Tag Archives: nanowires

Getting too hot? Strap on your personal cooling unit

Individual cooling units for firefighters, foundry workers, and others working in hot conditions are still in the future but if Pennsylvania State University (Penn State) researchers have their way that future is a lot closer than it was. From an April 29, 2016 news item on Nanotechnology Now,

Firefighters entering burning buildings, athletes competing in the broiling sun and workers in foundries may eventually be able to carry their own, lightweight cooling units with them, thanks to a nanowire array that cools, according to Penn State materials researchers.

An April 28, 2016 Penn State news release by A’ndrea Elyse Messer, which originated the news item, describes some of the concepts and details some of the technology,

“Most electrocaloric ceramic materials contain lead,” said Qing Wang, professor of materials science and engineering. “We try not to use lead. Conventional cooling systems use coolants that can be environmentally problematic as well. Our nanowire array can cool without these problems.”

Electrocaloric materials are nanostructured materials that show a reversible temperature change under an applied electric field. Previously available electrocaloric materials were single crystals, bulk ceramics or ceramic thin films that could cool, but are limited because they are rigid, fragile and have poor processability. Ferroelectric polymers also can cool, but the electric field needed to induce cooling is above the safety limit for humans.

Wang and his team looked at creating a nanowire material that was flexible, easily manufactured and environmentally friendly and could cool with an electric field safe for human use. Such a material might one day be incorporated into firefighting gear, athletic uniforms or other wearables. …

Their vertically aligned ferroelectric barium strontium titanate nanowire array can cool about 5.5 degrees Fahrenheit using 36 volts, an electric field level safe for humans. A 500 gram battery pack about the size of an IPad could power the material for about two hours.

The researchers grow the material in two stages. First, titanium dioxide nanowires are grown on fluorine doped tin oxide coated glass. The researchers use a template so all the nanowires grow perpendicular to the glass’ surface and to the same height. Then the researchers infuse barium and strontium ions into the titanium dioxide nanowires.

The researchers apply a nanosheet of silver to the array to serve as an electrode.

They can move this nanowire forest from the glass substrate to any substrate they want — including clothing fabric — using a sticky tape.

“This low voltage is good enough for modest exercise and the material is flexible,” said Wang. “Now we need to design a system that can cool a person and remove the heat generated in cooling from the immediate area.”

This solid state personal cooling system may one day become the norm because it does not require regeneration of coolants with ozone depletion and global warming potentials and could be lightweight and flexible.

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

Toward Wearable Cooling Devices: Highly Flexible Electrocaloric Ba0.67Sr0.33TiO3 Nanowire Arrays by Guangzu Zhang, Xiaoshan Zhang, Houbing Huang, Jianjun Wang, Qi Li, Long-Qing Chen, and Qing Wang. Advanced Materials DOI: 10.1002/adma.201506118 Article first published online: 27 APR 2016

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

This paper is behind a paywall.

One final comment, I’m trying to imagine a sport where an athlete would willingly wear any material that adds weight. Isn’t an athlete’s objective is to have lightweight clothing and footwear so nothing impedes performance?

Listening to bacteria for superior organic nanowires

Researchers at Michigan State University (MSU; US) claim to have  discovered organic nanowires that are superior to the engineered kind according to a March 24, 2016 news item on ScienceDaily,

A microbial protein fiber discovered by a Michigan State University scientist transports charges at rates high enough to be applied in humanmade nanotechnologies.

The discovery, featured in the current issue of Scientific Reports, describes the high-speed protein fiber produced by uranium-reducing Geobacter bacteria. The fibers are hair-like protein filaments called “pili” that have the unique property of transporting charges at speeds of 1 billion electrons per second.

A March 24, 2016 MSU news release, which originated the news item, provides more information,

“This microbial nanowire is made of but a single peptide subunit,” said Gemma Reguera, lead author and MSU microbiologist. “Being made of protein, these organic nanowires are biodegradable and biocompatible. This discovery thus opens many applications in nanoelectronics such as the development of medical sensors and electronic devices that can be interfaced with human tissues.”

Since existing nanotechnologies incorporate exotic metals into their designs, the cost of organic nanowires is much more cost effective as well, she added.

How the nanowires function in nature is comparable to breathing. Bacterial cells, like humans, have to breathe. The process of respiration involves moving electrons out of an organism. Geobacter bacteria use the protein nanowires to bind and breathe metal-containing minerals such as iron oxides and soluble toxic metals such as uranium. The toxins are mineralized on the nanowires’ surface, preventing the metals from permeating the cell.

Reguera’s team purified their protein fibers, which are about 2 nanometers in diameter. Using the same toolset of nanotechnologists, the scientists were able to measure the high velocities at which the proteins were passing electrons.

“They are like power lines at the nanoscale,” Reguera said. “This also is the first study to show the ability of electrons to travel such long distances — more than a 1,000 times what’s been previously proven — along proteins.”

