Tag Archives: US Dept. of Energy

Carbon nanotube optics and the quantum

A US-France-Germany collaboration has led to some intriguing work with carbon nanotubes. From a June 18, 2018 news item on ScienceDaily,

Researchers at Los Alamos and partners in France and Germany are exploring the enhanced potential of carbon nanotubes as single-photon emitters for quantum information processing. Their analysis of progress in the field is published in this week’s edition of the journal Nature Materials.

“We are particularly interested in advances in nanotube integration into photonic cavities for manipulating and optimizing light-emission properties,” said Stephen Doorn, one of the authors, and a scientist with the Los Alamos National Laboratory site of the Center for Integrated Nanotechnologies (CINT). “In addition, nanotubes integrated into electroluminescent devices can provide greater control over timing of light emission and they can be feasibly integrated into photonic structures. We are highlighting the development and photophysical probing of carbon nanotube defect states as routes to room-temperature single photon emitters at telecom wavelengths.”

A June 18, 2018 Los Alamos National Laboratory (LANL) news release (also on EurekAlert), which originated the news item, expands on the theme,

The team’s overview was produced in collaboration with colleagues in Paris (Christophe Voisin [Ecole Normale Supérieure de Paris (ENS)]) who are advancing the integration of nanotubes into photonic cavities for modifying their emission rates, and at Karlsruhe (Ralph Krupke [Karlsruhe Institute of Technology (KIT]) where they are integrating nanotube-based electroluminescent devices with photonic waveguide structures. The Los Alamos focus is the analysis of nanotube defects for pushing quantum emission to room temperature and telecom wavelengths, he said.

As the paper notes, “With the advent of high-speed information networks, light has become the main worldwide information carrier. . . . Single-photon sources are a key building block for a variety of technologies, in secure quantum communications metrology or quantum computing schemes.”

The use of single-walled carbon nanotubes in this area has been a focus for the Los Alamos CINT team, where they developed the ability to chemically modify the nanotube structure to create deliberate defects, localizing excitons and controlling their release. Next steps, Doorn notes, involve integration of the nanotubes into photonic resonators, to provide increased source brightness and to generate indistinguishable photons. “We need to create single photons that are indistinguishable from one another, and that relies on our ability to functionalize tubes that are well-suited for device integration and to minimize environmental interactions with the defect sites,” he said.

“In addition to defining the state of the art, we wanted to highlight where the challenges are for future progress and lay out some of what may be the most promising future directions for moving forward in this area. Ultimately, we hope to draw more researchers into this field,” Doorn said.

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

Carbon nanotubes as emerging quantum-light sources by X. He, H. Htoon, S. K. Doorn, W. H. P. Pernice, F. Pyatkov, R. Krupke, A. Jeantet, Y. Chassagneux & C. Voisin. Nature Materials (2018) DOI: https://doi.org/10.1038/s41563-018-0109-2 Published online June 18, 2018

This paper is behind a paywall.

Carbon nanotubes for water desalination

In discussions about water desalination and carbon nanomaterials,  it’s graphene that’s usually mentioned these days. By contrast, scientists from the US Department of Energy’s Lawrence Livermore National Laboratory (LLNL) have turned to carbon nanotubes,

There are two news items about the work at LLNL on ScienceDaily, this first one originated by the American Association for the Advancement of Science (AAAS) offers a succinct summary of the work (from an August 24, 2017 news item on ScienceDaily,

At just the right size, carbon nanotubes can filter water with better efficiency than biological proteins, a new study reveals. The results could pave the way to new water filtration systems, at a time when demands for fresh water pose a global threat to sustainable development.

A class of biological proteins, called aquaporins, is able to effectively filter water, yet scientists have not been able to manufacture scalable systems that mimic this ability. Aquaporins usually exhibit channels for filtering water molecules at a narrow width of 0.3 nanometers, which forces the water molecules into a single-file chain.

Here, Ramya H. Tunuguntla and colleagues experimented with nanotubes of different widths to see which ones are best for filtering water. Intriguingly, they found that carbon nanotubes with a width of 0.8 nanometers outperformed aquaporins in filtering efficiency by a factor of six.

These narrow carbon nanotube porins (nCNTPs) were still slim enough to force the water molecules into a single-file chain. The researchers attribute the differences between aquaporins and nCNTPS to differences in hydrogen bonding — whereas pore-lining residues in aquaporins can donate or accept H bonds to incoming water molecules, the walls of CNTPs cannot form H bonds, permitting unimpeded water flow.

