Tag Archives: NIST

US National Institute of Standards and Technology (NIST) and its whispering gallery for graphene electrons

I like this old introduction about research that invoked whispering galleries well enough to reuse it here. From a Feb. 8, 2012 post about whispering galleries for light,

Whispering galleries are always popular with all ages. I know that because I can never get enough time in them as I jostle with seniors, children, young adults, etc. For most humans, the magic of having someone across from you on the other side of the room sound as if they’re beside you whispering in your ear is ever fresh.

According to a May 12, 2015 news item on Nanowerk, the US Institute of National Standards and Technology’s (NIST) whispering gallery is not likely to cause any jostling for space as it exists at the nanoscale,

An international research group led by scientists at the U.S. Commerce Department’s National Institute of Standards and Technology (NIST) has developed a technique for creating nanoscale whispering galleries for electrons in graphene. The development opens the way to building devices that focus and amplify electrons just as lenses focus light and resonators (like the body of a guitar) amplify sound.

The NIST has provided a rather intriguing illustration of this work,

Caption: An international research group led by scientists at NIST has developed a technique for creating nanoscale whispering galleries for electrons in graphene. The researchers used the voltage from a scanning tunneling microscope (right) to push graphene electrons out of a nanoscale area to create the whispering gallery (represented by the protuberances on the left), which is like a circular wall of mirrors to the electron. credit: Jon Wyrick, CNST/NIST

Caption: An international research group led by scientists at NIST has developed a technique for creating nanoscale whispering galleries for electrons in graphene. The researchers used the voltage from a scanning tunneling microscope (right) to push graphene electrons out of a nanoscale area to create the whispering gallery (represented by the protuberances on the left), which is like a circular wall of mirrors to the electron.
credit: Jon Wyrick, CNST/NIST

A May 8, 2015 NIST news release, which originated the news item, gives a delightful introduction to whispering galleries and more details about this research (Note: Links have been removed),

In some structures, such as the dome in St. Paul’s Cathedral in London, a person standing near a curved wall can hear the faintest sound made along any other part of that wall. This phenomenon, called a whispering gallery, occurs because sound waves will travel along a curved surface much farther than they will along a flat one. Using this same principle, scientists have built whispering galleries for light waves as well, and whispering galleries are found in applications ranging from sensing, spectroscopy and communications to the generation of laser frequency combs.

“The cool thing is that we made a nanometer scale electronic analogue of a classical wave effect,” said NIST researcher Joe Stroscio. “These whispering galleries are unlike anything you see in any other electron based system, and that’s really exciting.”

Ever since graphene, a single layer of carbon atoms arranged in a honeycomb lattice, was first created in 2004, the material has impressed researchers with its strength, ability to conduct electricity and heat and many interesting optical, magnetic and chemical properties.

However, early studies of the behavior of electrons in graphene were hampered by defects in the material. As the manufacture of clean and near-perfect graphene becomes more routine, scientists are beginning to uncover its full potential.

When moving electrons encounter a potential barrier in conventional semiconductors, it takes an increase in energy for the electron to continue flowing. As a result, they are often reflected, just as one would expect from a ball-like particle.

However, because electrons can sometimes behave like a wave, there is a calculable chance that they will ignore the barrier altogether, a phenomenon called tunneling. Due to the light-like properties of graphene electrons, they can pass through unimpeded—no matter how high the barrier—if they hit the barrier head on. This tendency to tunnel makes it hard to steer electrons in graphene.

Enter the graphene electron whispering gallery.

To create a whispering gallery in graphene, the team first enriched the graphene with electrons from a conductive plate mounted below it. With the graphene now crackling with electrons, the research team used the voltage from a scanning tunneling microscope (STM) to push some of them out of a nanoscale-sized area. This created the whispering gallery, which is like a circular wall of mirrors to the electron.

“An electron that hits the step head-on can tunnel straight through it,” said NIST researcher Nikolai Zhitenev. “But if electrons hit it at an angle, their waves can be reflected and travel along the sides of the curved walls of the barrier until they began to interfere with one another, creating a nanoscale electronic whispering gallery mode.”

The team can control the size and strength, i.e., the leakiness, of the electronic whispering gallery by varying the STM tip’s voltage. The probe not only creates whispering gallery modes, but can detect them as well.

NIST researcher Yue Zhao fabricated the high mobility device and performed the measurements with her colleagues Fabian Natterer and Jon Wyrick. A team of theoretical physicists from the Massachusetts Institute of Technology developed the theory describing whispering gallery modes in graphene.

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

Creating and probing electron whispering-gallery modes in graphene by Yue Zhao, Jonathan Wyrick, Fabian D. Natterer1, Joaquin F. Rodriguez-Nieva, Cyprian Lewandowski, Kenji Watanabe, Takashi Taniguchi, Leonid S. Levitov, Nikolai B. Zhitenev, & Joseph A. Stroscio. Science 8 May 2015:
Vol. 348 no. 6235 pp. 672-675 DOI: 10.1126/science.aaa7469

This paper is behind a paywall.

