Tag Archives: CNTs

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.

Making spider silk stronger by feeding graphene and carbon nanotubes to spiders

Spider silk is already considered a strong and tough material but now scientists have found a way to enhance those properties. From an August 15, 2017 Institute of Physics Publishing press release (also on EurekAlert),

…  researchers in Italy and the UK have found a way to make Spidey’s silk a lot stronger, using various different spider species and carbon nanotubes or graphene.

The research team, led by Professor Nicola Pugno at the University of Trento, Italy, succeeded in having their spiders produce silk with up to three times the strength and ten times the toughness of the regular material.

Their discovery, published today in the journal 2D Materials, could pave the way for a new class of bionicomposites, with a wide variety of uses.

Professor Pugno said: “Humans have used silkworm silks widely for thousands of years, but recently research has focussed on spider silk, as it has extremely promising mechanical properties. It is among the best spun polymer fibres in terms of tensile strength, ultimate strain, and especially toughness, even when compared to synthetic fibres such as Kevlar.

“We already know that there are biominerals present in in the protein matrices and hard tissues of insects, which gives them high strength and hardness in their jaws, mandibles and teeth, for example. So our study looked at whether spider silk’s properties could be ‘enhanced’ by artificially incorporating various different nanomaterials into the silk’s biological protein structures.”

To do this, the team exposed three different spider species to water dispersions containing carbon nanotubes or graphene.

After collecting the spiders’ silk, the team tested its tensile strength and toughness.

Professor Pugno said: “We found that the strongest silk the spiders spun had a fracture strength up to 5.4 gigapascals (GPa), and a toughness modulus up to 1,570 joules per gram (J/g). Normal spider silk, by comparison, has a fracture strength of around 1.5 GPa and a toughness modulus of around 150 J/g.

“This is the highest fibre toughness discovered to date, and a strength comparable to that of the strongest carbon fibres or limpet teeth. These are still early days, but our results are a proof of concept that paves the way to exploiting the naturally efficient spider spinning process to produce reinforced bionic silk fibres, thus further improving one of the most promising strong materials.

“These silks’ high toughness and resistance to ultimate strain could have applications such as parachutes.”

“Furthermore, this process of the natural integration of reinforcements in biological structural materials could also be applied to other animals and plants, leading to a new class of “bionicomposites” for innovative applications.”

Remember this? “You are what you eat.” If you’ve ever had doubts about that saying, these spiders should be laying them to rest.

Sadly, this news release doesn’t explain much about the decision to feed the spiders graphene or carbon nanotubes, which are identical other than in their respective shapes (sheet vs tube)  and whether those shapes did or did not affect the strength of the silk.

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

Spider silk reinforced by graphene or carbon nanotubes by Emiliano Lepore, Federico Bosia, Francesco Bonaccorso, Matteo Bruna, Simone Taioli, Giovanni Garberoglio, Andrea C Ferrari, and Nicola Maria Pugno. 2D Materials, Volume 4, Number 3 DOI: https://doi.org/10.1088/2053-1583/aa7cd3 Published 14 August 2017

© 2017 IOP Publishing Ltd

This paper is behind a paywall.

Pugno was most recently mentioned here in a May 29, 2015 posting where he was listed as an author for a paper on synthesizing spider silk. Prior to 2015 I was familiar with Pugno’s name due to his work on adhesiveness in geckos.

Carbon nanotubes to repair nerve fibres (cyborg brains?)

Can cyborg brains be far behind now that researchers are looking at ways to repair nerve fibers with carbon nanotubes (CNTs)? A June 26, 2017 news item on ScienceDaily describes the scheme using carbon nanotubes as a material for repairing nerve fibers,

Carbon nanotubes exhibit interesting characteristics rendering them particularly suited to the construction of special hybrid devices — consisting of biological issue and synthetic material — planned to re-establish connections between nerve cells, for instance at spinal level, lost on account of lesions or trauma. This is the result of a piece of research published on the scientific journal Nanomedicine: Nanotechnology, Biology, and Medicine conducted by a multi-disciplinary team comprising SISSA (International School for Advanced Studies), the University of Trieste, ELETTRA Sincrotrone and two Spanish institutions, Basque Foundation for Science and CIC BiomaGUNE. More specifically, researchers have investigated the possible effects on neurons of the interaction with carbon nanotubes. Scientists have proven that these nanomaterials may regulate the formation of synapses, specialized structures through which the nerve cells communicate, and modulate biological mechanisms, such as the growth of neurons, as part of a self-regulating process. This result, which shows the extent to which the integration between nerve cells and these synthetic structures is stable and efficient, highlights the great potentialities of carbon nanotubes as innovative materials capable of facilitating neuronal regeneration or in order to create a kind of artificial bridge between groups of neurons whose connection has been interrupted. In vivo testing has actually already begun.

