Enhancing the Anhydrous Proton Conductivity of Sulfonated Polysulfone/Polyvinyl Phosphonic Acid Composite Membranes With Hexagonal Boron Nitride

Hexagonal boron nitride (h-BN) particles have attracted increasing interest due to mechanical properties, chemical stability, electrical features, thermal stability, and good lubrication property. In this work hexagonal boron nitride were used as inorganic fillers, which increase the mechanical and thermal stabilities of the membrane. The proton conducting polymer membranes were prepared by blending of sulfonated polysulfone, polyvinyl phosphonic acid, and boron nitride. Scanning electron microscopy indicated the homogeneous distribution of hBN nanoparticles in the polymer matrix. hBN increased the proton conductivity and in the anhydrous state the maximum proton conductivity was determined as 7.9 × 10^?3 S/cm at 150°C for PVPA-SPSU-5hBN.     

Enhancement of mechanical and wear resistance performance in hexagonal boron nitride‐reinforced epoxy nanocomposites

Hexagonal boron nitride (hBN), a two‐dimensional nanofiller with good mechanical properties, high thermal conductivity and excellent lubrication properties, has the potential to substantially reinforce polymers to form nanocomposites with advanced properties. In this study, we successfully prepared hBN nanosheets with a thickness of a few atoms by using amine‐capped aniline trimer (AT) as dispersant. Epoxy/hBN nanocomposites were prepared by curing reaction of epoxy E51, Jeffamine D230 and AT‐modified hBN nanosheets, where the hBN contents were 0.5, 1, 2 and 4 wt%. An increase in contact angle of the epoxy/hBN nanocomposites was evident in the presence of hBN nanosheets, implying an increase in the hydrophobic nature of the composites. The as‐prepared composites exhibited enhanced mechanical and tribological performance compared to pure epoxy resin. This effectiveness in improving the mechanical, friction and wear behavior of the epoxy composites could be attributed to the complementary action of excellent mechanical properties, lubrication and thermal conductivity of hBN nanofillers. © 2016 Society of Chemical Industry     

Effect of the particle size of Al2O3 on the properties of filled heat‐conductive silicone rubber

An elastomeric thermal pad with a thermal conductivity of 1.45 W/m K, needed for the heat dissipation of microelectronics, was obtained with hybrid alumina of different particle sizes as a filler and silicone rubber (vinyl‐end‐blocked polymethylsiloxane) as the matrix. The effects of the amount, particle size, and mixing mass ratio of the filler particles on the thermal conductivity and mechanical properties of silicone rubber were investigated. The results indicated that the thermal conductivity of the rubber filled with larger particles was superior to that of the rubber filled with the smaller grain size, and the rubber incorporated with a mixture of hybrid particles at a preferable mass ratio exhibited higher thermal conductivity than the rubber for which a filler with only a single particle size was used. In addition, the surface treatment of the hybrid filler with 3‐methacryloyloxypropyltrimethoxysilane could increase the thermal conductivity of the composite rubber. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1312–1318, 2007     

The synergistic effects on enhancing thermal conductivity and mechanical strength of hBN/CF/PE composite

In this work, a simple and novel method was applied to prepare polymer composites by taking the advantage of melt flow shear force driving orientation of the fillers. By using this method, hexagonal boron nitride/polyethylene (hBN/PE) and hexagonal boron nitride/carbon fibers/polyethylene (hBN/CF/PE) composites were fabricated to be possessed of high thermal conductivity and mechanical properties. A high thermal conductivity of 3.11 W/mK was realized in the composite containing 35 wt% hBN and 5 wt% CF, which was over 1,200% higher than that of unfilled PE matrix. Under this component, the compressive strength and modulus of hBN/CF/PE composite were determined to be 30.1 and 870.9 MPa, respectively, which were far higher than that of unfilled PE accordingly. The bending performance was also somewhat enhanced. Meanwhile, the bulk resistivity of the composite material reached 2.55 × 10¹¹ Ω·cm, which was basically the same as that of pure PE. The novel composites with high thermal conductivity, excellent mechanical properties, and controllable electrical insulation could be a potential thermal management material for electrical and electronics industries.     

