Comparing Multiple Weathering Techniques Among Various Coatings

JAN 14-17, 2013 SAN ANTONIO, TX HENRY B.
GONZALEZ CONVENTION CENTER
“Comparing Multiple Weathering Techniques Among Various Coatings

Chemistries“
By Veronica Lemmerman, Chemist, Sherwin Williams
Presented at SSPC 2013

January 14 -17, 2013
San Antonio, TX
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Comparing Multiple Weathering Techniques Among Various Coatings Chemistries
Veronica Lemmerman, Chemist

Sherwin Williams
Warrensville Heights, OH, USA
Abstract: It was requested that exposure testing be completed on various high durability coatings
products to evaluate gloss retention and color changes. Various systems were chosen to test, some with
clear coats and some without. They were placed in cyclic UV/condensation testing, concentrated natural
sunlight testing in Arizona, and outdoor exposure testing in South Florida. The coating systems that
exhibited the best results were those that included a fluoropolymer coating. Rank order correlations
among the various sites showed that results were very similar, with concentrated natural sunlight testing
and outdoor exposure in Florida having the best correlations for gloss and color retention results.
Calculated acceleration factors for this study were 1:2 for concentrated natural sunlight testing versus
cyclic UV/condensation, 1:7 between concentrated sunlight and Florida outdoor exposure, and 1:5
between cyclic UV/condensation and Florida.
Experimental Methods & Materials
PROCEDURE
Fifteen Sherwin Williams’s coatings systems were applied over an epoxy primer on hot rolled steel,
which had been prepared to SSPC SP 10 cleanliness with a 1.5-3.0 mil blast profile. These were then
allowed to cure for at least seven days, and were back-primed and edge-dipped with epoxy to seal the
metal to prevent failure due to blistering and rust. A variety of high performance topcoats were examined,
including fluoropolymers, polyurethanes, and polysiloxanes. Table 1 lists the fifteen coatings systems
involved in this study.
Table 1. Coating systems tested.
System # Chemistry
1 Moisture cured urethane
2 Acrylic polyurethane I
3 Acrylic polyurethane I w/ Acrylic polyurethane clear coat
4 Acrylic latex
5 Acrylic latex w/ Acrylic clear coat
6 Fluoropolymer urethane
7 Fluoropolymer urethane w/ Acrylic polyurethane clear coat
8 Fluoropolymer urethane w/ Fluoropolymer clear coat
9 Acrylic polyurethane II
10 High solids epoxy siloxane
11 Polyaspartic urethane
12 Polyurethane dispersion
13 Acrylic Polyurethane III
14 Polyester polyurethane
15 Waterbased acrylic polyurethane
Replicates of each system were prepared and placed on test in concentrated natural sunlight in Arizona,
cyclic UV/condensation, and South Florida (exterior exposure). Gloss and color retention were monitored
at each site. Panels completed 6 months of concentrated sunlight exposure, 54 months (39,000 hours) of
cyclic UV/condensation, and 48 months in Florida. This corresponds to 729 MJ/m2, 3197 MJ/m2, and
1292.89 MJ/m2 of Total UV at the respective locations.
TESTS
Details of each test are noted below.
ASTM G901 (concentrated natural sunlight, Arizona)

Q-Trac testing is an accelerated natural sunlight test. This uses mirrors to concentrate the outdoor
sunlight on the panels, therefore increasing the rate of failure of the coatings. The Q-Trac test cycle is as
follows: Between the hours of 5AM and 7 PM no water spray was used. Between the hours of 7 PM and
5 AM there was a 3-minute spray duration followed by 12-minute dry-time duration; this allows 4 cycles
to be completed per hour during this time interval. Each month panels were removed from testing and
rated for color and gloss.
ASTM D45872 (cyclic UV/condensation)

QUV testing is an accelerated weathering test, using UV bulbs to degrade the coating. The QUV test
cycle was as follows: For the duration of the test there were 4 hours of dry UV exposure followed by 4
hours of dark condensation at 60° C and 50° C respectively. This cycle was repeated continuously. At the
specific rating intervals, panels were removed from testing and rated for color and gloss.
ASTM D10143 (Florida exterior exposure)

