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      in Energy

      Moving perovskite advancements from the lab to the manufacturing floor

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      The following was issued as a joint announcement from MIT.nano and the MIT Research Laboratory for Electronics; CubicPV; Verde Technologies; Princeton University; and the University of California at San Diego.

      Tandem solar cells are made of stacked materials — such as silicon paired with perovskites — that together absorb more of the solar spectrum than single materials, resulting in a dramatic increase in efficiency. Their potential to generate significantly more power than conventional cells could make a meaningful difference in the race to combat climate change and the transition to a clean-energy future.

      However, current methods to create stable and efficient perovskite layers require time-consuming, painstaking rounds of design iteration and testing, inhibiting their development for commercial use. Today, the U.S. Department of Energy Solar Energy Technologies Office (SETO) announced that MIT has been selected to receive an $11.25 million cost-shared award to establish a new research center to address this challenge by using a co-optimization framework guided by machine learning and automation.

      A collaborative effort with lead industry participant CubicPV, solar startup Verde Technologies, and academic partners Princeton University and the University of California San Diego (UC San Diego), the center will bring together teams of researchers to support the creation of perovskite-silicon tandem solar modules that are co-designed for both stability and performance, with goals to significantly accelerate R&D and the transfer of these achievements into commercial environments.

      “Urgent challenges demand rapid action. This center will accelerate the development of tandem solar modules by bringing academia and industry into closer partnership,” says MIT professor of mechanical engineering Tonio Buonassisi, who will direct the center. “We’re grateful to the Department of Energy for supporting this powerful new model and excited to get to work.”

      Adam Lorenz, CTO of solar energy technology company CubicPV, stresses the importance of thinking about scale, alongside quality and efficiency, to accelerate the perovskite effort into the commercial environment. “Instead of chasing record efficiencies with tiny pixel-sized devices and later attempting to stabilize them, we will simultaneously target stability, reproducibility, and efficiency,” he says. “It’s a module-centric approach that creates a direct channel for R&D advancements into industry.”

      The center will be named Accelerated Co-Design of Durable, Reproducible, and Efficient Perovskite Tandems, or ADDEPT. The grant will be administered through the MIT Research Laboratory for Electronics (RLE).

      David Fenning, associate professor of nanoengineering at UC San Diego, has worked with Buonassisi on the idea of merging materials, automation, and computation, specifically in this field of artificial intelligence and solar, since 2014. Now, a central thrust of the ADDEPT project will be to deploy machine learning and robotic screening to optimize processing of perovskite-based solar materials for efficiency and durability.

      “We have already seen early indications of successful technology transfer between our UC San Diego robot PASCAL and industry,” says Fenning. “With this new center, we will bring research labs and the emerging perovskite industry together to improve reproducibility and reduce time to market.”

      “Our generation has an obligation to work collaboratively in the fight against climate change,” says Skylar Bagdon, CEO of Verde Technologies, which received the American-Made Perovskite Startup Prize. “Throughout the course of this center, Verde will do everything in our power to help this brilliant team transition lab-scale breakthroughs into the world where they can have an impact.”

      Several of the academic partners echoed the importance of the joint effort between academia and industry. Barry Rand, professor of electrical and computer engineering at the Andlinger Center for Energy and the Environment at Princeton University, pointed to the intersection of scientific knowledge and market awareness. “Understanding how chemistry affects films and interfaces will empower us to co-design for stability and performance,” he says. “The center will accelerate this use-inspired science, with close guidance from our end customers, the industry partners.”

      A critical resource for the center will be MIT.nano, a 200,000-square-foot research facility set in the heart of the campus. MIT.nano Director Vladimir Bulović, the Fariborz Maseeh (1990) Professor of Emerging Technology, says he envisions MIT.nano as a hub for industry and academic partners, facilitating technology development and transfer through shared lab space, open-access equipment, and streamlined intellectual property frameworks.

      “MIT has a history of groundbreaking innovation using perovskite materials for solar applications,” says Bulović. “We’re thrilled to help build on that history by anchoring ADDEPT at MIT.nano and working to help the nation advance the future of these promising materials.”

      MIT was selected as a part of the SETO Fiscal Year 2022 Photovoltaics (PV) funding program, an effort to reduce costs and supply chain vulnerabilities, further develop durable and recyclable solar technologies, and advance perovskite PV technologies toward commercialization. ADDEPT is one project that will tackle perovskite durability, which will extend module life. The overarching goal of these projects is to lower the levelized cost of electricity generated by PV.

      Research groups involved with the ADDEPT project at MIT include Buonassisi’s Accelerated Materials Laboratory for Sustainability (AMLS), Bulović’s Organic and Nanostructured Electronics (ONE) Lab, and the Bawendi Group led by Lester Wolfe Professor in Chemistry Moungi Bawendi. Also working on the project is Jeremiah Mwaura, research scientist in the ONE Lab. More

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      in Environment

      Even as temperatures rise, this hydrogel material keeps absorbing moisture

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      The vast majority of absorbent materials will lose their ability to retain water as temperatures rise. This is why our skin starts to sweat and why plants dry out in the heat. Even materials that are designed to soak up moisture, such as the silica gel packs in consumer packaging, will lose their sponge-like properties as their environment heats up.

      But one material appears to uniquely resist heat’s drying effects. MIT engineers have now found that polyethylene glycol (PEG) — a hydrogel commonly used in cosmetic creams, industrial coatings, and pharmaceutical capsules — can absorb moisture from the atmosphere even as temperatures climb.

      The material doubles its water absorption as temperatures climb from 25 to 50 degrees Celsius (77 to 122 degrees Fahrenheit), the team reports.

      PEG’s resilience stems from a heat-triggering transformation. As its surroundings heat up, the hydrogel’s microstructure morphs from a crystal to a less organized “amorphous” phase, which enhances the material’s ability to capture water.

      Based on PEG’s unique properties, the team developed a model that can be used to engineer other heat-resistant, water-absorbing materials. The group envisions such materials could one day be made into devices that harvest moisture from the air for drinking water, particularly in arid desert regions. The materials could also be incorporated into heat pumps and air conditioners to more efficiently regulate temperature and humidity.

      “A huge amount of energy consumption in buildings is used for thermal regulation,” says Lenan Zhang, a research scientist in MIT’s Department of Mechanical Engineering. “This material could be a key component of passive climate-control systems.”

