ANTI-CORROSIVE PAINT SYSTEMS

BASED ON CONDUCTING POLYMERS

Master of Science in Engineering Thesis

by M.Sc.Eng. Student Marie Louise Petersen

Supervisor: Per Mller The Danish Technical University Marts 2006

ABSTRACT
The corrosion protection of anti-corrosive paint systems based on conducting polymers is examined in the following four application areas: shopprimers, ballast tank protection, protection in off-shore environment and protection of aluminium. The conducting polymers used as an additive are polyaniline and polythiophene. Five possible hypotheses for the protection mechanism of conducting polymers are stated, and the aim is to examine the credibility of these hypotheses. For shopprimer applications, no improvement of the corrosion protection is established by the addition of polyaniline to a conventional shopprimer. In some of the applied shopprimers, polyaniline seems to accelerate the degradation of the paint film instead. The main explanation for these observations is a very low dispersibility of polyaniline in the paint. For protection of ballast tanks, addition of polyaniline to a conventional paint system seems to increase the resistance to cathodic disbonding. The assumption is made that polyaniline acts as an amphoteric material and reacts with the hydroxide ions, which are produced in the cathodic reaction. During this reaction, polyaniline is reduced to a non-conductive base form. For protection in off-shore environment, no improvement of the corrosion resistance is established by adding polyaniline to a conventional zinc primer. The effect of the cathodic protection is lowered, therefore polyaniline is not a suitable conductor between the zinc particles. Some positive effect is registered in the water based paint system with the addition of polythiophene in the primer. It is evaluated that a higher degree of dispersibility is the main explanation for this observation. Finally, the protective character of a conventional polyaniline containing primer is examined on aluminium. The efficiency is compared to other surface treatments that are especially designed for protection of aluminium. The results show that the polyaniline containing primer has a low adhesion to the substrate material, and the resistance to filiform corrosion is also not acceptable. The best corrosion protection is established by a conventional coating system with an anodizing pre-treatment.

II

PREFACE
This thesis, commenced in the autumn of 2005 at the Institute of Production and Management (IPL) at the Danish Technical University in Lyngby, is a 30 ECTS points project. This thesis is part of the education of Master of Science in Chemical Engineering, specializing in material science. The preparation and execution of the project is done in collaboration with the Danish company Hempel. Several people and companies in and outside IPL have been very helpful during the project period. I would among them like to thank my supervisor, professor Per Mller. I would like to thank the companies Chemetall, for providing standardized aluminium test panels, and Altitech, for performing the coating process altizizing. Thanks are also given to the German company Ormecon, which have provided paint to the project. Finally, I would like to thank Claus Weinell from Hempel for providing expertise and guidance, and the test department for their assistance during execution of the experiments.

_______________________________ Marie Louise Petersen, s031909 Lyngby, 1st of marts 2006

III

TABLE OF CONTENTS
Abstract .................................................................................................................................. I Preface ................................................................................................................................... II Table of contents................................................................................................................. III List of figures ........................................................................................................................ V List of tables .........................................................................................................................VI 1 Introduction.................................................................................................................... 1 1.1 Motivation..................................................................................................................................... 1 1.2 Problem formulation ................................................................................................................... 1 Theory............................................................................................................................. 2 2.1 Conductive polymers................................................................................................................... 2 2.1.1 Introduction to conductive polymers ........................................................................................... 2 2.1.2 Electrical conductivity .............................................................................................................. 3 2.1.3 Conjugated polymers ................................................................................................................ 4 2.1.4 Chemical structure of polyaniline and polythiophene .................................................................. 5 2.1.5 Doping of conjugated polymers.................................................................................................. 6 2.1.6 Mechanism of polymer conductivity ........................................................................................... 7 2.2 Corrosion theory........................................................................................................................ 11 2.2.1 What is corrosion?................................................................................................................. 11 2.2.2 Potential................................................................................................................................ 12 2.2.3 Pourbaix diagram ................................................................................................................. 14 2.2.4 Corrosion of steel ................................................................................................................... 15 2.2.5 Corrosion of aluminium ......................................................................................................... 16 2.2.6 Corrosion of painted steel and aluminium ............................................................................... 18 2.3 Anti-corrosive paint................................................................................................................... 21 2.3.1 What is paint? ...................................................................................................................... 21 2.3.2 Binders.................................................................................................................................. 22 2.3.3 Pigments................................................................................................................................ 23 2.3.4 Solvents ................................................................................................................................. 24 2.3.5 Additives............................................................................................................................... 25 2.4 Corrosion protection by conductive polymers...................................................................... 26 2.4.1 Hypotheses of anti-corrosive mechanisms ................................................................................. 26 2.4.2 Article review of conducting polymers ...................................................................................... 28 2.4.3 Research from Ormecon.......................................................................................................... 31 Experimental procedure............................................................................................... 33 3.1 Applied paint systems................................................................................................................ 33 3.1.1 Test panels and surface preparation ........................................................................................ 33 3.1.2 Shopprimer............................................................................................................................ 34 3.1.3 Paint for ballast tank ............................................................................................................ 35 3.1.4 Paint for off-shore environment ............................................................................................... 36 3.1.5 Paint for aluminium substrates .............................................................................................. 37 3.2 Paint film characterization........................................................................................................ 38 3.2.1 Electromagnetic induction....................................................................................................... 38 3.2.2 Eddy Current Test ................................................................................................................ 39

IV

3.2.3 Scanning Electron Microscopy ................................................................................................ 39 3.2.4 Pull-off test ............................................................................................................................ 40 3.3 Corrosion resistance .................................................................................................................. 40 3.3.1 Open Circuit Potential........................................................................................................... 41 3.3.2 Anodic polarization............................................................................................................... 41 3.3.3 Natural Weathering Test ...................................................................................................... 42 3.3.4 Mebon Prohesion Test ........................................................................................................... 42 3.3.5 Cathodic Protection Test ........................................................................................................ 43 3.3.6 Immersion Test...................................................................................................................... 43 3.3.7 Salt Spray Test ..................................................................................................................... 44 3.3.8 Cyclic Test............................................................................................................................. 44 3.3.9 Filiform Corrosion Test ......................................................................................................... 45 4 Results and discussion ................................................................................................. 46 4.1 Shopprimer ................................................................................................................................. 46 4.1.1 PVB shopprimers.................................................................................................................. 46 4.1.2 Zinc phosphate shopprimers ................................................................................................... 48 4.1.3 Zinc silicate shopprimers ........................................................................................................ 49 4.2 Paint for ballast tanks ................................................................................................................ 50 4.3 Paint for off-shore environments............................................................................................ 53 4.3.1 Solvent based paint system ..................................................................................................... 53 4.3.2 Water based paint system....................................................................................................... 57 4.4 Paint for aluminium substrates ................................................................................................ 62 Conclusion .................................................................................................................... 67 Perspective.................................................................................................................... 68

5 6

Abbreviations ..........................................................................................................................i Bibliography...........................................................................................................................ii List of appendix..................................................................................................................... vi

LIST OF FIGURES
Figure 1. Conductivity of conducting polymers compared to other materials. .................................... 3 Figure 2. Chemical structure of polythiophene and polyaniline. ............................................................ 5 Figure 3. Outline of the redox-reactions that combine the emeraldine form and the leuco form of polyaniline and their matching chemical structures. ........................................................................ 5 Figure 4. Chemical structure of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)................ 6 Figure 5. General energy band gap diagram for an insulator, a semi-conductor and a conductor. ... 8 Figure 6 Formation of a radical cation (polaron) by removal of a electron on the 5th carbon atom of an undecahexaene chain (ab). Migration of a polaron is shown in (ce). ......................... 9 Figure 7. A polaron on a polyparaphenylene chain. ................................................................................. 9 Figure 8. Illustration of the energy band gap of a quinoid and a benzene unit. ................................. 10 Figure 9. Intersoliton hopping between two undecahexaene chains.................................................... 10 Figure 10. Pourbaix diagram for aluminium in water............................................................................. 14 Figure 11. Pourbaix diagram for iron in water......................................................................................... 16 Figure 12. Illustration of a blister............................................................................................................... 18 Figure 13. Illustration of undercutting corrosion.................................................................................... 18 Figure 14. Reaction mechanism for filiform corrosion. ......................................................................... 19 Figure 15. Model for cathodic disbondment of a painted steel specimen........................................... 20 Figure 16. Reaction mechanism for passivation of iron using polyaniline according to Ormecon. 32 Figure 17. OCP potential of PVB based shopprimers in 3,5w% NaCl. .............................................. 47 Figure 18. Polarization curves of PVB based shopprimers in 3,5w% NaCl. ...................................... 47 Figure 19. Cathodic disbonding after exposure in CPT......................................................................... 50 Figure 20. Cathodic disbonding after seawater immersion.................................................................... 52 Figure 21. Undercutting corrosion of solvent based paint system.. ..................................................... 55 Figure 22. OCP measurements of water based paint in 3,5w% NaCl. ................................................ 58 Figure 23. Polarization curves of water based paint with 85w% Zn in 3,5w% NaCl........................ 58 Figure 24. Polarization curves of water based paint with 60w% Zn in 3,5w% NaCl........................ 59 Figure 25. Undercutting corrosion of water based paint system. ......................................................... 60 Figure 26. SEM pictures of a zinc primer in secondary signal and backscattered signal................... 61 Figure 27. Surface topography of altizized and anodized aluminium panels. ..................................... 64 Figure 28. OCP potential of aluminium specimens in 3,5w% NaCl.................................................... 65 Figure 29. Polarization curves of aluminium specimens in 3,5w% NaCl.......................................65

