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

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

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

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

Electrophoretic deposition of carbon nanotube–ceramic nanocomposites

The purpose of this paper is to present an up-to-date comprehensive overview of current research progress in the development of carbon nanotube (CNT)–ceramic nanocomposites by electrophoretic deposition (EPD). Micron-sized and nanoscale ceramic particles have been combined with CNTs, both multiwalled and single-walled, using EPD for a variety of functional, structural and biomedical applications. Systems reviewed include SiO₂/CNT, TiO₂/CNT, MnO₂/CNT, Fe₃O₄/CNT, hydroxyapatite (HA)/CNT and bioactive glass/CNT. EPD has been shown to be a very convenient method to manipulate and arrange CNTs from well dispersed suspensions onto conductive substrates. CNT–ceramic composite layers of thickness in the range <1–50 μm have been produced. Sequential EPD of layered nanocomposites as well as electrophoretic co-deposition from diphasic suspensions have been investigated. A critical step for the success of EPD is the prior functionalization of CNTs, usually by their treatment in acid solutions, in order to create functional groups on CNT surfaces so that they can be dispersed uniformly in solvents, for example water or organic media. The preparation and characterisation of stable CNT and CNT/ceramic particle suspensions as well as relevant EPD mechanisms are discussed. Key processing stages, including functionalization of CNTs, tailoring zeta potential of CNTs and ceramic particles in suspension as well as specific EPD parameters, such as deposition voltage and time, are discussed in terms of their influence on the quality of the developed CNT/ceramic nanocomposites. The analysis of the literature confirms that EPD is the technique of choice for the development of complex CNT–ceramic nanocomposite layers and coatings of high structural homogeneity and reproducible properties. Potential and realised applications of the resulting CNT–ceramic composite coatings are highlighted, including fuel cell and supercapacitor electrodes, field emission devices, bioelectrodes, photocatalytic films, sensors as well as a wide range of functional, structural and bioactive coatings.     

Compressive residual thermal stress induced crack deflection in carbon nanotube-doped carbon/carbon composites

Introducing carbon nanotubes (CNTs) by electrophoretic deposition (EPD) is a promising method to improve the strength and toughness of carbon/carbon (C/C) composites. Herein, a new reinforcing mechanism called “compressive residual thermal stress (RTS) induced crack deflection” has been reported. Concretely, CNTs, with different loading content, were introduced by EPD method. Results showed that the CNT content had little influence on CNT-induced matrix refinement. However, the strength of the CNT-doped C/C composites increased with the rising content of CNTs and cracks could only deflect when the CNT interface reached a certain thickness. A theory based on compressive RTS induced crack deflection was built to interpret this discrepancy. Tensile stress existed at the interface in pure C/C composites, while compressive stress occurred and increased with the rising thickness of the CNT interface, which were verified by finite element analysis and Raman test. Calculation revealed that compressive stress exceeded 30 MPa at the crack tip could make the crack deflection happen more easily since it released more strain energy than penetration.     

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

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

Effects of surface modification on rheological and mechanical properties of CNT/epoxy composites

Despite superior properties of carbon nanotubes (CNTs), physical properties of the CNT/epoxy composites are not improved significantly because interfacial bonding between the CNTs and the polymer matrix is weak. CNTs were treated by an acidic solution to remove impurities and modified subsequently by amine treatment or plasma oxidation to improve interfacial bonding and dispersion of nanotubes in the epoxy matrix. The functional groups on the surface of treated CNTs were investigated by X-ray photoelectron spectroscopy. The surface modified CNTs were embedded in the epoxy resin by ultra-sonication and the cured nanotube containing composites were characterized by field emission scanning electron microscopy. Rheological properties of nanotube containing epoxy resin and mechanical properties of the modified CNT/epoxy composites were improved because the modification of CNTs improved dispersion and interaction between the CNT and the epoxy resin.     

Thermal and ablative properties of binary carbon nanotube and nanodiamond reinforced carbon fibre epoxy matrix composites

