Ablative and mechanical evaluation of CNT/phenolic composites by thermal and microstructural analyses

Highly ablation resistant carbon nanotube (CNT)/phenolic composites were fabricated by the addition of low concentrations of CNTs. Tensile and compressive mechanical properties as well as ablation resistance were significantly improved by the addition of only 0.1 and 0.3 wt% of uniformly dispersed CNTs. An oxygen–kerosene-flame torch and a scanning electron microscope (SEM) were used to evaluate the ablative properties and microstructures. Thermal gravimetric analysis (TGA) revealed that the ablation rate was lower for the 0.3 wt% CNT/phenolic composites than for neat phenolic or the composite with 0.1 wt% CNTs. Ablation mechanisms for all three materials were investigated using TGA in conjunction with microstructural studies using a SEM. The microstructural studies revealed that CNTs acted as an ablation resistant phase at high temperatures, and that the uniformity of the CNT dispersion played an important role in this ablation resistance.     

Enhanced conductivity behavior of polydimethylsiloxane (PDMS) hybrid composites containing exfoliated graphite nanoplatelets and carbon nanotubes

Polydimethylsiloxane (PDMS) hybrid composites consisting of exfoliated graphite nanoplatelets (xGnPs) and multiwalled carbon nanotubes functionalized with hydroxyl groups (MWCNTs-OH) were fabricated, and the effects of the xGnP/MWCNT-OH ratio on the thermal, electrical, and mechanical properties of polydimethylsiloxane (PDMS) hybrid composites were investigated. With the total filler content fixed at 4 wt%, a hybrid composite consisting of 75% × GnP/25% MWCNT-OH showed the highest thermal conductivity (0.392 W/m K) and electrical conductivity (1.24 × 10⁻³ S/m), which significantly exceeded the values shown by either of the respective single filler composites. The increased thermal and electrical conductivity found when both fillers are used in combination is attributed to the synergistic effect between the fillers that forms an interconnected hybrid network. In contrast, the various different combinations of the fillers only showed a modest effect on the mechanical behavior, thermal stability, and thermal expansion of the PDMS composite.     

Thermal and mechanical properties of phenolic-based composites reinforced by carbon fibres and multiwall carbon nanotubes

The thermal, mechanical and ablation properties of carbon fibre/phenolic composites filled with multiwall carbon nanotubes (MWCNTs) were investigated. Carbon fibre/phenolic/MWCNTs were prepared using different weight percentage of MWCNTs by compression moulding. The samples were characterized by scanning electron microscopy (SEM), flexural tests, thermal gravimetric analysis and oxyacetylene torch tests. The thermal stability and flexural properties of the nanocomposites increased by increasing MWCNTs content (wt% ⩽1), but they decreased when the content of MWCNTs was 2 wt%. The linear and mass ablation rates of the nanocomposites after modified with 1 wt% MWCNTs decreased by about 80% and 52%, respectively. To investigate the material post-test microstructure, a morphological characterization was carried out using SEM. It was shown that the presence of MWCNTs in the composite led to the formation of a strong network char layer without any cracks or opening.     

Morphology and thermal conductivity of polyacrylate composites containing aluminum/multi-walled carbon nanotubes

Polyacrylate composites with various fillers such as multi-walled carbon nanotube (CNT), aluminum flake (Al-flake), aluminum powders and Al–CNT were prepared by a ball milling. The thermal decomposition temperature increased by as much as 64 °C for polyacrylate/Al-flake 70 wt% composite compared to polyacrylate. The thermal conductivity of polyacrylate/Al–CNT composites increased from 0.50 to 1.67 W/m K as the Al–CNT content increases from 50 to 80 wt%. The thermal conductivity of the composite sheet increases with the sheet thickness. At the given filler concentration (90 wt%), the composite filled with aluminum powder of 13 μm has a higher thermal conductivity than the one filled 3 μm powder, and the composite filled with mixture of two powders showed a synergistic effect on the thermal conductivity. The morphology indicates that the dispersion of CNT in the polyacrylate/Al-flake + CNT composite is not perfect, and agglomeration of CNTs was observed.     