The researchers also identified metal traps on the surface of the protein nanowires that bind uranium with great affinity and could potentially trap other metals. These findings could provide the basis for systems that integrate protein nanowires to mine gold and other precious metals, scrubbers that can be deployed to immobilize uranium at remediation sites and more.

Reguera’s nanowires also can be modified to seek out other materials in which to help them breathe.

“The Geobacter cells are making these protein fibers naturally to breathe certain metals. We can use genetic engineering to tune the electronic and biochemical properties of the nanowires and enable new functionalities. We also can mimic the natural manufacturing process in the lab to mass-produce them in inexpensive and environmentally friendly processes,” Reguera said. “This contrasts dramatically with the manufacturing of humanmade inorganic nanowires, which involve high temperatures, toxic solvents, vacuums and specialized equipment.”

This discovery came from truly listening to bacteria, Reguera said.

“The protein is getting the credit, but we can’t forget to thank the bacteria that invented this,” she said. “It’s always wise to go back and ask bacteria what else they can teach us. In a way, we are eavesdropping on microbial conversations. It’s like listening to our elders, learning from their wisdom and taking it further.”

Asking what else bacteria can teach us? That’s a lovely thought and  different from the still common ‘let’s wipe them all out’ approach to bacteria. It suggests scientific research that is more amenable to sharing the planet with all forms of life.

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

Thermally activated charge transport in microbial protein nanowires by Sanela Lampa-Pastirk, Joshua P. Veazey, Kathleen A. Walsh, Gustavo T. Feliciano, Rebecca J. Steidl, Stuart H. Tessmer, & Gemma Reguera. Scientific Reports 6, Article number: 23517 (2016) doi:10.1038/srep23517 Published online: 24 March 2016

This paper is open access.

Korean researchers fabricate cross-shaped memristors

I’ve been a bit late getting this Korean research concerning memristors into a posting. A Jan. 30, 2016 news item on Nanotechnology Now announces a new means of fabricating memristors,

Along with the fast development of modern information technology, charge-based memories, such as DRAM and flash memory, are being aggressively scaled down to meet the current trend of small size devices. A memory device with high density, faster speed, and low power consumption is desired to satisfy Moore’s law in the next few decades. Among the candidates of next-generation memory devices, cross-bar-shaped non-volatile resistive memory (memristor) is one of the most attractive solutions for its non-volatility, faster access speed, ultra-high density and easier fabrication process.

Conventional memristors are usually fabricated through conventional optical, imprint, and e-beam lithographic approaches. However, to meet Moore’s law, the assembly of memristors comprised of 1-dimensional (1D) nanowires must be demonstrated to achieve cell dimensions beyond limit of state-of-art lithographic techniques, thus allowing one to fully exploit the scaling potential of high density memory array.

Prof. Tae-Woo Lee (Dept. of Materials Science and Engineering) and his research team have developed a rapid printing technology for high density and scalable memristor array composed of cross-bar-shaped metal nanowires. The research team, which consists of Prof. Tae-Woo Lee, research professor Wentao Xu, and doctoral student Yeongjun Lee at POSTECH [Pohang University of Science and Technology], Korea, published their findings in Advanced Materials.

A Jan. 28, 2016 POSTECH news release, which originated the news item, expands on the theme,

They applied an emerging technique, electrohydrohynamic nanowire printing (e-NW printing), which directly prints highly-aligned nanowire array on a large scale into the fabrication of microminiature memristors, with cross-bar-shaped conductive Cu nanowires jointed with a nanometer-scale CuxO layer. The metal-oxide-metal structure resistive memory device exhibited excellent electrical performance with reproducible resistive switching behavior.

This simple and fast fabrication process avoids conventional vacuum techniques to significantly reduce the industrial-production cost and time. This method paved the way to the future down-scaling of electronic circuits, since 1D conductors represent a logical way to extreme scaling of data processing devices in the single-digit nanometer scale.

They also succeeded in printing memristor array with various shapes, such as parallel lines with adjustable pitch, grids, and waves which can offer a future stretchable memory for integration into textile to serve as a basic building block for smart fabrics and wearable electronics.

“This technology reduces lead time and cost remarkably compared with existing manufacturing methods of cross-bar-shaped nanowire memory and simplifies its method of construction,” said Prof. Lee. “In particular, this technology will be used as a source technology to realize smart fabric, wearable computers, and textile electronic devices.”

