基于第一抗热震因子的BN纳米管/Si_3N_4复合材料抗热震性能评价

利用Kingery抗热震断裂理论构建了BN纳米管(BNNTs)强韧化陶瓷复合材料的第一抗热震因子模型,通过真空热压烧结法制备了四组BNNTs含量分别为0.5wt%、1.0wt%、1.5wt%和2.0wt%的BNNTs/Si_3N_4复合材料,并采用水浴淬冷法和三点弯曲法测试了复合材料的抗热震性能(震后弯曲强度和临界热震断裂温差)。测试结果验证了在急剧加热和急剧冷却条件下第一抗热震因子模型的正确性。结果表明:添加BNNTs使BNNTs/Si_3N_4复合材料第一抗热震因子增大,抗热震性能提升。分布在晶界上的BNNTs起到裂纹钉扎、桥联和裂纹偏转作用,增加了裂纹扩展的阻力;纳米管孔隙的存在改变了裂纹扩展路径,提高了BNNTs/Si_3N_4的断裂韧度,从而有效提高了其抗热震断裂能力。     

Self-Catalytic Ternary Compounds for Efficient Synthesis of High-Quality Boron Nitride Nanotubes

The large-scale synthesis of high-quality boron nitride nanotubes (BNNTs) has attracted considerable interests due to their applications in nanocomposites, thermal management, and so on. Despite decades of development, efficient preparation of high-quality BNNTs, which relies on the effective design of precursors and catalysts and deep insights into the catalytic mechanisms, is still urgently needed. Here, a self-catalytic process is designed to grow high-quality BNNTs using ternary W–B–Li compounds. W–B–Li compounds provide boron source and catalyst for BNNTs growth. High-quality BNNTs are successfully obtained via this approach. Density functional theory-based molecular dynamics (DFT-MD) simulations demonstrate that the Li intercalation into the lattice of W₂B₅ promotes the formation of W–B–Li liquid and facilitates the compound evaporation for efficient BNNTs growth. This work demonstrates a high-efficient self-catalytic growth of high-quality BNNTs via ternary W–B–Li compounds, providing a new understanding of high-quality BNNTs growth.     

Bulk synthesis, growth mechanism and properties of highly pure ultrafine boron nitride nanotubes with diameters of sub-10 nm

As a structural analogue of the carbon nanotube (CNT), the boron nitride nanotube (BNNT) has become one of the most intriguing non-carbon nanostructures. However, up to now the pre-existing restrictions/limitations of BNNT syntheses have made the progress in their research rather modest. This work presents a new route toward the synthesis of highly pure ultrafine BNNTs based on a modified boron oxide (BO) CVD method. A new effective precursor--a mixture of Li?O and B--has been proposed for the growth of thin, few-layer BNNTs in bulk amounts. The Li?O utilized as the precursor plays the crucial role for the present nanotube growth. The prepared BNNTs have average external diameters of sub-10 nm and lengths of up to tens of μm. Electron energy loss spectrometry and Raman spectroscopy demonstrate the ultimate phase purity of the ultrafine BNNTs. Property studies indicate that the ultrafine nanotubes are perfect electrical insulators exhibiting superb resistance to oxidation and strong UV emission. Moreover, their reduced diameters lead to a dramatically decreased population of defects within the tube walls and result in the observation of near-band-edge (NBE) emission at room temperature.     

Effective Synthesis of Vertically Aligned Boron Nitride Nanotubes via a Simple CCVD

A simple catalytic chemical vapor deposition technique based on the combined logic of previously synthesized vertically aligned carbon nanotubes and pattern growth of boron nitride nanotubes (BNNTs) along with a few simple modifications in the experimental setup is successfully used for the synthesis of vertically aligned BNNTs. Field emission scanning electron microscope images show the top and side view of the as grown pure BNNTs. High-resolution transmission electron microscope images confirm the tubular structure as well as the highly crystalline nature of the tubes. X-ray photon spectroscopy and Raman spectroscopy indicate h-BN as a main constituent of BNNTs synthesized in the present work.     

