Tag Archives: US Department of Energy

Saharan silver ants: the nano of it all (science and technology)

Researchers at Columbia University (US) are on quite a publishing binge lately. The latest is a biomimicry story where researchers (from Columbia amongst other universities and including Brookhaven National Laboratory, which has issued its own news release) have taken a very close look at Saharan silver ants to determine how they stay cool in one of the hottest climates in the world. From a June 18, 2015 Columbia University news release (also on EurekAlert), Note: Links have been removed,

Nanfang Yu, assistant professor of applied physics at Columbia Engineering, and colleagues from the University of Zürich and the University of Washington, have discovered two key strategies that enable Saharan silver ants to stay cool in one of the hottest terrestrial environments on Earth. Yu’s team is the first to demonstrate that the ants use a coat of uniquely shaped hairs to control electromagnetic waves over an extremely broad range from the solar spectrum (visible and near-infrared) to the thermal radiation spectrum (mid-infrared), and that different physical mechanisms are used in different spectral bands to realize the same biological function of reducing body temperature. Their research, “Saharan silver ants keep cool by combining enhanced optical reflection and radiative heat dissipation,” is published June 18 [2015] in Science magazine.

The Columbia University news release expands on the theme,

“This is a telling example of how evolution has triggered the adaptation of physical attributes to accomplish a physiological task and ensure survival, in this case to prevent Saharan silver ants from getting overheated,” Yu says. “While there have been many studies of the physical optics of living systems in the ultraviolet and visible range of the spectrum, our understanding of the role of infrared light in their lives is much less advanced. Our study shows that light invisible to the human eye does not necessarily mean that it does not play a crucial role for living organisms.”

The project was initially triggered by wondering whether the ants’ conspicuous silvery coats were important in keeping them cool in blistering heat. Yu’s team found that the answer to this question was much broader once they realized the important role of infrared light. Their discovery that there is a biological solution to a thermoregulatory problem could lead to the development of novel flat optical components that exhibit optimal cooling properties.

“Such biologically inspired cooling surfaces will have high reflectivity in the solar spectrum and high radiative efficiency in the thermal radiation spectrum,” Yu explains. “So this may generate useful applications such as a cooling surface for vehicles, buildings, instruments, and even clothing.”

Saharan silver ants (Cataglyphis bombycina) forage in the Saharan Desert in the full midday sun when surface temperatures reach up to 70°C (158°F), and they must keep their body temperature below their critical thermal maximum of 53.6°C (128.48°F) most of the time. In their wide-ranging foraging journeys, the ants search for corpses of insects and other arthropods that have succumbed to the thermally harsh desert conditions, which they are able to endure more successfully. Being most active during the hottest moment of the day also allows these ants to avoid predatory desert lizards. Researchers have long wondered how these tiny insects (about 10 mm, or 3/8” long) can survive under such thermally extreme and stressful conditions.

Using electron microscopy and ion beam milling, Yu’s group discovered that the ants are covered on the top and sides of their bodies with a coating of uniquely shaped hairs with triangular cross-sections that keep them cool in two ways. These hairs are highly reflective under the visible and near-infrared light, i.e., in the region of maximal solar radiation (the ants run at a speed of up to 0.7 meters per second and look like droplets of mercury on the desert surface). The hairs are also highly emissive in the mid-infrared portion of the electromagnetic spectrum, where they serve as an antireflection layer that enhances the ants’ ability to offload excess heat via thermal radiation, which is emitted from the hot body of the ants to the cold sky. This passive cooling effect works under the full sun whenever the insects are exposed to the clear sky.

“To appreciate the effect of thermal radiation, think of the chilly feeling when you get out of bed in the morning,” says Yu. “Half of the energy loss at that moment is due to thermal radiation since your skin temperature is temporarily much higher than that of the surrounding environment.”

The researchers found that the enhanced reflectivity in the solar spectrum and enhanced thermal radiative efficiency have comparable contributions to reducing the body temperature of silver ants by 5 to 10 degrees compared to if the ants were without the hair cover. “The fact that these silver ants can manipulate electromagnetic waves over such a broad range of spectrum shows us just how complex the function of these seemingly simple biological organs of an insect can be,” observes Norman Nan Shi, lead author of the study and PhD student who works with Yu at Columbia Engineering.

Yu and Shi collaborated on the project with Rüdiger Wehner, professor at the Brain Research Institute, University of Zürich, Switzerland, and Gary Bernard, electrical engineering professor at the University of Washington, Seattle, who are renowned experts in the study of insect physiology and ecology. The Columbia Engineering team designed and conducted all experimental work, including optical and infrared microscopy and spectroscopy experiments, thermodynamic experiments, and computer simulation and modeling. They are currently working on adapting the engineering lessons learned from the study of Saharan silver ants to create flat optical components, or “metasurfaces,” that consist of a planar array of nanophotonic elements and provide designer optical and thermal radiative properties.

Yu and his team plan next to extend their research to other animals and organisms living in extreme environments, trying to learn the strategies these creatures have developed to cope with harsh environmental conditions.

“Animals have evolved diverse strategies to perceive and utilize electromagnetic waves: deep sea fish have eyes that enable them to maneuver and prey in dark waters, butterflies create colors from nanostructures in their wings, honey bees can see and respond to ultraviolet signals, and fireflies use flash communication systems,” Yu adds. “Organs evolved for perceiving or controlling electromagnetic waves often surpass analogous man-made devices in both sophistication and efficiency. Understanding and harnessing natural design concepts deepens our knowledge of complex biological systems and inspires ideas for creating novel technologies.”

Next, there’s the perspective provided by Brookhaven National Laboratory in a June 18, 2015 news item on Nanowerk (Note: It is very similar to the Columbia University news release but it takes a turn towards the technical challenges as you’ll see if you keep reading),

The paper, published by Columbia Engineering researchers and collaborators—including researchers from the U.S. Department of Energy’s (DOE) Brookhaven National Laboratory—describes how the nanoscale structure of the hairs helps increase the reflectivity of the ant’s body in both visible and near-infrared wavelengths, allowing the insects to deflect solar radiation their bodies would otherwise absorb. The hairs also enhance emissivity in the mid-infrared spectrum, allowing heat to dissipate efficiently from the hot body of the ants to the cool, clear sky.

