A comparative study on the effect of carbon fillers on electrical and thermal conductivity of a cyanate ester resin

Carbon fillers including multi-walled carbon nanotubes (MWCNTs), carbon black (CB) and graphite were introduced in a cyanate ester (CE) resin, respectively. The effects of the fillers on the electrical and thermal conductivity of the resin were measured and analyzed based on the microscopic observations. MWCNTs, CB and graphite exhibited percolation threshold at 0.1 wt%, 0.5 wt% and 10 wt%, respectively. The maximal electrical conductivity of the composites was 1.08 S/cm, 9.94 × 10⁻³ S/cm and 1.70 × 10⁻⁵ S/cm. MWCNTs showed the best enhancement on the electrical conductivity. The thermal behavior of the composites was analyzed by calorimetry method. Incorporation of MWCNTs, CB and graphite increased the thermal conductivity of CE resin by 90%, 15% and 92%, respectively. Theoretical models were introduced to correlate the thermal conductivity of the CE/MWCNTs composite. The interfacial thermal resistance between CE resin and MWCNTs was 8 × 10⁻⁸ m²K/W and the straightness ratio was 0.2. The MWCNTs were seriously entangled and agglomerated. Simulation results revealed that thermal conductivity of the CE/MWCNTs composites can be substantially elevated by increasing the straightness ratio and/or filler content of MWCNTs.     

Confinement crystallization of poly(l-lactide) induced by multiwalled carbon nanotubes and graphene nanosheets

Journal of Thermal Analysis and Calorimetry - Two sets of multiwalled carbon nanotubes (MWCNTs)/PLLA nanocomposites and graphene nanosheets (GNSs)/PLLA nanocomposites with various MWCNTs and GNSs...     

The addition of functionalized graphene oxide to polyetherimide to improve its thermal conductivity and mechanical properties

The thermal and electrical conductivity and mechanical properties of polyetherimide (PEI) containing either alkyl‐aminated (enGO) or phenyl‐aminated graphene (pnGO) oxides were studied. A solution casting method was used to prepare functionalized graphene oxide/PEI composites with different filler contents. The introduction of functionalized graphene oxide to the PEI matrix improved the thermal conductivity, electrical conductivity, and mechanical properties. The thermal conductivities of the enGO 3 wt%/PEI and pnGO 3 wt%/PEI composites were 0.324 W/mK and 0.329 W/mK, respectively, due to the high thermal conductivity of the graphene‐based materials and the strong interface adhesion due to the filler surface treatment between the fillers and the matrix. The electrical conductivities of the functionalized graphene oxide/PEI composites were larger than that of PEI, but the electrical conductivity values were generally low, which is consistent with the magnitude of the insulator. The strong interfacial adhesion between the fillers and the matrix led to improved mechanical properties. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of Different Hybrid Method on Properties of Carbon Nanotubes/Dolomite Hybrid Filled Phenolic Composites

Hybridization of multi wall carbon nanotubes (MWCNTs) with other filler in polymer matrix composites (PMC) is one of the techniques for combining different properties of fillers for making more unique composites. In this work, the hybrid filler (CNTs–dolomite) are prepared via chemical vapour deposition (CVD hybrid) and the milling method (physically hybrid). The effect of different hybrid method on properties of multi wall carbon nanotubes/dolomite hybrid filled phenolic composites were studied. Phenolic/CVD hybrid composites and phenolic/physically hybrid composites with different filler loadings were prepared using hot mounting press. The prepared samples were characterized for their thermal conductivity and hardness. The thermal conductivity was measured using the Transient Plane Source (TPS) method, using a Hot-DiskTM Thermal Constant Analyzer and the hardness was measured using Rockwell micro-hardness. The results showed that at 5% filler loading, the phenolic/CVD hybrid composites were capable of increasing the thermal conductivity and micro-hardness up to 7.22% and 101.6% respectively compared to pure phenolic.     