Making x-ray measurements more accurate

Apparently the method for establishing x-ray measurements is from the 1970s and the folks at the US National Institute of Standards and Technology (NIST) feel it’s time for a new technique. From a March 9, 2015 NIST news release (also on EurekAlert),

Criminal justice, cosmology and computer manufacturing may not look to have much in common, but these and many other disparate fields all depend on sensitive measurements of X-rays. Scientists at the National Institute of Standards and Technology (NIST) have developed a new method* to reduce uncertainty in X-ray wavelength measurement that could provide improvements awaited for decades.

Accurate measurement of X-ray wavelengths depends critically on the ability to measure angles very precisely and with very little margin for error. NIST’s new approach is the first major advance since the 1970s in reducing certain sources of error common in X-ray angle measurement.

Many of us associate X-rays with a doctor’s office, but the uses for these energetic beams go far beyond revealing our skeletons. The ability to sense X-rays at precise wavelengths allows law enforcement to detect and identify trace explosives, or astrophysicists to better understand cosmic phenomena. It all comes down to looking very closely at the X-ray spectrum and measuring the precise position of lines within it. Those lines represent specific wavelengths–which are associated with specific energies–of X-rays that are emitted by the subject being studied. Each material has its own, unique X-ray “fingerprint.”

But a slight error in angle measurement can skew the results, with consequences for quantum theories, research and manufacturing. “While many fields need good X-ray reference data, many of the measurements that presently fill standard reference databases are not great–most data were taken in the 1970s and are often imprecise,” says NIST’s Larry Hudson.

X-ray wavelengths are measured by passing the beam through special crystals and very carefully measuring the angle that exiting rays make with the original beam. While the physics is different, the technique is analogous to the way a prism will split white light into different colors coming out at different angles.

The crystal is typically mounted on a rotating device that spins the crystal to two different positions where a spectral line is observed. The angle between the two is measured–this is a neat geometry trick that determines the line’s position more precisely than a single measurement would, while also cancelling out some potential errors. One inevitable limit is the accuracy of the digital encoder, the device that translates the rotation of the crystal to an angle measurement.

The news release goes on to describe the new technique,

Hudson and his co-authors have found a way to dramatically reduce the error in that measurement. Their new approach uses laser beams bouncing off a mirrored polygon that is rotated on the same shaft that would carry the crystal. The approach allows the team to use additional mathematical shortcuts to their advantage. With new NIST sensing instrumentation and analysis, X-ray angles can now be measured routinely with an uncertainty of 0.06 arcseconds–an accuracy more than three times better than the uncalibrated encoder.

Hudson describes this reduction as significant enough to set world records in X-ray wavelength measurement. “If a giant windshield wiper stretched from Washington D.C. to New York City (364 kilometers) and were to sweep out the angle of one of these errors, its tip would move less than the width of a DVD,” he says.

What do these improvements mean for the fields that depend on X-ray sensing? For one thing, calibrating measurement devices to greater precision will provide better understanding of a host of newly designed materials, which often have complicated crystal structures that give rise to unusual effects such as high-temperature superconductivity. The team’s efforts will permit better understanding of the relationship between the structures and properties of novel materials.

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

A simple method for high-precision calibration of long-range errors in an angle encoder using an electronic nulling by Mark N Kinnane, Lawrence T Hudson, Albert Henins, and Marcus H Mendenhall. Metrologia Volume 52 Number 2 doi:10.1088/0026-1394/52/2/244

This is an open access paper,

For anyone curious about arcseconds, you can find an explanation in this Wikipedia entry titled Minute of art. Briefly, imagine a 360 degree circle where one degree equals one arcminute and one arcsecond is 1/60 of that minute.

Silver nanoparticle reference materials

When comparing silver nanoparticle toxicity studies, it would be good to know that the studies are all looking at the same type of nanoparticle. Happily, the US National Institute of Standards and Technology (NIST) has developed a silver nanoparticle reference material for just that purpose. From a March 5, 2015 news item on Azonano,

The National Institute of Standards and Technology (NIST) has issued a new silver nanoparticle reference material to support researchers studying potential environmental, health and safety risks associated with the nanoparticles, which are being incorporated in a growing number of consumer and industrial products for their antimicrobial properties. The new NIST test material is believed to be the first of its kind to stabilize the highly reactive silver particles in a freeze-dried, polymer coated, nanoparticle cake for long-term storage.

Nanoparticulate silver is a highly effective bactericide. It is, by some estimates, the most widely used nanomaterial in consumer products. These include socks and shoe liners (it combats foot odor), stain-resistant fabrics, coatings for handrails and keyboards, and a plethora of other applications.

