Thermal behavior and dielectric property analysis of boron nitride‐filled bismaleimide‐triazine resin composites

Bismaleimide‐triazine (BT) resin/hexagonal boron nitride (h‐BN) composites are prepared, and the effects of h‐BN content on the thermal and dielectric properties are studied in the view of structure–property relationship. It is found that the introduction of the BN in the BT resin dramatically improve the thermal conductivity of BT resin. The thermal conductivity of the composites is up to 1.11 W/m.K, with an h‐BN concentration of 50 wt %, which is increased by six times compared with the pure BT resin. The BT resin/h‐BN composites also exhibit excellent thermal properties, with the glass transition temperatures above 200°C, and thermal decomposition temperatures over 390°C. Moreover, the composites possess good dielectric properties. Their dielectric constant and loss tangent (tan δ) are less than 4.5 and 0.015, respectively. The results indicate that the BT resin/h‐BN composites are promising as efficient heat‐releasing materials in the high‐density electronic packaging technology. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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

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

Properties and application of polyimide‐based composites by blending surface functionalized boron nitride nanoplates

Ball milling was used to decrease the particle size of boron nitride (BN) nanoplates and to form more silylated functionalization of their surface. Such functionalized BN nanoplates enhanced their homogeneous dispersion in polyimide (PI) matrix. Thermal conductivities, thermal stabilities, and dielectric properties were characterized to investigate the particular effects on the performance of PI‐based composites with functionalized BN nanoplates. When the concentration of functionalized BN nanoplates increased to 50 wt %, thermal conductivity of the composite increased up to 1.583 W m^?1 K^?1, and the temperature of final thermal decomposition was improved to 600°C. An increasing trend was found in the dielectric constant of the composites while the dielectric loss decreased with the increase in the fraction. An appropriate fraction of functionalized BN nanoplates in PI‐based composites were necessary to meet the requirement of withstanding drilling forces for the interconnecting through holes of flexible circuits. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41889.     

Machinable α-SiAlON/BN Composites

Dense machinable α-SiAlON/BN composites were fabricated by hot-pressing using turbostratic boron nitride (tBN) obtained from nitridation of melamine diborate. The tBN was added to the starting powders, or introduced as a coating that formed in situ on α-Si₃N₄ carrier powders during nitridation, and was subsequently converted to hexagonal boron nitride (hBN) during hot pressing by solution reprecipitation. These composites maintain high strength at 1000°C and their strength/hardness are much higher than similar composites prepared using commercial hBN powder, which yielded a coarser microstructure. Good machinability was achieved despite a flat R curve.     

Enhanced thermal conductivity of boron nitride epoxy‐matrix composite through multi‐modal particle size mixing

Castable particulate‐filled epoxy resins exhibiting excellent thermal conductivity have been prepared using hexagonal boron nitride (hBN) and cubic boron nitride (cBN) as fillers. The thermal conductivity of boron nitride filled epoxy matrix composites was enhanced up to 217% through silane surface treatment of fillers and multi‐modal particle size mixing (two different hBN particle sizes and one cBN particle size) prior to fabricating the composite. The measurements and interpretation of the curing kinetics of anhydride cured epoxies as continuous matrix, loaded with BN having multi‐modal particle size distribution, as heat conductive fillers, are highlighted. This study evidences the importance of surface engineering and multi‐modal mixing distribution applied in inorganic fillered epoxy‐matrix composite. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Low‐Temperature Deposition of Hexagonal Boron Nitride via Sequential Injection of Triethylboron and N2/H2 Plasma

Hexagonal boron nitride (hBN) thin films were deposited on silicon and quartz substrates using sequential exposures of triethylboron and N₂/H₂ plasma in a hollow‐cathode plasma‐assisted atomic layer deposition reactor at low temperatures (≤450°C). A non‐saturating film deposition rate was observed for substrate temperatures above 250°C. BN films were characterized for their chemical composition, crystallinity, surface morphology, and optical properties. X‐ray photoelectron spectroscopy (XPS) depicted the peaks of boron, nitrogen, carbon, and oxygen at the film surface. B 1s and N 1s high‐resolution XPS spectra confirmed the presence of BN with peaks located at 190.8 and 398.3 eV, respectively. As deposited films were polycrystalline, single‐phase hBN irrespective of the deposition temperature. Absorption spectra exhibited an optical band edge at ~5.25 eV and an optical transmittance greater than 90% in the visible region of the spectrum. Refractive index of the hBN film deposited at 450°C was 1.60 at 550 nm, which increased to 1.64 after postdeposition annealing at 800°C for 30 min. These results represent the first demonstration of hBN deposition using low‐temperature hollow‐cathode plasma‐assisted sequential deposition technique.     