基于第二抗热震因子的BNNTs/Si3N4复合材料抗热震性能评价

利用Kingery抗热震断裂理论构建了氮化硼纳米管（BNNTs）强韧化陶瓷复合材料的第二抗热震因子模型,通过真空热压烧结法制备了BNNTs质量分数分别为0.5wt%、1.0wt%、1.5wt%和2.0wt%的BNNTs/Si₃N₄复合材料,并采用预制裂纹法测试了复合材料的抗热震性能,测试结果证实了在平稳状态下模型的正确性。结果表明,BNNTs的存在使复合材料第二抗热震因子增大,抗热震性能提升。分布在晶界上的BNNTs起到裂纹钉扎、桥联和裂纹偏转作用,增加了裂纹扩展的阻力,从而有效提高了BNNTs/Si₃N₄复合材料抗热震断裂能力。     

Measurement of wetting properties of individual boron nitride nanotubes with the wilhelmy method using a nanotube-based force sensor

The wetting properties of individual boron nitride nanotubes (BNNTs) were studied with the Wilhelmy method in ambient conditions. A nanotube-based force sensor having a force resolution of 0.1 nN, calibrated with the wetting force method, was used to study the interactions between BNNTs and liquids in situ. The static contact angles of the liquids on BNNTs were evaluated, and the surface tension of the BNNT along with its surface tension components was determined based on the Owens and Wendt method and the van Oss-Chaudhury-Good acid-base theory.     

Synthesis of multiwall boron nitride nanotubes dependent on crystallographic structure of boron

Synthesis and growth of multiwall boron nitride nanotubes (BNNTs) under the B and ZrO₂ seed system in the milling–annealing process were investigated. BNNTs were synthesized by annealing a mechanically activated boron powder under nitrogen environment. We explored the aspects of the mechanical activation energy transferred to milled crystalline boron powder producing structural disorder and borothermal reaction of the ZrO₂ seed particles on the synthesis of BNNTs during annealing. Under these circumstances, the chemical reaction of amorphous boron coated on the seed nanoparticles with nitrogen synthesizing amorphous BN could be enhanced. It was found that amorphous BN was crystallized to the layer structure and then grown to multiwall BNNTs during annealing. Especially, bamboo-type multiwall BNNTs were mostly produced and grown to the tail-side of the nanotube not to the round head-side. Open gaps with ∼0.3 nm of the bamboo side walls of BNNTs were also observed. Based on these understandings, it might be possible to produce bamboo-type multiwall BNNTs by optimization of the structure and shape of boron coat on the seed nanoparticles.     

Boron nitride nanotubes coated with organic hydrophilic agents: Stability and cytocompatibility studies

In the present study, Boron Nitride Nanotubes (BNNTs) were synthesized and functionalized with organic hydrophilic agents constituted by glucosamine (GA), polyethylene glycol (PEG)₁₀₀₀, and chitosan (CH) forming new singular systems. Their size, distribution, and homogeneity were determined by photon correlation spectroscopy, while their surface charge was determined by laser Doppler anemometry. The morphology and structural organization were evaluated by Transmission Electron Microscopy. The functionalization was evaluated by Thermogravimetry analysis and Fourier Transformer Infrared Spectroscopy. The results showed that BNNTs were successfully obtained and functionalized, reaching a mean size and dispersity deemed adequate for in vitro studies. The in vitro stability tests also revealed a good adhesion of functionalized agents on BNNT surfaces. Finally, the in vitro cytocompatibility of functionalized BNNTs against MCR-5 cells was evaluated, and the results revealed that none of the different functionalization agents disturbed the propagation of normal cells up to the concentration of 50 μg/mL. Furthermore, in this concentration, no significantly chromosomal or morphologic alterations or increase in ROS (Reactive Oxygen Species) could be observed. Thus, findings from the present study reveal an important stability and cytocompatibility of functionalized BNNTs as new potential drugs or radioisotope nanocarriers to be applied in therapeutic procedures.     

