SINTEF REPORT

TITLE

Coating systems for long lifetime:
Thermally Sprayed Duplex Systems

Final report

AUTHOR(S)
Ole ystein Knudsen
CLIENT(S)
SINTEF Materials Technology
Corrosion, J oining,
and Surface Technology

Address: NO-7465 Trondheim
NORWAY
Location: Richard Birkelands vei 3A
Telephone: +47 73 59 27 80
Fax: +47 73 59 68 92

Enterprise No.: NO 948 007 029 MVA

Spray Service, Statoil, Petrobras, Esso, Jotun, Carboline, International, Hempel,
R&M, Bjrge Norcoat, NSL Gruppen, Rotorkontroll, Vegdirektoratet,
Jernbaneverket
REPORT NO. CLASSIFICATION CLIENTS REF.
SINTEF A14189 Open Stein Paulsen
CLASS. THIS PAGE ISBN PROJ ECT NO. NO. OF PAGES/APPENDICES
Open 978-82-14-04760-8 243908 40
ELECTRONIC FILE CODE PROJ ECT MANAGER (NAME, SIGN.) CHECKED BY (NAME, SIGN.)
I:\2400\prosjekt\243908\adm\notat_rapport\FinalReport
OK040625.doc
Ole ystein Knudsen Astrid Bjrgum
FILE CODE DATE APPROVED BY (NAME, POSITION, SIGN.)
2010-01-20 Brd Tveiten, Research Director
ABSTRACT

Thermally sprayed zinc or aluminium in combination with organic coatings, TS Duplex Coating
Systems, is a common method used for corrosion protection of bridges, ships and oil- and gas
installations. These systems are supposed to provide a long lifetime (>20 years), and with that, be both
cost effective and environment friendly. However, so far the potential market for these protective
systems has not been reached. Potential users of such systems may have become sceptical because of
some reported cases with rapid degradation. Particularly for systems were TS aluminium has been used,
there have been problems. The main goals of this project have been to solve these problems, and to find
an optimal protective system, which combines thermally sprayed metals with paint, and still have a
relatively low price.


KEYWORDS ENGLISH NORWEGIAN
GROUP 1 Materials technology Materialteknologi
GROUP 2 Corrosion Korrosjon
SELECTED BY AUTHOR Duplex coatings Dupleks belegg

Thermally sprayed metal Termisk sprytet metal

Organic coating Organisk belegg

2

TABLE OF CONTENTS
Preface .........................................................................................................................................................3
List of reports from the project..................................................................................................................4
Publications and presentations from the project......................................................................................5
1 Summary and conclusions..................................................................................................................6
2 Background ......................................................................................................................................9
3 Approach ....................................................................................................................................10
4 State of the art ...................................................................................................................................11
4.1 Experiences with TSA duplex coatings ......................................................................................11
4.1.1 Sleipner Riser Platform......................................................................................................11
4.1.2 sgard A............................................................................................................................12
4.1.3 Risers at Jotun B................................................................................................................12
4.1.4 Nidelv bridge in Trondheim..............................................................................................13
4.1.5 Troms bridge....................................................................................................................13
4.2 Experiences with TSZ duplex coatings.......................................................................................14
4.2.1 Road bridges......................................................................................................................14
4.3 Failure or success what are the determining factors? ..............................................................14
5 Rapid degradation of TSA duplex coatings the mechanism......................................................16
5.1 Galvanic corrosion between duplex coating and bare steel ........................................................16
5.2 Properties of the thermally sprayed metal ..................................................................................16
5.3 TSA with sealer ..........................................................................................................................17
5.4 Recommendations for TS duplex coatings based on the degradation mechanism.....................18
6 Sealers ....................................................................................................................................22
6.1 Sealer penetration .......................................................................................................................22
6.1.1 Recommendations regarding sealers .................................................................................23
7 Testing of TS duplex coatings ..........................................................................................................24
7.1 Phase 1 Effect of TSM, organic coating and structure of TSM...............................................24
7.1.1 Effect of composition and structure of TSM.....................................................................24
7.1.2 Effect of organic coating ...................................................................................................24
7.1.3 Reference systems .............................................................................................................25
7.2 Phase 2 TSZ duplex coatings...................................................................................................28
7.2.1 Test results.........................................................................................................................28
7.2.2 Effect of paint film thickness.............................................................................................29
7.2.3 Cracking and flaking .........................................................................................................30
7.2.4 Low VOC coatings ............................................................................................................31
7.3 Properties of zinc coatings..........................................................................................................31
7.3.1 General experiences with zinc coatings.............................................................................31
7.3.2 Risk for zinc steel polarity reversal ...................................................................................32
7.3.3 Corrosion of zinc coatings exposed above 70C...............................................................32
8 TS Duplex systems expected lifetime............................................................................................33
9 Maintenance of duplex coatings.......................................................................................................34
9.1 Degradation of topcoat only no corrosion of TSA...................................................................34
9.2 Corroded TSA.............................................................................................................................34
9.2.1 State of TSA after degradation ..........................................................................................34
9.2.2 Maintenance without removing the TSA...........................................................................34
9.2.3 Maintenance by removing the TSA...................................................................................35
9.3 Repair systems for TSA duplex coating .....................................................................................35
9.3.1 Experiences and test results...............................................................................................35
9.3.2 Recommendations .............................................................................................................37
9.4 Maintenance of TSZ duplex coatings .........................................................................................37
10 References ....................................................................................................................................39

3

List of reports from the project:

1. O.. Knudsen, T.G. Eggen: "Duplex coating systems - State of art", SINTEF report
STF24 F01328, Confidential (2001)
2. H. Vold: "Coating systems for long lifetime: Thermal sprayed duplex systems - Field
exposure in sea water splash zone. DnV report BGN-R2701576, Restricted (2002)
3. J.E. Scheie, I. Lien: Coating systems for long lifetime: Thermal sprayed duplex systems
Testing of 12 sealers on TSA and TSZ win accordance to ISO 7253, TI Report no. 410-02-
0019, Confidential (2002)
4. B.S. Tanem, O.. Knudsen: Penetration of sealer at the surface of thermally sprayed
metal, SINTEF report STF24 F02248, Confidential (2002)
5. G. Soleng, O.. Knudsen: Corrosion properties of various thermally sprayed metals,
SINTEF Report STF24 F02334, Confidential (2002)
6. O.. Knudsen: Mechanism for degradation of thermally sprayed duplex coatings,
SINTEF Report STF24 F02331, Confidential (2002)
7. A. Mikkelsen, O.. Knudsen: Penetration of organic coating into TSM on samples
prepared at R&M in May, Memo, Confidential (2002)
8. O.. Knudsen: "Duplex coatings test results from phase 1". SINTEF report STF24
F03316, Confidential (2003).
9. O.. Knudsen: "Maintenance of thermally sprayed duplex coatings", SINTEF report
STF24 F03256 (2003).
10. B. Schei: "Coating systems for long lifetime: TS duplex systems Field testing status
report", DNV report no BGN-R2703356 (2003)
11. O.. Knudsen: Transport of ions through rubber coating, SINTEF report STF24 F03344
(2003)
12. K. Kaltenborn and J. Scheie: "Duplex coating systems for long life time. Testing in
accordance with NORSOK M 501 rev. 4 cyclic test for 4200 hours" Report no. 410-03-
0226 Mt01 Rev.1 (2004)
13. K. Kaltenborn and J. Scheie: "Duplex coating systems for long life time. Testing in
accordance with NORSOK M 501 rev. 4 cyclic test for 4200 hours" Report no. 410-03-
0019 Mt01 Rev.3 (2004)
14. O.. Knudsen: "Duplex coatings Test results from phase 2: TSZ systems", SINTEF
report STF24 F04256 (2004)
15. O.. Knudsen: "Coating systems for long lifetime: Thermally Sprayed Duplex Systems.
Final report", SINTEF report STF24 F04258, Confidential (2004)
16. Q. Dong: Coating systems for long lifetime: TS duplex systems, DNV report no 2008-
5320 (2008)

4

Publications and presentations from the project

O.. Knudsen: Bruk av termisk sprytet aluminium kombinert med organisk belegg for
redusere vedlikeholdskostnadene offshore. Hvorfor har dette gtt galt?, Materialdagen, Forus, 27
October 2004.

O.. Knudsen: "Metallisering/termisk spryting. Hvorfor ser vi tidlig nedbrytning av malt TSA?",
Overflatedagene 2004.

J.E. Scheie: "Metallisering/termisk spryting. Hva ser vi p lab av TSA og TSZ?",
Overflatedagene 2004.

O.. Knudsen, T. Rssland: "Rapid Degradation of Painted TSA", Paper no. 04023,
CORROSION/2004, 28/3 1/4 2004, New Orleans, NACE Houston TX

O.. Knudsen: "Hva kan vi forvente av duplex-systemer?" Presentation at Korrosjonsteknisk
Forening, Bergen. 6 May 2003.

R. Klinge: "Hva er riktig korrosjonsbeskyttelse i dag?", Presentation at Brukonferansen, Oslo, 30-
31 October 2002.

O.. Knudsen: Forskning innen organiske belegg ved SINTEF. Presentation at the annual
meeting in Norsk Maling- og Lakkteknisk Forening, Voss, 25 October, 2002.

O.. Knudsen: Fra den korrosjonstekniske forskningsfronten. Presentation at Korrosjonsteknisk
Forening, Haugesund, 19 September 2002



5

Preface
This project called "Coating systems for long lifetime: Thermally Sprayed Duplex Systems" has
been a joint industry project, financed by the Norwegian Research Council and a consortium of
Norwegian and international companies. Spray Service AS has been contract partner. The project
was initiated by "Forum for Overflate- og Beleggteknologi", and has lasted from 2001 to 2004.
The project is a continuation of a project with the same title running at TI and SINTEF Marintek
1997 2000.

The project has had a total budget of 4.43 MNOK, where 1.77 MNOK has been spent by the
industry partners and 2.66 MNOK by the R&D performing companies. The Norwegian Research
Council has supported the project by totally 1.27 MNOK.

The industry consortium has consisted of Spray Service, Statoil, Esso, Petrobras, Jotun, Carboline,
International, Hempel, R&M, Bjrge Norcoat, NSL Gruppen, Rotorkontroll, The Public Roads
Administration and Jernbaneverket. Their contribution by finances, knowledge and experiences
are gratefully acknowledged.

