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J. Adhesion Sci. Technol., Vol. 21, No. 10, pp. 961 981 (2007) VSP 2007.

Polar interactions at liquid/polymer interfaces


ALAIN CARR
Corning SAS, Corning European Technology Center, 7 bis, Avenue de Valvins, 77210 Avon, France Received in nal 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 dened for polymers. Using the surface polarizability approach rather than the polar component for the solid surface, we nd also that the dispersion (non-polar) component of the polymer surface free energy is obtained with a better condence, 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

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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 lm 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 quantied by the polar component of the liquid surface free energy. However, this result which apparently did not t 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 difculties, and there is no unanimously recognized model.

Polar interactions at liquid/polymer interfaces

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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 , I12

(1)

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 veried 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 = 22 L . 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: nS d N M
2/3

(5)

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where N is the Avogadro number (6.02 1023 ). 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 P D P , of the surface free energy, L (= L + L ), i.e.: component, L
P P = 2L . ILL

(6)

The comparison of these two calculations is presented in Table 1 with water P P P = 51 mJ/m2 ), formamide (L = 18.7 mJ/m2 ) and ethylene glycol (L = (L 2 19 mJ/m ) [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 t in Table 1) is necessary to get the correct agreement (rLL t = 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 P 1 2 and Ijj 2 surface free energies because as I12 j , it is easily concluded that [17]:
P = I12 P P I11 I22 = 2 1P 2P .

(7)

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 P As noted by Fowkes [12], a direct proportionality between ISL and L 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

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) nS (molecules/m2 ) 1.04 1019 6.11 1018 4.88 1018 3.10 1010 4.04 1010 4.53 1010 2.29 1020 4.21 1020 1.12 1020 rLL = v 1/3 (m) iLL aligned (J)
P = 2 P ILL L (mJ/m2 )

Liquid

P L (mJ/m2 )

L (Debye)

rLL t (m) 102 37.4 38 3.27 1010 6.10 1010 4.06 1010

Polar interactions at liquid/polymer interfaces

Water Formamide Ethylene glycol

51 18.7 19

1.85 3.73 2.28

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

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corresponds to the following Debye interaction energy [16]:


i = i12

2 2 2 2 1 1 = . 3 2 3 3 (40 r12 ) 40 r12 40 r12

(9)

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

(10)

where kS will be dened 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 Pi P = 2 S L . ISL

(13)

Pi , is induced by However, the polar component of the solid surface free energy, S P . the contacting liquid. It is a variable which depends on the liquid polarity, L 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: Pi = S 2 kS 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 P P L (1 + cos ) = 2 S L + 2 S L

(16)

according to the theory of permanent dipole interactions between the liquid and the solid [19], or
P D D L + kS L , L (1 + cos ) = 2 S

(17)

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 puried 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 at 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).

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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: L
D L D P (1 + cos ) = 2 S + 2 S P L . D L

(18)

The hypothesis of the induced polarity of polymer surfaces was veried with the linear form of equation (17) written as: L
D L D (1 + cos ) = 2 S + kS P L D L

(19)

We can expect that the best description of polar interactions (permanent polarity versus induced polarity at the polymer surface) is associated to the best t of experimental data with equations (18) and (19). The rst 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 uoride) (PVDF), poly(vinyl uoride) (PVF) and poly(hexamethylene adipamide) (PHMA). The liquid probes and their D P corresponding L , L and L 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 D P , and polar component, S (hypothesis of permanent solid surface component, S D polarity), or in terms of dispersion component, S , and surface polarizability, kS D (hypothesis of induced surface polarity). The dispersion component S is deduced
D from the ordinate at the origin (2 S ) of the linear regressions of equations (18) P P and kS are deduced from the slopes (2 S and kS , respectively). All and (19), S

