Tag Archives: rare earths

Alternative to rare earth magnets synthesized at Virginia Commonwealth University (US)

There’s a lot of interest in finding alternatives to rare earths given that China has been restricting exports (this Nov. 25, 2010 post describes the situation which hasn’t changed much, as far as I know). Should the research at the Virginia Commonwealth University highlighted in a June 1, 2015 news item on Nanotechnology Now present a viable alternative to rare earths the geopolitical situation should undergo some interesting changes,

A team of scientists at Virginia Commonwealth University has synthesized a powerful new magnetic material that could reduce the dependence of the United States and other nations on rare earth elements produced by China.

“The discovery opens the pathway to systematically improving the new material to outperform the current permanent magnets,” said Shiv Khanna, Ph.D., a commonwealth professor in the Department of Physics in the College of Humanities and Sciences.

A June 1, 2015 Virginia Commonwealth University news release by Brian McNeill (also on EurekAlert), which originated the news item, describes the achievement in more detail,

The new material consists of nanoparticles containing iron, cobalt and carbon atoms with a magnetic domain size of roughly 5 nanometers. It can store information up to 790 kelvins with thermal and time-stable, long-range magnetic order, which could have a potential impact for data storage application.

When collected in powders, the material exhibits magnetic properties that rival those of permanent magnets that generally contain rare earth elements. The need to generate powerful magnets without rare earth elements is a strategic national problem as nearly 70 to 80 percent of the current rare earth materials are produced in China.

Permanent magnets, specifically those containing rare earth metals, are an important component used by the electronics, communications and automobile industries, as well as in radars and other applications.

Additionally, the emergence of green technology markets – such as hybrid and electric vehicles, direct drive wind turbine power systems and energy storage systems – have created an increased demand for permanent magnets.

However, China is the main supplier of world rare earth demands and has tried to impose restrictions on their export, creating an international problem.

The current paper is a joint experimental theoretical effort in which the new material was synthesized, characterized and showed improved characteristics following the theoretical prediction.

“This is good science along with addressing a problem with national importance,” said Ahmed El-Gendy, a former postdoctoral associate in the Department of Chemistry in the College of Humanities and Sciences and a co-author of the paper.

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

Experimental evidence for the formation of CoFe2C phase with colossal magnetocrystalline-anisotropy by Ahmed A. El-Gendy, Massimo Bertino, Dustin Clifford, Meichun Qian, Shiv N. Khanna, and Everett E. Carpenter. Appl. Phys. Lett. 106, 213109 (2015); http://dx.doi.org/10.1063/1.4921789

This is an open access paper.

Europe’s search for raw materials and hopes for nanotechnology-enabled solutions

A Feb. 27, 2015 news item on Nanowerk highlights the concerns over the availability of raw materials and European efforts to address those concerns,

Critical raw materials’ are crucial to many European industries but they are vulnerable to scarcity and supply disruption. As such, it is vital that Europe develops strategies for meeting the demand for raw materials. One such strategy is finding methods or substances that can replace the raw materials that we currently use. With this in mind, four EU projects working on substitution in catalysis, electronics and photonics presented their work at the Third Innovation Network Workshop on substitution of Critical Raw Materials hosted by the CRM_INNONET project in Brussels earlier this month [February 2015].

A Feb. 26, 2015 CORDIS press release, which originated the news item, goes on to describe four European Union projects working on nanotechnology-enabled solutions,

NOVACAM

NOVACAM, a coordinated Japan-EU project, aims to develop catalysts using non-critical elements designed to unlock the potential of biomass into a viable energy and chemical feedstock source.

The project is using a ‘catalyst by design’ approach for the development of next generation catalysts (nanoscale inorganic catalysts), as NOVACAM project coordinator Prof. Emiel Hensen from Eindhoven University of Technology in the Netherlands explained. Launched in September 2013, the project is developing catalysts which incorporate non-critical metals to catalyse the conversion of lignocellulose into industrial chemical feedstocks and bio-fuels. The first part of the project has been to develop the principle chemistry while the second part is to demonstrate proof of process. Prof. Hensen predicts that perhaps only two of three concepts will survive to this phase.

The project has already made significant progress in glucose and ethanol conversion, according to Prof. Hensen, and has produced some important scientific publications. The consortium is working with and industrial advisory board comprising Shell in the EU and Nippon Shokubai in Japan.

FREECATS

The FREECATS project, presented by project coordinator Prof. Magnus Rønning from the Norwegian University of Science and Technology, has been working over the past three years to develop new metal-free catalysts. These would be either in the form of bulk nanomaterials or in hierarchically organised structures – both of which would be capable of replacing traditional noble metal-based catalysts in catalytic transformations of strategic importance.

Prof. Magnus Rønning explained that the application of the new materials could eliminate the need for the use for platinum group metals (PGM) and rare earth metals – in both cases Europe is very reliant on other countries for these materials. Over the course of its research, FREECATS targeted three areas in particular – fuel cells, the production of light olefins and water and wastewater purification.