      Zhang and his colleagues detail their work in a study appearing today in Advanced Materials. MIT co-authors include Xinyue Liu, Bachir El Fil, Carlos Diaz-Marin, Yang Zhong, Xiangyu Li, and Evelyn Wang, along with Shaoting Lin of Michigan State University.

      Against intuition

      Evelyn Wang’s group in MIT’s Device Research Lab aims to address energy and water challenges through the design of new materials and devices that sustainably manage water and heat. The team discovered PEG’s unusual properties as they were assessing a slew of similar hydrogels for their water-harvesting abilities.

      “We were looking for a high-performance material that could capture water for different applications,” Zhang says. “Hydrogels are a perfect candidate, because they are mostly made of water and a polymer network. They can simultaneously expand as they absorb water, making them ideal for regulating humidity and water vapor.”

      The team analyzed a variety of hydrogels, including PEG, by placing each material on a scale that was set within a climate-controlled chamber. A material became heavier as it absorbed more moisture. By recording a material’s changing weight, the researchers could track its ability to absorb moisture as they tuned the chamber’s temperature and humidity.

      What they observed was typical of most materials: as the temperature increased, the hyrogels’ ability to capture moisture from the air decreased. The reason for this temperature-dependence is well-understood: With heat comes motion, and at higher temperatures, water molecules move faster and are therefore more difficult to contain in most materials.

      “Our intuition tells us that at higher temperatures, materials tend to lose their ability to capture water,” says co-author Xinyue Liu. “So, we were very surprised by PEG because it has this inverse relationship.”

      In fact, they found that PEG grew heavier and continued to absorb water as the researchers raised the chamber’s temperature from 25 to 50 degrees Celsius.

      “At first, we thought we had measured some errors, and thought this could not be possible,” Liu says. “After we double-checked everything was correct in the experiment, we realized this was really happening, and this is the only known material that shows increasing water absorbing ability with higher temperature.”

      A lucky catch

      The group zeroed in on PEG to try and identify the reason for its unusual, heat-resilient performance. They found that the material has a natural melting point at around 50 degrees Celsius, meaning that the hydrogel’s normally crystal-like microstructure completely breaks down and transforms into an amorphous phase. Zhang says that this melted, amorphous phase provides more opportunity for polymers in the material to grab hold of any fast-moving water molecules.

      “In the crystal phase, there might be only a few sites on a polymer available to attract water and bind,” Zhang says. “But in the amorphous phase, you might have many more sites available. So, the overall performance can increase with increased temperature.”

      The team then developed a theory to predict how hydrogels absorb water, and showed that the theory could also explain PEG’s unusual behavior if the researchers added a “missing term” to the theory. That missing term was the effect of phase transformation. They found that when they included this effect, the theory could predict PEG’s behavior, along with that of other temperature-limiting hydrogels.

      The discovery of PEG’s unique properties was in large part by chance. The material’s melting temperature just happens to be within the range where water is a liquid, enabling them to catch PEG’s phase transformation and its resulting super-soaking behavior. The other hydrogels happen to have melting temperatures that fall outside this range. But the researchers suspect that these materials are also capable of similar phase transformations once they hit their melting temperatures.

      “Other polymers could in theory exhibit this same behavior, if we can engineer their melting points within a selected temperature range,” says team member Shaoting Lin.

      Now that the group has worked out a theory, they plan to use it as a blueprint to design materials specifically for capturing water at higher temperatures.

      “We want to customize our design to make sure a material can absorb a relatively high amount of water, at low humidity and high temperatures,” Liu says. “Then it could be used for atmospheric water harvesting, to bring people potable water in hot, arid environments.”

      This research was supported, in part, by U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy. More

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      in Energy

      MIT engineers devise technology to prevent fouling in photobioreactors for CO2 capture

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      Algae grown in transparent tanks or tubes supplied with carbon dioxide can convert the greenhouse gas into other compounds, such as food supplements or fuels. But the process leads to a buildup of algae on the surfaces that clouds them and reduces efficiency, requiring laborious cleanout procedures every couple of weeks.

      MIT researchers have come up with a simple and inexpensive technology that could substantially limit this fouling, potentially allowing for a much more efficient and economical way of converting the unwanted greenhouse gas into useful products.

      The key is to coat the transparent containers with a material that can hold an electrostatic charge, and then applying a very small voltage to that layer. The system has worked well in lab-scale tests, and with further development might be applied to commercial production within a few years.

      The findings are being reported in the journal Advanced Functional Materials, in a paper by recent MIT graduate Victor Leon PhD ’23, professor of mechanical engineering Kripa Varanasi, former postdoc Baptiste Blanc, and undergraduate student Sophia Sonnert.

      No matter how successful efforts to reduce or eliminate carbon emissions may be, there will still be excess greenhouse gases that will remain in the atmosphere for centuries to come, continuing to affect global climate, Varanasi points out. “There’s already a lot of carbon dioxide there, so we have to look at negative emissions technologies as well,” he says, referring to ways of removing the greenhouse gas from the air or oceans, or from their sources before they get released into the air in the first place.

      When people think of biological approaches to carbon dioxide reduction, the first thought is usually of planting or protecting trees, which are indeed a crucial “sink” for atmospheric carbon. But there are others. “Marine algae account for about 50 percent of global carbon dioxide absorbed today on Earth,” Varanasi says. These algae grow anywhere from 10 to 50 times more quickly than land-based plants, and they can be grown in ponds or tanks that take up only a tenth of the land footprint of terrestrial plants.

      What’s more, the algae themselves can then be a useful product. “These algae are rich in proteins, vitamins and other nutrients,” Varanasi says, noting they could produce far more nutritional output per unit of land used than some traditional agricultural crops.

      If attached to the flue gas output of a coal or gas power plant, algae could not only thrive on the carbon dioxide as a nutrient source, but some of the microalgae species could also consume the associated nitrogen and sulfur oxides present in these emissions. “For every two or three kilograms of CO2, a kilogram of algae could be produced, and these could be used as biofuels, or for Omega-3, or food,” Varanasi says.

      Omega-3 fatty acids are a widely used food supplement, as they are an essential part of cell membranes and other tissues but cannot be made by the body and must be obtained from food. “Omega 3 is particularly attractive because it’s also a much higher-value product,” Varanasi says.