Table 2. Liquid properties (from Ref. [13]) Water Glycerol Formamide Diiodomethane -Bromonaphthalene TCP Hexadecane L (mJ/m2 ) 72.8 D (mJ/m2 ) 21.8 L P (mJ/m2 ) 51 L 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 Table 3. Equilibrium contact angles on polar polymer surfaces (from Ref. [17]) Polimers Contact angle ( )

969

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
P = 2 P P Geometric mean ISL S L (equation (18)) D (mJ/m2 ) S P (mJ/m2 ) S P = k P Surface polarizability ISL S L (equation (19))

R2 0.90 0.89 0.82 0.83 0.88 0.96 0.94 0.89

D (mJ/m2 ) S

kS 0.46 0.47 0.31 0.50 0.61 0.57 0.73

R2 0.98 0.95 0.91 0.95 0.88 0.97 0.99 0.95

PET PVDC PVC PMMA PVDF PVF PHMA Average of R 2

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

41.4 42.9 41.6 39.1 31.0 37.7 41.1

the liquids are taken into consideration to calculate the linear regressions. The parameter R 2 is the coefcient of correlation of the linear regression. Except for PVDF where the coefcient 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) ts the contact angle data better than equation (18). For the series of 7 polar polymers, the average coefcient 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

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(A)

(B)
Figure 1. Comparison of the linear ts 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

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and 1B and the R 2 coefcients 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 D (Table 4). the surface free energy, S When considering liquids of low polarity, such as TCP, diiodomethane and D , both equations (18) and (19) can be -bromonaphthalene, for which L L simplied as L
D L D (1 + cos ) 2 S D (L L ),

(20)

as the polar interactions, irrespective of their nature, are negligible relatively to dispersion interactions. In general, this simplied 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 D , for the same series of polar polymers estimated from the contact components, S 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. D (mJ/m2 ), deduced from the contact angles of low polarity Estimation of the dispersion component, S liquids (TCP, diiodomethane and -bromonaphthalene) and equation (20) Equation and liquid probe
D from equation (20) S and TCP D from equation (20) S and diiodomethane D from equation (20) S and -bromonaphthalene D (average) from S equation (20) and nonpolar liquids D from equation (19) S (induced polarity) and all liquids D from equation (18) S (permanent polarity) and all liquids

PET 42.5 43.1 42.8

PVDC 42.1 46.7 43.9 44.3

PVC 41.9 43.5 43.3 42.9

PMMA 40.4 41.0 42.9 41.4

PVDF 37.8 28.1 33.9 33.3

PVF 37.8 36.5 37.7 37.3

PHMA 41.0 42.9 42.0 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.

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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 D (average) from equaaverage difference between the following sets of values: S D tion (20) and non-polar liquids, S from equation (19) (induced polarity) and all D from equation (18) (permanent polarity) and all liquids. is expressed liquids, S 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 coefcient 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 is deduced from the ordinate summarized in Table 8. The dispersion component S
D P ) of the linear regressions of equations (18) and (19), S at the origin (2 S P and kS are deduced from the slopes (2 S and kS , respectively). For this series

Table 6. Liquid properties on polymer substrates used in this study Water L (mJ/m2 ) D (mJ/m2 ) L P (mJ/m2 ) L 72.8 21.8 51 Glycerol 63.4 37.0 26.4 Formamide 58.2 39.5 18.7 Ethylene glycol 48.0 29.0 19.0 Diiodomethane 50.8 48.5 2.3 TCP 40.9 39.2 1.7

Table 7. Equilibrium contact angles on polymer substrates used in this study Polymer Contact angles on polymers ( ) Water PS g-PS TCT PS CellBIND ULA 85.4 0.7 75.9 0.6 54.3 0.9 37.4 1.0 18.0 0.7 Glycerol Formamide Ethylene glycol Diiodomethane TCP 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

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

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(A)

(B)
Figure 2. Comparison of the linear ts 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.

