In situ sintered silver decorated 3D structure of cellulose scaffold for highly thermoconductive electromagnetic interference shielding epoxy nanocomposites

This study presents a 3-dimensional (3D) network structure of cellulose scaffold (CS), which was in situ decorated with silver nanoparticles (AgNPs). The scaffold was then infiltrated with epoxy matrix and cured at elevated temperature to sinter the AgNPs; finally, highly thermoconductive epoxy composites (Ag@CS/epoxy) was obtained. The resultant Ag@CS20/epoxy composite reached a thermal conductivity of 2.52 W·m⁻¹·K⁻¹ at 2.2 vol% of filler loading, which shows an enhancement of over 11-folds in the thermal conductivity compared to the neat epoxy. The superb electrical conductivity value of over 53,691 S·m⁻¹ of the Ag@CS20/epoxy was achieved, which led to exceptional EMI SE values of 69.1 dB. Furthermore, surface temperatures during heating and cooling were also investigated to demonstrate the superior heat dissipating capacity of the Ag@CS/epoxy composite, which can be potentially put an application as thermal dissipating material in the next generation of electronics.     

Enhanced thermal conductive 3D-SiC/Al-Si-Mg interpenetrating composites fabricated by pressureless infiltration

A high thermal conductive 3D-SiC/Al-Si-Mg interpenetrating composite (IPC) with three dimensional mutually interpenetrated structure was fabricated by mold-forming and pressureless infiltration method. Al-15Si-10Mg was used as the infiltration aluminum alloy. The obtained composite was treated with a T6 procedure. The composed phases, microstructure, thermal conductivity, mechanical strength and fractography of the prepared 3D-SiC/Al-Si-Mg IPC were either analyzed or measured with X-ray diffraction (XRD), optical metallography, laser thermal conductivity instrument, universal testing machine, field emission electron scanning microscopy (SEM) with energy dispersive spectroscopy (EDS), high-resolution transmission electron microscopy (HRTEM), and etc. The results showed that both SiC ceramic and aluminum alloy phases distribute evenly and form a three-dimensional mutually interpenetrated structure in the obtained IPC. No clear brittle and harmful Al₄C₃ phase was found in the composite. The obtained IPC contains a SiC volume fraction of 67 vol% and has the properties of a density of 3.02 g/cm², a thermal conductivity of 233.6 W/(m °C), a thermal expansion coefficient (RT~300 °C) of 7.03×10⁻⁶/°C and a bending strength of 288 MPa.     

Thermal conductivity of several geopolymer composites and discussion of their formulation

We fabricated 50.8-mm cube-shaped samples of metakaolin geopolymer (GP) composites with various additives chosen to increase or decrease the thermal conductivity of the composite. Sodium-based GP (NaGP) and GP composites were more conductive than potassium-based GP (KGP) composites for a given phase fraction of filler, but the maximum amount of filler phase was higher with KGP due to the lower viscosity of the KGP mixture. The highest thermal conductivity achieved was about 8 W/m K by KGP + 44-vol% graphite flakes, whereas NaGP + 27 vol% graphite flakes reached 4.7 W/m K. The thermal conductivity was strongly affected by the moisture remaining in the composite, which appeared to have a greater effect at higher filler content. On the other hand, the size of alumina particles (6, 40, or 120 μm) did not have any apparent effect on thermal conductivity for the same filler content. Larger particles caused less change in mixture viscosity, though, thus permitting incorporation of higher filler phase fractions and therefore higher thermal conductivity.     

