Tag Archives: Van Der Waals Forces

Change the shape of water with nanotubes

An August 24, 2018 news item on ScienceDaily describes a ‘shapeshifting’ water technique,

First, according to Rice University engineers, get a nanotube hole. Then insert water. If the nanotube is just the right width, the water molecules will align into a square rod.

Rice materials scientist Rouzbeh Shahsavari and his team used molecular models to demonstrate their theory that weak van der Waals forces between the inner surface of the nanotube and the water molecules are strong enough to snap the oxygen and hydrogen atoms into place.

Shahsavari referred to the contents as two-dimensional “ice,” because the molecules freeze regardless of the temperature. He said the research provides valuable insight on ways to leverage atomic interactions between nanotubes and water molecules to fabricate nanochannels and energy-storing nanocapacitors.

An August 24, 2018 Rice University news release (also on EurekAlert and received via email), which originated the news item, delves further,

Shahsavari and his colleagues built molecular models of carbon and boron nitride nanotubes with adjustable widths. They discovered boron nitride is best at constraining the shape of water when the nanotubes are 10.5 angstroms wide. (One angstrom is one hundred-millionth of a centimeter.)

The researchers already knew that hydrogen atoms in tightly confined water take on interesting structural properties. Recent experiments by other labs showed strong evidence for the formation of nanotube ice and prompted the researchers to build density functional theory models to analyze the forces responsible.

Shahsavari’s team modeled water molecules, which are about 3 angstroms wide, inside carbon and boron nitride nanotubes of various chiralities (the angles of their atomic lattices) and between 8 and 12 angstroms in diameter. They discovered that nanotubes in the middle diameters had the most impact on the balance between molecular interactions and van der Waals pressure that prompted the transition from a square water tube to ice.

“If the nanotube is too small and you can only fit one water molecule, you can’t judge much,” Shahsavari said. “If it’s too large, the water keeps its amorphous shape. But at about 8 angstroms, the nanotubes’ van der Waals force [if you’re not familiar with the term, see below the link and citation for my brief explanation] starts to push water molecules into organized square shapes.”

He said the strongest interactions were found in boron nitride nanotubes due to the particular polarization of their atoms.

Shahsavari said nanotube ice could find use in molecular machines or as nanoscale capillaries, or foster ways to deliver a few molecules of water or sequestered drugs to targeted cells, like a nanoscale syringe.

Lead author Farzaneh Shayeganfar, a former visiting scholar at Rice, is an instructor at Shahid Rajaee Teacher Training University in Tehran, Iran. Co-principal investigator Javad Beheshtian is a professor at Amirkabir University, Tehran.

Supercomputer resources were provided with support from the [US] National Institutes of Health and an IBM Shared Rice University Research grant.

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

First Principles Study of Water Nanotubes Captured Inside Carbon/Boron Nitride Nanotubes by Farzaneh Shayeganfar, Javad Beheshtian, and Rouzbeh Shahsavari. Langmuir, DOI: 10.1021/acs.langmuir.8b00856 Publication Date (Web): August 23, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

For the purposes of the posting, van der Waals force(s) are weak adhesive forces measured at the nanoscale. Humans don’t feel them (we’re too big) but gecko lizards can exploit those forces which is why they are able to hang from the ceiling by a single toe.  There’s a more informed description here in the van der Waals force entry on Wikipedia.

Stronger than steel and spider silk: artificial, biodegradable, cellulose nanofibres

This is an artificial and biodegradable are two adjectives you don’t usually see united by the conjunction, and. However, it is worth noting that the artificial material is initially derived from a natural material, cellulose. Here’s more from a May 16, 2018 news item on ScienceDaily,

At DESY’s [Deutsches Elektronen-Synchrotron] X-ray light source PETRA III, a team led by Swedish researchers has produced the strongest bio-material that has ever been made. The artifical, but bio-degradable cellulose fibres are stronger than steel and even than dragline spider silk, which is usually considered the strongest bio-based material. The team headed by Daniel Söderberg from the KTH Royal Institute of Technology in Stockholm reports the work in the journal ACS Nano of the American Chemical Society.

A May 16, 2018 DESY press release (also on EurekAlert), which originated the news item, provides more detail,

The ultrastrong material is made of cellulose nanofibres (CNF), the essential building blocks of wood and other plant life. Using a novel production method, the researchers have successfully transferred the unique mechanical properties of these nanofibres to a macroscopic, lightweight material that could be used as an eco-friendly alternative for plastic in airplanes, cars, furniture and other products. “Our new material even has potential for biomedicine since cellulose is not rejected by your body”, explains Söderberg.

The scientists started with commercially available cellulose nanofibres that are just 2 to 5 nanometres in diameter and up to 700 nanometres long. A nanometre (nm) is a millionth of a millimetre. The nanofibres were suspended in water and fed into a small channel, just one millimetre wide and milled in steel. Through two pairs of perpendicular inflows additional deionized water and water with a low pH-value entered the channel from the sides, squeezing the stream of nanofibres together and accelerating it.

This process, called hydrodynamic focussing, helped to align the nanofibres in the right direction as well as their self-organisation into a well-packed macroscopic thread. No glue or any other component is needed, the nanofibres assemble into a tight thread held together by supramolecular forces between the nanofibres, for example electrostatic and Van der Waals forces.

With the bright X-rays from PETRA III the scientists could follow and optimise the process. “The X-rays allow us to analyse the detailed structure of the thread as it forms as well as the material structure and hierarchical order in the super strong fibres,” explains co-author Stephan Roth from DESY, head of the Micro- and Nanofocus X-ray Scattering Beamline P03 where the threads were spun. “We made threads up to 15 micrometres thick and several metres in length.”

