Tag Archives: Francesco Fornasiero

Carbon nanotubes for water desalination

In discussions about water desalination and carbon nanomaterials,  it’s graphene that’s usually mentioned these days. By contrast, scientists from the US Department of Energy’s Lawrence Livermore National Laboratory (LLNL) have turned to carbon nanotubes,

There are two news items about the work at LLNL on ScienceDaily, this first one originated by the American Association for the Advancement of Science (AAAS) offers a succinct summary of the work (from an August 24, 2017 news item on ScienceDaily,

At just the right size, carbon nanotubes can filter water with better efficiency than biological proteins, a new study reveals. The results could pave the way to new water filtration systems, at a time when demands for fresh water pose a global threat to sustainable development.

A class of biological proteins, called aquaporins, is able to effectively filter water, yet scientists have not been able to manufacture scalable systems that mimic this ability. Aquaporins usually exhibit channels for filtering water molecules at a narrow width of 0.3 nanometers, which forces the water molecules into a single-file chain.

Here, Ramya H. Tunuguntla and colleagues experimented with nanotubes of different widths to see which ones are best for filtering water. Intriguingly, they found that carbon nanotubes with a width of 0.8 nanometers outperformed aquaporins in filtering efficiency by a factor of six.

These narrow carbon nanotube porins (nCNTPs) were still slim enough to force the water molecules into a single-file chain. The researchers attribute the differences between aquaporins and nCNTPS to differences in hydrogen bonding — whereas pore-lining residues in aquaporins can donate or accept H bonds to incoming water molecules, the walls of CNTPs cannot form H bonds, permitting unimpeded water flow.

The nCNTPs in this study maintained permeability exceeding that of typical saltwater, only diminishing at very high salt concentrations. Lastly, the team found that by changing the charges at the mouth of the nanotube, they can alter the ion selectivity. This advancement is highlighted in a Perspective [in Science magazine] by Zuzanna Siwy and Francesco Fornasiero.

The second Aug. 24, 2017 news item on ScienceDaily offers a more technical  perspective,

Lawrence Livermore scientists, in collaboration with researchers at Northeastern University, have developed carbon nanotube pores that can exclude salt from seawater. The team also found that water permeability in carbon nanotubes (CNTs) with diameters smaller than a nanometer (0.8 nm) exceeds that of wider carbon nanotubes by an order of magnitude.

The nanotubes, hollow structures made of carbon atoms in a unique arrangement, are more than 50,000 times thinner than a human hair. The super smooth inner surface of the nanotube is responsible for their remarkably high water permeability, while the tiny pore size blocks larger salt ions.

There’s a rather lovely illustration for this work,

An artist’s depiction of the promise of carbon nanotube porins for desalination. The image depicts a stylized carbon nanotube pipe that delivers clean desalinated water from the ocean to a kitchen tap. Image by Ryan Chen/LLNL

An Aug. 24, 2017 LLNL news release (also on EurekAlert), which originated the second news item, proceeds

Increasing demands for fresh water pose a global threat to sustainable development, resulting in water scarcity for 4 billion people. Current water purification technologies can benefit from the development of membranes with specialized pores that mimic highly efficient and water selective biological proteins.

“We found that carbon nanotubes with diameters smaller than a nanometer bear a key structural feature that enables enhanced transport. The narrow hydrophobic channel forces water to translocate in a single-file arrangement, a phenomenon similar to that found in the most efficient biological water transporters,” said Ramya Tunuguntla, an LLNL postdoctoral researcher and co-author of the manuscript appearing in the Aug. 24 [2017]edition of Science.

Computer simulations and experimental studies of water transport through CNTs with diameters larger than 1 nm showed enhanced water flow, but did not match the transport efficiency of biological proteins and did not separate salt efficiently, especially at higher salinities. The key breakthrough achieved by the LLNL team was to use smaller-diameter nanotubes that delivered the required boost in performance.

“These studies revealed the details of the water transport mechanism and showed that rational manipulation of these parameters can enhance pore efficiency,” said Meni Wanunu, a physics professor at Northeastern University and co-author on the study.