The outdoor exposure testing in South Florida was a real world test. Panels were mounted on racks, at a
45º angle, facing south and left to be exposed to the natural outdoor conditions for up to 5 years. These
racks are open backed to allow air to cool the panel as it is weathered. The panels were taken off test at
specified times and rated for both gloss and color changes. Before evaluation, half of each panel was
washed with soap and water, and while the other have was allowed to build up dirt over the course of the
entire test. We will focus on the results of the washed half of each panel in this study.
RESULTS
The results are plotted in Charts 1-6 below. Performance rankings are tabulated in Tables 2 & 3.
Figure 1. Gloss Retention Cyclic UV/Condensation
120
Moisture cured urethane
Acrylic polyurethane I
Acrylic polyurethane I with an acrylic

100 polyurethane clearcoat
Acrylic latex
Acrylic latex with an acrylic clearcoat
80
Fluoropolymer urethane
Gloss Retention (%)
Fluoropolymer urethane with an acrylic

polyurethane clearcoat
Fluoropolymer urethane with an
60 fluoropolymer clearcoat
Acrylic polyurethane II
High solids epoxy siloxane
Polyurethane dispersion
Acrylic Polyurethane III

20
Polyester polyurethane
Waterbased acrylic polyurethane
0
0 5000 10000 15000 20000 25000 30000 35000 40000 45000
Hours on Test
Figure 2. Color Change CIE Lab Cyclic UV/Condensation
80
70 Moisture cured urethane

60 polyurethane clearcoat
Acrylic latex

50 Fluoropolymer urethane

Delta E

40 fluoropolymer clearcoat


20

10
0
0 5000 10000 15000 20000 25000 30000 35000 40000 45000
Hours on Test
Figure 3. Gloss Retention Concentrated Natural Sunlight
120.0
100.0
Acrylic latex
80.0 Acrylic latex with an acrylic clearcoat
Gloss Retention (%)
60.0 Fluoropolymer urethane with an

acrylic polyurethane clearcoat
fluoropolymer clearcoat
40.0
Polyaspartic urethane
20.0
0.0
0 1 2 3 4 5 6 7
-20.0
Months on Test
Figure 4. Color Change CIE Lab Concentrated Natural Sunlight
25.00

20.00 polyurethane clearcoat
Acrylic latex
15.00
acrylic polyurethane clearcoat
Delta E

10.00
5.00 Acrylic Polyurethane III
0.00
0 1 2 3 4 5 6 7
Months on Test
Figure 5. Gloss Retention Florida Outdoor Exposure
120

100

Acrylic latex
80
Gloss Retention (%)

60 Fluoropolymer urethane with an
40
20
0
0 10 20 30 40 50 60
Months on Test
Figure 6. Delta E CIE Lab Florida Outdoor Exposure
50
45
40
Acrylic latex
35
30
Delta E