The explosion of “nanosilver” products has driven a like expansion of research to better understand what happens to the material in the environment. “Silver nanoparticles transform, dissolve and precipitate back into nanoparticles again, combine or react with other materials—our understanding of these processes is limited,” says NIST chemist Vince Hackley. “However, in order to study their biological and environmental behavior and fate, one needs to know one is starting with the same material and not some modified or oxidized version. This new reference material targets a broad range of research applications.” [emphasis mine]

A March 3, 2015 NIST news release, which originated the news item, elaborates,

Silver nanoparticles are highly reactive. In the presence of oxygen or moisture they rapidly oxidize, subsequently releasing silver ions. This is the basis for their antimicrobial properties, but it also makes it difficult to create a standardized silver nanoparticle suspension with a long shelf life as a basis for doing comparative environmental studies. The new NIST product is the first to be stabilized by coating and freeze-drying—a technique commonly used in the pharmaceutical industry to preserve blood products and protein-based drugs. The NIST material uses polyvinylpyrrolidone (PVP), a polymer approved by the Food and Drug Administration for many uses, including as a food additive. The freeze-dried PVP-nanosilver cakes are flushed with an inert gas and sealed under a vacuum. Mixing the cake with water reconstitutes the original suspension.

NIST reference materials are designed to be homogeneous and stable. NIST provides the best available estimates for key properties of reference materials. In this case those include the mean silver particle size measured by four different methods, the total silver mass per vial, and the percentage distribution of nanoparticle sizes. The particles have a nominal diameter of 75 nanometers. NIST expects the material to be stable indefinitely when properly stored and handled, but will continue to monitor it for substantive changes in the reported values.

More information on NIST RM 8017, “Polyvinylpyrrolidone Coated Silver Nanoparticles” is available at https://www-s.nist.gov/srmors/view_report.cfm?srm=8017.

Given this development, I’m beginning to question all of the silver studies I’ve seen previously.

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.

Nanosafety research: a quality control issue

Toxicologist Dr. Harald Krug has published a review of several thousand studies on nanomaterials safety exposing problematic research methodologies and conclusions. From an Oct. 29, 2014 news item on Nanowerk (Note: A link has been removed),

Empa [Swiss Federal Laboratories for Materials Science and Technology] toxicologist Harald Krug has lambasted his colleagues in the journal Angewandte Chemie (“Nanosafety Research—Are We on the Right Track?”). He evaluated several thousand studies on the risks associated with nanoparticles and discovered no end of shortcomings: poorly prepared experiments and results that don’t carry any clout. Instead of merely leveling criticism, however, Empa is also developing new standards for such experiments within an international network.

An Oct. 29, 2014 Empa press release (also on EurekAlert), which originated the news item, describes the new enthusiasm for research into nanomaterials and safety,

Researching the safety of nanoparticles is all the rage. Thousands of scientists worldwide are conducting research on the topic, examining the question of whether titanium dioxide nanoparticles from sun creams can get through the skin and into the body, whether carbon nanotubes from electronic products are as hazardous for the lungs as asbestos used to be or whether nanoparticles in food can get into the blood via the intestinal flora, for instance. Public interest is great, research funds are flowing – and the number of scientific projects is skyrocketing: between 1980 and 2010, a total of 5,000 projects were published, followed by another 5,000 in just the last three years. However, the amount of new knowledge has only increased marginally. After all, according to Krug the majority of the projects are poorly executed and all but useless for risk assessments.

The press release goes on to describe various pathways into the body and problems with research methodologies,

How do nanoparticles get into the body?

Artificial nanoparticles measuring between one and 100 nanometers in size can theoretically enter the body in three ways: through the skin, via the lungs and via the digestive tract. Almost every study concludes that healthy, undamaged skin is an effective protective barrier against nanoparticles. When it comes to the route through the stomach and gut, however, the research community is at odds. But upon closer inspection the value of many alarmist reports is dubious – such as when nanoparticles made of soluble substances like zinc oxide or silver are being studied. Although the particles disintegrate and the ions drifting into the body are cytotoxic, this effect has nothing to do with the topic of nanoparticles but is merely linked to the toxicity of the (dissolved) substance and the ingested dose.

Laboratory animals die in vain – drastic overdoses and other errors

Krug also discovered that some researchers maltreat their laboratory animals with absurdly high amounts of nanoparticles. Chinese scientists, for instance, fed mice five grams of titanium oxide per kilogram of body weight, without detecting any effects. By way of comparison: half the amount of kitchen salt would already have killed the animals. A sloppy job is also being made of things in the study of lung exposure to nanoparticles: inhalation experiments are expensive and complex because a defined number of particles has to be swirled around in the air. Although it is easier to place the particles directly in the animal’s windpipe (“instillation”), some researchers overdo it to such an extent that the animals suffocate on the sheer mass of nanoparticles.

While others might well make do without animal testing and conduct in vitro experiments on cells, here, too, cell cultures are covered by layers of nanoparticles that are 500 nanometers thick, causing them to die from a lack of nutrients and oxygen alone – not from a real nano-effect. And even the most meticulous experiment is worthless if the particles used have not been characterized rigorously beforehand. Some researchers simply skip this preparatory work and use the particles “straight out of the box”. Such experiments are irreproducible, warns Krug.

