Eco-Friendly Dispersant-Free Purification Method of Boron Nitride Nanotubes through Controlling Surface Tension and Steric Repulsion with Solvents.

Boron nitride nanotubes (BNNTs) were purified without the use of a dispersant by controlling the surface tension and steric repulsion of solvent molecules. This method effectively enhanced the difference in solubilities of impurities and BNNTs. The purification process involved optimizing the alkyl-chains of alcohol solvents and adjusting the concentration of alcohol solvent in water to regulate surface tension and steric repulsion. Among the solvents tested, a 70 wt% t-butylalcohol in water mixture exhibited the highest selective isolation of BNNTs from impurities based on differences in solubilities. This favorable outcome was attributed to the surface tension matching with BNNTs, steric repulsion from bulky alkyl chain structures, and differences in interfacial energy between BNNT-liquid and impurity-liquid interfaces. Through this optimized purification process, impurities were removed to an extent of up to 93.3%. Additionally, the purified BNNTs exhibited a distinct liquid crystal phase, which was not observed in the unpurified BNNTs.

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.

Lyotropic Boron Nitride Nanotube Liquid Crystals: Preparation, Characterization, and Wet-Spinning for Fabrication of Composite Fiber.

Microfiber fabrication via wet-spinning of lyotropic liquid crystals (LCs) with anisotropic nanomaterials has gained increased attention due to the microfibers' excellent physical/chemical properties originating from the unidirectional alignment of anisotropic nanomaterials along the fiber axis with high packing density. For wet-spinning of the microfibers, however, preparing lyotropic LCs by achieving high colloidal stability of anisotropic nanomaterials, even at high concentrations, has been a critically unmet prerequisite, especially for recently emerging nanomaterials. Here, we propose a cationically charged polymeric stabilizer that can efficiently be adsorbed on the surface of boron nitride nanotubes (BNNTs), which provide steric hindrance in combination with Coulombic repulsion leading to high colloidal stability of BNNTs up to 22 wt %. The BNNT LCs prepared from the dispersions with various stabilizers were systematically compared using optical and rheological analysis to optimize the phase behavior and rheological properties for wet-spinning of the BNNT LCs. Systematic optical and mechanical characterizations of the BNNT microfibers with aligned BNNTs along the fiber axis revealed that properties of the microfibers, such as their tensile strength, packing density, and degree of BNNT alignment, were highly dependent on the quality of BNNT LCs directly related to the types of stabilizers.

Scalable, Highly Pure, and Diameter-Sorted Boron Nitride Nanotube by Aqueous Polymer Two-Phase Extraction.

Boron nitride nanotube (BNNT) has attracted recent attention owing to its exceptional material properties; yet, practical implementation in real-life applications has been elusive, mainly due to the purity issues associated with its large-scale synthesis. Although different purification methods have been discussed so far, there lacks a scalable solution method in the community. In this work, a simple, high-throughput, and scalable purification of BNNT is reported via modification of an established sorting technique, aqueous polymer two-phase extraction. A complete partition mapping of the boron nitride species is established, which enables the segregation of the highly pure BNNT with a major impurity removal efficiency of > 98%. A successful scaling up of the process is illustrated and provides solid evidence of its diameter sorting behavior. Last, towards its macroscopic assemblies, a liquid crystal of the purified BNNT is demonstrated. The effort toward large-scale solution purification of BNNT is believed to contribute significantly to the macroscopic realization of its exceptional properties in the near future.

Insight into BN Impurity Formation during Boron Nitride Nanotube Synthesis by High-Temperature Plasma.

