Tag Archives: Junichiro Kono

Carbon nanotubes (CNTs) in 466 colours

Caption: A color map illustrates the inherent colors of 466 types of carbon nanotubes with unique (n,m) designations based their chiral angle and diameter. Credit: Image courtesy of Kauppinen Group/Aalto University

This is, so to speak, a new angle on carbon nanotubes (CNTs). It’s also the first time I’ve seen two universities place identical news releases on EurekAlert under their individual names.

From the Dec. 14, 2020 Rice University (US) news release or the Dec. 14, 2020 Aalto University (Finland) press release on EurekAlert,

Nanomaterials researchers in Finland, the United States and China have created a color atlas for 466 unique varieties of single-walled carbon nanotubes.

The nanotube color atlas is detailed in a study in Advanced Materials about a new method to predict the specific colors of thin films made by combining any of the 466 varieties. The research was conducted by researchers from Aalto University in Finland, Rice University and Peking University in China.

“Carbon, which we see as black, can appear transparent or take on any color of the rainbow,” said Aalto physicist Esko Kauppinen, the corresponding author of the study. “The sheet appears black if light is completely absorbed by carbon nanotubes in the sheet. If less than about half of the light is absorbed in the nanotubes, the sheet looks transparent. When the atomic structure of the nanotubes causes only certain colors of light, or wavelengths, to be absorbed, the wavelengths that are not absorbed are reflected as visible colors.”

Carbon nanotubes are long, hollow carbon molecules, similar in shape to a garden hose but with sides just one atom thick and diameters about 50,000 times smaller than a human hair. The outer walls of nanotubes are made of rolled graphene. And the wrapping angle of the graphene can vary, much like the angle of a roll of holiday gift wrap paper. If the gift wrap is rolled carefully, at zero angle, the ends of the paper will align with each side of the gift wrap tube. If the paper is wound carelessly, at an angle, the paper will overhang on one end of the tube.

The atomic structure and electronic behavior of each carbon nanotube is dictated by its wrapping angle, or chirality, and its diameter. The two traits are represented in a “(n,m)” numbering system that catalogs 466 varieties of nanotubes, each with a characteristic combination of chirality and diameter. Each (n,m) type of nanotube has a characteristic color.

Kauppinen’s research group has studied carbon nanotubes and nanotube thin films for years, and it previously succeeded in mastering the fabrication of colored nanotube thin films that appeared green, brown and silver-grey.

In the new study, Kauppinen’s team examined the relationship between the spectrum of absorbed light and the visual color of various thicknesses of dry nanotube films and developed a quantitative model that can unambiguously identify the coloration mechanism for nanotube films and predict the specific colors of films that combine tubes with different inherent colors and (n,m) designations.

Rice engineer and physicist Junichiro Kono, whose lab solved the mystery of colorful armchair nanotubes in 2012, provided films made solely of (6,5) nanotubes that were used to calibrate and verify the Aalto model. Researchers from Aalto and Peking universities used the model to calculate the absorption of the Rice film and its visual color. Experiments showed that the measured color of the film corresponded quite closely to the color forecast by the model.

The Aalto model shows that the thickness of a nanotube film, as well as the color of nanotubes it contains, affects the film’s absorption of light. Aalto’s atlas of 466 colors of nanotube films comes from combining different tubes. The research showed that the thinnest and most colorful tubes affect visible light more than those with larger diameters and faded colors.

“Esko’s group did an excellent job in theoretically explaining the colors, quantitatively, which really differentiates this work from previous studies on nanotube fluorescence and coloration,” Kono said.

Since 2013, Kono’s lab has pioneered a method for making highly ordered 2D nanotube films. Kono said he had hoped to supply Kauppinen’s team with highly ordered 2D crystalline films of nanotubes of a single chirality.

“That was the original idea, but unfortunately, we did not have appropriate single-chirality aligned films at that time,” Kono said. “In the future, our collaboration plans to extend this work to study polarization-dependent colors in highly ordered 2D crystalline films.”

The experimental method the Aalto researchers used to grow nanotubes for their films was the same as in their previous studies: Nanotubes grow from carbon monoxide gas and iron catalysts in a reactor that is heated to more than 850 degrees Celsius. The growth of nanotubes with different colors and (n,m) designations is regulated with the help of carbon dioxide that is added to the reactor.

