J. Adhesion Sci. Technol., Vol. 21, No. 10, pp.

961 981 (2007)

VSP 2007.

Also available online - www.brill.nl/jast

Polar interactions at liquid/polymer interfaces

ALAIN CARR
Corning SAS, Corning European Technology Center, 7 bis, Avenue de Valvins, 77210 Avon, France
Received in final form 28 May 2007
AbstractNumerous relationships have been proposed in the literature to interpret wettability in
terms of solid and liquid surface free energies. In the classical approach based on surface free energy
components, the energy of interactions between the liquid and the solid is obtained from the geometric
mean of the dispersion and polar contributions of the liquid and solid surface free energies. In this
work, it is shown that the surface polarity of polar liquids can be modeled by the interaction of aligned
permanent dipoles. A good agreement is found between the surface polarity characterized by polar
component of the surface free energy of polar liquids (water, formamide and ethylene glycol) and the
dipolar energy of interactions calculated from their dipole moment. At the liquid/polymer interfaces,
polar interactions are better described by a simple relationship of proportionality with the polar
component of the liquid surface free energy. This observation leads us to evaluate the hypothesis of
induced polar interactions at liquid/polymer interfaces, the surface polarity of the solid being induced
by the polar liquid in contact with the solid surface. Thus, the variation of the contact angle of a series
of polar and non-polar liquids on various polymer substrates appears to be in better agreement when
compared to the classical description of permanent polar interactions, so that a surface polarizability
is defined for polymers. Using the surface polarizability approach rather than the polar component
for the solid surface, we find also that the dispersion (non-polar) component of the polymer surface
free energy is obtained with a better confidence, especially by taking into account the contact angles
of both non-polar and polar liquid probes, or even by considering only polar liquid probes.
Keywords: Wetting; wettability; contact angle; surface free energy; surface tension; polar forces;
dispersion forces; interfaces.

1. INTRODUCTION

There are various approaches in the literature to evaluate the surface free energy
of solid materials from wetting experiments. Contact angle measurements with
different liquid probes with known surface tension form the basis for the calculation
of the surface free energy of solids. However, the solid surface free energy, or
parameters related to the surface free energy, can be different depending on the
Tel.:

(33-1) 6469-7371; Fax: (33-1) 6469-7455; e-mail: carrea@corning.com

962

A. Carr

model chosen. One basic problem is that the Young equation (SV = L cos +SL )
describing the equilibrium of a liquid drop, L, having a contact angle on a
solid surface, S, involves two unknowns: the solid surface free energy, SV , and
the interface free energy between the liquid and the solid, SL (L is the liquid
surface free energy). As one equation having two unknowns cannot be solved,
several theories taking the Young equation as the starting point have been proposed.
Depending on the theoretical basis, three major approaches are still under debate:
the Fowkes type approach [1 3], involving the geometric mean of the liquid and
solid polar and non-polar components of the surface free energy, the Equationof-State of Neumann [4, 5] and the Lifshitzvan der Waals/acidbase approach
proposed by van Oss, Chaudhury and Good [6, 7]. In a comprehensive paper,
Sharma and Hanumantha Rao [8] exposed the arguments and the objections for each
of these different approaches. Etzler [9] also published a review on both theoretical
approaches and experimental methods for determining the surface free energy of
solids. Recently, Chibowski [10, 11] has developed another theory based on contactangle hysteresis and on the supposed existence of a liquid film left behind a receding
liquid front to deduce the value of the solid surface free energy.
Interestingly, it was mentioned by Fowkes [12], on the basis of data published
by Dann [13], that the polar energy of interaction between polar liquids (the
classical series of liquid probes used in wetting studies) and polymers including
polystyrene, polyamides, polyesters and poly(vinyl chloride) was proportional to
the liquid polarity quantified by the polar component of the liquid surface free
energy. However, this result which apparently did not fit with the geometric mean
approach was never deeply analyzed. We made similar observations, and propose
here an alternative to describe polar interactions between polar liquids and polar
polymers.
After presenting the theoretical background of intermolecular interactions, we
will show that a better coherence between theory and experiments is obtained when
the polar interaction at a liquid/polymer interface is considered to be proportional
to the liquid polarity. One possible explanation is that the polar liquid/polymer
interactions result from polar forces induced by the liquid at the solid surface.

2. THEORETICAL

With the surface energy component approaches, there is a general agreement

with the description of the non-polar solid/liquid interactions from the dispersion
contributions of the surface free energies of the solid and liquid. The calculation of
the dispersion interactions with the geometric mean relationship was successfully
established by Fowkes [14, 15]. The description of non-dispersion or polar
interactions raises more difficulties, and there is no unanimously recognized model.