      Most algae grown commercially are cultivated in shallow ponds, while others are grown in transparent tubes called photobioreactors. The tubes can produce seven to 10 times greater yields than ponds for a given amount of land, but they face a major problem: The algae tend to build up on the transparent surfaces, requiring frequent shutdowns of the whole production system for cleaning, which can take as long as the productive part of the cycle, thus cutting overall output in half and adding to operational costs.

      The fouling also limits the design of the system. The tubes can’t be too small because the fouling would begin to block the flow of water through the bioreactor and require higher pumping rates.

      Varanasi and his team decided to try to use a natural characteristic of the algae cells to defend against fouling. Because the cells naturally carry a small negative electric charge on their membrane surface, the team figured that electrostatic repulsion could be used to push them away.

      The idea was to create a negative charge on the vessel walls, such that the electric field forces the algae cells away from the walls. To create such an electric field requires a high-performance dielectric material, which is an electrical insulator with a high “permittivity” that can produce a large change in surface charge with a smaller voltage.

      “What people have done before with applying voltage [to bioreactors] has been with conductive surfaces,” Leon explains, “but what we’re doing here is specifically with nonconductive surfaces.”

      He adds: “If it’s conductive, then you pass current and you’re kind of shocking the cells. What we’re trying to do is pure electrostatic repulsion, so the surface would be negative and the cell is negative so you get repulsion. Another way to describe it is like a force field, whereas before the cells were touching the surface and getting shocked.”

      The team worked with two different dielectric materials, silicon dioxide — essentially glass — and hafnia (hafnium oxide), both of which turned out to be far more efficient at minimizing fouling than conventional plastics used to make photobioreactors. The material can be applied in a coating that is vanishingly thin, just 10 to 20 nanometers (billionths of a meter) thick, so very little would be needed to coat a full photobioreactor system.

      “What we are excited about here is that we are able to show that purely from electrostatic interactions, we are able to control cell adhesion,” Varanasi says. “It’s almost like an on-off switch, to be able to do this.”

      Additionally, Leon says, “Since we’re using this electrostatic force, we don’t really expect it to be cell-specific, and we think there’s potential for applying it with other cells than just algae. In future work, we’d like to try using it with mammalian cells, bacteria, yeast, and so on.” It could also be used with other valuable types of algae, such as spirulina, that are widely used as food supplements.

      The same system could be used to either repel or attract cells by just reversing the voltage, depending on the particular application. Instead of algae, a similar setup might be used with human cells to produce artificial organs by producing a scaffold that could be charged to attract the cells into the right configuration, Varanasi suggests.

      “Our study basically solves this major problem of biofouling, which has been a bottleneck for photobioreactors,” he says. “With this technology, we can now really achieve the full potential” of such systems, although further development will be needed to scale up to practical, commercial systems.

      As for how soon this could be ready for widespread deployment, he says, “I don’t see why not in three years’ timeframe, if we get the right resources to be able to take this work forward.”

      The study was supported by energy company Eni S.p.A., through the MIT Energy Initiative. More

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      in Security

      Scientists uncover the amazing way sandgrouse hold water in their feathers

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      Many birds’ feathers are remarkably efficient at shedding water — so much so that “like water off a duck’s back” is a common expression. Much more unusual are the belly feathers of the sandgrouse, especially Namaqua sandgrouse, which absorb and retain water so efficiently the male birds can fly more than 20 kilometers from a distant watering hole back to the nest and still retain enough water in their feathers for the chicks to drink and sustain themselves in the searing deserts of Namibia, Botswana, and South Africa.

      How do those feathers work? While scientists had inferred a rough picture, it took the latest tools of microscopy, and patient work with a collection of sandgrouse feathers, to unlock the unique structural details that enable the feathers to hold water. The findings appear today in the Journal of the Royal Society Interface, in a paper by Lorna Gibson, the Matoula S. Salapatas Professor of Materials Science and Engineering and a professor of mechanical engineering at MIT, and Professor Jochen Mueller of Johns Hopkins University.

      The unique water-carrying ability of sandgrouse feathers was first reported back in 1896, Gibson says, by E.G.B. Meade-Waldo, who was breeding the birds in captivity. “He saw them behaving like this, and nobody believed him! I mean, it just sounded so outlandish,” Gibson says.

      In 1967, Tom Cade and Gordon MacLean reported detailed observations of the birds at watering holes, in a study that proved the unique behavior was indeed real. The scientists found that male sandgrouse feathers could hold about 25 milliliters of water, or about a tenth of a cup, after the bird had spent about five minutes dipping in the water and fluffing its feathers.

      About half of that amount can evaporate during the male bird’s half-hour-long flight back to the nest, where the chicks, which cannot fly for about their first month, drink the remainder straight from the feathers.

      Cade and MacLean “had part of the story,” Gibson says, but the tools didn’t exist at the time to carry out the detailed imaging of the feather structures that the new study was able to do.

      Gibson and Mueller carried out their study using scanning electron microscopy, micro-computed tomography, and video imaging. They borrowed Namaqua sandgrouse belly feathers from Harvard University’s Museum of Comparative Zoology, which has a collection of specimens of about 80 percent of the world’s birds.

      Bird feathers in general have a central shaft, from which smaller barbs extend, and then smaller barbules extend out from those. Sandgrouse feathers are structured differently, however. In the inner zone of the feather, the barbules have a helically coiled structure close to their base and then a straight extension. In the outer zone of the feather, the barbules lack the helical coil and are simply straight. Both parts lack the grooves and hooks that hold the vane of contour feathers together in most other birds.
      Video of water spreading through the specialized sandgrouse feathers, under magnification, shows the uncoiling and spreading of the feather’s barbules as they become wet. Initially, most barbules in the outer zone of the feather form tubular features.Credit: Specimen #142928, Museum of Comparative Zoology, Harvard University © President and Fellows of Harvard College.

      When wetted, the coiled portions of the barbules unwind and rotate to be perpendicular to the vane, producing a dense forest of fibers that can hold water through capillary action. At the same time, the barbules in the outer zone curl inward, helping to hold the water in.

      The microscopy techniques used in the new study allowed the dimensions of the different parts of the feather to be measured. In the inner zone, the barb shafts are large and stiff enough to provide a rigid base about which the other parts of the feather deform, and the barbules are small and flexible enough that surface tension is sufficient to bend the straight extensions into tear-like structures that hold water. And in the outer zone, the barb shafts and barbules are smaller still, allowing them to curl around the inner zone, further retaining water.

