Barrier properties of thermal and electrical conductive hydrophobic multigraphitic/epoxy coatings

Epoxy composites doped with different content of graphene nanoplatelets (GNPs) and/or carbon nanotubes (CNTs) have been manufactured. Their chemical, thermal, electrical, and mechanical behaviors have been studied, evaluating also their performance as coatings of glass fiber composite substrates. It is confirmed that the graphitic nanofillers present different efficiency as nanofillers as a function of their geometry. CNTs are much higher efficient electrical nanofillers than graphene, but an important synergetic effect is determined in the electrical conductivity of hybrid GNP/CNT/epoxy composites. In contrast, the thermal conductivity scarcely depends on the geometry of graphitic nanofillers but on the graphitic nanofiller content. Adding up to 12 wt% GNP and 1 wt% CNT, the thermal conductivity of the epoxy resin can be increased more than 300%. GNP presents high efficiency to increase the barrier properties, reducing the water absorption up to 30%. The stiffness of nanocomposites proportionally increases with graphitic addition, up to 50%, regard to the modulus of the neat epoxy resin. The adherence of coatings over glass fiber composite substrates increases by nanofiller addition due to the nanomechanical anchoring. However, the water uptake induces a higher weakening on nanodoped composites due to the preferential water absorption by the interface.     

Synergistic electrical and thermal transport properties of hybrid polymeric nanocomposites based on carbon nanotubes and graphite nanoplatelets

In this study hybrid ternary polymeric nanocomposites based on carbon nanotubes (CNTs) and graphite nanoplatelets (GNPs) are examined for their enhanced transport properties, over mono-nanofiller composite systems, originated via a synergy mechanism. Using an epoxy as the host matrix, a number of CNTs/epoxy, GNPs/epoxy and hybrid CNTs/GNPs/epoxy specimens are processed and their electrical and thermal properties are characterized. Furthermore, these transport properties are also estimated using a set of recently developed computational models based on percolation analysis and statistical continuum mechanics. Results suggest that the models, in agreement with the experimental observations, confirm the presence of the synergy effect for both the electrical and thermal transport properties. Both the computational and experimental studies suggest incorporating miniscule amount of auxiliary nanofiller (ex. 10%wt CNTs compared to GNPs), boosts the electricalconductivity of the hybrid composites by several orders of magnitudes.Furthermore, the experimental measurements and the strong contrast computational models suggest that, owing to the formation of the hybrid CNT/GNP network, the hybrid CNT/GNP/polymer nanocomposites outperform their single-nanofiller counterpart configurations. The investigation affirms that the particle agglomeration severely affects the transport properties of the hybrid nanocomposites and it is the root cause for the conflicting results in the literature.     

Epoxy composites with carbon nanotubes and graphene nanoplatelets – Dispersion and synergy effects

Carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs) at different mix ratios were dispersed by ultrasonication into an epoxy matrix and the effects of CNT:GNP ratios on the mechanical and electrical properties of the hybrid composites were investigated. The combination of CNT and GNP in a ratio 8:2 was observed to synergistically increase flexural properties and to reduce the electrical percolation threshold for the epoxy composites, indicating easier formation of a conductive network due to the improved state of CNT dispersion in the presence of GNPs. The state of dispersion was evaluated at different length scales by using optical microscopy, UV–Vis spectroscopy, rheological measurements, scanning electron microscopy, transmission electron microscopy and sedimentation tests. The Fourier transform infrared spectra for CNT and GNP indicate that the GNPs contain oxygen moieties responsible for better interactions with the epoxy matrix.     

Joule effect self-heating of epoxy composites reinforced with graphitic nanofillers

Self-heating of conductive nanofilled resins due to the Joule effect is interesting for numerous applications, including computing, self-reparation, self-post-curing treatment of resins, fabrication of adhesive joints, de-icing coatings and so on. In this work, we study the effect of the nature and amount of graphitic nanofiller on the self-heating of epoxy composites.The addition of graphitic nanofillers induced an increase in the thermal conductivity of the epoxy resins, directly proportional to the nanofiller content. Percolation was not observed because of the heat transport through phonons. In contrast, the electrical conductivity curves present a clear percolation threshold, due to the necessity of an electrical percolation network. The electrical threshold is much lower for composites reinforced with carbon nanotubes (CNTs, 0.1 wt.%) than for the resin filled with graphene nanoplatelets (GNPs, 5 %). This fact is due to their very different specific areas.The composites filled with CNTs reach higher temperatures than the ones reinforced with GNPs, applying low electrical voltage because of their higher electrical conductivity. In contrast, the self-heating is more homogeneous for the GNP/epoxy resins due to their higher thermal conductivity. It was also confirmed that the self-heating is repetitive in several cycles, reaching the same temperature when the same voltage is applied.     

