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All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

Thermodynamic Approach to Boron Nitride Nanotube Solubility and Dispersion

Inadequate dispersion of nanomaterials is a critical issue that significantly limits the potential properties of nanocomposites and when overcome, will enable further enhancement of material properties. The most common methods used to improve dispersion include surface functionalization, surfactants, polymer wrapping, and sonication. Although these approaches have proven effective, they often achieve dispersion by altering the surface or structure of the nanomaterial and ultimately, their intrinsic properties. Co-solvents are commonly utilized in the polymer, paint, and art conservation industries to selectively dissolve materials. These co-solvents are utilized based on thermodynamic interaction parameters and are chosen so that the original materials are not affected. The same concept was applied to enhance the dispersion of boron nitride nanotubes (BNNTs) to facilitate the fabrication of BNNT nanocomposites. Of the solvents tested, dimethylacetamide (DMAc) exhibited the most stable, uniform dispersion of BNNTs, followed by N,N-dimethylformamide (DMF), acetone, and N-methyl-2-pyrrolidone (NMP). Utilizing the known Hansen solubility parameters of these solvents in comparison to the BNNT dispersion state, a region of good solubility was proposed. This solubility region was used to identify co-solvent systems that led to improved BNNT dispersion in poor solvents such as toluene, hexane, and ethanol. Incorporating the data from the co-solvent studies further refined the proposed solubility region. From this region, the Hansen solubility parameters for BNNTs are thought to lie at the midpoint of the solubility sphere: 16.8, 10.7, and 9.0 MPa(exp 1/2) for delta d, delta p, and delta h, respectively, with a calculated Hildebrand parameter of 21.8 MPa)exp 1/2).

Tiano, A. L.↗
NASA NTRS2005

Synthesis of Boron Nitride Nanotubes for Engineering Applications

Boron Nitride nanotubes (BNNT) are of interest to the scientific and technical communities for many of the same reasons that carbon nanotubes (CNT) have attracted large amounts of attention. Both materials have potentially unique and significant properties which may have important structural and electronic applications in the future. However of even more interest than their similarities may be the differences between carbon and boron nanotubes. Whilt boron nitride nanotubes possess a very high modulus similaar to CNT, they are also more chemically and thermally inert. Additionally BNNT possess more uniform electronic properties, having a uniform band gap of approximately 5.5 eV while CNT vary from semi-conductin to conductor behavior. Boron Nitride nanotubes have been synthesized by a variety of methods such as chemical vapor deposition, arc discharge and reactive milling. Consistently producing a reliable product has proven difficult. Progress in synthesis of 1-2 gram sized batches of Boron Nitride nanotubes will be discussed as well as potential uses for this unique material.

Hurst, Janet↗
NASA NTRS2015

Multifunctional Electroactive Nanocomposites Based on Piezoelectric Boron Nitride Nanotubes

Space exploration missions require sensors and devices capable of stable operation in harsh environments such as those that include high thermal fluctuation, atomic oxygen, and high-energy ionizing radiation. However, conventional or state-of-the-art electroactive materials like lead zirconate titanate, poly(vinylidene fluoride), and carbon nanotube (CNT)-doped polyimides have limitations on use in those extreme applications. Theoretical studies have shown that boron nitride nanotubes (BNNTs) have strength-to-weight ratios comparable to those of CNTs, excellent high-temperature stability (to 800 C in air), large electroactive characteristics, and excellent neutron radiation shielding capability. In this study, we demonstrated the experimental electroactive characteristics of BNNTs in novel multifunctional electroactive nanocomposites. Upon application of an external electric field, the 2 wt % BNNT/polyimide composite was found to exhibit electroactive strain composed of a superposition of linear piezoelectric and nonlinear electrostrictive components. When the BNNTs were aligned by stretching the 2 wt % BNNT/polyimide composite, electroactive characteristics increased by about 460% compared to the nonstretched sample. An all-nanotube actuator consisting of a BNNT buckypaper layer between two single-walled carbon nanotube buck-paper electrode layers was found to have much larger electroactive properties. The additional neutron radiation shielding properties and ultraviolet/visible/near-infrared optical properties of the BNNT composites make them excellent candidates for use in the extreme environments of space missions. utilizing the unique characteristics of BNNTs.

