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Surface Tension of Polymers

Abhinandan Agrawal

Hatsopoulos Microfluids Laboratory


Department of Mechanical Engineering
Massachusetts Institute of Technology

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June 29, 2005
Physical origin of surface tension/surface energy

• “Unhappy” molecules at the surface: they are


missing half their attractive interactions

• Unbalanced forces for the molecules at the


surface lead to additional energy

• The additional free energy at the surface is


Examples of “minimal surfaces” known as surface energy

• This is the fundamental reason behind liquids


adjusting their shapes to expose the smallest
possible area

www.fairfied.edu
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full dry hair vs. sticky wet hair spherical shape
June 29, 2005
Jose Bico, Nature, 2004 of bubbles
Mechanical definition: as a surface energy

Supply of energy is necessary to create surfaces

dW = γ ⋅ dA γ = specific free energy or surface tension (mJ/m2)

Specific surface energy of a material is the excess energy per unit area due to the
existence of the free surface

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Estimation of surface tension based on intermolecular forces
U/2
U is the cohesion energy per molecule inside the liquid

Energy shortfall for a molecule sitting at the surface ~ U/2


U
a is the size of a molecule; a2 is the exposed area of a
molecule
U
Surface tension is then of order γ ≅ For van der Waals type interactions, U ≅ kT
2a 2
At a temperature of 25 oC, kT is equal to 1/40 eV, which gives γ = 20 mJ /m2
(close to actual value for oils and alcohols)

Surface tension of a few common liquids in mJ/m2


Helium Ethanol Acetone Glycerol Water Water Molten Mercury
(4 K) (100oC) glass
0.1 23 24 63 73 58 ~300 485

U ≈ 1eV 4
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hydrogen bonding strongly cohesive liquid
Mechanical definition: as a capillary force

Surface tension (γ) can also be viewed as a force per unit length (mN/m or N/m)

The term “surface tension” is tied to the concept that the surface stays under
a tension
Examples where surface tension manifests itself
as force
1) Slider 2) Capillary adhesion 3) Objects on water

(F1+F2) cosθ

θ F
F2 1

W
F dx = 2 γ l dx F end view of the leg

F1=F2=γl

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June 29, 2005
Contents

Relationship of surface tension with other material properties

Derivation of surface tension theoretically from knowledge of


intermolecular forces

1) Surface energy of polymer liquids and melts

2) Surface energy of solid polymers

3) Interfacial tension between a solid and a liquid

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1. Surface energy of liquids and melts

Existing methods for determining the surface tension of liquids


F
1) Wilhelmy’s method, in which one dips a thin plate or p is the perimeter of the plate
ring in the liquid and measures the capillary force acting = 2(length + width)
on the plate
θ pγ cos(θ )

2) The rise of a liquid in a small capillary tube h


θ
hρ gr
γ=
2cosθ r

3) The method of drops, in which one characterizes washing-liquid water


the shape of drops
rzz 1
γ C = ρ gz C=−
(1 + r )
z
2 3/ 2
+
r (1 + r z )
2 1/ 2 r
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June 29, 2005 z
Estimation of surface tension from related properties
Since the surface tension is a manifestation of intermolecular forces, it may be expected to be
related to other properties derived from intermolecular forces, such as work of cohesion
internal pressure, and compressibility.

1) Relationship between work of cohesion and surface tension (Grunberg 1949)


2/3
= molecular vol.; ⎛⎜ A ⎞⎟
V N
V = molar vol.; NA = molecules/unit surf. area;
⎝ V ⎠
Wcoh = 2γ N 1/A 3V 2 / 3 γ = surf. energy per unit area; γ V / N A = surface energy per molecule;
2/3 2/3

γ N 1/A 3V 2 / 3 = molar surf. energy; 2γ N 1/A 3V 2 / 3 = work of cohesion;

2) Relationship between surface tension and solubility parameter (Hildebrand 1950)

0.43 γ / V 1/ 3 ∼ molar surf. energy/V = ∆Ev /V = δ 2 ;


⎛ γ ⎞
δ = 4.1⎜ 1/ 3 ⎟
(cgs units)
⎝V ⎠ ∆Ev is the energy of vaporization; δ is the solubility parameter;

3) Relationship between compressibility and surface tension (McGowan 1967)


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June 29, 2005 κγ 3/ 2 −8
= 1.33 × 10 (cgs units) κ ↑→ γ ↓
Introduction to parachor

