Category Archives: graphene

New water treatment with 3D-printed graphene aerogels

Caption: Graphene aerogel on a single tissue. Credit: University at Buffalo

That image of the graphene aerogel on a tissue shows off its weightlessness very well.

Here’s more about the graphene aerogel water treatment from an April 14, 2021 news item on Nanowerk,

Graphene excels at removing contaminants from water, but it’s not yet a commercially viable use of the wonder material.

That could be changing.

In a recent study, University at Buffalo [UB] engineers report a new process of 3D printing graphene aerogels that they say overcomes two key hurdles — scalability and creating a version of the material that’s stable enough for repeated use — for water treatment.

“The goal is to safely remove contaminants from water without releasing any problematic chemical residue,” says study co-author Nirupam Aich, PhD, assistant professor of environmental engineering at the UB School of Engineering and Applied Sciences. “The aerogels we’ve created hold their structure when put in water treatment systems, and they can be applied in diverse water treatment applications.”

An April 14, 2021 UB news release (also on EurekAlert) by Melvin Bankhead III, which originated the news item, explains the breakthrough in more detail,

An aerogel is a light, highly porous solid formed by replacement of liquid in a gel with a gas so that the resulting solid is the same size as the original. They are similar in structural configuration to Styrofoam: very porous and lightweight, yet strong and resilient.

Graphene is a nanomaterial formed by elemental carbon and is composed of a single flat sheet of carbon atoms arranged in a repeating hexagonal lattice.

To create the right consistency of the graphene-based ink, the researchers looked to nature. They added to it two bio-inspired polymers — polydopamine (a synthetic material, often referred to as PDA, that is similar to the adhesive secretions of mussels), and bovine serum albumin (a protein derived from cows).

In tests, the reconfigured aerogel removed certain heavy metals, such as lead and chromium, that plague drinking water systems nationwide. It also removed organic dyes, such as cationic methylene blue and anionic Evans blue, as well as organic solvents like hexane, heptane and toluene.

To demonstrate the aerogel’s reuse potential, the researchers ran organic solvents through it 10 times. Each time, it removed 100% of the solvents. The researchers also reported the aerogel’s ability to capture methylene blue decreased by 2-20% after the third cycle.

The aerogels can also be scaled up in size, Aich says, because unlike nanosheets, aerogels can be printed in larger sizes. This eliminates a previous problem inherent in large-scale production, and makes the process available for use in large facilities, such as in wastewater treatment plants, he says. He adds the aerogels can be removed from water and reused in other locations, and that they don’t leave any kind of residue in the water.

Aich is part of a collaboration between UB and the University of Pittsburgh, led by UB chemistry professor Diana Aga, PhD, to find methods and tools to degrade per- and polyfluoroalkyl substances (PFAS), toxic materials so difficult to break down that they are known as “forever chemicals.” Aich notes the similarities to his work with 3D aerogels, and he hopes results from the two projects can be brought together to create more effective methods of removing waterborne contaminants.

“We can use these aerogels not only to contain graphene particles but also nanometal particles which can act as catalysts,” Aich says. “The future goal is to have nanometal particles embedded in the walls and the surface of these aerogels and they would be able to degrade or destroy not only biological contaminants, but also chemical contaminants.”

Aich, Chi, and Masud [Arvid Masud, PhD] hold a pending patent for the graphene aerogel described in the study, and they are looking for industrial partners to commercialize this process.

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

Emerging investigator series: 3D printed graphene-biopolymer aerogels for water contaminant removal: a proof of concept by Arvid Masud, Chi Zhoub and Nirupam Aich. Environ. Sci.: Nano, 2021,8, 399-414 DOI: https://doi.org/10.1039/D0EN00953A First published online: 09 Dec 2020

This paper is behind a paywall.

Concrete collapse and research into durability

I have two items about concrete buildings, one concerns the June 24, 2021 collapse of a 12-storey condominium building in Surfside, close to Miami Beach in Florida. There are at least 20 people dead and, I believe, over 120 are still unaccounted for (July 2, 2021 Associated Press news item on Canadian Broadcasting Corporation news online website).

Miami collapse

Nate Berg’s June 25, 2021 article for Fast Company provides an instructive overview of the building collapse (Note: A link has been removed),

Why the building collapsed is not yet known [emphasis mine]. David Darwin is a professor of civil engineering at the University of Kansas and an expert in reinforced concrete structures, and he says the eventual investigation of the Surfside collapse will explore all the potential causes, ranging from movement in the foundation before the collapse, corrosion in the debris, and excessive cracking in the part of the building that remains standing. “There are all sorts of potential causes of failure,” Darwin says. “At this point, speculation is not helpful for anybody.”

Sometimes I can access the entire article, and at other times, only a few paragraphs; I hope you get access to all of it as it provides a lot of information.

The Surfside news puts this research from Northwestern University (Chicago, Illinois) into much sharper relief than might otherwise be the case. (Further on I have some information about the difference between cement and concrete and how cement leads to concrete.)

Smart cement for more durable roads and cities

Coincidentally, just days before the Miami Beach building collapse, a June 21, 2021 Northwestern University news release (also on EurekAlert), announced research into improving water and fracture resistance in cement,

Forces of nature have been outsmarting the materials we use to build our infrastructure since we started producing them. Ice and snow turn major roads into rubble every year; foundations of houses crack and crumble, in spite of sturdy construction. In addition to the tons of waste produced by broken bits of concrete, each lane-mile of road costs the U.S. approximately $24,000 per year to keep it in good repair.

Engineers tackling this issue with smart materials typically enhance the function of materials by increasing the amount of carbon, but doing so makes materials lose some mechanical performance. By introducing nanoparticles into ordinary cement, Northwestern University researchers have formed a smarter, more durable and highly functional cement.

The research was published today (June 21 [2021]) in the journal Philosophical Transactions of the Royal Society A.

With cement being the most widely consumed material globally and the cement industry accounting for 8% of human-caused greenhouse gas emissions, civil and environmental engineering professor Ange-Therese Akono turned to nanoreinforced cement to look for a solution. Akono, the lead author on the study and an assistant professor in the McCormick School of Engineering, said nanomaterials reduce the carbon footprint of cement composites, but until now, little was known about its impact on fracture behavior.