Enhanced thermal conductivity of PE/BN composites through controlling crystallization behavior of PE matrix

In this article, in order to enhance the thermal conductivity of the polyethylene (PE)/boron nitride (BN) composites through controlling the crystallization behavior of the PE matrix, the crystallization and melting behavior of the PE in the PE/BN composites was investigated. When the BN content was more than 10 wt%, an extra weak exothermic peak (T _h) at 130°C was observed. Moreover, after the annealing of the PE/BN composites at 130°C, the extra weak melting peaks (T _mh) of the PE in the PE/BN composites were also observed and shifted to the high temperature with increasing annealing time, which proved that the T _h was induced by PE crystallization. Meanwhile, the results of temperature‐dependent absorbance IR spectra of the PE/BN composites showed that the crystallization peak (729 cm⁻¹) remarkably appeared at 130.2°C, indicating that the crystallization of the PE in the PE/BN composites can occur at 130.2°C. When the annealing time and temperature were 20 min and 130°C, the thermal conductivity of the PE/BN composite was 16% higher than that of the unannealed PE/BN composites. In addition, the results of the wide angle X‐ray diffraction (WAXD) showed that the BN particles had no influence on the PE crystalline form in the PE/BN composites. POLYM. COMPOS., 38:2806–2813, 2017. © 2015 Society of Plastics Engineers     

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.     

Influence of hBN content on mechanical and tribological properties of Si3N4/BN ceramic composites

Silicon nitride materials containing 1–5 wt% of hexagonal boron nitride (micro-sized or nano-sized) were prepared by hot-isostatic pressing at 1700 °C for 3 h. Effect of hBN content on microstructure, mechanical and tribological properties has been investigated. As expected, the increase of hBN content resulted in a sharp decrease of hardness, elastic modulus and bending strength of Si₃N₄/BN composites. In addition, the fracture toughness of Si₃N₄/micro BN composites was enhanced comparing to monolithic Si₃N₄ because of toughening mechanisms in the form of crack deflection, crack branching and pullout of large BN platelets. The friction coefficient was not influenced by BN addition to Si₃N₄/BN ceramics. An improvement of wear resistance (one order of magnitude) was observed when the micro hBN powder was added to Si₃N₄ matrix. Mechanical wear (micro-failure) and humidity-driven tribochemical reaction were found as main wear mechanisms in all studied materials.     

Improved dielectric and mechanical properties of Ti3C2Tx MXene/silicone rubber composites achieved by adding a few boron nitride nanoplates

MXenes have attracted great attentions in the fabrication of dielectric polymer composites because of their excellent electrical conductivity. However, the high dielectric loss tangent would suppress the application of such polymer-based composites. Incorporating insulating fillers might be a solution. Herein, Ti₃C₂T_x MXene/silicone rubber (SR) composites incorporated with boron nitride (BN) nanoplates were prepared. The homogeneous distribution of fillers was obtained in the composites, which was also thermally stable up to 400 °C. Dielectric constant of 7.06 (2.54 times of pure SR) and dielectric loss tangent of 0.00131 were achieved when the filling contents of MXene and BN in SR composite were 1.2 wt% and 5 wt%, respectively. The improved dielectric constant can be ascribed to the enhanced interfacial polarization and the formation of conductive network, while the low dielectric loss tangent can be due to the insulating interlayers of BN which could inhibit the transfer of free electrons from conductive fillers to the insulating polymer matrices. BN/MXene/SR composites displayed improved mechanical properties (tensile stress of 671 kPa and elongation at break of 353%) and good flexibility (elastic modulus of 540 kPa) due to the low filling content of fillers. This work is promising for preparing dielectric polymer composites in applications of electronic devices.     

Modeling of anisotropic thermal conductivity of polymer composites containing aligned boron nitride platelets: Effect of processing methods

Hexagonal boron nitride (h‐BN) can remarkably enhance the thermal conductivity (TC) of polymer composites, while maintaining high electrical insulation. In this article, the previously developed analytical model, which can simultaneously solve the anisotropic TC of polymer composites containing aligned h‐BN platelets, was improved by introducing a power function to define the polymer thickness ratio in the unit cell. The modified model was validated by an excellent agreement with the experimental results from three independent literatures, in which the samples were prepared by either casting (including tape casting and spin casting) or injection molding. The influence of key parameters on the composite TCs was analyzed. It was found that the power n closely relates to the possessing methods for the polymer composites, which are also well correlated with the behavior of anisotropic TC. POLYM. COMPOS., 38:2670–2678, 2017. © 2015 Society of Plastics Engineers     