The high-temperature plasma process has demonstrated great potential in growing high-quality boron nitride nanotubes (BNNTs) with small diameters (∼5 nm) and few walls (3-4 walls) and led to successful commercialization with a high production rate approaching 20 g/h. However, the process is still accompanied by the production of BN impurities (e.g., a-BN, BN shell, BN flakes) whose physicochemical properties are similar to those of BNNTs. This renders the post-purification process very challenging and thus hampers the development of their practical applications. In this study, we have employed both experimental and numerical approaches for a mechanistic understanding of BN impurity formation in the high-temperature plasma process. This study suggests that the flow structure of the plasma jet (e.g., laminar or turbulent) plays a key role in the formation of BN impurities by dictating the transport phenomena of BNNT seeds (e.g., B droplets), which play an important role in BNNT nucleation. We discussed that the turbulence enhances the radial diffusion of B droplets as well as their interparticle coagulation, which leads to a significant reduction in the population of effective BNNT seeds in the BNNT growth zone (T < 4000 K). This results in the generation of unreacted BN precursors (e.g., B-N-H species) in the BNNT growth zone that eventually self-assemble into BN impurities. Our numerical simulation also suggests that a higher thermal energy input makes the flow more turbulent in the BNNT growth zone due to the elevated velocity difference between the plasma jet and ambient cold gas. This finding provides critical insight into the process design that can suppress the BN impurity formation in the high-temperature plasma process.

Stabilization of liquid instabilities with ionized gas jets.

Impinging gas jets can induce depressions in liquid surfaces, a phenomenon familiar to anyone who has observed the cavity produced by blowing air through a straw directly above a cup of juice. A dimple-like stable cavity on a liquid surface forms owing to the balance of forces among the gas jet impingement, gravity and surface tension1,2. With increasing gas jet speed, the cavity becomes unstable and shows oscillatory motion, bubbling (Rayleigh instability) and splashing (Kelvin-Helmholtz instability)3,4. However, despite its scientific and practical importance-particularly in regard to reducing cavity instability growth in certain gas-blown systems-little attention has been given to the hydrodynamic stability of a cavity in such gas-liquid systems so far. Here we demonstrate the stabilization of such instabilities by weakly ionized gas for the case of a gas jet impinging on water, based on shadowgraph experiments and computational two-phase fluid and plasma modelling. We focus on the interfacial dynamics relevant to electrohydrodynamic (EHD) gas flow, so-called electric wind, which is induced by the momentum transfer from accelerated charged particles to neutral gas under an electric field. A weakly ionized gas jet consisting of periodic pulsed ionization waves5, called plasma bullets, exerts more force via electrohydrodynamic flow on the water surface than a neutral gas jet alone, resulting in cavity expansion without destabilization. Furthermore, both the bidirectional electrohydrodynamic gas flow and electric field parallel to the gas-water interface produced by plasma interacting 'in the cavity' render the surface more stable. This case study demonstrates the dynamics of liquids subjected to a plasma-induced force, offering insights into physical processes and revealing an interdependence between weakly ionized gases and deformable dielectric matter, including plasma-liquid systems.

Highly Aligned Array of Heterostructured Polyflourene-Isolated Boron Nitride and Carbon Nanotubes.

Boron nitride nanotubes (BNNTs) have attracted increasing attention for their exceptional thermal, electronic, and optical properties. However, the progress in BNNTs applications has largely been limited by the low purity of as-synthesized BNNTs and inefficient solution-processing protocols due mainly to the instability of BNNTs in most of the solvents. Therefore, fabrication of highly pure, stable, and fully individualized BNNTs in a rational manner is required. Here, we report a significant improvement in the preparation of well-dispersed BNNTs, utilizing conjugated polymers that interact with BNNTs, allowing selective sorting and individualization of the nanotubes. Evidence of strong interactions between the polymers and BNNTs was observed by optical absorption and photoluminescence spectroscopies, while effective individualization was observed by electron microscopy. The sorted BNNTs were successfully used in a solution-processing protocol called dose-controlled, floating evaporative self-assembly (DFES) previously established for single-walled carbon nanotubes (SWCNT) array fabrication. A device fabricated via DFES from the sorted BNNTs mixed with polymer-wrapped, semiconducting single-walled carbon nanotubes (s-SWCNTs) exhibited an on-state conductance of 253 ± 6 µS µm-1 and an on/off ratio of 106.6±0.4 for a gate voltage of -0.1 V. This breakthrough in BNNT dispersion and isolation is a significant advancement toward the exploitation of BNNTs in future applications.

