Tag Archives: droplets

Stanford researchers solve the mystery of the dancing droplets

Years of research satisfy a graduate student’s curiosity about the molecular minuet he observed among drops of ordinary food coloring.


A puzzling observation, pursued through hundreds of experiments, has led Stanford researchers to a simple yet profound discovery: Under certain circumstances, droplets of fluid will move like performers in a dance choreographed by molecular physics.

“These droplets sense one another, they move and interact, almost like living cells,” said Manu Prakash, an assistant professor of bioengineering and senior author of an article published in Nature.

The unexpected findings may prove useful in semiconductor manufacturing and self-cleaning solar panels, but what truly excites Prakash is that the discovery resulted from years of persistent effort to satisfy a scientific curiosity.

Video: Stanford researchers solve the mystery of the dancing droplets

The research began in 2009 when Nate Cira, then an undergraduate at the University of Wisconsin, was doing an unrelated experiment. In the course of that experiment Cira deposited several droplets of food coloring onto a sterilized glass slide and was astonished when they began to move.

Cira replicated and studied this phenomenon alone for two years until he became a graduate student at Stanford, where he shared this curious observation with Prakash. The professor soon became hooked by the puzzle, and recruited a third member to the team: Adrien Benusiglio, a postdoctoral scholar in the Prakash Lab.

Together they spent three years performing increasingly refined experiments to learn how these tiny droplets of food coloring sense one another and move. In living cells these processes of sensing and motility are known as chemotaxis.

“We’ve discovered how droplets can exhibit behaviors akin to artificial chemotaxis,” Prakash said.

As the Nature article explains, the critical fact was that food coloring is a two-component fluid. In such fluids, two different chemical compounds coexist while retaining separate molecular identities

The droplets in this experiment consisted of two molecular compounds found naturally in food coloring: water and propylene glycol.

The researchers discovered how the dynamic interactions of these two molecular components enabled inanimate droplets to mimic some of the behaviors of living cells.

Surface tension and evaporation

Essentially, the droplets danced because of a delicate balance between surface tension and evaporation.

Evaporation is easily understood. On the surface of any liquid, some molecules convert to a gaseous state and float away.

Surface tension is what causes liquids to bead up. It arises from how tightly the molecules in a liquid bind together.

Water evaporates more quickly than propylene glycol. Water also has a higher surface tension.  These differences create a tornado-like flow inside the droplets, which not only allows them to move but also allows a single droplet to sense its neighbors.

To understand the molecular forces involved, imagine shrinking down to size and diving inside a droplet.

There, water and propylene glycol molecules try to remain evenly distributed but differences in evaporation and surface tension create turmoil within the droplet.

On the curved dome of each droplet, water molecules become gaseous and float away faster than their evaporation-averse propylene glycol neighbors.

This evaporation happens more readily on the thin lower edges of the domed droplet, leaving excess of propylene glycol there. Meanwhile, the peak of the dome has a higher concentration of water.

The water at the top exerts its higher surface tension to pull the droplet tight so it doesn’t flatten out. This tugging causes a tumbling molecular motion inside the droplet. Thus surface tension gets the droplet ready to roll.

Evaporation determines the direction of that motion. Each droplet sends aloft gaseous molecules of water like a radially emanating signal announcing the exact location of any given droplet. The droplets converge where the signal is strongest.

So evaporation provided the sensing mechanism and surface tension the pull to move droplets together in what seemed to the eye to be a careful dance.

Rule for two-component fluids

The researchers experimented with varied proportions of water and propylene glycol. Droplets that were 1 percent propylene glycol (PG) to 99 percent water exhibited much the same behavior as droplets that were two-thirds PG to just one-third water.

Based on these experiments the paper describes a “universal rule” to identify any two-component fluids that will demonstrate sensing and motility.

Adding colors to the mixtures made it easier to tell how the droplets of different concentrations behaved and created some visually striking results.

In one experiment, a droplet with more propylene glycol seems to chase a droplet with more water. In actuality, the droplet with more water exerts a higher surface tension tug, pulling the propylene droplet along.

In another experiment, researchers showed how physically separated droplets could align themselves using ever-so-slight signals of evaporation.

In a third experiment they used Sharpie pens to draw black lines on glass slides. The lines changed the surface of the slide and created a series of catch basins. The researchers filled each basin with fluids of different concentrations to create a self-sorting mechanism. Droplets bounced from reservoir to reservoir until they sensed the fluid that matched their concentration and merged with that pool.

What started as a curiosity-driven project may also have many practical implications.

The deep physical understanding of two component fluids allows the researchers to predict which fluids and surfaces will show these unusual effects. The effect is present on a large number of common surfaces and can be replicated with a number of chemical compounds.

