Lecture on Contact Angles, May 4, 2005

A) Liquid and Solid Surface Energies

B) Liquid Contact Angles on Solid Surfaces
Prof. Allan S. Hoffman
(with some slides by Buddy Ratner)

Lecture on Contact Angles, May 4, 2005

A) Liquid and Solid Surface Energies
B) Liquid Contact Angles on Solid Surfaces
Prof. Allan S. Hoffman
(with some slides by Buddy Ratner)

The unusual properties

of surfaces and interfaces
are due to unbalanced
intermolecular interaction
forces (or energies) across
the surface or interface.

vapor

Forces within liquids and solids

and across their interfaces
include:
Polar Interactions:
Ion-ion (+ -)
Ion-dipole (H-bond)
Dipole-dipole
Dipole-induced dipole
Non-Polar interactions:
Hydrophobic (dispersion forces)

liquid

solid

Polar

Higher energy
stronger

weaker
Non-polar
Lower energy

These forces exist between individual molecules

The energy to bring one molecule to the surface and then to volatile it

Break 6 nearest neighbor bonds

and move 1 molecule to surface

Remake 4 nearest neighbor

bonds in surface: Net cost-->2 bonds

Break 4 nearest neighbor bonds

and volatilize molecule: Net cost-->4 bonds

Fill surface vacancy

with another molecule

Thus, the energy to evaporate a molecule is composed of two parts:

1) The energy to bring the molecule to the surface (approx 1/3 of total)
2) The energy to volatilize the molecule (approx 2/3 of total)

Conclusions: 1) The surface is always higher energy than the bulk.

2) The surface is only a few molecular layers thick (or thin).

High energy surfaces in air

H2O, hydrogels, clean glass, and metal
oxides. They are all hydrophilic and have
significant ionic, H-bonding and polar
forces. BUT they also have important
hydrophobic forces.
These surfaces form low energy interfaces
under water.

Low energy surfaces in air

P.E., Teflon, S.R., HC oils. They are all
hydrophobic and most have high
hydrophobic or dispersion forces and low or
zero polar forces.
These surfaces form high energy interfaces
under water.

These surfaces
are readily
contaminated
in air
but difficult
to contaminate
under water
These surfaces
are difficult to
contaminate
in air
but may become
contaminated
under water

1)

What are "high" energy groups?

Polar, H-bonding, ionized, hydrophilic
groups as:
-OH -NH2 -COOH -OSO3H
-NH3+ -COO- -OSO3-

2)

What are "low" energy groups?

Non-polar, hydrophobic
groups as:
-CmH2m+1

hydrocarbons

CH3
-(Si -O)CH3

silicones

-CmF2m+1

fluorocarbons

Always remember this:

Mother Nature (and thermodynamics) drives all
systems to a minimum energy state.
In order to
MINIMIZE
SURFACE ENERGY,
polar groups orient
away from the surface
in air,
or
toward the more polar phase,
at aqueous interfaces.

Simple liquids illustrate surface orientation

of polar and non-polar groups
to minimize surface energies
Water
Ethanol (CH3CH2-OH)
n-Octanol (C8H17-OH)
n-Octane (C8H18)
H

octane
H

The non polar, HC portion of the molecule

tries to escape the highly polar water
environment by orienting into the air phase.

Surface tensions
72.8 dynes/cm
22.1 dynes/cm
27.5 dynes/cm
21.8 dynes/cm

High Energy Surfaces in Air:

Clean metals or metal oxides (very high)
readily
Clean glasses or ceramics (high)
contaminated
Clean surface oxidized polymers (moderately high)
in air
Clean water (high)
Clean mercury (very high)

Low Energy Surfaces in Air:

Hydrocarbon-based polymers
Fluorocarbon-based polymers (very low)
Silicone-based polymers & silicone oils

not readily
contaminated
in air

These generalizations may be the opposite under water, ie, high energy
surfaces are not readily contaminated while the opposite is the case for
low energy surfaces. The exception is when surface groups can flip to
expose polar groups and lower interfacial energy under water.

