Tag Archives: superhydrophobic

A superhydrophobic coating for glass from the University of Pennsylvania (US) with promises that it’s better than others

Anyone who’s read this blog with any frequency has likely encountered my obsession with self-cleaning glass (specifically, windows). Frankly, I’ve almost given up hope of ever seeing the product in my lifetime several times and then I see another announcement such as this in a Nov. 26, 2013 news item on Nanowerk,

Hanging hundreds of feet off the ground to wash a skyscraper’s windows or pumping water out to a desert solar array to keep its panels and mirrors clean is more than just a hassle—it’s an expensive problem with serious ecological implications.

A spin-off company from Penn has found a way to solve the problem of keeping surfaces clean, while also keeping them transparent.

The undated University of Pennsylvania article by Evan Lerner, which originated the news item, describes both the university’s spin-off company and the research which it is exploiting (Note: Links have been removed),

Nelum Sciences, created under an UPstart program in Penn’s Center for Technology Transfer, has developed a superhydrophobic coating that can be sprayed onto any surface. The water-based solution contains nanoscopic particles that add a nearly invisible layer of roughness to a surface. This increases the contact angle of the material to which these particles are applied.

A contact angle is the angle the edges of a resting drop of liquid make with a surface. When the angle is low, a drop resembles a flattened hemisphere, with edges that are stuck to the surface. But as the angle increases, a drop begins to look more like a ball, until it literally rolls away instead of sticking.

When these balls of liquid roll off a superhydrophobic surface, they pick up any debris they encounter in their paths, keeping a surface clean.

Co-founded in 2011 by Shu Yang, professor of materials science and engineering in Penn’s School of Engineering and Applied Science, Nelum Science’s coating is based on her nanotechnology research. Fabricating the coating’s nanoparticles at sizes smaller than the wavelength of light—the quality that makes them transparent—is the product of cutting-edge laboratory techniques. The company’s inspiration, however, came from structures created by nature.

“Some plants, like lotuses, and other biological structures, like butterfly wings, have this kind of nano-roughness to keep them clean and dry,” Yang says. “That’s why we named the company after the lotus’ Latin name, nelumbo.”

Other superhydrophobic sprays have recently come on the market, but they give surfaces a hazy, frosted appearance, making them inappropriate for applications where cleanliness is critical, such as windows, lenses, safety goggles, and solar panels.

Here’s a University of Pennsylvanis video illustrating the technology,

I wasn’t able to find much information about Nelum Sciences but there is this page on the University of Pennsylvania’s Center for Technology Transfer website, which leads me to suspect I may not be seeing the product in the market place any time soon.

Staying stuck when it’s wet; learning from the geckos

Researchers from the University of Akron have published another study on geckos and their ‘stickability’ in watery environments. Last mentioned here in my Aug. 10, 2012 posting, doctoral candidate Alyssa Stark  and her colleagues were then testing the geckos by placing them on wetted glass plate surfaces and also by immersing them on water-filled tubs with glass bottom,

Next, the trio sprayed the glass plate with a mist of water and retested the lizards, but this time the animals had problems holding tight: the attachment force varied each time they took a step. The droplets were interfering with the lizards’ attachment mechanism, but it wasn’t clear how. And when the team immersed the geckos in a bath of room temperature water with a smooth glass bottom, the animals were completely unable to anchor themselves to the smooth surface. ‘The toes are superhydrophobic [water repellent]’, explains Stark, who could see a silvery bubble of air around their toes, but they were unable to displace the water surrounding their feet to make the tight van der Waals contacts that usually keep the geckos in place.

Then, the team tested the lizard’s adhesive forces on the dry surface when their feet had been soaking for 90 min and found that the lizards could barely hold on, detaching when they were pulled with a force roughly equalling their own weight. ‘That might be the sliding behaviour that we see when the geckos climb vertically up misted glass’, says Stark. So, geckos climbing on wet surfaces with damp feet are constantly on the verge of slipping and Stark adds that when the soggy lizards were faced with the misted and immersed horizontal surfaces, they slipped as soon as the rig started pulling.

In this latest research, from the Ap. 1, 2013 news release issued by the University of Akron on EurekAlert, Stark and her colleagues announce they’ve discovered the conditions under which geckos can adhere to wet surfaces,

Principal investigator Stark and her fellow UA researchers Ila Badge, Nicholas Wucinich, Timothy Sullivan, Peter Niewiarowski and Ali Dhinojwala study the adhesive qualities of gecko pads, which have tiny, clingy hairs that stick like Velcro to dry surfaces. In a 2012 study, the team discovered that geckos lose their grip on wet glass. This finding led the scientists to explore how the lizards function in their natural environments.