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

[Nanowires:] Simple, Inexpensive, and Rapid Approach to Fabricate Cross-Shaped Memristors Using an Inorganic-Nanowire-Digital-Alignment Technique and a One-Step Reduction Process by Wentao Xu, Yeongjun Lee, Sung-Yong Min, Cheolmin Park, andTae-Woo Lee. Advanced Materials Volume 28, Issue 3 January 20, 2016 Page 591  DOI: 10.1002/adma.201503153 Article first published online: 20 NOV 2015

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Better neuroprostheses for brain diseases and mental illneses

I don’t often get news releases from Sweden but I do on occasion and, sometimes, they even come in their original Swedish versions. In this case, Lund University sent me an English language version about their latest work making brain implants (neural prostheses) safer and effective. From a Sept. 29, 2015 Lund University news release (also on EurekAlert),

Neurons thrive and grow in a new type of nanowire material developed by researchers in Nanophysics and Ophthalmology at Lund University in Sweden. In time, the results might improve both neural and retinal implants, and reduce the risk of them losing their effectiveness over time, which is currently a problem

By implanting electrodes in the brain tissue one can stimulate or capture signals from different areas of the brain. These types of brain implants, or neuro-prostheses as they are sometimes called, are used to treat Parkinson’s disease and other neurological diseases.

They are currently being tested in other areas, such as depression, severe cases of autism, obsessive-compulsive disorders and paralysis. Another research track is to determine whether retinal implants are able to replace light-sensitive cells that die in cases of Retinitis Pigmentosa and other eye diseases.

However, there are severe drawbacks associated with today’s implants. One problem is that the body interprets the implants as foreign objects, resulting in an encapsulation of the electrode, which in turn leads to loss of signal.

One of the researchers explains the approach adopted by the research team (from the news release),

“Our nanowire structure prevents the cells that usually encapsulate the electrodes – glial cells – from doing so”, says Christelle Prinz, researcher in Nanophysics at Lund University in Sweden, who developed this technique together with Maria Thereza Perez, a researcher in Ophthalmology.

“I was very pleasantly surprised by these results. In previous in-vitro experiments, the glial cells usually attach strongly to the electrodes”, she says.

To avoid this, the researchers have developed a small substrate where regions of super thin nanowires are combined with flat regions. While neurons grow and extend processes on the nanowires, the glial cells primarily occupy the flat regions in between.

“The different types of cells continue to interact. This is necessary for the neurons to survive because the glial cells provide them with important molecules.”

So far, tests have only been done with cultured cells (in vitro) but hopefully they will soon be able to continue with experiments in vivo.

The substrate is made from the semiconductor material gallium phosphide where each outgrowing nanowire has a diameter of only 80 nanometres (billionths of a metre).

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

Support of Neuronal Growth Over Glial Growth and Guidance of Optic Nerve Axons by Vertical Nanowire Arrays by Gaëlle Piret, Maria-Thereza Perez, and Christelle N. Prinz. ACS Appl. Mater. Interfaces, 2015, 7 (34), pp 18944–18948 DOI: 10.1021/acsami.5b03798 Publication Date (Web): August 11, 2015

Copyright © 2015 American Chemical Society

This paper appears to be open access as I was able to link to the PDF version.

LEDs (light-emitting diodes) that need less energy and give better light

A June 24, 2015 University of Copenhagen Niels Bohr Institute press release (also on EurekAlert), announces research that could lead to a brighter future (pun intended),

The researchers [from the Niels Bohr Institute] studied nanowires using X-ray microscopy and with this method they can pinpoint exactly how the nanowire should be designed to give the best properties. …

Nanowires are very small – about 2 micrometers high (1 micrometer is a thousandth of a millimetre) and 10-500 nanometers in diameter (1 nanometer is a thousandth of a micrometer). Nanowires for LEDs are made up of an inner core of gallium nitride (GaN) and a layer of indium-gallium-nitride (InGaN) on the outside, both of which are semiconducting materials.

“The light in such a diode is dependent on the mechanical strain that exists between the two materials and the strain is very dependent on how the two layers are in contact with each other. We have examined a number of nanowires using X-ray microscopy and even though the nanowires should in principle be identical, we can see that they are different and have very different structure,” explains Robert Feidenhans’l, professor and head of the Niels Bohr Institute at the University of Copenhagen.

Surprisingly efficient

The studies were performed using nanoscale X-ray microscopy in the electron synchrotron at DESY in Hamburg, Germany. The method is usually very time consuming and the results are often limited to very few or even a single study subject. But here researchers have managed to measure a series of upright nanowires all at once using a special design of a nanofocused X-ray without destroying the nanowires in the process.

“We measured 20 nanowires and when we saw the images, we were very surprised because you could clearly see the details of each nanowire. You can see the structure of both the inner core and the outer layer. If there are defects in the structure or if they are slightly bent, they do not function as well. So we can identify exactly which nanowires are the best and have the most efficient core/shell structure,” explains Tomas Stankevic, a PhD student in the research group ‘Neutron and X-ray Scattering’ at the Niels Bohr Institute at the University of Copenhagen.

The nanowires are produced by a company in Sweden and this new information can be used to tweak the layer structure in the nanowires. Professor Robert Feidenhans’l explains that there is great potential in such nanowires. They will provide a more natural light in LEDs and they will use much less power. In addition, they could be used in smart phones, televisions and many forms of lighting.