Simultaneously Improved Thermal Conductivity and Dielectric Properties of NBR Composites by Constructing 3D Hybrid Filler Networks

This work aims to address the heat accumulation issue in electronic components during high-frequency operation through the preparation of novel thermally conductive composites. First, polydopamine (PDA) and in-situ growth of silver (Ag) nanoparticles are applied for the surface modification of graphene oxide (GO) and carbon nanotube (CNT) to prepare pGO@Ag and pCNT@Ag hybrid filler, respectively. Then, nitrile butadiene rubber (NBR) is chosen as the polymeric matrix and simultaneously incorporated with both pGO@Ag and pCNT@Ag to prepare polymeric composites with excellent thermal conductivity (TC) and dielectric constant (ɛ_r). Due to the construction of 3D heat conduction networks by utilizing 2D pGO@Ag and 1D pCNT@Ag, the fabricated NBR composites achieved the maximum TC of 1.0112 W/(mK), which is 636% higher than that of neat NBR (0.1373 W (mK)⁻¹). At the filler loading of 9 vol%, the TC of pGO@Ag/pCNT@Ag/NBR composite is 152% that of GO/CNT/NBR composite (0.6660 W (mK)⁻¹). Moreover, due to electron polarization effect of GO and CNT and micro-capacitor effect of Ag nanoparticles, a large ɛ_r of 147.12 is attained at 10 Hz for NBR composites. Overall, the development of dielectric polymer materials with high TC is beneficial for enhancing the service life and safety stability of the electronic components.     

High-thermal conductivities of epoxy composites via p-phenylenediamine interfacial modification and process intensification

High loadings of fillers are usually needed to achieve high-thermal conductivity (TC) of polymer-based composites, which inevitably sacrifices processability and meanwhile causes high-cost. Therefore, it is of great significance to achieve high-TC composites under low-filler loading. Here, a novel p-phenylenediamine (PPD) modified expanded graphite (EG-PPD)/epoxy (EP) composite with high TC and low-filler content was successfully prepared via pre-dispersion and vacuum assisted mixing strategy. With the improved interfacial compatibility between EG and EP by PPD, the prepared EG-PPD/EP composite exhibited excellent thermal management performance, resulting in the TC of which reached 4.00 W·m⁻¹·K⁻¹ with only 10 wt% (5.59 vol%) of EG-PPD, which is approximately 19 times higher than that of pure EP. Meantime, the interface thermal resistance of EG-PPD/EP composite between EG-PPD and EP is reduced by 33% compared with EG/EP composite. This composite with excellent TC property is expected to be used in thermal management field.     

The Preparation and Cure Kinetics Researches of Thermal Conductivity Epoxy/AlN Composites

The aluminum nitride (AlN) was employed to prepare epoxy/AlN composites by blending-casting moulding method, two different coupling agents were used to functionalize the surface of AlN. The thermal conductivity and mechanical properties of the composites were investigated. And the cure kinetics of the EP/AlN composites was studied by means of isothermal DSC. Results revealed that the thermal conductivity of EP improved remarkably with the addition of AlN, a higher thermal conductivity of 1.05 W/mK can be achieved with 42 vol% AlN, about 5 times higher than that of native epoxy resin. And the flexural and impact strength of the EP/AlN composites were optimal with 3.3 vol% AlN. The curing process of the EP/AlN composites contained autocatalytic mechanism, the whole process was according with the Kamal model. The presence of AlN did not change the cure reaction mechanism, and had little effecting on the activation energy, but decreased the rate constants k_l and k₂.     

Thermal and Mechanical Properties of SiC–TiC0.5N0.5 Composites

SiC–TiC_0.5N_0.5 composites were fabricated from β‐SiC and TiN powders with 2 vol% equimolar Y₂O₃–Sc₂O₃ additives by conventional hot pressing. Thermal and mechanical properties of the SiC–TiC_0.5N_0.5 composites were investigated as a function of initial TiN content. Relative densities of ≥98.9% were achieved for all samples. The addition of a small amount of TiN increased thermal conductivity, flexural strength, and fracture toughness of SiC ceramics. However, further addition of TiN in excess of 10 and 20 vol% deteriorated both thermal conductivity and flexural strength of the composites, respectively. In contrast, the fracture toughness of the composites increased continuously from 4.2 to 6.2 MPa?m^1/2 with increasing initial TiN content from 0 to 35 vol%, due to crack deflection by TiC_0.5N_0.5. The maximum values of thermal conductivity and flexural strength were 224 W/m K for a 2 vol% TiC_0.5N_0.5 and 599 MPa for a 10 vol% TiC_0.5N_0.5 composite.     