The thermal and ablative properties of carbon nanotube (CNT) and nanodiamond (ND) reinforced carbon fibre epoxy matrix composites were investigated by simulating shear forces and high temperatures using oxyacetylene torch apparatus. Three types of composite specimens—(i) carbon fibre epoxy matrix composite (CF/Epoxy), (ii) carbon fibre epoxy matrix composite containing 0.1 wt-% CNTs and 0.1 wt-% NDs, and (iii) carbon fibre epoxy matrix composite containing 0.2 wt-% CNTs and 0.2 wt-% NDs—were explored. The ablative response of composites was studied through pre- and post-burnt SEM analysis and further related with thermogravimetric analysis, weight loss profile and thermal conductivity measurements. The novel nanofiller composites showed marked improvement in their thermal and ablative properties. A 22% and 30% increase in thermal conductivity was observed for composites containing 0.1 wt-% CNTs/0.1 wt-% NDs and 0.2 wt-% CNTs/0.2 wt-% NDs respectively. These nanofillers also improved the thermal stability of thermosetting epoxy matrix, and an increase of 13% and 20% was recorded in the erosion rate of composites containing 0.1 wt-% CNTs/0.1 wt-% NDs and 0.2 wt-% CNTs/0.2 wt-% NDs respectively. This improvement is due to the increased char yield produced by the increase in the loading of nanofillers, i.e. CNTs and NDs. Insulation index and insulation to density performance have also been improved due to increased thermal conductivity and char yield.     

Interlaminar fracture toughness of woven fabric composite laminates with carbon nanotube/epoxy interleaf films

The Mode I interlaminar fracture behavior of woven carbon fiber/epoxy composite laminates incorporating partially cured carbon nanotube/epoxy composite films has been investigated. Laminates with films containing carbon nanotubes (CNTs) in the as‐received state and functionalized with polyamidoamine were evaluated, as well as laminates with neat epoxy films. Double‐cantilever beam (DCB) specimens were used to measure G_Ic, the critical strain energy release rate (fracture toughness) versus crack length. Post‐fracture microscopic inspection of the fracture surfaces was performed. Results show that initial fracture toughness was improved with the amino‐functionalized CNT/epoxy interleaf films, but the important factor appears to be the polyamidoamine functionalization, not the CNTs. The initial fracture toughness remained relatively unaffected with the incorporation of neat epoxy and as‐received CNT/epoxy interleaf films. Plateau fracture toughness was unchanged with the use of functionalized CNT/epoxy interleaf films, and was reduced with the use of neat epoxy and as‐received CNT/epoxy interleaf films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The reduction of carbon nanotube (CNT) length during the manufacture of CNT/polymer composites and a method to simultaneously determine the resulting CNT and interfacial strengths

Carbon nanotube/epoxy composites with an excellent dispersion of carbon nanotubes (CNTs) were prepared using a three-roll calandering technique. CNT length after processing of composites is measured and then characterized using a two-parameter Weibull distribution function. Significant reduction of the CNT length is observed as a result of the processing and it is thus suggested that great attention should be paid to the retention of CNT length after processing in order to obtain good mechanical properties. Because of the difficulties in manipulating nanometer sized CNTs during measurement of CNT strength and CNT-polymer interfacial strength, CNT strength and CNT-polymer interfacial strength have previously been determined using complicated methods with expensive or specially designed equipments. In this work a simple methodology based on the modified rule of mixtures is proposed to simultaneously determine the CNT strength and CNT-polymer interfacial strength.     

Fabrication of patterned carbon nanotube thin films using electrophoretic deposition and ultrasonic radiation

A simple wet-deposition method for preparing patterned carbon nanotube (CNT) thin films is reported. Using electrophoretic deposition (EPD), CNTs were deposited over indium tin oxide (ITO) plates that had been patterned with a photoresist; consequently, CNTs covered not only the exposed ITO areas but also the photoresist areas because thinness of the photoresists could not prevent the transverse deposition of CNTs over the photoresist areas. The ultrasonic treatment for the samples removed only CNTs on the photoresist areas, resulting in the formation of patterned CNT thin films, because Ni metal formed during EPD connects CNTs to ITO plates.     

Influence of carbon nanotube reinforcement on the processing and the mechanical behaviour of carbon fiber/epoxy composites

Carbon nanotubes (CNTs) were incorporated in an epoxy matrix that was then reinforced with carbon fibers. A fixed amount (0.5 wt.%) of different types of CNTs (functionalized and non-functionalized) were dispersed in the epoxy matrix, and unidirectional prepregs are produced. The key issues like CNT dispersion and its stability during the processing steps and the final mechanical properties of composites are discussed in detail. The temperature-viscosity profile of the epoxy matrix reinforced with different types of CNTs indicated a strong dependency on the type of CNTs. The pronounced effect of the presence of CNTs in the matrix is reflected by the decrease of the coefficient of thermal expansion by ∼32% for the double-walled CNTs epoxy system. There is also a substantial increase in fracture toughness Mode-1 by over 80% for the pristine multi-walled CNTs in combination with the epoxy resin modified by using a compatibilizer. The influence of such CNT-resin modification also induced overall positive trends in all the mechanical properties that were evaluated.     