Simultaneous, efficient and continuous oil-water separation via antagonistically functionalized membranes prepared by atmospheric-pressure cold plasma.

For decades, oil and water separation has remained a challenge. Not only oil spills but also industrial oily wastewaters are threatening our environment. Over the years, oil-water separation methods have been developed, however, there are still considerable hurdles to overcome to provide a low cost and efficient process able to treat a large amount of liquid. In this work, we suggest a continuous, simultaneous and effective oil-water separation method based on the antagonistic functionalization of meshes using atmospheric pressure cold plasmas. Using this robust plasma method, superhydrophobic/underwater-superoleophilic or superhydrophilic/underwater-superoleophobic functionalized meshes are obtained. Antagonistically functionalized meshes can simultaneously separate oil and water and show continuous separation flow rates of water (900 L m-2 h-1) and oil (400 L m-2 h-1) with high purities (> 99.9% v/v). This fast, low-cost and continuous plasma-based process can be readily and widely adopted for the selective functionalization of membranes at large scale for oil-spill cleanup and water purification.

Fabrication of Noncovalently Functionalized Boron Nitride Nanotubes with High Stability and Water-Redispersibility.

Boron nitride nanotubes (BNNTs) have attracted significant interest because of the remarkable difference in their physical properties compared with carbon nanotubes and their far-reaching potential applications, including electrical insulators; thermally conducting, catalytic, and piezoelectric materials; and neutron absorbers. Despite their unique physical properties, the bundling and insolubility of BNNTs in water because of its substantial van der Waals attraction and hydrophobicity, respectively, give rise to many limitations in practical applications. Here, we present a new way to produce a highly stable BNNT dispersion by the noncovalent functionalization of the BNNT surface in water. The noncovalently functionalized BNNTs (p-BNNTs) have been found to be highly stable in water for a long time (>1 year) and easily water-redispersible by mild vortex mixing for a few minutes even after freeze-drying at -45 °C. The p-BNNTs were cylindrically encapsulated with polymerizable surfactants (BNNT diameter = ca. 3 nm and surfactant thickness = 0.8 nm).

Development of a probe-type optical absorption spectroscopic system for spatially resolved CF2 density measurement in inductively coupled C4F8/Ar plasmas.

A spatially resolvable optical probe is developed for the measurement of absolute CF2 radical density in inductively coupled plasmas using the broadband ultraviolet absorption spectroscopic method. The probe-type system is implemented inside a low-pressure inductively coupled plasma chamber and is built using a series of optical fibers, feedthroughs, collimators, and an ultraviolet light emitting diode. Using the CF2 A(0, v2', 0) ← X(0, 0, 0) absorption spectra, the spatial profile of CF2 density in the remote region of an inductively coupled C4F8/Ar plasma is investigated. The CF2 density is found to decrease from 4.06 × 1013 cm-3, around the chamber center, to 2.66 × 1013 cm-3, near the chamber wall. The spatial profile of the measured CF2 density, layer thickness, and composition of deposited films are compared. Plasma properties such as electron temperature and ion density are also discussed.

Plasma-assisted advanced oxidation process by a multi-hole dielectric barrier discharge in water and its application to wastewater treatment.

Advanced oxidation process (AOP) is a promising technology to decolorize and reduce organic contaminants in water. It is carried out using hydroxyl radicals (•OH) with an oxidizing potential of 2.80 V. Non-thermal plasma can directly generate •OH while maintaining a low temperature, and O3, H2O2, and UV light are also generated; these are necessary for AOP. In this study, we developed a multi-hole dielectric barrier discharge (DBD) system capable of generating radicals and active species in water for assisting AOP. We confirmed the optimized operating conditions based on critical parameters, including electrical and optical properties and O3 concentration. Furthermore, we described the plasma-based AOP through experimental results. We performed wastewater treatment using the multi-hole DBD: turbidity, BOD, and COD, were reduced by 60%, 40%, and 60%, respectively, after 20 min of treatment. Finally, 99.99% of Escherichia coli were eliminated after plasma treatment.

