Tag Archives: single-walled carbon nanotubes (SWCNTs)

Wearable electronic textiles from the UK, India, and Canada: two different carbon materials

It seems wearable electronic textiles may be getting nearer to the marketplace. I have three research items (two teams working with graphene and one working with carbon nanotubes) that appeared on my various feeds within two days of each other.

UK/China

This research study is the result of a collaboration between UK and Chinese scientists. From a May 15, 2019 news item on phys.org (Note: Links have been removed),


Wearable electronic components incorporated directly into fabrics have been developed by researchers at the University of Cambridge. The devices could be used for flexible circuits, healthcare monitoring, energy conversion, and other applications.

The Cambridge researchers, working in collaboration with colleagues at Jiangnan University in China, have shown how graphene – a two-dimensional form of carbon – and other related materials can be directly incorporated into fabrics to produce charge storage elements such as capacitors, paving the way to textile-based power supplies which are washable, flexible and comfortable to wear.

The research, published in the journal Nanoscale, demonstrates that graphene inks can be used in textiles able to store electrical charge and release it when required. The new textile electronic devices are based on low-cost, sustainable and scalable dyeing of polyester fabric. The inks are produced by standard solution processing techniques.

Building on previous work by the same team, the researchers designed inks which can be directly coated onto a polyester fabric in a simple dyeing process. The versatility of the process allows various types of electronic components to be incorporated into the fabric.

Schematic of the textile-based capacitor integrating GNP/polyesters as electrodes and h-BN/polyesters as dielectrics. Credit: Felice Torrisi

A May 16, 2019 University of Cambridge press release, which originated the news item, probes further,

Most other wearable electronics rely on rigid electronic components mounted on plastic or textiles. These offer limited compatibility with the skin in many circumstances, are damaged when washed and are uncomfortable to wear because they are not breathable.

“Other techniques to incorporate electronic components directly into textiles are expensive to produce and usually require toxic solvents, which makes them unsuitable to be worn,” said Dr Felice Torrisi from the Cambridge Graphene Centre, and the paper’s corresponding author. “Our inks are cheap, safe and environmentally-friendly, and can be combined to create electronic circuits by simply overlaying different fabrics made of two-dimensional materials on the fabric.”

The researchers suspended individual graphene sheets in a low boiling point solvent, which is easily removed after deposition on the fabric, resulting in a thin and uniform conducting network made up of multiple graphene sheets. The subsequent overlay of several graphene and hexagonal boron nitride (h-BN) fabrics creates an active region, which enables charge storage. This sort of ‘battery’ on fabric is bendable and can withstand washing cycles in a normal washing machine.

“Textile dyeing has been around for centuries using simple pigments, but our result demonstrates for the first time that inks based on graphene and related materials can be used to produce textiles that could store and release energy,” said co-author Professor Chaoxia Wang from Jiangnan University in China. “Our process is scalable and there are no fundamental obstacles to the technological development of wearable electronic devices both in terms of their complexity and performance.”

The work done by the Cambridge researchers opens a number of commercial opportunities for ink based on two-dimensional materials, ranging from personal health and well-being technology, to wearable energy and data storage, military garments, wearable computing and fashion.

“Turning textiles into functional energy storage elements can open up an entirely new set of applications, from body-energy harvesting and storage to the Internet of Things,” said Torrisi “In the future our clothes could incorporate these textile-based charge storage elements and power wearable textile devices.”

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

Wearable solid-state capacitors based on two-dimensional material all-textile heterostructures by Siyu Qiang, Tian Carey, Adrees Arbab, Weihua Song, Chaoxia Wang and Felice Torris. Nanoscale, 2019, Advance Article DOI: 10.1039/C9NR00463G First published on 18 Apr 2019

This paper is behind a paywall.

India

Prior to graphene’s reign as the ‘it’ carbon material, carbon nanotubes (CNTs) ruled. It’s been quieter on the CNT front since graphene took over but a May 15, 2019 Nanowerk Spotlight article by Michael Berger highlights some of the latest CNT research coming out of India,


The most important technical challenge is to blend the chemical nature of raw materials with fabrication techniques and processability, all of which are diametrically conflicting for textiles and conventional energy storage devices. A team from Indian Institute of Technology Bombay has come out with a comprehensive approach involving simple and facile steps to fabricate a wearable energy storage device. Several scientific and technological challenges were overcome during this process.