25

20
15 Polyurethane dispersion
10 Polyester polyurethane
0
0 10 20 30 40 50 60
Months on Test
Table 2. Rank Order of Gloss Retention Results
Concentrated Sunlight (6 months) Cyclic UV/Condensation (39,000 hours) Florida Exterior Exposure (4 year)
%Gloss % Gloss %Gloss
Coating Retention Coating Retention Coating Retention
Fluoropolymer urethane w/ Acrylic polyurethane
Acrylic latex w/ Acrylic clearcoat 109.5 69.8 Fluoropolymer urethane w/ Fluoropolymer clearcoat 97.6
clearcoat
Acrylic polyurethane I w/ Acrylic polyurethane Acrylic Polyurethane I w/ Acrylic Polyurethane Fluoropolymer urethane w/ Acrylic polyurethane
101.3 13.3 82.5
clearcoat clearcoat clearcoat
Fluoropolymer urethane w/ Acrylic polyurethane Fluoropolymer urethane w/ Fluoropolymer Acrylic polyurethane I w/ Acrylic polyurethane
100.0 23.7 80.9
clearcoat clearcoat* clearcoat
Fluoropolymer urethane 100.0 Fluoropolymer urethane** 44.2 Fluoropolymer urethane 76.2
Fluoropolymer urethane w/ Fluoropolymer
99.4 Waterbased acrylic polyurethane** 26.3 Acrylic latex w/ Acrylic clearcoat 64.8
clearcoat
Waterbased acrylic polyurethane 87.9 Polyurethane dispersion*** 29.1 Polyester polyurethane 45.5
Polyester polyurethane 82.0 Acrylic latex⁺ 48.3 Acrylic latex 23.0
Polyurethane dispersion 47.6 Polyester polyurethane⁺ 33.6 Waterbased acrylic polyurethane 22.4
Acrylic Polyurethane III 40.7 High Solids Epoxy Siloxane⁺ 29.6 Polyurethane dispersion 17.9
High Solids Epoxy Siloxane 33.6 Acrylic latex w/ Acrylic clearcoat⁺ 23.2 Acrylic Polyurethane III 9.8
Acrylic latex 18.3 Acrylic Polyurethane III⁺ 17.2 Moisture cured urethane 3.4
Acrylic Polyurethane II 2.7 Acrylic Polyurethane II⁺ 6.3 Acrylic polyurethane II 3.1
Polyaspartic urethane 1.7 Moisture cured urethane⁺ 4.6 Polyaspartic urethane 1.5
Moisture cured urethane 1.2 Polyaspartic urethane⁺ 1.2 Acrylic Polyurethane I 1.3
Acrylic polyurethane I 1.2 Acrylic Polyurethane I⁺ 1.1 High Solids Epoxy Siloxane⁺⁺ 6.2
* Removed at 33000 hours

** Removed at 18000 hours
*** Removed at 9000 hours
⁺Removed at 8000 hours
⁺⁺Removed from testing in Florida at 36 months
Table 3. Rank Order of Color Change Results
Concentrated Sunlight (6 months) Cyclic UV/Condensation (39,000 hours) Florida Exterior Exposure (4 year)
Coating ΔE Coating ΔE Coating ΔE
Fluoropolymer urethane w/ Acrylic polyurethane Fluoropolymer urethane w/ Acrylic polyurethane
1.56 11.06 Fluoropolymer urethane 1.79
clearcoat clearcoat
Acrylic polyurethane I w/ Acrylic polyurethane Fluoropolymer urethane w/ Fluoropolymer
Fluoropolymer urethane 1.82 40.16 2.25
clearcoat clearcoat
Fluoropolymer urethane w/ Fluoropolymer Fluoropolymer urethane w/ Acrylic polyurethane
Fluoropolymer urethane w/ Fluoropolymer clearcoat 1.97 23.31 2.70
clearcoat* clearcoat
Acrylic latex 4.81 Waterbased acrylic polyurethane** 22.64 Acrylic latex w/ Acrylic clearcoat 5.84
Acrylic latex w/ Acrylic clearcoat 5.06 Fluoropolymer urethane** 36.88 Polyurethane dispersion 6.40
Waterbased acrylic polyurethane 5.79 Polyurethane dispersion*** 16.05 Waterbased acyrlic polyurethane 6.69
Polyurethane dispersion 8.88 Acrylic latex⁺ 15.97 Acrylic latex 6.85

Acrylic polyurethane I w/ Acrylic polyurethane Acrylic polyurethane I w/ Acrylic polyurethane
clearcoat
10.26 Polyester polyurethane⁺ 18.52
clearcoat
12.40
Acrylic polyurethane I 14.69 High Solids Epoxy Siloxane⁺ 18.77 Acrylic polyurethane I 21.61
Moisture cured urethane 14.87 Acrylic polyurethane III⁺ 22.29 Moisture cured urethane 23.88
High Solids Epoxy Siloxane 15.00 Acrylic polyurethane II⁺ 25.12 Acrylic polyurethane II 25.05
Polyaspartic urethane 15.12 Moisture cured urethane⁺ 28.33 Acrylic polyurethane III 31.63
Polyester polyurethane 18.85 Polyaspartic urethane⁺ 39.89 Polyester polyurethane 33.64
Acrylic polyurethane III 20.50 Acrylic polyurethane I⁺ 41.38 Polyaspartic urethane 43.22
Acrylic polyurethane II 21.17 Acrylic latex w/ Acrylic clearcoat⁺ 66.83 High Solids Epoxy Siloxane⁺⁺ 38.52
* Removed at 33000 hours

