Thermal properties and moisture absorption of nanofillers‐filled epoxy composite thin film for electronic application

This current study aimed to enhance the thermal conductivity of thin film composites without compromising other polymer qualities. The effect of adding high thermal conductivity nanoparticles on the thermal properties and moisture absorption of thin film epoxy composites was investigated. Three types of fillers in nanosize with high thermal conductivity properties, boron nitride (BN), synthetic diamond (SD), and silicon nitride (Si₃N₄) were studied. SN was later used as an abbreviation for Si₃N₄. The contents of fillers varied between 0 and 2 vol.%. An epoxy nanocomposite solution filled with high thermal conductivity fillers was spun at 1500–2000 rpm to produce thin film 40–60 µm thick. The effects of the fillers on thermal properties and moisture absorption were studied. The addition of 2 vol.% SD produced the largest improvement with 78% increment in thermal conductivity compared with the unfilled epoxy. SD‐filled epoxy thin film also showed good thermal stability with the lowest coefficients of thermal expansion, 19 and 124 ppm, before and after T_g, respectively, which are much lower compared with SN‐filled and BN‐filled epoxy thin film composites. However the SD‐filled epoxy film has its drawback as it absorbs more moisture compared with BN‐filled and SN‐filled epoxy film. Copyright © 2012 John Wiley & Sons, Ltd.     

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。     

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.     

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.     

Effect of AlN content on the performance of brominated epoxy resin for printed circuit board substrate

Polymer matrix composites, based on brominated epoxy, a type of material widely used in printed circuit boards (PCBs), as matrix and AlN particle as filler were prepared. The influences of AlN content on the mechanical, thermal, and electrical properties of the composites were investigated by uniaxial tensile test, TMA, thermal conductivity measurement, DMA, and dielectric properties measurement. It was found that the properties of composites monotonically varied with AlN content except that maximum tensile strength and strain of composites corresponded to a filler content of 10 wt %. The results of DMA also showed the AlN reinforcement was more pronounced above T_g, and the peak area of tan δ versus T curves decreased with AlN content, which implied the damping capacity of the composite gradually decreased. The increase in T_g and decrease in damping were probably due to strong interaction between the AlN and epoxy matrix inhibiting the mobility of the epoxy chain. In addition, different theoretical models reported in the literature were used to predict the E, CTE, k, and D_k, and compared with the experimental data. Finally, suitable models were recommended in the present materials system. For the significant improvement of performance of epoxy, we can conclude that these composite materials may be promising for PCB substrate. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1662–1674, 2007     

Thermal conductivity behavior of SiC–Nylon 6,6 and hBN–Nylon 6,6 composites

A study was performed to determine the effect of the content and orientation of fillers on the thermal conductivity of a polymeric composite packed with hexagonal boron nitride (hBN) and silicon carbide (SiC) fillers. The thermal conductivity behavior of SiC–Nylon 6,6 and hBN–Nylon 6,6 composites was more dependent on the orientation and shape of the filler than on its thermal conductivity. The thermal conductivity of SiC–Nylon 6,6 composites with 59 % (v/v) isotropic SiC fillers increased from 0.25 to 3.83 W/m K. That of hBN–Nylon 6,6 composites with 62 % (v/v) anisotropic hBN fillers increased from 0.25 to 2.16 W/m K in the perpendicular direction whereas in the parallel direction it increased rapidly to 8.55 W/m K .     

Study on insulating thermal conductive BN/HDPE composites

Thermal conductivity of boron nitride (BN) reinforced high density polyethylene (HDPE) composites was investigated under a special dispersion state of BN particles in HDPE, i.e., BN particles surrounding HDPE matrix particles. The results indicated that the special dispersion of BN in matrix gives the composites high thermal conductivity at low filler content; moreover, the smaller BN particles can more easily form conductive chains of filler compared to the larger filler particles. Examining the dependence of electrical insulation and mechanical properties of the composites on BN content demonstrated that the reinforced composites containing 30% by volume of filler has good electrical insulation and mechanical properties.     

Heat Capacity Measurement of Boron Nitride-filled Polybenzoxazine: The composite structure-insensitive property

Specific heat capacity of boron nitride-filled polybenzoxazine has been investigated by using temperature-modulated differential scanning calorimetry, TMDSC, to study that it is a composite structure-insensitive property, i.e. independent of the degree of filler network formation. Many aspects of boron nitride filler such as particle size, particle surface area, particle shape, and filler loading are investigated. At the same filler loading, we observe insignificant change in composite specific heat capacity due to the effect of particle size, particle surface area, and particle shape. Filler loading is found to be the only aspect of filler that can change the specific heat capacity of this filled system. A linear relationship between the composite heat capacities and filler loading is observed and can be predicted by the rule of mixture with an error within ±1%. Within the temperature range betwen 0 and 80°C, the temperature dependent heat capacity of this composite can simply be expressed in the form of a linear equation: C _p=A+BT.This revised version was published online in November 2005 with corrections to the Cover Date.     