First, to achieve user-comfort and computability with clothing, the scaffold employed was the the same as what a regular fabric is made up of – cellulose fibers. However, cotton yarns are electrical insulators and therefore practically useless for any electronics. Therefore, the yarns are coated with single-wall carbon nanotubes (SWNTs).

SWNTs are hollow, cylindrical allotropes of carbon and combine excellent mechanical strength with electrical conductivity and surface area. Such a coating converts the electrical insulating cotton yarn to a metallic conductor with high specific surface area. At the same time, using carbon-based materials ensures that the final material remains light-weight and does not cause user discomfort that can arise from metallic wires such as copper and gold. This CNT-coated cotton yarn (CNT-wires) forms the electrode for the energy storage device.

Next, the electrolyte is composed of solid-state electrolyte sheets since no liquid-state electrolytes can be used for this purpose. However, solid state electrolytes suffer from poor ionic conductivity – a major disadvantage for energy storage applications. Therefore, a steam-based infiltration approach that enhances the ionic conductivity of the electrolyte is adopted. Such enhancement of humidity significantly increases the energy storage capacity of the device.


The integration of the CNT-wire electrode with the electrolyte sheet was carried out by a simple and elegant approach of interweaving the CNT-wire through the electrolyte (see Figure 1). This resulted in cross-intersections which are actually junctions where the electrical energy can be stored. Each such junction is now an energy storage unit, referred to as sewcap.

The advantage of this process is that several 100s and 1000s of sewcaps can be made in a small area and integrated to increase the total amount of energy stored in the system. This scalability is unique and critical aspect of this work and stems from the approach of interweaving.

Further, this process is completely adaptable with current processes used in textile industries. Hence, a proportionately large energy-storage is achieved by creating sewcap-junctions in various combinations.

All components of the final sewcap device are flexible. However, they need to be protected from environmental effects such as temperature, humidity and sweat while retaining the mechanical flexibility. This is achieved by laminating the entire device between polymer sheets. The process is exactly similar to the one used for protecting documents and ID cards.

The laminated sewcap can be integrated easily on clothing and fabrics while retaining the flexibility and sturdiness. This is demonstrated by the unchanged performance of the device during extreme and harsh mechanical testing such as striking repeatedly with a hammer, complete flexing, bending and rolling and washing in a laundry machine.

In fact, this is the first device that has been proven to be stable under rigorous washing conditions in the presence of hot water, detergents and high torque (spinning action of washing machine). This provides the device with comprehensive mechanical stability.


CNTs have high surface area and electrical conductivity. The CNT-wire combines these properties of CNTs with stability and porosity of cellulose yarns. The junction created by interweaving is essentially comprised of two such CNT-wires that are sandwiching an electrolyte. Application of potential difference leads to polarization of the electrolyte thus enabling energy storage similar to the way in which a conventional capacitor acts.

“We use the advantage of the interweaving process and create several such junctions. So, with each junction being able to store a certain amount of electrical energy, all the junctions synchronized are able to store a large amount of energy. This provides high energy density to the device,” Prof. C. Subramaniam, Department of Chemistry, IIT Bombay and corresponding author of the paper points out.

The device has also been employed for lighting up an LED [light-emitting diode]. This can be potentially scaled to provide electrical energy demanded by the application.

This image accompanies the paper written by Prof. C. Subramaniam and his team,

Courtesy: IACS Applied Materials Interfaces

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

Interwoven Carbon Nanotube Wires for High-Performing, Mechanically Robust, Washable, and Wearable Supercapacitors by Mihir Kumar Jha, Kenji Hata, and Chandramouli Subramaniam. ACS Appl. Mater. Interfaces, Article ASAP DOI: 10.1021/acsami.8b22233 Publication Date (Web): April 29, 2019 Copyright © 2019 American Chemical Society

This paper is behind a paywall.

Canada

A research team from the University of British Columbia (UBC at the Okanagan Campus) joined the pack with a May 16, 2019 news item on ScienceDaily,

Forget the smart watch. Bring on the smart shirt.