** Removed at 18000 hours
*** Removed at 9000 hours
⁺Removed at 8000 hours
⁺⁺Removed from testing in Florida at 36 months
DISCUSSION
In general, fluoropolymers performed the best, followed by polyurethanes, and finally polysiloxanes,
although there were some exceptions (two of the acrylic polyurethanes that were tested without a clear
coat performed relatively poorly). The industrial grade acrylic latex fell toward the middle in
performance, and when coated with an industrial acrylic latex clear coat, there was little change in the
performance. It should be noted that this product had a lower initial gloss than the others in this study.
Three systems showed high gloss retention at all exposure sites. These were the acrylic polyurethane I
with an acrylic polyurethane clear coat, the fluoropolymer urethane with a fluoropolymer clear coat, and
the fluoropolymer without a clear coat. A similar trend was noticed with color retention, in which these
same three systems exhibited a small color change. In addition, the waterbased acrylic polyurethane
showed good performance in retaining color and gloss in cyclic UV/condensation testing and Florida
outdoor exposure.
Not surprisingly, fluoropolymer based coating systems outperformed the other coatings tested.
Fluoropolymers are very durable due to the carbon-fluorine bonds that are found within them. This strong
bond tends to be characterized by its short length and partial ionic nature, and is one of the strongest
bonds in organic chemistry. The C-F bond energy is found to be much larger than the energy of UV rays.
Also, this chemically stable bond can protect neighboring components, which are usually attacked by
these rays. Therefore, the C-F bond will show a high resistance to breakdown from sunlight.4
Another trend was the significant difference in the results of the acrylic polyurethane I with and without
the acrylic polyurethane clear coat. The acrylic polyurethane I showed much better gloss and color
retention with the clear coat than without. This is most likely due to the leaching of the pigment upon
polymer breakdown when a clear coat is not present, which can cause chalking on the coating. On the
other hand, a clear topcoat does not have a pigment to be leached, and therefore would not show the
chalking impression.
Results for gloss showed similar performance ranking throughout all of the sites. The rank order
correlation coefficients over time among the sites can be found in Table 4 and 5. In Figure 7 and 8 these
coefficients have been graphed. The graphs indicate that as testing continues at the various sites the
correlation moves closer to 1, representing a perfect correlation. As the Florida test continues, the results
become more in line with the results of the accelerated weathering tests of cyclic UV/condensation and
concentrated sunlight, showing that the coating are behaving similar in the accelerated testing as they
would in real world exposure. Calculated acceleration factors for this study can be found in Table 6.
These would illustrate that it takes longer for Floridea exterior exposure to show the same results that
would be shown in either concentrated natural sunlight or cyclic UV/condensation testing, causing the
rank order correlation factors to improve the longer testing in conducted.
Table 4. Gloss Correlation

0 3 6 12 24 36 48
Site mo mo mo mo mo mo mo Average
Concentrated sunlight and Cyclic 0.00 0.90 0.97 0.96 0.96 0.96 0.96 0.95
UV/condensation
Concentrated sunlight and Florida exterior 0.00 0.90 0.93 0.96 0.98 0.98 0.97 0.95
exposure
Cyclic UV/condensation and Florida
0.00 0.96 0.96 0.97 0.98 0.97 0.97 0.97
exterior exposure
Figure 7. Gloss Correlation Over Time
1.05
1.00
Concentrated Natural
Sunlight and Cyclic
UV/Condensation
Rank Order Correlation
0.95
Sunlight and Florida Exterior
Exposure
0.90
Cyclic UV/condensation and
Florida Exterior Exposure
0.85
0.80
0 10 20 30 40 50 60
Time on Test (Months)
Table 5. Color Correlation

