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%.     

Surface-diffusion mechanism for synthesis of substrate-free and catalyst-free boron nitride nanosheets

This study presents an innovative surface-diffusion mechanism for the growth of substrate-free and catalyst-free boron nitride nanosheets (BNNSs) by annealing an ammonium borate hydroxide hydrate precursor in a NH₃ chemical vapor deposition system. At elevated temperatures, part of NH₄B₅O₈ slowly decomposes and forms B₂O₃, and flowing NH₃ gradually diffuses to the B₂O₃ surface to form vertically aligned BNNSs. The lateral dimension and crystallinity of the BNNSs increase, while their thickness decreases with the continuous surface-diffusion reaction. The residual NH₄B₅O₈ and B₂O₃ absorbs moisture in the air to constitute NH₄B₅O₈·4H₂O and H₃BO₃ substrates. With increasing annealing temperature and soaking time (at 1400 °C for 7 h), all NH₄B₅O₈ decomposes and the surface-diffusion reaction between B₂O₃ and NH₃ completely occurs, forming substrate-free BNNSs with a lateral dimension of 1 μm and a thickness of 10 nm. This reliable approach for synthesizing BNNSs paves the way for future applications in advanced ceramic composites.     

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.     

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。     

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.     

Large-scale fabrication of boron nitride nanotubes with high purity via solid-state reaction method

An effective solid-state reaction method is reported for synthesizing boron nitride nanotubes (BNNTs) in large scale and with high purity by annealing amorphous boron powder and ferric chloride (FeCl₃) catalyst in ammonia atmosphere at elevated temperatures. FeCl₃ that has rarely been utilized before is introduced not only as a catalyst but also as an efficient transforming agent which converts boron powder into boron chloride (BCl₃) vapor in situ. The nanotubes are bamboo in shape and have an average diameter of about 90 nm. The effect of synthetic temperatures on nanotube morphology and yield is investigated. The photoluminescence (PL) measurement shows emission bands of the nanotubes at 354, 423, 467, and 666 nm. A combined growth mechanism of vapor–liquid-solid (VLS) and solid–liquid-solid (SLS) model is proposed for the formation of the BNNTs.     

Interfacial diffusion-limited vapor-liquid-solid mechanism for the growth of tadpole-shaped boron nitride nanostructures

Here, tadpole-shaped boron nitride (BN) nanostructures, with a length of ∼10 µm and a diameter ranging from 0.05 µm (tail) to 1.0 µm (head), were prepared by a facile two-step process, involving the synthesis of a cobalt carbonate-boron precursor, and its annealing using chemical vapor deposition in an ammonia atmosphere. Based on phase composition changes and microstructural evolution during annealing, and thermodynamic analysis, an interfacial diffusion-limited vapor-liquid-solid mechanism was proposed for the growth of the tadpole-shaped BN nanostructures. An understanding of the growth mechanism of the nano-tadpoles supplements the knowledge base of the BN nanostructure family and provides a new opportunity for the synthesis of analogous inorganic nanomaterials.     

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

We report the thermal properties of boron nitride nanotube (BNNT) reinforced ceramic composites using the polymer derived ceramic (PDC) processing route. The nano-composites had a BNNT loading of up to 35.4 vol.%. TGA results showed that nano-composites have good thermal stability up to 900°C in air. BNNTs in nano-composites survived in an oxidizing environment up to 900°C, revealing that nano-composites can be used for high temperature applications. Thermal conductivity of PDC reinforced with 35.4 vol.% BNNT was measured as 4.123 W/(m·K) at room temperature, which is a 2100 % increase compared to that of pristine PDC. The thermal conductivity value increases with the increase of BNNT content. A thermal conductivity percolation phenomenon appeared when the BNNT content increased to 36 ± 5 vol.%. The results of this study showed that BNNTs could effectively improve the thermal conductivity of PDC materials. BNNT reinforced PDC could be used as thermal structural materials in a harsh environment at temperatures up to 900°C.     

