Tag Archives: copper oxides

Canadian research into nanomaterial workplace exposure in the air and on surfaces

An August 30, 2018 news item on Nanowerk announces the report,

The monitoring of air contamination by engineered nanomaterials (ENM) is a complex process with many uncertainties and limitations owing to the presence of particles of nanometric size that are not ENMs, the lack of validated instruments for breathing zone measurements and the many indicators to be considered.

In addition, some organizations, France’s Institut national de recherche et de sécurité (INRS) and Québec’s Institut de recherche Robert-Sauvé en santé et en sécurité du travail (IRSST) among them, stress the need to also sample surfaces for ENM deposits.

In other words, to get a better picture of the risks of worker exposure, we need to fine-tune the existing methods of sampling and characterizing ENMs and develop new one. Accordingly, the main goal of this project was to develop innovative methodological approaches for detailed qualitative as well as quantitative characterization of workplace exposure to ENMs.

A PDF of the 88-page report is available in English or in French.

An August 30, 2018 (?) abstract of the IRSST report titled An Assessment of Methods of Sampling and Characterizing Engineered Nanomaterials in the Air and on Surfaces in the Workplace (2nd edition) by Maximilien Debia, Gilles L’Espérance, Cyril Catto, Philippe Plamondon, André Dufresne, Claude Ostiguy, which originated the news item, outlines what you can expect from the report,

This research project has two complementary parts: a laboratory investigation and a fieldwork component. The laboratory investigation involved generating titanium dioxide (TiO2) nanoparticles under controlled laboratory conditions and studying different sampling and analysis devices. The fieldwork comprised a series of nine interventions adapted to different workplaces and designed to test a variety of sampling devices and analytical procedures and to measure ENM exposure levels among Québec workers.

The methods for characterizing aerosols and surface deposits that were investigated include: i) measurement by direct-reading instruments (DRI), such as condensation particle counters (CPC), optical particle counters (OPC), laser photometers, aerodynamic diameter spectrometers and electric mobility spectrometer; ii) transmission electron microscopy (TEM) or scanning transmission electron microscopy (STEM) with a variety of sampling devices, including the Mini Particle Sampler® (MPS); iii) measurement of elemental carbon (EC); iv) inductively coupled plasma mass spectrometry (ICP-MS) and (v) Raman spectroscopy.

The workplace investigations covered a variety of industries (e.g., electronics, manufacturing, printing, construction, energy, research and development) and included producers as well as users or integrators of ENMs. In the workplaces investigated, we found nanometals or metal oxides (TiO2, SiO2, zinc oxides, lithium iron phosphate, titanate, copper oxides), nanoclays, nanocellulose and carbonaceous materials, including carbon nanofibers (CNF) and carbon nanotubes (CNT)—single-walled (SWCNT) as well as multiwalled (MWCNT).

The project helped to advance our knowledge of workplace assessments of ENMs by documenting specific tasks and industrial processes (e.g., printing and varnishing) as well as certain as yet little investigated ENMs (nanocellulose, for example).

Based on our investigations, we propose a strategy for more accurate assessment of ENM exposure using methods that require a minimum of preanalytical handling. The recommended strategy is a systematic two-step assessment of workplaces that produce and use ENMs. The first step involves testing with different DRIs (such as a CPC and a laser photometer) as well as sample collection and subsequent microscopic analysis (MPS + TEM/STEM) to clearly identify the work tasks that generate ENMs. The second step, once work exposure is confirmed, is specific quantification of the ENMs detected. The following findings are particularly helpful for detailed characterization of ENM exposure:

  1. The first conclusive tests of a technique using ICP-MS to quantify the metal oxide content of samples collected in the workplace
  2. The possibility of combining different sampling methods recommended by the National Institute for Occupational Safety and Health (NIOSH) to measure elemental carbon as an indicator of NTC/NFC, as well as demonstration of the limitation of this method stemming from observed interference with the black carbon particles required to synthesis carbon materials (for example, Raman spectroscopy showed that less than 6% of the particles deposited on the electron microscopy grid at one site were SWCNTs)
  3. The clear advantages of using an MPS (instead of the standard 37-mm cassettes used as sampling media for electron microscopy), which allows quantification of materials
  4. The major impact of sampling time: a long sampling time overloads electron microscopy grids and can lead to overestimation of average particle agglomerate size and underestimation of particle concentrations
  5. The feasibility and utility of surface sampling, either with sampling pumps or passively by diffusion onto the electron microscopy grids, to assess ENM dispersion in the workplace

These original findings suggest promising avenues for assessing ENM exposure, while also showing their limitations. Improvements to our sampling and analysis methods give us a better understanding of ENM exposure and help in adapting and implementing control measures that can minimize occupational exposure.

