Ask the Coatings Experts

Edited by L.D. Lou Vincent, Technical Editor, CoatingsPro

his month we asked our panel of experts to explore the properties of polyurethanes, polysiloxanes, and fluoropolyers, with particular emphasis on their intended use as a finish coat for both weather resistance and color/gloss retention purposes. In a future article we will discuss the use of fluoropolymers and silicones in anti-fouling coatings and tank linings.

Topic of the Month: Fluoropolymers, Polysiloxanes, and Polyurethanes

Fluoropolymers, polysiloxanes, and polyurethanes are not pure resins of one type. They are, in fact, combinations of two or more resins along with a curing agent designed to give a specific service in a specific environment. The performance properties are quite different for each resin. For example, the base resin (also called backbone resin) for polyurethane coatings is normally either an acrylic or a polyester resin. The base resin for a polysiloxane coating is typically either an epoxy resin or a polyurethane resin. In the case of fluoropolymers, the critical component is a modification with fluorine and the performance rises dramatically with the amount of fluorine in the product. Polyurethanes in various forms have been around since the early 1940s from Bayer in Germany so their properties are fairly well known, particularly with regard to color and gloss retention. They are by far the most commonly used topcoat over other organic coatings where color and gloss retention are needed for aesthetic purposes. For purposes of this article, we will limit the discussion to thin film products, reserving the elastomeric polyurethanes for another article. When comparing fluoropolymers and polysiloxanes, we are basically evaluating two generic types that have extraordinary weathering (gloss and color retentive) properties. It makes sense therefore to include a short paragraph on polyurethanes as a base model or measuring stick that will probably be familiar to most readers; particularly if we bring in the SSPC Paint-361 standard that measures polyurethane performance or the AAMA 605.22 standard for fluoro polymers (extreme performance). What are fluoropolymers and polysiloxanes? By chemical definition, fluoropolymers are polymers that contain carbonfluorine bonds (C-F), whereas siloxane polymers contain silicon-oxygen bonds (Si-O). The polymer backbone of the fluoropolymer consists of the carboncarbon chain wherein the fluorine atoms are attached to the carbons in the chain. On the other hand, polysiloxanes contain a Si-O backbone where the carbon from the organic modification is attached to the silicon atoms. While they are different technologies, both take advantage of the inherent stability of their respective backbones. The chemical bonds within the basic polymers of these two types are incredibly strong and extremely resistant to ultraviolet (UV) radiation that is otherwise severely damaging to organic resins. While their resistance to UV is based on their inherently stable resins, they attain these properties through different chemistries. The ambient-cure fluoropolymers currently on the market are fluoroethylene vinyl ether (FEVE) resins reacted with an isocyanate to create a fluorourethane. For toxicity reasons in various countries, newer versions based on a silanol functionality are being introduced to overcome the resistance to isocyanates. The first generation fluoropolymers that have been around for 30 to 35 or more years were based on polyvinylene fluoride (pVDF) resins and typically were bakedon finishes for coil steel used on exterior building facades. In 1983, ambient-cured fluoropolymers (through the use of isocyanate resins) entered the scene and brought the benefits of fluoropolymer chemistry out of the shop and into the field. The coating world truly had a 25-year weathering finish for the first time. Current testing and field experience indicates a practical service life of 50 to 60 years in ambient environments. Beginning in 1978, polysiloxanes were pioneered by Ameron with its patented
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Experts of the Month

Adrian Andrews, AkzoNobel Earl Bowry, Consultant Liza Capino, Sherwin-Williams Kat Coronado, AkzoNobel Steve Harrison, Carboline Co. Hiroyuki Tanabe, Dai Nippon Toryo Nick Tatavak, AkzoNobel

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PSX series. The epoxy-based resin in this product required a minimum of 40% relative humidity to cure properly. It took other manufacturers a few years to work around the patent with their own modified versions based on epoxy resin bases, whereas International Paint concentrated on acrylic polyurethane base resins in order to gain greater flexibility, particularly as the coatings aged in service. While polysiloxanes are less understood than polyurethanes, the proper use of polysiloxanes has become well established. Manufacturers differ somewhat on their recommended systems for polysiloxanes, with several recommending epoxy-based products for direct application to abrasive This ship is protected with a red polyurethane coating. Photo courtesy of Carboline Co. blasted steel and others concentrating on Continued on p. 44 the topcoat qualities of the polysiloxane over either a zinc-rich primer or an epoxy intermediate coat. One-component polysiloxanes are moisture cure systems that usually contain an acrylic modification, whereas the two-component polysiloxanes are more often epoxy siloxanes crosslinked with amines. Fluoropolymers (ambient-cured versions) are a more recent development. The early patents from Asahi Glass and Dai Nippon Toryo in Japan, beginning in 1983, have case histories up to 25 years, but widespread use by multinational manufacturers did not gain substantial market penetration until around 2000. There are currently over 2,000,000 m2 of structures painted with Dai Nippons V-Flon coating. The Japanese government has now standardized all topcoats on bridges to be fluoropolymers due to the savings in long-term maintenance and increased visibility to the public. The Japanese standard requires 18% fluorine for extreme weatherability service. The earlier versions could only be applied up to 25 m dry film thickness (DFT). The newest version can be applied up to 55 m DFT. This topcoat will be applied to the Tokyo Sky Tree currently under