Multifunctional epoxy composites modified with a graphene nanoplatelet/carbon nanotube hybrid

Epoxies are a class of thermoset polymers which find use in high performance applications. However, epoxies are inherently brittle and are poor conductors of electricity, which limits their ability to be employed in functional applications. Carbon nanomaterials have attracted considerable attention as filler materials, due to their combination of outstanding properties. In the present work, an epoxy polymer was modified with a hybrid nanofiller, consisting of graphene nanoplatelets (GNPs) and carbon nanotubes (CNTs) at a mass ratio of 9:1, using three-roll milling. Addition of 1 wt% resulted in an increase of eight orders of magnitude in the electrical conductivity and a 182% increase in the fracture energy, G_IC, of the epoxy. CNTs contributed greatly in the reduction of the percolation threshold, which was 10 times lower than that of conventional GNP/epoxy composites, while the increase in toughness was entirely attributed to the GNPs, predominantly through the mechanism of crack deflection. The toughening contribution of the hybrid nanofiller was theoretically calculated using analytical modeling, which showed excellent agreement between the predicted and experimental values of G_IC.     

Size and synergy effects of nanofiller hybrids including graphene nanoplatelets and carbon nanotubes in mechanical properties of epoxy composites

We study mechanical reinforcement in a widely used epoxy matrix with the addition of graphene nanoplatelets (GnPs) and various mixture ratios of carbon nanotubes (CNTs) with GnPs. Two different dimensions of GnPs were used with flake sizes of 5 μm and 25 μm to investigate the influence of nanofiller size on composite properties. In GnP reinforced composites, bigger flakes showed greater reinforcement at all GnP concentrations as they actively control the failure mechanisms in the composite. In the mixture samples, highest CNT content (9:1) showed marked improvement in fracture toughness of 76%. The CNT:GnP ratio is an interesting factor significantly influencing the properties of the epoxy based nanocomposites. The combination of high aspect ratio of CNTs and larger surface area of GnPs contribute to the synergistic effect of the hybrid samples. Thermal conductivity consistently increases with incorporation of GnPs in the matrix. Transmission electron microscopy (TEM) images confirm the uniform nanofiller dispersion achieved in the composites. For the hybrid samples CNTs are seen to align themselves on the GnP flakes creating an inter-connected strong nanofiller network in the matrix. The homogeneous nanofiller dispersions have been achieved by high shear calendaring which is a method capable of being industrially scaled up.     

Effects of ultrasound vibration on the structure and properties of polypropylene/graphene nanoplatelets composites

An ultrasound‐assisted extrusion system was added to melt extrusion process to prepare polypropylene (PP) nanocomposites reinforced with graphene nanoplatelets (GNPs). The relationships among the ultrasound vibration, exfoliation, and dispersion morphology of GNPs in PP matrix, the crystallinity, and the macroscopic properties of nanocomposites were investigated. The properties measurement results showed that the present of ultrasound vibrations increased the conductive properties, decreased the apparent viscosity and crystallinity of PP/GNPs nanocomposites. FESEM results revealed that the ultrasound vibration increased the exfoliation and dispersion of GNPs in PP matrix. This morphology was benefit for forming electrical and thermal network, therefore the electrical conductivity and thermal conductivity of PP/GNP nanocomposites were increased. But the powerful vibration that provided by 300 W ultrasound power would reduce the diameter of GNPs, then reduce its conductive properties. FTIR and TGA results showed that ultrasound vibration had less effect on the chemical bond and the degradation of PP/GNPs nanocomposites. POLYM. ENG. SCI., 58:377–386, 2018. © 2017 Society of Plastics Engineers     

Enhanced thermal and electrical properties of epoxy composites reinforced with graphene nanoplatelets

We reported a facile approach to fabricate graphene nanoplatelets (GNPs)/epoxy composites with a novel blend method. The influence of GNPs on the thermal and electrical properties was investigated. Compounds with different GNPs content (0–8 wt%) were mixed with a Flacktek speedmixer at a speed of 3000 rpm for 5 min. The thermal conductivity of the epoxy composites with 8 wt% GNPs was 1.181 W/m K, which is increased by 627% compared with those of the neat epoxy. It is found that the thermal stability and electrical property also have a certain degree of improvement. Scanning electron microscopy images demonstrate that the structures of the composites have a closed relationship with their properties. In addition, the incorporation of GNPs in epoxy matrix indicated excellent Vickers hardness at the low weight fractions of GNPs. POLYM. COMPOS. 36:556–565, 2015. © 2014 Society of Plastics Engineers     

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.     

