An April 27, 2022 news item on ScienceDaily announces research into a solution to a vexing problem associated with the production of carbon nanotubes (CNTs),
Carbon nanotubes that are prone to tangle like spaghetti can use a little special sauce to realize their full potential.
Rice University scientists have come up with just the sauce, an acid-based solvent that simplifies carbon nanotube processing in a way that’s easier to scale up for industrial applications.
The Rice lab of Matteo Pasquali reported in Science Advances on its discovery of a unique combination of acids that helps separate nanotubes in a solution and turn them into films, fibers or other materials with excellent electrical and mechanical properties.
The study co-led by graduate alumnus Robert Headrick and graduate student Steven Williams reports the solvent is compatible with conventional manufacturing processes. That should help it find a place in the production of advanced materials for many applications.
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An April 22, 2022 Rice University news release (received via email and also published on April 27, 2022 on EurekAlert), which originated the news item, delves further into how the research has environmental benefits and into its technical aspects (Note Links have been removed),
“There’s a growing realization that it’s probably not a good idea to increase the mining of copper and aluminum and nickel,” said Pasquali, Rice’s A.J. Hartsook Professor and a professor of chemical and biomolecular engineering, chemistry and materials science and nanoengineering. He is also director of the Rice-based Carbon Hub, which promotes the development of advanced carbon materials to benefit the environment.
“But there is this giant opportunity to use hydrocarbons as our ore,” he said. “In that light, we need to broaden as much as possible the range in which we can use carbon materials, especially where it can displace metals with a product that can be manufactured sustainably from a feedstock like hydrocarbons.” Pasquali noted these manufacturing processes produce clean hydrogen as well.
“Carbon is plentiful, we control the supply chains and we know how to get it out in an environmentally responsible way,” he said.
A better way to process carbon will help. The solvent is based on methanesulfonic (MSA), p-toluenesulfonic (pToS)and oleum acids that, when combined, are less corrosive than those currently used to process nanotubes in a solution. Separating nanotubes (which researchers refer to as dissolving) is a necessary step before they can be extruded through a needle or other device where shear forces help turn them into familiar fibers or sheets.
Oleum and chlorosulfonic acids have long been used to dissolve nanotubes without modifying their structures, but both are highly corrosive. By combining oleum with two weaker acids, the team developed a broadly applicable process that enables new manufacturing for nanotubes products.
“The oleum surrounds each individual nanotube and gives it a very localized positive charge,” said Headrick, now a research scientist at Shell. “That charge makes them repel each other.”
After detangling, the milder acids further separate the nanotubes. They found MSA is best for fiber spinning and roll-to-roll film production, while pToS, a solid that melts at 40 degrees Celsius (104 degrees Fahrenheit), is particularly useful for 3D printing applications because it allows nanotube solutions to be processed at a moderate temperature and then solidified by cooling.
The researchers used these stable liquid crystalline solutions to make things in both modern and traditional ways, 3D printing carbon nanotube aerogels and silk screen printing patterns onto a variety of surfaces, including glass.
The solutions also enabled roll-to-roll production of transparent films that can be used as electrodes. “Honestly, it was a little surprising how well that worked,” Headrick said. “It came out pretty flawless on the very first try.”
The researchers noted oleum still requires careful handling, but once diluted with the other acids, the solution is much less aggressive to other materials.
“The acids we’re using are so much gentler that you can use them with common plastics,” Headrick said. “That opens the door to a lot of materials processing and printing techniques that are already in place in manufacturing facilities.
“It’s also really important for integrating carbon nanotubes into other devices, depositing them as one step in a device-manufacturing process,” he said.
They reported the less-corrosive solutions did not give off harmful fumes and were easier to clean up after production. MSA and pToS can also be recycled after processing nanotubes, lowering their environmental impact and energy and processing costs.
Williams said the next step is to fine-tune the solvent for applications, and to determine how factors like chirality and size affect nanotube processing. “It’s really important that we have high-quality, clean, large diameter tubes,” he said.
Co-authors of the paper are alumna Lauren Taylor and graduate students Oliver Dewey and Cedric Ginestra of Rice; graduate student Crystal Owens and professors Gareth McKinley and A. John Hart at the Massachusetts Institute of Technology; alumna Lucy Liberman, graduate student Asia Matatyaho Ya’akobi and Yeshayahu Talmon, a professor emeritus of chemical engineering, at the Technion-Israel Institute of Technology, Haifa, Israel; and Benji Maruyama, autonomous materials lead in the Materials and Manufacturing Directorate, Air Force Research Laboratory.
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Here’s a link to and a citation for the paper,
Versatile acid solvents for pristine carbon nanotube assembly by Robert J. Headrick, Steven M. Williams, Crystal E. Owens, Lauren W. Taylor, Oliver S. Dewey, Cedric J. Ginestra, Lucy Liberman, Asia Matatyaho Ya’akobi, Yeshayahu Talmon, Benji Maruyama, Gareth H. McKinley, A. John Hart, Matteo Pasquali. Science Advances • 27 Apr 2022 • Vol 8, Issue 17 • DOI: 10.1126/sciadv.abm3285
Rice University (Texas, US) has a pretty image illustrating the process of making 2D nanoflakes,
Caption: The image displays the exfoliation of hexagonal boron nitride into atomically thin nanosheets aided by surfactants, a process refined by chemists at Rice University. Credit: Ella Maru Studio
Just a little soap helps clean up the challenging process of preparing two-dimensional hexagonal boron nitride (hBN).
Rice University chemists have found a way to get the maximum amount [number] of quality 2D hBN nanosheets from its natural bulk form by processing it with surfactant (aka soap) and water. The surfactant surrounds and stabilizes the microscopic flakes, preserving their properties.
Experiments by the lab of Rice chemist Angel Martí identified the “sweet spot” for making stable dispersions of hBN, which can be processed into very thin antibacterial films that handle temperatures up to 900 degrees Celsius (1,652 degrees Fahrenheit).
