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    In nanotube science, is boron nitride the new carbon?

    Engineers at MIT and the University of Tokyo have produced centimeter-scale structures, large enough for the eye to see, that are packed with hundreds of billions of hollow aligned fibers, or nanotubes, made from hexagonal boron nitride.

    Hexagonal boron nitride, or hBN, is a single-atom-thin material that has been coined “white graphene” for its transparent appearance and its similarity to carbon-based graphene in molecular structure and strength. It can also withstand higher temperatures than graphene, and is electrically insulating, rather than conductive. When hBN is rolled into nanometer-scale tubes, or nanotubes, its exceptional properties are significantly enhanced.

    The team’s results, published today in the journal ACS Nano, provide a route toward fabricating aligned boron nitride nanotubes (A-BNNTs) in bulk. The researchers plan to harness the technique to fabricate bulk-scale arrays of these nanotubes, which can then be combined with other materials to make stronger, more heat-resistant composites, for instance to shield space structures and hypersonic aircraft.

    As hBN is transparent and electrically insulating, the team also envisions incorporating the BNNTs into transparent windows and using them to electrically insulate sensors within electronic devices. The team is also investigating ways to weave the nanofibers into membranes for water filtration and for “blue energy” — a concept for renewable energy in which electricity is produced from the ionic filtering of salt water into fresh water.

    Brian Wardle, professor of aeronautics and astronautics at MIT, likens the team’s results to scientists’ decades-long, ongoing pursuit of manufacturing bulk-scale carbon nanotubes.

    “In 1991, a single carbon nanotube was identified as an interesting thing, but it’s been 30 years getting to bulk aligned carbon nanotubes, and the world’s not even fully there yet,” Wardle says. “With the work we’re doing, we’ve just short-circuited about 20 years in getting to bulk-scale versions of aligned boron nitride nanotubes.”

    Wardle is the senior author of the new study, which includes lead author and MIT research scientist Luiz Acauan, former MIT postdoc Haozhe Wang, and collaborators at the University of Tokyo.

    A vision, aligned

    Like graphene, hexagonal boron nitride has a molecular structure resembling chicken wire. In graphene, this chicken wire configuration is made entirely of carbon atoms, arranged in a repeating pattern of hexagons. For hBN, the hexagons are composed of alternating atoms of boron and nitrogen. In recent years, researchers have found that two-dimensional sheets of hBN exhibit exceptional properties of strength, stiffness, and resilience at high temperatures. When sheets of hBN are rolled into nanotube form, these properties are further enhanced, particularly when the nanotubes are aligned, like tiny trees in a densely packed forest.

    But finding ways to synthesize stable, high quality BNNTs has proven challenging. A handful of efforts to do so have produced low-quality, nonaligned fibers.

    “If you can align them, you have much better chance of harnessing BNNTs properties at the bulk scale to make actual physical devices, composites, and membranes,” Wardle says.

    In 2020, Rong Xiang and colleagues at the University of Tokyo found they could produce high-quality boron nitride nanotubes by first using a conventional approach of chemical vapor deposition to grow a forest of short, few micron-long carbon nanotubes. They then coated the carbon-based forest with “precursors” of boron and nitrogen gas, which when baked in an oven at high temperatures crystallized onto the carbon nanotubes to form high-quality nanotubes of hexagonal boron nitride with carbon nanotubes inside.

    Burning scaffolds

    In the new study, Wardle and Acauan have extend and scale Xiang’s approach, essentially removing the underlying carbon nanotubes and leaving the long boron nitride nanotubes to stand on their own. The team drew on the expertise of Wardle’s group, which has focused for years on fabricating high-quality aligned arrays of carbon nanotubes. With their current work, the researchers looked for ways to tweak the temperatures and pressures of the chemical vapor deposition process in order to remove the carbon nanotubes while leaving the boron nitride nanotubes intact.

    “The first few times we did it, it was completely ugly garbage,” Wardle recalls. “The tubes curled up into a ball, and they didn’t work.”

    Eventually, the team hit on a combination of temperatures, pressures, and precursors that did the trick. With this combination of processes, the researchers first reproduced the steps that Xiang took to synthesize the boron-nitride-coated carbon nanotubes. As hBN is resistant to higher temperatures than graphene, the team then cranked up the heat to burn away the underlying black carbon nanotube scaffold, while leaving the transparent, freestanding boron nitride nanotubes intact.
    By using carbon nanotubes as a scaffold, MIT engineers grow forests of “white graphene” that emerge (in MIT pattern) after burning away the black carbon scaffold. Courtesy of the researchersIn microscopic images, the team observed clear crystalline structures — evidence that the boron nitride nanotubes have a high quality. The structures were also dense: Within a square centimeter, the researchers were able to synthesize a forest of more than 100 billion aligned boron nitride nanotubes, that measured about a millimeter in height — large enough to be visible by eye. By nanotube engineering standards, these dimensions are considered to be “bulk” in scale.

    “We are now able to make these nanoscale fibers at bulk scale, which has never been shown before,” Acauan says.

    To demonstrate the flexibility of their technique, the team synthesized larger carbon-based structures, including a weave of carbon fibers, a mat of “fuzzy” carbon nanotubes, and sheets of randomly oriented carbon nanotubes known as “buckypaper.” They coated each carbon-based sample with boron and nitrogen precursors, then went through their process to burn away the underlying carbon. In each demonstration, they were left with a boron-nitride replica of the original black carbon scaffold.