Enhanced directional thermal conductivity of polylactic acid/polybutylene adipate terephthalate ternary composite filled with oriented and surface treated boron nitride

A combination of solution casting and melt extrusion technique was used to fabricate Boron nitride (BN)-filled Polylactic acid (PLA)/polybutylene adipate terephthalate (PBAT) blend composites. The BN particles were surface treated with a silane coupling agent and functionalization was confirmed via spectroscopic analysis. Field emission scanning electron microscopy confirmed that the BN surface treatment improved the particle adhesion with the polymer matrices and acted as a compatibilizer for the polymers. Moreover, changes in the particle orientation in the blend composite yielded improved thermal conductivity in different directions. The inclusion of the treated BN particles enhanced the in-plane (~1.1 W m⁻¹K⁻¹) and through-plane (~0.8 W m⁻¹K⁻¹) thermal conductivity of the composites as compared to the neat PLA. In addition, the storage modulus of the composite become more than 3 GPa that is twice that of the PLA/PBAT blend with a reasonable tensile property. In general, compared with the PLA/PBAT blend, the blend composites exhibited superior thermal and mechanical properties.     

Very high thermal conductivity obtained by boron nitride-filled polybenzoxazine

A thermal conductivity of 32.5 W/mK is achieved for a boron nitride-filled polybenzoxazine at its maximum filler loading of 78.5% by volume (88% by weight). The extraordinarily high conductivity value results from outstanding properties of the polybenzoxazine matrix and the boron nitride filler. The bisphenol-A–methylamine-based polybenzoxazine possesses very low A-stage viscosity which aids in filler wetting and mixing. The filler particles with an average size of ca. 225 μm are large aggregates of boron nitride flake-like crystals. It has bimodal particle size distribution which assists in increasing the particle packing density. This filler–matrix system provides a highly thermally conductive composite due to the capability of forming conductive networks with low thermal resistance along the conductive paths. The SEM picture of the composite fracture surface reveals good interfacial adhesion between the boron nitride filler and polybenzoxazine matrix. Water absorption of the filled systems at 24 h is <0.1% and decreases with increasing filler content.     

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.     

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.     

Enhancement of the thermal and mechanical properties of a surface‐modified boron nitride–polyurethane composite

Thermoplastic polyurethane (PU) elastomer, prepared from poly(tetramethylene glycol) and methyl diphenyl diisocyanate, was blended with boron nitride (BN) to fabricate a thermally conductive interface material. BN treated by a silane coupling agent (BN―NH₂) and PU‐grafted BN were prepared to fabricate a composite that has better thermal conductivity and mechanical strength. The surface‐modified filler showed enhanced dispersibility and affinity because of the surface treatment with functional groups that affected the surface free energy, along with the structural similarity of the doped crystallized diisocyanate molecule with the matrix. The thermal conductivity increased from 0.349 to 0.467 W mk^?1 on 20 wt% PU‐grafted BN loading that is a 1.34‐fold higher value than in the case of pristine BN loading at the same weight fraction. Moreover, the number of BN particles acting as defects, thereby reducing the mechanical strength, is decreased because of strong adhesion. We can conclude that these composite materials may be promising materials for a significant performance improvement in terms of both the thermal and mechanical properties of PU‐based polymers. Copyright © 2014 John Wiley & Sons, Ltd.     

Thermal stability of poly(methyl methacrylate)/silica nano- and microcomposites as investigated by dynamic-mechanical experiments

The thermal stability of poly(methyl methacrylate) (PMMA) filled with silicon dioxide particles was investigated by means of rheological tests. The change in the storage modulus G′ was measured, which is a very sensitive method to detect molecular changes in polymers. The long-term thermal stability of the composites was found to depend on the temperature of the melt, the size of the silica particles, which ranged from nano- to micrometers, and the volume fraction of the filler. For high temperatures and a large surface area of the silica particles the behaviour of the composites differs significantly from that of the pure polymer. Pure PMMA degrades at high temperatures, which correlates with a decrease of G′. In contrast an increase in G′ with increasing temperature and filler surface was measured for the composite materials. This behaviour is explained by chemical reactions of the PMMA molecules with the silica particles. Effects of that kind were not found for SiO₂ filled polystyrene.     

Thermal stability and conductivity of hot-pressed Si3N4–graphene composites

This study concerns new Si₃N₄–graphene composites manufactured using the hot-pressing method. Because of future applications of silicon nitride for cutting tools or specific parts of various devices having contact with high temperatures there is a need to find a ceramic composite material with good mechanical and especially thermal properties. Excellent thermal properties in the major directions are characteristic of graphene. In this study, the graphene phase is added to the silicon nitride phase in a quantity of up to 10 mass%, and the materials are sintered under uniaxial pressure. The mixture of AlN and Y₂O₃ is added as sintering activator to the composite matrix. The studies focus on thermal stability of produced composites in argon and air conditions up to the temperature of 1,000 °C. The research also concerns the influence of applied uniaxial pressure during the sintering process on the orientation of graphene nanoparticles in the Si₃N₄ matrix. The study also presents research on anisotropy of thermal diffusivity and following thermal conductivity of ceramic matrix composites versus the increasing graphene quantity. Most of the presented results have not been published in the literature yet.     