As noted in the news item, the scientists at Empa have devised a solution to some to of the problems (from the press release),

The solution: inter-laboratory tests with standard materials
Empa is thus collaborating with research groups like EPFL’s Powder Technology Laboratory, with industrial partners and with Switzerland’s Federal Office of Public Health (FOPH) to find a solution to the problem: on 9 October the “NanoScreen” programme, one of the “CCMX Materials Challenges”, got underway, which is expected to yield a set of pre-validated methods for lab experiments over the next few years. It involves using test materials that have a closely defined particle size distribution, possess well-documented biological and chemical properties and can be altered in certain parameters – such as surface charge. “Thanks to these methods and test substances, international labs will be able to compare, verify and, if need be, improve their experiments,” explains Peter Wick, Head of Empa’s laboratory for Materials-Biology Interactions.

Instead of the all-too-familiar “fumbling around in the dark”, this would provide an opportunity for internationally coordinated research strategies to not only clarify the potential risks of new nanoparticles in retrospect but even be able to predict them. The Swiss scientists therefore coordinate their research activities with the National Institute of Standards and Technology (NIST) in the US, the European Commission’s Joint Research Center (JRC) and the Korean Institute of Standards and Science (KRISS).

Bravo! and thank you Dr. Krug and Empa for confirming something I’ve suspected due to hints from more informed commentators. Unfortunately my ignorance. about research protocols has not permitted me to undertake a better analysis of the research. ,

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

Nanosafety Research—Are We on the Right Track? by Prof. Dr. Harald F. Krug. Angewandte Chemie International Edition DOI: 10.1002/anie.201403367 Article first published online: 10 OCT 2014

This is an open access paper.

Smallest known reference material issued

I betray some of my occupational origins with this comment; a reference material is not necessarily a reference book. A Sept. 25, 2014, news item on Nanowerk clarifies the use of the term reference material in relationship to the US National Institute of Standards and technology while describing a new set designed for use at the nanoscale,

If it’s true that good things come in small packages, then the National Institute of Standards and Technology (NIST) can now make anyone working with nanoparticles very happy. NIST recently issued Reference Material (RM) 8027, the smallest known reference material ever created for validating measurements of these man-made, ultrafine particles between 1 and 100 nanometers in size.

RM 8027 consists of five hermetically sealed ampoules containing one milliliter of silicon nanoparticles—all certified to be close to 2 nanometers in diameter—suspended in toluene.

A Sept. 24, 2014 NIST news release (also on EurekAlert but dated Sept. 25, 2014), which originated the news item, provides a more detailed description and purchasing instructions

To yield the appropriate sizes for the new RM, the nanocrystals are etched from a silicon wafer, separated using ultrasound and then stabilized within an organic shell. Particle size and chemical composition are determined by dynamic light scattering, analytical centrifugation, electron microscopy and inductively coupled plasma mass spectrometry (ICP-MS), a powerful technique that can measure elements at concentrations as low as several parts per billion.

“For anyone working with nanomaterials at dimensions 5 nanometers or less, our well-characterized nanoparticles can ensure confidence that their measurements are accurate,” says NIST research chemist Vytas Reipa, leader of the team that developed and qualified RM 8027.

Silicon nanoparticles such as those in RM 8027 are being studied as alternative semiconductor materials for next-generation photovoltaic solar cells and solid-state lighting, and as a replacement for carbon in the cathodes of lithium batteries. Another potential application comes from the fact that silicon crystals at dimensions of 5 nanometers or less fluoresce under ultraviolet light. Because of this property, silicon nanoparticles may one day serve as easily detectable “tags” for tracking nanosized substances in biological, environmental or other dynamic systems.

RM 8027 maybe ordered from the NIST Standard Reference Materials Program by phone, (301) 975-2200; by fax, (301) 948-3730; or online at http://www.nist.gov/srm.

NIST has provided an illustration,

Caption: A structural model of a typical silicon nanocrystal (yellow) was stabilized within an organic shell of cyclohexane (blue). Credit: NIST

Caption: A structural model of a typical silicon nanocrystal (yellow) was stabilized within an organic shell of cyclohexane (blue).
Credit: NIST

NIST also supplied this image,

Caption: This is a high-resolution transmission electron microscope photograph of a single silicon nanoparticle. Credit: NIST

Caption: This is a high-resolution transmission electron microscope photograph of a single silicon nanoparticle. Credit: NIST

As is common with the images that scientists actually use in their work, the colour palette is gray.

Carbon capture with nanoporous material in the oilfields

Researchers at Rice University (Texas) have devised a new technique for carbon capture according to a June 3, 2014 news item on Nanowerk,

Rice University scientists have created an Earth-friendly way to separate carbon dioxide from natural gas at wellheads.