Air
Low surface energy

High surface energy

Teflon

Any metal oxide

Low surface energy

Poly(hydroxyethyl methacrylate)

High interfacial energy

Teflon

Water
Low interfacial energy
Any metal oxide

Low interfacial energy

Poly(hydroxyethyl methacrylate)

CH3
(CH2C)

Poly(HEMA)--soft contact lens

C=O

Poly(hydroxyethyl methacrylate)

OCH2CH2OH

Low surface energy in air

CH3CH3CH3 CH3CH3

Poly(HEMA)

Low

interfacial energy in water

H H H H H H H HH H H H
O O O O O O O OO O O O

Poly(HEMA)

CH3CH3CH3CH3CH3
O O OOO O OOO O OO
H H HHHH HHHH HH
To minimize surface energy in air, non-polar groups are exposed,
and to minimize interfacial energy in water, polar groups are exposed.

In 1972, we were funded to modify the blood contacting surfaces

(eg, silicone rubber) of the AEC artificial heart by radiation grafting PHEMA
and immobilizing biological agents such as Heparin onto the -OH groups.

Diagram by Allan Hoffman

Grafted polyHEMA hydrogel layer on silicone rubber

Schematic showing
poly(HEMA) grafting on PDMS
followed by immobilization of
biological agents such as
Heparin or PGE1 onto the
Poly(HEMA) -OH groups

Hoffman, et al., Trans Amer Soc Artif Int Organs, 18, 10 (1972)

Poly(2-hydroxyethyl methacrylate) C1s ESCA Spectrum

2500

Poly(HEMA)

CH3
(CH2C)

2000
1500

C=O
OCH2CH2OH

O=C-O

C-O

1000

C-H

500
0
292

290

288

286

284

282

280

CH3
Si - O
CH3
Poly(dimethyl siloxane) (PDMS or Silicone Rubber)

Surface Mobility of HEMA-g-PDMS Studied by ESCA

PolyHEMA grafted to PDMS
(frozen at -120C while hydrated)

PolyHEMA grafted to PDMS

(dried at ambient temperature)

42

hema_c1s.r01

...
.. .
.
.
.. ... ...
.....
.....
.
.....
.
. ......... ... ............
. .
. ....... ....... ....
.
. .......................... ............
2500

p-HEMA C1s

silicone rubber C1s

1500
1000

counts

counts

2000

500

0
292

290

288

286

284

282

280

295

295

290

285

280

290

285

295

280

290

285

Binding Energy (eV)

Ratner,BD; Weathersby,PK; Hoffman,AS; Kelly,MA; Scharpen,LH (1978): Radiation-grafted
hydrogels for biomaterial applications as studied by the ESCA technique. J. Appl. Polym. Sci.
22, 643-664.

280

Surface Mobility of HEMA-g-PDMS Studied by ESCA

PolyHEMA grafted to PDMS
(frozen at -120C while hydrated)

PolyHEMA grafted to PDMS

(dried at ambient temperature)

Another example of how Mother Nature

...
drives all systems
to a minimum energy
..

42

hema_c1s.r01
2500

p-HEMA C1s
2000

silicone rubber C1s

1000

counts

counts

.
.
.
.. ... ...
.....
.....
.
.....
.
. ......... ... ............
. .
. ....... ....... ....
.
. .......................... ............
1500

500

0
292

290

288

286

284

282

280

295

295

290

285

280

290

285

295

280

290

285

Binding Energy (eV)

Ratner,BD; Weathersby,PK; Hoffman,AS; Kelly,MA; Scharpen,LH (1978): Radiation-grafted
hydrogels for biomaterial applications as studied by the ESCA technique. J. Appl. Polym. Sci.
22, 643-664.

280

Summary
Summary of
Surface Fundamentals
1)

Surfac es and interfac es are at a h igher free energy leve l than

bulk phases.