The researchers expect that things could go very quickly and that they may already be in use within five years.

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

Fast Strain Mapping of Nanowire Light-Emitting Diodes Using Nanofocused X-ray Beams by Tomaš Stankevič, Emelie Hilner, Frank Seiboth, Rafal Ciechonski, Giuliano Vescovi, Olga Kryliouk, Ulf Johansson, Lars Samuelson, Gerd Wellenreuther, Gerald Falkenberg, Robert Feidenhans’l, and Anders Mikkelsen.
ACS Nano, Article ASAP DOI: 10.1021/acsnano.5b01291
Publication Date (Web): June 19, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

Sensing smoke with nanoscale sensors

A Feb. 17, 2015 news item on Nanowerk notes that current smoke sensors are ultra-violet light detectors in the context of research about developing better ones,

Researchers at the University of Surrey’s [UK] Advanced Technology Institute manipulated zinc oxide, producing nanowires from this readily available material to create a ultra-violet light detector which is 10,000 times more sensitive to UV light than a traditional zinc oxide detector.

A Feb. 17, 2015 University of Surrey press release (also on EurekAlert), which originated the news item, provides more detail about the work and the theory (Note: Links have been removed),

Currently, photoelectric smoke sensors detect larger smoke particles found in dense smoke, but are not as sensitive to small particles of smoke from rapidly burning fires.

Researchers believe that this new material could increase sensitivity and allow the sensor to detect distinct particles emitted at the early stages of fires, paving the way for specialist sensors that can be deployed in a number of applications.

“UV light detectors made from zinc oxide have been used widely for some time but we have taken the material a step further to massively increase its performance,” said Professor Ravi Silva, co-author of the study and head of the Advanced Technology Institute. “Essentially, we transformed zinc oxide from a flat film to a structure with bristle-like nanowires, increasing surface area and therefore increasing sensitivity and reaction speed.”

The team predict that the applications for this material could be far-reaching. From fire and gas detection to air pollution monitoring, they believe the sensor could also be incorporated into personal electronic devices – such as phones and tablets – to increase speed, with a response time 1,000 times faster than traditional zinc oxide detectors.

“This is a great example of a bespoke, designer nanomaterial that is adaptable to personal needs, yet still affordable. Due to the way in which this material is manufactured, it is ideally suited for use in future flexible electronics – a hugely exciting area,” added Professor Silva.

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

On-chip Fabrication of High Performance Nanostructured ZnO UV Detectors by Mohammad R. Alenezi, Simon J. Henley, & S. R. P. Silva. Scientific Reports 5, Article number: 8516 doi:10.1038/srep08516 Published 17 February 2015

This paper is open access.

Shrinky Dinks* instrumental for new nanowires technique

Shrinky Dinks, a material used for children’s arts and crafts projects, has proved instrumental for developing a new technique to close the gap between nanowires. From a July 1, 2014 news item on Nanowerk (Note: A link has been removed),

How do you put a puzzle together when the pieces are too tiny to pick up? Shrink the distance between them.

Engineers at the University of Illinois at Urbana-Champaign are using Shrinky Dinks, plastic that shrinks under high heat, to close the gap between nanowires in an array to make them useful for high-performance electronics applications. The group published its technique in the journal Nano Letters (“Assembly and Densification of Nanowire Arrays via Shrinkage”).

A July 1, 2014 University of Illinois at Urbana-Champaign news release, which originated the news item, provides more details about the new technique,

Nanowires are extremely fast, efficient semiconductors, but to be useful for electronics applications, they need to be packed together in dense arrays. Researchers have struggled to find a way to put large numbers of nanowires together so that they are aligned in the same direction and only one layer thick.

“Chemists have already done a brilliant job in making nanowires exhibit very high performance. We just don’t have a way to put them into a material that we can handle,” said study leader SungWoo Nam, a professor of mechanical science and engineering at the U. of I. “With the shrinking approach, people can make nanowires and nanotubes using any method they like and use the shrinking action to compact them into a higher density.”

The researchers place the nanowires on the Shrinky Dinks plastic as they would for any other substrate, but then shrink it to bring the wires much closer together. This allows them to create very dense arrays of nanowires in a simple, flexible and very controllable way.

The shrinking method has the added bonus of bringing the nanowires into alignment as they increase in density. Nam’s group demonstrated how even wires more than 30 degrees off-kilter can be brought into perfect alignment with their neighbors after shrinking.

“There’s assembly happening at the same time as the density increases,” Nam said, “so even if the wires are assembled in a disoriented direction we can still use this approach.”

The plastic is clamped before baking so that it only shrinks in one direction, so that the wires pack together but do not buckle. Clamping in different places could direct the arrays into interesting formations, according to Nam. The researchers also can control how densely the wires pack by varying the length of time the plastic is heated. They also are exploring using lasers to precisely shrink the plastic in specific patterns.

