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

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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.

Not ageing gracefully; the lithium-ion battery story

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There’s an alphabet soup’s worth of agencies involved in research on lithium-ion battery ageing which has resulted in two papers as noted in a May 30, 2014 news item Azonano,

Batteries do not age gracefully. The lithium ions that power portable electronics cause lingering structural damage with each cycle of charge and discharge, making devices from smartphones to tablets tick toward zero faster and faster over time. To stop or slow this steady degradation, scientists must track and tweak the imperfect chemistry of lithium-ion batteries with nanoscale precision.

In two recent Nature Communications papers, scientists from several U.S. Department of Energy national laboratories—Lawrence Berkeley, Brookhaven, SLAC, and the National Renewable Energy Laboratory—collaborated to map these crucial billionths-of-a-meter dynamics and lay the foundation for better batteries.

A May 29, 2014 Brookhaven National Laboratory news release by Justin Eure, which originated the news item, describes the research techniques in more detail,

“We discovered surprising and never-before-seen evolution and degradation patterns in two key battery materials,” said Huolin Xin, a materials scientist at Brookhaven Lab’s Center for Functional Nanomaterials (CFN) and coauthor on both studies. “Contrary to large-scale observation, the lithium-ion reactions actually erode the materials non-uniformly, seizing upon intrinsic vulnerabilities in atomic structure in the same way that rust creeps unevenly across stainless steel.”

Xin used world-leading electron microscopy techniques in both studies to directly visualize the nanoscale chemical transformations of battery components during each step of the charge-discharge process. In an elegant and ingenious setup, the collaborations separately explored a nickel-oxide anode and a lithium-nickel-manganese-cobalt-oxide cathode—both notable for high capacity and cyclability—by placing samples inside common coin-cell batteries running under different voltages.

“Armed with a precise map of the materials’ erosion, we can plan new ways to break the patterns and improve performance,” Xin said.

In these experiments, lithium ions traveled through an electrolyte solution, moving into an anode when charging and a cathode when discharging. The processes were regulated by electrons in the electrical circuit, but the ions’ journeys—and the battery structures—subtly changed each time.

The news release first describes the research involving the nickel-oxide anode, one of the two areas of interest,

For the nickel-oxide anode, researchers submerged the batteries in a liquid organic electrolyte and closely controlled the charging rates. They stopped at predetermined intervals to extract and analyze the anode. Xin and his collaborators rotated 20-nanometer-thick sheets of the post-reaction material inside a carefully calibrated transmission electron microscope (TEM) grid at CFN to catch the contours from every angle—a process called electron tomography.

To see the way the lithium-ions reacted with the nickel oxide, the scientists used a suite of custom-written software to digitally reconstruct the three-dimensional nanostructures with single-nanometer resolution. Surprisingly, the reactions sprang up at isolated spatial points rather than sweeping evenly across the surface.

“Consider the way snowflakes only form around tiny particles or bits of dirt in the air,” Xin said. “Without an irregularity to glom onto, the crystals cannot take shape. Our nickel oxide anode only transforms into metallic nickel through nanoscale inhomogeneities or defects in the surface structure, a bit like chinks in the anode’s armor.”

The electron microscopy provided a crucial piece of the larger puzzle assembled in concert with Berkeley Lab materials scientists and soft x-ray spectroscopy experiments conducted at SLAC’s Stanford Synchrotron Radiation Lightsource (SSRL). The combined data covered the reactions on the nano-, meso-, and microscales.

Next, there’s this about the second area of interest, a lithium-nickel-manganese-cobalt-oxide (NMC) cathode (from the news release),

In the other study, scientists sought the voltage sweet-spot for the high-performing lithium-nickel-manganese-cobalt-oxide (NMC) cathode: How much power can be stored, at what intensity, and across how many cycles?

The answers hinged on intrinsic material qualities and the structural degradation caused by cycles at 4.7 volts and 4.3 volts, as measured against a lithium metal standard.

As revealed through another series of coin-cell battery tests, 4.7 volts caused rapid decomposition of the electrolytes and poor cycling—the higher power comes at a price. A 4.3-volt battery, however, offered a much longer cycling lifetime at the cost of lower storage and more frequent recharges.

In both cases, the chemical evolution exhibited sprawling surface asymmetries, though not without profound patterns.

“As the lithium ions race through the reaction layers, they cause clumping crystallization—a kind of rock-salt matrix builds up over time and begins limiting performance,” Xin said. “We found that these structures tended to form along the lithium-ion reaction channels, which we directly visualized under the TEM. The effect was even more pronounced at higher voltages, explaining the more rapid deterioration.”

Identifying this crystal-laden reaction pathways hints at a way forward in battery design.

“It may be possible to use atomic deposition to coat the NMC cathodes with elements that resist crystallization, creating nanoscale boundaries within the micron-sized powders needed at the cutting-edge of industry,” Xin said. “In fact, Berkeley Lab battery experts Marca Doeff and Feng Lin are working on that now.”

