Category Archives: graphene

Graphene: a long story

For a change this October 19, 2021 item on phys.org isn’t highlighting a single research paper so much as it provides a history of graphene and context for research being done at the Joint Quantum Institute (JQI) at the University of Maryland (US),

Carbon is not the shiniest element, nor the most reactive, nor the rarest. But it is one of the most versatile.

Carbon is the backbone of life on earth and the fossil fuels that have resulted from the demise of ancient life. Carbon is the essential ingredient for turning iron into steel, which underlies technologies from medieval swords to skyscrapers and submarines. And strong, lightweight carbon fibers are used in cars, planes and windmills. Even just carbon on its own is extraordinarily adaptable: It is the only ingredient in (among other things) diamonds, buckyballs and graphite (the stuff used to make pencil lead).

This last form, graphite, is at first glance the most mundane, but thin sheets of it host a wealth of uncommon physics. Research into individual atom-thick sheets of graphite—called graphene—took off after 2004 when scientists developed a reliable way to produce it (using everyday adhesive tape to repeatedly peel layers apart). In 2010 early experiments demonstrating the quantum richness of graphene earned two researchers the Nobel Prize in physics.

In recent years, graphene has kept on giving. Researchers have discovered that stacking layers of graphene two or three at a time (called, respectively, bilayer graphene or trilayer graphene) and twisting the layers relative to each other opens fertile new territory for scientists to explore. Research into these stacked sheets of graphene is like the Wild West, complete with the lure of striking gold and the uncertainty of uncharted territory.

Researchers at JQI and the Condensed Matter Theory Center (CMTC) at the University of Maryland, including JQI Fellows Sankar Das Sarma and Jay Sau and others, are busy creating the theoretical physics foundation that will be a map of this new landscape. And there is a lot to map; the phenomena in graphene range from the familiar like magnetism to more exotic things like strange metallicity, different versions of the quantum Hall effect, and the Pomeranchuk effect—each of which involve electrons coordinating to produce unique behaviors. One of the most promising veins for scientific treasure is the appearance of superconductivity (lossless electrical flow) in stacked graphene.

“Here is a system where almost every interesting quantum phase of matter that theorists ever could imagine shows up in a single system as the twist angle, carrier density, and temperature are tuned in a single sample in a single experiment,” says Das Sarma, who is also the Director of the CMTC. “Sounds like magic or science fantasy, except it is happening every day in at least ten laboratories in the world.”

The richness and diversity of the electrical behaviors in graphene stacks has inspired a stampede of research. The 2021 American Physical Society March Meeting included 13 sessions addressing the topics of graphene or twisted bilayers, and Das Sarma hosted a day long virtual conference in June for researchers to discuss twisted graphene and the related research inspired by the topic. The topic of stacked graphene is extensively represented in scientific journals, and the online arXiv preprint server has over 2,000 articles posted about “bilayer graphene”—nearly 1,000 since 2018.

Perhaps surprisingly, graphene’s wealth of quantum research opportunities is tied to its physical simplicity.

An October 18, 2021 JQI news release by Bailey Bedford, which originated the news item, explains why researchers have described a twist found in graphene as ‘magic’,

Researchers have discovered that at a special, small twist angle (about 1.1 degrees)—whimsically named the “magic angle”—the environment is just right to create strong interactions that radically change its properties. When that precise angle is reached, the electrons tend to cluster around certain areas of the graphene, and new electrical behaviors suddenly appear as if summoned with a dramatic magician’s flourish. Magic angle graphene behaves as a poorly-conducting insulator in some circumstances and in other cases goes to the opposite extreme of being a superconductor—a material that transports electricity without any loss of energy.

The discovery of magic-angle graphene and that it has certain quantum behaviors similar to a high-temperature superconductor was the Physics World 2018 Breakthrough of the Year. Superconductors have many valuable potential uses, like revolutionizing energy infrastructure and making efficient maglev trains. Finding a convenient, room-temperature superconductor has been a holy grail for scientists.