By working to replace the platinum in fuel cells, the project is supporting the EU’s aim of replacing the internal combustion engine by 2050. However, as Prof. Rønning noted, while platinum has been optimized for use over several decades, the materials FREECATS are using are new and thus come with their new challenges which the project is addressing.

HARFIR

Prof. Atsufumi Hirohata of the University of York in the United Kingdom, project coordinator of HARFIR, described how the project aims to discover an antiferromagnetic alloy that does not contain the rare metal Iridium. Iridium is becoming more and more widely used in numerous spin electronic storage devices, including read heads in hard disk drives. The world supply depends on Platinum ore that comes mainly from South Africa. The situation is much worse than for other rare earth elements as the price has been shooting up over recent years, according to Prof. Hirohata.

The HARFIR team, divided between Europe and Japan, aims to replace Iridium alloys with Heusler alloys. The EU team, led by Prof. Hirohata, has been working on the preparation of polycrystalline and epitaxial thin films of Heusler Alloys, with the material design led by theoretical calculations. The Japanese team, led by Prof. Koki Takanashi at Tohoku University, is meanwhile working on the preparation of epitaxial thin films, measurements of fundamental properties and structural/magnetic characterisation by neutron and synchrotron x-ray beams.

One of the biggest challenges has been that Heusler alloys have a relatively complicated atomic structure. In terms of HARFIR’s work, if any atomic disordering at the edge of nanopillar devices, the magnetic properties that are needed are lost. The team is exploring solutions to this challenge.

IRENA

Prof. of Esko Kauppinen Aalto University in Finland closed off the first session of the morning with his presentation of the IRENA project. Launched in September 2013, the project will run until mid 2017 working towards the aim of developing high performance materials, specifically metallic and semiconducting single-walled carbon nanotube (SWCNT) thin films to completely eliminate the use of the critical metals in electron devices. The ultimate aim is to replace Indium in transparent conducting films, and Indium and Gallium as a semiconductor in thin film field effect transistors (TFTs).

The IRENA team is developing an alternative that is flexible, transparent and stretchable so that it can meet the demands of the electronics of the future – including the possibility to print electronics.

IRENA involves three partners from Europe and three from Japan. The team has expertise in nanotube synthesis, thin film manufacturing and flexible device manufacturing, modelling of nanotube growth and thin film charge transport processes, and the project has benefitted from exchanges of team members between institutions. One of the key achievements so far is that the project has succeeded in using a nanotube thin film for the first time as the both the electrode and hole blocking layer in an organic solar cell.

You’ll note that Japan is a partner in all of these projects. In all probability, these initiatives have something to do with rare earths which are used in much of today’s electronics technology and Japan is sorely lacking in those materials. China, by comparison, has dominated the rare earths export industry and here’s an excerpt from my Nov. 1, 2013 posting where I outline the situation (which I suspect hasn’t changed much since),

As for the short supply mentioned in the first line of the news item, the world’s largest exporter of rare earth elements at 90% of the market, China, recently announced a cap according to a Sept. 6, 2013 article by David Stanway for Reuters. The Chinese government appears to be curtailing exports as part of an ongoing, multi-year strategy. Here’s how Cientifica‘s (an emerging technologies consultancy, etc.) white paper (Simply No Substitute?) about critical materials published in 2012 (?), described the situation,

Despite their name, REE are not that rare in the Earth’s crust. What has happened in the past decade is that REE exports from China undercut prices elsewhere, leading to the closure of mines such as the Mountain Pass REE mine in California. Once China had acquired a dominant market position, prices began to rise. But this situation will likely ease. The US will probably begin REE production from the Mountain Pass mine later in 2012, and mines in other countries are expected to start operation soon as well.

Nevertheless, owing to their broad range of uses REE will continue to exert pressures on their supply – especially for countries without notable REE deposits. This highlights two aspects of importance for strategic materials: actual rarity and strategic supply issues such as these seen for REE. Although strategic and diplomatic supply issues may have easier solutions, their consideration for manufacturing industries will almost be the same – a shortage of crucial supply lines.

Furthermore, as the example of REE shows, the identification of long-term supply problems can often be difficult, and not every government has the same strategic foresight that the Chinese demonstrated. And as new technologies emerge, new elements may see an unexpected, sudden demand in supply. (pp. 16-17)

Meanwhile, in response to China’s decision to cap its 2013 REE exports, the Russian government announced a $1B investment to 2018 in rare earth production,, according to a Sept. 10, 2013 article by Polina Devitt for Reuters.

I’m not sure you’ll be able to access Tim Harper’s white paper as he is now an independent, serial entrepreneur. I most recently mentioned him in relation to his articles (on Azonano) about the nanotechnology scene in a Feb. 12, 2015 posting where you’ll also find contact details for him.

