CONTACT ANGLES:

Laplace-Young Equation and

Dupre-Young
Dupre
Young Relationship.
R. L. Cerro
Chemical and Materials Engineering
The Universityy of Alabama in Huntsville

Santa Fe
16 de Abril de 2010

Acknowledgements:

Dr.Javier Fuentes (PhD-2003)Univ. Simon Bolivar,, Caracas,,

VE. School of Chemical
Engineering and Analytical
Science, The Univ. of
Manchester, UK
D El
Dr.
Elena Diaz
Di Martin
M ti (PhD(PhD
2004)-Depto. de Ing. Quimica &
Textil, Universidad de
Salamanca, Spain.
Dr Michael D.
Dr.
D Savage,
Savage Physics
and Astronomy Dept. Leeds
University, UK.

OUTLINE OF PRESENTATION
Introduction/Motivation: What is wetting? Why is it
important?
The
Th

F ll A
Fully-Augmented
d Young-Laplace
Y
L l
Equation
E
i

Youngs relationship: static contact angles.

A 2D sessile drop = puddle.

C ill
Capillary
rise
i

The future behind

Wetting applications: boiling and condensation

Cooling electronic circuits

Heat
eat pipes
p pes rely
ey o
on
boiling and
condensation of the
cooling liquid.
Micro heat pipes are
Micro-heat
about 1 mm in
diameter.

Super-hydrophobic
Super
hydrophobic surfaces:

Super-hydrophobicity is the result

of chemistry and structure.

Self-cleaning
Self
cleaning superhydrophobic surfaces

Structure & Chemistry

Wetting precedes adhesion:

Feet of a geico and

the threads of a
mussel are examples
of natural adhesives.

Vapor/Liquid Interfaces
Interfaces are:
1.Diffuse (3D)
2.Dynamic
3 Asymmetric
3.Asymmetric

Static Contact Angles:Young relationship

and the Young-Laplace
Young Laplace equation.
equation
WETTING: The contact angle for a
th
three-phase
h
region
i is
i the
th main
i
variable in Youngs equation.
THOMAS YOUNG,, 1805
CAPILLARITY: The curvature of
the interface and the specific
interfacial free energy of the
interface, are related to the
pressure jump between the
inside and outside of a liquid
drop.
YOUNG-LAPLACE EQUATION

( pin pout ) 2 H VL = 0

SV SL = LV cos

Young-Laplace Equation in Differential Form:

pinside = poutside 2 H
1 1
2H =
+
R1 R2

pinside = in g z

{R1 , R2 :principal radius of curvature

;

poutside = out g z

in g zo

2
d z
dz

d x2
dx
+

g z ( in out ) = in g ( z zo ) =

3/2
1/2
1/2
dz 1/2
dz
z 1 +
1 + dx
dx

The equation of Young and Laplace:

Historical introduction.
introduction

Thomas Young

[Phil. Trans. Roy. Soc, vol 95, pp. 65-87

(1805)]

Born in Milverton, Somerset (1773) youngest of 10 children

Studied medicine in London, Edinburgh and physics in Gottingen

Entered Emmanuel College in Cambridge and practiced medicine in London

A
Appointed
i d professor
f
off Natural
N
l philosophy
hil
h at Royal
R
l Institution
I i i (1801)
Foreign associate in French Academy of Sciences (1827)
Wave theory of light, Young modulus, translated hieroglyphs, etc.

Pierre Simon de Laplace

Young never wrote the equation!

[Ouvres Completes,
Completes pp.
pp 394

(1807)]

Born in Normandy, 1749.

Univ. of Caen (16 years old)

U i off Paris
Univ.
P i (18 years old).
ld)

Rejected by Acad. of Sciences (22 yr old)

Accepted to Berlin Acad. of Sci. (24 yr)

On the attribution of an equation of capillarity to Young and Laplace, Pujado, Huh

and Scriven, JCISvol. 38, pp 662-663, (1972).