Polar interactions at liquid/polymer interfaces

963

2.1. Non-polar (dispersion) interactions

The intermolecular attractions, which cause surface tension, arise from a variety of
well-known intermolecular forces. London dispersion forces exist in all types of
materials and always produce an attractive force. Fowkes [15] demonstrated that
D
, between two phases, 1 and 2, was given by:
the dispersion interaction, I12


D
= 2 1D 2D ,
(1)
I12
where jD (j = 1 or 2) is the dispersion component of the surface free energy. The
usefulness of the geometric mean approach for calculating dispersion interactions
was demonstrated for both liquid/liquid and liquid/solid interfaces. As an example,
its validity is easily verified by measuring the interfacial tension between water and
saturated hydrocarbons where only dispersion forces are operative.
2.2. Permanent dipole/dipole interactions
The energy of interaction between two aligned dipoles, of dipole moments 1 and
2 , is given by [16, 17]:
i12 =

21 2
,
3
40 r12

(2)

where 0 is the permittivity of free space (0 = 8.854 1012 C2 J1 m1 ) and r12

the interacting, center to center, distance of dipoles. Equation (2) applies in a polar
medium when i12 is higher than the thermal energy kT , k being the Boltzmanns
constant (1.381 1023 J/K) and T the temperature in K.
Therefore, in a polar liquid the interaction for a pair of aligned dipoles is written
as:
iLL =

22L
.
3
40 rLL

(3)

First, we propose to test the validity of equation (3) with pure polar liquids. We can
estimate the polar interaction energy per unit area at the surface of a polar liquid,
P
ILL
, by considering that:
nS
P
= iLL ,
(4)
ILL
2
where nS is the number of molecules per unit area (the number of dipoles per
unit area is half of nS ). This number can be obtained from the density d and the
2/3
molecular weight M of the liquid, and considering that nS nV , nV being the
number of molecules per unit volume. Therefore, nS can be deduced from:
2/3

d
nS
N
,
(5)
M

964

A. Carr

where N is the Avogadro number (6.021023 ). The average molecular distance can
also be estimated by considering that rLL a 1/2 = (1/nS )1/2 = v 1/3 = (1/nV )1/3 ,
a and v being the molecular area and volume, respectively.
The polar interaction energy per unit area obtained from equations (4) and (5)
can be compared with the experimental polar interaction obtained from the polar
component, LP , of the surface free energy, L (= LD + LP ), i.e.:
P
= 2LP .
ILL

(6)

The comparison of these two calculations is presented in Table 1 with water

(LP = 51 mJ/m2 ), formamide (LP = 18.7 mJ/m2 ) and ethylene glycol (LP =
19 mJ/m2 ) [13]. Their permanent dipole moments L are 1.85, 3.73 and 2.28 Debye,
respectively [18] (1 Debye (D) = 3.336 1030 C m). The polar interactions in
water, formamide and ethylene glycol include hydrogen bonds which are no more
than a particularly strong type of directional dipole/dipole interactions [16]. The
values of polar interactions obtained from the components of liquid surface free
energies (equation (6)) are relatively close to the energy of interactions deduced
from the dipole moments (equations (3) and (4)), especially for water and ethylene
glycol. The agreement is not as good for formamide. A small adjustment of the
interaction distance (rLL fit in Table 1) is necessary to get the correct agreement
(rLL fit = 6.1 1010 m versus rLL v 1/3 = 4.04 1010 m for formamide).
This simple analysis shows that we can consider the polar interactions at the surface
of polar liquids simply as resulting from the interaction between aligned dipoles.
The description of polar interactions at the interface between two phases having
permanent dipoles is compatible with the geometric mean of polar contributions of
P
1 2 and IjjP 2j , it is easily concluded
surface free energies because as I12
that [17]:




P
P P
= I11
I22 = 2 1P 2P .
(7)
I12
However, equation (7) assumes implicitly that:

r12 = r11 r22 .

(8)

Equations (1) and (7) constitute the basis of the Owens and Wendt theory of
solid/liquid interactions [19]. However, it is usually recognized that the use of the
geometric mean is not really satisfactory to describe polar liquid/solid interactions.
P
As noted by Fowkes [12], a direct proportionality between ISL
and LP seems to be
more accurate. The following section would explain this experimental result.
2.3. Dipole/induced dipole interactions
i
, between a polar molecule of permanent dipole moment 1
The interaction, i12
(of a polar liquid, for example) and a polarizable molecule of polarizability 2

LP
(mJ/m2 )

51
18.7
19

Liquid

Water
Formamide
Ethylene glycol

1.85
3.73
2.28

L
(Debye)

iLL aligned
(J)
2.29 1020
4.21 1020
1.12 1020

rLL = v 1/3
(m)
3.10 1010
4.04 1010
4.53 1010

nS
(molecules/m2 )
1.04 1019
6.11 1018
4.88 1018

P
ILL
(equation (4))
(mJ/m2 )
118.8
128.6
27.3

102
37.4
38

P = 2 P
ILL
L
(mJ/m2 )

3.27 1010
6.10 1010
4.06 1010

rLL fit
(m)

Table 1.
P at polar liquid surfaces deduced from their dipole moment, , or from the polar component of their surface free energy, P
Polar interaction energy ILL
L
L
(kT = 4.05 1021 J at 293 K)

Polar interactions at liquid/polymer interfaces

965

966

A. Carr

corresponds to the following Debye interaction energy [16]:

i
=
i12

2 21
2
21
=
.
3 2
3
3
(40 r12
)
40 r12
40 r12

(9)

As LP 2L (equations (3) and (4)) and assuming that rSL rLL , it can be deduced
that the induced solid/liquid polar interaction has the form:
P
= kS LP ,
ISL

(10)

where kS will be defined as the surface polarizability of the solid.

