Growth methodologies of boron nitride nanotubes and their neutron shielding applications: a review.

This review provides a comprehensive overview of the growth methodologies and neutron shielding applications of Boron Nitride Nanotubes (BNNTs). BNNTs have garnered significant attention because of their unique combination of high thermal stability, mechanical strength, and exceptional neutron absorption properties. Synthesis methods for BNNTs, including laser ablation, thermal plasma treatment, chemical vapour deposition (CVD), and ball milling have been thoroughly examined, highlighting their mechanisms, advantages, and challenges. Each method contributes uniquely to the quality and applicability of BNNTs in terms of scalability and production efficiency. This study focused on the applications of BNNTs in neutron absorption, particularly in aerospace engineering. BNNTs have shown promising potential in enhancing the safety and longevity of space missions by providing effective radiation protection. Furthermore, their potential in medical applications, particularly in Boron Neutron Capture Therapy (BNCT) for cancer treatment, has been explored. BNCT offers a targeted approach to cancer therapy by utilizing the high boron-10 content of BNNTs for precise and localized treatment. This review also provides an outlook on the future of BNNT research, emphasizing the need for more efficient growth methods to facilitate wider adoption and commercialization. The versatility of BNNTs across various fields, from space exploration to medical science, underscores their potential as materials of significant scientific and technological importance. As research progresses, BNNTs are expected to play a pivotal role in advancing materials science and offer innovative solutions to complex challenges.

Synthesis of Double-Walled Boron Nitride Nanotubes from Ammonia Borane by Thermal Plasma Methods.

Highly crystalline double-walled boron nitride nanotubes (DWBNNTs ∼60%) were synthesized from ammonia borane (AB; H3B-NH3) precursors using a high-temperature thermal plasma method. The differences between the synthesized BNNTs using the hexagonal boron nitride (h-BN) precursor and AB precursor were compared using various techniques such as thermogravimetric analysis, X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and in situ optical emission spectroscopy (OES). The synthesized BNNTs were longer and had fewer walls when the AB precursor was used than when the conventional method was used (with the h-BN precursor). The production rate significantly improved from ∼20 g/h (h-BN precursor) to ∼50 g/h (AB precursor), and the content of amorphous boron impurities was significantly reduced, implying a self-assembly mechanism of BN radicals rather than the conventional mechanism involving boron nanoballs. Through this mechanism, the BNNT growth, which was accompanied by an increased length, a decreased diameter, and a high growth rate, could be understood. The findings were also supported by in situ OES data. Considering the increased production yield, this synthesis method using AB precursors is expected to make an innovative contribution to the commercialization of BNNTs.

Spontaneous formation of boron nitride nanotube fibers by boron impurity reduction in laser ablation of ammonia borane.

Highly crystalline and few-walled boron nitride nanotubes (BNNTs) had been synthesized by laser ablation using only ammonia borane as a precursor. As a molecular precursor, ammonia borane supplied both B and N atoms with a ratio of 1:1, and BNNTs were formed via the homogeneous nucleation of BN radicals, not the growth from boron nano-droplets, which is a generally accepted growth mechanism of the laser-grown BNNTs. Owing to the absence of amorphous boron impurities, the van der Waals interaction among BNNTs became effective and thus a BNNT fibers was formed spontaneously during the BNNT synthesis. The BNNT growth and the subsequent fiber formation are found to occur only at high pressures of a surrounding gas. The mechanism behind the critical role of pressure was elucidated from the perspective of reaction kinetics and thermal fluid behaviors. A polarized Raman study confirmed that the BNNT fiber formed exhibits a good alignment of BNNTs, which implies great potential for continuous production of high-quality BNNT fibers for various applications.

Ultrahigh strength, modulus, and conductivity of graphitic fibers by macromolecular coalescence.

Theoretical considerations suggest that the strength of carbon nanotube (CNT) fibers be exceptional; however, their mechanical performance values are much lower than the theoretical values. To achieve macroscopic fibers with ultrahigh performance, we developed a method to form multidimensional nanostructures by coalescence of individual nanotubes. The highly aligned wet-spun fibers of single- or double-walled nanotube bundles were graphitized to induce nanotube collapse and multi-inner walled structures. These advanced nanostructures formed a network of interconnected, close-packed graphitic domains. Their near-perfect alignment and high longitudinal crystallinity that increased the shear strength between CNTs while retaining notable flexibility. The resulting fibers have an exceptional combination of high tensile strength (6.57 GPa), modulus (629 GPa), thermal conductivity (482 W/m·K), and electrical conductivity (2.2 MS/m), thereby overcoming the limits associated with conventional synthetic fibers.

Investigation of shear-induced rearrangement of carbon nanotube bundles using Taylor-Couette flow.