I haven’t done to justice to this piece and, so, for anyone interested in graphene, superconductors, and electronics I recommend reading the piece (October 18, 2021 JQI news release by Bailey Bedford) in its entirety where you’ll also find references to these articles and more,

Reference Publication

Related JQI Articles

Sticky tape, hackers, and quantum communications

I always appreciate a low technology solution to a problem. In this case, it’s a piece of sticky tape which halts compute hackers in their tracks. Here’s more from an August 30, 2021 University of Technology Sydney press release (also on EurekAlert but published August 26, 2021), Note: Links have been removed,

Researchers from the University of Technology Sydney (UTS) and TMOS, an Australian Research Council Centre of Excellence [specifically, the Australian Research Council Centre of Excellence for Transformative Meta-Optical Systems (TMOS)], have taken the fight to online hackers with a giant leap towards realizing affordable, accessible quantum communications, a technology that would effectively prevent the decryption of online activity. Everything from private social media messaging to banking could become more secure due to new technology created with a humble piece of adhesive tape.

Quantum communication is still in its early development and is currently feasible only in very limited fields due to the costs associated with fabricating the required devices. The TMOS researches have developed new technology that integrates quantum sources and waveguides on chip in a manner that is both affordable and scalable, paving the way for future everyday use.

The development of fully functional quantum communication technologies has previously been hampered by the lack of reliable quantum light sources that can encode and transmit the information.

In a paper published today in ACS Photonics, the team describes a new platform to generate these quantum emitters based on hexagonal boron nitride, also known as white graphene. Where current quantum emitters are created using complex methods in expensive clean rooms, these new quantum emitters can be created using $20 worth of white graphene pressed on to a piece of adhesive tape.

These 2D materials can be pressed onto a sticky surface such as the [sic] adhesive tape [emphasis mine] and exfoliated, which is essentially peeling off the top layer to create a flex. Multiple layers of this flex can then be assembled in a Lego-like style, offering a new bottom up approach as a substitute for 3D systems.

TMOS Chief Investigator Igor Aharonovich said: “2D materials, like hexagonal boron nitride, are emerging materials for integrated quantum photonics, and are poised to impact the way we design and engineer future optical components for secured communication.”

In addition to this evolution in photon sources, the team has developed a high efficiency on-chip waveguide, a vital component for on-chip optical processing.

Lead author Chi Li said: “Low signal levels have been a significant barrier preventing quantum communications from evolving into practical, workable models. We hope that with this new development, quantum comms will become an everyday technology that improves people’s lives in new and exciting ways.”

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

Integration of hBN Quantum Emitters in Monolithically Fabricated Waveguides by Chi Li, Johannes E. Fröch, Milad Nonahal, Thinh N. Tran, Milos Toth, Sejeong Kim, and Igor Aharonovich. ACS Photonics 2021, XXXX, XXX, XXX-XXX DOI: https://doi.org/10.1021/acsphotonics.1c00890 Publication Date:August 20, 2021 © 2021 American Chemical Society

This paper is behind a paywall.

Sticky or adhesive tape is part of graphene lore and seems to exert a great fascination for scientists as I note in my June 12, 2018 posting.

Artificial ionic neuron for electronic memories

This venture into brain-like (neuromorphic) computing comes from France according to an August 17, 2021 news item on Nanowerk (Note: A link has been removed),

Brain-inspired electronics are the subject of intense research. Scientists from CNRS (Centre national de la recherche scientifique; French National Centre for Scientific Research) and the Ecole Normale Supérieure – PSL have theorized how to develop artificial neurons using, as nerve cells, ions to carry the information.

Their work, published in Science (“Modeling of emergent memory and voltage spiking in ionic transport through angstrom-scale slits”), reports that devices made of a single layer of water transporting ions within graphene nanoslits have the same transmission capacity as a neuron.

Caption Artificial neuron prototype: nanofluidic slits can play the role of ion channels and allow neurons to communicate. Ion clusters achieve the ion transport that causes this communication. Credit © Paul Robin, ENS Laboratoire de Physique (CNRS/ENS-PSL/Sorbonne Université/Université de Paris).

