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.

Long-wave infrared transparent sulfur polymers enabled by symmetric thiol cross-linker.

Infrared (IR) transmissive polymeric materials for optical elements require a balance between their optical properties, including refractive index (n) and IR transparency, and thermal properties such as glass transition temperature (Tg). Achieving both a high refractive index (n) and IR transparency in polymer materials is a very difficult challenge. In particular, there are significant complexities and considerations to obtaining organic materials that transmit in the long-wave infrared (LWIR) region, because of high optical losses due to the IR absorption of the organic molecules. Our differentiated strategy to extend the frontiers of LWIR transparency is to reduce the IR absorption of the organic moieties. The proposed approach synthesized a sulfur copolymer via the inverse vulcanization of 1,3,5-benzenetrithiol (BTT), which has a relatively simple IR absorption because of its symmetric structure, and elemental sulfur, which is mostly IR inactive. This strategy resulted in approximately 1 mm thick windows with an ultrahigh refractive index (nav > 1.9) and high mid-wave infrared (MWIR) and LWIR transmission, without any significant decline in thermal properties. Furthermore, we demonstrated that our IR transmissive material was sufficiently competitive with widely used optical inorganic and polymeric materials.

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.

Facile Preparation of a Bispherical Silver-Carbon Photocatalyst and Its Enhanced Degradation Efficiency of Methylene Blue, Rhodamine B, and Methyl Orange under UV Light.

The combination of organic and inorganic materials is attracting attention as a photocatalyst that promotes the decomposition of organic dyes. A facile thermal procedure has been proposed to produce spherical silver nanoparticles (AgNPs), carbon nanospheres (CNSs), and a bispherical AgNP-CNS nanocomposite. The AgNPs and CNSs were each synthesized from silver acetate and glucose via single- and two-step annealing processes under sealed conditions, respectively. The AgNP-CNS nanocomposite was synthesized by the thermolysis of a mixture of silver acetate and a mesophase, where the mesophase was formed by annealing glucose in a sealed vessel at 190 °C. The physicochemical features of the as-prepared nanoparticles and composite were evaluated using several analytical techniques, revealing (i) increased light absorption, (ii) a reduced bandgap, (iii) the presence of chemical interfacial heterojunctions, (iv) an increased specific surface area, and (v) favorable band-edge positions of the AgNP-CNS nanocomposite compared with those of the individual AgNP and CNS components. These characteristics led to the excellent photocatalytic efficacy of the AgNP-CNS nanocomposite for the decomposition of three pollutant dyes under ultraviolet (UV) radiation. In the AgNP-CNS nanocomposite, the light absorption and UV utilization capacity increased at more active sites. In addition, effective electron-hole separation at the heterojunction between the AgNPs and CNSs was possible under favorable band-edge conditions, resulting in the creation of reactive oxygen species. The decomposition rates of methylene blue were 95.2, 80.2, and 73.2% after 60 min in the presence of the AgNP-CNS nanocomposite, AgNPs, and CNSs, respectively. We also evaluated the photocatalytic degradation efficiency at various pH values and loadings (catalysts and dyes) with the AgNP-CNS nanocomposite. The AgNP-CNS nanocomposite was structurally rigid, resulting in 93.2% degradation of MB after five cycles of photocatalytic degradation.

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.

Fluorescence Switchable Block Copolymer Particles with Doubly Alternate-Layered Nanoparticle Arrays.

The precise self-assembly of block copolymers (BCPs) and inorganic nanoparticles (NPs) under 3D confinement offers microparticles with programmable nanostructures and functionalities. Here, fluorescence-switchable hybrid microspheres are developed by forming doubly alternating arrays of Au NPs and CdSe/ZnS quantum dots (QDs) within polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) BCP domains. These doubly alternating arrays afford controlled nonradiative energy transfer (NRET) between the QDs and Au NPs that is dependent on the layer-to-layer distance. Solvent-selective swelling of the hybrid particles tunes the distance between layers, modulating their NRET behavior and affording switchable fluorescence. The particle fluorescence is "OFF" in water through strong NRET from the QDs to Au NPs, but is "ON" in alcohols due to the increased distance between the Au NP and QD arrays in the swollen P4VP domains. The experimentally observed NRET intensity as a function of interparticle distance shows larger quenching efficiencies than those theoretically predicted due to the enhanced quenching within a 3D-confined system. Finally, the robust and reversible fluorescence switching of the hybrid particles in different solvents is demonstrated, highlighting their potentials for bioimaging, sensing, and diagnostic applications.