Macleod et al. (Trans. Faraday So., 1923, 19, 38)


γ is the surface tension, D and d are
γ = C(D − d)
4
the density of liquid and vapor at same
temperature. C is a a characteristic
valid for different compounds constant for a given liquid.
and at different temperatures

Sugden S. J. (Chem. Soc., 1924, 125, 1177) Unit of Ps (cm3/mol)×(erg/cm2)1/4 or


(m3/mol)×(mJ/m2)1/4
M at low temperature,
Ps = C M =
1/ 4
γ 1/ 4
D−d d becomes small molecular
volume V
Ps for different substances is a comparison of molecular volumes at temperatures at
which liquids have the same surface tension

Ps = 0.78Vc Ps bears an constant ratio to the critical volume, which


suggests that it is a true measure of the molecular volume

Ps is called parachor (from παρα = by the side of, and χορος = space to signify 9
comparative volumes)
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Useful properties of parachor

Ps is only a function of chemical composition and it is an additive function

From experimental data for Ps, it is found that

X R • Ps can be reproduced by adding together two sets of


constants, one for the atoms in the molecule, the other
for the unsaturation or ring closure.
H C C
• The values for a particular atom is independent of the
O R1 manner in which it is situated

• The values for individual element


are same from compound to compound.

The molecular parachor is a useful means ⎛ Ps ⎞


4

of estimating surface tensions γ =⎜ ⎟


⎝V ⎠
M is the molecular weight, V is the molar volume, ρ is the density. If the
group contributions of Ps and V are known, γ results from the above expression
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Atomic and structural contributions to the parachor

Deduction of atomic constants:


Difference for CH2 in paraffins, esters, ethers, and ketones has a mean value of 40.0

Subtracting nCH2 from a series of values for the paraffins CnH2n+2, values for 2H can
be calculated
Unit Value Unit Value
CH2 40.0 Br 68.0
C 9.0 I 90.3
H 15.5 Double bond 16.3–19.1
O 19.8 Triple bond 40.6
O2 (in esters) 54.8 Three-membered ring 12.5
N 17.5 Four-membered ring 6.0
S 49.1 Five-membered ring 3.0
F 26.1 Six-membered ring 0.8
Cl 55.2 Seven-membered ring 4.0
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June 29, 2005
Quayle O.R. Chem. Revs. 53 (1953) 439
Example: ethanol

H H Unit Contribution to
parachor
O 19.8
H C C O H
C 9.0
H H H 15.5

Ps = 1 × 19.8 + 6 × 15.5 + 2 × 9 = 130.8(cm3 /mol)×(erg/cm 2 )1/4


ρ = 0.789 g/cm3 ; M = 46 g/mol
M
V= = 58.3 cm3 /mol
ρ
4 4
⎛ Ps ⎞ ⎛ 130.8 ⎞
( )
4
γ =⎜ =
⎟ ⎜ ⎟ = 2.24 =25.3 erg/cm 2
or 25.3mJ/m 2

⎝ ⎠ ⎝
V 58.3 ⎠

close to the actual value of 24 mJ/m2


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June 29, 2005
Example: poly (ethylene oxide)

H H Unit Contribution to
parachor
O 19.8
C C O
C 9.0
H H H 15.5

Ps = 1 × 19.8 + 4 × 15.5 + 2 × 9 = 99.8(cm 3/mol)×(erg/cm 2 )1/4


ρ = 1.12 g/cm3 ; M = 44 g/mol
M
V= = cm3 /mol
ρ
4 4
⎛ Ps ⎞ ⎛ 99.8 ⎞
( )
4
γ =⎜ =
⎟ ⎜ ⎟ = 2.54 =41.6 erg/cm 2
or 41.6 mJ/m 2

⎝ ⎠ ⎝
V 39.28 ⎠

close to the actual value of 43 mJ/m2


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June 29, 2005
Contact between solids and liquids

Solid/liquid
pair

wetting partially wetting non-wetting

air
Change in Gibbs free energy dG when the drop spreads
γl
liquid an infinitesimal amount
dA cos θ
θ' θ dG = γ sl dA − γ s dA + γ l dA cos θ
γs
dA γsl At equilibrium dG / dA = 0 → γ sl − γ s + γ l cos θ = 0

