SSPC-TU 12

May 4, 2015

SSPC: The Society for Protective Coatings

Technology Update No. 12
Ambient-Curing Fluoropolymer Finish Coats
Applied to Metal Substrates

1. Scope these thermoplastic fluoropolymers offered extremely high

performance in severe environments, primarily due to their
This technology update provides a fundamental discussion resistance to a widely diverse range of harsh chemicals, resis-
of ambient-curing fluoropolymer finish coats applied to metal tance to elevated temperature, low surface energy and low
substrates, including recent developments. It is intended as coefficient of friction (i.e., “non-stick” capability).
a resource for architects, specification writers, facility owners,
and others charged with the selection and field application 3.1.1 Original Development of Ambient-Cured Fluo-
of coating systems requiring superior weathering resistance ropolymers: The first generation fluoropolymer-based coating
and appearance retention in both architectural and industrial materials were produced in the 1960s. They were solvent-
applications. It includes background information about the borne liquid dispersions of polyvinylidene fluoride (PVDF)
development of fluoropolymer materials, a basic description of thermoplastic resin (see Figure 1). These PVDF dispersions
fluoropolymer coating technology, the different types of fluo- were later formulated into coatings by blending with acrylic
ropolymers used in coatings today, application methods, and resins typically at a 70:30 PVDF:acrylic ratio by weight as
performance testing procedures. finish topcoats for exterior metal substrates on commercial
buildings. Formulations with less than 70% PVDF in the resin
2. Description are generally regarded as having reduced gloss retention and
increased levels of chalking.
“Ambient-cured fluoropolymer finish coats” describes a
class of coating materials based on resins (i.e., polymers) with H H H
a high fluorine content that have been formulated into liquid F F F
applied finishes that “air-dry” or cure under ambient conditions. C C
C
Finish coats based upon fluoropolymer resin technology are
C C C
designed to retain color and gloss after years of direct sunlight
(UV) exposure. The two principal fluoropolymer resin types for H H H
finish coatings used at the time of publication are polyvinyli- F F F
dene fluoride (PVDF), and fluoroethylene-vinyl ether (FEVE).
Fluoropolymer resin-based coatings are most frequently Figure 1. Polyvinylidene Fluoride Chemical Structure.
selected as finish coats to be applied over compatible primers
or intermediate coats in service environments where long-term The need to bake these coatings at high temperatures
color and gloss retention and chalking resistance are required. limited their applicability to uses that could accommodate
Additionally, the barrier properties of fluoropolymer resin-based factory application and high-temperature bake processes.
coatings provide corrosion resistance, making them suitable They were not an alternative to more conventional air-dry
for use as finish coats in marine and offshore environments. finish coats. The PVDF finish coatings were factory-applied to
The chemical resistance of thermoset fluoropolymer resin thin-gauge steel sheets coated with zinc or its alloys using a
coatings is similar to that of standard polyurethanes (such as coil-coating process, or spray-applied to extruded aluminum.
SSPC-Paint 36)1, and their application in severely corrosive The coatings were then baked in an oven at 230-250 ºC
environments may be limited. (approximately 450-500 ºF) to develop the final properties of
the thermoplastic coating.
3. Fluoropolymer Technology A coating that offered comparable performance to
the baked PVDF coatings that would air dry under ambient
conditions and could be applied by conventional application
3.1 HISTORY OF FLUOROPOLYMERS: Thermoplastic
methods was highly desirable. This led to the development of
fluoropolymers are a family of hydrocarbon polymers having
solvent-borne PVDF-acrylic coatings that formed a dry film by
high fluorine content, first developed by the DuPont Company
solvent evaporation without a high-temperature bake. These
in the 1930s, that were initially limited to the production of
early air-dry coatings began to approach the performance of
extruded or molded plastic parts. As a family of materials,
the baked coatings, but exhibited relatively lower adhesion,
lower tensile strength and limited scratch and mar resistance,
1
SSPC-Paint 36 (latest revision), Two-Component Weatherable Aliphatic Polyurethane
Topcoat, Performance-Based.