High thermally conductive graphite nanoplatelet/polyetherimide composite by precoating: Effect of percolation and particle size

Graphite nanoplatelets (GNPs) with different sizes were compounded with polyetherimide (PEId) by melt‐blending and precoating in order to investigate their effect on the electrical and thermal conductivity of the composites. Precoating compounding successfully created a percolated GNP network with an electrical percolation threshold at 1 wt%, while melt‐blended samples required concentrations over 5 wt% to achieve percolation. The precoated samples also show higher thermal conductivity than the melt‐blended ones. Smaller GNP particle size results in lower thermal conductivity. An improvement of 1,600% in thermal conductivity was recorded for precoated 10 wt% GNP‐15/PEId composite as compared to the neat polymer and a polynomial dependence on GNP concentration was found to predict thermal conductivity. POLYM. COMPOS., 34:2148–2153, 2013. © 2013 Society of Plastics Engineers     

Toughness and roughness in hybrid nanocomposites of an epoxy matrix

The present paper investigates the relationship between roughness and toughening mechanisms in hybrid epoxy nanocomposites with carbon nanotubes (CNT) and graphene nanoplatelets (GNPs). The role of adding a block copolymer (BC) to the studied systems was also investigated. The nanocomposites were prepared by means of high‐energy sonication and in situ polymerization. All nanocomposites presented higher numerical values for K_Ic than untoughened systems. The system containing 0.5 wt% of CNTs presented an increase of 35% in K_Ic compared to neat epoxy, and the hybrid nanocomposite, at the proportion of 1:1 (CNT:GNP), with 0.5 wt% total of nanoparticles and also containing 0.5 wt% of BC, had an increase of 34% compared to the neat epoxy. Systems with higher amounts of graphene showed the highest roughness values, having crack deflection/exfoliation between the GNP layers as the main toughening mechanism. On the other hand, systems with more CNTs presented a lower fracture surface roughness, and the main toughening mechanism was bridging/break‐up of the nanotubes. Hybrid systems have more types of mechanisms than simple ones. With only one type of nanoparticle, however, some of those mechanisms are not effective in increasing the toughness, only increasing the fracture surface roughness. POLYM. ENG. SCI., 59:1258–1269 2019. © 2019 Society of Plastics Engineers     

Mechanical properties of graphene nanoplatelet/epoxy composites

Because of their high‐specific stiffness, carbon‐filled epoxy composites can be used in structural components in fixed‐wing aircraft. Graphene nanoplatelets (GNPs) are short stacks of individual layers of graphite that are a newly developed, lower cost material that often increases the composite tensile modulus. In this work, researchers fabricated neat epoxy (EPON 862 with Curing Agent W) and 1–6 wt % GNP in epoxy composites. The cure cycle used for this aerospace epoxy resin was 2 h at 121°C followed by 2 h at 177°C. These materials were tested for tensile properties using typical macroscopic measurements. Nanoindentation was also used to determine modulus and creep compliance. These macroscopic results showed that the tensile modulus increased from 2.72 GPa for the neat epoxy to 3.36 GPa for 6 wt % (3.7 vol %) GNP in epoxy composite. The modulus results from nanoindentation followed this same trend. For loadings from 10 to 45 mN, the creep compliance for the neat epoxy and GNP/epoxy composites was similar. The GNP aspect ratio in the composite samples was confirmed to be similar to that of the as‐received material by using the percolation threshold measured from electrical resistivity measurements. Using this GNP aspect ratio, the two‐dimensional randomly oriented filler Halpin–Tsai model adjusted for platelet filler shape predicts the tensile modulus well for the GNP/epoxy composites. Per the authors' knowledge, mechanical properties and modeling for this GNP/epoxy system have never been reported in the open literature. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Characterisation of graphite nanoplatelets and the physical properties of graphite nanoplatelet/silicone composites for thermal interface applications