Nam first had the idea for using Shrinky Dinks plastic to assemble nanomaterials after seeing a microfluidics device that used channels made of shrinking plastic. He realized that the high degree of shrinking and the low cost of plastic could have a huge impact on nanowire assembly and processing for applications.

“I’m interested in this concept of synthesizing new materials that are assembled from nanoscale building blocks,” Nam said. “You can create new functions. For example, experiments have shown that film made of packed nanowires has properties that differ quite a bit from a crystal thin film.”

One application the group is now exploring is a thin film solar cell, made of densely packed nanowires, that could harvest energy from light much more efficiently than traditional thin-film solar cells.

I have featured the Shrinky Dinks product and its use for nanoscale fabrication before in an Aug. 16, 2010 posting which featured this reply from the lead researcher for that project on nanopatterning,

ETA Aug.17.10: I also contacted Teri W. Odom, professor at Northwestern University about why they use Slinky Dinks in their work. She very kindly responded with this:

Part of what we are interested in is the development of low-cost nanofabrication tools that can create macroscale areas of nanoscale patterns in a single step. For a variety of reasons, this end-product is hard to obtain—even though we and others have chipped away at this problem for years.

As an example, to achieve smaller and smaller separations between patterns, either expensive, top-down serial tools (such as electron beam lithography or scanning probe techniques) or bottom-up assembly methods need to be used. However, the former cannot easily create large areas of patterns, and the latter cannot readily control the separations of patterns.

We needed a way to obtain nanopatterns separated by specific distances on-demand. Here is where the Shrinky Dinks material comes in. My student had read a paper (published in 2007 in Lab on a Chip) about how this material was used to make microscale patterns starting from a pattern printed using a laser printer. I imagine his thought was: if this material could be used for microscale patterns, why not for nanoscale ones? It would be cheap, and it’s easy to order.

So, we combined this substrate with our new molding method—solvent assisted nanoscale embossing (SANE)—and could now heat the material to shrink the spacing between patterns. And thus, in some sense, we made available to any lab some of the capabilities of the billion-dollar nanofabrication industry for less than one-hundred dollars.

Getting back to this latest use of Shrinky Dinks, here’s a link to and a citation for the ‘nanowires’ research paper,

Assembly and Densification of Nanowire Arrays via Shrinkage by Jaehoon Bang, Jonghyun Choi, Fan Xia, Sun Sang Kwon, Ali Ashraf, Won Il Park, and SungWoo Nam. Nano Lett., 2014, 14 (6), pp 3304–3308 DOI: 10.1021/nl500709p Publication Date (Web): May 16, 2014
Copyright © 2014 American Chemical Society

This paper is behind a paywall.

* ‘dinks’ in headline changed to ‘Dinks’ on July 2, 2014 at 1150 hours PDT.

Solar cells and copper sprouts

First, Washington University in St. Louis (WUSTL; located in Missouri, US) announced a discovery about solar cells, then, the university announced a commitment to increase solar output by Fall 2014. Whether these two announcements are linked by some larger policy or strategy is not clear to me but it’s certainly an interesting confluence of events.

An April 26, 2014 news item on Azonano describes the researchers’ discovery,

By looking at a piece of material in cross section, Washington University in St. Louis engineer Parag Banerjee, PhD, and his team discovered how copper sprouts grass-like nanowires that could one day be made into solar cells.

Banerjee, assistant professor of materials science and an expert in working with nanomaterials, Fei Wu, graduate research assistant, and Yoon Myung, PhD, a postdoctoral research associate, also took a step toward making solar cells and more cost-effective.

An April 21, 2014 WUSTL news release by Beth Miller, which originated the news item, describes the research in some detail,

Banerjee and his team worked with copper foil, a simple material similar to household aluminum foil. When most metals are heated, they form a thick metal oxide film. However, a few metals, such as copper, iron and zinc, grow grass-like structures known as nanowires, which are long, cylindrical structures a few hundred nanometers wide by many microns tall. They set out to determine how the nanowires grow.

“Other researchers look at these wires from the top down,” Banerjee says. “We wanted to do something different, so we broke our sample and looked at it from the side view to see if we got different information, and we did.”

The team used Raman spectroscopy, a technique that uses light from a laser beam to interact with molecular vibrations or other movements. They found an underlying thick film made up of two different copper oxides (CuO and Cu2O) that had narrow, vertical columns of grains running through them. In between these columns, they found grain boundaries that acted as arteries through which the copper from the underlying layer was being pushed through when heat was applied, creating the nanowires.

“We’re now playing with this ionic transport mechanism, turning it on and off and seeing if we can get some different forms of wires,” says Banerjee, who runs the Laboratory for Emerging and Applied Nanomaterials (L.E.A.N.).

Like solar cells, the nanowires are single crystal in structure, or a continuous piece of material with no grain boundaries, Banerjee says.

“If we could take these and study some of the basic optical and electronic properties, we could potentially make solar cells,” he says. “In terms of optical properties, copper oxides are well-positioned to become a solar energy harvesting material.”

