Letter | Published:

Vapour-mediated sensing and motility in two-component droplets

Nature volume 519, pages 446450 (26 March 2015) | Download Citation

This article has been updated

Abstract

Controlling the wetting behaviour of liquids on surfaces is important for a variety of industrial applications such as water-repellent coatings1 and lubrication2. Liquid behaviour on a surface can range from complete spreading, as in the ‘tears of wine’ effect3,4, to minimal wetting as observed on a superhydrophobic lotus leaf5. Controlling droplet movement is important in microfluidic liquid handling6, on self-cleaning surfaces7 and in heat transfer8. Droplet motion can be achieved by gradients of surface energy9,10,11,12,13. However, existing techniques require either a large gradient or a carefully prepared surface9 to overcome the effects of contact line pinning, which usually limit droplet motion14. Here we show that two-component droplets of well-chosen miscible liquids such as propylene glycol and water deposited on clean glass are not subject to pinning and cause the motion of neighbouring droplets over a distance. Unlike the canonical predictions for these liquids on a high-energy surface, these droplets do not spread completely but exhibit an apparent contact angle. We demonstrate experimentally and analytically that these droplets are stabilized by evaporation-induced surface tension gradients and that they move in response to the vapour emitted by neighbouring droplets. Our fundamental understanding of this robust system enabled us to construct a wide variety of autonomous fluidic machines out of everyday materials.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Change history

  • 17 November 2015

    An equation was corrected in the HTML on 17 November 2015.

References

  1. 1.

    Resistance of solid surfaces to wetting by water. Ind. Eng. Chem. 28, 988–994 (1936)

  2. 2.

    , & Dynamic surface phenomena in the spontaneous spreading of oils on solids. , DTIC document number NRL-5963 (Naval Research Laboratory, 1963)

  3. 3.

    On certain curious motions observable at the surfaces of wine and other alcoholic liquors. Phil. Mag. 10, 330 (1855)

  4. 4.

    Über die Ausbreitung der Tropfen einer Flüssigkeit auf der Oberfläche einer anderen. Ann. Phys. 219, 337–354 (1871)

  5. 5.

    & Purity of the sacred lotus, or escape from contamination in biological surfaces. Planta 202, 1–8 (1997)

  6. 6.

    , & Electrowetting-based actuation of liquid droplets for microfluidic applications. Appl. Phys. Lett. 77, 1725–1726 (2000)

  7. 7.

    , , , & Superhydrophobic surfaces: from structural control to functional application. J. Mater. Chem. 18, 621–633 (2008)

  8. 8.

    , & Fast drop movements resulting from the phase change on a gradient surface. Science 291, 633–636 (2001)

  9. 9.

    & How to make water run uphill. Science 256, 1539–1541 (1992)

  10. 10.

    , & Light-driven motion of liquids on a photoresponsive surface. Science 288, 1624–1626 (2000)

  11. 11.

    et al. Electrochemical principles for active control of liquids on submillimeter scales. Science 283, 57–60 (1999)

  12. 12.

    , & Motions of droplets on hydrophobic model surfaces induced by thermal gradients. Langmuir 9, 2220–2224 (1993)

  13. 13.

    et al. Patterning droplets with durotaxis. Proc. Natl Acad. Sci. USA 110, 12541–12544 (2013)

  14. 14.

    & Contact angle hysteresis. IV. Contact angle measurements on heterogeneous surfaces. J. Phys. Chem. 69, 1507–1515 (1965)

  15. 15.

    , & Capillarity and Wetting Phenomena: Drops, Bubbles, Pearls, Waves (Springer, 2004)

  16. 16.

    & Surface tensions of propylene-glycol plus water. J. Chem. Eng. Data 37, 331–333 (1992)

  17. 17.

    et al. Capillary flow as the cause of ring stains from dried liquid drops. Nature 389, 827–829 (1997)

  18. 18.

    & Influence of surfactants on an evaporating drop: Fluorescence images and particle deposition patterns. Langmuir 19, 8271–8279 (2003)

  19. 19.

    & Analysis of the effects of Marangoni stresses on the microflow in an evaporating sessile droplet. Langmuir 21, 3972–3980 (2005)

  20. 20.