Mechanical properties of carbon fiber reinforced bisphenol A dicyanate ester composites modified with multiwalled carbon nanotubes

A novel electrophoretic deposition (EPD) method was employed for grafting multiwalled carbon nanotubes (MWCNTs) on carbon fibers, which, after impregnation with bisphenol A dicyanate ester (BADCy), synergistically reinforced BADCy matrix composites (CNT‐C/BADCy). The effect of MWCNT presence on the mechanical properties of the composites was investigated. Composite tensile strength increased by 45.2% for an EPD duration of 2 min, while flexural strength exhibited a decreasing trend with EPD duration. Optical microscopy revealed that the existence of MWCNTs enhanced the fiber‐matrix interface while a large number of CNTs were observed to have pulled‐out from the matrix, a finding which explained the observed tensile strength increase in terms of energy dissipation by the specific toughening mechanism. The flexural strength decrease of the composites with CNTs as compared to specimens without nanotubes was found linked to the increased stress concentration in the BADCy matrix due to tube presence which weakens the adhesion between carbon fabrics. In a word, carbon nanotubes will enhance the micro interface and weaken the macro interface of the composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45100.     

Synergistic effect of graphene and carbon nanotube on lap shear strength and electrical conductivity of epoxy adhesives

In this study, synergy between graphene platelets (GnPs) and carbon nanotubes (CNTs) in improving lap shear strength and electrical conductivity of epoxy composite adhesives is demonstrated. Adding two-dimensional GnPs with one-dimensional CNTs into epoxy matrix helped to form global three-dimensional network of both GnPs and CNTs, which provide large contact surface area between the fillers and the matrix. This has been evidenced by comparing the mechanical properties and electrical conductivity of epoxy/GnP, epoxy/CNT, and epoxy/GnP-CNT composites. Scanning electron microscopic images of lap shear fracture surfaces of the composite adhesives showed that GnP-CNT hybrid nanofillers demonstrated better interaction to the epoxy matrix than individual GnP and CNT. The lap shear strength of epoxy/GnP-CNT composite adhesive was 89% higher than that of the neat epoxy adhesive, compared with only 44 and 30% increase in the case of epoxy/GnP and epoxy/CNT composite adhesives, respectively. Electrical percolation threshold of epoxy/GnP-CNT composite adhesive is recorded at 0.41 vol %, which is lower than epoxy/GnP composite adhesive (0.58 vol %) and epoxy/CNT composite adhesive (0.53 vol %), respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48056.     

Microwave curing of epoxy polymers reinforced with carbon nanotubes

The driver for this study is the observation that heating of carbon nanotubes (CNTs) with electromagnetic field can offer a more efficient and cost‐effective alternative in heat transfer for the production of composites. The idea of this study is twofold; CNT can work as microwave (MW) radiation susceptors and they can act as nanoreinforcements in the final system. To test these assumptions, a household oven was modified to control the curing schedule. Polymers with different CNT concentrations were prepared (0.5 and 1.0 wt %). The dispersion of the CNTs in the epoxy was achieved using shear‐mixing dissolver technique. MW and conventionally cured specimens were also produced in a convection oven for reference. Thermal and mechanical tests were used as control point. A curing schedule investigation was further performed to quantify the energy and time‐saving capabilities using CNT and MWs. The presence of CNTs into epoxy matrix has been proven beneficial for the shortening of the curing time. MW‐cured composites showed the same degree of polymerization with the conventionally cured composites in a shorter time period and this time was reduced as the CNT concentration was increased. A good distribution of the CNT is required to avoid hot spot effects and local degradation. Mechanical performance was, in some cases, favored by the use of CNT. The benefit from the use of MWs and CNT could reach at least 40% in terms of energy needed and time without sacrificing mechanical performance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Raman microscopy of residual strains in carbon nanotube/epoxy composites

Carbon nanotube (CNT) strain variations with temperature, as measured with Raman microscopy, are reported for pristine and functionalized CNT/epoxy composites. The CNT strain is derived from the difference in frequencies of the CNT vibrational G⁺-mode in the composite and that of a relaxed CNT, and shown to serve as a measure of the local residual strains in the composites. The magnitudes of these strains vary with both CNT functionalization and CNT concentration. At room temperature and with the same local concentration of CNTs in the composite, the strains of oxidized and polyamidoamine-functionalized CNTs are found to be 2.5 times higher than that of the composite containing pristine CNTs. The higher residual strain of the composites loaded with functionalized CNTs reflects their better adhesion and integration in the polymer matrix. These findings are in accordance with the improved tensile properties measured for the functionalized CNT composites.     