γl and θ are directly measurable; γ s − γ sl


γs and γsl are not cos θ =
γl
wetting behavior dependent on
interfacial and solid surface energy as well 14
June 29, 2005
2. Surface tension of solid surfaces (γs)

Methods for determining the surface tension of solids

a) By measuring the contact angle between the solid and liquid

b) By determining critical surface tension (γ cr ) according to Zisman (1964),


with the assumption that γ cr ≈ γ s

c) By extrapolating surface tension data of polymer melts to room


temperature (Roe, 1965; Wu, 1969–71)

No direct method available for measurement of surface tension of solid polymers

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June 29, 2005
2a. Estimation of solid surface energy from contact angle
1/ 3
γ sl = γ s + γ l − 2Φ(γ sγ l )
1/ 2 4(VV
s l)
Φ=
γ sl − γ s + γ l cosθ = 0 (V 1/ 3
+V )
1/ 3 2
s l

Girifalco and Good (1956)


⎛ (1 + cosθ )2 ⎞
γs ≈γl ⎜ ⎟
⎜ 4Φ2 ⎟
⎝ ⎠

Example: PMMA VPMMA =


M PMMA
= 86.5 cm3 /mol
ρ PMMA = 1.17 g/cm3 ; M PMMA = 100.1g/mol ρ PMMA
68–72o
M
ρ H O = 1g/cm3 ; M H O = 18g/mol VH 2O = = 18 cm3 /mol; γ H 2O = 72 mJ/m 2
2 2
ρ
4(18 × 86.5)1/ 3 ⎛ (1 + cos(69 ))2 ⎞
Φ= = 0.93 γ s ≈ 72.8 ⎜ ⎟ ≈ 38 mJ/m2
(181/ 3
)
1/ 3 2
+ 86.5 ⎜ 4 × 0.93

2

By means of the boxed equation, surface tension of solid surface can be


calculated from measurements of contact angle and surface tension of liquid
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June 29, 2005
2b. Determining solid surface tension using Zisman plot

Toluene Propylene carbonate Zisman found that cosθ is usually a


1.0 monotonic function of γl
Dimethyl sulfoxide
0.8 Ethylene glycol cosθ = a − bγ l = 1 − β (γ l − γ cr )
cos(θ )

γcr is called the “critical surface tension”


0.6
Glycerol of a solid and is a characteristic property
of any given solid
0.4 Water
γ cr = 38 mJ/m2 Any liquid with γl <γcr will wet the
surface
30 40 50 60 70 80
Surface Tension (mN/m) It is found that critical surface tension is
close to the solid surface tension of
Zisman plot for PMMA using various testing liquids
polymer
γ s ≈ γ cr

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June 29, 2005
2c. Estimation of γ from extrapolating data of polymer melt

Extrapolation of surface tensions of melts to room temperature leads to


reliable values for solid polymers
4
⎛P ⎞
Hence, surface tension of solid polymers may be calculated using γ =⎜ s⎟
⎝V ⎠
Example: PMMA
CH3
Ps = 8 × H + 5 × C + 2 × O + 1 × double bond
CH2 C

C O Ps = 8 × 17.1 + 5 × 4.8 + 2 × 20 + 1 × 23.2


O CH3
Unit Contribution = 220.8(cm 3 /mol)×(erg/cm 2 )1/4
to parachor
O 20 ρ = 1.17 g/cm3 ; M = 100.1g/mol
4 4
C 9 M ⎛ P ⎞ ⎛ 220.8 ⎞
( )
4
V= = 86.5 cm3 /mol γ =⎜ s ⎟ = ⎜ ⎟ = 2.55
H 17.1 ρ ⎝ V ⎠ ⎝ 86.5 ⎠
Double 23.2
bond = 42.5 erg/cm 2 or 42.5mJ/m 2
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June 29, 2005
Example: contact angle of water on PMMA