Purple promises and bioimaging from Singapore’s A*STAR

A May 7, 2014 news item on Nanowerk describes a promising new approach to bioimaging,

Labeling biomolecules with light-emitting nanoparticles is a powerful technique for observing cell movement and signaling under realistic, in vivo conditions. The small size of these probes, however, often limits their optical capabilities. In particular, many nanoparticles have trouble producing high-energy light with wavelengths in the violet to ultraviolet range, which can trigger critical biological reactions.

Now, an international team led by Xiaogang Liu from the A*STAR Institute of Materials Research and Engineering and the National University of Singapore has discovered a novel class of rare-earth nanocrystals that preserve excited energy inside their atomic framework, resulting in unusually intense violet emissions …

A May 7, 2014 A*STAR (Agency for Science, Technology and Research) news release (h/t Imagist), which originated the news item, describes the problems with current bioimaging techniques and the new approach in more detail (Note: Links have been removed)

Nanocrystals selectively infused, or ‘doped’, with rare-earth ions have attracted the attention of researchers, because of their low toxicity and ability to convert low-energy laser light into violet-colored luminescence emissions — a process known as photon upconversion. Efforts to improve the intensity of these emissions have focused on ytterbium (Yb) rare-earth dopants, as they are easily excitable with standard lasers. Unfortunately, elevated amounts of Yb dopants can rapidly diminish, or ‘quench’, the generated light.

This quenching probably arises from the long-range migration of laser-excited energy states from Yb and toward defects in the nanocrystal. Most rare-earth nanocrystals have relatively uniform dopant distributions, but Liu and co-workers considered that a different crystal arrangement — clustering dopants into multi-atom arrays separated by large distances — could produce localized excited states that do not undergo migratory quenching.

The team screened numerous nanocrystals with different symmetries before discovering a material that met their criteria: a potassium fluoride crystal doped with Yb and europium rare earths (KYb2F7:Eu). Experiments revealed that the isolated Yb ‘energy clusters’ inside this pill-shaped nanocrystal (see image) enabled substantially higher dopant concentrations than usual — Yb accounted for up to 98 per cent of the crystal’s mass — and helped initiate multiphoton upconversion that yielded violet light with an intensity eight times higher than previously seen.

The researchers then explored the biological applications of their nanocrystals by using them to detect alkaline phosphatases, enzymes that frequently indicate bone and liver diseases. When the team brought the nanocrystals close to an alkaline phosphate-catalyzed reaction, they saw the violet emissions diminish in direct proportion to a chemical indicator produced by the enzyme. This approach enables swift and sensitive detection of this critical biomolecule at microscale concentration levels.

“We believe that the fundamental aspects of these findings — that crystal structures can greatly influence luminescence properties — could allow upconversion nanocrystals to eventually outperform conventional fluorescent biomarkers,” says Liu.

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

Enhancing multiphoton upconversion through energy clustering at sublattice level by Juan Wang, Renren Deng, Mark A. MacDonald, Bolei Chen, Jikang Yuan, Feng Wang, Dongzhi Chi, Tzi Sum Andy Hor, Peng Zhang, Guokui Liu, Yu Han, & Xiaogang Liu. Nature Materials 13, 157–162 (2014) doi:10.1038/nmat3804 Published online 24 November 2013

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

Biomining for rare earth elements with Alberta’s (Canada) Ingenuity Lab

Alberta’s Ingenuity Lab and its biomining efforts are being featured in a Feb. 3, 2014 Nanowerk Spotlight article which was supplied by Ingenuity Lab (Note: A link has been removed),

Scientists at Ingenuity Lab in Edmonton, Alberta are taking cues from nature, as they focus on nanotechnology gains in the area of biomining. Using microorganisms and biomolecules, the group is making significant advances in the recovery of rare earth and precious metals from industrial processes and the environment thanks to superior molecular recognition techniques.

In recent decades, the utility of protein/peptide molecules and their inorganic material recognition and binding abilities has come to light. Combinatorial biology tools have enabled researchers to select peptides for various materials such as ceramics, metal oxides, alloys and pure metals. Even though the binding mechanism of peptides hasn’t yet been fully resolved, studies are ongoing and these peptides continue to be used in many nanotechnology applications.

The Spotlight article further describes the approach being undertaken,

… researchers at Alberta’s first nanotechnology accelerator laboratory (Ingenuity Lab) are looking to take advantage of inorganic binding peptides for mining valuable and rare earth elements/metals that exist in nature or synthetic materials.

Rare earth elements (REE) are sought after materials that facilitate the production of electrical car batteries, high power magnets, lasers, fiber optic technology, MRI contrast agents, fluorescent lightening and much more. Despite increasing demand, mining and processing yields are not enough to satisfy the growing need. This is mainly due to the great loss during mining (25-50%) and beneficiation (10-30%).