“Since the previous study, we have pondered how we might explain the emergence of the colors of the nanotubes,” said Nan Wei, an assistant research professor at Peking University who previously worked as a postdoctoral researcher at Aalto. “Of the allotropes of carbon, graphite and charcoal are black, and pure diamonds are colorless to the human eye. However, now we noticed that single-walled carbon nanotubes can take on any color: for example, red, blue, green or brown.”

Kauppinen said colored thin films of nanotubes are pliable and ductile and could be useful in colored electronics structures and in solar cells.

“The color of a screen could be modified with the help of a tactile sensor in mobile phones, other touch screens or on top of window glass, for example,” he said.

Kauppinen said the research can also provide a foundation for new kinds of environmentally friendly dyes.

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

Colors of Single‐Wall Carbon Nanotubes by Nan Wei, Ying Tian, Yongping Liao, Natsumi Komatsu, Weilu Gao, Alina Lyuleeva‐Husemann, Qiang Zhang, Aqeel Hussain, Er‐Xiong Ding, Fengrui Yao, Janne Halme. Kaihui Liu, Junichiro Kono, Hua Jiang, Esko I. Kauppinen. Advanced Materials DOI: https://doi.org/10.1002/adma.202006395 First published: 14 December 2020

Thi8s paper is open access.

Quadruple the amount of electrical current by using carbon nanotube-based fibers

The announcement from Rice University was written in an interesting fashion. The good news is that you can quadruple the amount of electrical current being carried by substituting copper with carbon nanotube-based fibers. Unfortunately, expectations are set for a much higher rate before the good news is revealed in this Feb.  14, 2013 news item on ScienceDaily,

On a pound-per-pound basis, carbon nanotube-based fibers invented at Rice University have greater capacity to carry electrical current than copper cables of the same mass, according to new research.

While individual nanotubes are capable of transmitting nearly 1,000 times more current than copper, the same tubes coalesced into a fiber using other technologies fail long before reaching that capacity.

But a series of tests at Rice showed the wet-spun carbon nanotube fiber still handily beat copper, carrying up to four times as much current as a copper wire of the same mass. [emphasis mine]

That, said the researchers, makes nanotube-based cables an ideal platform for lightweight power transmission in systems where weight is a significant factor, like aerospace applications.

The Feb. 13, 2014 Rice University news release (dated as Feb. 14, 2014 on EurekAlert), which originated the news item, provides context for this discovery (Note: Links have been removed),

The analysis led by Rice professors Junichiro Kono and Matteo Pasquali appeared online this week [week of Feb. 10 – 14, 2014] in the journal Advanced Functional Materials. Just a year ago [2013] the journal Science reported that Pasquali’s lab, in collaboration with scientists at the Dutch firm Teijin Aramid, created a very strong conductive fiber out of carbon nanotubes.

Present-day transmission cables made of copper or aluminum are heavy because their low tensile strength requires steel-core reinforcement.

Scientists working with nanoscale materials have long thought there’s a better way to move electricity from here to there. Certain types of carbon nanotubes can carry far more electricity than copper. The ideal cable would be made of long metallic “armchair” nanotubes that would transmit current over great distances with negligible loss, but such a cable is not feasible because it’s not yet possible to manufacture pure armchairs in bulk, Pasquali said.

I have a couple of notes (1) the 2013 work on ‘armchair’ carbon nanotubes was featured here in a Feb. 6, 2013 posting and (2) Teijin Aramid is located in the Netherlands while its parent company, Teijin, is located in Japan (you can find more about Teijin in this Wikipedia essay).

Getting back to this latest work from Rice (from the news release),

In the meantime, the Pasquali lab has created a method to spin fiber from a mix of nanotube types that still outperforms copper. The cable developed by Pasquali and Teijin Aramid is strong and flexible even though at 20 microns wide, it’s thinner than a human hair.

Pasquali turned to Kono and his colleagues, including lead author Xuan Wang, a postdoctoral researcher at Rice, to quantify the fiber’s capabilities.

Pasquali said there has been a disconnect between electrical engineers who study the current carrying capacity of conductors and materials scientists working on carbon nanotubes. “That has generated some confusion in the literature over the right comparisons to make,” he said. “Jun and Xuan really got to the bottom of how to do these measurements well and compare apples to apples.”