Comparing equations (2) and (9), it can also be deduced that the induced dipole
acquires a dipole moment i2 having the following magnitude:
2 1
,
(11)
i2 =
3 2
40 r12
such as the induced polar interaction can also be described by:
i
=
i12

21 i2
.
3
40 r12

(12)

Thus, when a polar liquid is in contact with a polarizable solid surface, the induced
solid/liquid polar interaction is compatible with the geometric mean as:


P
= 2 SPi LP .
(13)
ISL
However, the polar component of the solid surface free energy, SPi , is induced by
the contacting liquid. It is a variable which depends on the liquid polarity, LP .
Equations (10) and (13) show that the induced polar contribution to the surface free
energy of the solid is related to the solid surface polarizability, kS , and to the liquid
polarity by:
SPi =

kS2 P
.
4 L

(14)

2.4. Consequences with respect to the interpretation of contact-angle

measurements on polymer surfaces
The energy of interactions between a liquid and a solid in a partial wetting situation
( = 0) is usually related to the contact angle by combining the Young and Dupre
equations as
D
P
+ ISL
,
L (1 + cos ) = ISL

(15)

by assuming that the spreading pressure on low surface free energy solids (polymers) is negligible (the spreading pressure is the reduction of the solid surface free
energy resulting from the adsorption of liquid vapor on the solid). The dispersion
D
, is described by the geometric mean relationship. As we
(non-polar) interaction, ISL

Polar interactions at liquid/polymer interfaces

967

P
propose to discuss the nature of the polar interaction term, ISL
, as resulting either
from permanent dipole/dipole interactions or possibly from dipoleinduced dipole
interactions as described above, we will compare the accuracy of equation (15) by
considering the following two possible expressions, i.e.:




D D
L (1 + cos ) = 2 S L + 2 SP LP
(16)

according to the theory of permanent dipole interactions between the liquid and the
solid [19], or


(17)
L (1 + cos ) = 2 SD LD + kS LP ,
following the hypothesis of the solid surface polarity induced by the liquid in
contact.

3. EXPERIMENTAL

The contact angles of a series of polar and non-polar liquids (water, glycerol, formamide, ethylene glycol, diiodomethane, tricresylphosphate (TCP)) were measured
on different substrates of varying hydrophilicity. Water was purified by ionic exchange followed by organic removal leading to a resistivity of 18 M cm (Elgastat, UHP). The organic liquids were of the following grades and origins: glycerol
(99.5%, Prolabo), formamide (99.5%, Sigma), ethylene glycol (99%, Aldrich), Diiodomethane (99%, Sigma) and tricresylphosphate (98%, Acros Organics).
Our own contact angle measurements were made on polymer surfaces currently
used as substrates for cell culture. These included non-treated sterile polystyrene
(PS) (35 mm culture dish, Nalge Nunc International), PS exposed to gamma
radiation (g-PS) (35 mm culture dish, Corning), tissue culture treated (TCT) PS
(6-well clear TC-treated microplate, Corning), CellBIND substrate (6-well clear
microplate, Corning) and Ultra Low Attachment substrates (6-well clear flat bottom
Ultra Low Attachment microplate, Corning). The CellBIND had received a
proprietary plasma surface treatment to improve cell spreading and attachment. The
Ultra Low Attachment (ULA) substrate has a covalently bonded hydrogel layer that
is hydrophilic and neutrally charged so that it inhibits attachment of anchoragedependent cell lines. The substrates for cell cultures are sterile and ready for use
and no special procedures need to be followed to use these surfaces. Therefore,
they were used as received.
Contact angle measurements were made using a Ram-Hart contact angle goniometer at a controlled temperature of 22 1 C. The average contact angle was
obtained from measurements on 10 drops of each liquid, measuring the contact angles on both sides of the drop. The liquid drops had a volume of 2 l. The contact
angle values correspond to the advancing contact angles at equilibrium measured
at the end of the spreading process. The standard deviation was always lower than
1.7 , irrespective of the liquid/substrate pair (see Results and Discussion).