VI

LIST OF TABLES
Table 1. Standard electrode potential of various metals......................................................................... 12 Table 2. Classification scheme of binders according to their chemical reactions............................... 22 Table 3. Classification scheme of pigments according to their functionality...................................... 23 Table 4. Classification scheme of solvents with a description of their application range. ................ 24 Table 5. Classification scheme of additives according to functionality................................................ 25 Table 6. Review of articles related to corrosion protection of aluminium by polyaniline................. 29 Table 7. Review of articles related to corrosion protection of steel by polyaniline. .......................... 30 Table 8. Review of articles related to corrosion protection of steel by polythiophene. .................... 31 Table 9. Requirements and specifications of shopprimers. ................................................................... 34 Table 10. Overview of applied shopprimers............................................................................................ 35 Table 11. Requirements and specifications of paints for ballast tanks................................................. 35 Table 12. Overview of applied paints for ballast tank protection......................................................... 36 Table 13. Requirements and specifications of paint systems for off-shore protection. .................... 36 Table 14. Overview of applied paint systems for off-shore protection. .............................................. 37 Table 15. Overview of water based paint systems for off-shore applications. ................................... 37 Table 16. Overview of applied coating systems for protection of aluminium.................................... 38 Table 17. Test methods used for characterization of the corrosive behaviour in the different application areas. ................................................................................................................................. 41 Table 18. Test conditions of the Mebon Prohesion Test. ..................................................................... 42 Table 19. Test description and applied conditions for the cyclic test. ................................................. 44 Table 20. Measurements of the cathodic disbonding after the cathodic protection test. ................. 51 Table 21. Measurements of the cathodic disbonding after the immersion test. ................................. 52 Table 22. Measurements of adhesion by pull-off test after the salt spray test. ................................... 54 Table 23. Measurements of undercutting corrosion after the cyclic test. ............................................ 56 Table 24. Measurements of the adhesion by pull-off test after the cyclic test. ................................... 56 Table 25. Measurements of undercutting corrosion after the cyclic test. ............................................ 61 Table 26. Evaluation of the adhesion after the salt spray test. .............................................................. 63 Table 27. Evaluation of the adhesion after the cyclic test...................................................................... 63

1 INTRODUCTION

1 INTRODUCTION
1.1 Motivation
The corrosion and degradation of metals is an important issue and constitutes a big expense to society. In order to improve the corrosion resistance of metals, continuous research is necessary in order to develop new types of protective surface treatments. One type of protective surface treatment is the application of anti-corrosive paint systems. The protective character of these paint systems has, up until now, primarily been based on zinc rich paints which provide cathodic protection of, for instance, steel. However, this protection is only present if unused zinc particles are present in the paint. The lifetime is therefore limited and continuous maintenance is needed in order to retain the cathodic protection. The development of anti-corrosive paint systems based on electrically conducting polymers is therefore an interesting alternative to conventional zinc paints. These new paint systems are also more environmentally friendly and cheaper to manufacture than zinc paints. Besides these advantages, there is a great scepticism about the efficiency of the paint systems and the application is still at research level. This report will try to uncover some of the problems related to these new paint systems and find possible application areas in relation to corrosion protection of metals.

1.2 Problem formulation

The aim of this project is to examine the corrosion protection of steel and aluminium by paint systems based on conducting polymers. Different paint systems are produced and tested in order to uncover the possible application areas of these paint systems. The conducting polymers used in this project are polyaniline and polythiophene, and the different paint formulations are prepared at the facilities of Hempel. A commercial paint system named CORRPASSIV from Ormecon, which contains polyaniline, is also tested and evaluated. On the basis of a thorough information retrieval, possible hypotheses about the anti-corrosive effect of polyaniline and polythiophene are stated. This project will examine the credibility of these hypotheses by several experiments performed at Hempel and DTU. Finally, the efficiency of the formulated paint systems is evaluated in relation to other anti-corrosive paint systems and surface treatments. In the case of steel protection, zinc rich paint systems are used for comparison, and for protection of aluminium, the efficiency is evaluated in comparison to three surface treatment methods named anodizing, chromatizing and altizizing.

2 THEORY

2 THEORY
This introductory theory section tries to give the reader a deeper understanding of the basic concepts of conducting polymers and the application of conducting polymers in anticorrosive paint systems for the protection of steel and aluminium. The theory section is divided into 4 sections, each with their own subject area. Section 2.1 concerns general aspects of conducting polymers, section 2.2 describes basic corrosion theory and mechanisms, and section 2.3 describes the composition and formulation of anti-corrosive paint system. Section 2.4 presents previous results and hypotheses about corrosion protection by conducting polymers.

2.1 Conductive polymers

This section describes the basic chemical and physical characteristics of conducting polymers, exemplified by polyaniline and polythiophene. In particular, the chemical structure and its importance for different physical and chemical properties are presented.

2.1.1 Introduction to conductive polymers

What is a conductive polymer and how is it possible that a polymer can behave as an electrically conductive material? These are the basic questions when conductive polymers are introduced as a new subject. This introductory chapter attempts to explain the basic principles of conductive polymers and describes how conductive polymers act and how they differentiate from other polymer materials. A polymer is, in chemical terms, a long molecule formed of repeating smaller units called monomers. Most of the polymers are known as electrical insulators due to their chemical structure and nature. Polymers normally contain electrons which are closely packed to the atoms by covalent bonds. This lack of mobility of the electrons is the reason why most of the polymers behave like insulators. An interesting discovery was however made in 1977 by Hideki Shirakawa, Alan MacDiarmid and Alan Heeger. These three scientists discovered that an oxidation of polyacetylene with iodide, bromide or chloride vapour increases the conductivity of the material by a factor 109. This is due to the fact that electrons are jerked out of the polymer chain, leaving holes in form of positive charges that can move along the chain. The experiments thus demonstrated that polyacetylene has the ability to possess both insolating and conductive properties, depending on the degree of

2 THEORY

oxidation. The three scientists received in 2000 the Nobel Prize in chemistry for the discovery and development of electrically conductive polymers. [1] Other polymers such as polyaniline and polythiophene possess the same conductive properties as polyacetylene. Each of these polymers is characterized by a chemical structure based on conjugated double bonds and named conjugated polymers. Figure 1 illustrates the conductivity range of these conjugated polymers ranging from insulating to conductive materials.

Figure 1. Conductivity of conducting polymers compared to other materials from quartz (insulator) to copper (conductor). [1]

The potential of these conductive polymers is very broad and includes different fields such as corrosion inhibitors, antistatic coatings, sensing devices and electromagnetic shielding. The main advantage of these conductive polymers is their cheap manufacturing cost and their high degree of flexibility. This makes them suitable in many fields and they will probably be used as a replacement for metals and other materials in the future. [1]

2.1.2 Electrical conductivity

Electrical conductivity can be described as the ability of a substance to conduct an electrical current. The conductivity is defined by Ohms law: U = RI (2.1)

where U is the drop in potential (in Volts), I is the current (in Amperes) and R is the resistance of the system (in Ohms). It is important to note that Ohms law is an empirical law and not all

2 THEORY

materials obey Ohms law. Examples of materials that deviate from Ohms law are vacuum tubes, semiconductors and one-dimensional conductors. For Ohmic materials the resistance is proportional to the length of the sample (l) and inverse proportional to the cross-section area (A), according to equation 2.2: R = (l/A) = (1/ ) (l/A) (2.2)

where is a proportionality factor called the resistivity. The inverse value of the resistivity is the conductivity () with the unit S/m. Generally, the conductivity depends on the number of charge carriers (n), the mobility () and the charge (q) of these carriers according to equation 2.3.

= n q

(2.3)

For highly conductive materials such as metals, the conductivity will increase as the temperature decreases, while the opposite is valid for semiconductors and insulators. Conductive polymers such as polyacetylene follow the same temperature dependence as semiconductors i.e. decreasing conductivity with falling temperature. [1]

2.1.3 Conjugated polymers

Each of the conducting polymers is characterized from a structural point of view as being a conjugated polymer. Conjugated polymers are materials which contain conjugated -bonds in their chemical structure. These -bonds are essential for the ability of the polymer to behave as an electrically conductive material. Conjugated polymers are constructed by conjugated double bonds, i.e. double bonds between every second C-atom. By visualizing one of the bonds in these double bonds, one finds that the electrons are moving in a special shell called a p-orbital. This type of orbital differentiates a lot from the molecule shells in which the remaining binding electrons travel through. A p-orbital has the ability to overlap similar p-orbitals from the following C-atoms, and forms a big coherent shell spread along the carbon chain. The electrons in this coherent shell are described as -electrons and are characterized by their free mobility in the polymer chain. This free mobility of the -electrons is important if the polymers shall behave as a conductive material. If a charge is introduced to the polymer chain, it can move along the -electron clouds. The charge can also move from one polymer chain to another if the -electron clouds from each

2 THEORY

polymer chain are overlapping each other. These properties are essential in order to create a conducting polymer. [2], [3]

2.1.4 Chemical structure of polyaniline and polythiophene

The two polymers polyaniline and polythiophene are used in this project and are examined according to their anti-corrosive effect. Both polymers are conjugated polymers which contain conjugated structure -bonds. of The chemical and
Figure 2. Chemical structure of polythiophene (top) and polyaniline (bottom).

polyaniline

polythiophene are illustrated in figure 2.