The researchers analyzed the fiber’s “current carrying capacity” (CCC), or ampacity, with a custom rig that allowed them to test it alongside metal cables of the same diameter. The cables were tested while they were suspended in the open air, in a vacuum and in nitrogen or argon environments.

Electric cables heat up because of resistance. When the current load exceeds the cable’s safe capacity, they get too hot and break. The researchers found nanotube fibers exposed to nitrogen performed best, followed by argon and open air, all of which were able to cool through convection. The same nanotube fibers in a vacuum could only cool by radiation and had the lowest CCC.

“The outcome is that these fibers have the highest CCC ever reported for any carbon-based fibers,” Kono said. “Copper still has better resistivity by an order of magnitude, but we have the advantage that carbon fiber is light. So if you divide the CCC by the mass, we win.”

Kono plans to further investigate and explore the fiber’s multifunctional aspects, including flexible optoelectronic device applications.

Pasquali suggested the thread-like fibers are light enough to deliver power to aerial vehicles. “Suppose you want to power an unmanned aerial vehicle from the ground,” he mused. “You could make it like a kite, with power supplied by our fibers. I wish Ben Franklin were here to see that!”

Pasquali and his team’s latest research can be found here,

High-Ampacity Power Cables of Tightly-Packed and Aligned Carbon Nanotubes by Xuan Wang, Natnael Behabtu, Colin C. Young, Dmitri E. Tsentalovich, Matteo Pasqua, & Junichiro Kono. Advanced Functional Materials, Article first published online: 13 FEB 2014 DOI: 10.1002/adfm.201303865

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This study is behind a paywall.

Rice U and the US National Institute of Standards and Technology settle into armchairs, the carbon nanotube kind

An armchair carbon nanotube is amongst the most desirable of carbon nanotubes. You’ll have to look carefully to see the resemblance to an armchair,

Armchair carbon nanotubes, so named for the arrangement of atoms that make their ends look like armchairs, are the most desirable among nanotube researchers for their superior electrical properties. Image by Erik Hároz [downloaded from http://news.rice.edu/2013/02/05/essential-armchair-reading-for-nanotube-researchers-2/]

Armchair carbon nanotubes, so named for the arrangement of atoms that make their ends look like armchairs, are the most desirable among nanotube researchers for their superior electrical properties. Image by Erik Hároz [downloaded from http://news.rice.edu/2013/02/05/essential-armchair-reading-for-nanotube-researchers-2/]

The Feb. 6, 2013 news item on phys.org about the armchair carbon nanotubes notes that this latest research is an early outcome from a recently announced (Oct. 2012) partnership between Rice University and the US National Institute of Standards and Technology (NIST). Trom the news item (Note: Links have been removed),

The first fruits of a cooperative venture between scientists at Rice University and the National Institute of Standards and Technology (NIST) have appeared in a paper that brings together a wealth of information for those who wish to use the unique properties of metallic carbon nanotubes.

The feature article published recently in the Royal Society of Chemistry journal Nanoscale gathers research about the separation and fundamental characteristics of armchair carbon nanotubes, which have been of particular interest to researchers trying to tune their electronic and optical properties.

The Rice University Feb. 5, 2013 news release by Mike Williams, which originated the news item, describe s the process the scientists undertook,

This paper, said Rice physicist Junichiro Kono, provides scientists a valuable resource for detailed information about metallic carbon nanotubes, especially armchair nanotubes. “Basically, we summarized all our recent findings as well as all information we could find in the literature about metallic nanotubes, along with detailed accounts of preparation methods for metal-enriched nanotube samples, to show the community just how much we now understand about these one-dimensional metals,” he said.

As part of the lengthy work, the team compiled and published tables of essential statistics, including optical properties, for a variety of metallic nanotubes. “We provide fundamental theoretical backgrounds and then show very detailed experimental results on unique properties of metallic nanotubes,” Kono said. “This paper summarizes what kind of aspects are understood, and what is not, about fundamental optical processes in nanotubes and will make it easier for researchers to identify their spectroscopic features and transition energies.”

For this of us who are less well versed on armchair carbon nanotubes and their electronic and optical properties, the news releases provides some information (Note: Links have been removed),

Nanotubes come in many flavors, depending on their chirality. Chirality is a characteristic akin to the angles at which a flat sheet of paper might align when wrapped into a tube. Cut the tube in half and the atoms at the open edge would line up in the shape of an armchair, a zigzag or some variant. Even though their raw material is identical – chicken-wire-like hexagons of carbon – the chirality makes all the difference in how nanotubes transmit electricity.