“Carbon nanotubes are a unique platform for studying molecular transport and nanofluidics,” said Alex Noy, LLNL principal investigator on the CNT project and a senior author on the paper. “Their sub-nanometer size, atomically smooth surfaces and similarity to cellular water transport channels make them exceptionally suited for this purpose, and it is very exciting to make a synthetic water channel that performs better than nature’s own.”

This discovery by the LLNL scientists and their colleagues has clear implications for the next generation of water purification technologies and will spur a renewed interest in development of the next generation of high-flux membranes.

Here’s a link to and a citation for the paper,

Enhanced water permeability and tunable ion selectivity in subnanometer carbon nanotube porins by Ramya H. Tunuguntla, Robert Y. Henley, Yun-Chiao Yao, Tuan Anh Pham, Meni Wanunu, Aleksandr Noy. Science 25 Aug 2017: Vol. 357, Issue 6353, pp. 792-796 DOI: 10.1126/science.aan2438

This paper is behind a paywall.

And, Northeastern University issued an August 25, 2017 news release (also on EurekAlert) by Allie Nicodemo,

Earth is 70 percent water, but only a tiny portion—0.007 percent—is available to drink.

As potable water sources dwindle, global population increases every year. One potential solution to quenching the planet’s thirst is through desalinization—the process of removing salt from seawater. While tantalizing, this approach has always been too expensive and energy intensive for large-scale feasibility.

Now, researchers from Northeastern have made a discovery that could change that, making desalinization easier, faster and cheaper than ever before. In a paper published Thursday [August 24, 2017] in Science, the group describes how carbon nanotubes of a certain size act as the perfect filter for salt—the smallest and most abundant water contaminant.

Filtering water is tricky because water molecules want to stick together. The “H” in H2O is hydrogen, and hydrogen bonds are strong, requiring a lot of energy to separate. Water tends to bulk up and resist being filtered. But nanotubes do it rapidly, with ease.

A carbon nanotube is like an impossibly small rolled up sheet of paper, about a nanometer in diameter. For comparison, the diameter of a human hair is 50 to 70 micrometers—50,000 times wider. The tube’s miniscule size, exactly 0.8 nm, only allows one water molecule to pass through at a time. This single-file lineup disrupts the hydrogen bonds, so water can be pushed through the tubes at an accelerated pace, with no bulking.

“You can imagine if you’re a group of people trying to run through the hallway holding hands, it’s going to be a lot slower than running through the hallway single-file,” said co-author Meni Wanunu, associate professor of physics at Northeastern. Wanunu and post doctoral student Robert Henley collaborated with scientists at the Lawrence Livermore National Laboratory in California to conduct the research.

Scientists led by Aleksandr Noy at Lawrence Livermore discovered last year [2016] that carbon nanotubes were an ideal channel for proton transport. For this new study, Henley brought expertise and technology from Wanunu’s Nanoscale Biophysics Lab to Noy’s lab, and together they took the research one step further.

In addition to being precisely the right size for passing single water molecules, carbon nanotubes have a negative electric charge. This causes them to reject anything with the same charge, like the negative ions in salt, as well as other unwanted particles.

“While salt has a hard time passing through because of the charge, water is a neutral molecule and passes through easily,” Wanunu said. Scientists in Noy’s lab had theorized that carbon nanotubes could be designed for specific ion selectivity, but they didn’t have a reliable system of measurement. Luckily, “That’s the bread and butter of what we do in Meni’s lab,” Henley said. “It created a nice symbiotic relationship.”

“Robert brought the cutting-edge measurement and design capabilities of Wanunu’s group to my lab, and he was indispensable in developing a new platform that we used to measure the ion selectivity of the nanotubes,” Noy said.

The result is a novel system that could have major implications for the future of water security. The study showed that carbon nanotubes are better at desalinization than any other existing method— natural or man-made.

