New Investigations of Liquid Marbles

Ed. Bormashenko, The Ariel University, Ariel, Israel Харьковский национальный университет имени В. Н. Каразина, Октябрь, 2013

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

Deformation of water marbles by gravity

V=10 μl V=50 μl

Marbles Sit on Air!

Hydrophobic particles liquid Solid substrate

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

E. Bormashenko, Ye. Bormashenko, A. Musin, Z. Barkay, ChemPhysChem 2009, 10, 654 30 μl marble containing 0.1 M CaCl 2 water solution floating on the 0.1 M Na 2 CO 3 water solution before puncturing with a needle CaCO 3 precipitate formed after puncturing the marble

Floating Marbles

Journal of Colloid and Interface Science , 333, 2009 , 419. Ed. Bormashenko, Ye. Bormashenko, Al. Musin

Revealing Water Surface Pollution with Liquid Marbles E. Bormashenko, A. Musin Applied Surface Science , 255, 12 , 2009 , 6429-6431

Superhydrophobic Behavior of Liquid Marbles

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

Materials:

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

)

Lycopodium Particles

ESEM Image of the Marble Surface (Coated with Lycopodium)

ESEM Image of Marble Surface (Coated with PVDF) Ed. Bormashenko, R. Pogreb, G. Whyman, Al. Musin, Ye. Bormashenko, Z. Barkay, 2009, 25 Langmuir , , 1893–1896

Liquid Marble Coated With Carbon Black

ρ ~170 Ω∙m Air pockets Hydrophilic particles

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.

Surface Tension of Marbles Established with Vibrations  

h

(  2 

Vf

)( 1  2 cos  )

R θ θ δθ

θ+δθ

Ed. Bormashenko, R. Pogreb, G. Whyman, Al. Musin, Ye. Bormashenko, Z., Langmuir , 2009, 25 (4), 1893–1896.

Values of surface tension measured with different methods.

Marbles γ, mJ/m2 maximal height method marble shape analysis vibration method PVDF 70±7 79±5 75±3 PE 66±5 63±3 60±4 Teflon Lycopodium Carbon black 60±6 50±5 66±4 53±5 60±5 68±3 53±3 43±3 -

Effective Surface Tension of Marbles

A B Pendant marbles: (A) lycopodium and (B) carbon black

Establishment of the effective surface tension with the pendant marble method   

r

( 1  1

r

 2 )  ( 1 

r



r

 2 ) 3 / 2    

gz

E. Bormashenko, Al. Musin, G. Whyman, Z. Barkay, A. Starostin, V. Valtsifer, Vl. Strelnikov Colloids and Surfaces A: 425 (2013) 15-23

Dependence of the effective surface tension on the volume during inflation (open circles) and evaporation (solid circles) for the lycopodium coated marbles .

Dependence of the effective surface tension on the volume during inflation (open circles) and evaporation (solid circles) for the PVDF coated marbles .

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

Actuation of Liquid Marbles

Ferrofluidic Marbles

V=25 cm/s magnetic powder PVDF Ed. Bormashenko, R. Pogreb, Ye. Bormashenko, Al. Musin, T. Stein, Langmuir , 2008, 24 , 12119–12122

Ferrofluidics with Liquid Marbles

g

Ferrofluidic marble magnet superhydrophobic surface

Ed. Bormashenko, R. Pogreb, Ye. Bormashenko, Al. Musin, T. Stein, Langmuir , 2008, 24 , 12119–12122

T



E

c 4  0  T=1.63-1.65

r

0

Jetting Liquid Marbles (Taylor Instability) water marbles immersed in PDMS Colloid Polymer Sci. (2013) 291:1535–1539

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.

E

c 2  1

A r

0 

B

 eff  4  0

A T

2 300000 200000 100000 400 450 500 550 1 /r 0 , m -1 600 Lycopodium marble PVDF marble Teflon marble Water droplet 650 700

Micro-Pump Based on Liquid

Bormashenko, E. et al,

Applied Physics Letters

, 97 (2010) 091908

Marbles

Parameters of the Micro-Pump



p

 2 ( 

eff

,

PVDF

 

eff

,

lyc

)

R

 20

Pa Q

  

p

8 

l r

4

Q

 100 

l s

Marbles Swallowing One Another

Composite Liquid Marbles and Their Actuation

PTFE (white) and carbon black coated (black) 20 µl liquid marbles

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), 7–10

Composite 40 µl Janus liquid marble

Watermelon-like marble obtained by merging of two Janus marbles

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), 7–10

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 CH 2 I 2 ( white) of the same volume of 10 µl. B. Water marble climbed on the MI one.

A B

10 µl MI (white) and 10 µl water (red) marbles exposed to the electric field. The initial state exposed to E =7 C. 10 µl MI (white) and 40 µl water (red) marbles exposed to the electric field. The initial state marbles exposed to × 10 E= 7 5 E × =0, B. The marbles V/m 10 5 V/m E =0, D. The

Sensitivity of water and diiodomethane (CH 2 I 2 ) marbles to electric field

G



G S



G gr



G el G el

  0 

E

2

V

2

G gr

 

Vgh

    0 

gR E

2

Sensitivity of water and diiodomethane (CH 2 I 2 ) marbles to electric field  

water MI

   

MI water



MI water R MI R water

 

water MI

  

water



MI



MI water

 50 same radii  

water MI

 30

V MI V water

 1 4

Manufacturing “sandwich marbles” containing solid particles

powder foamed PS ball liquid

Sandwich water marbles containing spherical particle of foamed PS

Manufacturing “sandwich marbles”

FD-POSS powder Liquids: Hexadecane or Toluene DMSO

Sandwich Marbles: Hexadecane Marble Comprising DMSO (Red)

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 .

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) 196–199.

Lycopodium-coated shaped marbles

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

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

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



Thanks for Invitation!