The chemical structure of polyaniline is arranged by coherent aniline monomers. The illustrated structure of polyaniline in figure 2 is called leucoemeraldine or leuco due to its oxidation stage. Polyaniline is proven to assess three different oxidation stages with leucoemeraldine as the fully reduced form. If polyaniline appears in a fully oxidized form it is termed pernigraniline, while the half oxidized form is termed emeraldine. Polyaniline normally exists as leucoemeraldine or emeraldine. The transformation between these two oxidation forms takes place through a series of redox-reactions according to the reaction scheme on figure 3. [4], [5]

Figure 3. Outline of the redox-reactions that combine the emeraldine form and the leuco form of polyaniline and their matching chemical structures. [4]

2 THEORY

The illustrated forms of polyaniline on figure 3 will in practice possess very different chemical and physical properties. Only polyaniline on an emeraldine salt form has the functionality of an electrically conductive material with a conductivity of 10-1000 S/cm. In comparison, the conductivity of the base form is about 10-10 S/cm. [6] Polythiophene has a chemical structure which is arranged by coherent units of thiophene, as recalled on figure 2. A modified polythiophene product is used in this project in order to achieve a better degree of dispersion in the paint formulation. The applied polythiophene product is called Baytron P and is an aqueous dispersion of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), in short PEDOT/PSS. Figure 4 shows the chemical structure of the complex between poly(3,4-ethylenedioxythiophene) in the bottom and poly(styrenesulfonate) in the top.

Figure 4. Chemical structure of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate). [7]

The conductivity of PEDOT/PSS is maximum 10 S/cm, but is strongly dependant on the type of coating formulation. [7]

2.1.5 Doping of conjugated polymers

In order for a conjugated polymer to behave as an electroactive conducting material, it must be exposed to a process called doping. During the doping process, an ionization of the polymer chain takes place. This introduces charge carriers to the chain, which in turn increases the conductivity of the polymer.

2 THEORY

Different kinds of doping methods exist, but common to all of them is that they are reversible processes. The doping can be divided into two sub-classes called p-doping and n-doping. In p-doping an oxidation of the polymer chain takes place for example by means of halogens such as I2. In contrast, n-doping causes a reduction of the polymer chain and normally used reduction mediums are alkali metals such as lithium and potassium. P-doping is the most useful method to ionize the polymer chain because experiments have revealed that p-doping leads to more stable compounds compared to n-doping. Alkali metals used in n-doping are unstable in the atmosphere, and furthermore oxygen acts as an oxidant which neutralizes the n-doping. [2] The doping process can also be described as a redox process and is carried out by either chemical or electrochemical processes. In the context of the application of polyaniline in anti-corrosive paint systems, doping will normally take place chemically. A very useful chemical method for doping of polyaniline is by addition of acid which liberates protons to the polymer chain. Doping of polyaniline by means of camphor sulphonic acid has proved to give a very high conductivity (200-400 S/cm) and is stable at the same time. [8] A de-doping of the conducting polymers can also take place. In the case of polyaniline, addition of base (e.g. NH4OH) is the normal method for de-doping. De-doping can also take place due to pHchanges in the surrounding environment. An increase in the degree of protonation will appear if the pH is dropping in the surrounding environment, making the polymer more conductive. At the same time, an alkaline environment causes a de-doping and lowers the conductivity. Polyaniline is therefore able to adjust its conductivity from the chemical changes in the environment during application.

2.1.6 Mechanism of polymer conductivity

Materials can be classified according to their electrical conductivity as conductors, semiconductors and insulators. Metals are typically good conductors, while polymers often act as insulators. The development of conducting polymers is therefore an important step in the polymer technology. The electrical properties of a material can always be determined according to its electronic structure. A method to describe the electrical conductivity of a material is the energy band gap theory. This theory describes the energy states of the electrons in a material. The outer shell of electrons in a material contains the so called valence electrons. Valance electrons can be placed theoretically in the valence band which defines the lowest energy state. The valence band describes

2 THEORY

the highest occupied band, while the lowest unoccupied band is called the conduction band. In order for a material to conduct electricity, the electrons in the valence band must contain sufficient energy to reach the conduction band and the difference between the valence and conduction band must be small. The difference between the two bands is called the band gap. In a metal, the density of electronic states is very high and the electrons which have relative low binding energy can move freely from one atom to another. According to the energy band gap theory, this means that the valance band and the conduction band are partly overlapping each other and the electrons can easily pass into the conduction band. In insulating materials, the band gap is so big that the electrons are fixed into the valence band. Therefore, an electrical current can not be conducted through the material. Finally, semi-conductors will contain a moderate band gap. This allows a partial transfer of electrons to the conductive band, leaving an electron hole in the valence band. The three energy band gap states are illustrated in figure 5. [9], [10]

Figure 5. General energy band gap diagram for an insulator, a semi-conductor and a conductor. [11]

Conducting polymers obtain their electrically conductive properties through a combination of a conjugated -electron structure and the doping of the polymer chain. When the polymer is doped, for instance by an oxidation with iodine, an electron is removed from the top of the valence band. This creates a vacancy (hole) which does not delocalize completely. If an electron is removed locally from one carbon atom on the polymer chain, a radical cation will be formed (see figure 6 b).

2 THEORY

Figure 6 Formation of a radical cation (polaron) by removal of a electron on the 5th carbon atom of an undecahexaene chain (ab). Migration of a polaron is shown in (ce). [1]

A radical cation, which is also called a polaron, is localized by a Coulomb attraction to its counterion (e.g. I3-) and by a local change in the equilibrium geometry of the polaron relative to the neutrale molecule. The mobility of the polaron is normally quite high and the charge is carried along the polymer chain according to figure 6 c-e. [1]

Figure 7. A polaron on a polyparaphenylene chain. [12]

If another electron is removed from the oxidized polymer chain, a second independent polaron or a new bipolaron is created. Figure 7 shows the presence of a bipolaron in polyparaphenylene. A bipolaron is more stable than two polarons in spite of the repelling coulomb forces between the two ions. A bipolaron has the charge +2e and spin 0 while a positive polaron will have the charge +e and spin . The spin condition refers to where the bonding defect is placed in the band gap. Thus, spin means that the defect is placed in the middle of the band gap. [12] Other important polymer chain defects for the conductivity of conjugated polymers are solitary wave defects called solitons. Solitons can either be neutral or charged, both having a spin of 0. A

2 THEORY

10

soliton is characterized by its free mobility and that no disorder of the structure is created when a soliton moves along the polymer chain. [2], [13] When defects such as solitons, polarons and bipolarons are present in the polymer chain, they will act as charge carriers and increase the conductivity. In the case of polyaniline, the movement of defects will cause the conjugated bindings to move about and form quinoid units instead of benzene units. Quinoid units will have a smaller band gap and a higher energy in the valance band than benzene units (see figure 8). A doping of polyaniline will therefore increase the amount of quinoid units, and thus the conductivity. [14], [15]
Figure 8. Illustration of the energy band gap of a quinoid and a benzene unit. [14]

The actual conductivity of the polymer is limited by intermolecular charge transfer reactions, i.e. the need for the electrons to jump from one polymer chain to another. Other important factors are related to macroscopic terms such as bad contact between different crystalline domains in the material. One mechanism to account for the conductivity of conjugated polymers is called intersoliton hopping. This describes the charge-hopping between different polymer chains. Figure 9 illustrates the principle where a charged soliton (bottom) is trapped by two dopant counterions and a neutral soliton (top) are free to move. When a neutral soliton is placed on a chain close to another chain with a charged soliton, interactions can take place. Interactions between the two polymer chains will cause the electron to jump from one defect to the other. [1]

Figure 9. Intersoliton hopping between two undecahexaene chains. [1]

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11

2.2 Corrosion theory

This section is a pre-study of the basic theory about corrosion kinetics and thermodynamics. The general corrosion behaviour of steel and aluminium is described, and the most common failure mechanisms of paint are explained in the end of the section.

2.2.1 What is corrosion?

Corrosion of metals is defined as an electrochemical reaction between the metal and the surrounding environment. These electrochemical reactions are driven by charged and neutral particles, in both the metal and the environment. Free electrons are, for instance, located in the metal and are able to move through the metal. In the surrounding environment, positive and negative ions as well as neutral molecules are present, leading to a corrosive environment. Corrosion of metals can only occur if an anode/cathode relation is established, where the metal works as an anode and oxidizes. During oxidation, metal ions will form and be released to the surrounding environment, in the course of electron release: M Mn+ + ne(2.4)

The anodic reaction will thus drive an anodic current, ia, running in the direction metal solution. To compensate for the anodic reaction, a cathodic reaction will simultaneously take place. Electrons, when released in the anodic reaction, will form part of the cathodic reaction and reduce another chemical substance. Examples of cathodic reactions are the reduction of hydrogen or oxygen. In the cathodic reaction, a cathodic current, ic, will run in the direction solution metal. Anodic and cathodic reactions will take place simultaneously and in electrical equilibrium so that the electron- and current fluxes are in balance, i.e. ia = ik. The electrochemical reactions will result in an electrical current in any given system. This current depends on the potential difference between the metal and the surrounding environment. The kinetics of the different anodic and cathodic reactions is therefore an expression of the relation between the potential, E, and the reaction rate with the corresponding electrical intensity, i. An E-i mapping is used to graph the anodic and cathodic polarization curves through which the corrosion potential and corrosion rate can be determined. The point where the anodic and cathodic polarization curves cross each other is the point where the anodic and cathodic currents are equal. A reading of the corrosion potential, E, and the corrosion current, icor, can be done at the point of intersection.