The R&D has been performed jointly by: SINTEF, The National Institute of Technology and Det
Norske Veritas. I would like to thank Jan Scheie, Isabel Lien, Kristian Kaltenborn at TI and Helge
Wold and Birgith Schei at DNV for the cooperation. I would also like to thank all colleagues at
SINTEF who have contributed to the project: Sten B. Axelsen (now Statoil), Tor Gunnar Eggen,
Gro Soleng (now Optirock), Andre Mikkelsen, Erling Abusland and Bjrn Steinar Tanem.

Some contributions to the project deserve special mentioning. I would like to thank my colleague
Trond Rogne for taking the initiative to the project, for his contributions during the application
process and later during the course of the project. Stein Paulsen at Spray Service has been contract
partner for the project, and has taken care of the formal contact with the Research Council. Thank
you for volunteering for the job and for good cooperation. Finally, special thanks go to Reidar
Klinge. He has been a careful reviewer of all written deliveries from the project, in addition to
generously sharing his long experience regarding thermally sprayed duplex coatings. All these
contributions have been of great value to the project and are gratefully acknowledged.




Trondheim 20 January, 2010


Ole ystein Knudsen

6

1 Summary and conclusions
Thermally sprayed zinc (TSZ) or aluminium (TSA) in combination with organic coatings,
Thermally Sprayed (TS) Duplex Coating Systems, is a common method used for corrosion
protection of bridges, ships and oil- and gas installations. These systems are supposed to provide a
long lifetime (>20 years), and with that, be both cost effective and environment friendly.
However, so far the potential market for these protective systems has not been reached. Potential
users of such systems may have become sceptical because of some reported cases with rapid
degradation. Particularly for systems were TS aluminium has been used, there have been
problems. The main objectives with this project has been to solve these problems, and to find an
optimal protective system, which combines thermally sprayed metals with paint, and still have a
relatively low price.

In the attempt to reach this objective the following more technical objectives were defined:
1. To find the corrosion mechanisms causing problems on painted TSA.
2. To find optimal sealers for thermally sprayed coats exposed in seawater or in marine
atmosphere.
3. To determine which paint systems that are suitable for use on TS coats.
4. To optimise application parameters for TSA.
5. To optimise the application of, and the alloying constituent of aluminium and zinc in the
new alloys.

The experiences with TSZ duplex coating systems are very good. The Public Roads
Administration has used TSZ duplex coating systems for more than 40 years, and has examples of
bridges where the coating has performed excellent during three decades without maintenance.
TSZ duplex coatings have also performed well in various field tests and accelerated tests
performed at SINTEF, TI and DnV.

With TSA duplex coating systems the experiences are mixed. Statoil has installations where such
coating systems have degraded severely after only a few years of exposure. However, there are
also examples where TSA duplex coating systems have performed well. The Public Roads
Administration has good experiences with their TSA duplex systems in atmosphere. The reason
may be choice of different organic coatings, where physically drying coatings have been used.
Compared to offshore, the environment may also be somewhat less corrosive, though this has not
been investigated. The performance in various test projects at SINTEF, TI and DnV has also
varied from acceptable to very bad.

Evidently, the degradation problems with TS duplex coating systems are limited to TSA duplex
coatings. The degradation mechanism was investigated in a laboratory study.

When duplex coatings are galvanically coupled to bare steel, a galvanic corrosion mechanism of
the thermally sprayed metal starts. Cathodic oxygen reduction takes place at the bare steel, while
anodic corrosion of the thermally sprayed metal takes place under the organic coating. In chloride
containing environments, like in marine atmosphere, the chloride ions migrate in under the
organic coating to balance the positive charge on the metal ions. So far the degradation
mechanism is the same for TSA and TSZ duplex coatings. For TSA duplex coatings, aluminium
chloride is formed under the organic coating as the aluminium corrodes. However, aluminium
chloride is highly unstable in the presence of water. The aluminium chloride reacts with water and
forms hydrochloric acid. The electrolyte under the organic coating will therefore be acidic (low
pH). A new cathodic reaction, hydrogen evolution, will then start under the organic coating.
Aluminium is not passive at pH < 4 and will corrode actively.

7


TSZ duplex coatings will not suffer the same rapid degradation. When chlorides migrate in under
the organic coating on TSZ duplex coatings, zinc chloride is formed. Zinc chloride dissolves in
water, but does not acidify the electrolyte, and hydrochloric acid is not formed. Cathodic
hydrogen evolution under the organic coating will therefore not start, and the degradation of the
TSZ duplex coating is not accelerated.

In the mechanism outlined in this project, we have described a situation where the duplex coating
is galvanically coupled to bare steel. The bare steel may be equipment in stainless steel mounted
in the structure, mechanical damages in the duplex coating exposing the steel substrate or an area
where the duplex coating has corroded away. Other metals that are efficient cathodes, e.g. copper
and copper alloys, will have the same effect. The mechanism is similar to the traditional
mechanism for crevice corrosion and pitting corrosion. Other initiation mechanisms may also
exist.

TSA with only a thin sealer will not be degraded by this mechanism. If the sealer is applied in a
very thin coat, like it is supposed to, it will not be able to hold an aggressive electrolyte at the
TSA surface. No crevice will be formed and acidification will probably never take place.
Investigation of samples exposed offshore showed that aluminium oxide had been formed on top
of the sealer, which means that aluminium ions probably penetrate the sealer. No significant
corrosion of the TSA was found.

Based on these findings the project has recommended that TSA should not be painted with thick
organic coatings. Due to this recommendation the activities on optimising the application
parameters and studies of TS alloys with a high content of aluminium was stopped or not started.

TS coatings have a rough surface structure with pores and narrow crevices. In order to fill these
pores a sealer is usually applied. Incomplete penetration of the organic coating will lead to pores
in the interface between the thermally sprayed metal (TSM) and the organic coating where
corrosion may initiate. To improve the penetration into the TSM surface structure a thin sealer
with low viscosity should be applied. An investigation to evaluate the penetration of various
sealer products into porous thermally sprayed metal coatings was therefore started, in order to
help the selection of sealers to be used later in the project in combination with thicker organic
coatings.

The clear unpigmented sealers had the best penetrating properties. However, good penetration was
also observed for some of the pigmented sealers. Flake shaped pigments and large pigment
particles in the sealer seemed to inhibit the penetration. Generic type of the sealer did not seem to
be the most important factor for pore formation. Good penetration was also found with
waterborne sealers. Proper dilution of the sealer before application to decrease the viscosity seems
to be important to improve the penetrating properties. Sealers applied with high film thickness had
more pores than the ones applied in a thin coat. Too thin film will give insufficient amount of
sealer to fill the larger pores in the TSM surface.

Testing of TS duplex systems has been a large activity in the project. The testing was conducted
in two phases. Phase 1 was started before we found the degradation mechanism for TSA duplex
coatings, so a large number of TSA duplex systems were tested. In Phase 2 we focused on TSZ
duplex systems. Coatings with zinc rich primers have been used as reference coating systems.

The purpose with the testing in Phase 1 was to study the effect of type of TSM, type of organic
coating and effect of porous TSM on corrosion properties of the coatings. The results showed that
duplex coatings with TSZ performed well. None of the TSZ duplex coatings had more than 1 mm

8

scribe creep, neither in the NORSOK test nor in the field test. All the duplex coatings with
thermally sprayed aluminium (both AlMg5 and 99.5% aluminium) showed severe degradati
particularly in the 5 years field test. Porosity of the TSA does not seem to affect the result
significantly.

on,
here was little difference between the TSZ duplex coatings, and most of them performed well,
ere
ne duplex coating with TS ZnAl15 was tested and performed equally well as the pure TSZ

nd
ater borne and high solid coatings gave good performance. The experimental results so far

hermally sprayed zinc has been avoided on offshore installations, because in the highly corrosive
f
s to
ted
the
ue to the severe degradation of TSA duplex coatings, developing efficient maintenance
lex
oat
n
nc
he
entire structure to Sa 2 and application of a new coating system will probably give the best
T
both in the field test and in the NORSOK test. In Phase 2 of the project seven different duplex
coating systems were prepared with TSZ and various organic coatings. The coating suppliers w
asked to select organic coatings that will comply with future environmental legislation, e.g. high
solid or waterborne products. The test results showed very little corrosion creep from scribe for
the TSZ duplex samples. None of the TSZ duplex coatings showed any corrosion creep on the
steel, and corrosion creep on the zinc was less than 1 mm. Hence, the results indicate that TSZ
duplex coatings will have long lifetime. One of the TSZ duplex coatings showed general
degradation in the field test, due to initiation of corrosion on the zinc in random spots.

O
duplex coatings. Hence, TS ZnAl15 duplex coatings should be regarded as equally resistant to
degradation as TSZ duplex coatings. ZnAl15 has some advantages with respect to application a
will in most cases be economically beneficial to the pure TSZ.

W
indicate that TSZ duplex coatings are less susceptible to degradation by corrosion than coating
systems based on zinc rich primers.

T
environment zinc coatings usually only last for 5-10 years. Therefore only TSA have been used
for metallizing offshore structures. TSZ duplex coatings therefore represent a new generic type o
coatings on offshore installations. Painted TSZ will have different properties from bare TSZ, but
some questions have been put forward regarding the use of TSZ duplex coatings offshore. In
duplex coatings the zinc will be coated with an organic coating. As long as the coating adhere
the zinc there can be no corrosion of the zinc. All results from this project indicate very low
degradation rates for TSZ duplex coatings. Offshore TS duplex coatings may be exposed to
temperatures up to 120C. However, no reports of rapid degradation of TSZ coatings at eleva
temperatures have been found. On the contrary, experimental results and practical experiences
indicate that zinc coatings can be used without any problems up to 200C. Polarity reversal
between zinc and steel has been reported in some instances, where zinc becomes cathode and
steel anode, i.e. causing corrosion of the steel. This has only been observed in water above 65C
with low chloride concentrations. Hence, there is no risk for polarity reversal in corrosive
environments or below 65C

D
procedures is important. A study of various options for maintenance, focusing on TSA dup
coatings, was therefore conducted. The main conclusions from this study were: If only the topc
is degraded, it is important not to damage the rest of the organic coating during the maintenance.
Damages in the organic coating, exposing bare TSA may initiate rapid degradation. Gentle
cleaning with water and soap and application of a new topcoat will give the best result. Whe
corrosion of the TSA has started, but not propagated far, local cleaning of corroded areas and
application of a repair system will probably temporarily stop or slow down the degradation. Zi
rich primers may be applied on TSA. To remove the organic coating from the TSA, leaving the
TSA more or less intact on the structure is in practice difficult. Degraded TSA duplex coatings
often give a mixed surface consisting of intact coating, bare TSA and bare steel. Blast cleaning t

9

result and should be considered. If that is not an option, bare steel and TSA should be primed with
a zinc rich primer. An epoxy mastic or equivalent barrier coat may be applied on the primer,
before the entire structure is coated with a topcoat. Applying the barrier coat on the entire
structure may decrease the chance for initiation of new degradation.

