Chemical vapor deposition of pyrolytic boron nitride ceramics from single source precursor

Pyrolytic boron nitride ceramics were prepared on graphite substrates from borazine as the single source precursor by hot-wall chemical vapor deposition in deposition temperature range from 1300 °C to 1600 °C with a total pressure of 200 Pa. The chemical composition and the effect of deposition temperature on the morphology, phase, and structure of the pyrolytic boron nitride were investigated. A high purity product with stoichiometric B/N ratio is obtained. The deposition surface of the product exhibited a pebble-like structure, and the fracture surface showed an apparent laminar structure having a preferential (002) orientation parallel to the surface of the substrate at temperatures above 1400 °C. The product contained some turbostratic and amorphous boron nitride as evidenced from XRD and FTIR examinations. With the increase of deposition temperature, the crystallinity of the pyrolytic boron nitride increased with the turbostratic and amorphous boron nitride turned into hexagonal structure, and the crystallinity of the product became higher.     

Synthesis of poly(borazinylamine)

1,3,5-Trichloroborazine (TCB) was prepared from the reaction of ammonia chloride with boron trichloride. TCB along with hexamethyldisilazane and boron trichloride were used to synthesize boron nitride (BN) preceramic polymer poly(borazinylamine). This study showed that, the lower the reaction temperature, the higher the synthetic yield. Poly(borazinylamine)'s solubility mainly depended on the ratio of TCB, (Me₃Si)₂NH, and BCl₃. The solvent used in the reaction had a large effect on the ceramic yield of poly(borazinylamine). A soluble poly(borazinylamine) with good synthesis and ceramic yields was obtained when the reaction temperature was −15°C, cyclohexane was the solvent, and the ratio of TCB : (Me₃Si)₂NH : BCl₃ was 1 : 6 : 1. By means of infrared and mass spectroscopy analyses, the structure of the poly(borazinylamine) was identified. Thermal decomposition of the poly(borazinylamine) precursor to hydrolyzed BN was also examined. Hydrolyzed BN was obtained at 1000°C, where the ceramic yield was 35–45%. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 863–868, 1999     

The effect of boron nitride nanosheets on the mechanical and thermal properties of aluminum nitride ceramics

The boron nitride nanosheets (BNNSs)/aluminum nitride (AlN) composites were prepared by hot press sintering at 1600°C. The microstructure, mechanical properties, and thermal conductivity of the samples were measured, and the effect of adding BNNSs to AlN ceramics on the properties was studied. It is found that the addition of BNNSs can effectively improve the mechanical properties of AlN. When the additional amount is 1 wt%, the bending strength of the sample reaches the maximum value of 456.6 MPa, which is 23.1% higher than that of the AlN sample without BNNSs. The fracture toughness of the sample is 4.47 MPa m^1/2, a 68.7% improvement over the sample without BNNSs. The composites obtained in the experiment have brilliant mechanical properties.     

氮化硼纳米片改性复合材料导热性能的研究进展

氮化硼纳米片（BNNSs）是一种二维片状纳米材料，具有较高的导热性和热稳定性。将其作为填料加入聚合物中，可显著提高复合材料的导热性能。本文基于近年来对BNNSs改性复合材料的导热性能的研究进展，总结了BNNSs制备和改性的方法以及建立导热路径的方法，介绍了该体系复合材料的导热机理，分析了影响复合材料导热性能的因素，最后对提高复合材料的导热性能进行了展望。     

Controllable preparation of boron nitride microspheres and their epoxy-based thermoconductive composites

How to prepare spherical boron nitride (BN) particle with different size is an extremely challenging work. In this paper, the controllable preparation of spherical BN particle from nanospheres to microsphere was realized by changing the synthesis temperature of trimethyl borate (B(OMe)₃) and ammonia. The spherical precursor (SP) with high oxygen content was obtained first, and then it was heated under flowing ammonia atmosphere to form stable boron nitride microspheres (BNMS). The BNMS exhibits onion-like cavitation structure with a diameter of 0.8–3.4 μm. The effects of the lower reaction temperature (700–825 °C) and gas flow rate on the spherical precursor are discussed. A possible mechanism is proposed to explain the formation of precursors and the appearance of onion-like structure. It is believed that the formation of microsphere is due to the deposition and growth of BO species during the flow process of nanosphere. In addition, the effect of the addition of BNMS on the thermal conductivity of epoxy resin (EP) composites was investigated.     