    Spreading of silicone oil drops on horizontal surfaces. J. Phys. D 12, 1473–1484 (1979)

  21. 21.

    & Prevention of liquid spreading or creeping. Contact angle, wettability and adhesion. Adv. Chem. Ser. 43, 332–340 (1964)

  22. 22.

    & Marangoni effects in the spreading of liquid mixtures on a solid. Langmuir 3, 519–524 (1987)

  23. 23.

    & The behaviour of liquid drops and adsorbed films at cleavage surfaces of mica. Trans. Faraday Soc. 34, 0554–0569 (1938)

  24. 24.

    & Spreading involving the Marangoni effect—some preliminary results. Colloids Surf. 41, 97–105 (1989)

  25. 25.

    & Evaporation of a sessile droplet on a substrate. J. Phys. Chem. B 106, 1334–1344 (2002)

  26. 26.

    Motions of droplets on solid surfaces induced by chemical or thermal gradients. Langmuir 5, 432–438 (1989)

  27. 27.

    & Quantitative experimental study on the transition between fast and delayed coalescence of sessile droplets with different but completely miscible liquids. Langmuir 26, 11823–11829 (2010)

  28. 28.

    & Delayed coalescence behavior of droplets with completely miscible liquids. Langmuir 24, 6395–6398 (2008)

  29. 29.

    , & Clusters, asters and collective oscillations in chemotactic colloids. Phys. Rev. E 89, 062316 (2014)

  30. 30.

    & Actin microfilament dynamics in locomoting cells. Nature 352, 126–131 (1991)

  31. 31.

    coli in Motion (Springer, 2004)

  32. 32.

    , , , & Influence of substrate conductivity on circulation reversal in evaporating drops. Phys. Rev. Lett. 99, 234502 (2007)

Download references

Acknowledgements

We thank all members of the Prakash Laboratory for discussions. We thank J. C. Williams for early support of this work, B. Buisson for discussions, and G. R. Dick for discussions and reagents. N.J.C. is supported by a National Science Foundation Graduate Research Fellowship Program fellowship. A.B. is supported by the Pew Foundation. M.P. is supported by the Pew Program in Biomedical Sciences, the Terman Fellowship, Keck Foundation, the Gordon and Betty Moore Foundation and a National Science Foundation Career Grant.

Author information

Affiliations

  1. Department of Bioengineering, Stanford University, 450 Serra Mall, California 94305, USA

    • N. J. Cira
    • , A. Benusiglio
    •  & M. Prakash

Authors

  1. Search for N. J. Cira in:

  2. Search for A. Benusiglio in:

  3. Search for M. Prakash in:

Contributions

N.J.C. made the original observation. All authors designed the research. N.J.C. and A.B. conducted experiments, and all authors interpreted the data; N.J.C. and A.B. developed the models. N.J.C and A.B. wrote the manuscript, and all authors commented on it.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to M. Prakash.

Extended data

Supplementary information

PDF files

  1. 1.

    Supplementary Information

    This file contains Supplementary Methods, a Supplementary Discussion and Supplementary Video legends – see Contents page for details.

Videos

  1. 1.

    Long-range and short-range interactions in two-component droplets.

    Part 1) Complex movement of droplets Highly dynamic behaviour of PG/water droplets of various concentrations and sizes when placed simultaneously on a corona treated glass slide. (Slide dimensions: 25 x 75 mm, 4x speed). Part 2) Long-range attraction, different concentrations. Two 0.5 µL droplets of 25% PG (blue) and 1% PG (orange) are placed near each other on a corona treated glass slide. First the droplets move toward each other, then the droplet of higher PG concentration ‘chases’ the droplet of lower PG concentration which ‘flees’. (1x speed). Part 3) Long-range attraction, same concentration. Two 0.5 µL droplets of 10% PG are placed near each other on a corona treated glass slide. Both droplets move toward each other, and then they merge. (1x speed).

  2. 2.