Covalent functionalization of boron nitride nanotubes through photo-initiated chemical vapour deposition

Boron nitride nanotubes (BNNTs) are analogous nanostructures to carbon nanotubes (CNTs), possessing similar properties such as Young's modulus and thermal conductivity, but superior resistance to oxidation and thermal stability. In addition, BNNTs are insulating materials, whereas CNTs are electrically conductive. They could be used as reinforcements in polymeric matrices as heat dissipators or as protective coatings in harsh environments. However, when incorporating them into polymers, one main drawback is their tendency to agglomerate. To improve their dispersion, covalent surface modification can be applied, with solvent-free approaches being preferred. Herein, we used syngas photo-initiated chemical vapour deposition (PICVD) to incorporate oxygen functionalities on the surface of BNNT. X-ray photoelectron spectroscopy analysis showed a highly oxidized BNNT surface after treatment. In addition, a decrease in water contact angle and an increase in surface energy were observed for the treated material. These results open new possibilities to incorporate hydrophilic BNNTs surfaces into polar polymers or other matrices of interest.     

Mechanical and dielectric properties of functionalized boron nitride nanosheets/silicon nitride composites

Uniformly dispersed boron nitride nanosheets (BNNSs) reinforced silicon nitride (Si₃N₄) composites were prepared by surface modification assisted flocculation combined with SPS sintering. In order to improve the dispersibility of the BNNSs in the composites, the liquid phase stripped BNNSs are surface functionalized by a two-step covalently modification. The amino-modified BNNSs (NH₂-BNNSs) and Si₃N₄ powders have opposite surface potential, mixed evenly by electrostatic interaction during flocculation. The results showed that mechanical properties of Si₃N₄ composites were obviously enhanced by adding NH₂-BNNSs. The fracture toughness and bending strength of Si₃N₄ composites added 0.75 wt% NH₂-BNNSs were increased by 34% and 28%, respectively, compared with monolithic Si₃N₄. Toughening mechanisms are synergistic action of the torn, pull-out or bridging of BNNSs and crack deflection mechanisms with microstructural analyzes. The dielectric properties of the Si₃N₄ ceramics are also improved after the addition of NH₂-BNNSs.     

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.     

Enhancing mechanical properties of fused silica composites by introducing well-dispersed boron nitride nanosheets

Well-dispersed boron nitride nanosheets (BNNSs) reinforced fused silica composites were successfully fabricated by surface modification assisted flocculation method. Surface modification can enhance the performance of flocculation process. BNNSs were homogeneously mixed with fused silica through the electrostatic interaction between hydroxylated BNNSs with negative charge and amino-modified fused silica with positive charge. The BNNSs can act as excellent nanofillers for enhancing the mechanical properties of fused silica composites. Approximately 74% and 48% increases in flexure strength and fracture toughness can be achieved for the 1.5 wt% BNNSs/fused silica composite, respectively. The toughening mechanisms were analyzed by microstructural characterization, especially for pull-out mechanism.     

Scalable production of boron nitride nanosheets in ionic liquids by shear-assisted thermal treatment

Due to their intriguing properties, boron nitride nanosheets (BNNSs) with large lateral size and high crystallinity have great promise for many applications. However, the quantitative exfoliation of hexagonal boron nitride (h-BN) into good quality BNNSs still remains a key challenge. Herein, we report a scalable method to exfoliate BNNSs in ionic liquids (ILs) via shear-assisted thermal treatment. Few-layer BNNSs with well-preserved structural integrity are successfully prepared by this method. The synergistic effects of strong physical adsorption and intercalation of IL molecules, chemical interactions between hydrogen fluoride (HF) and h-BN, activation energy provided by heat treatment, and shear forces generated by repetitive stirring effect contribute to the exfoliation of BNNSs.     

Synthesis of boron nitride nanotubes by combining citrate-nitrate combustion reaction and catalytic chemical vapor deposition

High-quality boron nitride nanotubes were successfully synthesized via a novel two-step method, including citrate-nitrate combustion reaction and catalytic chemical vapor deposition. The composition, bonding features and microstructures of as-synthesized sample were investigated by X-ray diffraction, Fourier transform infrared spectroscopy, Raman microscopy, X-ray photoelectron spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, transmission electron microscopy and selected area electron diffraction techniques. The results show that the as-synthesized boron nitride nanotubes with smooth surface are relatively pure. The diameter ranges between 20 and 80?nm, while the length is about dozens of micrometers. During the synthesis process of boron nitride nanotubes, citric acid chelates the cobalt ions and reacts with nitrate to form the cobalt oxide, depositing on the surface of boron powder homogeneously. The catalyst content and annealing temperature have a significant impact on the composition and microstructures of the final products. Based on the experimental results and thermodynamic analysis, the possible chemical reactions are listed, and vapor-liquid-solid mechanism is proposed to be dominant for the formation of boron nitride nanotubes.     