The researchers have included a gorgeous image to illustrate their work,

Caption: Scientists have proven that these nanomaterials may regulate the formation of synapses, specialized structures through which the nerve cells communicate, and modulate biological mechanisms, such as the growth of neurons, as part of a self-regulating process. Credit: Pixabay

A June 26, 2017 SISSA press release (also on EurekAlert), which originated the news item, describes the work in more detail while explaining future research needs,

“Interface systems, or, more in general, neuronal prostheses, that enable an effective re-establishment of these connections are under active investigation” explain Laura Ballerini (SISSA) and Maurizio Prato (UniTS-CIC BiomaGUNE), coordinating the research project. “The perfect material to build these neural interfaces does not exist, yet the carbon nanotubes we are working on have already proved to have great potentialities. After all, nanomaterials currently represent our best hope for developing innovative strategies in the treatment of spinal cord injuries”. These nanomaterials are used both as scaffolds, a supportive framework for nerve cells, and as means of interfaces releasing those signals that empower nerve cells to communicate with each other.

Many aspects, however, still need to be addressed. Among them, the impact on neuronal physiology of the integration of these nanometric structures with the cell membrane. “Studying the interaction between these two elements is crucial, as it might also lead to some undesired effects, which we ought to exclude”. Laura Ballerini explains: “If, for example, the mere contact provoked a vertiginous rise in the number of synapses, these materials would be essentially unusable”. “This”, Maurizio Prato adds, “is precisely what we have investigated in this study where we used pure carbon nanotubes”.

The results of the research are extremely encouraging: “First of all we have proved that nanotubes do not interfere with the composition of lipids, of cholesterol in particular, which make up the cellular membrane in neurons. Membrane lipids play a very important role in the transmission of signals through the synapses. Nanotubes do not seem to influence this process, which is very important”.

There is more, however. The research has also highlighted the fact that the nerve cells growing on the substratum of nanotubes, thanks to this interaction, develop and reach maturity very quickly, eventually reaching a condition of biological homeostasis. “Nanotubes facilitate the full growth of neurons and the formation of new synapses. This growth, however, is not indiscriminate and unlimited since, as we proved, after a few weeks a physiological balance is attained. Having established the fact that this interaction is stable and efficient is an aspect of fundamental importance”. Maurizio Prato and Laura Ballerini conclude as follows: “We are proving that carbon nanotubes perform excellently in terms of duration, adaptability and mechanical compatibility with the tissue. Now we know that their interaction with the biological material, too, is efficient. Based on this evidence, we are already studying the in vivo application, and preliminary results appear to be quite promising also in terms of recovery of the lost neurological functions”.

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

Sculpting neurotransmission during synaptic development by 2D nanostructured interfaces by Niccolò Paolo Pampaloni, Denis Scaini, Fabio Perissinotto, Susanna Bosi, Maurizio Prato, Laura Ballerini. Nanomedicine: Nanotechnology, Biology and Medicine, DOI: http://dx.doi.org/10.1016/j.nano.2017.01.020 Published online: May 25, 2017

This paper is open access.

Sustainable water desalination with self-cleaning membranes

This desalination technology comes from the United Arab Emirates (UAE). from an April 13, 2017 news item on Nanowerk,

An advanced water treatment membrane made of electrically conductive nanofibers developed at Masdar Institute was highlighted by Dr. Raed Hashaikeh, Professor of Mechanical and Materials Engineering at Masdar Institute, in his keynote speech during the 3rd International Conference on Desalination using Membrane Technology held last week in Spain.

An April 13, 2017 Masdar Institute press release by Erica Solomon, which originated the news item, expands on the theme,

Self-cleaning membranes offer a critically needed solution to the problem of fouling, which is the unwanted build-up of organic and inorganic deposits on a membrane’s surface that reduces the membrane’s ability to filter impurities. Water treatment and purification membranes that can easily clean themselves when fouled could make pressure-driven membrane filtration systems used to treat and desalinate water more energy-efficient.

“Keeping membranes clean, permeable and functional is a great challenge to membrane desalination technologies. When a membrane becomes fouled, its pores get blocked and its flux is severely reduced, which means that much less water can pass through the membrane at a constant pressure,” Dr. Hashaikeh explained.

Conventional methods for cleaning fouled membranes involve expensive and harsh chemical treatments, and often lead to water treatment plant shut-downs, which can cost millions of dollars in lost operational hours. In the UAE, annual spending on desalination is already estimated to cost AED12 billion, indicating a pressing need for solutions that avoid costly shut-downs and treatments.

In addition to posing a heavy financial burden, fouled membranes are also a sustainability issue, as once a membrane becomes fouled, the higher pressure needed to push water through clogged pores significantly increases the plant’s energy consumption. The harsh chemicals used to clean a fouled membrane are also bad for the environment and require neutralizing. Thus, finding a way to easily and quickly clean fouled membranes not only makes financial sense, but environmental sense.

In a country like the UAE, where natural gas-powered thermal desalination produces over 80% of the country’s domestic water, innovative technologies like self-cleaning membranes to support a shift toward lower-energy and lower-cost membrane-based desalination are essential for achieving economic and environmental balance while meeting the UAE’s water demands.

And now, Dr. Hashaikeh’s research group may have brought the UAE closer towards realizing a more sustainable and economic approach to membrane desalination through their research on the application of advanced nanofibers for enhanced, self-cleaning membranes.

The group has leveraged the electrically conductive nature of a special kind of nanofiber, called carbon nanotubes (CNT). CNTs are tiny cylindrical tubes made of tightly bonded carbon atoms, measuring just one atom thick. But the CNTs Dr. Hashaikeh’s team used, which were provided by global security, aerospace, and information technology company Lockheed Martin, are not ordinary CNTs.