Measurements showed a tensile stiffness of 86 gigapascals (GPa) for the material and a tensile strength of 1.57 GPa. “The bio-based nanocellulose fibres fabricated here are 8 times stiffer and have strengths higher than natural dragline spider silk fibres,” says Söderberg. “If you are looking for a bio-based material, there is nothing quite like it. And it is also stronger than steel and any other metal or alloy as well as glass fibres and most other synthetic materials.” The artificial cellulose fibres can be woven into a fabric to create materials for various applications. The researchers estimate that the production costs of the new material can compete with those of strong synthetic fabrics. “The new material can in principle be used to create bio-degradable components,” adds Roth.

The study describes a new method that mimics nature’s ability to accumulate cellulose nanofibres into almost perfect macroscale arrangements, like in wood. It opens the way for developing nanofibre material that can be used for larger structures while retaining the nanofibres’ tensile strength and ability to withstand mechanical load. “We can now transform the super performance from the nanoscale to the macroscale,” Söderberg underlines. “This discovery is made possible by understanding and controlling the key fundamental parameters essential for perfect nanostructuring, such as particle size, interactions, alignment, diffusion, network formation and assembly.” The process can also be used to control nanoscale assembly of carbon tubes and other nano-sized fibres.

(There are some terminology and spelling issues, which are described at the end of this post.)

Let’s get back to a material that rivals spider silk and steel for strength (for some reason that reminded me of an old carnival game where you’d test your strength by swinging a mallet down on a ‘teeter-totter-like’ board and sending a metal piece up a post to make a bell ring). From a May 16, 2018 DESY press release (also on EurekAlert), which originated the news item,

The ultrastrong material is made of cellulose nanofibres (CNF), the essential building blocks of wood and other plant life. Using a novel production method, the researchers have successfully transferred the unique mechanical properties of these nanofibres to a macroscopic, lightweight material that could be used as an eco-friendly alternative for plastic in airplanes, cars, furniture and other products. “Our new material even has potential for biomedicine since cellulose is not rejected by your body”, explains Söderberg.

The scientists started with commercially available cellulose nanofibres that are just 2 to 5 nanometres in diameter and up to 700 nanometres long. A nanometre (nm) is a millionth of a millimetre. The nanofibres were suspended in water and fed into a small channel, just one millimetre wide and milled in steel. Through two pairs of perpendicular inflows additional deionized water and water with a low pH-value entered the channel from the sides, squeezing the stream of nanofibres together and accelerating it.

This process, called hydrodynamic focussing, helped to align the nanofibres in the right direction as well as their self-organisation into a well-packed macroscopic thread. No glue or any other component is needed, the nanofibres assemble into a tight thread held together by supramolecular forces between the nanofibres, for example electrostatic and Van der Waals forces.

With the bright X-rays from PETRA III the scientists could follow and optimise the process. “The X-rays allow us to analyse the detailed structure of the thread as it forms as well as the material structure and hierarchical order in the super strong fibres,” explains co-author Stephan Roth from DESY, head of the Micro- and Nanofocus X-ray Scattering Beamline P03 where the threads were spun. “We made threads up to 15 micrometres thick and several metres in length.”

Measurements showed a tensile stiffness of 86 gigapascals (GPa) for the material and a tensile strength of 1.57 GPa. “The bio-based nanocellulose fibres fabricated here are 8 times stiffer and have strengths higher than natural dragline spider silk fibres,” says Söderberg. “If you are looking for a bio-based material, there is nothing quite like it. And it is also stronger than steel and any other metal or alloy as well as glass fibres and most other synthetic materials.” The artificial cellulose fibres can be woven into a fabric to create materials for various applications. The researchers estimate that the production costs of the new material can compete with those of strong synthetic fabrics. “The new material can in principle be used to create bio-degradable components,” adds Roth.

The study describes a new method that mimics nature’s ability to accumulate cellulose nanofibres into almost perfect macroscale arrangements, like in wood. It opens the way for developing nanofibre material that can be used for larger structures while retaining the nanofibres’ tensile strength and ability to withstand mechanical load. “We can now transform the super performance from the nanoscale to the macroscale,” Söderberg underlines. “This discovery is made possible by understanding and controlling the key fundamental parameters essential for perfect nanostructuring, such as particle size, interactions, alignment, diffusion, network formation and assembly.” The process can also be used to control nanoscale assembly of carbon tubes and other nano-sized fibres.

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

Multiscale Control of Nanocellulose Assembly: Transferring Remarkable Nanoscale Fibril Mechanics to Macroscale Fibers by Nitesh Mittal, Farhan Ansari, Krishne Gowda V, Christophe Brouzet, Pan Chen, Per Tomas Larsson, Stephan V. Roth, Fredrik Lundell, Lars Wågberg, Nicholas A. Kotov, and L. Daniel Söderberg. ACS Nano, Article ASAP DOI: 10.1021/acsnano.8b01084 Publication Date (Web): May 9, 2018

Copyright © 2018 American Chemical Society

This paper is open access and accompanied by this image illustrating the work,

Courtesy: American Chemical Society and the researchers [Note: The bottom two images of cellulose nanofibres, which are constittuents of an artificial cellulose fibre, appear to be from a scanning tunneling microsscope. Credit: Nitesh Mittal, KTH Stockholm

This news has excited interest at General Electric (GE) (its Wikipedia entry), which has highlighted the work in a May 25, 2018 posting (The 5 Coolest Things On Earth This Week) by Tomas Kellner on the GE Reports blog.

Terminology and spelling

I’ll start with spelling since that’s the easier of the two. In some parts of the world it’s spelled ‘fibres’ and in other parts of the world it’s spelled ‘fibers’. When I write the text in my post, it tends to reflect the spelling used in the news/press releases. In other words, I swing in whichever direction the wind is blowing.

For diehards only

As i understand the terminology situation, nanocellulose and cellulose nanomaterials are interchangeable generic terms. Further, cellulose nanofibres (CNF) seems to be another generic term and it encompasses both cellulose nanocrystals (CNC) and cellulose nanofibrils (CNF). Yes, there appear to be two CNFs. Making matters more interesting is the fact that cellulose nanocrystals were originally christened nanocrystalline cellulose (NCC). For anyone who follows the science and technology scene, it becomes obvious that competing terminologies are the order of the day. Eventually the dust settles and naming conventions are resolved. More or less.