Shirley Meng, a professor at UC San Diego’s Department of NanoEngineering, added, “This beautiful study combines several complementary tools that probe both the bulk and surface of the NMC layered oxide—one of the most promising cathode materials for high-voltage operation that enables higher energy density in lithium-ion batteries. The meaningful insights provided by this study will significantly impact the optimization strategies for this type of cathode material.”

The TEM measurements revealed the atomic structures while electron energy loss spectroscopy helped pinpoint the chemical evolution—both carried out at the CFN….

The scientists next want to observe these changes in real-time which will necessitate the custom design of some new equipment (“electrochemical contacts and liquid flow holders”).

Here are links to and citations for the papers,

Phase evolution for conversion reaction electrodes in lithium-ion batteries by Feng Lin, Dennis Nordlund, Tsu-Chien Weng, Ye Zhu, Chunmei Ban, Ryan M. Richards, & Huolin L. Xin. Nature Communications 5, Article number: 3358 doi:10.1038/ncomms4358 Published 24 February 2014

Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries by Feng Lin, Isaac M. Markus, Dennis Nordlund, Tsu-Chien Weng, Mark D. Asta, Huolin L. Xin & Marca M. Doeff. Nature Communications 5, Article number: 3529 doi:10.1038/ncomms4529 Published 27 March 2014

Both of these articles are behind a paywall and they both offer previews via ReadCube Access.

Mixing and matching your nanoparticles

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An Oct. 20, 2013 Brookhaven National Laboratory (BNL; US Dept. of Energy) news release (also on EurekAlert) describes a technique for combining different kinds of nanoparticles into a single nanocomposite,

Scientists at the U.S. Department of Energy’s Brookhaven National Laboratory have developed a general approach for combining different types of nanoparticles to produce large-scale composite materials. The technique, described in a paper published online by Nature Nanotechnology on October 20, 2013, opens many opportunities for mixing and matching particles with different magnetic, optical, or chemical properties to form new, multifunctional materials or materials with enhanced performance for a wide range of potential applications.

The approach takes advantage of the attractive pairing of complementary strands of synthetic DNA—based on the molecule that carries the genetic code in its sequence of matched bases known by the letters A, T, G, and C. After coating the nanoparticles with a chemically standardized “construction platform” and adding extender molecules to which DNA can easily bind, the scientists attach complementary lab-designed DNA strands to the two different kinds of nanoparticles they want to link up. The natural pairing of the matching strands then “self-assembles” the particles into a three-dimensional array consisting of billions of particles. Varying the length of the DNA linkers, their surface density on particles, and other factors gives scientists the ability to control and optimize different types of newly formed materials and their properties.

The news release details some of the challenges the researchers faced,

… the scientists explored the effect of particle shape. “In principle, differently shaped particles don’t want to coexist in one lattice,” said Gang [Brookhaven physicist Oleg Gang]. “They either tend to separate into different phases like oil and water refusing to mix or form disordered structures.” The scientists discovered that DNA not only helps the particles mix, but it can also improve order for such systems when a thicker DNA shell around the particles is used.

They also investigated how the DNA-pairing mechanism and other intrinsic physical forces, such as magnetic attraction among particles, might compete during the assembly process. For example, magnetic particles tend to clump to form aggregates that can hinder the binding of DNA from another type of particle. “We show that shorter DNA strands are more effective at competing against magnetic attraction,” Gang said.

For the particular composite of gold and magnetic nanoparticles they created, the scientists discovered that applying an external magnetic field could “switch” the material’s phase and affect the ordering of the particles. “This was just a demonstration that it can be done, but it could have an application—perhaps magnetic switches, or materials that might be able to change shape on demand,” said Zhang [[Yugang Zhang, first author of the paper].

The third fundamental factor the scientists explored was how the particles were ordered in the superlattice arrays: Does one type of particle always occupy the same position relative to the other type—like boys and girls sitting in alternating seats in a movie theater—or are they interspersed more randomly? “This is what we call a compositional order, which is important for example for quantum dots because their optical properties—e.g., their ability to glow—depend on how many gold nanoparticles are in the surrounding environment,” said Gang. “If you have compositional disorder, the optical properties would be different.” In the experiments, increasing the thickness of the soft DNA shells around the particles increased compositional disorder.

These fundamental principles give scientists a framework for designing new materials. The specific conditions required for a particular application will be dependent on the particles being used, Zhang emphasized, but the general assembly approach would be the same.

Said Gang, “We can vary the lengths of the DNA strands to change the distance between particles from about 10 nanometers to under 100 nanometers—which is important for applications because many optical, magnetic, and other properties of nanoparticles depend on the positioning at this scale. We are excited by the avenues this research opens up in terms of future directions for engineering novel classes of materials that exploit collective effects and multifunctionality.”

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

A general strategy for the DNA-mediated self-assembly of functional nanoparticles into heterogeneous systems by Yugang Zhang, Fang Lu, Kevin G. Yager, Daniel van der Lelie, & Oleg Gang. Nature Nanotechnology (2013) doi:10.1038/nnano.2013.209 Published online 20 October 2013.

This article can be viewed/previewed on ReadCube or purchased.