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(A)

(B)
Figure 3. Comparison of the linear ts 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

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Table 8. Comparison between geometric mean ((equation (18)) and surface polarizability (equation (19)) to describe polar interactions Polymer
P = 2 P P Geometric mean ISL S L (equation (18)) D (mJ/m2 ) S P (mJ/m2 ) S P = k P Surface polarizability ISL S L (equation (19))

R2 0.83 0.83 0.96 0.97 0.95 0.91

D (mJ/m2 ) S

kS 0.39 0.58 1.06 1.40 1.62

R2 0.94 0.92 0.96 0.98 0.99 0.96

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

33.8 33.3 31.6 25.9 22.8

2.1 4.9 17.9 31.0 40.3

37.6 39.3 44.6 41.8 39.8

Table 9. D (mJ/m2 ), from the contact angles of TCP and diEstimation of the dispersion component, S iodomethane and equation (20) Equation and liquid probe from equation (20) and TCP D from equation (20) and S diiodomethane D (average) from equation S (20) and non-polar liquids D from equation (19) S (induced polarity) and all liquids D from equation (18) S (permanent polarity) and all liquids
D S

PS 40.3 40.7 40.5 37.6

g-PS 41.5 45.2 43.4 39.3

TCT PS 42.1 45.2 43.7 44.6

CellBIND 40.8 42.9 41.8 41.8

ULA 41.6 43.8 40.3 39.8 0

(%)

4.0

33.8

33.3

31.6

25.9

22.8

29.7

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 coefcient 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)). D , from the contact angles of In Table 9, are given the dispersion components, S 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,

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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. D (mJ/m2 ), obtained from non-polar liquids only (TCP, Comparison of the dispersion component, S 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
D (average) from equation S (20) and non-polar liquids D from equation (19) S (induced polarity) and polar liquids (w, g, f) D from equation (18) S (permanent polarity) and polar liquids (w, g, f)

PET 42.8 38.2

PVDC 44.3 39.9

PVC 42.9 37.9

PMMA 41.4 32.7

PVDF 33.3 34.0

PVF 37.3 41.9

PHMA 42.0 40.5 0

(%)

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. D (mJ/m2 ), obtained from non-polar liquids only (TCP Comparison of the dispersion component, S 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
D (average) from equation S (20) and non-polar liquids D from equation (19) S (induced polarity) and polar liquids only (w, g, f, e-g) D from equation (18) S (permanent polarity) and polar liquids only (w, g, f, e-g)

PS 40.5 33.8

g-PS 43.4 34.1

TCT PS 43.7 50.6

CellBIND 41.8 46.9

ULA 40.3 40.0 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

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contact angles taken from the literature (Table 10) and using our own measurements D values are deduced from the ordinate at the origin (Table 11). With polar liquids, S 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:
+ + LW LW L + 2 S L + 2 S L , L (1 + cos ) = 2 S

(21)

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 + LW , L , L ), equation (21) can be used to determine the tension parameters (L , L 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 LW , of the surface free energy of Lifshitzvan der Waals (non-polar) component, S polymers. This result can be compared to the value obtained with the next equation
LW LW L , L (1 + cos ) = 2 S

(22)

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 LW of the surface free energy of polymers obtained from non-polar component S 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] Water L (mJ/m2 ) LW (mJ/m2 ) L + L (mJ/m2 ) L (mJ/m2 ) 72.8 21.8 25.5 25.5 Glycerol 64 34 3.92 57.4 Formamide 58 39 2.28 39.6 Ethylene glycol 48 29 1.92 47.0 Diiodomethane 50.8 50.8 0 0 -Bromonaphthalene 44.4 44.4 0 0

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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
LW S

PET 40.6 43.1 41.9

PVDC 44.6 43.9 44.3

PVC 41.6 43.3 42.5

PMMA 39.1 42.9 41.0

PVDF 26.8 33.9 30.4

PVF 34.8 37.7 36.3

PHMA 39.1 42.9 41.0 0

(%)

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

15.7

7.8

8.4

18.2

59.2

40.6

34.3

57.6

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 Equation and liquid probe
LW S