The nCNTPs in this study maintained permeability exceeding that of typical saltwater, only diminishing at very high salt concentrations. Lastly, the team found that by changing the charges at the mouth of the nanotube, they can alter the ion selectivity. This advancement is highlighted in a Perspective [in Science magazine] by Zuzanna Siwy and Francesco Fornasiero.

The second Aug. 24, 2017 news item on ScienceDaily offers a more technical  perspective,

Lawrence Livermore scientists, in collaboration with researchers at Northeastern University, have developed carbon nanotube pores that can exclude salt from seawater. The team also found that water permeability in carbon nanotubes (CNTs) with diameters smaller than a nanometer (0.8 nm) exceeds that of wider carbon nanotubes by an order of magnitude.

The nanotubes, hollow structures made of carbon atoms in a unique arrangement, are more than 50,000 times thinner than a human hair. The super smooth inner surface of the nanotube is responsible for their remarkably high water permeability, while the tiny pore size blocks larger salt ions.

There’s a rather lovely illustration for this work,

An artist’s depiction of the promise of carbon nanotube porins for desalination. The image depicts a stylized carbon nanotube pipe that delivers clean desalinated water from the ocean to a kitchen tap. Image by Ryan Chen/LLNL

An Aug. 24, 2017 LLNL news release (also on EurekAlert), which originated the second news item, proceeds

Increasing demands for fresh water pose a global threat to sustainable development, resulting in water scarcity for 4 billion people. Current water purification technologies can benefit from the development of membranes with specialized pores that mimic highly efficient and water selective biological proteins.

“We found that carbon nanotubes with diameters smaller than a nanometer bear a key structural feature that enables enhanced transport. The narrow hydrophobic channel forces water to translocate in a single-file arrangement, a phenomenon similar to that found in the most efficient biological water transporters,” said Ramya Tunuguntla, an LLNL postdoctoral researcher and co-author of the manuscript appearing in the Aug. 24 [2017]edition of Science.

Computer simulations and experimental studies of water transport through CNTs with diameters larger than 1 nm showed enhanced water flow, but did not match the transport efficiency of biological proteins and did not separate salt efficiently, especially at higher salinities. The key breakthrough achieved by the LLNL team was to use smaller-diameter nanotubes that delivered the required boost in performance.

“These studies revealed the details of the water transport mechanism and showed that rational manipulation of these parameters can enhance pore efficiency,” said Meni Wanunu, a physics professor at Northeastern University and co-author on the study.

“Carbon nanotubes are a unique platform for studying molecular transport and nanofluidics,” said Alex Noy, LLNL principal investigator on the CNT project and a senior author on the paper. “Their sub-nanometer size, atomically smooth surfaces and similarity to cellular water transport channels make them exceptionally suited for this purpose, and it is very exciting to make a synthetic water channel that performs better than nature’s own.”

This discovery by the LLNL scientists and their colleagues has clear implications for the next generation of water purification technologies and will spur a renewed interest in development of the next generation of high-flux membranes.

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

Enhanced water permeability and tunable ion selectivity in subnanometer carbon nanotube porins by Ramya H. Tunuguntla, Robert Y. Henley, Yun-Chiao Yao, Tuan Anh Pham, Meni Wanunu, Aleksandr Noy. Science 25 Aug 2017: Vol. 357, Issue 6353, pp. 792-796 DOI: 10.1126/science.aan2438

This paper is behind a paywall.

And, Northeastern University issued an August 25, 2017 news release (also on EurekAlert) by Allie Nicodemo,

Earth is 70 percent water, but only a tiny portion—0.007 percent—is available to drink.

As potable water sources dwindle, global population increases every year. One potential solution to quenching the planet’s thirst is through desalinization—the process of removing salt from seawater. While tantalizing, this approach has always been too expensive and energy intensive for large-scale feasibility.

Now, researchers from Northeastern have made a discovery that could change that, making desalinization easier, faster and cheaper than ever before. In a paper published Thursday [August 24, 2017] in Science, the group describes how carbon nanotubes of a certain size act as the perfect filter for salt—the smallest and most abundant water contaminant.

Filtering water is tricky because water molecules want to stick together. The “H” in H2O is hydrogen, and hydrogen bonds are strong, requiring a lot of energy to separate. Water tends to bulk up and resist being filtered. But nanotubes do it rapidly, with ease.