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SSPC-TU 12
May 4, 2015

when compared to the baked PVDF coatings. lower molecular weight fluoropolymers are preferred for ther-
mosetting systems.
3.1.2 Development of Second-Generation Ambient 3.2 CURING MECHANISM OF ARCHITECTURAL AND
Cured Fluoropolymers: The second advancement in INDUSTRIAL FLUOROPOLYMERS: Most fluoropolymer
ambient-cured fluoropolymers occurred in Japan circa 1980. products for thermosetting systems are hydroxy functional.
These newer resins were designated fluoroethylene vinyl This means that they can be cross-linked with the same prod-
ethers, or FEVE (see Figure 2). They were also formulated ucts used with standard acrylic or polyester polyols. Examples
with solvents, but could undergo thermosetting reactions of cross-linkers include oligomers of isophorone diisocyanate
during ambient temperature cure. Early FEVE thermosetting (IPDI), hexamethylene diisocyanate (HDI), and hydrogenated
coatings show marked improvement in many physical proper- methylene diphenyl diisocyanate (HMDI). Ambient-curing
ties (such as higher gloss capabilities) compared to the earlier coatings of this type are generally two-component or “2-k.”
PVDF thermoplastic solution coatings. For water-borne thermosetting systems, a number of special-
Today, most FEVE products are cross-linked with poly- ized crosslinker products have been developed, which are
isocyanates, yielding coatings with superior transparency, adapted to better incorporate the hydrophobic crosslinker into
gloss, and hardness, with many FEVE systems now demon- an aqueous medium.
strating outdoor weatherability comparable to the 70% PVDF Thermoplastic systems do not “cure” via crosslinking,
technology. but rather develop their properties by means of increasing
polymer chain entanglements during and after a physical
3.1.3 Third-Generation Water-borne Ambient-Cured drying, a process known as “coalescence.” Solution coatings
Fluoropolymer Systems: Environmental concerns have and dispersions have different mechanisms for film formation.
led to severe restrictions in the amount of volatile organic Thermoplastic systems are generally single-component or
compounds (VOCs) that can be released to the atmosphere “1-k.”
as solvent-borne coatings cure. Considerable work has been
done to adapt both the FEVE and the PVDF resin technolo- 3.3 FACTORS AFFECTING THE FINAL COATING
gies for use in water-borne fluoropolymer coatings to reduce PERFORMANCE
the amounts of solvent released, and hence the VOCs emitted
to the environment. The FEVE technology can be adapted 3.3.1 Resin Structure and Fluorine Content:
to water, either in an FEVE emulsion form (higher molecular Fluoropolymer resins derive their weatherability from their
weight), or in water dispersion form (lower molecular weight). chemical structure. The unique properties of fluorine atoms
The PVDF technology can be adapted to water by making not only make the resin much more hydrophobic (important
LUMIFLON® FLUOROPOLYMER for both RESINS
corrosion resistance and weathering), but also impart
PVDF-acrylic hybrid dispersions (latex), which incorporate a
Long Term Performance
miscible blend of fluoropolymer and acrylic polymer in each
Vs.
increased PVDF
chemical and UV resistance to the resin, including
latex particle. Either resin chemistry can be adapted to make nearby non-fluorinated segments on the polymer chain. For
either LUMIFLON resins are known
thermoplastic (non-crosslinking) generically
or thermoset as fluoroethylene vinyl ether (FEVE) resins.
(cross- instance, the regularly alternating structure of FEVE resins
The
linking) name
coating derives
systems. from the
Generally reactants
speaking, higherused to form the polymer. These materials form the to protect
molecular allows the fluorinated segments of the molecule
weightregularly
fluoropolymers are used for
alternating thermoplastic
structure shownsystems, and The alternating structure is critical to the
below.
weatherability of coatings made with LUMIFLON resins.

F F F ᨸF F ᨸ
F
ᨸ ᨸ ᨸ ᨸ
C᧩ C H H C᧩ C H H C᧩ C H H
ᨸ ᨸ ᨸ ᨸ ᨸ ᨸ ᨸ ᨸ ᨸ ᨸ ᨸ ᨸ
F X C ᧩C
ᨸ ᨸ
F X C ᧩C
ᨸ ᨸ
F X C ᧩C
ᨸ ᨸ
H O H O H O
ᨸ ᨸ ᨸ
R1 R2 R3
ᨸ
OH

Weatherability Solubility Flexibility Crosslinking Sites

Durability Transparency Adhesion
Gloss
Hardness

Physical properties of the LUMIFLON resin can be modified by changes in the nature of
Figure 2. Structure of Fluorolymer Resin Polymer.The fluoroethylene segments (en-
the vinyl ether closed
units.byUltra-weatherability,
boxes in figure above)provide durability,
weatherability,and chemical
durability resistance
and chemical are derived
resistance.
from the alternating fluorinated
Each of the units.(notLUMIFLON
vinyl ether segments enclosed by boxes) resins aredifferent
contributes usually reacted with
attributes:
clarity; gloss and hardness; flexibility; and crosslinking.
aliphatic isocyanates to form crosslinked fluorourethane coatings.
2
Recently, claims have been made that FEVE resins do not offer the same weatherability
as PVDF coatings because they are lower in fluorine content. These claims are
 SSPC-TU 12
May 4, 2015