PS 38.9 26.6 1.6 32.3 28.5 22.3

g-PS 43.2 38.9 175.6 28.0 34.9 69.4

TCT PS 43.2 91.6 16.8 106.2 96.6 77.8

CellBIND 40.9 55.0 No solution* 98.2 68.7 74.0

ULA 41.8 54.1 No solution* 89.2 65.4 69.6 0

(%)

from (equation (22)) and diiodomethane LW from (equation (21)) and S 3 polar liquids (w, g, f) LW from (equation (21)) and S 3 polar liquids (w, g, e-g) LW from (equation (21)) and S 3 polar liquids (w, f, e-g) LW from (equation (21)) and S 3 polar liquids (g, f, e-g) LW (average) from (equation S (21)) and polar liquids
* No

53.8

is the average difference by taking the mean values obtained from equation (22) as the reference. solution; solution of the system of three equations with three unknowns leads to a negative
LW . S

value of

LW the system of three polar liquids used to calculate the non-polar component S 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

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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 rst evidence is a better t of expressions relating contact angles to the surface properties of liquids and solids. The second argument in favor of polymer polarizability is the D , deduced from the contact angles similarity between the dispersion components, S 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 rst 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 xed and random orientation of dipoles in a solid may explain why polymers do not exhibit a signicant 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

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signicantly the linear t 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 dened 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 dening 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 coefcient of surface polarizability, kS , can be dened. 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.

REFERENCES
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. F. M. Fowkes, J. Phys. Chem. 66, 382 (1962). F. M. Fowkes, Ind. Eng. Chem. 56 (12), 40 (1964). F. M. Fowkes, D. C. McCarthy and M. A. Mostafa, J. Colloid Interface Sci. 78, 200 (1980). A. W. Neumann, R. J. Good, C. J. Hope and M. Sejpal, J. Colloid Interface Sci. 49, 291 (1974). A. W. Neumann, O. S. Hum, D. W. Francis, W. Zingg and C. J. van Oss, J. Biomed. Mater. Res. 14, 499 (1980). C. J. van Oss, R. J. Good and M. K. Chaudhury, J. Colloid Interface Sci. 111, 378 (1986). C. J. van Oss, M. K. Chaudhury and R. J. Good, Adv. Colloid Interface Sci. 28, 35 (1987). P. K. Sharma and K. Hanumantha Rao, Adv. Colloid Interface Sci. 98, 341 (2002). F. M. Etzler, in: Contact Angle, Wettability and Adhesion, K. L. Mittal (Ed.), Vol. 3, pp. 219264. VSP, Utrecht (2003). E. Chibowski, in: Contact Angle, Wettability and Adhesion, K. L. Mittal (Ed.), Vol. 2, pp. 265 288. VSP, Utrecht (2002). H. Radelczuk, L. Holysz and E. Chibowski, J. Adhesion Sci. Technol. 16, 1547 (2002). F. M. Fowkes, J. Adhesion 4, 155 (1972). J. R. Dann, J. Colloid Interface Sci. 32, 321 (1970). F. M. Fowkes, in: Contact Angle, Wettability and Adhesion, Advances in Chemistry Series No. 43, pp. 99. American Chemical Society, Washington, DC (1964).

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15. F. M. Fowkes, in: Surfaces and Interfaces: Chemical and Physical Characteristics, J. J. Burke, N. L. Reed and V. Weiss (Eds), p. 197. Syracuse University Press, Syracuse, NY (1967). 16. J. Israelachvili, Intermolecular and Surface Forces, 2nd edition. Academic Press, San Diego, CA (1992). 17. S. Wu, Polymer Interface and Adhesion. Marcel Dekker, New York, NY (1982). 18. R. C. Weast (Ed.), Handbook of Chemistry and Physics, 58th edition. CRC Press, Cleveland, OH (1977). 19. D. K. Owens and R. C. Wendt, J. Appl. Polym. Sci. 13, 1741 (1969).