Thermally conducting and highly compliant composites were developed by dispersing graphite nanoplatelets (GNPs) into a silicone matrix by mechanical mixing. X-ray diffraction (XRD) indicates that the average thickness of the GNPs decreased from 60 to 35 nm during mechanical mixing. XRD-texture analysis demonstrated that GNP/silicone composites at 8 wt.% GNPs have a higher degree of basal plane alignment than at 20 wt.%. Differential scanning calorimetry showed that GNPs raised the curing temperature of silicone with no significant effect on the glass transition temperature. The thermal conductivity of the 20 wt.% composites reached 1.909 W/m.K, an 11-fold increase over silicone suggesting an improved dispersion compared to similar composites prepared by dual asymmetric centrifuge mixing. The percolation threshold for electrical conductivity of the composites was at ∼15 wt.%. The compressive modulus of the composite increased to twice that of silicone at 20 wt.%. The corresponding strength decreased by a factor of two compared to silicone and this can be attributed to the weak bonding at the GNP-silicone interface. Overall, these GNP/silicone composites, with a high thermal conductivity, low electrical conductivity and compliant nature are promising materials for use as thermal pads for thick gap filling thermal interface applications.     

Plasma sprayed graphene/carbon nanotube reinforced lanthanum-cerate hybrid composite coating

Lanthanum cerate (LC: La₂Ce₂O₇) is a potential material for thermal barrier coating, whose improved toughness is a crucial necessity for the pathway of its industrialization. Herein, we demonstrated a promising approach to develop graphene/carbon nanotube hybrid composite coating using a large throughput and atmospheric plasma spraying method. Graphene nanoplatelets (GNP: 1 wt %) and carbon nanotube (CNT: 0.5 wt %) reinforced lanthanum cerate (LCGC) hybrid composite coatings were deposited on the Inconel substrate. Addition of 1 wt % GNP and 0.5 wt % CNT in LC matrix has significantly increased its relative density, hardness, and elastic modulus up to 97.2%, 2–3 folds, 3–4 folds, respectively. An impressive improvement of indentation toughness (8.04 ± 0.2 MPa m^0.5) was observed on LCGC coating, which is ～8 times higher comparing the LC coating. The toughening was attributed to the factors: such as the distribution of GNPs and CNTs in the LC matrix, synergistic toughening offered by the GNPs and CNTs; (i) GNP/CNT pull-out, (ii) crack bridging and arresting, (iii) splat sandwiching, mechanical interlocking, etc. Finally, this improved toughness offered an exceptional thermal shock performance up to 1721 cycles at 1800 °C, without any major failure on the coating. Therefore, the GNP and CNT-reinforced LC hybrid composite coating can be recommended to open a path for turbine industries.     

Study of the synergistic effect of boron nitride and carbon nanotubes in the improvement of thermal conductivity of epoxy composites

The enhancement of the thermal conductivity, keeping the electrical insulation, of epoxy thermosets through the addition of pristine and oxidized carbon nanotubes (CNTs) and microplatelets of boron nitride (BN) was studied. Two different epoxy resins were selected: a cycloaliphatic (ECC) epoxy resin and a glycidylic (DGEBA) epoxy resin. The characteristics of the composites prepared were evaluated and compared in terms of thermal, thermomechanical, rheological and electrical properties. Two different dispersion methods were used in the addition of pristine and oxidized CNTs depending on the type of epoxy resin used. Slight changes in the kinetics of the curing reaction were observed in the presence of the fillers. The addition of pristine CNTs led to a greater enhancement of the mechanical properties of the ECC composite whereas the oxidized CNTs presented a greater effect in the DGEBA matrix. The addition of CNTs alone led to a marked decrease of the electrical resistivity of the composites. Nevertheless, in the presence of BN, which is an electrically insulating material, it was possible to increase the proportion of pristine CNTs to 0.25 wt% in the formulation without deterioration of the electrical resistivity. A small but significant synergic effect was determined when both fillers were added together. Improvements of about 750% and 400% in thermal conductivity were obtained in comparison to the neat epoxy matrix for the ECC and DGEBA composites, respectively. © 2019 Society of Chemical Industry     

