We recently demonstrated scalable manufacturing of boron nitride nanotubes (BNNTs) directly from hexagonal BN (hBN) powder by using induction thermal plasma, with a high-yield rate approaching 20 g/h. The main finding was that the presence of hydrogen is crucial for the high-yield growth of BNNTs. Here we investigate the detailed role of hydrogen by numerical modeling and in situ optical emission spectroscopy (OES) and reveal that both the thermofluidic fields and chemical pathways are significantly altered by hydrogen in favor of rapid growth of BNNTs. The numerical simulation indicated improved particle heating and quenching rates (∼10 K/s) due to the high thermal conductivity of hydrogen over the temperature range of 3500-4000 K. These are crucial for the complete vaporization of the hBN feedstock and rapid formation of nanosized B droplets for the subsequent BNNT growth. Hydrogen is also found to extend the active BNNT growth zone toward the reactor downstream, maintaining the gas temperature above the B solidification limit (∼2300 K) by releasing the recombination heat of H atoms, which starts at 3800 K. The OES study revealed that H radicals also stabilize B or N radicals from dissociation of the feedstock as BH and NH radicals while suppressing the formation of N or N species. Our density functional theory calculations showed that such radicals can provide faster chemical pathways for the formation of BN compared with relatively inert N.

Current processes to manufacture nanotubes at commercial scales are unfortunately imperfect and commonly generate undesirable byproducts. After manufacturing, purification is necessary and is a rate and cost determining step in advancing the development of commercial products based on nanotubes. Boron nitride nanotubes (BNNTs) produced without metal catalysts from high-temperature processes are known to contain a significant amount (e.g., 50 wt %) of various boron derivatives. Herein we report a simple yet efficient and scalable process to purify these types of BNNT materials at commercial scales, from a few grams to hundreds of grams, at purity over 85 wt % in a single step. The process relies on a vertically mounted flow tube reactor and scrubber system that can be operated under pure or diluted chlorine gas flow at temperatures up to 1100 °C. The main chemical reactions driving the purification are the conversion of boron and BN derivatives into BCl3 and HCl, which are removed as gaseous species, while pristine BNNTs are left behind. The preferential etching of impurities over pristine BNNTs shows the extreme chemical resistance of BNNTs in this harsh environment and opens up new applications for this nanomaterial. The process has been examined at various temperatures, up to 1050 °C, and the resulting materials display improved BNNT purity and quality across a range of imaging and spectroscopic assessments. The recommended temperature to optimize quality with yield is 950 °C, although higher quality material is obtained at a higher temperature.

Single-walled carbon nanotubes (SWCNT) have been reduced with sodium naphthalide in THF. The reduced SWCNT are not only soluble in dimethylsulfoxide (DMSO) to form a stable solution/suspension, but also react spontaneously at room temperature with DMSO to evolve hydrocarbon gases and are converted into functionalized SWCNT. The degree of functionalization is about 2C% and the addends are mainly methyl and small oxygen-containing hydrocarbons. The functionalized SWCNT are apparently more soluble and stable in DMSO solution. It may open a new era for further processing and applications.

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