To keep their momentum going, the two labs have partnered with a leading water purification organization based in Israel. And the group was recently awarded a National Science Foundation/Binational Science Foundation grant to conduct further studies and develop water filtration platforms based on their new method. As they continue the research, the researchers hope to start programs where students can learn the latest on water filtration technology—with the goal of increasing that 0.007 percent.

As is usual in these cases there’s a fair degree of repetition but there’s always at least one nugget of new information, in this case, a link to Israel. As I noted many times, the Middle East is experiencing serious water issues. My most recent ‘water and the Middle East’ piece is an August 21, 2017 post about rainmaking at the Masdar Institute in United Arab Emirates. Approximately 50% of the way down the posting, I mention Israel and Palestine’s conflict over water.

Protecting soldiers from biological and chemical agents with a ‘second skin’ made of carbon nanotubes

There are lots of ‘second skins’ which promise to protect against various chemical and biological agents, the big plus for this ‘skin’ from the US Lawrence Livermore National Laboratory is breathability. From an Aug. 3, 2016 news item on Nanowerk (Note: A link has been removed),

This material is the first key component of futuristic smart uniforms that also will respond to and protect from environmental chemical hazards. The research appears in the July 27 [2016] edition of the journal, , Advanced Materials (“Carbon Nanotubes: Ultrabreathable and Protective Membranes with Sub-5 nm Carbon Nanotube Pores”).

An Aug. 3, 2016 Lawrence Livermore National Laboratory (LLNL) news release (also on EurekAlert), which originated the news item, explains further (Note: Links have been removed),

High breathability is a critical requirement for protective clothing to prevent heat-stress and exhaustion when military personnel are engaged in missions in contaminated environments. Current protective military uniforms are based on heavyweight full-barrier protection or permeable adsorptive protective garments that cannot meet the critical demand of simultaneous high comfort and protection, and provide a passive rather than active response to an environmental threat.

The LLNL team fabricated flexible polymeric membranes with aligned carbon nanotube (CNT) channels as moisture conductive pores. The size of these pores (less than 5 nanometers, nm) is 5,000 times smaller than the width of a human hair [if 1 nm is 1/100,000 or 1/60,000 of a human hair {the two most commonly used measurements} then wouldn’t 5 nm be between 1/20,000 or1/15,000 of a human hair?] .

“We demonstrated that these membranes provide rates of water vapor transport that surpass those of commercial breathable fabrics like GoreTex, even though the CNT pores are only a few nanometers wide,” said Ngoc Bui, the lead author of the paper.

To provide high breathability, the new composite material takes advantage of the unique transport properties of carbon nanotube pores. By quantifying the membrane permeability to water vapor, the team found for the first time that, when a concentration gradient is used as a driving force, CNT nanochannels can sustain gas-transport rates exceeding that of a well-known diffusion theory by more than one order of magnitude.

These membranes also provide protection from biological agents due to their very small pore size — less than 5 nanometers (nm) wide. Biological threats like bacteria or viruses are much larger and typically more than 10-nm in size. Performed tests demonstrated that the CNT membranes repelled Dengue virus from aqueous solutions during filtration tests. This confirms that LLNL-developed CNT membranes provide effective protection from biological threats by size exclusion rather than by merely preventing wetting.

Furthermore, the results show that CNT pores combine high breathability and bio-protection in a single functional material.

However, chemical agents are much smaller in size and require the membrane pores to be able to react to block the threat. To encode the membrane with a smart and dynamic response to small chemical hazards, LLNL scientists and collaborators are surface modifying these prototype carbon nanotube membranes with chemical-threat-responsive functional groups. These functional groups will sense and block the threat like gatekeepers on the pore entrance. A second response scheme also is in development — similar to how living skin peels off when challenged with dangerous external factors. The fabric will exfoliate upon reaction with the chemical agent.

“The material will be like a smart second skin that responds to the environment,” said Kuang Jen Wu, leader of LLNL’s Biosecurity & Biosciences Group. “In this way, the fabric will be able to block chemical agents such as sulfur mustard (blister agent), GD and VX nerve agents, toxins such as staphylococcal enterotoxin and biological spores such as anthrax.”

