The Theory of Adhesion 5.1 Contact Angle Equilibrium 51 5.2 Forces of Attraction 53 Carl A. Dahlquist 5.3 Real and Ideal Adhesive Bond Strengths 58 3M Company References 59 When pressure-sensitive adhesive is applied to a smooth surface it sticks immediately. The application, pressure can be very slight, not more than the pressure due to the weight of the tape itself The adhesive is said to “wet” the surface, and, indeed, ifthe tape is applied to clea glass and one views the attached. area through the glass, itis found that in certain areas the adhesive-glass interface looks like aliquid-glass interface. From this one would infer that a pressute-sensitive adhesive, even though itis a soft, highly compliant solid, also has liqudlike characteristics. Some knowledge of the interaction between liquids and solids is beneficial to the understanding of adhesion, 5.1 Contact Angle Equilibrium When a drop of liquid is placed on a surface of a solid that is smooth, planar, and level, the liquid either spreads out to a thin surface film, or it forms a sessile droplet on the surface. The droplet has a finite angle of contact (Figure 5.1). The magnitude of the contact angle depends on the force of attraction, between the solid and the liquid and the surface tension of the liquid. The contact angle equilibrium has received a great deal of attention, principally because it is perhaps the simplest direct experimental approach to the thermodynamic work of adhesion, “Many years ago Young’ proposed that the contact angle represents the vectorial balance of three tensors, the surface tension of the solid in air (7,), the surface tension of the liquid in equilibrium with the vapor (i) and the interfacial tension between the solid and the liquid (>), The force balance can be written joa pcos Hy 6) ‘Young’ equation has come under criticism on the grounds that the surface tension of a solid is ill defined, but most surface chemists find his equation acceptable on theoretical grounds, ‘The equation can be written as a force equilibrium or as an energy equilibrium, because the surface tension, expressed asa force per unit of length, will require an energy expenditure of the same numerical value when it acts to generate a unit area of new surface. Harkins and Livingston? recognized that Young's equation must be corrected when the exposed surface of the solid carries an adsorbed film of the liquid’s vapor. The solid-“air plus-vapor” tensor, ys less than the solid-air tensor, 7. Harkins and Livingston introduced a term, 7, to indicate the reduction thus: = fa Me (52) Bl52 Coatings Technology Handbook, Third Edition Sous FIGURES. Contact angle equiv of surface and inefaci ensons. and the modified Young equation becomes acordingly Yor woos ttt re 63) ‘The work of adhesion (W,) is the thermodynamic work necessary to separate the liquid from the solid without performing any additional work, such as viscous or elastic deformation of either the liquid or the solid, Dupré is credited with the definition of the work of adhesion. When a liquid is separated. from a solid, new solid-air and liquid-air interfaces are created, and solid-liquid interface is destroyed (Figure 5.2), ‘The Dupré equation becomes Watt y Ga) ‘Combining Equations 5.4 and 5.3 yield. Ww, Le WL +t cos) HF ne 63) Under some circumstances, me is negligible, and Equation 5.5 simply reduces to the original Young-Dupré equation: Wy, i (1 +# 608) 6.6) ‘The work of adhesion can then be obtained by measuring the surface tension of the liquid and the contact angle; need not be known ‘Zismman and his associates! at the Naval Research Laboratories have done extensive and cateful investigation of the contact angles of liquids on solids. They found that when the surface tensions of a family of liquids were ploted against the cosines oftheir contact angles on a given solid, the data fal, with some scater, along a relatively straight line. The surface tension value at which this line intersected the ordinate [ie where cos 6 = 1.00 (or 8= 0°] was designated the critical surface tension, 7 Some have equated “of a solid to is surface tension of surface energy, but this was never done or condoned by Zisman, The critical surface tension of a solid is simply the highest surface tension among the susface tensions of liquids that will spread on the solid. Is, of course, a measure of the attractive force aliquid experiences when it comes in contact with the solid Liquid FIGURES2 W,‘The Theory of Adhesion 53 70 60 waergslon 50 40 rr ar a a oe Contact Angle FIGURES. Work of adhesion of liquids om a surface having a of 21.5 ergsem’ Some have postulated that a contact angle of O° is essential for the formation of a strong adhesive bond. This is said to be requisite for wetting. Wetting, however, is a relative term. Surely the molecules, of a liquid and a solid will be in close contact atthe interface even though the contact angle is greater than 0°. In fac, if one measures the works of adhesion between a family of liquids and a solid, one finds, as illustrated in Figure 5.3, that the work of adhesion can maximize at a relatively high contact angle ‘Thus, spreading is not requisite for good adhesion on thermodynamic grounds, but it may be highly desirable in real situations for maximizing contact area and minimizing interfacial flaws and defects. 