This work may be useful in other applications according to the news release,

The find may also benefit other engineers who want to use single crystal oxides in scientific research. Manufacturing single crystal Cu2O for research is very expensive, Banerjee says, costing up to about $1,500 for one crystal.

“But if you can live with this form that’s a long wire instead of a small crystal, you can really use it to study basic scientific phenomena,” Banerjee says.

Banerjee’s team also is looking for other uses for the nanowires, including acting as a semiconductor between two materials, as a photocatalyst, a photovoltaic or an electrode for splitting water.

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

Unravelling transient phases during thermal oxidation of copper for dense CuO nanowire growth by Fei Wu, Yoon Myunga and Parag Banerjee.  CrystEngComm, 2014,16, 3264-3267. DOI: 10.1039/C4CE00275J First published online 26 Feb 2014

This article is behind a paywall.

Shortly after the research announcement, WUSTL made this ‘solar’ announcement via an April 29, 2014 news release by Neil Schoenherr,

Washington University in St. Louis is moving forward with a bold and impactful plan to increase solar output on all campuses by 1,150 percent over current levels by this fall. The project demonstrates the university’s commitment to sustainable operations and to reducing its environmental impact in the St. Louis region and beyond.

This spring and early summer, the university will add a total of 379 kilowatts (kw) of solar on university-owned property throughout the region. Prior to this installation, the university had 33 kw that were installed as demonstration projects.

I suspect the two announcements reflect synchronicity or, perhaps, my tendency to see and develop patterns.

Ahoy me hearties! A new theory for Damascus steel

I hope I got that right. It’s been a long time since I’ve seen a pirate movie but talk of Damascus steel meant that I had to have at least one movie pirate-type phrase in this piece.

I first came across Damascus steel outside the pirate movie domain in 2007 about the time that researchers declared blades made of Damascus steel sported carbon nanotubes giving  the blades their legendary qualities. From a Nov. 16, 2006 National Geographic article by Mason Inman,

New studies of Damascus swords are revealing that the legendary blades contain nanowires, carbon nanotubes, and other extremely small, intricate structures that might explain their unique features.

Damascus swords, first made in the eighth century A.D., are renowned for their complex surface patterns and sharpness. According to legend, the blades can cut a piece of silk in half as it falls to the ground and maintain their edge after cleaving through stone, metal, or even other swords.

Now studies of the swords’ molecular structure are uncovering the tiny structures that may explain these properties.

Peter Paufler, a crystallographer at Technical University in Dresden, Germany, and his colleagues had previously found tiny nanowires and nanotubes when they used an electron microscope to examine samples from a Damascus blade made in the 17th century.

It seems that while researchers were able to answer some questions about the blade’s qualities, researchers in China believe they may have answered the question about the blade’s unique patterns, from a March 12, 2014 news release on EurekAlert,

Blacksmiths and metallurgists in the West have been puzzled for centuries as to how the unique patterns on the famous Damascus steel blades were formed. Different mechanisms for the formation of the patterns and many methods for making the swords have been suggested and attempted, but none has produced blades with patterns matching those of the Damascus swords in the museums. The debate over the mechanism of formation of the Damascus patterns is still ongoing today. Using modern metallurgical computational software (Thermo-Calc, Stockholm, Sweden), Professor Haiwen Luo of the Central Iron and Steel Research Institute in Beijing, together with his collaborator, have analyzed the relevant published data relevant to the Damascus blades, and present a new explanation that is different from other proposed mechanisms.

Before the development of tanks, guns, and cannons, humans fought with swords, and there was one type of sword in particular that everyone wanted, a Damascus sword. Western Europeans first encountered these swords in the hands of Muslim warriors in Damascus about a thousand years ago. Damascus swords were prized for their strength and sharpness. They were famous for being so sharp that they could cut a silk scarf in half as it fell to ground, something that European swords could not do. Both Mediterranean and European blacksmiths believed that the outstanding strength and sharpness of the swords resulted from their beauty, i.e., the Damascus pattern. This presents as a wavy pattern like a rose and ladder on the surface of Damascus blades, as shown in Fig. 1. It was recorded that blacksmiths in Persia made the best Damascus steel swords by hammering a small cake of Wootz steel, which was a high-quality steel ingot imported from ancient India. The best European blade smiths from the Middle Ages onwards were not able to fabricate similar blades, even though they carefully studied examples made in the East. Damascus blades became even more mysterious when the art of making them actually died out. Despite all the knowledge and technological advances of the 21st century, people are still debating the mechanism through which such beautiful patterns were formed on Damascus blades.

