Boron nitride nanotubes : pronounced resistance to oxidation

Boron nitride (BN) nanotubes have the same nanostructure as carbon nanotubes but are found to exhibit significant resistance to oxidation at high temperatures. Our systematic study has revealed that BN nanotubes are stable at 700 °C in air and that some thin nanotubes (diameter less than 20 nm) with perfect multiwalled cylindrical structure can survive up to 900 °C. Thermogravimetric analysis reveals an onset temperature for oxidation of BN nanotubes of 800 °C compared with only 400 °C for carbon nanotubes under the same conditions. This more pronounced resistance of BN nanotubes to oxidation is inherited from the hexagonal BN and also depends on the nanocrystalline structure. This high level of resistance to oxidation allows promising BN nanotube applications at
high temperatures

Purification of boron nitride nanotubes

A purification process was developed for the first time for boron nitride (BN) nanotubes. BN nanotubes, prepared using a ball milling and annealing method, contain a high yield of nanotubes and a small amount of BN and metal catalyst particles. The metal particles can be dissolved in an HCl solution. Fine BN nanoparticles and thin layers were first converted to water soluble B₂O₃ via a partial oxidation treatment at 800 °C. The oxide particles and layers can then be dissolved in hot water. Thermogravimetric analysis has been used to determine an adequate oxidation temperature at which fine BN particles were oxidized.

An effective approach to grow boron nitride nanowires directly on stainless-steel substrates

When growing one-dimensional (1D) nanomaterials via the vapour–liquid–solid (VLS) model, the substrates usually need to be coated with a layer of catalyst film. In this study, however, an effective approach for the synthesis of boron nitride (BN) nanowires directly onto commercial stainless-steel foils has been demonstrated. Growth occurs by heating boron and zinc oxide (ZnO) powders at 1100 °C under a mixture of nitrogen and hydrogen gas flow (200 ml min−1). The stainless-steel foils played an additional role of catalyst besides substrate during the VLS growth of these BN nanowires. The as-synthesized nanowires emit strong photoluminescence (PL) bands at 515, 535 and 728 nm. In addition, we found that the gas flow rate and the hydrogen content in the gas mixture strongly affected the diameter and yield of the nanowires by changing the relative concentration of the nanowire growth species in the chamber.

Pure boron nitride nanowires produced from boron triiodide

A thick layer of pure boron nitride (BN) nanowires with a uniform diameter of 20 nm was synthesized for the first time using a CVD process with a new precursor of boron triiodide (BI3). Transmission electron microscopy revealed a nanocrystalline structure in the BN nanowires and the absence of any catalyst particle. Some BN nanowires self-assembled into thick threads up to several hundred micrometres long on top of the nanowire layer. The nitriding reactions and lack of catalyst suggest new formation mechanisms of the BN nanowires.

11B nuclear magnetic resonance study of boron nitride nanotubes prepared by mechano-thermal method

We reported ¹¹B nuclear magnetic resonance studies of boron nitride (BN) nanotubes prepared by mechano-thermal route. The NMR lineshape obtained at 192.493 MHz (14.7 T) was fitted with two Gaussian functions, and the ¹¹B nuclear magnetization relaxations were satisfied with the stretched–exponential function, exp[-(tlT₁)^(D+1)/6] (D: space dimension) at all temperatures. In addition, the temperature dependence of spin–lattice relaxation rates was well described by T_i^-1 = aT (a: constant, T: temperature) and could be understood in terms of direct phonon process. All the 11BNMR results were explained by considering the inhomogeneous distribution of the paramagnetic metal catalysts, such as α-Fe, Fe–N, and Fe₂ B, that were incorporated during the process of high-energy ball milling of boron powder and be synthesized during subsequent thermal annealing. X-ray powder diffraction as well as electron paramagnetic resonance (EPR) on BN nanotubes were also conducted and the results obtained supported these conclusions.

Influence of nitriding gases on the growth of boron nitride nanotubes

Boron nitride (BN) nanotubes of different sizes and tubular structures exhibit very different mechanical and chemical properties, as well as different applications. BN nanotubes of different sizes and nanostructures have been produced in different nitriding gases in a milling and annealing process, in which elemental boron powder was first milled in NH₃ for 150 h and subsequently annealed at 1,200 °C for 6 h. The influence of nitriding gases was investigated by using N₂, NH₃, N₂–H₂ mixture gases. A relatively slow nitriding reaction in NH₃ gas leaded to a 2D growth of BN (002) basal planes and the formation of thin BN nanotubes without the help of metal catalysts. Fast nitriding reactions occurred in N₂ or N₂–H₂ mixture gases, catalyzed by metal particles, resulted in 3D crystal growth and the formation of many large cylindrical and bamboo tubes.

Conical boron nitride nanorods synthesized via the ball-milling and annealing method

A boron nitride (BN) nanostructure, conical BN nanorod, has been synthesized in a large quantity on Si substrates for the first time via the ball-milling and annealing method. Nitridation of milled boron carbide (B₄C) powders was performed in nitrogen gas at 1300°C on the surface of the substrates to form the BN nanorods. The highly crystallized nanorods consist of conical BN basal layers stacked along the nanorod axis. Ball milling of the B₄C powders can significantly enhance the nitridation of the powders and thus facilitate the formation of nanorods during the annealing process.