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     

Thermal conductivity of polypropylene composites with hybrid fillers of boron nitride and vapor‐grown carbon fiber

High thermal conductivity fillers of boron nitride (BN) and vapor‐grown carbon fiber (VGCF) were used alone or incorporate to prepare polypropylene (PP) composites. The effects of filler content, particle size and shape, and single vs. hybrid BN/VGCF fillers were investigated with respect to the thermal conductivity of the PP composites. The thermal conductivity of PP/BN composites depended upon the content and particle size of the BN. Increased content and length of VGCF had the effect of increasing the thermal conductivity of the PP composites. Hybrid fillers were created with a mixture of medium‐sized BN and long‐length VGCF; hybrid BN/VGCF fillers enhanced the thermal conductivity of PP composites with a lower total content compared with PP composites containing only medium‐sized BN particles. POLYM. COMPOS., 37:936–942, 2016. © 2014 Society of Plastics Engineers     

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)。     

不同粒径氮化硼填充环氧树脂/玻璃纤维绝缘导热复合材料的研究

以聚砜改性环氧树脂为基体,通过高温模压制备了环氧树脂/玻璃纤维/氮化硼复合材料,研究了不同粒径及不同氮化硼导热粒子用量对复合材料导热性能、力学性能和电性能的影响。结果表明,大粒径粒子有利于复合材料力学性能的提高,小粒径有利于导热性能的提高;随着氮化硼用量的增加,复合材料的导热性能升高,力学性能呈现先增后降趋势,当氮化硼用量为10%(质量分数,下同)时,复合材料的冲击强度和弯曲强度均达到最佳,当氮化硼用量为20%时,复合材料仍保持较好的电性能。     

Synergistic effects of hybrid fillers on the development of thermally conductive polyphenylene sulfide composites

The future of integrated circuits with three‐dimensional chip architecture hinges on the development of practical solutions for the management of excessive amounts of heat generation. This requires new polymer–matrix composites (PMCs), with good processibility, high effective thermal conductivity (k_eff), and low but tailored electrical conductivity (σ). This article explores the synergy of hybrid fillers: (i) hexagonal boron nitride (hBN) platelets with different sizes and shapes; (ii) hBN platelets with carbon‐based fillers promoting the k_eff of the polyphenylene sulfide (PPS) composites. It explores the promotion of interconnectivity among the fillers in the PPS matrix, leading to higher k_eff, by the uses of hybrid fillers. It discusses using carbon‐based fillers as secondary fillers to tailor the PMCs' σ. Finally, it presents the effects of hybrid fillers on the PMCs' coefficient of thermal expansion. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synergistic effects of boron nitride sheets and reduced graphene oxide on reinforcing the thermal conduction,SERS performance and thermal property of polyimide composite films

Polyimide (PI) composite films with hybrid fillers containing hBN (hexagonal boron nitride) sheets and rGO (reduced graphene oxide) were successfully fabricated by in-situ polymerization. Herein, hBN sheets and rGO were obtained by ball milling and chemical reduction, respectively. In PI composite films, hBN can be tightly attached onto the surface of rGO via π-π interaction, which can benefit the construction of heat-conduction pathways and reduce boundary of heat resistance. The results show that the addition of rGO and hBN could enhance the thermal conductivity by synergistic effects. Specially, hBN and rGO are at the weight ratio of 1:1 and at the total loading of 33 wt%, thermal conductivity of PI composites can reach up to 1.19 Wm⁻¹ K⁻¹, which is 5.61 times higher than that of pure PI. Thermal property and dynamic mechanical property of composite films were also investigated. Besides, compared with pure PI, mixed fillers have obvious surface-enhanced Raman scattering signals, indicating the synergistic effect of the mixed fillers. Overall, this study gives insights into heat dissipative and high sensitivity analysis components which may be used in the field of high-temperature micro fabrication.     

Rice‐husk‐ash‐based silica as a filler for embedding composites in electronic devices

We carried out a feasibility study of the use of black rice husk ash (RHA) as a filler in epoxy resin for embedding material in electrical and electronic applications. We made a comparison by mixing RHA and two commercial fillers, fused and crystalline silica, with epoxy resin at weight fractions ranging from 20–60%. RHA‐filled epoxy resin had higher mixing viscosity, coefficient of thermal expansion, and water absorption percentage than commercial‐silica‐filled epoxy composite. However, the impact strength of all composites was comparable, but the tensile strength and elongation at break of silica‐filled epoxy were slightly superior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3013–3020, 2002     

High‐performance heat‐sink composites incorporating micron‐sized inorganic fillers and Sn/In metal particles