Manufacture of a polymer-based carbon nanocomposite as bipolar plate of proton exchange membrane fuel cells

The aim of this paper is to prepare a polymer-based carbon nanocomposite reinforced by carbon fiber cloth (CF) to be utilized as bipolar plate of proton exchange membrane (PEM) fuel cell. For this purpose, some single, double, and triple-filler composites were manufactured by using phenolic resin as polymer (P) and graphite (G), carbon fiber (CF) and expanded graphite (EG) as fillers. The production method was compression-molding technique. The electrical conductivity, flexural strength, toughness, hardness, porosity, and hydrogen permeability tests were then measured to determine the mechanical and physical properties. A triple-filler composite containing 45 wt.% G, 10 wt.% CF, 5 wt.% EG, reinforced by a layer of CF cloth, was selected as composite bipolar plate. The electrical conductivity, thermal conductivity, and flexural strength of this composite were 74 S/cm, 9.6 W/m K, and 74 MPa, respectively, which are higher than the specified value by department of energy in USA (DOE). The composite bipolar plate used in the single fuel cell assembly showed a maximum power density 810 mW/cm². In this paper, a material selection was performed on the different materials of bipolar plates. It can be concluded that the composite bipolar plates are more suitable for high life time stationary applications.     

Synergistic effect of hybrid graphene nanoplatelet and multi-walled carbon nanotube fillers on the thermal conductivity of polymer composites and theoretical modeling of the synergistic effect

We found that the thermal conductivity of polymer composites was synergistically improved by the simultaneous incorporation of graphene nanoplatelet (GNP) and multi-walled carbon nanotube (MWCNT) fillers into the polycarbonate matrix. The bulk thermal conductivity of composites with 20 wt% GNP filler was found to reach a maximum value of 1.13 W/m K and this thermal conductivity was synergistically enhanced to reach a maximum value of 1.39 W/m K as the relative proportion of MWCNT content was increased but the relative proportion of GNP content was decreased. The synergistic effect was theoretically estimated based on a modified micromechanics model where the different shapes of the nanofillers in the composite system could be taken into account. The waviness of the incorporated GNP and MWCNT fillers was found to be one of the most important physical factors determining the thermal conductivity of the composites and must be taken into consideration in theoretical calculations.     

Properties of polypropylene composites containing aluminum/multi-walled carbon nanotubes

Polypropylene/aluminum–multi-walled carbon nanotube (PP/Al–CNT) composites were prepared by a twin-screw extruder. The morphology indicates that the CNTs are well embedded or implanted within Al-flakes rather than attached on the surface. During preparation of composites, the CNTs came apart from Al–CNT so that free CNTs as well as Al–CNT were observed in PP/Al–CNT composite. The crystallization temperatures of PP/CNT and PP/Al–CNT composites were increased from 111 °C for PP to 127 °C for the composites. The decomposition temperature increased by 55 °C for PP/CNT composite and 75 °C for PP/Al–CNT composite. The PP/Al–CNT composite showed higher thermal conductivity than PP/CNT and PP/Al-flake composites with increasing filler content. PP/Al–CNT composites showed the viscosity values between PP/CNT and PP/Al-flake composites. PP/Al–CNT composite showed higher tensile modulus and lower tensile strength with increasing filler content compared to PP/CNT and PP/Al-flake composites.     

Novel phenolic impregnated 3-D Fine-woven pierced carbon fabric composites: Microstructure and ablation behavior

The processing, microstructure and ablative properties of novel phenolic impregnated 3-D Fine-woven pierced carbon fabric ablator (PICA) with different bulk density were investigated. The density of PICA material ranges from 0.352 to 0.701 g/cm³ that having uniform resin distribution within the fibrous substrate. An oxyacetylene torch was used to explore the ablative characteristics in terms of linear/mass ablation rate and microscopic pattern of ablation. Surface and in-depth temperatures during ablation were measured by using optical pyrometers and thermocouples. The experimental results showed that the linear ablation rate varied between 0.019 and 0.036 mm/s and the mass ablation rate increased from 0.045 to 0.061 g/s for the tested PICA composites. It suggests that the PICA composites with lower density may significantly contribute to improving the thermal insulation and ablative properties.     