Improved de-inking of inkjet-printed paper using environmentally friendly atmospheric pressure low temperature plasma for paper recycling.

Nowadays, due to environmental pollution and natural energy consumption caused by waste paper, many researches are being conducted on the reuse of printed-paper. To recycle the paper, de-inking has to be performed. In this article, in order to reduce the use of the commonly used de-inking chemicals, the effect of an atmospheric pressure helium plasma treatment on the de-inking enhancement of printed-paper is studied. Through colorimeter and UV-visible spectrometer measurements the plasma treatment is shown to speed up the de-inking. While SEM observations and FTIR measurements suggest that the paper quality is retained upon plasma treatment, the increase of surface hydrophilicity measured by water contact angle measurements, compared to non-treated paper, is believed to enhance the fiber swelling of the paper and lead to a faster ink removal.

Insights into the Role of Plasma in Atmospheric Pressure Chemical Vapor Deposition of Titanium Dioxide Thin Films.

In this work, the effect of plasma on the chemistry and morphology of coatings deposited by Atmospheric Pressure Plasma Enhanced Chemical Vapor Deposition (AP-PECVD) is investigated. To do so, plasma deposited amorphous titanium dioxide (TiO2) thin films are compared to thin films deposited using Atmospheric Pressure Chemical Vapor Deposition (AP-CVD) not involving the use of plasma. We focus here on the effect and the interest of plasma in the AP-PECVD process over AP-CVD for low substrate temperature deposition. The advantages of AP-PECVD over AP-CVD are often suggested in many articles however no direct evidence of the role of the plasma for TiO2 deposition at atmospheric pressure was reported. Hence, herein, the deposition via both methods is directly compared by depositing coatings with and without plasma using the same CVD reactor. Through the control of the plasma parameters, we are able to form low carbon coatings at low temperature with a deposition rate twice faster than AP-CVD, clearly showing the interest of plasma. Plasma enhanced methods are promising for the deposition of coatings at industrial scale over large surface and at high rate.

Electron Information in Single- and Dual-Frequency Capacitive Discharges at Atmospheric Pressure.

Determining the electron properties of weakly ionized gases, particularly in a high electron-neutral collisional condition, is a nontrivial task; thus, the mechanisms underlying the electron characteristics and electron heating structure in radio-frequency (rf) collisional discharges remain unclear. Here, we report the electrical characteristics and electron information in single-frequency (4.52 MHz and 13.56 MHz) and dual-frequency (a combination of 4.52 MHz and 13.56 MHz) capacitive discharges within the abnormal α-mode regime at atmospheric pressure. A continuum radiation-based electron diagnostic method is employed to estimate the electron density (ne) and temperature (Te). Our experimental observations reveal that time-averaged ne (7.7-14 × 1011 cm-3) and Te (1.75-2.5 eV) can be independently controlled in dual-frequency discharge, whereas such control is nontrivial in single-frequency discharge, which shows a linear increase in ne and little to no change in Te with increases in the rf input power. Furthermore, the two-dimensional spatiotemporal evolution of neutral bremsstrahlung and associated electron heating structures is demonstrated. These results reveal that a symmetric structure in electron heating becomes asymmetric (via a local suppression of electron temperature) as two-frequency power is simultaneously introduced.

The creation of electric wind due to the electrohydrodynamic force.

Understanding the interactions between ionized matter and neutral particles is a prerequisite for discovering their impact on natural phenomena. One such phenomenon is the electric wind, which supposedly occurs due to the charged particle-neutral coupling in systems of weakly ionized gases, but this mechanism remains unclear. Here, we report direct evidence that electric wind is caused by an electrohydrodynamic force generated by the charged particle drag as a result of the momentum transfer from electrons/ions to neutrals. The model experiment is based on a pulsed plasma jet as a source of weakly ionized gases generated in the helium gas at atmospheric pressure using Schlieren photography. Studying the helium gas flow trajectories at different discharge parameters allows one to distinguish between the effects of streamer propagation or space charge drift causing the electric wind as well as to determine the role of electrons and (positive) ions in wind generation.