0 3 6 12 24 36 48
Site mo mo mo mo mo mo mo Average
Concentrated sunlight and Cyclic UV/condensation 0.00 0.92 0.93 0.93 0.93 0.93 0.92 0.93
Concentrated sunlight and Florida exterior
0.00 0.89 0.89 0.97 0.98 0.98 0.98 0.95
exposure
Cyclic UV/condensation and Florida exterior
0.00 0.97 0.93 0.96 0.94 0.92 0.92 0.94
exposure
Figure 8. Color Correlation Over Time
1.05
1.00
Sunlight and Cyclic
Rank Order Correlation
UV/Condensation
0.95
Sunlight and Florida Exterior
Exposure
0.90
Cyclic UV/condensation and

Florida Exterior Exposure
0.85
0.80
0 10 20 30 40 50 60
Time on Test (Months)
Table 6. Calculated Acceleration Rates
Sites Acceleration Rate*
Concentrated sunlight and Cyclic UV/condensation 1:2
Concentrated sunlight and Florida exterior exposure 1:7
Cyclic UV/condensation and Florida exterior exposure 1:5
* Approximate
The best correlation for this study was between concentrated natural sunlight and Florida outdoor
exposure, as shown in the plots. This is due to the fact that both concentrated sunlight and outdoor
exposure testing use the same spectrum of light to degrade the coating, while cyclic UV/condensation has
a spectrum with a spike around 340nm. This is part of the UV spectrum of light, which is considered the
most destructive of natural light. However, UV testing showed very similar results to both the
concentrated sunlight and Florida test sites.
SERVICE LIFE PREDICTION
An attempt was made to determine the service life precition of the coatings using the following equation7:
L 2 I 2 x(b+mTOW 2 ){T f (T2-T1)}

t 1 =t 2 [ L 1 I 1 x(b+mTOW 1 )
]
t 1 = Outdoor test time
t2= Accelerated test time
L1= Light on fraction outdoors
L2= Light on fraction accelerated test
I1= Irradiance in outdoor test
I2= Irradiance in accelerated test
TOW 1 = Time of wetness outdoors
TOW 2 = Time of wetness accelerated test
T 1 = Temperature outdoors
T 2 = Temperature accelerated test
x= Power law exponent
It was found that the results of this testing did not fit a linear correlation, and therefore no accurate
prediction could be made on the service of a coating strictly based on the failure rate of a coating in
accelerated testing. This is shown in Figures 9-11. (In figure 9, the red point represents the best fit line
for model predictions.)
Figure 9. Concentrated Sunlight/Florida Model
30
Florida failure time (months) 25

y = 3.2687x + 2.9552
R² = 0.2871
20
15
10
0
0 1 2 3 4 5 6 7
Arizona failure time (months)
Figure 10. Cyclic UV /Florida Model

40000
Florida Failure Time (hours)
35000
y = 0.3932x 1.2226
30000 R² = 0.9335
25000
20000
15000
10000
5000
0
0 2000 4000 6000 8000 10000
QUV Failure Time (hours)
Figure 11. Cyclic UV/Concentrated sunlight Model
5000
4500
Arizona Failure Time (hours) R² = 0.4249
4000
3500
3000
2500
2000
1500
1000
500
0
0 2000 4000 6000 8000
QUV Failure Time (hours)
A factor that may affect service life prediction are the various environtmental conditions the coatings
would be used in. This is mostly due to time of wetness, temperature, and salinity of the atmosphere. For
instance, Seattle, WA is a very wet city that can have average high temperatures of 60°F most of the
year5, while Phoenix, AZ is a very dry atmosphere with average high temperatures around 87°F yearly.6
CONCLUSIONS
1. The systems that included fluoropolymers and/or a clear topcoat had the highest durability in
these exposures. This is due in part to the very strong carbon-fluorine bond found within the
coatings.
2. Rank order correlations among the various sites were very similar. However, the test sites that use
natural sunlight to degrade the coatings showed a better correlation to each other in both color
and gloss retention.
3. Rank order correlation factors trended closer to 1.00 (perfect correlation) the longer the testing
was conducted, specifically in Florida. This is due to the face that the real world testing results
will begin to line up with the accelerated testing the longer the coatings are tested.
4. It is difficult to determine the service life prediction for a coating using the Zielnik equation based
on the accelerated testing results. This is partly due to the various environtmental conditions that
the coatings are used in.
Acknowledgements & References
1. ASTM G90-05 Standard Practice for Performing Accelerated Outdoor Weathering of Nonmetallic
Materials Using Concentrated Natural Sunlight, Cycle 3 (Q-Trac)
2. ASTM D4587-05 Standard Practice for Fluorescent UV-Condensation Exposures of Paint and Related
Coatings (QUV)
3. ASTM D1014 Standard Practice for Conducting Exterior Exposure Tests of Paint and Coatings on Metal
Substrates (Florida and Chicago Exterior Exposure)
4. Wassar, Hundert. (2002). “Lumiflon and PFEVE Structure.” Lumiflon Introduction. 16 October, 2009.
http://www.lumiflon.com/what_us/
5. The Weather Channel. (1995-2012). Average Weather for Seattle, WA—Temperature and Precipitation.
Retrieved September 4, 2012, from
http://www.weather.com/weather/wxclimatology/monthly/graph/USWA0395
6. The Weather Channel. (1995-2012). Average Weather for Phoenix, AZ—Temperature and Precipitation.
Retrieved September 4, 2012, from
http://www.weather.com/weather/wxclimatology/monthly/graph/USAZ0166
7. Zielnik, Allen (2008). Service Life Prediction: Concepts & Methodologies [PowerPoint slides].
Veronica Lemmerman
Veronica Lemmerman graduated from Case Western Reserve University with a Bachelors of Science degree
in Chemistry in 2007. She began working at Sherwin Williams in 2008, testing industrial coatings for
performance specifications. In January she will have worked in Weathering and testing for 5 years.