Boron Nitride Nanotube-Based Separator for High-Performance Lithium-Sulfur Batteries.

To prevent global warming, ESS development is in progress along with the development of electric vehicles and renewable energy. However, the state-of-the-art technology, i.e., lithium-ion batteries, has reached its limitation, and thus the need for high-performance batteries with improved energy and power density is increasing. Lithium-sulfur batteries (LSBs) are attracting enormous attention because of their high theoretical energy density. However, there are technical barriers to its commercialization such as the formation of dendrites on the anode and the shuttle effect of the cathode. To resolve these issues, a boron nitride nanotube (BNNT)-based separator is developed. The BNNT is physically purified so that the purified BNNT (p-BNNT) has a homogeneous pore structure because of random stacking and partial charge on the surface due to the difference of electronegativity between B and N. Compared to the conventional polypropylene (PP) separator, the p-BNNT loaded PP separator prevents the dendrite formation on the Li metal anode, facilitates the ion transfer through the separator, and alleviates the shuttle effect at the cathode. With these effects, the p-BNNT loaded PP separators enable the LSB cells to achieve a specific capacity of 1429 mAh/g, and long-term stability over 200 cycles.

Single- and double-walled boron nitride nanotubes: Controlled synthesis and application for water purification.

Research interest in boron nitride nanotubes (BNNTs) has increased after the recent success of large-scale BNNT syntheses using high-temperature-pressure laser ablation or high-temperature plasma methods. Nonetheless, there are limits to the application and commercialization of these materials because of the difficulties associated with their fine structural control. Herein, the growth kinetics of BNNTs were systemically studied for this purpose. The growth pressure of the nitrogen feed gas was varied while the growth temperature remained constant, which was confirmed by black body radiation measurements and calculations based on a heat loss model. Changing from the diffusion-limited regime to the supply-limited regime of growth kinetics based on the optimized BNNT synthesis condition afforded the control of the number of BNNT walls. The total amount of BNNTs possessing single and double walls was over 70%, and the BNNT surface area increased to 278.2 m2/g corresponding to small wall numbers and diameters. Taking advantage of the large surface area and high-temperature durability of the material, BNNTs utilized as a recyclable adsorbent for water purification. The efficiency of the BNNTs for capturing methylene blue particles in water was approximately 94%, even after three repetition cycles, showing the potential of the material for application in the filter industry.

Effect of Polymeric In Situ Stabilizers on Dispersion Homogeneity of Nanofillers and Thermal Conductivity Enhancement of Composites.

Boron nitride (BN) nanofiller-based polymer composites have been considered promising candidates for efficient heat-dissipating packaging materials because of their superior thermal conductivity, mechanical strength, and chemical resistance. However, strong aggregation of the BN nanofillers in the composite matrix as well as the difficulty in the modification of the chemically inert surface prevents their effective use in polymer composites. Herein, we report an effective method by using in situ stabilizers to achieve homogeneous dispersion of boron nitride (BN) nanofillers in an epoxy-based polymeric matrix and demonstrate their use as efficient heat-dissipating materials. Poly(4-vinylpyridine) (P4VP) is designed and added into the epoxy resin to produce in situ stabilizers during preparation of hexagonal BNs (h-BNs) and BN nanotubes (BNNTs) dispersion. In-depth experimental and theoretical studies indicated that the homogeneous distribution of BN nanofillers in epoxy composites achieved by using the in situ stabilizer enhanced the thermal conductivity of the composite by ∼27% at the same concentration of the BN nanofillers. In addition, the thermal conductivity of the h-BN/epoxy composite (∼3.3 W/mK) was dramatically improved by ∼48% (4.9 W/mK) when the homogeneously dispersed BNNTs (∼1.8 vol %) were added. The concept of the proposed in situ stabilizer can be further utilized to prepare the epoxy composites with the homogeneous distribution of BN nanofillers, which is critical for reproducible and position-independent composite properties.

Dual growth mode of boron nitride nanotubes in high temperature pressure laser ablation.