Au August 16, 2021 CNRS press release (also on EurekAlert but published August 6, 2021), which originated the news item, provides insight into the international interest in neuromorphic computing along with a few technical details about this latest research,

With an energy consumption equivalent to two bananas per day, the human brain can perform many complex tasks. Its high energy efficiency depends in particular on its base unit, the neuron, which has a membrane with nanometric pores called ion channels, which open and close according to the stimuli received. The resulting ion flows create an electric current responsible for the emission of action potentials, signals that allow neurons to communicate with each other.

Artificial intelligence can do all of these tasks but only at the cost of energy consumption tens of thousands of times that of the human brain. So the entire research challenge today is to design electronic systems that are as energy efficient as the human brain, for example, by using ions, not electrons, to carry the information. For this, nanofluidics, the study of how fluids behave in channels less than 100 nanometers wide, offer many perspectives. In a new study, a team from the ENS Laboratoire de Physique (CNRS/ENS-PSL/Sorbonne Université/Université de Paris) shows how to construct a prototype of an artificial neuron formed of extremely thin graphene slits containing a single layer of water molecules1. The scientists have shown that, under the effect of an electric field, the ions from this layer of water assemble into elongated clusters and develop a property known as the memristor effect: these clusters retain some of the stimuli that have been received in the past. To repeat the comparison with the brain, the graphene slits reproduce the ion channels, clusters and ion flows. And, using theoretical and digital tools, scientists have shown how to assemble these clusters to reproduce the physical mechanism of emission of action potentials, and thus the transmission of information.

This theoretical work continues experimentally within the French team, in collaboration with scientists from the University of Manchester (UK). The goal now is to prove experimentally that such systems can implement simple learning algorithms that can serve as the basis for tomorrow’s electronic memories.

1 Recently invented in Manchester by the group of André Geim (Nobel Prize in Physics 2010)

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

Modeling of emergent memory and voltage spiking in ionic transport through angstrom-scale slits by Paul Robin, Nikita Kavokine, Lydéric Bocquet. Science 06 Aug 2021: Vol. 373, Issue 6555, pp. 687-691 DOI: 10.1126/science.abf7923

This paper is behind a paywall.

Season’s Greetings with the world’s thinnest Christmas tree

Courtesy: Technical University of Denmark

I haven’t seen one of these in a while. It used to be a relatively common occurrence (especially during a holiday) that scientists would create the world’s smallest XXX and send a press release. I’ve missed them so I’m glad to see this one pop up.

A December 23, 2021 news item on phys.org announces the world’s thinnest Christmas tree,

A Christmas tree with a thickness of one atom has been made at DTU [Technical University of Denmark]. It shows how terahertz measurements can be used to ensure the quality of graphene.

A December 22, 2021 DTU press release by by Tore Vind Jensen, which originated the news item, provides more technical detail,

The Christmas tree in the pictures above is 14 centimeters long. Since it is made of graphene, it consists of carbon atoms in only one layer and is only a third of a nanometer thick. It is cut out of a 10-meter long roll of graphene, transferred in one piece using a rebuilt laminating machine and then scanned with terahertz radiation.

The experiment shows that continuous quality control can be done during the production of graphene, which is expected to play a significant role in future high-speed electronics, i.e. medical instruments and sensors.

Graphene is a so-called two-dimensional material, i.e. it consists of atoms in one cohesive layer that is only one atom thin. It is more robust, stiffer and better at conducting electricity and heat than any other material we know of. Therefore, graphene is an obvious candidate for electronic circuits that take up less space, weigh less, are bendable and are more efficient than the electronics we know today.

“Even if you could make a pencil drawing of a Christmas tree and lift it off the paper—which, figuratively, is what we have done—it would be much thicker than one atom. A bacterium is, e.g. 3000 times thicker than the graphene layer we used. That’s why I dare call this the world’s thinnest Christmas tree. And although the starting point is carbon, just like the graphite in a pencil, graphene is at the same time even more conductive than copper. The “drawing” is made in one perfect layer in one piece, ” says Professor Peter Bøggild who lead the team behind the Christmas tree experiment.