A June 18, 2015 BNL news release by Alasdair Wilkins, which originated the Nanowerk news item, describes the collaboration between the researchers and the special adjustments made to the equipment in service of this project (Note: A link has been removed),

In a typical experiment involving biological material such as nanoscale hairs, it would usually be sufficient to use an electron microscope to create an image of the surface of the specimen. This research, however, required Yu’s group to look inside the ant hairs and produce a cross-section of the structure’s interior. The relatively weak beam of electrons from a standard electron microscope would not be able to penetrate the surface of the sample.

The CFN’s dual beam system solves the problem by combining the imaging of an electron microscope with a much more powerful beam of gallium ions.  With 31 protons and 38 neutrons, each gallium ion is about 125,000 times more massive than an electron, and massive enough to create dents in the nanoscale structure – like throwing a stone against a wall. The researchers used these powerful beams to drill precise cuts into the hairs, revealing the crucial information hidden beneath the surface. Indeed, this particular application, in which the system was used to investigate a biological problem, was new for the team at CFN.

“Conventionally, this tool is used to produce cross-sections of microelectronic circuits,” said Camino. “The focused ion beam is like an etching tool. You can think of it like a milling tool in a machine shop, but at the nanoscale. It can remove material at specific places because you can see these locations with the SEM. So locally you remove material and you look at the under layers, because the cuts give you access to the cross section of whatever you want to look at.”

The ant hair research challenged the CFN team to come up with novel solutions to investigate the internal structures without damaging the more delicate biological samples.

“These hairs are very soft compared to, say, semiconductors or crystalline materials. And there’s a lot of local heat that can damage biological samples. So the parameters have to be carefully tuned not to do much damage to it,” he said. “We had to adapt our technique to find the right conditions.”

Another challenge lay in dealing with the so-called charging effect. When the dual beam system is trained on a non-conducting material, electrons can build up at the point where the beams hit the specimen, distorting the resulting image. The team at CFN was able to solve this problem by placing thin layers of gold over the biological material, making the sample just conductive enough to avoid the charging effect.

Revealing Reflectivity

While Camino’s team focused on helping Yu’s group investigate the structure of the ant hairs, Matthew Sfeir’s work with high-brightness Fourier transform optical spectroscopy helped to reveal how the reflectivity of the hairs helped Saharan silver ants regulate temperature. Sfeir’s spectrometer revealed precisely how much those biological structures reflect light across multiple wavelengths, including both visible and near-infrared light.

“It’s a multiplexed measurement,” Sfeir said, explaining his team’s spectrometer. “Instead of tuning through this wavelength and this wavelength, that wavelength, you do them all in one swoop to get all the spectral information in one shot. It gives you very fast measurements and very good resolution spectrally. Then we optimize it for very small samples. It’s a rather unique capability of CFN.”

Sfeir’s spectroscopy work draws on knowledge gained from his work at another key Brookhaven facility: the original National Synchrotron Light Source, where he did much of his postdoc work. His experience was particularly useful in analyzing the reflectivity of the biological structures across many different wavelengths of the electromagnetic spectrum.

“This technique was developed from my experience working with the infrared synchrotron beamlines,” said Sfeir. “Synchrotron beamlines are optimized for exactly this kind of thing. I thought, ‘Hey, wouldn’t it be great if we could develop a similar measurement for the type of solar devices we make at CFN?’ So we built a bench-top version to use here.”

Fascinating, non? At last, here’s a link to and a citation for the paper,

Keeping cool: Enhanced optical reflection and heat dissipation in silver ants by Norman Nan Shi, Cheng-Chia Tsai, Fernando Camino, Gary D. Bernard, Nanfang Yu, and Rüdiger Wehner. Science DOI: 10.1126/science.aab3564 Published online June 18, 2015

This paper is behind a paywall.

Platinum catalysts and their shortcomings

The problem boils down to the fact that platinum isn’t cheap and so US Dept. of Energy research laboratories are looking for alternatives to or ways of making more efficient use of platinum according to a June 16, 2015 news item on Nanowerk,

Visions of dazzling engagement rings may pop to mind when platinum is mentioned, but a significant share of the nearly half a million pounds of the rare metalExternal link [sic] mined each year ends up in vehicle emission systems and chemical manufacturing plants. The silvery white metal speeds up or enhances reactions, a role scientists call serving as a catalyst, and platinum is fast and efficient performing this function.

Because of its outstanding performance as a catalyst, platinum plays a major role in fuel cells. Inside a fuel cell, tiny platinum particles break apart hydrogen fuel to create electricity. Leftover protons are combined with oxygen ions to create pure water.

Fuel cells could let scientists turn wind into fuel. Right now, electricity generated by wind turbines is not stored. If that energy could be converted into hydrogen to power fuel cells, it would turn a sporadic source into a continuous one.

The problem is the platinum – a scarce and costly metal. Scientists funded by the U.S. Department of Energy’s Office of Science are seeing if something more readily available, such as iron or nickel, could catalyze the reaction.

But, earth-abundant metals cannot simply be used in place of platinum and other rare metals. Each metal works differently at the atomic level. It takes basic research to understand the interactions and use that knowledge to create the right catalysts.

A June 15, 2015 US Department of Energy Office of Science news release, which originated the news item, describes various efforts,

At the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, scientists are gaining new understanding of catalysts based on common metals and how they move protons, the positively charged, oft-ignored counterpart to the electron.

Center Director Morris Bullock and his colleagues showed that protons’ ability to move through the catalyst greatly influences the catalyst’s speed and efficiency. Protons move via relays — clusters of atoms that convey protons to or from the active site of catalysts, where the reaction of interest occurs. The constitution, placement, and number of relays can let a reaction zip along or grind to a halt. Bullock and his colleagues are creating “design guidelines” for building relays.

