, ∼1.5% weight fraction, of CNTs) that can be used for multifunctional applications such as de-icing and electromagnetic shielding. The thermal conductivity enhancement (∼1 W/m K) suggests that carbon-fiber based laminates can significantly benefit from aligned CNTs. Application of such new nano-engineered, multi-scale, multi-functional CNT composites can be extended to system health monitoring with electrical or thermal resistance change induced by damage, fire-resistant structures among other multifunctional attributes.     

Preparation and electrical properties of xCaRuO3/(1 − x)CaTiO3 perovskite composites

CaRuO₃-CaTiO₃ ceramic composites were prepared by sintering for short times for potential applications in the areas of electronic ceramics. Scanning electron microscopy and energy dispersive X-ray analysis showed two separate phases, CaRuO₃ and CaTiO₃ in the composite. Conductivity data, measured by the four-probe method, showed that the composites have high electrical conductivity when x ≥ 0.19 in xCaRuO₃-(1 − x)CaTiO₃ composites. Furthermore, the nanoparticle of calcium ruthenate prepared by reverse micelle synthesis was used to be conductive agent for the composite. The result shows that the use of nano-sized calcium ruthenate enabled higher electrical conductivity to be maintained down to x = 0.09.     

Fabrication of nature-inspired bulk laminar composites by a powder processing

Among many kinds of “nano-laminar” composites inspired by the brick and mortar structure of nacre in mollusk shells, a bulky, dense and ceramics–base composite has been a missing piece despite its importance. Here we report that such a composite with a submicron-order layered structure can be fabricated by a simple method, sintering aligned flake-like inorganic powder coated with ductile matrix material. The composites fabricated by this method had crack extension resistance by interface delamination, crack deflection, and ligament bridging by the ductile matrix. They showed non-brittle fracture behavior in a bending test despite a quite high flake volume fraction of over 80%, and had a work of fracture (WOF) of more than 300 J/m², several hundreds times as large as that of monolithic glass.     

Effects of aluminium nitride inclusions on thermal and electrical properties of epoxy and polypropylene: An experimental investigation

Thermal and dielectric properties of polymers reinforced with micro-sized aluminium nitride (AlN) particles have been studied. A set of epoxy–AlN composites, with filler content ranging from 0 to 25 vol% is prepared by hand lay-up technique. With similar filler loading, polypropylene -AlN composites are fabricated by compression molding technique. Density (ρ_c), effective thermal conductivity (k_eff), glass transition temperature (T_g), coefficient of thermal expansion (CTE) and dielectric constant (ε_c) of these composites are measured experimentally. The various experimental data were interpreted using appropriate theoretical models. Incorporation of AlN in both the resin increases the k_eff and T_g whereas CTE of composite decreases favourably. The dielectric constant of the composite also found to get modified with filler content. With improved thermal and modified dielectric characteristics, these AlN filled polymer composites can possibly be used for microelectronics applications.     

The poly(urethane-ionic liquid)/multi-walled carbon nanotubes composites

In the paper, a novel kind of imidazolium based poly(urethane-ionic liquid)/multi-walled carbon nanotubes (PUIL/MWCNT) composites was facilely prepared by uncovalent ways. The imidazolium based ionic liquid (IL) greatly improved the dispersion of pristine MWCNTs in PUIL by the π-cation interaction formed between the imidazolium cation and the π-electron of MWCNTs. The PUIL/MWCNT composites showed obviously increased modulus, glass transition temperature and tensile strength in comparison with PU/MWCNT composites. The thermal and mechanical properties of the PUIL/MWCNT composites presented significant increase with low load of the MWCNTs. It indicated the interactions between PUIL and MWCNTs played an important role to enhance the performances of the composites.     

Flexural properties of hemp fibre reinforced polylactide and unsaturated polyester composites

In this work, flexural strength and flexural modulus of chemically treated random short and aligned long hemp fibre reinforced polylactide and unsaturated polyester composites were investigated over a range of fibre content (0-50 wt%). Flexural strength of the composites was found to decrease with increased fibre content; however, flexural modulus increased with increased fibre content. The reason for this decrease in flexural strength was found to be due to fibre defects (i.e. kinks) which could induce stress concentration points in the composites during flexural test, accordingly flexural strength decreased. Alkali and silane fibre treatments were found to improve flexural strength and flexural modulus which could be due to enhanced fibre/matrix adhesion.     