The morphological analysis of the end of boron nitride nanotubes (BNNTs) using high-resolution transmission electron microscopy (HR-TEM) can provide valuable insight into the growth mechanism in high temperature pressure (HTP) laser ablation where the best quality of BNNT materials can be obtained so far. Two growth modes of BNNT coexisting during the synthesis process have been proposed based on HR-TEM observation and length analysis. One is the root growth mode, in which boron nitride (BN) species formed via the surface interaction between surrounding N2 molecules and boron nanodroplets incorporate into the tubular structure. Another mode called open-end growth mode means the prolongation of tube growth from the exposed BN edge surrounding the surface of boron nanodroplets which is constructed by the heterogeneous nucleation of absorbed BN radicals from the gas plume. The statistical data, the proportions of end structures and the length of BNNTs, could be fitted to two growth modes, and the open-end growth mode is found to be especially effective in producing longer nanotubes with a higher growth rate. The scientific understanding of the growth mechanism is believed to provide the control for optimized production of BNNTs.

Light-Responsive, Shape-Switchable Block Copolymer Particles.

A robust strategy is developed for preparing light-responsive block copolymer (BCP) particles in which shape and color can be actively controlled with high spatial and temporal resolution. The key to achieving light-responsive shape transitions of BCP particles is the design and synthesis of surfactants containing light-active groups (i.e., nitrobenzyl esters and coumarin esters) that modulate the amphiphilicity and interfacial activity of the surfactants in response to light of a specific wavelength. These light-induced changes in surfactant structure modify the surface and wetting properties of BCP particles, affording both shape and morphological transitions of the particles, for example from spheres with an onion-like inner morphology to prolate or oblate ellipsoids with axially stacked nanostructures. In particular, wavelength-selective shape transformation of the BCP particles can be achieved with a mixture of two light-active surfactants that respond to different wavelengths of light (i.e., 254 and 420 nm). Through the use of light-emitting, photoresponsive surfactants, light-induced changes in both color and shape are further demonstrated. Finally, to demonstrate the potential of the light-triggered shape control of BCP particles in patterning features with microscale resolution, the shape-switchable BCP particles are successfully integrated into a patterned, free-standing hydrogel film, which can be used as a portable, high-resolution display.

Enhanced Thermal Conductivity of Liquid Crystalline Epoxy Resin using Controlled Linear Polymerization.

A powerful strategy to enhance the thermal conductivity of liquid crystalline epoxy resin (LCER) by simply replacing the conventional amine cross-linker with a cationic initiator was developed. The cationic initiator linearly wove the epoxy groups tethered on the microscopically aligned liquid crystal mesogens, resulting in freezing of the ordered LC microstructures even after curing. Owing to the reduced phonon scattering during heat transport through the ordered LC structure, a dramatic improvement in the thermal conductivity of neat cation-cured LCER was achieved to give a value ∼141% (i.e., 0.48 W/mK) higher than that of the amorphous amine-cured LCER. In addition, at the same composite volume fraction in the presence of a 2-D boron nitride filler, an approximately 130% higher thermal conductivity (maximum ∼23 W/mK at 60 vol %) was observed. The nanoarchitecture effect of the ordered LCER on the thermal conductivity was then examined by a systematic investigation using differential scanning calorimetry, polarized optical microscopy, X-ray diffraction, and thermal conductivity measurements. The linear polymerization of LCER can therefore be considered a practical strategy to enable the cost-efficient mass production of heat-dissipating materials, due to its high efficiency and simple process without the requirement for complex equipment.

Boron nitride nanotubes as a heat sinking and stress-relaxation layer for high performance light-emitting diodes.

High-density threading dislocations, the presence of biaxial compressive strain, and heat generation are the major limitations obstructing the performance and reliability of light emitting diodes (LEDs). Herein, we demonstrate a facile epitaxial lateral overgrowth (ELOG) method by incorporating boron nitride nanotubes (BNNTs) on a sapphire substrate by spray coating to resolve the above issues. Atomic force microscopy, X-ray diffraction, micro-Raman, and photoluminescence measurements confirmed the growth of a high quality GaN epilayer on the BNNT-coated sapphire substrate with reduced threading dislocations and compressive strain owing to the ELOG process. GaN LEDs fabricated using this approach showed a significant enhancement in the internal quantum efficiency and electroluminescence intensity compared to conventional LEDs grown on sapphire. Moreover, reduced efficiency droop and surface temperature at high injection currents were achieved due to the excellent thermal stability and conductivity of BNNTs. Based on our findings we infer that the BNNTs would be a promising material for high power devices vulnerable to self-heating problems.

Stimuli-Responsive, Shape-Transforming Nanostructured Particles.