Further, the team is expanding the guidelines to examine proton movement related to the solutions and surfaces where the catalyst resides. For example, matching the proton-donating abilityExternal link [sic] of a nickel-based catalyst to that of the surrounding liquid, much like matching your clothing choice with the event you’re attending, eases protons’ travels. The benefit? Speed. A coordinated catalyst pumped out 96,000 hydrogen molecules a second — compared to just 27,000 molecules a second without the adjustment.

This and other research at the Energy Frontier Research Center is funded by the DOE Office of Science’s Office of Basic Energy Sciences. The Center is led by Pacific Northwest National Laboratory.

At two other labs, research shows how changing the catalyst’s superstructure, which contains the proton relays and wraps around the active site, can also increase the speed of the reaction. Led by Argonne National Lab’s Vojislav Stamenkovic and Berkeley Lab’s Peidong Yang, researchers created hollow platinum and nickel nanoparticles, a thousand times smaller in diameter than a human hair. The 12-sided particles split oxygen molecules into charged oxygen ions, a reaction that’s needed in fuel cells. The new catalyst is far more active and uses far less platinum than conventional platinum-carbon catalysts.

Building the catalysts begins with tiny structures made of platinum and nickel held in solution. Oxygen from the air dissolves into the liquid and selectively etches away some of the nickel atoms. The result is a hollow framework with a highly active platinum skin over the surface. The open design of the catalyst allows the oxygen to easily access the platinum. The new catalyst has a 36-fold increase in activity compared to traditional platinum–carbon catalysts. Further, the new hollow structure continues to work far longer in operating fuel cells than traditional catalysts.

I think we’re entering the ‘slow’ season newswise so there are likely to be more of these ’roundup’ pieces being circulated in the online nanosciencesphere and, consequently, here. too.

DNA (deoxyribonucleic acid) scaffolding for nonbiological construction

DNA (deoxyribonucleic acid) is being exploited in ways that would have seemed unimaginable to me when I was in high school. Earlier today (June 3, 2015), I ran a piece about DNA and data storage as imagined in an art/science project (DNA (deoxyribonucleic acid), music, and data storage) and now I have this work from the US Department of Energy’s (DOE) Brookhaven National Laboratory, from a June 1, 2015 news item on Nanowerk,

You’re probably familiar with the role of DNA as the blueprint for making every protein on the planet and passing genetic information from one generation to the next. But researchers at Brookhaven Lab’s Center for Functional Nanomaterials have shown that the twisted ladder molecule made of complementary matching strands can also perform a number of decidedly non-biological construction jobs: serving as a scaffold and programmable “glue” for linking up nanoparticles. This work has resulted in a variety of nanoparticle assemblies, including composite structures with switchable phases whose optical, magnetic, or other properties might be put to use in dynamic energy-harvesting or responsive optical materials. Three recent studies showcase different strategies for using synthetic strands of this versatile building material to link and arrange different types of nanoparticles in predictable ways.

The researchers have provided an image of the DNA building blocks,

Controlling the self-assembly of nanoparticles into superlattices is an important approach to build functional materials. The Brookhaven team used nanosized building blocks—cubes or octahedrons—decorated with DNA tethers to coordinate the assembly of spherical nanoparticles coated with complementary DNA strands.

Controlling the self-assembly of nanoparticles into superlattices is an important approach to build functional materials. The Brookhaven team used nanosized building blocks—cubes or octahedrons—decorated with DNA tethers to coordinate the assembly of spherical nanoparticles coated with complementary DNA strands.

A June 1, 2015 article (which originated the news item) in DOE Pulse Number 440 goes on to highlight three recent DNA papers published by researchers at Brookhaven National Laboratory,

The first [leads to a news release], published in Nature Communications, describes how scientists used the shape of nanoscale building blocks decorated with single strands of DNA to orchestrate the arrangement of spheres decorated with complementary strands (where bases on the two strands pair up according to the rules of DNA binding, A to T, G to C). For example, nano-cubes coated with DNA tethers on all six sides formed regular arrays of cubes surrounded by six nano-spheres. The attractive force of the DNA “glue” keeps these two dissimilar objects from self-separating to give scientists a reliable way to assemble composite materials in which the synergistic properties of different types of nanoparticles might be put to use.

In another study [leads to a news release], published in Nature Nanotechnology, the team used ropelike configurations of the DNA double helix to form a rigid geometrical framework, and added dangling pieces of single-stranded DNA to glue nanoparticles in place on the vertices of the scaffold. Controlling the code of the dangling strands and adding complementary strands to the nanoparticles gives scientists precision control over particle placement. These arrays of nanoparticles with predictable geometric configurations are somewhat analogous to molecules made of atoms, and can even be linked end-to-end to form polymer-like chains, or arrayed as flat sheets. Using this approach, the scientists can potentially orchestrate the arrangements of different types of nanoparticles to design materials that regulate energy flow, rotate light, or deliver biomolecules.

“We may be able to design materials that mimic nature’s machinery to harvest solar energy, or manipulate light for telecommunications applications, or design novel catalysts for speeding up a variety of chemical reactions,” said Oleg Gang, the Brookhaven physicist who leads this work on DNA-mediated nano-assembly.

Perhaps most exciting is a study [leads to a news release] published in Nature Materials in which the scientists added “reprogramming” strands of DNA after assembly to rearrange and change the phase of nanoparticle arrays. This is a change at the nanoscale that in some ways resembles an atomic phase change—like the shift in the atomic crystal lattice of carbon that transforms graphite into diamond—potentially producing a material with completely new properties from the same already assembled nanoparticle array. Inputting different types of attractive and repulsive reprogramming DNA strands, scientists could selectively trigger the transformation to the different resulting structures.

“The ability to dynamically switch the phase of an entire superlattice array will allow the creation of reprogrammable and switchable materials wherein multiple, different functions can be activated on demand,” Gang said.