2 Background
ms, consisting of TSM and a full organic coating system, have been used
bridges in Norway. For offshore installations
n

ngs and their combination with paints.
esults from the pre-project Coating System for long lifetime: TS Duplex Systems, initiated by
isk of
, salt
this project has been to develop new procedures and protective systems for corrosion
rotection in aggressive atmosphere. For the owners of steel structures this means that the
e in
ese goals it is mandatory to develop an optimal protective system, which combines
ermally sprayed aluminium, zinc or alloys of these metals with sealers and paint. The objective
four coats of alkyd or
lkyd/chlorinated rubber paints have been frequently used. During the last decade epoxymastic /
gs with long lifetime, the following more technical
ub-goals were defined:
ealers for thermally sprayed coats exposed in marine atmosphere.
.
and zinc in the
Duplex coating syste
mainly for protecting offshore installations and road
duplex systems with TSA have been applied. On road bridges duplex systems with TSZ has bee
used most frequently, but TSA systems have also been applied on a few bridges. The experiences
with TSZ duplex coating systems are very good. The Public Roads Administration has used TSZ
duplex coating systems for more than 40 years, and has examples of bridges where the coating has
performed excellent for more than three decades without maintenance. Within the oil- and gas
industry severe problems have occurred on painted TSA. In fact the paint has reduced the lifetime
of the protective system due to high local corrosion rates.

Previous projects have investigated thermally sprayed coati
R
National Institute of Technology, Norway (TI) and MARINTEKs Laboratory for Material
Technology, showed that some Duplex Systems with TSZ and paint performed well in the
accelerated tests. However, good results were not achieved with TSA. The results showed r
blistering and corrosion of aluminium when these systems are used in seawater or in marine
spray containing atmosphere. The results did also reveal that these systems are vulnerable to
mechanical damages. High underfilm corrosion rates around the scribe in the coatings were
observed.

The aim of
p
protection will be carried out cost effective and with less environmental impact. For material
suppliers this means better understanding of the corrosion process and the paint performanc
TS duplex systems. For applicators of the coatings the project will provide better application
procedures.

To achieve th
th
was to reach a lifetime (with lifetime of the duplex systems we understand the time to the first
necessary maintenance of the paint) of the system of more than 20 years.

In Norway, road bridges thermally sprayed with zinc in combination with
a
polyurethane coatings have also been used.

In order to reach the goal of TS duplex coatin
s
1. To find the corrosion mechanisms causing problems on painted TSA.
2. To find optimal s
3. To determine which paint systems that are suitable for use on TS coats
4. To optimise application parameters for TSA.
5. To optimise the application of, and the alloying constituent of aluminium
new alloys.

10

3 Approach
In order to fulfil the objectives of the project the following research activities have been carried
out:

State-of-Art: A study of previous experiences with TS duplex coatings on various installations
and test results. Motivation: Collect experiences and get an overview of degradation problems
with TS dupelx coatings.

Sealers: An investigation of various sealers and their ability to penetrate into narrow crevices
found in the surface of TS coatings. Motivation: Pores at the TSM/coating interface may serve as
initiation points for corrosion. Improving sealer penetration may therefore decrease coating
degradation by corrosion.

Corrosion of various types of thermally sprayed metal: The corrosion rate of thermally
sprayed aluminium, zinc and alloys of these were investigated. Motivation: By using TSM with
high corrosion resistance the corrosion resistance of the TS duplex coating could probably be
improved.

Degradation mechanisms: The mechanism for rapid degradation of TSA duplex coatings was
found. Motivation: Rapid degradation of TSA duplex coatings have been observed in some cases,
which has decreased the confidence in duplex coatings. Finding the degradation mechanism was
important in order to know how to avoid the degradation.

Testing: A number of TS duplex coating systems have been tested in the NORSOK test and a
field test, and compared to coating systems with zinc rich primers. Motivation: Understanding
how duplex coating systems should be composed in order to obtain long lifetime.

Maintenance: Give recommendations for maintenance of TS duplex coatings. Motivation:
Decreasing maintenance costs by using the optimal cleaning method and applying the optimal
repair coating system.


11

4 State of the art

plex coatings have also been studied in research projects. The performance of such coating
ystems have not always been as good as expected, and this has decreased the confidence in this
thorough review of these experiences was given in a State-of-Art report (Knudsen and Eggen,
duplex coatings
ed
nce. In order to achieve this a duplex coating system consisting of TSA and an organic
oating was chosen. The specification for the coating system was:
olyurethane topcoat 80 m
e
om the
SA lift the organic coating and blisters are formed. The blisters are particularly numerous around
h is
eople in Statoil have suggested that the degradation of the coating is connected to adhesion loss
between TSA and the steel substrate. In order to obtain proper adhesion between TSA and steel you
need:
A proper roughness and a sharp profile formed during grit blasting
During metal spraying the metal droplets must penetrate into the profile
The impact angle both during grit blasting and metal spraying is important in order to obtain this. In
both cases a high impact angle gives the best result. On complex structures it will be difficult to have
the optimal impact angle in all areas, which may result in adhesion problems and corrosion. The
distance between the spray gun and the steel substrate is also critical.

If this is correct, the coating degradation observed is not connected to the organic coating system, but
to the thermal spraying and/or the grit blasting.

A number of offshore installations and road bridges are protected by TS duplex coating systems.
TS du
s
type of protective coatings. The objective with this activity in the project was to find common
denominators for the successful cases on one hand and the failures on the other.

A
2002). A collection of field experiences with duplex coating systems is given in the following
sections, followed by a discussion of similarities and differences.
4.1 Experiences with TSA
4.1.1 Sleipner Riser Platform
The Sleipner Riser Platform was put in service in 1992. The platform was built with a design life of
50 years. Statoil wished to have a corrosion protection system on the platform with a minimum ne
for maintena
c

TSA, arc spray AlMg5 200 m
Epoxy primer 50 m
Epoxymastic 200 m
P

After seven years in service, Statoil was experiencing severe degradation of the coating system. Th
coating system had started to develop blisters after relatively short time. Corrosion products fr
T
edges, corners and near details in stainless steel. A white salt is found under intact blisters, whic
assumed to be aluminium hydroxide. Pictures of coating with degradation are shown in Figure 1.

P

12




Figure 1: Coating degradation of TSA duplex syste
ainless st nected to the st
m at Sleipner Riser Platform.
ructure.
poxy tiecoat 20 m
ll was installed in 1999 and was in excellent condition after three years exposure. However,
of the coating system.
vel
r coating was approximately
2 mm thick. Above this level, a coating consisting of TSA/polyester duplex coating was applied
polyester duplex coating and a TSA/rubber duplex
oating. The production at the Jotun field started in 1999.

The risers were inspected during the summer 2003 and severe degradation of the duplex coatings
was reported. In addition, subsequent corrosion of the risers had resulted in a material loss of up
to 5-6 mm wall thickness. The degradation probably started in the TSA polyester coating, and
corrosion of the TSA later spread under the rubber coating as well. The corrosion products caused
the polyester coating to crack, whereas the thick and somewhat elastic rubber coating developed
Degradation near st eel con
4.1.2 sgard A
On the sgard A platform a duplex coating system has been used on a wall protecting one of the
decks from wind and sea waves. The coating system is as follows:

TSA, arc spray Al 99.5 200 m
E
Fluoropolymer topcoat 80 m

The wa
three years is too short time toconclude anything about the performance
4.1.3 Risers at Jotun B
Two risers at Jotun B were coated with TSA duplex coatings in the splash zone. From
approximately 4 meters below the sea level and up to approximately 6-meters above the sea le
the riser were coated with a TSA rubber duplex coating. The rubbe
1
over a length of 0.5 meter. From here to the platform the risers were coated with the polyester.
Hence, in the splash zone the risers had a TSA/
c

13

very large blisters, filled with corrosion products. The corrosion under the rubber coating had
started at the top of the coating and spread downwards.

Due to the rapid coating degradation and severe corrosion of the risers, maintenance of the
coatings was performed later during the summer. The TSA duplex coating was removed by blast
cleaning. The rubber coating was cut and peeled of, down to where no corrosion of the TSA could
be found, and the exposed steel was blast cleaned. The intact TSA rubber duplex coating was
left on the riser.
4.1.4 Nidelv bridge in Trondheim
Nidelv bridge was built in 1975/76 and coated with a TSA duplex coating system. The TSA was
applied by arc spraying with a closed nozzle, which gave severe dusting problems. Investigation of
cross sections of the metal coating showed that up to 50% of the coating consisted of dust particles
(aluminium oxide). The organic coating consisted of a wash primer and four coats of
alkyd/chlorinated rubber 1:1 pigmented with zinc-chromate.

In spite of the dusting problems during application, the coating system has performed well during 30
years of exposure near the Trondheim harbour.

.1.5 Troms bridge
bridge is a concrete bridge that was opened to traffic in 1960. Concrete fenders protect the
tructure was
en into the seabed. Already during
construction of the concrete rings, severe degradation of the TSA duplex coating system was found
the tidal zone (Klinge 1976). The following coating system had been applied:
: 225 m
40 m
435 m


ar
ted in Australia. Pores, cracks or
4
Troms
main columns of the bridge from ships passing under the bridge. A new concrete fender s
built in 1975. The concrete fenders are standing on steel piles driv
on the steel piles in

TSA flamesprayed: 160 m
ashprimer: 10 m W
3 coats vinyl tar @ 75 m
Topcoat:
Total:

The piles were coated with this system down to 1 m below lowest tide. The organic coating started to
blister and inside the blisters there was a liquid with pH 3.5 4. The TSA was corroded away inside
the blisters and the steel surface was exposed.

The Association of Metal Sprayers has reported a similar case in Australia, on a bridge ne
Adelaide. Within three weeks of exposure, severe degradation of the vinyl topcoat was found in the
tidal zone. In this case intense galvanic corrosion between the TSA and the bare steel areas was
assumed to cause the degradation. They have also reported about other cases where TSA and TSZ
coatings have failed due to electrical contact to bare steel surfaces also immersed in water.