Here’s the figure showing a blade and its pattern,

Caption: This is an example of a Damascus sword with a typical Damascus pattern of Muhammad ladder and rose. Microstructural examination of the blade indicates that rows of cementite particles (in black) form the Damascus patterns[11]. Credit: ©Science China Press

Caption: This is an example of a Damascus sword with a typical Damascus pattern of Muhammad ladder and rose. Microstructural examination of the blade indicates that rows of cementite particles (in black) form the Damascus patterns[11].
Credit: ©Science China Press

The news release goes on,

The compositions and microstructures of many existing Damascus steel blades have been examined previously. Their C contents are within the range of 1 wt.%, and often around 1.6 wt.%. It is also known that the Damascus pattern results from the band-like formation of coarse cementite particles. The high C content leads to a large amount of cementite particles being precipitated during hot hammering. After proper etching, the coarse cementite bands appear white within the dark matrix, such that they form a visible pattern on the surface. After the 1970s, the mechanism for the formation of the Damascus pattern was revisited and debated, particularly by Professors Verhoeven from Iowa State University and Sherby from Stanford University. Sherby and his co-workers[1-4] thought that a coarse cementite network was formed around the large austenite grains, when the Wootz steel cake was cooled slowly in crucibles for several days after melting. Later, the continuous cementite network was broken into spheroidal particles during extensive hammering at relatively low temperatures between cherry (850 °C) and blood red (650 °C), rather than the white heat customarily used by European blacksmiths. Furthermore, Wootz steel cake must be used in the manufacture of genuine Damascus blades. The low-temperature hammering was also a key technology, by which Wootz steels were easily hot deformed without cracking, and finer carbide particles precipitated to make the steel stronger and tougher. However, Verhoeven et al. though that the Damascus pattern was related to the microsegregation of solutes during solidification. They carried out experiments on two genuine Damascus blades during which the carbides were removed completely by dissolution treatment, followed by quenching. It was shown that the planar arrays of carbide particles could be made to return, together with the surface pattern, by thermal cycling, whereas the Sherby mechanism requires the cementite particles formed on the boundaries of the large austenite grains to be retained during deformation. Hence, they argued strongly that the surface patterns formed on genuine Damascus steel blades should result from a type of microsegregation-induced carbide banding that requires thermal cycling[5-10]. In particular, the dendritic segregation of V was considered the most likely reason for carbide banding[11].

However, compositional examinations of some existing Damascus steel blades revealed that many of them contain almost no V or any other carbide-forming elements. Moreover, it is apparent that the ancient craftsmen making Wootz steels had no concept of alloying with particular elements such as V. As Wootz steel cakes have been discovered in many parts of the ancient Indian region, it is unlikely that the iron ores in all those places happened to contain V or other certain types of carbide-forming elements. Therefore, the explanation proposed by Verhoeven et al. is also less than convincing.

Luo et al. adopted a new method to approach this puzzle. Using an advanced metallurgical computational software package (Thermo-Calc), all possible factors, such as the influence of S, P, and V elements on the Fe-C phase diagram, precipitation of V(CN), diffusion of V in austenite, and the dendritic segregation of S and P during solidification were quantified, because they have all been considered as possible prerequisites for forming Damascus patterns. The calculations indicated that V(CN) particles precipitate or dissolve at temperatures much lower than cementite in cases with a low content of V, as is commonly found in Damascus steels (see Fig. 2a). Instead, the sulfide and phosphide could precipitate at the dendritic zone because of the severe segregation during slow solidification. In particular, the remaining P-rich liquid at the end of solidification might transform to a eutectic product of phosphide and cementite (Fig. 2b), which cannot be distinguished from cementite under an optical microscope. The high concentration of P will not be homogenized by diffusion after a short dissolution treatment, such that cementite might re-precipitate in the P-segregated regions. Therefore, the dendritic segregation of P influences the spatial distribution of cementite in Damascus blades and thus, the patterns are formed.

Luo et al. also suggested that their method could be widely employed to tackle other puzzles similar to that of the Damascus patterns, because today’s knowledge is so well developed that reliable theoretical computations are now possible. Although people were capable of making Damascus steel swords containing ultrahigh carbon contents (1 wt.%) a long time ago, it is surprising that almost all modern steels in use contain C contents below 1 wt.%. However, with future developments of knowledge and technology, it is expected that ultrahigh carbon steels. e.g., Wootz steels, will once again find important applications, because the best of the new is often the long-forgotten past.

I want to draw attention to two elements that distinguish this news release, the request from the authors and the bibliographic notes (I don’t recall seeing bibliographies appended to a news release before),

Note from the authors: It would be much appreciated if anyone would like to donate a piece of genuine Damascus blade for our research.