New insights into synthesis of nanocrystalline hexagonal BN

Uncovering the mechanism behind nanocrystalline hexagonal boron nitride (h-BN) formation at relatively low temperatures is of great scientific and practical interest. Herein, the sequence of phase transformations occurring during the interaction of boric acid with ammonia in a temperature range of 25–1000 °C has been studied in detail by means of thermo-gravimetric analysis, X-ray diffraction, infrared spectroscopy, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The results indicate that at room temperature boric acid reacts with ammonia to form an ammonium borate hydrate (NH₄)₂B₄O₇x4H₂O. Its interaction with ammonia upon further heating at 550 °C for 1 h leads to the formation of turbostratic BN. Nanocrystalline h-BN is obtained either during heating in ammonia at 550 °C for 24 h or at 1000 °C for 1 h. This result is important for the development of novel cost-effective and scalable syntheses of h-BN nanostructures, such as nanosheets, nanoparticles, nanofibers, and nanofilms, as well as for sintering h-BN ceramic materials.     

Recrystallization behaviour of cubic boron nitride under high pressure

The recrystallization behaviour of micron-sized cubic boron nitride (cBN) was studied by analysing the grain size and morphology of samples treated at 8−16 GPa/1500–2200 °C. The results show that the recrystallization temperature of cBN under a pressure of 8 GPa is approximately 1650 °C and increases by approximately 100 °C with every 2 GPa increase in pressure. Once grain recrystallization starts, the grains grow abnormally quickly as the temperature rises, and the strengthening effects of grain refinement and defect structure are greatly weakened. The recrystallization behaviour of cBN at high pressure is helpful to understand the sintering mechanism and control the microstructure and mechanical properties of sintered polycrystalline cBN compacts. In addition, the melting curve for cBN under high pressure is inferred according to the empirical relationship between recrystallization temperature and melting temperature, and the phase diagram for boron nitride is revised based on this new melting curve.     

Novel Poly(m‐phenyleneisophthalamide) Dielectric Composites with Enhanced Thermal Conductivity and Breakdown Strength Utilizing Functionalized Boron Nitride Nanosheets

Dielectric polymer‐based composites with high breakdown strengths and thermal conductivities have attracted considerable attention when applied in electronic devices. In this study, a novel poly(m‐phenyleneisophthalamide) (PMIA) dielectric nanocomposite is successfully fabricated by introducing functionalized hexagonal boron nitride nanosheet (fBNNS) fillers. Due to effective functionalization of hexagonal boron nitride nanosheets (BNNSs), fBNNSs fillers are homogeneously dispersed in the PMIA matrix. The breakdown strength and thermal conductivity of PMIA/fBNNSs dielectric nanocomposite are investigated. Research results indicate that the breakdown strength of fBNNSs‐12 reaches 105.6 MV m^?1, which is 1.34 times that of pure PMIA. Moreover, owing to high thermal conductivity of fBNNSs, the thermal conductivities of fBNNSs‐12 are observably increased to 8.06 W m^?1 K of in‐plane direction and 0.84 W m^?1 K of through‐plane direction, respectively. Considering these properties, the manufactured PMIA/fBNNSs dielectric nanocomposites show potential applications in field of electronics.     

Crystallization and thermal conductivity of poly (vinylidene fluoride)/boron nitride nanosheets composites

ABSTRACT

In this work, boron nitride (BN) and exfoliated boron nitride nanosheets (BNNs) were employed as thermal conductive fillers to improve the thermal conductivity of poly(vinylidene fluoride) (PVDF) composites. Results suggested that the thermal conductivity of PVDF increases significantly with an increase in loading content of functional fillers. When the mass ratio of fillers was more than 30 wt%, the heat conduction network was formed. BNNs were capable of forming denser heat conduction network as per the SEM observations. In this scenario, PVDF/BNNs composites demonstrated excellent thermal conductivity. For example, the thermal conductivity of PVDF/BNNs (60/40) was 0.82 W/mK, which was 2.4 times and 17% higher than that of neat PVDF and PVDF/BN (60/40) counterpart, respectively. The non-isothermal crystallization of corresponding composite was studied by Mo method. Combining with XRD results, both BN and BNNs acted as the nucleation agents but had no effect on crystal forms.     

Pyrolysis process for boron nitride fiber derived from tris(methylamino)borane: Evolution of the molecular structure

To provide molecular-scale insight into the structural evolution from tris(methylamino)borane to boron nitride (BN) fiber during the chemical thermal-treating process, polymeric green fiber is cured in hot synthetic air at 300°C and then treats to 400, 600, 800, and 1000°C in ammonia. The chemical composition and structure of the volatile compounds and residual products are analyzed during the pyrolysis process for the polymeric green fiber. It is demonstrated that oxygen can be used to cure polymeric green fiber rapidly under the premise of ensuring a final fiber content of less than 1 wt% carbon and 2 wt% oxygen while maintaining the fiber tensile strength at 1000°C. The molecular structure evolution during the pyrolysis process for polymeric green fiber after oxygen curing is determined. Specifically, in hot synthetic air, introducing oxygen and releasing methylamine generates a B–O six-membered ring structure in the polymer in the first stage. Then, the removal of methyl results in the formation of a B–N–O network in hot ammonia. Afterward, nitridation of the B–O six-membered ring promotes the evolution of the B–N six-membered ring structure with the release of water and carbon dioxide. Finally, the growth and rearrangement of the BN structure are achieved.     