2 THEORY

12

Faradays law can subsequently calculate an estimate of the corrosion rate:

m=

1 A I t 96500 n

(2.5)

where m is the weight loss, A is the atomic mass of the metal, n is the valence, I is the intensity ( = icor) and t is the time. It is important to point out that the weight loss determination in equation 2.5 is only valid for uniform corrosion. If the metal is exposed to local corrosion such as pitting and crevice corrosion, a true estimate is not possible by using this equation. [16], [21]

2.2.2 Potential
The potential difference between the metal and surrounding environment is called the absolute potential or just the metal potential. In order to determine the absolute potential of a given metal, a connection between the metal and a stable electrode must be established. A reference electrode with a constant potential in stable conditions of temperature and pressure is therefore used for potential measurements. The hydrogen equilibrium in reaction 2.6 is, per definition, chosen to have a potential of 0V at 1013 bar and 20 C. 2H+ + ne- H2 (2.6)

The standard electrode potential can be arranged for a number of different metals and their respective oxidation reactions. A selection of different standard electrode potentials is listed in table 1.
Table 1. Standard electrode potential of various metals. [21]

Reaction Au Au3+ + 3eAg Ag2+ + 2eCu Cu2+ + 2eFe Fe2+ + 2eZn Zn2+ + 2eAl Al3+ + 3eMg Mg2+ + 2e-

Potential vs. SHE (V) +1,42 +0,80 +0,34 -0,44 -0,76 -1,66 -2,38

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13

The standard electrode potentials in table 1 can be used to determine the electrochemical character of different metals. Metals with a high and positive potential, such as gold, have a very poor tendency to oxidize and are therefore noble metals. In contrast, metals with a strongly electronegative potential, such as magnesium, will have a great affinity for oxidation, and are therefore un-noble metals. Table 1 is, in practice, a useful tool for anticipating whether two metals will evolve a galvanic coupling. As an example, zinc will function as an anode in connection with more noble metals such as iron and copper. This property is employed for cathodic protection of, for example, steel tanks, where sacrificial anodes of zinc are mounted to the tank. Sacrificial anodes will therefore corrode in favour of the steel tank. It is, however, important to state that the standard electrode potential is a thermodynamic parameter which only expresses whether a reaction is possible or not in theory. Standard electrode potentials are not valid for determining the kinetics of a given reaction. Aluminium is a very good example, which, according to table 1, is very unstable and easily corrodes. But general practice shows that the corrosion of aluminium is reduced by a natural oxide layer which is formed on the surface of aluminium. Aluminium is therefore a so-called passive metal. [21] Reality, however, rarely relies on standard conditions and the metal potential therefore deviates from the standard electrode potential. To determine the metal potential of non-standard activities or concentrations, an expression called Nernst equation can be used:

E = E0 +

RT log(a M n +1 ) nF

(2.7)

where E0 is the standard electrode potential, R is the gas constant, T is the temperature, n is the valence of the ion, F is Faradays constant and a is the activity of metal ions. At 20 C, equation 2.7 can be rewritten as the following expression:

E = E0 +

0,058 log(a M n +1 ) n

(2.8)

If the activity is 1, it is clear that Nernst equation is reduced to E = E0. The real potential is often influenced by different factors which complicate the application of Nernst equation. These factors are primarily related to changes in the surrounding environment, but different material properties also have a major effect on the potential. [16]

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2.2.3 Pourbaix diagram

A way to determine the corrosion properties of a metal is by means of the so called Pourbaix diagram. A Pourbaix diagram illustrates the connection between E and pH for a metal in an aqueous environment at a given pressure, temperature and concentration. The diagram is based on thermodynamic equilibrium data and considers three types of equilibrium states: 1) equilibrium between solid substances, 2) equilibrium between two substances in solution and 3) equilibrium between a solid and a substance in solution. A Pourbaix diagram is therefore based on three domain areas: a) corrosion, b) passivity and c) immunity. Figure 10 shows the Pourbaix diagram for aluminium and water at 25 C. The red areas mark the conditions where aluminium has a risk of corroding and changing to an ion state as Al3+ or AlO2depending on the environment. In the light blue area, aluminium forms a protective oxide layer that is insoluble in water. Finally, aluminium remains immune in surroundings that are strongly reducing i.e. where the potential is very low.

Figure 10. Pourbaix diagram for aluminium in water.

It is important to state that the Pourbaix diagram is based on thermodynamic equilibrium data, where the stable compounds and their domain areas and reaction ways are calculated. The diagrams do not give information about reaction kinetics and make no allowances for impurities or additives in the liquid or the metal. [21]

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2.2.4 Corrosion of steel

Corrosion of steel is a well-known problem, and can normally be recognized by the formation of red rust on the surface. In order for the steel to corrode and form rust, anodic and cathodic reactions must occur. In the anodic reaction, iron is oxidized and forms divalent cation Fe2+ with the liberation of two electrons (cf. reaction 2.9). In reality, the most frequent cathodic reaction is the reduction of oxygen, as shown in reaction 2.10. Fe Fe2+ + 2eO2 + 2H2O + 4e- 4OH(2.9) (2.10)

The iron ions given in reaction 2.9 will subsequently react with the hydroxide ions and form the complex iron hydroxide: Fe2+ + 2OH- Fe(OH)2 (2.11)

Since oxygen dissolves readily in water, there is normally an excess of it. A further reaction with the formation of the well known red rust can therefore take place according to reaction 12. 4Fe(OH)2 + O2 + 2H2O 2Fe2O3H2O + 4H2O (2.12)

The stability of iron can be illustrated by means of a Pourbaix diagram. Figure 11 on the following page shows the Pourbaix diagram for iron in water at 30C with an ion molarity of 1,0E-06. As illustrated on figure 11, iron is only immune at a potential below -650 mV. Above the immune area, iron will corrode in acidic environments with the formation of Fe2+ or Fe3+. In neutral environments, iron will have the tendency to form oxides normally as Fe2O3 or Fe3O4. In strongly alkaline environments, iron will corrode and form either FeO2- or HFeO2-. It is important to state that the presence of chloride ions in the environment has a big influence on the stability of iron and increases the risk of active corrosion. The ability of iron to form oxides will additionally decrease, and the passive properties are harder to reach. [16], [17]

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Figure 11. Pourbaix diagram for iron in water.

2.2.5 Corrosion of aluminium

Aluminium and its alloys are normally resistant to corrosive attack. This is due to the fact that aluminium is a passive metal which forms a protective oxide layer on the substrate surface. Corrosion can however occur in conditions where the passive layer is unstable. In aqueous environments, corrosion of aluminium can occur according to the succeeding reactions. Reaction 2.13 shows the anodic reaction where aluminium with oxidation stage 0 oxidizes and forms trivalent cation Al3+ in the course of electron release. Al Al3+ + 3e(2.13)

In order to obtain balance in the system, a matching cathodic reaction takes place simultaneously. Two types of reduction reactions will normally dominate in aqueous and neutral environments: 3H+ + 3e- 3/2H2 O2 + 2H2O + 4e- 4OH(2.14) (2.15)

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Adding written anodic and cathodic reactions results in a total reaction scheme. Reactions 2.16 and 2.17 show the two possible reactions for corrosion of aluminium in aqueous neutral and acidic environments. Al + 3H+ Al3+ + 3/2H2 Al + 3H2O Al(OH)3 + 3/2H2 (2.16) (2.17)

As it appears in reaction 2.17, corrosion of aluminium will in some cases cause a formation of aluminium hydroxide, Al(OH)3, which is insoluble in water and precipitates as a white gel on the metal surface. As mentioned earlier, aluminium is a metal that easily passivates. Aluminium, when in contact with oxygen, will spontaneously form a natural oxide layer that functions as a protective barrier layer, which reduces the substrate corrosion. Reaction 2.18 shows the reaction between aluminium and oxygen with the formation of aluminium oxide. 2Al + 3/2O2 Al2O3 (2.18)

Reaction 2.18 has a very high free energy of -1675 kJ which indicates that aluminium is a metal with great affinity to oxygen. [21] The structure of this oxide layer is based on two layers, with a total thickness of 4 to 10 nm. The first layer is a compact and amorphous layer that works as a barrier layer. It is formed instantaneously by contact with oxygen and the reaction rate is independent of the oxygen partial pressure. This means that the layer is able to repair itself if, for instance, the metal is exposed to mechanical stress in different machining operations. The growth of the layer is due to migration of Al3+ ions through the oxide layer and a maximum thickness of about 4 nm can be achieved. The second layer is contrary to the first, porous and less compact. This layer is formed by a reaction between the first layer and the surrounding environment. The growth rate depends on different factors and a maximum thickness of about 10 nm can only be achieved after several weeks. Temperature and humidity have proved to be effective promoters on the second layer. The composition of this layer can be very complex and contains different contaminants from the surroundings. [19] The corrosion of aluminium depends strongly on the stability and solubility of the natural oxide layer which is a function of different factors, e.g. pH. The solubility of the oxide layer will normally be greatest in strong acidic or alkaline environments, but the type of acid or base is also of great

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importance. For instance, a solution of hydrochloride acid is much more aggressive than a solution of acetic acid at the same pH value.

