Tag Archives: Tao Xu

Silver nanoparticles: liquid on the outside, crystal on the inside

Research from the Massachusetts Institute of Technology (MIT) has revealed a new property of metal nanoparticles, in this case, silver. From an Oct. 12, 2014 news item on ScienceDaily,

A surprising phenomenon has been found in metal nanoparticles: They appear, from the outside, to be liquid droplets, wobbling and readily changing shape, while their interiors retain a perfectly stable crystal configuration.

The research team behind the finding, led by MIT professor Ju Li, says the work could have important implications for the design of components in nanotechnology, such as metal contacts for molecular electronic circuits.

The results, published in the journal Nature Materials, come from a combination of laboratory analysis and computer modeling, by an international team that included researchers in China, Japan, and Pittsburgh, as well as at MIT.

An Oct. 12, 2014 MIT news release (also on EurekAlert), which originated the news item, offers both more information about the research and a surprising comparison of nanometers to the width of a human hair,

The experiments were conducted at room temperature, with particles of pure silver less than 10 nanometers across — less than one-thousandth of the width of a human hair. [emphasis mine] But the results should apply to many different metals, says Li, senior author of the paper and the BEA Professor of Nuclear Science and Engineering.

Silver has a relatively high melting point — 962 degrees Celsius, or 1763 degrees Fahrenheit — so observation of any liquidlike behavior in its nanoparticles was “quite unexpected,” Li says. Hints of the new phenomenon had been seen in earlier work with tin, which has a much lower melting point, he says.

The use of nanoparticles in applications ranging from electronics to pharmaceuticals is a lively area of research; generally, Li says, these researchers “want to form shapes, and they want these shapes to be stable, in many cases over a period of years.” So the discovery of these deformations reveals a potentially serious barrier to many such applications: For example, if gold or silver nanoligaments are used in electronic circuits, these deformations could quickly cause electrical connections to fail.

It was a bit surprising to see the reference to 10 nanometers as being less than 1/1,000th (one/one thousandth) of the width of a human hair in a news release from MIT. Generally, a nanometer has been described as being anywhere from less than 1/50,000th to 1/120,000th of the width of a human hair with less than 1/100,000th being one of the most common descriptions. While it’s true that 10 nanometers is less than 1/1,000th of the width of a human hair, it seems a bit misleading when it could be described, in keeping with the more common description, as less than 1/10,000th.

Getting back to the research, the news release offers more details as to how it was conducted,

The researchers’ detailed imaging with a transmission electron microscope and atomistic modeling revealed that while the exterior of the metal nanoparticles appears to move like a liquid, only the outermost layers — one or two atoms thick — actually move at any given time. As these outer layers of atoms move across the surface and redeposit elsewhere, they give the impression of much greater movement — but inside each particle, the atoms stay perfectly lined up, like bricks in a wall.

“The interior is crystalline, so the only mobile atoms are the first one or two monolayers,” Li says. “Everywhere except the first two layers is crystalline.”

By contrast, if the droplets were to melt to a liquid state, the orderliness of the crystal structure would be eliminated entirely — like a wall tumbling into a heap of bricks.

Technically, the particles’ deformation is pseudoelastic, meaning that the material returns to its original shape after the stresses are removed — like a squeezed rubber ball — as opposed to plasticity, as in a deformable lump of clay that retains a new shape.

The phenomenon of plasticity by interfacial diffusion was first proposed by Robert L. Coble, a professor of ceramic engineering at MIT, and is known as “Coble creep.” “What we saw is aptly called Coble pseudoelasticity,” Li says.

Now that the phenomenon has been understood, researchers working on nanocircuits or other nanodevices can quite easily compensate for it, Li says. If the nanoparticles are protected by even a vanishingly thin layer of oxide, the liquidlike behavior is almost completely eliminated, making stable circuits possible.

There are some benefits to this insight (from the news release),

On the other hand, for some applications this phenomenon might be useful: For example, in circuits where electrical contacts need to withstand rotational reconfiguration, particles designed to maximize this effect might prove useful, using noble metals or a reducing atmosphere, where the formation of an oxide layer is destabilized, Li says.

The new finding flies in the face of expectations — in part, because of a well-understood relationship, in most materials, in which mechanical strength increases as size is reduced.