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A brief grammatical moment: I can see where someone might view it as arguable (see second paragraph of the above excerpt) but for me ‘amount’ is for something like ‘flour’ for an ‘amount of flour’. ‘Number’ is for something like a ‘number of sheets’. The difference lies in your ability to count the items. Generally speaking, you can’t count the number of flour, therefore, it’s the amount of flour, but you can count the number of sheets. Can count these hexagonal boron nitride (hBN) sheets? If not, is what makes this arguable.
The work led by Martí, alumna Ashleigh Smith McWilliams and graduate student Cecilia Martínez-Jiménez is detailed in the American Chemical Society journal ACS Applied Nano Materials.
“Boron nitride materials are interesting, particularly because they are extremely resistant to heat,” Martí said. “They are as light as graphene and carbon nanotubes, but you can put hBN in a flame and nothing happens to it.”
He said bulk hBN is cheap and easy to obtain, but processing it into microscopic building blocks has been a challenge. “The first step is to be able to exfoliate and disperse them, but research on how to do that has been scattered,” Martí said. “When we decided to set a benchmark, we found the processes that have been extremely useful for graphene and nanotubes don’t work as well for boron nitride.”
Sonicating bulk hBN in water successfully exfoliated the material and made it soluble. “That surprised us, because nanotubes or graphene just float on top,” Martí said. “The hBN dispersed throughout, though they weren’t particularly stable.
“It turned out the borders of boron nitride crystals are made of amine and nitric oxide groups and boric acid, and all of these groups are polar (with positive or negative charge),” he said. “So when you exfoliate them, the edges are full of these functional groups that really like water. That never happens with graphene.”
Experiments with nine surfactants helped them find just the right type and amount to keep 2D hBN from clumping without cutting individual flakes too much during sonication. The researchers used 1% by weight of each surfactant in water, added 20 milligrams of bulk hBN, then stirred and sonicated the mix.
Spinning the resulting solutions at low and high rates showed the greatest yield came with the surfactant known as PF88 under 100-gravity centrifugation, but the highest-quality nanosheets came from all the ionic surfactants under 8,000 g centrifugation, with the greatest stability from common ionic surfactants SDS and CTAC.
DTAB — short for dodecyltrimethylammonium bromide — under high centrifugation proved best at balancing the yield and quality of 2D hBN. The researchers also produced a transparent film from hBN nanosheets dispersed in SDS and water to demonstrate how they can be processed into useful products.
“We describe the steps you need to do to produce high-quality hBN flakes,” Martí said. “All of the steps are important, and we were able to bring to light the consequences of each one.”
Boron nitride nanotubes are primed to become effective building blocks for next-generation composite and polymer materials based on a new discovery at Rice University – and a previous one.
Scientists at known-for-nano Rice have found a way to enhance a unique class of nanotubes using a chemical process pioneered at the university. The Rice lab of chemist Angel Martí took advantage of the Billups-Birch reaction process to enhance boron nitride nanotubes.
The work is described in the American Chemical Society journal ACS Applied Nano Materials.
Boron nitride nanotubes, like their carbon cousins, are rolled sheets of hexagonal arrays. Unlike carbon nanotubes, they’re electrically insulating hybrids made of alternating boron and nitrogen atoms.
Insulating nanotubes that can be functionalized will be a valuable building block for nanoengineering projects, Martí said. “Carbon nanotubes have outstanding properties, but you can only get them in semiconducting or metallic conducting types,” he said. “Boron nitride nanotubes are complementary materials that can fill that gap.”
Until now, these nanotubes have steadfastly resisted functionalization, the “decorating” of structures with chemical additives that allows them to be customized for applications. The very properties that give boron nitride nanotubes strength and stability, especially at high temperatures, also make them hard to modify for their use in the production of advanced materials.
But the Billups-Birch reaction developed by Rice Professor Emeritus of Chemistry Edward Billups, which frees electrons to bind with other atoms, allowed Martí and lead author Carlos de los Reyes to give the electrically inert boron nitride nanotubes a negative charge.
That, in turn, opened them up to functionalization with other small molecules, including aliphatic carbon chains.
“Functionalizing the nanotubes modifies or tunes their properties,” Martí said. “When they’re pristine they are dispersible in water, but once we attach these alkyl chains, they are extremely hydrophobic (water-avoiding). Then, if you put them in very hydrophobic solvents like those with long-chain hydrocarbons, they are more dispersible than their pristine form.
“This allows us to tune the properties of the nanotubes and will make it easier to take the next step toward composites,” he said. “For that, the materials need to be compatible.”
After he discovered the phenomenon, de los Reyes spent months trying to reproduce it reliably. “There was a period where I had to do a reaction every day to achieve reproducibility,” he said. But that turned out to be an advantage, as the process only required about a day from start to finish. “That’s the advantage over other processes to functionalize carbon nanotubes. There are some that are very effective, but they may take a few days.”
The process begins with adding pure ammonia gas to the nanotubes and cooling it to -70 degrees Celsius (-94 degrees Fahrenheit). “When it combines with sodium, lithium or potassium — we use lithium — it creates a sea of electrons,” Martí said. “When the lithium dissolves in the ammonia, it expels the electrons.”
The freed electrons quickly bind with the nanotubes and provide hooks for other molecules. De los Reyes enhanced Billups-Birch when he found that adding the alkyl chains slowly, rather than all at once, improved their ability to bind.
The researchers also discovered the process is reversible. Unlike carbon nanotubes that burn away, boron nitride nanotubes can stand the heat. Placing functionalized boron nitride tubes into a furnace at 600 degrees Celsius (1,112 degrees Fahrenheit) stripped them of the added molecules and returned them to their nearly pristine state.
“We call it defunctionalization,” Martí said. “You can functionalize them for an application and then remove the chemical groups to regain the pristine material. That’s something else the material brings that is a little different.”