2.2.6 Corrosion of painted steel and aluminium

The protective nature of anti-corrosive paint systems is only valid for a given time, and the destruction of the paint film will eventually take place leaving free entrance for corrosive medias to the substrate material. Normal failure mechanisms related to organic coatings include blistering and undercutting corrosion, which are catastrophic for the protective character of the coating, and chalking or fading, which are less risky. Blisters in the paint are formed when water and other corrosive elements penetrate the paint film during time of wetness. Access of corrosive medias cause a corrosive reaction to take place beneath the coating and cause the paint film to swell, as illustrated on figure 12. As the blister grows, it often tends to combine with other blisters and the paint will eventually fall off
Figure 12. Illustration of a blister.

in flakes. Three types of blisters can be formed: 1) Osmotic blister 2) Anodic blister and 3) Cathodic blister. The osmotic blister is most common and is created near contaminants on the metal surface. An osmotic blister is formed when water penetrates the paint and dissolves soluble substances in the paint. This creates a dense fluid beneath the paint film which is drawn to the water outside the paint by osmosis. The blister is formed as an attempt to equalize the density between these two fluids. [18] Undercutting corrosion is formed near scratches or sheared edges as illustrated on figure 13. The corrosion will normally occur either by a chemical reaction in the interface between substrate material and paint, or by corrosion of the substrate material itself. Both situations will decrease the adhesion, or
Figure 13. Illustration of undercutting corrosion.

in worst case, completely disconnect the paint film. The mechanism of undercutting corrosion can be

described as a crevice corrosion scenario. Crevice corrosion is characterized by the presence of a small local anode and a large external cathode. Formation of an acidic environment and gaseous hydrogen in the crevice will further accelerate the corrosion. [19] Another kind of crevice corrosion is often present on painted aluminium and is called filiform corrosion. Filiform corrosion is initiated near defects and mechanical damages in the paint from

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which fine tunnels containing corrosive products are spread in a streaked pattern. The mechanism behind filiform corrosion is driven by an active head, which acts as an anode, while the tail and the surrounding regions acts as a cathode. A potential difference of 0,1 to 0,2 V is typically obtained between the head and tail region. The presence of oxygen is essential for the maintenance of cathodic reactions, and is therefore the driving force behind the mechanism of filiform corrosion. The cathodic reactions take place in the tail region, which is supplied with oxygen and condensed vapour through cracks and crevices in the coating. The head of the filament is filled with floating flakes of opal aluminium gel which are moving towards the tail region. Reactions between aluminium ions (Al3+) and hydroxide ions (OH-) will also take place in the tail region, producing aluminium trihydroxide (Al(OH)3) and aluminium oxide (Al2O3). Figure 14 illustrates the reactions which take place during filiform corrosion of aluminium. [20]

Figure 14. Reaction mechanism for filiform corrosion. [21]

Filiform corrosion is mostly dependent on the relative humidity and the quality of the applied surface treatment. Serious attacks appear in warm coast areas, where the combination of saltwater and high relative humidity increases the development of filiform corrosion. Filiform corrosion is only present in the atmosphere and occurs especially at a relative humidity of 85 to 95%. [22] Cathodic protection of steel by means of sacrificial anodes (e.g. zinc) or impressed current can result in a cathodic disbondment which decreases the adhesion of the paint film. The loss of adhesion between the paint and substrate material, is caused by formation of cathodic reaction products (e.g. OH-) near damaged areas in the paint film. Cathodic protection thus increases the

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risk of disbondment since a cathodic polarized steel surface has a higher exposure to cathodic reactions. A model for the mechanism of cathodic disbondment is illustrated in figure 15, with the presence of cathodic reaction products beneath the paint film.

Figure 15. Model for cathodic disbondment of a painted steel specimen.

Studies of the mechanism behaviour have shown that production of hydroxyl ions is the primary cause of cathodic disbondment. A direct proportionality is present between the OH- concentration and the rate of disbondment. It is believed that the generated hydroxyl ions interact with the paint and thus weaken and break the bonds between the paint and the steel substrate. The oxygen concentration in the environment is another factor that enhances the risk of cathodic disbondment. [23]

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2.3 Anti-corrosive paint

An introduction to general aspects of paint composition and properties is needed in order to understand the mechanism of anti-corrosive paint systems. Paint is a complex formulation based on many different components which contribute to the overall efficiency of the system. This section describes the different components and their mode of operation.

2.3.1 What is paint?

Paint is an organic coating that primarily protects equipment and constructions from environmental damage and provides a decorative surface. For protection purposes, paint is used in a wide range of industrial applications such as ships, ballast tanks, drilling rigs and concrete constructions. Selecting the right kind of paint system requires a comprehensive knowledge about the environment and its demands. Protection is a wide area of expertise and requires information about problems related to corrosion, fouling, contaminations, wear and abrasion. Paint is, per definition, composed of a liquid material which transforms to a thin coherent and adherent film when applied to a surface. The composition of paint can generally be divided into four main components: binder, pigment, solvent and additive. The binder is the backbone of a paint system and is therefore used to classify the system. Generally, organic solvent based paint can be divided into two groups: physically drying paint and chemically curing paint. This categorization concerns the action of film formation and describes whether the transition from liquid to solid state takes place either by evaporation or by chemical reaction. Physically drying paints form a film exclusively by evaporation of solvents. The binder molecules have therefore the same composition and size both before and after solidification of the film. The mechanism of physically drying paint is a physical process where the solvents evaporate and leave behind long chains of resin molecules, which pack together and form a coherent plastic film. Chemically curing paint is based on a curing mechanism where the film formation takes place by a chemical reaction between the binder and a curing agent. The final binder molecules in the dry film are therefore different from the initial binder molecules. The final binder molecules are much bigger and contain a high degree of cross-linking, forming a strong and non-reversible paint film. [24] A description of the four main components is given in the following four sub-sections. Each section describes the most common components, their mechanism and application.

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2.3.2 Binders
The binder is an essential component that provides uniformity and coherence to the paint system. It holds the pigments together when a dry film is formed, and provides adhesion to the substrate material. The type of binder often determines the durability of the final product. The ability of a binder to form a dense and tight film is directly related to its molecular weight and complexity. Binders with a high molecular weight often tend to form film by evaporation, while low-molecular binders generally will form film by a reaction in situ. A way to classify a binder is according to its chemical reactions. Table 2 lists some important binders, their grouping and chemical reactions. [25]
Table 2. Classification scheme of binders according to their chemical reactions. [25]

Classification Oxygen reactive binders Lacquers

Examples Alkyds Epoxy esters Urethane alkyds Polyvinyl chloride polymers Chlorinated rubbers Acrylics

Chemical reactions The binder molecules react with oxygen and a cross-linking of the resin molecules takes place. Drying mechanism by solvent evaporation. The long chain resins entangle with each other but no crosslinking exists. Curing takes place upon heating as the components melt. Both cross-linked and non cross-linked coatings are possible. The film is formed by a polymerization between the resin and a curing agent. A three-dimensional network is formed. The binders are usually used in zinc-dust pigmented primers where a reaction between zinc and binder takes place forming a very hard film. Film formation by coalescence of binder particles dispersed in water.

Heat conversion binders Co-reactive binders

Hot melts Organisols and plastisols Powder coatings Epoxies Polyurethanes

Inorganic binders

Post-cured silicates Self-curing water silicates Self-curing solvent based silicates

Coalescent binders

Latex

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2.3.3 Pigments
Pigments constitute a broad group of dry powder materials which are added to the paint in order to provide functionality and appearance to the paint system. The pigments are insoluble in the paint system and range from naturally occurring minerals to synthetic organic materials. Besides the obvious purpose of providing colour and opacity, pigments are also an important additive for corrosion protection, film reinforcement, coverage and adhesion. In anti-corrosive paint systems, pigments mainly provide protection by one or more of the following mechanisms; 1) Inhibition of corrosion; 2) Passivation of substrate metal; 3) Barrier against water permeability and 4) Cathodic protection. Certain pigments also enhance heat, abrasion, acid or alkali resistance to the final dry film. Important properties for all pigments are particle size and shape, wet ability by the binder and bulking. Some important pigments, their grouping and functionality are listed in table 3. [25]
Table 3. Classification scheme of pigments according to their functionality. [25]

Classification Colour pigments

Examples Titanium dioxide, iron oxides, organic azo pigments.

Functionality Provide colour to the paint. Titanium dioxide is the most popular white pigment because of its high refractive index. Provide active corrosion inhibition to the metal substrate. The pigments are slightly water soluble. Dissolved ion species thus react with the metal to form passivating reaction products.

Inhibitive pigments

Zinc phosphate, aluminium phosphate, zinc molybdate.

Barrier pigments Sacrificial pigments Hiding pigments Extender pigments

Aluminium flake, micaceous iron oxide. High purity zinc dust. Rutile titanium dioxide, zinc oxide. Carbonates, silicates, sulphates, barytes and mica.

Increase the permeation path length to the substrate for incoming moisture. Function as sacrificial anodes which provide cathodic protection of the substrate metal. Pigments with a high light refractive index to provide good hiding. Acts as reinforcement and flow control pigments. They are relatively inexpensive.

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2.3.4 Solvents
Solvents are volatile liquid substances with the purpose to dissolve solid paint constituents, reduce the viscosity and make the paint fluid for satisfactory appliance. After application, the solvent must evaporate to allow the coating to cure and achieve hardness. If a solvent has low volatility it can cause runs and sags in the drying coating film. In contrast, solvents can not be too volatile and cause solvent pops, loss of gloss, dry spray, poor surface wetting and penetration, poor film flow and inhibit cure. A blend of different solvents is therefore normally used in order to achieve optimum properties. Solvents are usually categorized according to their chemical composition. Table 4 lists some important groups of solvents, their advantages and disadvantages. [25], [26]
Table 4. Classification scheme of solvents with a description of their application range. [25], [26]

Classification Aliphatic hydrocarbons Aromatic hydrocarbons Ketones

Examples Naphtha, mineral spirits, hexane, heptane. Toluene, xylene. Acetone, methyl ethyl ketone, methyl isobutyl ketone.

Solvent description Used with asphalt, oil and vinyl based coatings. Poor to moderate solvency and wide range of evaporating rates. Least expensive of all solvents. Used with chlorinated rubbers, coal tars and certain alkyds. Greater solvent power than the aliphatics. Effectively used with vinyls and some epoxies. Exhibit varying evaporation rates and relatively strong solubility parameters. Strong hydrogen bonding and high polarity. Used as latent solvents with epoxy and polyurethane. Solvency power between aromatic hydrocarbons and ketones. Strong hydrogen bonding and a relatively high polarity.

Esters

Ethyl acetate, isobutyl acetate, ethylene glycol.

Alcohols

Ethanol, isopropanol, n-butanol.