Here are links to and citation for all three papers,

Superlattices assembled through shape-induced directional binding by Fang Lu, Kevin G. Yager, Yugang Zhang, Huolin Xin, & Oleg Gang. Nature Communications 6, Article number: 6912 doi:10.1038/ncomms7912 Published 23 April 2015

Prescribed nanoparticle cluster architectures and low-dimensional arrays built using octahedral DNA origami frames by Ye Tian, Tong Wang, Wenyan Liu, Huolin L. Xin, Huilin Li, Yonggang Ke, William M. Shih, & Oleg Gang. Nature Nanotechnology (2015) doi:10.1038/nnano.2015.105 Published online 25 May 2015

Selective transformations between nanoparticle superlattices via the reprogramming of DNA-mediated interactions by Yugang Zhang, Suchetan Pal, Babji Srinivasan, Thi Vo, Sanat Kumar & Oleg Gang. Nature Materials (2015) doi:10.1038/nmat4296 Published online 25 May 2015

The first study is open access, the second is behind a paywall but there is a free preview via ReadCube Acces, and the third is behind a paywall.

Large(!)-scale graphene composite fabrication at the US Oak Ridge National Laboratory (ORNL)

When you’re talking about large-scale production of nanomaterials, it would be more accurate term to say ‘relatively large when compared to the nanoscale’. A May 15, 2015 news item on ScienceDaily, trumpets the news,

One of the barriers to using graphene at a commercial scale could be overcome using a method demonstrated by researchers at the Department of Energy’s Oak Ridge National Laboratory [ORNL].

Graphene, a material stronger and stiffer than carbon fiber, has enormous commercial potential but has been impractical to employ on a large scale, with researchers limited to using small flakes of the material.

Now, using chemical vapor deposition, a team led by ORNL’s Ivan Vlassiouk has fabricated polymer composites containing 2-inch-by-2-inch sheets of the one-atom thick hexagonally arranged carbon atoms. [emphasis mine]

Once you understand where these scientists are coming from in terms of the material size, it becomes easier to appreciate the accomplishment and its potential. From a May 14, 2015 ORNL news release (also on EurekAlert), which originated the news item,

The findings, reported in the journal Applied Materials & Interfaces, could help usher in a new era in flexible electronics and change the way this reinforcing material is viewed and ultimately used.

“Before our work, superb mechanical properties of graphene were shown at a micro scale [one millionth of a metre],” said Vlassiouk, a member of ORNL’s Energy and Transportation Science Division. “We have extended this to a larger scale, which considerably extends the potential applications and market for graphene.”

While most approaches for polymer nanocomposition construction employ tiny flakes of graphene or other carbon nanomaterials that are difficult to disperse in the polymer, Vlassiouk’s team used larger sheets of graphene. This eliminates the flake dispersion and agglomeration problems and allows the material to better conduct electricity with less actual graphene in the polymer.

“In our case, we were able to use chemical vapor deposition to make a nanocomposite laminate that is electrically conductive with graphene loading that is 50 times less compared to current state-of-the-art samples,” Vlassiouk said. This is a key to making the material competitive on the market.

If Vlassiouk and his team can reduce the cost and demonstrate scalability, researchers envision graphene being used in aerospace (structural monitoring, flame-retardants, anti-icing, conductive), the automotive sector (catalysts, wear-resistant coatings), structural applications (self-cleaning coatings, temperature control materials), electronics (displays, printed electronics, thermal management), energy (photovoltaics, filtration, energy storage) and manufacturing (catalysts, barrier coatings, filtration).

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

Strong and Electrically Conductive Graphene-Based Composite Fibers and Laminates by Ivan Vlassiouk, Georgios Polizos, Ryan Cooper, Ilia Ivanov, Jong Kahk Keum, Felix Paulauskas, Panos Datskos, and Sergei Smirnov. ACS Appl. Mater. Interfaces, Article ASAP DOI: 10.1021/acsami.5b01367 Publication Date (Web): April 28, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

Stress makes quantum dots ‘breathe’

A March 19, 2015 news item on ScienceDaily describes some new research on quantum dots,

Researchers at the Department of Energy’s SLAC National Accelerator Laboratory watched nanoscale semiconductor crystals expand and shrink in response to powerful pulses of laser light. This ultrafast “breathing” provides new insight about how such tiny structures change shape as they start to melt — information that can help guide researchers in tailoring their use for a range of applications.

In the experiment using SLAC’s Linac Coherent Light Source (LCLS) X-ray laser, a DOE Office of Science User Facility, researchers first exposed the nanocrystals to a burst of laser light, followed closely by an ultrabright X-ray pulse that recorded the resulting structural changes in atomic-scale detail at the onset of melting.

“This is the first time we could measure the details of how these ultrasmall materials react when strained to their limits,” said Aaron Lindenberg, an assistant professor at SLAC and Stanford who led the experiment. The results were published March 12 [2015] in Nature Communications.

A March 18, 2015 SLAC news release, which originated the news item, provides a general description of quantum dots,

The crystals studied at SLAC are known as “quantum dots” because they display unique traits at the nanoscale that defy the classical physics governing their properties at larger scales. The crystals can be tuned by changing their size and shape to emit specific colors of light, for example.

So scientists have worked to incorporate them in solar panels to make them more efficient and in computer displays to improve resolution while consuming less battery power. These materials have also been studied for potential use in batteries and fuel cells and for targeted drug delivery.

Scientists have also discovered that these and other nanomaterials, which may contain just tens or hundreds of atoms, can be far more damage-resistant than larger bits of the same materials because they exhibit a more perfect crystal structure at the tiniest scales. This property could prove useful in battery components, for example, as smaller particles may be able to withstand more charging cycles than larger ones before degrading.

The news release then goes on to describe the latest research showing the dots ‘breathe’ (Note: A link has been removed),

In the LCLS experiment, researchers studied spheres and nanowires made of cadmium sulfide and cadmium selenide that were just 3 to 5 nanometers, or billionths of a meter, across. The nanowires were up to 25 nanometers long. By comparison, amino acids – the building blocks of proteins – are about 1 nanometer in length, and individual atoms are measured in tenths of nanometers.