    Internal flow

    The first clip shows flow in a droplet on clean corona treated glass as visualized in bright field by 5 µm diameter tracer beads. The beads are initially well distributed but collect into a ring at the liquid/vapour interface. Flow can be seen moving both toward the centre and toward the edge of the droplet. The second clip shows a fluorescent movie of 2 µm diameter tracer beads visualizing flow in a droplet on high energy treated glass. Like this first clip, beads move both toward the centre and the edge of the droplet, collecting in a ring at the liquid/vapour interface. The third clip shows the same droplet as in the second clip, but on an untreated, unclean glass slide (lower energy surface). The bead velocity is much slower and beads do not collect into a ring. The droplets are 10% PG. (All clips are 2x speed).

  3. 3.

    Long-range attraction.

    Part 1) Attraction across a break Two 10% PG droplets moving toward each other despite a break/gap in the substrate. (1x speed). Part 2) Pipette tip control. A droplet of 10% PG moves to follow a pipette tip which contains a droplet of water. (Slide dimensions: 25 x 75 mm, 4x speed).

  4. 4.

    Short-range chasing fluid exchange

    Transfer of fluorescein arises from the back droplet (25 % PG, dyed with fluorescein) to the front droplet (1% PG, initially no fluorescein) during a short-range chasing interaction. The camera is panning to the right, following the droplet. (1x speed).

  5. 5.

    Devices.

    Part 1) Self-alignment device 25% PG droplets are placed in lanes and allowed to move. From initially random positions they spontaneously arrange themselves in a line. (Slide dimensions: 25 x 75 mm, 4x speed). Part 2) Circular chasing. A 25% PG droplet (blue) pursues a 1% PG droplet (red) around a 2.1 cm mean diameter circular ring several times before merging. (16x speed). Part 3) Vertical oscillator. A 1% PG droplet (red) is chased up by a 25% PG droplet (blue) which remains at the bottom of a vertical lane due to gravity. The 1% PG droplet is eventually overcome by gravity and falls back, only to oscillate again once it contacts the 25% PG droplet. (8x speed). Part 4) Movement on flexible substrates. Here we show short-range chasing on flexible strips of ITO/PET which have been treated in a plasma oven for 5 min (droplets move on the high energy ITO side). Here a 25% PG droplet chases a 1% PG droplet in two different configurations. (4x speed).

  6. 6.

    Self-sorting device

    0.25 µL droplets are deposited at the top of the device and gravity acts to bring them down. As they slide down the device, they sample each well. They are chased away if the surface tension of the well is lower than their own surface tension. They merge when they have reached the well of like surface tension (same [PG]). As in all videos and figures, the colour is only present to aid in visualization and not important in the phenomena. (4x speed).

  7. 7.

    Repulsive long-range positioning

    Here we demonstrate contactless remote droplet positioning. The top plate has droplets of pure PG, which act to repel the 10% PG red droplet via vapour through long-range repulsion interactions. When we arrange these PG droplets in a circle, they form a vapour trap which we move around to demonstrate positioning. (8x speed).

  8. 8.

    Parallel plate devices.

    Part 1) Parallel plate alignmentTwo 0.5 μL 10% PG droplets (blue on top, yellow on the bottom) interact across an air gap via their vapour clouds on the adjacent side of two parallel glass slides. Here the slides are repositioned several times to show several examples of alignment. (8x speed). Part 2) Self-assembled, self-aligned 2-lens system. Here we use a similar configuration to the parallel plate aligner but use clear droplets and arrange the distance between the plates to create an image only once alignment has occurred. This system shows how lenses can be placed far apart and will self-assemble and self-align to produce images of various magnifications, depending on distances and curvatures of the lenses. (2x speed, and 4x speed). Part 3) Self-assembled, self-aligned 3-lens system with scanning. Here we show an optical system where 3 lenses with 4 optical surfaces self-assemble and self-align. The setup is similar to the 2-lens system with an additional plate inserted between the top and bottom plates. This additional plate has a hole drilled through it in which sits a pinned droplet with two optical surfaces. We then demonstrate the ability of this system to scan an area much larger than the lens itself by moving the center plate. When the center plate is moved, the other lenses follow then automatically realign (2x speed, and 8x speed).

  9. 9.

    Easy way to recreate

    Here we demonstrate an easy method to create the simplest version of this system and run basic experiments. For more detailed methods please refer to the methods section (Supplementary Information Section 1). (various speeds).

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nature14272

Further reading

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.