      While previous work had suggested that surface tension produced the water retention characteristics, “what we did was make measurements of the dimensions and do some calculations to show that that’s what is actually happening,” Gibson says. Her group’s work demonstrated that the varying stiffnesses of the different feather parts plays a key role in their ability to hold water.

      The study was mostly driven by intellectual curiosity about this unique behavioral phenomenon, Gibson says. “We just wanted to see how it works. The whole story just seemed so interesting.” But she says it might lead to some useful applications. For example, in desert regions where water is scarce but fog and dew regularly occur, such as in Chile’s Atacama Desert, some adaptation of this feather structure might be incorporated into the systems of huge nets that are used to collect water. “You could imagine this could be a way to improve those systems,” she says. “A material with this kind of structure might be more effective at fog harvesting and holding the water.”

      “This fascinating and in-depth study reveals how the different parts of the sandgrouse’s belly feathers — including the microscopic barb shafts and barbules — work together to hold water,” says Mary Caswell Stoddard, an evolutionary biologist at Princeton University, who was not associated with this study. “By using a suite of advanced imaging techniques to describe the belly feathers and estimate their bending stiffnesses, Mueller and Gibson add rich new details to our understanding of the sandgrouse’s water-carrying feathers. … This study may inspire others to take a closer look at diverse feather microstructures across bird species — and to wonder whether these structures, as in sandgrouse, help support unusual or surprising functions.”

      The work was partly supported by the National Science Foundation and the Matoula S. Salapatas Professorship in Materials Science and Engineering at MIT. More

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      in Energy

      Using combustion to make better batteries

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      For more than a century, much of the world has run on the combustion of fossil fuels. Now, to avert the threat of climate change, the energy system is changing. Notably, solar and wind systems are replacing fossil fuel combustion for generating electricity and heat, and batteries are replacing the internal combustion engine for powering vehicles. As the energy transition progresses, researchers worldwide are tackling the many challenges that arise.

      Sili Deng has spent her career thinking about combustion. Now an assistant professor in the MIT Department of Mechanical Engineering and the Class of 1954 Career Development Professor, Deng leads a group that, among other things, develops theoretical models to help understand and control combustion systems to make them more efficient and to control the formation of emissions, including particles of soot.

      “So we thought, given our background in combustion, what’s the best way we can contribute to the energy transition?” says Deng. In considering the possibilities, she notes that combustion refers only to the process — not to what’s burning. “While we generally think of fossil fuels when we think of combustion, the term ‘combustion’ encompasses many high-temperature chemical reactions that involve oxygen and typically emit light and large amounts of heat,” she says.

      Given that definition, she saw another role for the expertise she and her team have developed: They could explore the use of combustion to make materials for the energy transition. Under carefully controlled conditions, combusting flames can be used to produce not polluting soot, but rather valuable materials, including some that are critical in the manufacture of lithium-ion batteries.

      Improving the lithium-ion battery by lowering costs

      The demand for lithium-ion batteries is projected to skyrocket in the coming decades. Batteries will be needed to power the growing fleet of electric cars and to store the electricity produced by solar and wind systems so it can be delivered later when those sources aren’t generating. Some experts project that the global demand for lithium-ion batteries may increase tenfold or more in the next decade.

      Given such projections, many researchers are looking for ways to improve the lithium-ion battery technology. Deng and her group aren’t materials scientists, so they don’t focus on making new and better battery chemistries. Instead, their goal is to find a way to lower the high cost of making all of those batteries. And much of the cost of making a lithium-ion battery can be traced to the manufacture of materials used to make one of its two electrodes — the cathode.

      The MIT researchers began their search for cost savings by considering the methods now used to produce cathode materials. The raw materials are typically salts of several metals, including lithium, which provides ions — the electrically charged particles that move when the battery is charged and discharged. The processing technology aims to produce tiny particles, each one made up of a mixture of those ingredients, with the atoms arranged in the specific crystalline structure that will deliver the best performance in the finished battery.

      For the past several decades, companies have manufactured those cathode materials using a two-stage process called coprecipitation. In the first stage, the metal salts — excluding the lithium — are dissolved in water and thoroughly mixed inside a chemical reactor. Chemicals are added to change the acidity (the pH) of the mixture, and particles made up of the combined salts precipitate out of the solution. The particles are then removed, dried, ground up, and put through a sieve.

      A change in pH won’t cause lithium to precipitate, so it is added in the second stage. Solid lithium is ground together with the particles from the first stage until lithium atoms permeate the particles. The resulting material is then heated, or “annealed,” to ensure complete mixing and to achieve the targeted crystalline structure. Finally, the particles go through a “deagglomerator” that separates any particles that have joined together, and the cathode material emerges.

      Coprecipitation produces the needed materials, but the process is time-consuming. The first stage takes about 10 hours, and the second stage requires about 13 hours of annealing at a relatively low temperature (750 degrees Celsius). In addition, to prevent cracking during annealing, the temperature is gradually “ramped” up and down, which takes another 11 hours. The process is thus not only time-consuming but also energy-intensive and costly.

      For the past two years, Deng and her group have been exploring better ways to make the cathode material. “Combustion is very effective at oxidizing things, and the materials for lithium-ion batteries are generally mixtures of metal oxides,” says Deng. That being the case, they thought this could be an opportunity to use a combustion-based process called flame synthesis.

      A new way of making a high-performance cathode material

      The first task for Deng and her team — mechanical engineering postdoc Jianan Zhang, Valerie L. Muldoon ’20, SM ’22, and current graduate students Maanasa Bhat and Chuwei Zhang — was to choose a target material for their study. They decided to focus on a mixture of metal oxides consisting of nickel, cobalt, and manganese plus lithium. Known as “NCM811,” this material is widely used and has been shown to produce cathodes for batteries that deliver high performance; in an electric vehicle, that means a long driving range, rapid discharge and recharge, and a long lifetime. To better define their target, the researchers examined the literature to determine the composition and crystalline structure of NCM811 that has been shown to deliver the best performance as a cathode material.

      They then considered three possible approaches to improving on the coprecipitation process for synthesizing NCM811: They could simplify the system (to cut capital costs), speed up the process, or cut the energy required.

