Tag Archives: Robert A. Welch Foundation

How small can a carbon nanotube get before it stops being ‘electrical’?

Research, which began as an attempt to get reproducible electronics (?) measurements, yielded some unexpected results according ta January 3, 2018 news item on phys.org,

Carbon nanotubes bound for electronics not only need to be as clean as possible to maximize their utility in next-generation nanoscale devices, but contact effects may limit how small a nano device can be, according to researchers at the Energy Safety Research Institute (ESRI) at Swansea University [UK] in collaboration with researchers at Rice University [US].

ESRI Director Andrew Barron, also a professor at Rice University in the USA, and his team have figured out how to get nanotubes clean enough to obtain reproducible electronic measurements and in the process not only explained why the electrical properties of nanotubes have historically been so difficult to measure consistently, but have shown that there may be a limit to how “nano” future electronic devices can be using carbon nanotubes.

Swansea University Issued a January 3, 2018 press release (also on EurekAlert), which originated the news item, explains the work in more detail,

Like any normal wire, semiconducting nanotubes are progressively more resistant to current along their length. But conductivity measurements of nanotubes over the years have been anything but consistent. The ESRI team wanted to know why.

“We are interested in the creation of nanotube based conductors, and while people have been able to make wires their conduction has not met expectations. We were interested in determining the basic sconce behind the variability observed by other researchers.”

They discovered that hard-to-remove contaminants — leftover iron catalyst, carbon and water — could easily skew the results of conductivity tests. Burning them away, Barron said, creates new possibilities for carbon nanotubes in nanoscale electronics.

The new study appears in the American Chemical Society journal Nano Letters.

The researchers first made multiwalled carbon nanotubes between 40 and 200 nanometers in diameter and up to 30 microns long. They then either heated the nanotubes in a vacuum or bombarded them with argon ions to clean their surfaces.

They tested individual nanotubes the same way one would test any electrical conductor: By touching them with two probes to see how much current passes through the material from one tip to the other. In this case, their tungsten probes were attached to a scanning tunneling microscope.

In clean nanotubes, resistance got progressively stronger as the distance increased, as it should. But the results were skewed when the probes encountered surface contaminants, which increased the electric field strength at the tip. And when measurements were taken within 4 microns of each other, regions of depleted conductivity caused by contaminants overlapped, further scrambling the results.

“We think this is why there’s such inconsistency in the literature,” Barron said.

“If nanotubes are to be the next generation lightweight conductor, then consistent results, batch-to-batch, and sample-to-sample, is needed for devices such as motors and generators as well as power systems.”

Annealing the nanotubes in a vacuum above 200 degrees Celsius (392 degrees Fahrenheit) reduced surface contamination, but not enough to eliminate inconsistent results, they found. Argon ion bombardment also cleaned the tubes, but led to an increase in defects that degrade conductivity.

Ultimately they discovered vacuum annealing nanotubes at 500 degrees Celsius (932 Fahrenheit) reduced contamination enough to accurately measure resistance, they reported.

To now, Barron said, engineers who use nanotube fibers or films in devices modify the material through doping or other means to get the conductive properties they require. But if the source nanotubes are sufficiently decontaminated, they should be able to get the right conductivity by simply putting their contacts in the right spot.

“A key result of our work was that if contacts on a nanotube are less than 1 micron apart, the electronic properties of the nanotube changes from conductor to semiconductor, due to the presence of overlapping depletion zones” said Barron, “this has a potential limiting factor on the size of nanotube based electronic devices – this would limit the application of Moore’s law to nanotube devices.”

Chris Barnett of Swansea is lead author of the paper. Co-authors are Cathren Gowenlock and Kathryn Welsby, and Rice alumnus Alvin Orbaek White of Swansea. Barron is the Sêr Cymru Chair of Low Carbon Energy and Environment at Swansea and the Charles W. Duncan Jr.–Welch Professor of Chemistry and a professor of materials science and nanoengineering at Rice.

The Welsh Government Sêr Cymru National Research Network in Advanced Engineering and Materials, the Sêr Cymru Chair Program, the Office of Naval Research and the Robert A. Welch Foundation supported the research.

Rice University has published a January 4, 2018 Rice University news release (also on EurekAlert), which is almost (95%) identical to the press release from Swansea. That’s a bit unusual as collaborating institutions usually like to focus on their unique contributions to the research, hence, multiple news/press releases.

Dexter Johnson, in a January 11, 2018 post on his Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers] website,  adds a detail or two while writing in an accessible style.

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

Spatial and Contamination-Dependent Electrical Properties of Carbon Nanotubes by Chris J. Barnett, Cathren E. Gowenlock, Kathryn Welsby, Alvin Orbaek White, and Andrew R. Barron. Nano Lett., Article ASAP DOI: 10.1021/acs.nanolett.7b03390 Publication Date (Web): December 19, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.

Carbon nanotubes for enhanced wheat growth?