The researchers have provided this pretty illustration of boron nitride nanotube,
Caption: Rice University researchers have discovered a way to ‘decorate’ electrically insulating boron nitride nanotubes with functional groups, making them more suitable for use with polymers and composite materials. Credit: Martí Research Group/Rice University
I have two items about implants and brains and an item about being able to exert remote control of the brain, all of which hint at a cyborg future for at least a few of us.
e-Dura, the spinal column, and the brain
The first item concerns some research, at the École Polytechnique de Lausanne (EPFL) which features flexible electronics. From a March 24, 2015 article by Ben Schiller for Fast Company (Note: Links have been removed),
Researchers at the Swiss Federal Institute of Technology, in Lausanne, have developed the e-Dura—a tiny skinlike device that attaches directly to damaged spinal cords. By sending out small electrical pulses, it stimulates the cord as if it were receiving signals from the brain, thus allowing movement.
“The purpose of the neuro-prosthesis is to excite the neurons that are on the spinal cord below the site of the injury and activate them, just like if they were receiving information from the brain,” says Stéphanie Lacour, a professor at the institute.
EPFL scientists have managed to get rats walking on their own again using a combination of electrical and chemical stimulation. But applying this method to humans would require multifunctional implants that could be installed for long periods of time on the spinal cord without causing any tissue damage. This is precisely what the teams of professors Stéphanie Lacour and Grégoire Courtine have developed. Their e-Dura implant is designed specifically for implantation on the surface of the brain or spinal cord. The small device closely imitates the mechanical properties of living tissue, and can simultaneously deliver electric impulses and pharmacological substances. The risks of rejection and/or damage to the spinal cord have been drastically reduced. An article about the implant will appear in early January [2015] in Science Magazine.
So-called “surface implants” have reached a roadblock; they cannot be applied long term to the spinal cord or brain, beneath the nervous system’s protective envelope, otherwise known as the “dura mater,” because when nerve tissues move or stretch, they rub against these rigid devices. After a while, this repeated friction causes inflammation, scar tissue buildup, and rejection.
Here’s what the implant looks like,
Courtesy: EPFL
The press release describes how the implant is placed (Note: A link has been removed),
Flexible and stretchy, the implant developed at EPFL is placed beneath the dura mater, directly onto the spinal cord. Its elasticity and its potential for deformation are almost identical to the living tissue surrounding it. This reduces friction and inflammation to a minimum. When implanted into rats, the e-Dura prototype caused neither damage nor rejection, even after two months. More rigid traditional implants would have caused significant nerve tissue damage during this period of time.
The researchers tested the device prototype by applying their rehabilitation protocol — which combines electrical and chemical stimulation – to paralyzed rats. Not only did the implant prove its biocompatibility, but it also did its job perfectly, allowing the rats to regain the ability to walk on their own again after a few weeks of training.
“Our e-Dura implant can remain for a long period of time on the spinal cord or the cortex, precisely because it has the same mechanical properties as the dura mater itself. This opens up new therapeutic possibilities for patients suffering from neurological trauma or disorders, particularly individuals who have become paralyzed following spinal cord injury,” explains Lacour, co-author of the paper, and holder of EPFL’s Bertarelli Chair in Neuroprosthetic Technology.
The press release goes on to describe the engineering achievements,
Developing the e-Dura implant was quite a feat of engineering. As flexible and stretchable as living tissue, it nonetheless includes electronic elements that stimulate the spinal cord at the point of injury. The silicon substrate is covered with cracked gold electric conducting tracks that can be pulled and stretched. The electrodes are made of an innovative composite of silicon and platinum microbeads. They can be deformed in any direction, while still ensuring optimal electrical conductivity. Finally, a fluidic microchannel enables the delivery of pharmacological substances – neurotransmitters in this case – that will reanimate the nerve cells beneath the injured tissue.
The implant can also be used to monitor electrical impulses from the brain in real time. When they did this, the scientists were able to extract with precision the animal’s motor intention before it was translated into movement.
“It’s the first neuronal surface implant designed from the start for long-term application. In order to build it, we had to combine expertise from a considerable number of areas,” explains Courtine, co-author and holder of EPFL’s IRP Chair in Spinal Cord Repair. “These include materials science, electronics, neuroscience, medicine, and algorithm programming. I don’t think there are many places in the world where one finds the level of interdisciplinary cooperation that exists in our Center for Neuroprosthetics.”
For the time being, the e-Dura implant has been primarily tested in cases of spinal cord injury in paralyzed rats. But the potential for applying these surface implants is huge – for example in epilepsy, Parkinson’s disease and pain management. The scientists are planning to move towards clinical trials in humans, and to develop their prototype in preparation for commercialization.
EPFL has provided a video of researcher Stéphanie Lacour describing e-Dura and expressing hopes for its commercialization,
Here’s a link to and a citation for the paper,
Electronic dura mater for long-term multimodal neural interfaces by Ivan R. Minev, Pavel Musienko, Arthur Hirsch, Quentin Barraud, Nikolaus Wenger, Eduardo Martin Moraud, Jérôme Gandar, Marco Capogrosso, Tomislav Milekovic, Léonie Asboth, Rafael Fajardo Torres, Nicolas Vachicouras, Qihan Liu, Natalia Pavlova, Simone Duis, Alexandre Larmagnac, Janos Vörös, Silvestro Micera, Zhigang Suo, Grégoire Courtine, Stéphanie P. Lacour. Science 9 January 2015: Vol. 347 no. 6218 pp. 159-163 DOI: 10.1126/science.1260318
This paper is behind a paywall.
Carbon nanotube fibres could connect to the brain
Researchers at Rice University (Texas, US) are excited about the possibilities that carbon nanotube fibres offer in the field of implantable electronics for the brain. From a March 25, 2015 news item on Nanowerk,
Carbon nanotube fibers invented at Rice University may provide the best way to communicate directly with the brain.
