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

Patterned growth and cathodoluminescence of conical boron nitride nanorods

We demonstrate a simple and effective approach for growing large-scale, high-density, and well-patterned conical boron nitride nanorods. A catalyst layer of Fe(NO₃)₃ was patterned on a silicon substrate by using a copper grid as a mask. The nanorods were grown via annealing milled boron carbide powders at 1300 °C in a flow of nitrogen gas. The as-grown nanorods exhibit uniform morphology and the catalyst pattern precisely defines the position of nanorod deposition. Cathodoluminescence (CL) spectra of the nanorods show two broad emission bands centered at 3.75 and 1.85 eV. Panchromatic CL images reveal clear patterned structure

Light emission and excitonic effect of boron nitride nanotubes observed by photoluminescent spectra

Photoluminescent (PL) and optical absorption spectra of high-yield multi-wall BN nanotubes (BNNTs) were systematically investigated at room temperature in comparison with commercial hexagonal BN (h-BN) powder. The direct band gap of the BNNTs was determined to be 5.75 eV, just slightly narrower than that of h-BN powder (5.82 eV). Two Frenkel excitons with the binding energy of 1.27 and 1.35 eV were also determined. However, they were not a distinctive characteristic of the BNNTs as reported previously. Observed broad UV–visible–NIR light emission demonstrates the potential of the BNNTs as a nano light source.

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.

Boron carbide nanowires with uniform CNχ coatings

Boron carbide nanowires with uniform carbon nitride coating layers were synthesized on a silicon substrate using a simple thermal process. The structure and morphology of the as-synthesized nanowires were characterized using x-ray diffraction, scanning and transmission electron microscopy and electron energy loss spectroscopy. A correlation between the surface smoothness of the nanowire sidewalls and their lateral sizes has been observed and it is a consequence of the anisotropic formation of the coating layers. A growth mechanism is also proposed for these growth phenomena.

Field-emission characteristics of conical boron nitride nanorods

We present the electron field-emission (FE) characteristics of conical boron nitride nanorods grown on a (1 0 0) n-type silicon substrate. The emission current can be up to ~60 µA at an applied voltage of ~3 kV. Two distinct slopes are evident in the Fowler–Nordheim (FN) plot. The FE characteristics can be explained using a site-related tunnelling-controlled mechanism. The occurrence of two FN slopes is attributed to the switchover from tip emission to side emission, which results from the differences in interface barrier, geometry, as well as the total emission area of the two emission interfaces.

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.

Growth and structure of prismatic boron nitride nanorods

Prismatic boron nitride nanorods have been grown on single crystal silicon substrates by mechanical ball-milling followed by annealing at 1300 °C. Growth takes place by rapid surface diffusion of BN molecules, and follows heterogeneous nucleation at catalytic particles of an Fe/Si alloy. Lattice imaging transmission electron microscopy studies reveal a central axial row of rather small truncated pyramidal nanovoids on each nanorod, surrounded by three basal planar BN domains which, with successive deposition of epitaxial layers adapt to the void geometry by crystallographic faceting. The bulk strain in the nanorods is taken up by the presence of what appear to be simple nanostacking faults in the external, near-surface domains which, like the nanovoids are regularly repetitive along the nanorod length. Growth terminates with a clear cuneiform tip for each nanorod. Lateral nanorod dimensions are essentially determined by the size of the catalytic particle, which remains as a foundation essentially responsible for base growth. Growth, structure, and dominating facets are shown to be consistent with a system which seeks lowest bulk and surface energies according to the well-known thermodynamics of the capillarity of solids.