Since REEs exist as a mixture in mineral ores, their beneficiation and separation into individual metals requires unique processes. Depending on the chemical form of the metal, different compounds are necessary during beneficiation steps to convert minerals into metal nitrates, oxides, chlorides and fluorides, which would be further extracted individually. Furthermore, this process must be followed with solvent separation to obtain individual metals. These excessive steps not only increase the production cost and energy consumption but also decrease the yield and generate environmental pollution due to the use of various chemicals and organic solvents.

…  Ingenuity Lab is working on generating smart biomaterials composed of inorganic binding peptides coated on the core of magnetic nanoparticles. These smart materials will expose two functions; first they will recognize and bind to a specific REE through the peptide region and they will migrate to magnetic field by the help of Iron Oxide core.

You can find more detail and illustrations in the Spotlight article.

There is biomining research being performed in at least one other lab (in China) as I noted in a Nov. 1, 2013 posting about some work to remove REEs from wastewater and where I noted that China had announced a cap on its exports of REEs.

Tim Harper’s Cientifica emerging technologies and business consultancy offers a white paper (free), Simply No Substitute? [2013?], which contextualizes and provides insight into the situation with REEs and other other critical materials. From Cientifica’s Simply No Substitute? webpage,

There is increasing concern that restricted supplies of certain metals and other critical minerals could hinder the deployment of future technologies. This new white paper by Cientifica and Material Value,  Simply No Substitute? takes a critical look at the current technology and policy landscape in this vital area, and in particular, the attempts to develop substitutes for critical materials.

A huge amount of research and development is currently taking place in academic and industrial research laboratories, with the aim of developing novel, innovative material substitutes or simply to ‘engineer-out’ critical materials with new designs.  As an example, our analysis shows the number of patents related to substitutes for rare earth elements has doubled in the last two years. However, the necessity and effectiveness of this research activity is still unclear and requires greater insight. Certainly, as this white paper details, there is no universal agreement between Governments and other stakeholders on what materials are at risk of future supply disruptions.

In an effort to ensure the interests of end-users are represented across this increasingly complex and rapidly developing issue, the publication proposes the creation of a new industry body. This will benefit not just end-users, but also primary and secondary producers  of critical materials, for who it is currently only feasible to have sporadic and inconsistent interaction with the diverse range of industries that use their materials.

You can download the white paper from here.

Getting back to Ingenuity Lab, there is no research paper mentioned in the Spotlight article. Their website does offer this on the Mining page,

The extraction of oil and gas is key to the economic prosperity of Alberta and Canada. We have the third largest oil reserves in the world behind Saudi Arabia and Venezuela. Not only is our oil and gas sector expected to generate $2.1 trillion in economic activity across Canada over the next 25 years, Canadian employment is expected to grow from 75,000 jobs in 2010 to 905,000 in 2035. However, it’s not without its impacts to the environment. This, we know. There are great strides being made in technology and innovation in this sector, but what if we could do more?

Then, there’s this from the site’s Biomining subpage,

Using a process called biomining, the research team at Ingenuity Lab is engineering new nano particles that have the capability to detect, extract or even bind to rare earth and precious metals that exist in nature or found in man-made materials.

Leveraging off of the incredible advances in targeted medical therapies, active nanoparticle and membrane technologies offer the opportunity to recover valuable resources from mining operations while leading to the remediation of environmentally contaminated soil and water.

Biomining technology offers the opportunity to maximize the utility of our natural resources, establish a new path forward to restore the pristine land and water of our forefathers and redefine Canada’s legacy of societal environmental, and economic prosperity.

Finally, there’s this page (Ingenuity Attracts Attention with Biomining Advances)  which seems to have originated the Spotlight article and is the source of the images in the Spotlight article.  I am curious as to whose attention they’ve attracted although I can certainly understand why various groups and individuals might be,

… Ingenuity’s system will also be able to work in a continuous flow process. There will be a constant input of metal mixture, which could be mine acid drain, tailing ponds or polluted water sources, and smart biomaterial. Biomaterial will be recovered from the end point of the chamber together with the targeted metal. Since the interaction between the peptide and the metal of interest is not covalent bonding, metal will be removed from the material without the need for harsh chemicals. This means valuable materials, currently discarded as waste, will be accessible and the reuse of the smart biomaterial will be an option, lowering the purification cost even more.

These exciting discoveries are welcome news for the mining industry and the environment, but also for communities around the world and generations to come.  Thanks to ingenuity, we will soon be able to maximize the utility of our precious resources as we restore damaged lands and water.

In any event I hope to hear more about this promising work with more details (such as:  At what stage is this work?, Is it scalable?) and the other research being performed at Ingenuity Lab.

Alberta’s (Canada) Ingenuity Lab and its nanotechnology dreams

I believe the Nov. 6, 2013 news release from Alberta’s Ingenuity Lab was meant to announce this new lab’s existence (why does Alberta need another nanotechnology-focused institution?),

Alberta’s first accelerator laboratory brings together some of nanotechnology’s leading players to make small science have a big impact in Alberta, by harnessing and commercializing emerging technologies, and simultaneously addressing some of the grand challenges faced by our province.