Kang, Jin Ho↗
NASA NTRS2020

Implementation Concept of Operation for a Multi-Purpose Cassegrain Solar Concentrator, Micro-Spectrometers, and Electrostatic Neutralizers to Enable In Situ Construction Activities plus Lunar, Planetary, and Deep Space Science Exploration on the Moon

The ability to utilize regolith would support human missions to the Moon and Mars by both stabilizing the surface as well as the use of indigenous resources. Precision landing requirements include surface stabilization to prevent damage or contamination due to regolith projectiles as a result of plume interaction with regolith. The use of indigenous resources rather than hauling materials from Earth appears to be economically a palatable option by converting indigenous resources to usable products. However, such activities have new technical challenges to overcome the issues related to lunar environmental conditions, a wide range of temperature fluctuation, extremely high vacuum, and electrostatically charged fine regolith dusts. For both the regolith sintering and extraction of resources onsite, a Cassegrain solar concentrator was studied for not only sintering lunar regolith into a hardened stabilized surface, but also other multiple applications. This report illustrates a Cassegrain solar concentrator that has multi-functional capabilities for space missions. Proper design and implementation of high-performance lightweight composite materials for the primary mirror of the Cassegrain concentrator can offer multiple capabilities to be performed on the Moon. The multiple applications studied with Cassegrain concentrators are (1) Solar sintering for landing pad and habitats, (2) Harvest of volatiles: H2O, O2, H2, and He-3, (3) Space antenna for telemetry and telecommunication, and (4) Space telescope with 20-meter aperture that exceeds the space telescopes to date in terms of the State-of-Art (SOA) in resolution and aperture diameter. In this study, a key emphasis was placed on the NASA Langley-developed boron nitride nanotube (BNNT) nanocomposite technology which is ideal for the segmented primary mirror structure of the Cassegrain system because it promises a very low coefficient of thermal expansion (CTE) and negligible Poisson ratio. Also, BNNT nanocomposites offer several noticeable benefits, such as light weight, radiation shielding capability, and mechanical strength for structural applications. Additionally, the NASA Langley-developed bullet-like micro-spectrometer and electrostatic power generator were reviewed for mineral mapping applications and electrostatic power generation and dust mitigation from electrostatically charged regolith.

landing pad↗
NASA NTRS2022

Liquid crystals of neat boron nitride nanotubes and their assembly into ordered macroscopic materials

Boron nitride nanotubes (BNNTs) have attracted attention for their predicted extraordinary properties; yet, challenges in synthesis and processing have stifled progress on macroscopic materials. Recent advances have led to the production of highly pure BNNTs. Here we report that neat BNNTs dissolve in chlorosulfonic acid (CSA) and form birefringent liquid crystal domains at concentrations above 170 ppmw. These tactoidal domains merge into millimeter- sized regions upon light sonication in capillaries. Cryogenic electron microscopy directly shows nematic alignment of BNNTs in solution. BNNT liquid crystals can be processed into aligned films and extruded into neat BNNT fibers. This study of nematic liquid crystals of BNNTs demonstrates their ability to form macroscopic materials to be used in high- performance applications.

Cedric J. Simonsen Ginestra↗
NASA NTRS2025

The Shape Effect: Influence of 1D and 2D Boron Nitride Nanostructures on the Radiation Shielding, Thermal, and Damping Properties of High-Temperature Epoxy Composites

