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This month, we will discuss the effect of small molecules as penetrants into the dry film. Peter wilson: the film's response to such penetration parallels its response to humidity. He says the extent of penetrant accumulation and swelling will depend on the solubility of the penetrant in the coating and the rate of its diffusion within the film.
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Quantrong - Trouble With Paint Effects of Solvents on Coating Films
This month, we will discuss the effect of small molecules as penetrants into the dry film. Peter wilson: the film's response to such penetration parallels its response to humidity. He says the extent of penetrant accumulation and swelling will depend on the solubility of the penetrant in the coating and the rate of its diffusion within the film.
This month, we will discuss the effect of small molecules as penetrants into the dry film. Peter wilson: the film's response to such penetration parallels its response to humidity. He says the extent of penetrant accumulation and swelling will depend on the solubility of the penetrant in the coating and the rate of its diffusion within the film.
fects of compressive and ten- sile stresses resulting from the ex- pansion and contraction of paint films as they respond to changes in humidity. This month, we will con- sider in more detail the effect of small molecules as penetrants into the dry film. While the films re- sponse to such penetration parallels its response to humidity, the magni- tude of the response may be signifi- cantly greater, and the consequences may be more catastrophic. This article will review the action of penetrants through films, the in- fluence of free volume and glass transition temperature (T g ), penetra- tion-related primer failures, and the measurement of solvent resistance of coatings. Free Volume and Penetrant The January 1996 column intro- duced the concept of free volume. In discussing the volumetric expan- sion of a film caused by the entry and accumulation of penetrants into the film, we revisit free volume. It is largely through free volume holes that small penetrants enter in- tact films, working their way down- wards into the film through adjacent free volume sites in successively deeper molecular layers. These sites or holes become available as the polymeric structure of the film vi- brates with the kinetic energy of the molecule. (These vibrations are of a very high order, 10 12 times each second.) As the molecule or pene- trant moves from one molecular ingress and the accumulation of even more penetrant. In the case of thermoplastic sys- tems, active solvent penetrants pro- gressively dissolve the film. In cross- linked systems and in thermoplastics where the penetrant is not an active solvent, the extent of penetrant accu- mulation and therefore swelling will depend on the solubility of the pen- etrant in the coating and the rate of its diffusion within the film. These are affected by the molecular struc- ture of the polymer and penetrant, the size and shape of the penetrant, the affinity of the penetrant for groups within the polymer, the cross-link density of the film, and the relationship T-T g . In less amorphous thermoplastics, film structure is very important, as is the molecular weight of the polymer, the preponderance of crystalline areas, the degree of secondary valency bonding between chains, and again T-T g . These factors will largely dictate the rate of entry and diffusion of the penetrant. layer to the next deeper layer, the vacant site in the original layer is taken up by a new molecule of pen- etrant that enters the film at the lo- cation being vacated. The insertion of a highly polar molecule, like water, into the poly- meric continuum may provide a site to which other water molecules are attracted. This site will feature a hy- drogen-bonded accumulation of water molecules. In other cases, functional groups on the polymer structure of the binder will facilitate the ingress and accumulation of penetrants, for ex- ample, hydroxyl groups on epoxies and amide groups on urethanes. The accumulation of penetrant molecules at such hospitable sites within the polymeric matrix may eventually pry apart the chains of the polymer. The penetrants overcome some of the secondary associations that, espe- cially in thermoplastics, hold the film together and thus reduce the T g of the film by plasticization. The weak- ening of the film allows increased MAY 1997 / 69 T continued TROUBLE with PAINT Effects of Solvents on Coating Films Fig. 1 - Solvent attack on a cross-linked epoxy film Figures courtesy of the author by Clive H. Hare, Coating System Design Inc. Copyright 1997, Technology Publishing Company Copyright 1997, Technology Publishing Company When the take-up of penetrant is sufficient to induce severe changes in non-soluble films, severe compres- sive stresses build up within the solvated film and cause mechanical failure. Initially, this failure is centered at the interface of the film and its substrate and is first manifested as blistering from localized de-adhesion. In some cases, the stress-induced de- adhesion may be facilitated by an accumulation of penetrant at this in- terface, which displaces the coating film. With the more aggressive sol- vents, this effect is often secondary to film distention, which precedes any interfacial accumulation. In the more severe cases, the