Current work is directed toward designing this multifunctional material to undergo a rapid transition from the breathable state to the protective state.

“These responsive membranes are expected to be particularly effective in mitigating a physiological burden because a less breathable but protective state can be actuated locally and only when needed,” said Francesco Fornasiero, LLNL’s principal investigator of the project.

The new uniforms could be deployed in the field in less than 10 years.

“The goal of this science and technology program is to develop a focused, innovative technological solution for future chemical biological defense protective clothing,” said Tracee Whitfield, the DTRA [US Defense Threat Reduction Agency] science and technology manager for the Dynamic Multifunctional Material for a Second Skin Program. “Swatch-level evaluations will occur in early 2018 to demonstrate the concept of ‘second skin,’ a major milestone that is a key step in the maturation of this technology.”

The researchers have prepared a video describing their work,

Here’s a link to and a citation for the paper,

Ultrabreathable and Protective Membranes with Sub-5 nm Carbon Nanotube Pores by Ngoc Bui, Eric R. Meshot, Sangil Kim, José Peña, Phillip W. Gibson, Kuang Jen Wu, and Francesco Fornasiero. Advanced Materials Volume 28, Issue 28, pages 5871–5877, July 27, 2016 DOI: 10.1002/adma.201600740 Version of Record online: 9 MAY 2016

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Smart suits for US soldiers—an update of sorts from the Lawrence Livermore National Laboratory

The US military has funded a program named: ‘Dynamic Multifunctional Material for a Second Skin Program’ through its Defense Threat Reduction Agency’s (DTRA) Chemical and Biological Technologies Department and Sharon Gaudin’s Feb. 20,  2014 article for Computer World offers a bit of an update on this project,which was first reported in 2012,

A U.S. soldier is on patrol with his squad when he kneels to check something out, unknowingly putting his knee into a puddle of contaminants.

The soldier isn’t harmed, though, because he or she is wearing a smart suit that immediately senses the threat and transforms the material covering his knee into a protective state that repels the potential deadly bacteria.

Scientists at the Lawrence Livermore National Laboratory, a federal government research facility in Livermore, Calif., are using nanotechnology to create clothing designed to protect U.S. soldiers from chemical and biological attacks.

“The threat is nanoscale so we need to work in the nano realm, which helps to keep it light and breathable,” said Francesco Fornasiero, a staff scientist at the lab. “If you have a nano-size threat, you need a nano-sized defense.”

Fornasiero said the task is a difficult one, and the suits may not be ready for the field for another 10 to 20 years. [emphasis mine]

One option is to use carbon nanotubes in a layer of the suit’s fabric. Sweat and air would be able to easily move through the nanotubes. However, the diameter of the nanotubes is smaller than the diameter of bacteria and viruses. That means they would not be able to pass through the tubes and reach the person wearing the suit.

However, chemicals that might be used in a chemical attack are small enough to fit through the nanotubes. To block them, researchers are adding a layer of polymer threads that extend up from the top of the nanotubes, like stalks of grass coming up from the ground.

The threads are designed to recognize the presence of chemical agents. When that happens, they swell and collapse on top of the nanotubes, blocking anything from entering them.

A second option that the Lawrence Livermore scientists are working on involves similar carbon nanotubes but with catalytic components in a polymer mesh that sits on top of the nanotubes. The components would destroy any chemical agents they come in contact with. After the chemicals are destroyed, they are shed off, enabling the suit to handle multiple attacks.

An October 6, 2012 (NR-12-10-06) Lawrence Livermore National Laboratory (LLNL) news release details the -project and the proponents,

Lawrence Livermore National Laboratory scientists and collaborators are developing a new military uniform material that repels chemical and biological agents using a novel carbon nanotube fabric.