“But behind the Christmas joke hides an important breakthrough. For the first time, we managed to make an in-line quality control of the graphene layer while we transferred it. Doing this is the key to gaining stable, reproducible and usable material properties, which is the prerequisite for utilizing graphene in, e.g. electronic circuits.”

30,000 times thinner than kitchen film

As the researchers have done in this case, the graphene can be “grown” on copper film. The graphene is deposited on a roll of copper foil at around 1000 ° C. That process is well known and well-functioning. But a lot can go wrong when the ultra-thin graphene film is moved from the copper roller to where it is used. Since graphene is 30,000 times thinner than kitchen film, it is a demanding process. Researcher Abhay Shivayogimath has been behind several new inventions in DTU’s transfer process, ensuring a stable transfer of the graphene layers from the copper roll.

Moreover, there has been no technology that could control the electrical quality of graphene on the go—while transferring it. This year Peter Bøggild and his colleague Professor Peter Uhd Jepsen from DTU Fotonik, one of the world’s leading terahertz researchers, established a way to do it.

The colored images are measurements of how the graphene layer absorbs terahertz radiation. The absorption is directly related to the electric conductivity: the better the conductive graphene, the better it absorbs.

Terahertz rays are high-frequency radio waves that lie between infrared radiation and microwaves. Like X-rays, they can be used to scan human bodies, as we know it from airport security. Terahertz rays can also take pictures of the electrical resistance of the graphene layer. By connecting the terahertz scanner to the machine that transfers the graphene film, it is possible to image the electrical properties of the film during the transfer process.

Official international measurement standard

Suppose the implementation of graphene and other 2D materials is to be accelerated. In that case, ongoing quality assurance is a prerequisite, says Peter Bøggild. Quality control precedes trust, he says. The technology can guarantee that graphene-based technologies are manufactured more uniformly and predictably with fewer errors. This year, the DTU researchers’ method was approved as the first official international measurement standard for graphene. Their method was described earlier this year in the article ‘Terahertz imaging of graphene paves the way to industrialisation.’

The potential is excellent. Graphene and other two-dimensional materials can e.g. enable the manufacturing of high-speed electronics performing lightning-fast calculations with far less power consumption than the technologies we use today. But before graphene can become more widespread on an industrial scale and be used in electronics, we encounter in everyday life three main problems must be solved.

First, the price is too high. More and faster production is needed to bring the price down. But with that, you face the second problem: When you increase the speed and can not at the same time check the quality, the risk of error also increases dramatically. At high high-speed transfer, everything must be set precisely.This brings us to the third problem: How do you know what is precise?

It requires measurements. And preferably measurements during the actual transfer process. The DTU team is convinced that the best bet on that method is quality control using terahertz radiation.

Peter Bøggild emphasizes that these three problems have not been solved with the new method alone: “We have taken a very significant step. We have converted a laminating machine into a so-called roll-2-roll transfer system. It gently lifts the graphene layer from the copper roll on which the graphene layer is grown and moves it onto plastic foil without it breaking, becoming wrinkled or dirty. When we combine this with the terahertz system, we can immediately see if the process has gone well. That is, whether we have unbroken graphene with low electrical resistance,” says Peter Bøggild.

Joyeux Noël et une bonne année 2022!

Radiation-free quantum technology with graphene

A July 8, 2021 news item on Nanowerk announces research from Finland and Switzerland that could have an impact on real world quantum technologies (Note: A link has been removed),

Rare-earth compounds have fascinated researchers for decades due to the unique quantum properties they display, which have so far remained totally out of reach of everyday compounds. One of the most remarkable and exotic properties of those materials is the emergence of exotic superconducting states, and particularly the superconducting states required to build future topological quantum computers.

While these specific rare-earth compounds, known as heavy fermion superconductors, have been known for decades, making usable quantum technologies out of them has remained a critically open challenge. This is because these materials contain critically radioactive compounds, such as uranium and plutonium, rendering them of limited use in real-world quantum technologies.