1/ 2 1/ 3
⎛γ ⎞ 4(VV )
cosθ ≈ 2Φ ⎜ s ⎟ −1 Φ= s l

⎝ γl ⎠ (V
s
1/ 3
+V
l )
1/ 3 2

4(18 × 86.5)1/ 3
ρ H O = 1g/cm ; M H O = 18g/mol
3
Φ= = 0.93
2

M
2
(18 1/ 3
)
1/ 3 2
+ 86.5
VH 2O = = 18 cm /mol; γ H 2O = 72 mJ/m
3 2

ρ 1/ 2
⎛ 42.5 ⎞
cosθ ≈ 2 × 0.93⎜ ⎟ − 1 = 0.43
VPMMA = 86.5 cm3 /mol; γ PMMA = 42.5 mJ/m 2 ⎝ 72 ⎠
θ = 65o

contact angle of water on PMMA = 68–72 o

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June 29, 2005
Temperature dependence of surface tension
4
⎛ Ps ⎞
1) Since the parachor Ps is independent of the temperature γ =⎜ ⎟
⎝V ⎠
4
⎛ ρ (T ) ⎞
γ = γ (298) ⎜ ⎟
⎝ ρ (298) ⎠

2) Guggenheim (1945) relationship


1+ r
⎛ T ⎞
--surface tension of a liquid decreases with temperature γ = γ (0) ⎜1 − ⎟
⎝ Tcr ⎠
--surface tension vanishes at the critical point
r=2/9
Tcr is the imaginary critical
2/9
d γ 11 γ (0) ⎛ T ⎞ temperature of the polymer
− = ⎜ 1 − ⎟
dT 9 Tcr ⎝ Tcr ⎠

for low values of T/Tcr , dγ/dT will be constant


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June 29, 2005
Molecular mass dependence of surface tension

The surface tension of homologous series tends to increase with increasing molecular
weight

The bulk properties (e.g. heat capacity, tensile strength, specific volume etc.) vary linearly
with the reciprocal of molecular weight

The surface tension, instead, varies linearly with Mn-2/3

At infinite molecular weight, surface tension is finite, γ∞

ke Polymer γ∞ ke
γ = γ ∞ − 2/ 3
Mn polyethylene 36 386
polystyrene 30 373

ke is a constant Polydimethylsiloxane 21 166

polyethylene oxide 43 343

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June 29, 2005 “Polymer Interface and Adhesion” Wu S.
3. Estimation of interfacial surface energy

The additional free energy at the interface between two condensed phases is
known as interfacial energy
1/ 3
4(VV
s l)
Φ=
γ sl − γ s + γ l cosθ = 0 γ sl = γ s + γ l − 2Φ(γ sγ l )1/ 2
(V
s
1/ 3
+V
l )
1/ 3 2

eliminating γs

⎛ (1 + cosθ )2 ⎞
γ sl = γ l ⎜ − cosθ ⎟
⎜ 4Φ 2 ⎟
⎝ ⎠

By means of this equation, interfacial tension can be calculated from measurements


of contact angle and surface tension of liquid
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June 29, 2005
Estimation of interfacial tension

Lorentz-Berthelot Mixing Rules


Aab Aab = interaction energy between unlike molecules
=1
( Aaa Abb ) Aaa , Abb = interaction energy between like molecules
1/ 2

Girifalco and Good (1956)


∆Fab ∆Fab = free energy of adhesion ∆Faa = free energy of cohesion
− =Φ
( ∆Faa ∆Fbb )
1/ 2
Φ = interaction parameter

γab adhesion
γb
∆Fab = γ ab − γ b − γ a
γa
γa cohesion
∆Faa = −2γ a
γa

1/ 3
4(VV
s l)
γ ab = γ a + γ b − 2Φ(γ aγ b ) 1/ 2
Φ=
(Vs1/ 3 + Vl1/ 3 )
2

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June 29, 2005
General expression for the interfacial tension

Equation is only valid for substances


γ sl = γ s + γ l − 2Φ (γ sγ l )1/ 2
interacting with additive dispersive forces and
without hydrogen bonds. (Fowkes, 1964)
γ sl ≈ (γ l1/ 2 − γ s1/ 2 )
2
since Φ ≈ 1for most polymers

Fowkes has suggested that total free energy at a surface is the sum of contributions
from the different intermolecular forces at the surface.

d and a refer to the dispersion forces and a-scalar forces (the


γ = γ +γ d a
combined polar interactions: dipole, induction, and hydrogen
bonding

γ sl = γ s + γ l − 2 (γ γ )
d d 1/ 2
l s γ sl = γ s + γ l − 2 (γ γ )
d d 1/ 2
l s − 2 (γ γ )
a a 1/ 2
l s

for apolar liquids/solids Owens and Wendt extended the formulation

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June 29, 2005
General expression for the interfacial tension