“The role of nanoparticles in this application has not been understood before now, so this is a major breakthrough,” Akono said. “As a fracture mechanics expert by training, I wanted to understand how to change cement production to enhance the fracture response.”

Traditional fracture testing, in which a series of light beams is cast onto a large block of material, involves lots of time and materials and seldom leads to the discovery of new materials.

By using an innovative method called scratch testing, Akono’s lab efficiently formed predictions on the material’s properties in a fraction of the time. The method tests fracture response by applying a conical probe with increasing vertical force against the surface of microscopic bits of cement. Akono, who developed the novel method during her Ph.D. work, said it requires less material and accelerates the discovery of new ones.

“I was able to look at many different materials at the same time,” Akono said. “My method is applied directly at the micrometer and nanometer scales, which saves a considerable amount of time. And then based on this, we can understand how materials behave, how they crack and ultimately predict their resistance to fracture.”

Predictions formed through scratch tests also allow engineers to make changes to materials that enhance their performance at the larger scale. In the paper, graphene nanoplatelets, a material rapidly gaining popularity in forming smart materials, were used to improve the resistance to fracture of ordinary cement. Incorporating a small amount of the nanomaterial also was shown to improve water transport properties including pore structure and water penetration resistance, with reported relative decreases of 76% and 78%, respectively.

Implications of the study span many fields, including building construction, road maintenance, sensor and generator optimization and structural health monitoring.

By 2050, the United Nations predicts two-thirds of the world population will be concentrated in cities. Given the trend toward urbanization, cement production is expected to skyrocket.

Introducing green concrete that employs lighter, higher-performing cement will reduce its overall carbon footprint by extending maintenance schedules and reducing waste.

Alternately, smart materials allow cities to meet the needs of growing populations in terms of connectivity, energy and multifunctionality. Carbon-based nanomaterials including graphene nanoplatelets are already being considered in the design of smart cement-based sensors for structural health monitoring.

Akono said she’s excited for both follow-ups to the paper in her own lab and the ways her research will influence others. She’s already working on proposals that look into using construction waste to form new concrete and is considering “taking the paper further” by increasing the fraction of nanomaterial that cement contains.

“I want to look at other properties like understanding the long-term performance,” Akono said. “For instance, if you have a building made of carbon-based nanomaterials, how can you predict the resistance in 10, 20 even 40 years?”

The study, “Fracture toughness of one- and two-dimensional nanoreinforced cement via scratch testing,” was supported by the National Science Foundation Division of Civil, Mechanical and Manufacturing Innovation (award number 18929101).

Akono will give a talk on the paper at The Royal Society’s October [2021] meeting, “A Cracking Approach to Inventing Tough New Materials: Fracture Stranger Than Friction,” which will highlight major advances in fracture mechanics from the past century.

I don’t often include these kinds of photos (one or more of the researchers posing (sometimes holding something) for the camera but I love the professor’s first name, Ange-Therese (which means angel in French, I don’t know if she ever uses the French spelling for Thérèse),

Caption: Professor Ange-Therese Akono holds a sample of her smart cement. Credit: Northwestern University

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

Fracture toughness of one- and two-dimensional nanoreinforced cement via scratch testing by Ange-Therese Akono. Philosophical Transactions of the Royal Society A: Mathematical, Physical & Engineering Sciences 2021 379 (2203): 20200288 DOI: 10.1098/rsta.2020.0288 Published June 21, 2021

This paper appears to be open access.

Cement vs. concrete

Andrew Logan’s April 3, 2020 article for MIT (Massachusetts Institute of Technology) News is a very readable explanation of how cement and concrete differ and how they are related,

There’s a lot the average person doesn’t know about concrete. For example, it’s porous; it’s the world’s most-used material after water; and, perhaps most fundamentally, it’s not cement.

Though many use “cement” and “concrete” interchangeably, they actually refer to two different — but related — materials: Concrete is a composite made from several materials, one of which is cement. [emphasis mine]

Cement production begins with limestone, a sedimentary rock. Once quarried, it is mixed with a silica source, such as industrial byproducts slag or fly ash, and gets fired in a kiln at 2,700 degrees Fahrenheit. What comes out of the kiln is called clinker. Cement plants grind clinker down to an extremely fine powder and mix in a few additives. The final result is cement.

“Cement is then brought to sites where it is mixed with water, where it becomes cement paste,” explains Professor Franz-Josef Ulm, faculty director of the MIT Concrete Sustainability Hub (CSHub). “If you add sand to that paste it becomes mortar. And if you add to the mortar large aggregates — stones of a diameter of up to an inch — it becomes concrete.”

Final thoughts

I offer my sympathies to the folks affected by the building collapse and my hopes that research will lead the way to more durable cement and, ultimately, concrete buildings.

2021 version of graphene-enhanced sports shoes/sneakers/running shoes/runners/trainers

My June 21, 2018 posting was the last time these graphene-enhanced sports shoes/sneakers/running shoes/runners/trainers were mentioned here (it was also the first time). The latest version features newly graphene-enhanced shoe soles that last twice as long as the industry standard according to a March 30, 2021 article by Robert Lea for Azonano (Note: A link has been removed),

Thanks to researchers at the University of Manchester and UK-based sportswear manufacturer Inov-8, graphene can now be found at the tips of your toes as well as your fingers.

In 2017 Inov-8 brought to the market the first running shoe that utilizes graphene in its grips, and 4 years later the manufacturer is still innovating, offering a wide range of products that rely on the wonder material. 

Now, as well as finding its way into the grips of the company’s running shoes, graphene is also found in the soles of the company’s latest long-distance running shoe too¹. 

Using graphene as part of the cushioning insole in trail running shoes has led to a shoe that lasts twice as long as leading competitors’ footwear, the company says.

When Inov-8 began their quest to use graphene to improve running shoes, the initial goal was to employ the material to create improved rubber grips that would not wear down as quickly as other running shoes and retain grip for longer during this slower wearing process.