New research has now revealed an alternative pathway to engineer the fundamental phenomena of these rare-earth compounds solely with graphene, which has none of the safety problems of traditional rare-earth compounds.

The exciting result in the new paper shows how a quantum state known as a “heavy fermion” can be produced by combining three twisted graphene layers. A heavy fermion is a particle – in this case an electron – that behaves like it has a lot more mass than it actually does. The reason it behaves this way stems from unique quantum many-body effects that were mostly only observed in rare-earth compounds until now.

This heavy fermion behavior is known to be the driving force of the phenomena required to use these materials for topological quantum computing. This new result demonstrates a new, non-radioactive way of achieving this effect using only carbon, opening up a pathway for sustainably exploiting heavy fermion physics in quantum technologies.

A July 8, 2021 Aalto University press release (also on EurekAlert), which originated the news item, provides more details,

In the paper authored by Aline Ramires, (Paul Scherrer Institute, Switzerland) and Jose Lado (Aalto University), the researchers show how it is possible to create heavy fermions with cheap, non-radioactive materials. To do this, they used graphene, which is a one-atom thick layer of carbon. Despite being chemically identical to the material that is used in regular pencils, the sub-nanometre thickness of graphene means that it has unexpectedly unique electrical properties. By layering the thin sheets of carbon on top of one another in a specific pattern, where each sheet is rotated in relation to the other, the researchers can create the quantum properties effect that results in the electrons in the graphene behaving like heavy fermions.

“Until now, practical applications of heavy fermion superconductors for topological quantum computing has not been pursued much, partially because it required compounds containing uranium and plutonium, far from ideal for applications due to their radioactive nature”, says Professor Lado, “In this work we show that one can aim to realize the exactly very same physics just with graphene. While in this work we only show the emergence of heavy fermion behavior, addressing the emergence of topological superconductivity is a natural next step, which could potentially have a groundbreaking impact for topological quantum computing.”

Topological superconductivity is a topic of critical interest for quantum technologies, also tackled by alternative strategies in other papers from Aalto University Department of Applied Physics, including a previous paper by Professor Lado. “These results potentially provide a carbon-based platform for exploitation of heavy fermion phenomena in quantum technologies, without requiring rare-earth elements”, concludes Professor Lado.

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

Emulating Heavy Fermions in Twisted Trilayer Graphene by Aline Ramires and Jose L. Lado. Phys. Rev. Lett. 127, 026401 DOI: https://doi.org/10.1103/PhysRevLett.127.026401 Published 7 July 2021 © 2021 American Physical Society

This paper is behind a paywall.

Quick and efficient nanographene synthesis

Thank you to Nagoya University (Japan) for making this image available.

Caption: APEX reactions are carried out on the K, M and bay regions of the polycyclic aromatic hydrocarbon, synthesizing multiple nanographenes. These reactions can then be repeated, further increasing the number of potential nanographene structures that can be synthesized. Credit: Issey Takahashi

From a June 28, 2021 Nagoya University press release (also on EurekAlert),

A group of researchers at Nagoya University, Japan, have developed a new method for quickly and efficiently synthesizing nanographenes, a type of nanocarbon with great potential as a next generation material.

Nanographenes are the part structures of graphene, which is a sheet of carbon atoms around 3 nanometers thick with particular potential for use in semiconductor development, having electron mobility several hundred times better than current generation materials. Graphene was first isolated in 2004, a discovery which received the 2010 Nobel Prize in physics, making it a very new material which is currently the subject of a great deal of research.

With magnetic and electric characteristics beyond those of graphene, nanographenes are equally of interest to scientists in the nanocarbon research field. The biggest obstacle, albeit an exciting one, faced by researchers is the sheer number of potential nanographenes. The number of potentially possible nanographene structures increases with the number of benzene rings (6 atoms of carbon in a hexagonal formation) to make them. For example, even a relatively small 10 benzene ring nanographene may have up to 16,000 variants. As each nanographene has different physical characteristics, the key to applied nanographene research is to identify the relationship between the structure and characteristics of as many nanographenes as possible.