A novel thermal‐barrier composite system was developed by incorporating fusible metal particles in the epoxy matrix system. Using the latent heat of melting, the Sn/In metal particles having melting temperature at 125°C were imbedded in the polymer matrix to suppress the thermal shock and transient temperature variation. The high‐density metal particles were successfully dispersed in the polymer matrix without sinking by incorporating inorganic particles of aluminum nitride (AlN) and boron nitride (BN), which desirably facilitated the heat dissipation to give a high thermal conductivity at around 10 W/m‐K. Under the repeated melting and cooling cycles, the spherical shape of metal particles and the latent heat of melting were retained demonstrating the reversible thermal‐barrier capability of the developed composite system. Under the constant‐heating conditions, it was validated that the temperature rise was delayed by the endothermic melting of Sn/In particles. The developed composite system could find various applications since it could minimize damages caused by the repeated thermal fatigue and/or accidental thermal shock. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Consolidation of cubic and hexagonal boron nitride composites

Consolidating cubic boron nitride (cBN) typically requires either a matrix of metal bearing materials that are undesirable for certain applications, or very high pressures within the cBN phase stability field that are prohibitive to manufacturing size and cost. We present new methodology for consolidating high stiffness cBN composites within a hexagonal boron nitride (hBN) matrix (15–25 vol%) with the aid of a binder phase (0–6 vol%) at moderate pressures (0.5–1.0 GPa) and temperatures (900–1300 °C). The composites are demonstrated to be highly tailorable with a range of compositions and resulting physical/mechanical properties. Ultrasonic measurements indicate that in some cases these composites have elastic mechanical properties that exceed those of the highest strength steel alloys. Two methods were identified to prevent phase transformation of the metastable cBN phase into hBN during consolidation: 1. removal of hydrocarbons, and 2. increased cBN particle size. Lithium tetraborate worked better as a binder than boron oxide, aiding consolidation without enhancing cBN to hBN phase transformation kinetics. These powder mixtures consolidated within error of their full theoretical mass densities at 1 GPa, and had only slightly lower densities at 0.5 GPa. This shows potential for consolidation of these composites into larger parts, in a variety of shapes, at even lower pressures using more conventional manufacturing methods, such as hot-pressing.     

High hardness cubic boron nitride with nanograin microstructure produced by high‐energy milling

High‐energy shaker milling of hexagonal boron nitride (hBN) powders was used to produce powders rich in sp³ bonding. The powders contained up to 68% sp³ bonding and were found to nucleate nanosize cBN grains during consolidation at 5.5 GPa and 1400°C. The effect of hBN starting particle size, milling time, and powder‐to‐milling ball ratio were studied. The amount of sp³ bonding for milled hBN powders was determined, using ¹¹B solid‐state NMR. The milled material was also analyzed by XRD, Raman spectroscopy, and HRTEM. The results indicate that the material has a nanosized microstructure comprised of a disordered hBN matrix and cBN nuclei in the form of sp³‐rich domains. Eight different milled powders were produced and consolidated at pressures of either 5.5 or 6.5 GPa and temperatures of either 1400°C or 1450°C into 12 mm diameter and 5 mm thick pellets. Consolidated pellets formed from milled hBN with 68% sp³ bonding had Vickers hardness of 42 ± 1 GPa and fracture toughness 3.8 ± 0.1 MPa.m^1/2. Vickers hardness of 49 ± 1 GPa and fracture toughness of 4.6 ± 0.1 MPa.m^1/2 was achieved with a precursor that contained milled hBN and 50 vol. % of 0.5 μm diameter cBN crystals.     

ROMP‐based boron nitride composites

The present work focuses on the investigation of the thermal and dielectric properties of composites obtained by surface‐modified hexagonal boron nitride (hBN) and ring‐opening metathesis polymerization (ROMP) based polymer. A new kind of high performance composites was developed based on using amino silane functionalized hBN (AS‐hBN) and bromine functional group possessing homo and copolymers synthesized via ROMP pathway. Aminosilane capped boron nitride (BN) and bromine bearing polymer backbone enhance the interaction between filler and the polymer chains. The effects of surface‐modified BN (AS‐hBN) and its content on the dielectric properties, and thermal resistance of composites, are systematically investigated and discussed. The resultant composites possess high electrical break over voltages. While all of the ROMP‐based films exhibit low ?′ value in a wide frequency range, in the case of the composite with 20% AS‐hBN and poly(bromooxanorbornene‐co‐cyclooctadiene) (ROMP‐BN‐6) displays very low dielectric constants in around 1.5 up to 1 MHz at 20 °C. This value is significantly lower than that of common polymer dielectrics, which is usually in the range of 3–6. Besides the lowest dielectric constant of ROMP‐BN‐6, it has also the smallest dielectric loss tangent even at high temperatures. Tan δ of ROMP‐BN‐6 is 0.003 and 0.0067 at 10 Hz–1 MHz at 20 °C, respectively. Thermal stability of polymers was also improved by introducing surface‐modified hBN. Polymers bearing 20% AS‐hBN are highly thermally stable up to ～350 °C and gave 25% char yield at 800 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45658.     