“The carbon nanostructures supplied by Lockheed Martin are special; they are networked. This means that they are composed of many interconnecting channels that branch off in all directions. This interconnectivity is what enables the entire membrane to become completely cleaned when electricity is applied to it,” Dr. Hashaikeh said.

The networked CNTs, also known as carbon nanostructures (CNS), coupled with the team’s expert membrane fabrication know-how, resulted in the development of two different types of membranes that can clean themselves when a low-voltage electric current is run through them.

The first type is a microfiltration membrane, which has pores sizes ranging from 100 nanometers to 10 micrometers, where a nanometer is approximately one hundred thousand times smaller than the width of a human hair and a micrometer one thousand times larger than a nanometer. The second is a nanofiltration membrane with pore sizes ranging from one to ten nanometers. Both membranes demonstrated the ability to clean themselves in response to an electric shock, which resulted in the immediate restoration of the membranes’ flux.

Dr. Hashaikeh’s investigation of a self-cleaning membrane began four years ago, when he realized that electrolytic cleaning – which is the process of removing soil, scale or corrosion from a metal’s surface by subjecting it to an electric current – could also be used to clean membranes. To prove his theory, he coated a membrane with ordinary CNTs. When a voltage was applied to the membrane, the parts of the membranes that were coated with CNTs were successfully cleaned. Dr. Hashaikeh filed a patent for this in-situ electrolytic cleaning process with the United States Patent and Trademark Office (USPTO) in 2014.

However, there were limitations to this discovery, namely that only specific areas in the coated CNTs were cleaned, not the entire membrane. Thus, to develop an efficient, self-cleaning membrane with commercial potential, Dr. Hashaikeh required a material that would easily allow electric shockwaves to penetrate through the entire membrane’s surface area.

The unique, interconnected structure of Lockheed Martin’s carbon nanostructures proved to be just the right type of electrically conductive, nano-fibrous material required.

“We immediately recognized that Lockheed Martin’s CNTs might enable electricity to pass through the entire surface, but we had to modify the nanostructures to transform the material into a membrane. To do this, we controlled certain properties, such as wettability and pore size, and improved its mechanical strength by incorporating polymer materials,” he explained.

Dr. Haishaikeh’s team successfully developed a self-cleaning microfiltration membrane in 2014 and a paper describing the research was published in the Journal of Membrane Science. But they did not stop there; they wanted to take their research a step further and find a way to develop a self-cleaning nanofiltration membrane. While microfiltration membranes are useful for removing larger particles, including sand, silt, clays, algae and some forms of bacteria, nanofiltration membranes can go a step further, removing most organic molecules, nearly all viruses, most of the natural organic matter and a range of salts. Nanofiltration membranes also remove divalent ions, which make water hard, making nanofiltration a popular and eco-friendly option to soften hard water.

To create self-cleaning nanofiltration membranes out of Lockheed Martin’s networked CNTs, the team needed to overcome the problem of the CNTs’ large pore sizes, which prevented the material from functioning as a nanofiltration membrane.

To achieve this they looked to a second advanced nanofiber material previously developed by Dr. Hashaikeh’s research group, known as networked cellulose. Networked cellulose is a modified type of cellulose made from wood pulp. When dried, the networked cellulose gel shrinks in volume, but maintains its integrity and shape, becoming harder as it shrinks. The research team asserted that the networked cellulose gel could reduce the membrane’s pore sizes while maintaining its structural integrity.

The researchers then mixed the carbon nanostructures with the networked cellulose gel and as the mixture dried, the networked cellulose shrank. The shrinking of the network cellulose in turn pressurized the nanostructures in the membrane. The resulting membrane is strong with much smaller pore sizes. Dr. Hashaikeh reports that the pore size dropped from 60 nanometers to just three nanometers with the addition of the networked cellulose in a paper describing the study, which was published in the journal Desalination last month. Co-authors from Masdar Institute include PhD student Farah Ahmad and postdoctoral researcher Boor Lalia, along with Dr. Nidal Hilal of Swansea University.

Dr. Hashaikeh’s prolific scientific contribution to the field of membrane desalination has led to his recent appointment as an associate editor for the journal Desalination; a position that is essential to the quality of the international journal and its peer review process.

The innovative research conducted by Dr. Hashaikeh and the team will help position Abu Dhabi as a leader in membrane desalination research and technology development. This project has already yielded a patent filing, and is hoped to provide the emirate with novel intellectual property in the critical industry of desalination.

Here are the links and citations for the 2014 and 2017 papers,

A novel in situ membrane cleaning method using periodic electrolysis by Raed Hashaikeh, Boor Singh Lalia, Victor Kochkodan, Nidal Hilal. Journal of Membrane Science Volume 471, 1 December 2014, Pages 149–154 https://doi.org/10.1016/j.memsci.2014.08.017

Electrically conducting nanofiltration membranes based on networked cellulose and carbon nanostructures by Farah Ejaz Ahmed, Boor Singh Lalia, Nidal Hilal, Raed Hashaikeh. Desalination Volume 406, 16 March 2017, Pages 60–66 https://doi.org/10.1016/j.desal.2016.09.005

Both papers a behind a paywall.