“We still have an incredible amount to learn from nature. This we know,” says Ingenuity Lab Director, Dr. Carlo Montemagno. “The opportunity in front of us is the potential to create a bio-enabled, globally-competitive and value-added industry while training the next generation of researchers and innovators in Alberta.”

With a research team of 25 strong and growing, Ingenuity Lab is focusing its research on the mining, energy, agriculture and health sectors, and is a $40 million provincial government led initiative working in partnership with the National Institute for Nanotechnology (NINT), Campus Alberta and industry.

Alberta already hosts the National Institute of Nanotechnology (which was and perhaps still is partially funded by the province of Alberta) and there’s ACAMP “(Alberta Centre for Advanced MNT Products) is a not for profit organization that provides specialized services to micro nano technology clients. Clients have access to world-class equipment, facilities …” Both the University of Alberta and the University of Calgary have any number of labs dedicated to nanotechnology research and then there’s nanoAlberta which now lives on as part of  Alberta Innovates where* it’s listed on their Programs and Services page. It seems to me they have a number of organizations devoted to nanotechnology research and/or commercialization in Alberta. By the way, Canada’s National Institute of Nanotechnology (NINT) can still be found on two different websites; there’s the NINT on the National Research Council of Canada website and there’s the NINT on the University of Alberta website.

While the lab’s Nov. 19, 2013 news release (h/t Nanowerk) explores the lab’s goals, it doesn’t really answer the question: why another one?,

Dr. Carlo Montemagno and a world-class team of researchers are working across disciplines to identify innovative solutions to some of the province’s most difficult issues, including optimal resource extraction while enhancing environmental stewardship of Alberta’s signature natural resources [oil sands].

“Nanotechnology will have a significant impact on Canada’s economic prosperity and global competitive advantage,” says Ingenuity Lab Director, Dr. Carlo Montemagno.  “This enhanced understanding of matter will provide the necessary underpinning for revolutionary discoveries across disciplines that will forever change the way we envisage the future.”

Ingenuity Lab is applying recent advances in targeted drug delivery and other areas to develop novel technologies that will enable the recovery of valuable materials, currently discarded as waste, from our industrial operations and the environment.

The Ingenuity research team is engineering new materials that have the capability to detect, extract and bind to rare earth and precious metals that exist in nature or synthetic materials. As this approach is refined, it will spawn a variety of applications like reclamation of trace amounts of valuable or harmful materials from soil, water and industrial process streams, including tailing ponds.

“Our molecular recognition techniques, what we call biomining, offer the ability to maximize the utility of our resources, establish a new path forward to restore damaged lands and water and to reaffirm Canada’s commitment to societal and economic prosperity,” says Dr. Montemagno. “The further we delve into the very makeup of the natural and inorganic components of our universe, the more opportunities we uncover. This radical shift away from conventional thinking means that we leverage research gains beyond their intended purpose. We achieve a multiplier effect that increases the capacity of nanotechnology to address the grand challenges facing modern industrial societies.”

I became a little curious about Dr. Montemagno and found this on the Ingenuity Lab’s About the Director page,

Dr. Carlo Montemagno

“The purpose of scientific study is to create new knowledge by working at the very edge where world-changing knowledge unfolds.” – C. Montemagno

Driven by the principles of excellence, honor and responsibility and an unwavering commitment to education as an engine of economic prosperity, Dr. Montemagno has become a world-renowned expert in nanotechnology and is responsible for creating groundbreaking innovations which solve complex challenges in the areas of informatics, agriculture, chemical refining, transportation, energy, and healthcare.

He was Founding Dean of the College of Engineering and Applied Sciences at University of Cincinnati; received a Bachelor of Science degree in Agriculture and Bio Engineering from Cornell University; a Master’s Degree  in Petroleum and Natural Gas Engineering from Penn State and a Ph.D. in Civil Engineering and Geological Sciences from Notre Dame.

“Research and education are critical to success because the transfer of knowledge creates economic prosperity.” — C. Montemagno

Dr. Montemagno has been recognized with prestigious awards including the Feynman Prize (for creating single molecule biological motors with nano-scale silicon devices); the Earth Award Grand Prize (for cell-free artificial photosynthesis with over 95% efficiency); the CNBC Business Top 10 Green Innovator award (for Aquaporin Membrane water purification and desalination technology); and named a Bill & Melinda Gates Grand Challenge Winner (for a pH sensing active microcapsule oral vaccine delivery system which increased vaccine stability and demonstrated rapid uptake in the lower GI tract.)

Despite my doubts, I wish the Ingenuity Lab folks good luck with their efforts.