A carbon nanotube is like an impossibly small rolled up sheet of paper, about a nanometer in diameter. For comparison, the diameter of a human hair is 50 to 70 micrometers—50,000 times wider. The tube’s miniscule size, exactly 0.8 nm, only allows one water molecule to pass through at a time. This single-file lineup disrupts the hydrogen bonds, so water can be pushed through the tubes at an accelerated pace, with no bulking.

“You can imagine if you’re a group of people trying to run through the hallway holding hands, it’s going to be a lot slower than running through the hallway single-file,” said co-author Meni Wanunu, associate professor of physics at Northeastern. Wanunu and post doctoral student Robert Henley collaborated with scientists at the Lawrence Livermore National Laboratory in California to conduct the research.

Scientists led by Aleksandr Noy at Lawrence Livermore discovered last year [2016] that carbon nanotubes were an ideal channel for proton transport. For this new study, Henley brought expertise and technology from Wanunu’s Nanoscale Biophysics Lab to Noy’s lab, and together they took the research one step further.

In addition to being precisely the right size for passing single water molecules, carbon nanotubes have a negative electric charge. This causes them to reject anything with the same charge, like the negative ions in salt, as well as other unwanted particles.

“While salt has a hard time passing through because of the charge, water is a neutral molecule and passes through easily,” Wanunu said. Scientists in Noy’s lab had theorized that carbon nanotubes could be designed for specific ion selectivity, but they didn’t have a reliable system of measurement. Luckily, “That’s the bread and butter of what we do in Meni’s lab,” Henley said. “It created a nice symbiotic relationship.”

“Robert brought the cutting-edge measurement and design capabilities of Wanunu’s group to my lab, and he was indispensable in developing a new platform that we used to measure the ion selectivity of the nanotubes,” Noy said.

The result is a novel system that could have major implications for the future of water security. The study showed that carbon nanotubes are better at desalinization than any other existing method— natural or man-made.

To keep their momentum going, the two labs have partnered with a leading water purification organization based in Israel. And the group was recently awarded a National Science Foundation/Binational Science Foundation grant to conduct further studies and develop water filtration platforms based on their new method. As they continue the research, the researchers hope to start programs where students can learn the latest on water filtration technology—with the goal of increasing that 0.007 percent.

As is usual in these cases there’s a fair degree of repetition but there’s always at least one nugget of new information, in this case, a link to Israel. As I noted many times, the Middle East is experiencing serious water issues. My most recent ‘water and the Middle East’ piece is an August 21, 2017 post about rainmaking at the Masdar Institute in United Arab Emirates. Approximately 50% of the way down the posting, I mention Israel and Palestine’s conflict over water.

Ferroelectric roadmap to neuromorphic computing

Having written about memristors and neuromorphic engineering a number of times here, I’m  quite intrigued to see some research into another nanoscale device for mimicking the functions of a human brain.

The announcement about the latest research from the team at the US Department of Energy’s Argonne National Laboratory is in a Feb. 14, 2017 news item on Nanowerk (Note: A link has been removed),

Research published in Nature Scientific Reports (“Ferroelectric symmetry-protected multibit memory cell”) lays out a theoretical map to use ferroelectric material to process information using multivalued logic – a leap beyond the simple ones and zeroes that make up our current computing systems that could let us process information much more efficiently.

A Feb. 10, 2017 Argonne National Laboratory news release by Louise Lerner, which originated the news item, expands on the theme,

The language of computers is written in just two symbols – ones and zeroes, meaning yes or no. But a world of richer possibilities awaits us if we could expand to three or more values, so that the same physical switch could encode much more information.

“Most importantly, this novel logic unit will enable information processing using not only “yes” and “no”, but also “either yes or no” or “maybe” operations,” said Valerii Vinokur, a materials scientist and Distinguished Fellow at the U.S. Department of Energy’s Argonne National Laboratory and the corresponding author on the paper, along with Laurent Baudry with the Lille University of Science and Technology and Igor Lukyanchuk with the University of Picardie Jules Verne.

This is the way our brains operate, and they’re something on the order of a million times more efficient than the best computers we’ve ever managed to build – while consuming orders of magnitude less energy.

“Our brains process so much more information, but if our synapses were built like our current computers are, the brain would not just boil but evaporate from the energy they use,” Vinokur said.