Al2O3/h-BN/epoxy based electronic packaging material with high thermal conductivity and flame retardancy

The long-term and stable operation of integrated circuits and microelectronics requires packaging epoxy resin (EP) exhibit high thermal conductivity for efficient heat dissipation, and excellent flame retardancy in case of thermal runaway. We achieved such EP composite via filling poly-dopamine (PDA) modified nanoscale Al₂O₃ spheres and microscale h-BN sheets. The PDA modification increases the compatibility between fillers and EP and largely reduces the viscosity, improving the dispersion of fillers in EP thus the thermal conductivity of EP composites. In addition, NH₃, H₂O, and N₂ generated during the combustion of phenolic hydroxyls and aminos in PDA combined with the physical barrier effect of Al₂O₃ and h-BN can improve the flame retardancy of EP composites. As a consequence, the EP composite filled with PDA modified Al₂O₃ (26.67 wt%) and h-BN (13.33 wt%) (i.e., PDA-BNAO/EP) shows a thermal conductivity of 1.192 W/mK (654.9% of EP), a peak heat release rate of 194.9 W/g (33.8% of EP), and total heat release of 15.2 kJ/g (54.5% of EP), respectively. What's more, the viscosity of PDA-BNAO/EP is 20,443 mPa s, which is only 20% of BNAO/EP (whose viscosity is 102,281 mPa s). More importantly, the PDA-BNAO/EP has good dynamic mechanical properties with the storage modulus of 14.69 Gpa, glass transition temperature of 91.9°C and good electrical insulation, which is desired for packaging of microelectronics. PDA-BNAO/EP composite should be a promising candidate for widespread packaging materials of microelectronics.     

Tuning the electronic and thermal transport behaviors of metal-dispersed Ti2O3 composites derived by metal–insulator transition

Thermal management requires an understanding of the relations among the thermal energy transfer, electronic properties, and structures of thermoconductive materials. Here, we enhanced the metal–insulator transition (MIT)-induced effect on the thermal conductivities of microstructure-controlled Ti₂O₃ composites containing W as a thermal conductive filler at approximately 450 K. To change the electronic and thermal transport properties, we varied the particle radii of the conductive phases in the raw material. The change in the calculated electronic thermal conductivity relative to the electrical conductivity of the W_x(Ti₂O₃)_1?x composite was enhanced by compounding the material. When x was reduced from 50 vol% to 20 vol% and the W particle diameter was reduced from 150 μm to 5 μm, the variation in the estimated electronic thermal conductivity of the W_x(Ti₂O₃)_1?x composite was increased by a factor of 2.01. The total thermal conductivity was also changed by the MIT. At x = 50 vol% and a W particle diameter of 5 μm, the maximum thermal conductivity change was 6.34 times larger than that of pure Ti₂O₃. The detailed relation between the MIT-induced changes in thermal transport and the microstructure were elucidated in classical effective medium approximations.     

A graphite nanoplatelet/epoxy composite with high dielectric constant and high thermal conductivity

A simple strategy for the preparation of composites with high dielectric constant and thermal conductivity was developed through a typical interface design. Graphite nanoplatelets (GNPs) with a thickness of 20–50 nm are fabricated and homogeneously dispersed in the epoxy matrix. A high dielectric constant of more than 230 and a high thermal conductivity of 0.54 W/mK (a 157% increase over that of pure epoxy) could be obtained for the composites with a lower filler content of 1.892 vol.%. The dielectric constant still remains at more than 100 even in the frequency range of 10⁵–10⁶ Hz. When loaded at 2.703 vol.%, GNP/epoxy composites have a dielectric constant higher than 140 in the frequency range of 10²–10⁴ Hz and a high thermal conductivity of 0.72 W/mK, which is a 240% increase over that of pure epoxy. The high dielectric constant and low loss tangent are observed in the composite with the GNPs content of 0.949 vol.% around 10⁴ Hz. It is believed that high aspect ratio of GNPs and oxygen functional groups on their basal planes are critical issues of the constitution of a special interface region between the GNPs and epoxy matrix and the high performance of the composites.     