      “Our first thought was, what if we can mix together all of the substances — including the lithium — at the beginning?” says Deng. “Then we would not need to have the two stages” — a clear simplification over coprecipitation.

      Introducing FASP

      One process widely used in the chemical and other industries to fabricate nanoparticles is a type of flame synthesis called flame-assisted spray pyrolysis, or FASP. Deng’s concept for using FASP to make their targeted cathode powders proceeds as follows.

      The precursor materials — the metal salts (including the lithium) — are mixed with water, and the resulting solution is sprayed as fine droplets by an atomizer into a combustion chamber. There, a flame of burning methane heats up the mixture. The water evaporates, leaving the precursor materials to decompose, oxidize, and solidify to form the powder product. The cyclone separates particles of different sizes, and the baghouse filters out those that aren’t useful. The collected particles would then be annealed and deagglomerated.

      To investigate and optimize this concept, the researchers developed a lab-scale FASP setup consisting of a homemade ultrasonic nebulizer, a preheating section, a burner, a filter, and a vacuum pump that withdraws the powders that form. Using that system, they could control the details of the heating process: The preheating section replicates conditions as the material first enters the combustion chamber, and the burner replicates conditions as it passes the flame. That setup allowed the team to explore operating conditions that would give the best results.

      Their experiments showed marked benefits over coprecipitation. The nebulizer breaks up the liquid solution into fine droplets, ensuring atomic-level mixing. The water simply evaporates, so there’s no need to change the pH or to separate the solids from a liquid. As Deng notes, “You just let the gas go, and you’re left with the particles, which is what you want.” With lithium included at the outset, there’s no need for mixing solids with solids, which is neither efficient 
nor effective.

      They could even control the structure, or “morphology,” of the particles that formed. In one series of experiments, they tried exposing the incoming spray to different rates of temperature change over time. They found that the temperature “history” has a direct impact on morphology. With no preheating, the particles burst apart; and with rapid preheating, the particles were hollow. The best outcomes came when they used temperatures ranging from 175-225 C. Experiments with coin-cell batteries (laboratory devices used for testing battery materials) confirmed that by adjusting the preheating temperature, they could achieve a particle morphology that would optimize the performance of their materials.

      Best of all, the particles formed in seconds. Assuming the time needed for conventional annealing and deagglomerating, the new setup could synthesize the finished cathode material in half the total time needed for coprecipitation. Moreover, the first stage of the coprecipitation system is replaced by a far simpler setup — a savings in capital costs.

      “We were very happy,” says Deng. “But then we thought, if we’ve changed the precursor side so the lithium is mixed well with the salts, do we need to have the same process for the second stage? Maybe not!”

      Improving the second stage

      The key time- and energy-consuming step in the second stage is the annealing. In today’s coprecipitation process, the strategy is to anneal at a low temperature for a long time, giving the operator time to manipulate and control the process. But running a furnace for some 20 hours — even at a low temperature — consumes a lot of energy.

      Based on their studies thus far, Deng thought, “What if we slightly increase the temperature but reduce the annealing time by orders of magnitude? Then we could cut energy consumption, and we might still achieve the desired crystal structure.”

      However, experiments at slightly elevated temperatures and short treatment times didn’t bring the results they had hoped for. In transmission electron microscope (TEM) images, the particles that formed had clouds of light-looking nanoscale particles attached to their surfaces. When the researchers performed the same experiments without adding the lithium, those nanoparticles didn’t appear. Based on that and other tests, they concluded that the nanoparticles were pure lithium. So, it seemed like long-duration annealing would be needed to ensure that the lithium made its way inside the particles.

      But they then came up with a different solution to the lithium-distribution problem. They added a small amount — just 1 percent by weight — of an inexpensive compound called urea to their mixture. In TEM images of the particles formed, the “undesirable nanoparticles were largely gone,” says Deng.

      Experiments in the laboratory coin cells showed that the addition of urea significantly altered the response to changes in the annealing temperature. When the urea was absent, raising the annealing temperature led to a dramatic decline in performance of the cathode material that formed. But with the urea present, the performance of the material that formed was unaffected by any temperature change.

      That result meant that — as long as the urea was added with the other precursors — they could push up the temperature, shrink the annealing time, and omit the gradual ramp-up and cool-down process. Further imaging studies confirmed that their approach yields the desired crystal structure and the homogeneous elemental distribution of the cobalt, nickel, manganese, and lithium within the particles. Moreover, in tests of various performance measures, their materials did as well as materials produced by coprecipitation or by other methods using long-time heat treatment. Indeed, the performance was comparable to that of commercial batteries with cathodes made of NCM811.

      So now the long and expensive second stage required in standard coprecipitation could be replaced by just 20 minutes of annealing at about 870 C plus 20 minutes of cooling down at room temperature.

      Theory, continuing work, and planning for scale-up

      While experimental evidence supports their approach, Deng and her group are now working to understand why it works. “Getting the underlying physics right will help us design the process to control the morphology and to scale up the process,” says Deng. And they have a hypothesis for why the lithium nanoparticles in their flame synthesis process end up on the surfaces of the larger particles — and why the presence of urea solves that problem.

      According to their theory, without the added urea, the metal and lithium atoms are initially well-mixed within the droplet. But as heating progresses, the lithium diffuses to the surface and ends up as nanoparticles attached to the solidified particle. As a result, a long annealing process is needed to move the lithium in among the other atoms.

      When the urea is present, it starts out mixed with the lithium and other atoms inside the droplet. As temperatures rise, the urea decomposes, forming bubbles. As heating progresses, the bubbles burst, increasing circulation, which keeps the lithium from diffusing to the surface. The lithium ends up uniformly distributed, so the final heat treatment can be very short.

      The researchers are now designing a system to suspend a droplet of their mixture so they can observe the circulation inside it, with and without the urea present. They’re also developing experiments to examine how droplets vaporize, employing tools and methods they have used in the past to study how hydrocarbons vaporize inside internal combustion engines.

      They also have ideas about how to streamline and scale up their process. In coprecipitation, the first stage takes 10 to 20 hours, so one batch at a time moves on to the second stage to be annealed. In contrast, the novel FASP process generates particles in 20 minutes or less — a rate that’s consistent with continuous processing. In their design for an “integrated synthesis system,” the particles coming out of the baghouse are deposited on a belt that carries them for 10 or 20 minutes through a furnace. A deagglomerator then breaks any attached particles apart, and the cathode powder emerges, ready to be fabricated into a high-performance cathode for a lithium-ion battery. The cathode powders for high-performance lithium-ion batteries would thus be manufactured at unprecedented speed, low cost, and low energy use.

