Epoxy nanocomposites with high thermal conductivity and low loss factor: Realize 3D thermal conductivity network at low content through core-shell structure and micro-nano technology

Dielectric polymers with high thermal conductivity are very promising in the fields of aerospace and electronic device packaging. However, composites with excellent dielectric properties usually have low thermal conductivity. It is usually to fill the polymer with thermal conductivity particles to improve the thermal conductivity, but the high content of filler often reduces the mechanical properties of the polymer. In this paper, the traditional insulating polymer epoxy resin was used as the matrix, by covering the surface of silicon carbide with graphene to form a core-shell structure and co-filled with nano diamonds to achieve the preparation of high-performance epoxy resin at low content. The results showed that at the filling content of 30 wt%, the thermal conductivity of epoxy nanocomposites showed a dramatic thermal conductivity enhancement of 1263%, the energy storage modulus increased by 1.1 GPa, and the dielectric loss remained unchanged at 50 Hz. The advantages of the composite are the structural design and surface modification of the filler, which not only take advantage of its inherent advantages, but also improve the interface area with the epoxy matrix. The composite materials with excellent properties are expected to provide theoretical guidance for the application of high thermal conductivity dielectric materials.     

Effect of arrangement of nano and micro barium titanate (BaTiO3) particles on the enhanced dielectric constant of high‐density polyethylene (HDPE)/BaTiO3

The aim of this study is to improve the dielectric and mechanical properties of HDPE/BaTiO₃ composites by binary BaTiO₃ particles, when the volume fraction of BaTiO₃ is constant. In this study, it was found that the pack density of binary BaTiO₃ particles in HDPE/BaTiO₃ composite relies on particle ratio and volume fraction of small particles. It is found that the addition of 50 vol % 1600 nm BaTiO₃ particles can boost the dielectric constant of HDPE control from 2 to 30 (14 times higher) at 40 Hz and 19 (8.5 times higher) at 40 MHz, respectively. When the particle ratio was 4, the substitution of 10 vol % 1600 nm BaTiO₃ particles by 10 vol % 400 nm BaTiO₃ particles can further enhance the dielectric constant of HDPE/L‐BT (10/10) from 30 to 50 (67% increase) at 40 Hz and from 19 to 42 (121% increase) at 40 MHz, respectively, without greatly influencing the volume resistivity of HDPE composites. In addition, the thermal conductivity of HDPE with binary BaTiO₃ particles were all above 2.0 W/(m•K). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1101–1108     

Enhanced dielectric performance of TPU composites filled with Graphene@poly(dopamine)-Ag core-shell nanoplatelets as fillers

A new type of graphene@poly(dopamine)-Ag (Gns@PDA-Ag) core-shell nanoplatelets was designed to improve the dielectric properties of thermoplastic polyurethane (TPU) composites. The microstructure, dielectric performances and the effects of Ag nanoparticles’ content on the dielectric properties of composites were investigated. Results showed that the addition of Gns@PDA-Ag nanoplatelets could effectively improve the dielectric constant of the composite. When tested at low frequency (below 100 Hz), the highest dielectric constant of the TPU/Gns@PDA-0.78Ag (3 wt%) composite was 118.82, which was 14 times higher than that of pure TPU (8.39). This increase in dielectric constant should be attributed to the strong polarization effect of conductive graphene nanoflakes (Gns) and Ag nanoparticles to TPU molecules. The PDA shell could prevent direct contact between Gns and Ag nanoparticles, limit the formation of conductive pathways, which kept the dielectric loss of the composites at a low level and maintained the breakdown strength in a stable state. Compared with pure TPU (0.29), the minimum dielectric loss of composites was only 0.36. Moreover, after Gns@PDA-Ag nanoplatelets with higher Ag content were doped into TPU, the composite showed a higher dielectric constant, and due to the existence of the Coulomb blocking effect, the dielectric loss did not increase significantly. The scalability and simplicity of the described method will provide a promising route to polymer composites for highspeed integrated circuits and energy storage applications.     

Thermal conductivity epoxy resin composites filled with boron nitride

Boron nitride (BN) micro particles modified by silane coupling agent, γ‐aminopropyl triethoxy silane (KH550), are employed to prepare BN/epoxy resin (EP) thermal conductivity composites. The thermal conductivity coefficient of the composites with 60% mass fraction of modified BN is 1.052 W/mK, five times higher than that of native EP (0.202 W/mK). The mechanical properties of the composites are optimal with 10 wt% BN. The thermal decomposition temperature, dielectric constant, and dielectric loss increase with the addition of BN. For a given BN loading, the surface modification of BN by KH550 exhibits a positive effect on the thermal conductivity and mechanical properties of the BN/EP composites. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermodynamic properties of liquid Au-Cu-Sn alloys determined from electromotive force measurements

