The Progress of Newly Developed

Fluoro-polymer Topcoat Systems

－Weathering performance and track records since the 1980’s－

Hiroyuki Tanabe, Masanori Nagai

Dai Nippon Toryo Co.,R & D Division

Winn Darden, Takashi Takayanagi

AGC Chemicals Americas

NACE
CORROSION 2011
March 13-17, 2011
Houston, Texas, USA 1
 Outline of Presentation
 FLUORO-POLYMER COATINGS
 Composition of Fluoro-polymer
 Fundamental Chemistry of Fluoro-polymer
 Results of Molecular Weight Change of Fluoro-polymer
Compared with Polyurethane
 FLUORO-POLYMER TOPCOAT OF SYSTEM
 General Performance
 Corrosion Protective Performance of Fluoro-polymer
Coatings Weather-ability of Fluoro-polymer Coating
 TRACK RECORDS OF USE IN THE FIELD
 Advanced Application
 FURTHER DEVELOPMENTS
2
FLUORO-POLYMER FOR COATINGS

・ Composition of Fluoro-polymer
・ Fundamental Chemistry of Fluoro-polymer
・ Results of Molecular Weight Change of Fluoro-polymer
Compared with Polyurethane

3
Figure 1

Structure of Fluoro-polymer

Fluoro ethylene Segment

Weather ability, durability, chemical resistance
Vinyl Ether Segments
R1=Clarity, gloss, hardness R2=Flexibility, R3=Cross linking site (-OH)

4
Table 1

Bond Energy of Fluoro-Chemicals

and Commodity-Chemicals

Resin C-C Chain KJ/mol C-F. C-H KJ/mol

Fluoro- CF3-CF3 414 F-CF2-CH3 523
Compound CF3-CH3 424 CF3CH2-H 447
Commodity CH3-CH3 379 CH3CH2-H 411

Natural strongest UV energy in the outdoor: 411KJ/mol (290nm)

5
Table 2

Change of molecular weight on

Fluoro-polymer and Polyurethane resins

Over sea
Binder Resins
Exposure Fluoro-
Polyurethane
polymer
Exposed period
0 3 0 3
(years)
Molecular weight
9,000 8,400 3,600 600
(Mn)

6
FLUORO-POLYMER TOPCOAT OF SYSTEM
・ General Performance
・ Corrosion Protective Performance of Fluoro-polymer Coatings
・ Weather-ability of Fluoro-polymer Coating

7
Table 3

Coating systems used for the outdoor

exposure test

Topcoat Polyurethane Chlorinated Alkyd

System Fluoro-polymer rubber

Substrate steel panel

Primer zinc-rich primer Wash primer

Undercoat Epoxy resin Epoxy resin Chlorinated Anti corrosive

rubber Undercoating

Intermediate Coat Epoxy resin Epoxy resin Chlorinated Alkyd

rubber

Top coat Fluoro-polymer Polyurethane Chlorinated Alkyd

rubber

Total Film 255 255 245 170

thickness(μｍ)

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Table 4

Performance of Fluoro-polymer
Topcoats in coating systems

Test items Test contents Test result

Gloss 60° 80%
Adhesion 2mm cross cut 25/25
Bend 10mm No defect
Shock resistance Du Pont 300gx50cmx1/2in. Excellent
Hardness Pencil hardness H
5%NaOH Soln./six months. ＞6 months
Chemical resistance
5%HCl Soln./six months. ＞6 months
3%NaCl Immersion ＞12 months
Protective performance
Salt Spray/1000h. ＞10,000 hrs.
Sunshine Weather Meter,
Weathering performance Gloss Retention 90%
4000h.

Test specimen: OZRP/75μm + Epoxy/120μm +Fluoro-polymer/55μm

9
Figure 2

Impedance reduction for each Top

coat system after accelerated testing

b) Sunshine WM 1000 hrs

a) Sunshine WM 2000 hrs
+ Salt spray test 1000 hrs
10
Figure 3

SEM observation of surface

for each coating system
Fluoro-polymer Polyurethane Chlorinated rubber Alkyd

Initial surface: 0 hrs

Exposure surface with SWM after 2000hrs 11

Table 5

Time period ratio of corrosion

protection for each coating system

Top coat tan θ from slope in The period ratio of

system Fig 2 a) Protection
Fluoro-
5.7 2.2
polymer
Polyurethane 2.6 1.0
Chlorinated
1.8 0.75
Rubber
Alkyd 1.3 0.5
12
Figure 4,5

Film resistance
after outdoor Exposure test (Miyakojima)
Film Resistance (W･cm2)

108
107
106
105
104

0 1 2 3 4
Exposure Time (Years)
:Fluoro-polymer System
: Polyurethane System
:Chlorinated Rubber System
13
 Measurements of film consumption
（by observing the section of 15y exposure samples at Hiroshima）