solvated film may expand so much that it delami- nates entirely, wrinkling into furrows (Fig. 1). Delamination may be accom- panied by concomitant vertical cohe- sive failure, cracking, or breaking of the film, as the film is strained be- yond its elongation at break. (The mechanical properties of the film, in- cluding modulus, yield values, tensile strength, and elongation properties, constantly change during solvent at- tack. The film becomes softer and weaker, if more flexible, than before solvent impact.) This type of failure is typical of the action of paint re- movers. (See pp. 73-74.) T g and Penetrant Action Because free volume availability and molecular mobility within the coat- ing film are greatly reduced at tem- peratures below the T g of the film, it follows that penetration is signifi- cantly reduced as T-T g becomes negative. There is some free volume (about 2.5 percent of the volume of the film) below the T g . Some re- searchers 1,2 have concluded that minimization of diffusion is found at some secondary threshold below the T g , T
, at which there is no configu-
rational entropy. If impermeability to solvent is the paramount design criterion, the binder selection should ensure that film T g is above the service tempera- ture (i.e., T-T g is negative). It should also remain above the service tem- perature. The plasticization of a film by the absorption of a penetrant that depresses the T g of the film below the service temperature may initiate significantly increased absorption and system failure. This degree of plasticization may occur in immer- sion service, where the temperature of the liquid is temporarily increased above the T g . Without post curing, in fact, some researchers such as Wicks believe that maintaining the T g well above T can be difficult with films cured at ambient temperature. Cross-linking of a thermosetting polymer becomes 2 or 3 times slow- er as the T g rises during cure above the ambient temperature. Essentially, air drying thermosets never achieve T g levels much above the tempera- ture at which the film is formed. This, Wicks believes, is a factor in the superior corrosion resistance of a baked system compared to air dry- ing offsets. 3 TROUBLE with PAINT 70 / Journal of Protective Coatings & Linings continued Fig. 2 - Wrinkling of oil-based primer recoated with a high performance thermoplastic coating (lacquer) Copyright 1997, Technology Publishing Company MAY 1997 / 73 TROUBLE with PAINT The ingress of penetrants into a coating film decreases T g in both thermosets and thermoplastics. Not only does decreased T g reduce the systems resistance to the penetra- tion of additional molecules of the same penetrant, but also the in- creased free volume will facilitate the penetration of other types of small molecules. The corrosion resis- tance of a highly solvated film will be poorer than one that is free of solvents. Residual hydrophilic solvents such as cellosolve acetate in high-build vinyls have compromised the perfor- mance of such systems in water service, for example. Similarly, the depression of T g from the ingress of moisture into the film also de- creases the films resistance to inva- sion by oxygen. In extreme cases, high T g ther- mosets of high cross-link density (e.g., trimerized cyanate esters and thermosetting polyimides) will take up little water and solvent and will change little dimensionally, even in immersion service. In films of highly crystalline polymers, such as those based on the fluoropolymers, acrylonitrile, or polyolefins, the polymer will exhibit little take-up of even the most powerful pene- trants, and consequent swelling will again be minor. Systems having lower cross-link density, such as epoxy polyamides and those lower density systems rich in polar groups (alkyds), will, conversely, exhibit considerable volumetric expansion in the presence of water and sol- vents. Fortunately, certain amine- cured epoxies, polyesters, and vinyl esters give adequate imperme- ability to oxygen, solvents, and, relatively speaking, to water, after ambient cure. Lifting Failure with Solvent-Sensitive Primers In recoating one film with another, the absorption of carrier solvent from the recoat systems into the al- ready applied films of the primer, undercoat, or old coating is to some degree inevitable, as is the conse- quent deformation of the existing film. Solvent absorption may or may not cause problems. Lacquers and latex system films may partially or completely redissolve in the solvent systems of the newly applied finish, even allowing some interfacial asso- ciations between molecules of one coat and another. These films rarely give problems. The resultant solvent weld or disappearing interface be- tween the 2 layers will normally guarantee adhesion. Old, well-cured oxidized systems, baked systems, and other thermosets continued Paint Removers An extreme example of penetrant attack on coating films is seen in the action of paint removers (Fig. a). Such removers are based on designed solvent mixtures primarily made up of small molecules such as methylene chloride and methanol. These mole- cules readily insert themselves into the free volume spaces within the polymeric matrix. Strong electronega- tive groups (chlorine, hydroxyls) allow for good secondary valency bonding of the solvent with the poly- mer, which encourages absorption. Evaporation of the solvent (a process that opposes absorption) is reduced by trapping the