Tag Archives: Pin Ann Lin

Oh so cute! Baby nanotubes!

Scientists from the US National Institute of Standards and Technology and from two US universities have successfully filmed the formation of single-walled carbon nanotubes (SWCNTs) according to a Dec. 2, 2014 news item on Nanowerk,

Single-walled carbon nanotubes are loaded with desirable properties. In particular, the ability to conduct electricity at high rates of speed makes them attractive for use as nanoscale transistors. But this and other properties are largely dependent on their structure, and their structure is determined when the nanotube is just beginning to form.

In a step toward understanding the factors that influence how nanotubes form, researchers at the National Institute of Standards and Technology (NIST), the University of Maryland, and Texas A&M have succeeded in filming them when they are only a few atoms old. These nanotube “baby pictures” give crucial insight into how they germinate and grow, potentially opening the way for scientists to create them en masse with just the properties that they want.

A Dec. 1, 2014 NIST news release, which originated the news item, explains how scientists managed to make movies of SWCNTs as they formed,

To better understand how carbon nanotubes grow and how to grow the ones you want, you need to understand the very beginning of the growth process, called nucleation. To do that, you need to be able to image the nucleation process as it happens. However, this is not easy because it involves a small number of fast-moving atoms, meaning you have to take very high resolution pictures very quickly.

Because fast, high-resolution cameras are expensive, NIST scientists instead slowed the growth rate by lowering the pressure inside their instrument, an environmental scanning transmission electron microscope. Inside the microscope’s chamber, under high heat and low pressure, the team watched as carbon atoms generated from acetylene rained down onto 1.2-nanometer bits of cobalt carbide, where they attached, formed into graphene, encircled the nanoparticle, and began to grow into nanotubes.

“Our observations showed that the carbon atoms attached only to the pure metal facets of the cobalt carbide nanoparticle, and not those facets interlaced with carbon atoms,” says NIST chemist Renu Sharma, who led the research effort. “The burgeoning tube then grew above the cobalt-carbon facets until it found another pure metal surface to attach to, forming a closed cap. Carbon atoms continued to attach at the cobalt facets, pushing the previously formed graphene along toward the cap in a kind of carbon assembly line and lengthening the tube. This whole process took only a few seconds.”

According to Sharma, the carbon atoms seek out the most energetically favorable configurations as they form graphene on the cobalt carbide nanoparticle’s surface. While graphene has a mostly hexagonal, honeycomb-type structure, the geometry of the nanoparticle forces the carbon atoms to arrange themselves into pentagonal shapes within the otherwise honeycomb lattice. Crucially, these pentagonal irregularities in the graphene’s structure are what allows the graphene to curve and become a nanotube.

Because the nanoparticles’ facets also appear to play a deciding role in the nanotube’s diameter and chirality, or direction of twist, the group’s next step will be to measure the chirality of the nanotubes as they grow. The group also plans to use metal nanoparticles with different facets to study their adhesive properties to see how they affect the tubes’ chirality and diameter.

The researchers have made one of their movies available for viewing, but, despite my efforts, I cannot find a way to embed the silent movie. Happily, you can find the ‘baby carbon nanotube’ movie alongside NIST’s Dec. 1, 2014 NIST news release,

As for the research paper, here’s a link and a citation for it,

Nucleation of Graphene and Its Conversion to Single-Walled Carbon Nanotubes by Matthieu Picher, Pin Ann Lin, Jose L. Gomez-Ballesteros, Perla B. Balbuena, and Renu Sharma. Nano Lett., 2014, 14 (11), pp 6104–6108 DOI: 10.1021/nl501977b Publication Date (Web): October 20, 2014

Copyright © 2014 American Chemical Society

This paper is behind a paywall.

Nanodiamond grow-ops possible now nanodiamonds can be made in ambient conditions

Living in a area where marijuana grow-ops are a serious issue and something to be considered when you buy your condo, house, etc. (dangerous people showing up at odd times and structural issues are amongst two of the most feared problems), an Oct. 22, 2013 news item on Azonano featuring nanodiamonds grown at almost room-level temperatures caught my attention,

Instead of having to use tons of crushing force and volcanic heat to forge diamonds, researchers at Case Western Reserve University [Case] have developed a way to cheaply make nanodiamonds on a lab bench at atmospheric pressure and near room temperature.

The nanodiamonds are formed directly from a gas and require no surface to grow on.

The discovery holds promise for many uses in technology and industry, such as coating plastics with ultrafine diamond powder and making flexible electronics, implants, drug-delivery devices and more products that take advantage of diamond’s exceptional properties.

Their investigation is published today in the scientific journal Nature Communications. The findings build on a tradition of diamond research at Case Western Reserve.

The Oct. 21, 2013 Case University press release (also on EurekAlert), which originated the news item, explaining why this discovery is so exciting and describing the technique for creating nanodiamonds without “crushing force and volcanic heat” in more detail,

Beyond its applications, the discovery may offer some insight into our universe: an explanation of how nanodiamonds seen in space and found in meteorites may be formed.

“This is not a complex process: ethanol vapor at room temperature and pressure is converted to diamond,” said Mohan Sankaran, associate professor of chemical engineering at Case Western Reserve and leader of the project. “We flow the gas through a plasma, add hydrogen and out come diamond nanoparticles. We can put this together and make them in almost any lab.”