It is reasonable to assume that the degradation of the coating on the fender structure of the Troms
ridge was caused by a mechanism similar to what was repor b
mechanical damages in the organic coating that lead to exposure of the TSA, may have been the
initiating points for the degradation. When the seawater has access to the TSA, a galvanic cell
between TSA and bare steel is established. Since we have a large bare steel area acting as cathode,
and a small TSA area acting as anode (damages in the organic coating), the corrosion rate of the TSA
will be very high. Severe coating degradation can then be expected within a few days or weeks.


14

4.2 Experiences with TSZ duplex coatings
4.2.1 Road bridges
d
n of the bridge in 1998, after 28 years of service without maintenance, no
y the topcoat was degraded and a new topcoat was
coating system consisted of:
eplaced with alkyd/chlorinated rubber 1:1 mixtures. In 1977 the toxic
ere replaced with harmless zinc phosphate, and the alkyd/chlorinated
lkyd/chlorinated rubber 50 m
bber

Alkyd 50 m
Alkyd 50 m
kyd 50 m
Alkyd 50 m
SZ/TSA, arc or flame 100 m
as
.3 Failure or success what are the determining factors?
.

The Public Roads Administration in Norway has used duplex coating systems with thermally spraye
zinc for protecting bridges extensively since 1965. Many of these bridges are located near/at the coast
and are therefore exposed in a highly corrosive marine environment. Their experiences with duplex
coating systems are very good. E.g. Rombak Bridge was coated with a duplex system in 1970 and
during an inspectio
corrosion was found (Klinge 1999). Onl
recommended for aesthetic reasons. The

TSZ, flame sprayed 100 m
Phosphoric acid wash primer max 10 m
Alkyd, zinc chromate 2 x 50 m
Alkyd, MIO Al flake 2 x 50 m

Several other bridges have been coated with this or similar systems, showing the same good
performance.

In 1972 the alkyd coats were r
zinc chromate pigments w
rubber ratio was changed to 2:1. The duplex coating systems specified until recently were:

System 1
TSZ/TSA, arc or flame 100 m
Phosphoric acid wash primer 10 m
System 2
TSZ/TSA, arc or flame 100 m
Phosphoric acid wash primer 10 m
A
Alkyd/chlorinated ru 50 m
Alkyd/chlorinated rubber 50 m Al
Alkyd/chlorinated rubber 50 m

System 3
T
Epoxy tiecoat/sealer 25-30 m
Epoxymastic 100-125 m
PU or PU/acryllic 60-100 m

In tenders where system 3 with TSA have been one of the possible solutions, this system h
always been offered with a much higher price, and has never been chosen by the Public Roads
Administration.

4
The experiences with TSZ duplex coating systems are very good. The Public Roads
Administration has used TSZ duplex coating systems for more than 30 years, and has examples of
bridges where the coating has performed excellent for this period of time without maintenance

With TSA duplex coating systems the experiences are mixed. Statoil has installations where such
coating systems have degraded severely after only a few years of exposure. However, there are
also examples where TSA duplex coating systems have performed well. The Public Roads

15

Administration has good experiences with their TSA duplex systems, but these have been applied
on two bridges only.
o thick coats or too short overcoating intervals, which may cause solvent
s paint systems

However, the problem is limited to TSA duplex coatings and is therefore probably caused by
properties of the TSA or the TSA/organic coating combination. The following theories for the
poor performance of TSA duplex coating systems were suggested:

1. Unfilled pores or crevices in the TSA surface, which may
- serve as initiation points for corrosion.
- later formation of cracks and pinholes in subseqent paint layers
. Adhesion loss between steel and TSA. 2
3. Application of to
retention and pore formation.
uitable ea 4. Application of uns lers and/or






16

5 Rapid degradation of TSA duplex coatings the mechanism
ct.
eel
Sta stainless steel
ating. Aluminium is a poor
d
ion
ilm is present on the
TSZ duplex coatings were galvanically
onnected to bare steel, as shown in Figure 2. The coating systems are described in Table 1. The
are steel and the duplex coating were glued to a 1 mm thick PVC film and electrically connected
rough an ampere meter. The samples were exposed in a salt spray cabinet, where they were
ontinuously sprayed with synthetic seawater (ASTM D1141-90) for 900 hours. The galvanic
urrent was automatically logged every six hours. Figure 3 shows the galvanic current measured
in the experiment.

Cathodic reduction of oxygen takes place at the bare steel, while anodic dissolution of the
thermally sprayed metal takes place at the duplex sample, as shown in Figure 4. Initially the
galvanic current is very high for the TSZ sample, but as Figure 3 shows, it decreases rapidly. Most
likely this is due to formation of corrosion products or calcareous deposits on the bare steel
surface, decreasing the cathodic reaction rate.

For the TSA sample the current is initially low, but increasing. A passivating oxide film on the
surface probably protects the TSA to some degree. The chlorides in the electrolyte attack the
oxide, and corrosion initiates gradually, which causes the galvanic current to increase. Later, the
galvanic current starts to decrease. As for the TSZ sample, formation of corrosion products or
calcareous deposits most likely explains the reduction.

Figure 3 shows that the galvanic current is about twice as high for the TSA sample as for the TSZ
sample. In Table 2, the galvanic corrosion rate (mm/year laterally from the edge of exposed TSM)
of the thermally sprayed zinc and aluminium is calculated, based on the galvanic current
measured in the experiment. The corrosion rate calculated for the TSA is not significantly
different from the TSZ, when the difference in thickness, density and valence between TSA and
TSZ is included. Hence, there is no significant difference in galvanic corrosion between the two
coating systems. Figure 5 shows pictures of the samples after the test. Contrary to the calculated
galvanic corrosion rates, the pictures show that the TSA duplex coating is much more degraded
than the TSZ duplex coating. Galvanic corrosion cannot explain the rapid degradation of this TSA
duplex sample. The cathodic reaction responsible for the severe degradation of the TSA duplex
coating must therefore take place under the organic coating.

5.2 Properties of the thermally sprayed metal
The samples tested in the galvanic corrosion test were identical, except for the thermally sprayed
metal. The properties of the thermally sprayed metal must therefore be important for the
degradation process.

In order to avoid the rapid degradation of TS duplex coatings in the future, it is important to know
the degradation mechanism. The mechanism study was therefore an important part of the proje
The first hypothesis that was tested was that galvanic corrosion between TSM and bare steel
caused the rapid degradation.
5.1 Galvanic corrosion between duplex coating and bare st
toil has reported that the coating degradation at Sleipner was most severe around
unted into the structure, in galvanic contact with the duplex co mo
cathode, but steel is a reasonably efficient cathode. When steel and aluminium are connecte
together, the steel surface will act as cathode and the aluminium as anode. Galvanic corros
y then start wherever the TSA is exposed, assu ma ming a conducting water f
surface. This was tested in an experiment where TSA and
c
b
th
c
c

17

The galvanic corrosion mechanism described in Figure 4 shows that chlorides are transported
plex coatings, this
umid
that it is relatively stable. Aluminium chloride, on the other hand,
ents. When dry aluminium chloride is added to water a violent

s we found in the previous section. The overall corrosion reaction will be
as there is a supply of water, the corrosion reaction
steel mounted in the structure,
The two upper images in Figure 6 shows cross sections of the left and the right side of the scribe
ealer is shown as a thin bright line on top of the
nalysed.
under the organic coating as the thermally sprayed metal corrodes. For TSA du
means that aluminium chloride (AlCl
3
) should be formed under the organic coating, while for
TSZ duplex coatings zinc chloride (ZnCl
2
) should be formed. Aluminium chloride and zinc
chloride have very different properties. Zinc chloride is a salt that may dissolve in h
environments/water, but beside
is not stable in humid environm
reaction according to Eq. 1 starts, and hydrochloric acid is formed.

(1)

The reaction is more complicated than indicated here, but a detailed description is beyond our
scope. During corrosion of TSA under the organic coating, hydrochloric acid and various
aluminium ydroxyl-chloride complexes are probably formed directly.

Hence, for the TSA duplex coating hydrochloric acid will be formed, acidifying the environment
under the organic coating. The low pH in the electrolyte under the organic coating has two effects.
Firstly, the aluminium will corrode actively, since the protecting aluminium oxide is unstable at
pH below 4. Secondly, hydrogen evolution from the acidic electrolyte will provide an effective
cathodic reaction. Hence, the corrosion of the aluminium does not depend on any external
athodic reaction, a
AlCl
3
+ 3 H
2
O Al(OH)
3
+ 3 HCl
c
according to Eq. 2.

(2)

In the corrosion reaction the aggressive environment is regenerated, represented by aluminium
hloride in the equation above. Hence, as long
2 Al + 6 HCl 2AlCl
3
+ 3 H
2

c
will maintain itself. The mechanism is similar to the traditional mechanism for localized corrosion
of aluminium.

In the mechanism outlined in Figure 4, we have described a situation where the duplex coating is
galvanically coupled to bare steel. The galvanic corrosion initiates rapid degradation caused by
e hydrochloric acid. The bare steel may be equipment in stainless th
mechanical damage in the duplex coating down to the steel or an area where the duplex coating
has corroded away. Other materials that may act as cathodes, e.g. copper and copper alloys, will
have the same effect.

5.3 TSA with sealer
TSA only coated with a thin sealer has given very good corrosion resistance and little coating
degradation, even after very long exposure, as summarised in the introduction. In order to study
corrosion of sealed TSA, a sample exposed offshore for five years was investigated. The sample
was exposed with a scribe, and a cross section was made across the scribe. The cross section was
studied by electron probe micro analysis (EPMA).

The TSA had a thickness of about 200 m. The s
TSA, as indicated in the upper right hand image. The lower images show the distribution of
aluminium and oxygen in the two upper images. Bright contrast indicates a high concentration,
while dark shades indicate low concentration. Black means no signal from the element that is
a

18


The oxygen rich phase on top of the TSA is aluminium oxide. The thickness of the oxide varied
between 20 and 50 m. The oxide is located partly on top of the sealer and partly penetrating it.
Aluminium oxide is also found in the scribe, though much of the oxygen signal in the scribe is
from corrosion products of the steel.

Evidently the degradation mechanism for duplex coatings outlined above will not take place on
sealed TSA. This is probably because the sealer is too thin to hold an aggressive electrolyte at the
etal surface. Chlorides may be washed away by water on the coating surface. Since no
aggressive electrolyte is formed, th
plex coatings is caused
y the chemical properties of aluminium. Galvanic corrosion is an initiation mechanism for the
ating systems that were tested in the galvanic corrosion test.
Code TSM Sealer opcoat
m
e TSA will remain passive.