While the advantages of this type of computing, called multivalued logic, have long been known, the problem is that we haven’t discovered a material system that could implement it. Right now, transistors can only operate as “on” or “off,” so this new system would have to find a new way to consistently maintain more states – as well as be easy to read and write and, ideally, to work at room temperature.

Hence Vinokur and the team’s interest in ferroelectrics, a class of materials whose polarization can be controlled with electric fields. As ferroelectrics physically change shape when the polarization changes, they’re very useful in sensors and other devices, such as medical ultrasound machines. Scientists are very interested in tapping these properties for computer memory and other applications; but the theory behind their behavior is very much still emerging.

The new paper lays out a recipe by which we could tap the properties of very thin films of a particular class of ferroelectric material called perovskites.

According to the calculations, perovskite films could hold two, three, or even four polarization positions that are energetically stable – “so they could ‘click’ into place, and thus provide a stable platform for encoding information,” Vinokur said.

The team calculated these stable configurations and how to manipulate the polarization to move it between stable positions using electric fields, Vinokur said.

“When we realize this in a device, it will enormously increase the efficiency of memory units and processors,” Vinokur said. “This offers a significant step towards realization of so-called neuromorphic computing, which strives to model the human brain.”

Vinokur said the team is working with experimentalists to apply the principles to create a working system

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

Ferroelectric symmetry-protected multibit memory cell by Laurent Baudry, Igor Lukyanchuk, & Valerii M. Vinokur. Scientific Reports 7, Article number: 42196 (2017) doi:10.1038/srep42196 Published online: 08 February 2017

This paper is open access.

Heat, evolution, and the shape of gold nanorods

A Feb. 23, 2015 news item on Azonano features gold nanorods and their shapeshifting ways when releasing heat,

Researchers at the U.S. Department of Energy’s Argonne National Laboratory have revealed previously unobserved behaviors that show how details of the transfer of heat at the nanoscale cause nanoparticles to change shape in ensembles.

The new findings depict three distinct stages of evolution in groups of gold nanorods, from the initial rod shape to the intermediate shape to a sphere-shaped nanoparticle. The research suggests new rules for the behavior of nanorod ensembles, providing insights into how to increase heat transfer efficiency in a nanoscale system.

A Feb. 18, 2015 Argonne National Laboratory news release by Justin H. S. Breaux, which originated the news item, provides more details about the work,

At the nanoscale, individual gold nanorods have unique electronic, thermal and optical properties. Understanding these properties and managing how collections of these elongated nanoparticles absorb and release this energy as heat will drive new research towards next-generation technologies such as water purification systems, battery materials and cancer research.

A good deal is known about how single nanorods behave—but little is known about how nanorods behave in ensembles of millions. Understanding how the individual behavior of each nanorod, including how its orientation and rate of transition differ from those around it, impacts the collective kinetics of the ensemble and is critical to using nanorods in future technologies.

“We started with a lot of questions,” said Argonne physicist Yuelin Li, “like ‘How much power can the particles sustain before losing functionality? How do individual changes at the nanoscale affect the overall functionality? How much heat is released to the surrounding area?’ Each nanorod is continuously undergoing a change in shape when heated beyond melting temperature, which means a change in the surface area and thus a change in its thermal and hydrodynamic properties.”

The researchers used a laser to heat the nanoparticles and X-rays to analyze their changing shapes. Generally, nanorods transition into nanospheres more quickly when supplied with a higher intensity of laser power. In this case, completely different ensemble behaviors were observed when this intensity increased incrementally. The intensity of the heat applied changes not only the nanoparticles’ shape at various rates but also affects their ability to efficiently absorb and release heat.

“For us, the key was to understand just how efficient the nanorods were at transferring light into heat in many different scenarios,” said nanoscientist Subramanian Sankaranarayanan of Argonne’s Center for Nanoscale Materials. “Then we had to determine the physics behind how heat was transferred and all the different ways these nanorods could transition into nanospheres.”

To observe how the rod makes this transition, researchers first shine a laser pulse at the nanorod suspended in a water solution at Argonne’s Advanced Photon Source. The laser lasts for less than a hundred femtoseconds, nearly one trillion times faster than a blink of the eye. What follows is a series of focused and rapid X-ray bursts using a technique called small angle X-ray scattering. The resulting data is used to determine the average shape of the particle as it changes over time.

