ECTrieste 2

Liquid flows on surfaces:
the boundary condition
E. CHARLAIX
University of Lyon, France
NANOFLUIDICS SUMMER SCHOOL August 20-24 2007

THE ABDUS SALAM INTERNATIONAL CENTER FOR THEORETICAL PHYSICS
The no-slip boundary condition (bc):
a long lasting empiricism regularly questionned
Some examples of importance of the b.c. in nanofluidics

Pressure drop in nanochannels
Elektrokinetics effects
Dispersion & mixing
Theory of the h.b.c. for simple liquids
Slippage effects in macroscopic flows ?

Microchannels…
…nanochannels 500 nm
Miniaturization increases surface to volume ratio:

importance of surface phenomena
The description of flows requires

constitutive equation (bulk property of fluid)
+ boundary condition (surface property)
Yesterday we saw that N.S. equation for simple liquids is very
robust constitutive equation down to (some) molecular scale.
What about boundary condition ?

Hydrodynamic boundary condition (h.b.c.)
at a solid-liquid interface
v(z)
VS = 0
Usual b.c. : the fluid velocity vanishes at wall

 Phenomenological : derived from experiments on low molecular
mass liquids
 OK at a macroscopic scale and for simple fluids

The nature of hydrodynamics bc’s has been widely debated in 19th century
Goldstein S. 1969. Fluid mechanics in the first half of this century. Annu. Rev. Fluid Mech 1:1–
28
Lauga & al, in Handbook of Experimental Fluid Dynamics, 2005
M. Denn, 2001 Annu. Rev. Fluid Mech. 33:265–87
Batchelor, An introduction to fluid dynamics, 1967
Goldstein 1938
But wall slippage occurs in polymer flows…
Shark-skin effect in
extrusion of polymer melts
Pudjijanto & Denn 1994
J. Rheol. 38:1735
… and some time suspected on non-wetting surfaces
And also
Bulkley (1931),Chen & Emrich (1963), Debye & Cleland (1958)…
Drainage experiments with SFA
Ag
mica
Ag
C. Chan and R. Horn no-slip flow with liquid monolayer

J. Chem. Phys. (83) 5311, 1985 sticking at wall
various organic liquids/mica
J.N. Israelachvili
J. Colloid Interf. Sci. (110) 263, 1986 Water on mica: no-slip within 2 Å
George et al., no-slip flow w. monolayer sticking at wall

J. Chem. Phys. 1994 various organic liquids/ metal surfaces
N.V. Churaev, V.D; Sobolev and A.NSomov
J. Colloid Interf. Sci. (97) 574, 1984
∆P
Water slips in hydrophobic capillaries

slip length 70 nm
Partial slip and solid-liquid friction
Navier 1823
z Maxwell 1856
v(z)
b VS ≠ 0
Tangentiel stress at interface
∂V
σS = η = λ VS
∂z
VS : slip velocity
S : tangential stress at the solid surface
∂V
 : liquid viscosity VS = b
€ ∂z
 : liquid-solid friction coefficient
b : slip length η
∂V =  € b=
∂z : shear rate λ
Interpretation of the slip length
From Lauga & al, Handbook of Experimental Fluid Dynamics, 2005

Some properties of the slip length
 No-slip bc (b=0) is associated to very large liquid-solid friction
 The bc is an interface property.

The slip length has not to be related to an internal scale in the fluid
On a mathematically smooth surface, b=∞ (perfect slip).
 The hydrodynamic b.c. is fully characterized by b()
 The hydrodynamic bc is linear if the slip length does not depend on

the shear rate.

Dispersion & mixing

Slit z
b
d x
∆P
Tube
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décompresseur TIFF (non compressé)
sont requis pour visionner cette image.
r
Exemple 1 d=1 µm %error on permeability : 12%
slit
b=20 nm
Exemple 2 r = 2 nm Error factor on permeability : 80
tube b=20 nm (2 order of magnitude)

Exemple 3 Forced imbibition of hydrophobic mesoporous medium
mesoporous silica: MCM41
10nm
B. Lefevre et al, J. Chem. Phys 120 4927 2004

Water in silanized MCM41
The intrusion-extrusion cycle of water in
of various radii (1.5 to 6 nm)
hydrophobic MCM41
quasi-static cycle, does not depend on

frquency up to kHz
Porous grain
L ~ 2-10 µm
Dispersion of transported species - Mixing
d
Taylor dispersion
t=0 time t
injection
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Without molecular diffusion: décompresseur TIFF (non compressé)
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requis pourTIFF
Molecular diffusion spreads the solute through the width within sont visionner cette
Solute motion is analogous to random walk:

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b
d
With partial slip b.c.
t=0 time t
b
d
With partial slip b.c.
t=0 time t QuickTime™ et un