Effect of preparation method on the mechanism for oxidation of C/C-BN composites

C/C-BN composites and C_f/BN/PyC composites exhibiting different structures for pyrolytic carbon (PyC) and boron nitride (BN) were studied comparatively to determine their oxidation behavior. This study used five types of samples. Porous C/C composites were modified with silane coupling agents (APS) and then fully impregnated in water-based slurry of hexagonal boron nitride (h-BN); the resulting C/C-BN preforms were densified by depositing PyC by chemical vapor infiltration (CVI), resulting in three types of C/C-BN composites. The other two C_f/BN/PyC composites were obtained by depositing a BN interphase and PyC in carbon fiber preforms by CVI; one was treated with heat, and the other was not. This study was focused on determining how the PyC deposition mechanism, morphology and pore structure were affected by the method of BN introduction. In the 600–900 °C temperature range, the C_f/BN/PyC composites and C/C composites underwent oxidation via a mixed diffusion/reaction mode. The C/C-BN composites had a different pore structure due to the formation of nodules comprising h-BN particles; both interfacial debonding and cracking were reduced, resulting in higher resistance to gas diffusion, lower oxidation rate and larger activation energy (Ea) in the temperature range 600–800 °C. In addition, the mechanism for oxidation of C/C-BN composites gradually exhibited diffusion control at 800–900 °C because the formation of h-BN oxidation products healed the defects. The oxidation mechanism was more dependent on pore structure than on BN structure or content.     

Reinforced thermal conductivity and mechanical properties of in situ microfibrillar composites through multistage stretching extrusion

To surmount difficulty of the melt processing and deterioration of mechanical properties of polymer composites induced by high fraction of the reinforced fibers and thermal conductive fillers, polyethylene (PE)/boron nitride (BN)/polyamide 6 (PA6) and PE/BN/poly(‐hydroxybenzate‐co‐DOPO‐benzenediol dihydrodiphenyl ether terephthalate) (PHDDT) in situ microfibrillar composites were prepared through multistage stretching extrusion. The experimental results showed that both the tensile and impact strength of the PE/BN/PA6 and PE/BN/PHDDT composites were improved. Meanwhile, the thermal conductivities of the PE/BN, PE/BN/PA6, and PE/BN/PHDDT composites were also reinforced. Based on the equation proposed by Y. Agari, the new modified equations can well predict the thermal conductivity of the composites prepared through multistage stretching extrusion with different number of laminating‐multiplying elements. In addition, it was found that PHDDT can act as a “processing aid” to reduce the viscosity of the PE/BN composites. POLYM. COMPOS., 38:2663–2669, 2017. © 2015 Society of Plastics Engineers     

Thermal and electrical properties of aluminum nitride/boron nitride filled polyamide 6 hybrid polymer composites

The effects of boron nitride (BN) and aluminum nitride fillers on polyamide 6 (PA6) hybrid polymer composites were investigated. In particular, the thermal and electrical conductivity, thermal transition, thermal degradation, mechanical and morphological properties and chemical bonds characteristic of the materials with crystal structure of BN and aluminum nitride (AlN) filled PA6 prepared at different concentrations were characterized. Thermal conductivity of hybrid systems revealed a 1.6-fold gain compared to neat PA6. The highest thermal conductivity value was obtained for the composite containing 50 vol% additives (1.040 W/m K). A slight improvement in electrical conductive properties of composites appears and the highest value was obtained for the 50 vol% filled composite with only an increase by 3%. The microstructure of these composites revealed a homogeneous dispersion of AlN and BN additives in PA6 matrix. For all composites, one visible melting peak around 220°C related to the α-form crystals of PA6 was detected in correlation with the X-ray diffraction results. An improved thermal stability was obtained for 10 vol% AlN/BN filled PA6 composite (from 405.41°C to 409.68°C). The tensile strength results of all composites were found to be approximately 22% lower than pure PA6.     

Thermal shock resistance of the porous boron nitride/silicon oxynitride ceramic composites

The thermal shock resistance of the porous boron nitride/silicon oxynitride (BN/Si₂N₂O) ceramic composites were tested by the quenching‐strength method with temperature differences of 600‐1400°C. The residual flexural strength of the composites decreased with increasing temperature difference from 600°C to 900°C. This weakening in flexural strength was attributed to the formation of microcracks in the matrix caused by thermal stress damage. Afterward, as the formation of a dense oxidized layer sealed the surface and hindered further oxidation, the residual flexural strength increased with the further increase of temperature difference from 900°C to 1100°C. Finally, when the temperature differences were above 1100°C, the residual flexural strength gradually decreased with increasing temperature difference, which was attributed to the further oxidation and large thermal stress damage. And the thermal shock resistance of the porous BN/Si₂N₂O ceramic can be improved by the introduction of high contents of sintering aids and h‐BN.     