Effect of MoO3 on the synthesis of boron nitride nanotubes over Fe and Ni catalysts

Synthesis of boron nitride nanotubes at reduced temperature is important for industrial manufactures. In this study boron nitride nanotubes were synthesized by thermal evaporation method using B/Fe2O3/MoO3 and B/Ni2O3/MoO3 mixtures separately with ammonia as the nitrogen source. The growth of boron nitride nanotubes occurred at 1100 degrees C, which was relatively lower than other metal oxides assisted growth processes requiring higher than 1200 degrees C. MoO3 promoted formation of B2O2 and aided boron nitride nanotubes growth at a reduced temperature. The boron nitride nanotubes with bamboo shaped, nested cone structured and straight tubes like forms were evident from the high resolution transmission electron microscopy. Metallic Fe and Ni, formed during the process, were the catalysts for the growth of boron nitride nanotubes. Their formation was established by X-ray diffraction. FT Raman showed a peak due to B-N vibration of BNNTs close to 1370 cm(-1). Hence MoO3 assisted growth of boron nitride nanotubes is advantageous, as it significantly reduced the synthesis temperature.     

Functionalization of BN nanotubes with dichlorocarbenes

The geometric and electronic structures of dichlorocarbene (CCl(2)) functionalized BN nanotubes (BNNTs) were studied using density functional theory within the generalized gradient approximation. We found that the CCl(2) addition favors slanted B-N bonds in zigzag tubes, and the CCl(2)-attached BNNTs prefer open rather than closed three-membered-ring (3MR) structures in all the zigzag (n,0) BNNTs studied, whereas closed 3MR structure occurs in the CCl(2)-attached BN graphene layer. The binding energies decrease with increase of the CCl(2) coverage, but the electronic properties of BNNTs do not change significantly, irrespective of the CCl(2) coverage.     

Platinum nanoparticle modified polyaniline-functionalized boron nitride nanotubes for amperometric glucose enzyme biosensor

A novel amperometric biosensor based on the BNNTs-Pani-Pt hybrids with Pt nanoparticle homogeneously decorated on polyaniline (Pani)-wrapped boron nitride nanotubes (BNNTs), was developed. It is shown that π interactions take place between BNNTs and polyaniline (Pani) located at N atoms from BNNTs and C atoms from Pani, resulting in the water solubility for the Pani wrapped BNNTs hybrids. The developed glucose biosensor displayed high sensitivity and stability, good reproducibility, anti-interference ability, especially excellent acid stability and heat resistance. The resulted BNNTs-Pani-Pt hybrid amperometric glucose biosensor exhibited a fast response time (within 3 s) and a linear calibration range from 0.01 to 5.5 mM with a high sensitivity and low detection limit of 19.02 mA M(-1) cm(-2) and 0.18 μM glucose (S/N = 3). Surprisedly, the relative activity of the GC/BNNTs-Pani-Pt-GOD electrode keeps almost no change in a range from pH 3 to 7. Futhermore, the BNNTs-Pani-Pt hybrid biosensor maintains a high GOD enzymatic activity even at a relatively high temperature of 60 °C. This might be attributed to the effect of electrostatic field and hydrophobia of BNNTs. The unique acid stability and heat resistance of this sensor indicate great promising application in numerous industrial and biotechnological operations involving harsh conditions.     

Synthesis of boron nitride nanotubes with SiC nanowire as template

A novel template method for the preparation of boron nitride nanotubes (BNNTs) using SiC nanowire as template and ammonia borane as precursor is reported. We find out that the SiC nanowires could be effectively etched out by the vapors decomposed from ammonia borane, leading to the formation of BNNTs. The as-prepared products are well characterized by means of complementary analytical techniques. A possible formation mechanism is disclosed. The method developed here paves the way for large scale production of BNNTs.     