Towards efficient electromagnetic interference shielding performance for polyethylene composites by structuring segregated carbon black/graphite networks

An electromagnetic interference (EMI) shielding composite based on ultrahigh molecular weight polyethylene (UHMWPE) loaded with economical graphite-carbon black (CB) hybrid fillers was prepared via a green and facile methodology, i.e., high-speed mechanical mixing combined with hot compression thus avoiding the assistance of the intensive ultrasound dispersion in volatile organic solvents. In this composite, the graphite-CB hybrid fillers were selectively distributed in the interfacial regions of UHMWPE domains resulting a typical segregated structure. Thanks to the specific morphology of segregated conductive networks along with the synergetic effect of large-sized graphite flakes and small-sized CB nanoparticles, a low filler loading of 7.7 vol% (15 wt%) yielded the graphite-CB/UHMWPE composites with a satisfactory electrical conductivity of 33.9 S/m and a superior shielding effectiveness of 40.2 dB, manifesting the comparable value of the pricey large-aspect-ratio carbon nanofillers (e.g., carbon nanotubes and graphene nanosheets) based polymer composites. More interestingly, with the addition of 15 wt% graphite-CB (1/3, W/W) hybrid fillers, the tensile strength and elongation at break of the composite reached 25.3 MPa and 126%, respectively; with a remarkable increase of 58.1% and 2420% over the conventional segregated graphite/UHMWPE composites. The mechanical reinforcement could be attributed to the favor of the small-sized CB particles in the polymer molecular diffusion between UHMWPE domains which in turn provided a stronger interfacial adhesion. This work provides a facile, green and affordable strategy to obtain the polymer composites with high electrical conductivity, efficient EMI shielding, and balanced mechanical performance.     

High thermal conductivity polylactic acid composite for 3D printing: Synergistic effect of graphene and alumina

With the continuous development of the electronics industry, in order to meet the requirements of electronic equipment to reduce the size and increase power consumption, the development of high thermal conductivity materials is crucial. In this study, thermally conductive polylactic acid (PLA) composites were prepared by constructing graphene and alumina (Al₂O₃) hybrid filler network, and it was further successfully used in additive manufacturing. Due to the synergistic effect of Al₂O₃ and graphene, the resulting composite achieved the thermal conductivity of 2.4 Wm^?1 K^?1 with 70 wt% Al₂O₃ and 1 wt% graphene, which are superior to data reported in the literature in the same filler condition. The Al₂O₃ and graphene hybrid filler network reduced the agglomeration of graphene and the thermal contact resistance between the fillers, thereby leading a faster cooling rate. Furthermore, the obtained thermally conductive PLA composite has good thermal stability at a normal temperature. The PLA composite powder obtained by the cryogenic pulverization can be used in the laser sintering additive manufacturing process to prepare a heat conductive material with a complicated shape.     

Influence of graphene reinforcement in conductive polymer: Synthesis and characterization

Lightweight conductive polymers are considered for lightning strike mitigation in composites by synthesizing intrinsically conductive polymers (ICPs) and by the inclusion of conductive fillers in insulating matrices. Conductive films based on polyaniline (PANI) and graphene have been developed to improve through‐thickness conductivity of polymer composites. The result shows that the conductivity of PANI enhanced by blending polyvinylpyrrolidone (PVP) and PANI in 3:1 ratio. Conductive composite thin films are prepared by dispersing graphene in PANI. The conductivity of composite films was found to increase by 40× at 20 wt% of graphene inclusion compared with PVP and PANI blend. Fourier‐transform‐infrared (FTIR) spectra confirmed in situ polymerization of the polymer blend. The inclusion of graphene also exhibits an increase in Tg by 21°C. Graphene additions also showed an increase in thermal stability by approximately 148°C in the composite films. The mechanical result obtained from DMA shows that inclusion of graphene increases the tensile strength by 48% at 20 wt% of graphene reinforcement. A thin, highly conductive surface that is compatible with a composite resin system can enhance the surface conductivity of composites, improving its lightning strike mitigation capabilities.     

Noncovalent functionalization of multiwalled and double‐walled carbon nanotubes: Positive effect of the filler functionalization on high glass transition temperature epoxy resins

Double‐walled carbon nanotubes (DWCNTs) and multiwalled carbon nanotubes (MWCNTs) were modified using melamine to attach ? NH₂ to the surface of these fillers, without previous oxidation of their graphene layers. FT‐Raman, elemental (chemical) and thermogravimetric analysis, confirmed the modification, which was more extensive for DWCNTs. The potential of this modification was evaluated by adding the melamin‐modified nanotubes to thermosets based on diglycidyl ether of bisphenol A (resin) and polycyclic amine (hardener). Broadening of the glass transition interval and an increase between 7 and 8 °C of the glass transition temperatures show better filler/matrix interaction for the nanocomposites based on melamine‐modified nanotubes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1860–1868, 2009     