Liquid crystal epoxy composites based on functionalized boron nitride: Synthesis and thermal properties

A composite was prepared by in-situ polymerization of liquid crystal epoxy (LCE₄) with a low dielectric and high thermal conductivity boron nitride (BN) filler, which the filler (f-BN) was surface-functionalized by γ-glycidoxypropyltrimethoxysilane (KH560) and aminopropylisobutyl polyhedral oligomeric silsesquioxane (NH₂-POSS). The surface-functionalized BN was more uniformly dispersed in LCE₄, which improved the interfacial compatibility between inorganic and organic phases. Compared with pure LCE₄, KH560, and NH₂-POSS modified f-BN/LCE₄ composites exhibited a higher glass transition temperature, better thermal stability, and higher thermal conductivity. For example, when the f-BN content reached 30 wt%, the energy storage modulus of the composite increased to 2580 MPa, and the glass transition temperature was 103°C. The thermal conductivity of this 30 wt% f-BN composite was 0.48 W m⁻¹ K⁻¹, 128.6% higher than that of pure LCE₄. In addition, thermal stability, low hygroscopicity, and dielectric properties of the composites were characterized and analyzed to explore the application prospects of f-BN/LCE₄ composites in electronic packaging and in high-performance microelectronic devices.     

Design and preparation of low-filled magnetic oriented BN@Fe3O4/EP insulating composite with improved thermal conductivity and thermal stability

As an excellent two-dimensional insulating material with high thermal conductivity, high temperature stability and high hardness, hexagonal boron nitride(h-BN) is widely applied in semiconductor manufacturing, aerospace, metallurgical manufacturing and other cutting-edge fields. However, the unique surface structure of h-BN leads to poor lubricity and easy agglomeration, which limits the application of h-BN especially in the field of electronic packaging. To address key issues boosted above, this study designed and prepared the BN@Fe₃O₄ magnetic insulating particles and doped it into the reduced viscosity epoxy resin to prepare the composites. By selecting appropriate external magnetic field strength and BN@Fe₃O₄ particles’ content, a novel 3D structure of fillers like dominoes in epoxy resin composite was successfully constructed. The microstructure of the BN@Fe₃O₄ particles and composites were analyzed, the thermal conductivity, the mechanical and the electrical properties of composites were simultaneously tested. Results manifested that the core-shell structures with BN as core and Fe₃O₄ as shell was successfully prepared, linking through the PDA middle layer between the BN core and Fe₃O₄ shell. Under the influence of magnetic orientation, the BN@Fe₃O₄ magnetic particles were preferred an out-of-plane oriented in the epoxy resin composites, resulted an enormously enhanced on thermal conductivity of composites. At a magnetic field strength of 60 mT and 25 vol% BN@Fe₃O₄ content, the thermal conductivity of BN@Fe₃O₄/EP composites is as lofty as 1.832 W/(m K), which is 1023.46% higher than that of pure epoxy resin. Meanwhile, the thermal stability has also been slightly improved, the elastic modulus and insulation performances remain at the same level.     

环氧树脂/氧化锌晶须/氮化硼导热绝缘复合材料的研究

以环氧树(脂EP)为基体,分别以氧化锌晶(须ZnOw)和ZnOw/氮化硼(BN)混合物为导热填料,制备了EP导热绝缘复合材料。研究了填料含量对复合材料导热性能、电绝缘性能及力学性能的影响,并利用扫描电镜对复合材料的断面形貌进行了观察。结果表明:随着导热填料含量的增大,复合材料的导热系数和介电常数增大,体积电阻率下降,而拉伸强度呈先增大后减小的趋势;在填料含量相同的情况下,EP/ZnOw/BN复合材料比EP/ZnOw复合材料具有更好的导热性能;当填料体积分数为15%时,EP/ZnOw/BN复合材料的热导率为1.06W/(mK)而,EP/ZnOw复合材料的热导率仅为0.98W/(mK)。     