The scientists studied the clinging power of six geckos, which they outfitted with harnesses and tugged upon gently as the lizards clung to surfaces in wet and dry conditions. The researchers found that the effect of water on adhesive strength correlates with wettability, or the ability of a liquid to maintain contact with a solid surface. On glass, which has high wettability, a film of water forms between the surface and the gecko’s foot, decreasing adhesion. Conversely, on surfaces with low wettability, such as waxy leaves on tropical plants, the areas in contact with the gecko’s toes remain dry and adhesion, firm. [emphasis mine]

“The geckos stuck just as well under water as they did on a dry surface, as long as the surface was hydrophobic,” Stark explains. “We believe this is how geckos stick to wet leaves and tree trunks in their natural environment.”

For interested parties, this is where the paper can be found,

The discovery, “Surface Wettability Plays a Significant Role in Gecko Adhesion Underwater,” was published April 1, 2013 by the Proceedings of the National Academy of Sciences. The study has implications for the design of a synthetic gecko-inspired adhesive.

Here’s an image of a gecko (from the University of Akron’s webpage with their Ap. 1, 2013 news release),

Courtesy University of Akron [downloaded from http://www.uakron.edu/im/online-newsroom/news_details.dot?newsId=ec9fd559-e4af-487f-a9cc-2ea5f5c9612d&pageTitle=Top%20Story%20Headline&crumbTitle=Geckos%20keep%20firm%20grip%20in%20wet%20natural%20habitat]

Courtesy University of Akron [downloaded from http://www.uakron.edu/im/online-newsroom/news_details.dot?newsId=ec9fd559-e4af-487f-a9cc-2ea5f5c9612d&pageTitle=Top%20Story%20Headline&crumbTitle=Geckos%20keep%20firm%20grip%20in%20wet%20natural%20habitat]


Not mentioned in this news release, one of the relevant applications for this work would be getting bandages and dressings  to adhere to wet surfaces.

Liquipel’s latest superhydrophobic advance for mobile devices

The Jan. 7, 2013 news item on Azonano spells out Liquipel’s new development,

Liquipel LLC, the sole owner and licensor of the Liquipel technology, announced today new scientific breakthroughs in nanotechnology protection, dubbing them “Liquipel 2.0.” The science behind Liquipel 2.0 represents significant advancements in durability, corrosion resistance and water protection. Extensive company testing has shown Liquipel 2.0 to be up to 100 times more effective than its predecessor, Liquipel 1.0, while maintaining component integrity and RF sensitivity.

“Liquipel version 2.0 is a huge advancement for super-hydrophobic nanotechnology,” said Danny McPhail, Liquipel’s Head of Product Development and Co-Founder. …

Liquipel’s description of its own technology can be found on the company home page,

Liquipel™ is a Nano-Coating that is applied though a propriety process. This process starts by placing devices into the chamber of the Liquipel™ Machine. The machine removes the air inside the chamber to create a vacuum and our special Liquipel formula is introduced in vapor form. The Liquipel coating permeates the entire device and bonds to it on a molecular level leaving it watersafe™ for years to come.

How did they determine that Liquipel 2.0 is 100 times more effective than the 1.0 version of the product as claimed in the news item? What tests do they conduct to confirm that component integrity and RF sensitivity are maintained? Have they published any research papers about their work?

It would be nice to see some data about the technology.

NBD Nano startup company and the Namib desert beetle

In 2001, Andrew Parker and Chris Lawrence published an article in Nature magazine about work which has inspired a US startup company in 2012 to develop a water bottle that fills itself up with water by drawing moisture from the air. Parker’s and Lawrence’s article was titled Water capture by a desert beetle. Here’s the abstract (over 10 years later the article is still behind a paywall),

Some beetles in the Namib Desert collect drinking water from fog-laden wind on their backs1. We show here that these large droplets form by virtue of the insect’s bumpy surface, which consists of alternating hydrophobic, wax-coated and hydrophilic, non-waxy regions. The design of this fog-collecting structure can be reproduced cheaply on a commercial scale and may find application in water-trapping tent and building coverings, for example, or in water condensers and engines.