Surfaces in 3D space:
Surface geometry

Surfaces in 3D space:

Orientable in space
Locally have two sides
Globally have in general two sides with famous
exceptions (Mobius strip)
If they are closed
closed, separate an inside space
from an outside space with famous exceptions
(Klein bottle)
They have shape

Globaly shape distinguishes a torus from a sphere

Locally it is distinguished by its curvature

Surface curvature
1. Location: a point on the surface is described by
the vector R
R.
2. Orientation: the top and bottom are described
by a unit vector n, normal to the surface

R = R ( x, y , z )

3. Two tangents unit vectors, a1 and a2 are

normal to each other and both are normal to
the vector n.

r = R ( u1 , u2 )

4. Points on the
h surface
f
can be
b described
d
b d on the
h
basis of a two dimensional system.

1 = 1/ R1 ; 2 =1/ R2
1 1
1 1
H = + = ( 1 + 2 )
2 R1 R2 2
1
K = 1 2 =
R1 R2

5. The rate of change of orientation (normal)

corresponds
d to
t th
the iintuitive
t iti notion
ti off shape.
h
6. Curvature is defined as the inverse, 1/R, of the
radius of a circle tangent to the surface.
7. There are two independent radius of curvature
and their directions are normal to each other.

Young-Laplace equation:simplified
derivation Butt et al
derivation.
al. pp10
pp10. 2003
F = er Fn + et Ft
df n = 2 dl sin + 2 dl sin
sin d / R1 ; sin d / R2

Fn

1
1
dff n 2 d dl +
R1 R2
d /2
1
1
1
2 1
0 0 2 d R1 + R2 d dl = d R1 + R2

1
Fn
1
P =
= + = ( 2H )
2
d
R1 R2

Minimal surfaces (soap films):

Lagrange Nitsche
Lagrange,
Nitsche, others
Lagrange: Lectures on a novel method for the
g formulae,, 1762
determination of maxima of integral

z = z ( x, y ) I ( ) =
S

z z
1 + + dxdy
x y

Definition: A minimal surface is a surface whose mean curvature is zero

at every point of the surface.
Theorem: If there is a portion of a surface of minimum area among
all portions of surfaces bounded by the same closed curve, then the
surface is a minimal surface.
Minimal surfaces are sometimes defined as surfaces with the
property that any portion of them bounded by a closed curve has
the minimum area.

2H =

z xx
2 1/ 2

1 + ( z ) + ( z )
x
y

2 z x z y z xy
1 + ( z ) + ( z )
x
y

3/ 2

z yy
2 1/ 2

1 + ( z ) + ( z )
x
y

Static Contact Angles

Youngss relationship (1805):
Young
SV SL = VL cos o

An Essay on the
Cohesion of Fluids
Phil. Trans. Roy. Soc.
v. 95, 65-87

We
We may therefore inquire into the conditions of
equilibrium of the three forces acting on the angular
particles, one on the direction of the surface of the
fluid only, a second in that of the common surface
off th
the solid
lid and
d fl
fluid,
id and
d th
the third
thi d in
i that
th t off the
th
exposed surface of the solid. Now supposing the
angle of the fluid to be obtuse, the whole superficial
cohesion of the fluid being
g represented
p
byy the
radius, the part of which acts in the direction of the
surface of the solid will be proportional to the
cosine of the inclination; and its force added to the
force of the solid
solid, will be equal to the force of the
common surface of the solid and fluid, or to the
difference of their forces; consequently, the cosine
added to twice the force of the fluid; will be equal
to ....

Interfaces are not 2D surfaces!

Interfaces are:
1.Diffuse (3D)
2.Dynamic
3 Asymmetric
3.Asymmetric

Macroscopic definition of contact angles

SV SL = LV cos
Young (1805) derived relation as
a balance of forces.
s

Equation can be derived using

macroscopic arguments.
Specific interfacial free energies
are macroscopic/thermodynamic
parameters.
Contact angles are macroscopic
parameters and thermodynamic
functions.

Surface forces of the second kind:

Derjaguin et al.
al Surface Forces,
Forces (1987) Plenum

Derjaguin and
Obuchov (1936)
At the contact line
line, there is an
interaction of molecular force
fields due to the presence of a
thi d phase.
third
h
Forces of the second kind are the same
forces determining surface tension:
(1) Dipole-dipole, nonpolar or chargedipole interactions.(van der Waals)
((2)) Electrical double layers
y
(3) Structural forces induced by
molecular order.

Augmented and Fully-augmented YoungLaplace equation:

Static Jump-Momentum balance:
Normal component:

Derjaguin
j g
et al. Surface
Forces (1987)
Teletzke, Davis and Scriven
(1988)

2 H gVL ( r , ) + ( p B p A + ( r , ) ) = 0

Tangential component:

gVL ( r , ) =
= VL +

+ L

( ( r , ) ) r d

Miller and
Ruckenstein (1974)
Jameson and del
Cerro (1976).