The company teamed with the University of Manchester to make this goal a reality, …

The graphene-enhanced grip proved such a hit with consumers that in the four years since its induction, shoes featuring the outer-sole now account for 50% of overall sales.

Building upon the success of Inov-8’s graphene gripped running shoe, the company has expanded its use of the material to a midsole foam. The graphene replaces EVA foam plates of carbon which are traditionally used in this form of long-distance running shoe.

A March 24, 2021 University of Manchester press release describes the latest use of graphene in Inov-8’s shoes,

Sports footwear firm inov-8 has unveiled the world’s first running shoe to use a graphene-enhanced foam in the sole, bucking the widespread trend for carbon-plate technology and doubling the industry standard for longevity.

Developed in collaboration with graphene experts at The University of Manchester, the cushioned foam, called G-FLY™, features as part of inov-8’s new trail shoe, the TRAILFLY ULTRA G 300 MAX™, designed for ultramarathon and long-distance runners.

Tests have shown the foam delivers 25% greater energy return than standard EVA foams and is far more resistant to compressive wear. It therefore maintains optimum levels of underfoot bounce and comfort for much longer.

This helps runners maintain a faster speed over greater distances, aid their feet in feeling fresher for longer, and prolong the life of their footwear.

Michael Price, COO of Lake District-based inov-8, said: …

“We’ve worked incredibly hard for the past two years with the university and leading footwear industry veteran Doug Sheridan in developing this innovation. A team of 40 athletes from across the world tested prototype shoes and more than 50 mixes of graphene-enhanced foam. Trail test reports show G-FLY foam still performing well after 1,200km – double the industry standard.”

Dr Aravind Vijayaraghavan, Reader in Nanomaterials at the University, home to both the National Graphene Institute and Graphene Engineering Innovation Centre, said: “As well as on the trail, we also tested extensively in the laboratory, including subjecting the foam to aggressive ageing tests that mimic extensive use. Despite being significantly aged, the G-FLY foam still delivered more energy return than some unaged foams.

The company inov-8 can be found here.

Mechano-photonic artificial synapse is bio-inspired

The word ‘memristor’ usually pops up when there’s research into artificial synapses but not in this new piece of research. I didn’t see any mention of the memristor in the paper’s references either but I did find James Gimzewski from the University of California at Los Angeles (UCLA) whose research into brainlike computing (neuromorphic computing) is running parallel but separately to the memristor research.

Dr. Thamarasee Jeewandara has written a March 25, 2021 article for phys.org about the latest neuromorphic computing research (Note: Links have been removed)

Multifunctional and diverse artificial neural systems can incorporate multimodal plasticity, memory and supervised learning functions to assist neuromorphic computation. In a new report, Jinran Yu and a research team in nanoenergy, nanoscience and materials science in China and the US., presented a bioinspired mechano-photonic artificial synapse with synergistic mechanical and optical plasticity. The team used an optoelectronic transistor made of graphene/molybdenum disulphide (MoS2) heterostructure and an integrated triboelectric nanogenerator to compose the artificial synapse. They controlled the charge transfer/exchange in the heterostructure with triboelectric potential and modulated the optoelectronic synapse behaviors readily, including postsynaptic photocurrents, photosensitivity and photoconductivity. The mechano-photonic artificial synapse is a promising implementation to mimic the complex biological nervous system and promote the development of interactive artificial intelligence. The work is now published on Science Advances.

The human brain can integrate cognition, learning and memory tasks via auditory, visual, olfactory and somatosensory interactions. This process is difficult to be mimicked using conventional von Neumann architectures that require additional sophisticated functions. Brain-inspired neural networks are made of various synaptic devices to transmit information and process using the synaptic weight. Emerging photonic synapse combine the optical and electric neuromorphic modulation and computation to offer a favorable option with high bandwidth, fast speed and low cross-talk to significantly reduce power consumption. Biomechanical motions including touch, eye blinking and arm waving are other ubiquitous triggers or interactive signals to operate electronics during artificial synapse plasticization. In this work, Yu et al. presented a mechano-photonic artificial synapse with synergistic mechanical and optical plasticity. The device contained an optoelectronic transistor and an integrated triboelectric nanogenerator (TENG) in contact-separation mode. The mechano-optical artificial synapses have huge functional potential as interactive optoelectronic interfaces, synthetic retinas and intelligent robots. [emphasis mine]

As you can see Jeewandara has written quite a technical summary of the work. Here’s an image from the Science Advances paper,

Fig. 1 Biological tactile/visual neurons and mechano-photonic artificial synapse. (A) Schematic illustrations of biological tactile/visual sensory system. (B) Schematic diagram of the mechano-photonic artificial synapse based on graphene/MoS2 (Gr/MoS2) heterostructure. (i) Top-view scanning electron microscope (SEM) image of the optoelectronic transistor; scale bar, 5 μm. The cyan area indicates the MoS2 flake, while the white strip is graphene. (ii) Illustration of charge transfer/exchange for Gr/MoS2 heterostructure. (iii) Output mechano-photonic signals from the artificial synapse for image recognition.

You can find the paper here,

Bioinspired mechano-photonic artificial synapse based on graphene/MoS2 heterostructure by Jinran Yu, Xixi Yang, Guoyun Gao, Yao Xiong, Yifei Wang, Jing Han, Youhui Chen, Huai Zhang, Qijun Sun and Zhong Lin Wang. Science Advances 17 Mar 2021: Vol. 7, no. 12, eabd9117 DOI: 10.1126/sciadv.abd9117

This appears to be open access.

Stronger concrete with graphene derived from tires

I’ve become strangely fascinated with concrete these last few months. Possibly, this is a consequence of a lot more ‘concrete’ research being published. Here’s a March 29, 2021 news item on phys.org featuring work from Rice University (Texas, US),

This could be where the rubber truly hits the road.

Rice University scientists have optimized a process to convert waste from rubber tires into graphene that can, in turn, be used to strengthen concrete.

The environmental benefits of adding graphene to concrete are clear, chemist James Tour said.

“Concrete is the most-produced material in the world, and simply making it produces as much as 9% of the world’s carbon dioxide emissions,” Tour said. “If we can use less concrete in our roads, buildings and bridges, we can eliminate some of the emissions at the very start.”