The fibers have proven superior to metal electrodes for deep brain stimulation and to read signals from a neuronal network. Because they provide a two-way connection, they show promise for treating patients with neurological disorders while monitoring the real-time response of neural circuits in areas that control movement, mood and bodily functions.
New experiments at Rice demonstrated the biocompatible fibers are ideal candidates for small, safe electrodes that interact with the brain’s neuronal system, according to the researchers. They could replace much larger electrodes currently used in devices for deep brain stimulation therapies in Parkinson’s disease patients.
They may also advance technologies to restore sensory or motor functions and brain-machine interfaces as well as deep brain stimulation therapies for other neurological disorders, including dystonia and depression, the researchers wrote.
The fibers created by the Rice lab of chemist and chemical engineer Matteo Pasquali consist of bundles of long nanotubes originally intended for aerospace applications where strength, weight and conductivity are paramount.
The individual nanotubes measure only a few nanometers across, but when millions are bundled in a process called wet spinning, they become thread-like fibers about a quarter the width of a human hair.
“We developed these fibers as high-strength, high-conductivity materials,” Pasquali said. “Yet, once we had them in our hand, we realized that they had an unexpected property: They are really soft, much like a thread of silk. Their unique combination of strength, conductivity and softness makes them ideal for interfacing with the electrical function of the human body.”
The simultaneous arrival in 2012 of Caleb Kemere, a Rice assistant professor who brought expertise in animal models of Parkinson’s disease, and lead author Flavia Vitale, a research scientist in Pasquali’s lab with degrees in chemical and biomedical engineering, prompted the investigation.
“The brain is basically the consistency of pudding and doesn’t interact well with stiff metal electrodes,” Kemere said. “The dream is to have electrodes with the same consistency, and that’s why we’re really excited about these flexible carbon nanotube fibers and their long-term biocompatibility.”
Weeks-long tests on cells and then in rats with Parkinson’s symptoms proved the fibers are stable and as efficient as commercial platinum electrodes at only a fraction of the size. The soft fibers caused little inflammation, which helped maintain strong electrical connections to neurons by preventing the body’s defenses from scarring and encapsulating the site of the injury.
The highly conductive carbon nanotube fibers also show much more favorable impedance – the quality of the electrical connection — than state-of-the-art metal electrodes, making for better contact at lower voltages over long periods, Kemere said.
The working end of the fiber is the exposed tip, which is about the width of a neuron. The rest is encased with a three-micron layer of a flexible, biocompatible polymer with excellent insulating properties.
The challenge is in placing the tips. “That’s really just a matter of having a brain atlas, and during the experiment adjusting the electrodes very delicately and putting them into the right place,” said Kemere, whose lab studies ways to connect signal-processing systems and the brain’s memory and cognitive centers.
Doctors who implant deep brain stimulation devices start with a recording probe able to “listen” to neurons that emit characteristic signals depending on their functions, Kemere said. Once a surgeon finds the right spot, the probe is removed and the stimulating electrode gently inserted. Rice carbon nanotube fibers that send and receive signals would simplify implantation, Vitale said.
The fibers could lead to self-regulating therapeutic devices for Parkinson’s and other patients. Current devices include an implant that sends electrical signals to the brain to calm the tremors that afflict Parkinson’s patients.
“But our technology enables the ability to record while stimulating,” Vitale said. “Current electrodes can only stimulate tissue. They’re too big to detect any spiking activity, so basically the clinical devices send continuous pulses regardless of the response of the brain.”
Kemere foresees a closed-loop system that can read neuronal signals and adapt stimulation therapy in real time. He anticipates building a device with many electrodes that can be addressed individually to gain fine control over stimulation and monitoring from a small, implantable device.
“Interestingly, conductivity is not the most important electrical property of the nanotube fibers,” Pasquali said. “These fibers are intrinsically porous and extremely stable, which are both great advantages over metal electrodes for sensing electrochemical signals and maintaining performance over long periods of time.”
The paper is open access provided you register on the website.
Remote control for stimulation of the brain
Mo Costandi, neuroscientist and freelance science writer, has written a March 24, 2015 post for the Guardian science blog network focusing on neuronal remote control,
Two teams of scientists have developed new ways of stimulating neurons with nanoparticles, allowing them to activate brain cells remotely using light or magnetic fields. The new methods are quicker and far less invasive than other hi-tech methods available, so could be more suitable for potential new treatments for human diseases.
Researchers have various methods for manipulating brain cell activity, arguably the most powerful being optogenetics, which enables them to switch specific brain cells on or off with unprecedented precision, and simultaneously record their behaviour, using pulses of light.
This is very useful for probing neural circuits and behaviour, but involves first creating genetically engineered mice with light-sensitive neurons, and then inserting the optical fibres that deliver light into the brain, so there are major technical and ethical barriers to its use in humans.
Nanomedicine could get around this. Francisco Bezanilla of the University of Chicago and his colleagues knew that gold nanoparticles can absorb light and convert it into heat, and several years ago they discovered that infrared light can make neurons fire nervous impulses by heating up their cell membranes.
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Polina Anikeeva’s team at the Massachusetts Institute of Technology adopted a slightly different approach, using spherical iron oxide particles that give off heat when exposed to an alternating magnetic field.
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Although still in the experimental stages, research like this may eventually allow for wireless and minimally invasive deep brain stimulation of the human brain. Bezanilla’s group aim to apply their method to develop treatments for macular degeneration and other conditions that kill off light-sensitive cells in the retina. This would involve injecting nanoparticles into the eye so that they bind to other retinal cells, allowing natural light to excite them into firing impulses to the optic nerve.
Costandi’s article is intended for an audience that either understands the science or can deal with the uncertainty of not understanding absolutely everything. Provided you fall into either of those categories, the article is well written and it provides links and citations to the papers for both research teams being featured.