solvent against the film using wax additives. The addi- tives float to the top of the paint re- mover surface. There, they precipitate and form a barrier above the solvent. Excessive free volume expan- sion, resulting from the absorption of sensitive substrate. The characteristic wrinkling or puckering of the film be- large quantities of solvent by the coating, produces interfacial failure of the paint system with a less solvent- Fig. a - Mechanism of paint remover activity PAINT REMOVERS continued on page 74 Copyright 1997, Technology Publishing Company are also rarely affected by solvent at- tack in recoating. However, their cross-link density is usually high enough to resist excessive solvent absorption and consequent film de- formation. In fact, it is often more of a problem to secure good adhesion to these films because of the ab- sence of solvent attack. A recoat window related to the degree of primer cure is often utilized when recoating epoxies and urethanes. Entirely more vulnerable to attack by a wide range of solvents are ther- mosetting systems of very low cross- link density, such as recently ap- plied oxidizing films (long oil alkyds). These films are slow to de- velop appreciable cross-link density and, therefore, solvent resistance. Vinylated alkyd copolymers (styrene and vinyl toluenated alkyds) are particularly vulnerable in this respect. Here, a rapid full cure is sacrificed for fast initial dry. 4 The films are sensitive to solvent during a long intermediate cure period be- tween the initial drying (lacquer mechanism) and full cure (oxidative mechanism). The large amounts of vinylation reduce the available un- saturation, so that oxidation takes far longer than with the equivalent oil- modified alkyds. Other systems showing fast touch-dry/slow through-dry properties, such as very high-solids medium and long oil alkyds, are also very susceptible to this type of attack. Here, aromatic solvents and oxygenated solvents will rapidly penetrate the still incom- pletely cured primer, producing se- vere swelling of the film and, as a consequence, a wrinkling and lifting from the subfilm (Fig. 2). Less attack is likely using finish coats based on aliphatic hydrocar- bons such as mineral spirits and VM&P naphtha. While a slightly more aggressive solvent than mineral spir- its, VM&P naphtha evaporates very rapidly, which diminishes contact time. Made up of larger, more un- wieldy branch chain molecules in- stead of the small, compact structures that typify the aromatics, these sol- vents are similarly far less dangerous to use over sensitive, newly applied films because they are less easily in- serted into the polymeric matrix. Factory-primed with alkyds and oil paints, structural steel members, light miscellaneous metal pieces, or other equipment often exhibit lifting failure in demanding environments where surfaces are to be refinished with epoxies, urethanes, and other high performance topcoats. During application of the finish coat or soon after, the primer wrinkles and lifts from the metal as if it had been TROUBLE with PAINT 74 / Journal of Protective Coatings & Linings trays the large increase in surface area (as compared to the area of the substrate) that accompanies the volu- metric increase of the film. The film may remain locally adherent at dis- crete points where stress has been dissipated locally by the loss of adhe- sion of the film in adjacent areas. Lo- calized adhesion leads to locally un- restricted film distortion and reduced stress on the remaining adjacent ad- hesive anchorages. However, lateral propagation of adhesion loss at the remaining anchorages usually results in eventual total delamination. In this case, the film puckers up. Solvents used in paint removers are readily imbibed into even highly cross-linked films, such as epoxies and polyurethanes, as well as into aged oxidizing films. These solvents will dissolve lacquers and latex. Methylene chloride is, of course, the target of regulation. (Toxicity con- These groups may attack vulnerable sites on the polymer, causing hydrol- ysis and thereby further facilitating solvent ingress and deformation of the film. This type of remover is rarely necessary with alkyds or even polyamide-cured epoxies. Carboxylic acids may, however, be valuable in removing more highly cross-linked epoxies. Paint removers based on so- lutions of sodium and potassium hy- droxide in gelled solvents may be used to remove urethanes and oil systems. Small amounts of water and surfactants may be introduced to fa- cilitate alkaline hydrolysis of the ester or amide groups within the film. The same principle without the solvent is used in poultice-type removers popu- lar for the field removal of lead-based paint systems. These highly alkaline materials are trapped against the film with water-impermeable paper or plastic sheet, and the hydrolysis of the polymer proceeds over a more extended period of time. cerns have always limited the use of methanol in these compositions to about 4 percent.) Finding non-toxic re- placement solvents of equal effective- ness poses some difficulty. Methylene chloride and methanol are small, streamlined, highly polar materials that are low in molecular weight and effec- tively penetrate and expand the free volume of even the most cross-linked systems. Some small, compact mole- cules, such as the cyclic lactam, n- methyl-2-pyrrolidone, have similar properties but are slower to evaporate than methylene