Ordinarily I would reference the Nanocellulose Wikipedia entry in my attempts to clarify the issues but it seems that the writers for the entry have not caught up to the current naming convention for cellulose nanocrystals, still referring to the material as nanocrystalline cellulose. This means, I can’t trust the rest of the entry, which has only one CNF (cellulose nanofibres).

I have paid more attention to the NCC/CNC situation and am not as familiar with the CNF situation. Using, NCC/CNC as an example of a terminology issue, I believe it was first developed in Canada and it was Canadian researchers who were pushing their NCC terminology while the international community pushed back with CNC.

In the end, NCC became a brand name, which was trademarked by CelluForce, a Canadian company in the CNC market. From the CelluForce Products page on Cellulose Nanocrystals,

CNC are not all made equal. The CNC produced by CelluForce is called CelluForce NCCTM and has specific properties and are especially easy to disperse. CelluForce NCCTM is the base material that CelluForce uses in all its products. This base material can be modified and tailored to suit the specific needs in various applications.

These, days CNC is almost universally used but NCC (not as a trademark) is a term still employed on occasion (and, oddly, the researchers are not necessarily Canadian).

Should anyone have better information about terminology issues, please feel free to comment.

Upending the textbooks on Van Der Waals interactions

It’s always exciting when textbook information has to be changed due to a discovery; it’s also a reminder that science is constantly changing. From a June 29, 2017 news item on Nanowerk (Note: A link has been removed),

Van der Waals interactions between molecules are among the most important forces in biology, physics, and chemistry, as they determine the properties and physical behavior of many materials. For a long time, it was considered that these interactions between molecules are always attractive. Now, for the first time, Mainak Sadhukhan and Alexandre Tkatchenko from the Physics and Materials Science Research Unit at the University of Luxembourg found that in many rather common situations in nature the van der Waals force between two molecules becomes repulsive. This might lead to a paradigm shift in molecular interactions.

“The textbooks so far assumed that the forces are solely attractive. For us, the interesting question is whether you can also make them repulsive,” Prof Tkatchenko explains. “Until recently, there was no evidence in scientific literature that van der Waals forces could also be repelling.”

Now, the researchers have shown in their paper, published in Physical Review Letters (“Long-Range Repulsion Between Spatially Confined van der Waals Dimers”), that the forces are, in fact, repulsive when they take place under confinement.

A June 30, 2017 Université de Luxembourg press release, which originated the news item, expands on the theme,

The ubiquitous van der Waals force was first explained by the German-American physicist Fritz London in 1930. Using quantum mechanics, he proved the purely attractive nature of the van der Waals force for any two molecules interacting in free space. “However, in nature molecules in most cases interact in confined spaces, such as cells, membranes, nanotubes, etc. In is this particular situation, van der Waals forces become repulsive at large distances between molecules,” says Prof. Tkatchenko.

Mainak Sadhukhan, the co-author of the study, developed a novel quantum-mechanical method that enabled them to model van der Waals forces in confinement. “We could rationalise many previous experimental results that remained unexplained until now. Our new theory allows, for the first time, for an interpretation of many interesting phenomena observed for molecules under confinement,” Mainak Sadhukhan says.

The discovery could have many potential implications for the delivery of pharmaceutical molecules in cells, water desalination and transport, and self-assembly of molecular layers in photovoltaic devices.

Prof. Tkatchenko’s research group is working on methods that model the properties of a wide range of intermolecular interactions. Only in 2016, they found that the true nature of these van der Waals forces differs from conventional wisdom in chemistry and biology, as they have to be treated as coupling between waves rather than as mutual attraction (or repulsion) between particles.

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

Long-Range Repulsion Between Spatially Confined van der Waals Dimers by Mainak Sadhukhan and Alexandre Tkatchenko. Phys. Rev. Lett. 118, 210402 (Vol. 118, Iss. 21 — 26 May 2017) DOI:https://doi.org/10.1103/PhysRevLett.118.210402 Published 25 May 2017

This paper is behind a paywall.

The brittleness of molybdenum diselenide

With the finding that molybdenum diselenide is not as strong as previously believed, industry may want to reconsider 2D materials before incorporating them in new products according to a Rice University (Texas, US) scientist. From a Nov. 14, 2016 news item on Nanowerk,

Scientists at Rice University have discovered that an atom-thick material being eyed for flexible electronics and next-generation optical devices is more brittle than they expected.

The Rice team led by materials scientist Jun Lou tested the tensile strength of two-dimensional, semiconducting molybdenum diselenide and discovered that flaws as small as one missing atom can initiate catastrophic cracking under strain.

The finding may cause industry to look more carefully at the properties of 2-D materials before incorporating them in new technologies, he said.

 

A Nov. 14, 2016 Rice University news release (also on EurekAlert), which originated the news item, provides more insight into the research,

“It turns out not all 2-D crystals are equal,” said Lou, a Rice professor of materials science and nanoengineering. “Graphene is a lot more robust compared with some of the others we’re dealing with right now, like this molybdenum diselenide. We think it has something to do with defects inherent to these materials.”

The defects could be as small as a single atom that leaves a vacancy in the crystalline structure, he said. “It’s very hard to detect them,” he said. “Even if a cluster of vacancies makes a bigger hole, it’s difficult to find using any technique. It might be possible to see them with a transmission electron microscope, but that would be so labor-intensive that it wouldn’t be useful.”

Molybdenum diselenide is a dichalcogenide, a two-dimensional semiconducting material that appears as a graphene-like hexagonal array from above but is actually a sandwich of metallic atoms between two layers of chalcogen atoms, in this case, selenium. Molybdenum diselenide is being considered for use as transistors and in next-generation solar cells, photodetectors and catalysts as well as electronic and optical devices.

Lou and colleagues measured the material’s elastic modulus, the amount of stretching a material can handle and still return to its initial state, at 177.2 (plus or minus 9.3) gigapascals. Graphene is more than five times as elastic. They attributed the large variation to pre-existing flaws of between 3.6 and 77.5 nanometers.