968

A. Carr

4. RESULTS AND DISCUSSION

The hypothesis of surface polarizability was evaluated with the literature data as
well as with our own contact angle measurements. The current permanent polarity
theory of the solid surface was tested with the linear form of equation (16) written
as:





LP
L
 (1 + cos ) = 2 SD + 2 SP
.
(18)
LD
LD
The hypothesis of the induced polarity of polymer surfaces was verified with the
linear form of equation (17) written as:


P
L
 (1 + cos ) = 2 SD + kS  L .
(19)
LD
LD
We can expect that the best description of polar interactions (permanent polarity
versus induced polarity at the polymer surface) is associated to the best fit of
experimental data with equations (18) and (19).
The first evaluation of the validity of equations (18) and (19) with polar polymers was made by considering the wettability data available in the literature
[17]. The study is limited to polar polymer surfaces when the water contact
angle is lower than 90 , but it can be applied to any type of polymer surface.
The series of polar polymers considered comprised poly(ethylene terephthalate)
(PET), poly(vinylidene chloride) (PVDC), poly(vinyl chloride) (PVC), poly(methyl
methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly(vinyl fluoride)
(PVF) and poly(hexamethylene adipamide) (PHMA). The liquid probes and their
corresponding L , LD and LP values are presented in Table 2 [13].
The contact angle data of Table 3 were used to compare the validity of equations
(18) and (19). The surface properties of the series of polar polymers are gathered
in Table 4 in which the surface properties are given either in terms of dispersion
component, SD , and polar component, SP (hypothesis of permanent solid surface
polarity), or in terms of dispersion component, SD , and surface polarizability, kS
(hypothesis of induced surface polarity).
The dispersion component SD is deduced


from the ordinate at the origin (2 SD ) of the linear regressions of equations (18)


and (19), SP and kS are deduced from the slopes (2 SP and kS , respectively). All
Table 2.
Liquid properties (from Ref. [13])
Water Glycerol Formamide Diiodomethane -Bromonaphthalene TCP Hexadecane
L (mJ/m2 ) 72.8
LD (mJ/m2 ) 21.8
LP (mJ/m2 ) 51

63.4
37
26.4

58.2
39.5
18.7

50.8
48.5
2.3

44.6
44.6
0

40.9 27.6
39.2 27.6
1.7 0

Polar interactions at liquid/polymer interfaces

969

Table 3.
Equilibrium contact angles on polar polymer surfaces (from Ref. [17])
Polimers Contact angle ( )
Water Glycerol Formamide Diiodomethane -Bromonaphthalene TCP Hexadecane
PET
PVDC
PVC
PMMA
PVDF
PVF
PHMA
* ,

81
80
87
80
82
80
70

65
61
67
69
75
66
60

61
61
66
64
59
54
50

38
29
36
41
63
49
41

15
9
11
16
42
33
16

*
10
14
19
28
28

24

no data reported.

Table 4.
Comparison between geometric mean (equation (18)) and surface polarizability (equation (19)) to
describe polar interactions
Polymer

PET
PVDC
PVC
PMMA
PVDF
PVF
PHMA
Average of R 2

P = 2 P P
Geometric mean ISL
S L
(equation (18))

P = k P
Surface polarizability ISL
S L
(equation (19))

SD (mJ/m2 )

SP (mJ/m2 )

R2

SD (mJ/m2 )

kS

R2

38.4
39.7
39.7
36.3
28.1
33.7
36.2

2.7
3.4
2.2
3.0
4.8
4.8
7.0

0.90
0.89
0.82
0.83
0.88
0.96
0.94
0.89

41.4
42.9
41.6
39.1
31.0
37.7
41.1

0.46
0.47
0.31
0.50
0.61
0.57
0.73

0.98
0.95
0.91
0.95
0.88
0.97
0.99
0.95

the liquids are taken into consideration to calculate the linear regressions. The
parameter R 2 is the coefficient of correlation of the linear regression. Except for
PVDF where the coefficient of correlation (R 2 = 0.88) is the same with both
models of polar interactions, the induced polarity at the polymer surface leads to
a better correlation, meaning that equation (19) fits the contact angle data better
than equation (18). For the series of 7 polar polymers, the average coefficient of
correlation is 0.89 with the model of permanent solid surface polarity described by
the geometric mean relationship versus 0.95 for the model considering that polar
interactions at liquid/polymer interfaces are induced by the polarity of the liquid.
As examples, the linear relationships corresponding to the description of permanent polar interactions with the geometric mean (equation (18)) are presented in
Fig. 1A for PHMA and PET. For the same polymers (PHMA, PET), the hypothesis of induced polar interactions (equation (19)) corresponds to Fig. 1B. Figure 1A

970

A. Carr

(A)

(B)
Figure 1. Comparison of the linear fits of equations (18) (A) and (19) (B) according to the nature of
dipolar solid/liquid interactions (permanent (A) or induced (B) solid polarity) for PHMA and PET.