It’s been a long time (Oct. 22, 2009 posting; scroll down about 20% of the way) since I’ve written about carbon nanotubes and their possible use in agriculture but now a December 6, 2017 news item on ScienceDaily raises the topic again,

The introduction of purified carbon nanotubes appears to have a beneficial effect on the early growth of wheatgrass, according to Rice University scientists. But in the presence of contaminants, those same nanotubes could do great harm.

The Rice lab of chemist Andrew Barron grew wheatgrass in a hydroponic garden to test the potential toxicity of nanoparticles on the plant. To their surprise, they found one type of particle dispersed in water helped the plant grow bigger and faster.

They suspect the results spring from nanotubes’ natural hydrophobic (water-avoiding) nature that in one experiment apparently facilitated the plants’ enhanced uptake of water.

The research appears in the Royal Society of Chemistry journal Environmental Science: Nano.

A December 6, 2017 Rice University news release (also on EurekAlert), which originated the news item, expands on the theme,

The lab mounted the small-scale study with the knowledge that the industrial production of nanotubes will inevitably lead to their wider dispersal in the environment. The study cited rapid growth in the market for nanoparticles in drugs, cosmetic, fabrics, water filters and military weapons, with thousands of tons produced annually.

Despite their widespread use, Barron said few researchers have looked at the impact of environmental nanoparticles — whether natural or man-made — on plant growth.

The researchers planted wheatgrass seeds in multiple replicates in cotton wool and fed them with dispersions that contained raw single-walled or multi-walled nanotubes, purified single-walled nanotubes or iron oxide nanoparticles that mimicked leftover catalyst often attached to nanotubes. The solutions were either water or tetrahydrofuran (THF), an industrial solvent. Some of the seeds were fed pure water or THF as a control.

Rice University researchers tested the effects of carbon nanotubes on the growth of wheatgrass. While some showed no effect, purified single-walled nanotubes in water (5) enhanced the plants' growth, while the same nanotubes in a solvent (6) retarded their development. The photos at left show the plants after four days and at right after eight days, with odd-numbered plants growing in water and evens in a solvent. Numbers 1 and 2 are controls without nanotubes; 3-4 contain raw single-walled tubes; 5-6 purified single-walled tubes; 7-8 raw multi-walled tubes; 9-10 low-concentration iron-oxide nanoparticles and 11-12 high-concentration iron-oxide nanoparticles.

Rice University researchers tested the effects of carbon nanotubes on the growth of wheatgrass. While some showed no effect, purified single-walled nanotubes in water (5) enhanced the plants’ growth, while the same nanotubes in a solvent (6) retarded their development. The photos at left show the plants after four days and at right after eight days, with odd-numbered plants growing in water and evens in a solvent. Numbers 1 and 2 are controls without nanotubes; 3-4 contain raw single-walled tubes; 5-6 purified single-walled tubes; 7-8 raw multi-walled tubes; 9-10 low-concentration iron-oxide nanoparticles and 11-12 high-concentration iron-oxide nanoparticles. Click on the image for a larger version. Photos by Seung Mook Lee

After eight days, the plantings showed that purified single-walled nanotubes in water enhanced the germination rate and shoot growth of wheatgrass, which grew an average of 13 percent larger than plants in plain water. Raw single- and multi-walled nanotubes and particles in either solution had little effect on the plants’ growth, they found.

However, purified single-walled nanotubes in THF retarded plant development by 45 percent compared to single-walled nanotubes in water, suggesting the nanotubes act as a carrier for the toxic substance.

The concern, Barron said, is that if single-walled nanotubes combine with organic pollutants like pesticides, industrial chemicals or solvents in the environment, they may concentrate and immobilize the toxins and enhance their uptake by plants.

Nothing seen in the limited study indicated whether carbon nanotubes in the environment, and potentially in plants, will rise up the food chain and be harmful to humans, he said.

On the other hand, the researchers said it may be worth looking at whether hydrophobic substrates that mimic the positive effects observed in single-walled nanotubes could be used for high-efficiency channeling of water to seeds.

“Our work confirms the importance of thinking of nanomaterials as part of a system rather in isolation,” Barron said. “It is the combination with other compounds that is important to understand.”

Seung Mook Lee, a former visiting student research assistant from Memorial High School in Houston and now an undergraduate student at the University of California, Berkeley, is lead author of the paper. Co-authors are Rice research scientist Pavan Raja and graduate student Gibran Esquenazi. Barron is the Charles W. Duncan Jr.–Welch Professor of Chemistry and a professor of materials science and nanoengineering at Rice and the Sêr Cymru Chair of Low Carbon Energy and Environment at Swansea University, Wales (UK).

The Welsh Government Sêr Cymru Program and the Robert A. Welch Foundation supported the research.

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

Effect of raw and purified carbon nanotubes and iron oxide nanoparticles on the growth of wheatgrass prepared from the cotyledons of common wheat (triticum aestivum) by Seung Mook Lee, Pavan M. V. Raja, Gibran L. Esquenazi, and Andrew R. Barron. Environ. Sci.: Nano, 2018, Advance Article DOI: 10.1039/C7EN00680B First published on 09 Nov 2017

This paper appears to be behind a paywall.

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.