Thus, scientists’ task is to create a nanographene library, containing data on the properties of as many nanographenes as possible. However, the current method of nanographene synthesis, known as a coupling reaction, is a multi-step process which produces one single nanographene. Thus, to create a 100-nanographene library, 100 separate coupling reactions would have to be carried out. Even this would be a significant undertaking, rendering the construction of a truly comprehensive nanographene library practically impossible.

To solve this problem, the Nagoya University research group, led by Professor Kenichiro Itami, have been working on the APEX reaction, a reaction which uses polycyclic aromatic hydrocarbons as templates to synthesize nanographenes. Polycyclic aromatic hydrocarbons have three areas of their structure – known as the K region, M region and bay region – which can be elongated in an APEX reaction, producing three nanographenes. These nanographenes can then be further elongated in a second reaction, meaning that a large number of nanographenes can be synthesized from a single polycyclic aromatic hydrocarbon template molecule.

With Professor Itami’s group having already developed the K region APEX reaction, and another group of scientists having done so for the bay region, they turned their attention to the M region. They activated the M region using the 1950 Nobel Prize winning Diels-Alder reaction, and succeeded in carrying out an elongation reaction on the activated M region, thus rendering all three possible sites on the polycyclic aromatic hydrocarbons capable of synthesizing nanographenes.

The researchers were able to produce 13 nanographenes with three APEX reactions, with most of these being previously unseen structures, thus proving both the efficiency and usefulness of this new method.

This exciting new piece of research and its potential to accelerate the creation of nanographene libraries is a step towards the development of the next generation of materials, which have the potential to revolutionize semiconductors and solar energy and improve lives all around the world.

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

Diversity-oriented synthesis of nanographenes enabled by dearomative annulative π-extension by Wataru Matsuoka, Hideto Ito, David Sarlah & Kenichiro Itami. Nature Communications volume 12, Article number: 3940 (2021) DOI: https://doi.org/10.1038/s41467-021-24261-y Published 24 June 2021

This paper is open access.

Graphene in art preservation and restoration

A July 5, 2021 news item on phys.org announces a new technology for preserving and restoring your paintings,

The exposure of colors used in artworks to ultraviolet (UV) and visible light in the presence of oxidizing agents triggers color degradation, fading and yellowing. These degradation mechanisms can lead to irreversible alteration of artworks. Protective varnishes and coatings currently used to protect art paintings are not acceptable solutions, since their removal requires the use of solvents, which can affect adversely the underlying work surface.

A team of researchers from the Institute of Chemical Engineering Sciences of Foundation for Research and Technology-Hellas (FORTH/ ICE-HT), the Department of Chemical Engineering of the University of Patras, and the Center for Colloid and Surface Science (CSGI) of the University of Florence, led by Professor Costas Galiotis, had the innovative ideato use graphene veils for the protection of paintings against environmental degradation.

A July 2, 2021 Foundation for Research and Technology – Hellas (FORTH) press release, which originated the news item, provides more details,

Since its isolation in 2004 by Geim [Andre Geim] and Novoselov [Konstantin Novoselov] from the University of Manchester (Nobel Prize in Physics in 2010), graphene has been termed as a ‘wonder material’ due to its exceptional properties that have already been used in many applications and products. The graphene veil used in this work is a flexible, transparent film, produced by the technique of chemical vapor deposition. It has a monoatomic thickness and, since there are no size limitations in the other dimensions (length and width), it can cover any required large surface areas.

The results from measurements performed in the above mentioned laboratories, showed that this membrane is impermeable to moisture, the oxidizing agents and other harmful pollutants and also can absorb a large amount of harmful ultraviolet radiation. Finally, in contrast to other protective means, it is demonstrated that these graphene coatings are relatively easy to remove without damaging the surface of the artworks.