Polar interactions at liquid/polymer interfaces

971

and 1B and the R 2 coefficients show the improvement of linearity obtained with the
solid polarizability approach (equation (19)).
The model chosen has also an impact on the determination of the dispersion
component of the surface free energy of polymer materials. The induced dipole
hypothesis leads systematically to a higher value of the dispersion component of
the surface free energy, SD (Table 4).
When considering liquids of low polarity, such as TCP, diiodomethane and
-bromonaphthalene, for which L LD , both equations (18) and (19) can be
simplified as


L
 (1 + cos ) 2 SD (LD L ),
(20)
LD
as the polar interactions, irrespective of their nature, are negligible relatively to dispersion interactions. In general, this simplified approach to estimate the dispersion
contribution to the surface free energy slightly overestimates the dispersion component of the solid surface free energy as the liquid/solid work of adhesion is assumed
to result only from dispersion interactions, which is not exactly true. The dispersion
components, SD , for the same series of polar polymers estimated from the contact
angles of low polarity liquids are presented in Table 5. It is obvious that the dispersion components of the surface free energy of polymers obtained from the contact
angles of low polarity liquids and from equation (20) are closer to the values deTable 5.
Estimation of the dispersion component, SD (mJ/m2 ), deduced from the contact angles of low polarity
liquids (TCP, diiodomethane and -bromonaphthalene) and equation (20)
Equation and liquid
probe

PET

PVDC

PVC

PMMA

PVDF

PVF

PHMA

 (%)

SD from equation (20)

and TCP
SD from equation (20)
and diiodomethane
SD from equation (20)
and -bromonaphthalene
SD (average) from
equation (20) and nonpolar liquids
SD from equation (19)
(induced polarity)
and all liquids
SD from equation (18)
(permanent polarity)
and all liquids

42.1

41.9

40.4

37.8

37.8

42.5

46.7

43.5

41.0

28.1

36.5

41.0

43.1

43.9

43.3

42.9

33.9

37.7

42.9

42.8

44.3

42.9

41.4

33.3

37.3

42.0

41.4

42.9

41.6

39.1

31.0

37.7

41.1

3.5

38.4

39.7

39.7

36.3

28.1

33.7

36.2

11.2

Comparison with the values obtained from the complete series of liquids of Table 2 and equations
(19) and (18).  is the average difference by taking the mean values obtained from non-polar liquids
and equation (20) as the reference.

972

A. Carr

duced from the contact angles of the entire series of non-polar and very polar liquids
with the surface induced polarity hypothesis (equation (19)). In Table 5,  is the
average difference between the following sets of values: SD (average) from equation (20) and non-polar liquids, SD from equation (19) (induced polarity) and all
liquids, SD from equation (18) (permanent polarity) and all liquids.  is expressed
in %, by taking the mean values obtained from non-polar liquids and equation (20)
as the reference.
Secondly, the concept of surface polarizability was also evaluated with contact
angle measurements that we made on the series of polymers described in the
Experimental section. The liquid properties and the contact angle data are presented
in Tables 6 and 7. The results are presented in Figs 2 and 3. In Figs 2A and
3A, polar interactions are described with the geometric mean of solid and liquid
polar components and the polymer surface polarizability is used in Figs 2B and 3B.
Figure 2 relates to PS and ULA substrates. Figure 3 relates to the other substrates,
i.e., g-PS, TCT PS and CellBIND . In all cases, except with TCT PS for which
the coefficient of linear regression is high and of the same level (R 2 = 0.96),
a better linear correlation is obtained when the polar interactions are considered
as resulting from a solid surface polarity induced by the liquid polarity (Figs 2B
and 3B versus Figs 2A and 3A). Following both descriptions of polar interactions
at liquid/polymer interfaces, the surface properties of the polymer substrates are
D
summarized in Table

8. The dispersion component S is deduced from the ordinate

at the origin (2 SD ) of the linear regressions of equations (18) and (19), SP

and kS are deduced from the slopes (2 SP and kS , respectively). For this series
Table 6.
Liquid properties on polymer substrates used in this study

L (mJ/m2 )
LD (mJ/m2 )
LP (mJ/m2 )

Water

Glycerol

Formamide

Ethylene glycol

Diiodomethane

TCP

72.8
21.8
51

63.4
37.0
26.4

58.2
39.5
18.7

48.0
29.0
19.0

50.8
48.5
2.3

40.9
39.2
1.7

Table 7.
Equilibrium contact angles on polymer substrates used in this study
Polymer

PS
g-PS
TCT PS
CellBIND
ULA

Contact angles on polymers ( )

Water

Glycerol

Formamide Ethylene glycol Diiodomethane TCP

85.4 0.7
75.9 0.6
54.3 0.9
37.4 1.0
18.0 0.7

73.4 1.3 65.3 1.6

70.5 1.7 59.4 1.0
48.9 0.8 15.6 1.5
35.4 0.8 5.0 0.0
34.2 1.1 4.2 0.8

59.5 0.7
50.2 0.6
21.3 1.1
11.6 1.1
6.8 0.9

41.4 1.5
32.4 0.5
32.4 1.2
37.3 0.7
35.4 0.5

19.3 1.2
13.3 1.7
9.8 0.7
17.2 0.8
13.0 1.6

Polar interactions at liquid/polymer interfaces

973

(A)

(B)
Figure 2. Comparison of the linear fits of equations (18) (A) and (19) (B) according to the nature
of dipolar solid/liquid interactions (permanent (A) or induced (B) solid polarity) for PS and ULA
substrates.