By examining the nanocrystals from many different angles with X-ray pulses, researchers reconstructed how they change shape when hit with an optical laser pulse. They were surprised to see the spheres and nanowires expand in width by about 1 percent and then quickly contract within femtoseconds, or quadrillionths of a second. They also found that the nanowires don’t expand in length, and showed that the way the crystals respond to strain was coupled to how their structure melts.

In an earlier, separate study, another team of researchers had used LCLS to explore the response of larger gold particles on longer timescales.

“In the future, we want to extend these experiments to more complex and technologically relevant nanostructures, and also to enable X-ray exploration of nanoscale devices while they are operating,” Lindenberg said. “Knowing how materials change under strain can be used together with simulations to design new materials with novel properties.”

Participating researchers were from SLAC, Stanford and two of their joint institutes, the Stanford Institute for Materials and Energy Sciences (SIMES) and Stanford PULSE Institute; University of California, Berkeley; University of Duisburg-Essen in Germany; and Argonne National Laboratory. The work was supported by the DOE Office of Science and the German Research Council.

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

Visualization of nanocrystal breathing modes at extreme strains by Erzsi Szilagyi, Joshua S. Wittenberg, Timothy A. Miller, Katie Lutker, Florian Quirin, Henrik Lemke, Diling Zhu, Matthieu Chollet, Joseph Robinson, Haidan Wen, Klaus Sokolowski-Tinten, & Aaron M. Lindenberg. Nature Communications 6, Article number: 6577 doi:10.1038/ncomms7577 Published 12 March 2015

This paper is behind a paywall but there is a free preview available through ReadCube Access.

Solar cells and ‘tinkertoys’

A Nov. 3, 2014 news item on Nanowerk features a project researchers hope will improve photovoltaic efficiency and make solar cells competitive with other sources of energy,

 Researchers at Sandia National Laboratories have received a $1.2 million award from the U.S. Department of Energy’s SunShot Initiative to develop a technique that they believe will significantly improve the efficiencies of photovoltaic materials and help make solar electricity cost-competitive with other sources of energy.

The work builds on Sandia’s recent successes with metal-organic framework (MOF) materials by combining them with dye-sensitized solar cells (DSSC).

“A lot of people are working with DSSCs, but we think our expertise with MOFs gives us a tool that others don’t have,” said Sandia’s Erik Spoerke, a materials scientist with a long history of solar cell exploration at the labs.

A Nov. 3, 2014 Sandia National Laboratories news release, which originated the news item, describes the project and the technology in more detail,

Sandia’s project is funded through SunShot’s Next Generation Photovoltaic Technologies III program, which sponsors projects that apply promising basic materials science that has been proven at the materials properties level to demonstrate photovoltaic conversion improvements to address or exceed SunShot goals.

The SunShot Initiative is a collaborative national effort that aggressively drives innovation with the aim of making solar energy fully cost-competitive with traditional energy sources before the end of the decade. Through SunShot, the Energy Department supports efforts by private companies, universities and national laboratories to drive down the cost of solar electricity to 6 cents per kilowatt-hour.

DSSCs provide basis for future advancements in solar electricity production

Dye-sensitized solar cells, invented in the 1980s, use dyes designed to efficiently absorb light in the solar spectrum. The dye is mated with a semiconductor, typically titanium dioxide, that facilitates conversion of the energy in the optically excited dye into usable electrical current.

DSSCs are considered a significant advancement in photovoltaic technology since they separate the various processes of generating current from a solar cell. Michael Grätzel, a professor at the École Polytechnique Fédérale de Lausanne in Switzerland, was awarded the 2010 Millennium Technology Prize for inventing the first high-efficiency DSSC.

“If you don’t have everything in the DSSC dependent on everything else, it’s a lot easier to optimize your photovoltaic device in the most flexible and effective way,” explained Sandia senior scientist Mark Allendorf. DSSCs, for example, can capture more of the sun’s energy than silicon-based solar cells by using varied or multiple dyes and also can use different molecular systems, Allendorf said.

“It becomes almost modular in terms of the cell’s components, all of which contribute to making electricity out of sunlight more efficiently,” said Spoerke.

MOFs’ structure, versatility and porosity help overcome DSSC limitations

Though a source of optimism for the solar research community, DSSCs possess certain challenges that the Sandia research team thinks can be overcome by combining them with MOFs.

Allendorf said researchers hope to use the ordered structure and versatile chemistry of MOFs to help the dyes in DSSCs absorb more solar light, which he says is a fundamental limit on their efficiency.

“Our hypothesis is that we can put a thin layer of MOF on top of the titanium dioxide, thus enabling us to order the dye in exactly the way we want it,” Allendorf explained. That, he said, should avoid the efficiency-decreasing problem of dye aggregation, since the dye would then be locked into the MOF’s crystalline structure.

MOFs are highly-ordered materials that also offer high levels of porosity, said Allendorf, a MOF expert and 29-year veteran of Sandia. He calls the materials “Tinkertoys for chemists” because of the ease with which new structures can be envisioned and assembled. [emphasis mine]

Allendorf said the unique porosity of MOFs will allow researchers to add a second dye, placed into the pores of the MOF, that will cover additional parts of the solar spectrum that weren’t covered with the initial dye. Finally, he and Spoerke are convinced that MOFs can help improve the overall electron charge and flow of the solar cell, which currently faces instability issues.

“Essentially, we believe MOFs can help to more effectively organize the electronic and nano-structure of the molecules in the solar cell,” said Spoerke. “This can go a long way toward improving the efficiency and stability of these assembled devices.”

In addition to the Sandia team, the project includes researchers at the University of Colorado-Boulder, particularly Steve George, an expert in a thin film technology known as atomic layer deposition.

The technique, said Spoerke, is important in that it offers a pathway for highly controlled materials chemistry with potentially low-cost manufacturing of the DSSC/MOF process.

“With the combination of MOFs, dye-sensitized solar cells and atomic layer deposition, we think we can figure out how to control all of the key cell interfaces and material elements in a way that’s never been done before,” said Spoerke. “That’s what makes this project exciting.”