A thermally conductive linear low-density polyethylene (LLDPE) composite with aluminum nitride (AlN) as filler was prepared in a heat press molding. Differential scanning calorimeter results indicated that the AlN filler decreases the degree of crystallinity of LLDPE, and has no obvious influence on the melting temperature of LLDPE. Experimental results demonstrated that the LLDPE composites display a high thermal conductivity of 1.25 W/m K and improved thermal stability at 70 wt% AlN content as compared to pure LLDPE. The dielectric constant and dissipation factor increased with AlN content, however, they still remained at relatively low levels, i.e., <5 in wider frequency range from 10 to 10⁶ Hz. The surface treatment of AlN particles had a beneficial effect on improving the thermal conductivity and dielectric constant, whereas, the dissipation factor was less affected. Additionally, the obtained AlN/LLDPE composites have possessed rather low dielectric constant and high electrical insulation, which is suitable for substrate and packaging materials.     

聚乙二醇/氮化硼复合材料相变导热性能及其结晶行为

本文采用熔融共混浇筑的方法制备了聚乙二醇/氮化硼(PEG/BN)相变复合材料,并研究了不同尺度片状BN对相变复合材料导热性能和结晶行为的影响。 通过扫描电子显微镜(SEM)、热常数分析仪、红外热成像分析仪和差示扫描量热仪(DSC)研究了相变复合材料的微观形貌、导热系数和相变过程,并利用莫志深法对DSC结果进行了非等温结晶动力学分析。 结果表明,较大片状直径(50 μm)的BN可以更有效地提高聚乙二醇的导热系数,当BN填料质量分数为40%时,相变复合材料的导热系数可达到5.04 W/(m·K)。 在快速降温条件下,片径为50 μm的BN填料可以缩短PEG的半结晶时间,提高结晶速率,使相变复合材料具有较大的相变焓。     

Enhanced thermal conductivity and mechanical properties of polymeric composites through formation of covalent bonds between boron nitride and rubber chains

Hexagonal boron nitride (BN) platelets, also known as white graphite, are often used to improve the thermal conductivities of polymeric matrices. Due to the poor interfacial compatibility between BN platelets and polymeric matrices, in this study, polyrhodanine (PRd) was used to modify BN platelets and prepared functionalized BN-PRd platelets, thereby enhancing the interfacial interaction between the thermal conductive filler and polymeric matrix. Then, BN-PRd platelets were dispersed into the nitrile butadiene rubber (NBR) matrix to yield high thermally conductive composites. The presence of N? C═S groups in PRd allowed the combination of PRd and NBR chains containing stable covalent bonds via vulcanization reaction. The thermal conductivity of the as-prepared 30 vol% BN-PRd/NBR composite reached 0.40 W/mK, representing an increment of 135% over pure NBR (0.17 W/mK). In addition, the largest tensile strength of NBR composite containing 30 vol% BN-PRd platelets was 880% times of pure NBR. The 30 vol% BN-PRd/NBR composite also displayed a relatively high dielectric constant (9.35 at 100 Hz) and a low dielectric loss tangent value (0.07 at 100 Hz), indicating their usefulness as dielectric flexible materials of microelectronics. In sum, the simplicity and good efficiency of formation of covalent bonds between boron nitride and rubber chains look very promising for large-scale industrial production of high thermally conductive composites.     

Effect of nano/micro‐mixed ceramic fillers on the dielectric and thermal properties of epoxy polymer composites

Nano/micro ceramic‐filled epoxy composite materials have been processed with various percentage additions of SiO₂, Al₂O₃ ceramic fillers as reinforcements selected from the nano and micro origin sources. Different types of filler combinations, viz. only nano, only micro, nano/micro, and micro/micro particles, were designed to investigate their influence on the thermal expansion, thermal conductivity, and dielectric properties of epoxy polymers. Thermal expansion studies were conducted using thermomechanical analysis that revealed a two‐step expansion pattern consecutively before and after vitreous transition temperatures. The presence of micro fillers have shown vitreous transition temperature in the range 70–80°C compared with that of nano structured composites in which the same was observed as ~90°C. Similarly, the bulk thermal conductivity is found to increase with increasing percentage of micron‐size Al₂O₃. It was established that the addition of micro fillers lead to epoxy composite materials that exhibited lower thermal expansion and higher thermal conductivity compared with nano fillers. Moreover, nano fillers have a significantly decisive role in having low bulk dielectric permittivity. In this study, epoxy composites with a thermal expansion coefficient of 2.5 × 10^?5/K, thermal conductivity of 1.18 W/m · K and dielectric permittivity in the range 4–5 at 1 kHz have been obtained. The study confirms that although the micro fillers seem to exhibit good thermal conductivity and low expansion coefficient, the nano‐size ceramic fillers are candidate as cofillers for low dielectric permittivity. However, a suitable proportion of nano/micro‐mixed fillers is necessary for achieving epoxy composites with promising thermal conductivity, controlled coefficient of thermal expansion and dielectric permittivity. Copyright © 2013 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.     