A March 29, 2021 Rice University news release (also on EurekAlert), which originated the news item, provides context for the work and more technical details,

Recycled tire waste is already used as a component of Portland cement, but graphene has been proven to strengthen cementitious materials, concrete among them, at the molecular level.

While the majority of the 800 million tires discarded annually are burned for fuel or ground up for other applications, 16% of them wind up in landfills.

“Reclaiming even a fraction of those as graphene will keep millions of tires from reaching landfills,” Tour said.

The “flash” process introduced by Tour and his colleagues in 2020 has been used to convert food waste, plastic and other carbon sources by exposing them to a jolt of electricity that removes everything but carbon atoms from the sample.

Those atoms reassemble into valuable turbostratic graphene, which has misaligned layers that are more soluble than graphene produced via exfoliation from graphite. That makes it easier to use in composite materials.

Rubber proved more challenging than food or plastic to turn into graphene, but the lab optimized the process by using commercial pyrolyzed waste rubber from tires. After useful oils are extracted from waste tires, this carbon residue has until now had near-zero value, Tour said.

Tire-derived carbon black or a blend of shredded rubber tires and commercial carbon black can be flashed into graphene. Because turbostratic graphene is soluble, it can easily be added to cement to make more environmentally friendly concrete.

The research led by Tour and Rouzbeh Shahsavari of C-Crete Technologies is detailed in the journal Carbon.

The Rice lab flashed tire-derived carbon black and found about 70% of the material converted to graphene. When flashing shredded rubber tires mixed with plain carbon black to add conductivity, about 47% converted to graphene. Elements besides carbon were vented out for other uses.

The electrical pulses lasted between 300 milliseconds and 1 second. The lab calculated electricity used in the conversion process would cost about $100 per ton of starting carbon.

The researchers blended minute amounts of tire-derived graphene — 0.1 weight/percent (wt%) for tire carbon black and 0.05 wt% for carbon black and shredded tires — with Portland cement and used it to produce concrete cylinders. Tested after curing for seven days, the cylinders showed gains of 30% or more in compressive strength. After 28 days, 0.1 wt% of graphene sufficed to give both products a strength gain of at least 30%.

“This increase in strength is in part due to a seeding effect of 2D graphene for better growth of cement hydrate products, and in part due to a reinforcing effect at later stages,” Shahsavari said.

Set of tires on a sky background

I’m not sure where I got this stock shot but it is pretty (if tires can ever be described that way).

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

Flash Graphene from Rubber Waste by Paul A. Advincula, Duy Xuan Luong, Weiyin Chen, Shivaranjan Raghuraman, Rouzbeh Shahsavari, James M.Tour. Carbon Available online 28 March 2021 In Press, Journal Pre-proof DOI: https://doi.org/10.1016/j.carbon.2021.03.020

This paper is behind a paywall.

Impact of graphene flakes (nanoparticles) on neurons

This research suggests that graphene flakes might have an impact on anxiety-related behaviour. If I read the work correctly, the graphene flakes don’t exacerbate anxiety but, instead, may provide relief.

A March 10, 2021 news item on phys.org announces the research into graphene flakes and neurons (rat), Note: Links have been removed,

Effective, specific, with a reversible and non-harmful action: the identikit of the perfect biomaterial seems to correspond to graphene flakes, the subject of a new study carried out by SISSA—International School for Advanced Studies of Trieste, Catalan Institute of Nanoscience and Nanotechnology (ICN2) of Barcelona, and the National Graphene Institute of the University of Manchester, as part of the European Graphene Flagship project. This nanomaterial has demonstrated the ability to interact with the functions of the nervous system in vertebrates in a very specific manner, interrupting the building up of a pathological process that leads to anxiety-related behavior.

“We previously showed that when graphene flakes are delivered to neurons they interfere spontaneously with excitatory synapses by transiently preventing glutamate release from presynaptic terminals,” says Laura Ballerini of SISSA, the leader of the team that carried out the research study “Graphene oxide prevents lateral amygdala dysfunctional synaptic plasticity and reverts long lasting anxiety behavior in rats,” recently published in Biomaterials.

A March 10, 2021 Scuola Internazionale Superiore di Studi Avanzati (SISSA) press release (also on EurekAlert), which originated the news item, provides more detail,

“We investigated whether such a reduction in synaptic activity was sufficient to modify related behaviours, in particular the pathological ones that develop due to a transient and localised hyper-function of excitatory synapses”. This approach would fortify the strategy of selective and transient targeting of synapses to prevent the development of brain pathologies by using the so-called precise medicine treatments.

To test this hypothesis, the team focused on post-traumatic stress disorder (PTSD) and carried out the experiments in two phases, in vivo and in vitro.

“We analysed defensive behaviours caused in rats [emphasis mine] by the presence of a predator, using the exposure to cat odour, to induce an aversive memory” explains Audrey Franceschi Biagioni of SISSA, the first author of the study. “If exposed to the predator odour, the rat has a defensive response, holing up, and this experience is so well-imprinted in the memory, that when the animal is placed in the same context even six days later, the animal remembers the odour of the predator and acts the same protective behaviour. This is a well-known and consolidated model, that we used to reproduce a stress behaviour. Exposure to the predator can modify neuronal connections – a phenomenon that is technically known as plasticity – and increases synaptic activity in a specific area of the amygdala that therefore represented the target of our study to test the effects of the nanomaterial”.

Laura Ballerini adds: “We hypothesised that graphene flakes that we showed to temporarily inhibit excitatory synapses (without causing inflammation, damage to neurons or other side effects) could be injected in the lateral amygdala when the plasticity associated with memory was consolidated. If the nanomaterial was efficient in blocking excitatory synapses, it should inhibit plasticity and decrease the anxiety related response. And this is what happened: the animals that were administered with graphene flakes, after six days, “forgot” the anxiety related responses, rescuing their behaviour”.