Its fracture strength, the amount of stretching a material can handle before breaking, was measured at 4.8 (plus or minus 2.9) gigapascals. Graphene is nearly 25 times stronger.

Part of the project led by Rice postdoctoral researcher Yingchao Yang required moving molybdenum diselenide from a growth chamber in a chemical vapor deposition furnace to a microscope without introducing more defects. Yang solved the problem using a dry transfer process in place of a standard acid washing that would have ruined the samples.

To test samples, Yang placed rectangles of molybdenum diselenide onto a sensitive electron microscope platform invented by the Lou group. Natural van der Waals forces held the samples in place on springy cantilever arms that measured the applied stress.

Lou said the group attempted to measure the material’s fracture toughness, an indicator of how likely cracks are to propagate, as they had in an earlier study on graphene. But they found that pre-cutting cracks into molybdenum diselenide resulted in it shattering before stress could be applied, he said.

“The important message of this work is the brittle nature of these materials,” Lou said. “A lot of people are thinking about using 2-D crystals because they’re inherently thin. They’re thinking about flexible electronics because they are semiconductors and their theoretical elastic strength should be very high. According to our calculations, they can be stretched up to 10 percent.

“But in reality, because of the inherent defects, you rarely can achieve that much strength. The samples we have tested so far broke at 2 to 3 percent (of the theoretical maximum) at most,” Lou said. “That should still be fine for most flexible applications, but unless they find a way to quench the defects, it will be very hard to achieve the theoretical limits.”

 

When seen from above, the atoms in two-dimensional molybdenum diselenide resemble a hexagonal grid, like graphene. But in reality, the darker molybdenum atoms are sandwiched between top and bottom layers of selenide atoms. Rice University researchers tested the material for its tensile strength. Courtesy of the Lou Group

When seen from above, the atoms in two-dimensional molybdenum diselenide resemble a hexagonal grid, like graphene. But in reality, the darker molybdenum atoms are sandwiched between top and bottom layers of selenide atoms. Rice University researchers tested the material for its tensile strength. Courtesy of the Lou Group

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

 

Brittle Fracture of 2D MoSe2 by Yingchao Yang, Xing Li, Minru Wen, Emily Hacopian, Weibing Chen, Yongji Gong, Jing Zhang, Bo Li, Wu Zhou, Pulickel M. Ajayan, Qing Chen, Ting Zhu, and Jun Lou. Advanced Materials DOI: 10.1002/adma.201604201 Version of Record online: 3 NOV 2016

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Measuring the van der Waals forces between individual atoms for the first time

A May 13, 2016 news item on Nanowerk heralds the first time measuring the van der Waals forces between individual atoms,

Physicists at the Swiss Nanoscience Institute and the University of Basel have succeeded in measuring the very weak van der Waals forces between individual atoms for the first time. To do this, they fixed individual noble gas atoms within a molecular network and determined the interactions with a single xenon atom that they had positioned at the tip of an atomic force microscope. As expected, the forces varied according to the distance between the two atoms; but, in some cases, the forces were several times larger than theoretically calculated.

A May 13, 2016 University of Basel press release (also on EurekAlert), which originated the news item, provides an explanation of van der Waals forces (the most comprehensive I’ve seen) and technical details about how the research was conducted,

Van der Waals forces act between non-polar atoms and molecules. Although they are very weak in comparison to chemical bonds, they are hugely significant in nature. They play an important role in all processes relating to cohesion, adhesion, friction or condensation and are, for example, essential for a gecko’s climbing skills.

Van der Waals interactions arise due to a temporary redistribution of electrons in the atoms and molecules. This results in the occasional formation of dipoles, which in turn induce a redistribution of electrons in closely neighboring molecules. Due to the formation of dipoles, the two molecules experience a mutual attraction, which is referred to as a van der Waals interaction. This only exists temporarily but is repeatedly re-formed. The individual forces are the weakest binding forces that exist in nature, but they add up to reach magnitudes that we can perceive very clearly on the macroscopic scale – as in the example of the gecko.

Fixed within the nano-beaker

To measure the van der Waals forces, scientists in Basel used a low-temperature atomic force microscope with a single xenon atom on the tip. They then fixed the individual argon, krypton and xenon atoms in a molecular network. This network, which is self-organizing under certain experimental conditions, contains so-called nano-beakers of copper atoms in which the noble gas atoms are held in place like a bird egg. Only with this experimental set-up is it possible to measure the tiny forces between microscope tip and noble gas atom, as a pure metal surface would allow the noble gas atoms to slide around.

Compared with theory

The researchers compared the measured forces with calculated values and displayed them graphically. As expected from the theoretical calculations, the measured forces fell dramatically as the distance between the atoms increased. While there was good agreement between measured and calculated curve shapes for all of the noble gases analyzed, the absolute measured forces were larger than had been expected from calculations according to the standard model. Above all for xenon, the measured forces were larger than the calculated values by a factor of up to two.

The scientists are working on the assumption that, even in the noble gases, charge transfer occurs and therefore weak covalent bonds are occasionally formed, which would explain the higher values.

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

Van der Waals interactions and the limits of isolated atom models at interfaces by Shigeki Kawai, Adam S. Foster, Torbjörn Björkman, Sylwia Nowakowska, Jonas Björk, Filippo Federici Canova, Lutz H. Gade, Thomas A. Jung, & Ernst Meyer. Nature Communications 7, Article number: 11559  doi:10.1038/ncomms11559 Published 13 May 2016

This is an open access paper.

Self-assembly with porphine molecules

A Jan. 12, 2016 American Institute of Physics (AIP) news release by John Arnst (also on EurekAlert but dated Jan. 14, 2016) describes computational research into self-assembling nanodevices based on porphine molecules,

As we continue to shrink electronic components, top-down manufacturing methods begin to approach a physical limit at the nanoscale. Rather than continue to chip away at this limit, one solution of interest involves using the bottom-up self-assembly of molecular building blocks to build nanoscale devices.