Electrically conductive composites of polyethylene filled with polyamide particles coated with silver

New types of electrically conductive polymeric composites were prepared on a base of high-density polyethylene (HDPE) matrix filled with silver-coated polyamide (PA) particles. The electrical, mechanical and adhesive properties of those composites are reported in this paper. The percolation concentration of the filler within a matrix was found to be 4 vol.%. Composites filled with high filler content were highly electrically conductive; their electrical conductivity reached the value of 6.8 × 10² S cm⁻¹. Mechanical properties and rheology of these composites were discussed. The adhesive properties of the composites to metal sharply increased with an increase in the filler content.     

Polylactide compositions. II. Correlation between morphology and main properties of PLA/calcium sulfate composites

Starting from calcium sulfate (gypsum) as fermentation by‐product of lactic acid production process, high performance composites have been produced by melt‐blending polylactide (PLA, L/D isomer ratio of 96:4) and β‐anhydrite II (AII) filler, that is, calcium sulfate hemihydrate previously dehydrated at 500 °C. Characterized by attractive mechanical and thermal properties due to good filler dispersion throughout the polyester matrix, these composites are interesting for potential use as biodegradable rigid packaging. Physical characterization of selected composites filled with 20 and 40 wt % AII has been performed and compared to processed unfilled PLA with similar amorphous structure. State of dispersion of the filler particles and interphase characteristic features have been investigated using light microscopy (LM) and scanning electron microscopy (SEM). Addition of AII did not decrease PLA thermal stability as revealed by thermogravimetry analyses (TGA) and allowed reaching a slight increase of PLA crystallizability during melt crystallization and upon heating from the glassy, amorphous state (DSC). It was found by thermomechanical measurements (DMTA) that the AII filler increased pronouncedly storage modulus (E′) of the composites in comparison with PLA in a broad temperature range. The X‐ray investigations showed stable/unchanged crystallographic structure of AII during processing with molten PLA and in the composite system. The notable thermal and mechanical properties of PLA–AII composites are accounted for by the good filler dispersion throughout the polyester matrix confirmed by morphological studies, system stability, and favorable interactions between components. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2770–2780, 2007     

Thermal resistance and mechanical stability of tungsten oxide filled polymer composite radiation shields

Abstract

The influence of tungsten oxide on thermal and mechanical properties of Isophthalic polyester was studied in detail. Ultrasonication technique was successful in dispersing WO₃ filler particles upto 40?wt% into the polymer matrix and was confirmed through the Scanning Electron Microscopy technique. The mechanical strength of the composites was found to increase with increase in the WO3 content and is acting as a reinforcer. About 77.4%, 65.4% and 7–8 times increase was observed in tensile, flexural and compressive strength respectively with respect to pristine. The thermogram of the composites reveal two stages of degradation. Maximum weight loss was observed in the first stage of degradation in almost all the composites. The initial degradation temperature of the composites range from 151?°C–226?°C. Activation energy was estimated using Horowitz–Metzger kinetic theory and was found to range from 25.31 to 78.58?kJ/Mol. The 50?wt% WO3 filled composite exhibits excellent thermal stability and mechanical strength. Thus, WO₃ filler particles were successful in enhancing the thermal and mechanical strength of Isophthalic polyester.     

Carbon nanofibers–SiO<Subscript>2</Subscript> composites: Preparation and characterization

A method has been developed for preparing carbon fibers–SiO₂ composites using oligomethylhydridesiloxane (OMHS) as the precursor for SiO₂. The presence of active hydrogen in OMHS made it possible to attain chemical interaction between the surface of carbon nanofibers (CNFs) and the applied silicon oxide layer. The oxidation rate of CNF–SiO₂ composite is found to be lower by about one order of magnitude compared to that of the as-synthesized CNF. The thermal stability of CNF–SiO₂ composites has been studied. Under an inert atmosphere, CNF–SiO₂ composite has thermal stability up to 1300°C. At temperatures above 1350°C, silicon carbide (SiC) fibers are formed as a result of the carbothermal reduction of silicon oxide.     

Thermal expansion of epoxy-resin/particle composites—a size effect

The thermal expansion of epoxy-resin (Epikote 828)/particle composites has been measured in the range 77 to 450 K. The fillers used were Cu spheres (seven sizes from 5 to 150 μm diameter) and glass ballotini spheres (three sizes from 3.5 to 200 μm diameter). The volume concentrations used were 0.3 and 0.5 for Cu and 0.3 for glass. The experiments show that the addition of filler raises the glass transition temperature T_g, especially for fine particles. Below the normal value of T_g the thermal expansion is independent of particle size while above T_g the expansion is considerably smaller for samples containing the smaller particles. The effect is more pronounced for Cu than for glass filler. In addition a rapid heating rate reduces the expansion for specimens containing smaller particles but it does not effect the expansion for those containing large particles. The results, which are discussed in the light of the work of other authors, suggest that the addition of particles increases T_g by changing the nature of the polymer not only immediately at the particle surface but also for a considerable distance into the polymer itself. This probably occurs because the epoxy bonds strongly to the particles and this inhibits segmental rotations of the polymer even at considerable distances from the particle surface.