The second part of the research was performed in vitro. “In vivo we could observe only behavioural changes and could not evaluate the impact of the graphene flakes on synapses,” explains Giada Cellot, researcher at SISSA and first author of the study together with Audrey Franceschi Biagioni. “In vitro experiments allowed to work on a simplified model, to get insight about the mechanisms through which the graphene flakes can interact with neurons. We used neuronal cultures obtained from the amygdala, the region of the brain where the stress response occurs, and we observed that the effects of nanomaterials were specific for the excitatory synapses and a short exposure to graphene flakes could prevent the pathological plasticity of the synapses”.

Thanks to these findings, graphene flakes have shown their potential as nanotools (biomedical tools composed of nanomaterials) that could act in a specific and reversible way on synaptic activity to interrupt a pathological process and therefore they might be used also to transport drugs or for other applications in the field of precision medicine.

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

Graphene oxide prevents lateral amygdala dysfunctional synaptic plasticity and reverts long lasting anxiety behavior in rats by Audrey Franceschi Biagionia1, Giada Cellot, Elisa Pati, Neus Lozano, Belén Ballesteros, Raffaele Casani, Norberto Cysne Coimbra, Kostas Kostarelos, Laura Ballerini. Biomaterials Volume 271, April 2021, 120749 DOI: https://doi.org/10.1016/j.biomaterials.2021.120749

This paper is open access.

A standard for determining what it means to be graphene

How do you know if your ‘graphene’ light bulb has any graphene in it? How do you know if your orange juice is 100% orange juice? The answer to those questions is that you don’t. So, you must hope there are standards and regulations governing the answers. You must also hope that there are incentives (fines and/or jail time) for obeying those regulations.

In a March 15, 2021 news item on Nanowerk, you’ll find an announcement from the UK’s National Physical Laboratory about an international standard for graphene (Note: A link has been removed),

The National Physical Laboratory (NPL) in the UK in collaboration with international partners, have developed an ISO/IEC [International Standards Organization/International Electrotechnical Commission] standard, ISO/TS 21356-1:2021, for measuring the structural properties of graphene, typically sold as powders or in a liquid dispersion. The ISO/IEC standard allows the supply chain to answer the question ‘what is my material?’ and is based on methods developed with The University of Manchester in the NPL Good Practice Guide 145.

A March ??, 2021 NPL press release, which originated the news item, provides more details,

Over the last few years, graphene, a 2D material with many exciting properties and just one atom thick, has moved from the laboratory into real-world products such as cars and smartphones. However, there is still a barrier affecting the rate of its commercialisation, namely, understanding the true properties of the material. There is not just one type of material, but many, each with different properties that need matching to the many different applications where graphene can provide an improvement.

With hundreds of companies across the globe selling different materials labelled as ‘graphene’, and manufacturing it in different ways, end users who want to improve their products by incorporating few-layer graphene flakes are unable to compare and subsequently select the right material for their product.

Through standardised methods to enable the reliable and repeatable measurement of properties, such as the lateral flake size, flake thickness, level of disorder and specific surface area, industry will be able to compare the many materials available and instil trust in the supply chain.  In conjunction with the international ISO/IEC terminology standard led by NPL, ISO/TS 80004-13:2017, it will be possible for commercially available material to be correctly measured and labelled as graphene, few-layer graphene or graphite.

As the UK’s National Metrology Institute, NPL has been developing and standardising the required metrologically-robust methods for the measurement of graphene and related 2D materials to enable industry to use these materials and realise novel and improved products across many application areas.

The continuation of the NPL-led standardisation work within ISO TC229 (nanotechnologies) will allow the chemical properties of graphene related 2D materials to be determined, as well as the structural properties for different forms of graphene material, such as CVD-grown graphene. This truly international effort to standardise the framework of measurements for graphene is described in more detail in Nature Reviews Physics, including further technical discussion on the new ISO graphene measurement standard.

Dr Andrew J Pollard, Science Area Leader at NPL said: “It is exciting to see this new measurement standard now available for the growing graphene industry worldwide. Based on rigorous metrological research, this standard will allow companies to confidently compare technical datasheets for the first time and is the first step towards verified quality control methods.”

Dr Charles Clifford, Senior Research Scientist at NPL said: “It is fantastic to see this international standard published after several years of development.  To reach international consensus especially across the 37 member countries of ISO TC229 (nanotechnologies) is a testament both to the global interest in graphene and the importance of international cooperation.”

James Baker, CEO of Graphene@Manchester said: “Standardisation is crucial for the commercialisation of graphene in many different applications such as construction, water filtration, energy storage and aerospace. Through this international measurement standard, companies in the UK and beyond will be able to accelerate the uptake of this 21st Century material, now entering many significant markets.”

Here are links to the new standard ISO/TS 21356-1:2021 (Nanotechnologies — Structural characterization of graphene — Part 1: Graphene from powders and dispersions} and the NPL/University of Manchester’s 2017 edition of the Good Practice Guide.

Here’s a second link to the article along with a citation,

The importance of international standards for the graphene community by Charles A. Clifford, Erlon H. Martins Ferreira, Toshiyuki Fujimoto, Jan Herrmann, Angela R. Hight Walker, Denis Koltsov, Christian Punckt, Lingling Ren, Gregory J. Smallwood & Andrew J. Pollard. Nature Reviews Physics (2021) DOI: https://doi.org/10.1038/s42254-021-00278-6 Published 15 March 2021

This paper is behind a paywall.

Making carbon capture more efficient and cheaper with graphene filters

Years ago someone asked me if there was any nanotechnology research into carbon capture. I couldn’t answer the question at the time but since then I’ve been on the lookout for more on the topic. So, I’m happy to add this February 25, 2021 news item on Nanowerk to my growing number of carbon capture posts (Note: A link has been removed),

One of the main culprits of global warming is the vast amount of carbon dioxide pumped out into the atmosphere mostly from burning fossil fuels and the production of steel and cement. In response, scientists have been trying out a process that can sequester waste carbon dioxide, transporting it into a storage site, and then depositing it at a place where it cannot enter the atmosphere.

The problem is that capturing carbon from power plants and industrial emissions isn’t very cost-effective. The main reason is that waste carbon dioxide isn’t emitted pure, but is mixed with nitrogen and other gases, and extracting it from industrial emissions requires extra energy consumption – meaning a pricier bill.