5.4 Recommendations for TS duplex coatings based on the degradation mechanism
The results from this investigation showed that the degradation of TSA du
b
degradation, but there may be others as well. Based on these findings, we recommend not to use
TSA duplex coatings in corrosive environments in the future. Dupelx coating is here defined as
thermally sprayed metal with thick, protective organic coatings. TSA with a thin sealer only
provides excellent corrosion protection.


able 1: Duplex co T
Barrier coat T
E2 200 m TSA 35 m epoxy 125 m epoxymastic 100 m polysiloxane
M1 100 m TSZ 35 m epoxy 125 m epoxymastic 100 m polysiloxane


Figure 2: Test set-up for duplex coating galvanically coupled to bare steel. The samples were
exposed in a salt spray cabinet for 900 hours. The two duplex coating systems tested are
described in Table 1.

A
Steel
Duplex coating
PVC (1 mm thick)
50 mm
5 mm
Steel
Paint
TSM

19

-200
-100
0
TSZ
-500
-400
-300
C
u
r
r
e
n
t

[

A
]
-600
-700
0 100 200 300 400 500 600 700 800 900
Time [hrs]

Figure 3: Galvanic current between bare steel and TSA duplex coating (A) and TSZ dup
coating (B).
TSA
lex
able 2: Calculation of corrosion rate of the TSA and TSZ based on the current
Sample
m)
Molecu
gh
o
Corrosion
/yr)
T
measurements shown in Figure 3.
Galvanic
current
(A)
TSM
thickness
(m)
width
(m
Density

(g/cm
3
)
wei
(g/m
lar
t
Valence

l)
rate
(mm
TSA 0 250 200 5 2.7 27 3+ 27
TSZ 100 100 50 7.1 65 2+ 30






Figure 4: Galvanic corrosion of TSA duplex coatings in electrical contact with bare steel.
Organic coating
TSA

Steel
Al Al
3+
+ 3 e
-

O
2
+ 2 H
2
O + 4 e
-
4 OH
-

Cl
-

e
-


20


TSA duplex
coating
Bare steel


1 cm

TSZ duplex
coating
Bare steel
Figure 5: Picture of TSZ and TSA duplex coatings galvanically coupled to bare steel, after
38 days of exposure in continuos salt spray. The TSZ duplex coating has protected
approximately 2 cm of the bare steel cathodically. The protected distance is seen as the onset
of red corrosion products. The TSA duplex coating is severely degraded, while the TSZ
duplex coating is in much better condition.

21




Figure 6: Electron microscopy of cross section of sample coated with TSA and sealer
exposed offshore for five years. The upper micrographs show SEM backscatter images of
the left and right side of the scribe in the TSA sample. The other four images show the
distribution of aluminium and oxygen on the left and e of the scribe.



TSA
Steel
Embedding
resin
Sealer
Scribe
TSA
right sid

22

6 Sealers
Proper sealing of the porous surface will likely increase the lifetime of TS duplex coatings.
Corrosion may initate in pores in the TSM surface. Hence a study of the ability of various sealers
to penetrate pores and crevices was performed. The paint suppliers selected or developed new
and TSZ. Cross sections of the sealed TS coatings were then
studied in an optical microscope in order to characterise the penetration. m with this study
was to find effective sealers for later application in duplex coatings.

6.1 Sealer penetration
In this section the penetration of two of the sealers are shown in order to give an impression of the
complexity of the TSM surface and the ability of sealers to fill the structure of the TSM. The
complete study has been reported earlier (B.S. Tanem, O.. Knudsen, 2002).

Figure 7 shows an optical micrographs of sealer 2B, which was a unpigmented epoxy. The dark
line defines the surface of the sealer. The sealer seems to fill out the surface towards TSA in a
very good manner, even where the TSA/sealer interface is rather complex. Figure 7b shows that
there are a few large pores in the sealer, but not all these pores are located at the TSA/sealer
interface. There is a thin layer of sealer between the pore and the TSA and the pore will therefore
probably not affect the corrosion properties of the coating system.

sealers that were applied on TSA
The ai
Steel

a
TSA
Sealer
Sealer
Sealer surface
Large pore
Sealer surface
Embedding resin
b
Embedding resin

Figure 7: Picture in a) shows optical micrograph of Sealer 2B, indicating that the sealer
penetrates the surface towards TSA in a very good manner. There are a few large pores as
shown in b), but some of these pores are located inside the sealer and not at the TSA/sealer
interface.

Cross sections of sealer 3C are shown in Figure 8. The optical micrographs show that the sealer is
only partly able to fill the complex geometry of the TSA. As a result of this, many small and large
pores appear at the TSA/sealer interface, especially where there are many pores in the TSA
surface and where the sealer locally is thick (~100 m). Pigments in the sealer might be partly
responsible for the incomplete penetration.



23

Steel
a
Sealer
TSA
100m
Embedding resin

b
TSA
Small and large
pores at TSA sealer
interface
Pigments
Sealer
20 m
Embedding resin


igure 8: Picture in a) shows optical micrograph of Sealer 3C, identifying F the sealer.
e (8 sealers), waterborne
poxy (2), silicone (1) and vinyl phenoxy copolymer (1). The penetration of the epoxy polyamide
based sealers varied from excellent to poor, which shows that the binder itself is not decisive for
the penetration. Both the waterborne sealers (2C and 2D) gave good penetration, which shows that
good penetration can be obtained with waterborne sealers as well. The silicone and vinyl phenoxy
copolymer based sealers gave pores in this test, but since only one sealer with these binders were
tested, it is difficult to say anything in general about the pore filling properties of these binders. In
general all organic binders have low surface energy, which imply that they wet metallic surfaces
well.

Some of the sealers were clear, some contained filler particles and some were pigmented with
flake shaped pigments. We found that all the clear unpigmented sealers gave very good
penetration and little pores. However, also some of the pigmented sealers gave rather good
penetration. The sealers with large flake shaped igments were among the sealers that gave most
ores. In the microscope we saw that pores were situated behind pigments that blocked complex
etry in the TSM. We therefore conclude that pigmentation is not beneficial for the

ess seen in a microscope will then vary from zero at the peaks in the thermally sprayed
etal to several tens of microns between the peaks. For some of the samples we investigated the
of a sealer to penetrate narrow crevices and complex
eometry in the TSM surface. However, we have not measured the viscosity of the applied sealers
(after dilution). The amount of solvent added before application is reported, but this is probably
not a good parameter for discussing viscosity. The sealers that were least diluted were among the
sealers that gave most pores. This is an indication that proper dilution of the sealer in order to
decrease the viscosity improves the performance with respect to penetration properties.
Pigments are present in the sealer. Small and large pores tend to appear at the TSA/sealer
interface, especially where the TSA surface is complex, as shown in b), or where the sealer
locally is thick (~100 m).
6.1.1 Recommendations regarding sealers
Sealers of four different generic types were tested: Epoxy polyamid
e
p
p
geom
penetrating properties of the sealer. At least large flake shape pigments should be avoided.

A sealer is supposed to be applied in a non-measurable film thickness, according to BS 5493. The
film thickn
m
film thickness was according to this specification, while for others the films were thicker. Sealers
applied in film thickness above 50 m were among the products with most pores. Hence, there
seems to be a correlation between amount of pores and applied film thickness.

The viscosity probably also affect the ability
g

24

7 Testing of TS duplex coatings
The testing in Phase 1 was started before we found the degradation mechanism for TSA duplex
coatings, so a large number of TSA duplex systems were tested. In Phase 2 we focused on TSZ
duplex systems. The overall purpose with the testing has been to find duplex coating systems with
long lifetime expectancy.

7.1 Phase 1 Effect of TSM, organic coating and structure of TSM
The purpose with the testing in Phase 1 was to study the effect of composition and structure of the
metal coating and the generic type of the organic coating on the performance of the duplex
coatings. Coatings with zinc rich primers were used as reference coating systems. The samples
were tested in the NORSOK test (rev. 4) and in a 5 years field test.
o
ne (Al, porous Al, AlMg5, Zn, ZnAl15)
ated rubber (Zn, Al)
the results indicate that the porosity of the TSM is less important than anticipated.
est
y little
mples.
he results clearly demonstrate that TSA should not be painted with thick protective coatings,
igure 10 shows how the various organic coatings performed when applied on TSA. In both tests
ng

7.1.1 Effect of composition and structure of TSM
Figure 9 shows how the various TSMs performed when tested with the same organic coating. Tw
organic coating systems were tested with more than one TSM:

Epoxy polyamide + epoxymastic + polysiloxa
Washprimer + 4 coats of alkyd / chlorin

In the NORSOK test the TSA duplex coatings performed surprisingly well, compared to what was
expected, based on the degradation mechanism described earlier. However, in the field test more
degradation of TSA duplex coatings was found. There was no significant difference between
99.5% Al and AlMg5, and both types of TSM evidently are subject to the same type of
degradation, resulting in give rapid and severe degradation in corrosive environments.

The samples with extra porous TSA did not degrade more than the other TSA duplex coatings.
Hence,

The field test was more discriminating with respect to type of TSM than the NORSOK test.
In the NORSOK test the two best coating systems were both TSZ duplex coatings. The t
indicates that TSZ duplex coatings are superior to TSA duplex coatings. In the field test ver
degradation was found on the TSZ systems. The ZnAl15 coating performed similar to the pure
TSZ. Corrosion creep was less than 1 mm for all TSZ systems. All the TSA systems had much
more degradation, and up to 30 mm around the scribe was severely degraded on some sa

T
confirming the conclusions from the mechanism study. Duplex coatings with TSZ or TS ZnAl15
will give long lifetime, while TSA duplex coatings will degrade rapidly.


7.1.2 Effect of organic coating
F
there were significant differences between the various coatings, but the differences were not
consistent between the two tests.

In the NORSOK test most of the TSA duplex coatings passed the 3 mm average scribe creep
qualification limit. However, in the field test significant degradation was found. Severe blisteri

25

around the scribe was found on all nine TSA duplex coatings shown in the diagram. In addition
NORSOK testing of the coating systems with zinc rich primers.
the NORSOK test are shown in the figure. All the systems have performed
um scribe creep. The

ep from the scribe. Including
listering of the topcoat the degradation of the organic coating spread 4.5 mm from the scribe.
moved, probably due to corrosion

some of the TSA duplex coatings are suffering from general blistering.