2 2
γ 12 = ⎡⎢(γ )
d 1/ 2
− (γ ) ⎤ + ⎡( γ
d 1/ 2
⎥⎦ ⎢⎣ )
a 1/ 2
− (γ ) ⎤
a 1/ 2
⎥⎦
⎣ 1 2 1 2

Substances 1 and 2 may either be liquids, or solids, or they may be a


combination of a solid and a liquid

Liquid γ1 γ 1d γ 1a
n-hexane 18.4 18.4 0
cyclohexane 25.5 25.5 0 γ 12 = ⎡⎢(γ 1d )
1/ 2 2
− (γ 2d ) ⎤⎥ + ⎡⎢ (γ 1a ) − (γ 2a ) ⎤⎥
1/ 2 1/ 2 1/ 2 2

⎣ ⎦ ⎣ ⎦

glycol 48 33.8 14.2


methylene iodide 50.8 49.5 1.3
glycerol 63.4 37.0±4 26 γ 12 = ⎡⎢ (γ 1d )

γ 12 = ⎢⎡ (γ 1d )

1/ 2

1/ 2

1/ 2

⎦ ⎣
2 1/ 2
2
− (γ 2d ) ⎤⎥ + ⎡⎢ (γ 1a ) − (γ 2a ) ⎤⎥
1/ 2

⎦ ⎣
− (γ 2d ) ⎥⎤ + ⎢⎡(γ 1a ) − (γ 2a ) ⎥⎤
1/ 2


1/ 2

2
1/ 2


2

water 72.8 21.8±0.7 51

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June 29, 2005
Calculation of force components of surface tension

Liquid 1 (e.g. water): γ 1a ,γ 1d


• Measure the surface tension of this liquid (γ 1 = 72.3 mJ/m 2 )

• Take another liquid (e.g. cyclohexane) which is immiscible with Liquid 1


and is apolar (γ 2a = 0; γ 2 = 25mJ/m2 ; → γ 2d = 25mJ/m2 )

Measure the interfacial tension by one of the available methods (γ 12 = 50.2 mJ/m )
2

• Solve the following the two equations simultaneously

2 2
γ 12 = ⎡⎢(γ )
d 1/ 2
− (γ ) ⎤ + ⎡(γ
d 1/ 2
⎥⎦ ⎢⎣ )
a 1/ 2
− (γ )
a 1/ 2⎤
⎥⎦ γ 1 = γ 1d + γ 1a
⎣ 1 2 1 2

γ H O ,ch = 50.2 = 25 + 72 − 2 ( 25γ )


1/ 2
2
d
H 2O γ Hd O = 22.7, γ Ha O = 72 − 22.7 = 49.3
2 2

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June 29, 2005
Conclusions

• The specific energy of a polymer can be estimated by means of an


additive quantity, the parachor

• It may be alternatively calculated from different related material


properties e.g. cohesive energy, compressibility, solubility
parameter

• Rules are given for the estimation of the interfacial tension and the
contact angle of a liquid on a solid

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June 29, 2005
Extra slides: estimation of Φ

∞ ∞ ∞ ∂ε ab
Fab ( z ) = 2π ∫ nbd j ∫ f df ∫ na dr
z j f ∂r
∞ ∞ ∞ ∞ ∂ε ab
−∆Fab ( z ) = 2π ∫ dx∫ nbd j ∫ f df ∫ na dr
z x j f ∂r

A B
Lennnard-Jones ε ab = − 6 + m
ab ab
Carrying out the integrations and equating the net force to 0
when z=dAB (equilibrium distance) potential r r

Interaction ∂ε ab 6 Aab mBab


n n A ⎛1 1 ⎞ = 7 − m+1
∆ Fab = a b 2 ab ⎜ − ⎟ force ∂r r r
6 d ab ⎝ 2 m − 4 ⎠
n a2 Aaa ⎛ 1 1 ⎞
∆ Faa = ⎜ − ⎟
⎝2 m−4⎠
2
6 d aa

∆Fab d d Aab 4(VsVl )1/ 3


− =Φ Φ = aa 2 bb × Φ=
( Aaa Abb ) (V + Vl1/ 3 )
2 2
( ∆Faa ∆Fbb ) d ab
1/ 2 1/ 3
s

28
June 29, 2005 Girifalco and Good (1956)
1) Floating needles l

(F1+F2) cosθ

θ F
F2 1

W
end view of needle
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June 29, 2005 F1=F2=γl