Scientists have been trying to develop an energy-efficient carbon dioxide-filter. Referred to as a “membrane”, this technology can extract carbon dioxide out of the gas mix, which can then be either stored or converted into useful chemicals. “However, the performance of current carbon dioxide filters has been limited by the fundamental properties of currently available materials,” explains Professor Kumar Varoon Agrawal at EPFL’s School of Basic Sciences (EPFL Valais Wallis).

Now, Agrawal has led a team of chemical engineers to develop the world’s thinnest filter from graphene, the world-famous “wonder material” that won the Physics Nobel in 2010. But the graphene filter isn’t just the thinnest in the world, it can also separate carbon dioxide from a mix of gases such as those coming out of industrial emissions and do so with an efficiency and speed that surpasses most current filters.

A March 3, 2021 Ecole Polytechnique Fédérale de Lausanne (EPFL) press release (also on EurekAlert but published February 25, 2021), which originated the news item, delves further into the topic,

“Our approach was simple,” says Agrawal. “We made carbon dioxide-sized holes in graphene, which allowed carbon dioxide to flow through while blocking other gases such as nitrogen, which are larger than carbon dioxide.” The result is a record-high carbon dioxide-capture performance.

For comparison, current filters are required to exceed 1000 gas permeation units (GPUs), while their carbon-capturing specificity, referred to as their “carbon dioxide/nitrogen separation factor” must be above 20. The membranes that the EPFL scientists developed show more than ten-fold higher carbon dioxide permeance at 11,800 GPUs, while their separation factor stands at 22.5.

“We estimate that this technology will drop the cost of carbon capture close to $30 per ton of carbon dioxide, in contrast to commercial processes where the cost is two-to-four time higher,” says Agrawal. His team is now working on scaling up the process by developing a pilot plant demonstrator to capture 10 kg carbon dioxide per day, in a project funded by the Swiss government and Swiss industry.

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

Millisecond lattice gasification for high-density CO2– and O2-sieving nanopores in single-layer graphene by Shiqi Huang, Shaoxian Li, Luis Francisco Villalobos, Mostapha Dakhchoune, Marina Micari, Deepu J. Babu, Mohammad Tohidi Vahdat, Mounir Mensi, Emad Oveisi and Kumar Varoon Agrawal. Science Advances 24 Feb 2021: Vol. 7, no. 9, eabf0116 DOI: 10.1126/sciadv.abf0116

This paper appears to be open access.

Graphene and its magnetism

I have two news bits about graphene and magnetism. If I understood what I was reading, one is more focused on applications and the other is focused on further establishing the field of valleytronics.

University of Cambridge and superconductivity

A February 8, 2021 news item on Nanowerk announces ‘magnetic work’ from the University of Cambridge (Note: A link has been removed),

The researchers, led by the University of Cambridge, were able to control the conductivity and magnetism of iron thiophosphate (FePS3), a two-dimensional material which undergoes a transition from an insulator to a metal when compressed. This class of magnetic materials offers new routes to understanding the physics of new magnetic states and superconductivity.

Using new high-pressure techniques, the researchers have shown what happens to magnetic graphene during the transition from insulator to conductor and into its unconventional metallic state, realised only under ultra-high pressure conditions. When the material becomes metallic, it remains magnetic, which is contrary to previous results and provides clues as to how the electrical conduction in the metallic phase works. The newly discovered high-pressure magnetic phase likely forms a precursor to superconductivity so understanding its mechanisms is vital.

Their results, published in the journal Physical Review X, also suggest a way that new materials could be engineered to have combined conduction and magnetic properties, which could be useful in the development of new technologies such as spintronics, which could transform the way in which computers process information.

A February 8, 2021 University of Cambridge press release (also on EurekAlert), which originated the news item, delves into the topic,

Properties of matter can alter dramatically with changing dimensionality. For example, graphene, carbon nanotubes, graphite and diamond are all made of carbon atoms, but have very different properties due to their different structure and dimensionality.

“But imagine if you were also able to change all of these properties by adding magnetism,” said first author Dr Matthew Coak, who is jointly based at Cambridge’s Cavendish Laboratory and the University of Warwick. “A material which could be mechanically flexible and form a new kind of circuit to store information and perform computation. This is why these materials are so interesting, and because they drastically change their properties when put under pressure so we can control their behaviour.”

In a previous study by Sebastian Haines of Cambridge’s Cavendish Laboratory and the Department of Earth Sciences, researchers established that the material becomes a metal at high pressure, and outlined how the crystal structure and arrangement of atoms in the layers of this 2D material change through the transition.

“The missing piece has remained however, the magnetism,” said Coak. “With no experimental techniques able to probe the signatures of magnetism in this material at pressures this high, our international team had to develop and test our own new techniques to make it possible.”

The researchers used new techniques to measure the magnetic structure up to record-breaking high pressures, using specially designed diamond anvils and neutrons to act as the probe of magnetism. They were then able to follow the evolution of the magnetism into the metallic state.

“To our surprise, we found that the magnetism survives and is in some ways strengthened,” co-author Dr Siddharth Saxena, group leader at the Cavendish Laboratory. “This is unexpected, as the newly-freely-roaming electrons in a newly conducting material can no longer be locked to their parent iron atoms, generating magnetic moments there – unless the conduction is coming from an unexpected source.”

In their previous paper, the researchers showed these electrons were ‘frozen’ in a sense. But when they made them flow or move, they started interacting more and more. The magnetism survives, but gets modified into new forms, giving rise to new quantum properties in a new type of magnetic metal.

How a material behaves, whether conductor or insulator, is mostly based on how the electrons, or charge, move around. However, the ‘spin’ of the electrons has been shown to be the source of magnetism. Spin makes electrons behave a bit like tiny bar magnets and point a certain way. Magnetism from the arrangement of electron spins is used in most memory devices: harnessing and controlling it is important for developing new technologies such as spintronics, which could transform the way in which computers process information.