“In general, the smaller the size, the higher the strength,” Li says, but “at very small sizes, a material component can get very much weaker. The transition from ‘smaller is stronger’ to ‘smaller is much weaker’ can be very sharp.”

That crossover, he says, takes place at about 10 nanometers at room temperature — a size that microchip manufacturers are approaching as circuits shrink. When this threshold is reached, Li says, it causes “a very precipitous drop” in a nanocomponent’s strength.

The findings could also help explain a number of anomalous results seen in other research on small particles, Li says.

For more details about the various attempts to create smaller computer chips, you can read my July 11, 2014 posting about IBM and its proposed 7 nanometer chip where you will also find links to announcements and posts about Intel’s smaller chips and HP Labs’ attempt to recreate computers.

As for the research into liquid-like metallic (silver) nanoparticles, here’s a link to and a citation for the paper,

Liquid-like pseudoelasticity of sub-10-nm crystalline ​silver particle by Jun Sun, Longbing He, Yu-Chieh Lo, Tao Xu, Hengchang Bi, Litao Sun, Ze Zhang, Scott X. Mao, & Ju Li. Nature Materials (2014) doi:10.1038/nmat4105 Published online 12 October 2014

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

Printing new knee cartilage

I was reminded of the 1992 Olympics in Barcelona while reading the Nov. 22, 2012 news item on Nanowerk about printing cartilage for knees. Some years ago I knew a Canadian wrestler who’d participated in those games and he had a story about knee cartilage that featured amputation.

Apparently, wrestlers in earlier generations had knee surgeries that involved removal of cartilage for therapeutic purposes. Unfortunately, decades later, these retired wrestlers found that whatever cartilage had remained was now worn through and bones were grinding on bones causing such pain that more than one wrestler agreed to amputation. I never did check out the story but it rang true largely because I’d come across a similar story from a physiotherapist regarding  a shoulder joint and the consequences of losing cartilage in there (very, very painful).

It seems that scientists are now working on a solution for those of us unlucky enough to have damaged or worn through cartilage in our joints, from the Nov. 22, 2012 IOP science news release, (Institute of Physics) which originated the news item,

The printing of 3D tissue has taken a major step forward with the creation of a novel hybrid printer that simplifies the process of creating implantable cartilage.

The printer is a combination of two low-cost fabrication techniques: a traditional ink jet printer and an electrospinning machine. Combining these systems allowed the scientists to build a structure made from natural and synthetic materials. …

In this study, the hybrid system produced cartilage constructs with increased mechanical stability compared to those created by an ink jet printer using gel material alone. The constructs were also shown to maintain their functional characteristics in the laboratory and a real-life system.

The key to this was the use of the electrospinning machine, which uses an electrical current to generate very fine fibres from a polymer solution. Electrospinning allows the composition of polymers to be easily controlled and therefore produces porous structures that encourage cells to integrate into surrounding tissue.

In this study, flexible mats of electrospun synthetic polymer were combined, layer-by-layer, with a solution of cartilage cells from a rabbit ear that were deposited using the traditional ink jet printer. The constructs were square with a 10cm diagonal and a 0.4mm thickness.

The researchers tested their strength by loading them with variable weights and, after one week, tested to see if the cartilage cells were still alive.

The constructs were also inserted into mice for two, four and eight weeks to see how they performed in a real life system. After eight weeks of implantation, the constructs appeared to have developed the structures and properties that are typical of elastic cartilage, demonstrating their potential for insertion into a patient.

The researchers state that in a future scenario, cartilage constructs could be clinically applied by using an MRI scan of a body part, such as the knee, as a blueprint for creating a matching construct. A careful selection of scaffold material for each patient’s construct would allow the implant to withstand mechanical forces while encouraging new cartilage to organise and fill the defect.

The researchers’ article in the IOP science jouBiofrarnal, Biofabrication, is freely available for 30 days after its date of publication, Nov. 21, 2012. You do need to register with IOP science to gain access. Here’s the citation and a link,

Hybrid printing of mechanically and biologically improved constructs for cartilage tissue engineering applications by Tao Xu, Kyle W Binder, Mohammad Z Albanna, Dennis Dice, Weixin Zhao, James J Yoo and Anthony Atala in 2013 Biofabrication 5 015001 doi:10.1088/1758-5082/5/1/015001

I believe all of the scientists involved in this bioprinting project are with the Wake Forest Institute for Regenerative Medicine.