Successful self-assembly is an elaborately choreographed dance, in which the attractive and repulsive forces within molecules, between each molecule and its neighbors, and between molecules and the surface that supports them, have to all be taken into account. To better understand the self-assembly process, researchers at the Technical University of Munich have characterized the contributions of all interaction components, such as covalent bonding and van der Waals interactions between molecules and between molecules and a surface.

“In an ideal case, the smallest possible device has the size of a single atom or molecule,” said Katharina Diller, who worked as a postdoctoral researcher in the group of Karsten Reuter at the Technical University of Munich. Reuter and his colleagues present their work this week in The Journal of Chemical Physics, from AIP Publishing.

One such example is a single-porphyrin switch, which occupies a surface area of only one square nanometer. [emphasis mine] The porphine molecule, which was the object of this study, is even smaller than this. Porphyrins are a group of ringed chemical compounds which notably include heme – responsible for transporting oxygen and carbon dioxide in the bloodstream – and chlorophyll. In synthetically-derived applications, porphyrins are studied for their potential uses as sensors, light-sensitive dyes in organic solar cells, and molecular magnets.

The researchers from TU Munich assessed the interactions of the porphyrin molecule 2H-porphine by using density functional theory, a quantum mechanical computational modelling method used to describe the electronic properties of molecules and materials. Their simulations were performed at the high-performance supercomputer SuperMUC at Leibniz-Rechenzentrum in Garching.

The metallic substrates the researchers chose for the porphyrin molecules to assemble on, the close packed single crystal surfaces of copper and silver, are widely used as substrates in surface science. This is due to the densely packed nature of the surfaces, which allow the molecules to exhibit a smooth adsorption environment. Additionally, copper and silver each react differently with porhyrins – the molecule adsorbs more strongly on copper, whereas silver does a better job of keeping the electronic structure of the molecule intact – allowing the researchers to monitor a variety of competing effects for future applications.

In their simulation, porphyrin molecules were placed on a copper or silver slab, which was repeated periodically to simulate an extended surface. After finding the optimal geometry in which the molecules would adsorb on the surface, the researchers altered the size of the metal slab to increase or decrease the distance between molecules, thus simulating different molecular coverages. The computational setup gave them a switch to turn the energy contributions of neighboring molecules on and off, in order to observe the interplay of the individual interactions.

Diller and Reuter, along with colleagues Reinhard Maurer and Moritz Müller, who is first author on the paper, found that the weak long-range van der Waals interactions yielded the largest contribution to the molecule-surface interaction, and showed that the often employed methods to quantify the electronic charges in the system have to be used with caution. Surprisingly, while interactions directly between molecules are negligible, the researcher found indications for surface-mediated molecule-molecule interactions at higher molecular coverages.

“The analysis of the electronic structure and the individual interaction components allows us to better understand the self-assembly of porphine adsorbed on copper and silver, and additionally enables predictions for more complex porphyrine analogues,” Diller said. “These conclusions, however, come without yet considering the effects of atomic motion at finite temperature, which we did not study in this work.”

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

Interfacial charge rearrangement and intermolecular interactions: Density-functional theory study of free-base porphine adsorbed on Ag(111) and Cu(111) by Moritz Müller, Katharina Diller, Reinhard J. Maurer, and Karsten Reuter. J. Chem. Phys. 144, 024701 (2016); http://dx.doi.org/10.1063/1.4938259

This paper appears to be open access.

Finally, the researchers have made this illustrative diagram titled ‘Energy’ available,

Caption: Schematic depiction of different energy terms contributing to the adsorption energy, and charge density difference of 2H-P after adsorption onto Cu(111) at 12.8 Angstrom separation. Credit: M. Müller/TU Munich

Caption: Schematic depiction of different energy terms contributing to the adsorption energy, and charge density difference of 2H-P after adsorption onto Cu(111) at 12.8 Angstrom separation. Credit: M. Müller/TU Munich

Scaling graphene production up to industrial strength

If graphene is going to be a ubiquitous material in the future, production methods need to change. An Aug. 7, 2015 news item on Nanowerk announces a new technique to achieve that goal,

Producing graphene in bulk is critical when it comes to the industrial exploitation of this exceptional two-dimensional material. To that end, [European Commission] Graphene Flagship researchers have developed a novel variant on the chemical vapour deposition process which yields high quality material in a scalable manner. This advance should significantly narrow the performance gap between synthetic and natural graphene.

An Aug. 7, 2015 European Commission Graphene Flagship press release by Francis Sedgemore, which originated the news item, describes the problem,

Media-friendly Nobel laureates peeling layers of graphene from bulk graphite with sticky tape may capture the public imagination, but as a manufacturing process the technique is somewhat lacking. Mechanical exfoliation may give us pristine graphene, but industry requires scalable and cost-effective production processes with much higher yields.

On to the new method (from the press release),

Flagship-affiliated physicists from RWTH Aachen University and Forschungszentrum Jülich have together with colleagues in Japan devised a method for peeling graphene flakes from a CVD substrate with the help of intermolecular forces. …

Key to the process is the strong van der Waals interaction that exists between graphene and hexagonal boron nitride, another 2d material within which it is encapsulated. The van der Waals force is the attractive sum of short-range electric dipole interactions between uncharged molecules.

Thanks to strong van der Waals interactions between graphene and boron nitride, CVD graphene can be separated from the copper and transferred to an arbitrary substrate. The process allows for re-use of the catalyst copper foil in further growth cycles, and minimises contamination of the graphene due to processing.

Raman spectroscopy and transport measurements on the graphene/boron nitride heterostructures reveals high electron mobilities comparable with those observed in similar assemblies based on exfoliated graphene. Furthermore – and this comes as something of a surprise to the researchers – no noticeable performance changes are detected between devices developed in the first and subsequent growth cycles. This confirms the copper as a recyclable resource in the graphene fabrication process.