974

A. Carr

(A)

(B)
Figure 3. Comparison of the linear fits of equations (18) (A) and (19) (B) according to the nature of
dipolar solid/liquid interactions (permanent (A) or induced (B) solid polarity) for g-PS, TCT PS and
CellBIND substrates.

Polar interactions at liquid/polymer interfaces

975

Table 8.
Comparison between geometric mean ((equation (18)) and surface polarizability (equation (19)) to
describe polar interactions
Polymer

PS
g-PS
TCT PS
CellBIND
ULA
Average of R 2

P = 2 P P
Geometric mean ISL
S L
(equation (18))

P = k P
Surface polarizability ISL
S L
(equation (19))

SD (mJ/m2 )

SP (mJ/m2 )

R2

SD (mJ/m2 )

kS

R2

33.8
33.3
31.6
25.9
22.8

2.1
4.9
17.9
31.0
40.3

0.83
0.83
0.96
0.97
0.95
0.91

37.6
39.3
44.6
41.8
39.8

0.39
0.58
1.06
1.40
1.62

0.94
0.92
0.96
0.98
0.99
0.96

Table 9.
Estimation of the dispersion component, SD (mJ/m2 ), from the contact angles of TCP and diiodomethane and equation (20)
Equation and liquid probe

PS

g-PS

TCT PS

CellBIND

ULA

SD

40.3

41.5

42.1

40.8

41.6

40.7

45.2

45.2

42.9

43.8

40.5

43.4

43.7

41.8

40.3

37.6

39.3

44.6

41.8

39.8

4.0

33.8

33.3

31.6

25.9

22.8

29.7

from equation (20) and

TCP
SD from equation (20) and
diiodomethane
SD (average) from equation
(20) and non-polar liquids
SD from equation (19)
(induced polarity) and all
liquids
SD from equation (18)
(permanent polarity) and
all liquids

 (%)

Comparison with the values obtained from the complete series of liquids of Table 6 and equations
(19) and (18).  is the average difference by taking the mean values obtained from non-polar liquids
and equation (20) as the reference.

of polymers, the average coefficient of correlation is 0.91 when permanent polar

interactions are described with the geometric mean (equation (18)) and 0.96 when
polar interactions are considered as being induced by the liquid (equation (19)).
In Table 9, are given the dispersion components, SD , from the contact angles of
TCP and diiodomethane and from equation (20). It appears also that the dispersion
components of the surface free energy of polymers obtained from the contact angles
of these low polarity liquids and from equation (20) are closer to the values deduced
from the contact angles of the entire series of non-polar and polar liquids by
considering that the polymer surface polarity is induced (equation (19)). In Table 9,

976

A. Carr

 is the average difference between the two sets of values, expressed in %, by taking
the mean values obtained from non-polar liquids and equation (20) as the reference.
There is no fundamental reason preventing a priori determination of the nonpolar component of the surface free energy of a solid from the contact angles
of polar liquid probes, as polar liquids interact also with non-polar interactions.
Thus, the description of intermolecular interactions at liquid/polymer interfaces
must allow determining the dispersion (non-polar) components of the surface free
energy of solids from the contact angles of polar liquids. Thus, it is possible to
compare the dispersion components obtained, on the one hand, from the contact
angle of non-polar liquids and equation (20) and, on the other hand, the dispersion
components deduced from the contact angles of polar liquids only (water, glycerol,
formamide, ethylene glycol). This comparison is made in Tables 10 and 11 with the
Table 10.
Comparison of the dispersion component, SD (mJ/m2 ), obtained from non-polar liquids only (TCP,
diiodomethane and -bromonaphthalene) and equation (20), and from polar liquids only (water (w),
glycerol (g), formamide (f)) by considering induced polarity (equation (19)) or permanent polarity
(equation (18))
Equation and liquid probe

PET

PVDC

PVC

PMMA

PVDF

PVF

PHMA

 (%)

SD (average) from equation

(20) and non-polar liquids
SD from equation (19)
(induced polarity) and
polar liquids (w, g, f)
SD from equation (18)
(permanent polarity) and
polar liquids (w, g, f)

42.8

44.3

42.9

41.4

33.3

37.3

42.0

38.2

39.9

37.9

32.7

34.0

41.9

40.5

10.3

27.4

28.7

29.8

21.1

23.6

31.4

25.2

34.0

 is the average difference by taking the mean values obtained from equation (20) as the reference.
Table 11.
Comparison of the dispersion component, SD (mJ/m2 ), obtained from non-polar liquids only (TCP
and diiodomethane) and equation (20), and from polar liquids only (water (w), glycerol (g),
formamide (f), ethylene glycol (e-g)) by considering induced (equation (19)) or permanent (equation
(18)) polar interactions
Equation and liquid probe