Lightweight carbon-bonded carbon fiber composites with quasi-layered and network structure

Lightweight carbon-bonded carbon fiber (CBCF) composites were fabricated with chopped carbon fibers and dilute phenolic resin solution by pressure filtration, followed by carbonization at 1000 °C in argon. The as-prepared CBCF composites had a homogenous fiber network distribution in xy direction and quasi-layered structure in z direction. The pyrolytic carbon derived from phenolic resin was mainly accumulated at the intersections and surfaces of chopped carbon fibers. The composites possessed compressive strengths ranged from 0.93–6.63 MPa in xy direction to 0.30–2.01 MPa in z direction with a density of 0.162–0.381 g cm^− 3. The thermal conductivity increased from 0.314–0.505 to 0.139–0.368 Wm^− 1 K^− 1 in xy and z directions, respectively. The experimental results indicate that the CBCF composites prepared by this technique can significantly contribute to improve the thermal insulation and mechanical properties at high temperature.     

Ablation,mechanical and thermal conductivity properties of vapor grown carbon fiber/phenolic matrix composites

The ablation, mechanical and thermal properties of vapor grown carbon fiber (VGCF) (Pyrograf III™ Applied Sciences, Inc.)/phenolic resin (SC-1008, Borden Chemical, Inc.) composites were evaluated to determine the potential of using this material in solid rocket motor nozzles. Composite specimens with varying VGCF loadings (30–50% wt.) including one sample with ex-rayon carbon fiber plies were prepared and exposed to a plasma torch for 20 s with a heat flux of 16.5 MW/m² at approximately 1650°C. Low erosion rates and little char formation were observed, confirming that these materials were promising for rocket motor nozzle materials. When fiber loadings increased, mechanical properties and ablative properties improved. The VGCF composites had low thermal conductivities (approximately 0.56 W/m-K) indicating they were good insulating materials. If a 65% fiber loading in VGCF composite could be achieved, then ablative properties are projected to be comparable to or better than the composite material currently used on the Space Shuttle Reusable Solid Rocket Motor (RSRM).     

A comparative study on the electrical,thermal and mechanical properties of ethylene–octene copolymer based composites with carbon fillers

Conducting polymer composites (CPC) were prepared with an ethylene–octene copolymer (EOC) matrix and with either carbon fibers (CFs) or multiwall carbon nanotubes (MWCNTs) as fillers. Their electrical and thermal conductivities, mechanical properties and thermal stabilities were evaluated and compared. CF/EOC composites showed percolation behavior at a lower filler level (5 wt.%) than the MWCNT/EOC composites (10 wt.%) did. Alternating current (AC) conductivity and real part of permittivity (dielectric constant) of these composites were found to be frequency-dependent. Dimensions and electrical conductivities of individual fillers have a great influence on the conductivities of the composites. CF/EOC composites possessed higher conductivity than the MWCNT-composites at all concentrations, due to the higher length and diameter of the CF filler. Both electrical and thermal conductivities were observed to increase with increasing filler level. Tensile moduli and thermal stabilities of both (CF/EOC and MWCNT/EOC) composites increase with rising filler content. Improvements in conductivities and mechanical properties were achieved without any significant increase in the hardness of the composites; therefore, they can be potentially used in pressure/strain sensors. Thermoelectric behavior of the composites was also studied. Accordingly, CF and MWCNT fillers are versatile and playing also other roles in their composites than just being conducting fillers.     

