Tag Archives: titanium dioxide (TiO2)

Historic and other buildings get protection from pollution?

This Sept. 15, 2017 news item on Nanowerk announces a new product for protecting buildings from pollution,

The organic pollution decomposing properties of titanium dioxide (TiO2 ) have been known for about half a century. However, practical applications have been few and hard to develop, but now a Greek paint producer claims to have found a solution

A Sept. 11, 2017 Youris (European Research Media Center) press release by Koen Mortelmans which originated the news item expands on the theme,

The photocatalytic properties of anatase, one of the three naturally occurring forms of titanium dioxide, were discovered in Japan in the late 1960s. Under the influence of the UV-radiation in sunlight, it can decompose organic pollutants such as bacteria, fungi and nicotine, and some inorganic materials into carbon dioxide. The catalytic effect is caused by the nanostructure of its crystals.

Applied outdoors, this affordable and widely available material could represent an efficient self-cleaning solution for buildings. This is due to the chemical reaction, which leaves a residue on building façades, a residue then washed away when it rains. Applying it to monuments in urban areas may save our cultural heritage, which is threatened by pollutants.

However, “photocatalytic paints and additives have long been a challenge for the coating industry, because the catalytic action affects the durability of resin binders and oxidizes the paint components,” explains Ioannis Arabatzis, founder and managing director of NanoPhos, based in the Greek town of Lavrio, in one of the countries home to some of the most important monuments of human history. The Greek company is testing a paint called Kirei, inspired by a Japanese word meaning both clean and beautiful.

According to Arabatzis, it’s an innovative product because it combines the self-cleaning action of photocatalytic nanoparticles and the reflective properties of cool wall paints. “When applied on exterior surfaces this paint can reflect more than 94% of the incident InfraRed radiation (IR), saving energy and reducing costs for heating and cooling”, he says. “The reflection values are enhanced by the self-cleaning ability. Compared to conventional paints, they remain unchanged for longer.”

The development of Kirei has been included in the European project BRESAER (BREakthrough Solutions for Adaptable Envelopes in building Refurbishment) which is studying a sustainable and adaptable “envelope system” to renovate buildings. The new paint was tested and subjected to quality controls following ISO standard procedures at the company’s own facilities and in other independent laboratories. “The lab results from testing in artificial, accelerated weathering conditions are reliable,” Arabatzis claims. “There was no sign of discolouration, chalking, cracking or any other paint defect during 2,000 hours of exposure to the simulated environmental conditions. We expect the coating’s service lifetime to be at least ten years.”

Many studies are being conducted to exploit the properties of titanium dioxide. Jan Duyzer, researcher at the Netherlands Organisation for Applied Scientific Research (TNO) in Utrecht, focused on depollution: “There is no doubt about the ability of anatase to decrease the levels of nitrogen oxides in the air. But in real situations, there are many differences in pollution, wind, light, and temperature. We were commissioned by the Dutch government specifically to find a way to take nitrogen oxides out of the air on roads and in traffic tunnels. We used anatase coated panels. Our results were disappointing, so the government decided to discontinue the research. Furthermore, we still don’t know what caused the difference between lab and life. Our best current hypothesis is that the total surface of the coated panels is very small compared to the large volumes of polluted air passing over them,” he tells youris.com.

Experimental deployment of titanium dioxide panels on an acoustic wall along a Dutch highway – Courtesy of Netherlands Organisation for Applied Scientific Research (TNO)

“In laboratory conditions the air is blown over the photocatalytic surface with a certain degree of turbulence. This results in the NOx-particles and the photocatalytic material coming into full contact with one another,” says engineer Anne Beeldens, visiting professor at KU Leuven, Belgium. Her experience with photocatalytic TiO2 is also limited to nitrogen dioxide (NOx) pollution.

In real applications, the air stream at the contact surface becomes laminar. This results in a lower velocity of the air at the surface and a lower depollution rate. Additionally, not all the air will be in contact with the photocatalytic surfaces. To ensure a good working application, the photocatalytic material needs to be positioned so that all the air is in contact with the surface and flows over it in a turbulent manner. This would allow as much of the NOx as possible to be in contact with photocatalytic material. In view of this, a good working application could lead to a reduction of 5 to 10 percent of NOx in the air, which is significant compared to other measures to reduce pollutants.”

The depollution capacity of TiO2 is undisputed, but most applications and tests have only involved specific kinds of substances. More research and measurements are required if we are to benefit more from the precious features of this material.

I think the most recent piece here on protecting buildings, i.e., the historic type, from pollution is an Oct. 21, 2014 posting: Heart of stone.

Nanoparticles from tattoo inks circulate through your body

English: Tattoo of Hand of Fatima,. Model: Casini. Date: 4 July 2017, 18:13:41. Source : Own work. Author: Stephencdickson.