2)

There is always a thermodynamic drivin g force to minimize

surface a nd interfacial energie s.
a)

Surfac e/vol ume ratios minimize (e .g., l iquid drople ts are

spherical )

b)

High energy surfaces are hard to k eep clean and are

easily c ontami nated wi th low e nergy substances.

c)

Surfac e molecules wi ll orient so as to minimize surface

or interfac ial e nergy (polar groups inwar d, nonpolar
groups outwa rd in air -- the o pposite in w ater.)

d)

"Surface-a ctive " molecules will a dsorb and sim ilarl y

orient at high energy surfaces o r h igh energy in terface s.

3)

High energy surfaces in a ir tend to form low energy interfaces

in aqueous solutions, a nd vice v ersa.

4)

Surfac
a nd
interfacare
esusua
a re lly
u sual
nlymolecu
a fewlar
molecula
r (or thin).
Sur
faceses
and
interfaces
onlylya o
few
laye rs thick
lay ers thick (or thin).

Contaminated
Surface?

Pure water

Teflon

PTFE

The Teflon Film Test

Contaminated
water

Teflon

Lecture on Contact Angles, May 4, 2005

A) Liquid and Solid Surface Energies
B) Liquid Contact Angles on Solid Surfaces
Prof. Allan S. Hoffman
(with some slides by Buddy Ratner)

Contact angles
AFM, STM
static SIMS

Contact angles,
AFM, STM,
Static SIMS

ESCA, Auger

ESCA
100

SURFACE ANALYSIS
TECHNIQUES

ATR-IR

200

Each technique
probes a unique
depth into the
surface. Spatial
resolution of the
technique is also
important.

ATR-IR
300

x 40

400

500

1 cm

Contact angles and water wettability are important for:

Industrial/Commercial
Adhesion
Printing
Paints
Absorbancy
Textile processing
Static dissipation
Water repellancy
Stain repellancy
Laundering

Biomedical
Protein adsorption
Blood compatibility
Cell-surface interactions

Contact Angles
The CONTACT ANGLE () is the angle that a small drop of
liquid makes as it meets the surface or interface of another
phase, usually a solid.
The contact angle
is always measured
through the droplet
(or air bubble)

vapor

liquid

solid

Contact Angles ()
vapor

Note that
is always
measured
through the
droplet or air
bubble

water
solid

solid

solid

air bubble
or oil droplet

water

Contact Angles ()
vapor

Note that
is always
measured
through the
droplet.

water
solid

ce
a
f
r
u
s
d
li
o
s
t?
i
c
i
l
e
i
r
ph easu
o
r
d
y
m solid
h
o
t
y
er bble
v
solid
a
u
r
b
o
f
ir

a
s
i
n

a
at
g
h
n
W
air bubble
usi

or oil droplet

water

Some interesting observations

about contact angles
The contact angle of water on skin is about 90 degrees.
(If it were zero, external water could penetrate the pores).
The contact angle of water on Teflon is about 110 degrees.
A birds feather has a contact angle of water as high as 150 degrees.

In measuring contact angles, you are creating

and altering the free total surface of a drop:

solid
Why does the
drop spread
on some
surfaces?

Non-wetting
surface -- a sphere has
minimum surface
to volume

solid

Drop volume
is constant

solid

Thus, drop
surface area
must increase

In measuring contact angles, you are creating

and altering the free total surface of a drop:
Same solid

Same liquid

solid
Why does the
drop spread
on some
surfaces?
Solid surface
energy
increasing

solid

solid

Non-wetting
surface -- a sphere has
minimum surface
to volume

Drop volume
is constant

Liquid surface
Thus, drop
tension
surface area
must increase
decreasing

There are many techniques for

measuring the contact angle

Droplet or bubbleb.contact angles

a.

lv
sv

c.

Capillary rise

Figure 5

air or
octane

sl

d.

Wilhelmy Plate

View here

Add liquid drop here

Eyepiece has a
crosshair +
Protractor

Goniometer

This drop will appear

upside down in the
goniometer objective.

Phase Transition Behavior of

PNIPAAm-PDMS
Above the LCST

Below the LCST

Photographs of Water Drops on

PNIPAAm-grafted PDMS Surfaces
20oC

40oC

Data of M. Ebara, UW, 1/05 (Stayton/Hoffman group)

Capillary rise of water in the grafted channel is

reduced as temperature is raised above the LCST.