Light proof

Ｌｉｈｔ ｅｘｐｏｓｕｒe Ｐａｒｔｓ

Cutting process

Observation of
The cross section

Exposure specimen 10Ｘ30 cm

Figure 6

Consumption of topcoat in film thickness

after15 year exposure (Cross section)

a) Fluoro-polymer b) Polyurethane
Light sealed label

Film
Film
consumption:
consumption:
22～28μm
A B 0～1.1μm D
C /15 years
/15 years

← 1/20 shrinking →
A, B, C, D area were for Imaging IR measurement as below (Figure 7)

15
Figure 7

Isocyanates retention of each cross section of

coats about light seal or irradiated surface area
Light sealed area Light irradiated area
A: Fluoro-polymer B: Fluoro-polyme
Line of
Top coat / air surface
Red Color indicates
good retention of
isocyanate
40µm
C: Polyurethane D: Polyurethane
Line of
Top coat / air surface
Yellow Color indicates
poor retention of
isocyanate
16
Figure 8

Change in Amide ll Retention (QUV)

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 Summary of degradation phenomena
for Fluoro-polymer vs. Polyurethane

Issue Unit Exposure Fluoro-polymer Polyurethane

Mol. weight ― 3 years 9000 → 8400 3600 → 600
Consumption of DFT μｍ 0.1 22
15 years
cross-linking ― no change large degradation
Retention of cross- ％ 5 years 75% 25%
linking
adhesiveness ％ Miyako 93% 83%
Impedance Ω/cm2 4 years EXP10*7 EXP10*6
SWM
Impedance slopes 2000 hrs
1 1/2.5

Gloss retention ％ 20 > 20% / 15years < 20% / 2years

Years
Rate at marine
Chalking number environment 10 / 20years 0 / 10years
18
Figure 9

TRACK RECORDS OF USE IN THE FIELD

Outdoor Exposure Test1

of Marine test station
in service since 1983

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Figure 10,11

Gloss retention and Chalking Rate of

Outdoor Exposure Test1

100 10
Gloss Retention (%)

80 8

60 6

Chalking
40 4
20 2
0 0
0 5 10 15 20 0 5 10 15 20
Exposure Time (years) Exposure Time (year)
Fluoro-polymer Coating Fluoro-polymer Coating
Polyurethane Coating Polyurethane Coating
20
Table 6, Figure 12:

Tokiwa Bridge after 20 years, Photo: in 2008

Old film was Chlorinated Rubber 8 years past

Good Light Refraction

on the Surface

Gloss retention and color change after 20 years

20 years after Wiped with wet cloth Un wiped
Gloss retention (%) 100 92
Color difference ΔE 2.8 3.2 21
Figure 13

Some of applications for bridges

Hirado Bridge (10 years)

Akashi Straits Bridge (12 years) Gateway Bridge; Nashville, TN

22
Longest Suspension Bridge in the world
Table 8, Figure 14 Advanced Application

A new coating system

applied to structures
Coating
Name of coating DFT
system
Organic or Inorganic
Primer 75μm
zinc rich primer
Intermediat
Epoxy 120μm
e coat
Top coat Fluoro-polymer 55μm

“The Tokyo Sky Tree®”

The advantage of using the fluoro-polymer topcoat
・ the workability is saving the number of coats
・ the weather-ability is longer and longer
which means dry film thickness of 55 μm per a coat.

Ref： N. Hori, A. Okuda, M. Keii “ The construction and protection

coating technology for outer surface of The Tokyo Sky Tree®” Figure 14: “The Tokyo Sky Tree®” rendering
Rust Prevention and Control Japan vol.54,No.2, pp9-17, (2010) by TOBU RAILWAY Co.,LTD(2) &
TOBU TOWER SKY TREE Co. ,LTD. 23
 FURTHER DEVELOPMENTS
Environmental approach
An important area is to reduce VOC.
・ A weak solvent type consisting of mineral spirits
for repainting top coat system,
that has a small MIR VOC value
(i.e. generation of g-ozone/1g solution)
・ Water borne paint of fluoro-polymer
with hardener as 2K system
as protection top coat for many steel structures.
・LCC consideration
Workability for saving cost
High durability and cost performances
as total coating system

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 SUMMARY
 The fluoro-polymer topcoat was extremely superior to other topcoats
such as polyurethane, chlorinated rubber and alkyd in weather-ability.
 The decrease of film thickness by surface degradation after 18 years
outdoor exposure was surprisingly less one micron.
 Protective performance of fluoro-polymer topcoat system was
evaluated at a marine testing station. Degradation, such as rust,
blistering, and chalking, were not obvious after 20 years.
 The protective performance was affected by the weather-ability of top
coating. Fluoro-polymer coating was excellent in weather-ability and its
top coated coating system showed much better protective
performance compared with polyurethane top coated coating system.
 Life cycle cost is expected to be reduced by adopting the fluoro-
polymer. We suggest we should focus on the importance of top coat
durability in coating systems. 25