A porous material invented by the Rice lab of chemist James Tour sequesters carbon dioxide, a greenhouse gas, at ambient temperature with pressure provided by the wellhead and lets it go once the pressure is released. The material shows promise to replace more costly and energy-intensive processes.

A June 3, 2014 Rice University news release, which originated the news item, provides a general description of how carbon dioxide is currently removed during fossil fuel production and adds a few more details about the new technology,

Natural gas is the cleanest fossil fuel. Development of cost-effective means to separate carbon dioxide during the production process will improve this advantage over other fossil fuels and enable the economic production of gas resources with higher carbon dioxide content that would be too costly to recover using current carbon capture technologies, Tour said. Traditionally, carbon dioxide has been removed from natural gas to meet pipelines’ specifications.

The Tour lab, with assistance from the National Institute of Standards and Technology (NIST), produced the patented material that pulls only carbon dioxide molecules from flowing natural gas and polymerizes them while under pressure naturally provided by the well.

When the pressure is released, the carbon dioxide spontaneously depolymerizes and frees the sorbent material to collect more.

All of this works in ambient temperatures, unlike current high-temperature capture technologies that use up a significant portion of the energy being produced.

The news release mentions current political/legislative actions in the US and the implications for the oil and gas industry while further describing the advantages of this new technique,

“If the oil and gas industry does not respond to concerns about carbon dioxide and other emissions, it could well face new regulations,” Tour said, noting the White House issued its latest National Climate Assessment last month [May 2014] and, this week [June 2, 2014], set new rules to cut carbon pollution from the nation’s power plants.

“Our technique allows one to specifically remove carbon dioxide at the source. It doesn’t have to be transported to a collection station to do the separation,” he said. “This will be especially effective offshore, where the footprint of traditional methods that involve scrubbing towers or membranes are too cumbersome.

“This will enable companies to pump carbon dioxide directly back downhole, where it’s been for millions of years, or use it for enhanced oil recovery to further the release of oil and natural gas. Or they can package and sell it for other industrial applications,” he said.

This is an epic (Note to writer: well done) news release as only now is there a technical explanation,

The Rice material, a nanoporous solid of carbon with nitrogen or sulfur, is inexpensive and simple to produce compared with the liquid amine-based scrubbers used now, Tour said. “Amines are corrosive and hard on equipment,” he said. “They do capture carbon dioxide, but they need to be heated to about 140 degrees Celsius to release it for permanent storage. That’s a terrible waste of energy.”

Rice graduate student Chih-Chau Hwang, lead author of the paper, first tried to combine amines with porous carbon. “But I still needed to heat it to break the covalent bonds between the amine and carbon dioxide molecules,” he said. Hwang also considered metal oxide frameworks that trap carbon dioxide molecules, but they had the unfortunate side effect of capturing the desired methane as well and they are far too expensive to make for this application.

The porous carbon powder he settled on has massive surface area and turns the neat trick of converting gaseous carbon dioxide into solid polymer chains that nestle in the pores.

“Nobody’s ever seen a mechanism like this,” Tour said. “You’ve got to have that nucleophile (the sulfur or nitrogen atoms) to start the polymerization reaction. This would never work on simple activated carbon; the key is that the polymer forms and provides continuous selectivity for carbon dioxide.”

Methane, ethane and propane molecules that make up natural gas may try to stick to the carbon, but the growing polymer chains simply push them off, he said.

The researchers treated their carbon source with potassium hydroxide at 600 degrees Celsius to produce the powders with either sulfur or nitrogen atoms evenly distributed through the resulting porous material. The sulfur-infused powder performed best, absorbing 82 percent of its weight in carbon dioxide. The nitrogen-infused powder was nearly as good and improved with further processing.

Tour said the material did not degrade over many cycles, “and my guess is we won’t see any. After heating it to 600 degrees C for the one-step synthesis from inexpensive industrial polymers, the final carbon material has a surface area of 2,500 square meters per gram, and it is enormously robust and extremely stable.”

Apache Corp., a Houston-based oil and gas exploration and production company, funded the research at Rice and licensed the technology. Tour expected it will take time and more work on manufacturing and engineering aspects to commercialize.

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

Capturing carbon dioxide as a polymer from natural gas by Chih-Chau Hwang, Josiah J. Tour, Carter Kittrell, Laura Espinal, Lawrence B. Alemany, & James M. Tour. Nature Communications 5, Article number: 3961 doi:10.1038/ncomms4961 Published 03 June 2014

This paper is behind a paywall.

The researchers have made an illustration of the material available,

 Illustration by Tanyia Johnson/Rice University

Illustration by Tanyia Johnson/Rice University

This morning, Azonano posted a June 6, 2014 news item about a patent for carbon capture,

CO2 Solutions Inc. ( the “Corporation”), an innovator in the field of enzyme-enabled carbon capture technology, today announced it has received a Notice of Allowance from the U.S. Patent and Trademark Office for its patent application No. 13/264,294 entitled Process for CO2 Capture Using Micro-Particles Comprising Biocatalysts.

