Tag Archives: Benji Maruyama

Detangling carbon nanotubes (CNTs)

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.

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.

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

This paper is open access.

Yarns that harvest and generate energy

The researchers involved in this work are confident enough about their prospects that they will be  patenting their research into yarns. From an August 25, 2017 news item on Nanowerk,

An international research team led by scientists at The University of Texas at Dallas and Hanyang University in South Korea has developed high-tech yarns that generate electricity when they are stretched or twisted.

In a study published in the Aug. 25 [2017] issue of the journal Science (“Harvesting electrical energy from carbon nanotube yarn twist”), researchers describe “twistron” yarns and their possible applications, such as harvesting energy from the motion of ocean waves or from temperature fluctuations. When sewn into a shirt, these yarns served as a self-powered breathing monitor.

“The easiest way to think of twistron harvesters is, you have a piece of yarn, you stretch it, and out comes electricity,” said Dr. Carter Haines, associate research professor in the Alan G. MacDiarmid NanoTech Institute at UT Dallas and co-lead author of the article. The article also includes researchers from South Korea, Virginia Tech, Wright-Patterson Air Force Base and China.

An August 25, 2017 University of Texas at Dallas news release, which originated the news item, expands on the theme,

Yarns Based on Nanotechnology

The yarns are constructed from carbon nanotubes, which are hollow cylinders of carbon 10,000 times smaller in diameter than a human hair. The researchers first twist-spun the nanotubes into high-strength, lightweight yarns. To make the yarns highly elastic, they introduced so much twist that the yarns coiled like an over-twisted rubber band.

In order to generate electricity, the yarns must be either submerged in or coated with an ionically conducting material, or electrolyte, which can be as simple as a mixture of ordinary table salt and water.

“Fundamentally, these yarns are supercapacitors,” said Dr. Na Li, a research scientist at the NanoTech Institute and co-lead author of the study. “In a normal capacitor, you use energy — like from a battery — to add charges to the capacitor. But in our case, when you insert the carbon nanotube yarn into an electrolyte bath, the yarns are charged by the electrolyte itself. No external battery, or voltage, is needed.”

When a harvester yarn is twisted or stretched, the volume of the carbon nanotube yarn decreases, bringing the electric charges on the yarn closer together and increasing their energy, Haines said. This increases the voltage associated with the charge stored in the yarn, enabling the harvesting of electricity.

Stretching the coiled twistron yarns 30 times a second generated 250 watts per kilogram of peak electrical power when normalized to the harvester’s weight, said Dr. Ray Baughman, director of the NanoTech Institute and a corresponding author of the study.

“Although numerous alternative harvesters have been investigated for many decades, no other reported harvester provides such high electrical power or energy output per cycle as ours for stretching rates between a few cycles per second and 600 cycles per second.”

Lab Tests Show Potential Applications

In the lab, the researchers showed that a twistron yarn weighing less than a housefly could power a small LED, which lit up each time the yarn was stretched.

To show that twistrons can harvest waste thermal energy from the environment, Li connected a twistron yarn to a polymer artificial muscle that contracts and expands when heated and cooled. The twistron harvester converted the mechanical energy generated by the polymer muscle to electrical energy.

“There is a lot of interest in using waste energy to power the Internet of Things, such as arrays of distributed sensors,” Li said. “Twistron technology might be exploited for such applications where changing batteries is impractical.”

The researchers also sewed twistron harvesters into a shirt. Normal breathing stretched the yarn and generated an electrical signal, demonstrating its potential as a self-powered respiration sensor.

“Electronic textiles are of major commercial interest, but how are you going to power them?” Baughman said. “Harvesting electrical energy from human motion is one strategy for eliminating the need for batteries. Our yarns produced over a hundred times higher electrical power per weight when stretched compared to other weavable fibers reported in the literature.”

