Tag Archives: nanoribbons

Self-assembled molecular nanofibers that are stronger than steel

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A January 26, 2021 news item on Nanowerk announces a promising discovery in ‘self-assembly research’ (Note: A link has been removed,

Self-assembly is ubiquitous in the natural world, serving as a route to form organized structures in every living organism. This phenomenon can be seen, for instance, when two strands of DNA — without any external prodding or guidance — join to form a double helix, or when large numbers of molecules combine to create membranes or other vital cellular structures. Everything goes to its rightful place without an unseen builder having to put all the pieces together, one at a time.

For the past couple of decades, scientists and engineers have been following nature’s lead, designing molecules that assemble themselves in water, with the goal of making nanostructures, primarily for biomedical applications such as drug delivery or tissue engineering.

“These small-molecule-based materials tend to degrade rather quickly,” explains Julia Ortony, assistant professor in [Massachusetts Institute of Technology] MIT’s Department of Materials Science and Engineering (DMSE), “and they’re chemically unstable, too. The whole structure falls apart when you remove the water, particularly when any kind of external force is applied.”

She and her team, however, have designed a new class of small molecules that spontaneously assemble into nanoribbons with unprecedented strength, retaining their structure outside of water. The results of this multi-year effort, which could inspire a broad range of applications, were described in Nature Nanotechnology (“Self-assembly of aramid amphiphiles into ultra-stable nanoribbons and aligned nanoribbon threads”) by Ortony and coauthors.

“This seminal work — which yielded anomalous mechanical properties through highly controlled self-assembly — should have a big impact on the field,” asserts Professor Tazuko Aida, deputy director for the RIKEN Center for Emergent Matter Science and professor of chemistry and biotechnology at the University of Tokyo, who was not involved in the research.

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A January 26, 2021 MIT news release, which originated the news item, describe the work in more detail,

The material the MIT group constructed — or rather, allowed to construct itself — is modeled after a cell membrane. Its outer part is “hydrophilic,” which means it likes to be in water, whereas its inner part is “hydrophobic,” meaning it tries to avoid water. This configuration, Ortony comments, “provides a driving force for self-assembly,” as the molecules orient themselves to minimize interactions between the hydrophobic regions and water, consequently taking on a nanoscale shape.

The shape, in this case, is conferred by water, and ordinarily the whole structure would collapse when dried. But Ortony and her colleagues came up with a plan to keep that from happening. When molecules are loosely bound together, they move around quickly, analogous to a fluid; as the strength of intermolecular forces increases, motion slows and molecules assume a solid-like state. The idea, Ortony explains, “is to slow molecular motion through small modifications to the individual molecules, which can lead to a collective, and hopefully dramatic, change in the nanostructure’s properties.”

One way of slowing down molecules, notes Ty Christoff-Tempesta, a PhD student and first author of the paper, “is to have them cling to each other more strongly than in biological systems.” That can be accomplished when a dense network of strong hydrogen bonds join the molecules together. “That’s what gives a material like Kevlar — constructed of so-called ‘aramids’ — its chemical stability and strength,” states Christoff-Tempesta.

Ortony’s team incorporated that capability into their design of a molecule that has three main components: an outer portion that likes to interact with water, aramids in the middle for binding, and an inner part that has a strong aversion to water. The researchers tested dozens of molecules meeting these criteria before finding the design that led to long ribbons with nanometer-scale thickness. The authors then measured the nanoribbons’ strength and stiffness to understand the impact of including Kevlar-like interactions between molecules. They discovered that the nanoribbons were unexpectedly sturdy — stronger than steel, in fact. 

This finding led the authors to wonder if the nanoribbons could be bundled to produce stable macroscopic materials. Ortony’s group devised a strategy whereby aligned nanoribbons were pulled into long threads that could be dried and handled. Notably, Ortony’s team showed that the threads could hold 200 times their own weight and have extraordinarily high surface areas — 200 square meters per gram of material. “This high surface-to-mass ratio offers promise for miniaturizing technologies by performing more chemistry with less material,” explains Christoff-Tempesta. To this end, they have already developed nanoribbons whose surfaces are coated with molecules that can pull heavy metals, like lead or arsenic, out of contaminated water. Other efforts in the research group are aimed at using bundled nanoribbons in electronic devices and batteries.