Activation of boron nitride nanotubes and their polymer composites for improving mechanical performance

Boron nitride nanotubes (BNNTs) are inappropriate for further chemical derivatization because of their chemical inertness. We demonstrate covalent activation of chemically inert BNNTs by isophorone diisocyanate (IPDI) to form isocyanate group (NCO)-terminated BNNT precursors with an 'NCO anchor' ready for further functionalization. As identified by Fourier transform infrared spectroscopy, a number of molecules or polymers with -COOH, -OH or -NH? groups are readily attached to the activated IPDI-BNNTs. The IPDI-BNNT-involving polymer composites have shown mechanical properties are considerably improved due to the good dispersibility of IPDI-BNNTs in the polymer matrix and the strong interfacial interactions between BNNTs and polymers. The methodology reported here provides a promising method to promote the chemical reactivity of BNNTs and covalently modify polymer nanocomposites with improved mechanical performance.     

Field emission and strain engineering of electronic properties in boron nitride nanotubes

The electrical properties of boron nitride (BN) nanostructures, particularly BN nanotubes (NTs), have been studied less in comparison to the counterpart carbon nanotubes. The present work investigates the field emission (FE) behavior of BNNTs under multiple cycles of FE experiments and demonstrates a strain-engineering pathway to tune the electronic properties of BNNTs. The electrical probing of individual BNNTs were conducted inside a transmission electron microscope (TEM) using an in?situ electrical holder capable of applying a bias voltage of up to 110?V. Our results indicate that in the first cycle a single BNNT can exhibit the current density of ～1?mA?cm(-2) at 110?V and the turn-on voltage of 325?V?μm(-1). However, field emission properties reduced considerably in subsequent cycles. Real-time imaging revealed the structural degradation of individual BNNTs during FE experiments. The electromechanical measurements show that the conductivity of BNNTs can be tuned by means of mechanical straining. The resistance of individual BNNTs reduced from 2000 to 769?MΩ and the carrier concentration increased from 0.35?×?10(17) to 1.1?×?10(17)?cm(-3) by straining the samples up to 2.5%.     

Radial elasticity of multi-walled boron nitride nanotubes

We investigated the radial mechanical properties of multi-walled boron nitride nanotubes (MW-BNNTs) using atomic force microscopy. The employed MW-BNNTs were synthesized using pressurized vapor/condenser (PVC) methods and were dispersed in aqueous solution using ultrasonication methods with the aid of ionic surfactants. Our nanomechanical measurements reveal the elastic deformational behaviors of individual BNNTs with two to four tube walls in their transverse directions. Their effective radial elastic moduli were obtained through interpreting their measured radial deformation profiles using Hertzian contact mechanics models. Our results capture the dependences of the effective radial moduli of MW-BNNTs on both the tube outer diameter and the number of tube layers. The effective radial moduli of double-walled BNNTs are found to be several-fold higher than those of single-walled BNNTs within the same diameter range. Our work contributes directly to a complete understanding of the fundamental structural and mechanical properties of BNNTs and the pursuits of their novel structural and electronics applications.     

Controlled surface modification of boron nitride nanotubes

Controlled surface modification of boron nitride nanotubes has been achieved by gentle plasma treatment. Firstly, it was shown that an amorphous surface layer found on the outside of the nanotubes can be removed without damaging the nanotube structure. Secondly, it was shown that an oxygen plasma creates nitrogen vacancies that then allow oxygen atoms to be successfully substituted onto the surface of BNNTs. The percentage of oxygen atoms can be controlled by changing the input plasma energy and by the Ar plasma pre-treatment time. Finally, it has been demonstrated that nitrogen functional groups can be introduced onto the surface of BNNTs using an N(2) + H(2) plasma. The N(2) + H(2) plasma also created nitrogen vacancies, some of which led to surface functionalization while some underwent oxygen healing.     