Armchairs are the most coveted because they have no band gap; electrons flow through without resistance. Cables made with armchair nanotubes have the potential to move electricity over great distances with virtually no loss. That makes them the gold standard as the basic element of armchair quantum wire. The ongoing development of this very strong, lightweight, high-capacity cable could improve further the record properties of multifunctional carbon nanotube fibers that are being developed by the group of Rice Professor Matteo Pasquali.

For the project-specific work the scientists performed (Note: Links have been removed),

The new work led by Kono and Robert Hauge, a distinguished faculty fellow in chemistry at Rice, along with scientists at NIST and Los Alamos National Laboratory, looks beyond the armchair’s established electrical properties to further detail their potential for electronic, sensing, optical and photonic devices.

“Of course, to get there, we need really good samples,” Kono said. “Many applications will rely on our ability to separate carbon nanotubes and then assemble macroscopically ordered structures consisting of single-chirality nanotubes. Nobody can do that at this point.”

When a batch of nanotubes comes out of a furnace, it’s a jumble of types. That makes detailed analysis of their characteristics — let alone their practical use — a challenge.

But techniques developed in recent years at Rice and by NIST scientist Ming Zheng to purify metallic nanotubes are beginning to change that. Rice graduate student Erik Hároz said recent experiments established “unambiguous evidence” that a process he and Kono are using called density gradient ultracentrifugation can enrich ensemble samples of armchairs. Taking things further, Zheng’s method of DNA-based ion-exchange chromatography provides very small samples of ultrapure armchair nanotubes of a single chirality.

You can read more about the work at phys.org or at Rice University using the links already provided. For those who’d like to read the research,

Fundamental optical processes in armchair carbon nanotubes by Erik H. Hároz ,  Juan G. Duque,  Xiaomin Tu ,  Ming Zheng ,  Angela R. Hight Walker ,  Robert H. Hauge ,  Stephen K. Doorn and Junichiro Kono. Nanoscale, 2013,5, 1411-1439 DOI: 10.1039/C2NR32769D First published on the web 04 Jan 2013

This article is behind a paywall of sorts.  RSC (Royal Society of Chemistry) Publishing (which publishes Nanoscale) has an open access policy but there are various options, from the RSC Publishing’s Open Access Policy webpage,

RSC Open Access statement

Open Access is the term given to making electronic versions of articles accessible to readers, without any subscription or ‘access side’ fees.

RSC supports Open Access models which seek to ensure that scholarly publishing activities operate in a long term sustainable way.

  • Our fundamental goal is to advance the chemical sciences, through the effective dissemination of high quality research content
  • We seek to maximise the dissemination of the research that we publish
  • We support any and all sustainable and fair models of access. We believe that the integrity and archiving of scholarly content must be maintained throughout
  • We support ‘Gold’* Open Access and encourage funding to be made available to support authors during any transition from reader to author side payments
  • We support the author’s ability to choose where they publish their work to the benefit of the advancement of science. We do not wish authors to be discriminated against if they are unable to pay author-side fees
  • We seek to work closely with other parties, including funders and government agencies, to achieve the above goals

RSC Publishing provides authors with the option to make their article Open Access, through payment of a fee on acceptance. Authors following the traditional route still have deposition options – details are on the ‘Deposition and Licence to Publish’ page of the website.

*There are several types of Open Access:

  • Gold Open Access: Publication costs are covered by an ‘Article Processing Fees’ being paid by authors upon acceptance. The final ‘article of record’ is made available to all, immediately, without any barriers to access
  • Green Open Access: A version of the paper (often the author’s manuscript) is made available via a subject or institutional repository. An embargo period is often involved, typically 6-24 months. No payment is made, and publishers should strive to recoup their investment through traditional sales during the embargo period
  • Delayed Open Access: The final version of the paper is made available by the publisher after an embargo period (e.g. publisher deposit the paper in PubMed after 12 months)

It would seem the option for this article is ‘Delayed Open Access’.

Prima donna of nanomaterials (carbon nanotubes) tamed by scientists at Rice University (Texas, US), Teijin Armid (Dutch/Japanese company), and Technion Institute (based in Israel)

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,

A more commercial perspective is covered in the Teijin Armid Jan. 11, 2013 news release (Note: A link has been removed),

“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.