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Progress in Organic Coatings, 19 (1991) 59-68 59

Surface defects and surface flows in coatings*

Gordon P. Bierwagen**
Department of Polymers & Coatings, North Dakota State University, Fargo, ND 5’8105
(U.S.A.)

Contents

1 ~trodu~tion .............................................. 59
2 Coating application methods. ................................... 59
3 Basic physical phenomena of coating processes ....................... 61
4 Origins of surface flows. .................................. . ... 62
5 The variables controlling surface ilow phenomena, ..................... 64
6 Surface defects caused by surface flow effects ........................ 65
7 Methods of eliminating surface flow-Induced defects .................... 66
References ................................................. 67

1 Introduction

There have been several articles written in the past reviewing the
relationship between surface defects in coatings and the surface flow phe-
nomena. This review is an update and extension of this author’s earlier paper
on this topic [ 11. That gave a review of the literature through 1974, and
other more recent reviews are given in the bibliography [Z-4]. The basic
premise of this review is that the creation of new surfaces in coating application
processes gives nonequilibrium surfaces over which surface flows (desirable
and undesirable) occur as films are transferred to the substrate and film
formation processes occur (see Fig. 1 and Table 1). Even in powder coatings,
surface flows are very important in film-formation processes. To understand,
control and eliminate defect formation in coating application processes, one
must understand the physical phenomena that occur in these processes and
in the resulting thin liquid films prior to coffin fo~ation.

2 Coating application methods

Surface flows in coatings are the interactions of surfaces with fluid
motion as applied to the conversion of a bulk liquid to a thin protective or
functional organic film [5]. We will consider first the various types of coating

*Presented, in part, at Friends and Students qf.Prof. R. S. Hansen Symp., Div. Colloid
SUT$. Chem., Am. Chem. Sot. Meet., Los Angeles, 1988.
**Part of this work was completed white the author was at Avery International Inc.,
Decorative Films Division, 650 W. 67th PI., Scherervihe, IN 46375 (U.S.A.).

0033-0655/91/$3.50 0 Elsevler Sequoia/Printed ln The Netherlands

) During this zt. Other methods are hand brushed [ 111 and hand roller. Schematic diagram of the curtain coating process. special features of the coating application methods. 161. spray coatings [ 131 .wetting motion of coating device/substrate causes new surface formation in thin liquid film dilation/extensional flow equilibratiou/leveling drying/curing applications. We must also consider electrodeposited coatings. Coatings are thin films that use a minimum of material to achieve a desired effect such as the protection of a substrate. with and without electrostatic assist . most propertiez of the fluld are not in equilibrium --surface tension is time dependent Surface Flow3 may occ~ t: : : in applied film during fii formation steps (COATING m< BUBBTBATB 3 COntlnuouscoa &ysUedonsu ?!!sz!z Fig. dip coating [ 15. flow coating. the characteristics of coating flows. TABLE 1 Events in coating formation bulk liquid brought into contact with substrate . One point that must be considered carefully is the high surface-to-volume ratio in coating films [ 61. either direct or reverse [ 7-101. spin coating (commonly used in the electronics area) [ 121. such as decorative films printed onto polyester web for transfer coating. slot dye coating. 1. bead . These methods are strongly affected by surface flows. slide coating [ 5 1.ep. Included in the latter are roll coatings. doctor blade [ lo]. the variables involved. unlike a metal. surface flow phenomenon occur in the deposition process because the deposition involves a layer which can exhibit flow.there are several different variations on this general method. organic coatings deposited by methods very similar to metal electrodeposition techniques. Again.air and airless. and some comments. There are many techniques that involve the change of a bulk liquid to a thin film of organic material on a solid substrate or a continuous sheet/film or carrier web (see Table 2). Curtain coating [ 141. and gravure applications.60 I Before Coating I lD%inn CoatinE 1 1 ApL?lication.