Researchers at UBC Okanagan’s School of Engineering have developed a low-cost sensor that can be interlaced into textiles and composite materials. While the research is still new, the sensor may pave the way for smart clothing that can monitor human movement.

A May 16, 2019 UBC news release (also on EurekAlert), which originated the news item, describes the work in more detail,


“Microscopic sensors are changing the way we monitor machines and humans,” says Hoorfar, lead researcher at the Advanced Thermo-Fluidic Lab at UBC’s Okanagan campus. “Combining the shrinking of technology along with improved accuracy, the future is very bright in this area.”

This ‘shrinking technology’ uses a phenomenon called piezo-resistivity—an electromechanical response of a material when it is under strain. These tiny sensors have shown a great promise in detecting human movements and can be used for heart rate monitoring or temperature control, explains Hoorfar.

Her research, conducted in partnership with UBC Okanagan’s Materials and Manufacturing Research Institute, shows the potential of a low-cost, sensitive and stretchable yarn sensor. The sensor can be woven into spandex material and then wrapped into a stretchable silicone sheath. This sheath protects the conductive layer against harsh conditions and allows for the creation of washable wearable sensors.

While the idea of smart clothing—fabrics that can tell the user when to hydrate, or when to rest—may change the athletics industry, UBC Professor Abbas Milani says the sensor has other uses. It can monitor deformations in fibre-reinforced composite fabrics currently used in advanced industries such as automotive, aerospace and marine manufacturing.

The low-cost stretchable composite sensor has also shown a high sensitivity and can detect small deformations such as yarn stretching as well as out-of-plane deformations at inaccessible places within composite laminates, says Milani, director of the UBC Materials and Manufacturing Research Institute.

The testing indicates that further improvements in its accuracy could be achieved by fine-tuning the sensor’s material blend and improving its electrical conductivity and sensitivity This can eventually make it able to capture major flaws like “fibre wrinkling” during the manufacturing of advanced composite structures such as those currently used in airplanes or car bodies.

“Advanced textile composite materials make the most of combining the strengths of different reinforcement materials and patterns with different resin options,” he says. “Integrating sensor technologies like piezo-resistive sensors made of flexible materials compatible with the host textile reinforcement is becoming a real game-changer in the emerging era of smart manufacturing and current automated industry trends.”

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

Graphene‐Coated Spandex Sensors Embedded into Silicone Sheath for Composites Health Monitoring and Wearable Applications by Hossein Montazerian, Armin Rashidi, Arash Dalili, Homayoun Najjaran, Abbas S. Milani, Mina Hoorfar. Small Volume15, Issue17 April 26, 2019 1804991 DOI: https://doi.org/10.1002/smll.201804991 First published: 28 March 2019

This paper is behind a paywall.

Will there be one winner or will they find CNTs better for one type of wearable tech textile while graphene excels for another type of wearable tech textile?

Carbon nanotube optics and the quantum

A US-France-Germany collaboration has led to some intriguing work with carbon nanotubes. From a June 18, 2018 news item on ScienceDaily,

Researchers at Los Alamos and partners in France and Germany are exploring the enhanced potential of carbon nanotubes as single-photon emitters for quantum information processing. Their analysis of progress in the field is published in this week’s edition of the journal Nature Materials.

“We are particularly interested in advances in nanotube integration into photonic cavities for manipulating and optimizing light-emission properties,” said Stephen Doorn, one of the authors, and a scientist with the Los Alamos National Laboratory site of the Center for Integrated Nanotechnologies (CINT). “In addition, nanotubes integrated into electroluminescent devices can provide greater control over timing of light emission and they can be feasibly integrated into photonic structures. We are highlighting the development and photophysical probing of carbon nanotube defect states as routes to room-temperature single photon emitters at telecom wavelengths.”

A June 18, 2018 Los Alamos National Laboratory (LANL) news release (also on EurekAlert), which originated the news item, expands on the theme,

The team’s overview was produced in collaboration with colleagues in Paris (Christophe Voisin [Ecole Normale Supérieure de Paris (ENS)]) who are advancing the integration of nanotubes into photonic cavities for modifying their emission rates, and at Karlsruhe (Ralph Krupke [Karlsruhe Institute of Technology (KIT]) where they are integrating nanotube-based electroluminescent devices with photonic waveguide structures. The Los Alamos focus is the analysis of nanotube defects for pushing quantum emission to room temperature and telecom wavelengths, he said.