Enhanced thermal conductivity of epoxy–matrix composites with hybrid fillers

The results of thermal conductivity study of epoxy–matrix composites filled with different type of powders are reported. Boron nitride and aluminum nitride micro‐powders with different size distribution and surface modification were used. A representative set of samples has been prepared with different contents of the fillers. The microstructure was investigated by SEM observations. Thermal conductivity measurements have been performed at room temperature and for selected samples it was also measured as a function of temperature from 300 K down to liquid helium temperatures. The most spectacular enhancement of the thermal conductivity was obtained for composites filled with hybrid fillers of boron nitride–silica and aluminum nitride–silica. In the case of sample with 31 vol.% of boron nitride–silica hybrid filler it amounts to 114% and for the sample with 45 vol.% of hybrid filler by 65% as compared with the reference composite with silica filler. However, in the case of small aluminum nitride grains application, large interfacial areas were introduced, promoting creation of thermal resistance barriers and causing phonon scattering more effective. As a result, no thermal conductivity improvement was obtained. Different characters of temperature dependencies are observed for hybrid filler composites which allowed identifying the component filler of the dominant contribution to the thermal conductivity in each case. The data show a good agreement with predictions of Agari‐Uno model, indicating the importance of conductive paths forming effect already at low filler contents. Copyright © 2014 John Wiley & Sons, Ltd.     

Epoxy‐based composite adhesives: Effect of hybrid fillers on thermal conductivity,rheology, and lap shear strength

Thermal management is an important parameter in an electronic packaging application. In this work, three different types of fillers such as natural graphite powder (Gr) of 50‐μm particle size, boron nitride powder (h‐BN) of 1‐μm size, and silver flakes (Ag) of 10‐μm particle size were used for thermal conductivity enhancement of neat epoxy resin. The thermal properties, rheology, and lap shear strength of the neat epoxy and its composite were investigated. The analysis showed that the loading of different wt% of Gr‐based fillers can effectively increase the thermal conductivity of the epoxy resin. It has also been observed that the thermal conductivity of the hybrid filler (Gr/h‐BN/Ag) reinforced epoxy adhesive composite increased six times greater than that of neat epoxy resin composite. Further, the viscosity of hybrid filler reinforced epoxy resin was found to be increased as compared with its virgin counterpart. The adhesive composite with optimized filler content was then subsequently subjected to determine single lap shear strength. The degree of filler dispersion and alignment in the matrix were determined by scanning electron microscopy (SEM) analysis.     

Significant enhancement of electrical and thermal conductivities of polyethylene carbon nanotube composites by the addition of a low amount of silver nanoparticles

Electrically and thermally conductive high‐density polyethylene composites filled with hybrid fillers, multiwall carbon nanotubes (MWCNTs) and silver nanoparticles (Ag‐NPs), have been prepared in the melt state. The investigation of their electrical and thermal conductivities while comparing with high‐density polyethylene/MWCNT binary composites shows that the addition of only 3 vol% of Ag‐NPs does not reduce the electrical percolation threshold (P_c) that remains as low as 0.40 vol% of MWCNTs but leads to an increase in the maximum dc electrical conductivity of PE/MWCNT composites by two orders of magnitudes. Moreover, the association of both Ag‐NPs and carbon nanotube particles improved our composite's thermal conductivity. Copyright © 2014 John Wiley & Sons, Ltd.     

Synergetic effect of thermal conductivity and flame retardancy of cyanate ester composites containing DOPO and BN with great dielectric properties

DOPO and boron nitride (BN) fillers with different particle sizes and several loadings were employed to improve the properties of cyanate ester (CE) resin. The effects of BN content and particle size on the thermal conductivity of the BN‐DOPO/CE ternary composites were discussed. The influence of enhancing the thermal conductivity of the ternary composites on their flame retardancy was studied. The consequences showed that increasing the thermal conductivity of BN‐DOPO/CE composites had an active impact on their flame retardancy. Approving flame retardancy of the ternary composites was certified by the high limiting oxygen index (LOI), UL‐94 rating of V‐0, and low heat release rate (HRR) and total heat release (THR). For instance, in contrast with pure CE matrix, peak of HRR (pk‐HRR), average of HRR (av‐HRR), THR, and average of effective heat of combustion (av‐EHC) of CEP/BN_{0.5 μm}/10 composite were decreased by 51.7%, 33.8%, 18.7%, and 18.9%, respectively. Thermal gravimetry analysis (TGA) showed that the addition of BN fillers improves the thermal stability of the composites. Moreover, the ternary composites possess good dielectric properties. Their dielectric constants (ε) are less than 3, and dielectric loss tangent (tgδ) values are lower than neat CE resin.     