*where’s changed to where, Feb. 3, 2014

News of nanotechnology-enabled recovery of rare earth elements from industrial wastewater and some rare earths context

An Oct. 31, 2013 news item on Azonano features information about rare earth elements and their use in technology along with a new technique for recycling them from wastewater,

Many of today’s technologies, from hybrid car batteries to flat-screen televisions, rely on materials known as rare earth elements (REEs) that are in short supply, but scientists are reporting development of a new method to recycle them from wastewater.

The process, which is described in a study in the journal ACS [American Chemical Society] Applied Materials & Interfaces, could help alleviate economic and environmental pressures facing the REE industry.

… Attempts so far to recycle them from industrial wastewater are expensive or otherwise impractical. A major challenge is that the elements are typically very diluted in these waters. The team knew that a nanomaterial known as nano-magnesium hydroxide, or nano-Mg(OH)2, was effective at removing some metals and dyes from wastewater. So they set out to understand how the compound worked and whether it would efficiently remove diluted REEs, as well.

The Oct. 30, 2013 ACS PressPac news release, which originated the news item, provides a few details about how the scientists tested their approach,

To test their idea, they produced inexpensive nano-Mg(OH)2 particles, whose shapes resemble flowers when viewed with a high-power microscope. They showed that the material captured more than 85 percent of the REEs that were diluted in wastewater in an initial experiment mimicking real-world conditions. “Recycling REEs from wastewater not only saves rare earth resources and protects the environment, but also brings considerable economic benefits,” the researchers state. “The pilot-scale experiment indicated that the self-supported flower-like nano-Mg(OH)2 had great potential to recycle REEs from industrial wastewater.”

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

Recycling Rare Earth Elements from Industrial Wastewater with Flowerlike Nano-Mg(OH)2 by Chaoran Li †‡, Zanyong Zhuang, Feng Huang, Zhicheng Wu, Yangping Hong, and Zhang Lin. ACS Appl. Mater. Interfaces, 2013, 5 (19), pp 9719–9725 DOI: 10.1021/am4027967 Publication Date (Web): September 13, 2013

Copyright © 2013 American Chemical Society

As for the short supply mentioned in the first line of the news item, the world’s largest exporter of rare earth elements at 90% of the market, China, recently announced a cap according to a Sept. 6, 2013 article by David Stanway for Reuters. The Chinese government appears to be curtailing exports as part of an ongoing, multi-year strategy. Here’s how Cientifica‘s (an emerging technologies consultancy, etc.) white paper (Simply No Substitute?) about critical materials published in 2012 (?), described the situation,

Despite their name, REE are not that rare in the Earth’s crust. What has happened in the past decade is that REE exports from China undercut prices elsewhere, leading to the closure of mines such as the Mountain Pass REE mine in California. Once China had acquired a dominant market position, prices began to rise. But this situation will likely ease. The US will probably begin REE production from the Mountain Pass mine later in 2012, and mines in other countries are expected to start operation soon as well.

Nevertheless, owing to their broad range of uses REE will continue to exert pressures on their supply – especially for countries without notable REE deposits. This highlights two aspects of importance for strategic materials: actual rarity and strategic supply issues such as these seen for REE. Although strategic and diplomatic supply issues may have easier solutions, their consideration for manufacturing industries will almost be the same – a shortage of crucial supply lines.

Furthermore, as the example of REE shows, the identification of long-term supply problems can often be difficult, and not every government has the same strategic foresight that the Chinese demonstrated. And as new technologies emerge, new elements may see an unexpected, sudden demand in supply. (pp. 16-17)

Meanwhile, in response to China’s decision to cap its 2013 REE exports, the Russian government announced a $1B investment to 2018 in rare earth production,, according to a Sept. 10, 2013 article by Polina Devitt for Reuters.

For those who like to get their information in a more graphic form, here’s an infographic from Thomson Reuters from a May 13, 2012 posting on their eponymous blog,

Rare Earth Metals - Graphic of the Day Credit:  Thomson Reuters [downloaded from http://blog.thomsonreuters.com/index.php/rare-earth-metals-graphic-of-the-day/]

Rare Earth Metals – Graphic of the Day Credit: Thomson Reuters [downloaded from http://blog.thomsonreuters.com/index.php/rare-earth-metals-graphic-of-the-day/]

There is a larger version on  their blog.

All of this serves to explain the interest in recycling REE from industrial wastewater. Surprisingly,, the researchers who developed this new recycling technique are based in China which makes me wonder if the Chinese government sees a future where it too will need to import rare earths as its home sources diminish.

Buckyball legal suit: all about toys, rare earths, and magnets

The July 27, 2012 news item by Gary Thomas on Azonano highlights a legal suit involving Maxfield & Obertontoys that happen to be called Buckyballs and Buckycubes. From the news item,

The United States Consumer Product Safety Commission (CPSC) has filed a complaint against New York based Maxfield & Oberton Holdings LLC over their Buckyballs and Buckycube desk toys subsequent to a 3-1 Commission vote approving the filing of complaint.