Good solvents for highly polar binders such as phenolics. Alcohols are highly polar with a strong affinity for water. Excellent solvents for some of the natural resins, oils and fats. Used in latex paint.

Ether and alcohol ethers Water

Ethyl ether. Water

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2.3.5 Additives
The final component in a paint system is the additives which normally make less than 1% of the entire paint formulation. Additives are used to stabilize the paint fluid and affect different physical and chemical properties such as viscosity, surface and interfacial tensions, gloss and drying time. Addition of additives is only done when necessary since unwanted effects on the paint properties are likely to take place. The most common additives are listed in table 5 with an explanation of their functionality. [27]

Table 5. Classification scheme of additives according to functionality. [27]

Classification Examples Antifoam additives Thickeners Mineral oils, silicone oil, wax dispersions Bentonite, cellulose derivates, polyacrylates Dispersion additives Siccatives Cold stabilizers Metal salts of organic acids Ethylene glycol, propylene glycol Tensides

Functionality Prevent the formation of foam e.g. by coalescence of small bubbles to larger bubbles which increases the buoyancy of the bubbles. Increase the viscosity of the paint by creating a network between hydrophobic and hydrophilic parts of the paint. Increase the wetability of pigments to the binder phase by formation of micelles. Used in paints with oxygen reactive binders. Improves the curing process. Used in water based paint to improve the stability to freezing

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2.4 Corrosion protection by conductive polymers

The application of conducting polymers for corrosion protection has been examined during the last decade. This section introduces the reader to the different protection mechanisms which are proposed by a number of scientists. The chosen articles examine the anti-corrosive behaviour of polyaniline and polythiophene on both steel and aluminium.

2.4.1 Hypotheses of anti-corrosive mechanisms

The aim of this project is to uncover the different anti-corrosive mechanisms of conducting polymers. The following five hypotheses are believed to be the most important and are the most documented mechanisms for corrosion protection of metals by means of conducting polymers. 1. Anodic protection and passivation of the substrate metal. 2. Formation of a protective metal/polymer complex. 3. Absorption of OH- and inhibiting of cathodic disbondment. 4. Inhibition of the cathodic reactions. 5. Improve the conduction between zinc particles in zinc pigmented paints. Hypothesis 1: According to several studies, conducting polymers are able to raise the surface potential and provide an anodic protection of the substrate material. Tallman [28] has reported that the redox potential of polyaniline is 0,4 to 1,0 V (vs. SHE at pH 7) and 0,8 to 1,2 V for polythiophene. Both values are higher when compared to the corrosion potential of steel and aluminium. This indicates that both polyaniline and polythiophene are able to ennoble the surface of both steel and aluminium. Anodic protection alone can be fatal if the coating is damaged. A local damage in the coating will accelerate the corrosion of the underlying metal since the metal appears as an anode due to its lower potential. An effective corrosion protection can therefore only be provided if passivation of the metal takes place simultaneously. According to theory, the metal potential is stabilized in the passive potential range and a protective barrier of metal oxides is formed on the surface which prevents the active corrosion. The passivation takes place with an oxidation of the metal (M) and a reduction of the electrically conducting polymer (ECP) as illustrated in reaction 2.21. [29]

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y y 1 1 1 1 M + ECP m + + H 2 O M (OH ) (yn y ) + + ECP 0 + H + n m n n m n

(2.21)

Hypothesis 2: Another theory claims that a protective complex between the metal and the conducting polymer is formed in the metal/polymer interface. Kinlen [30] found by electron spectroscopy chemical analysis (ESCA) that an iron-polyaniline complex in the intermediate layer between the steel surface and the polymer coating is formed. By isolating the complex, Kinlen found that the complex has an oxidation potential 250 mV more positive than polyaniline. According to Kinlen, this complex more readily reduces oxygen and produces a more efficient electrocatalyst. Hypothesis 3: In addition to the electrocatalytic character of polyaniline, some studies claim that polyaniline has the ability to absorb OH- from the O2 reduction. The absorption of OH- causes a reduction of polyaniline (PANI) from emeraldine salt (ES) to emeraldine base (EB), as illustrated in reaction 2.22, where A describes the dopant ion. PANI-ES + OH- PANI-EB + H2O + A(2.22)

The reaction between polyaniline and the hydroxide ions limits the increase in pH at the polymer/metal interface and creates a buffering effect on the electrolyte pH. This is a very important quality for inhibition of cathodic disbondment which strongly depends on the concentration of OH- in the interface. [31] Hypothesis 4: Another approach to the protection mechanisms of conducting polymer is a theory which claims that conducting polymers inhibit the cathodic reactions. By limiting the cathodic reactions, one also limits the anodic reactions since both reactions are in balance. This relation reduces the corrosion rate of the metal. Seegmiller [32] used SECM (Scanning Electrochemical Microscopy) to analyze the hydrogen production across a scratch in a polyaniline coated aluminium specimen. The specimen was exposed to a 10 mM H2SO4 solution, and a redox mediator in the SECM tip electrode was used to locate the surface during approach curves. The SECM data indicated that hydrogen production was inhibited by the polyaniline coating. Seegmiller therefore suggested that polyaniline works as an inhibitor towards cathodic reactions and reduces the decomposition of a protective oxide layer.

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Hypothesis 5: The final hypothesis is only present in the case of zinc pigmented paint systems, which provide cathodic protection of steel. In cathodic protection the substrate material is placed in galvanic coupling with a low potential metal, such as zinc. In this way, zinc provides the anode and corrodes in favour of the substrate material. The zinc is added as a fine powder to the paint system. In order for the paint to reach a high efficiency, the zinc particles must be in close contact to each other. Different aids have been tested to raise the conductance between the zinc particles. One theory adds conductive additives to the paint. The addition of carbon black has shown good results but no research is done on the basis of conducting polymers. This project will try to examine the efficiency of polyaniline and polythiophene as a conductive additive in zinc-rich paint systems.

2.4.2 Article review of conducting polymers

This section gives the reader a review of the most comparable articles which have studied the corrosion behaviour of conducting polymers. It is important to note that a complete comparison between these articles and this project is not to be recommended. The results of the following articles are based on very different coating formulations and different film thicknesses. However, the results in these articles are good indicators for understanding the anti-corrosive mechanisms of conductive polymers. The results based on polyaniline coatings on aluminium substrates are listed in table 6 on the following page. Both articles state that a ennobling of aluminium takes place but Seegmiller [32] measures a much lower potential than Tallman [33]. This difference is probably caused by the difference in the electrolyte and the coating formulation. Seegmiller uses sulphuric acid as en electrolyte, which is a reducing acid. Polyaniline is mixed with polymethylmethacrylate (PMMA), and this can possibly lead to a decrease in the corrosion potential. Both articles claim that polyaniline is reduced in a corrosive environment which supports the presence of a redox reaction between polyaniline and aluminium. According to Seegmiller, polyaniline also acts as an inhibitor towards hydrogen production. This final statement is not to be found elsewhere.

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Table 6. Review of articles related to corrosion protection of aluminium by polyaniline.

Coating Polyaniline coating on aluminium (40-50 m)

Results and observations - An oxidation of aluminium and a reduction of polyaniline are found by EIS. - An OCP potential of 0,2 V (vs. SCE) is measured at the polyaniline coated aluminium specimen in a solution of 0,35% ammonium sulphate and 5% sodium chloride. - The pH in the immersion electrolyte decreases, indicating that an interaction between polyaniline and aluminium takes place.

Reference Tallmann et al 2000 [33]

Polyaniline /PMMA blend on aluminium (10m)

- An OCP potential of -0,12 V (vs. Ag/AgCl) is measured on polyaniline coated aluminium in 10 mM H2SO4. - Raman spectroscopy indicates an increase of reduced benzenoid groups and a decrease of oxidative cation radicals in the polymer chain. - SECM indicates that the hydrogen production is inhibited by the polyaniline coating.

Seegmiller et al 2005 [32]

Several studies have also examined the anti-corrosive behaviour of polyaniline on steel substrates. The different articles show no remarkable difference in the protection mechanisms regardless of whether the substrate material is steel or aluminium. Table 7 on the following page lists the results of three articles which examine the corrosion protection of steel by different polyaniline blends. These articles give the best comparable measurements in relation to this project which are based on paint formulations and not pure polyaniline coatings. An interesting discovery is made by Samui [34], who found that the best corrosion protection is provided with a low loaded polyaniline blend. At higher loadings of polyaniline, the compatibility of polyaniline and the styrene-butyl acrylate copolymer matrix is very low and the film becomes porous. This allows water and other contaminants to permeate the coating to a higher degree and decrease the corrosion protection.

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Table 7. Review of articles related to corrosion protection of steel by polyaniline.

Coating Polyaniline /PVB blend on steel (305 m)

Results and observations - The potential increases from 0,2 to 0,56 V (vs. SHE) as the polyaniline content is raised from 0 to 0,2. Measured by a Scanning Kelvin Probe in 96% RH and 20C. - The potential in the defect zone is equal to iron. - Cathodic disbondment is inhibited by polyaniline but not prevented. - As the alkalizing of the coating proceeds polyaniline is converted into the emeraldine base.

Reference Holness et al 2005 [31]

Polyaniline /St-BuA blend on steel (805 m)

- More porous film and higher water permeability with increasing polyaniline content. - Better corrosion performance in low loaded polyaniline paint. - Potentiodynamic measurements in 3,5 wt% NaCl shows a higher corrosion potential and a lower corrosion rate at low loadings. - Best performance is obtained in a 0,1 part polyaniline loaded paint.

Samui et al 2003 [34]

Polyaniline primer blends + topcoat on steel (0,5 -3,4 mm primer + 1,7-7,2 mm topcoat)

- An iron/polyaniline complex is found by ESCA. The complex is 250 mV more noble compared to pure polyaniline. - An epoxy topcoated PANI/thermoplastic primer has equal performance to inorganic zinc in a salt fog exposure.