Elevated-Temperature Mechanical Properties of Silicon Nitride/Boron Nitride Fibrous Monolithic Ceramics

A unique, all-ceramic material capable of nonbrittle fracture via crack deflection and delamination has been mechanically characterized from 25° through 1400°C. This material, fibrous monoliths, was comprised of unidirectionally aligned 250 μm diameter silicon nitride cells surrounded by 10 to 20 μm thick boron nitride cell boundaries. The average flexure strengths of fibrous monoliths were 510 and 290 MPa for specimens tested at room temperature and 1300°C, respectively. Crack deflection in the BN cell boundaries was observed at all temperatures. Characteristic flexural responses were observed at temperatures between 25° and 1400°C. Changes in the flexural response at different temperatures were attributed to changes in the physical properties of either the silicon nitride cells or boron nitride cell boundary.     

Micro-sized polycrystalline cubic boron nitride with properties comparable to nanocrystalline counterparts

High-performance polycrystalline cubic boron nitride (PcBN) was sintered without binders at 1500 °C in a pressure range from 11 to 15 GPa using commercial micrometre cubic boron nitride (cBN) with a diameter of approximately 2–4 μm. The results demonstrated that the sample sintered at 12 GPa and 1500 °C had the best mechanical properties and thermal stability. Its average Vickers hardness, fracture toughness, and thermal stability was 63 GPa, 15 MPa m^1/2, and 1315 °C, respectively. The considerable improvement in the mechanical properties was mostly attributed to the high compactness, close bonding between grains, and the sample's internal defect structures. The relatively small specific surface area of the micron grains provides an advantage due to its high thermal stability. The amorphous regions observed in the sample's local areas may provide a new strengthening mechanism under high pressure and temperature.     

表面有丝状吸附物的氮化硼纳米管的制备

采用简单工艺,即：将块体氧化硼（B2O3）在氮气气氛中球磨后,在1200℃、流动的氨气中热处理,成功合成了表面有大量丝状吸附物的BN纳米管。纳米管为六方BN晶体且呈竹节形貌,其直径为80～120nm,长度近1μm。纳米管表面丝状的吸附层也是六方BN晶体,细丝的长度为100nm左右,直径不到10nm。     

Excellent electrical conductivity of the exfoliated and fluorinated hexagonal boron nitride nanosheets

The insulator characteristic of hexagonal boron nitride limits its applications in microelectronics. In this paper, the fluorinated hexagonal boron nitride nanosheets were prepared by doping fluorine into the boron nitride nanosheets exfoliated from the bulk boron nitride in isopropanol via a facile chemical solution method with fluoboric acid; interestingly, these boron nitride nanosheets demonstrate a typical semiconductor characteristic which were studied on a new scanning tunneling microscope-transmission electron microscope holder. Since this property changes from an insulator to a semiconductor of the boron nitride, these nanosheets will be able to extend their applications in designing and fabricating electronic nanodevices.     

Urchin-like boron nitride hierarchical structure assembled by nanotubes-nanosheets for effective removal of heavy metal ions

Water pollution has become a serious global issue owing to the large amounts of contaminants generated from industrial and agricultural development. Recently, various boron nitride-based micro/nano-materials have exhibited efficient sorption capacity for contaminants from water. Herein, novel urchin-like boron nitride hierarchical structure assembled by free-growing boron nitride nanotubes and crapy boron nitride nanosheets is firstly fabricated via a sample two-step approach, including the synthesis of analogous "core-shell" structured boron-containing precursor and thermal catalytic chemical vapor deposition. A combined growth mechanism of vapor-liquid-solid and vapor-solid is proposed to control the formation of BN hierarchical structure. The unique structure exhibits superior removal capacity of 115.07?mg?g^?1 and 92.85?mg?g^?1 for Pb²⁺ and Cu²⁺ in water solution, respectively. The excellent adsorption performance of the product mainly derives from the vast lattice imperfections, the high-density edge active sites, the expanded interplanar spacing, as well as the unique structural characteristics. They are beneficial for structural stability and enough space for accommodating the adsorbed heavy metal ions. These results indicate that the urchin-like boron nitride hierarchical structure is a promising adsorption material for water treatment.     