Taken together, the research at EPFL, Rice University, University of Chicago, and Massachusetts Institute of Technology provides a clue as to how much money and intellectual power is being directed at the brain.
Queensland University of Technology* (QUT; Australia) researchers are hopeful they can adapt supercapacitors in the form of a fine film tor use in electric vehicles making them more energy-efficient. From a Nov. 6, 2014 news item on ScienceDaily,
A car powered by its own body panels could soon be driving on our roads after a breakthrough in nanotechnology research by a QUT team.
Researchers have developed lightweight “supercapacitors” that can be combined with regular batteries to dramatically boost the power of an electric car.
The discovery was made by Postdoctoral Research Fellow Dr Jinzhang Liu, Professor Nunzio Motta and PhD researcher Marco Notarianni, from QUT’s Science and Engineering Faculty — Institute for Future Environments, and PhD researcher Francesca Mirri and Professor Matteo Pasquali, from Rice University in Houston, in the United States.
A Nov. 6, 2014 QUT news release, which originated the news item, describes supercapacitors, the research, and the need for this research in more detail,
The supercapacitors – a “sandwich” of electrolyte between two all-carbon electrodes – were made into a thin and extremely strong film with a high power density.
The film could be embedded in a car’s body panels, roof, doors, bonnet and floor – storing enough energy to turbocharge an electric car’s battery in just a few minutes.
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“Vehicles need an extra energy spurt for acceleration, and this is where supercapacitors come in. They hold a limited amount of charge, but they are able to deliver it very quickly, making them the perfect complement to mass-storage batteries,” he said.
“Supercapacitors offer a high power output in a short time, meaning a faster acceleration rate of the car and a charging time of just a few minutes, compared to several hours for a standard electric car battery.”
Dr Liu said currently the “energy density” of a supercapacitor is lower than a standard lithium ion (Li-Ion) battery, but its “high power density”, or ability to release power in a short time, is “far beyond” a conventional battery.
“Supercapacitors are presently combined with standard Li-Ion batteries to power electric cars, with a substantial weight reduction and increase in performance,” he said.
“In the future, it is hoped the supercapacitor will be developed to store more energy than a Li-Ion battery while retaining the ability to release its energy up to 10 times faster – meaning the car could be entirely powered by the supercapacitors in its body panels.
“After one full charge this car should be able to run up to 500km – similar to a petrol-powered car and more than double the current limit of an electric car.”
Dr Liu said the technology would also potentially be used for rapid charges of other battery-powered devices.
“For example, by putting the film on the back of a smart phone to charge it extremely quickly,” he said.
The discovery may be a game-changer for the automotive industry, with significant impacts on financial, as well as environmental, factors.
“We are using cheap carbon materials to make supercapacitors and the price of industry scale production will be low,” Professor Motta said.
“The price of Li-Ion batteries cannot decrease a lot because the price of Lithium remains high. This technique does not rely on metals and other toxic materials either, so it is environmentally friendly if it needs to be disposed of.”
A Nov. 10, 2014 news item on Azonano describes the Rice University (Texas, US) contribution to this work,
Rice University scientist Matteo Pasquali and his team contributed to two new papers that suggest the nano-infused body of a car may someday power the car itself.
Rice supplied high-performance carbon nanotube films and input on the device design to scientists at the Queensland University of Technology in Australia for the creation of lightweight films containing supercapacitors that charge quickly and store energy. The inventors hope to use the films as part of composite car doors, fenders, roofs and other body panels to significantly boost the power of electric vehicles.
A Nov. 7, 2014 Rice University news release, which originated the news item, offers a few technical details about the film being proposed for use as a supercapacitor on car panels,
Researchers in the Queensland lab of scientist Nunzio Motta combined exfoliated graphene and entangled multiwalled carbon nanotubes combined with plastic, paper and a gelled electrolyte to produce the flexible, solid-state supercapacitors.
“Nunzio’s team is making important advances in the energy-storage area, and we were glad to see that our carbon nanotube film technology was able to provide breakthrough current collection capability to further improve their devices,” said Pasquali, a Rice professor of chemical and biomolecular engineering and chemistry. “This nice collaboration is definitely bottom-up, as one of Nunzio’s Ph.D. students, Marco Notarianni, spent a year in our lab during his Master of Science research period a few years ago.”
“We built on our earlier work on CNT films published in ACS Nano, where we developed a solution-based technique to produce carbon nanotube films for transparent electrodes in displays,” said Francesca Mirri, a graduate student in Pasquali’s research group and co-author of the papers. “Now we see that carbon nanotube films produced by the solution-processing method can be applied in several areas.”
As currently designed, the supercapacitors can be charged through regenerative braking and are intended to work alongside the lithium-ion batteries in electric vehicles, said co-author Notarianni, a Queensland graduate student.
“Vehicles need an extra energy spurt for acceleration, and this is where supercapacitors come in. They hold a limited amount of charge, but with their high power density, deliver it very quickly, making them the perfect complement to mass-storage batteries,” he said.
Because hundreds of film supercapacitors are used in the panel, the electric energy required to power the car’s battery can be stored in the car body. “Supercapacitors offer a high power output in a short time, meaning a faster acceleration rate of the car and a charging time of just a few minutes, compared with several hours for a standard electric car battery,” Notarianni said.
The researchers foresee such panels will eventually replace standard lithium-ion batteries. “In the future, it is hoped the supercapacitor will be developed to store more energy than an ionic battery while retaining the ability to release its energy up to 10 times faster – meaning the car would be powered by the supercapacitors in its body panels,” said Queensland postdoctoral researcher Jinzhang Liu.
Here’s an image of graphene infused with carbon nantoubes used in the supercapacitor film,
A scanning electron microscope image shows freestanding graphene film with carbon nanotubes attached. The material is part of a project to create lightweight films containing super capacitors that charge quickly and store energy. Courtesy of Nunzio Motta/Queensland University of Technology
Here are links to and citations for the two papers published by the researchers,
High performance all-carbon thin film supercapacitors by Jinzhang Liu, Francesca Mirri, Marco Notarianni, Matteo Pasquali, and Nunzio Motta. Journal of Power Sources Volume 274, 15 January 2015, Pages 823–830 DOI: 10.1016/j.jpowsour.2014.10.104
Both articles are behind paywalls.