The complaint seeks an order on the firm to prohibit sale of Buckyballs and Buckycubes, to inform the public about the defect and also refund the consumers in full for purchases made. …

Despite cooperative efforts by CPSC and Maxfield & Oberton to educate buyers that the products are meant for adults, reports of swallowing incidents and injuries kept coming in.

Before I go further, here’s what the toy looks like,

downloaded from Maxfield & Oberton’s http://www.getbuckyballs.com/ home page

The problem is that the small spherical magnets contain rare earths and are being swallowed by children and teenagers resulting in serious injury. I found more details about the situation in the July 25, 2012 news release issued by the CPSC (Note: I have removed some links) ,

In May 2010, CPSC and Maxfield & Oberton announced a cooperative recall of about 175,000 Buckyball high powered magnets sets, because they were labeled “Ages 13+” and did not meet the federal mandatory toy standard, F963-08. The standard requires that such powerful loose as received magnets not be sold for children younger than 14.

The Buckyballs and Buckycubes sets contain up to 216 powerful rare earth magnets.

In November 2011, CPSC and Maxfield & Oberton worked cooperatively to inform and educate consumers that Buckyballs were intended for adult use only, and although the risk scenarios differ by age group, the danger when multiple rare earth magnets are ingested is the same. However, even after the safety alert, ingestions and injuries continued to occur.

Here’s more about the number of injuries associated with the Maxfield & Oberton toys and more about how children and why teenagers accidentally swallow the magnets (from the CPSC news release),

Since 2009, CPSC staff has learned of more than two dozen ingestion incidents, with at least one dozen involving Buckyballs. Surgery was required in many of incidents. The Commission staff alleges in its complaint that it has concluded that despite the attempts to warn purchasers, warnings and education are ineffective and cannot prevent injuries and incidents with these rare earth magnets.

CPSC has received reports of toddlers finding loose magnets left within reach and placing them in their mouths. It can be extremely difficult for a parent to tell if any of the tiny magnets are missing from a set. In some of the reported incidents, toddlers have accessed loose magnets left on a refrigerator and other parts of the home.

Use of the product by tweens and teenagers to mimic piercings of the tongue, lip or cheek has resulted in incidents where the product is unintentionally inhaled and swallowed. These ingestion incidents occur when children receive it as a gift or gain access to the product in their homes or from friends.

When two or more magnets are swallowed, they can attract to one another through the stomach and intestinal walls, resulting in serious injuries, such as holes in the stomach and intestines, intestinal blockage, blood poisoning and possibly death. Medical professionals may not diagnose the need for immediate medical intervention in such cases, resulting in worsening of the injuries.

Here’s how the CPSC explains the reason for filing suit (from the CPSC news release),

The Commission staff filed the administrative complaint against Maxfield & Oberton after discussions with the company and its representatives failed to result in a voluntary recall plan that CPSC staff considered to be adequate. This type of legal action against a company is rare, as this is only the second administrative complaint filed by CPSC in the past 11 years.

Michelle Castillo’s July 26, 2012 news item for CBS News provides more background,

Currently marketed to adults, the CPSC reported that more than 2 million Buckyballs have been sold in the U.S., as well as 200,000 Buckycubes. Each container has anywhere from between 10 to 216 small magnets.

CPSC spokesperson Alex Filip told CBSNews.com that there were 22 cases of swallowing these magnets from 2009 to October 2011. One of the most high-profile cases was that of a 3-year-old from Portland, Ore., who swallowed 37 magnets. The girl needed surgery after the balls ripped three holes through her intestines.

The American Academy of Pediatrics (AAP)said in a statement that they agreed with the CSPS complaint, adding that the minute size of the magnets made it hard for caregivers to see if one is missing. A survey of North American Society for Pediatric Gastroenterology, Hepatology, and Nutrition members found that there have been more than 60 magnet ingestion cases over the last two years, which necessitated 26 surgeries and involved 23 bowel perforations. It wasn’t stated how many of these cases were related to Buckyball or Buckycube magnets. [emphasis mine]

According to the CPSC information, there were a dozen or more  incidents associated with the Buckyball/Buckycube magnets. I’m unclear as to how many incidents that is per year since 2009 – 2011 could be considered either two years (e.g. July 2009 – July 2011) or three years (Jan. – Dec. of 2009, 2010, and 2011). Regardless,  either four or six incidents per year in the US have been attributed to these Maxfield & Oberton toys (or, seven to eleven incidents based on the total number [22] of accidents involving the ingestion of these kinds of magnets).

Maxfield & Oberton’s response covers a number of points,

“We are deeply disappointed that the CPSC has decided to go after our firm – and magnets in general. Magnets have been around for centuries and are used for all sorts of purposes. Our products are marketed to those 14 and above and out of over half a billion magnets in the market place CPSC has received reports of less than two-dozen cases of misuse. We worked with the Commission in order to do an education video less than 9 months ago, so we are shocked they are taking this action. We find it unfair, unjust and un-American,” added Zucker [Craig Zucker, founder and Chief Executive Officer]. “We will vigorously fight this action taken by President Obama’s hand picked agency.”