Macroscopic assemblies of carbon nanotubes (CNTs) usually have a poor alignment and a low packing density due to their hierarchical structure. To realize the inherent properties of CNTs at the macroscopic scale, the CNT assemblies should have a highly aligned and densified structure. Shear-aligning processes are commonly employed for this purpose. This work investigates how shear flows affect the rearrangement of CNT bundles in macroscopic assemblies. We propose that buckling behavior of CNT bundles in a shear flow causes the poor alignment of CNT bundles and a low packing density of CNT assemblies; the flow pattern and the magnitude of shear stress induced by the flow are key factors to regulate this buckling behavior. To obtain CNT assemblies with a high packing density, the CNTs should undergo a laminar flow that has a sufficiently low shear stress. Understanding the effect of shear flow on the structure of CNT bundles may guide improvement of fabrication strategies.

Super-Strong Carbon Nanotube Fibers Achieved by Engineering Gas Flow and Postsynthesis Treatment.

Carbon nanotube fibers (CNTFs) are directly spun from a floating-catalyst chemical vapor deposition apparatus using gas-phase carbon and an iron nanocatalyst. The essential synthesis and post-treatment factors that affect the strength of CNTFs are investigated to obtain CNTFs with greater strength than those of any previously reported high-performance fibers. The key factors optimized included the degree of rotational flow inside the reactor, the ratio of the starting materials, and the postsynthesis treatment conditions. The formation of rotational gas flow inside the reactor was confirmed by computational fluid dynamics simulations, and the feed ratio of the starting materials was optimized through response surface methodology. In addition, a reproducible and highly efficient postsynthesis treatment method was established. Pristine CNTFs with a high specific strength (SS) (average 2.2 N/tex, max. 2.3 N/tex) were synthesized through decreased rotational flow and optimization of the CNTF synthesis conditions. To improve the SS of the CNTFs further, we adopted an acid wet-stretching method that included washing and heat treatment. This drastically increased the SS of the CNTFs (average 5.5 N/tex, max. 6.4 N/tex) because of the decrease in the volume of the pores between the CNT bundles.

Effects of Wet-Pressing and Cross-Linking on the Tensile Properties of Carbon Nanotube Fibers.

To increase the strength of carbon nanotube (CNT) fibers (CNTFs), the mean size of voids between bundles of CNTs was reduced by wet-pressing, and the CNTs were cross-linked. Separate and simultaneous physical (roller pressing) and chemical methods (cross-linking) were tested to confirm each method's effects on the CNTF strength. By reducing the fraction of pores, roller pressing decreased the cross-sectional area from 160 µm² to 66 µm² and increased the average load-at-break from 2.83 ± 0.25 cN to 4.41 ± 0.16 cN. Simultaneous injection of crosslinker and roller pressing augmented the cross-linking effect by increasing the infiltration of the crosslinker solution into the CNTF, so the specific strength increased from 0.40 ± 0.05 N/tex to 0.67 ± 0.04 N/tex. To increase the strength by cross-linking, it was necessary that the size of the pores inside the CNTF were reduced, and the infiltration of the solution was increased. These results suggest that combined physical and chemical treatment is effective to increase the strength of CNTFs.

Estimation of degree of polymerization of poly-acrylonitrile-grafted carbon nanotubes using Guinier plot of small angle x-ray scattering.

Small angle x-ray scattering (SAXS) was used to estimate the degree of polymerization of polymer-grafted carbon nanotubes (CNTs) synthesized using a 'grafting from' method. This analysis characterizes the grafted polymer chains without cleaving them from CNTs, and provides reliable data that can complement conventional methods such as thermogravimetric analysis or transmittance electron microscopy. Acrylonitrile was polymerized from the surface of the CNTs by using redox initiation to produce poly-acrylonitrile-grafted CNTs (PAN-CNTs). Polymerization time and the initiation rate were varied to control the degree of polymerization. Radius of gyration (R g ) of PAN-CNTs was determined using the Guinier plot obtained from SAXS solution analysis. The results showed consistent values according to the polymerization condition, up to a maximum R g  = 125.70 Å whereas that of pristine CNTs was 99.23 Å. The dispersibility of PAN-CNTs in N,N-dimethylformamide was tested using ultraviolet-visible-near infrared spectroscopy and was confirmed to increase as the degree of polymerization increased. This analysis will be helpful to estimate the degree of polymerization of any polymer-grafted CNTs synthesized using the 'grafting from' method and to fabricate polymer/CNT composite materials.

Facile fabrication of superhydrophobic surfaces with hierarchical structures.