Thermal conductivity enhancement of liquid crystalline epoxy/MgO composites by formation of highly ordered network structure

To develop a high thermal conductive composite, an MgO filler was incorporated into a liquid crystalline (LC) epoxy containing a mesogenic moiety. The thermal conductivity of the obtained composite was 1.41 W/(m∙K) at 33 vol% content, which was remarkably higher than the value predicted using Bruggeman's model. To investigate the reason for this significant enhancement of the thermal conductivity in the LC epoxy composites, the LC phase structure of the composite was analyzed by a polarized optical microscope, an X-ray diffractometry (XRD) and a polarized IR mapping measurement. An XRD analysis indicated the local formation of a highly ordered smectic phase structure, even in the high-loading composite. This result indicated the promotion of the self-assembly of the mesogenic network polymer chains by the MgO filler loading. We considered that this highly ordered structural formation can lead to an increase in the matrix resin's thermal conductivity, which can result in the effective enhancement of the thermal conductivity in the LC epoxy/MgO composite.     

Optical transmittance and electrical conductivity of silica glass with biserial and hierarchical network structures made of carbon nanofibers

Silica glass composites, with biserial and hierarchical percolative network made of carbon nanofibers (CNFs), was fabricated using a layer-by-layer technique and spark plasma sintering to obtain high optical transmittance and electrical conductivity. Owing to the network, the critical volume fraction, V_c, for the CNF percolation in the silica glass-matrix composite (0.5–0.7 vol%), when the electrical conductivity of the composite drastically increased with change from insulator (～10^?10 S/m) to conductor (～10^?1 S/m), is smaller than theoretical V_c predicted for the three-dimensional random orientation of CNFs (2.6 vol% for the CNF aspect ratio of 30). The conductivity of the composite with above the V_c of CNFs (～10 S/m) is higher than that reported for the polymer-matrix composite (～10^?5–～10^?3 S/m). Furthermore, high optical transmittance was observed for the electrically conductive composite with V_c of CNFs.     

Effect of Al2O3 addition on thermo‐electrical properties of polymer composites: An experimental investigation

To develop a new class of composites with adequately high thermal conductivity and suitably controlled dielectric constant for electronic packages and printed circuit board applications, polymer composites are prepared with microsized Al₂O₃ particle as filler having an average particle size of 80–100 μm. Epoxy and polypropylene (PP) are chosen as matrix materials for this study. Fabrication of epoxy‐based composite is done by hand lay‐up technique and its counterpart PP‐based composite are fabricated by compression molding technique with filler content ranging from 2.5–25 vol%. Effects of filler loading on various thermal properties like effective thermal conductivity (k_eff), glass transition temperature (T_g), coefficient of thermal expansion (CTE) and electrical property like dielectric constant (ε_c) of composites are investigated experimentally. In addition, physical properties like density and void fraction of the composites along with there morphological features are also studied. The experimental findings obtained under controlled laboratory conditions are interpreted using appropriate theoretical models. Results show that with addition of 25 vol% of Al₂O₃, k_eff of epoxy and PP improve by 482% and 498% respectively, T_g of epoxy increases from 98°C to 116°C and that of PP increases from −14.9°C to 3.4°C. For maximum filler loading of 25 vol% the CTE decreases by 14.8% and 26.4% for epoxy and PP respectively whereas the dielectric constants of the composites get suitably controlled simultaneously. POLYM. COMPOS., 36:102–112, 2015. © 2014 Society of Plastics Engineers     

Cactus-like double-oriented magnetic SiC and BN networks leading to simultaneously enhanced dielectric strength and thermal conductivity of epoxy composites

Epoxy-based composites with high insulation and thermal conductivity are desirable materials for electronic and electrical applications. However, resolving the tradeoff between insulation and thermal conductivity remains challenging. Based on the functional requirement, we designed and fabricated a cactus-like double-oriented epoxy composite by combining magnetic orientation and ice-templated methods. Semiconducting SiC endowed the composite with field-grading characteristics, thus relieving local electric field stress along the horizontal direction, while BN with high thermal conductivity promoted heat dissipation along the vertical direction. The composite exhibited its highest performance with 15 vol% filler, improving the breakdown voltage and thermal conductivity by 43.7% and 1312% compared with pure epoxy, respectively, outperforming recently developed packaging materials. It is believed that this work offers an efficient strategy for the fabrication of the filler structure and provides insights on the simultaneous enhancement in insulation and thermal conductivity of polymer composites.     

