Droplets that

Sprout Millimetre
Paul S.Tubes
Clegg
Scale
University of Edinburgh

Particles on Interfaces

B. P. Binks, Current Opinion in Colloid & Interface Science, 2002, 7, 21 41

Pickering emulsions

Rigid interfaces
As colloids are
pulled apart
new interface is
exposed

When an interface of closepacked colloids is strained it

is predominantly the
interfacial tension that leads
to the elastic properties.
Youngs Modulus E ~ / dD. Vella et al, Europhys. Lett. 68,

Demonstrations of elastic
interfaces

Pickering
emulsions dont
need to be made
of spherical
droplets!

Ostwald ripening

Laplace pressure is higher in smaller droplets

Oils with non-zero partition coefficient will dissolve from small droplets and
condense in large droplets
Change in size distribution with time

Pickering emulsions &

ripening
Ostwald
ripening

Particles rarely come off

emulsion droplets
At the same time Ostwald
ripening begins to reduce
the volume of oil

The liquid-liquid interface

that is exposed between
particles changes shape
Laplace pressure goes to
zero and can become
negative

Pickering emulsions &

ripening
Compositional
ripening

Surprisingly this effect still occurs with particle-stabilized droplets

Yellow completely insoluble oil

Green very slightly soluble oil

Effect of insoluble oil as a solute

drives soluble oil into yellow droplets

Outline
1.Growing droplets
2.Changing the solute
3.When two droplets meet

Marangoni Instability

1.8 mm diameter needle with a water droplet hanging off it

Continuous phase oil (toluene) containing 20vol% alcohol (ethanol)

Ethanol partitions into the droplet modifying the interfacial tension on the wa

vidence of the Particles at the Interf

Needle
1.8mm

20x real time

Bath: 0.2 vol% fumed silica and 5 vol% ethanol in toluene

Droplet: Water

Sessile drop
Scale bar 5mm

Initial droplet diameter ~ 3mm

10x real time

Bath: 0.2 vol% fumed

silica &
15 vol% ethanol in

10x real time

Ternary Phase Diagram

Ruschak &
Millar, Ind. Eng.
Chem. Fundem.
11, 534, (1972)

Solubilities of inorganic and organic compounds Vol. 2, Ternary systems Part 1, ed H.

Stephen and T. Stephen, Pergamon Press, Oxford, 1963

Composition profile at
the interface
Liquid-liquid interface

Composition halo

Growth Behaviour
Ethanol
partitions into
droplet

Low density
layer rich in
ethanol rises

Toluene layer
depleted in
ethanol

Water
layer
rich in
ethan
ol

Drople
t
sprout
s tube

Buckling
A regular buckling pattern appears on the tube as
it topples
Scale bar 5mm

Bath: 0.2 vol% fumed silica & 15 vol% ethanol

in toluene
Droplet: Water

Interfacial Rheology
Via interfacial shear experiments we can show that
the interfaces are more difficult to deform at higher
particle concentrations

Interfacial Rheology

A floppy interface cant support growth; and

undeformable interface isnt very useful either!

Shuffling

Scale bar 5mm

Bath: 0.2 vol% fumed silica & 15 vol% ethanol

in toluene

Droplet army

Scale bar 5mm

Bath: 0.2 vol% fumed silica & 15 vol% ethanol

in toluene

Other regimes

Outline
1.Growing droplets
2.Changing the solute
3.When two droplets meet

Changing the Solute

Changes the rate of partitioning
Changes the particle
interactions
Changes the interfacial tension
Does not change density based

effects
Solute

Distribution
Coefficient

Solute

Density
(g/mL)

Methan
ol

0.04

Propano
l

0.802

Ethanol

0.11

Methan
ol

0.791

Propan
0.90
A. W. ol
Islam, A. Zavvadi and V. N. Kabadi, Chem. ProcessEthanol
Eng., 2012, 33, 243
253
0.789

Solute: Propanol

Critical Point

Distribution
Coefficient
0.90
41x real time

Bath: 0.2 vol% fumed silica and 10 vol% propanol in toluene

Droplet: Water

Solute: Methanol

Critical Point

Distribution
Coefficient
0.04
33x real time

Bath: 0.2 vol% fumed silica and 25 vol% methanol in toluene

Droplet: Water

Interfacial tension

Mixtures of Alcohols

Outline
1.Growing droplets
2.Changing the solute
3.When two droplets meet

Droplet contact
Pendant droplet

Sessile droplet

Droplet contact

Old
droplet

New
droplet

Composition profile at
the interface
Liquid-liquid interface

Composition halo

Droplet contact
Bridge building is followed by:
- Large scale transfer of solvent
- Bridge breaking and retraction

Droplet contact
The extent of solvent transfer could well vary

Self assembly
You can try to
tune interactions
to give exciting
assemblies of
bits
A different
approach is to
try to shake your
lego bits the
right way
A driven system
can self
assemble in new

Conclusion
This system does self-organization to an
unprecedented degree
We have four successive steps:
1). Droplet growth
2). Bridge building
3). Transfer of solvent
4). Collapse / retraction

Future plans
We have sprouting droplet behaviour is
controlled by:
Density differences within the droplet
Particle coverage
Solute partitioning rate
Particle interactions
Large scale fluid movement between phases.
To now investigate
Dramatic compositional ripening
Droplets whose interactions depend on
contents

Acknowledgements

Iliya Stoev
Migle Grauzinyte
Katherine Rumble
Joe Forth
M. Grauinyt, J. Forth, K. A. Rumble, P.
S. Clegg, Angew. Chem. Int. Ed., 2015,