ANGLE DE CONTACT

Introduction
The contact angle is a measure of the ability of a liquid to spread on a surface. The method consists to measure the angle between the outline tangent of a drop deposited on a solid and the surface of this solid. The contact angle is linked to the surface energy and so one can calculate the surface energy and discriminate between polar and apolar interactions.

Principle
When a drop is deposited on a planar solid surface, the angle between the outline tangent of the drop at the contact location and the solid surface is called contact angle ().

The contact angle measurements give 3 informations : The affinity of a liquid to a solid surface : if water is used to measure the contact angle one can deduce the hydrophobic (great angle) or hydrophilic (small angle) character of the surface. If several reference liquids are used, the surface energy of the solid can be calculated, discriminating between polar and dispersive components. The most common models are Good & Van Oss model or Owens & Wendt model. The measure of the hysteresis between advancing angle and recessing angle give informations on non homogeneity of the surface (rugosity, contamination,...).

Surface energy calculations

Three parameters influence the shape of drop at solid surface is : - Solid-Liquid interfacial tension SL - Solid-Vapour interfacial tension SV (S) - Liquid-Vapour interfacial tension LV (L) These three parameters are linked with the contact angle by the Young equation :

 SV + SL + LV cos = 0 Solely LV and are measurable, so additionnal equations are necessary to determine SL and SV. Several model were developed to calculate these parameters. Neumann Model: In this model there is no distinction between the various components of surface energy and there also no relation with the material physico-chemical properties. The contact angle equation is written as : (0.015S 2) S L + L cos = L 0.015 S L 1 This equation is limited to system with low polar components like fluorinated surface and it is difficult to compare values obtained with different liquid.

Owens & Wendt Model

The OW model considers that surface energy can be expressed as : d nd S = S + S with : - Sd dispersive component (Lifshitz-Van der Waals interactions) - Sp non-dispersive component (polar interactions, Lewis acid-base) The equation between tension components and contact angle is then :
d p L (1 + cos ) = 2 S d + 2 S p L L

In this model the measure of contact angle of two different liquids are necessary to calculate the surface energy. However there is an approximation on non dispersives interactions considering that it is the geometrical mean of Snd and Lnd. This approximation can not predict the behaviour of polar polymer in aqueous environment.

Good Van Oss Model

In the Good & Van Oss model the surface energy is written as :
+ d S = S + 2 S S with :

- Sd dispersive component (Lifshitz-Van der Waals interactions) - S+, S- polar components (polar interactions, Lewis acid-base) The relation between surface energy components, liquid components and contact angle is written as:
d + + L (1 + cos ) = 2 S d + S L + L S L

Depositing a drop of 3 different liquids with known dispersive and polar components, one can calculate the solid surface energy.

The Table 1 gives values of components of typical liquids used in the determination of surface energy and Table 2 some exemples of polymer surface energy (C.J. Van Oss Interfacial forces in aqueous media - Marcel Dekker, Inc 1994).
Table 1 : Energy components of typical liquids

Liquides Eau Glycerol Formamide Ethylene Glycol a-Bromonaphtalene Diiodomethane Cis-decaline

L (mJ/m2) 72.8 64.0 58 48.0 44.4 50.8 32.2

Ld (mJ/m2) 21.8 34.0 39 29 44.4 50.8 32.2

Lp (mJ/m2) 51 30.0 19 19 0 0 0

Lp+ (mJ/m2) 25.5 3.92 2.28 1.92 0 0 0

Lp- (mJ/m2) 25.5 57.4 39.6 47 0 0 0

Table 2 : Surface energy of some polymers

Polymer Teflon FEP Polypropylene Polypropylene (Corona treated) Polythylne Nylon 6-6 PMMA Polystyrene PNVP PVC Cellulose

17.9 25.7 33.0 33.0 37.7 41.4 42.0 43.4 43.8 54.5

d 17.9 25.7 33.0 33.0 36.4 41.4 42.0 43.4 43.0 44.0

p 0.0 0.0 0.0 0.0 1.3 0.0 0.0 0.0 0.8 10.5

+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.6

0.0 0.0 11.1 0.0 21.6 12.2 1.1 29.7 3.5 17.2

Apparatus
A typical apparatus is shown on the following picture and the principle of the apparatus is shown in the drawing below :

Drop deposition system Camera Sample Illuminating Light

Bibliography
1) Neumann et al. J. Colloid Interface Sci. 49, (1979), 291 2) D.K. Owens, R.C. Wendt J. Appl. Polymer Sci. 13, (1979), 1741 3) Van Oss et al. Advan.Colloid Interface Sci. 1987