Boron Nitride Powders Formed by Aerosol Decomposition of Poly(borazinylamine) Solutions

Micrometer-sized aerosol droplets of a liquid ammonia solution of poly(borazinylamine) were formed in a nitrogen carrier gas by using an aerosol generator. The resulting droplets were thermally decomposed in a flow reactor at 1000°C. The white powder obtained was amorphous to X-rays and spherical with particle sizes on the order of 0.5 μm. The particles at this stage were porous, and some appeared to exhibit a hollow-shell morphology. Subsequent calcining at 1600°C yielded dense, crystalline boron nitride powder with partial sintering.     

Characterization of boron nitride nanosheets synthesized by boron-ammonia reaction

Boron nitride nanosheets (BNNS) with thickness 5–11 nm were successfully produced when pure boron powder (1–2 μm) interacted with ammonia gas in chemical vapour deposition set up. Under the optimized parameters, at 1200 °C and for uninterrupted 1 h of reaction duration, 2D BNNS with thickness of ca.11 nm were synthesized. BNNS were characterized by X-ray diffraction (XRD) for crystal structure, scanning electron microscopy for dimensions and morphology, energy dispersive X-ray analysis for chemical composition and Fourier transform infrared spectroscopy for sp² BN bond detection. The thickness of BNNS determined from both XRD data (using Scherrer equation) and atomic force microscopic analysis confirmed the stated product thickness. The BNNS obtained at 1200 °C had high crystallinity, purity and yield.     

Effect of temperature on the growth of boron nitride interfacial coatings on SiC fibers by chemical vapor infiltration

In order to improve bonding property between SiC fibers and matrix of SiC_f/SiC composites, boron nitride (BN) interfacial coatings were synthesized by chemical vapor infiltration. BN coatings were fabricated from BCl₃–NH₃ gaseous mixtures at four different temperatures (843 °C, 900 °C, 950 °C and 1050 °C) with different deposition times. Growth kinetics, nucleation and growth processes, microstructure and chemical composition of boron nitride coatings were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Raman spectrometry. Results showed that deposition rate increased as the temperature increased from 843 °C to 950 °C. However, deposition rate decreased slightly from 23.10 ± 0.85 nm/min (950 °C) to 21.39 ± 0.67 nm/min when the temperature was increased further to 1050 °C. It could be due to the nucleation occurring in the gas and the consumption of a large amount of BCl₃ and NH₃. When deposition temperature was 843 °C, BN grains deposited on top layer of the coating could not completely cross Ehrlich-Schwoebel barrier and grew in island growth mode. On the other hand, the deposition pattern followed a layer-by-layer growth mode when deposition temperature was 1050 °C. Deposition temperature significantly affected the microstructure of as-deposited BN coatings. At 843 °C, 950 °C and 1050 °C, the coatings presented amorphous, polycrystalline and hexagonal structures, respectively.     

Dielectric properties of polymer-derived ceramic reinforced with boron nitride nanotubes

The electrical and dielectric properties of boron nitride nanotubes (BNNTs) reinforced ceramic composites using the polymer-derived ceramic (PDC) processing route were investigated in this work. The electrical resistivity of the pristine PDC increases from 10⁶ to 10⁸ Ω m after the addition of BNNTs. When the BNNT loading was increased to 5 wt%, the average real relative permittivity of the PDC decreased from 2.94 to 2.80, while the quality factor (Q) of the PDC increased from 134.40 to 176.77. The BNNTs can increase the Q factor of the PDC due to the reduction in the porosity cause by the introduction of the BNNTs. Further increasing the BNNT content decreases the real relative permittivity of the nanocomposites and increases the Q factor at high frequency. The average real relative permittivity decreases to 2.29, while the average Q factor increases to 208.60 when the BNNT content is increased to 30 wt%. The dielectric loss after the addition of high fraction of BNNTs can be explained by the Lorentz resonance relaxation process. Results of this work showed that PDC-BNNT nanocomposites are satisfactory electromagnetic transparent materials when the BNNT fraction is less than 10 wt%.     

Synthesis of highly purified and crystallized h-BN using calcium-assisted carbothermal reduction nitridation

Highly purified and crystallized hexagonal boron nitride (h-BN) powder is suitable as thermally conductive filler in resins. To obtain h-BN powder with large particle size, as well as high purity and crystallinity, high-temperature heat treatment over 1800°C in a N₂ gas atmosphere is effective. The carbothermal reduction nitridation (CRN) involves the carbothermic reduction of boric oxide in a N₂ gas atmosphere. In CRN using a CaO promoter, h-BN particles with high crystallinity can be obtained by a simple heat treatment process. CaO prevents the evaporation of boron oxide and aids in h-BN particle growth at high temperatures. However, CaB₆ is formed as byproduct or impurity when CRN using the CaO promoter is performed at temperatures higher than 1800°C. In this study, the relationship between the products and the reaction temperature was clarified via thermodynamic considerations and experimentation. The results clarified the ideal reaction process of CRN using a CaO promoter to obtain highly purified and crystallized h-BN powder.