Multi-contact hybrid thermal conductive filler Al2O3@AgNPs optimized three-dimensional thermal network for flexible thermal interface materials

In this work, a multi-contact Al₂O₃@AgNPs hybrid thermal conductive filler was synthesized by in-situ growth method to fill high thermal conductivity polydimethylsiloxane (PDMS)-based composites to prepare TIMs. And the thermal conductivity, electrical conductivity, and mechanical properties of the composite materials were studied. During the synthesis process of the multi-contact hybrid filler, different concentrations of silver ions were reduced to generate silver nanoparticles and attached to the surface of Al₂O₃. Al₂O₃@AgNPs/PDMS thermally conductive composites were prepared by changing the filler addition. Using SEM, XPS, and XRD is used to characterize the morphology and chemical composition of Al₂O₃@AgNPs hybrid filler. The thermal conductivity of PDMS-based composites with different AgNPs content under 70 wt% filler loading was studied. The results show that the thermal conductivity of PDMS-based composites filled with 7owt%Al₂O₃@3AgNPs/PDMS multi-contact hybrid filler is 0.67 W/m·K, which is 3.72 times that of pure PDMS, and is higher than that of unmodified Al₂O₃ with the same addition amount. /PDMS composite material has a high thermal conductivity of 24%. This work provides a new idea for the design and manufacture of high thermal conductivity hybrid fillers for TIMs.     

Electrical,rheological and electromagnetic interference shielding properties of thermoplastic polyurethane/carbon nanotube composites

Electrically conducting rubbery composites based on thermoplastic polyurethane (TPU) and carbon nanotubes (CNTs) were prepared through melt blending using a torque rheometer equipped with a mixing chamber. The electrical conductivity, morphology, rheological properties and electromagnetic interference shielding effectiveness (EMI SE) of the TPU/CNT composites were evaluated and also compared with those of carbon black (CB)‐filled TPU composites prepared under the same processing conditions. For both polymer systems, the insulator–conductor transition was very sharp and the electrical percolation threshold at room temperature was at CNT and CB contents of about 1.0 and 1.7 wt%, respectively. The EMI SE over the X‐band frequency range (8–12 GHz) for TPU/CNT and TPU/CB composites was investigated as a function of filler content. EMI SE and electrical conductivity increased with increasing amount of conductive filler, due to the formation of conductive pathways in the TPU matrix. TPU/CNT composites displayed higher electrical conductivity and EMI SE than TPU/CB composites with similar conductive filler content. EMI SE values found for TPU/CNT and TPU/CB composites containing 10 and 15 wt% conductive fillers, respectively, were in the range ?22 to ?20 dB, indicating that these composites are promising candidates for shielding applications. © 2013 Society of Chemical Industry     

Dynamic percolation phenomenon of poly(methyl methacrylate)/surface fluorinated carbon black composite

The electrical resistivity of polymer filled with conductive filler, such as carbon black (CB) particles, is greatly decreased by incorporating the conductive filler. This is called the percolation phenomenon and the critical CB concentration is called the percolation threshold concentration (Φ*). For CB particle–filled insulating polymer composite at lower than Φ*, the conductive CB network is constructed in the polymer matrix when the composite is maintained at a temperature higher than the glass‐transition temperature or the melting temperature of the polymer matrix. This phenomenon is called dynamic percolation and the time to reach the substantial decrease in resistivity is called percolation time (t_p). To investigate the relationship between the dynamic percolation process and the surface state of CB particles, we used three kinds of carbon black particles such as original carbon black (CB0) and fluorinated carbon black (FCB010 and FCB025)–filled poly(methyl methacrylate) (PMMA). It was observed that the dynamic percolation curves for CB0‐filled PMMA and FCB‐filled PMMA composites shifted to a shorter percolation time with increases in both the annealing temperature and the filler concentration. However, the dynamic percolation curves of FCB‐filled PMMA showed a gradually decreasing trend compared to that of CB0‐filled PMMA composites. The activation energy calculated from an Arrhenius plot of the t_p against the inverse of the annealing temperature was decreased by surface fluorine treatment. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1151–1155, 2003     