“If necessity is the mother of invention, then curiosity is the father,” Prakash observed.

Source: Stanford News

Solid nanoparticles can deform like a liquid|Unexpected finding shows tiny particles keep their internal crystal structure while flexing like droplets.

By David Chandler

CAMBRIDGE, Mass–A surprising phenomenon has been found in metal nanoparticles: They appear, from the outside, to be liquid droplets, wobbling and readily changing shape, while their interiors retain a perfectly stable crystal configuration.

The research team behind the finding, led by MIT professor Ju Li, says the work could have important implications for the design of components in nanotechnology, such as metal contacts for molecular electronic circuits.

The results, published in the journal Nature Materials, come from a combination of laboratory analysis and computer modeling, by an international team that included researchers in China, Japan, and Pittsburgh, as well as at MIT.

The experiments were conducted at room temperature, with particles of pure silver less than 10 nanometers across — less than one-thousandth of the width of a human hair. But the results should apply to many different metals, says Li, senior author of the paper and the BEA Professor of Nuclear Science and Engineering.

Silver has a relatively high melting point — 962 degrees Celsius, or 1763 degrees Fahrenheit — so observation of any liquidlike behavior in its nanoparticles was “quite unexpected,” Li says. Hints of the new phenomenon had been seen in earlier work with tin, which has a much lower melting point, he says.

The use of nanoparticles in applications ranging from electronics to pharmaceuticals is a lively area of research; generally, Li says, these researchers “want to form shapes, and they want these shapes to be stable, in many cases over a period of years.” So the discovery of these deformations reveals a potentially serious barrier to many such applications: For example, if gold or silver nanoligaments are used in electronic circuits, these deformations could quickly cause electrical connections to fail.

Only skin deep

The researchers’ detailed imaging with a transmission electron microscope and atomistic modeling revealed that while the exterior of the metal nanoparticles appears to move like a liquid, only the outermost layers — one or two atoms thick — actually move at any given time. As these outer layers of atoms move across the surface and redeposit elsewhere, they give the impression of much greater movement — but inside each particle, the atoms stay perfectly lined up, like bricks in a wall.

“The interior is crystalline, so the only mobile atoms are the first one or two monolayers,” Li says. “Everywhere except the first two layers is crystalline.”

By contrast, if the droplets were to melt to a liquid state, the orderliness of the crystal structure would be eliminated entirely — like a wall tumbling into a heap of bricks.

Technically, the particles’ deformation is pseudoelastic, meaning that the material returns to its original shape after the stresses are removed — like a squeezed rubber ball — as opposed to plasticity, as in a deformable lump of clay that retains a new shape.

The phenomenon of plasticity by interfacial diffusion was first proposed by Robert L. Coble, a professor of ceramic engineering at MIT, and is known as “Coble creep.”  “What we saw is aptly called Coble pseudoelasticity,” Li says.

Now that the phenomenon has been understood, researchers working on nanocircuits or other nanodevices can quite easily compensate for it, Li says. If the nanoparticles are protected by even a vanishingly thin layer of oxide, the liquidlike behavior is almost completely eliminated, making stable circuits possible.

Possible benefits

On the other hand, for some applications this phenomenon might be useful: For example, in circuits where electrical contacts need to withstand rotational reconfiguration, particles designed to maximize this effect might prove useful, using noble metals or a reducing atmosphere, where the formation of an oxide layer is destabilized, Li says.

The new finding flies in the face of expectations — in part, because of a well-understood relationship, in most materials, in which mechanical strength increases as size is reduced.

“In general, the smaller the size, the higher the strength,” Li says, but “at very small sizes, a material component can get very much weaker. The transition from ‘smaller is stronger’ to ‘smaller is much weaker’ can be very sharp.”

That crossover, he says, takes place at about 10 nanometers at room temperature — a size that microchip manufacturers are approaching as circuits shrink. When this threshold is reached, Li says, it causes “a very precipitous drop” in a nanocomponent’s strength.

The findings could also help explain a number of anomalous results seen in other research on small particles, Li says.

The research team included Jun Sun, Longbing He, Tao Xu, Hengchang Bi, and Litao Sun, all of Southeast University in Nanjing, China; Yu-Chieh Lo of MIT and Kyoto University; Ze Zhang of Zhejiang University; and Scott Mao of the University of Pittsburgh. It was supported by the National Basic Research Program of China; the National Natural Science Foundation of China; the Chinese Ministry of Education; the National Science Foundation of Jiangsu Province, China; and the U.S. National Science Foundation.

Source: MIT News Office