Tag Archives: Parambath M. Sudeep

Graphene fatigue

Graphene fatigue operates under the same principle as metal fatigue. Subject graphene to stress over and over and at some point it (just like metal) will fail. Scientists at the University of Toronto (Ontatrio, Canada) and Rice University (Texas, US) have determined just how much stress graphene can withstand before breaking according to a January 28, 2020 University of Toronto news release by Tyler Irving (also on EurekAlert but published on January 29, 2020),

Graphene is a paradox. It is the thinnest material known to science, yet also one of the strongest. Now, research from University of Toronto Engineering shows that graphene is also highly resistant to fatigue — able to withstand more than a billion cycles of high stress before it breaks.

Graphene resembles a sheet of interlocking hexagonal rings, similar to the pattern you might see in bathroom flooring tiles. At each corner is a single carbon atom bonded to its three nearest neighbours. While the sheet could extend laterally over any area, it is only one atom thick.

The intrinsic strength of graphene has been measured at more than 100 gigapascals, among the highest values recorded for any material. But materials don’t always fail because the load exceeds their maximum strength. Stresses that are small but repetitive can weaken materials by causing microscopic dislocations and fractures that slowly accumulate over time, a process known as fatigue.

“To understand fatigue, imagine bending a metal spoon,” says Professor Tobin Filleter, one of the senior authors of the study, which was recently published in Nature Materials. “The first time you bend it, it just deforms. But if you keep working it back and forth, eventually it’s going to break in two.”

The research team — consisting of Filleter, fellow University of Toronto Engineering professors Chandra Veer Singh and Yu Sun, their students, and collaborators at Rice University — wanted to know how graphene would stand up to repeated stresses. Their approach included both physical experiments and computer simulations.

“In our atomistic simulations, we found that cyclic loading can lead to irreversible bond reconfigurations in the graphene lattice, causing catastrophic failure on subsequent loading,” says Singh, who along with postdoctoral fellow Sankha Mukherjee led the modelling portion of the study. “This is unusual behaviour in that while the bonds change, there are no obvious cracks or dislocations, which would usually form in metals, until the moment of failure.”

PhD candidate Teng Cui, who is co-supervised by Filleter and Sun, used the Toronto Nanofabrication Centre to build a physical device for the experiments. The design consisted of a silicon chip etched with half a million tiny holes only a few micrometres in diameter. The graphene sheet was stretched over these holes, like the head of a tiny drum.

Using an atomic force microscope, Cui then lowered a diamond-tipped probe into the hole to push on the graphene sheet, applying anywhere from 20 to 85 per cent of the force that he knew would break the material.

“We ran the cycles at a rate of 100,000 times per second,” says Cui. “Even at 70 per cent of the maximum stress, the graphene didn’t break for more than three hours, which works out to over a billion cycles. At lower stress levels, some of our trials ran for more than 17 hours.”

As with the simulations, the graphene didn’t accumulate cracks or other tell-tale signs of stress — it either broke or it didn’t.

“Unlike metals, there is no progressive damage during fatigue loading of graphene,” says Sun. “Its failure is global and catastrophic, confirming simulation results.”

The team also tested a related material, graphene oxide, which has small groups of atoms such as oxygen and hydrogen bonded to both the top and bottom of the sheet. Its fatigue behaviour was more like traditional materials, in that the failure was more progressive and localized. This suggests that the simple, regular structure of graphene is a major contributor to its unique properties.

“There are no other materials that have been studied under fatigue conditions that behave the way graphene does,” says Filleter. “We’re still working on some new theories to try and understand this.”

In terms of commercial applications, Filleter says that graphene-containing composites — mixtures of conventional plastic and graphene — are already being produced and used in sports equipment such as tennis rackets and skis.

In the future, such materials may begin to be used in cars or in aircraft, where the emphasis on light and strong materials is driven by the need to reduce weight, improve fuel efficiency and enhance environmental performance.

“There have been some studies to suggest that graphene-containing composites offer improved resistance to fatigue, but until now, nobody had measured the fatigue behaviour of the underlying material,” he says. “Our goal in doing this was to get at that fundamental understanding so that in the future, we’ll be able to design composites that work even better.”

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

Fatigue of graphene by Teng Cui, Sankha Mukherjee, Parambath M. Sudeep, Guillaume Colas, Farzin Najafi, Jason Tam, Pulickel M. Ajayan, Chandra Veer Singh, Yu Sun & Tobin Filleter. Nature Materials (2020) DOI: DOIhttps://doi.org/10.1038/s41563-019-0586-y Published: 20 January 2020

This paper is behind a paywall.