PS

g-PS

TCT PS

CellBIND

ULA

SD (average) from equation

(20) and non-polar liquids
SD from equation (19)
(induced polarity) and polar
liquids only (w, g, f, e-g)
SD from equation (18)
(permanent polarity) and polar
liquids only (w, g, f, e-g)

40.5

43.4

43.7

41.8

40.3

33.8

34.1

50.6

46.9

40.0

13.6

23.7

19.8

28.1

18.9

10.2

52.0

 (%)

 is the average difference by taking the mean values obtained from equation (20) as the reference.

Polar interactions at liquid/polymer interfaces

977

contact angles taken from the literature (Table 10) and using our own measurements
(Table 11). With polar liquids, SD values are deduced from the ordinate at the origin
of the linear regressions corresponding to equations (18) and (19). In Tables 10
and 11,  is the average difference for the series of polymers considered by taking
the mean values obtained from non-polar liquids and equation (20) as the reference.
The agreement between the two sets of values of the dispersion components is
much better when the dispersion component is deduced from the contact angles
of polar liquids with the hypothesis of induced polar interactions (equation (19)).
The discrepancy reaches more than 50% with the constant polarity and is lower
than 14% with the hypothesis of induced polarity.
A similar comparison can be made by considering the van Oss, Chaudhury and
Good [6, 7] model in which the solid/liquid work of adhesion is expressed as a sum
of three terms:






(21)
L (1 + cos ) = 2 SLW LLW + 2 S+ L + 2 S L+ ,
where iLW is the Lifshitzvan der Waals (non-polar) component of the surface free
energy and i+ and i are the Lewis acid parameter and the Lewis base parameter,
respectively. From the contact angles of at least three liquids of known surface
tension parameters (L , LLW , L+ , L ), equation (21) can be used to determine the
van Oss, Chaudhury and Good parameters for the surface free energy of the solid.
The van Oss, Chaudhury and Good parameters of liquids are presented in Table 12.
Thus, by considering three polar liquids, it is theoretically possible to determine the
Lifshitzvan der Waals (non-polar) component, SLW , of the surface free energy of
polymers. This result can be compared to the value obtained with the next equation


(22)
L (1 + cos ) = 2 SLW LLW ,
established for non-polar liquids (diiodomethane, -bromonaphthalene). This
comparison is made in Table 13 with the series of polar polymers considered in
the literature [17]. The results show in most cases a large discrepancy between the
non-polar component SLW of the surface free energy of polymers obtained from
non-polar or polar liquids. The same conclusion can be drawn with the results
concerning the series of polymers used in this study as shown in Table 14. Whatever
Table 12.
Van Oss, Chaudhury and Good surface tension parameters [9] of liquids used in this study and in [17]

L (mJ/m2 )
LLW (mJ/m2 )
L+ (mJ/m2 )
L (mJ/m2 )

Water

Glycerol

Formamide

Ethylene
glycol

Diiodomethane

-Bromonaphthalene

72.8
21.8
25.5
25.5

64
34
3.92
57.4

58
39
2.28
39.6

48
29
1.92
47.0

50.8
50.8
0
0

44.4
44.4
0
0

978

A. Carr

Table 13.
Comparison of the Lifshitzvan der Waals (non-polar) component of the surface free energy of
polar polymers determined from the contact angles of three polar liquids (water (w), glycerol (g),
formamide (f)) and equation (21), and from the contact angles of non-polar liquids (diiodomethane,
-bromonaphthalene) and equation (22), by using the van Oss, Chaudhury and Good approach
Equation and liquid probe

PET

PVDC

PVC

PMMA

PVDF

PVF

PHMA

SLW

40.6

44.6

41.6

39.1

26.8

34.8

39.1

43.1

43.9

43.3

42.9

33.9

37.7

42.9

41.9

44.3

42.5

41.0

30.4

36.3

41.0

15.7

7.8

8.4

18.2

59.2

40.6

34.3

57.6

from equation (22)

and diiodomethane
SLW from equation (22)
and -bromonaphthalene
SLW (average) from
equation (22) and
non-polar liquids
SLW from equation (21)
and polar liquids (w, g, f)

 (%)

 is the average difference by taking the mean values obtained from equation (22) as the reference.
Table 14.
Comparison of the Lifshitzvan der Waals (non-polar) component of the surface free energy of
polar polymers determined from the contact angles of three polar liquids (water (w), glycerol (g),
formamide (f), ethylene glycol (e-g)) and equation (21), and obtained form the contact angles of nonpolar liquids (TCP, diiodomethane, -bromonaphthalene) and equation (22), by using the van Oss,
Chaudhury and Good approach
CellBIND