Silane surface modification of boron nitride for high thermal conductivity with polyphenylene sulfide via melt mixing method

Polyphenylene sulfide (PPS) is a promising engineering polymer, which is used for various industrial applications. In this study, we developed a highly thermally conductive PPS composite containing boron nitride (BN) as a thermally conductive ceramic filler. (3‐Aminopropyl) triethoxysilane was doped onto the surface of hydroxyl‐functionalized BN using a simple sol–gel process. The modified BN particles were embedded in a PPS matrix via a melt mixing process using a twin extruder to form BN‐Si composites. The maximum thermal conductivity 3.09 W/m·K was exhibited by the surface‐modified BN‐Si containing 60 wt%. This value was 116% higher than the thermal conductivities of the pristine BN and PPS matrix, respectively. The surface‐treated composites also showed an improved storage modulus because of an improvement in the interfacial adhesion and interaction between the BN filler and the PPS matrix. Copyright © 2017 John Wiley & Sons, Ltd.     

A conductive polymer composite derived from polyurethane and cathodically exfoliated graphene

Composite electrodes represent an important class of electromaterials, with enhanced functional properties tailored for targeted applications. Introduction of graphene as a conductive nanofiller into the thermoplastic polyurethane (PU) provides electrodes with interesting properties. In this study, a highly conductive cathodically exfoliated graphene (CEG) of ～2–8 μm lateral size was employed to prepare CEG-PU composites. The use of this larger graphene sheet requires loading of at least 20% w/w graphene to promote contact between the sheets, hence the conductivity. The CEG-PU composite electrodes were tested to determine their electrochemical capacitance and it was found that the 40% (w/w) CEG-PU composite shows areal capacitance, energy density, and power density of 2.51 mF/cm², 1.56 μW/h/cm², and 0.48 mW/cm², respectively, at a current density of 0.2 mA/cm² and an operating voltage of 1.0 V. In summary, the CEG-PU composite electrodes have excellent conductivity, chemical/mechanical properties, and capacitive performance.     

Barium Titanate-reinforced Acrylonitrile-Butadiene Rubber: Synergy Effect of Carbon-based Secondary Filler

Acrylonitrile rubber(NBR) composites filled with barium titanate(BT) were prepared using an internal mixer and a two-roll mill. Also, a secondary filler, namely carbon nanotubes(CNT), was added in order to find a potential synergistic blend ratio of BT and CNT. The cure characteristics, tensile and dielectric properties(dielectric constant and dielectric loss) of the composites were determined. It was found that NBR/BT composites with CNT secondary filler, at a proper BT:CNT ratio, exhibited shorter scorch time(t_(s1)) and cure time(t_(c90)) together with superior tensile properties and reinforcement efficiency, relative to the one with only the primary filler. In addition, the NBR/BT-CNT composite with 80 phr BT and 1-2 phr CNT had dielectric constant of 100-500, dielectric loss of 12-100 and electrical conductivity below 10~(-4) S/m together with high thermal stability. Thus, with a proper BT:CNT mix and filler loading, we can produce mechanically superior rubber composites that are easy to process and low-cost, for flexible dielectric materials application.     

An interlayer model for the complex dielectric constant of composites: An extension to ellipsoidally shaped particles

A theoretical interlayer model (IL) has been developed for the complex dielectric constant of a composite in which the filler particles are enveloped with a layer of interfacial material. The filler particles can be of any ellipsoidal shape. Special cases such as spherical particles, needles, and fabrics are shown to be covered by the model.The analytical formula as derived describes the composite properties as a function of the volume fractions of the filler, the layer and the matrix material, their dielectric properties and the filler particle shape factor.In the case of a two-phase composite the model reduces to the well-known Sillars relation for the complex dielectric constant of composite which contains filler particles of ellipsoidal shape.The effect of an interfacial layer on the static dielectric constant of the composite is discussed using the model. Next, the special case of a conductive interfacial layer in an otherwise non-conductive composite is discussed; it illustrates the effect of interfacially adsorbed water on the electrical properties of composites. Some practical examples are shown.     

Thermal conductivity of polyurethane composites containing nanometer- and micrometer-sized silver particles

Polyurethane composites containing spherical and flake-shaped silver fillers of micrometer and nanometer sizes were prepared by reacting suspensions of the silver filler in tetraethylene glycol with Desmodur^? HL BA. Both the thermal conductivity and the stability of the silver composites are increased in comparison with a reference polyurethane sample without filler. Unexpectedly, the largest increases in thermal conductivity and stability are observed for the spherical silver particles of micrometer size but not for the silver nanoparticles, which is reasoned with larger aggregates of silver particles and a higher degree of crystallinity in the sample containing micrometer-sized silver particles.     