Carbon nanotubes self-assembling into transistors on a gold substrate

I’m not sure this work is ready for commercialization (I think not) but it’s certainly intriguing. From an April 5, 2017 news item on ScienceDaily,

Carbon nanotubes can be used to make very small electronic devices, but they are difficult to handle. University of Groningen scientists, together with colleagues from the University of Wuppertal and IBM Zurich, have developed a method to select semiconducting nanotubes from a solution and make them self-assemble on a circuit of gold electrodes. …

An April 5, 2017 University of Groningen (Netherlands) press release on EurekAlert, which originated the news item, explains the work in more detail,

The results look deceptively simple: a self-assembled transistor with nearly 100 percent purity and very high electron mobility. But it took ten years to get there. University of Groningen Professor of Photophysics and Optoelectronics Maria Antonietta Loi designed polymers which wrap themselves around specific carbon nanotubes in a solution of mixed tubes. Thiol side chains on the polymer bind the tubes to the gold electrodes, creating the resultant transistor.

Patent

‘In our previous work, we learned a lot about how polymers attach to specific carbon nanotubes’, Loi explains. These nanotubes can be depicted as a rolled sheet of graphene, the two-dimensional form of carbon. ‘Depending on the way the sheets are rolled up, they have properties ranging from semiconductor to semi-metallic to metallic.’ Only the semiconductor tubes can be used to fabricate transistors, but the production process always results in a mixture.

‘We had the idea of using polymers with thiol side chains some time ago’, says Loi. The idea was that as sulphur binds to metals, it will direct polymer-wrapped nanotubes towards gold electrodes. While Loi was working on the problem, IBM even patented the concept. ‘But there was a big problem in the IBM work: the polymers with thiols also attached to metallic nanotubes and included them in the transistors, which ruined them.’

Solution

Loi’s solution was to reduce the thiol content of the polymers, with the assistance of polymer chemists from the University of Wuppertal. ‘What we have now shown is that this concept of bottom-up assembly works: by using polymers with a low concentration of thiols, we can selectively bring semiconducting nanotubes from a solution onto a circuit.’ The sulphur-gold bond is strong, so the nanotubes are firmly fixed: enough even to stay there after sonication of the transistor in organic solvents.

The production process is simple: metallic patterns are deposited on a carrier , which is then dipped into a solution of carbon nanotubes. The electrodes are spaced to achieve proper alignment: ‘The tubes are some 500 nanometres long, and we placed the electrodes for the transistors at intervals of 300 nanometres. The next transistor is over 500 nanometres away.’ The spacing limits the density of the transistors, but Loi is confident that this could be increased with clever engineering.

‘Over the last years, we have created a library of polymers that select semiconducting nanotubes and developed a better understanding of how the structure and composition of the polymers influences which carbon nanotubes they select’, says Loi. The result is a cheap and scalable production method for nanotube electronics. So what is the future for this technology? Loi: ‘It is difficult to predict whether the industry will develop this idea, but we are working on improvements, and this will eventually bring the idea closer to the market.’

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

On-Chip Chemical Self-Assembly of Semiconducting Single-Walled Carbon Nanotubes (SWNTs): Toward Robust and Scale Invariant SWNTs Transistors by Vladimir Derenskyi, Widianta Gomulya, Wytse Talsma, Jorge Mario Salazar-Rios, Martin Fritsch, Peter Nirmalraj, Heike Riel, Sybille Allard, Ullrich Scherf, and Maria A. Loi. Advanced Materials DOI: 10.1002/adma.201606757 Version of Record online: 5 APR 2017

© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Understanding how carbon nanotubes grow and self-organize is key to better production

This research may help to commercialize use of carbon nanotubes (CNTs), a  ‘magical’ nanoscale material with great promise and great difficulties (standardizing production being one of the main difficulties). A Feb. 10, 2017 news item on phys.org describes how researchers at the Lawrence Livermore National Laboratory (LLNL) and other collaborators have recorded carbon nanotubes self-organizing,

For the first time, Lawrence Livermore National Laboratory scientists and collaborators have captured a movie of how large populations of carbon nanotubes grow and align themselves.

Understanding how carbon nanotubes (CNT) nucleate, grow and self-organize to form macroscale materials is critical for application-oriented design of next-generation supercapacitors, electronic interconnects, separation membranes and advanced yarns and fabrics.

A Feb. 9, 2017 LLNL news release, which originated the news item, provides more information about the research (Note: Links have been removed),

New research by LLNL scientist Eric Meshot and colleagues from Brookhaven National Laboratory (link is external) (BNL) and Massachusetts Institute of Technology (link is external) (MIT) has demonstrated direct visualization of collective nucleation and self-organization of aligned carbon nanotube films inside of an environmental transmission electron microscope (ETEM).

In a pair of studies reported in recent issues of Chemistry of Materials (link is external) and ACS Nano (link is external), the researchers leveraged a state-of-the-art kilohertz camera in an aberration-correction ETEM at BNL to capture the inherently rapid processes that govern the growth of these exciting nanostructures.

Among other phenomena discovered, the researchers are the first to provide direct proof of how mechanical competition among neighboring carbon nanotubes can simultaneously promote self-alignment while also frustrating and limiting growth.