The material will be designed to undergo a rapid transition from a breathable state to a protective state. The highly breathable membranes would have pores made of a few-nanometer-wide vertically aligned carbon nanotubes that are surface modified with a chemical warfare agent-responsive functional layer. Response to the threat would be triggered by direct chemical warfare agent attack to the membrane surface, at which time the fabric would switch to a protective state by closing the CNT pore entrance or by shedding the contaminated surface layer.

High breathability is a critical requirement for protective clothing to prevent heat-stress and exhaustion when military personnel are engaged in missions in contaminated environments. Current protective military uniforms are based on heavyweight full-barrier protection or permeable adsorptive protective overgarments that cannot meet the critical demand of simultaneous high comfort and protection, and provide a passive rather than active response to an environmental threat.

To provide high breathability, the new composite material will take advantage of the unique transport properties of carbon nanotube pores, which have two orders of magnitude faster gas transport rates when compared with any other pore of similar size.

“We have demonstrated that our small-size prototype carbon nanotube membranes can provide outstanding breathability in spite of the very small pore sizes and porosity,” said Sangil Kim, another LLNL scientist in the Biosciences and Biotechnology Division. “With our collaborators, we will develop large area functionalized CNT membranes.”

Biological agents, such as bacteria or viruses, are close to 10 nanometers in size. Because the membrane pores on the uniform are only a few nanometers wide, these membranes will easily block biological agents.

However, chemical agents are much smaller in size and require the membrane pores to be able to react to block the threat. To create a multifunctional membrane, the team will surface modify the original prototype carbon nanotube membranes with chemical threat responsive functional groups. The functional groups on the membrane will sense and block the threat like gatekeepers on entrance. A second response scheme also will be developed: Similar to how a living skin peels off when challenged with dangerous external factors, the fabric will exfoliate upon reaction with the chemical agent. In this way, the fabric will be able to block chemical agents such as sulfur mustard (blister agent), GD and VX nerve agents, toxins such as staphylococcal enterotoxin and biological spores such as anthrax.

The project is funded for $13 million over five years with LLNL as the lead institution. The Livermore team is made up of Fornasiero [Francesco Fornasiero], Kim and Kuang Jen Wu. Other collaborators and institutions involved in the project include Timothy Swager at Massachusetts Institute of Technology, Jerry Shan at Rutgers University, Ken Carter, James Watkins, and Jeffrey Morse at the University of Massachusetts-Amherst, Heidi Schreuder-Gibson at Natick Soldier Research Development and Engineering Center, and Robert Praino at Chasm Technologies Inc.

“Development of chemical threat responsive carbon nanotube membranes is a great example of novel material’s potential to provide innovative solutions for the Department of Defense CB needs,” said Tracee Harris, the DTRA science and technology manager for the Dynamic Multifunctional Material for a Second Skin Program. “This futuristic uniform would allow our military forces to operate safely for extended time periods and successfully complete their missions in environments contaminated with chemical and biological warfare agents.”

The Laboratory has a history in developing carbon nanotubes for a wide range of applications including desalination. “We have an advanced carbon nanotube platform to build and expand to make advancements in the protective fabric material for this new project,” Wu said.

The new uniforms could be deployed in the field in less than 10 years. [emphasis mine]

Since Gaudin’s 2014 article quotes one of the LLNL’s scientists, Francesco Fornasiero, with an estimate for the suit’s deployment into the field as 10 – 20 years as opposed to the “less than 10 years” estimated in the news release, I’m guessing the problem has proved more complex than was first anticipated.

For anyone who’s interested in more details about  US soldiers and nanotechnology,

  • May 1, 2013 article by Max Cacas for Signal Online provides more details about the overall Smart Skin programme and its goals.
  • Nov. 15, 2013 article by Kris Walker for Azonano.com describes the Smart Skin project along with others including the intriguingly titled: ‘Warrior Web’.
  • website for MIT’s (Massachusetts Institute of Technology) Institute for Soldier Nanotechnologies Note: The MIT researcher mentioned in the LLNL news release is a faculty member of the Institute for Soldier Nanotechnologies.
  • website for the Defense Threat Reduction Agency