Some five years later, there was a June 15, 2006 news item on phys.org about the development of a new material based on the Namib desert beetle,

When that fog rolls in, the Namib Desert beetle is ready with a moisture-collection system exquisitely adapted to its desert habitat. Inspired by this dime-sized beetle, MIT [Massachusetts Institute of Technology] researchers have produced a new material that can capture and control tiny amounts of water.

The material combines a superhydrophobic (water-repelling) surface with superhydrophilic (water-attracting) bumps that trap water droplets and control water flow. The work was published in the online version of Nano Letters on Tuesday, May 2 [2006] {behind a paywall}.

Potential applications for the new material include harvesting water, making a lab on a chip (for diagnostics and DNA screening) and creating microfluidic devices and cooling devices, according to lead researchers Robert Cohen, the St. Laurent Professor of Chemical Engineering, and Michael Rubner, the TDK Professor of Polymer Materials Science and Engineering.

The MIT June 14, 2006 news release by Anne Trafton, which originated the news item about the new material, indicates there was some military interest,

The U.S. military has also expressed interest in using the material as a self-decontaminating surface that could channel and collect harmful substances.

The researchers got their inspiration after reading a 2001 article in Nature describing the Namib Desert beetle’s moisture-collection strategy. Scientists had already learned to copy the water-repellent lotus leaf, and the desert beetle shell seemed like another good candidate for “bio-mimicry.”

When fog blows horizontally across the surface of the beetle’s back, tiny water droplets, 15 to 20 microns, or millionths of a meter, in diameter, start to accumulate on top of bumps on its back.

The bumps, which attract water, are surrounded by waxy water-repelling channels. “That allows small amounts of moisture in the air to start to collect on the tops of the hydrophilic bumps, and it grows into bigger and bigger droplets,” Rubner said. “When it gets large, it overcomes the pinning force that holds it and rolls down into the beetle’s mouth for a fresh drink of water.”

To create a material with the same abilities, the researchers manipulated two characteristics — roughness and nanoporosity (spongelike capability on a nanometer, or billionths of a meter, scale).

By repeatedly dipping glass or plastic substrates into solutions of charged polymer chains dissolved in water, the researchers can control the surface texture of the material. Each time the substrate is dipped into solution, another layer of charged polymer coats the surface, adding texture and making the material more porous. Silica nanoparticles are then added to create an even rougher texture that helps trap water droplets.

The material is then coated with a Teflon-like substance, making it superhydrophobic. Once that water-repellent layer is laid down, layers of charged polymers and nanoparticles can be added in certain areas, using a properly formulated water/alcohol solvent mixture, thereby creating a superhydrophilic pattern. The researchers can manipulate the technique to create any kind of pattern they want.

The research is funded by the Defense Advanced Research Projects Agency and the National Science Foundation.

I’m not sure what happened with the military interest or the group working out of MIT in 2006 but on Nov. 23, 2012, BBC News online featured an article about a US startup company, NBD Nano, which aims to bring a self-filling water bottle based on Namib desert beetle to market,

NBD Nano, which consists of four recent university graduates and was formed in May, looked at the Namib Desert beetle that lives in a region that gets about half an inch of rainfall per year.

Using a similar approach, the firm wants to cover the surface of a bottle with hydrophilic (water-attracting) and hydrophobic (water-repellent) materials.

The work is still in its early stages, but it is the latest example of researchers looking at nature to find inspiration for sustainable technology.

“It was important to apply [biomimicry] to our design and we have developed a proof of concept and [are] currently creating our first fully-functional prototype,” Miguel Galvez, a co-founder, told the BBC.

“We think our initial prototype will collect anywhere from half a litre of water to three litres per hour, depending on local environments.”

According to the Nov. 25, 2012 article by Nancy Owano for phys.org, the company is at the prototype stage now,

NBD Nano plans to enter the worldwide marketplace between 2014 and 2015.

You can find out more about NBD Nano here.

Hands off the bubbles in my boiling water!

The discovery that boiling water bubbled was important to me. I’ve never really thought about it until now when researchers at Northwestern University have threatened to take my bubbles away, metaphorically speaking. From the Sept. 13, 2012 news item on ScienceDaily,

Every cook knows that boiling water bubbles, right? New research from Northwestern University turns that notion on its head.