Noncovalent functionalization of boron nitride and its effect on the thermal conductivity of polycarbonate composites

Polycarbonate (PC) is an engineering thermoplastic with excellent insulation and mechanical properties. However, the low thermal conductivity restricted its application in electronic devices. Hexagonal boron nitride (h ‐BN) microparticle, a promising material with high thermal conductivity, was functionalized with cationic polyacrylamide (CPAM) and introduced into PC matrix to improve the thermal conductivity. SEM and XRD analysis showed that the modified BN (CBN) particles oriented and formed thermal conductive pathways within PC matrix. The formation of large‐area oriented CBN significantly improved the thermal conductivity and thermal stability of composites. At 20 wt % CBN loading, the thermal conductivity of 0.7341 Wm^?1 K^?1 and the temperature for 5% weight loss (T ₅) of 498.6 °C were obtained, which was 3.1 times and 77 °C higher than that of pure PC, respectively. Furthermore, outstanding electrical insulation property of matrix was retained in the composites. These results revealed that PC/CBN composite was a promising material for thermal management and electrical enclosure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44978.     

Effects of heat treatment on mechanical and dielectric properties of 3D Si3N4f/BN/Si3N4 composites by CVI

In this study, three-dimensional silicon nitride fiber-reinforced silicon nitride matrix (3D Si₃N_4f/BN/Si₃N₄) composites with a boron nitride (BN) interphase were fabricated through chemical vapor infiltration. Through comparing the changes of microstructure, thermal residual stress, interface bonding state, and interface microstructure evolution of composites before and after heat treatment, the evolution of mechanical and dielectric properties of Si₃N_4f/BN/Si₃N₄ composites was analyzed. Flexural strength and fracture toughness of composites acquired the maximum values of 96 ± 5 MPa and 3.8 ± 0.1 MPa·m^1/2, respectively, after heat treatment at 800 °C; however, these values were maintained at 83 ± 6 MPa and 3.1 ± 0.2 MPa·m^1/2 after heat treatment at 1200 °C, respectively. The relatively low mechanical properties are mainly attributed to the strong interface bonding caused by interfacial diffusion of oxygen and subsequent interfacial reaction and generation of turbostratic BN interphase with relatively high fracture energy. Moreover, the Si₃N_4f/BN/Si₃N₄ composites also displayed moderate dielectric constant and dielectric loss fluctuating irregularly around 5.0 and 0.04 before and after heat treatment, respectively. They were mainly determined based on the intrinsic properties of materials system and complex microstructure of composites.     

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     

Reaction behavior during Spark Plasma Sintering of cBN-TiCN-Ni powders

Polycrystalline cubic boron nitride (PcBN) is the designation given to composites constituted by cBN hard particles within a ceramic/metallic matrix. These composites are normally processed in severe pressure and temperature conditions to achieve full densification and prevent hexagonal BN formation, which would decrease the composite hardness. In this work, the Spark Plasma Sintering (SPS) technique was investigated as an alternative to sinter cBN-TiCN based composites, with and without addition of metallic Ni. The initial compositions were selected according with calculated phase diagrams, using the Thermo-calc software. The thermal behavior during SPS was studied up to 2000°C, namely the densification, reactivity and phase transformations. A larger densification was achieved with Ni addition, but full removal of open porosity was only possible at 1700 °C, where the cBN phase transformation to hBN completely occurred. In agreement with the thermodynamic calculations, other matrix phases, as TiB₂ and Ni₃B, were formed during sintering.     

A Novel Polymeric Precursor for Boron Nitride Ceramics: Synthesis,Characterization, and Ceramic Conversion

A new polymeric boron nitride (BN) precursor poly[(phenylamino)borazine] (PPAB) with good melt‐processing performance was successfully synthesized by reaction of B‐trichloroborazine (TCB), aniline, and N‐methylaniline under mild conditions. The as‐synthesized PPAB as well as its structural evolution during the ceramic conversion was studied by means of various complementary techniques. The effect of process parameters including monomer ratio, reaction time, and reaction temperature on the properties of polymers was investigated, and the optimized parameters were obtained. Gel permeation chromatography (GPC) analysis of typical PPAB revealed that the number‐average molecular weight (M_n) was 30,520 Da and the polymerization degree was 319. The polymer could be converted to BN ceramics under ammonia atmosphere at 1200°C with carbon content as low as 0.9wt%. The PPAB polymer could be melt‐spun into continuous polymer fibers by hand drawing, which could be further transformed into BN ceramic fibers with good quality. The PPAB polymer is promising for applications that require BN precursor with stable melt processability.