Effects of poly(oxyethylene)-block structure in polyetheramines on the modified carbon nanotube/poly(lactic acid) composites

The hybrids of multi-walled carbon nanotube and poly(lactic acid) (MWCNT/PLA) were prepared by a melt-blending method. In order to enhance the compatibility between the PLA and MWCNTs, the surface of the MWCNTs was covalently modified by Jeffamine® polyetheramines by functionalizing MWCNTs with carboxylic groups. Different molecular weights and hydrophilicity of the polyethermaines were grafted onto MWCNTs with the assistance of a dehydrating agent. The results showed that low-molecular-weight Jeffamine® polyetheramine modified MWCNTs can effectively improve the thermal properties of PLA composites. On the other hand, high-molecular-weight and poly(oxyethylene)-segmented polyetheramine could render the modified MWCNTs of well dispersion in PLA, and consequently affecting the improvements of mechanical properties and conductivity of composite materials. With the addition of 3.0 wt% MWCNTs, the increment of E′ of the composite at 40 °C was 79%. For conductivity, the surface resistivity decreased from 1.27 × 10¹² Ω/sq for neat PLA to 8.30 × 10⁻³ Ω/sq for the composites.     

Effect of silica coating thickness on the thermal conductivity of polyurethane/SiO2 coated multiwalled carbon nanotube composites

Silica coated multiwalled carbon nanotubes (SiO₂@MWCNTs) with different coating thicknesses of ∼4 nm, 30–50 nm, and 70–90 nm were synthesized by a sol–gel method and compounded with polyurethane (PU). The effects of SiO₂@MWCNTs on the electrical properties and thermal conductivity of the resulting PU/SiO₂@MWCNT composites were investigated. The SiO₂ coating maintained the high electrical resistivity of pure PU. Meanwhile, incorporating 0.5, 0.75 and 1.0 wt% SiO₂@MWCNT (70–90 nm) into PU, produced thermal conductivity values of 0.287, 0.289 and 0.310 W/mK, respectively, representing increases of 62.1%, 63.3% and 75.1%. The thermal conductivity of PU/SiO₂@MWCNT composites was also increased by increasing the thickness of the SiO₂ coating.     

Heterogeneously structured conductive carbon fiber composites by using multi-scale silver particles

This paper reports a new approach to enhance the through-thickness thermal conductivity of laminated carbon fabric reinforced composites by using nanoscale and microscale silver particles in combination to create heterogeneously structured continuous through-thickness thermal conducting paths. High conductivity of 6.62 W/(m K) with a 5.1 v% silver volume fraction can be achieved by incorporating these nanoscale and microscale silver particles in EWC-300X/Epon862 composite. Silver flakes were distributed within the inter-tow area, while nanoscale silver particles penetrated into the fiber tows. The combination of different sizes of silver fillers is able to effectively form continuous through-thickness conduction paths penetrating fiber tows and bridging the large inter-tow resin rich areas. Positive hybrid effects to thermal conductivity were found in IM7/EWC300X/sliver particle hybrid composites. In addition, microscale fillers in resin rich areas showed less impact on tensile performance than nanoscale particles applied directly on fiber surface.     

Fabrication and mechanical/conductive properties of multi-walled carbon nanotube (MWNT) reinforced carbon matrix composites

Multi-walled carbon nanotube (MWNT) reinforced carbon matrix (MWNT/C) composites have been explored using mesophase pitch as carbon matrix precursor in the present work. Results show that carbon nanotubes (CNTs)can enhance the mechanical properties of carbon matrix significantly. The maximal increment of the bending strength and stiffness of the composites, compared with the carbon matrix, are 147% and 400%, respectively. Whereas the highest in-plane thermal conductivity of the composites is 86 W m^− 1 K^− 1 which much lower than that of carbon matrix (253 W m^− 1 K^− 1).At the same time the electrical resistivity of the composites is much higher than that of matrix. It is implicated that CNTs seem to play the role of thermal/electrical barrier in the composites. FSEM micrograph of the fracture surface for the composites shows that the presence of CNTs restrains the crystallite growth of carbon matrix, which is one of factors that improve mechanical properties and decrease the conductive properties of the composites. The defects and curved shape of CNTs are also the affecting factors on the conductive properties of the composites.     

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.     

