Interactions between Particles with an Undulated

Contact Line at a Fluid Interface: Capillary

Multipoles of Arbitrary Order

Paper Submitted to: Journal of Colloid and Interface Science

by Krassimir Danov, Peter Kralchevsky, Boris Naydenov and Günter Brenn

Capillary force between particles:

Force mediated

by a fluid interface
 Kinds of Capillary Forces

KEY: The lateral capillary forces are due to the overlap of the menisci formed
around the separate particles attached to a fluid interface.
 Origin of the Lateral Capillary Force

F(1) = F(2) = F

F = F() + F(p) F()  e x   dlm F(p)  e x   ds (nP)

L S

(force due to surface tension) (force due to pressure)

Presence of second particle breaks the axial symmetry  nonzero integral force
 Capillary Immersion Forces and 2D Crystallization

evaporation

(a) Brownian motion - thick layer (2R > h) (b) Aggregation after particle protrusion (2R < h)

Two consecutive stages of 2D array formation (latex particles 1.7 m in diameter)

 Convective Self-Assembly of Colloids and Proteins

Role of Water Evaporation:

Drives convective flow from
the suspension toward array.
N. Denkov et al., Nature 361 (1993) 26.

Protein ferritin, 2R = 12 nm 

Latex beads, 2R = 1.7 m 

 Meniscus Overlap around Particles of Undulated Contact Line

Rough-edged particles have

undulated contact line when Copolymer latex particles (PS/HEMA):
Cardoso et al. Langmuir 15 (1999) 4447.
attached to a fluid interface.
Capillary Multipoles

Meniscus around a particle of undulated contact line:


H(r,) =  K m (qr ) (Am cos m + Bm sin m)
m 0
(q 2  g /  )
Analogy with electrostatics:
m = 0 – “capillary charges”
m = 1 – “capillary dipoles”
m = 2 – “capillary quadrupoles”
m = 3 – “capillary hexapoles”
..................................................
The capillary force spontaneously rotates a floating
particle to annihilate its dipole moment (m = 1)

 The leading multipole orders are the charges and

quadrupoles.
 Interaction between “Capillary Quadrupoles”

The signs “+” and “” = local deviations of the contact line from planarity.
(a) Initial state. (b) After rotation of the particles at angles  A and  B =   A.

Asymptotic formula, Stamou et al. Phys. Rev. E 62 (2000) 5263:

rc4
W ( L)  12H cos(2 A  2 B ) 4 , m  2, L  2rc
2
L
For typical parameter values W becomes greater than the thermal energy kT
for undulation amplitude H > 3 Å. (Even minimal roughness  capillary force).
See also: P. Kralchevsky, N. Denkov, K. Danov, Langmuir 17 (2001) 7694–7705.
2D arrays: capillary quadrupoles (m = 2) and hexapoles (m = 3)

Quadrupoles form square array Hexapoles form hexagonal array

Bowden, Whitesides et al., J. Am. Chem. Soc. 121 (1999) 5373-5391.

A.B.D. Brown, C.G. Smith, et al., Phys. Rev. E 62 (2000) 951-960:

curved disks,
having one
hydrophilic and
one hydrophobic
side.
Generalization of the Theory to Arbitrary Capillary Multipoles

 2  2
2
 2
 0
 

The Laplace equation is

solved in bipolar coordinates
( , )
Boundary conditions:  A  H A cos[mA (   A )];  B  H B cos[mB (   B )]
 Expression for the Interaction Energy W(L, A, B)

The meniscus shape, z =  ( , ), is found by solving the Laplace equation.

Next, the interaction energy (the surface excess surface energy) is calculated:

W ( L )  W ( L )  W (  )


W ( )  ( mA H A2  mB H B2 )
2
 
W ( L)   ds  ( ) 
2S
 
2 Y  A, B C
dl n ( )
m Y

W ( L)
Results:  H A2 S A ( L)  H B2 S B ( L)  H A H B G ( L) cos(mB B  mA A )

where SA(L), SB(L), and G (L) are known functions, given by infinite series;

The dependence of W(L) on  A and  B is given explicitly by the cosine.

 Example: Hexapoles   3 A  3 B For 5 <   < 25, the
dependence W(L) has
a minimum.
0.6
Dimensionless energy, W(L)/( H2)

HA = HB = H For 0    < 5 the

0.4 interaction is attraction
20o at all distances.
0.2
30o
The energy of capillary
interaction is very large
25o
0.0 compared to the
15o thermal energy kT, even
-0.2 for undulations of 10
10o nm amplitude.
-0.4 Long-distance asymptotics The asymptotic
5o
formula becomes
0o
-0.6 sufficiently accurate for
1.0 1.2 1.4 1.6 1.8 2.0 L/(2rc) > 1.5.
Dimensionless distance, L/(2rc)

Energy of interaction between two capillary hexapoles (mA = mB = 3) for

two identical particles: HA = HB = H; rA = rB = rc. The different curves
correspond to different phase angle   , denoted in the figure; the
dashed line is the asymptotic expression for large L and   = 0.
Asymptotic expressions for W(L) for some values of mA and mB

Type of (mA, mB) Interaction Energy W(L)

interaction
2
charge – (0, 2)  r 
quadrupole   QA H B cos[2( B   )] B 
2 L
mB
charge – (0, mB)  r 
multipole   QA H B cos[mB ( B   )] B 
2 L
quadrupole – (2, 2) (rA rB ) 2
quadrupole  12 H A H B cos[2( A   B )]
L4
quadrupole – (2, 3) rA2 rB3
hexapole 24 H A H B cos(2 A  3 B )
L5
hexapole – (3, 3) rA3 rB3
hexapole  60 H A H B cos(3 A  3 B )
L6
multipole – (mA, mB) rAmA rBmB
multipole  G0  H A H B cos(mA A  mB B )
L( mA  mB )
 Rheology of Particulate Monolayers
(response of a “quadrupole” monolayer to deformations)

Shear
deformation 

2
Yield Stress: H  ES / *  169
 *  0.137   
(small effect)  rc 
H/rc = 0.1 and  = 70 mN/m
2
ES  16.1 mN/m
Shear Elasticity: H
ES  23   Predictions which have to be
(considerable effect)  rc 
checked experimentally !
 Rheology of Particulate Monolayers
(response of a “hexapole” monolayer to deformations)

Shear
deformation 

Shear Elasticity:
(considerable effect)

2
H
ES  64   
 rc 

H/rc = 0.1 and  = 70 mN/m

ES  44.8 mN/m

Predictions that have to be

checked experimentally !
 Conclusions

1. As a generalization of previous studies, here, we derive expressions for

the interaction between two capillary multipoles of arbitrary order.
2. Simpler asymptotic expressions for the interaction energy at not-too-
short interparticle distances are also derived.
3. Depending on   , the interaction is either monotonic attraction, or it is
attraction at long distances but repulsion at short distances.
4. Typically, for H  5 nm, the interaction energy is much greater than the
thermal energy kT.
5. Owing to the angular dependence of the interaction energy, the
adsorption monolayer of capillary multipoles has a considerable shear
elasticity, and should behave as a 2D elastic solid, rather than 2D fluid.
6. The forces between capillary multipoles could influence many
phenomena with particles, particle monolayers and arrays at fluid
interfaces, but experimentally, these effects are insufficiently explored.