7.1.3 Reference systems
igure 11 shows the results from F
Only the results from
reasonably well, and neither of the systems have more than 3 mm maxim
figure shows maximum scribe creep, while NORSOK qualification is based on average scribe
creep. Average scribe creep is given in the report from TI, showing that except for A1, all systems
had less than 1 mm average scribe creep [Kaltenborn 2003]. For system R4 one of the samples
had large scribe creep locally on one of the samples, which explains the large standard deviation
or this sample. System F1 had less than 3 mm average corrosion cre f
b

Very little degradation was found after 5 years exposure in the field test. None of the samples
showed had more than 0.5 mm corrosion creep on the steel outside the scribe. For most of the
amples up to 1 mm of the topcoat/intermediate coat could be re s
of the zinc in the primer. Hence, all the reference systems have performed very well in the field
test.



26


0
2
4
6
8
10
S
c
r
i
b
e

c
r
e
e
p

(
m
m
)
12
14
99.5 Al AlMg5 ZnAl15 TSZ TSA TSZ TSA
porous
NORSOK test
Epoxy +epoxymastic +polysiloxane
4 x alkyd / CR



Figure 9: Effect of Thermally sprayed metal on degradation of duplex coatings. Tw
different organic coatings were tested. The bars show maximum co
scribe (average of the three samples tested).


o
rrosion attack from
12
m
)
0
2
4
6
8
10
99.5 Al AlMg5 ZnAl15 TSZ TSA
porous
TSZ TSA
B
l
i
s
t
e
r
i
n
g

a
r
o
u
n
d

s
c
r
i
b
e

(
m
Field test, 5 years
Epoxy +epoxymastic +polysiloxane
4 x alkyd / CR

27

0
2
4
6
8
10
12
14
B1 B2 C1 C2 D1 D2 E1 E2 R2
S
c
r
i
b
e

c
r
e
e
p

(
m
m
)
NORSOK test


pt for
k
0
5
10
15
20
25
30
B1 B2 C1 C2 D1 D2 E1 E2 R2
B
l
i
s
t
e
r
i
n
g

a
r
o
u
n
d

s
c
r
i
b
e

(
m
m

Figure 10: Effect of type of organic coating on degradation of duplex coating in the
ed).
NORSOK test and five years field test. All coatings were applied on 200 m TSA, exce
R2 where the TSA thickness was only 100 m. The bars show maximum corrosion attac
from scribe (average of the three samples test
)
Field test, 5 years

28


0
1
2
3
4
5
6
A1 A2 R3 R4 R5 R6 F1
S
c
r
i
b
e

c
r
e
e
p

(
m
m
)
NORSOK test


Figure 11: Systems with zinc rich primers. The bars show maximum corrosion attack from
scribe (average of the three samples tested) in the NORSOK test. None of the samples
showed any degradation after one year in the field test.

7.2 Phase 2 TSZ duplex coatings
Due to the risk for rapid degradation of TSA duplex coatings, focus in the project was shifted
from TSA duplex systems to duplex coatings based on TSZ. In phase 2 of the project a set of
duplex coated samples was prepared with TSZ and various organic coatings. The coating
suppliers were asked to select organic coatings that will comply with future environmental
legislation, e.g. high solid or waterborne products. Test results from laboratory testing (NORSOK
M-501, Kaltenborn and Scheie 2004) and one year field exposure have been reported (O..
Knudsen, 2004).

Thermally sprayed zinc has been avoided on offshore installations, because in the highly corrosive
nvironment zinc coatings usually only last for 5-10 years. Only TSA have been used for
etallising offshore structures. TSZ duplex coatings therefore represent a new generic type of
aviour
7.2.1 Test results
Figure 12 shows the test results from the NORSOK test. Neither of the TSZ duplex coating
systems showed significant corrosion creep from the scribe.

System C2 showed white zinc corrosion products all over the coating surface, which means that
zinc oxide penetrated the organic coating. The organic coating system was only specified to be
105 m thick, and this was probably too thin. The zinc coating has a rough surface structure, and
over peaks in the TSZ the organic coating may have been very thin, i.e. less than specified.

e
m
coatings on offshore installations. Questions regarding steel/zinc polarity reversal and beh
at temperatures up to 120C have been put forward, which have been investigated by literature
studies.


29

For system H4 the topcoat (50 m oxirane ester) was flaking off, starting from the scribe, on all
three parallels tested. Due to the 110 m thick epoxy polyamide coat under, there was little
corrosion of the zinc.

For system I5 one of the parallels showed severe cracking of the topcoat, starting at the scribe and
propagating more than 20 mm on either side of the scribe. The topcoat was also flaking off in this
area. Some of the cracks also penetrated the epoxy barrier coat, and the zinc was corroding in the
cracks. On the two other samples there were no cracking, but around the scribe the topcoat could
be removed by a scalpel, indicating decreased intercoat adhesion.

System H3, I6, J1 and J2 showed very little degradation after the NORSOK test. Scribe creep on
the zinc was reported to be 0.1 to 0.4 mm, which is very good. As noted above, neither of the TSZ
duplex samples showed any corrosion creep on the steel.

After the 5 years field test very little degradation was found on the TSZ duplex coatings. None of
the samples had any corrosion of the steel around the scribe. Most samples had about 0.5 - 1 mm
corrosion of the TSZ around the scribe. Outside the scribe area no degradation was found. The
nly exception was system I6, where the zinc started to corrode at spots all over the sample, and
on. No thorough investigation about
e cause of this degradation has been performed, so this should only be considered as
o
the corrosion products caused the coating to crack over these spots. The explanation for this
degradation may have been incomplete penetration into the TSZ coating. During exposure these
pores will be filled with water and the zinc may start to corrode. The I6 coating system was
entirely water borne, which also may be part of the explanati
th
speculations.

There was little correlation between the field test and the NORSOK test.

0
5
10
15
D
e
g
r
a
d
a
t
i
o
n

f
r
o
m
20
25
30

s
c
r
i
b
e

(
m
m
)
C2 H3 H4 I5 I6 J 1 J 2
Corrosion on steel
Corrosion on zinc
Degradation of
organic coating
h
e

c
o
a
t
i
n
g
W
h
i

t

. 4

ystem the specified total film thickness was only 105 m, consisting of 30 m sealer and 75 m
topcoat, which evidently is too thin. The topcoat may have only just covered the largest peaks in
the coarse structure of the thermally sprayed zinc. Due to the low film thickness of the sealer and
t
e

r
u
s
t

p
e
n
e
t
r
a
t
i
n
g
Figure 12: Test results from cyclic testing of TSZ duplex coatings (NORSOK M-501 rev
est cycle). t

7.2.2 Effect of paint film thickness
For system C2 zinc corrosion products penetrated the coating during the test. For this coating
s

30

the coarse structure of the TSZ the sealer is not a continuous film. Hence, the organic coating
system should be considered to be a one coat system, and not a two coat system.

Coating films below 80 m formed from solvent borne binders have in earlier studies been shown
polymer film is not uniform in structure. It can rather be considered as consisting of microgels
). The film formation is not a
omogeneous process. Formation of microgels starts at a number of different sites in the wet film.
nt of
ctive
,
es above a
veral layers of microgels may be formed and block the conductive pathways.
ultiple coats will have the same effect.
7.2.3 Cracking and flaking
Cracking or flaking was found on two of the tested TSZ duplex coating systems, but only in the
NORSOK test. These forms of degradation were probably not related to the duplex nature of the
coating systems, but rather properties of the coats or the application.

For system I5 the topcoat cracked on one of the parallels in the NORSOK test, starting at the
scribe and propagating more than 50 mm. The crack penetrated the entire organic coating, causing
the zinc to corrode inside the crack. The topcoat is a 100 m polysiloxane. The same coating
product was applied on system E1, E2, M1, M2, M3 and P1 in Phase 1 of the project (TI report
from Phase 1: Kaltenborn and Scheie 2004), where we found cracking on all samples after the
NORSOK test.

For system H4 the topcoat (50 m oxirane ester) was flaking off in the NORSOK test, starting at
the scribe. At the end of the test the adhesion loss had spread about 20 mm on each side of the
scribe. For system I5 the cracking was combined with flaking, and the two samples without
y
ince the adhesion loss seems to be spreading from the scribe, it seems likely that it is linked to
th corrosion products from the zinc, probably a
rbonate. This may have attacked the coating, e.g. by the

the scribe.
to have low ionic resistance (Mills and Mayne 1981). This was attributed to formation of
conductive pathways through the organic coating. Mills also found that coating resistivity
increases significantly when the film thickness increased above 80 m, or when multiple coat
films were tested.

A
(high molecular weight and high crosslinking density) connected via a low molecular weight and
low cross-linked (LMW/LC) polymer fraction. The inhomogenity is due to a phase separation
during film formation, according to Bascom (Bascom 1970
h
As the microgels approach each other from their initiation sites, they are unable to merge into a
homogeneous structure. When the microgels meet, the reactive groups in the polymer chains
either already have reacted or are immobilized, so the polymerisation reaction is terminated.
Unreacted or partly reacted resin is then left at the periphery. This unreacted or partly reacted
resin is the LMW/LC fraction described above. The LMW/LC fraction takes up a large amou
water, has a low resistance to ion transport, and is susceptible to water attack, e.g. hydrolysis and
dissolution (Nguyen et al 1996). Nguyen has linked this inhomogenity to formation of condu
pathways and transport of ions through coatings. If the microgels are in the order of 50 m in size
conductive pathways may penetrate the entire coating. When the film thickness increas
certain value se
M

cracking also showed signs of poor adhesion between the polysiloxane and the intermediate epox
coat.

S
processes at the scribe. The scribe was filled wi
mixture of zinc oxide, hydroxide and ca
slightly alkaline properties of zinc corrosion products. However, we would then have expected
more degradation on the lower part of the samples, since the corrosion products were running
down from the scribe. This was not the case. The degradation was the same at the upper side of

31


7.2.4 Low VOC coatings
The coating suppliers were asked to select coating systems that are likely to comply with future
ts gave
olvent

test and I6 in the field test. Thus, water based systems performed just as well
s the best solvent based systems. Also the high solid systems applied with mist coats instead of
d in
s is
ay in
istance to atmospheric corrosion to the formation of an insoluble
ntal conditions that interfere with the formation of such films may

he
sphere on the initiation and growth of the protective carbonate film.
evere than in most types of domestic or river water, which contains some scale-forming
environmental legislation, e.g. high solid or waterborne systems. As far as I know, most of the
applied coating products can be classified under one of these two categories. The test resul
no indications that the water based systems were more susceptible to degradation than the s
based systems. On the contrary, the water based systems performed very well, except for system
C2 in the NORSOK
a
diluted sealers performed well.