Hierarchical structures were fabricated on the surfaces of SUS304 plates using a one-step process of direct microwave irradiation under a carbon dioxide atmosphere. The surface nanostructures were composed of chrome-doped hematite single crystals. Superhydrophobic surfaces with a water contact angle up to 169° were obtained by chemical modification of the hierarchical structures. The samples maintained superhydrophobicity under NaCl solution up to 2 weeks.

High-strength carbon nanotube/carbon composite fibers via chemical vapor infiltration.

In this study, we have developed an efficient and scalable method for improving the mechanical properties of carbon nanotube (CNT) fibers. The mechanical properties of as-synthesized CNT fibers are primarily limited by their porous structures and the weak bonding between adjacent CNTs. These result in inefficient load transfer, leading to low tensile strength and modulus. In order to overcome these limitations, we have adopted chemical vapor infiltration (CVI) to efficiently fill the internal voids of the CNT fibers with carbon species which are thermally decomposed from gas phase hydrocarbon. Through the optimization of the processing time, temperature, and gas flow velocity, we have confirmed that carbon species formed by the thermal decomposition of acetylene (C2H2) gas successfully infiltrated into porous CNT fibers and densified them at relatively low temperatures (650-750 °C). As a result, after CVI processing of the as-synthesized CNT fibers under optimum conditions, the tensile strength and modulus increased from 0.6 GPa to 1.7 GPa and from 25 GPa to 127 GPa, respectively. The CVI technique, combined with the direct spinning of CNT fibers, can open up a route to the fast and scalable fabrication of high performance CNT/C composite fibers. In addition, the CVI technique is a platform technology that can be easily adapted into other nano-carbon based yarn-like fibers such as graphene fibers.

Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids.

Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes.

Gas hydrate inhibition by perturbation of liquid water structure.

Natural gas hydrates are icy crystalline materials that contain hydrocarbons, which are the primary energy source for this civilization. The abundance of naturally occurring gas hydrates leads to a growing interest in exploitation. Despite their potential as energy resources and in industrial applications, there is insufficient understanding of hydrate kinetics, which hinders the utilization of these invaluable resources. Perturbation of liquid water structure by solutes has been proposed to be a key process in hydrate inhibition, but this hypothesis remains unproven. Here, we report the direct observation of the perturbation of the liquid water structure induced by amino acids using polarized Raman spectroscopy, and its influence on gas hydrate nucleation and growth kinetics. Amino acids with hydrophilic and/or electrically charged side chains disrupted the water structure and thus provided effective hydrate inhibition. The strong correlation between the extent of perturbation by amino acids and their inhibition performance constitutes convincing evidence for the perturbation inhibition mechanism. The present findings bring the practical applications of gas hydrates significantly closer, and provide a new perspective on the freezing and melting phenomena of naturally occurring gas hydrates.

Abnormal incorporation of amino acids into the gas hydrate crystal lattice.

Gas hydrates are crystalline ice-like solid materials enclosing gas molecules inside. The possibility of the presence of gas hydrates with amino acids in the universe is of interest when revealing the potential existence of life as they are evidence of a source of water and organic precursors, respectively. However, little is known about how they can naturally coexist, and their crystallization behavior would become far more complex as both crystallize with formation of hydrogen bonds. Here, we report abnormal incorporation of amino acids into the gas hydrate crystal lattice that is contrary to the generally accepted crystallization mode, and this resulted in lattice distortion and expansion. The present findings imply the potential for their natural coexistence by sharing the crystal lattice, and will be helpful for understanding the role of additives in the gas hydrate crystallization.

Aqueous-solution route to zinc telluride films for application to CO2 reduction.

As a photocathode for CO2 reduction, zinc-blende zinc telluride (ZnTe) was directly formed on a Zn/ZnO nanowire substrate by a simple dissolution-recrystallization mechanism without any surfactant. With the most negative conduction-band edge among p-type semiconductors, this new photocatalyst showed efficient and stable CO formation in photoelectrochemical CO2 reduction at -0.2--0.7 V versus RHE without a sacrificial reagent.

Hydrophobic amino acids as a new class of kinetic inhibitors for gas hydrate formation.

As the foundation of energy industry moves towards gas, flow assurance technology preventing pipelines from hydrate blockages becomes increasingly significant. However, the principle of hydrate inhibition is still poorly understood. Here, we examined natural hydrophobic amino acids as novel kinetic hydrate inhibitors (KHIs), and investigated hydrate inhibition phenomena by using them as a model system. Amino acids with lower hydrophobicity were found to be better KHIs to delay nucleation and retard growth, working by disrupting the water hydrogen bond network, while those with higher hydrophobicity strengthened the local water structure. It was found that perturbation of the water structure around KHIs plays a critical role in hydrate inhibition. This suggestion of a new class of KHIs will aid development of KHIs with enhanced biodegradability, and the present findings will accelerate the improved control of hydrate formation for natural gas exploitation and the utilization of hydrates as next-generation gas capture media.