Ortony, for her part, is still amazed that they’ve been able to achieve their original research goal of “tuning the internal state of matter to create exceptionally strong molecular nanostructures.” Things could easily have gone the other way; these materials might have proved to be disorganized, or their structures fragile, like their predecessors, only holding up in water. But, she says, “we were excited to see that our modifications to the molecular structure were indeed amplified by the collective behavior of molecules, creating nanostructures with extremely robust mechanical properties. The next step, figuring out the most important applications, will be exciting.”

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

Self-assembly of aramid amphiphiles into ultra-stable nanoribbons and aligned nanoribbon threads by Ty Christoff-Tempesta, Yukio Cho, Dae-Yoon Kim, Michela Geri, Guillaume Lamour, Andrew J. Lew, Xiaobing Zuo, William R. Lindemann & Julia H. Ortony. Nature Nanotechnology (2021) DOI: https://doi.org/10.1038/s41565-020-00840-w Published: 18 January 2021

This paper is behind a paywall.

De-icing film for radar domes adapted for use on glass

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Interesting to see that graphene is in use for de-icing. From a Sept. 16, 2014 news item  on ScienceDaily,

Rice University scientists who created a deicing film for radar domes have now refined the technology to work as a transparent coating for glass.

The new work by Rice chemist James Tour and his colleagues could keep glass surfaces from windshields to skyscrapers free of ice and fog while retaining their transparency to radio frequencies (RF).

A Sept. 16, 2014 Rice University news release on EurekAlert, which originated the news item, describes the technology and its new application in more detail,

The material is made of graphene nanoribbons, atom-thick strips of carbon created by splitting nanotubes, a process also invented by the Tour lab. Whether sprayed, painted or spin-coated, the ribbons are transparent and conduct both heat and electricity.

Last year the Rice group created films of overlapping nanoribbons and polyurethane paint to melt ice on sensitive military radar domes, which need to be kept clear of ice to keep them at peak performance. The material would replace a bulky and energy-hungry metal oxide framework.

The graphene-infused paint worked well, Tour said, but where it was thickest, it would break down when exposed to high-powered radio signals. “At extremely high RF, the thicker portions were absorbing the signal,” he said. “That caused degradation of the film. Those spots got so hot that they burned up.”

The answer was to make the films more consistent. The new films are between 50 and 200 nanometers thick – a human hair is about 50,000 nanometers thick – and retain their ability to heat when a voltage is applied. The researchers were also able to preserve their transparency. The films are still useful for deicing applications but can be used to coat glass and plastic as well as radar domes and antennas.

In the previous process, the nanoribbons were mixed with polyurethane, but testing showed the graphene nanoribbons themselves formed an active network when applied directly to a surface. They were subsequently coated with a thin layer of polyurethane for protection. Samples were spread onto glass slides that were then iced. When voltage was applied to either side of the slide, the ice melted within minutes even when kept in a minus-20-degree Celsius environment, the researchers reported.

“One can now think of using these films in automobile glass as an invisible deicer, and even in skyscrapers,” Tour said. “Glass skyscrapers could be kept free of fog and ice, but also be transparent to radio frequencies. It’s really frustrating these days to find yourself in a building where your cellphone doesn’t work. This could help alleviate that problem.”

Tour noted future generations of long-range Wi-Fi may also benefit. “It’s going to be important, as Wi-Fi becomes more ubiquitous, especially in cities. Signals can’t get through anything that’s metallic in nature, but these layers are so thin they won’t have any trouble penetrating.”

He said nanoribbon films also open a path toward embedding electronic circuits in glass that are both optically and RF transparent.

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

Functionalized Graphene Nanoribbon Films as a Radiofrequency and Optically Transparent Material by Abdul-Rahman O. Raji, Sydney Salters, Errol L. G. Samuel, Yu Zhu, Vladimir Volman, and James M. Tour. ACS Appl. Mater. Interfaces, Article ASAP DOI: 10.1021/am503478w Publication Date (Web): September 4, 2014
Copyright © 2014 American Chemical Society

This paper is behind a paywall.