Here’s a picture showing an early Tinkertoy set,

Original Tinkertoy, Giant Engineer #155. Questor Education Products Co., c.1950 [downloaded from http://en.wikipedia.org/wiki/Tinkertoy#mediaviewer/File:Tinkertoy_300126232168.JPG]

Original Tinkertoy, Giant Engineer #155. Questor Education Products Co., c.1950 [downloaded from http://en.wikipedia.org/wiki/Tinkertoy#mediaviewer/File:Tinkertoy_300126232168.JPG]

The Tinkertoy entry on Wikipedia has this,

The Tinkertoy Construction Set is a toy construction set for children. It was created in 1914—six years after the Frank Hornby’s Meccano sets—by Charles H. Pajeau and Robert Pettit and Gordon Tinker in Evanston, Illinois. Pajeau, a stonemason, designed the toy after seeing children play with sticks and empty spools of thread. He and Pettit set out to market a toy that would allow and inspire children to use their imaginations. At first, this did not go well, but after a year or two over a million were sold.

Shrinky Dinks, tinkertoys, Lego have all been mentioned here in conjunction with lab work. I’m always delighted to see scientists working with or using children’s toys as inspiration of one type or another.

Single layer graphene as a solid lubricant

Graphite (from which graphene springs) has been used as a solid lubricant for many years but it has limitations which researchers at the US Dept. of Energy’s Argonne National Laboratory are attempting to overcome by possibly replacing it with graphene. An Oct. 14, 2014 news item on phys.org describes the research (Note: A link has been removed),

Nanoscientist Anirudha Sumant and his colleagues at Argonne’s Center for Nanoscale Materials and Argonne’s Energy Systems division applied a one-atom-thick layer of graphene, a two-dimensional form of carbon, in between a steel ball and a steel disk. They found that just the single layer of graphene lasted for more than 6,500 “wear cycles,” a dramatic improvement over conventional lubricants like graphite or molybdenum disulfide.

An Oct. 13, 2014 Argonne National Laboratory news release by Jared Sagoff, which originated the news item, provides more information about this research (Note: A link has been removed),

“For comparison,” Sumant said, “conventional lubricants would need about 1,000 layers to last for 1,000 wear cycles. That’s a huge advantage in terms of cost savings with much better performance.”

Graphite has been used as an industrial lubricant for more than 40 years, but not without certain drawbacks, Sumant explained.  “Graphite is limited by the fact that it really works only in humid environments. If you have a dry setting, it’s not going to be nearly as effective,” he said.

This limitation arises from the fact that graphite – unlike graphene – has a three-dimensional structure.  The water molecules in the moist air create slipperiness by weaving themselves in between graphite’s carbon sheets. When there are not enough water molecules in the air, the material loses its slickness.

Molybdenum disulfide, another common lubricant, has the reverse problem, Sumant said. It works in dry environments but not well in wet ones. “Essentially the challenge is to find a single all-purpose lubricant that works well for mechanical systems, no matter where they are,” he said.

Graphene’s two-dimensional structure gives it a significant advantage. “The material is able to bond directly to the surface of the stainless steel ball, making it so perfectly even that even hydrogen atoms are not able to penetrate it,” said Argonne materials scientist Ali Erdemir, a collaborator on the study who tested graphene-coated steel surfaces in his lab.

In a previous study in Materials Today, Sumant and his colleagues showed that a few layers of graphene works equally well in humid and dry environments as a solid lubricant, solving the 40-year-old puzzle of finding a flawless solid lubricant. However, the team wanted to go further and test just a single graphene layer.

While doing so in an environment containing molecules of pure hydrogen, they observed a dramatic improvement in graphene’s operational lifetime. When the graphene monolayer eventually starts to wear away, hydrogen atoms leap in to repair the lattice, like stitching a quilt back together. “Hydrogen can only get into the fabric where there is already an opening,” said Subramanian Sankaranarayanan, an Argonne computational scientist and co-author in this study. This means the graphene layer stays intact longer.

Researchers had previously done experiments to understand the mechanical strength of a single sheet of graphene, but the Argonne study is the first to explain the extraordinary wear resistance of one-atom-thick graphene.

Here’s a link to and a citation for the August 2014 study,

Extraordinary Macroscale Wear Resistance of One Atom Thick Graphene Layer by Diana Berman, Sanket A. Deshmukh, Subramanian K. R. S. Sankaranarayanan, Ali Erdemir, and Anirudha V. Sumant. Advanced Funtional Materials DOI: 10.1002/adfm.201401755 Article first published online: 26 AUG 2014

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This article is behind a paywall.

Trapping gases left from nuclear fuels

A July 20, 2014 news item on ScienceDaily provides some insight into recycling nuclear fuel,

When nuclear fuel gets recycled, the process releases radioactive krypton and xenon gases. Naturally occurring uranium in rock contaminates basements with the related gas radon. A new porous material called CC3 effectively traps these gases, and research appearing July 20 in Nature Materials shows how: by breathing enough to let the gases in but not out.

The CC3 material could be helpful in removing unwanted or hazardous radioactive elements from nuclear fuel or air in buildings and also in recycling useful elements from the nuclear fuel cycle. CC3 is much more selective in trapping these gases compared to other experimental materials. Also, CC3 will likely use less energy to recover elements than conventional treatments, according to the authors.

A July 21, 2014 US Department of Energy (DOE) Pacific Northwest National Laboratory (PNNL) news release (also on EurekAlert), which originated the news item despite the difference in dates, provides more details (Note: A link has been removed),

The team made up of scientists at the University of Liverpool in the U.K., the Department of Energy’s Pacific Northwest National Laboratory, Newcastle University in the U.K., and Aix-Marseille Universite in France performed simulations and laboratory experiments to determine how — and how well — CC3 might separate these gases from exhaust or waste.

“Xenon, krypton and radon are noble gases, which are chemically inert. That makes it difficult to find materials that can trap them,” said coauthor Praveen Thallapally of PNNL. “So we were happily surprised at how easily CC3 removed them from the gas stream.”

Noble gases are rare in the atmosphere but some such as radon come in radioactive forms and can contribute to cancer. Others such as xenon are useful industrial gases in commercial lighting, medical imaging and anesthesia.