Kinlen et al 1997 [30]

Only a few articles deal with the action of polythiophene as an anti-corrosive additive. Table 8 lists the results of two articles which examine the corrosion protection of steel by polythiophene. As indicated in table 8, the same protection mechanisms are observed for both polyaniline and polythiophene.

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Table 8. Review of articles related to corrosion protection of steel by polythiophene.

Coating Paints modified with a polythiophene deviate on steel (100-200 m) Polythiophene coatings on steel (10-24 m)

Results and observations - Problems with homogeneity in the paint blends. - FTIR indicates that polythiophene enhances the protecting role of the resin by delaying resin degradation. - Colour chance from yellowish grey to violet after exposure in a cyclic test. - Potentiodynamic measurements in 3,5 wt% NaCl indicate an ennobling of steel by the polythiophene coating. - The best corrosion resistance are obtained with a 22 m coating at a corrosion potential of -346 mV (vs. SCE). - EIS indicates the presence of a passive oxide layer.

Reference Ocampo et al 2005 [35]

Kousik et al 2001 [36]

2.4.3 Research from Ormecon

Ormecon, the German manufacturer of the CORRPASSIV paint systems, has performed a number of tests in order to prove the anti-corrosive effect of their paint systems. The following results and claims are recited by Ormecon on their homepage and in their publications. [37] Ormecon states that a primer containing their organic metal (red. doped polyaniline) will enhance the surface potential of steel by up to 800 mV. The internal specifications of the company demand a potential shift of at least +100mV, which is stable over time. Ormecon also claims that the CORRPASSIV paint system produces a passive layer of Fe2O3 about 1 m thick, between the steel surface and the primer. The formation of stable iron oxides is according to Ormecon, possible due to the following reaction mechanism (see figure 16). As seen in the reaction scheme, polyaniline oxidizes the iron to Fe2+ and is reduced to leucoemeraldine (LE) in return. The iron ions are oxidized further to Fe3+ which is able to form Fe2O3 in the presence of OH-. The leucoemeraldine form of polyaniline will by means of oxygen undergo an oxidation to the emeraldine base (EB) form, which in the presence of H+ will oxidize polyaniline back to its original emeraldine salt (ES) form. According to the reaction scheme, polyaniline is thus a catalyst for the production of Fe2O3. [38]

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Figure 16. Reaction mechanism for passivation of iron using polyaniline according to Ormecon. [38]

A closer look at the reaction mechanism proposed by Ormecon reveals that the reactions are not in balance. As recalled on figure 3, the same amount of hydrogen is produced and used in the catalytic circle of polyaniline. The release of two hydrogen ions for reduction of oxygen (cf. figure 16) will thus put an end to the catalytic circle. A supply of hydrogen ions from the environment is therefore necessary if polyaniline has to act as a catalyst. According to Ormecon, a topcoat on the polyaniline primer is needed for obtaining an effective corrosion protection. Without a topcoat, H+ ions penetrate the primer layer to the surrounding media and the catalytic circle in figure 16 will stop. An optimal utilization of the anti-corrosive character of polyaniline can therefore only be obtained if an acidic pH is maintained in the primer. According to Ormecon, a low pH can be retained within the primer by a powerful barrier coating which forces the H+ ions to stay in the primer. Ormecon also claims that their paint systems are capable of protecting even non-painted areas, for instance scratches in the paint film. According to their specifications, the formation of rust in a 1-2 mm broad score is inhibited. [39]

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3 EXPERIMENTAL PROCEDURE
A number of experiments are performed in order to uncover the applications and efficiency of anti-corrosive paint systems based on conducting polymers. Another purpose of these experiments is to disprove or confirm the mechanisms which have been proposed in section 2.4.1.

3.1 Applied paint systems

Different paint systems are formulated and applied to steel and aluminium substrates. For protection of steel, the paint systems are divided into three sections of applications: shopprimers, paint for ballast tanks and paint for off-shore environments. A brief introduction to each of these application areas and their characteristics are given in the following.

3.1.1 Test panels and surface preparation

Two types of test panels, made of steel or aluminium, are used in this project. The steel panels, which are standardized test panels from Hempel, are made of normal carbon steel (St37) and blast cleaned to a designation SA3 according to ISO8501-1. A grit blasting provides the panels with a surface roughness of designation N9 or N10 according to Rugotest 3. Designation N9 and N10 corresponds to a Ra-value of 6,3m and 12,5m respectively. The Ra value describes the arithmetical mean deviation of the profile. Only the shopprimer uses a designation N9 while the paint systems for ballast tanks and off-shore protection uses a N10 profile. The size and thickness of the steel panels depends on the test procedure. The aluminium panels are made of the alloy AA 6016 and provided by Chemetall. This type of alloy contains magnesium and silicon as the main alloying elements (0,25-0,6 wt% Mg and 1-1,5 wt% Si), but smaller amounts of copper, chromium or manganese can also be present. Magnesium and silicon are added in order to increase the strength of aluminium by precipitation of Mg2Si particles in the alloy. The test panels have the dimensions 105 x 190mm and a thickness of 0,75 mm.

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3.1.2 Shopprimer
A shopprimer is a thin organic coating that provides temporary corrosion protection of steel plates and profiles during storage, transport and production. The application of shopprimers is related to marine and industrial use, where a protective coating is needed in order to retain a smooth and viable surface workable for further machining. Applying a shopprimer pre-treatment to steel plates makes additional surface treatment, cutting and welding operations less complicated. The requirements to a shopprimer and its specifications are listed in table 9.
Table 9. Requirements and specifications of shopprimers.

Requirements Coating thickness Corrosion protection

Specifications - Max. 20 m and no pinholes. - Protection against atmospheric corrosion for 3-12 months depending on the environment. Temporary corrosion protection against salt and fresh water during building period.

Weldability

- High temperature resistance and less than 5 mm burn damage along the cutting edge. - Low gas and fume production with low toxicity. - No influence of arc stability and low splatter.

This project examines the corrosion resistance of shopprimers based on three different binder systems with and without the addition of polayniline as described in table 10. Polyaniline is added as a powder with the name Panipol F, which is produced by the Finnish company Panipol. A detailed product description of the standardized shopprimers, which are stated in table 10, is found in the respective data sheets in appendix H, J, K and L.

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Table 10. Overview of applied shopprimers.

Classification

Product description

Polyvinyl butyral Polyaniline containing PVB paint from Ormecon (CORRPASSIV 4000) (PVB) Zinc phosphate pigmented epoxy polyamide Low-zinc ethyl silicate Standard PVB shopprimer from Hempel Standard zinc phosphate shopprimer from Hempel Standard zinc phosphate shopprimer with 10vol% Panipol F Standard zinc silicate shopprimer with 50w% zinc Standard zinc silicate shopprimer with 40w% zinc and 5vol% Panipol F Standard zinc silicate shopprimer with 30w% zinc and 5vol% Panipol F

3.1.3 Paint for ballast tank

A ballast tank is a tank that is filled with sea water to provide stability when the ship is unloaded. The corrosion of ballast tanks is not evenly distributed since the environment in the tank contains areas with different electrochemical loadings. When the tank is full, the upper regions are anodic and the lower regions are cathodic. The upper regions therefore tend to corrode, and the lower regions tend to blister and delaminate. In order to control this problem, ballast tanks are provided with sacrificial anodes or impressed current in order to establish cathodic protection of the tank. To fulfil the application requirements, the paint specifications in table 11 must be fulfilled.
Table 11. Requirements and specifications of paints for ballast tanks.

Requirements Film thickness Corrosion protection

Specifications Min. 2 x 150 m In accordance with ISO15711. No disbonding with an equivalent diameter <20mm.

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The paint system used within this project is a polyamide-adduct cured epoxy paint from Hempel especially designed for protection of ballast tanks. Three versions are prepared according to table 12. A detailed product description of the conventional paint system is stated in appendix N.
Table 12. Overview of applied paints for ballast tank protection.

System 1 2 3

Primer -----

Barrier coating Polyamide-adduct cured epoxy paint Polyamide-adduct cured epoxy paint with 10vol% Panipol F

Barrier coating Polyamide-adduct cured epoxy paint Polyamide-adduct cured epoxy paint Polyamide-adduct cured epoxy paint

Polyaniline/PVB paint Polyamide-adduct cured epoxy (CORRPASSIV 4000) paint with 10vol% Panipol F

3.1.4 Paint for off-shore environment

An off-shore environment is a very broad term, and includes many different corrosive scenarios. This project only examines the effect of an off-shore environment above the waterline. Examples of application areas are drilling rigs and marine windmills. Both are placed in an environment which is highly corrosive due to continuous exposure to salt spray and high relative humidity. The protective coating also needs to withstand thermal stress due to varying temperature conditions. The paint must therefore be able to withstand the requirements and paint specifications listed in table 13.
Table 13. Requirements and specifications of paint systems for off-shore protection.

Requirements Film thickness Corrosion protection

Specifications Min. 60 m primer and min. 280 m of complete paint system Requirements after qualification testing (according to ISO 20340): Undercutting corrosion: M < 3mm. M = (C-2)/2, where C is the average corrosion from the scribe. Adhesion: Min. 5 MPa and max. 50% reduction from original value.

The paint system applied in this project for protection in the off-shore environment is a commercial paint system from Hempel. This paint system is composed of three layers: 1) a zinc-

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rich epoxy primer, 2) an epoxy polyamide barrier coating and 3) an acrylic polyurethane topcoat. Two versions of the paint system are prepared according to table 14. A detailed description of the paint system is found in the respective data sheets in appendix M, Q and R.
Table 14. Overview of applied paint systems for off-shore protection.