Enhanced thermal conductivity of low-temperature sintered borosilicate glass–AlN composites with β-Si3N4 whiskers

The effects of β-Si₃N₄ whiskers on the thermal conductivity of low-temperature sintered borosilicate glass–AlN composites were systematically investigated. The thermal conductivity of borosilicate glass–AlN ceramic composite was increased from 11.9 to 18.8 W/m K by incorporating 14 vol% β-Si₃N₄ whiskers, and high flexural strength up to 226 MPa were achieved along with low relative dielectric constant of 6.5 and dielectric loss of 0.16% at 1 MHz. Microstructure characterization and percolation model analysis indicated that thermal percolation network formation in the ceramic composites led to the high thermal conductivity. The crystallization of the borosilicate microcrystal glass also contributed to the enhancement of thermal conductivity. Such ceramic composites with low sintering temperature and high thermal conductivity might be a promising material for electronic packaging applications.     

MgO-Y2O3:Eu composite ceramics with high quantum yield and excellent thermal performance

MgO-Y₂O₃:Eu composite ceramics with high quantum yield and excellent thermal performance were successfully synthesized by vacuum sintering. All samples exhibited uniform composite microstructures and pure binary phase. Eu³⁺ ions were completely incorporated into Y₂O₃ phase, and the optimal Eu concentration is 15 at%. Sintered at 1800 °C, the fluorescent properties of MgO- z vol% Y₂O₃: Eu (z = 30, 40, 50, 60, 70, 100) composites proved to be independent on component proportion, including the similar fluorescence lifetimes (953–983 μs), quantum yield (70%−80%), and activation energy (ΔE) of thermal quenching (0.163 eV). Significantly, thermal conductivity of composites with 30 vol%, 50 vol% and 70 vol% MgO attained 11.58, 17.45, and 29.65 W/(m∙K) at room temperature, which are nearly 2, 3, and 5 times as high as that of 15 at% Eu:Y₂O₃ ceramic (5.90 W/(m∙K)), respectively, demonstrating their potential for application in high-power-density display and lighting technology.     

Improvement in thermal conductivity and mechanical properties of ethylene‐propylene–diene monomer rubber by expanded graphite

Thermally conductive fillers are usually employed in the preparation of rubber composites to enhance thermal conductivity. In this work, ethylene‐propylene‐diene monomer rubber (EPDM)/expanded graphite (EG) and EPDM/graphite composites with up to 100 phr filler loading were prepared. Compared to EPDM/graphite compounds with the same filler loading, stronger filler network was demonstrated for EPDM/EG compounds. Thermal conductivity and mechanical properties of EPDM/graphite and EPDM/EG composites were compared and systematically investigated as a function of the filler loading. The thermal conductivity of both EPDM/graphite and EPDM/EG composites increased with increasing volume fraction of fillers, and could be well fitted by Geometric Mean Model. The thermal conductivity as high as 0.910 W · m⁻¹ · K⁻¹ was achieved for the EPDM/EG composite with 25.8 vol% EG, which was ∼4.5 times that of unfilled EPDM. Compared to EPDM/graphite composites, EPDM/EG composites exhibited much more significant improvement in thermal conductivity and mechanical properties, which could be well correlated with the better filler‐matrix interfacial compatibility and denser structure in EPDM/EG composites, as revealed in the SEM images of tensile fracture surfaces. POLYM. COMPOS., 38:870–876, 2017. © 2015 Society of Plastics Engineers