Porous ZnO-ZnSe nanocomposites for visible light photocatalysis.

We report the synthesis of porous ZnO-ZnSe nanocomposites for use in visible light photocatalysis. Porous ZnO nanostructures were synthesized by a microwave-assisted hydrothermal reaction then converted into porous ZnO-ZnSe nanocomposites by a microwave-assisted dissolution-recrystallization process using an aqueous solution containing selenium ions. ZnO and ZnSe nanocrystallites of the nanocomposites were well-mixed (rather than forming simple core-shell (ZnO-ZnSe) structures), particularly, in the outer regions. Both ZnO and ZnSe were present at the surface and exposed to the environment. The porous ZnO-ZnSe nanocomposites showed absorption bands in the visible region as well as in the UV region. The porous ZnO-ZnSe nanocomposites had much higher activities than the porous ZnO nanostructures. Control experiments using cutoff filters revealed that the main photocatalytic activity of the synthesized nanostructures arose from photo-excitation of the semiconductor (ZnO or ZnSe) via absorption of light of an energy equal to or exceeding the band gap energy.

Turning refuse plastic into multi-walled carbon nanotube forest.

A novel and effective method was devised for synthesizing a vertically aligned carbon nanotube (CNT) forest on a substrate using waste plastic obtained from commercially available water bottles. The advantages of the proposed method are the speed of processing and the use of waste as a raw material. A mechanism for the CNT growth was also proposed. The growth rate of the CNT forest was ∼2.5 µm min-1. Transmission electron microscopy images indicated that the outer diameters of the CNTs were 20-30 nm on average. The intensity ratio of the G and D Raman bands was 1.27 for the vertically aligned CNT forest. The Raman spectrum showed that the wall graphitization of the CNTs, synthesized via the proposed method was slightly higher than that of commercially available multi-walled carbon nanotubes (MWCNTs). We expect that the proposed method can be easily adapted to the disposal of other refuse materials and applied to MWCNT production industries.

The cages, dynamics, and structuring of incipient methane clathrate hydrates.

Interest in describing clathrate hydrate formation mechanisms spans multiple fields of science and technical applications. Here, we report findings from multiple molecular dynamics simulations of spontaneous methane clathrate hydrate nucleation and growth from fully demixed and disordered two-phase fluid systems of methane and water. Across a range of thermodynamic conditions and simulation geometries and sizes, a set of seven cage types comprises approximately 95% of all cages formed in the nucleated solids. This set includes the ubiquitous 5(12) cage, the 5(12)6(n) subset (where n ranges from 2-4), and the 4(1)5(10)6(n) subset (where n also ranges from 2-4). Transformations among these cages occur via water pair insertions/removals and rotations, and may elucidate the mechanisms of solid-solid structural rearrangements observed experimentally. Some consistency is observed in the relative abundance of cages among all nucleation trajectories. 5(12) cages are always among the two most abundant cage types in the nucleated solids and are usually the most abundant cage type. In all simulations, the 5(12)6(n) cages outnumber their 4(1)5(10)6(n) counterparts with the same number of water molecules. Within these consistent features, some stochasticity is observed in certain cage ratios and in the long-range ordering of the nucleated solids. Even when comparing simulations performed at the same conditions, some trajectories yield swaths of multiple adjacent sI unit cells and long-range order over 5 nm, while others yield only isolated sI unit cells and little long-range order. The nucleated solids containing long-range order have higher 5(12)6(2)/5(12) and 5(12)6(3)/4(1)5(10)6(2) cage ratios when compared to systems that nucleate with little long-range order. The formation of multiple adjacent unit cells of sI hydrate at high driving forces suggests an alternative or addition to the prevailing hydrate nucleation hypotheses which involve formation through amorphous intermediates.

Formation of quasi-single crystalline porous ZnO nanostructures with a single large cavity.

We report a method for synthesizing quasi-single crystalline porous ZnO nanostructures containing a single large cavity. The microwave-assisted route consists of a short (about 2 min) temperature ramping stage (from room temperature to 120 °C) and a stage in which the temperature is maintained at 120 °C for 2 h. The structures produced by this route were 200-480 nm in diameter. The morphological yields of this method were very high. The temperature- and time-dependent evolution of the synthesized powders and the effects of an additive, vitamin C, were studied. Spherical amorphous/polycrystalline structures (70-170 nm in diameter), which appeared transitorily, may play a key role in the formation of the single crystalline porous hollow ZnO nanostructures. Studies and characterization of the nanostructures suggested a possible mechanism for formation of the quasi-single crystalline porous ZnO nanostructures with an interior space.