and transfer coating from one solid carrier to another all involve heat and mass transfer in which surface effects are important. surface tension is a time-dependent quantity. At a freshly formed surface. The fundamental equations needed to describe surface flows are + +?A+-VPf?P~ (1) and ?7(VXzJ)= -v.air. use on many lack of film .direct film base web dip flat parts simplicity non-uniform films bead web feed stock film thickness control limited speeds Curtain flat rigid stock simple controls speed. Further.electrostatic slide multilayered films thin films web stock only brush general use ease of use lack of control roller (hand) walls. Equation (2) tells us that a surface tension gradient can induce fluid motion at a surface. . easy. rigid parts spin electronic coatings uniform parts simple shapes only spray general use portable. and the diffusion-controlled transport of surfactants in liquid coatings must be taken into account if an accurate description of the flows is to be made. 3 Basic physical phenomena of coating processes The bases of surface flow phenomena have been discussed by several authors [ 17-191.c+ (2) with the symbols used defined in Table 3.sheet metal. etc. The work of Hansen [21] and others [22-241 describes this phenomenon. airless shapes thickness control . fast film non-uniformity coating..2RTc (3) can be used to approximate this effect.reverse stock . and indicates a relationship such as a(t) = cro. . 61 TABLE 2 Characteristics of coating application methods Application Use/products Advantages Disadvantages type gravure transfer films & pattern & color control thin films only precision printing roll coating continuous feed roll speed. curvature effects can induce pressure gradients which will also induce flow [20]. film thickness flow instabilities .

extensional contact angle. 0 surface tension. Temperature gradients will also create gradients in surface tension and viscosity which can subsequently cause surface flows to occur during film curing/drying (see Fig. the coating film will tend to withdraw to the minimum surface under surface tension forces. p surface lifetimes. If the film breaks. Local hot spots in the substrate or carrier web during a coating process can also cause defects. r 4 Origins of surface flows What are the origins of surface flows in coatings? Consider Fig. In the formation of new surfaces. d lnA/dt concentrations. or impurities either in the coating or substrate. If thermal gradients are present. a temperature gradient will induce a gradient in surface tension from hot to cold which will. surface flows and sometimes defects.solvent .dilational relative velocities. 7 duldc . caused by wetting and surface flows of all types including those around sharp edges in which the surface pressure effects become very important. there is dilation of the new and existing surfaces. 3 . induce flow along the . h da/dT bulk viscosity.62 TABLE 3 Characteristic variables of surface flows in coatings film thickness. a schematic diagram of the curtain coating process describing some of the steps of this application technique [5] which involve coating flows typical of many application processes. t edge radii of substrate. creating surface flows and instabilities and. duld lnA temperature. one must also account for the temperature dependence of both the coating surface tension and coating viscosity. the coating process itself creates new surfaces during the very creation of the film. Gradients in temperature may give gradients in both surface tension and viscosity. 1.shear. T rate of surface area (A) formation. VII diffusion coefficients. 2). c surface viscosities .surfactant . Thus. D time. Other origins of flows are the Laplace forces on these liquids as they are forming films by surface tension curvature effects [ 171.shear dTldr . In most materials surface tension decreases with temperature. in turn. As illustrated by this diagram. thus. 7 gradient in the surface. u surface modulus. u radius of curvature at surface. Another source of surface flows are gradients in temperature and surfactant concentrations along the interfaces created by evaporation or heating effects.

~~..lul . 1”1 .I il . As shown in the schematic drawing of Fig..e.l ” (. If there is a surface tension gradient in one direction d&lx. evaporation phenomena can induce local surface tension gradients.1.a.il :. Surface flows induced by water evaporation in a water-reduced coating. This can be thought of in thermodynamic terms as the response induced in a liquid system moving to the condition of lowest free energy. The general statement describing the flows induced by surface tension differences is that these flows occur in the direction proceeding from regions of lower surface tension to regions of higher surface tension.’ .:.‘I’//.r. 2.I> .L’..I.i . b.. This effect can .1:~‘.I .. h. ‘8 . 3.j .. since the term aA (A = surface area) is minimized at constant A at the lowest avalues.li I:‘11 /I 8.h .# . ‘i Fig. Surface flows induced by temperature gradients.‘. . from low to high surface tension regions). a surface flow is induced in the opposite direction to the gradient (i. ..:I~1. u h?gh 1 r. surface... 3..d b. When the water in a water-borne or latex coating evaporates./. 63 Fig.L 1 1. “.. the concentration of organic materials increases in the liquid film causing a decrease in surface tension.~.~.‘.