      Deng notes that every component in their integrated system is already used in industry, generally at a large scale and high flow-through rate. “That’s why we see great potential for our technology to be commercialized and scaled up,” she says. “Where our expertise comes into play is in designing the combustion chamber to control the temperature and heating rate so as to produce particles with the desired morphology.” And while a detailed economic analysis has yet to be performed, it seems clear that their technique will be faster, the equipment simpler, and the energy use lower than other methods of manufacturing cathode materials for lithium-ion batteries — potentially a major contribution to the ongoing energy transition.

      This research was supported by the MIT Department of Mechanical Engineering.

      This article appears in the Winter 2023 issue of Energy Futures, the magazine of the MIT Energy Initiative. More

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      in Energy

      How to pull carbon dioxide out of seawater

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      As carbon dioxide continues to build up in the Earth’s atmosphere, research teams around the world have spent years seeking ways to remove the gas efficiently from the air. Meanwhile, the world’s number one “sink” for carbon dioxide from the atmosphere is the ocean, which soaks up some 30 to 40 percent of all of the gas produced by human activities.

      Recently, the possibility of removing carbon dioxide directly from ocean water has emerged as another promising possibility for mitigating CO2 emissions, one that could potentially someday even lead to overall net negative emissions. But, like air capture systems, the idea has not yet led to any widespread use, though there are a few companies attempting to enter this area.

      Now, a team of researchers at MIT says they may have found the key to a truly efficient and inexpensive removal mechanism. The findings were reported this week in the journal Energy and Environmental Science, in a paper by MIT professors T. Alan Hatton and Kripa Varanasi, postdoc Seoni Kim, and graduate students Michael Nitzsche, Simon Rufer, and Jack Lake.

      The existing methods for removing carbon dioxide from seawater apply a voltage across a stack of membranes to acidify a feed stream by water splitting. This converts bicarbonates in the water to molecules of CO2, which can then be removed under vacuum. Hatton, who is the Ralph Landau Professor of Chemical Engineering, notes that the membranes are expensive, and chemicals are required to drive the overall electrode reactions at either end of the stack, adding further to the expense and complexity of the processes. “We wanted to avoid the need for introducing chemicals to the anode and cathode half cells and to avoid the use of membranes if at all possible” he says.

      The team came up with a reversible process consisting of membrane-free electrochemical cells. Reactive electrodes are used to release protons to the seawater fed to the cells, driving the release of the dissolved carbon dioxide from the water. The process is cyclic: It first acidifies the water to convert dissolved inorganic bicarbonates to molecular carbon dioxide, which is collected as a gas under vacuum. Then, the water is fed to a second set of cells with a reversed voltage, to recover the protons and turn the acidic water back to alkaline before releasing it back to the sea. Periodically, the roles of the two cells are reversed once one set of electrodes is depleted of protons (during acidification) and the other has been regenerated during alkalization.

      This removal of carbon dioxide and reinjection of alkaline water could slowly start to reverse, at least locally, the acidification of the oceans that has been caused by carbon dioxide buildup, which in turn has threatened coral reefs and shellfish, says Varanasi, a professor of mechanical engineering. The reinjection of alkaline water could be done through dispersed outlets or far offshore to avoid a local spike of alkalinity that could disrupt ecosystems, they say.

      “We’re not going to be able to treat the entire planet’s emissions,” Varanasi says. But the reinjection might be done in some cases in places such as fish farms, which tend to acidify the water, so this could be a way of helping to counter that effect.

      Once the carbon dioxide is removed from the water, it still needs to be disposed of, as with other carbon removal processes. For example, it can be buried in deep geologic formations under the sea floor, or it can be chemically converted into a compound like ethanol, which can be used as a transportation fuel, or into other specialty chemicals. “You can certainly consider using the captured CO2 as a feedstock for chemicals or materials production, but you’re not going to be able to use all of it as a feedstock,” says Hatton. “You’ll run out of markets for all the products you produce, so no matter what, a significant amount of the captured CO2 will need to be buried underground.”

      Initially at least, the idea would be to couple such systems with existing or planned infrastructure that already processes seawater, such as desalination plants. “This system is scalable so that we could integrate it potentially into existing processes that are already processing ocean water or in contact with ocean water,” Varanasi says. There, the carbon dioxide removal could be a simple add-on to existing processes, which already return vast amounts of water to the sea, and it would not require consumables like chemical additives or membranes.

      “With desalination plants, you’re already pumping all the water, so why not co-locate there?” Varanasi says. “A bunch of capital costs associated with the way you move the water, and the permitting, all that could already be taken care of.”

      The system could also be implemented by ships that would process water as they travel, in order to help mitigate the significant contribution of ship traffic to overall emissions. There are already international mandates to lower shipping’s emissions, and “this could help shipping companies offset some of their emissions, and turn ships into ocean scrubbers,” Varanasi says.

      The system could also be implemented at locations such as offshore drilling platforms, or at aquaculture farms. Eventually, it could lead to a deployment of free-standing carbon removal plants distributed globally.

      The process could be more efficient than air-capture systems, Hatton says, because the concentration of carbon dioxide in seawater is more than 100 times greater than it is in air. In direct air-capture systems it is first necessary to capture and concentrate the gas before recovering it. “The oceans are large carbon sinks, however, so the capture step has already kind of been done for you,” he says. “There’s no capture step, only release.” That means the volumes of material that need to be handled are much smaller, potentially simplifying the whole process and reducing the footprint requirements.

      The research is continuing, with one goal being to find an alternative to the present step that requires a vacuum to remove the separated carbon dioxide from the water. Another need is to identify operating strategies to prevent precipitation of minerals that can foul the electrodes in the alkalinization cell, an inherent issue that reduces the overall efficiency in all reported approaches. Hatton notes that significant progress has been made on these issues, but that it is still too early to report on them. The team expects that the system could be ready for a practical demonstration project within about two years.

      “The carbon dioxide problem is the defining problem of our life, of our existence,” Varanasi says. “So clearly, we need all the help we can get.”