Electrical properties of carbon black‐filled polymer composites

This work deals with the dielectric properties of conductive composite materials, which consist of thermoplastic polypropylene (PP) matrix filled with carbon black (CB). The CB concentration was systematically varied in a wide range. Our main interest is focused on the investigation of electrical conductivity mechanism and related percolation phenomena in these materials. To study the electrical and dielectric properties of composites we used broadband ac dielectric relaxation spectroscopy (DRS) techniques in a wide temperature range. By measurements of complex dielectric permittivity, ϵ*, the dependence of ac conductivity, σ_ac, and dc conductivity, σ_dc, on the frequency, the temperature and the concentration of the conductive filler was investigated. The behavior of this system is described by means of percolation theory. The percolation threshold, P_C, value was calculated to be 6.2 wt.% CB. Both, dielectric constant and dc conductivity follow power‐law behavior, yielding values for the critical exponents, which are in good agreement with the theoretical ones. Indications for tunneling effect in the charge carriers transport through the composites are presented. The temperature dependence of dc conductivity gives evidence for the presence of positive temperature coefficient (PTC) effect.     

Role,effect, and influences of micro and nano‐fillers on various properties of polymer matrix composites for microelectronics: A review

Ever since the discovery of polymer composites, its potential has been anticipated for numerous applications in various fields such as microelectronics, automobiles, and industrial applications. In this paper, we review filler reinforced polymer composites for its enormous potential in microelectronic applications. The interface and compatibility between matrix and filler have a significant role in property alteration of a polymer nanocomposites. Ceramic reinforced polymeric nanocomposites are promising candidate dielectric materials for several micro‐ and nano‐electronic devices. Because of its synergistic effect like high thermal conductivity, low thermal expansion, and dielectric constant of ceramic fillers with the polymer matrix, the resultant nanocomposites have high dielectric breakdown strength. The thermal and dielectric properties are discussed in the view of filler alignment techniques and its effect on the composites. Furthermore, the effect of various surface modified filler materials in polymer matrix, concepts of network forming using filler, and benefits of filler alignment are also discussed in this work. As a whole, this review article addresses the overall view to novice researchers on various properties such as thermal and dielectric properties of polymer matrix composites and direction for future research to be carried out.     

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.     

Enhancement of thermal conductivity and tensile strength of liquid silicone rubber by three-dimensional alumina network

ABSTRACT

Rapidly increasing demands for higher integration density and stability of electronic devices embrace higher requirements for thermally conductive silicone rubber, which is promisingly used in ultra-thin components. In this work, alumina whiskers (AWs) and alumina flakes (AFs) are used to modify liquid silicone rubber (LSR) by fabricating binary (AFs/LSR) or ternary (AWs/AFs/LSR) composites. The thermal conductivity and mechanical strength of the binary and ternary composites were investigated. Thermal conductivity of the binary AFs/LSR composite (25AFs/LSR) was 0.1990 W m^?1 K^?1, while the thermal conductivity of the ternary AFs/AWs/LSR composite (20AFs/5AWs/LSR) was 0.2655 W m^?1 K^?1. Furthermore, the tensile strength of the ternary AWs/AFs/LSR composites increased by 180.9% as compared with the binary system, increased to 7.81 MPa from 2.78 MPa due to the introduction of 1 wt% AWs. As a reason, a significant synergistic effect of AWs and AFs in the enhancement of both thermal and mechanical properties of the LSR was proved. Furthermore, the dielectric property measurements demonstrated that the ternary composites exhibited a lower dielectric constant and dielectric loss, indicating that the AWs/AFs/LSR composites were qualified to be applied in the field of electronic devices.     

Rheological properties of wood polymer composites at high shear rates

This paper presents the rheological properties of wood-polymer composites (WPC) with a polypropylene (PP) matrix in the corrected shear rate range from approx. 20 s⁻¹ to 150 000 s⁻¹. Tests were conducted using a capillary rheometer and a rheological head of the author's construction, for which the working element is a thermoplastic injection moulding machine. The constructed tool was found to be very useful, especially for the determination of the processing characteristics of WPC composites containing a large particle-size filler. It was observed that the rheological properties of wood-polymer composites in the shear rate range of up to several thousand s⁻¹ significantly depended on the filler content of the polymer matrix; at the same time, at higher shear rate, a clear decrease in the effect of the wood filler content on the viscosity of the composites and on the flow behaviour, as described by the power law, took place.