Corresponding Author:

LUO Haiwen
Email: haiwenluo@126.com

References

1. Sherby O D, Wadsworth J. Damascus Steels. Sci Amer, 1985,252:112-118

2. Wadsworth J, Sherby O D. On the Bulat Damascus steels revisited. Prog Mater Sci, 1980,25:35-68

3. Sherby O D, Wadsworth J. Ancient blacksmiths, the Iron Age, Damascus steels, and modern metallurgy. J of Mater Processing Techno, 2001,117:347-352

4. Wadsworth J, Sherby O D. Response to Verhoeven comments on Damascus steel. Mater Charact, 2001, 47: 163

5. Verhoeven J D, Pendary A H. Origin of the Damask pattern in Damascus steel blades. Mater Charact, 2001, 47: 423

6. Verhoeven J D, Pendary A H. On the origin of the Damask pattern of Damascus steels. Mater Charact, 2001, 47: 79

7. Verhoeven J D, Baker H H, Peterson D T, et al. Damascus Steel, Part III—The Wadsworth-Sherby mechanism. Mater Charact, 1990, 24:205

8. Verhoeven J D, Pendary A H, Gibson E D. Wootz Damascus steel blades. Mater Charact, 1996, 37: 9

9. Verhoeven J D, Pendary A H. Studies of Damascus steel blades: Part I—Experiments on reconstructed blades. Mater Charact, 1993, 30:175

10. Verhoeven J D, Pendary A H, Berge P M. Studies of Damascus steel blades: Part II—Destruction and reformation of the patterns. Mater Charact, 1993, 30: 187

11. Verhoeven J D, Pendray A. The mystery of the Damascus sword. Muse, 1998, 2: 35

Here’s a link to and a citation for the paper (you will likely need Chinese language skills to read it, although there is an English language abstract on the page),

Theoretic analysis on the mechanism of particular pattern formed on the ancient Damascus steel blades by LUO HaiWen, QIAN Wei, and DONG Han. Chinese Science Bulletin, 2014(9)

I believe the paper is behind a paywall. Finally, I hope the researchers are able to obtain a piece of genuine Damascus steel blade for their studies.

Biology and lithium-air batteries

Firstly, the biology in question is that of viruses and, secondly, research in lithium-air batteries has elicited big interest according to David Chandler’s November 13, 2013 Massachusetts Institute of Technology (MIT) news piece (also on EurekAlert and Nanowerk),

Lithium-air batteries have become a hot research area in recent years: They hold the promise of drastically increasing power per battery weight, which could lead, for example, to electric cars with a much greater driving range. But bringing that promise to reality has faced a number of challenges, ….

Now, MIT researchers have found that adding genetically modified viruses to the production of nanowires — wires that are about the width of a red blood cell, and which can serve as one of a battery’s electrodes — could help solve some of these problems.

Lithium-air batteries can also be referred to as lithiium-oxygen batteries, although Chandler does not choose to mix terms as he goes on to describe the process the researchers developed,

The researchers produced an array of nanowires, each about 80 nanometers across, using a genetically modified virus called M13, which can capture molecules of metals from water and bind them into structural shapes. In this case, wires of manganese oxide — a “favorite material” for a lithium-air battery’s cathode, Belcher says — were actually made by the viruses. But unlike wires “grown” through conventional chemical methods, these virus-built nanowires have a rough, spiky surface, which dramatically increases their surface area.

Belcher, the W.M. Keck Professor of Energy and a member of MIT’s Koch Institute for Integrative Cancer Research, explains that this process of biosynthesis is “really similar to how an abalone grows its shell” — in that case, by collecting calcium from seawater and depositing it into a solid, linked structure.

The increase in surface area produced by this method can provide “a big advantage,” Belcher says, in lithium-air batteries’ rate of charging and discharging. But the process also has other potential advantages, she says: Unlike conventional fabrication methods, which involve energy-intensive high temperatures and hazardous chemicals, this process can be carried out at room temperature using a water-based process.

Also, rather than isolated wires, the viruses naturally produce a three-dimensional structure of cross-linked wires, which provides greater stability for an electrode.

A final part of the process is the addition of a small amount of a metal, such as palladium, which greatly increases the electrical conductivity of the nanowires and allows them to catalyze reactions that take place during charging and discharging. Other groups have tried to produce such batteries using pure or highly concentrated metals as the electrodes, but this new process drastically lowers how much of the expensive material is needed.

Altogether, these modifications have the potential to produce a battery that could provide two to three times greater energy density — the amount of energy that can be stored for a given weight — than today’s best lithium-ion batteries, a closely related technology that is today’s top contender, the researchers say.

MIT has produced a video highlighting the researchers’ work (this runs longer than most of the materials I embed here at approximately 11 mins. 25 secs.),

For those who want to know more about this intriguing and speculative work,

Biologically enhanced cathode design for improved capacity and cycle life for lithium-oxygen batteries by Dahyun Oh, Jifa Qi, Yi-Chun Lu, Yong Zhang, Yang Shao-Horn, & Angela M. Belcher. Nature Communications 4, Article number: 2756 doi:10.1038/ncomms3756 Published 13 November 2013

This article is behind a paywall.

ETA Nov. 15, 2013: Dexter Johnson offers more context and information, including commercialization issues, about lithium-air batteries and lithium-ion batteries in his Nov. 14, 2013 posting on the Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers] website).