As the paper notes, “With the advent of high-speed information networks, light has become the main worldwide information carrier. . . . Single-photon sources are a key building block for a variety of technologies, in secure quantum communications metrology or quantum computing schemes.”

The use of single-walled carbon nanotubes in this area has been a focus for the Los Alamos CINT team, where they developed the ability to chemically modify the nanotube structure to create deliberate defects, localizing excitons and controlling their release. Next steps, Doorn notes, involve integration of the nanotubes into photonic resonators, to provide increased source brightness and to generate indistinguishable photons. “We need to create single photons that are indistinguishable from one another, and that relies on our ability to functionalize tubes that are well-suited for device integration and to minimize environmental interactions with the defect sites,” he said.

“In addition to defining the state of the art, we wanted to highlight where the challenges are for future progress and lay out some of what may be the most promising future directions for moving forward in this area. Ultimately, we hope to draw more researchers into this field,” Doorn said.

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

Carbon nanotubes as emerging quantum-light sources by X. He, H. Htoon, S. K. Doorn, W. H. P. Pernice, F. Pyatkov, R. Krupke, A. Jeantet, Y. Chassagneux & C. Voisin. Nature Materials (2018) DOI: https://doi.org/10.1038/s41563-018-0109-2 Published online June 18, 2018

This paper is behind a paywall.

Canadian research into nanomaterial workplace exposure in the air and on surfaces

An August 30, 2018 news item on Nanowerk announces the report,

The monitoring of air contamination by engineered nanomaterials (ENM) is a complex process with many uncertainties and limitations owing to the presence of particles of nanometric size that are not ENMs, the lack of validated instruments for breathing zone measurements and the many indicators to be considered.

In addition, some organizations, France’s Institut national de recherche et de sécurité (INRS) and Québec’s Institut de recherche Robert-Sauvé en santé et en sécurité du travail (IRSST) among them, stress the need to also sample surfaces for ENM deposits.

In other words, to get a better picture of the risks of worker exposure, we need to fine-tune the existing methods of sampling and characterizing ENMs and develop new one. Accordingly, the main goal of this project was to develop innovative methodological approaches for detailed qualitative as well as quantitative characterization of workplace exposure to ENMs.

A PDF of the 88-page report is available in English or in French.

An August 30, 2018 (?) abstract of the IRSST report titled An Assessment of Methods of Sampling and Characterizing Engineered Nanomaterials in the Air and on Surfaces in the Workplace (2nd edition) by Maximilien Debia, Gilles L’Espérance, Cyril Catto, Philippe Plamondon, André Dufresne, Claude Ostiguy, which originated the news item, outlines what you can expect from the report,

This research project has two complementary parts: a laboratory investigation and a fieldwork component. The laboratory investigation involved generating titanium dioxide (TiO2) nanoparticles under controlled laboratory conditions and studying different sampling and analysis devices. The fieldwork comprised a series of nine interventions adapted to different workplaces and designed to test a variety of sampling devices and analytical procedures and to measure ENM exposure levels among Québec workers.

The methods for characterizing aerosols and surface deposits that were investigated include: i) measurement by direct-reading instruments (DRI), such as condensation particle counters (CPC), optical particle counters (OPC), laser photometers, aerodynamic diameter spectrometers and electric mobility spectrometer; ii) transmission electron microscopy (TEM) or scanning transmission electron microscopy (STEM) with a variety of sampling devices, including the Mini Particle Sampler® (MPS); iii) measurement of elemental carbon (EC); iv) inductively coupled plasma mass spectrometry (ICP-MS) and (v) Raman spectroscopy.

The workplace investigations covered a variety of industries (e.g., electronics, manufacturing, printing, construction, energy, research and development) and included producers as well as users or integrators of ENMs. In the workplaces investigated, we found nanometals or metal oxides (TiO2, SiO2, zinc oxides, lithium iron phosphate, titanate, copper oxides), nanoclays, nanocellulose and carbonaceous materials, including carbon nanofibers (CNF) and carbon nanotubes (CNT)—single-walled (SWCNT) as well as multiwalled (MWCNT).

