Tag Archives: nanocavity

Water that freezes solid at over 100 degrees Celsius

The ‘magical property’ of water that freezes at temperatures higher than 100 degrees Celsius occurs at the nanoscale according to this Nov. 28, 2016 news item on Nanowerk,

It’s a well-known fact that water, at sea level, starts to boil at a temperature of 212 degrees Fahrenheit, or 100 degrees Celsius. And scientists have long observed that when water is confined in very small spaces, its boiling and freezing points can change a bit, usually dropping by around 10 C or so.

But now, a team at MIT [Massachusetts Institute of Technology] has found a completely unexpected set of changes: Inside the tiniest of spaces — in carbon nanotubes whose inner dimensions are not much bigger than a few water molecules — water can freeze solid even at high temperatures that would normally set it boiling.

A Nov. 28, 2016 MIT news release (also on EurekAlert), which originated the news item, expands on the theme,

The discovery illustrates how even very familiar materials can drastically change their behavior when trapped inside structures measured in nanometers, or billionths of a meter. And the finding might lead to new applications — such as, essentially, ice-filled wires — that take advantage of the unique electrical and thermal properties of ice while remaining stable at room temperature.

“If you confine a fluid to a nanocavity, you can actually distort its phase behavior,” Strano says, referring to how and when the substance changes between solid, liquid, and gas phases. Such effects were expected, but the enormous magnitude of the change, and its direction (raising rather than lowering the freezing point), were a complete surprise: In one of the team’s tests, the water solidified at a temperature of 105 C or more. (The exact temperature is hard to determine, but 105 C was considered the minimum value in this test; the actual temperature could have been as high as 151 C.)

“The effect is much greater than anyone had anticipated,” Strano says.

It turns out that the way water’s behavior changes inside the tiny carbon nanotubes — structures the shape of a soda straw, made entirely of carbon atoms but only a few nanometers in diameter — depends crucially on the exact diameter of the tubes. “These are really the smallest pipes you could think of,” Strano says. In the experiments, the nanotubes were left open at both ends, with reservoirs of water at each opening.

Even the difference between nanotubes 1.05 nanometers and 1.06 nanometers across made a difference of tens of degrees in the apparent freezing point, the researchers found. Such extreme differences were completely unexpected. “All bets are off when you get really small,” Strano says. “It’s really an unexplored space.”

In earlier efforts to understand how water and other fluids would behave when confined to such small spaces, “there were some simulations that showed really contradictory results,” he says. Part of the reason for that is many teams weren’t able to measure the exact sizes of their carbon nanotubes so precisely, not realizing that such small differences could produce such different outcomes.

In fact, it’s surprising that water even enters into these tiny tubes in the first place, Strano says: Carbon nanotubes are thought to be hydrophobic, or water-repelling, so water molecules should have a hard time getting inside. The fact that they do gain entry remains a bit of a mystery, he says.

Strano and his team used highly sensitive imaging systems, using a technique called vibrational spectroscopy, that could track the movement of water inside the nanotubes, thus making its behavior subject to detailed measurement for the first time.

The team can detect not only the presence of water in the tube, but also its phase, he says: “We can tell if it’s vapor or liquid, and we can tell if it’s in a stiff phase.” While the water definitely goes into a solid phase, the team avoids calling it “ice” because that term implies a certain kind of crystalline structure, which they haven’t yet been able to show conclusively exists in these confined spaces. “It’s not necessarily ice, but it’s an ice-like phase,” Strano says.

Because this solid water doesn’t melt until well above the normal boiling point of water, it should remain perfectly stable indefinitely under room-temperature conditions. That makes it potentially a useful material for a variety of possible applications, he says. For example, it should be possible to make “ice wires” that would be among the best carriers known for protons, because water conducts protons at least 10 times more readily than typical conductive materials. “This gives us very stable water wires, at room temperature,” he says.

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

Observation of extreme phase transition temperatures of water confined inside isolated carbon nanotubes by Kumar Varoon Agrawal, Steven Shimizu, Lee W. Drahushuk, Daniel Kilcoyne, & Michael S. Strano. Nature Nanotechnology (2016)  doi:10.1038/nnano.2016.254 Published online 28 November 2016

This paper is behind a paywall.

Peacocks and their structural colour inspire better resolution in e-readers

Thank goodness birds, insects, and other denizens of the natural world have not taken to filing patents otherwise we’d be having some serious problems in the courts as I have hinted in previous postings including this March 29, 2012 posting titled, Butterflies give and give … .