“Chemical vapour deposition is a highly scalable and cost-efficient technology,” says Christoph Stampfer, head of the 2nd Institute of Physics A in Aachen, and co-author of the technical article. “Until now, graphene synthesised this way has been significantly lower in quality than that obtained with the scotch-tape method, especially when it comes to the material’s electronic properties. But no longer. We demonstrate a novel fabrication process based on CVD that yields ultra-high quality synthetic graphene samples. The process is in principle suitable for industrial-scale production, and narrows the gap between graphene research and its technological applications.”

With their dry-transfer process, Banszerus and his colleagues have shown that the electronic properties of CVD-grown graphene can in principle match those of ultrahigh-mobility exfoliated graphene. The key is to transfer CVD graphene from its growth substrate in such a way that chemical contamination is avoided. The high mobility of pristine graphene is thus preserved, and the approach allows for the substrate material to be recycled without degradation.

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

Ultrahigh-mobility graphene devices from chemical vapor deposition on reusable copper by Luca Banszerus, Michael Schmitz, Stephan Engels, Jan Dauber, Martin Oellers, Federica Haupt, Kenji Watanabe, Takashi Taniguchi, Bernd Beschoten, and Christoph Stampfer. Science Advances  31 Jul 2015: Vol. 1, no. 6, e1500222 DOI: 10.1126/sciadv.1500222

This article appears to be open access.

For those interested in finding out more about chemical vapour deposition (CVD), David Chandler has written a June 19, 2015 article for the Massachusetts Institute of Technology (MIT) titled:  Explained: chemical vapor deposition (Technique enables production of pure, uniform coatings of metals or polymers, even on contoured surfaces.)

Catch a falling gecko

While discussions of gecko lizards in the ‘nanotechnology world’ are almost always focused on the creature’s adhesive properties, a recent research article in Physical Review E explores the gecko’s ‘loss of grip’. From a July 9, 2014 news item on Nanowerk (Note: A link has been removed),

Geckos and spiders that seem to be able to sit still forever, and walk around upside down have fascinated researchers worldwide for many years. We will soon be able to buy smart new fasteners that hold the same way as the gecko’s foot. But the fact is, sooner or later the grip is lost, no matter how little force is acting on it. Stefan Lindström and Lars Johansson, researchers at the Division of Mechanics, Linköping University, together with Nils Karlsson, recent engineering graduate, have demonstrated this in an article just published in Physical Review E (“Metastable states and activated dynamics in thin-film adhesion to patterned surfaces”).

A June 24, 2014 Linköping University press release (also on EurekAlert but dated July 9, 2014), which originated the news item, describes how this ‘grip loss’ could have implications for graphene production,

…, it’s a phenomenon that can have considerable benefits, for instance in the production of graphene. Graphene consists only of one layer of atom, and which must be easily detached from the substrate.

In his graduation project at the Division of Mechanics, Nils Karlsson studied both the mechanics of the gecko’s leg as well as the adhesion of its foot to the substrate. The gecko’s foot has five toes, all with transverse lamellae. A scanning electron microscope shows that these lamellae consist of a number of small hair-like setae, each with a little film at the end, which resembles a small spatula. These spatulae, roughly 10 nm thick, are what adheres to the substrate.

”At the nano level, conditions are a bit different. The movement of the molecules is negligible in our macroscopic world, but it’s not in the nano world. Nils Karlsson’s graduation project suggested that heat, and consequently the movement of the molecules, has an effect on the adhesion of these spatulae. We wanted to do further analyses, and calculate what actually happens,” explains Stefan Lindström.

They refined the calculations, so they applied to a thin film in contact with an uneven surface (…). So, the film only contacts the uppermost parts of the uneven surface. The researchers also chose to limit the calculations to the type of weak forces that exist between all atoms and molecules – van der Waals forces.

”It’s true, they are small, but they are always there and we know that they are extremely reliant on distance,” says Lars Johansson.

This means that the force is much stronger where the film is very close to a single high point, than when it is quite close to a number of high points. Then, when the film detaches, it does this point by point. This is because both contact surfaces are moving – vibrating. These are tiny movements, but at some stage the movements are in sync, so the surfaces actually lose contact. Then the van der Waals force is so small that the film releases.

”So in reality, we can detach a thin film from the substrate simply by waiting for the right moment. This doesn’t require a great deal of force. The part of the film that remains on the substrate vibrates constantly, and the harder I pull on this part, the faster the film will detach. But how long it takes for the film to detach also depends on the structure of the substrate and the film’s stiffness,” says Stefan Lindström.

In practice this means that even a small force over a long period will cause the film, or for that matter the gecko’s foot, to lose its grip. Which is fine for the gecko, who can scoot off, but maybe not so good for a fastening system. Still – in the right application, this knowledge can be of great industrial benefit.

This is what a gecko’s foot looks like when viewed through a scanning electron microscope,

The pictures of the gecko’s foot is taken by Oskar Geller, Lund University, with a scanning electron microscope.  Linköping University

The pictures of the gecko’s foot is taken by Oskar Geller, Lund University, with a scanning electron microscope. Linköping University

The image looks like a candidate for entry into a nano art show.

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

Metastable states and activated dynamics in thin-film adhesion to patterned surfaces by Stefan B. Lindström, Lars Johansson, and Nils R. Karlsson. DOI 10.1103/PhysRevE.89.062401 Phys. Rev. E 89, 062401 – Published 6 June 2014

This paper is behind a paywall.