1 mm x 5 mm

Advancing contact angles (in air) sense the

hydrophobic portion of surface properties
Water drop on surface at equilibrium
water
CH3 CH3 CH3 CH3

O O O O O O O CH3 CH3 CH3 CH3

H H H H H H H

Add water to the drop (to make it advance)

Drop probes hydrophobic regions and adv is high.

water
CH3 CH3 CH3 CH3

O O O O O O O CH3 CH3 CH3 CH3

H H H H H H H

Receding contact angles (in air) sense the

hydrophilic portion of surface properties
Water drop on surface at equilibrium
water
CH3 CH3 CH3 CH3

O O O O O O O CH3 CH3 CH3 CH3

H H H H H H H

Remove water from the drop (to make it recede)

Drop is held back by hydrophilic regions and rec is low.

water
CH3 CH3 CH3 CH3 O O O O O O O O O CH3 CH3
H H H H H H H HH

CH3

Contact angles on hydrogels made by crosslinking three-arm

PEG acrylates of different PEG MWs

Large
hysteresis

Advancing

Receding

1000

10,000

100,000

PEG molecular weight

Drumheller and Hubbell, J. Bioed. Mater. Res. 29, 207 (1995)

a.

b.

adv

rec

Advancing (adv)
and receding (rec)
contact angles

adv

rec

Tilting plane gives both

advancing and receding
contact angles in same drop.

Concerns and considerations in

contact angle measurements
Liquid penetrating the surface
Liquid dissolving the surface
Contamination of liquid
Size of drop and effect of gravity
Evaporation
Usually limited to ambient temperature
Usually limited to flat surfaces
Surface roughness
Surface heterogeneity
Surface group mobility and kinetics
Advancing vs. receding contact angles
Limited to relatively low energy solids (polymers)
Individual eyeball bias

Concerns and considerations in

contact angle measurements
Liquid penetrating the surface
Liquid dissolving the surface
Contamination of liquid
Size of drop and effect of gravity
ctly
e
r
i
d
Evaporation
t
no
o
d
s
n
o
le
i
t
g
i
n
s
a
o
Usually limited
to
ambient
temperature
t
mp
ac
t
o
n
c
o
e
C
c
rfasurfaces
u
s
Usually
to
flat
NOTE: limited
e
z
analy
Surface roughness
Surface heterogeneity
Surface group mobility and kinetics
Advancing vs. receding contact angles
Limited to relatively low energy solids (polymers)
Individual eyeball bias

Force Balance at the Contact Angle ()

lv is for liquid in equilibrium

lv

with its own vapor

liquid

l/s
sl

is for solid-liquid interface

l/s

sv is for solid in equilibrium

with vapor of liquid

vapor
of liquid

sv

solid

at equilibrium (assume no
swelling of solid by liquid)

At equilibrium:

sv

so

sv = l/s + lv cos

(Young-Dupr Eqn)

Equil. Spreading Pressure

Young-Dupre Equation

sv - ls
cos =
lv

Note that for solving

this equation, we know

and lv , but we are

missing two values!
We want

sv

We do not know

= 180 cos = -1
= 90 cos = 0
= 0 cos = 1

ls

Molecules in liquid
and molecules on the
surface have very
different forces!

Molecules in liquid and

molecules on the surface
have similar forces!

a vs.
vs. cos , and adv
rec

Practical application of the Young-Dupre equation

We will use contact angles to estimate solid surface energies:

s = i

+ H + p + d + m

s = i

+ a + b + d + m

Critical surface tension

(Zisman)

Polar + Dispersive
(Good, Fowkes)

s = p

Acid-Base + Dispersive
(Fowkes)

s = a

Critical Surface Tension, c

A concept developed in the 1960s by Walter Zisman at the NRL
Critical surface tension, c = surface tension of a liquid
that would just completely wet a solid being tested.
When the liquid just spreads on the solid, then one could say
that the solid surface energy is just matched by the liquid

surface tension*. However, Zisman never believed c was a

measure of solid surface energy, but only an empirical
approximation of it, and this is the best way to view

c .