Green and efficient production of boron nitride nanosheets via oxygen doping-facilitated liquid exfoliation

As the structural analogue of graphene, boron nitride nanosheets (BNNSs) are anticipated to have a wide range of potential applications. BNNSs exhibit good mechanical properties, outstanding thermal conductivity, oxidation and chemical stability and are excellent electrical insulators. While BNNSs have gained recognition as one of the most versatile 2D materials in recent years, their application in research and industry is still hampered by the lack of methods to produce BNNSs in large quantity and a cost-effective way. In this study, we report highly efficient h-BN exfoliation via the oxygen doping-facilitated liquid exfoliation. Oxygen atoms are introduced into the hexagonal boron nitride (h-BN) structure via a facile thermal treatment. The relationship of thermal treatment, structural changes and h-BN exfoliation are studied to elucidate the key factor for advancing the BNNS production. The optimum concentration of hydroxyl groups and weakening of interlayer interactions have synergistically facilitated the delamination of h-BN in water under mild exfoliation conditions, resulting in up to 1255% yield increment and without noticeable new defects in the BNNS structure as compared with the untreated control. An efficient and environmentally friendly exfoliation process of h-BN is a crucial starting point towards the cost-effective and mass production of BNNSs which is needed for the currently identified and myriad future applications of BNNSs.     

Hexagonal boron nitride nanosheets exfoliated by sodium hypochlorite ball mill and their potential application in catalysis

The unique physicochemical properties of two-dimensional (2D) h-BN and its promising applications in future optoelectronics have motivated an extensive study of its properties. However, a major limiting factor is its high quality and scalable preparation of few-layer h-BN. Herein, a facile, low cost, and high yield process is developed by using a sodium hypochlorite aqueous solution-assisted ball milling exfoliation process. The facile process results in scalable production of few-layer (2–4 sheets) h-BN from commercial BN powders, with little damage of its in-plane structure and high yield amounting to 21%. Furthermore, few-layer h-BN has been demonstrated to be good carrier to support and disperse Ag nanoparticles with high catalytic activity for the reduction of p-nitrophenol to p-aminophenol with NaBH₄. The pseudo-first-order reaction rate constant of the pre-prepared catalyst was calculated to be 7.13×10⁻³ s⁻¹, larger than that of pristine BN supported Ag nanoparticles. The results indicate that stable exfoliation process could open the way to a range of important applications of h-BN based materials.     

Few-layer boron nitride nanosheets: Preparation,characterization and application in epoxy resin

Large-scale exfoliated boron nitride nanosheets were achieved via a liquid exfoliation sonication method by using sodium fluoride and ammonium hydroxide as Lewis base compounds. The crystal structure, surface functional groups, morphology and thickness of the as-prepared samples were characterized by X-ray diffraction, fourier transform infrared spectroscopy, transmission electron microscopy and atomic force microscopy, respectively. The as-prepared samples were introduced into epoxy resin to fabricate the polymer-based composites. Experimental results showed that the layer thickness of the as-prepared nanosheets was in the range of 1 to 3 layers. Moreover, it could improve the tensile properties of the matrix. When the loading of the as-prepared nanoparticles was 0.4 wt%, the tensile strength and elongation at break of the composites reached to their maximum values 65.6 MPa and 25.9%, which were increased by 118% and 192% more than that of pure resin. In addition, the as-prepared boron nitride samples could improve the thermostability and promote the curing of the matrix.     

In situ preparation of intrinsic flame-retardant urea formaldehyde/carbon nanotubes nanocomposite foam: structure and reinforcing mechanism

ABSTRACT

Urea-formaldehyde (UF)/carboxylated carbon nanotubes (CNTs-COOH) nanocomposite foams were prepared via in-situ polymerization. Chemical bonding and hydrogen bonding interactions formed between CNTs-COOH and UF matrix. UF resin adhered onto the ektexine of CNTs-COOH and grafting ratio of 496.41% was achieved. UF/CNTs-COOH foam showed smaller cell size, narrower cell size distribution and lower water absorption compared with UF foam. Introduction of 0.25 wt% CNTs-COOH resulted in 58.43% increase in compressive strength. CNTs-COOH were pulled out with surface covered with UF resin under stress and the failure mode was the destruction of matrix around interfacial layer. UL-94V-0 rating was achieved for the composite foams.