There is quite a list . Figure 4 also shows an inverse situation which can exist in solvent- borne coatings. wetting phenomena are also involved. with moving contact lines. in the coating process. one may then have a localized gradient in surface tension causing an increase in thickness due to flow from areas of low surface tension in the film to the localized area of high surface tension/high evaporation. u= u(D. when the liquid coating film is applied to a moving solid substrate. one has a local defect. Thus. one gets local defects in the film. As many paint scientists know from unfortunate experience. In these types of coatings the low surface tension material may very often be the organic solvent. As the film forms after the application process. Again. An important issue with respect to the origins of surface flows is that a coating film as created is very often in a non-equilibrium condition. and as it evaporates in film drying/ curing it leaves the higher surface tension polymer. there are often those surface flows associated with the process of ‘leveling’ [25]. Thus.see Table 3. This can give a local build- up of film material and again. and there are expressions for dcldt as a function of diffusion coefficient and concentration by which one has an expression for u as a function of time. Further. The surface tension gradients discussed above can become time-dependent phenomena as the controlling variable or coupling due to flow becomes time- dependent. 5 The variables controlling surface flow phenomena Let us now consider the variables necessary for describing surface flows in coatings. and one has the relationship: da _=_. The surface tension of a solution of a surface-active material has a definite time-dependence due to the diffusion of surfactants to a fresh interface. If that film thickness decrease happens to be frozen-in by any sort of drying phenomena. Polymeric types of surfactants can have a significant time-dependency in their surface tension because of their molecular size. concentration of the surface-active species become time-dependent. dynamic phenomena. the film thickness is a very important variable when considering the effects of surface flows and the manner in . i. One has to consider the diffusion control of surface tension and many other effects that will impinge on the quality of the coating which are very definitely time-dependent.c. dilational flows and some extensional flows in the coating liquid.64 generate flow away from areas of localized evaporation giving a localized decrease in the thickness of the coating.e. thermal gradients or concentration gradients induced by the mass transfer of drying can cause local defects in a coating film. at a fresh surface._ do dc (4) dt dc dt The fresh surface problem has been discussed quite extensively.t). if frozen-in by the drying/curing process.

temperature and temper- a~~~~d~pendence of both surface tension and viscosity. ‘orange peel’ foami. the diffusion coefficient of the surfactants in the system. the surface elastic modulus [ 171. 4). A thin coating is also very sensitive to surface impurities. surface tension.n@ir entrapment dew&t&g&&y spot formation fe~&~g problems (not enough surface flrnv] others . the contact angle. the rate of surface area formation and the radius of curvature developed in the liquid itself during the coating process. For example. Other important variables are the viscosity of the bulk liquid. the more dependent the quality of the coating on the proper control of surface flows. further problems may ensue. r) on wares are closely tied to Laplace pressure effects @ = crier’) causing fluid motion. A thicker coating will ‘level’ far more readily than a thin coating. wetting phenomena. These effects are crucial to the coatings formulation scientist. the shear and dilational surface viscosities. Thin films near sharp edges (small radii of curvature.‘picture framing’ roll cells. The thinner the film. 65 which they can cause defects in films. 6 Smrface defects caused by surface flow effects One of the major reasons for the considerable amount of time expended in the analysis of surface flows and coatings are the types of defect and coating failure caused by ~controll@d surface flows. Further. The tendency toward reflow to a level surface after a surface has been disturbed or distorted in application (leveiingf proceeds as the inverse cube of the thickness [25]. If local fluctuations in condensation and temperature due to evaporation cause undesired surface flows. When coupled with curvature effects. as summ~zed in Table 4. Wetting and meniscus instabilities will cause the well- TABLE 4 Defects in coatings caused by surface flows cratering ribbing flows curt&n/sheet breaks edge flowa . variations in film thickness may occur which may destroy a coating’s performance (see Fig. and the concentrations of both solvents and surfactants in the system. in hand roll or hand brushing the brush marks have a radius of curvature which affect the manner in which the coatings will flow to a level film. one must consider the velocity components both from the viewpoint of the substrate and the coating liquid7the age of the surface. and meniscus stability and shape. Cratering may occur at fresh surfaces or ‘curtain’ breakage may occur in a curtain coater. convection cells. the radius of curvature of the object(s) being coated.