One might almost think these announcements were timed to coincide with the US White House’s moves.

As for CO2 Solutions, this company is located in Québec, Canada.  You can find out more about the company here (you may want to click on the English language button).

Competition, collaboration, and a smaller budget: the US nano community responds

Before getting to the competition, collaboration, and budget mentioned in the head for this posting, I’m supplying some background information.

Within the context of a May 20, 2014 ‘National Nanotechnology Initiative’ hearing before the U.S. House of Representatives Subcommittee on Research and Technology, Committee on Science, Space, and Technology, the US General Accountability Office (GAO) presented a 22 pp. précis (PDF; titled: NANOMANUFACTURING AND U.S. COMPETITIVENESS; Challenges and Opportunities) of its 125 pp. (PDF version report titled: Nanomanufacturing: Emergence and Implications for U.S. Competitiveness, the Environment, and Human Health).

Having already commented on the full report itself in a Feb. 10, 2014 posting, I’m pointing you to Dexter Johnson’s May 21, 2014 post on his Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers] website) where he discusses the précis from the perspective of someone who was consulted by the US GAO when they were writing the full report (Note: Links have been removed),

I was interviewed extensively by two GAO economists for the accompanying [full] report “Nanomanufacturing: Emergence and Implications for U.S. Competitiveness, the Environment, and Human Health,” where I shared background information on research I helped compile and write on global government funding of nanotechnology.

While I acknowledge that the experts who were consulted for this report are more likely the source for its views than I am, I was pleased to see the report reflect many of my own opinions. Most notable among these is bridging the funding gap in the middle stages of the manufacturing-innovation process, which is placed at the top of the report’s list of challenges.

While I am in agreement with much of the report’s findings, it suffers from a fundamental misconception in seeing nanotechnology’s development as a kind of race between countries. [emphases mine]

(I encourage you to read the full text of Dexter’s comments as he offers more than a simple comment about competition.)

Carrying on from this notion of a ‘nanotechnology race’, at least one publication focused on that aspect. From the May 20, 2014 article by Ryan Abbott for CourthouseNews.com,

Nanotech Could Keep U.S. Ahead of China

WASHINGTON (CN) – Four of the nation’s leading nanotechnology scientists told a U.S. House of Representatives panel Tuesday that a little tweaking could go a long way in keeping the United States ahead of China and others in the industry.

The hearing focused on the status of the National Nanotechnology Initiative, a federal program launched in 2001 for the advancement of nanotechnology.

As I noted earlier, the hearing was focused on the National Nanotechnology Initiative (NNI) and all of its efforts. It’s quite intriguing to see what gets emphasized in media reports and, in this case, the dearth of media reports.

I have one more tidbit, the testimony from Lloyd Whitman, Interim Director of the National Nanotechnology Coordination Office and Deputy Director of the Center for Nanoscale Science and Technology, National Institute of Standards and Technology. The testimony is in a May 21, 2014 news item on insurancenewsnet.com,

Testimony by Lloyd Whitman, Interim Director of the National Nanotechnology Coordination Office and Deputy Director of the Center for Nanoscale Science and Technology, National Institute of Standards and Technology

Chairman Bucshon, Ranking Member Lipinski, and Members of the Committee, it is my distinct privilege to be here with you today to discuss nanotechnology and the role of the National Nanotechnology Initiative in promoting its development for the benefit of the United States.

Highlights of the National Nanotechnology Initiative

Our current Federal research and development program in nanotechnology is strong. The NNI agencies continue to further the NNI’s goals of (1) advancing nanotechnology R&D, (2) fostering nanotechnology commercialization, (3) developing and maintaining the U.S. workforce and infrastructure, and (4) supporting the responsible and safe development of nanotechnology. …

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The sustained, strategic Federal investment in nanotechnology R&D combined with strong private sector investments in the commercialization of nanotechnology-enabled products has made the United States the global leader in nanotechnology. The most recent (2012) NNAP report analyzed a wide variety of sources and metrics and concluded that “… in large part as a result of the NNI the United States is today… the global leader in this exciting and economically promising field of research and technological development.” n10 A recent report on nanomanufacturing by Congress’s own Government Accountability Office (GAO) arrived at a similar conclusion, again drawing on a wide variety of sources and stakeholder inputs. n11 As discussed in the GAO report, nanomanufacturing and commercialization are key to capturing the value of Federal R&D investments for the benefit of the U.S. economy. The United States leads the world by one important measure of commercial activity in nanotechnology: According to one estimate, n12 U.S. companies invested $4.1 billion in nanotechnology R&D in 2012, far more than investments by companies in any other country.  …

There’s cognitive dissonance at work here as Dexter notes in his own way,

… somewhat ironically, the [GAO] report suggests that one of the ways forward is more international cooperation, at least in the development of international standards. And in fact, one of the report’s key sources of information, Mihail Roco, has made it clear that international cooperation in nanotechnology research is the way forward.