“This knowledge may enable new pathways toward mitigating self-termination and promoting growth of ultra-dense and aligned carbon nanotube materials, which would directly impact several application spaces, some of which are being pursued here at the Laboratory,” Meshot said.

Meshot has led the CNT synthesis development at LLNL for several projects, including those supported by the Laboratory Directed Research and Development (LDRD) program and the Defense Threat Reduction Agency (link is external) (DTRA) that use CNTs as fluidic nanochannels for applications ranging from single-molecule detection to macroscale membranes for breathable and protective garments.

Here’s a link to and a citation for the both of the papers mentioned in the news release,

Measurement of the Dewetting, Nucleation, and Deactivation Kinetics of Carbon Nanotube Population Growth by Environmental Transmission Electron Microscopy by Mostafa Bedewy, B. Viswanath, Eric R. Meshot, Dmitri N. Zakharov, Eric A. Stach, and A. John Hart. Chem. Mater., 2016, 28 (11), pp 3804–3813 DOI: 10.1021/acs.chemmater.6b00798 Publication Date (Web): May 23, 2016

Copyright © 2016 American Chemical Society

Real-Time Imaging of Self-Organization and Mechanical Competition in Carbon Nanotube Forest Growth by Viswanath Balakrishnan, Mostafa Bedewy, Eric R. Meshot, Sebastian W. Pattinson, Erik S. Polsen, Fabrice Laye, Dmitri N. Zakharov, Eric A. Stach, and A. John Hart. ACS Nano, 2016, 10 (12), pp 11496–11504 DOI: 10.1021/acsnano.6b07251 Publication Date (Web): November 23, 2016

Copyright © 2016 American Chemical Society

Both papers are behind a paywall.

The researchers have also provided this image which allows you to appreciate the difference between a ‘scientific’ version of the work and an artistic version,

This transmission electron microscope image shows growth of a dense carbon nanotube population. Courtesy: LLNL

Drive to operationalize transistors that outperform silicon gets a boost

Dexter Johnson has written a Jan. 19, 2017 posting on his Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers]) about work which could lead to supplanting silicon-based transistors with carbon nanotube-based transistors in the future (Note: Links have been removed),

The end appears nigh for scaling down silicon-based complimentary metal-oxide semiconductor (CMOS) transistors, with some experts seeing the cutoff date as early as 2020.

While carbon nanotubes (CNTs) have long been among the nanomaterials investigated to serve as replacement for silicon in CMOS field-effect transistors (FETs) in a post-silicon future, they have always been bogged down by some frustrating technical problems. But, with some of the main technical showstoppers having been largely addressed—like sorting between metallic and semiconducting carbon nanotubes—the stage has been set for CNTs to start making their presence felt a bit more urgently in the chip industry.

Peking University scientists in China have now developed carbon nanotube field-effect transistors (CNT FETs) having a critical dimension—the gate length—of just five nanometers that would outperform silicon-based CMOS FETs at the same scale. The researchers claim in the journal Science that this marks the first time that sub-10 nanometer CNT CMOS FETs have been reported.

More importantly than just being the first, the Peking group showed that their CNT-based FETs can operate faster and at a lower supply voltage than their silicon-based counterparts.

A Jan. 20, 2017 article by Bob Yirka for phys.org provides more insight into the work at Peking University,

One of the most promising candidates is carbon nanotubes—due to their unique properties, transistors based on them could be smaller, faster and more efficient. Unfortunately, the difficulty in growing carbon nanotubes and their sometimes persnickety nature means that a way to make them and mass produce them has not been found. In this new effort, the researchers report on a method of creating carbon nanotube transistors that are suitable for testing, but not mass production.

To create the transistors, the researchers took a novel approach—instead of growing carbon nanotubes that had certain desired properties, they grew some and put them randomly on a silicon surface and then added electronics that would work with the properties they had—clearly not a strategy that would work for mass production, but one that allowed for building a carbon nanotube transistor that could be tested to see if it would verify theories about its performance. Realizing there would still be scaling problems using traditional electrodes, the researchers built a new kind by etching very tiny sheets of graphene. The result was a very tiny transistor, the team reports, capable of moving more current than a standard CMOS transistor using just half of the normal amount of voltage. It was also faster due to a much shorter switch delay, courtesy of a gate capacitance of just 70 femtoseconds.

Peking University has published an edited and more comprehensive version of the phys.org article first reported by Lisa Zyga and edited by Arthars,

Now in a new paper published in Nano Letters, researchers Tian Pei, et al., at Peking University in Beijing, China, have developed a modular method for constructing complicated integrated circuits (ICs) made from many FETs on individual CNTs. To demonstrate, they constructed an 8-bits BUS system–a circuit that is widely used for transferring data in computers–that contains 46 FETs on six CNTs. This is the most complicated CNT IC fabricated to date, and the fabrication process is expected to lead to even more complex circuits.

SEM image of an eight-transistor (8-T) unit that was fabricated on two CNTs (marked with two white dotted lines). The scale bar is 100 μm. (Copyright: 2014 American Chemical Society)

Ever since the first CNT FET was fabricated in 1998, researchers have been working to improve CNT-based electronics. As the scientists explain in their paper, semiconducting CNTs are promising candidates for replacing silicon wires because they are thinner, which offers better scaling-down potential, and also because they have a higher carrier mobility, resulting in higher operating speeds.

