Fluid+and+Interface+Laboratory
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Nanoscale Self-Assembling Salt-Crystal ‘Origami’ Balls Envelop Liquids
Mechanical engineers have devised a ‘crystal capillary origami’ technique where salt crystals spontaneously encapsulate liquid droplets
Researchers have developed a technique whereby they can spontaneously encapsulate microscopic droplets of water and oil emulsion in a tiny sphere made of salt crystals—sort of like a minute, self-constructing origami soccer ball filled with liquid. The process, which they are calling ‘crystal capillary origami,’ could be used in a range of fields from more precise drug delivery to nanoscale medical devices.The technique is described in a paper appearing in the journal Nanoscale on September 21.
Capillary action, or ‘capillarity,’ will be familiar to most people as the way that water or other liquids can move up narrow tubes or other porous materials seemingly in defiance of gravity (for example within the vascular systems of plants, or even more simply, the drawing up of paint between the hairs of a paintbrush). This effect is due to the forces of cohesion (the tendency of a liquid’s molecules to stick together), which results in surface tension, and adhesion (their tendency to stick to the surface of other substances). The strength of the capillarity depends on the chemistry of the liquid, the chemistry of the porous material, and on the other forces acting on them both. For example, a liquid with lower surface tension than water would not be able to hold up a water strider insect.
Less well known is a related phenomenon, elasto-capillarity, that takes advantage of the relationship between capillarity and the elasticity of a very tiny flat sheet of a solid material. In certain circumstances, the capillary forces can overcome the elastic bending resistance of the sheet.
This relationship can be exploited to create ‘capillary origami,’ or three-dimensional structures. When a liquid droplet is placed on the flat sheet, the latter can spontaneously encapsulate the former due to surface tension. Capillary origami can take on other forms including wrinkling, buckling, or self-folding into other shapes. The specific geometrical shape that the 3D capillary origami structure ends up taking is determined by both the chemistry of the flat sheet and that of the liquid, and by carefully designing the shape and size of the sheet.
There is one big problem with these small devices, however. “These conventional self-assembled origami structures cannot be completely spherical and will always have discontinuous boundaries, or what you might call ‘edges,’ as a result of the original two-dimensional shape of the sheet,” said Kwangseok Park, a lead researcher on the project. He added, “These edges could turn out to be future defects with the potential for failure in the face of increased stress.” Non-spherical particles are also known to be more disadvantageous than spherical particles in terms of cellular uptake.
Professor Hyoungsoo Kim from the Department of Mechanical Engineering explained, “This is why researchers have long been on the hunt for substances that could produce a fully spherical capillary origami structure.”
The authors of the study have demonstrated such an origami sphere for the first time. They showed how instead of a flat sheet, the growth of salt-crystals can perform capillary origami action in a similar manner. What they call ‘crystal capillary origami’ spontaneously constructs a smooth spherical shell capsule from these same surface tension effects, but now the spontaneous encapsulation of a liquid is determined by the elasto-capillary conditions of growing crystals.
Here, the term ‘salt’ refers to a compound of one positively charged ion and another negatively charged. Table salt, or sodium chloride, is just one example of a salt. The researchers used four other salts: calcium propionate, sodium salicylate, calcium nitrate tetrahydrate, and sodium bicarbonate to envelop a water-oil emulsion. Normally, a salt such as sodium chloride has a cubical crystal structure, but these four salts form plate-like structures as crystallites or ‘grains’ (the microscopic shape that forms when a crystal first starts to grow) instead. These plates then self-assemble into perfect spheres.
Using scanning electron microscopy and X-ray diffraction analysis, they investigated the mechanism of such formation and concluded that it was ‘Laplace pressure’ that drives the crystallite plates to cover the emulsion surface. Laplace pressure describes the pressure difference between the interior and exterior of a curved surface caused by the surface tension at the interface between the two substances, in this case between the salt water and the oil.
The researchers hope that these self-assembling nanostructures can be used for encapsulation applications in a range of sectors, from the food industry and cosmetics to drug delivery and even tiny medical devices.
-Publication
Kwangseok Park, Hyoungsoo Kim “Crystal capillary origami capsule with self-assembled nanostructure,” Nanoscale, 13(35), 14656-14665 (DOI: 10.1039/d1nr02456f)
-Profile
Professor Hyoungsoo Kim
Fluid and Interface Laboratory
http://fil.kaist.ac.kr
Department of Mechanical Engineering
KAIST
2021.11.04 View 7452 -
Solutal Marangoni Flows of Miscible Liquid Drive Transport without Surface Contamination
(Professor Hyoungsoo Kim, Department of Mechanical Engineering, KAIST)
A research team led by Hyoungsoo Kim, a professor of Mechanical Engineering at KAIST, succeeded in quantifying the phenomenon called, the Marangoni effect, which occurs at the interface between alcohol and water. It is expected that this finding will be a valuable resource used for effectively removing impurities from a surface fluid without any contamination, and developing materials that can replace surfactants.
This research, co-conducted with a research team led by Professor Howard A. Stone at Princeton University, was published online in Nature Physics on July 31.
The Marangoni effect, also known as tears of wine, is generated when two fluids having a different surface tension meet, causing finite mixing, spreading time and length scale. Typically, people believe that infinitely miscible liquids immediately mix together; however, it is not always true according to this paper.
The typical surface tension of alcohol is three times lower than that of water, and this different surface tension generates the Marangoni-driven convection flow at the interface of the two liquids. In addition, there is a certain amount of time required for them to mix.
This phenomenon has been discussed many times since it was discovered in early the 20th century, yet there was a limit to quantifying and explaining it.
Professor Kim, considering the mixing and spreading mechanism, used various flow visualization techniques and equipment for capturing high speed images in his experiment.
Through the flow visualization methods, the team succeeded in quantifying and explaining the complex, physicochemical phenomenon generated between water and alcohol. Moreover, they developed a theoretical model to predict the physicochemical hydrodynamic phenomena.
The theoretical model can predict the speed of Marangoni-driven convection flow, the area of a drop of alcohol and the time required to develop the flow field. Hence, this model can map out types of materials (e.g., alcohol) and the volume of a drop of liquid as applicable to target a specific situation.
Moreover, the research team believes that the interfacial flow enables the driving of bulk flows and that it can be a source of technology for effectively delivering drugs and removing impurities from a surface of substance without causing secondary contamination.
Above all, the results show a possibility for replacing surfactant with alcohol as a material used for delivering drugs. In the case of the drug delivery, some drugs are encapsulated with a surfactant in order to be effectively transported in vivo; however, the surfactant accumulates in the body, which can cause various side effects, such as heart disease. Therefore, using new materials like alcohol for drug delivery will contribute to preventing the side effects caused by the surfactant.
“The surfactant is used for delivering drugs, but it is difficult to be expelled from the body. This will cause various side effects, such as heart diseases in asthmatic patients,” said Professor Kim. “I hope that using new materials, like alcohol, will free people from these side effects.”
(Marangoni-driven convection flow generated at the interface between water and alcohol, and the flow visualization results)
- A drop of alcohol on a water surface
- Comparison of mixing structures on the surface
- Marangoni mixing flow under the free surface
2017.08.18 View 7452