Development of particles that change shape in response to external stimuli has been a long-thought goal for producing bioinspired, smart materials. Herein, the temperature-driven transformation of the shape and morphology of polymer particles composed of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block copolymers (BCPs) and temperature-responsive poly(N-isopropylacrylamide) (PNIPAM) surfactants is reported. PNIPAM acts as a temperature-responsive surfactant with two important roles. First, PNIPAM stabilizes oil-in-water droplets as a P4VP-selective surfactant, creating a nearly neutral interface between the PS and P4VP domains together with cetyltrimethylammonium bromide, a PS-selective surfactant, to form anisotropic PS-b-P4VP particles (i.e., convex lenses and ellipsoids). More importantly, the temperature-directed positioning of PNIPAM depending on its solubility determines the overall particle shape. Ellipsoidal particles are produced above the critical temperature, whereas convex lens-shaped particles are obtained below the critical temperature. Interestingly, given that the temperature at which particle shape change occurs depends solely on the lower critical solution temperature (LCST) of the polymer surfactants, facile tuning of the transition temperature is realized by employing other PNIPAM derivatives with different LCSTs. Furthermore, reversible transformations between different shapes of PS-b-P4VP particles are successfully demonstrated using a solvent-adsorption annealing with chloroform, suggesting great promise of these particles for sensing, smart coating, and drug delivery applications.

Processable high internal phase Pickering emulsions using depletion attraction.

High internal phase emulsions have been widely used as templates for various porous materials, but special strategies are required to form, in particular, particle-covered ones that have been more difficult to obtain. Here, we report a versatile strategy to produce a stable high internal phase Pickering emulsion by exploiting a depletion interaction between an emulsion droplet and a particle using water-soluble polymers as a depletant. This attractive interaction facilitating the adsorption of particles onto the droplet interface and simultaneously suppressing desorption once adsorbed. This technique can be universally applied to nearly any kind of particle to stabilize an interface with the help of various non- or weakly adsorbing polymers as a depletant, which can be solidified to provide porous materials for many applications.

Particles with Tunable Porosity and Morphology by Controlling Interfacial Instability in Block Copolymer Emulsions.

A series of porous block copolymer (BCP) particles with controllable morphology and pore sizes was fabricated by tuning the interfacial behavior of BCP droplets in oil-in-water emulsions. A synergistic adsorption of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) BCPs and sodium dodecyl sulfate (SDS) to the surface of the emulsion droplet induced a dramatic decrease in the interfacial tension and generated interfacial instability at the particle surface. In particular, the SDS concentration and the P4VP volume fraction of PS-b-P4VP were key parameters in determining the degree of interfacial instability, leading to different types of particles including micelles, capsules, closed-porosity particles, and open-porosity particles with tunable pore sizes ranging from 10 to 500 nm. The particles with open-porosity could be used as pH-responsive, high capacity delivery systems where the uptake and release of multiple dyes could be achieved.

Size-controlled nanoparticle-guided assembly of block copolymers for convex lens-shaped particles.

The tuning of interfacial properties at selective and desired locations on the particles is of great importance to create the novel structured particles by breaking the symmetry of their surface property. Herein, a dramatic transition of both the external shape and internal morphology of the particles of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) was induced by precise positioning of size-controlled Au nanoparticle surfactants (Au NPs). The size-dependent assembly of the Au NPs was localized preferentially at the interface between the P4VP domain at the particle surface and the surrounding water, which generated a balanced interfacial interaction between two different PS/P4VP domains of the BCP particles and water, producing unique convex lens-shaped BCP particles. In addition, the neutralized interfacial interaction, in combination with the directionality of the solvent-induced ordering of the BCP domains from the interface of the particle/water, generated defect-free, vertically ordered porous channels within the particles. The mechanism for the formation of these novel nanostructures was investigated systemically by varying the size and the volume fraction of the Au NPs. Furthermore, these convex lens-shaped particles with highly ordered channels can be used as a microlens, in which the light can be concentrated toward the focal point with enhanced near-field signals. And, these particles can possess additional optical properties such as unique distribution of light scattering as a result of the well-ordered Au cylinders that filled into the channels, which hold great promise for use in optical, biological-sensing, and imaging applications.

A facile synthesis of dynamic, shape-changing polymer particles.

We herein report a new facile strategy to ellipsoidal block copolymer nanoparticles that exhibit a pH-triggered anistropic swelling profile. In a first step, elongated particles with an axially stacked lamellae structure are selectively prepared by utilizing functional surfactants to control the phase separation of symmetric polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) in dispersed droplets. In a second step, the dynamic shape change is realized by cross-linking the P2VP domains, thereby connecting glassy PS discs with pH-sensitive hydrogel actuators.