Moving contact lines are special sources of instability related to surface flow. thinning the film about the edge. Spray droplet formation. surface flows that are surface tension driven due to curvature near a sharp edge. Evaporation effects in solvent coating. proper droplet break-up. cratering. Examples of surface defects are well described in ref.e.66 Loodized Ewapordion atdeh . Other specific important examples of surface defects occurring due to surface flows are ‘ribbing’ [ 7-101. Electrostatic charge build-up during spraying induces surface tension gradients and contributes to. 2. undesired manner in an organic coating. Stabilization of coatings with respect to undesired surface-flow-related effects is a crucial task for the coating formulation scientist. edge coverage phenomena and ‘curtain’ stability in curtain coatings are all effects related to surface flow. 7 Methods of eliminating surface flow-induced defects There is a large litany of this type of problem which arises when surface flows occur in an uncontrolled. 4. Instabilities with respect to surface flows occur in coatings during the period from application until the coating viscosity increase causes all flows to cease. known ribbing effects in coil coating. 6 and 18. Surface flows affect all types of coatings from trade sales latex coatings to powder coatings. i. leveling. This is a most difficult problem since it involves stabilizing coatings with respect to the coupling of several dynamic phenomena. of Organic sdvent Fig. Further examples are given in refs. 3. which is a direct dynamic effect related to surface tension forces in the deposition process in the roll coating. One must consider all of the issues discussed above and look to the guidance of the surface chemist/engineer for assistance in eliminating potential sources . and what is called ‘picture framing’ [20]. each of which may have to be controlled separately. 6. 1. or interferes with.

Hansen and P. induce surface flows. in turn. Prog. and post-cure exposure sensitivity. Res. 3 (1975) 101. 8 (1980) 275. Komum and H.c. plus interference effects in other coating parameters (dispersions. E. . concentra- tion. 5 S. velocity) and coating parameters (surface tension. It would be better to match the method of eliminating a surface-flow- induced instability in a coating to its cause. Rev.. Numerical Methods in Fluids. This has some logical basis when one realizes that most A versu-s c curves at high surfactant concentration (surface saturation da. Annu.. 67 TABLE 5 Methods of eliminating surface defects viscosity control housekeeping/environment control surface tension control through coating operation raw material purity temperature control in curing operations close control of all coating equipment careful analysis of solubility and evaporation effects of undesired surface flows. Ind. and to consider the eventual effects of what is done in eliminating the instability. 3 C. By considering the controlling parameters of a given surface flow instability. K.). Prod. Org. Ruschak. High surfactant levels also tend to level out thermal effects on surface tension. Coat.. References 1 G. there is a price to pay for these high surfactant levels . Adding a surfactant to reduce surface flow effects may cause destabilization of pigment dispersion.. shear instabilities during application. dc + 0). or fluctuations in c with distance x. Striven. Org. Int. Prog. M. This coupling of parameters of the coating behavior by physical relationships such as u= ~(t. such as temperature gradients inducing surface tension gradients which. 4 (1984) 20’7. Pierce. F’luid Mech. Kistler and L.greater water sensitivity and more foaming in the film (especially in aqueous systems). One must also look for coupled phenomena. Chem. or evaporation which causes concentration gradients which induce surface tension gradients which cause surface flow. 4 K. Bierwagen. Dev.Z’) forces the formulator to consider at all time the dependence between application parameters (temperature. 13 (1974) 218. viscosity). Coat. J. E. excess foaming. A summary of the methods available to eliminate surface- flow-induced defects is given in Table 5. Eng. P. Raaschou Nielsen. 2 L. 17 (1985) 65. not an ‘overkill’. L. one can focus on an ‘exact cure’ to a problem.. But. The traditional response by coating formulators has often been to reduce surface flow effects by the addition of large amounts of surfactant. will not propagate to significant variations in surface tension with distance. J. F. etc.

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