“The combination of the two, the charge and the spin, is key to how this material behaves,” said co-author Dr David Jarvis from the Institut Laue-Langevin, France, who carried out this work as the basis of his PhD studies at the Cavendish Laboratory. “Finding this sort of quantum multi-functionality is another leap forward in the study of these materials.”

“We don’t know exactly what’s happening at the quantum level, but at the same time, we can manipulate it,” said Saxena. “It’s like those famous ‘unknown unknowns’: we’ve opened up a new door to properties of quantum information, but we don’t yet know what those properties might be.”

There are more potential chemical compounds to synthesise than could ever be fully explored and characterised. But by carefully selecting and tuning materials with special properties, it is possible to show the way towards the creation of compounds and systems, but without having to apply huge amounts of pressure.

Additionally, gaining fundamental understanding of phenomena such as low-dimensional magnetism and superconductivity allows researchers to make the next leaps in materials science and engineering, with particular potential in energy efficiency, generation and storage.

As for the case of magnetic graphene, the researchers next plan to continue the search for superconductivity within this unique material. “Now that we have some idea what happens to this material at high pressure, we can make some predictions about what might happen if we try to tune its properties through adding free electrons by compressing it further,” said Coak.

“The thing we’re chasing is superconductivity,” said Saxena. “If we can find a type of superconductivity that’s related to magnetism in a two-dimensional material, it could give us a shot at solving a problem that’s gone back decades.”

The citation and link to the paper are at the end of this blog posting.

Aalto University’s valleytronics

Further north in Finland, researchers at Aalto University make some advances applicable to the field of valleytronics, from a February 5, 2021 Aalto University press release (also on EurekAltert but published February 8, 2021),

Electrons in materials have a property known as ‘spin’, which is responsible for a variety of properties, the most well-known of which is magnetism. Permanent magnets, like the ones used for refrigerator doors, have all the spins in their electrons aligned in the same direction. Scientists refer to this behaviour as ferromagnetism, and the research field of trying to manipulate spin as spintronics.

Down in the quantum world, spins can arrange in more exotic ways, giving rise to frustrated states and entangled magnets. Interestingly, a property similar to spin, known as “the valley,” appears in graphene materials. This unique feature has given rise to the field of valleytronics, which aims to exploit the valley property for emergent physics and information processing, very much like spintronics relies on pure spin physics.

‘Valleytronics would potentially allow encoding information in the quantum valley degree of freedom, similar to how electronics do it with charge and spintronics with the spin.’ Explains Professor Jose Lado, from Aalto’s Department of applied physics, and one of the authors of the work. ‘What’s more, valleytronic devices would offer a dramatic increase in the processing speeds in comparison with electronics, and with much higher stability towards magnetic field noise in comparison with spintronic devices.’

Structures made of rotated, ultra-thin materials provide a rich solid-state platform for designing novel devices. In particular, slightly twisted graphene layers have recently been shown to have exciting unconventional properties, that can ultimately lead to a new family of materials for quantum technologies. These unconventional states which are already being explored depend on electrical charge or spin. The open question is if the valley can also lead to its own family of exciting states.

Making materials for valleytronics

For this goal, it turns out that conventional ferromagnets play a vital role, pushing graphene to the realms of valley physics. In a recent work, Ph.D. student Tobias Wolf, together with Profs. Oded Zilberberg and Gianni Blatter at ETH Zurich, and Prof. Jose Lado at Aalto University, showed a new direction for correlated physics in magnetic van der Waals materials.

The team showed that sandwiching two slightly rotated layers of graphene between a ferromagnetic insulator provides a unique setting for new electronic states. The combination of ferromagnets, graphene’s twist engineering, and relativistic effects force the “valley” property to dominate the electrons behaviour in the material. In particular, the researchers showed how these valley-only states can be tuned electrically, providing a materials platform in which valley-only states can be generated. Building on top of the recent breakthrough in spintronics and van der Waals materials, valley physics in magnetic twisted van der Waals multilayers opens the door to the new realm of correlated twisted valleytronics.

‘Demonstrating these states represents the starting point towards new exotic entangled valley states.’ Said Professor Lado, ‘Ultimately, engineering these valley states can allow realizing quantum entangled valley liquids and fractional quantum valley Hall states. These two exotic states of matter have not been found in nature yet, and would open exciting possibilities towards a potentially new graphene-based platform for topological quantum computing.’

Citations and links

Here’s a link to and a citation for the University of Cambridge research,

Emergent Magnetic Phases in Pressure-Tuned van der Waals Antiferromagnet FePS3 by Matthew J. Coak, David M. Jarvis, Hayrullo Hamidov, Andrew R. Wildes, Joseph A. M. Paddison, Cheng Liu, Charles R. S. Haines, Ngoc T. Dang, Sergey E. Kichanov, Boris N. Savenko, Sungmin Lee, Marie Kratochvílová, Stefan Klotz, Thomas C. Hansen, Denis P. Kozlenko, Je-Geun Park, and Siddharth S. Saxena. Phys. Rev. X 11, 011024 DOI: https://doi.org/10.1103/PhysRevX.11.011024 Published 5 February 2021

This article appears to be open access.

Here’s a link to and a citation for the Aalto University research,

Spontaneous Valley Spirals in Magnetically Encapsulated Twisted Bilayer Graphene by Tobias M. R. Wolf, Oded Zilberberg, Gianni Blatter, and Jose L. Lado. Phys. Rev. Lett. 126, 056803 DOI: https://doi.org/10.1103/PhysRevLett.126.056803 Published 4 February 2021

This paper is behind a paywall.

The need for Wi-Fi speed

Yes, it’s a ‘Top Gun’ movie quote (1986) or more accurately, a paraphrasing of Tom Cruise’s line “I feel the need for speed.” I understand there’s a sequel, which is due to arrive in movie theatres or elsewhere at sometime in this decade.

Where wireless and WiFi are concerned I think there is a dog/poodle situation. ‘Dog’ is a general description where ‘poodle’ is a specific description. All poodles (specific) are dogs (general) but not all dogs are poodles. So, wireless is a general description and Wi-Fi is a specific type of wireless communication. All WiFi is wireless but not all wireless is Wi-Fi. That said, onto the research.