Kudos to anyone who recognized the paraphrasing of the song title, ‘Catch a falling star’ in the head for this posting,

Climb like a gecko (in DARPA’s [US Defense Advanced Research Projects Agency] Z-Man program)

I’m not entirely certain why DARPA (US Defense Advanced Research Projects Agency) has now issued a news release (h/t June 5, 2014 news item on Nanowerk) about this achievement (a human climbing like a Gecko) which seems to have first occurred in 2012 but perhaps they want to emphasize that this particular demonstration occurred on a glass wall. In any event, I’m happy to get more news about DARPA’s Z-Man program. From the June 5, 2014 DARPA news release,

DARPA’s Z-Man program has demonstrated the first known human climbing of a glass wall using climbing devices inspired by geckos. The historic ascent involved a 218-pound climber ascending and descending 25 feet of glass, while also carrying an additional 50-pound load in one trial, with no climbing equipment other than a pair of hand-held, gecko-inspired paddles. [emphasis mine] The novel polymer microstructure technology used in those paddles was developed for DARPA by Draper Laboratory of Cambridge, Mass. [Massachusetts]

Historically, gaining the high ground has always been an operational advantage for warfighters, but the climbing instruments on which they’re frequently forced to rely—tools such as ropes and ladders—have not advanced significantly for millennia. Not only can the use of such tools be overt and labor intensive, they also only allow for sequential climbing whereby the first climber often takes on the highest risk.

DARPA created the Z-Man program to overcome these limitations and deliver maximum safety and flexibility for maneuver and rapid response to warfighters operating in tight urban environments. The goal of the program is to develop biologically inspired climbing aids to enable warfighters carrying a full combat load to scale vertical walls constructed from typical building materials.

“The gecko is one of the champion climbers in the Animal Kingdom, so it was natural for DARPA to look to it for inspiration in overcoming some of the maneuver challenges that U.S. forces face in urban environments,” said Dr. Matt Goodman, the DARPA program manager for Z-Man. “Like many of the capabilities that the Department of Defense pursues, we saw with vertical climbing that nature had long since evolved the means to efficiently achieve it. The challenge to our performer team was to understand the biology and physics in play when geckos climb and then reverse-engineer those dynamics into an artificial system for use by humans.”

Geckos can climb on a wide variety of surfaces, including smooth surfaces like glass, with adhesive pressures of 15-30 pounds per square inch for each limb, meaning that a gecko can hang its entire body by one toe. The anatomy of a gecko toe consists of a microscopic hierarchical structure composed of stalk-like setae (100 microns in length, 2 microns in radius). From individual setae, a bundle of hundreds of terminal tips called spatulae (approximately 200 nanometers in diameter at their widest) branch out and contact the climbing surface.

A gecko is able to climb on glass by using physical bond interactions—specifically van der Waals intermolecular forces—between the spatulae and a surface to adhere reversibly, resulting in easy attachment and removal of the gecko’s toes from the surface. The van der Waals mechanism implied that it is the size and shape of the spatulae tips that affect adhesive performance, not specific surface chemistry. This suggested that there were design principles and physical models derived from nature that might enable scientists to fabricate an adhesive inspired by gecko toes.

Humans, of course, have much more weight to carry than a gecko. One of the initial challenges in developing a device to support human climbing was the issue of scaling: a typical Tokay gecko weighs 200 grams, while an average human male weighs 75 kilograms. To enable dynamic climbing like a gecko at this larger scale required that the engineers create climbing paddles capable of balancing sufficient adhesive forces in both the shear (parallel to the vertical surface) and normal (perpendicular to the vertical surface) directions. That feature is necessary for a climber to remain adhered on a surface without falling off while in the act of attaching and detaching the paddles with each movement.

The Draper Laboratory team was also challenged to create novel micro- and nanofabrication technologies to produce the high-aspect-ratio microstructures found in the gecko toe. In the process of achieving that capability, the Z-Man performers transformed the fundamental design and development of reversible adhesives for potential biomedical, industrial, and consumer applications.

The first human climbing demonstration occurred in February 2012 and tests of the technology are ongoing. [emphasis mine]

I’m guessing that glass is difficult to photograph because the image which accompanies the DARPA news release doesn’t highlight the achievement in quite the way one would expect,

During testing, an operator climbed 25 feet vertically on a glass surface using no climbing equipment other than a pair of hand-held, gecko-inspired paddles. The climber wore, but did not require, the use of a safety belay. Image: DARPA

During testing, an operator climbed 25 feet vertically on a glass surface using no climbing equipment other than a pair of hand-held, gecko-inspired paddles. The climber wore, but did not require, the use of a safety belay. Image: DARPA

I last wrote about Z-man in an April 3, 2012 posting highlighting some DARPA-funded work being done at the University of Massachusetts at Amherst while also mentioning work being done in other labs not associated (to my knowledge) with DARPA.

I was not successful in my attempts to find a video highlighting this ‘glass wall’ achievement but I did find this episode of Science Friction, where the host, Rusty Ward, does a very nice job of describing the technology (van der Waals forces, the nanostructures allowing spiders and geckos to climb all sorts of surfaces, etc.) along with some pop culture references (Spider-Man),

This runs for approximately 5 mins. 30 secs., a bit longer than usual for a video embedded here.

One last note, for anyone curious the laboratory referenced in the news release, you can find more here at the (Charles Stark) Draper Laboratory Wikipedia entry.

Research into the properties of water at the nanoscale and water droplet networks

I have two pieces of research with the only common element being water. First, there’s a May 9, 2014 news release on EurekAlert issued by the Politecnico di Torino (Italy; rough translation: Turin Polytechnic),

Swimming in a honey pool. That’s the sensation a water molecule should “feel” while approaching a solid surface within a nanometer (i.e. less than a ten-thousandth of hair diameter). The reduction in water mobility in the very close proximity of surfaces at the nanoscale is the well-known phenomenon of “nanoconfinement”, and it is due to both electrostatic and van der Waals attractive forces ruling matter interactions at that scale.

In this context, scientists from Politecnico di Torino and Houston Methodist Research Institute have taken a further step forward, by formulating a quantitative model and a physical interpretation able of predicting the nanoconfinement effect in a rather general framework. In particular, geometric and chemical characteristics as well as physical conditions of diverse nanoconfining surfaces (e.g. proteins, carbon nanotubes, silica nanopores or iron oxide nanoparticles) have been quantitatively related to mobility reduction and “supercooling” conditions of water, namely the persistence of water in a liquid state at temperatures far below 0°C, when close to a solid surface.