Dynamic percolation in highly oriented conductive networks formed with different carbon nanofillers

Dynamic percolation in highly oriented conductive networks formed with different carbon nanofillers is investigated during disorientation upon annealing. Conductive networks are constructed by solid-state drawing, subsequent annealing, and using fillers with different dimensions (multiwalled carbon nanotubes (MWCNTs) and carbon black (CB)) in a bicomponent tape. Interestingly, it is observed that a less entangled network work is formed by mixed filler containing CB; consequently, this result in an accelerated dynamic percolation process and reduced activation energy of such process. Three different analytical approaches have been utilized to analyze this interesting behavior. It is concluded that the dynamic percolation process in highly oriented conductive polymer composites filled with MWCNTs can indeed be accelerated by the addition of CB, since less entangled networks are formed in a hybrid filler system compared with MWCNTs alone.     

Dielectric,mechanical and electro-stimulus response properties studies of polyurethane dielectric elastomer modified by carbon nanotube-graphene nanosheet hybrid fillers

The typical nano-carbon materials, 1D fiber-like carbon nanotubes (CNTs) and 2D platelet-like graphene nanosheets (GRNs), that have attracted tremendous attention in the field of polymer nanocomposites due to their unprecedented properties, are used as conducting filler to induce a considerable improvement in the mechanical, thermal and electrical properties of the resulting graphene/polymer nanocomposites at very low loading contents. This study deals with the preparation and electro-stimulus response properties of polyurethane (PU) dielectric elastomer films with such 1D and 2D nanocarbon fillers embedded in the polymer matrix. The various forms of carbon used in composite preparation include CNT, GRN and CNT-GRN hybrid fillers. Results indicate that the dielectric, mechanical and electromechanical properties depend on the carbon filler type and the carbon filler weight fraction. Here, it has been also established that embedding CNT-GRN hybrid fillers into pristine polyurethane endows somewhat better dispersion of CNTs and GRNs as well as better interfacial adhesion between the carbon fillers and matrix, which results in an improvement in electric-induced strain. Therefore, the nanocomposites seem to be very attractive for microelectromechanical systems applications.     

A comprehensive study on the impact of RGO/MWCNT hybrid filler reinforced polychloroprene rubber multifunctional nanocomposites

Flexible dielectric chloroprene rubber (CR) nanocomposites reinforced by one-dimensional carbon nanotube (CNT)/two dimensional reduced graphene oxide hybrids have been prepared using two-roll mill mixing technique. Non-covalent π-π interaction between multiwalled carbon nanotubes (MWCNTs) and reduced graphene oxide (RGO) nanosheets and the secondary interaction between fillers and chloroprene rubber matrix are responsible for generating the effective load transfer between RGO/MWCNTs and CR. The prepared RGO-MWCNT hybrid nanocomposites with high dielectric constant (≈650), low dielectric loss (≈0.42) and high energy storage efficiency (78.6%) values are practically good enough to use as a low cost polymeric dielectric layer in transistors. Furthermore, the prepared nanocomposites showed excellent electromagnetic effectiveness; a maximum shielding efficiency of 11.87 dB @ 3.5 GHz was achieved at 4 phr of MWCNT loading. This excellent electromechanical performance can be ascribed to the synergistic effect of RGO-MWCNT hybrid suggesting that this novel hybrid nanocomposite serves as an attractive candidate in modern electronics and electric power systems.     

Structural and electrochemical properties of SnO2/nanocarbon families as lithium-ion battery anodes

Hybrid SnO₂/nanocarbon families (graphene nanosheets (GNSs), single-wall carbon nanotubes (SWCNTs), multi-wall carbon nanotubes (MWCNTs) and carbon nanospheres (CNSs)) have been synthesized by a similar wet chemical method. SnO₂ nanoparticles are uniformly loaded on the surface of the nanocarbon families. As lithium battery anodes, their electrochemical properties of the reaction of lithium are investigated under the same conditions. To compare between them, SnO₂/GNSs have the largest capacity; SnO₂/GNSs and SnO₂/SWCNTs have high cyclability; and SnO₂/MWCNTs can maintain the capacity at high current density. Such behaviors are ascribed to their surface-to-volume ratio, structure flexibility, ion mobility and electron conductivity. The present results are the bases for their practical applications in lithium-ion battery anodes.     