    They also were able to “knock down” the forests of BNNTs, producing horizontally aligned fiber films that are a preferred configuration for incorporating into composite materials.

    “We are now working toward fibers to reinforce ceramic matrix composites, for hypersonic and space applications where there are very high temperatures, and for windows for devices that need to be optically transparent,” Wardle says. “You could make transparent materials that are reinforced with these very strong nanotubes.”

    This research was supported, in part, by Airbus, ANSYS, Boeing, Embraer, Lockheed Martin, Saab AB, and Teijin Carbon America through MIT’s Nano-Engineered Composite aerospace STructures (NECST) Consortium. More

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    New maps show airplane contrails over the U.S. dropped steeply in 2020

    As Covid-19’s initial wave crested around the world, travel restrictions and a drop in passengers led to a record number of grounded flights in 2020. The air travel reduction cleared the skies of not just jets but also the fluffy white contrails they produce high in the atmosphere.

    MIT engineers have mapped the contrails that were generated over the United States in 2020, and compared the results to prepandemic years. They found that on any given day in 2018, and again in 2019, contrails covered a total area equal to Massachusetts and Connecticut combined. In 2020, this contrail coverage shrank by about 20 percent, mirroring a similar drop in U.S. flights.  

    While 2020’s contrail dip may not be surprising, the findings are proof that the team’s mapping technique works. Their study marks the first time researchers have captured the fine and ephemeral details of contrails over a large continental scale.

    Now, the researchers are applying the technique to predict where in the atmosphere contrails are likely to form. The cloud-like formations are known to play a significant role in aviation-related global warming. The team is working with major airlines to forecast regions in the atmosphere where contrails may form, and to reroute planes around these regions to minimize contrail production.

    “This kind of technology can help divert planes to prevent contrails, in real time,” says Steven Barrett, professor and associate head of MIT’s Department of Aeronautics and Astronautics. “There’s an unusual opportunity to halve aviation’s climate impact by eliminating most of the contrails produced today.”

    Barrett and his colleagues have published their results today in the journal Environmental Research Letters. His co-authors at MIT include graduate student Vincent Meijer, former graduate student Luke Kulik, research scientists Sebastian Eastham, Florian Allroggen, and Raymond Speth, and LIDS Director and professor Sertac Karaman.

    Trail training

    About half of the aviation industry’s contribution to global warming comes directly from planes’ carbon dioxide emissions. The other half is thought to be a consequence of their contrails. The signature white tails are produced when a plane’s hot, humid exhaust mixes with cool humid air high in the atmosphere. Emitted in thin lines, contrails quickly spread out and can act as blankets that trap the Earth’s outgoing heat.

    While a single contrail may not have much of a warming effect, taken together contrails have a significant impact. But the estimates of this effect are uncertain and based on computer modeling as well as limited satellite data. What’s more, traditional computer vision algorithms that analyze contrail data have a hard time discerning the wispy tails from natural clouds.

    To precisely pick out and track contrails over a large scale, the MIT team looked to images taken by NASA’s GOES-16, a geostationary satellite that hovers over the same swath of the Earth, including the United States, taking continuous, high-resolution images.

    The team first obtained about 100 images taken by the satellite, and trained a set of people to interpret remote sensing data and label each image’s pixel as either part of a contrail or not. They used this labeled dataset to train a computer-vision algorithm to discern a contrail from a cloud or other image feature.

    The researchers then ran the algorithm on about 100,000 satellite images, amounting to nearly 6 trillion pixels, each pixel representing an area of about 2 square kilometers. The images covered the contiguous U.S., along with parts of Canada and Mexico, and were taken about every 15 minutes, between Jan. 1, 2018, and Dec. 31, 2020.

    The algorithm automatically classified each pixel as either a contrail or not a contrail, and generated daily maps of contrails over the United States. These maps mirrored the major flight paths of most U.S. airlines, with some notable differences. For instance, contrail “holes” appeared around major airports, which reflects the fact that planes landing and taking off around airports are generally not high enough in the atmosphere for contrails to form.

    “The algorithm knows nothing about where planes fly, and yet when processing the satellite imagery, it resulted in recognizable flight routes,” Barrett says. “That’s one piece of evidence that says this method really does capture contrails over a large scale.”

    Cloudy patterns

    Based on the algorithm’s maps, the researchers calculated the total area covered each day by contrails in the US. On an average day in 2018 and in 2019, U.S. contrails took up about 43,000 square kilometers. This coverage dropped by 20 percent in March of 2020 as the pandemic set in. From then on, contrails slowly reappeared as air travel resumed through the year.

    The team also observed daily and seasonal patterns. In general, contrails appeared to peak in the morning and decline in the afternoon. This may be a training artifact: As natural cirrus clouds are more likely to form in the afternoon, the algorithm may have trouble discerning contrails amid the clouds later in the day. But it might also be an important indication about when contrails form most. Contrails also peaked in late winter and early spring, when more of the air is naturally colder and more conducive for contrail formation.

    The team has now adapted the technique to predict where contrails are likely to form in real time. Avoiding these regions, Barrett says, could take a significant, almost immediate chunk out of aviation’s global warming contribution.  

    “Most measures to make aviation sustainable take a long time,” Barrett says. “(Contrail avoidance) could be accomplished in a few years, because it requires small changes to how aircraft are flown, with existing airplanes and observational technology. It’s a near-term way of reducing aviation’s warming by about half.”

    The team is now working towards this objective of large-scale contrail avoidance using realtime satellite observations.

    This research was supported in part by NASA and the MIT Environmental Solutions Initiative. More