In space exploration, lightweight multifunctional materials capable of shielding neutron radiation, dissipating heat, and providing damping are essential. Polymer composites reinforced with boron nitride (BN) nanomaterials—specifically one-dimensional boron nitride nanotubes (BNNTs) and two-dimensional boron nitride nanoplatelets (BNNPs)—offer promising solutions. This study investigates how BN nanomaterial morphology influences the performance of high-temperature (HT) epoxy composites. We developed ultralightweight, three-dimensional BN foams comprising 1D BNNTs, 2D BNNPs, and hybrid 1D BNNT/2D BNNP structures via freeze-drying, then infiltrated them with HT epoxy to form dense composites. The BNNT foam exhibited the highest neutron radiation shielding, with a mass absorption coefficient of 26.64 cm2 g −1 , outperforming the hybrid foam (18.18 cm 2 g −1 ) and the BNNP foam (11.12 cm 2 g −1 ). A similar trend was observed in the HT epoxy composites; incorporating these foams at least doubled the mass absorption coefficient compared to the neat polymer. In terms of thermal conductivity, the BNNT/BNNP foam-epoxy composite achieved the highest value of 0.34 W m −1 K −1 , a 2.13-fold increase over neat HT epoxy. The BNNT/BNNP foam-epoxy composites also improved by 1.88 and 1.75 times, respectively. Mechanical testing revealed that BNNP foams withstood the highest loads during nanoindentation (3.53 kN), followed by BNNT/BNNP foams (1.93 kN) and BNNT foams (1.56 kN). All BN foam-epoxy composites exhibited enhanced damping properties, with tan δ increasing by at least 30 % compared to neat HT epoxy. These findings elucidate the impact of BN nanomaterial morphology on the multifunctional performance of HT epoxy composites, offering insights for developing high-performance, tailorable materials for demanding environments.

Kazue Orikasa↗
NASA NTRS2021

Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes (BNNTs) for Structural Applications: Part III

The emergence of commercial quantities of BNNTs facilitates the exploration of structural material applications. BNNT-reinforced composites must exhibit extraordinary mechanical properties in order to justify the cost premium. Prevailing theory indicates that suitable BNNTs must possess an aspect ratio (AR= length/diameter) approaching 10,000 to provide effective discontinuous reinforcement under tensile loading. A survey of commercial products shows that although the quantities are sufficient, lots of uniform morphology are unavailable. Therefore, the opportunity exists to supplement procedures either during synthesis operations or post-synthesis processing in order to deliver homogeneous batches of high AR BNNTs. An assessment of relevant technologies reveals established methods compatible with sorting of BNNTs by physical dimensions, i.e., size and/or shape. Electrostatic fractionation emerges as the leading candidate, with the potential to isolate high-purity, low-defect, high AR product. The adaptation of existing equipment to the handling of fibrous particulate on the nanoscale will be paramount to success. Although currently focused on BNNTs, the concepts outlined may be applied to nanotubes synthesized from any organic or inorganic compounds. This survey sets the stage for delivering reproducible lots of BNNTs that satisfy the dimensional requirements for use in acreage structural materials.

induction plasma, BNNT, aspect ratio, fractionatio↗
NASA NTRS2004

Boron Nitride Nanotubes Synthesized by Pressurized Reactive Milling Process

Nanotubes, because of their very high strength, are attractive as reinforcement materials for ceramic matrix composites (CMCs). Recently there has been considerable interest in developing and applying carbon nanotubes for both electronic and structural applications. Although carbon nanotubes can be used to reinforce composites, they oxidize at high temperatures and, therefore, may not be suitable for ceramic composites. Boron nitride, because it has a higher oxidation resistance than carbon, could be a potential reinforcement material for ceramic composites. Although boron nitride nanotubes (BNnT) are known to be structurally similar to carbon nanotubes, they have not undergone the same extensive scrutiny that carbon nanotubes have experienced in recent years. This has been due to the difficulty in synthesizing this material rather than lack of interest in the material. We expect that BNnTs will maintain the high strength of carbon nanotubes while offering superior performance for the high-temperature and/or corrosive applications of interest to NASA. At the NASA Glenn Research of preparing BN-nTs were investigated and compared. These include the arc jet process, the reactive milling process, and chemical vapor deposition. The most successful was a pressurized reactive milling process that synthesizes BN-nTs of reasonable quantities.

Hurst, Janet B.↗
NASA NTRS2009

Very Long Single and Few-Walled Boron Nitride Nanotubes via the Pressurized Vapor/Condenser Method

A new method for producing long, small diameter, single and few-walled, boron nitride nanotubes (BNNTs) in macroscopic quantities is reported. The pressurized vapor/condenser (PVC) method produces, without catalysts, highly crystalline, very long, small diameter, BNNTs. Palm-sized, cotton-like masses of BNNT raw material were grown by this technique and spun directly into centimeters-long yarn. Nanotube lengths were observed to be 100 times that of those grown by the most closely related method. Self-assembly and growth models for these long BNNTs are discussed.