A comprehensive analysis of the CVD growth of boron nitride nanotubes

Boron nitride nanotube (BNNT) films were grown on silicon/silicon dioxide (Si/SiO(2)) substrates by a catalytic chemical vapor deposition (CVD) method in a horizontal electric furnace. The effects of growth temperature and catalyst concentration on the morphology of the films and the structure of individual BNNTs were systematically investigated. The BNNT films grown at 1200 and 1300?°C consisted of a homogeneous dispersion of separate tubes in random directions with average outer diameters of ~30 and ~60 nm, respectively. Meanwhile, the films grown at 1400?°C comprised of BNNT bundles in a flower-like morphology, which included thick tubes with average diameters of ~100 nm surrounded by very thin ones with diameters down to ~10 nm. In addition, low catalyst concentration led to the formation of BNNT films composed of entangled curly tubes, while high catalyst content resulted in very thick tubes with diameters up to ~350 nm in a semierect flower-like morphology. Extensive transmission electron microscopy (TEM) investigations revealed the diameter-dependent growth mechanisms for BNNTs; namely, thin and thick tubes with closed ends grew by base-growth and tip-growth mechanisms, respectively. However, high catalyst concentration motivated the formation of filled-with-catalyst BNNTs, which grew open-ended with a base-growth mechanism.     

In situ observation of reversible rippling in multi-walled boron nitride nanotubes

The recent observation of high flexibility in buckled boron nitride nanotubes (BNNTs) contradicts the pre-existing belief about BN nanotube brittleness due to the partially ionic character of bonding between the B and N atoms. However, the underlying mechanisms and relationships within the nanotube remained unexplored. This study reports for the first time the buckling mechanism in multi-walled BNNTs upon severe mechanical deformation. Individual BNNTs were deformed inside a transmission electron microscope (TEM) equipped with an in situ atomic force microscopy holder. High-resolution TEM images revealed that bent BNNTs form multiple rippling upon buckling. The critical strain to form the first ripple was measured as 4.1% and the buckling process was reversible up to 26% strain. As opposed to carbon nanotubes, the BNNTs buckled into V-shaped ripples rather than smooth wavy shapes. The rippling wavelength was quantified in terms of the outer diameter and thickness of the nanotubes. The BNNTs showed a larger rippling wavelength compared to that of CNTs with the same number of walls. This difference was explained by the tendency of BN structures to reduce the number of thermodynamically unfavorable B-B and N-N bonds at the sharp corners in the rippling regions. The BNNTs' structure also exhibited a higher fracture strain compared to their counterpart.     

Selective growth of boron nitride nanotubes by plasma-enhanced chemical vapor deposition at low substrate temperature

Hexagonal boron nitride nanotubes (BNNTs) were synthesized at a low substrate temperature of 800?°C on nickel (Ni) coated oxidized Si(111) wafers in a microwave plasma-enhanced chemical vapor deposition system (MPCVD) by decomposition and reaction of gas mixtures consisting of B(2)H(6)-NH(3)-H(2). The 1D BN nanostructures grew preferentially on Ni catalyst islands with a small thickness only. In situ mass spectroscopic analysis and optical emission spectroscopy were used to identify the gas reactions responsible for the BNNT formation. The morphology and structural properties of the deposits were analyzed by SEM, TEM, EDX, SAD and Raman spectroscopy. The growth mechanism of the BNNTs was identified.     

Low temperature growth of boron nitride nanotubes on substrates

High growth temperatures (>1100 degrees C), low production yield, and impurities have prevented research progress and applications of boron nitride nanotubes (BNNTs) in the past 10 years. Here, we show that BNNTs can be grown on substrates at 600 degrees C. These BNNTs are constructed of high-order tubular structures and can be used without purification. Tunneling spectroscopy indicates that their band gap ranges from 4.4 to 4.9 eV.