ULA

43.2

40.9

41.8

38.9

91.6

55.0

54.1

1.6

175.6

16.8

No solution*

No solution*

32.3

28.0

106.2

98.2

89.2

28.5

34.9

96.6

68.7

65.4

22.3

69.4

77.8

74.0

69.6

Equation and liquid probe

PS

SLW

38.9

43.2

26.6

from (equation (22)) and

diiodomethane
SLW from (equation (21)) and
3 polar liquids (w, g, f)
SLW from (equation (21)) and
3 polar liquids (w, g, e-g)
SLW from (equation (21)) and
3 polar liquids (w, f, e-g)
SLW from (equation (21)) and
3 polar liquids (g, f, e-g)
SLW (average) from (equation
(21)) and polar liquids

g-PS

TCT PS

 (%)
0

53.8

 is the average difference by taking the mean values obtained from equation (22) as the reference.
* No solution; solution of the system of three equations with three unknowns leads to a negative


value of

SLW .

the system of three polar liquids used to calculate the non-polar component SLW
of the surface free energy of polymers, the results largely disagree with the
value obtained from equation (22) and the contact angle of the non-polar liquid,
diiodomethane.

Polar interactions at liquid/polymer interfaces

979

Thus, it appears that only the description of liquid/polymer polar interactions as

polar interactions induced by the liquid leads to coherent results when the non-polar
component of the surface free energy of polymers is calculated from the contact
angles of polar liquids. Both constant polarity and acid/base descriptions failed
in allowing to determine the non-polar component of the surface free energy of
polymers from the contact angles of liquids interacting with the polymer surfaces
via non-polar and polar interactions.
The literature data, as well as our own measurements, show that liquid/polymer
polar interactions are better described when we consider that the surface polymer
polarity is induced by the polarity of the contacting liquids. The first evidence
is a better fit of expressions relating contact angles to the surface properties of
liquids and solids. The second argument in favor of polymer polarizability is the
similarity between the dispersion components, SD , deduced from the contact angles
of the complete series of polar and non-polar liquids or from the contact angles of
only polar liquids, and the values deduced from contact angles of only low polarity
liquids. This approach is in agreement with the remark made in the seventies by
Fowkes who mentioned the proportionality between polar interaction energy and
the liquid polarity [12].
It may be possible to further improve the description of induced polar interactions,
for example by taking into account the actual values of intermolecular interaction
distances between similar and dissimilar molecules. These distances are presently
considered identical (r11 r12 ).
Of course, the idea of induced polar interactions at the interface between a
polar liquid and a solid raises numerous fundamental questions. The first one
is to understand why liquids exhibit a permanent polarity at their surface and
why this would be different at polymer surfaces. The answer may be in the
molecular mobility or in the molecular size and structure, obviously quite different
for molecular liquids and solid polymers. A fixed and random orientation of dipoles
in a solid may explain why polymers do not exhibit a significant permanent polarity
at their surface.

5. CONCLUSIONS

At liquid surfaces, polar interactions including hydrogen bonds are well described
by the interactions between aligned dipoles. For liquid/polymer interfaces, the
hypothesis of induced polar interactions, between a liquid having a permanent
dipole and a polarizable polymer surface, appears reasonable when compared to
literature data as well as to our own measurements. Therefore, polar interactions
at liquid/polymer interfaces seem to be essentially induced polar interactions. The
induced polar component of the solid surface free energy is found to be proportional
to the polarity of the liquid in contact with the solid.
Twelve different polymer surfaces are considered in this study. In most cases,
the proportionality between the polar interactions and the liquid polarity improves

980

A. Carr

significantly the linear fit of the expression relating the contact angle to the surface
properties of the liquid and the solid.
As second consequence, the non-polar component of the polymer surface energy
appears to be better defined with the hypothesis of induced polar interactions. The
values of the non-polar component obtained either from the contact angles of nonpolar liquids only or from both non-polar and polar liquid probes, or even from the
contact angles of polar liquids only are very similar. This is clearly not the case
when liquid/polymer interactions are considered as permanent dipole/dipole forces
or resulting from acidbase interactions with the formalism developed by van Oss,
Chaudhury and Good.
The concept of surface polarizability for polymers implies that defining an
absolute value of the surface free energy of a polymer may not be possible from
contact angle measurements as the liquid probe may impact directly the properties
of the material at the liquid/solid interface. Nevertheless, an intrinsic property of
a polymer substrate, the coefficient of surface polarizability, kS , can be defined.
Therefore, the surface polarity of polymers can be seen as a variable property
depending on the environment of the polymer surface. The induction of a solid
surface polarity by the contacting polar liquid has the consequence of reducing the
interfacial free energy between the liquid and the solid.
Acknowledgement
The contribution of Mrs Valrie Lacarrire in the measurements of the liquid contact
angles on polymer substrates is greatly appreciated.

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1.
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3.
4.
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Polar interactions at liquid/polymer interfaces

981

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