The Young-Laplace
g p
equation
q
is valid awayy
from the solid surface where disjoining
pressure is negligible and surface tension is
constant!

MOTIVATION: molecular interactions

Derjaguin and Obuchov (1936)

disjoining pressure
pressure,
[ ]
[ ]
ASL
ALL
=
6 h3
variable surface tension, gVL
6

d gVL
=
dh
Questions!
Is Young's
Young s equation really valid?
What is the proper definition for o ?

How is o to be measured?
Where is o located on the vapor/liquid interface?

Contact Angles (Merchant and Keller, 1992)

Used the method of matched asymptotic
expansions
i
to
t validate
lid t Youngs
Y
equation!
ti !
Leading term in the outer expansion for the interface
shape satisfies the Young-Laplace equation.
Leading term in the inner expansion satisfies an
integral equation.
equation
Matched the two solutions and confirmed that
the slope angle of the leading term in the
outer expansion is o
-as given
i
by
b Youngs
Y
equation.
i

Interesting relationships for 2D systems:

L E.
L.
E Scriven,
Scriven class notes UofM
UofM, circa 1980

d y
dx 2

d 2 y dy

dx 2 dx

=
2 3/2
dy
1 +
dx

d sin
i
=
1/2
dx
dy 2
1 +
dx
d2y
2
dx
=
= 2H
2 3/2
dy
1 +
dx

dy
h = y ( x),
tan =
dx
dy
d
dx
sin =
2 1/2
dy
1 +
dx
1
cos =
2 1/2
dy
1 +
dx

Macroscopic approach:
Two-dimensional
Two
dimensional fluid wedge.
Young-Laplace Equation:

de Gennes, Brochard,

Quere (2004) the

housewife
if problem.
bl
h

2 H = ( p L pV ) , p L pV = g ( hC h )
h h
2 H = 2 / 1 +
z z
2

2 3/2

Scriven, ChEn 8104 class notes (1982)

2H =

d cos
dh
;
= tan
dh
dz

d cos hC h
=
dh
L2C

hC h
h2
cos = 2 2 + C
LC 2 LC

{B.C.

L =
g
2
C

cos = 1 at h = hC

Integrate and introduce one

boundary condition at a time:
hC h
h2
cos = 2 2 + C
LC 2 LC

{B.C.

cos = 1 at h = hC

hC2
C =1 2
2 LC
hC2 hC h
hC2
h2
cos = 1 2 + 2 2 h = 0 cos o =1 2
2 LC
LC 2 LC
2 LC

Solution to Young Laplace equation

describes the gas-liquid interface of
a liquid puddle resting on a smooth,
horizontal surface.

Defines contact angle as the

angle of intersection between
solution of YL equation and
the solid surface
surface.

Second method:
hC h
h2
cos = 2 2 + C
LC 2 LC

{B.C.

cos = cos o at h 0

C = cos o
hC h
h2
cos o = cos 2 + 2 h = hC cos =1
LC 2 LC

Solution to Young Laplace equation

describes the gas-liquid interface of
a liquid puddle resting on a smooth,
h i
horizontal
t l surface.
f

Defines
D
fi
contact angle
l as the
h
angle of intersection
between gas-liquid interface
and the solid surface.

Consequences:
[1] Mathematical
definition of o

o is the B.C. at the solid

surface for solutions of the
Young-Laplace equation
= o when
h h = 0
Fluid wedge:

hC2
cos o =1
2 L2C

match data points to a solution of the

[ 2] Measurement of o

Young-Laplace equation.
extend
t d the
th solution
l ti to
t h=0
measure the angle.

MOTIVATION:

Questions

Questions!

Young's relation is macroscopically valid.

o defined as B.C.
B C for YL equation.
equation
o is measured intersecting YL with solid.

Where is o located on the vapor/liquid interface?