Yet CNT-based electronics still face challenges. One of the most significant challenges is obtaining arrays of semiconducting CNTs while removing the less-suitable metallic CNTs. Although scientists have devised a variety of ways to separate semiconducting and metallic CNTs, these methods almost always result in damaged semiconducting CNTs with degraded performance.

To get around this problem, researchers usually build ICs on single CNTs, which can be individually selected based on their condition. It’s difficult to use more than one CNT because no two are alike: they each have slightly different diameters and properties that affect performance. However, using just one CNT limits the complexity of these devices to simple logic and arithmetical gates.

The 8-T unit can be used as the basic building block of a variety of ICs other than BUS systems, making this modular method a universal and efficient way to construct large-scale CNT ICs. Building on their previous research, the scientists hope to explore these possibilities in the future.

“In our earlier work, we showed that a carbon nanotube based field-effect transistor is about five (n-type FET) to ten (p-type FET) times faster than its silicon counterparts, but uses much less energy, about a few percent of that of similar sized silicon transistors,” Peng said.

“In the future, we plan to construct large-scale integrated circuits that outperform silicon-based systems. These circuits are faster, smaller, and consume much less power. They can also work at extremely low temperatures (e.g., in space) and moderately high temperatures (potentially no cooling system required), on flexible and transparent substrates, and potentially be bio-compatible.”

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

Scaling carbon nanotube complementary transistors to 5-nm gate lengths by Chenguang Qiu, Zhiyong Zhang, Mengmeng Xiao, Yingjun Yang, Donglai Zhong, Lian-Mao Peng. Science  20 Jan 2017: Vol. 355, Issue 6322, pp. 271-276 DOI: 10.1126/science.aaj1628

This paper is behind a paywall.

Sniffing out disease (Na-Nose)

The ‘artificial nose’ is not a newcomer to this blog. The most recent post prior to this is a March 15, 2016 piece about Disney using an artificial nose for art conservation. Today’s (Jan. 9, 2016) piece concerns itself with work from Israel and ‘sniffing out’ disease, according to a Dec. 30, 2016 news item in Sputnik News,

A team from the Israel Institute of Technology has developed a device that from a single breath can identify diseases such as multiple forms of cancer, Parkinson’s disease, and multiple sclerosis. While the machine is still in the experimental stages, it has a high degree of promise for use in non-invasive diagnoses of serious illnesses.

The international team demonstrated that a medical theory first proposed by the Greek physician Hippocrates some 2400 years ago is true, certain diseases leave a “breathprint” on the exhalations of those afflicted. The researchers created a prototype for a machine that can pick up on those diseases using the outgoing breath of a patient. The machine, called the Na-Nose, tests breath samples for the presence of trace amounts of chemicals that are indicative of 17 different illnesses.

A Dec. 22, 2016 Technion Israel Institute of Technology press release offers more detail about the work,

An international team of 56 researchers in five countries has confirmed a hypothesis first proposed by the ancient Greeks – that different diseases are characterized by different “chemical signatures” identifiable in breath samples. …

Diagnostic techniques based on breath samples have been demonstrated in the past, but until now, there has not been scientific proof of the hypothesis that different and unrelated diseases are characterized by distinct chemical breath signatures. And technologies developed to date for this type of diagnosis have been limited to detecting a small number of clinical disorders, without differentiation between unrelated diseases.

The study of more than 1,400 patients included 17 different and unrelated diseases: lung cancer, colorectal cancer, head and neck cancer, ovarian cancer, bladder cancer, prostate cancer, kidney cancer, stomach cancer, Crohn’s disease, ulcerative colitis, irritable bowel syndrome, Parkinson’s disease (two types), multiple sclerosis, pulmonary hypertension, preeclampsia and chronic kidney disease. Samples were collected between January 2011 and June 2014 from in 14 departments at 9 medical centers in 5 countries: Israel, France, the USA, Latvia and China.

The researchers tested the chemical composition of the breath samples using an accepted analytical method (mass spectrometry), which enabled accurate quantitative detection of the chemical compounds they contained. 13 chemical components were identified, in different compositions, in all 17 of the diseases.

According to Prof. Haick, “each of these diseases is characterized by a unique fingerprint, meaning a different composition of these 13 chemical components.  Just as each of us has a unique fingerprint that distinguishes us from others, each disease has a chemical signature that distinguishes it from other diseases and from a normal state of health. These odor signatures are what enables us to identify the diseases using the technology that we developed.”

With a new technology called “artificially intelligent nanoarray,” developed by Prof. Haick, the researchers were able to corroborate the clinical efficacy of the diagnostic technology. The array enables fast and inexpensive diagnosis and classification of diseases, based on “smelling” the patient’s breath, and using artificial intelligence to analyze the data obtained from the sensors. Some of the sensors are based on layers of gold nanoscale particles and others contain a random network of carbon nanotubes coated with an organic layer for sensing and identification purposes.

The study also assessed the efficiency of the artificially intelligent nanoarray in detecting and classifying various diseases using breath signatures. To verify the reliability of the system, the team also examined the effect of various factors (such as gender, age, smoking habits and geographic location) on the sample composition, and found their effect to be negligible, and without impairment on the array’s sensitivity.