7.3 Properties of zinc coatings
7.3.1 General experiences with zinc coatings
The behavior of zinc and zinc coatings during atmospheric exposure has been closely examine
tests conducted throughout the world. Precise comparison of corrosion behavior in atmosphere
complex because of the many factors involved, such as prevailing wind direction, type and
intensity of corrosive fumes, the amount of sea spray, and the relative periods of moisture or
condensation and dryness. However, it is generally accepted that the corrosion rate of zinc is low;
particularly in less corrosive environments. In rural atmospheres corresponding to corrosion class
2 or less, the corrosion rate is in the order of 0.1 m/year. In moist industrial or marine
atmosphere, corresponding to corrosion class 5, corrosion rates up to 15 m/year has been
reported. Hence, in very corrosive environments a 100 m thick zinc coating may corrode aw
less than 10 years.

Zinc owes its high degree of res
zinc carbonate film. Environme
attack zinc quite rapidly. The important factors that control the rate at zinc corrodes in
atmospheric exposures are:

The duration and frequency of moisture
The rate at which the surface dries
Presence of industrial pollution or chlorides

Atmospheric corrosion has been defined to include corrosion by air at temperatures between -18
to 70C in the open and in enclosed spaces of all kinds. The corrosion rate of zinc is related to t
effect of the atmo

The corrosion of zinc in water is largely controlled by salinity, pH and impurities present in the
water. As in the atmosphere, the corrosion resistance of a zinc coating in water depends on its
initial ability to form a protective layer by reacting with the environment. In distilled water, which
cannot form a protective scale to reduce the access of oxygen to the zinc surface, the attack is
more s
salts. Seawater is more aggressive than freshwater. For example, in UK waters the zinc corrosion
rate normally lies in the range 10 - 15 m/year for continuous immersion.


32

7.3.2 Risk for zinc steel polarity reversal
In some cases it has been observed that the polarity has reversed between zinc and steel, i.e. steel
as become anode and zinc the cathode. This situation has been reported for zinc coated steel
5C (Corrosion and Corrosion Control, 1985). This reversal is
ons of carbonates and nitrates, and inhibited by chlorides and
f
7.3.3 Corrosion of zinc coatings exposed above 70C
efined to temperatures between -18C and 70C. Very little data
are published about the properties of zinc coatings above 70C, and most reported experiences are
to

G
ting
ermally sprayed zinc coatings do not, or to very small extent, form intermetallic phases with
en claimed that thermally sprayed zinc coatings should not be used
bove 60C due to degradation processes starting at this temperature. This may be a problem on
may be used on structures with temperature up
information or documentation that support this
gium, TSZ coatings may be used without
ny problems at 120C.
h
exposed in hot water above 6
favoured by high concentrati
sulphates. The corrosion failure is explained by passivation of the zinc surface by the formation o
a protective film consisting of zinc carbonates and possibly other zinc compounds. The
dissolution of iron will occur at defects of the film. Formation of ZnO rather than Zn(OH)
2
may
also contribute, where the ZnO may act as a semiconductor in aerated waters. The water quality is
characterized by a pH above 9.0, and low concentrations of chloride and sulfate. Presence of
aggressive ions such as chloride and sulfate will destroy or prevent the formation of the passive
film. Hence, this will not be a problem in marine environments or at structures below 60C.

Atmospheric exposure has been d
for ambient or room temperature.

Studies of hot dip galvanized coatings (HDG) have shown that such coatings will withstand
continuous exposure to temperatures of approximately 200C and occasional excursions up
275C without any effect on the coating. Above these temperatures there is a tendency for the
outer zinc layer to separate, but the alloy-layer, which comprises the majority of the coating,
remains intact. Adequate protection may often, therefore, be provided up to the melting point of
the alloy layer (around 530C). Exposure above 200C results in phase transitions in HD
coatings, and the amount of zinc iron intermetallic phases increase. This makes the zinc coa
become brittle and susceptible to mechanical damage and cracking.

Th
iron during applications. Phase transitions during exposure at elevated temperature should
therefore not be a problem.

Earlier in the project it has be
a
offshore installations, where NORSOK System 1
to 120C. However, we have not found any
conclusion. According to Paul Delpire in Zinacor Bel
a



33

8 TS Duplex systems expected lifetime
Compared to the reference systems with zinc rich primers, the TSA duplex coatings were
significantly more degraded, while the TSZ duplex coatings were less degraded or equally li
degraded. It should be noted that none of the duplex systems tested have given any corrosio
the steel substrate. The coating degradation was solely affecting the TSM and the organic coating.
However, based on offshore experiences degradation of TSA duplex coatings will devel
when it first starts, and when the TSA have been consumed the steel starts to corrode. It is
therefore reasonable to assume that the TSA duplex coatings tested here will degrade faster than
the reference systems. Based on the test results, we expect the TSA duplex coatings to have
shorter lifetime than this.

ttle
n of
op rapidly
ealed TSA has in many studies been shown to give excellent and long lasting protection. Hence,
there must be a limit to the film thickness that can be applied on TSA without causing the
ct of film thickness on degradation of
omewhat thicker than a sealer and still have an acceptable
sult. In order to avoid the rapid degradation the organic coating must probably have a
er,

g"
hed

ly will
he TSZ duplex coatings tested in Phase 1 and 2 showed very good performance. Based on the
, and
to assume that the lifetime will be longer than for the reference
ystems. The project was started with an objective to reach more than 20 years lifetime, which


evelops linearly. The experiences from The Public Roads
dministration indicate that 50 years lifetime is possible [Klinge 1999].

S
degradation problem described earlier. In section 7.1.2 effe
TSA duplex coatings were discussed. Based on the the experiences at sgard A, where a coating
system consisting of TSA + 20 m sealer + 80 m topcoat seems to be performing well, it seems
possible to apply a coating that is s
re
sufficiently open structure so that an aggressive electrolyte may penetrate the coating. Howev
the lifetime of such a coating will probably not be longer than for sealed TSA, since the organic
coating in a way must behave like a sealer. The only advantage with such a "lean duplex coatin
will probably be a more coloured surface. During application the film thickness must be watc
carefully in order to avoid too high film thickness, which may cause degradation. Maintenance of
such a coating will also be difficult, since the total thickness of the organic coating then easi
exceed a critical value for initiation of rapid degradation.

T
test results, they are therefore expected to have more than 20 years lifetime in highly corrosive
atmosphere. In fact, since the degradation only has affected the TSZ and the organic coating
not the steel, it is reasonable
s
very likely will be obtained with TSZ duplex coatings, based on the test results and the
experiences from road bridges. Another question is whether we can assume lifetimes significantly
longer than 20 years, e.g. approaching 50 years. An accelerated test and a 5 years field test do not
give experimental evidence to conclude for certain about this. However, the low degree of
degradation of the TSZ duplex coatings in the field test is promising, particularly if we can
assume that degradation d
A


34

9 Maintenance of duplex coatings
Due to severe degradation, good maintenance procedures for TSA duplex coatings for oil &
installations are needed. The task is extra challenging due to the limitations on surface cleaning
methods and coating products. With TSZ duplex coatings there has been less degradation and the
need for development of maintenance procedures is less urgent. The project has therefore focused
on maintenance of TSA duplex coatings. The purpose with this part of the project was to give
recommendations about maintenance of TSA duplex systems, with respect to cleaning meth
and selection of repair coatings. The extent of coating degradation will influence the maintenance
method. Recommendations were therefore given as function of the state of the coating.

gas

od

d only
ase
tion of
w coating. The first question that
eeds answering is whether to remove the remaining TSA or not. The TSA represents a value and
g

TSA
.2.2 Maintenance without removing the TSA
he TSA in the duplex system represents a potential value if the rapid degradation can be
prevented. A surface with a corroded TSA duplex coating will usually consist of areas with intact
coating, areas with corroded TSA and areas with corroded steel, as discussed above.

An attempt was made to remove only the organic coating at Sleipner R by blast cleaning during
the summer 2003. However, this turned out to be difficult, and it was decided to remove the entire
coating system, including the TSA, by blast cleaning. Ultra high pressure (UHP) water jetting will
remove corrosion products, degraded and intact organic coating and some TSA. It was shown that
UHP is able to remove the entire TSA coating, but this is a very slow process. Most of the TSA
will usually remain on the surface. Hence UHP will give a surface consisting of bare steel, bare
TSA and intact duplex coating.
9.1 Degradation of topcoat only no corrosion of TSA
If only the topcoat is degraded, i.e. the TSA is still totally covered by an organic coating an
the visual appearance of the structure is affected, then it is important to avoid excessive cleaning
of the surface, resulting in exposure of steel or TSA. Gentle cleaning with soap and water to
remove salts and other contaminants, rinsing of the soap and drying before application of a new
topcoat will give the best result. The additional film thickness of the organic coating will decre
the probability of pores penetrating the coating, which will decrease the chance for initia
corrosion of the TSA. This situation will not be discussed further in this report.

9.2 Corroded TSA
In the case of heavy corrosion of the TSA under the organic coating, as experienced on e.g.
Sleipner R, the situation is very different. A thorough cleaning with removal of loose paint and
corrosion products is necessary before application of the ne
n
potential long term corrosion protection, but also potentially rapid degradation of the new coatin
system.
9.2.1 State of TSA after degradation
Due to the heavy corrosion of the thermally sprayed metal in TSA duplex coatings, one may ask
how much aluminium is left. On offshore installation it has been reported that if the degradation is
allowed to develop for sufficiently long time, the aluminium will be consumed and the steel
substrate will start to corrode (Figure 1). Hence, when maintenance starts there will likely be a
situation where in some areas the duplex coating is intact, in some areas there are remaining
and in some areas bare steel is exposed.

9
T

35


micals. Paint removing chemicals are commercially

is
ethylene chloride but have other flammable chemicals, for example acetone, toluene, or
g only acetone, toluene or methanol, or

.
.2.3 Maintenance by removing the TSA
TSA duplex coating will provide a uniform surface with less restriction on
e to

P.
products and the organic coating. However, the
00 cm
2
in two minutes (50 min/m
2
).
described earlier (Knudsen 2002) hydrochloric acid is
rmed under the organic coating during degradation. A coating system that can absorb and
acid would probably perform better than the previously tested systems.
ave this ability. They will react with the
omate),
,

al
Another way of removing the paint is by che
available in a wide range of compositions. In order to be effective the formulation must contain
substances that are able to break bonds between the coating and the substrate. Protective coatings
usually have cross linked binders, which makes them more demanding to remove. Efficiency and
toxicity of paint removing chemicals are usually correlated, and many of the products contain
harmful substances like organic solvents, caustic soda or strong acids.