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JAN 14-17, 2013 SAN ANTONIO, TX HENRY B.

GONZALEZ CONVENTION CENTER

“Comparing Multiple Weathering Techniques Among Various Coatings

By Veronica Lemmerman, Chemist, Sherwin Williams

Presented at SSPC 2013

Veronica Lemmerman, Chemist

Experimental Methods & Materials

Table 1. Coating systems tested.

ASTM G901 (concentrated natural sunlight, Arizona)

ASTM D45872 (cyclic UV/condensation)

ASTM D10143 (Florida exterior exposure)

Acrylic polyurethane I with an acrylic

Acrylic latex with an acrylic clearcoat

Fluoropolymer urethane with an acrylic

High solids epoxy siloxane

Acrylic Polyurethane III

Waterbased acrylic polyurethane

Figure 2. Color Change CIE Lab Cyclic UV/Condensation

70 Moisture cured urethane

Acrylic polyurethane I with an acrylic

Acrylic latex with an acrylic clearcoat

Fluoropolymer urethane with an acrylic

Fluoropolymer urethane with an

High solids epoxy siloxane

Acrylic Polyurethane III

Waterbased acrylic polyurethane

80.0 Acrylic latex with an acrylic clearcoat

60.0 Fluoropolymer urethane with an

Acrylic Polyurethane III

Figure 4. Color Change CIE Lab Concentrated Natural Sunlight

Moisture cured urethane

Acrylic polyurethane I with an acrylic

Acrylic latex with an acrylic clearcoat

Fluoropolymer urethane with an

5.00 Acrylic Polyurethane III

Waterbased acrylic polyurethane

Moisture cured urethane

Acrylic polyurethane I with an acrylic

Fluoropolymer urethane with an acrylic

High solids epoxy siloxane

Acrylic Polyurethane III

Figure 6. Delta E CIE Lab Florida Outdoor Exposure

Fluoropolymer urethane with an

High solids epoxy siloxane

Acrylic Polyurethane III

Waterbased acrylic polyurethane

Polyester polyurethane 82.0 Acrylic latex⁺ 48.3 Acrylic latex 23.0

* Removed at 33000 hours

Polyurethane dispersion 8.88 Acrylic latex⁺ 15.97 Acrylic latex 6.85

Polyester polyurethane 18.85 Polyaspartic urethane⁺ 39.89 Polyester polyurethane 33.64

* Removed at 33000 hours

Table 4. Gloss Correlation

Table 5. Color Correlation

Figure 8. Color Correlation Over Time

Cyclic UV/condensation and

SERVICE LIFE PREDICTION

L 2 I 2 x(b+mTOW 2 ){T f (T2-T1)}

Florida failure time (months) 25