Electrical and mechanical properties of carbon nanotube‐epoxy nanocomposites

In this work, electrical conductivity and thermo‐mechanical properties have been measured for carbon nanotube reinforced epoxy matrix composites. These nanocomposites consisted of two types of nanofillers, single walled carbon nanotubes (SW‐CNT) and electrical grade carbon nanotubes (XD‐CNT). The influence of the type of nanotubes and their corresponding loading weight fraction on the microstructure and the resulting electrical and mechanical properties of the nanocomposites have been investigated. The electrical conductivity of the nanocomposites showed a significantly high, about seven orders of magnitude, improvement at very low loading weight fractions of nanotubes in both types of nanocomposites. The percolation threshold in nanocomposites with SW‐CNT fillers was found to be around 0.015 wt % and that with XD‐CNT fillers around 0.0225 wt %. Transmission optical microscopy of the nanocomposites revealed some differences in the microstructure of the two types of nanocomposites which can be related to the variation in the percolation thresholds of these nanocomposites. The mechanical properties (storage modulus and loss modulus) and the glass transition temperature have not been compromised with the addition of fillers compared with significant enhancement of electrical properties. The main significance of these results is that XD‐CNTs can be used as a cost effective nanofiller for electrical applications of epoxy based nanocomposites at a fraction of SW‐CNT cost. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermal conductivity and lap shear strength of GNP/epoxy nanocomposites adhesives

The addition of graphene nanoplatelets (GNPs) into the epoxy adhesives has been studied in order to increase their thermal conductivity. Thermally conductive adhesives are often used as thermal interface materials (TIMs). The incorporation of 8 and 10 wt% GNPs reinforcement caused a thermal conductivity enhancement of ~206 and ~306%, respectively. The wettability seems to decrease with low GNPs content (2–3 wt%) in comparison with the neat epoxy adhesive but the contact angle remains constant for higher GNPs contents. Lap shear strength remains constant for neat adhesives and resins doped with GNPs. The lack of enhancement of adhesive properties of doped resins is due to a weak interface reinforcement-matrix. In fact, the joint failure is in the adhesive except for high GNPs content (10 wt%) where a cohesive failure mode is observed.     

Alignment and properties of carbon nanotube buckypaper/liquid crystalline polymer composites

Carbon nanotubes (CNTs) have been recognized as a potential superior reinforcement for high‐performance, multifunctional composites. However, non‐uniform CNT dispersion within the polymer matrix, the lack of adequate adhesion between the constituents of the composites, and lack of nanotube alignment have hindered significant improvements in composite performance. In this study, we present the development of a layer‐by‐layer assembly method to produce high mechanical performance and electrical conductivity CNT‐reinforced liquid crystalline polymer (LCP) composites using CNT sheets or buckypaper (BP) and self‐reinforcing polyphenylene resin, Parmax. The Parmax/BP composite morphology, X‐ray diffraction, mechanical, thermal, and electrical properties have been investigated. SEM observations and X‐ray diffraction demonstrate alignment of the CNTs due to flow‐induced orientational ordering of LCP chains. The tensile strength and Young's modulus of the Parmax/BP nanocomposites with 6.23 wt % multi‐walled carbon nanotube content were 390 MPa and 33 GPa, respectively, which were substantially improved when compared to the neat LCP. Noticeable improvements in the thermal stability and glass transition temperature with increasing CNT content due to the restriction in chain mobility imposed by the CNTs was demonstrated. Moreover, the electrical conductivity of the composites increased sharply to 100.23 S/cm (from approximately 10^?13 S/cm) with the addition of CNT BP. These results suggest that the developed approach would be an effective method to fabricate high‐performance, multifunctional CNT/LCP nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical properties of graphene nanoplatelet/carbon fiber/epoxy hybrid composites: Multiscale modeling and experiments

Because of the relatively high specific mechanical properties of carbon fiber/epoxy composite materials, they are often used as structural components in aerospace applications. Graphene nanoplatelets (GNPs) can be added to the epoxy matrix to improve the overall mechanical properties of the composite. The resulting GNP/carbon fiber/epoxy hybrid composites have been studied using multiscale modeling to determine the influence of GNP volume fraction, epoxy crosslink density, and GNP dispersion on the mechanical performance. The hierarchical multiscale modeling approach developed herein includes Molecular Dynamics (MD) and micromechanical modeling, and it is validated with experimental testing of the same hybrid composite material system. The results indicate that the multiscale modeling approach is accurate and provides physical insight into the composite mechanical behavior. Also, the results quantify the substantial impact of GNP volume fraction and dispersion on the transverse mechanical properties of the hybrid composite while the effect on the axial properties is shown to be insignificant.