Thermal conductivity of graphene nanoplatelets filled composites fabricated by solvent-free processing for the excellent filler dispersion and a theoretical approach for the composites containing the geometrized fillers

The thermal conductivity of polymer composites containing nanofillers such as GNP (graphene nanoplatelet) and carbon black (CB) was investigated using experimental and theoretical approaches. We developed a fabrication method that allows different shapes and sizes of nanofillers to be highly dispersed in polymer resin. When the bulk and in-plane thermal conductivities of the fabricated composites were measured, they were found to increase rapidly as the GNP filler content increased. The in-plane thermal conductivity of composites with 20 wt.% GNP filler was found to reach a maximum value of 1.98 W/m K. The measured thermal conductivities were compared with the calculated values based on a micromechanics model where the waviness of nanofillers could be taken into account. The waviness of the incorporated GNP filler is an important physical factor that determines the thermal conductivity of composites and must be taken into consideration in theoretical calculations.     

Graphene woven fabric-reinforced polyimide films with enhanced and anisotropic thermal conductivity

Due to the growing needs of thermal management in modern electronics, polyimide-based (PI) composites are increasingly demanded in thermal interface materials (TIMs). Graphene woven fabrics (GWFs) with a mesh structure have been prepared by chemical vapor deposition and used as thermally conductive filler. With the incorporation of 10-layer GWFs laminates (approximate 12 wt%), the in-plane thermal conductivity of GWFs/PI composite films achieves 3.73 W/mK, with a thermal conductivity enhancement of 1418% compared to neat PI. However, the out-of-plane thermal conductivity of the composites is only 0.41 W/mK. The in-plane thermal conductivity exceeds its out-of plane counterpart by over 9 times, indicating a highly anisotropic thermal conduction of GWFs/PI composites. The thermal anisotropy and the enhanced in-plane thermal conductivity can be attributed to the layer-by-layer stacked GWFs network in PI matrix. Thus, the GWFs-reinforced polyimide films are promising for use as an efficient heat spreader for electronic cooling applications.     

Reduction of thermal residual stresses of laminated polymer composites by addition of carbon nanotubes

This paper studies the effects of multi-walled carbon nanotubes (MWCNTs) on the thermal residual stresses in polymeric fibrous composites. Reinforced ML-506 epoxy nanocomposites with different amounts of homogeneously dispersed MWCNTs (0.1 wt.%, 0.5 wt.% and 1 wt.%) were fabricated using the sonication technique. Thermo-mechanical analysis and tensile tests of the specimens were carried out to characterize the thermal and mechanical properties of MWCNTs/epoxy composites. Due to the negative thermal expansion and high modulus of MWCNTs, addition of MWCNTs resulted in a great reduction of the coefficient of thermal expansion (CTE) of epoxy. The MWCNTs also moderately increased the Young’s modulus of the epoxy. Then, the effects of adding MWCNTs on micro and macro-residual stresses in carbon fiber (CF)/epoxy laminated composites were investigated using the energy method and the classical lamination theory (CLT), respectively. The results indicated that the addition of low amounts of MWCNTs leads to a considerable reduction in thermal residual stress components in both micro and macro levels.     

Electrostatic self-assembled carbon nanotube/nano carbon black composite fillers reinforced cement-based materials with multifunctionality

Electrostatic self-assembled carbon nanotube (CNT)/nano carbon black (NCB) composite fillers are added into cement mortar to fabricate smart cement-based materials. The grape bunch structure of CNT/NCB composite fillers is beneficial for dispersing CNT/NCB in cement mortar matrix and achieving cooperative improvement effect. The mechanical, electrically conductive, and piezoresistive behaviors of the cement mortar are investigated. The CNT/NCB composite fillers can effectively enhance the flexural strength and electrical conductivity of cement mortars, and endow stable and sensitive piezoresistivity to cement mortar at a low filler content. However, they weaken the compressive strength of cement mortar to some extent. The percolation threshold zone of cement mortar with CNT/NCB composite fillers ranges in the amount of 0.39–1.52 vol.%. The optimal content of CNT/NCB composite fillers is 2.40 vol.% for piezoresistivity and the stress and strain sensitivities can reach 2.69% MPa⁻¹ and 704, respectively.