chloride and methanol. Delamination, therefore, may take much longer than is the case with conventional removers. Other small, active molecules have also been used in paint re- movers. These include the lower car- boxylic acids (formic acid and acetic acid) as well as substituted aromatics such as phenol and cresylic acid. These materials also have benefits be- cause of their functional groups. continued PAINT REMOVERS continued from page 73 Copyright 1997, Technology Publishing Company MAY 1997 / 77 TROUBLE with PAINT treated with paint remover. In some systems (e.g., the vinylated alkyds noted above), there is a viable recoat window both before and after the pe- riod of solvent sensitivity wherein these systems may be recoated safely. Shortly after application, the lacquer- type drying predominates without oxi- dation, and the film may be recoated without mishap. In the very long run, the film may become more fully oxi- dized, and here again resistance to sol- vent attack improves enough to allow good recoatability. In the long interme- diate period, however, the conse- quences of recoating with strong sol- vent topcoats may be lifting of the primer. Rapid recoating of such insuffi- ciently oxidized films with chemically curing systems may actually lock in a partially uncured state within a primer of this type. Thereafter, this type of de- ficient system will be unusually sensi- tive to lateral cohesive failure under applied stress. Still available is a class of universal lift-resistant primers that dry rapidly and may be satisfactorily coated with lacquers and other strong sol- vent-containing finish coats. They are generally inhibitive primers for- mulated from special phenolic and rosin-modified short to medium oil alkyds. Similar alkyds are sometimes externally modified with phenolic dispersion resins, giving still further improvements in recoatability. The use of solvents in a recoat film to obtain improved adhesion of the recoat to the primer (or undercoats) involves much the same considera- tions as are noted here, although in the former case, solvent attack is con- trolled and used productively. Solubility and Attack of Solvents Solvency and the judicious applica- tion of solubility parameters 5,6 are the keys to predicting solvent sensi- tivity of amorphous thermoplastics. These polymers remain soluble in the classes of solvents that character- ize the solubility of the dry resin type. Even high molecular weight systems, including thermoplastic powder coatings, organosols, plasti- sols, and latex paints, will soften, if not dissolve, in these solvents. The actual dissolution of ther- mosetting ambient-cured epoxies, urethanes, baked amino, and phenyl formaldehyde cross-linked films is precluded by the primary bonded network of the film structure. How- ever, solvents may penetrate and swell systems of this type, especially those of lower cross-link density. In the latter case, the more open, cross- linked structure allows the easier in- sertion of penetrants. Penetration is also partially dependent upon solu- bility characteristics, certainly on the affinity of the penetrant for the structural make-up of the film. As continued Copyright 1997, Technology Publishing Company noted above, cross-linked systems rich in alcohol groups, for example, will be vulnerable to alcohols and other polar solvents, while non- polar coatings will be more resistant to attack from this type of solvent. Testing for Solvent Sensitivity Solvent sensitivity in thermosetting systems is more likely, therefore, to be an indicator of the extent of cure. The rub test with an appropriate sol- vent (usually methyl ethyl ketone, or MEK) is a standard qualitative test for the assessment of cure. In this test, an MEK-soaked cotton, cloth, or felt tip of an engineered marker is reciprocal- ly rubbed across the film, and the number of rubs required for film re- moval, loss of gloss, or other change is noted. Systems showing no effect after 200 double rubs are considered cured, although this is hardly a measure of the extent of cross-link- ing. In addition, the test is not much good for differentiating between 2 or more systems that are satisfactorily cross-linked. In systems where a rea- sonable degree of cross-linking is ex- pected and the film is removed in 20 to 50 rubs, the result would indicate some problem in the cure condition (cure time and temperature or mixing ratio). Immediate solubility of the films supposedly laid down from two- pack mixes such as urethanes and epoxies is usually evidence that one or another of the components is miss- ing. Solvent rub techniques are often used in the field as part of the failure analysis process. The general degree of cure may be confirmed by infra- red spectrophotometry. Solvent immersion testing may be a better measure of relative solvent resistance in highly cross-linked sys- tems using either the watch glass test or preferably some kind of covered immersion test. Coatings are com- pared by their timed response to the solvent, which progresses from soft- ening or blistering to dissolution or delamination. Watch glass tests using volatile materials can be particularly frustrating because in spite of the cover, solvent evaporates rapidly. In addition, the test requires continual monitoring with many applications. The effect of repeated solvent ab- sorption and desorption is probably fatiguing to the film but thwarts even a rough qualitative assessment of