In this way, scientists can reconstruct the minute changes occurring in the shape of the nanorod. However, to understand the physics underlying this phenomenon, the researchers needed to look deeper at how individual atoms vibrate and move during the transition. For this, they turned to the field of molecular dynamics using the supercomputing power of the 10-petaflop Mira supercomputer at the Argonne Leadership Computing Facility.

Mira used mathematical equations to pinpoint the individual movements of nearly two million of the nanorods’ atoms in the water. Using factors such as the shape, temperature and rate of change, the researchers built simulations of the nanorod in many different scenarios to see how the structure changes over time.

“In the end,” said Sankaranarayanan, “we discovered the heat transfer rates for shorter but wider nanospheres are lower than for their rod-shaped predecessors. This decrease in heat transfer efficiency at the nanoscale plays a key role in accelerating the transition from rod to sphere when heated beyond the melting temperature.”

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

Femtosecond Laser Pulse Driven Melting in Gold Nanorod Aqueous Colloidal Suspension: Identification of a Transition from Stretched to Exponential Kinetics by Yuelin Li, Zhang Jiang, Xiao-Min Lin, Haidan Wen, Donald A. Walko, Sanket A. Deshmukh, Ram Subbaraman, Subramanian K. R. S. Sankaranarayanan, Stephen K. Gray, & Phay Ho. Scientific Reports 5, Article number: 8146 doi:10.1038/srep08146 Published 30 January 2015

This article is open access.

Dumbbells at the nanoscale according to researchers at the (US) Argonne National Laboratory

Researchers at the US Dept. of Energy’s Argonne National Laboratory are providing new insight into how nanoparticles ‘grow’. From a Dec. 5, 2014 news item on Nanowerk,

Like snowflakes, nanoparticles come in a wide variety of shapes and sizes. The geometry of a nanoparticle is often as influential as its chemical makeup in determining how it behaves, from its catalytic properties to its potential as a semiconductor component.

Thanks to a new study from the U.S. Department of Energy’s (DOE) Argonne National Laboratory, researchers are closer to understanding the process by which nanoparticles made of more than one material – called heterostructured nanoparticles – form. This process, known as heterogeneous nucleation, is the same mechanism by which beads of condensation form on a windowpane.

The scientists have provided an image which illustrates their findings,

This picture combines a transmission electron microscope image of a nanodumbbell with a gold domain oriented in direction. The seed and gold domains in the dumbbell in the image on the right are identified by geometric phase analysis. Image credit: Soon Gu Kwon.

This picture combines a transmission electron microscope image of a nanodumbbell with a gold domain oriented in direction. The seed and gold domains in the dumbbell in the image on the right are identified by geometric phase analysis. Image credit: Soon Gu Kwon.

A Dec. 4, 2014 Argonne National Laboratory news release by Jared Sagoff, which originated the news item, describes the structures being examined and the reason for doing so,

Heterostructured nanoparticles can be used as catalysts and in advanced energy conversion and storage systems. Typically, these nanoparticles are created from tiny “seeds” of one material, on top of which another material is grown.  In this study, the Argonne researchers noticed that the differences in the atomic arrangements of the two materials have a big impact on the shape of the resulting nanoparticle.

“Before we started this experiment, it wasn’t entirely clear what’s happening at the interface when one material grows on another,” said nanoscientist Elena Shevchenko of Argonne Center for Nanoscale Materials, a DOE Office of Science user facility.

In this study, the researchers observed the formation of a nanoparticle consisting of platinum and gold.  The researchers started with a platinum seed and grew gold around it. Initially, the gold covered the platinum seed’s surface uniformly, creating a type of nanoparticle known as “core-shell.” However, as more gold was deposited, it started to grow unevenly, creating a dumbbell-like structure.

Thanks to state-of-the-art X-ray analysis provided by Argonne’s Advanced Photon Source (APS), a DOE Office of Science user facility, the researchers identified the cause of the dumbbell formation as “lattice mismatch,” in which the spacing between the atoms in the two materials doesn’t align.

“Essentially, you can think of lattice mismatch as having a row of smaller boxes on the bottom layer and larger boxes on the top layer.  When you try to fit the larger boxes into the space for a smaller box, it creates an immense strain,” said Argonne physicist Byeongdu Lee.