Decoration of nitrogen vacancies by oxygen atoms in boron nitride nanotubes

Decoration of nitrogen vacancies by oxygen atoms has been studied by near-edge X-ray absorption fine structure (NEXAFS) around B K-edge in several boron nitride (BN) structures, including bamboo-like and multi-walled BN nanotubes. Breaking of B-N bonds and formation of nitrogen vacancies under low-energy ion bombardment reduces oxidation resistance of BN structures and promotes an efficient oxygen-healing mechanism, in full agreement with some recent theoretical predictions. The formation of mixed O-B-N and B-O bonds is clearly identified by well-resolved peaks in NEXAFS spectra of excited boron atoms.

Large-scale mechanical peeling of boron nitride nanosheets by low-energy ball milling

Mechanical cleavage by Scotch tape was the first method to produce graphene and is still widely used in laboratories. However, a critical problem of this method is the extremely low yield. We have tailored ball milling conditions to produce gentle shear forces that produce high quality boron nitride (BN) nanosheets in high yield and efficiency. The in-plane structure of the BN nanosheets has not been damaged as shown by near edge X-ray absorption fine structure measurements. The benzyl benzoate acts as the milling agent to reduce the ball impacts and milling contamination. This method is applicable to any layered materials for producing nanosheets.

Improving thermal conductivity of cotton fabrics using composite coatings containing graphene, multiwall carbon nanotube or boron nitride fine particles

Graphene, multi-wall carbon nanotube (MWCNT) and fine boron nitride (BN) particles were separately applied with a resin onto a cotton fabric, and the effect of the thin composite coatings on the thermal conductive property, air permeability, wettability and color appearance of the cotton fabric was examined. The existence of the fillers within the coating layer increased the thermal conductivity of the coated cotton fabric. At the same coating content, the increase in fabric thermal conductivity was in the order of graphene > BN > MWCNT, ranging from 132 % to 842 % (based on pure cotton fabric). The coating led to 73 %, 69 % and 64 % reduction in air permeability when it respectively contained 50.0 wt% graphene, BN and MWCNTs. The graphene and MWCNT treated fabrics had a black appearance, but the coating had almost no influence on the fabric hydrophilicity. The BN coating made cotton fabric surface hydrophobic, with little change in fabric color.

Strong oxidation resistance of atomically thin boron nitride nanosheets

Investigation of oxidation resistance of two-dimensional (2D) materials is critical for many of their applications because 2D materials could have higher oxidation kinetics than their bulk counterparts due to predominant surface atoms and structural distortions. In this study, the oxidation behavior of high-quality boron nitride (BN) nanosheets of 1-4 layers thick has been examined by heating in air. Atomic force microscopy and Raman spectroscopy analyses reveal that monolayer BN nanosheets can sustain up to 850 °C, and the starting temperature of oxygen doping/oxidation of BN nanosheets only slightly increases with the increase of nanosheet layer and depends on heating conditions. Elongated etch lines are found on the oxidized monolayer BN nanosheets, suggesting that the BN nanosheets are first cut along the chemisorbed oxygen chains and then the oxidative etching grows perpendicularly to these cut lines. The stronger oxidation resistance of BN nanosheets makes them more preferable for high-temperature applications than graphene.

Dielectric screening in atomically thin boron nitride nanosheets

Two-dimensional (2D) hexagonal boron nitride (BN) nanosheets are excellent dielectric substrate for graphene, molybdenum disulfide, and many other 2D nanomaterial-based electronic and photonic devices. To optimize the performance of these 2D devices, it is essential to understand the dielectric screening properties of BN nanosheets as a function of the thickness. Here, electric force microscopy along with theoretical calculations based on both state-of-the-art first-principles calculations with van der Waals interactions under consideration, and nonlinear Thomas-Fermi theory models are used to investigate the dielectric screening in high-quality BN nanosheets of different thicknesses. It is found that atomically thin BN nanosheets are less effective in electric field screening, but the screening capability of BN shows a relatively weak dependence on the layer thickness.

Oxygen-doped boron nitride nanosheets with excellent performance in hydrogen storage

Hydrogen is considered one of the best energy sources. However, the lack of effective, stable, and safe storage materials has severely prevented its practical application. Strong effort has been made to try new nanostructured materials as new storage materials. In this study, oxygen-doped boron nitride (BN) nanosheets with 2-6 atomic layers, synthesized by a facile sol-gel method, show a storage capacity of 5.7wt% under 5MPa at room temperature, which is the highest hydrogen storage ever reported for any BN materials. Importantly, 89% of the stored hydrogen can be released when the hydrogen pressure is reduced to ambient conditions. Furthermore, the BN nanosheets exhibit an excellent storage cycling stability due to the stable two-dimensional nanostructure. The first principles calculations reveal that the high hydrogen storage mainly origins from the oxygen-doping of the BN nanosheets with increased adsorption energies of H2 on BN by 20-80% over pure BN sheets at the different coverage. © 2014 Elsevier Ltd.

High-efficient production of boron nitride nanosheets via an optimized ball milling process for lubrication in oil

Although tailored wet ball milling can be an efficient method to produce a large quantity of two-dimensional nanomaterials, such as boron nitride (BN) nanosheets, milling parameters including milling speed, ball-to-powder ratio, milling ball size and milling agent, are important for optimization of exfoliation efficiency and production yield. In this report, we systematically investigate the effects of different milling parameters on the production of BN nanosheets with benzyl benzoate being used as the milling agent. It is found that small balls of 0.1-0.2 mm in diameter are much more effective in exfoliating BN particles to BN nanosheets. Under the optimum condition, the production yield can be as high as 13.8% and the BN nanosheets are 0.5-1.5 μm in diameter and a few nanometers thick and of relative high crystallinity and chemical purity. The lubrication properties of the BN nanosheets in base oil have also been studied. The tribological tests show that the BN nanosheets can greatly reduce the friction coefficient and wear scar diameter of the base oil.