De-icing is a matter of some interest in the airlines industry as I noted in my Nov. 19, 2012 posting about de-icing airplane wings.

Like water for graphene nanoribbons

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Reference to magical realism and fiction aside (Like Water for Chocolate by Laura Esquivel), it turns out that water is integral to the formation of very long, very thin graphene nanoribbons. A July 30, 2011 Rice University news release describes the phenomenon, a two year research odyssey, and the scientific ‘accident’ which led researchers to the discovery,

New research at Rice University shows how water makes it practical to form long graphene nanoribbons less than 10 nanometers wide.

And it’s unlikely that many of the other labs currently trying to harness the potential of graphene, a single-atom sheet of carbon, for microelectronics would have come up with the technique the Rice researchers found while they were looking for something else.

The discovery by lead author Vera Abramova and co-author Alexander Slesarev, both graduate students in the lab of Rice chemist James Tour, appears online this month in the American Chemical Society journal ACS Nano.

A bit of water adsorbed from the atmosphere was found to act as a mask in a process that begins with the creation of patterns via lithography and ends with very long, very thin graphene nanoribbons. The ribbons form wherever water gathers at the wedge between the raised pattern and the graphene surface.

The water formation is called a meniscus; it is created when the surface tension of a liquid causes it to curve [in a convex or concave manner]. In the Rice process, the meniscus mask protects a tiny ribbon of graphene from being etched away when the pattern is removed.

Tour said any method to form long wires only a few nanometers wide should catch the interest of microelectronics manufacturers as they approach the limits of their ability to miniaturize circuitry. “They can never take advantage of the smallest nanoscale devices if they can’t address them with a nanoscale wire,” he said. “Right now, manufacturers can make small features, or make big features and put them where they want them. But to have both has been difficult. To be able to pattern a line this thin right where you want it is a big deal because it permits you to take advantage of the smallness in size of nanoscale devices.”

Tour said water’s tendency to adhere to surfaces is often annoying, but in this case it’s essential to the process. “There are big machines that are used in electronics research that are often heated to hundreds of degrees under ultrahigh vacuum to drive off all the water that adheres to the inside surfaces,” he said. “Otherwise there’s always going to be a layer of water. In our experiments, water accumulates at the edge of the structure and protects the graphene from the reactive ion etching (RIE). So in our case, that residual water is the key to success.

…

Abramova and Slesarev had set out to fabricate nanoribbons by inverting a method developed by another Rice lab to make narrow gaps in materials. The original method utilized the ability of some metals to form a native oxide layer that expands and shields material just on the edge of the metal mask. The new method worked, but not as expected.

“We first suspected there was some kind of shadowing,” Abramova said. But other metals that didn’t expand as much, if at all, showed no difference, nor did varying the depth of the pattern. “I was basically looking for anything that would change something.”

It took two years to develop and test the meniscus theory, during which the researchers also confirmed its potential to create sub-10-nanometer wires from other kinds of materials, including platinum. They also constructed field-effect transistors to check the electronic properties of graphene nanoribbons.

To be sure that water does indeed account for the ribbons, they tried eliminating its effect by first drying the patterns by heating them under vacuum, and then by displacing the water with acetone to eliminate the meniscus. In both cases, no graphene nanoribbons were created.

The researchers are working to better control the nanoribbons’ width, and they hope to refine the nanoribbons’ edges, which help dictate their electronic properties.

“With this study, we figured out you don’t need expensive tools to get these narrow features,” Tour said. “You can use the standard tools [;] a fab line already has to make features that are smaller than 10 nanometers.”

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

Meniscus-Mask Lithography for Narrow Graphene Nanoribbons by Vera Abramova, Alexander S. Slesarev, and James M. Tour. ACS Nano, Article ASAP DOI: 10.1021/nn403057t Publication Date (Web): July 23, 2013
Copyright © 2013 American Chemical Society

This paper is behind a paywall.

Dexter Johnson in his July30, 2013 posting on the Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers]) notes that this use of water is counter-intuitive,

In [an] ironic twist, the water that most lithography processes try avoid and eliminate at great cost is the same water that makes this new lithography process work.