This time, it’s the peacock which is sharing its intellectual property as per this Feb. 5, 2013 news item on ScienceDaily,

Now, researchers at the University of Michigan have found a way to lock in so-called structural color, which is made with texture rather than chemicals. A paper on the work is published online in the current edition of the Nature journal Scientific Reports.

In a peacock’s mother-of-pearl tail, precisely arranged hairline grooves reflect light of certain wavelengths. That’s why the resulting colors appear different depending on the movement of the animal or the observer. Imitating this system—minus the rainbow effect—has been a leading approach to developing next-generation reflective displays.

The University of Michigan Feb. 5, 2013 news release, which originated the news item, provides information about potential applications and more details about the science,

The new U-M research could lead to advanced color e-books and electronic paper, as well as other color reflective screens that don’t need their own light to be readable. Reflective displays consume much less power than their backlit cousins in laptops, tablet computers, smartphones and TVs. The technology could also enable leaps in data storage and cryptography. Documents could be marked invisibly to prevent counterfeiting.

Led by Jay Guo, professor of electrical engineering and computer science, the researchers harnessed the ability of light to funnel into nanoscale metallic grooves and get trapped inside. With this approach, they found the reflected hues stay true regardless of the viewer’s angle.

“That’s the magic part of the work,” Guo said. “Light is funneled into the nanocavity, whose width is much, much smaller than the wavelength of the light. And that’s how we can achieve color with resolution beyond the diffraction limit. Also counterintuitive is that longer wavelength light gets trapped in narrower grooves.”

The diffraction limit was long thought to be the smallest point you could focus a beam of light to. Others have broken the limit as well, but the U-M team did so with a simpler technique that also produces stable and relatively easy-to-make color, Guo said.

“Each individual groove—much smaller than the light wavelength—is sufficient to do this function. In a sense, only the green light can fit into the nanogroove of a certain size,” Guo said.

The U-M team determined what size slit would catch what color light. Within the framework of the print industry standard cyan, magenta and yellow color model, the team found that at groove depths of 170 nanometers and spacing of 180 nanometers, a slit 40 nanometers wide can trap red light and reflect a cyan color. A slit 60 nanometers wide can trap green and make magenta. And one 90 nanometers wide traps blue and produces yellow. The visible spectrum spans from about 400 nanometers for violet to 700 nanometers for red.

“With this reflective color, you could view the display in sunlight. It’s very similar to color print,” Guo said.

Particularly interesting (for someone who worked in the graphic arts/printing industry as I did) are the base colours being used to create all the other colours,

To make color on white paper, (which is also a reflective surface), printers arrange pixels of cyan, magenta and yellow in such a way that they appear to our eyes as the colors of the spectrum. [emphasis mine] A display that utilized Guo’s approach would work in a similar way.

To demonstrate their device, the researchers etched nanoscale grooves in a plate of glass with the technique commonly used to make integrated circuits, or computer chips. Then they coated the grooved glass plate with a thin layer of silver. When light—which is a combination of electric and magnetic field components—hits the grooved surface, its electric component creates what’s called a polarization charge at the metal slit surface, boosting the local electric field near the slit. That electric field pulls a particular wavelength of light in.

The base colours in printing are CMYK (cyan, magenta, yellow, black). At least, that was the case when I worked in the graphic arts industry and quick search on the web suggests that standard still holds.(Have I missed a refinement?) In any event, here’s an image that demonstrates how this new colour scale can be used,

University of Michigan researchers created the color in these tiny Olympic rings using precisely-sized nanoscale slits in a glass plate coated with silver. Each ring is about 20 microns, smaller than the width of a human hair. They can produce different colors with different widths of the slits. Yellow is produced with slits that are each 90 nanometers wide. The technique takes advantage of a phenomenon called light funneling that can catch and trap particular wavelengths of light, and it could lead to reflective display screens with colors that stay true regardless of the viewer's angle. Image credit: Jay Guo, College of Engineering

University of Michigan researchers created the color in these tiny Olympic rings using precisely-sized nanoscale slits in a glass plate coated with silver. Each ring is about 20 microns, smaller than the width of a human hair. They can produce different colors with different widths of the slits. Yellow is produced with slits that are each 90 nanometers wide. The technique takes advantage of a phenomenon called light funneling that can catch and trap particular wavelengths of light, and it could lead to reflective display screens with colors that stay true regardless of the viewer’s angle. Image credit: Jay Guo, College of Engineering

You can find more about this work in the ScienceDaily news item, which includes a link to the abstract, or in the University of Michigan news release, which includes more images from the scientists.