Given what seems to be an insatiable desire for speed in the wireless world, the quote seems quite à propos in relation to the latest work on quantum tunneling and its impact on Wi-Fi speed from the Moscow Institute of Physics and Technology (from a February 3, 2021 news item on phys.org,

Scientists from MIPT (Moscow Institute of Physics and Technology), Moscow Pedagogical State University and the University of Manchester have created a highly sensitive terahertz detector based on the effect of quantum-mechanical tunneling in graphene. The sensitivity of the device is already superior to commercially available analogs based on semiconductors and superconductors, which opens up prospects for applications of the graphene detector in wireless communications, security systems, radio astronomy, and medical diagnostics. The research results are published in Nature Communications.

A February 3, 2021 MIPT press release (also on EurekAlert), which originated the news item, provides more technical detail about the work and its relation WiFi,

Information transfer in wireless networks is based on transformation of a high-frequency continuous electromagnetic wave into a discrete sequence of bits. This technique is known as signal modulation. To transfer the bits faster, one has to increase the modulation frequency. However, this requires synchronous increase in carrier frequency. A common FM-radio transmits at frequencies of hundred megahertz, a Wi-Fi receiver uses signals of roughly five gigahertz frequency, while the 5G mobile networks can transmit up to 20 gigahertz signals. This is far from the limit, and further increase in carrier frequency admits a proportional increase in data transfer rates. Unfortunately, picking up signals with hundred gigahertz frequencies and higher is an increasingly challenging problem.

A typical receiver used in wireless communications consists of a transistor-based amplifier of weak signals and a demodulator that rectifies the sequence of bits from the modulated signal. This scheme originated in the age of radio and television, and becomes inefficient at frequencies of hundreds of gigahertz desirable for mobile systems. The fact is that most of the existing transistors aren’t fast enough to recharge at such a high frequency.

An evolutionary way to solve this problem is just to increase the maximum operation frequency of a transistor. Most specialists in the area of nanoelectronics work hard in this direction. A revolutionary way to solve the problem was theoretically proposed in the beginning of 1990’s by physicists Michael Dyakonov and Michael Shur, and realized, among others, by the group of authors in 2018. It implies abandoning active amplification by transistor, and abandoning a separate demodulator. What’s left in the circuit is a single transistor, but its role is now different. It transforms a modulated signal into bit sequence or voice signal by itself, due to non-linear relation between its current and voltage drop.

In the present work, the authors have proved that the detection of a terahertz signal is very efficient in the so-called tunneling field-effect transistor. To understand its work, one can just recall the principle of an electromechanical relay, where the passage of current through control contacts leads to a mechanical connection between two conductors and, hence, to the emergence of current. In a tunneling transistor, applying voltage to the control contact (termed as ”gate”) leads to alignment of the energy levels of the source and channel. This also leads to the flow of current. A distinctive feature of a tunneling transistor is its very strong sensitivity to control voltage. Even a small “detuning” of energy levels is enough to interrupt the subtle process of quantum mechanical tunneling. Similarly, a small voltage at the control gate is able to “connect” the levels and initiate the tunneling current

“The idea of ??a strong reaction of a tunneling transistor to low voltages is known for about fifteen years,” says Dr. Dmitry Svintsov, one of the authors of the study, head of the laboratory for optoelectronics of two-dimensional materials at the MIPT center for photonics and 2D materials. “But it’s been known only in the community of low-power electronics. No one realized before us that the same property of a tunneling transistor can be applied in the technology of terahertz detectors. Georgy Alymov (co-author of the study) and I were lucky to work in both areas. We realized then: if the transistor is opened and closed at a low power of the control signal, then it should also be good in picking up weak signals from the ambient surrounding. “

The created device is based on bilayer graphene, a unique material in which the position of energy levels (more strictly, the band structure) can be controlled using an electric voltage. This allowed the authors to switch between classical transport and quantum tunneling transport within a single device, with just a change in the polarities of the voltage at the control contacts. This possibility is of extreme importance for an accurate comparison of the detecting ability of a classical and quantum tunneling transistor.

The experiment showed that the sensitivity of the device in the tunnelling mode is few orders of magnitude higher than that in the classical transport mode. The minimum signal distinguishable by the detector against the noisy background already competes with that of commercially available superconducting and semiconductor bolometers. However, this is not the limit – the sensitivity of the detector can be further increased in “cleaner” devices with a low concentration of residual impurities. The developed detection theory, tested by the experiment, shows that the sensitivity of the “optimal” detector can be a hundred times higher.

“The current characteristics give rise to great hopes for the creation of fast and sensitive detectors for wireless communications,” says the author of the work, Dr. Denis Bandurin. And this area is not limited to graphene and is not limited to tunnel transistors. We expect that, with the same success, a remarkable detector can be created, for example, based on an electrically controlled phase transition. Graphene turned out to be just a good launching pad here, just a door, behind which is a whole world of exciting new research.”

The results presented in this paper are an example of a successful collaboration between several research groups. The authors note that it is this format of work that allows them to obtain world-class scientific results. For example, earlier, the same team of scientists demonstrated how waves in the electron sea of ??graphene can contribute to the development of terahertz technology. “In an era of rapidly evolving technology, it is becoming increasingly difficult to achieve competitive results.” – comments Dr. Georgy Fedorov, deputy head of the nanocarbon materials laboratory, MIPT, – “Only by combining the efforts and expertise of several groups can we successfully realize the most difficult tasks and achieve the most ambitious goals, which we will continue to do.”

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

Tunnel field-effect transistors for sensitive terahertz detection by I. Gayduchenko, S. G. Xu, G. Alymov, M. Moskotin, I. Tretyakov, T. Taniguchi, K. Watanabe, G. Goltsman, A. K. Geim, G. Fedorov, D. Svintsov & D. A. Bandurin. Nature Communications volume 12, Article number: 543 (2021) DOI: https://doi.org/10.1038/s41467-020-20721-z Published: 22 January 2021

This paper is open access.

One last comment, I’m assuming since the University of Manchester is mentioned that A. K. Geim is Sir Andre K. Geim (you can look him up here is you’re not familiar with his role in the graphene research community).