      The work was supported by ARPA-E. More

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      in Energy

      Responsive design meets responsibility for the planet’s future

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      MIT senior Sylas Horowitz kneeled at the edge of a marsh, tinkering with a blue-and-black robot about the size and shape of a shoe box and studded with lights and mini propellers.

      The robot was a remotely operated vehicle (ROV) — an underwater drone slated to collect water samples from beneath a sheet of Arctic ice. But its pump wasn’t working, and its intake line was clogged with sand and seaweed.

      “Of course, something must always go wrong,” Horowitz, a mechanical engineering major with minors in energy studies and environment and sustainability, later blogged about the Falmouth, Massachusetts, field test. By making some adjustments, Horowitz was able to get the drone functioning on site.

      Through a 2020 collaboration between MIT’s Department of Mechanical Engineering and the Woods Hole Oceanographic Institute (WHOI), Horowitz had been assembling and retrofitting the high-performance ROV to measure the greenhouse gases emitted by thawing permafrost.

      The Arctic’s permafrost holds an estimated 1,700 billion metric tons of methane and carbon dioxide — roughly 50 times the amount of carbon tied to fossil fuel emissions in 2019, according to climate research from NASA’s Jet Propulsion Laboratory. WHOI scientists wanted to understand the role the Arctic plays as a greenhouse gas source or sink.

      Horowitz’s ROV would be deployed from a small boat in sub-freezing temperatures to measure carbon dioxide and methane in the water. Meanwhile, a flying drone would sample the air.

      An MIT Student Sustainability Coalition leader and one of the first members of the MIT Environmental Solutions Initiative’s Rapid Response Group, Horowitz has focused on challenges related to clean energy, climate justice, and sustainable development.

      In addition to the ROV, Horowitz has tackled engineering projects through D-Lab, where community partners from around the world work with MIT students on practical approaches to alleviating global poverty. Horowitz worked on fashioning waste bins out of heat-fused recycled plastic for underserved communities in Liberia. Their thesis project, also initiated through D-Lab, is designing and building user-friendly, space- and fuel-efficient firewood cook stoves to improve the lives of women in Santa Catarina Palopó in northern Guatemala.

      Through the Tata-MIT GridEdge Solar Research program, they helped develop flexible, lightweight solar panels to mount on the roofs of street vendors’ e-rickshaws in Bihar, India.

      The thread that runs through Horowitz’s projects is user-centered design that creates a more equitable society. “In the transition to sustainable energy, we want our technology to adapt to the society that we live in,” they say. “Something I’ve learned from the D-Lab projects and also from the ROV project is that when you’re an engineer, you need to understand the societal and political implications of your work, because all of that should get factored into the design.”

      Horowitz describes their personal mission as creating systems and technology that “serve the well-being and longevity of communities and the ecosystems we exist within.

      “I want to relate mechanical engineering to sustainability and environmental justice,” they say. “Engineers need to think about how technology fits into the greater societal context of people in the environment. We want our technology to adapt to the society we live in and for people to be able, based on their needs, to interface with the technology.”

      Imagination and inspiration

      In Dix Hills, New York, a Long Island suburb, Horowitz’s dad is in banking and their mom is a speech therapist. The family hiked together, but Horowitz doesn’t tie their love for the natural world to any one experience. “I like to play in the dirt,” they say. “I’ve always had a connection to nature. It was a kind of childlike wonder.”

      Seeing footage of the massive 2010 oil spill in the Gulf of Mexico caused by an explosion on the Deepwater Horizon oil rig — which occurred when Horowitz was around 10 — was a jarring introduction to how human activity can impact the health of the planet.

      Their first interest was art — painting and drawing portraits, album covers, and more recently, digital images such as a figure watering a houseplant at a window while lightning flashes outside; a neon pink jellyfish in a deep blue sea; and, for an MIT-wide Covid quarantine project, two figures watching the sun set over a Green Line subway platform.

      Art dovetailed into a fascination with architecture, then shifted to engineering. In high school, Horowitz and a friend were co-captains of an all-girls robotics team. “It was just really wonderful, having this community and being able to build stuff,” they say. Horowitz and another friend on the team learned they were accepted to MIT on Pi Day 2018.

      Art, architecture, engineering — “it’s all kind of the same,” Horowitz says. “I like the creative aspect of design, being able to create things out of imagination.”

      Sustaining political awareness

      At MIT, Horowitz connected with a like-minded community of makers. They also launched themself into taking action against environmental injustice.

      In 2022, through the Student Sustainability Coalition (SSC), they encouraged MIT students to get involved in advocating for the Cambridge Green New Deal, legislation aimed at reducing emissions from new large commercial buildings such as those owned by MIT and creating a green jobs training program.

      In February 2022, Horowitz took part in a sit-in in Building 3 as part of MIT Divest, a student-led initiative urging the MIT administration to divest its endowment of fossil fuel companies.

      “I want to see MIT students more locally involved in politics around sustainability, not just the technology side,” Horowitz says. “I think there’s a lot of power from students coming together. They could be really influential.”

      User-oriented design

      The Arctic underwater ROV Horowitz worked on had to be waterproof and withstand water temperatures as low as 5 degrees Fahrenheit. It was tethered to a computer by a 150-meter-long cable that had to spool and unspool without tangling. The pump and tubing that collected water samples had to work without kinking.

      “It was cool, throughout the project, to think, ‘OK, what kind of needs will these scientists have when they’re out in these really harsh conditions in the Arctic? How can I make a machine that will make their field work easier?’

      “I really like being able to design things directly with the users, working within their design constraints,” they say.

      Inevitably, snafus occurred, but in photos and videos taken the day of the Falmouth field tests, Horowitz is smiling. “Here’s a fun unexpected (or maybe quite expected) occurrence!” they reported later. “The plastic mount for the shaft collar [used in the motor’s power transmission] ripped itself apart!” Undaunted, Horowitz jury-rigged a replacement out of sheet metal.

      Horowitz replaced broken wires in the winch-like device that spooled the cable. They added a filter at the intake to prevent sand and plants from clogging the pump.

      With a few more tweaks, the ROV was ready to descend into frigid waters. Last summer, it was successfully deployed on a field run in the Canadian high Arctic. A few months later, Horowitz was slated to attend OCEANS 2022 Hampton Roads, their first professional conference, to present a poster on their contribution to the WHOI permafrost research.