It seems to me that much of the testimony and at least some of the anxiety about being left behind can be traced to a decreased 2015 budget allotment for nanotechnology (mentioned here in a March 31, 2014 posting [US National Nanotechnology Initiative’s 2015 budget request shows a decrease of $200M]).

One can also infer a certain anxiety from a recent presentation by Barbara Herr Harthorn, head of UCSB’s [University of California at Santa Barbara) Center for Nanotechnology in Society (CNS). She was at a February 2014 meeting of the Presidential Commission for the Study of Bioethical Issues (mentioned in parts one and two [the more substantive description of the meeting which also features a Canadian academic from the genomics community] of my recent series on “Brains, prostheses, nanotechnology, and human enhancement”). II noted in part five of the series what seems to be a shift towards brain research as a likely beneficiary of the public engagement work accomplished under NNI auspices and, in the case of the Canadian academic, the genomics effort.

The Americans are not the only ones feeling competitive as this tweet from Richard Jones, Pro-Vice Chancellor for Research and Innovation at Sheffield University (UK), physicist, and author of Soft Machines, suggests,

May 18

The UK has fewer than 1% of world patents on graphene, despite it being discovered here, according to the FT –

I recall reading a report a few years back which noted that experts in China were concerned about falling behind internationally in their research efforts. These anxieties are not new, CP Snow’s book and lecture The Two Cultures (1959) also referenced concerns in the UK about scientific progress and being left behind.

Competition/collaboration is an age-old conundrum and about as ancient as anxieties of being left behind. The question now is how are we all going to resolve these issues this time?

ETA May 28, 2014: The American Institute of Physics (AIP) has produced a summary of the May 20, 2014 hearing as part of their FYI: The AIP Bulletin of Science Policy News, May 27, 2014 (no. 93).

ETA Sept. 12, 2014: My first posting about the diminished budget allocation for the US NNI was this March 31, 2014 posting.

Textiles laced with carbon nanotubes for clothing that protects against poison gas

The last time I featured carbon nanotube-infused clothing was in a Nov. 4, 2013 post featuring a $20,000+ bulletproof business suit. It now seems that carbon nanotubes in clothing might also be used to protect the wearer against poison gases (from a May 7, 2014 news item on Nanowerk; Note:  A link has been removed),

Nerve agents are among the world’s most feared chemical weapons, but scientists at the National Institute of Standards and Technology (NIST) have demonstrated a way to engineer carbon nanotubes to dismantle the molecules of a major class of these chemicals (“Functionalized, carbon nanotube material for the catalytic degradation of organophosphate nerve agents”). In principle, they say, the nanotubes could be woven into clothing that destroys the nerve agents on contact before they reach the skin.

A May 6, 2014 US NIST news release, which originated the news item, describes the research in more detail,

The team’s experiments show that [carbon] nanotubes—special molecules that resemble cylinders formed of chicken wire—can be combined with a copper-based catalyst able to break apart a key chemical bond in the class of nerve agents that includes Sarin. A small amount of catalyst can break this bond in a large number of molecules, potentially rendering a nerve agent far less harmful. Because nanotubes further enhance the breakdown capability of the catalyst and can be woven into fabric easily, the NIST team members say the findings could help protect military personnel involved in cleanup operations.

Sarin—used in a 1995 Tokyo subway attack—is one of several deadly nerve agents of a group called organophosphates. Many are classified as weapons of mass destruction. While organophosphates are harmful if inhaled, they also are dangerous if absorbed through the skin, and can be even be re-released from clothing if not thoroughly decontaminated.

To protect themselves during research, the team did not work with actual nerve agents, but instead used a “mimic molecule” that contains a chemical bond identical to the one found in organophosphates. Breaking this bond splits the molecule into pieces that are far less dangerous.

The team developed a way to attach the catalyst molecule to the nanotubes and then tested the effectiveness of the tube-catalyst complex to break the bonds. To perform the test, the complex was deposited onto a small sheet of paper and put into a solution containing the mimic molecule. For comparison, the catalyst without nanotubes was tested simultaneously in a different solution. Then it was a simple matter of stirring and watching chemistry in action.

“The solution was initially transparent, almost like water,” says the team’s John Heddleston, “but as soon as we added the paper, the solution started to turn yellow as the breakdown product accumulated. Measuring this color change over time told us the amount and rate of catalysis. We began to see a noticeable difference within an hour, and the longer we left it, the more yellow it became.” The catalyst-nanotube complex far outperformed the catalyst alone.

Principal investigator Angela Hight Walker says that several questions will need to be addressed before catalytic nanotubes start showing up in clothing, such as whether it is better to add the catalyst to the nanotubes before or after they are woven into the fabric.

“We’d also like to find ways to make the catalytic reaction go faster, which is always better,” Hight Walker says. “But our research group has been focusing on the fundamental science of nanoparticles for years, so we are in a good position to answer these questions.”