Preparation of nano‐reinforced thermal conductive natural rubber composites

Natural rubber (NR) composites highly filled with nano‐α‐alumina (nano‐α‐Al₂O₃) modified in situ by the silane coupling agent bis‐(3‐triethoxysilylpropyl)‐tetrasulfide (Si69) were prepared. The effects of various modification conditions and filler loading on the properties of the nano‐α‐Al₂O₃/NR composites were investigated. The results indicated that the preparation conditions for optimum mechanical (both static and dynamic) properties and thermal conductivity were as follows: 100 phr of nano‐α‐Al₂O₃, 6 phr of Si69, heat‐treatment time of 5 min at 150°C. Furthermore, two other types of fillers were also investigated as thermally conductive reinforcing fillers for the NR systems: (1) hybrid fillers composed of 100 phr of nano‐α‐Al₂O₃ and various amounts of the carbon black (CB) N330 and (2) nano‐γ‐Al₂O₃, the particles of which are smaller than those of nano‐α‐Al₂O₃. The hybrid fillers had better mechanical properties and dynamic performance with higher thermal conductivity, which means that it can be expected to endow the rubber products serving under dynamic conditions with much longer service life. The smaller sized nano‐γ‐Al₂O₃ particles performed better than the larger‐sized nano‐α‐Al₂O₃ particles in reinforcing NR. However, the composites filled with nano‐γ‐Al₂O₃ had lower thermal conductivity than those filled with nano‐α‐Al₂O₃ and badly deteriorated dynamic properties at loadings higher than 50 phr, both indicating that nano‐γ‐Al₂O₃ is not a good candidate for novel thermally conductive reinforcing filler. POLYM. COMPOS., 37:771–781, 2016. © 2014 Society of Plastics Engineers     

Electrical conductivity and EMI shielding effectiveness of polyurethane foam–conductive filler composites

The morphological, electrical, and thermal properties of polyurethane foam (PUF)/single conductive filler composites and PUF/hybrid conductive filler composites were investigated. For the PUF/single conductive filler composites, the PUF/nickel‐coated carbon fiber (NCCF) composite showed higher electrical conductivity and electromagnetic interference shielding effectiveness (EMI SE) than did the PUF/multiwall carbon nanotube (MWCNT) and PUF/graphite composites; therefore, NCCF is the most effective filler among those tested in this study. For the PUF/hybrid conductive fillers PUF/NCCF (3.0 php)/MWCNT (3.0 php) composites, the values of electrical conductivity and EMI SE were determined to be 0.171 S/cm and 24.7 dB (decibel), respectively, which were the highest among the fillers investigated in this study. NCCF and MWCNT were the most effective primary and secondary fillers, and they had a synergistic effect on the electrical conductivity and EMI SE of the PUF/NCCF/MWCNT composites. From the results of thermal conductivity and cell size of the PUF/conductive filler composites, it is suggested that a reduction in cell size lowers the thermal conductivity of the PUF/conductive filler composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44373.     

Preparation of polydimethylsiloxane‐coated α‐alumina fillers with cold plasma for elastomer thermal interface materials

A novel method for the organic modification of a ceramic thermal conductive filler (α‐alumina) with cold plasma was developed for the preparation of elastomer thermal interface materials with high thermal conductivities and low moduli. The α‐alumina fillers were first coated with low‐molecular‐weight polydimethylsiloxane (PDMS) by solution dispersion and then treated in argon plasma for different time. The modified α‐alumina fillers were characterized with high‐resolution transmission electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. The results revealed that a thin PDMS film with several nanometers thick was tightly coated on the surface of the alumina filler after plasma treatment, and this thin film could not be removed by 48 h of Soxhlet extraction with n‐hexane at 120°C. Plasma modification of the alumina could dramatically weaken the strength of the filler–filler networks and, thus, remarkably reduce the modulus of the alumina‐filled silicone rubber composites but did not affect the thermal conductivity of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrical conductivity and rheology of carbon‐filled liquid crystal polymer composites

One emerging market for electrically conductive resins is for bipolar plates for use in fuel cells. Adding carbon fillers to thermoplastic resins increases composite electrical conductivity and viscosity. Current technology often adds as much of a single type of carbon filler as possible to achieve the desired conductivity, while still allowing the carbon‐filled thermoplastic matrix material to be extruded and molded into a bipolar plate. In this study, varying amounts of two different types of carbon, one carbon black and one synthetic graphite, were added to Vectra A950RX liquid crystal polymer. The resulting single filler composites were then tested for electrical conductivity and rheological properties. The electrical conductivity followed that typically seen in polymer composites with a percolation threshold at 4 vol % for carbon black and at 15 vol % for synthetic graphite. Over the range of shear rates studied, the viscosity followed a shear‐thinning power law model with power‐law exponent (n ? 1) = ?0.5 for neat Vectra A950RX and (n ? 1) = ?0.7 for highly filled composite materials. Viscosity increased with increasing filler volume fraction for all shear rates. The viscosity–enhancement effect was more rapid for the composites containing carbon black when compared with those containing synthetic graphite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2680–2688, 2006     