Electrophoretic deposition of carbon nanotubes

Electrophoretic deposition (EPD) has been gaining increasing interest as an economical and versatile processing technique for the production of novel coatings or films of carbon nanotubes (CNTs) on conductive substrates. The purpose of the paper is to present an up-to-date comprehensive overview of current research progress in the field of EPD of CNTs. The paper specifically reviews the preparation and characterisation of stable CNT suspensions, and the mechanism of the EPD process; it includes discussion of pure CNT coatings and CNT/nanoparticle composite films. A complete discussion of the EPD parameters is presented, including electrode materials, deposition time, electrode separation, deposition voltage and resultant electric field. The paper highlights potential applications of the resulting CNT and CNT/composite structures, in areas such as field emission devices, fuel cells, and supercapacitors.     

Dispersion, interfacial interaction and re-agglomeration of functionalized carbon nanotubes in epoxy composites

The surface, interfacial and dispersion properties of carbon nanotubes (CNTs), and the mechanical properties of the CNT/epoxy composites affected by CNT functionalization are investigated. It is demonstrated that there exists strong correlations between amino-functionalization, dispersion, wettability, interfacial interaction and re-agglomeration behaviour of CNTs and the corresponding mechanical and thermo-mechanical properties of CNT/epoxy composites. The amino-functionalized CNTs exhibit higher surface energy and much better wettability with epoxy resin than the pristine CNTs, and the attached amine molecules arising from the functionalization effectively inhibit the re-agglomeration of CNTs during the curing of resin. These ameliorating effects along with improved interfacial adhesion between the matrix and functionalized CNTs through covalent bonds result in improved flexural and thermo-mechanical properties compared with those without functionalization.     

Structure and properties of aeronautical composites using carbon nanotubes/epoxy dispersion as nanocomposite matrix

The structure and properties of hybrid multiscale composites containing carbon nanotubes (CNTs) was reported. CNTs were dispersed in epoxy by using high energy ultrasonication, followed by the fabrication of CNT hybrid composites via resin transfer molding (RTM) processing. The processability of CNTs/epoxy systems was explored by a capillary experiment. The dependences of mechanical and electrical properties of the hybrid composites on CNT content were investigated. Microscopic observation confirms the formation of CNTs percolation network. The different roles of CNT networks in mechanical reinforcement and electrical amelioration were analyzed. One explanation based on the dispersion and distribution of CNTs is proposed. It is found that the variations of the hybrid composites with respect to mechanical and electrical properties are attributed to the hierarchical structure in the hybrid composites. As far as the hybrid multiscale composites produced via RTM process is concerned, the formation of CNT percolation network, subjected to dynamic impregnation, is hindered by the presence of continuous fibrous reinforcement. The hierarchical structure influenced by several competing factors reveals great potential in being able to tailor the structural and functional performance of the CNT hybrid composites. The effects of CNTs on the dimensional stability of polymer based composites are also assessed. POLYM. COMPOS., 34:1690–1697, 2013. © 2013 Society of Plastics Engineers     

Improved fracture toughness of carbon fiber composite functionalized with multi walled carbon nanotubes

Woven carbon fiber (CF) laminae are functionalized in situ with carbon nanotubes (CNTs) to test the hypothesis that growing CNTs on CF (i.e., carbon fiber bundles or tow) would enhance the properties of polymeric carbon composites, specifically epoxy–carbon composites that are used in aerospace applications. The CNT as-grown on the woven CF were shown to substantially improve the fracture toughness of the cured composite on the order of 50%. This was accompanied by no loss in structural stiffness of the final composite structure. In fact, the flexural modulus increased approximately 5%. The significant increase in the fracture toughness as tested under the ASTM D 5528 standard indicates that the damage tolerance of a composite structure would benefit from the CNT material applied in this way. Our approach has allowed for significantly larger samples to be uniformly functionalized with CNTs than is reported elsewhere in the open literature. In addition, this work demonstrated CNT functionalization on flexible substrates that remains flexible after functionalization, whereas most CNT growth substrates are rigid in order to withstand the high (>800 °C) growth temperatures often encountered in CNT synthesis.     

Simultaneous dispersion and alignment of carbon nanotubes in epoxy resin through chronoamperometry

A novel technique of dispersion, stretching and alignment of carbon nanotubes (CNTs) in an epoxy resin has been developed based on chronoamperometry. The procedure is to apply an electrical field in non-cured CNT/epoxy mixtures, using an electrode of large surface. CNT movements can be promoted by their intrinsic polarisation or by the introduction of electrical charges over their surfaces. The efficiency of the process can be monitored through the electrical current passing through the system as a function of time. Different experimental conditions, such as the applied voltage, have been analysed. The composites have been characterised through their thermal, mechanical and electrical behaviour. They show high dispersion degree of nanotubes, which are found to be stretched and untangled. CNTs show alignment along a preferred direction in the epoxy matrix, which affects to their electrical conductivity.