The conventional way to remove xenon from the air or recover it from nuclear fuel involves cooling the air far below where water freezes. Such cryogenic separations are energy intensive and expensive. Researchers have been exploring materials called metal-organic frameworks, also known as MOFs, that could potentially trap xenon and krypton without having to use cryogenics. Although a leading MOF could remove xenon at very low concentrations and at ambient temperatures admirably, researchers wanted to find a material that performed better.

Thallapally’s collaborator Andrew Cooper at the University of Liverpool and others had been researching materials called porous organic cages, whose molecular structures are made up of repeating units that form 3-D cages. Cages built from a molecule called CC3 are the right size to hold about three atoms of xenon, krypton or radon.

To test whether CC3 might be useful here, the team simulated on a computer CC3 interacting with atoms of xenon and other noble gases. The molecular structure of CC3 naturally expands and contracts. The researchers found this breathing created a hole in the cage that grew to 4.5 angstroms wide and shrunk to 3.6 angstroms. One atom of xenon is 4.1 angstroms wide, suggesting it could fit within the window if the cage opens long enough. (Krypton and radon are 3.69 angstroms and 4.17 angstroms wide, respectively, and it takes 10 million angstroms to span a millimeter.)

The computer simulations revealed that CC3 opens its windows big enough for xenon about 7 percent of the time, but that is enough for xenon to hop in. In addition, xenon has a higher likelihood of hopping in than hopping out, essentially trapping the noble gas inside.

The team then tested how well CC3 could pull low concentrations of xenon and krypton out of air, a mix of gases that included oxygen, argon, carbon dioxide and nitrogen. With xenon at 400 parts per million and krypton at 40 parts per million, the researchers sent the mix through a sample of CC3 and measured how long it took for the gases to come out the other side.

Oxygen, nitrogen, argon and carbon dioxide — abundant components of air — traveled through the CC3 and continued to be measured for the experiment’s full 45 minute span. Xenon however stayed within the CC3 for 15 minutes, showing that CC3 could separate xenon from air.

In addition, CC3 trapped twice as much xenon as the leading MOF material. It also caught xenon 20 times more often than it caught krypton, a characteristic known as selectivity. The leading MOF only preferred xenon 7 times as much. These experiments indicated improved performance in two important characteristics of such a material, capacity and selectivity.

“We know that CC3 does this but we’re not sure why. Once we understand why CC3 traps the noble gases so easily, we can improve on it,” said Thallapally.

To explore whether MOFs and porous organic cages offer economic advantages, the researchers estimated the cost compared to cryogenic separations and determined they would likely be less expensive.

“Because these materials function well at ambient or close to ambient temperatures, the processes based on them are less energy intensive to use,” said PNNL’s Denis Strachan.

The material might also find use in pharmaceuticals. Most molecules come in right- and left-handed forms and often only one form works in people. In additional experiments, Cooper and colleagues in the U.K. tested CC3’s ability to distinguish and separate left- and right-handed versions of an alcohol. After separating left- and right-handed forms of CC3, the team showed in biochemical experiments that each form selectively trapped only one form of the alcohol.

The researchers have provided an image illustrating a CC3 cage,

Breathing room: In this computer simulation, light and dark purple highlight the cavities within the 3D pore structure of CC3. Courtesy:  PNNL

Breathing room: In this computer simulation, light and dark purple highlight the cavities within the 3D pore structure of CC3. Courtesy: PNNL

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

Separation of rare gases and chiral molecules by selective binding in porous organic cages by Linjiang Chen, Paul S. Reiss, Samantha Y. Chong, Daniel Holden, Kim E. Jelfs, Tom Hasell, Marc A. Little, Adam Kewley, Michael E. Briggs, Andrew Stephenson, K. Mark Thomas, Jayne A. Armstrong, Jon Bell, Jose Busto, Raymond Noel, Jian Liu, Denis M. Strachan, Praveen K. Thallapally, & Andrew I. Cooper. Nature Material (2014) doi:10.1038/nmat4035 Published online 20 July 2014

This paper is behind a paywall.

Picasso, paint, and the hard x-ray nanoprobe

There’s the paint you put on your walls and there’s the paint you put on your body and there’s the paint artists use for their works of art. Well, it turns out that a very well known artist used common house paint to create some of his masterpieces,

Among the Picasso paintings in the Art Institute of Chicago collection, The Red Armchair is the most emblematic of his Ripolin usage and is the painting that was examined with APS X-rays at Argonne National Laboratory. To view a larger version of the image, click on it. Courtesy Art Institute of Chicago, Gift of Mr. and Mrs. Daniel Saidenberg (AIC 1957.72) © Estate of Pablo Picasso / Artists Rights Society (ARS), New York [downloaded from http://www.anl.gov/articles/high-energy-x-rays-shine-light-mystery-picasso-s-paints]

Among the Picasso paintings in the Art Institute of Chicago collection, The Red Armchair is the most emblematic of his Ripolin usage and is the painting that was examined with APS X-rays at Argonne National Laboratory. To view a larger version of the image, click on it. Courtesy Art Institute of Chicago, Gift of Mr. and Mrs. Daniel Saidenberg (AIC 1957.72) © Estate of Pablo Picasso / Artists Rights Society (ARS), New York [downloaded from http://www.anl.gov/articles/high-energy-x-rays-shine-light-mystery-picasso-s-paints]

The Art Institute of Chicago teamed with the US Argonne National Laboratory to solve a decades-long mystery as to what kind of paint Picasso used. From the Feb. 8, 2013 news item on Azonano,

The Art Institute of Chicago teamed up with Argonne National Laboratory to unravel a decades-long debate among art scholars about what kind of paint Picasso used to create his masterpieces.

The results published last month in the journal Applied Physics A: Materials Science & Processing adds significant weight to the widely held theory that Picasso was one of the first master painters to use common house paint rather than traditional artists’ paint. That switch in painting material gave birth to a new style of art marked by canvasses covered in glossy images with marbling, muted edges, and occasional errant paint drips but devoid of brush marks. Fast-drying enamel house paint enabled this dramatic departure from the slow-drying heavily blended oil paintings that dominated the art world up until Picasso’s time.