[downloaded from https://phys.org/news/2021-07-graphene-paving-methods-art.html]

Before getting to the link and citation for the paper, here’s the abstract, which helps fill n a few more details,

Modern and contemporary art materials are generally prone to irreversible colour changes upon exposure to light and oxidizing agents. Graphene can be produced in thin large sheets, blocks ultraviolet light, and is impermeable to oxygen, moisture and corrosive agents; therefore, it has the potential to be used as a transparent layer for the protection of art objects in museums, during storage and transportation. Here we show that a single-layer or multilayer graphene veil, produced by chemical vapour deposition, can be deposited over artworks to protect them efficiently against colour fading, with a protection factor of up to 70%. We also show that this process is reversible since the graphene protective layer can be removed using a soft rubber eraser without causing any damage to the artwork. We have also explored a complementary contactless graphene-based route for colour protection that is based on the deposition of graphene on picture framing glass for use when the directapplication of graphene is not feasible due to surface roughness or artwork fragility. Overall, the present results are a proof of concept of the potential use of graphene as an effective and removable protective advanced material to prevent colour fading in artworks.

And now, a link to and a citation for the paper,

Preventing colour fading in artworks with graphene veils by M. Kotsidi, G. Gorgolis, M. G. Pastore Carbone, G. Anagnostopoulos, G. Paterakis, G. Poggi, A. Manikas, G. Trakakis, P. Baglioni & C. Galiotis. Nature Nanotechnology (2021) DOI: https://doi.org/10.1038/s41565-021-00934-z Published 01 July 2021

This paper is behind a paywall.

A graphene ‘camera’ and your beating heart: say cheese

Comparing it to a ‘camera’, even with the quotes, is a bit of a stretch for my taste but I can’t come up with a better comparison. Here’s a video so you can judge for yourself,

Caption: This video repeats three times the graphene camera images of a single beat of an embryonic chicken heart. The images, separated by 5 milliseconds, were measured by a laser bouncing off a graphene sheet lying beneath the heart. The images are about 2 millimeters on a side. Credit: UC Berkeley images by Halleh Balch, Alister McGuire and Jason Horng

A June 16, 2021 news item on ScienceDaily announces the research,

Bay Area [San Francisco, California] scientists have captured the real-time electrical activity of a beating heart, using a sheet of graphene to record an optical image — almost like a video camera — of the faint electric fields generated by the rhythmic firing of the heart’s muscle cells.

A University of California at Berkeley (UC Berkeley) June 16, 2021 news release (also on EurekAlert) by Robert Sanders, which originated the news item, provides more detail,

The graphene camera represents a new type of sensor useful for studying cells and tissues that generate electrical voltages, including groups of neurons or cardiac muscle cells. To date, electrodes or chemical dyes have been used to measure electrical firing in these cells. But electrodes and dyes measure the voltage at one point only; a graphene sheet measures the voltage continuously over all the tissue it touches.

The development, published online last week in the journal Nano Letters, comes from a collaboration between two teams of quantum physicists at the University of California, Berkeley, and physical chemists at Stanford University.

“Because we are imaging all cells simultaneously onto a camera, we don’t have to scan, and we don’t have just a point measurement. We can image the entire network of cells at the same time,” said Halleh Balch, one of three first authors of the paper and a recent Ph.D. recipient in UC Berkeley’s Department of Physics.

While the graphene sensor works without having to label cells with dyes or tracers, it can easily be combined with standard microscopy to image fluorescently labeled nerve or muscle tissue while simultaneously recording the electrical signals the cells use to communicate.

“The ease with which you can image an entire region of a sample could be especially useful in the study of neural networks that have all sorts of cell types involved,” said another first author of the study, Allister McGuire, who recently received a Ph.D. from Stanford and. “If you have a fluorescently labeled cell system, you might only be targeting a certain type of neuron. Our system would allow you to capture electrical activity in all neurons and their support cells with very high integrity, which could really impact the way that people do these network level studies.”

Graphene is a one-atom thick sheet of carbon atoms arranged in a two-dimensional hexagonal pattern reminiscent of honeycomb. The 2D structure has captured the interest of physicists for several decades because of its unique electrical properties and robustness and its interesting optical and optoelectronic properties.