One final note, Dexter Johnson provides some insight into issues with graphene-based supercapacitors and what makes this proposed application attractive in his Nov. 7, 2014 post on the Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers] website; Note: Links have been removed),
The hope has been that someone could make graphene electrodes for supercapacitors that would boost their energy density into the range of chemical-based batteries. The supercapacitors currently on the market have on average an energy density around 28 Wh/kg, whereas a Li-ion battery holds about 200Wh/kg. That’s a big gap to fill.
The research in the field thus far has indicated that graphene’s achievable surface area in real devices—the factor that determines how many ions a supercapacitor electrode can store, and therefore its energy density—is not any better than traditional activated carbon. In fact, it may not be much better than a used cigarette butt.
Though graphene may not help increase supercapacitors’ energy density, its usefulness in this application may lie in the fact that its natural high conductivity will allow superconductors to operate at higher frequencies than those that are currently on the market. Another likely benefit that graphene will yield comes from the fact that it can be structured and scaled down, unlike other supercapacitor materials.
I recommend reading Dexter’s commentary in its entirety.
*’University of Queensland’ corrected to “Queensland University of Technology’ on Nov. 10, 2014 at 1335 PST.
* ‘super-capacitor’ changed to ‘supercapacitor’ on April 29, 2015.
Australian start-up company, Fabricor Workwear launched a Kickstarter campaign on Sept. 18, 2014 to raise funds for a stain-proof and water-repellent chef’s jacket according to a Sept. 25, 2014 news item on Azonano,
An Australian startup is using a patented nanotechnology to create ‘hydrophobic’ chef jackets and aprons. Fabricor says this means uniforms that stay clean for longer, and saving time and money.
The company was started because cofounder and MasterChef mentor Adrian Li, was frustrated with keeping his chef jackets and aprons clean.
“As a chef I find it really difficult to keep my chef jacket white, and we like our jackets white,” Li said. …
The nanotechnology application works by modifying the fabric at a molecular level by permanently attaching hydrophobic ‘whiskers’ to individual fibres which elevate liquids, causing them to bead up and roll off.
Thanks for taking the time check out our campaign.
Traditional chef jackets date back to the mid 19th century and since then haven’t changed much.
We’re tired of poor quality hospitality workwear that doesn’t last and hate spending our spare time and money washing or replacing our uniforms.
So we designed a range of stain-resistant Chef Jackets and Aprons using the world’s leading patented hydrophobic nanotechnology that repels water, dirt and oil.
Most stains either run off by themselves or can easily be rinsed off with a little water. This means they don’t need to be washed as often saving you time and money.
We’re really proud of what we’ve created and we hope you you’ll support us.
Adrian Li
Head Chef at Saigon Sally
Mentor on MasterChef Australia – Asian Street Food Challenge
Cofounder at Fabricor Workwear
At this point (Sept. 24, 2014), the campaign has raised approximately $2700US towards a $5000US goal and there are 22 days left to the campaign.
The fabric’s patented technology can extend the life of the apparel is because the apparel doesn’t have to be washed as often and can be washed in cooler temperatures, the company stated.
Fabricor’s products are not made with spray-application like many on the market which can destroy fabrics and contain carcinogenic chemical. Its hydrophobic properties are embedded into the weave during the production of the fabric.
…
Li said chefs spend too much money on chef jackets that are poorly designed and don’t last. The long-lasting fabric in Fabricor’s chef’s apparel retains its natural softness and breathability.
It seems to me that the claim about fewer washes can be made for all superhydrophobic textiles. As for carcinogenic chemicals in other superhydrophobic textiles, it’s the first I’ve heard of it, which may or may not be significant. I.e., I look at a lot of material but don’t focus on superhydrophobic textiles here and do not seek out research on risks specific to these textiles.
Teijin Aramid/Rice University
Still talking about textile fibres but on a completely different track, I received a news release this morning (Sept. 25, 2014) from Teijin Aramid about carbon nanotubes and fibres,
Researchers of Teijin Aramid, based in the Netherlands, and Rice University in the USA are awarded with the honorary ‘Paul Schlack Man-Made Fibers Prize’ for corporate-academic partnerships in fiber research. Their new super fibers are now driving innovation in aerospace, healthcare, automotive, and (smart) clothing.
The honorary Paul Schlack prize was granted by the European Man-made Fibers Association to Dr. Marcin Otto, Business Development Manager at Teijin Aramid and Prof. Dr. Matteo Pasquali from Rice University Texas, for the development of a new generation super fibers using carbon nanotubes (CNT). The new super fibers combine high thermal and electrical conductivity, as seen in metals, with the flexibility, robust handling and strength of textile fibers.
“The introduction of carbon nanotube fibers marked the beginning of a series of innovations in various industries”, says Marcin Otto, Business Development Manager at Teijin Aramid. “For example, CNT fibers can be lifesaving for heart patients: one string of CNT fiber in the cardiac muscle suffices to transmit vital electrical pulses to the heart. Or by replacing copper in data cables and light power cables by CNT fibers it’s possible to make satellites, aircraft and high end cars lighter and more robust at the same time.”
Since 1971, the Paul Schlack foundation annually grants one monetary prize to an individual young researcher for outstanding research in the field of fiber research, and an honorary prize to the leader(s) of excellent academic and corporate research partnerships to promote research at universities and research institutes.
For several years, leading researchers at Rice University and Teijin Aramid worked together on the development of CNT production. Teijin Aramid and Rice University published their research findings on carbon nanotubes fibers in the leading scientific journal, Science, beginning of 2013.