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.     

Polypyrrole/poly(vinyl alcohol-co-ethylene) nanofiber composites on polyethylene terephthalate substrate as flexible electric heating elements

Polypyrrole/poly(vinyl alcohol-co-ethylene) (PPy/PVA-co-PE) nanofiber composites on polyethylene terephthalate (PET) substrates were prepared using spray coating technique and in situ polymerization process. The electric heating behaviors of composites were investigated as functions of the amounts of nanofiber and PPy. It was observed that, the electrical resistivity of composites decreased significantly with increasing nanofiber and PPy contents. Scanning electron microscope images and infrared spectrum studies confirmed the formation of well dispersed network-like structure of PPy/PVA-co-PE nanofibers on PET substrate. Furthermore, maximum temperature attained at a given applied voltage for the composites could be well controlled by changing nanofibers and PPy amounts. PPy/PVA-co-PE nanofiber/PET composites exhibited excellent electric heating performance in aspects of rapid temperature response, long retaining behavior, thermal and operational stability. The incorporation of PPy on PVA-co-PE nanofibers/PET nonwoven substrates resulted in high conductivity and enhanced heating behavior, which have potential to be used as efficient electric heating elements.     

Evaluation of interfacial shear stress between multi-walled carbon nanotubes and epoxy based on strain distribution measurement using Raman spectroscopy

This study investigated the stress recovery of aligned multi-walled carbon nanotubes (MWCNTs) embedded in epoxy using Raman spectroscopy, and evaluated interfacial shear stress between MWCNTs and epoxy using shear-lag analysis. To this end, ultralong aligned MWCNTs (3.8 mm long) were embedded in epoxy to obtain Raman spectra at multiple points along the MWCNTs. Downshift of the G′-band due to tensile strain was measured from the nanotube end to the center, and the strain distribution of embedded MWCNTs was evaluated successfully. Interfacial shear stress was then estimated by minimizing the error between the shear-lag analysis and measured strain distribution. The maximum interfacial shear stress between the embedded MWCNTs and epoxy was 10.3–24.1 MPa at the failure strain of aligned MWCNT-reinforced epoxy composites (0.46% strain). Furthermore, the interfacial shear stress between an individual MWCNT and epoxy was investigated.     

Graphene sheets segregated by barium titanate for polyvinylidene fluoride composites with high dielectric constant and ultralow loss tangent

In this paper, we report a unique method to develop polyvinylidene fluoride (PVDF) composites with high dielectric constant and low loss tangent by loading relatively low content of graphene-encapsulated barium titanate (BT) hybrid fillers. BT particles encapsulated with graphene oxide (BT-GO) were prepared via electrostatic self-assembly and subsequent chemical reduction resulted in BT-RGO particles. SEM morphology revealed that RGO sheets were segregated by BT particles. The hybrid fillers have two advantages for tuning dielectric properties: loading extremely low content of RGO can be exactly controlled and individual RGO sheets segregated by BT particles would prevent leakage current. As a result, PVDF composites filled with BT-RGO displayed improved dielectric properties before percolative behavior occurred. Composites filled with 30 vol% BT-RGO have a dielectric constant and loss tangent (tan δ) value of 67.5 and 0.060 (1 kHz), respectively. By contrast, dielectric constant and tan δ of composites filled with 30 vol% BT-GO and BT were 57.7 and 38.3, 0.076 and 0.042 (1 kHz), respectively. The improvement of dielectric constant is attributable to the formation of microcapacitors by highly conductive RGO sheets segregated by BT particles. Meanwhile, the distance between adjacent RGO sheets is large enough to prevent leakage current from tunneling conductance, by which tan δ is remarkably constrained. The composites could achieve excellent dielectric properties by loading relatively low amount of ceramic fillers, which indicates that this method can be used as guideline for reduce the usage amount of ceramic fillers.