“Each of the sensors responds to a wide range of exhalation components,” explain Prof. Haick and his previous Ph.D student, Dr. Morad Nakhleh, “and integration of the information provides detailed data about the unique breath signatures characteristic of the various diseases. Our system has detected and classified various diseases with an average accuracy of 86%.

This is a new and promising direction for diagnosis and classification of diseases, which is characterized not only by considerable accuracy but also by low cost, low electricity consumption, miniaturization, comfort and the possibility of repeating the test easily.”

“Breath is an excellent raw material for diagnosis,” said Prof. Haick. “It is available without the need for invasive and unpleasant procedures, it’s not dangerous, and you can sample it again and again if necessary.”

Here’s a schematic of the study, which the researchers have made available,

Diagram: A schematic view of the study. Two breath samples were taken from each subject, one was sent for chemical mapping using mass spectrometry, and the other was analyzed in the new system, which produced a clinical diagnosis based on the chemical fingerprint of the breath sample. Courtesy: Tech;nion

There is also a video, which covers much of the same ground as the press release but also includes information about the possible use of the Na-Nose technology in the European Union’s SniffPhone project,

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

Diagnosis and Classification of 17 Diseases from 1404 Subjects via Pattern Analysis of Exhaled Molecules by Morad K. Nakhleh, Haitham Amal, Raneen Jeries, Yoav Y. Broza, Manal Aboud, Alaa Gharra, Hodaya Ivgi, Salam Khatib, Shifaa Badarneh, Lior Har-Shai, Lea Glass-Marmor, Izabella Lejbkowicz, Ariel Miller, Samih Badarny, Raz Winer, John Finberg, Sylvia Cohen-Kaminsky, Frédéric Perros, David Montani, Barbara Girerd, Gilles Garcia, Gérald Simonneau, Farid Nakhoul, Shira Baram, Raed Salim, Marwan Hakim, Maayan Gruber, Ohad Ronen, Tal Marshak, Ilana Doweck, Ofer Nativ, Zaher Bahouth, Da-you Shi, Wei Zhang, Qing-ling Hua, Yue-yin Pan, Li Tao, Hu Liu, Amir Karban, Eduard Koifman, Tova Rainis, Roberts Skapars, Armands Sivins, Guntis Ancans, Inta Liepniece-Karele, Ilze Kikuste, Ieva Lasina, Ivars Tolmanis, Douglas Johnson, Stuart Z. Millstone, Jennifer Fulton, John W. Wells, Larry H. Wilf, Marc Humbert, Marcis Leja, Nir Peled, and Hossam Haick. ACS Nano, Article ASAP DOI: 10.1021/acsnano.6b04930 Publication Date (Web): December 21, 2016

Copyright © 2017 American Chemical Society

This paper appears to be open access.

As for SniffPhone, they’re hoping that Na-Nose or something like it will allow them to modify smartphones in a way that will allow diseases to be detected.

I can’t help wondering who will own the data if your smartphone detects a disease. If you think that’s an idle question, here’s an excerpt from Sue Halpern’s Dec. 22, 2016 review of two books (“Weapons of Math Destruction: How Big Data Increases Inequality and Threatens Democracy” by Cathy O’Neil and “Virtual Competition: The Promise and Perils of the Algorithm-Driven Economy” by Ariel Ezrachi and Maurice E. Stucke) for the New York Times Review of Books,

We give our data away. We give it away in drips and drops, not thinking that data brokers will collect it and sell it, let alone that it will be used against us. There are now private, unregulated DNA databases culled, in part, from DNA samples people supply to genealogical websites in pursuit of their ancestry. These samples are available online to be compared with crime scene DNA without a warrant or court order. (Police are also amassing their own DNA databases by swabbing cheeks during routine stops.) In the estimation of the Electronic Frontier Foundation, this will make it more likely that people will be implicated in crimes they did not commit.

Or consider the data from fitness trackers, like Fitbit. As reported in The Intercept:

During a 2013 FTC panel on “Connected Health and Fitness,” University of Colorado law professor Scott Peppet said, “I can paint an incredibly detailed and rich picture of who you are based on your Fitbit data,” adding, “That data is so high quality that I can do things like price insurance premiums or I could probably evaluate your credit score incredibly accurately.”

Halpern’s piece is well worth reading in its entirety.

Spinach and plant nanobionics

Who knew that spinach leaves could be turned into electronic devices? The answer is: engineers at the Massachusetts Institute of Technology, according to an Oct. 31, 2016 news item on phys.org,

Spinach is no longer just a superfood: By embedding leaves with carbon nanotubes, MIT engineers have transformed spinach plants into sensors that can detect explosives and wirelessly relay that information to a handheld device similar to a smartphone.

This is one of the first demonstrations of engineering electronic systems into plants, an approach that the researchers call “plant nanobionics.”

An Oct. 31, 2016 MIT news release (also on EurekAlert), which originated the news item, describes the research further (Note: Links have been removed),

“The goal of plant nanobionics is to introduce nanoparticles into the plant to give it non-native functions,” says Michael Strano, the Carbon P. Dubbs Professor of Chemical Engineering at MIT and the leader of the research team.