While the lattice mismatch is only fractions of a nanometer, the effect accumulates as layer after layer of gold forms on the platinum. The mismatch can be handled by the first two layers of gold atoms – creating the core-shell effect – but afterwards it proves too much to overcome. “The arrangement of atoms is the same in the two materials, but the distance between atoms is different,” said Argonne postdoctoral researcher Soon Gu Kwon. “Eventually, this becomes unstable, and the growth of the gold becomes unevenly distributed.”

As the gold continues to accumulate on one side of the seed nanoparticle, small quantities “slide” down the side of the nanoparticle like grains of sand rolling down the side of a sand hill, creating the dumbbell shape.

The advantage of the Argonne study comes from the researchers’ ability to perform in situ observations of the material in realistic conditions using the APS. “This is the first time anyone has been able to study the kinetics of this heterogeneous nucleation process of nanoparticles in real-time under realistic conditions,” said Argonne physicist Byeongdu Lee. “The combination of two X-ray techniques gave us the ability to observe the material at both the atomic level and the nanoscale, which gave us a good view of how the nanoparticles form and transform.” All conclusions made based on the X-ray studies were further confirmed using atomic-resolution microscopy in the group of Professor Robert Klie of the University of Illinois at Chicago.

This analysis of nanoparticle formation will help to lay the groundwork for the formation of new materials with different and controllable properties, according to Shevchenko. “In order to design materials, you have to understand how these processes happen at a very basic level,” she said.

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

Heterogeneous nucleation and shape transformation of multicomponent metallic nanostructures by Soon Gu Kwon, Galyna Krylova, Patrick J. Phillips, Robert F. Klie, Soma Chattopadhyay, Tomohiro Shibata, Emilio E. Bunel, Yuzi Liu, Vitali B. Prakapenka, Byeongdu Lee, & Elena V. Shevchenko. Nature Materials (2014) doi:10.1038/nmat4115 Published online 02 November 2014

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

Not ageing gracefully; the lithium-ion battery story

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.

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.

Cleaner greener diesel by way of bi-functional nanoparticles

It’s always good to hear about cleaner greener diesel as per this May 13, 2014 news item on Azonano,

Ames Laboratory [US Dept. of Energy] scientists have developed a nanoparticle that is able to perform two processing functions at once for the production of green diesel, an alternative fuel created from the hydrogenation of oils from renewable feedstocks like algae.

The method is a departure from the established process of producing biodiesel, which is accomplished by reacting fats and oils with alcohols.

A May ??, 2014 Ames Laboratory news release,which originated the news item, describes the specifics of the problem the scientists are trying to solve,

“Conventionally, when you are producing biodiesel from a feedstock that is rich in free fatty acids like microalgae oil, you must first separate the fatty acids that can ruin the effectiveness of the catalyst, and then you can perform the catalytic reactions that produce the fuel,” said Ames Lab scientist Igor Slowing. “By designing multifunctional nanoparticles and focusing on green diesel rather than biodiesel, we can combine multiple processes into one that is faster and cleaner.” Contrary to biodiesel, green diesel is produced by hydrogenation of fats and oils, and its chemical composition is very similar to that of petroleum-based diesel. Green diesel has many advantages over biodiesel, like being more stable and having a higher energy density.

One of the research groups at Ames Laboratory stumbled across an exciting property while working with bi-functional nanoparticles (from the news release),

An Ames Lab research group, which included Slowing, Kapil Kandel, Conerd Frederickson, Erica A. Smith, and Young-Jin Lee, first saw success using bi-functionalized mesostructured nanoparticles. These ordered porous particles contain amine groups that capture free fatty acids and nickel nanoparticles that catalyze the conversion of the acids into green diesel. Nickel has been researched widely in the scientific community because it is approximately 2000 times less expensive as an alternative to noble metals traditionally used in fatty acid hydrogenation, like platinum or palladium.

Creating a bi-functional nanoparticle also improved the resulting green diesel. Using nickel for the fuel conversion alone, the process resulted in too strong of a reaction, with hydrocarbon chains that had broken down. The process, called “cracking,” created a product that held less potential as a fuel.

“A very interesting thing happened when we added the component responsible for the sequestration of the fatty acids,” said Slowing. “We no longer saw the cracking of molecules. So the result is a better catalyst that produces a hydrocarbon that looks much more like diesel. “

“It also leaves the other components of the oil behind, valuable molecules that have potential uses for the pharmaceutical and food industries,” said Slowing.