“We manipulated what has been known for a long, long time by using the right kind of texture and chemistry to prevent bubbling during boiling,” said Neelesh A. Patankar, professor of mechanical engineering at Northwestern’s McCormick School of Engineering and Applied Science and co-author of the study.

This discovery could help reduce damage to surfaces, prevent bubbling explosions and may someday be used to enhance heat transfer equipment, reduce drag on ships and lead to anti-frost technologies.

The Sept. 13, 2012 news release from McCormick University (which originated the news item) provides details,

This phenomenon is based on the Leidenfrost effect. In 1756 the German scientist Johann Leidenfrost observed that water drops skittered on a sufficiently hot skillet, bouncing across the surface of the skillet on a vapor cushion or film of steam. The vapor film collapses as the surface falls below the Leidenfrost temperature. When the water droplet hits the surface of the skillet, at 100 degrees Celsius, boiling temperature, it bubbles.

To stabilize a Leidenfrost vapor film and prevent bubbling during boiling, Patankar collaborated with Ivan U. Vakarelski of King Abdullah University of Science and Technology, Saudi Arabia. Vakarelski led the experiments and Patankar provided the theory. The collaboration also included Derek Chan, professor of mathematics and statistics from the University of Melbourne in Australia.

In their experiments, the stabilization of the Leidenfrost vapor film was achieved by making the surface of tiny steel spheres very water-repellant. The spheres were sprayed with a commercially available hydrophobic coating — essentially self-assembled nanoparticles — combined with other water-hating chemicals to achieve the right amount of roughness and water repellency. At the correct length scale this coating created a surface texture full of tiny peaks and valleys.

When the steel spheres were heated to 400 degrees Celsius and dropped into room temperature water, water vapors formed in the valleys of the textured surface, creating a stable Leidenfrost vapor film that did not collapse once the spheres cooled to the temperature of boiling water. In the experiments, researchers completely avoided the bubbly phase of boiling.

To contrast, the team also coated tiny steel spheres with a water-loving coating, heated the objects to 700 degrees Celsius, dropped them into room temperature water and observed that the Leidenfrost vapor collapsed with a vigorous release of bubbles.

The scientists have provided a video illustrating their work,

This movie shows the cooling of 20 mm hydrophilic (left) and superhydrophobic (right) steel spheres in 100 C water. The spheres’ initial temperature is about 380 C. The bubbling phase of boiling is completely eliminated for steel spheres with superhydrophobic coating. (from Vimeo, http://vimeo.com/49391913)

I understand there are advantages to not having bubbles in hot water but it somehow seems wrong. I’ve given up a lot over the years: gravity, boundaries between living and non-living (that was a very big thing to give up), and other distinctions that I have made based on traditional science but, today, this is one step too far.

It may seem silly but that memory of my mother explaining that you identify boiling water by its bubbles is important to me. It was one of my first science lessons. I imagine I will recover from this moment but it does remind me of how challenging it can be when your notions of reality/normalcy are challenged by various scientific endeavours. The process can get quite exhausting as you keep recalibrating everything you ‘know’ all the time.

Nanosponges clean up spilled oil and release the oil for future use

The nanosponges that have been developed by a joint team of Rice University and Penn State University researchers look pretty exciting (wish I could write a better headline about them). Here’s the researcher describing them,

I find the idea that the sponges can be reused and the oil still put to use quite compelling. From the April 16, 2012 news item on Nanowerk,

… Daniel Hashim, a graduate student in the Rice lab of materials scientist Pulickel Ajayan, said the blocks are both superhydrophobic (they hate water, so they float really well) and oleophilic (they love oil). The nanosponges, which are more than 99 percent air, also conduct electricity and can easily be manipulated with magnets.

To demonstrate, Hashim dropped the sponge into a dish of water with used motor oil floating on top. The sponge soaked it up. He then put a match to the material, burned off the oil and returned the sponge to the water to absorb more. The robust sponge can be used repeatedly and stands up to abuse; he said a sample remained elastic after about 10,000 compressions in the lab. The sponge can also store the oil for later retrieval, he said.

“These samples can be made pretty large and can be easily scaled up,” said Hashim, holding a half-inch square block of billions of nanotubes. “They’re super-low density, so the available volume is large. That’s why the uptake of oil can be so high.” He said the sponges described in the paper can absorb more than a hundred times their weight in oil.