You can download the full report in either or both English and French from the ‘Nanomaterials – A Guide to Good Practices Facilitating Risk Management in the Workplace, 2nd Edition‘ webpage.

Solar cells and copper sprouts

First, Washington University in St. Louis (WUSTL; located in Missouri, US) announced a discovery about solar cells, then, the university announced a commitment to increase solar output by Fall 2014. Whether these two announcements are linked by some larger policy or strategy is not clear to me but it’s certainly an interesting confluence of events.

An April 26, 2014 news item on Azonano describes the researchers’ discovery,

By looking at a piece of material in cross section, Washington University in St. Louis engineer Parag Banerjee, PhD, and his team discovered how copper sprouts grass-like nanowires that could one day be made into solar cells.

Banerjee, assistant professor of materials science and an expert in working with nanomaterials, Fei Wu, graduate research assistant, and Yoon Myung, PhD, a postdoctoral research associate, also took a step toward making solar cells and more cost-effective.

An April 21, 2014 WUSTL news release by Beth Miller, which originated the news item, describes the research in some detail,

Banerjee and his team worked with copper foil, a simple material similar to household aluminum foil. When most metals are heated, they form a thick metal oxide film. However, a few metals, such as copper, iron and zinc, grow grass-like structures known as nanowires, which are long, cylindrical structures a few hundred nanometers wide by many microns tall. They set out to determine how the nanowires grow.

“Other researchers look at these wires from the top down,” Banerjee says. “We wanted to do something different, so we broke our sample and looked at it from the side view to see if we got different information, and we did.”

The team used Raman spectroscopy, a technique that uses light from a laser beam to interact with molecular vibrations or other movements. They found an underlying thick film made up of two different copper oxides (CuO and Cu2O) that had narrow, vertical columns of grains running through them. In between these columns, they found grain boundaries that acted as arteries through which the copper from the underlying layer was being pushed through when heat was applied, creating the nanowires.

“We’re now playing with this ionic transport mechanism, turning it on and off and seeing if we can get some different forms of wires,” says Banerjee, who runs the Laboratory for Emerging and Applied Nanomaterials (L.E.A.N.).

Like solar cells, the nanowires are single crystal in structure, or a continuous piece of material with no grain boundaries, Banerjee says.

“If we could take these and study some of the basic optical and electronic properties, we could potentially make solar cells,” he says. “In terms of optical properties, copper oxides are well-positioned to become a solar energy harvesting material.”

This work may be useful in other applications according to the news release,

The find may also benefit other engineers who want to use single crystal oxides in scientific research. Manufacturing single crystal Cu2O for research is very expensive, Banerjee says, costing up to about $1,500 for one crystal.

“But if you can live with this form that’s a long wire instead of a small crystal, you can really use it to study basic scientific phenomena,” Banerjee says.

Banerjee’s team also is looking for other uses for the nanowires, including acting as a semiconductor between two materials, as a photocatalyst, a photovoltaic or an electrode for splitting water.

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

Unravelling transient phases during thermal oxidation of copper for dense CuO nanowire growth by Fei Wu, Yoon Myunga and Parag Banerjee.  CrystEngComm, 2014,16, 3264-3267. DOI: 10.1039/C4CE00275J First published online 26 Feb 2014

This article is behind a paywall.

Shortly after the research announcement, WUSTL made this ‘solar’ announcement via an April 29, 2014 news release by Neil Schoenherr,

Washington University in St. Louis is moving forward with a bold and impactful plan to increase solar output on all campuses by 1,150 percent over current levels by this fall. The project demonstrates the university’s commitment to sustainable operations and to reducing its environmental impact in the St. Louis region and beyond.

This spring and early summer, the university will add a total of 379 kilowatts (kw) of solar on university-owned property throughout the region. Prior to this installation, the university had 33 kw that were installed as demonstration projects.

I suspect the two announcements reflect synchronicity or, perhaps, my tendency to see and develop patterns.