Electricity from Ocean Waves

“In the lab we showed that our energy harvesters worked using a solution of table salt as the electrolyte,” said Baughman, who holds the Robert A. Welch Distinguished Chair in Chemistry in the School of Natural Sciences and Mathematics. “But we wanted to show that they would also work in ocean water, which is chemically more complex.”

In a proof-of-concept demonstration, co-lead author Dr. Shi Hyeong Kim, a postdoctoral researcher at the NanoTech Institute, waded into the frigid surf off the east coast of South Korea to deploy a coiled twistron in the sea. He attached a 10 centimeter-long yarn, weighing only 1 milligram (about the weight of a mosquito), between a balloon and a sinker that rested on the seabed.

Every time an ocean wave arrived, the balloon would rise, stretching the yarn up to 25 percent, thereby generating measured electricity.

Even though the investigators used very small amounts of twistron yarn in the current study, they have shown that harvester performance is scalable, both by increasing twistron diameter and by operating many yarns in parallel.

“If our twistron harvesters could be made less expensively, they might ultimately be able to harvest the enormous amount of energy available from ocean waves,” Baughman said. “However, at present these harvesters are most suitable for powering sensors and sensor communications. Based on demonstrated average power output, just 31 milligrams of carbon nanotube yarn harvester could provide the electrical energy needed to transmit a 2-kilobyte packet of data over a 100-meter radius every 10 seconds for the Internet of Things.”

Researchers from the UT Dallas Erik Jonsson School of Engineering and Computer Science and Lintec of America’s Nano-Science & Technology Center also participated in the study.

The investigators have filed a patent on the technology.

In the U.S., the research was funded by the Air Force, the Air Force Office of Scientific Research, NASA, the Office of Naval Research and the Robert A. Welch Foundation. In Korea, the research was supported by the Korea-U.S. Air Force Cooperation Program and the Creative Research Initiative Center for Self-powered Actuation of the National Research Foundation and the Ministry of Science.

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

Harvesting electrical energy from carbon nanotube yarn twist by Shi Hyeong Kim, Carter S. Haines, Na Li, Keon Jung Kim, Tae Jin Mun, Changsoon Choi, Jiangtao Di, Young Jun Oh, Juan Pablo Oviedo, Julia Bykova, Shaoli Fang, Nan Jiang, Zunfeng Liu, Run Wang, Prashant Kumar, Rui Qiao, Shashank Priya, Kyeongjae Cho, Moon Kim, Matthew Steven Lucas, Lawrence F. Drummy, Benji Maruyama, Dong Youn Lee, Xavier Lepró, Enlai Gao, Dawood Albarq, Raquel Ovalle-Robles, Seon Jeong Kim, Ray H. Baughman. Science 25 Aug 2017: Vol. 357, Issue 6353, pp. 773-778 DOI: 10.1126/science.aam8771

This paper is behind a paywall.

Dexter Johnson in an Aug. 25, 2017 posting on his Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers] website) delves further into the research,

“Basically what’s happening is when we stretch the yarn, we’re getting a change in capacitance of the yarn. It’s that change that allows us to get energy out,” explains Carter Haines, associate research professor at UT Dallas and co-lead author of the paper describing the research, in an interview with IEEE Spectrum.

This makes it similar in many ways to other types of energy harvesters. For instance, in other research, it has been demonstrated—with sheets of rubber with coated electrodes on both sides—that you can increase the capacitance of a material when you stretch it and it becomes thinner. As a result, if you have charge on that capacitor, you can change the voltage associated with that charge.

“We’re more or less exploiting the same effect but what we’re doing differently is we’re using an electric chemical cell to do this,” says Haines. “So we’re not changing double layer capacitance in normal parallel plate capacitors. But we’re actually changing the electric chemical capacitance on the surface of a super capacitor yarn.”

While there are other capacitance-based energy harvesters, those other devices require extremely high voltages to work because they’re using parallel plate capacitors, according to Haines.

Dexter asks good questions and his post is very informative.