      Ultimately, Horowitz hopes to pursue a career in renewable energy, sustainable design, or sustainable agriculture, or perhaps graduate studies in data science or econometrics to quantify environmental justice issues such as the disproportionate exposure to pollution among certain populations and the effect of systemic changes designed to tackle these issues.

      After completing their degree this month, Horowitz will spend six months with MIT International Science and Technology Initiatives (MISTI), which fosters partnerships with industry leaders and host organizations around the world.

      Horowitz is thinking of working with a renewable energy company in Denmark, one of the countries they toured during a summer 2019 field trip led by the MIT Energy Initiative’s Director of Education Antje Danielson. They were particularly struck by Samsø, the world’s first carbon-neutral island, run entirely on renewable energy. “It inspired me to see what’s out there when I was a sophomore,” Horowitz says. They’re ready to see where inspiration takes them next.

      This article appears in the Winter 2023 issue of Energy Futures, the magazine of the MIT Energy Initiative. More

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      in Environment

      Moving water and earth

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      As a river cuts through a landscape, it can operate like a conveyer belt, moving truckloads of sediment over time. Knowing how quickly or slowly this sediment flows can help engineers plan for the downstream impact of restoring a river or removing a dam. But the models currently used to estimate sediment flow can be off by a wide margin.

      An MIT team has come up with a better formula to calculate how much sediment a fluid can push across a granular bed — a process known as bed load transport. The key to the new formula comes down to the shape of the sediment grains.

      It may seem intuitive: A smooth, round stone should skip across a river bed faster than an angular pebble. But flowing water also pushes harder on the angular pebble, which could erase the round stone’s advantage. Which effect wins? Existing sediment transport models surprisingly don’t offer an answer, mainly because the problem of measuring grain shape is too unwieldy: How do you quantify a pebble’s contours?

      The MIT researchers found that instead of considering a grain’s exact shape, they could boil the concept of shape down to two related properties: friction and drag. A grain’s drag, or resistance to fluid flow, relative to its internal friction, the resistance to sliding past other grains, can provide an easy way to gauge the effects of a grain’s shape.

      When they incorporated this new mathematical measure of grain shape into a standard model for bed load transport, the new formula made predictions that matched experiments that the team performed in the lab.

      “Sediment transport is a part of life on Earth’s surface, from the impact of storms on beaches to the gravel nests in mountain streams where salmon lay their eggs,” the team writes of their new study, appearing today in Nature. “Damming and sea level rise have already impacted many such terrains and pose ongoing threats. A good understanding of bed load transport is crucial to our ability to maintain these landscapes or restore them to their natural states.”

      The study’s authors are Eric Deal, Santiago Benavides, Qiong Zhang, Ken Kamrin, and Taylor Perron of MIT, and Jeremy Venditti and Ryan Bradley of Simon Fraser University in Canada.

      Figuring flow

      Video of glass spheres (top) and natural river gravel (bottom) undergoing bed load transport in a laboratory flume, slowed down 17x relative to real time. Average grain diameter is about 5 mm. This video shows how rolling and tumbling natural grains interact with one another in a way that is not possible for spheres. What can’t be seen so easily is that natural grains also experience higher drag forces from the flowing water than spheres do.

      Credit: Courtesy of the researchers

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      Bed load transport is the process by which a fluid such as air or water drags grains across a bed of sediment, causing the grains to hop, skip, and roll along the surface as a fluid flows through. This movement of sediment in a current is what drives rocks to migrate down a river and sand grains to skip across a desert.

      Being able to estimate bed load transport can help scientists prepare for situations such as urban flooding and coastal erosion. Since the 1930s, one formula has been the go-to model for calculating bed load transport; it’s based on a quantity known as the Shields parameter, after the American engineer who originally derived it. This formula sets a relationship between the force of a fluid pushing on a bed of sediment, and how fast the sediment moves in response. Albert Shields incorporated certain variables into this formula, including the average size and density of a sediment’s grains — but not their shape.

      “People may have backed away from accounting for shape because it’s one of these very scary degrees of freedom,” says Kamrin, a professor of mechanical engineering at MIT. “Shape is not a single number.”

      And yet, the existing model has been known to be off by a factor of 10 in its predictions of sediment flow. The team wondered whether grain shape could be a missing ingredient, and if so, how the nebulous property could be mathematically represented.

      “The trick was to focus on characterizing the effect that shape has on sediment transport dynamics, rather than on characterizing the shape itself,” says Deal.

      “It took some thinking to figure that out,” says Perron, a professor of geology in MIT’s Department of Earth, Atmospheric and Planetary Sciences. “But we went back to derive the Shields parameter, and when you do the math, this ratio of drag to friction falls out.”

      Drag and drop

      Their work showed that the Shields parameter — which predicts how much sediment is transported — can be modified to include not just size and density, but also grain shape, and furthermore, that a grain’s shape can be simply represented by a measure of the grain’s drag and its internal friction. The math seemed to make sense. But could the new formula predict how sediment actually flows?

      To answer this, the researchers ran a series of flume experiments, in which they pumped a current of water through an inclined tank with a floor covered in sediment. They ran tests with sediment of various grain shapes, including beds of round glass beads, smooth glass chips, rectangular prisms, and natural gravel. They measured the amount of sediment that was transported through the tank in a fixed amount of time. They then determined the effect of each sediment type’s grain shape by measuring the grains’ drag and friction.

      For drag, the researchers simply dropped individual grains down through a tank of water and gathered statistics for the time it took the grains of each sediment type to reach the bottom. For instance, a flatter grain type takes a longer time on average, and therefore has greater drag, than a round grain type of the same size and density.

      To measure friction, the team poured grains through a funnel and onto a circular tray, then measured the resulting pile’s angle, or slope — an indication of the grains’ friction, or ability to grip onto each other.

      For each sediment type, they then worked the corresponding shape’s drag and friction into the new formula, and found that it could indeed predict the bedload transport, or the amount of moving sediment that the researchers measured in their experiments.

      The team says the new model more accurately represents sediment flow. Going forward, scientists and engineers can use the model to better gauge how a river bed will respond to scenarios such as sudden flooding from severe weather or the removal of a dam.

      “If you were trying to make a prediction of how fast all that sediment will get evacuated after taking a dam out, and you’re wrong by a factor of three or five, that’s pretty bad,” Perron says. “Now we can do a lot better.”

      This research was supported, in part, by the U.S. Army Research Laboratory. More