MT-0.

6081 Microfluidics and BioMEMS

Microfluidics 2
Surface tension, contact angle, capillary flow

20.1.2014
Ville Jokinen
 Scaling: surface forces vs body forces
• Surface area to volume ratio scales as d-1
• Microsystems often dominated by surface effects
• An example:

h
Reservoir droplet

Flow channel

Case 1: The flow channel is a microchannel: 100 μm x 100 μm x 100 mm, Volume 1 μl
Volume: Hydrostatic pressure from reservoir ≈ 10 Pa
Surface dominated!
Area: Capillary pressure from channel ≈ 3000 Pa
Case 2: The flow channel is a garden hose: 1 cm x 1 cm x 10 m , Volume 1 liter

Volume: Hydrostatic pressure from reservoir ≈ 1000 Pa

Volume dominated!
Area: Capillary pressure from channel ≈ 30 Pa
 Bond number: Does gravity matter?
• Dimensionless number that characterizes the ratio of surface forces to body
forces
a = acceleration (for gravity, 9.81m/s2) L = characteristic length scale
γ = surface tension ρ = density

ρaL2
Bo =
γ
If Bo < 1 the system is dominated by surface forces (opposed to body forces)
For water, Bo = 1 at around 1 mm range.

Example from previous page, water in a channel with 100 µm and 1 cm dimensions:
Bo ≈ 1.4 * 10-3 (for 100 µm)
Bo ≈ 14 (for 1 cm)
 Surface tension & Surface energy
Work required to create new surface =
surface energy x area created

δW = γ δA = γ Lδx
Fundamental definition of surface energy:

γ = δW / δA [ J / m2] Hunter: Introduction to Modern

Colloid Science, p.134

Surface energy is also known as surface tension:

γ = δF / δl [ N / m]

Concept applicable to all surfaces and interfaces:

solid-solid, solid-liquid, liquid-liquid, solid-gas, liquid-gas
Molecular basis of surface energy

The surface layer lacks some of the bonds

in bulk phase

This increased potential energy compared

to the bulk is called surface energy!
Temperature dependence: water: 68 mJ/m2 at 50oC, 59 mJ/m2 at 100oC

Water has a very high surface energy because of strong intermolecular bonds.
Surface energy, cohesion, adhesion
Surface energy is linked to adhesion between materials and intra material cohesion.

Work of cohesion, W11:

Material 1
Before separation: γ11=0 Material 1 γ1
After separation: 2γ1 γ11
Material 1 γ1
Material 1
W11= 2γ1- 0 = 2γ1

Work of adhesion, W12:

Before separation: γ12 Material 2

After separation: γ1 + γ2 Material 2 γ2
γ12
Material 1 γ1
W12= γ1 + γ2 - γ12 Material 1
 Laplace pressure
• There is a pressure difference across a curved liquid surface.

Young-Laplace equation Calculating radius of curvature

For a spherical droplet or bubble:

1 μl spherical water droplet in air, ∆P ≈ 140 Pa Pressure is higher inside a spherical

1 μl spherical air bubble in water, ∆P ≈ -140 Pa bubble or a droplet!
 Surface tension measurement:
force tensiometry
Drop weight method:
Gravity = perimeter x surface tension
mg = 2πr x γ
• Empirical correction factor needed

Wilhelmy plate method:

Force tensiometry:
The force a liquid exerts on a plate is measured
•F=2Lγ
• No correction factor needed
• Good method also in practice
 Surface tension measurement:
optical tensiometry
Drop shape analysis:
• Optical tensiometry: Surface tension measured from the shape of a hanging
droplet
• Shape determined by the balance of gravity (hydrostatic pressure) and
surface tension (laplace pressure).

Image from biolin scientific.

 Contact angle, experimental
• A liquid droplet makes a certain angle of contact with a solid surface
• The angle is called the apparent contact angle θ

• Property of a solid-liquid-fluid three phase system

• For a fixed liquid and fluid, contact angle is characteristic parameter of a
surface/material
 Contact angle, theoretical
Young’s equation:

γLG cos(θ) = γSG - γSL

θ Thermodynamical, or Young’s, contact angle

γLG Liquid-vapor surface energy (“liquid surface tension”) (often also γl, γlv)
γSG Solid-vapor surface energy (“solid surface energy”) (often also γs, γsv)
γSL Solid-liquid surface energy (“solid-liquid interface energy”)

• The thermodynamical contact angle does not necessarily equal the experimental
contact angle on real surfaces because of hysteresis.
 Contact angle hysteresis
On real surfaces: θrec < θeq < θadv
Hysteresis θadv – θrec

θrec = Receding contact angle

θeq = Equilibrium/static contact angle
θadv = Advancing contact angle

Reasons for contact angle hysteresis:

• Adsorption of molecules from the solution
• Desorption of molecules from the surface
• Chemical inhomogenities
• Physical surface topography

Which experimental contact angle is the one appearing in Young’s equation?

