New Investigations of Liquid Marbles

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New Investigations of Liquid Marbles
Ed. Bormashenko, The Ariel University, Ariel,
Israel
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What is a Liquid Marble? A liquid Marbles Are
Non-Stick Droplets Coated with Macro- or
Nano-Scaled Powder
P. Aussillous, D. Quéré, Nature, 411 (2001)
924-927
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Deformation of water marbles by gravity
V10 µl
V50 µl
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Marbles Sit on Air!
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E. Bormashenko, Ye. Bormashenko, A. Musin, Z.
Barkay, ChemPhysChem 2009, 10, 654

15 µl marble containing 0.3 M NaOH water solution floating on the water containing phenolphthalein alcohol solution (0.1 wt.) Coloring after puncturing the marble
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E. Bormashenko, Ye. Bormashenko, A. Musin, Z.
Barkay, ChemPhysChem 2009, 10, 654

30 µl marble containing 0.1 M CaCl2 water solution floating on the 0.1 M Na2CO3 water solution before puncturing with a needle CaCO3 precipitate formed after puncturing the marble
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Floating Marbles
Journal of Colloid and Interface Science, 333,
2009, 419. Ed. Bormashenko, Ye. Bormashenko, Al.
Musin
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Revealing Water Surface Pollution with Liquid
Marbles
E. Bormashenko, A. Musin Applied Surface Science,
255, 12, 2009, 6429-6431
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Superhydrophobic Behavior of Liquid Marbles
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Motivation

• Liquid marbles an alternative approach to
  manufacturing non-stick surfaces
• Study of physical properties of liquid marbles
• Study of the possibility of remote actuation of
  liquid marbles

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Materials

• Polyvinylidene fluoride (PVDF)
• Polytetrafluoroethylene (PTFE)
• Polyethylene (PE)
• Lycopodium
• Carbon black (hydrophilic!)

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Lycopodium Particles
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ESEM Image of the Marble Surface (Coated with
Lycopodium)
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ESEM Image of Marble Surface (Coated with PVDF)
Ed. Bormashenko, R. Pogreb, G. Whyman, Al. Musin,
Ye. Bormashenko, Z. Barkay, Langmuir, 2009, 25 ,
18931896
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Liquid Marble Coated With Carbon Black
? 170 Om
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Properties of Liquid Marbles

• What is the effective surface tension of liquid
  marbles?
• Aussillous and D. Quéré Proceedings Royal Soc.
  A, 2006, 462, 973.
• G. McHale, S. J. Elliott, M. I. Newton, D. L.
  Herbertson, K. Esmer, Langmuir, 2009, 25, 529.
• T. Arbatan, W. Shen Langmuir, 2011, 27, 12923
• C. Planchette, E. Lorenceau, A.-L. Biance, Soft
  Matter, 2012, 8, 2444.