Preparation of nylon MXD6/EG/CNTs ternary composites with excellent thermal conductivity and electromagnetic interference shielding effectiveness

In this article,hybrid fillers with different dimensions,namely,2-dimensional (2-D) expanded graphite (EG) and 1-dimensional (1-D) multi-walled carbon nanotubes (CNTs),were added to aromatic nylon MXD6 matrix via melt-blending,to enhance its thermal and electrical conductivity as well as electromagnetic interference shielding effectiveness (EMI SE).For ternary composites of MXD6/EG/CNTs,the electrical conductivity reaches up nine orders of magnitude higher compared to that of the neat MXD6 sample,which tumed the polymer-based composites from an insulator to a conductor,and the thermal conductivity has been enhanced by 477％ compared with that of neat MXD6 sample.Meanwhile,the EMI SE of ternary composite reaches ～50 dB at the overall filler loading of only 18 wt％.This work can provide guidance for the preparation of polymer composites with excellent thermal and electrical conductivity via using hybrid filler.     

Dissolution of MWCNTs by using polyoxadiazoles,and highly effective reinforcement of their composite films

Nonmodified multiwalled carbon nanotubes (MWCNTs)/sulfonated polyoxadiazole (sPOD) nanocomposites are successfully prepared by a facile solution route. The pristine MWCNTs are dispersed in a sPOD solution, and the mixtures are fabricated into thin films by solution casting. The homogeneous dispersion of nanotubes in the composites is confirmed by transmission electron microscopy. The mechanical properties, thermal stability, and electrical conductivity are investigated. Tensile strength, elongation at break, and tensile energy to break are shown to increase by more than 28, 45, and 73%, respectively, by incorporating up to 1.0 wt % pristine MWCNTs. The experimental values for sPOD/MWCNTs composite stiffness are compared with Halpin‐Tsai and modified Halpin‐Tsai predictions. The storage modulus is found to increase up to 10% at low CNT loading. The composite films, which have an outstanding thermal stability, show an increase of up to 57 °C in the initial degradation temperature. The addition of 1.0 wt % MWCNTs increases the electrical conductivity of the sPOD matrix by two orders of magnitude. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Catalyst-free fabrication of graphene nanosheets without substrates using multiwalled carbon nanotubes and a spark plasma sintering process

Catalyst-free graphene nanosheets without substrates were synthesized using pure solid carbon sources of multiwalled carbon nanotubes (MWCNTs) and a spark plasma sintering (SPS) process. Single and few-hundred-nanometer graphene nanosheets were formed from gas-phase carbon atoms which were directly evaporated from MWCNTs at a local high temperature.     

Enhanced toughness and strength of conductive cellulose-poly(butylene succinate) films filled with multiwalled carbon nanotubes

Cellulose (CE) composite films with high tensile strength, modulus, remarkable elongation as well as excellent electrical conductivity were successfully prepared by dispersing poly(butylene succinate) (PBS) and multiwalled carbon nanotubes (MWCNTs) in CE matrix via the help of ionic liquid 1-allyl-3-methylimidazolium chloride. Fourier transform infrared spectroscopy and differential scanning calorimetry results verified that a physical interaction junction existed between PBS and CE. Scanning electron micrograph (SEM) showed that the low content PBS was uniformly dispersed in CE matrix, leading to a tough and ductile fractured surface. The elongation at break of CE composite film with 1 wt% PBS was increased to 25.9 %, which showed an increase of 325 % compared to that of neat CE film (6.07 %). But high-content PBS acted as the structural defect in the CE matrix. MWCNTs were further added to improve the mechanical and conductive properties of the composite film. The tensile strength and Young’s modulus of MWCNT/CE-PBS composite film with 4 wt% MWCNTs were respectively increased by 33.6 and 140 % compared to CE-PBS film. The electrical conductivity of MWCNT/CE-PBS film was also improved by 8–9 orders of magnitude from 2.5 × 10^?14 to 1.3 × 10^?5 S/m.