Hybrid composites of ABS with carbonaceous fillers for electromagnetic shielding applications

This work evaluates the influence of two types of carbonaceous fillers, carbon black (CB) and carbon nanotubes (CNTs), on the electrical, electromagnetic, and rheological properties of composites based on poly(acrylonitrile‐co‐butadiene‐co‐styrene) (ABS) prepared by the melt mixing. Electrical conductivity, electromagnetic shielding efficiency (EMI SE) in the X‐band frequency range (8–12.4 GHz), and melt flow index (MFI) results showed that ABS/CNT composites exhibit higher electrical conductivity and EMI SE, but lower MFI when compared to ABS/CB composites. The electrical conductivity of the binary composites showed an increase of around 16 orders of magnitude, when compared to neat ABS, for both fillers. Binary composites with 5 and 15 wt % of filler showed an EMI SE of, respectively, ?44 and ?83 dB for ABS/CNT, and ?9 and ?34 dB for ABS/CB. MFI for binary composites with 5 wt % were 15.45 and 0.55 g/10 min for CB and CNT, respectively. Hybrid composites ABS/CNT.CB with 3 wt % total filler and fraction 50:50 and 75:25 showed good correlation between EMI SE and MFI. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46546.     

聚合物基导热复合材料的性能及导热机理

采用不同品种、粒径的导热填料和基体树脂,以熔融共混方法制备聚合物/填料体系导热功能复合材料。研究了复合材料热导率λ和体积电阻率ρ_v随不同填料、粒径等因素的变化规律及其内在原因。不同填充体系的热导率均随填料粒径的减小而降低,而电导率则相反;复合体系热导率随填料含量的增加始终呈逐步上升趋势,未表现出电导率那样的急剧变化。研究表明：复合体系热导率和电导率变化的差异主要是由于二者具有不同的传导机理;复合材料热导率的变化规律可以用热弹性复合增强机制进行合理解释。     

Effects of filler geometry on internal structure and physical properties of polycarbonate composites prepared with various carbon fillers

BACKGROUND: The effects of filler geometry are important for understanding the internal structure and physical properties of polymer composites. To investigate the effects of filler geometry on electrical conductivity as well as morphological and rheological properties, three types of polycarbonate (PC) composites were prepared by melt compounding with a twin‐screw extruder. RESULTS: The electrical conductivity of PC/carbon black (CB) and PC/graphite (carbon) nanofibre (CNF) composites did not show a percolation threshold through the entire filler loading ranges. However, PC‐blend‐carbon nanotube (CNT) composites showed a percolation electrical threshold for a filler loading of 1.0 to 3.0 wt% and their maximum electrical conductivity approached 10^?3 S m^?1. PC‐blend‐CB and PC‐blend‐CNF composites showed Newtonian behaviour like pure PC matrix, but PC‐blend‐CNT composites showed yield stress as well as increased storage modulus and strong shear thinning behaviour at low angular frequency and shear rate due to strong interactions generated between CNT–CNT particles as well as PC molecules and CNT particles on the nanometre scale. CONCLUSIONS: The electrical conductivity of the PC composites with different carbon constituents was well explained by the continuous network structure formed between filler particles. The network structure was confirmed by the good dispersion of fillers as well as by the yield stress and solid‐like behaviour observed in steady and dynamic shear flows. Copyright © 2009 Society of Chemical Industry     

Piezoresistive behavior of graphene nanoplatelets/carbon black/silicone rubber nanocomposite

Silicon rubber (SR) filled with carbon black (CB) and carbon black (CB)/graphene nanoplatelets (GNPs) hybrid fillers are synthesized via a liquid mixing method. The effects of filler type on the electrical properties and piezoresistive properties (near the region of the percolation) of the conductive SR composites are studied. It is suggested that the conductivity of the composite filled with CB/GNPs hybrid fillers in the mass ratio of 2 : 4 is much higher than that in other ratio. Percolation threshold for CB/GNPs/SR is found to be 0.18 volume fractions lower than CB/SR. Moreover, force rang and linearity of GNPs/CB/SR is higher than CB alone filling system. And the repeatability of the GNPs/CB/SR composites is better than CB/SR. Not repetitive index () of them is 0.1 and 0.18, respectively. The results suggest that the GNPs/CB/SR composites provide a new route toward fabrication of flexible piezoresistive sensors with high performance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39778.     