But Slowing, along with Kapil Kandel, James W. Anderegg, Nicholas C. Nelson, and Umesh Chaudhary, took the process further by using iron as the catalyst. Iron is 100 times cheaper than nickel. Using iron improved the end product even further, giving a faster conversion and also reducing the loss of CO2  in the process.

“As part of the mission of the DOE, [US Dept. of Energy] we are focused on researching the fundamental science necessary to create the process; but the resulting technology should in principle be scalable for industry,” he said.

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

Supported iron nanoparticles for the hydrodeoxygenation of microalgal oil to green diesel by Kapil Kandel, James W. Anderegg, Nicholas C. Nelson, Umesh Chaudhary, Igor I. Slowing. Journal of Catalysis Volume 314, May 2014, Pages 142–148 http://dx.doi.org/10.1016/j.jcat.2014.04.009

This paper is behind a paywall.

There is a patent pending on this technology (from the news release),

A patent application has been filed for this technology; it is available for licensing from the Iowa State University Research Foundation. Further information can be obtained at licensing@iastate.edu.

Patent or not, it would be nice to see at least one of these technologies successfully commercialized.

Studying corrosion from the other side

Corrosion can be beautiful as well as destructive,

Typically, the process of corrosion has been studied from the metal side of the equation - See more at: http://www.anl.gov/articles/core-corrosion#sthash.ZPqFF13I.dpuf. Courtesy of the Argonne National Laboratory

Typically, the process of corrosion has been studied from the metal side of the equation – See more at: http://www.anl.gov/articles/core-corrosion#sthash.ZPqFF13I.dpuf. Courtesy of the Argonne National Laboratory

A Feb. 18, 2014 news item on Nanowerk expands on the theme of corrosion as destruction (Note: Links have been removed),

Anyone who has ever owned a car in a snowy town – or a boat in a salty sea – can tell you just how expensive corrosion can be.

One of the world’s most common and costly chemical reactions, corrosion happens frequently at the boundaries between water and metal surfaces. In the past, the process of corrosion has mostly been studied from the metal side of the equation.

However, in a new study (“Chloride ions induce order-disorder transition at water-oxide interfaces”), scientists at the Center for Nanoscale Materials at the U.S. Department of Energy’s Argonne National Laboratory investigated the problem from the other side, looking at the dynamics of water containing dissolved ions located in the regions near a metal surface.

The Feb. 14, 2014 Argonne National Laboratory news release by Jared Sagoff, which originated the news item, describes how the scientists conducted their research,

A team of researchers led by Argonne materials scientist Subramanian Sankaranarayanan simulated the physical and chemical dynamics of dissolved ions in water at the atomic level as it corrodes metal oxide surfaces. “Water-based solutions behave quite differently near a metal or oxide surface than they do by themselves,” Sankaranarayanan said. “But just how the chemical ions in the water interact with a surface has been an area of intense debate.”

Under low-chlorine conditions, water tends to form two-dimensional ordered layers near solid interfaces because of the influence of its strong hydrogen bonds. However, the researchers found that increasing the proportion of chlorine ions above a certain threshold causes a change in which the solution loses its ordered nature near the surface and begins to act similar to water away from the surface. This transition, in turn, can increase the rate at which materials corrode as well as the freezing temperature of the solution.

This switch between an ordered and a disordered structure near the metal surface happens incredibly quickly, in just fractions of a nanosecond. The speed of the chemical reaction necessitates the use of high-performance computers like Argonne’s Blue/Gene Q supercomputer, Mira.

To further explore these electrochemical oxide interfaces with high-performance computers, Sankaranarayanan and his colleagues from Argonne, Harvard University and the University of Missouri have also been awarded 40 million processor-hours of time on Mira.

“Having the ability to look at these reactions in a more powerful simulation will give us the opportunity to make a more educated guess of the rates of corrosion for different scenarios,” Sankaranarayanan said. Such studies will open up for the first time fundamental studies of corrosion behavior and will allow scientists to tailor materials surfaces to improve the stability and lifetime of materials.

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

Chloride ions induce order-disorder transition at water-oxide interfaces by Sanket Deshmukh, Ganesh Kamath, Shriram Ramanathan, and Subramanian K. R. S. Sankaranarayanan. Phys. Rev. E 88 (6), 062119 (2013) [5 pages]

This article is behind a paywall on both the primary site and the beta site (the American Physical Society is testing a new website for its publications).

Mixing and matching your nanoparticles

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.

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