Figure 3. Baked (top row) and air-dry (2nd and 3rd row) PVDF-based paints with 30% added acrylic, after 25-30
years South Florida exposure. Topcoat formulations, 1-mil (25 microns) dry film thickness, on chromated aluminum.
Exposure at 45º south facing, unbacked. The top quarter of each panel is the original panel color. Source: Arkema, Inc.

the vinyl ether segment from degrading due to exposure to performance and formulate to a balance of properties for a
UV radiation and corrosives. This protective mechanism given application. The color and gloss stability of the coating is
continues to work even in the cross-linked coating. Because highly dependent on the light-fastness of the pigment chosen.
the ability of fluorine atoms to protect nearby groups depends It is important to use pigments that will not change color over
on details of the molecular structure, fluorine content alone is time. The pigment must withstand UV light and humidity. As a
not sufficient to predict how weatherable a coating system will general rule, inorganic oxide pigments are more durable (UV-
be. In some fluoropolymer coating systems, including nearly resistant) than organic pigments, but the organics give a wider
all PVDF coating systems, non-fluorinated blend resins such range of bright colors. In addition to highly durable pigments,
as thermoplastic acrylics or acrylic polyols are incorporated UV stabilizers can also be used in the formulations to improve
in order to modify the balance of properties.. In weathering both color and gloss retention.
studies, it was found that the lower the level of fluorinated
resin in the system, the more the performance tends toward 3.4 EXPOSURE STUDIES OF FLUOROPOLYMER:
that of a non-fluorinated system. However, the relationship is Fluoropolymer resin-based coatings have been evaluated in a
not always proportional. For example, paints based on air-dry range of accelerated exposure tests, as well as outdoor expo-
PVDF solution coatings, with 30% added acrylic, maintain sures. In these exposure tests, gloss retention, color retention,
color retention and chalk resistance for decades, as long as and chalking resistance can serve as the measure of coating
weatherable pigments are used (Figure 3). Nevertheless, for durability, particularly for coatings that have a decorative
any given fluoropolymer resin type, the total resin fluorine function.
content will often give a general idea of the weathering
performance. 3.4.1 Fresnel-type Exposure (ASTM G90)2: This method
of “natural accelerated weathering” involves concentrating
3.3.2 Examples of Effect of Formulation Variables on
Coating Performance: By using the proper components in a 2
ASTM G 90, “Standard Practice for Performing Accelerated Outdoor Weathering of Nonme-
tallic Materials Using Concentrated Natural Sunlight,” (latest edition), ASTM International,
coating formulation, coating manufacturers can maximize the 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959. Standards available online
from http://www.astm.org.

Figure 4. Fresnel-type (ASTM G90) Testing of Fluoropolymer Resin-Based Coatings.

Percent gloss retention is plotted vs. the total UV dose received by the coating. Source: Asahi Glass Chemicals Co.

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SSPC-TU 12
May 4, 2015

Figure 5. UV-Fluorescent Cabinet (UVB-313 nm bulbs) Testing of Fluoropolymer Resin-Based

Coatings. Percent gloss retention is plotted, vs. the number of exposure hours.
Source: Asahi Glass Chemicals Co.

sunlight via reflective mirrors onto the coating specimen, with the coating is exposed to a controlled spectrum and dose of
intensity approximately equal to that of 8 suns (5 suns in the UV light while undergoing intermittent water spray. The results
UV range of the spectrum). The unit mirrors track the solar for coatings properties, such as gloss and color, are reported
image as it moves across the sky, exposing the test specimen as a function of the number of hours of exposure. Typical test
to the full spectrum of radiation found in natural sunlight. results for an FEVE resin coating and a PVDF coil coating are
An oscillating nozzle sprays the specimens with deionized shown in Figure 5.
water on a preset schedule. Results are reported in units of The results of exposure tests based on accelerated
energy to which the coating is exposed. Figure 4 shows the testing should always be viewed with caution. In general, the
results of ASTM G90 testing on a typical FEVE fluoropolymer more accelerated that a test is, the more likely it is to distort the
resin-based coating, along with results for a PVDF-based coil degradation chemistry for at least some systems. As a result,
coating. no universal “acceleration factor” or multiplier can be applied to
accelerated test data to rigorously translate hours of acceler-
3.4.2 UV-Fluorescent Cabinet and “Weatherometer” ated exposure to months or years of outdoor exposure.
Testing: Accelerated methods to test fluoropolymer resin
coatings often make use of xenon arc weatherometers and 3.4.3 South Florida Weathering: The most common
UV fluorescent test cabinets such as those described in real-time weathering test used for evaluation of these coatings
ASTM G154 and G155.3 In one commonly used test cycle, is exposure of coated panels in South Florida. The panels are
3
ASTM G 154, “Standard Practice for Operating Fluorescent Light Apparatus for UV usually placed at a 45° angle on a rack on a south facing expo-
Exposure of Nonmetallic Materials,” (latest edition); ASTM G155 “Standard Practice for
Operating Xenon Arc Light Apparatus for Exposure of Nonmetallic Materials” ASTM Interna- sure, and then left in place for several years. The fluoropolymer
tional, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959. Standards available
online from http://www.astm.org.
resin-based coatings shown in Figure 6 were left in place for
10 years. The 10-year requirement comes from the American