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Surface Tension of Marbles Established with
Vibrations
Ed. Bormashenko, R. Pogreb, G. Whyman, Al. Musin,
Ye. Bormashenko, Z., Langmuir, 2009, 25 (4),
18931896.
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Values of surface tension measured with different
methods.
Marbles ?, mJ/m2
maximal height method marble shape analysis vibration method  
PVDF 707 795 753  
PE 665 633 604
Teflon 606 535 533  
Lycopodium 505 605 433
Carbon black 664 683 -  
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Effective Surface Tension of Marbles
A
B
Pendant marbles (A) lycopodium and (B) carbon
black
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Establishment of the effective surface tension
with the pendant marble method
E. Bormashenko, Al. Musin, G. Whyman, Z. Barkay,
A. Starostin, V. Valtsifer, Vl.
Strelnikov Colloids and Surfaces A 425 (2013)
15-23
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Dependence of the effective surface tension on
the volume during inflation (open circles) and
evaporation (solid circles) for the lycopodium
coated marbles.
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Dependence of the effective surface tension on
the volume during inflation (open circles) and
evaporation (solid circles) for the PVDF coated
marbles.
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Surface Tension of Liquid Marbles is of a
Pronounced Hysteretic Nature
E. Bormashenko, Al. Musin, G. Whyman, Z. Barkay,
A. Starostin, V. Valtsifer, Vl.
Strelnikov Colloids and Surfaces A 425 (2013)
15-23
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Actuation of Liquid Marbles
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Ferrofluidic Marbles
V25 cm/s
Ed. Bormashenko, R. Pogreb, Ye. Bormashenko, Al.
Musin, T. Stein, Langmuir, 2008, 24 , 1211912122
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Ferrofluidics with Liquid Marbles
Ed. Bormashenko, R. Pogreb, Ye. Bormashenko, Al.
Musin, T. Stein, Langmuir, 2008, 24 , 1211912122
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Jetting Liquid Marbles (Taylor
Instability)water marbles immersed in
PDMSColloid Polymer Sci. (2013) 29115351539
T1.63-1.65
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Squared critical electric field versus inverse
radius, of the spherical marble of an equivalent
volume. Different slopes resemble different
surface energies at the marble/oil interfaces.
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Micro-Pump Based on Liquid Marbles
Bormashenko, E. et al, Applied Physics Letters,
97 (2010) 091908
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Parameters of the Micro-Pump
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Marbles Swallowing One Another
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Composite Liquid Marbles and Their Actuation
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PTFE (white) and carbon black coated (black) 20
µl liquid marbles
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Preparing Janus Marbles
vibration
Ed Bormashenko, Ye. Bormashenko, R. Pogreb, O.
Gendelman, Janus Droplets Liquid Marbles Coated
with Dielectric/Semiconductor Particles Langmuir
2011, 27(1), 710
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Composite 40 µl Janus liquid marble
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Watermelon-like marble obtained by merging of two
Janus marbles
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The sequence of images demonstrating the rotation
of the Janus marble by the growing electric field
Ed Bormashenko, Ye. Bormashenko, R. Pogreb, O.
Gendelman, Janus Droplets Liquid Marbles Coated
with Dielectric/Semiconductor Particles Langmuir
2011, 27(1), 710
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The sequence of images illustrating the behavior
of composed marble exposed to electric field. A.
Initial state, the composite marble built of the
water (red) and CH2I2 ( white) of the same volume
of 10 µl. B. Water marble climbed on the MI one.
A
B
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10 µl MI (white) and 10 µl water (red) marbles
exposed to the electric field. The initial state
E0, B. The marbles exposed to E7 105 V/mC. 10
µl MI (white) and 40 µl water (red) marbles
exposed to the electric field. The initial state
E0, D. The marbles exposed to E7 105 V/m
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Sensitivity of water and diiodomethane (CH2I2)
marbles to electric field
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Sensitivity of water and diiodomethane (CH2I2)
marbles to electric field
same radii
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Manufacturing sandwich marbles containing solid
particles
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Sandwich water marbles containing spherical
particle of foamed PS
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Manufacturing sandwich marbles
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Sandwich Marbles Hexadecane Marble Comprising
DMSO (Red)
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Micro-Reactors Based on Marbles
The shell enwrapping the marble is permeable for
gases
Marbles containing a solution of ammonia acetate,
acetic acid and acetylacetone exposed to the
formaldehyde vapor Bormashenko E, et al
International Journal of Chemical Reactor
Engineering, 9 (2011) S10.
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Pickering-like emulsions obtained via liquid
marbles (water marbles immersed in PDMS)
Bormashenko E., Pogreb R., Musin Al., Stable
water and glycerol marbles immersed in organic
liquids From liquid marbles to Pickering-like
emulsions, Journal of Colloid and Interface
Science 366 (2012) 196199.
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Lycopodium-coated shaped marbles
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Conclusions
Liquid marbles are non-stick droplets coated with
hydrophobic or hydrophilic powder Marbles are
separated from a substrate by air pockets Janus
and composite marbles could be manufactured
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Conclusions
Surface Tension of Liquid Marbles is of a
Pronounced Hysteretic Nature Marbles could be
actuated with magnetic and electric
fields Possible applications of
marbles Micro-fluidic devices, Gas
sensing Precise transport of small quantities of
liquids, Revealing of water pollution, blood
typing
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Acknowledgements

• The authors are grateful to Professor M. Zinigrad
  for his continuous support of our research
  activity
• The authors are thankful to Mrs. Zahava Barkay
  for SEM and ESEM imaging

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• Thanks for Invitation!