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vapor
liquid
solid
Polar
Higher energy
stronger
weaker
Non-polar
Lower energy
The energy to bring one molecule to the surface and then to volatile it
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)
2)
hydrocarbons
CH3
-(Si -O)CH3
silicones
-CmF2m+1
fluorocarbons
octane
H
Surface tensions
72.8 dynes/cm
22.1 dynes/cm
27.5 dynes/cm
21.8 dynes/cm
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
Teflon
Poly(hydroxyethyl methacrylate)
Water
Low interfacial energy
Any metal oxide
CH3
(CH2C)
C=O
Poly(hydroxyethyl methacrylate)
OCH2CH2OH
Poly(HEMA)
Low
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.
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(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)
42
hema_c1s.r01
...
.. .
.
.
.. ... ...
.....
.....
.
.....
.
. ......... ... ............
. .
. ....... ....... ....
.
. .......................... ............
2500
p-HEMA 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
280
42
hema_c1s.r01
2500
p-HEMA C1s
2000
1000
counts
counts
.
.
.
.. ... ...
.....
.....
.
.....
.
. ......... ... ............
. .
. ....... ....... ....
.
. .......................... ............
1500
500
0
292
290
288
286
284
282
280
295
295
290
285
280
290
285
295
280
290
285
280
Summary
Summary of
Surface Fundamentals
1)
2)
b)
c)
d)
3)
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
Contaminated
water
Teflon
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
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
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
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
a.
lv
sv
c.
Capillary rise
Figure 5
air or
octane
sl
d.
Wilhelmy Plate
View here
Eyepiece has a
crosshair +
Protractor
Goniometer
40oC
1 mm x 5 mm
water
CH3 CH3 CH3 CH3
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
Large
hysteresis
Advancing
Receding
1000
10,000
100,000
a.
b.
adv
rec
Advancing (adv)
and receding (rec)
contact angles
adv
rec
lv
liquid
l/s
sl
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)
Young-Dupre Equation
sv - ls
cos =
lv
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!
a vs.
vs. cos , and adv
rec
s = i
+ H + p + d + m
s = i
+ a + b + d + m
Polar + Dispersive
(Good, Fowkes)
s = p
Acid-Base + Dispersive
(Fowkes)
s = a
c .
(adv = 0)
adv
72.9
63.7
58.4
53.5
51.7
49.8
45.0
42.9
38.9
32.7
27.6
24.1
Note c range
is relatively
narrow
(Baier, 1969)
25
(Baier, 1969)
s = i
+ H + p + d + m
s = i
+ a + b + d + m
Polar + Dispersive
(Good, Fowkes)
s = p
Acid-Base + Dispersive
(Fowkes)
s = a
=
d +
water
fomamide
CH2I2
C16H34
SOLIDS
=
d +
Nylon 66
46
Dacron
43
P.E.
31
PDMS
22
PTFE
18.5
Contact angle,
vapor adsn.
s = i
+ H + p + d + m
s = i
+ a + b + d + m
Polar + Dispersive
(Good, Fowkes)
s = p
Acid-Base + Dispersive
(Fowkes)
s = a
HCl + NH3
B-L
acid
B-L
base
HNH3+ + Cl-
HCl + :NH3
L. acid
H:NH3+ + Cl-
L. base
F3B + :N(CH3)3
F3B:N(CH3)3
Conclusions
or acid-base interns
force = f/2
x/2
L/2
SURFACE ENERGY/AREA