Smith, Michael W.↗
NASA NTRS2011

In Situ Mechanical Property Measurements of Amorphous Carbon-Boron Nitride Nanotube Nanostructures

To understand the mechanical properties of amorphous carbon (a-C)/boron nitride nanotube (BNNT) nanostructures, in situ mechanical tests are conducted inside a transmission electron microscope equipped with an integrated atomic force microscope system. The nanotube structure is modified with amorphous carbon deposited by controlled electron beam irradiation. We demonstrate multiple in situ tensile, compressive, and lap shear tests with a-C/BNNT hybrid nanostructures. The tensile strength of the a-C/BNNT hybrid nanostructure is 5.29 GPa with about 90 vol% of a-C. The tensile strength and strain of the end-to-end joint structure with a-C welding is 0.8 GPa and 5.2% whereas the lap shear strength of the side-by-side joint structure with a-C is 0.25 GPa.

Kim, Jae-Woo↗
NASA NTRS2012

Modeling of Laser Vaporization and Plume Chemistry in a Boron Nitride Nanotube Production Rig

Flow in a pressurized, vapor condensation (PVC) boron nitride nanotube (BNNT) production rig is modeled. A laser provides a thermal energy source to the tip of a boron ber bundle in a high pressure nitrogen chamber causing a plume of boron-rich gas to rise. The buoyancy driven flow is modeled as a mixture of thermally perfect gases (B, B2, N, N2, BN) in either thermochemical equilibrium or chemical nonequilibrium assuming steady-state melt and vaporization from a 1 mm radius spot at the axis of an axisymmetric chamber. The simulation is intended to define the macroscopic thermochemical environment from which boron-rich species, including nanotubes, condense out of the plume. Simulations indicate a high temperature environment (T > 4400K) for elevated pressures within 1 mm of the surface sufficient to dissociate molecular nitrogen and form BN at the base of the plume. Modifications to Program LAURA, a finite-volume based solver for hypersonic flows including coupled radiation and ablation, are described to enable this simulation. Simulations indicate that high pressure synthesis conditions enable formation of BN vapor in the plume that may serve to enhance formation of exceptionally long nanotubes in the PVC process.

Gnoffo, Peter A.↗
NASA NTRS2014

Chemical Sharpening, Shortening, and Unzipping of Boron Nitride Nanotubes

Boron nitride nanotubes (BNNTs), the one-dimensional member of the boron nitride nanostructure family, are generally accepted to be highly inert to oxidative treatments and can only be covalently modifi ed by highly reactive species. Conversely, it is discovered that the BNNTs can be chemically dispersed and their morphology modifi ed by a relatively mild method: simply sonicating the nanotubes in aqueous ammonia solution. The dispersed nanotubes are significantly corroded, with end-caps removed, tips sharpened, and walls thinned. The sonication treatment in aqueous ammonia solution also removes amorphous BN impurities and shortened BNNTs, resembling various oxidative treatments of carbon nanotubes. Importantly, the majority of BNNTs are at least partially longitudinally cut, or "unzipped". Entangled and freestanding BN nanoribbons (BNNRs), resulting from the unzipping, are found to be approximately 5-20 nm in width and up to a few hundred nanometers in length. This is the fi rst chemical method to obtain BNNRs from BNNT unzipping. This method is not derived from known carbon nanotube unzipping strategies, but is unique to BNNTs because the use of aqueous ammonia solutions specifi cally targets the B-N bond network. This study may pave the way for convenient processing of BNNTs, previously thought to be highly inert, toward controlling their dispersion, purity, lengths, and electronic properties.

