contact angle hysteresis

Jacco Snoeijer

Physics of Fluids - University of Twente

small droplets can ‘stick’ to window

 force on contact line

balance:
γ cos θe

γsv γsl
 force on contact line

balance:
γ cos θe

γsv γsl

γ cos θ

γsv γsl

force on contact line: fcl = γ (cos θ - cos θe)

advancing - receding angles

hysteresis: no unique value for contact angle

pinning force: H = γ (cos θr - cos θa)

’sticky’ drops
 microscopic origin
geometric heterogeneity

θe θe

small scale ‘roughness’

 microscopic origin
geometric heterogeneity chemical heterogeneity:
θe(x,y)

θe θe

small scale ‘roughness’ large θe smaller θe

contact line shape?
 contact line shape?
heterogeneity at larger scale: macroscopic ‘wetting defects’

single defect (500µm) many defects (10µm)

 contact line shape?
heterogeneity at larger scale: macroscopic ‘wetting defects’

single defect (500µm) many defects (10µm)

‘simple’ dynamics collective dynamics

contact line is very ‘rough’
 what will we do:

• contact line deformation of single defect

• Joanny - De Gennes model for hysteresis
• implications for dynamics...

literature:

Joanny & De Gennes,

J. Chem. Phys. 81, 552 (1984)

Bonn, Eggers, Indekeu, Meunier, Rolley,

to appear Rev. Mod. Phys. (2009)
contact line shape

θ0 y
 contact line shape

θ0 y

z
y
x
 contact line shape

z
y
η(x) contact line position
x
 interface

interface h(x,y) ?

h(x, y) = " 0 y + ....

η(x) contact line position

!
 interface

z
Δh ~ e-qy
y

interface h(x,y) ?

h(x, y) = " 0 y + Ae iqxe#qy

η(x) contact line position

!
 interface

z
change in local contact angle: Δθ(x)
y

η(x) contact line position

 interface

z
Δθ(x)
y
increase of area

Δ E ~ γ q A2

contact line ‘elasticity’

η(x) contact line position
Joanny & De Gennes 1984
 sinusoidal perturbations

increase of area: z
Δθ(x)
ΔE ~ γ q A2
y

contact line position

 sinusoidal perturbations

increase of area: z
Δθ(x)
ΔE ~ γ q A2
y

relaxation rate
σ

Delon et al. JFM 2008

q
 single defect
θ=0

wetting defect is ‘pulling’, but....

large deformations cost energy

 single defect
θ=0

η(x) contact line shape ?

 single defect
θ=0

η(x) contact line shape ?

h(x, y) = " 0 y + ...

!
 single defect
θ=0

η(x) contact line shape ?

"0 iqx #qy

h(x, y) = " 0 y #
2$
& dq ˜
% (q) e e

!
 single defect
θ=0

η(x) contact line shape ?

"0 iqx #qy

h(x, y) = " 0 y #
2$
& dq ˜
% (q) e e

imposing θ(x) at the contact line η(x)

!
 single defect
θ=0

η(x) contact line shape ?

"0 iqx #qy

h(x, y) = " 0 y #
2$
& dq ˜
% (q) e e

$h "0 iqx (qy

"#
$y
= "0 +
2%
' dq ˜
& (q) q e e
!
 single defect
θ=0

η(x) contact line shape ?

"0 iqx #qy

h(x, y) = " 0 y #
2$
& dq ˜
% (q) e e

"0 iqx
" (x) # " 0 +
2$
& dq {%˜ (q) q} e
!
 single defect
θ=0 η(x) Nadkarni & Garoff 1992

Fdefect
"(x) ~ ln( L / x )
#

Fdefect ~ d" (1# cos $ e )

!
 model for hysteresis

advancing receding

‘jump’

asymmetry between advancing and receding

(for defects that are strong enough)

 model for hysteresis

advancing receding

‘jump’

non-interacting defects,
density ρ

" (cos# r $ cos# a ) ~ % Fd &max

!
contact line dynamics, revisited

many defects (10µm)

contact line dynamics, revisited

many defects (10µm)

if we go very slowly...

... thermally activated ‘hopping’ of molecules

 contact line dynamics, revisited
thermally activated ‘hopping’ of molecules

Fcl ~ γ(cosθ - cosθe)

Rolley & Guthmann PRL 2007

# E " f cl lmicro
2 &
U ~ exp%" (
speed

$ k B T '

Fcl
!
 contact line dynamics, revisited
thermally activated ‘depinning’ of contact line

Rolley & Guthmann PRL 2007

# E " f cl lmicro
2 &
U ~ exp%" (
speed

$ k B T '

Fcl
!
coupling to hydrodynamics?
for significant Ca: lubrication + slip

microscopics shows up as ‘boundary conditions’

 conclusion

- microscopic description of hysteresis

- ’interacting defects’ are difficult...

depinning, contact line roughness

- coupling to hydrodynamics??