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public exposure purposes such as water tanks and storage tank exteriors, fascias, sports complexes, bridges, marine vessel topsides, and other transportation. What are the cost comparisons between the three technologies? While the costs vary according to the formula of each product, its fair to say that polyurethanes are the most economical on an initial applied basis, with polysiloxanes being in the mid range of cost and fluoropolymers being the most expensive. However, cost comparisons made on a cost per mil/ft2 per year of service make the comparisons swing in favor of polysiloxanes and fluoropolymers. The cost of labor and other logistical costs are relatively equal for all three technologies, but the extended service life of fluoropolymers is estimated to yield a savings of 37% over the life of the coating system. What are the differences in surface preparation requirements for the three technologies? When used as a topcoat there are some differences in surface preparation. All require a clean surface but the polyurethanes are a bit more forgiving than the polysiloxanes and much more forgiving than the fluoropolymers. Once the gloss level of polyurethanes has fallen below 50 degrees due to weathering and chalking, a good pressure washing presents a paintable surface. Epoxy-based polysiloxanes are more likely to require roughening of the surface in the early years of service, followed by pressure washing to achieve proper adhesion of the refresher coat. Polyurethane-based polysiloxanes are not as likely to require roughening. Ambient-cured fluoropolymers nearly always require roughening of the surface followed by pressure washing to achieve acceptable adhesion of the refresher coat in its early stages of exposure. After 25 years of exposure, pressure washing alone could be acceptable, but light roughening would be a good investment to extend the service life into the 50- to 60-year range.
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Bridges in Japan are typically coated with fluoropolymers due to the savings in long-term maintenance and increased visibility to the public. Photo courtesy of Dai Nippon Toryo.

construction, which will be the tallest structure in Japan at 634 m. The threepart coating system on this prominent building will consist of 75 m zinc-rich epoxy primer, 120 m epoxy intermediate, and 55 m fluoropolymer topcoat. What drives the durability of fluoropolymers is the degree of fluorine modification plus the migration of the fluorine groups to the surface. This creates lower surface energy with excellent exterior and hydrolytic durability. It becomes very difficult for UV light to break the carbon-fluorine bonds at the surface of the film. The first thing to understand when attempting to compare the service histories of these three coating types is that the formulas are very complex combinations of resins, pigments, additives, etc. intended to achieve a desired performance level. While polyurethane resins are flexible by nature, the coating does not consist of just polyurethane resin. Performance is driven by the combination of the resin polymer and the type of curing agent used. Pure polysiloxane resins are somewhat brittle, so various organic modifications are necessary to create a coating that can be easily applied with reasonable flexibility. Some manufactur-

ers modify epoxies with polysiloxanes and get a nice, hard film with very good color and gloss retention, but these coatings run the risk of becoming brittle as the epoxy resin ages. Other manufacturers use acrylic modifications of the polysiloxanes resin to achieve equivalent levels of color and gloss retention without the risk of embrittlement as the coating ages. Some of the acrylic-modified polysiloxanes meet the flexibility requirements of APAS 2920 3 whereas other epoxy-modified polysiloxanes coatings do not. Are these products limited to ambient service or can they be used in immersion service? A review of the literature from global scale manufacturers of polyurethanes, polysiloxanes, and fluoropolymers reveals that polyurethanes for the most part are limited to ambient service, while some polysiloxanes have immersion-resistant properties. Several epoxy-based polysiloxanes perform quite well in acidic splash and spillage service. Ambientcured fluoropolymers are used almost exclusively for ambient exposures on structures where the aesthetic properties of color and gloss retention are critical for

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A comparison of the performance of polyester urethane, fluorourethane, and acrylic urethane after exposure in an accelerated ultraviolet weathering chamber. Figure courtesy of Sherwin-Williams.