Liao, Yunlong↗
NASA NTRS2017

Boron Nitride Nanoribbons from Exfoliation of Boron Nitride Nanotubes

Two types of boron nitride nanotubes (BNNTs) were exfoliated into boron nitride nanoribbons (BNNR), which were identified using transmission electron microscopy: (1) commercial BNNTs with thin tube walls and small diameters. Tube unzipping was indicated by a large decrease of the sample's surface area and volume for pores less than 2 nm in diameter. (2) BNNTs with large diameters and thick walls synthesized at NASA Glenn Research Center. Here, tube unraveling was indicated by a large increase in external surface area and pore volume. For both, the exfoliation process was similar to the previous reported method to exfoliate commercial hexagonal boron nitride (hBN): Mixtures of BNNT, FeCl3, and NaF (or KF) were sequentially treated in 250 to 350 C nitrogen for intercalation, 500 to 750 C air for exfoliation, and finally HCl for purification. Property changes of the nanosized boron nitride throughout this process were also similar to the previously observed changes of commercial hBN during the exfoliation process: Both crystal structure (x-ray diffraction data) and chemical properties (Fourier-transform infrared spectroscopy data) of the original reactant changed after intercalation and exfoliation, but most (not all) of these changes revert back to those of the reactant once the final, purified products are obtained.

boron nitride nanotube↗
NASA NTRS2017

Quantitative Characterization of Structural and Mechanical Properties of Boron Nitride Nanotubes in High Temperature Environments

The structural stability and mechanical integrity of boron nitride nanotubes (BNNTs) in high temperature environments are of importance in pursuit of their applications that are involved with extreme thermal processing and/or working conditions, but remain not well understood. In this paper, we perform an extensive study of the impacts of high temperature exposure on the structural and mechanical properties of BNNTs with a full structural size spectrum from nano- to micro- to macro-scale by using a variety of in situ and ex situ material characterization techniques. Atomic force microscopy (AFM) and high resolution transmission electron microscopy measurements reveal that the structures of individual BNNTs can survive at up to 850 °C in air and capture the signs of their structural degradation at 900 °C or above. In situ Raman spectroscopy measurements reveal that the BN bonds in BNNT micro-fibrils undergo substantial softening at elevated temperatures of up to 900 °C. The AFM-based nanomechanical compression measurements demonstrate that the mechanical integrity of individual BNNTs remain intact after being thermally baked at up to 850 °C in air. The studies reveal that BNNTs are structurally and mechanically stable materials in high temperature environments, which enables their usages in high temperature applications.

Chen, Xiaoming↗
NASA NTRSDate not supplied

TPSAS-NF1676L-18391-DND

Vehicle weight is a primary driver for most NASA missions. Reducing vehicle weight can: - Expand mission capability - Reduce launch costs - Reduce fuel consumption - Systems analysis shows that reducing materials mass by 20% leads to a 30% reduction in launch vehicle gross weight - Same study indicates a 50% reduction in materials mass reduces launch vehicle gross weight by >60%, enables potential single stage to orbit designs - Additional multifunctionality: thermal, radiation protection, sensing capabilities, no corrosion Potential Impact: Produce advanced lightweight structural BNNT composites with higher thermal stability, no corrosion, high toughness, sensing/actuation, and radiation shielding effectiveness.

Cheol Park↗
NASA NTRSDate not supplied

Aligned Boron Nitride Nanotube Reinforced Polyethylene Nanocomposite for Space Radiation Shielding

With NASA’s Artemis program aiming to establish a human presence on the Moon and eventually on Mars, protecting astronauts from radiation is necessary. Flight-heritage materials, like those with high hydrogen content, such as polyethylene (PE), have proven to be effective radiation shields. This is due to hydrogen’s high charge-to-mass ratio, low secondary radiation production, efficient energy absorption, and high cross-section, which increases the probability of particle interactions to slow or stop ionized particles. Boron nitride nanotubes (BNNTs) and other boron-rich materials offer more effective thermal neutron radiation-stopping capabilities due to their high cross-section and neutron absorption properties. BNNTs also enhance the mechanical properties of radiation shielding material due to their high strength-to-weight ratios. However, integrating high volumes of nanotubes in a matrix without defects presents significant manufacturing challenges. To address this, a bulk nanocomposite laminate fabricating technique, involving synthesizing millimeter-long vertically aligned BNNTs, densifying the nanotubes to high-volume fractions, and infusing the nanotubes with PE while applying heat and pressure was utilized to fabricate the BNNT-PE nanocomposite that was tested for its radiation shielding properties at NASA Langley Research Center’s neutron radiation exposure lab. Results from these experiments will be discussed in the presentation.

Palak B Patel↗