Maxfield believes the CPSC is now taking the absurd position that warnings can never work. By doing so, CPSC has called into question the efficacy of all of the warnings the agency relies upon including its recently announced program to warn about the risk of strangulation posed by cords on baby monitors, cords that have been involved in 7 deaths.

What will CPSC do about drowning for which its remedy is warnings?

For balloons involved in several deaths each year, the Commission warns about the risk of suffocation from uninflated or broken balloons and says “Adult supervision required.” But for some reason when it comes to an American company that sells Buckyballs® exclusively to adults, the CPSC takes a different approach and decides that warnings don’t work. The Company believes the CPSC can’t have it both ways.

While this isn’t a nanotechnology story as such, despite what the toys are named, it  does illustrate issues around risk s, hazards, and regulations. What are the benefits? What risks are we prepared to tolerate? What are the hazards and how do we mitigate against them? How much regulation do we need? What are the impacts economically and socially?

Rare earths, China, and Nanosys

There’s been some discussion recently about rare earths in the light of tensions between China and Japan. Here’s a brief description of rare earths for anyone who’s not certain what they are, from the Wikipedia essay on rare earths,

… rare earth elements or rare earth metals are a collection of seventeen chemical elements in the periodic table, namely scandium, yttrium, and the fifteen lanthanides.

Despite their name, rare earth elements (with the exception of the highly unstable promethium) are relatively plentiful in the Earth’s crust, with cerium being the 25th most abundant element at 68 parts per million (similar to copper). However, because of their geochemical properties, rare earth elements are not often found in concentrated and economically exploitable forms, generally called rare earth minerals. It was the very scarcity of these minerals (previously called “earths”) that led to the term “rare earth”

Here’s what started the tensions (from the NY Times article by Keith Bradsher),

Chinese customs officials abruptly halted the processing of paperwork for shipments bound for Japan on Sept. 21 [2010]. The shipments were halted during an acrimonious dispute over Japan’s detention of a Chinese fishing trawler that rammed two Japanese coast guard vessels two weeks earlier near islands long controlled by Japan but claimed by China.

Here’s why they’re so important,

Rare earths are vital to the production of a wide range of industrial products, including automobiles, glass, oil refining, computers, smartphones, wind turbines and flat-screen televisions. The military needs them for missiles, sonar systems and the range finders of tanks.

Here are some of the consequences of the ban,

Many factories in China assemble products that require high-tech components from Japan that use rare earths. Some of these factories, which employ large numbers of workers in China, have begun running low on components as Japanese suppliers ran short on some of the more obscure rare earths needed to manufacture them, two rare earth industry executives said.

Electronics industries have been affected, particularly camera manufacturers, leading to a desperate scramble for raw materials that has even included buying tons of obscure rare earth compounds from corporate stockpiles in Europe and airlifting them to Japan.

All 32 of the authorized rare earth exporters in China have refused to increase their shipments to other countries during the unannounced ban on shipments to Japan, making it difficult for Japanese traders to obtain supplies indirectly.

As a result of the blocked shipments, some rare earths now cost up to 10 times as much outside China as inside; the Chinese government has started a vigorous campaign to prevent this from leading to smuggling.

Brasher’s article is very interesting and I do recommend reading all of it.

There has been one other consequence to this concern over a dependency on China’s rare earths (excerpted from the Nov. 23, 2010 article by Ariel Schwartz on Fast Company),

There’s just one problem: The metals are only found in high concentrations in a few sites in China, the U.S., and Australia–and China has threatened to stop exporting its supply. But instead of expanding rare earth metal mines, what if we look for more sustainable replacements?

Enter Nanosys, a company that offers process-ready materials for the LED and energy-storage markets, among other things. Nanosys has been thinking about rare earth material shortages for years, which is why the company manufactures synthetic phosphors out of common materials–not the rare earth materials (i.e. yttrium) usually used in phosphors.

“We make a semiconductor phosphor that employs a nanomaterial called a quantum dot,” explains Nanosys CEO Jason Hartlove. “It’s made out of indium phosphide and phosphorous, and the synthesis process is all in the lab. There’s no heavy metal mining, no destructive mining practices.”

Nanosys’s QuantumRail LED backlighting device is made out of quantum dots, which can purportedly generate brighter and richer colors than their rare earth metal counterparts–all while delivering a higher efficiency and lower cost.

I don’t know how close they are to producing these quantum dots in industrial quantities but the appeal of a process that lessens dependency on resources that have to be mined and/or be used to apply political pressure is undeniable. If you’re interested, you can visit the Nanosys website here.

(They talk about ‘architected’ materials. I view that word with the same enthusiasm I have for ‘impactful’. These people should never be allowed to invent another word, ever again.)