Unresolved, but some suggestions that have been made in the literature:
1. θadv
2. (θadv + θrec) /2
3. acos ((cos θadv + cosθrec)/2)
4. the most stable θ (e.g. after vibrations or other source of energy)
 Contact angle measurement
Same tools and methods as for surface tension:
• Force tensiometry, often Wilhelmy plate
• Optical goniometry of a sessile droplet

Optical goniometry Wilhelmy plate method

 Hydrophilic/ Hydrophobic terminology
For water: hydrophilic/hydrophobic
For oils: oleophilic/oleophobic
For liquids in general: hygrophilic/hygrophobic, omniphilic/omniphobic

θ = 0° 0° < θ < 90° 90° < θ < ≈ 150° 150° ≈ < θ < 180°
Completely wetting
θ ≈ 5° Hydrophilic Hydrophobic Superhydrophobic
Superhydrophilic Wetting Nonwetting Ultrahydrophobic

SiO2 SU-8, Si PDMS, Teflon roughness+chemistry

Clean metals
roughness+chemistry
 Measuring solid-vapor surface energies
• With some assumptions, γsv can be estimated by contact angle measurements

Zisman:
Surface energy of a solid
is the surface energy of the highest
surface tension liquid exhibiting
complete wetting.
(= critical surface tension)

Depending on the assumptions, many ways to calculate solid surface energies

from contact angles (Zisman, Owens-Wendt ,Good-vanOss etc.)
 Capillary rise and depression

Capillary pressure = Laplace pressure of a meniscus inside a capillary!

Note that θ is the only material parameter of the capillary that is needed, not eg. γSG or γSL
 Capillary filling of microfluidic channels
Main differences to classical capillary rise:

Horizontal vs vertical θt
• Capillary filling continues until the channel network is full h θl θr
θb
Geometry usually non circular and nonuniform materials
• Hydrophilic walls contribute to filling, hydrophobic oppose it w

cos θ t + cos θ b cos θ l + cos θ r

∆P = γ ( + )
h w
Channel architecture might be complex (wider and narrower areas)

• The capillary pressure is calculated at the filling front (and

possibly the de-wetting front), already filled areas only contribute
to flow resistance.
Application example: surface immunoassay
• Immunoassays

Bernard et al. Anal. Chem. 2001

 Contact angle on structured surfaces
• On the lowest surface energy planar surfaces, contact angles only go up to ≈ 120°
for water and ≈ 75° for oils.
• Beyond that, topography can be used to enhance contact angle

Cassie state: Wenzel state:

Possible on intrinsically Possible on any surface
hydrophobic surfaces
Results in enhanced
Results in increased intrinsic contact angle
hydrophobicity
cos(θw) = r cos(θ)
cos(θc) = f cos(θ) -1 +f
f = air fraction r = roughness factor

Note!
• The contact angle is enhanced but the chemical nature of the surface remains the same
• The enhanced contact angles are relevant for fluidics, but not directly in e.g. adsorption
 Superhydrophobicity
• Micro/nanostructures combined to hydrophobic surface properties can result in
superhydrophobic surfaces.
• Properties: θ > 150°, water repellent, water deposited on top stays as intact
droplets and moves easily → low sliding angles, self cleaning

Silicon nanopillars Left: Right:

(black silicon) oxidized silicon surface fluoropolymer coating
θ ≈ 0° θ ≈ 170°

Jokinen, Sainiemi, Franssila: Advanced Materials 2008

 Digital Microfluidics, 2-phase
• Microfluidics does not always mean continuous flow in a channel.
• Digital microfluidics increasingly common.
• Discrete droplets, either 2 immiscible liquid phases or liquid droplets and air.
• Each droplet can be viewed as a single experiment.

2-phase digital microfluidics. The surface tension keeps the droplets together.
Digital microfluidics, electrowetting
• Droplets on hydrophobic surfaces, surface tension holds the droplets together
(no spreading)
• Electrowetting used to move the droplets.
• Either one open surface or more commonly between 2 hydrophobic plates.

V = applied voltage
C = capacitance
γs =solid surface energy
γw = water surface energy
γ0ws = water solid interfacial energy with
no electric field.
 CD microfluidics
• Actuating force by centrifugation. Capillary valves and hydrophobic valves to control flow.
 Review
• The importance of surfaces in microfluidics/bio-MEMS
• The concept of surface energy, measurement, Laplace pressure
• Contact angle, theoretical and experimental aspects
• Capillary rise and capillary filling of microfluidic channels
• Superhydrophobicity
• Surface tension effects for microfluidics

Reading material (updated)

• For lecture 2, the reading material is:
Chapter 5, surface tension, from a book “Physics of Continuous matter” by B.
Lautrup. Pages 69-83
Available from link: http://www.cns.gatech.edu/~predrag/courses/PHYS-
4421-13/Lautrup/surface.pdf