The process for making these small “forever stones” won’t melt plastic so it is well suited for certain high-tech applications. Diamond, renowned for being hard, has excellent optical properties and the highest velocity of sound and thermal conductivity of any material.

Unlike the other form of carbon, graphite, diamond is a semiconductor, similar to silicon, which is the dominant material in the electronics industry, and gallium arsenide, which is used in lasers and other optical devices.

While the process is simple, finding the right concentrations and flows—what the researchers call the “sweet spot”—took time.

The other researchers involved were postdoctoral researcher Ajay Kumar, PhD student Pin Ann Lin, and undergraduate student Albert Xue, of Case Western Reserve; and physics professor Yoke Khin Yap and graduate student Boyi Hao, of Michigan Technological University.

Sankaran and John Angus, professor emeritus of chemical engineering, came up with the idea of growing nanodiamonds with no heat or pressure about eight years ago. Angus’ research in the 1960s and 1970s led him and others to devise a way to grow diamond films at low pressure and high temperature, a process known as chemical vapor deposition that is now used to make coatings on computer disks and razor blades. Sankaran’s specialty, meanwhile, is making nanoparticles using cool microplasmas.

It usually requires high pressures and high temperatures to convert graphite to diamond or a combination of hydrogen gas and a heated substrate to grow diamond rather than graphite.

“But at the nanoscale, surface energy makes diamond more stable than graphite,” Sankaran explained. “We thought if we could nucleate carbon clusters in the gas phase that were less than 5 nanometers, they would be diamond instead of graphite even at normal pressure and temperature.”

After several ups and downs with the effort, the process came together when Kumar joined Sankaran’s lab. The engineers produced diamond much like they’d produce carbon soot.

They first create a plasma, which is a state of matter similar to a gas but a portion is becoming charged, or ionized. A spark is an example of a plasma, but it’s hot and uncontrollable.

To get to cooler and safer temperatures, they ionized argon gas as it was pumped out of a tube a hair-width in diameter, creating a microplasma. They pumped ethanol—the source of carbon—through the microplasma, where, similar to burning a fuel, carbon breaks free from other molecules in the gas, and yields particles of 2 to 3 nanometers, small enough that they turn into diamond.

In less than a microsecond, they add hydrogen. The element removes carbon that hasn’t turned to diamond while simultaneously stabilizing the diamond particle surface.

The diamond formed is not the large perfect crystals used to make jewelry, but is a powder of diamond particles. Sankaran and Kumar are now consistently making high-quality diamonds averaging 2 nanometers in diameter.

The researchers spent about a year of testing to verify they were producing diamonds and that the process could be replicated, Kumar said. The team did different tests themselves and brought in Yap’s lab to analyze the nanoparticles by Raman spectroscopy.

Currently, nanodiamonds are made by detonating an explosive in a reactor vessel to provide heat and pressure. The diamond particles must then be removed and purified from contaminating elements massed around them. The process is quick and cheap but the nanodiamonds aggregate and are of varying size and purity.

The new research offers promising implications. Nanodiamonds, for instance, are being tested to carry drugs to tumors. Because diamond is not recognized as an invader by the immune system, it does not evoke resistance, the main reason why chemotherapy fails.

Sankaran said his nanodiamonds may offer an alternative to diamonds made by detonation methods because they are purer and smaller.

The group’s process produces three kinds of diamonds: about half are cubic, the same structure as gem diamonds, a small percentage are a form suspected of having hydrogen trapped inside and about half are lonsdaleite, a hexagonal form found in interstellar dust but rarely found on Earth.

A recent paper in the journal Physical Review Letters suggests that when interstellar dust collides, such high pressure is involved that the graphitic carbon turns into londsdaleite nanodiamonds.

Sankaran and Kumar contend that an alternative with no high pressure requirement, such as their method, should be considered, too.

“Maybe we’re making diamond in the way diamond is sometimes made in outer space,” Sankaran proposed. “Ethanol and plasmas exist in outer space, and our nanodiamonds are similar in size and structure to those found in space.”

The group is now investigating whether it can fine-tune the process to control which form of diamond is made, analyzing the structures and determining if each has different properties. Lonsdaleite, for instance, is harder than cubic diamond.

The researchers have made a kind of nanodiamond spray paint. “We can do this in a single step, by spraying the nanodiamonds as they are produced out of the plasma and purified with hydrogen, to coat a surface,” Kumar said.

“Will they be able to scale up? That’s always a crap shoot,” Angus said. “But I think it can be done, and at very high rates and cheaply. Ultimately, it may take some years to get there, but there is no theoretical reason it can’t be done.”

Here’s an image from the researchers illustrating the technique,

Caption: (Clockwise) Microplasma dissociates ethanol vapor, carbon particles are collected and dispersed in solution, and electron microscope image reveals nanosized diamond particles. Credit: Case Western Reserve University

Caption: (Clockwise) Microplasma dissociates ethanol vapor, carbon particles are collected and dispersed in solution, and electron microscope image reveals nanosized diamond particles.
Credit: Case Western Reserve University

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

Formation of nanodiamonds at near-ambient conditions via microplasma dissociation of ethanol vapour by Ajay Kumar, Pin Ann Lin, Albert Xue, Boyi Hao, Yoke Khin Yap, & R. Mohan Sankaran. Nature Communications 4, Article number: 2618 doi:10.1038/ncomms3618  Published 21 October 2013

This article is behind a paywall,