This result has been achieved after two years of in silico (i.e. computer-based) and in vitro (i.e. experiment-driven) activities by Eliodoro Chiavazzo, Matteo Fasano, Pietro Asinari (Multi-Scale Modelling Lab, Department of Energy at Politecnico di Torino) and Paolo Decuzzi (Center for the Rational Design of Multifunctional Nanoconstructs at Houston Methodist Research Institute).

I love the image of swimming in a ‘honey pool’ and while developing a schema for predicting a nanoconfinement effect may not seem all that exciting to an outsider the applications are varied according to the news release,

This study may soon find applications in the optimization and rational design of a broad variety of novel technologies ranging from applied physics (e.g. “nanofluids”, suspensions made out of water and nanoparticles for enhancing heat transfer) to sustainable energy (e.g. thermal storage based on nanoconfined water within sorbent materials); from detection and removal of pollutant from water (e.g. molecular sieves) to nanomedicine.

In fact this work is finding an immediate application in the field of medicine as pertaining to magnetic resonance imaging (MRI), from the news release,

The latter is the field where the research has indeed found a first important application. Every year, almost sixty millions of Magnetic Resonance Imaging (MRI) scans are performed, with diagnostic purposes. In the past decade, MRI technology benefitted from various significant scientific advances, which allowed more precise and sharper images of pathological tissues. Among other, contrast agents (i.e. substances used for improving contrast of structures or fluids within the body) importantly contributed in enhancing MRI performances.

This research activity has been able to explain and predict the increase in MRI performances due to nanoconfined contrast agents, which are currently under development at the Houston Methodist Research Institute. Hence, the discovery paves the way to further increase in the quality of MRI images, in order to possibly improve chances of earlier and more accurate detection of diseases in millions of patients, every year.

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

Scaling behaviour for the water transport in nanoconfined geometries by Eliodoro Chiavazzo, Matteo Fasano, Pietro Asinari & Paolo Decuzzi. Nature Communications 5 Article number: 4565 doi:10.1038/ncomms4565 Published 03 April 2014

This is an open access paper and, unusually, I am excerpting the Abstract as I find it helps to further explain this work (although the more technical aspects are lost on me),

The transport of water in nanoconfined geometries is different from bulk phase and has tremendous implications in nanotechnology and biotechnology. Here molecular dynamics is used to compute the self-diffusion coefficient D of water within nanopores, around nanoparticles, carbon nanotubes and proteins. For almost 60 different cases, D is found to scale linearly with the sole parameter θ as D(θ)=DB[1+(DC/DB−1)θ], with DB and DC the bulk and totally confined diffusion of water, respectively. The parameter θ is primarily influenced by geometry and represents the ratio between the confined and total water volumes. The D(θ) relationship is interpreted within the thermodynamics of supercooled water. As an example, such relationship is shown to accurately predict the relaxometric response of contrast agents for magnetic resonance imaging. The D(θ) relationship can help in interpreting the transport of water molecules under nanoconfined conditions and tailoring nanostructures with precise modulation of water mobility.

The second piece of ‘water’ research was featured in a May 13, 2014 news item on Nanowerk,

A simple new technique to form interlocking beads of water in ambient conditions could prove valuable for applications in biological sensing, membrane research and harvesting water from fog.

Researchers at the Department of Energy’s Oak Ridge National Laboratory have developed a method to create air-stable water droplet networks known as droplet interface bilayers. These interconnected water droplets have many roles in biological research because their interfaces simulate cell membranes. Cumbersome fabrication methods, however, have limited their use.

A May 13, 2014 Oak Ridge National Laboratory (ORNL) news release, which originated the news item, provides more details,

“The way they’ve been made since their inception is that two water droplets are formed in an oil bath then brought together while they’re submerged in oil,” said ORNL’s Pat Collier, who led the team’s study published in the Proceedings of the National Academy of Sciences. “Otherwise they would just pop like soap bubbles.”

Instead of injecting water droplets into an oil bath, the ORNL research team experimented with placing the droplets on a superhydrophobic surface infused with a coating of oil. The droplets aligned side by side without merging.

To the researchers’ surprise, they were also able to form non-coalescing water droplet networks without including lipids in the water solution. Scientists typically incorporate phospholipids into the water mixture, which leads to the formation of an interlocking lipid bilayer between the water droplets.

“When you have those lipids at the interfaces of the water drops, it’s well known that they won’t coalesce because the interfaces join together and form a stable bilayer,” ORNL coauthor Jonathan Boreyko said. “So our surprise was that even without lipids in the system, the pure water droplets on an oil-infused surface in air still don’t coalesce together.”

The team’s research revealed how the unexpected effect is caused by a thin oil film that is squeezed between the pure water droplets as they come together, preventing the droplets from merging into one. Watch a video of the process on ORNL’s YouTube channel.

With or without the addition of lipids, the team’s technique offers new insight for a host of applications. Controlling the behavior of pure water droplets on oil-infused surfaces is key to developing dew- or fog-harvesting technology as well as more efficient condensers, for instance.

“Our finding of this non-coalescence phenomenon will shed light on these droplet-droplet interactions that can occur on oil-infused systems,” Boreyko said.

The ability to create membrane-like water droplet networks by adding lipids leads to a different set of functional applications, Collier noted.

“These bilayers can be used in anything from synthetic biology to creating circuits to bio-sensing applications,” he said. “For example, we could make a bio-battery or a signaling network by stringing some of these droplets together. Or, we could use it to sense the presence of airborne molecules.”

The team’s study also demonstrated ways to control the performance and lifetime of the water droplets by manipulating oil viscosity and temperature and humidity levels.

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

Air-stable droplet interface bilayers on oil-infused surfaces by Jonathan B. Boreyko, Georgios Polizos, Panos G. Datskos, Stephen A. Sarles, and C. Patrick Collier.  PNAS 2014 ; published ahead of print May 12, 2014, doi: 10.1073/pnas.1400381111

This paper is behind a paywall.