In this case, the plants were designed to detect chemical compounds known as nitroaromatics, which are often used in landmines and other explosives. When one of these chemicals is present in the groundwater sampled naturally by the plant, carbon nanotubes embedded in the plant leaves emit a fluorescent signal that can be read with an infrared camera. The camera can be attached to a small computer similar to a smartphone, which then sends an email to the user.

“This is a novel demonstration of how we have overcome the plant/human communication barrier,” says Strano, who believes plant power could also be harnessed to warn of pollutants and environmental conditions such as drought.

Strano is the senior author of a paper describing the nanobionic plants in the Oct. 31 [2016] issue of Nature Materials. The paper’s lead authors are Min Hao Wong, an MIT graduate student who has started a company called Plantea to further develop this technology, and Juan Pablo Giraldo, a former MIT postdoc who is now an assistant professor at the University of California at Riverside.

Environmental monitoring

Two years ago, in the first demonstration of plant nanobionics, Strano and former MIT postdoc Juan Pablo Giraldo used nanoparticles to enhance plants’ photosynthesis ability and to turn them into sensors for nitric oxide, a pollutant produced by combustion.

Plants are ideally suited for monitoring the environment because they already take in a lot of information from their surroundings, Strano says.

“Plants are very good analytical chemists,” he says. “They have an extensive root network in the soil, are constantly sampling groundwater, and have a way to self-power the transport of that water up into the leaves.”

Strano’s lab has previously developed carbon nanotubes that can be used as sensors to detect a wide range of molecules, including hydrogen peroxide, the explosive TNT, and the nerve gas sarin. When the target molecule binds to a polymer wrapped around the nanotube, it alters the tube’s fluorescence.

In the new study, the researchers embedded sensors for nitroaromatic compounds into the leaves of spinach plants. Using a technique called vascular infusion, which involves applying a solution of nanoparticles to the underside of the leaf, they placed the sensors into a leaf layer known as the mesophyll, which is where most photosynthesis takes place.

They also embedded carbon nanotubes that emit a constant fluorescent signal that serves as a reference. This allows the researchers to compare the two fluorescent signals, making it easier to determine if the explosive sensor has detected anything. If there are any explosive molecules in the groundwater, it takes about 10 minutes for the plant to draw them up into the leaves, where they encounter the detector.

To read the signal, the researchers shine a laser onto the leaf, prompting the nanotubes in the leaf to emit near-infrared fluorescent light. This can be detected with a small infrared camera connected to a Raspberry Pi, a $35 credit-card-sized computer similar to the computer inside a smartphone. The signal could also be detected with a smartphone by removing the infrared filter that most camera phones have, the researchers say.

“This setup could be replaced by a cell phone and the right kind of camera,” Strano says. “It’s just the infrared filter that would stop you from using your cell phone.”

Using this setup, the researchers can pick up a signal from about 1 meter away from the plant, and they are now working on increasing that distance.

Michael McAlpine, an associate professor of mechanical engineering at the University of Minnesota, says this approach holds great potential for engineering not only sensors but many other kinds of bionic plants that might receive radio signals or change color.

“When you have manmade materials infiltrated into a living organism, you can have plants do things that plants don’t ordinarily do,” says McAlpine, who was not involved in the research. “Once you start to think of living organisms like plants as biomaterials that can be combined with electronic materials, this is all possible.”

“A wealth of information”

In the 2014 plant nanobionics study, Strano’s lab worked with a common laboratory plant known as Arabidopsis thaliana. However, the researchers wanted to use common spinach plants for the latest study, to demonstrate the versatility of this technique. “You can apply these techniques with any living plant,” Strano says.

So far, the researchers have also engineered spinach plants that can detect dopamine, which influences plant root growth, and they are now working on additional sensors, including some that track the chemicals plants use to convey information within their own tissues.

“Plants are very environmentally responsive,” Strano says. “They know that there is going to be a drought long before we do. They can detect small changes in the properties of soil and water potential. If we tap into those chemical signaling pathways, there is a wealth of information to access.”

These sensors could also help botanists learn more about the inner workings of plants, monitor plant health, and maximize the yield of rare compounds synthesized by plants such as the Madagascar periwinkle, which produces drugs used to treat cancer.

“These sensors give real-time information from the plant. It is almost like having the plant talk to us about the environment they are in,” Wong says. “In the case of precision agriculture, having such information can directly affect yield and margins.”

Once getting over the excitement, questions spring to mind. How could this be implemented? Is somebody  going to plant a field of spinach and then embed the leaves so they can detect landmines? How will anyone know where to plant the spinach? And on a different track, is this spinach edible? I suspect that if spinach can be successfully used as a sensor, it might not be for explosives but for pollution as the researchers suggest.

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

Nitroaromatic detection and infrared communication from wild-type plants using plant nanobionics by Min Hao Wong, Juan P. Giraldo, Seon-Yeong Kwak, Volodymyr B. Koman, Rosalie Sinclair, Tedrick Thomas Salim Lew, Gili Bisker, Pingwei Liu, & Michael S. Strano. Nature Materials (2016) doi:10.1038/nmat4771 Published online 31 October 2016

This paper is behind a paywall.

The last posting here which featured Strano’s research is in an Aug. 25, 2015 piece about carbon nanotubes and medical sensors.