A new equation for predicting electrical conductivity of carbon‐filled polymer composites used for bipolar plates of fuel cells

In this article, a statistical‐thermodynamic formula based on a new approach has been developed to predict electrical conductivity of carbon‐filled composites used for bipolar plate of proton exchange membrane fuel cell. In this model, based on percolation threshold phenomenon, it is assumed that the relationship between electrical conductivity of composite and filler volume fraction follows a sigmoidal equation. Afterwards, the four effective factors on composite conductivity including filler electrical conductivity, filler aspect ratio, wettability, as well as interface contact resistance are replaced upon constant parameters of sigmoidal function. In order to test the model, some single‐filler composites have been manufactured by using the phenolic resin as binder and graphite (G), expanded graphite (EG), and carbon fiber (CF) as fillers. The fitting quality is measured by R‐square, adjusted R‐square, SSE, and RMSE parameters. The results showed that there is a noteworthy agreement between the model and the experimental data. Compared to the other models, this model can be used for more types of fillers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improvement in physical and electrical properties of poly(vinyl alcohol) hydrogel conductive polymer composites

With an aim to develop anti‐electrostatic discharge materials based on biodegradable polymers, poly(vinyl alcohol) films composited with two different conductive fillers (carbon black and aluminium) at various fillers contents (20?60%wt), were manufactured using solvent‐casting technique. The mechanical properties of such the films were investigated through tensile stress‐strain tests. Wettability and morphology of the composite films were performed by water contact angle measurement and SEM, respectively. Young's modulus of the composite films can be increased with the addition of conductive fillers. The surface of the composite films showed non‐homogeneous appearance, in which the phase boundary within the composites was clearly observed and the conductive fillers formed aggregation structure at high filler concentration. In addition, the composite films exhibited better hydrophobicity when higher conductive filler content was added. TGA results suggested that both carbon black and aluminum have proven their efficiency to enhance thermal stability of poly(vinyl alcohol). Investigation of cross‐cut adhesion performance of the prepared composite films revealed that carbon black‐filled composites exhibited excellent adhesion strength. The effect of conductive filler content on surface resistivity of the composite films was also examined. The experimental results confirmed that both the fillers used in this study can improve the electrical conductivity of poly(vinyl alcohol) hydrogel. The surface resistivity of the composite films was reduced by several orders of magnitude when the filler of its critical concentration was applied. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42234.     

Cold plasma modification of boron nitride fillers and its effect on the thermal conductivity of silicone rubber/boron nitride composites

Hexagonal boron nitride (h‐BN) fillers were first coated with low‐molecular‐weight polydimethylsiloxane (PDMS) by solution dispersion and then treated in argon plasma for different times. The modified h‐BN fillers were characterized by high‐resolution transmission electron microscopy, X‐ray photoelectron spectroscopy, and contact angle analysis. The results revealed that a thin PDMS film several nanometers thick was tightly coated on the surface of the h‐BN filler after plasma treatment, and this thin film could not be removed by 48 h Soxhlet extraction with n‐hexane at 120°C. Furthermore, the effect of plasma modification on the h‐BN filled silicone rubber composites was investigated. The results indicated that the plasma modification improved the interfacial interaction between h‐BN and the matrix, but hardly affected the distribution state of the h‐BN in the composites. The composites filled with the modified h‐BN exhibit significantly higher thermal conductivity than the composites filled with untreated h‐BN. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

PE-HD/CNTs/CB复合材料的导电行为研究

用溶液超声分散法制备了高密度聚乙烯/碳纳米管/炭黑(PE-HD/CNTs/cB)导电复合材料,研究了CNTs与CB的比例以及两者的总含量对复合材料导电行为的影响.结果表明,CNTs与CB以不同比例混合的试样其渗流阈值较PE-HD/CNTs高,比PE-HD/CB的低,CNTs与CB在材料内部可能形成了共同的导电网络;当其...     

Kinetic and thermodynamic control in conductive PP/PMMA/EAA carbon black composites

Multiphase polymer blends provide unique morphologies to reduce the percolation concentration and increase conductivity of carbon‐based polymer composites via selective distribution of the conductive filler. In this work, the kinetic and thermodynamic effects on a series of multiphase conductive polymer composites were investigated. The electrical conductivity of carbon black (CB)‐filled conductive polymer blend composites comprising polypropylene, poly(methyl methacrylate), and ethylene–acrylic acid were determined as a function of compounding sequence and annealing time. Kinetic and thermodynamic parameters were found to influence the conductivity. Phase morphology and conductivity at short annealing times were influenced by the compounding sequence where the CB was added after being premixed with one of the polymer components or directly added to the three‐component polymer melt. However, they were thermodynamically driven at longer annealing times; the resistivity was found to decrease by a statistically significant amount to similar levels for all the composite systems with increasing annealing time. The increase in conductivity at longer annealing times was determined to be the result of changes in the phase morphology from sea‐island, dispersed microstructure to a tri‐continuous morphology rather than change in localization of CB, given that the CB was found to be entirely located in the EAA phase even at short annealing times (and independent of compounding sequence), where the conductivity was not measurable. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42134.     