5.2 Forces of Attraction All atoms or molecules, when brought into sufficiently close proximity, exhibit attraction for each other a8 a result of asymmetric charge distributions in their electron clouds. Under special circumstances, if there are fixed electrical charge distributions (ein electrets) oF fixed magnetic polarization, repulsion ‘may occur, but these are special and rare cases. Repulsion also occurs when matter is compressed to the point that the outer electron orbits begin to interpenetrate each other; but when electrical charges and. ‘magnetic domains ate randomly distributed, and the liquids and solids ate not under extremely high compressive forces, the forces of attraction prevail, ‘The forces take several forms. The forces due to the fluctuation in the electron cloud density are universal. These forces were first recognized by Fritz London® and are sometimes called the “London forces.” but more frequently, they are called “dispersion forces” The fluctuation in electron density produces temporary electrical dipoles, which give rise to universal attraction in matter. These are the forces that account for cohesion and adhesion in aliphatic hydrocarbons. They are relatively weak atomic Interactions, but because all the atoms are involved, the cumulative effect is great. The dispersion forces depend markedly on the distance of separation, decreasing asthe seventh power of the separation between isolated atom pairs, and asthe thied or fourth power of the separation between planar surfaces ‘The dispersion forces are common to all matter and can account for universal adhesion in condensed ‘media, but other forces can contsibute substantially to adhesion in specific cases. There may be attractive forces between permanent dipoles, where the potential energy of head-to-tail interaction of two dipoles having dipole moments j, and pis given in the lowest energy configuration, as54 Coatings Technology Handbook, Third Edition uy =e Where ris the center-to-center distance between the dipoles. If the rotational energy i less than the thermal energy of the system, then hit 3 Ug = Keesom potential Where k is Boltzmann's constant (0.0821 1-atm/mol deg), and T is absolute temperature (K). ‘There may be dipole-induced dipoles, where the potential energy of interaction is given by where cj and cy, are the molecular polarizabilities. ‘There may be acid-base interactions" across the interface that can lead to strong bonding. Examples are hydrogen bonding, Lewis acid-base interactions, and Bronsted-type acid-base interactions. Covalent bonding between adhesive and adherend, if achievable either by chemical reactions or by high energy radiation, can lead to very strong bonds. Interdiffusion, usually not achievable except between selected polymers, can also lead to high adhesion, ‘The force of attraction between planar surfaces has been derived from quantum mechanical consid: erations by Casimir, Polder? and Lifshitz." Lifthit calculated the atractive forces between nonmetallic solids at distances of separation sufficiently large that the phase lag due tothe finite velocity of electromagnetic waves becomes a factor. He obtained. the following relationship between the attractive force and the known physical constants hele, “Dlele. aod, +0 Where F isthe attractive force per unit of area, h is Planck's constant, Cis the velocity of light, d is the distance of separation, ¢, isthe dielectric constant, and o(e,) is a multiplying factor that depends on the dielectric constant as follows: Vez 0 0025 0.10 025 050 1 We): 1 053 041 037 035 025 Strictly speaking, the dielectric constant in this expression should be measured at electron orbital frequency, about 10° Hz. However, if we assume handbook values of the dielectric constant at 10* Hz, Which for nylon, polyethylene, and polytetrafluoroethylene, ae 3.5, 2.3, and 2.0, respectively, the corre: sponding Q(e,) values are 0.37, 0.36, and 0.35. The force values then stand in the ratios 0.11 to 0.056 to 0.039. When normalized to F (nylon) = 1.0, they fall to the following ratios: Finylon), = 1.00; F(PE), 0.51; FIPTFE), 0.35, ‘When the values (dynes/cm) of these three materials are similarly normalized to the 3, values for nylon, the values fallin remarkedly similar ratios. Nylon PE PTFE x 5 OSLO jylnorm) 1.00055 0.33 ©2009 Tyr Ar Gap.