CONTACT ANGLES: Laplace-Young Equation and Dupre-Young Dupre Young Relationship.

R. L. Cerro Chemical and Materials Engineering The University y 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

SV SL = LV cos

( pin pout ) 2 H VL = 0

Young-Laplace Equation in Differential Form:

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

{R1 , R2 :principal radius of curvature

; poutside = out g z

pinside = in 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

(1805)] Born in Milverton, Somerset (1773) youngest of 10 children Studied medicine in London, Edinburgh and physics in Gottingen

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

Pierre Simon de Laplace

Entered Emmanuel College in Cambridge and practiced medicine in London A Appointed i d professor f of f 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.

Young never wrote the equation!

(1807)] Born in Normandy, 1749. Univ. of Caen (16 years old) U i of Univ. f Paris P i (18 years old). ld) Rejected by Acad. of Sciences (22 yr old) Accepted to Berlin Acad. of Sci. (24 yr)

[Ouvres Completes, Completes pp. pp 394

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 )
r = R ( u1 , u2 )
1 = 1/ R1 ; 2 =1/ R2
1 1 1 1 H = + = ( 1 + 2 ) 2 R1 R2 2 1 K = 1 2 = R1 R2

3. Two tangents unit vectors, a1 and a2 are normal to each other and both are normal to the vector n. 4. Points on the h surface f can be b described d b d on the h basis of a two dimensional system. 5. The rate of change of orientation (normal) corresponds d to t th the i intuitive t iti notion ti of f 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
1 1 df f n 2 d dl + R1 R2 d /2 1 1 1 2 1 2 d + d dl = d + R1 R2 R1 R2 0 0

Fn

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

2 z x z y z xy 1 + ( z ) + ( z ) x y
2 2 3/ 2

z yy 1 + ( z ) + ( z ) x y
2 2 1/ 2

Static Contact Angles Youngs Young s relationship (1805):

SV SL = VL cos o
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 of f th the solid lid and d fl fluid, id and d th the third thi d in i that th t of f 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 by y 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 ....

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

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 and Obuchov (1936)

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

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

+ L

( ( r , ) ) r d
L

The Young-Laplace g p equation q is valid away y 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 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 sin i = 1/2 dx dy 2 1 + dx d2y 2 dx = = 2H 2 3/2 dy 1 + dx

d y dx 2

d 2 y dy dx 2 dx = 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 L2 C

L = g
2 C

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

{B.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
2 hC C =1 2 2 LC 2 2 hC hC h hC h2 cos = 1 2 + 2 2 h = 0 cos o =1 2 2 LC LC 2 LC 2 LC

{B.C.

cos = 1 at h = hC

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 C = cos o hC h h2 cos o = cos 2 + 2 h = hC cos =1 LC 2 LC
Defines D fi contact angle l as the h angle of intersection between gas-liquid interface and the solid surface.

{B.C.

cos = cos o at h 0

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

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:
2 hC cos o =1 2 L2 C

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

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

103 102

Molecular region:

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

gVL = specific interfacial free energy

[ ] [ ] A A 2 SL hm = LL 6
6 6

2 d gVL hm = 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

h hC ht = 2 1 h LC hC
2 m 3 t
2 2 h L ht3 = m C hC

Since

ht / hC

Transition region: Location of

2 hC h d cos hm = 3 2 dh h LC
2 hC cos o =1 2 2 LC

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

2 (1 cos o )

At h = ht and = t
2 smaller ht hm 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!

since o > t > for all on interface

But:

o t to O ( 2 )

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

2 g yo Yo2 sin 0 = 1 = 1 2 2

y Y= LC
2 o 2 o 2

cos o = Y (Y / 2 )

Capillary Rise: Molecular Approach

2 hm d cos g = y+ 3 dh h

{ = o
hS

at h = hS

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

2 m

y tan dy = 2 LC 0
y

(Y

Y Y3 / 2
2

(Y / 2 )
2 2

2 1/2

dY = Y (Y / 2 )
2 2

2 1/2

cos o YS2 (YS2 / 2 )

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

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
4

h C = cos o + ln + O m hL

Molecular region:
[ ] [ ] A A 2 SL hm = LL 6
6 6

h < 10

m
4

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

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 Heptane Octane Nonane Decane Undecane Dodecane Tetradec. Hexadec. 10-3 N/m 20.3 21.8 22.9 23.9 24.7 25.4 26.7 27.6 ASL 10-20 J 4.03 4.11 4.18 4.25 4.28 4.35 4.38 4.43 ALL 10-20 J 4.31 4.49 4.66 4.81 4.87 5.03 5.09 5.22 exper. comp. 10-10 m (deg) (deg) 2.979 2.811 2.656 2.617 2.501 2.489 2.421 2.402 21 26 32 35 39 42 44 46 20.8 25.8 31.7 34.5 38.7 41.8 43.7 46.2 D

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