A new graphene-based contrast agent for magnetic resonance imaging (MRI)

After teaching a continuing studies course on bioelectronics for Simon Fraser University (Vancouver, Canada), I’ve developed a mild interest in magnetic resonance imaging and contrast agents which this Nov. 11, 2016 news item on phys.org satisfies,

Graphene, the atomically thin sheets of carbon that materials scientists are hoping to use for everything from nanoelectronics and aircraft de-icers to batteries and bone implants, may also find use as contrast agents for magnetic resonance imaging (MRI), according to new research from Rice University.

“They have a lot of advantages compared with conventionally available contrast agents,” Rice researcher Sruthi Radhakrishnan said of the graphene-based quantum dots she has studied for the past two years. “Virtually all of the widely used contrast agents contain toxic metals, but our material has no metal. It’s just carbon, hydrogen, oxygen and fluorine, and in all of our tests so far it has shown no signs of toxicity.”

The initial findings for Rice’s nanoparticles—disks of graphene that are decorated with fluorine atoms and simply organic molecules that make them magnetic—are described in a new paper in the journal Particle and Particle Systems characterization.

A Nov. 10, 2016 Rice University (Texas, US) news release, which originated the news item, describes the work in more detail,

Pulickel Ajayan, the Rice materials scientist who is directing the work, said the fluorinated graphene oxide quantum dots could be particularly useful as MRI contrast agents because they could be targeted to specific kinds of tissues.

“There are tried-and-true methods for attaching biomarkers to carbon nanoparticles, so one could easily envision using these quantum dots to develop tissue-specific contrast agents,” Ajayan said. “For example, this method could be used to selectively target specific types of cancer or brain lesions caused by Alzheimer’s disease. That kind of specificity isn’t available with today’s contrast agents.”

MRI scanners make images of the body’s internal structures using strong magnetic fields and radio waves. As diagnostic tests, MRIs often provide greater detail than X-rays without the harmful radiation, and as a result, MRI usage has risen sharply over the past decade. More than 30 million MRIs are performed annually in the U.S.

Radhakrishnan said her work began in 2014 after Ajayan’s research team found that adding fluorine to either graphite or graphene caused the materials to show up well on MRI scans.

All materials are influenced by magnetic fields, including animal tissues. In MRI scanners, a powerful magnetic field causes individual atoms throughout the body to become magnetically aligned. A pulse of radio energy is used to disrupt this alignment, and the machine measures how long it takes for the atoms in different parts of the body to become realigned. Based on these measures, the scanner can build up a detailed image of the body’s internal structures.

MRI contrast agents shorten the amount of time it takes for tissues to realign and significantly improve the resolution of MRI scans. Almost all commercially available contrast agents are made from toxic metals like gadolinium, iron or manganese.

“We worked with a team from MD Anderson Cancer Center to assess the cytocompatibility of fluorinated graphene oxide quantum dots,” Radhakrishnan said. “We used a test that measures the metabolic activity of cell cultures and detects toxicity as a drop in metabolic activity. We incubated quantum dots in kidney cell cultures for up to three days and found no significant cell death in the cultures, even at the highest concentrations.”

The fluorinated graphene oxide quantum dots Radhakrishnan studies can be made in less than a day, but she spent two years perfecting the recipe for them. She begins with micron-sized sheets of graphene that have been fluorinated and oxidized. When these are added to a solvent and stirred for several hours, they break into smaller pieces. Making the material smaller is not difficult, but the process for making small particles with the appropriate magnetic properties is exacting. Radhakrishnan said there was no “eureka moment” in which she suddenly achieved the right results by stumbling on the best formula. Rather, the project was marked by incremental improvements through dozens of minor alterations.

“It required a lot of optimization,” she said. “The recipe matters a lot.”

Radhakrishnan said she plans to continue studying the material and hopes to eventually have a hand in proving that it is safe and effective for clinical MRI tests.

“I would like to see it applied commercially in clinical ways because it has a lot of advantages compared with conventionally available agents,” she said.

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

Metal-Free Dual Modal Contrast Agents Based on Fluorographene Quantum Dots by Sruthi Radhakrishnan, Atanu Samanta, Parambath M. Sudeep, Kiersten L. Maldonado, Sendurai A. Mani, Ghanashyam Acharya, Chandra Sekhar Tiwary, Abhishek K. Singh, and Pulickel M. Ajayan. Particle & Particle Systems Characterization DOI: 10.1002/ppsc.201600221 Version of Record online: 21 OCT 2016

This paper is behind a paywall.