Tag Archives: Sanket A. Deshmukh

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.

Single layer graphene as a solid lubricant

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

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

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

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

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

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

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

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

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

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

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

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

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

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

This article is behind a paywall.