Teijin Aramid and some of its carbon nanotube projects have been mentioned here before, notably, in a Jan. 11, 2013 posting and in a Feb. 17, 2014.
Good luck on the Kickstarter campaign and congratulations on the award!
Chemical engineers from Rice University and biophysicists from Georg-August Universität Göttingen in Germany and the VU University Amsterdam in the Netherlands have successfully tracked single molecules inside living cells with carbon nanotubes.
Through this new method, the researchers found that cells stir their interiors using the same motor proteins that serve in muscle contraction.
The team attached carbon nanotubes to transport molecules known as kinesin motors to visualize and track them as they moved through the cytoplasm of living cells.
…
Carbon nanotubes are hollow cylinders of pure carbon with one-atom-thick walls. They naturally fluoresce with near-infrared wavelengths when exposed to visible light, a property discovered at Rice by Professor Rick Smalley a decade ago and then leveraged by Rice Professor Bruce Weisman to image carbon nanotubes. When attached to a molecule, the hitchhiking nanotubes serve as tiny beacons that can be precisely tracked over long periods of time to investigate small, random motions inside cells.
“Any probe that can hitch the length and breadth of the cell, rough it, slum it, struggle against terrible odds, win through and still know where its protein is, is clearly a probe to be reckoned with,” said lead author Nikta Fakhri, paraphrasing “The Hitchhiker’s Guide to the Galaxy.” Fakhri, who earned her Rice doctorate in Pasquali’s lab in 2011, is currently a Human Frontier Science Program Fellow at Göttingen.
“In fact, the exceptional stability of these probes made it possible to observe intracellular motions from times as short as milliseconds to as long as hours,” she said.
For long-distance transport, such as along the long axons of nerve cells, cells usually employ motor proteins tied to lipid vesicles, the cell’s “cargo containers.” This process involves considerable logistics: Cargo needs to be packed, attached to the motors and sent off in the right direction.
“This research has helped uncover an additional, much simpler mechanism for transport within the cell interior,” said principal investigator Christoph Schmidt, a professor of physics at Göttingen. “Cells vigorously stir themselves, much in the way a chemist would accelerate a reaction by shaking a test tube. This will help them to move objects around in the highly crowded cellular environment.”
The researchers showed the same type of motor protein used for muscle contraction is responsible for stirring. They reached this conclusion after exposing the cells to drugs that suppressed these specific motor proteins. The tests showed that the stirring was suppressed as well.
The mechanical cytoskeleton of cells consists of networks of protein filaments, like actin. Within the cell, the motor protein myosin forms bundles that actively contract the actin network for short periods. The researchers found random pinching of the elastic actin network by many myosin bundles resulted in the global internal stirring of the cell. Both actin and myosin play a similar role in muscle contraction.
The highly accurate measurements of internal fluctuations in the cells were explained in a theoretical model developed by VU co-author Fred MacKintosh, who used the elastic properties of the cytoskeleton and the force-generation characteristics of the motors.
“The new discovery not only promotes our understanding of cell dynamics, but also points to interesting possibilities in designing ‘active’ technical materials,” said Fakhri, who will soon join the Massachusetts Institute of Technology faculty as an assistant professor of physics. “Imagine a microscopic biomedical device that mixes tiny samples of blood with reagents to detect disease or smart filters that separate squishy from rigid materials.”
There is an accompanying video,
This video is typical of the kind of visual image that nanoscientists look at and provides an interesting contrast to ‘nano art’ where colours and other enhancements are added. as per this example, NanoOrchard, from a May 13, 2014 news item on Nanowerk about the 2014 Materials Research Society spring meeting and their Science as Art competition,
NanoOrchard – Electrochemically overgrown CuNi nanopillars. (Image courtesy of the Materials Research Society Science as Art Competition and Josep Nogues, Institut Catala de Nanociencia i Nanotecnologia (ICN2), Spain, and A. Varea, E. Pellicer, S. Suriñach, M.D. Baro, J. Sort, Univ. Autonoma de Barcelona) [downloaded from http://www.nanowerk.com/nanotechnology-news/newsid=35631.php]
Getting back to the carbon nanotube hitchhikers, here’s a link to and a citation for the paper,
The big news is that a multinational team has managed to spin carbon nanotubes (after 10 years of work) into threads that look like black cotton and display both the properties of metal wires and of carbon fibers. Here’s more from the Jan. 10, 2013 news item on ScienceDaily,
“We finally have a nanotube fiber with properties that don’t exist in any other material,” said lead researcher Matteo Pasquali, professor of chemical and biomolecular engineering and chemistry at Rice. “It looks like black cotton thread but behaves like both metal wires and strong carbon fibers.”
The research team includes academic, government and industrial scientists from Rice; Teijin Aramid’s headquarters in Arnhem, the Netherlands; the Technion-Israel Institute of Technology in Haifa, Israel; and the Air Force Research Laboratory (AFRL) in Dayton, Ohio.
The Jan. 10, 2013 Rice University news release on EurekAlert, which originated the news item, describes some of the problems presented when trying to produce carbon nanotube fiber at an industrial scale,
The phenomenal properties of carbon nanotubes have enthralled scientists from the moment of their discovery in 1991. The hollow tubes of pure carbon, which are nearly as wide as a strand of DNA, are about 100 times stronger than steel at one-sixth the weight. Nanotubes’ conductive properties — for both electricity and heat — rival the best metal conductors. They also can serve as light-activated semiconductors, drug-delivery devices and even sponges to soak up oil.
Unfortunately, carbon nanotubes are also the prima donna of nanomaterials [emphasis mine]; they are difficult to work with, despite their exquisite potential. For starters, finding the means to produce bulk quantities of nanotubes took almost a decade. Scientists also learned early on that there were several dozen types of nanotubes — each with unique material and electrical properties; and engineers have yet to find a way to produce just one type. Instead, all production methods yield a hodgepodge of types, often in hairball-like clumps.