Figure 6. South Florida (South 45º) Testing of Fluoropolymer Resin-Based Coatings. Percent gloss
retention is plotted, vs. the number of years of exposure.
Source: Asahi Glass Chemicals Co.

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 SSPC-TU 12
May 4, 2015

Architectural Manufacturer’s Association (AAMA) standard for

aluminum extrusions4 and requires a minimum of 50% gloss 6. Bibliography
retention after 10 years of South Florida weathering.
AAMA 2605-02 “Performance Requirements and Test
5. Summary Procedures for Superior Performing Organic Coatings
on Aluminum Extrusions and Panels,” Schaumberg, IL:
The protection of substrate from corrosion and weather- American Architectural Manufacturers Association, 2002.
related degradation are very important in both industrial and Asakawa, Akihiko. “Performance of Durable Fluoropolymer
architectural applications, and organic coating systems play an Coatings,” Presented at 7th Nüremburg Congress,
essential role. Fluoropolymer coatings have achieved this goal European Coatings Show, April, 2003, Nüremburg,
over the course of the last few decades, and have evolved Germany.
into one of the major classes of coatings used in the high- Cocuzzi, D.A. and G.R. Pilcher, “Final Report on the Subject
performance segment for the coating of various substrates. of Accelerated Weathering: an ASTM D01.53 Ten-Year
Although no coating system is suitable for all environments, Exposure Study”, Chapter 4 of Service Life Prediction of
studies have shown that fluoropolymers can perform well in Polymeric Materials: Global Perspectives, J.W. Martin,
variety of difficult atmospheric conditions. R.A. Ryntz, J. Chin and R.A. Dickie, eds., Springer
Science +Business Media, New York, 2009, pp. 57-68.
5. Disclaimer Darden, Winn. “Style with Staying Power.” Journal of
Architectural Coatings vol. 2, no. 5, August/September,
5.1 This technology update is for information purposes
2006, pp. 78-83.
only. It is neither a standard nor a recommended practice.
Darden, Winn; Bob Parker, Naoko Sumi, Isao Kimura,
While every precaution is taken to ensure that all informa-
Masakazu Ataku, and Takashige Maekawa, “New
tion furnished in SSPC technology updates is as accurate,
Waterborne Fluoropolymer Resins for Ultra-Weatherable
complete, and useful as possible, SSPC cannot assume
Coatings.” Journal of Protective Coatings and Linings,
responsibility nor incur any obligation resulting from the use of
vol. 26, no. 9, December 2009, pp. 32-37.
any materials, coatings, or methods specified herein, or of the
Greigger, Paul; and Paul Wilson. “High Performance
technology update itself.
Fluoropolymer Coatings,” presented at Construction
Specifications Institute Conference, Chicago, IL 2004.
5.2 This technology update does not attempt to address
Munekata, Seiji. Progress in Organic Coatings, “Fluoropolymers
problems concerning safety and health associated with its use.
as Coating Materials,” 16 (1988), pp. 113-134.
The user of this technology update, as well as the user of all
Wood, Kurt; Ron Partridge, and Ravi Gupta, “Highly
products or practices described herein, is responsible for insti-
Weatherable Low-VOC Fluoropolymer Coatings for
tuting appropriate health and safety practices and for ensuring
Building Restoration”, Journal of Coatings Technology,
compliance with all appropriate governmental regulations.
vol. 6, no. 8, September 2009, pp. 32-39.
4
AAMA 2605 (latest edition), “Performance Requirements and Test Procedures for Superior Wood, Kurt A. “The Advantages of Networking: Poly(vinylidene
Performing Organic Coatings on Aluminum Extrusions and Panels.” American Architectural
Manufacturers’ Association, 1827 Walden Office Square, Suite 550, Schaumburg, Illinois fluoride)-Acrylic IPN Structures for Solvent and Waterborne
60173-4268, phone: (847) 303-5664, fax: (847) 303-5774. Standards available online from
http://www.aamanetstore.org/pubstore. Coatings”, European Coatings Journal, September 2005,
pp. 48-53.

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