The key to decoding this long-standing mystery was the development of a unique high-energy X-ray instrument, called the hard X-ray nanoprobe, at the U.S. Department of Energy’s Advanced Photon Source (APS) X-ray facility and the Center for Nanoscale Materials, both housed at Argonne. The nanoprobe is designed to advance the development of high-performance materials and sustainable energies by giving scientists a close up view of the type and arraignment of chemical elements in material.

At that submicroscopic level is where science and art crossed paths.

The Argonne National Laboratory Feb. 6, 2013 news release by Tona Kunz, which originated the news item,  provides more  technical detail,

Volker Rose, a physicist at Argonne, uses the nanoprobe at the APS [Advanced Photon Source]/CNM [Center for Nanoscale Materials] to study zinc oxide, a key chemical used in wide-band-gap semiconductors. White paint contains the same chemical in varying amounts, depending on the type and brand of paint, which makes it a valuable clue for learning about Picasso’s work.

By comparing decades-old paint samples collected through e-Bay purchases with samples from Picasso paintings, scientists were able to learn that the chemical makeup of paint used by Picasso matched the chemical makeup of the first commercial house paint, Ripolin. Scientists also learned about the correlation of the spacing of impurities at the nanoscale in zinc oxide, offering important clues to how zinc oxide could be modified to improve performance in a variety of products, including sensors for radiation detection, LEDs and energy-saving windows as well as liquid-crystal displays for computers, TVs and instrument panels.

“Everything that we learn about how materials are structured and how chemicals react at the nanolevel can help us in our quest to design a better and more sustainable future,” Rose said.

Physicists weren’t the first to investigate the question,

Many art conservators and historians have tried over the years to use traditional optical and electron microscopes to determine whether Picasso or one of his contemporaries was the first to break with the cultural tradition of professional painters using expensive paints designed specifically for their craft. Those art world detectives all failed, because traditional tools wouldn’t let them see deeply enough into the layers of paint or with enough resolution to distinguish between store-bought enamel paint and techniques designed to mimic its appearance.

“Appearances can deceive, so this is where art can benefit from scientific research,” said Francesca Casadio, senior conservator scientist at the Art Institute of Chicago, and co-lead author on the result publication. “We needed to reverse-engineer the paint so that we could figure out if there was a fingerprint that we could then go look for in the pictures around the world that are suspected to be painted with Ripolin, the first commercial brand of house paint.”

Just as criminals leave a signature at a crime scene, each batch of paint has a chemical signature determined by its ingredients and impurities from the area and time period it was made. These signatures can’t be imitated and lie in the nanoscale range.

Yet until now, it was difficult to differentiate the chemical components of the paint pigments from the chemical components in the binders, fillers, other additives and contaminates that were mixed in with the pigments or layered on top of them. Only the nanoprobe at the APS /CNM can distinguish that level of detail: elemental composition and nanoscale distribution of elements within individualized submicrometeric pigment particles.

“The nanoprobe at the APS and CNM allowed unprecedented visualization of information about chemical composition within a singe grain of paint pigment, significantly reducing doubt that Picasso used common house paint in some of his most famous works,” said Rose, co-lead author on the result publication titled “High-Resolution Fluorescence Mapping of Impurities in the Historical Zinc Oxide Pigments: Hard X-ray Nanoprobe Applications to the Paints of Pablo Picasso.”

The nanoprobe’s high spatial resolution and micro-focusing abilities gave it the unique ability to identify individual chemical elements and distinguish between the size of paint particles crushed by hand in artists’ studios and those crushed even smaller by manufacturing equipment. The nanoprobe peered deeper than previous similar paint studies limited to a one-micrometer viewing resolution. The nanoprobe gave scientists an unprecedented look at 30-nanometer-wide particles of paint and impurities from the paint manufacturing process. For comparison, a typical sheet of copier paper is 100,000 nanometers thick.

Using the nanoprobe, scientists were able to determine that Picasso used enamel paint to create in 1931 The Red Armchair, on display at the Art Institute of Chicago. They were also able to determine the paint brand and from what manufacturing region the paint originated.

X-ray analysis of white paints produced under the Ripolin brand and used in artists’ traditional tube paints revealed that both contained nearly contaminate-free zinc oxide pigment. However, artists’ tube paints contained more fillers of other white-colored pigments than did the Ripolin, which was mostly pure zinc oxide.

Casaido [sic] views this type of chemical characterization of paints as a having a much wider application than just the study of Picasso’s paintings. By studying the chemical composition of art materials, she said, historians can learn about trade movements in ancient times, better determine the time period a piece was created, and even learn about the artist themselves through their choice of materials.

Perhaps not so coincidentally, the Art Institute of Chicago is celebrating the 100 year relationship between Picasso and Chicago, excerpted from their Jan. 14, 2013 news release,


First Large-Scale Picasso Exhibition Presented by the Art Institute in 30 Years Commemorates Centennial Anniversary of the Armory Show

Picasso and Chicago on View Exclusively at the Art Institute February 20–May 12, 2013

This winter, the Art Institute of Chicago celebrates the unique relationship between Chicago and one of the preeminent artists of the 20th century—Pablo Picasso—with special presentations, singular paintings on loan from the Philadelphia Museum of Art, and programs throughout the museum befitting the artist’s unparalleled range and influence. The centerpiece of this celebration is the major exhibition Picasso and Chicago, on view from February 20 through May 12, 2013 in the Art Institute’s Regenstein Hall, which features more than 250 works selected from the museum’s own exceptional holdings and from private collections throughout Chicago. Representing Picasso’s innovations in nearly every media—paintings, sculpture, prints, drawings, and ceramics—the works not only tell the story of Picasso’s artistic development but also the city’s great interest in and support for the artist since the Armory Show of 1913, a signal event in the history of modern art.

The Art Institute of Chicago, Francesca Casadio, and art conservation (specifically in regard to Winslow Homer) were mentioned here in an April 11, 2011 posting.