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Same channel, same flow rate sont requis pour visionner cette image.
Hydrodynamic dispersion is significantly reduced if b ≥ d

b = 0.15 d reduction factor 2
b = 1.5 d reduction factor 10
Electrokinetic phenomena
Colloid science, biology, …
Electrostatic double layer

nm 1 µm
Electric field
electroosmotic flow
Electro-osmosis, streaming potential… are determined by interfacial

hydrodynamics at the scale of the Debye length
z
E vos
+ +
+ + x
+ + + + + +
- - - - - - - - -
z
E vos
no-slip plane
+ +
+ + x
+ + + + + +
- - - - - - - - -
zH
Case of a no-slip boundary condition:
zeta potential
z
E vos
+ +
+ + x
+ + + + + +
- - - - - - - - -
Case of a partial slip boundary condition:

 At constant s the electroosmotic
velocity depends on Debye length.
Pb for measuring surface charges 
 Possibility of very large el-osmotic

flow by decreasing 
Example: b=20nm
 = 3nm at 10-2M
os increased by 800%
Churaev et al, Adv. Colloid Interface Sci. 2002

L. Joly et al, Phys. Rev. Lett, 2004

Dispersion & mixing
What about macroscopic flows ?

Effect of surface roughness
Fluid mechanics calculation :
Far field flow : no-slip
locally: perfect slip
Richardson, J Fluid Mech 59 707 (1973),

Janson, Phys. Fluid 1988
roughness « kills » slip

Slip at a microscopic scale :
molecular dynamics on simple liquids
Robbins (1990)
Barrat, Bocquet (1994, 1999)
Thomson-Troian (Nature 1997)
u
q = 2 
Thermodynamic equilibrium determination of b.c.
with Molecular Dynamics simulations
Bocquet & Barrat, Phys Rev E 49 3079 (1994)
Be j(r,t) the fluctuating momentum density at point r

Assume that it obeys Navier-Stokes equation
And assume boundary condition

b
Then take its <x,y> average
And auto-correlation function
C(z,z’,t) obeys a diffusion equation
with boundary condition b
and initial value given by

thermal equilibrium
2D density
C(z,z’,t) can be solved analytically and obtained as a function of b

b can be determined by ajusting analytical solution to data
measured in equilibrium Molecular Dynamics simulation
b
Slip at a microscopic scale : linear response theory
Green-Kubo relation for the hydrodynamic b.c.:
Liquid-solid canonical
total force exerted equilibrium
Friction coefficient
by the solid on the liquid
(assumes that momentum fluctuations in fluid obey Navier-Stokes

equation + b.c. condition of Navier type)
Friction coefficient (i.e. slip length) can be computed at equilibrium from

time decay of correlation function of momentum tranfer
Slip at a microscopic scale : molecular dynamics
Barrat, Bocquet, PRE (1994)
 « soft sphere » liquid

interaction potential  (r) = (r)12
molecular size : 
 hard wall u
corrugation z=u cos qx
q = 2 
 attractive wall
interaction potential z)= sf (1/z9-1/z3)
u/ b/
 very small surface corrugation is
0 ∞
enough to suppress slip effects
0.01 40
 Strong wall-fluid attraction induces >0.03 0
an immobile fluid layer at wall >0.03 -2
sf =15
Effect of liquid-solid interaction
Barrat et al Farad. Disc. 112,119 1999
Simple Lennard-Jones fluid

with fluid-fluid and fluid-solid interactions
⎡⎛σ ⎞12 ⎡⎛σ ⎞6 ⎤⎤ D

vα β (r) = 4ε⎢⎜ ⎟ − cα β ⎢⎜ ⎟ ⎥⎥
⎣⎝ r ⎠
⎢ ⎣⎝ r ⎠ ⎦⎥
⎦
 = {fluid,solid}
c parameter controls wettability
€
Wettability is characterized by contact angle (c.a.)
cFS=1.0 : =90°
cFS=0.5 : =140°
cFS=0 : =180°
Two types of flow
Couette flow Poiseuille flow

F0
V(z)
U
V(z)
b=0
b=0
z/ z/
Here : =140°, P~7 MPa

Slip length b=11 is found (both case)
Slip at a microscopic scale: liquid-solid interaction effect
 essentially no (small) slip in

b/ =140° partial wetting systems ( < 90°)
 substantial slips occurs on

strongly non-wetting systems
 slip length increases with c.a.
130°
 slip length increases stronly as
=90°
pressure decreases
P0~MPa Po ~ MPa
P/P0
 Linear b.c. up to ~ 108 s-1

fluid density profile across the cell
Soft spheres on hard repulsive wall Lennard-Jones fluid  = 137°
QuickTime™ et un
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Slip increases with reduced fluid density at wall.