“This is maybe the first example where you can use an optical readout of 2D materials to measure biological electrical fields,” said senior author Feng Wang, UC Berkeley professor of physics. “People have used 2D materials to do some sensing with pure electrical readout before, but this is unique in that it works with microscopy so that you can do parallel detection.”

The team calls the tool a critically coupled waveguide-amplified graphene electric field sensor, or CAGE sensor.

“This study is just a preliminary one; we want to showcase to biologists that there is such a tool you can use, and you can do great imaging. It has fast time resolution and great electric field sensitivity,” said the third first author, Jason Horng, a UC Berkeley Ph.D. recipient who is now a postdoctoral fellow at the National Institute of Standards and Technology. “Right now, it is just a prototype, but in the future, I think we can improve the device.”

Graphene is sensitive to electric fields

Ten years ago, Wang discovered that an electric field affects how graphene reflects or absorbs light. Balch and Horng exploited this discovery in designing the graphene camera. They obtained a sheet of graphene about 1 centimeter on a side produced by chemical vapor deposition in the lab of UC Berkeley physics professor Michael Crommie and placed on it a live heart from a chicken embryo, freshly extracted from a fertilized egg. These experiments were performed in the Stanford lab of Bianxiao Cui, who develops nanoscale tools to study electrical signaling in neurons and cardiac cells.

The team showed that when the graphene was tuned properly, the electrical signals that flowed along the surface of the heart during a beat were sufficient to change the reflectance of the graphene sheet.

“When cells contract, they fire action potentials that generate a small electric field outside of the cell,” Balch said. “The absorption of graphene right under that cell is modified, so we will see a change in the amount of light that comes back from that position on the large area of graphene.”

In initial studies, however, Horng found that the change in reflectance was too small to detect easily. An electric field reduces the reflectance of graphene by at most 2%; the effect was much less from changes in the electric field when the heart muscle cells fired an action potential.

Together, Balch, Horng and Wang found a way to amplify this signal by adding a thin waveguide below graphene, forcing the reflected laser light to bounce internally about 100 times before escaping. This made the change in reflectance detectable by a normal optical video camera.

“One way of thinking about it is that the more times that light bounces off of graphene as it propagates through this little cavity, the more effects that light feels from graphene’s response, and that allows us to obtain very, very high sensitivity to electric fields and voltages down to microvolts,” Balch said.

The increased amplification necessarily lowers the resolution of the image, but at 10 microns, it is more than enough to study cardiac cells that are several tens of microns across, she said.

Another application, McGuire said, is to test the effect of drug candidates on heart muscle before these drugs go into clinical trials to see whether, for example, they induce an unwanted arrhythmia. To demonstrate this, he and his colleagues observed the beating chicken heart with CAGE and an optical microscope while infusing it with a drug, blebbistatin, that inhibits the muscle protein myosin. They observed the heart stop beating, but CAGE showed that the electrical signals were unaffected.

Because graphene sheets are mechanically tough, they could also be placed directly on the surface of the brain to get a continuous measure of electrical activity — for example, to monitor neuron firing in the brains of those with epilepsy or to study fundamental brain activity. Today’s electrode arrays measure activity at a few hundred points, not continuously over the brain surface.

“One of the things that is amazing to me about this project is that electric fields mediate chemical interactions, mediate biophysical interactions — they mediate all sorts of processes in the natural world — but we never measure them. We measure current, and we measure voltage,” Balch said. “The ability to actually image electric fields gives you a look at a modality that you previously had little insight into.”

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

Graphene Electric Field Sensor Enables Single Shot Label-Free Imaging of Bioelectric Potentials by Halleh B. Balch, Allister F. McGuire, Jason Horng, Hsin-Zon Tsai, Kevin K. Qi, Yi-Shiou Duh, Patrick R. Forrester, Michael F. Crommie, Bianxiao Cui, and Feng Wang. Nano Lett. 2021, XXXX, XXX, XXX-XXX OI: https://doi.org/10.1021/acs.nanolett.1c00543 Publication Date: June 8, 2021 © 2021 American Chemical Society

This paper is behind a paywall.

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.