Rapid and selective surface functionalization of the membrane for high efficiency oil-water separation via an atmospheric pressure plasma process.

Oil-water separation is a worldwide challenge because of the increasing production of industrial oily wastewater and frequent oil spills. The growing environmental and economic demands emphasize the need to develop effective solutions to separate oil and water. Recently, oil-water separation methods were developed by tuning the wettability of membranes via surface functionalization. However, the industrialization of such methods remains challenging due to the easy-fouling, high cost and complex fabrication. Herein, a simple and rapid pathway to separate oil from oil-water mixtures is reported using plasma surface functionalization in an open-air environment. The fine tuning and study of the plasma process parameters enables the selective functionalization of each side of the membranes which led respectively to a superhydrophobic-superoleophilic and superhydrophobic-oleophobic sides. The successful separation, without any external force, of a 50 mL oil-water solution in 6 minutes was achieved. This work paves the way for an efficient, low cost and easily upscalable method for oil-water separation due to the high versatility of the atmospheric pressure plasma processes.

Antitumorigenic effect of atmospheric-pressure dielectric barrier discharge on human colorectal cancer cells via regulation of Sp1 transcription factor.

Human colorectal cancer cell lines (HT29 and HCT116) were exposed to dielectric barrier discharge (DBD) plasma at atmospheric pressure to investigate the anticancer capacity of the plasma. The dose- and time-dependent effects of DBDP on cell viability, regulation of transcription factor Sp1, cell-cycle analysis, and colony formation were investigated by means of MTS assay, DAPI staining, propidium iodide staining, annexin V-FITC staining, Western blot analysis, RT-PCR analysis, fluorescence microscopy, and anchorage-independent cell transformation assay. By increasing the duration of plasma dose times, significant reductions in the levels of both Sp1 protein and Sp1 mRNA were observed in both cell lines. Also, expression of negative regulators related to the cell cycle (such as p53, p21, and p27) was increased and of the positive regulator cyclin D1 was decreased, indicating that the plasma treatment led to apoptosis and cell-cycle arrest. In addition, the sizes and quantities of colony formation were significantly suppressed even though two cancer promoters, such as TPA and epidermal growth factor, accompanied the plasma treatment. Thus, plasma treatment inhibited cell viability and colony formation by suppressing Sp1, which induced apoptosis and cell-cycle arrest in these two human colorectal cancer cell lines.

Evaluation of atmospheric pressure plasma to improve the safety of sliced cheese and ham inoculated by 3-strain cocktail Listeria monocytogenes.

The objective of this study was to evaluate the efficacy of atmospheric pressure plasma (APP), which is capable of operating at atmospheric pressure in air, in sliced cheese and ham inoculated by 3-strain cocktail of Listeria monocytogenes (ATCC 19114, 19115, and 19111, LMC). The process parameters considered were input power (75, 100, 125, and 150 W) and plasma exposure time (60, 90, and 120 s). Microbial log reduction increased with increases of input power and plasma exposure time. After 120 s APP treatments at 75, 100, and 125 W, the viable cells of LMC were reduced by 1.70, 2.78, and 5.82 log in sliced cheese, respectively. More than 8 log reductions can be achieved in 120 s at 150 W. In contrast, reductions after 120 s ranged from 0.25 to 1.73 log CFU/g in sliced ham. Calculated D values, the exposure time required to inactivate 90% of a population, from the survival curves of 75, 100, 125, and 150 W of APP treatments were 71.43, 62.50, 19.65, and 17.27 s for LMC in sliced cheese, respectively, and those in sliced ham were 476.19, 87.72, 70.92, and 63.69 s. No viable cells were detected at 125 and 150 W of APP treatment in sliced cheese, irrespective of plasma exposure time, after 1 week at a detection limit of 10(1) CFU/g. These results indicate that the inactivation effects of APP on L. monocytogenes are strongly dependent on the type of food.