*(Note that the act of wetting and spreading is not an

equilibrium phenomenon).

Critical Surface Tension, c

Measure adv on one surface for a series of liquids
varying in surface tension.
Plot cos adv vs. lv
Extrapolate to cos adv = 1.0 (adv = 0)
Define c =

lv at cos adv = 1.0

(adv = 0)

adv

Liquids used in critical surface tension measurements

Surface tension, dynes/cm (22C)
Water
Glycerol
Formamide
Thiodiglycol
Methylene iodide
Tetrabromoethane
1-bromonaphthalene
Dibromobenzene
1-methyl naphthalene
Dicyclohexyl
Hexadecane
Decane

72.9
63.7
58.4
53.5
51.7
49.8
45.0
42.9
38.9
32.7
27.6
24.1

Why these liquids?

Theyre stable, and can be purified. They have relatively low viscosity and
low volatility. Only pure liquids will have a well-known surface tension.

Note c range
is relatively
narrow

(Baier, 1969)

25

(Baier, 1969)

We will use contact angles to estimate solid surface energies:

s = i

+ H + p + d + m

s = i

+ a + b + d + m

Critical surface tension

(Zisman)

Polar + Dispersive
(Good, Fowkes)

s = p

Acid-Base + Dispersive
(Fowkes)

s = a

Some Polar and Dispersive Contributions to Liquid

and Solid Surface Energies @ 20 C
LIQUIDS

=
d +

water

72.8 = 21.8 + 51.0 (dynes/cm)

fomamide

58.2 = 39.5 + 18.7

CH2I2

50.8 = 48.5 + 2.3

C16H34

27.6 = 27.6 + 0.0

SOLIDS

=
d +

Nylon 66

41.4 = 33.6 + 7.8

46

Dacron

39.5 = 38.4 + 2.2

43

P.E.

32.4 = 31.3 + 1.1

31

PDMS

22.1 = 20.5 + 1.6

22

PTFE

15.6 = 14.6 + 1.0

18.5

Contact angle,

vapor adsn.

NOTE THAT EVEN OXIDES AND

SALTS OF METALS, AS WELL AS
GLASSES, HAVE AN IMPORTANT
DISPERSION COMPONENT
OF SURFACE ENERGY

We will use contact angles to estimate solid surface energies:

s = i

+ H + p + d + m

s = i

+ a + b + d + m

Critical surface tension

(Zisman)

Polar + Dispersive
(Good, Fowkes)

s = p

Acid-Base + Dispersive
(Fowkes)

s = a

The older acid-base principle applied to proton interactions:

Brnsted-Lowry acid is defined as a proton donor.
Brnsted-Lowry base is defined as a proton acceptor.

HCl + NH3
B-L
acid

B-L
base

HNH3+ + Cl-

The more modern acid-base principle applied to electron interns:

Lewis acid is an electron pair acceptor.
Lewis base is an electron pair donor.

HCl + :NH3
L. acid

H:NH3+ + Cl-

L. base

F3B + :N(CH3)3

F3B:N(CH3)3

Its clear that Fowkes theory relating surface

energies and contact angles through acid-base
(plus hydrophobic) interactions is just another way
to characterize polar (plus hydrophobic)
interactions between molecules at interfaces.

Conclusions

or acid-base interns

Definition of surface tension, : force in the surface of a liquid, to be

applied to a barrier perpendicular to it in order to increase surface area.
Thus, surface tension, = f/L = (f2)/(L2) = f/L
force = f

force = f/2

is the same as:

L

x/2
L/2

Definition of surface energy per unit area, : force applied to

a barrier of length L, perpendicular to it, acting over a
distance x, to increase surface area by xL.
The work to do this is the surface energy/area, .

= (fx)/(Lx) = (f2x)/(L2x) = (2f2x)/(2L2x) = f/L

THUS, SURFACE TENSION

SURFACE ENERGY/AREA