Nanosponges have been made from carbon nan0tubes before now (from the Feb. 8, 2010 article by Michael Berger on Nanowerk),

Carbon nanotubes (CNTs) are ‘strange’ nanostructures in a sense that they have both high mechanical strength and extreme flexibility. Deforming a carbon nanotube into any shape would not easily break the structure, and it recovers to original morphology in perfect manner. Researchers in China are exploiting this phenomenon by making CNT sponges consisting of a large amount of interconnected nanotubes, thus showing a combination of useful properties such as high porosity, super elasticity, robustness, and little weight (1% of water density).

The nanotube sponges not only show exciting properties as a porous material but they also are very promising to be used practically in a short time. The production method is simple and scalable, the cost is low, and the sponges can find immediate use in many fields related to water purification.

“We hope to give an example to industry that this sponge is a real thing they can prepare at low cost, make versatile products with high performance, and solve environmental problems utilizing nanotechnology,” [says] Anyuan Cao, a professor in the Department of Advanced Materials and Nanotechnology at Peking University …

The difference between the nanosponges made in 2010 and the ones made in 2012 is the fabrication process. From the April 16, 2012 news item on Nanowerk,

Ajayan, Rice’s Benjamin M. and Mary Greenwood Anderson Professor in Mechanical Engineering and Materials Science and of chemistry, said multiwalled carbon nanotubes grown on a substrate via chemical vapor deposition usually stand up straight without any real connections to their neighbors. But the boron-introduced defects induced the nanotubes to bond at the atomic level, which tangled them into a complex network. Nanotube sponges with oil-absorbing potential have been made before (see paper in Advanced Materials: “Carbon Nanotube Sponges”), but this is the first time the covalent junctions between nanotubes in such solids have been convincingly demonstrated, he said.

“The interactions happen as they grow, and the material comes out of the furnace as a solid,” Ajayan said. [emphasis mine] “People have made nanotube solids via post-growth processing but without proper covalent connections. The advantage here is that the material is directly created during growth and comes out as a cross-linked porous network.

By comparison, the team in China used this process (from the Feb. 8, 2012 article),

The scientists synthesized the sponges by a chemical vapor deposition (CVD) process during which the CNTs (multi-walled nanotubes with diameters in the range of 30 to 50nm and lengths of tens to hundreds of micrometers,) self-assembled into a porous, interconnected, three-dimensional framework.

The research team had collaborators from the US, Mexico, Japan, Spain, and Belgium. From the April 16, 2012 news release on EurekAlert,

When he was an undergraduate student of Ajayan’s at Rensselaer Polytechnic Institute, Hashim and his classmates discovered hints of a topological solution to the problem while participating in a National Science Foundation exchange program at the Institute of Scientific Research and Technology (IPICYT) in San Luis Potosí, Mexico. The paper’s co-author, Mauricio Terrones, a professor of physics, materials science and engineering at Penn State University with an appointment at Shinshu University, Japan, led a nanotechnology lab there.

“Our goal was to find a way to make three-dimensional networks of these carbon nanotubes that would form a macroscale fabric — a spongy block of nanotubes that would be big and thick enough to be used to clean up oil spills and to perform other tasks,” Terrones said. “We realized that the trick was adding boron — a chemical element next to carbon on the periodic table — because boron helps to trigger the interconnections of the material. To add the boron, we used very high temperatures and we then ‘knitted’ the substance into the nanotube fabric.”

For anyone who would like to read further about this work (from the April 16, 2012 news release on EurekAlert),

The paper’s co-authors are Narayanan Narayanan, Myung Gwan Hahm, Joseph Suttle and Robert Vajtai, all of Rice; Jose Romo-Herrera of the University of Vigo, Spain; David Cullen and Bobby Sumpter of Oak Ridge National Laboratory, Oak Ridge, Tenn.; Peter Lezzi and Vincent Meunier of Rensselaer Polytechnic Institute; Doug Kelkhoff of the University of Illinois at Urbana-Champaign; E. Muñoz-Sandoval of the Instituto de Microelectrónica de Madrid; Sabyasachi Ganguli and Ajit Roy of the Air Force Research Laboratory, Dayton, Ohio (on loan from IPICYT); David Smith of Arizona State University; and Humberto Terrones of Oak Ridge National Lab and the Université Catholique de Louvain, Belgium.

The article is titled, Covalently bonded three-dimensional carbon nanotube solids via boron induced nanojunctions, and has been published as an open access article in Nature’s Scientific Reports.

I did mention the nanosponges developed in China in my Feb. 9, 2010 posting.