Creating large-scale objects from these clumps of nanotubes has been a challenge. A threadlike fiber that is less than one-quarter the thickness of a human hair will contain tens of millions of nanotubes packed side by side. Ideally, these nanotubes will be perfectly aligned — like pencils in a box — and tightly packed. Some labs have explored means of growing such fibers whole, but the production rates for these “solid-state” fibers have proven quite slow compared with fiber-production methods that rely on a chemical process called “wet spinning.” In this process, clumps of raw nanotubes are dissolved in a liquid and squirted through tiny holes to form long strands.
Thank you to the writer of the Rice University news release for giving me the phrase “prima donna of nanomaterials.”
The news release goes on to describe the years of work and collaboration needed to arrive at this point,
Shortly after arriving at Rice in 2000, Pasquali began studying CNT wet-spinning methods with the late Richard Smalley, a nanotechnology pioneer and the namesake of Rice’s Smalley Institute for Nanoscale Science and Technology. In 2003, two years before his untimely death, Smalley worked with Pasquali and colleagues to create the first pure nanotube fibers. The work established an industrially relevant wet-spinning process for nanotubes that was analogous to the methods used to create high-performance aramid fibers — like Teijin’s Twaron — which are used in bulletproof vests and other products. But the process needed to be refined. The fibers weren’t very strong or conductive, due partly to gaps and misalignment of the millions of nanotubes inside them.
“Achieving very high packing and alignment of the carbon nanotubes in the fibers is critical,” said study co-author Yeshayahu Talmon, director of Technion’s Russell Berrie Nanotechnology Institute, who began collaborating with Pasquali about five years ago.
The next big breakthrough came in 2009, when Talmon, Pasquali and colleagues discovered the first true solvent for nanotubes — chlorosulfonic acid. For the first time, scientists had a way to create highly concentrated solutions of nanotubes, a development that led to improved alignment and packing.
“Until that time, no one thought that spinning out of chlorosulfonic acid was possible because it reacts with water,” Pasquali said. “A graduate student in my lab, Natnael Bahabtu, found simple ways to show that CNT fibers could be spun from chlorosulfonic acid solutions. That was critical for this new process.”
Pasquali said other labs had found that the strength and conductivity of spun fibers could also be improved if the starting material — the clumps of raw nanotubes — contained long nanotubes with few atomic defects. In 2010, Pasquali and Talmon began experimenting with nanotubes from different suppliers and working with AFRL scientists to measure the precise electrical and thermal properties of the improved fibers.
During the same period, Otto [Marcin Otto, Business Development Manager at Teijin Aramid] was evaluating methods that different research centers had proposed for making CNT fibers. He envisaged combining Pasquali’s discoveries, Teijin Aramid’s know-how and the use of long CNTs to further the development of high performance CNT fibers. In 2010, Teijin Aramid set up and funded a project with Rice, and the company’s fiber-spinning experts have collaborated with Rice scientists throughout the project.
“The Teijin scientific and technical help led to immediate improvements in strength and conductivity,” Pasquali said.
Study co-author Junichiro Kono, a Rice professor of electrical and computer engineering, said, “The research showed that the electrical conductivity of the fibers could be tuned and optimized with techniques that were applied after initial production. This led to the highest conductivity ever reported for a macroscopic CNT fiber.”
The fibers reported in Science have about 10 times the tensile strength and electrical and thermal conductivity of the best previously reported wet-spun CNT fibers, Pasquali said. The specific electrical conductivity of the new fibers is on par with copper, gold and aluminum wires, but the new material has advantages over metal wires.
Here’s an explanatory video the researchers have provided,
“Our carbon nanotube fibers combine high thermal and electrical conductivity, like that seen in metals, with the flexibility, robust handling and strength of textile fibers”, explained Marcin Otto, Business Development Manager at Teijin Aramid. “With that novel combination of properties it is possible to use CNT fibers in many applications in the aerospace, automotive, medical and (smart) clothing industries.”
Teijin’s cooperation and involvement was crucial to the project. Twaron technology enabled improved performance, and an industrially scalable production method. That makes it possible to find applications for CNT fibers in a range of commercial or industrial products. “This research and ongoing tests offer us a glimpse into the potential future possibilities of this new fiber. For example, we have been very excited by the interest of innovative medical doctors and scientists exploring the possibilities to use CNT fiber in surgical operations and other applications in the medical field”, says Marcin Otto. Teijin Aramid expects to replace the copper in data cables and light power cables used in the aerospace and automotive industries, to make aircraft and high end cars lighter and more robust at the same time. Other applications could include integrating light weight electronic components, such as antennas, into composites, or replacing cooling systems in electronics where the high thermal conductivity of carbon nanotube fiber can help to dissipate heat.
Teijin Aramid is currently trialing samples of CNT fiber on a small scale with the most active prospective customers. Building up a robust supply chain is high on the project team’s list of priorities. As well as their carbon fiber, aramid fiber and polyethylene tape, this new carbon nanotube fiber is expected to allow Teijin to offer customers an even broader portfolio of high performance materials.
Teijin Group (which is headquartered in Japan) has been mentioned here before notably in a July 19, 2010 posting about a textile inspired by a butterfly’s wing (Morphotex) which, sadly, is no longer being produced as noted in a more recent April 12, 2012 posting about Teijin’s then new fiber ‘Nanofront™’ for use in sports socks.
![NanoOrchard – Electrochemically overgrown CuNi nanopillars. (Image courtesy of the Materials Research Society Science as Art Competition and Josep Nogues, Institut Catala de Nanociencia i Nanotecnologia (ICN2), Spain, and A. Varea, E. Pellicer, S. Suriñach, M.D. Baro, J. Sort, Univ. Autonoma de Barcelona) [downloaded from http://www.nanowerk.com/nanotechnology-news/newsid=35631.php]](http://www.frogheart.ca/wp-content/uploads/2014/05/NanoOrchard.jpg)