influence on color stability. Color retention is only as good as the quality of the color pigments or tint pastes used in the formula. In general inorganic pigments have better color and chemical fastness than the organic pigments. There are less expensive universal tint pastes that are fine for most weathering needs but they fall far short for really long-term performance. Why spend the money on a 25-year resin system and only use a 10-year color recipe? Higher grade or even automotive-grade pigments are preferred. Likewise, you wouldnt use expensive color pigments in an epoxy used for exterior exposure. The epoxy will quickly chalk and mask the color of the original finish, which is a waste of money. Matching the type and quality of color pigments to the resin type is the job of the formulator and must satisfy the expectations of the customer. We recognize, however, that actual color retention is affected by the stability of the surface layer of resin, which exudes to the surface of an applied film during its curing process regardless of which color system is used. Once that resin-rich outer layer becomes degraded from UV attack, some of the underlying color pigments will also be degraded. As a result, we can reliably say that color retention of polysiloxanes will be better than polyurethanes, but Which of these three topcoats both will be poorer in color retention than will retain color the longest? fluoropolymers. One of the growth marThe choice of color pigments and kets for fluoropolymer topcoats is in the quality of those pigments has a dramatic anti-graffiti coatings market. Laboratory Which technology is likely to give longer service life? There is considerable evidence in papers and manufacturers literature to establish the following expected service life comparisons. Accelerated test results have indicated much better performance by the fluorourethane and polysiloxanes than the traditional urethanes. During actual exposure, fluoropolymer coatings are expected to last three to four times longer than the polyurethanes, and the polysiloxanes should last two to three times longer provided the coating application, including surface preparation, is optimized to the coating manufacturers recommendation. Fluoropolymer coatings service life depends greatly on the amount of fluorine in the formula. It is very, very expensive so the amount of fluorine in a fluoropolymer coating varies, but there is good reason to expect more than 25 years of service life in an ambient exposure. The first patented fluoropolymer finish coat from Japan has at least 18% fluorine in the polymer and is still defect free on the Akashi-Kaikyo Bridge after more than 20 years. The film structure of fluoropolymers is very dense and the resin rich outer layer does not readily accept refresher coats without proper surface preparation.
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tests prove that these topcoats have a far greater resistance to embedment of both spray and hand-applied paints typically used by graffiti aficionados, and ease of cleaning is excellent. How can they be repaired after being placed into service? While formulations can vary, we have seen repairability of polyurethanes to be quite easy with minimal surface preparation (clean and dry) once the initial gloss has begun to fade (usually in a matter of months). The acrylic-based versions are normally easier to repair without abrading than the polyester ones, but once the gloss level has fallen to less than 50 degrees, both can normally be topcoated after clean water washing at pressures below 3,000 psi. In most cases, abrading the surface is not necessary but it is certainly an acceptable method to ensure adhesion and long-term performance. Polysiloxanes based on an epoxy backbone may require a longer period of abrasion time than the ones based on a polyurethane backbone, but both are easily repaired with proper cleaning of the chalky residues on the resin-rich outer layer. Fluoropolymers are more likely to require surface abrasion many years after being placed into service if repairs need to be made, simply because of the density of the fluoropolymer resin-rich outer layer and the tightness of the carbon/fluorine Continued on p. 46
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bonding within that film. Based upon current experience with fluoropolymer finishes in the industry, repairs for color or gloss purposes are not expected until they approach their current 25-year durability record. How can we measure their performance? Actual weathering (which, of course, takes too long to wait for results) is one method to measure performance. Standard methods include accelerated cabinet testing (QUV-A, QUV-B, WOM) or accelerated exterior weathering (such as in the EMMAQUA test facility in Arizona) that intensifies/concentrates the actual radiation from the sun. Industry specifications may provide guidance in determining performance measurements. For instance, SSPC-Paint 36 covers the performance level for the aliphatic polyurethane. ANSI/AWWA D102-034

describes coating systems for recoating 3 APAS Specification 2920, Siloxane and Polysiloxane Coatings for the Long the inside and outside surfaces of steel Term Protection of Steel and Masonry tanks used for potable water storage, and (Highett, VIC, Australia: APAS, 2005). 5 AAMA 2605 describes the performance 4 ANSI/AWWA D102-03, AWWA requirements for aluminum extrusion Standard for Coating Steel Waterand panel for architectural structures. Storage Tanks (Denver, CO: AWWA). The performance of the fluoropolymers 5 AAMA 2605-05, Voluntary Specification, Performance Requirements and so far exceeds that of the SSPC-Paint 36 Test Procedures for Superior Performing standard that separate specifications are Organic Coatings on Aluminum being proposed for this type of coating. Extrusions and Panels (Schaumburg, Of course, you have to purchase the IL: AAMA). coatings from reputable manufacturers whose product technical information you can trust. Send Us Your Coatings Questions! References MP readers are invited to submit their coat1 SSPC-Paint 36, Two-Component ings-related questions for discussion in future Weatherable Aliphatic Polyurethane Ask the Coatings Experts columns. Please Topcoat, Performance-Based (Pittsburgh, PA: SSPC, 2004). send your questions to Lou Vincent at e-mail: 2 AAMA 605.2-92, Voluntary Specifilou.vincent@nace.org.
cation for High Performance Organic Coatings on Architectural Extrusions and Panesl (Schaumburg, IL: AAMA).

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