However slippage does not reduce to « air cushion » at wall.
Slip at a microscopic scale: theory for simple liquids
Analytical expression for slip length Barrat et al Farad. Disc. 112,119 1999
molecular size
//
density at wall, wall corrugation

fluid struct.factor
depends on a exp(q// • R//)
parallel to wall
wetting properties
Depends only on structural parameters, no dynamic parameter

Intrinsic b.c. on smooth surfaces : conclusion
.
 at moderate shear rate ( < 108 s-1 ) essentially no slip in wetting systems
 substantial slips occurs in strongly non-wetting systems

slip length increases with c.a.
slip length depends strongly on pressure
 slip length amplitude is moderate (~ 5 nm at  )
 slip length is not expected to depend on fluid viscosity (≠ polymers)
 non-linear slip develops above a (high) critical shear rate (~ 109 s-1 )
Thomson-Troian Nature 1997


Dispersion & mixing

Duez, Ybert, Clanet, Bocquet
Nature Physics 3, 180, 2007
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sont requis pour visionner cette image. décompresseur
MOVING CONTACT LINE INSTABILITY
U static contact angle

e
z LV SV SV - SL = LV cos e
d
d dynamic ‘ ‘
SL
QuickTime™ et un
Tangential stress on L/S surface diverges at c.l. sont requis pour visionner cette image.
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Adds a dynamic force at c.l.:

The dynamic c.a. increases QuickTime™ et un

with flow velocity: sont requis pour visionner cette image.
Above threshold Ca > Cac, d = 180° Capillary number

the c.l. destabilizes, a fluid film is trapped QuickTime™ et un
LANDAU-LEVITCH EFFECT
U
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décompresseur
sont et un(non cette
requis pourTIFF
visionner compressé)
image.
De Gennes, Brochart et Quéré,

Gouttes bulles perles et ondes, 2005
ANTI LANDAU-LEVITCH EFFECT
U
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Duez & al Nature Physics

3, 180, 2007
QuickTime™ et un
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décompresseur TIFF (non compressé) Duez & al Nature Physics
3, 180, 2007

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Liquid flows on surfaces:

the boundary condition

NANOFLUIDICS SUMMER SCHOOL August 20-24 2007

Some examples of importance of the b.c. in nanofluidics

Theory of the h.b.c. for simple liquids

Slippage effects in macroscopic flows ?

Miniaturization increases surface to volume ratio:

The description of flows requires

What about boundary condition ?

Usual b.c. : the fluid velocity vanishes at wall

 OK at a macroscopic scale and for simple fluids

M. Denn, 2001 Annu. Rev. Fluid Mech. 33:265–87

Batchelor, An introduction to fluid dynamics, 1967

… and some time suspected on non-wetting surfaces

C. Chan and R. Horn no-slip flow with liquid monolayer

George et al., no-slip flow w. monolayer sticking at wall

Water slips in hydrophobic capillaries

From Lauga & al, Handbook of Experimental Fluid Dynamics, 2005

 No-slip bc (b=0) is associated to very large liquid-solid friction

 The bc is an interface property.

On a mathematically smooth surface, b=∞ (perfect slip).

 The hydrodynamic b.c. is fully characterized by b()

 The hydrodynamic bc is linear if the slip length does not depend on

Some examples of importance of the b.c. in nanofluidics

Theory of the h.b.c. for simple liquids

Slippage effects in macroscopic flows ?

Exemple 2 r = 2 nm Error factor on permeability : 80

tube b=20 nm (2 order of magnitude)

mesoporous silica: MCM41

B. Lefevre et al, J. Chem. Phys 120 4927 2004

quasi-static cycle, does not depend on

Solute motion is analogous to random walk:

t=0 time t QuickTime™ et un

Hydrodynamic dispersion is significantly reduced if b ≥ d

Electrostatic double layer

Electro-osmosis, streaming potential… are determined by interfacial

Case of a partial slip boundary condition:

Pb for measuring surface charges 

 Possibility of very large el-osmotic

Churaev et al, Adv. Colloid Interface Sci. 2002

Some examples of importance of the b.c. in nanofluidics

Theory of the h.b.c. for simple liquids

What about macroscopic flows ?

Fluid mechanics calculation :

Far field flow : no-slip

locally: perfect slip

Richardson, J Fluid Mech 59 707 (1973),

roughness « kills » slip

Be j(r,t) the fluctuating momentum density at point r

And assume boundary condition

And auto-correlation function

C(z,z’,t) obeys a diffusion equation

with boundary condition b

and initial value given by

C(z,z’,t) can be solved analytically and obtained as a function of b

Green-Kubo relation for the hydrodynamic b.c.:

(assumes that momentum fluctuations in fluid obey Navier-Stokes

Friction coefficient (i.e. slip length) can be computed at equilibrium from

Barrat, Bocquet, PRE (1994)

 « soft sphere » liquid

Simple Lennard-Jones fluid

⎡⎛σ ⎞12 ⎡⎛σ ⎞6 ⎤⎤ D

Wettability is characterized by contact angle (c.a.)