For those who like their news in video format, there’s this Canadian Broadcasting Corporation (CBC) news item broadcast on Sep. 11, 2017 (after the commercials),

For those who like text and more detail, scientists at the European Synchrotron Radiation Facility (ESRF) have produced a study of the (at the nanoparticle scale) inks in tattoos. From a Sept. 12, 2017 news item on phys.org,

The elements that make up the ink in tattoos travel inside the body in micro and nanoparticle forms and reach the lymph nodes, according to a study published in Scientific Reports on 12 September [2017] by scientists from Germany and the ESRF, the European Synchrotron, Grenoble (France). It is the first time researchers have found analytical evidence of the transport of organic and inorganic pigments and toxic element impurities as well as in depth characterization of the pigments ex vivo in tattooed tissues. Two ESRF beamlines were crucial in this breakthrough.

A Sept. 12, 2017 ESRF press release (also on EurkeAlert), which originated the news item, explains further,

The reality is that little is known about the potential impurities in the colour mixture applied to the skin. Most tattoo inks contain organic pigments, but also include preservatives and contaminants like nickel, chromium, manganese or cobalt. Besides carbon black, the second most common ingredient used in tattoo inks is titanium dioxide (TiO2), a white pigment usually applied to create certain shades when mixed with colorants. Delayed healing, along with skin elevation and itching, are often associated with white tattoos, and by consequence with the use of TiO2. TiO2 is also commonly used in food additives, sun screens and paints. Scientists from the ESRF, the German Federal Institute for Risk Assessment, Ludwig-Maximilians University, and the Physikalisch-Technische Bundesanstalt have managed to get a very clear picture on the location of titanium dioxide once it gets in the tissue. This work was done on the ESRF beamlines ID21 and ID16B.

drawing tattookinetics.jpg

Translocation of tattoo particles from skin to lymph nodes. Upon injection of tattoo inks, particles can be either passively transported via blood and lymph fluids or phagocytized by immune cells and subsequently deposited in regional lymph nodes. After healing, particles are present in the dermis and in the sinusoids of the draining lymph nodes. Credits: C. Seim.

The hazards that potentially derive from tattoos were, until now, only investigated by chemical analysis of the inks and their degradation products in vitro. “We already knew that pigments from tattoos would travel to the lymph nodes because of visual evidence: the lymph nodes become tinted with the colour of the tattoo. It is the response of the body to clean the site of entrance of the tattoo. What we didn’t know is that they do it in a nano form, which implies that they may not have the same behaviour as the particles at a micro level. And that is the problem: we don’t know how nanoparticles react”, explains Bernhard Hesse, one of the two first authors of the study (together with Ines Schreiver, from the German Federal Institute for Risk Assessment) and ESRF visiting scientist.


Particle mapping and size distribution of different tattoo pigment elements.  a, d) Ti and the Br containing pigment phthalocyanine green 36 are located next to each other. b, e) Log scale mappings of Ti, Br and Fe in the same areas as displayed in a) and d) reveal primary particle sizes of different pigment species. c, f) Magnifications of the indicated areas in b) and e), respectively. Credits: C. Seim.

X-ray fluorescence measurements on ID21 allowed the team to locate titanium dioxide at the micro and nano range in the skin and the lymphatic environment. They found a broad range of particles with up to several micrometres in size in human skin, but only smaller (nano) particles transported to the lymph nodes. This can lead to the chronic enlargement of the lymph nodes and lifelong exposure. Scientists also used the technique of Fourier transform infrared spectroscopy to assess biomolecular changes in the tissues in the proximity of the tattoo particles.


Ines Schreiver doing experiments on ID16B with Julie Villanova. Credits: B. Hesse.

Altogether the scientists report strong evidence for both migration and long-term deposition of toxic elements and tattoo pigments as well as for conformational alterations of biomolecules that are sometimes linked to cutaneous adversities upon tattooing.

Then next step for the team is to inspect further samples of patients with adverse effects in their tattoos in order to find links with chemical and structural properties of the pigments used to create these tattoos.

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

Synchrotron-based ν-XRF mapping and μ-FTIR microscopy enable to look into the fate and effects of tattoo pigments in human skin by Ines Schreiver, Bernhard Hesse, Christian Seim, Hiram Castillo-Michel, Julie Villanova, Peter Laux, Nadine Dreiack, Randolf Penning, Remi Tucoulou, Marine Cotte, & Andreas Luch. Scientific Reports 7, Article number: 11395 (2017) doi:10.1038/s41598-017-11721-z Published online: 12 September 2017

This paper is open access.

Cicada wings for anti-reflective surfaces

This bioinspired piece of research comes courtesy of China. From an Oct. 11, 2016 news item on Nanowerk,

A team of Shanghai Jiao Tong University researchers has used the shape of cicada wings as a template to create antireflective structures fabricated with one of the most intriguing semiconductor materials, titanium dioxide (TiO2). The antireflective structures they produced are capable of suppressing visible light — 450 to 750 nanometers — at different angles of incidence.

An Oct. 11,2016 American Institute of Physics news release, which originated the news item, explains why the researchers focused on cicada wings and how their observations led to a new anti-reflective material,

Why cicada wings? The surfaces of the insect’s wings are composed of highly ordered, tiny vertical “nano-nipple” arrays, according to the researchers. As they report this week in Applied Physics Letters, from AIP Publishing, the resulting biomorphic TiO2 surface they created with antireflective structures shows a significant decrease in reflectivity.