the relative effect of different solvents on the same film or the response of multiple films to the same solvent. A more quantitative assessment of solvent sensitivity may be obtained by weighing small coupons of totally coated metal or glass before, during, and after solvent immersion, and plot- ting the weight change data against time (Fig. 3). In this way, both the amount of absorbed material and the rate of absorption may be assessed, as well as the extent of dissolution (or solid removal) after the test is termi- nated. Differences in the weight of the fully dried films before and after immersion may show the loss of ex- tractables. Some error may occur be- cause of weighing time, but this usu- ally takes less than 30 seconds with a modern analytical balance. Matching the temperature of the test with the service application is also important in testing for solvent sensitivity. Hot solvent is far more de- structive than cold solvent, and hot films (above their T g ) are more sensi- tive than cold films. Solvent contact at high temperature may yield quite dif- ferent results from low temperature testing on the same film. In applica- tions where solvent contact is not en- closed, the mitigating effects of evap- oration will also be magnified in the case of hot solvent. Recoatability Solvent sensitivity is often used to advantage in the design of coating systems, where it may be used to improve the intercoat adhesion be- tween successive films. In such recoating, there are no de- vices such as the wax used in paint removers to trap the solvent systems against the old coating and retard their evaporation long enough so that they may attack the existing film. Under most circumstances, the solvent system will evaporate from the finish before it can absorb ap- preciably into the paint film and produce the free volume expansion necessary to good intercoat adhesion, or, in extreme cases, compressive stresses sufficient to induce failure. TROUBLE with PAINT 78 / Journal of Protective Coatings & Linings continued Fig. 3 - Solvent resistanceweight change over time, before, during, and after immersion Copyright 1997, Technology Publishing Company MAY 1997 / 81 TROUBLE with PAINT Contact time between solvent and the exposed film will be increased with high film thickness recoats or where barrier-type pigmentations (aluminum flake) are used in the recoat. In some cases, such excessive contact time may be long enough to cause solvent attack on the primer, particularly where high boiling (slow evaporat- ing) solvents are used. Low molecular weight solvents (small molecules) such as acetone and toluene, which are more aggressive than larger mole- cules and which might easily pene- trate the film, usually evaporate too fast to do so. Conversely, larger mole- cules such as methyl isoamyl ketone, diisobutyl ketone, and high flash naphtha may stay in contact with the existing film long enough to facilitate entry, but they are often too large to readily penetrate the existing film. Compact solvents with cyclic struc- tures, such as cyclohexanone and n- methyl-2-pyrrolidone, are small enough to enter the film easily but are relatively slow to evaporate. These solvents may be more aggres- sive in solvating the surface of the existing film. They have been used to soften hard, well cured thermosets before coating. In lacquer-based sys- tems made up of amorphous ther- moplastic-based coatings, the poten- tial dissolution of a lower coat by the solvents of a subsequently applied coat ensure a good bond with sol- vent and solubilized binder intermin- gling across the interface. The swelling of thermosetting primers by solvents in the finish may also be used, especially where the state of cure of the primer film remains incomplete. As cure advances with time (as T g increases), the technique becomes progressively more difficult to apply. This fact is indicated in the recoat window of the system pub- lished by coating manufacturers. In many of the better product informa- tion sheets, this recoat window is ex- pressed in terms of cure temperatures involved. Recoat times become pro- gressively shorter as cure temperatures increase. It is, of course, possible that in recoating primers with T g values in the 80 to 90 F (27 to 32 C) range, ap- plications at 90 to 100 F (32 to 38 C) may actually facilitate recoating be- cause of T-T g effects. Shrewd use of solvents in the re- coat paint may also improve the re- coatability of well aged gloss films. Conclusion Next month, we will review aesthet- ic difficulties associated with solvent sensitivity in coating films. JPCL References 1. G. Adams and J.H. Gibbs, Journal of Chem. Phys. (Vol. 43, Number 139, 1965). 2. E.N. Dalal, On the Relationship between T g and T, Journal of Polymer Science, Polymer Letters Edition (Vol. 22, Number 547, 1984), 547-548. 3. Z.N. Wicks, Free Volume and the Coatings Formulator, Jour- nal of Coatings Technology (De- cember 1986), 23. 4. H.R. Hamburg and W.H. Mor- gans, Hess Paint Film Defects, 3rd Edition (London: Chapman & Hall, 1979), p. 284. 5. C.H. Hare, Protective Coatings Fundamentals of Chemistry and Composition (Pittsburgh, PA: Technol ogy Publ ishing Co., 1994), p. 141. 6. H. Burrell, Solubility Parameters for Film Formers, Official Digest (now the Journal of Coatings Technology) (Vol. 27, Number 369, 1955), 726. Back issues containing the earlier segments of the Trouble with Paint series are available from JPCL at 800/837-8303.