Most paint strippers are solvent based, and methylene chloride is the most commonly used
chemical in paint strippers. Methylene chloride products come in two varieties. One type
onflammable, while the other type is flammable. The flammable paint strippers have less n
m
methanol. There are also paint strippers available containin
mixtures of these. N-methylpyrrolidone or dimethyl sulfoxide are also used. Paint strippers based
on acids or alkaline solutions may attack the TSA as well as the organic coating, and are therefore
not possible to use on duplex coatings. Some products are claimed to be environmentally friendly
by the producers, e.g. water borne products containing weak organic acids and aromatic alcohols
According to DnV some of these products have been effective in lab testing. However, the content
of acids may exclude them, as mentioned above.

9
Removing the entire
selection of the new coating system. The TSA may easily be removed by grit blasting, but du
restrictions on blast cleaning offshore, it will be advantageous if UHP water jetting can be used.
This was investigated in a test where a sample with a TSA duplex coating was cleaned with UH
The water pressure was 200 bar, the flow was 11 litres/min, and the sample (20 x 20 cm) was
cleaned for approximately 2 minutes. Electron microscopy showed that there was no aluminium
left on the surface after the UHP water jetting. Hence, the UHP water jetting is capable of
removing metallic TSA, as well as the corrosion
method seems to be slow, cleaning only 4

9.3 Repair systems for TSA duplex coating
9.3.1 Experiences and test results
According to the degradation mechanism
fo
neutralise hydrochloric
Pigments like zinc, zinc oxide and zinc phosphate h
hydrochloric acid and form zinc chloride. Another possibility is hexavalent chromium (chr
known for its ability to form stabile complexes with chlorides (Williams 2003). Nidelv bridge in
Trondheim, which is coated with a TSA duplex system, has an organic coating pigmented with
inc chromate, which may partly explain the good performance of this coating system. However z
hexavalent chromium is now abandoned in organic coatings. A zinc phosphate pigmented coating
was tested in the first test series (reference system 2 TSA + washprimer + 4 coats
alkyd/chlorinated rubber). This system did not perform well in the NORSOK test and gave 5 11
mm scribe creep (Knudsen 2003).

Can TSA be coated with zinc rich primers? There is a certain difference in corrosion potenti
between the TSA and zinc epoxies, which may lead to galvanic corrosion. TSA has an open

36

circuit potential of about -1050 mV SCE, while zinc rich primers have potentials between -1000

r,

tested two TSA duplex
oating systems, one with a zinc rich epoxy primer and one with an epoxy primer. The barrier
s in a
vent the binder from penetrating the pores. The
cribe creep progression rates shown in Figure 13 indicates that the zinc rich primer to some
degree slow down the corrosion of the TSA. If the test is prolonged it seems that the zinc rich
er. Hence, zinc rich primers may decrease
and -800 mV SCE. The potential on the individual zinc particles are probably closer to -1000 mV
SCE. The zinc may then be cathode and aluminium anode in case of galvanic corrosion. Howeve
the potential difference is small and the zinc dust particles are to some degree insulated from the
steel by the epoxy binder.

In order to investigate whether galvanic corrosion is a problem, we have
c
coat was an epoxymastic and the topcoat was a polysiloxane. The zinc epoxy has been
documented to be able to polarise steel below the protection potential for more than 100 day
submersion test. The coating systems are described in .

After NORSOK testing both coating systems have an average scribe creep of approximately 4 mm
(Figure 13). During the first months of the test the zinc epoxy sample had more scribe creep than
the epoxy primer. However, after the scribe creep first initiated on the epoxy primed samples, the
corrosion has propagated faster than on the zinc epoxy samples. The rapid initiation of scribe
creep on the zinc epoxy samples may be due to a galvanic effect, but a more likely explanation is
insufficient penetration of the primer into the porous TSA surface. Zinc rich primers have a high
content of fairly large zinc particles which may pre
s
primer will perform better than the epoxy prim
corrosion to some degree.

Table 3: TSA duplex coatings with and without a zinc rich primer tested in the NORSOK
test. Except for the primer the two coating systems are identical.
Sample TSA
Thickness
Primer
Type DFT
Barrier coat
Type DFT
Topcoat
Type DFT
EP 200 Epoxy 35 Epoxymastic 200 Polysiloxane 75
Zn EP 200 Zn Epoxy 75 Epoxymastic 200 Polysiloxane 75


4.5
4
0
0.5
1
1.5
2
2.5
3
3.5
0 1000 2000 3000 4000 5000
Hours
S
c
r
i
b
e

c
r
e
e
p

(
m
m
)
EP primer
ZnEP primer

Figure 13: Scribe creep test results in the NORSOK test as function of time. The coatings
are described in Table 3.


37

9.3.2 Recommendations
Blast cleaning in order to remove all remaining TSA will give a homogeneous surface and remove
the chance for rapid corrosion of the TSA. Milder cleaning may give a surface consisting of bare
steel, bare TSA and intact duplex coating. On bare steel a zinc rich primer will be beneficial. Zinc
rich primers also seem to be beneficial on TSA, though we only have tested one coating system
ss on
for degradation.
ore

igure 14: Situation at a coating edge. On the drawing to the left the TSA is exposed at the
coating edge. On the drawing to the right the TSA is totally insulated under the organic
coating. The situation on the right will have better corrosion resistance.


9.4 Maintenance of TSZ duplex coatings
The typical situation for TSZ duplex coatings exposed for many years in atmosphere is:
Degradation of the topcoat only and decreased visual appearance
Some corrosion of the zinc around mechanical damages in the paint
Little or no bare steel exposed

Based on information from the Public Roads Administration and the paint suppliers the following
is recommended for maintenance of TSZ duplex coatings:
In case only the topcoat is degraded, the structure should be cleaned without removing any
ed with corrosion under surrounding organic coating, the surface
must be cleaned and any corrosion products and loose paint removed. Remaining metallic zinc
with zinc epoxy on TSA. Zinc rich primers should not be applied on remaining organic coating
due to low adhesion.

Intermediate- and topcoats may be applied on the entire surface. Additional film thickne
already painted TSA will not make the situation worse. On the contrary, additional film thickness
will contribute to insulate the TSA and decrease the risk

Offshore experience and this project has shown that degradation usually initiates near bare steel
and where the TSA is exposed, e.g. at damages in the coating or edges. The corrosion process and
surface cleaning during maintenance will remove most of the TSA in degraded areas. After
application of the maintenance coating system the remaining TSA is to a larger extent hidden
under the organic coatings, compared to a new structure. Hence, the TSA is better insulated from
bare steel. Rapid corrosion of the TSA will therefore not start until the maintained coating is
degraded in such a way that TSA is exposed again. It may therefore take a while before
degradation is initiated again, and probably longer than on the new built structure which has m
spots with exposed TSA. The situation is described in Figure 14.



F
paint and a new topcoat applied. The new topcoat must be of a generic type that adheres to the
original coating.
In case bare zinc is expos
Organ ng
TS


Ste
ic coati
A
el
Organic coating
e
TSA


Ste l
Coating edge

38

is still providing corrosion protection and must not be removed. A repair coating system is
and Sa 3 on their bridges.
applied on exposed zinc.
If the steel is also exposed, a zinc rich primer may be applied on the steel and a repair system
on top of that. Zinc rich primers should not be applied on remaining organic coating due to low
adhesion. Thermal spraying of new zinc on clean steel is the best alternative, when that is
possible. Thermal spraying requires blast cleaning to at least Sa 2. The Public Roads
Administration dem



39

10 References

ASM Handbook, Vol 13: Corrosion. ISBN: 0-08170-019-0. ASM International, USA (1987)
. Kaltenborn and J. Scheie: "Duplex coating systems for long life time. Testing in accordance
ith NORSOK M 501 rev. 4 cyclic test for 4200 hours" Report no. 410-03-0226 Mt01 Rev.1
(2004)

K. Kaltenborn and J. Scheie: "Duplex coating systems for long life time. Testing in accordance
with NORSOK M 501 rev. 4 cyclic test for 4200 hours" Report no. 410-03-0019 Mt01 Rev.3
(2004)

R. Klinge: "Sprayed Zinc and Aluminium Coatings for the Protection of Structural Steel in
Scandinavia", Eight International Thermal Spray Conference, Miami, USA, 27 September 1
October 1976

R. Klinge: "Protection of Norwegian Steel Bridges against Corrosion", Stahlbau, Vol: 68, No: 5,
p. 382-391 (1999)

O.. Knudsen, T.G. Eggen: "Duplex coating systems - State of art", SINTEF report STF24
F01328, Confidential (2001)

O.. Knudsen: Mechanism for degradation of thermally sprayed duplec coatings, SINTEF
Report STF24 F02331, Confidential (2002)

O.. Knudsen: "Duplex coatings test results from phase 1". SINTEF report STF24 F03316,
Confidential (2003).

O.. Knudsen: "Maintenance of thermally sprayed duplex coatings", SINTEF report STF24
F03256 (2003).

O.. Knudsen: "Duplex coatings Test results from phase 2: TSZ systems", SINTEF report
STF24 F04256 (2004)

A. Mikkelsen, O.. Knudsen: Penetration of organic coating into TSM on samples prepared at
R&M in May, Memo, Confidential (2002)

D. J. Mills and J. E. O. Mayne, In "Corrosion Control by Organic Coatings", Editor: H.
Leidheiser, p. 12-17, NACE, Houston, TX (1981)

T. Nguyen, J. B. Hubbard and J. M. Pommersheim, Journal of Coatings Technology, Vol 68, pp
45-56 (1996)

B. Schei: "Coating systems for long lifetime: TS duplex systems Field testing status report",
DNV report no BGN-R2703356 (2003)


W. D. Bascom, Journal of Adhesion, Vol. 2, pp 168 (1970)

Corrosion and Corrosion Control, 3rd Edn., pp. 239-240 (1985)

K
w

40

J.E. Scheie, I. Lien: Coating systems for long lifetime: Thermal sprayed duplex systems
rs on TSA and TSZ win accordance to ISO 7253, TI Report no. 410-02-0019,
onfidential (2002)
. Soleng, O.. Knudsen: Corrosion properties of various thermally sprayed metals, SINTEF
of thermally sprayed metal,
n
Testing of 12 seale
C

G
Report STF24 F02334, Confidential (2002)

B.S. Tanem, O.. Knudsen: Penetration of sealer at the surface
INTEF report STF24 F02248, Confidential (2002) S

H. Vold: "Coating systems for long lifetime: Thermal sprayed duplex systems - Field exposure i
sea water splash zone. DnV report BGN-R2701576, Restricted (2002)