“This can be attributed to an optimally graded refractive index profile between air and the TiO2 via antireflective structures on the surface,” explained Wang Zhang, associate professor at State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University in China.

Small spaces between the ordered nano-antireflective structures “can be thought of as a light-transfer path that let incident light rays into the interior surface of the biomorphic TiO2 — allowing the incident light rays to completely enter the structure,” Zhang continued. “The multiple reflective and scattering effects of the antireflective structures prevented the incident light from returning to the outside atmosphere.”

Significantly, the team’s work relies on “a simple and low-cost sol-gel (wet chemical) method to fabricate biomorphic TiO2 with precise subwavelength antireflective surfaces,” Zhang pointed out. “The TiO2 was a purely anatase phase (a mineral form of TiO2), which has unique antireflective surfaces. This led to an optimally graded refractive index and, ultimately, to angle-dependent antireflective properties within the visible light range.”

In terms of applications, the team’s biomorphic TiO2 antireflective structures “show great potential for photovoltaic devices such as solar cells,” Zhang said. “We expect our work to inspire and motivate engineers to develop antireflective surfaces with unique structures for various practical applications.”

Even after high calcination at 500 C, the antireflective structures retain their morphology and high-performance antireflection properties. These qualities should enable the coatings to withstand harsh environments and make them suitable for long-term applications.

In the future, the team plans “to reduce the optical losses in solar cells by using materials with a higher refractive index such as tantalum pentoxide or any other semiconductor materials,” Zhang said.

I. Photograph and scanning electron microscope characterizations of a black cicada wing (Cryptympana atrata Fabricius). II. Synthesis process of biomorphic TiO2 with ordered nano-nipple array structures. III. Counter map angle-dependent antireflection of biomorphic TiO2 and non-templated TiO2, respectively. CREDIT: Shanghai Jiao Tong University

I. Photograph and scanning electron microscope characterizations of a black cicada wing (Cryptympana atrata Fabricius).
II. Synthesis process of biomorphic TiO2 with ordered nano-nipple array structures.
III. Counter map angle-dependent antireflection of biomorphic TiO2 and non-templated TiO2, respectively.
CREDIT: Shanghai Jiao Tong University

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

Angle dependent antireflection property of TiO2 inspired by cicada wings by Imran Zada, Wang Zhang, Yao Li, Peng Sun, Nianjin Cai, Jiajun Gu, Qinglei Liu, Huilan Su, and Di Zhang.  Appl. Phys. Lett. 109, 153701 (2016); http://dx.doi.org/10.1063/1.4962903

This paper appears to be open access.

Nanosunscreen in swimming pools

Thanks to Lynn L. Bergeson’s Sept. 21, 2016 posting for information about the US Environmental Protection Agency’s (EPA) research into what happens to the nanoparticles when your nanosunscreen washes off into a swimming pool. Bergeson’s post points to an Aug. 15, 2016 EPA blog posting by Susanna Blair,

… It’s not surprising that sunscreens are detected in pool water (after all, some is bound to wash off when we take a dip), but certain sunscreens have also been widely detected in our ecosystems and in our wastewater. So how is our sunscreen ending up in our environment and what are the impacts?

Well, EPA researchers are working to better understand this issue, specifically investigating sunscreens that contain engineered nanomaterials and how they might change when exposed to the chemicals in pool water [open access paper but you need to register for free] … But before I delve into that, let’s talk a bit about sunscreen chemistry and nanomaterials….

Blair goes on to provide a good brief description of  nanosunscreens before moving onto her main topic,

Many sunscreens contain titanium dioxide (TiO2) because it absorbs UV radiation, preventing it from damaging our skin. But titanium dioxide decomposes into other molecules when in the presence of water and UV radiation. This is important because one of the new molecules produced is called a singlet oxygen reactive oxygen species. These reactive oxygen species have been shown to cause extensive cell damage and even cell death in plants and animals. To shield skin from reactive oxygen species, titanium dioxide engineered nanomaterials are often coated with other materials such as aluminum hydroxide (Al(OH)3).

EPA researchers are testing to see whether swimming pool water degrades the aluminum hydroxide coating, and if the extent of this degradation is enough to allow the production of potentially harmful reactive oxygen species. In this study, the coated titanium dioxide engineered nanomaterials were exposed to pool water for time intervals ranging from 45 minutes to 14 days, followed by imaging using an electron microscope.  Results show that after 3 days, pool water caused the aluminum hydroxide coating to degrade, which can reduce the coating’s protective properties and increase the potential toxicity.  To be clear, even with degraded coating, the toxicity measured from the coated titanium dioxide, was significantly less [emphasis mine] than the uncoated material. So in the short-term – in the amount of time one might wear sunscreen before bathing and washing it off — these sunscreens still provide life-saving protection against UV radiation. However, the sunscreen chemicals will remain in the environment considerably longer, and continue to degrade as they are exposed to other things.

Blair finishes by explaining that research is continuing as the EPA researches the whole life cycle of engineered nanomaterials.