Synthesis and Characterization of TiN‐coated Cubic Boron Nitride Powders

Titanium nitride‐coated cubic boron nitride (TiN/cBN) composite powders were prepared by nitridizing TiO₂/cBN powders in a NH₃ flow at 950°C. The TiO₂/cBN powders were synthesized via a sol‐gel process using tetra‐butyl titanate and concentrated‐HNO₃‐treated BN powders as starting materials. The techniques of XRD, SEM, TEM, FT‐IR, and TG‐DTA were used to characterize the products and their intermediates. The cBN powders were uniformly coated with TiN nanoparticles. During the nitridization, the morphology of the TiO₂/cBN powders is unchanged. The TiN/cBN powders can be used as starting materials to prepare polycrystalline cBN compacts, or as reinforcements to strengthen metal‐matrix composites.     

Low dielectric and high thermal conductivity epoxy nanocomposites filled with NH2‐POSS/n‐BN hybrid fillers

Hybrid fillers of mono‐amine polyhedral oligomeric silsesquioxane/nanosized boron nitride (NH₂‐POSS/n‐BN) were performed to fabricate NH₂‐POSS/n‐BN/epoxy nanocomposites. Results revealed that the dielectric constant and dielectric loss values were decreased with the increasing addition of NH₂‐POSS obviously, but increased with the increasing addition of BN fillers. For a given loading of NH₂‐POSS (5 wt %), the thermal conductivities of NH₂‐POSS/n‐BN/epoxy nanocomposites were improved with the increasing addition of n‐BN fillers, and the thermal conductivity of the nanocomposites was 1.28 W/mK with 20 wt % n‐BN fillers. Meantime, the thermal stability of the NH₂‐POSS/n‐BN/epoxy nanocomposites was also increased with the increasing addition of n‐BN fillers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41951.     

Thermal conductivity of boron nitride‐filled thermoplastics: Effect of filler characteristics and composite processing conditions

The thermal conductivity of boron nitride (BN)‐filled poly(butylene terephthalate) (PBT) was investigated as a function of particle size, aspect ratio, surface area, surface chemistry, and concentration of BN as well as composite processing methods and conditions. In the low filler concentration region, a larger BN surface area resulted in lower thermal conductivity of the composites as a result of phonon scattering at interfaces. In the high filler concentration region the ease in forming filler networks, as reflected by the aspect ratio of BN, played a more dominant role. A percolation‐like behavior was observed when BN networks were formed while the thermal conductivity at close vicinity of the percolation threshold was not completely governed by the scaling law of classic percolation theory. High shear force employed in extrusion was effective in dispersing BN agglomerates into fine platelets while also inducing PBT degradation. When a low screw speed was used in extrusion followed by injection molding, the samples exhibited significantly lower thermal conductivity, which may be attributed to flow‐induced orientation of BN platelets in the direction perpendicular to the heat flow, relatively low concentration of filler at sample surfaces (skin‐core effect), and agglomeration of the BN platelets. POLYM. COMPOS. 26:778–790, 2005. © 2005 Society of Plastics Engineers     

High pressure synthesis of cubic boron nitride from Si-hBN system

Cubic boron nitride (cBN) was synthesized from hexagonal boron nitride (hBN) in the presence of silicon. The cBN forming pressure-temperature region was determined at pressures up to 7.7 GPa. Near perfect octahedral cBN crystals could be synthesized under the P-T conditions near the low temperature boundary of the cBN-forming region. When the temperature was above 1700°C at 6.5 GPa, the transformation rate of cBN from hBN was very high and the cBN crystals had an oriented columnar morphology. This suggests that silicon has strong catalytic ability for cBN formation from hBN. The energy-disperse X-ray analysis (EDXA) identified that silicon was homogeneously distributed in the cBN crystals.     

Theoretical investigation of the hBN(0001)/cBN(111) interface

The interface between the (0001) surface of the hexagonal boron nitride (hBN) and the (111) surface of the cubic boron nitride (cBN) is studied through first principles plane-wave pseudopotentials within the density functional theory. Four different structural models for the pseudomorphic growth of the cBN on hBN have been investigated, two with tetrahedral and two with hexagonal arrangements of the atoms at the interface. The interfaces with N-terminated cBN(111) surface are seen to have the lowest formation energies. The studied interface models present a metallic character, with the levels at Fermi energy spatially confined in the interface region. The band offsets show type I band lineups, with large valence and conduction band discontinuities.