Fluid Wedge: 3-region model

3-Region Model: Characteristic

Film Thicknesses
3

hC 10 m
ht 3. 108 m
hm 1010 m
hm
=
ht

103 102

Molecular region:

Derjaguin
j g

gVL = specific interfacial free energy

[ 6]
[ 6]
dgVL
ALL
ASL
= ( h ) =
dh
6 h3

[ ]
[ ]
A

A
SL
hm2 = LL
6
6

d gVL
hm2
= 3
dh
h

B.C.

gVL as h

1 hm 2
gVL ( h ) = 1
2 h

Note:

gVL 0.995 when h = 109 m

Transition Region: Null Curvature Point

2 H = g ( hC h )
Augmented
d cos h hC h

= 2 Young-Laplace
dh
h
LC
equation
2
m
3

At the null curvature point; h = ht , 2H = 0

Since

ht / hC

h
hC
ht
= 2 1
h
LC hC
2
m
3
t

2
2
h
L
ht3 = m C
hC

Transition region: Location of

d cos hm2 hC h

= 3 2
dh
h
LC

hC2
cos o =1 2
2 LC

BC h = hC = 0
hm2
hm2 h
h2
cos cos o =
2 + 2
2
2 h 2 hC hC 2 hC

2 (1 cos o )

At h = ht and = t
smaller
hm2 ht

cos t cos o =
+ 2 (1 cos o ) +

2
terms
2 ht hC

3 hm
3
= 2
2 ht
2

Transition region: Location of 0

Where, on the vapor/liquid interface, is o to be found?

3 2
cos t cos o
2

3
o t +
2
2sin o

Nowhere!

But:

o t to O ( 2 )

since o > t >

for all on interface

Numerical Integration of FAYL equation

HEPTANE ON PTFE

*Continuous line: YL solution; Dotted line: FAYL solution

CAPILLARY RISE: MACROSC0PIC APPROACH

2H = g y
McNutt and Andes, J. of Chemical
Physics (1969)
Legendre transformation

d sin
y
2H =
= 2
y2 Y 2
LC 1 sin = 2 =
dy
2 LC
2

y 0 ; sin = 1

g yo2
Yo2
sin 0 = 1
= 1
2
2

y
Y=
LC

cos o = Y (Y / 2 )
2
o

2
o

Capillary Rise: Molecular Approach

hm2
d cos g

=
y+ 3
dh

{ = o

at h = hS

hS

2
m

h
y
cos o =
2 dh
2
2 hs LC
dh = ( dh / dy ) dy = cot ( / 2 ) dy = tan dy
y

y tan dy
=
2
LC
0

Y Y3 / 2

(Y

(Y / 2 )

cos o YS2 (YS2 / 2 )

2 1/2

dY = Y (Y / 2 )
2

2
hm2
2
2
+ 2 = Yo (Yo / 2 )
2 hs

2 1/2

Molecular region: Further Analysis

d cos
gVL
= ( h )
dh
dgVL
= ( h, )
dh

d gVL
d cos
= gVL
ln gVL = cos + C
d h
d h
1 hm 2
But: gVL ( h ) = 1
2 h
h = hL
Determine C:
= L

cos = ln
l

1 hm 2
1 + C
2 h

h
C = cos o + ln + O m
hL

Molecular region:
[ ]
[ ]
A

A
SL
hm2 = LL
6
6

h < 10

1 hm 2
hm
cos = cos 0 ln 1 + O
hL
2 h

Gives = ( h, hm , o ) in molecular region.

Proceed down to = 0!
h = hD ; = 0

1 h 2
cos o = 1 + ln 1 m
2 hD

Comparison with experiments:

Alkanes

10-3 N/m

ASL
10-20 J

ALL
10-20 J

exper. comp.
10-10 m (deg)
(deg)

Heptane

20.3

4.03

4.31

2.979

21

20.8

Octane

21.8

4.11

4.49

2.811

26

25.8

Nonane

22.9

4.18

4.66

2.656

32

31.7

Decane

23.9

4.25

4.81

2.617

35

34.5

Undecane

24.7

4.28

4.87

2.501

39

38.7

Dodecane

25.4

4.35

5.03

2.489

42

41.8

Tetradec.

26.7

4.38

5.09

2.421

44

43.7

Hexadec.

27.6

4.43

5.22

2.402

46

46.2

Conclusions:
Molecular Interactions ( close to the contact line )
f
tension
t i
gVL surface
give rise to variations in
- slope of interface
s.tt
o
as h hL
gVL

Macroscopic contact angle, o , is

the B.C. for solutions of YL equation at surface h = 0
obtained by matching data points to solutions
of the YL equation, extending the solution to h = 0
and measuring the angle.
may or may not be found anywhere in the interface.