Multiple percolation in a carbon‐filled polymer composites via foaming

This article describes an investigation into the effects of foaming on the electrical conductivity for a carbon‐filled cyclic olefin copolymer (COC) composite incorporating both chopped carbon fibers (cCF) and carbon black (CB). Foamed and solid samples were injection molded and then analyzed for cell size, fiber length, fiber orientation, and electrical conductivity. Foamed samples exhibited higher electrical conductivity in the through‐plane direction for materials containing only CB or composites containing both filler types, and reduced electrical conductivity in the cCF‐filled composites. The increased electrical property gained by foaming was attributed to multiple percolation with CB aggregates forming more effective conductive clusters and networks in the continuous polymer phase during growth of the gas domains. A mechanism for the phenomenon was proposed based on these experimental observations. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of nanoparticles on the performance of thermally conductive epoxy adhesives

Microsized or nanosized α‐alumina (Al₂O₃) and boron nitride (BN) were effectively treated by silanes or diisocyanate, and then filled into the epoxy to prepare thermally conductive adhesives. The effects of surface modification and particle size on the performance of thermally conductive epoxy adhesives were investigated. It was revealed that epoxy adhesives filled with nanosized particles performed higher thermal conductivity, electrical insulation, and mechanical strength than those filled with microsized ones. It was also indicated that surface modification of the particles was beneficial for improving thermal conductivity of the epoxy composites, which was due to the decrease of thermal contact resistance of the filler‐matrix through the improvement of the interface between filler and matrix by surface treatment. A synergic effect was found when epoxy adhesives were filled with combination of Al₂O₃ nanoparticles and microsized BN platelets, that is, the thermal conductivity was higher than that of any sole particles filled epoxy composites at a constant loading content. The heat conductive mechanism was proposed that conductive networks easily formed among nano‐Al₂O₃ particles and micro‐BN platelets and the thermal resistance decreased due to the contact between the nano‐Al₂O₃ and BN, which resulted in improving the thermal conductivity. POLYM. ENG. SCI., 50:1809–1819, 2010. © 2010 Society of Plastics Engineers     

Dispersion of fillers and the electrical conductivity of polymer blends filled with carbon black

Dispersion state of carbon black(CB) was studied in polymer blends which are incompatible with each other. It was found that CB distributes unevenly in each component of the polymer blend. There are two types of distribution. (1) One is almost predominantly distributed in one phase of the blend matrix, and in this phase fillers are relatively homogeneously distributed in the same manner as a single polymer composite. (2) In the second, the filler distribution concentrates at interface of two polymers. As long as the viscosities of two polymers are comparable, interfacial energy is the main factor determining uneven distribution of fillers in polymer blend matrices. This heterogeneous dispersion of conductive fillers has much effect on the electrical conductivity of CB filled polymer blends. The electrical conductivity of CB filled polymer blends is determined by two factors. One is concentration of CB in the filler rich phase and the other is phase continuity of this phase. These double percolations affect conductivity of conductive particle filled polymer blends.     

High electrical conductivity of nylon 6 composites obtained with hybrid multiwalled carbon nanotube/carbon fiber fillers

The synergetic effect of multiwalled carbon nanotubes (MWNTs) and carbon fibers (CFs) in enhancing the electrical conductivity of nylon 6 (PA6) composites was investigated. To improve the compatibility between the fillers and the PA6 resin, we grafted γ‐aminopropyltriethoxy silane (KH‐550) onto the MWNTs and CFs after carboxyl groups were generated on their surface by chemical oxidation with nitric acid. Fourier transform infrared spectroscopy and thermogravimetric analysis proved that the KH‐550 molecules were successfully grafted onto the surface of the MWNTs and CFs. Scanning electron microscopy and optical microscopy showed that the obtained modified fillers reduced the aggregation of fillers and resulted in better dispersion and interfacial compatibility. We found that the electrical percolation threshold of the MWNT/PA6 and CF/PA6 composites occurred when the volume fraction of the fillers were 4 and 5%, respectively. The MWNT/CF hybrid‐filler system exhibited a remarkable synergetic effect on the electrically conductive networks. The MWNT/7% CF hybrid‐filler system appeared to show a second percolation when the MWNT volume fraction was above 4% and a volume resistivity reduction of two orders of magnitude compared with the MWNT/PA6 system. The mechanical properties of different types of PA6 composites with variation in the filler volume content were also studied. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40923.