The project helped to advance our knowledge of workplace assessments of ENMs by documenting specific tasks and industrial processes (e.g., printing and varnishing) as well as certain as yet little investigated ENMs (nanocellulose, for example).

Based on our investigations, we propose a strategy for more accurate assessment of ENM exposure using methods that require a minimum of preanalytical handling. The recommended strategy is a systematic two-step assessment of workplaces that produce and use ENMs. The first step involves testing with different DRIs (such as a CPC and a laser photometer) as well as sample collection and subsequent microscopic analysis (MPS + TEM/STEM) to clearly identify the work tasks that generate ENMs. The second step, once work exposure is confirmed, is specific quantification of the ENMs detected. The following findings are particularly helpful for detailed characterization of ENM exposure:

  1. The first conclusive tests of a technique using ICP-MS to quantify the metal oxide content of samples collected in the workplace
  2. The possibility of combining different sampling methods recommended by the National Institute for Occupational Safety and Health (NIOSH) to measure elemental carbon as an indicator of NTC/NFC, as well as demonstration of the limitation of this method stemming from observed interference with the black carbon particles required to synthesis carbon materials (for example, Raman spectroscopy showed that less than 6% of the particles deposited on the electron microscopy grid at one site were SWCNTs)
  3. The clear advantages of using an MPS (instead of the standard 37-mm cassettes used as sampling media for electron microscopy), which allows quantification of materials
  4. The major impact of sampling time: a long sampling time overloads electron microscopy grids and can lead to overestimation of average particle agglomerate size and underestimation of particle concentrations
  5. The feasibility and utility of surface sampling, either with sampling pumps or passively by diffusion onto the electron microscopy grids, to assess ENM dispersion in the workplace

These original findings suggest promising avenues for assessing ENM exposure, while also showing their limitations. Improvements to our sampling and analysis methods give us a better understanding of ENM exposure and help in adapting and implementing control measures that can minimize occupational exposure.

You can download the full report in either or both English and French from the ‘Nanomaterials – A Guide to Good Practices Facilitating Risk Management in the Workplace, 2nd Edition‘ webpage.

Feed your silkworms graphene or carbon nanotubes for stronger silk

This Oct. 11, 2016 news item on Nanowerk may make you wonder about a silkworm’s standard diet,

Researchers at Tsinghua University in Beijing, China, have demonstrated that mechanically enhanced silk fibers could be naturally produced by feeding silkworms with diets containing single-walled carbon nanotubes (SW[C]NTs) or graphene.

The as-spun silk fibers containing nanofillers showed evidently increased fracture strength and elongation-at-break, demonstrating the validity of SWNT or graphene incorporation into silkworm silk as reinforcement through an in situ functionalization approach.

The researchers conclude that “by analyzing the silk fibers and the excrement of silkworms, … parts of the fed carbon nanomaterials were incorporated into the as-spun silk fibers, while others went into excrement.

Bob Yirka in an Oct. 11, 2016 article for phys.org provides a little information about silkworms and their eating habits,

In this new effort, the researchers sought to add new properties to silk by adding carbon nanotubes and graphene to their diet.

To add the materials, the researchers sprayed a water solution containing .2 percent carbon nanotubes or graphene onto mulberry leaves and then fed the leaves to the silkworms. They then allowed the silkworms to make their silk in the normal way. Testing of the silks that were produced showed they could withstand approximately 50 percent more stress than traditional silk. A closer look showed that the new silk was made of a more orderly crystal structure than normal silk. And taking their experiments one step further, the researchers cooked the new silk at 1,050 °C causing it to be carbonized—that caused the silk to conduct electricity.

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

Feeding Single-Walled Carbon Nanotubes or Graphene to Silkworms for Reinforced Silk Fibers by Qi Wang, Chunya Wang, Mingchao Zhang, Muqiang Jian, and Yingying Zhang. Nano Lett., Article ASAP DOI: 10.1021/acs.nanolett.6b03597 Publication Date (Web): September 13, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.