It’s not clear to me if this technique of combining carbon nanotubes with copper for protection against poison gas will affect, adversely or otherwise, the bulletproofing properties associated with carbon nanotubes. In any event, here’s a link to and a citation for the paper from the NIST researchers,

Functionalized, carbon nanotube material for the catalytic degradation of organophosphate nerve agents by Mark M. Bailey, John M. Heddleston, Jeffrey Davis, Jessica L. Staymates, & Angela R. Hight Walker.  Nano Research March 2014, Volume 7, Issue 3, pp 390-398

This paper is behind a paywall.

Getting to know your piezoelectrics

It took me a couple of tries before I could see the butterfly in the neutron scattering image (on the left), which illustrates work undertaken in an attempt to better understand piezoelectrics (found in hard drives, loud speakers, etc.) by researchers at Simon Fraser University (Vancouver area, Canada) and the US National Institute of Standards and Technology.

These two neutron scattering images represent the nanoscale structures of single crystals of PMN and PZT. Because the atoms in PMN deviate slightly from their ideal positions, diffuse scattering results in a distinctive "butterfly" shape quite different from that of PZT, in which the atoms are more regularly spaced. Credit: NIST

These two neutron scattering images represent the nanoscale structures of single crystals of PMN and PZT. Because the atoms in PMN deviate slightly from their ideal positions, diffuse scattering results in a distinctive “butterfly” shape quite different from that of PZT, in which the atoms are more regularly spaced.
Credit: NIST

A Jan. 30, 2014 news release on EurekAlert (also found on on the NIST website where it’s dated Jan. 29, 2014) describes piezoelectrics,

Piezoelectrics—materials that can change mechanical stress to electricity and back again—are everywhere in modern life. Computer hard drives. Loud speakers. Medical ultrasound. Sonar. Though piezoelectrics are a widely used technology, there are major gaps in our understanding of how they work. Now researchers at the National Institute of Standards and Technology (NIST) and Canada’s Simon Fraser University believe they’ve learned why one of the main classes of these materials, known as relaxors, behaves in distinctly different ways from the rest and exhibit the largest piezoelectric effect. And the discovery comes in the shape of a butterfly. …

The news release goes on to explain piezoelectrics and provide details about how the researchers made their discovery,

The team examined two of the most commonly used piezoelectric compounds—the ferroelectric PZT and the relaxor PMN—which look very similar on a microscopic scale. Both are crystalline materials composed of cube-shaped unit cells (the basic building blocks of all crystals) that contain one lead atom and three oxygen atoms. The essential difference is found at the centers of the cells: in PZT these are randomly occupied by either one zirconium atom or one titanium atom, both of which have the same electric charge, but in PMN one finds either niobium or manganese, which have very different electric charges. The differently charged atoms produce strong electric fields that vary randomly from one unit cell to another in PMN and other relaxors, a situation absent in PZT.

“PMN-based relaxors and ferroelectric PZT have been known for decades, but it has been difficult to identify conclusively the origin of the behavioral differences between them because it has been impossible to grow sufficiently large single crystals of PZT,” says the NIST Center for Neutron Research (NCNR)’s Peter Gehring. “We’ve wanted a fundamental explanation of why relaxors exhibit the greatest piezoelectric effect for a long time because this would help guide efforts to optimize this technologically valuable property.”

A few years ago, scientists from Simon Fraser University found a way to make crystals of PZT large enough that PZT and PMN crystals could be examined with a single tool for the first time, permitting the first apples-to-apples comparison of relaxors and ferroelectrics. That tool was the NCNR’s neutron beams, which revealed new details about where the atoms in the unit cells were located. In PZT, the atoms sat more or less right where they were expected, but in the PMN, their locations deviated from their expected positions—a finding Gehring says could explain the essentials of relaxor behavior.

“The neutron beams scatter off the PMN crystals in a shape that resembles a butterfly,” Gehring says. “It gives a characteristic blurriness that reveals the nanoscale structure that exists in PMN—and in all other relaxors studied with this method as well—but does not exist in PZT. It’s our belief that this butterfly-shaped scattering might be a characteristic signature of relaxors.”

Additional tests the team performed showed that PMN-based relaxors are over 100 percent more sensitive to mechanical stimulation compared to PZT, another first-time measurement. Gehring says he hopes the findings will help materials scientists do more to optimize the behavior of piezoelectrics generally.

Here’s a citation for the researchers’ paper,

Role of random electric fields in relaxors by Daniel Phelan, Christopher Stock, Jose A. Rodriguez-Rivera, Songxue Chia, Juscelino Leão, Xifa Long, Yujuan Xie, Alexei A. Bokov, Zuo-Guang Ye, Panchapakesan Ganesh, and Peter M. Gehring. Proceedings of the National Academy of Sciences, Jan. 21, 2014. DOI:10.1073/pnas.1314780111

This paper is behind a paywall.