System 1 2

Primer Zinc-rich epoxy primer Zinc-rich epoxy primer with 10vol% Panipol F

Barrier coating Epoxy polyamide barrier coating Epoxy polyamide barrier coating

Topcoat Acrylic polyurethane topcoat Acrylic polyurethane topcoat

A water based paint system is also formulated and tested in off-shore conditions. The paint system is a commercial paint system from Hempel composed of two layers: 1) a zinc-rich epoxy primer and 2) a polyamide cured epoxy barrier coating. According to table 15, four versions of the paint system are formulated with varying zinc content and addition of Baytron P (red. polythiophene). A detailed description of the paint system is given in the respective data sheets in appendix O and P.
Table 15. Overview of water based paint systems for off-shore applications.

System 1 2 3 4

Primer Zinc epoxy primer with 85w% Zn Zinc epoxy primer with 85w% Zn and 2vol% Baytron P. Zinc epoxy primer with 60w% Zn Zinc epoxy primer with 60w% Zn and 2vol% BAYTRON P

Barrier coating Polyamide cured epoxy paint Polyamide cured epoxy paint Polyamide cured epoxy paint Polyamide cured epoxy paint

Topcoat ---------

3.1.5 Paint for aluminium substrates

Corrosion of aluminium depends mainly on the type of aluminium alloy and the character of the corrosive environment. The aim of this project is to compare and examine the efficiency of four different protective coating systems (see table 15). Anodizing and chromatizing converts the surface of aluminium to Al2O3 and Cr2O3 while altizizing covers the surface with MnO2. Each of these three coatings has a very high potential and provides anodic protection to aluminium. All of

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the protective coating systems have a two layer paint system applied on top. This paint system is based on an epoxy polyamide barrier coating and an acrylic polyurethane topcoat. A more detailed product description is stated in the respective data sheets in appendix I, Q and R
Table 16. Overview of applied coating systems for protection of aluminium.

System 1 2 3 4

Pre-treatment --Anodizing Chromatizing (yellow) Altizizing

Primer Polyaniline/PVB primer (CORRPASSIV) -------

Barrier coating Epoxy polyamide barrier coating

Topcoat Acrylic polyurethane topcoat Acrylic polyurethane topcoat Acrylic polyurethane topcoat Acrylic polyurethane topcoat

Epoxy polyamide barrier coating Epoxy polyamide barrier coating Epoxy polyamide barrier coating

3.2 Paint film characterization

The different paint systems have been characterized according to their film thickness, structure and adhesion. Electromagnetic induction and the eddy current test are both used to determine the film thickness. The structure of the dry paint and its composition is examined by scanning electron microscopy and the adhesion is evaluated by a pull-off test.

3.2.1 Electromagnetic induction

Electromagnetic induction is a non-destructive method used to determine the dry film thickness (DFT) of paint on ferrous substrates. Standard test methods are described in ASTM B 499 and ISO 2178. Measurements are performed by a probe placed on the surface of the specimen. In the probe, a magnetic field is generated by a magnetizing coil. The magnetic substrate material influences the magnetic inductivity and the change in magnetic flux is registered by a measuring coil. The signal from the coil is transformed to an electric signal that indicates the distance from the probe to the magnetic substrate material, which is equal to the coating thickness.

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Thickness measurements by electromagnetic induction are a simple method with a good accuracy and a tolerance of 1%. [24]

3.2.2 Eddy Current Test

Measurements of the dry film thickness on a non-magnetic substrate material, such as aluminium, are performed by the non-destructive Eddy Current Test (ECT). Application and performance skills are described in ASTM B 244 and ISO 2360. In the ECT-technique, an AC-magnetic field is generated by a probe that induces an eddy current in the base material, which is proportional to the frequency and the resistance. When a nonconductive coating is present on the substrate material, the magnitude of the induced eddy current is reduced. This loss in permeability of the eddy current can be used to measure the coating thickness. The eddy current generates further an opposite electromagnetic field. This field reduces the reactant of the coil in the probe and thus the generated voltage output from the probe. The change in voltage from the probe is therefore also a basis for measuring the thickness of the coating. An ECT-instrument retains normally a tolerance of 1%, but the measurements are sensitive to different factors such as surface roughness, curvature, substrate thickness and material. Modern instruments are normally designed to incorporate both magnetic and eddy current principles in one unit. [24], [40]

3.2.3 Scanning Electron Microscopy

Scanning electron microscopy (SEM) is used to determine the microstructural topography and the composition of the different paint systems and surface treatments. A description of the method is presented in ASTM E-1508. In the SEM-technique, an electron beam is used to scan the sample surface. The electrons are produced in a beam gun by heating a filament made of either tungsten or lanthanum hexaboride. A column containing electromagnetic lenses is used to focus and direct the beam towards the sample. The surface scanning is performed at high vacuum and with an intensity of the electron beam of up to 30 keV. Once the beam hits the sample, secondary and backscattered electrons are ejected. A detector collects these electrons and converts them into a signal that can be displayed as a picture showing the surface topography with high resolution and depth. Interactions between the atoms in the sample and the primary electrons from the beam can furthermore result in an

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ionization of the atoms and emission of X-rays. Analysis of the wavelength or the energy of emitted X-rays can be used to identify the elements in the sample. The relative intensities of these X-rays are also a useful tool to make a qualitative analysis. [41], [42]

3.2.4 Pull-off test

Adhesion of the paint can be determined by means of a pull-off test. A standard method for application and performance of the pull-off test is described in ASTM-standard D45541. The pull-off test is performed by gluing a dolly to the surface of a paint film. In order to obtain reliable measurements, it is very important that the surfaces of both the paint and the dolly are clean and contain no grease or contaminants. Both surfaces are therefore slightly grinded and rinsed carefully with both water and spirit. A portable adhesion tester is subsequently fixed on top of the dolly, and the load is gradually increased until the dolly is detached. The force needed to detach the dolly is therefore an expression of the adhesion of paint to the underlying substrate material. Normally, the force is measured in psi or MPa and the load can be applied either by mechanical, hydraulic or pneumatic pressure. The most reliable results are obtained on test panels with a thickness of at least 5 mm. A pull-off test performed on a very thin test panel can cause deformation of the panel and thus a smaller adhesion value. [40]

3.3 Corrosion resistance

Examination of the corrosion resistance is performed by electrochemical measurements and different accelerated climatic tests. Electrochemical measurements are used to establish the corrosion rate and corrosion potential of the painted steel and aluminium substrates. The accelerated climatic tests are performed in order to reflect some of the worse climatic scenarios which are fatal for the paint performance. The chosen climatic test methods depend on the application area of the paint system. Table 17 on the following page lists the earlier mentioned application areas and their test methods. A description of the performance of the different tests is given in the following sub-sections.

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Table 17. Test methods used for characterization of the corrosive behaviour in the different application areas.

Application area Shopprimer Ballast tanks Off-shore environment Aluminium

Test method Natural Weathering Test Mebon Prohesion Test Immersion Test Cathodic Protection Test Salt Spray Test Cyclic Test Salt Spray Test Cyclic Test Filiform Corrosion Test

3.3.1 Open Circuit Potential

The Open Circuit Potential (OCP) is the potential at which there is no current, and can be used as an expression for the corrosion potential of the material in a given electrolyte. By determining the OCP potential of both painted and non-painted substrates, an evaluation of the galvanic coupling between the steel substrate and the paint can be made. The experiment is performed in an electrochemical cell containing a solution of 3,5wt% NaCl. The electrical potential of the test panel is measured against a reference electrode, when there is no current flowing through the test panel. A reference electrode of saturated calomel is used in this case and the experiment is performed at room temperature with access to air. The two electrodes are connected to a potentiostat which measures the potential of the test panel in proportion to the calomel electrode. The OCP potential is finally mapped as a function of time.

3.3.2 Anodic polarization

Anodic polarization is used to determine the corrosion rate and potential in a 3,5wt% NaCl solution. The experiment is performed according to ASTM standard G5-94. The polarization measurements are performed in an electrochemical cell containing a 3,5wt% NaCl solution at room temperature and with access to air. A reference electrode of saturated calomel, a counter electrode of graphite and a working electrode of the test material are placed in

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the electrochemical cell. In an anodic polarization experiment, the test material is polarized and the current is continuously measured as the potential is increased. The potential scan is performed from an initial potential around 300 mV beneath the open circuit potential. A potential around 800 mV above the initial potential is chosen as the final potential and the scanning is performed at a scanning rate of 10mV/min in a current interval from -300 to 300 mA. The potential is finally mapped as a function of the current density, illustrating the anodic and cathodic polarization curves of the test material.

3.3.3 Natural Weathering Test

The Natural Weathering Test is an atmospheric corrosion test performed on the roof of Hempel in Lundtofte, Denmark. The test is part of the test procedure for shopprimers and is comparable with standardized norms in ASTM D 1014. The painted steel panels are prepared with a 50 x 1 mm score in a 45 angle to the horizontal and placed in an exposure rack turning 45 to horizontal and facing south. Inspections are performed regularly and are evaluated according to rust formation and blistering as specified in ASTM D 61095 and ASTM 714-02. By the end of the test, the panels are evaluated with regards to rust creep and adhesion.

3.3.4 Mebon Prohesion Test

The Mebon Prohesion Test is a cyclic wet/dry corrosion test designed to match the conditions that exist in the atmosphere in industrial areas. The test is part of the standardized test procedure of shopprimers and follows the specifications in ASTM G5 ANNEX 5.

Each painted steel panel is applied with a 50 x 1 mm score in a 45 angle to the horizontal and is placed in a special chamber with the conditions described in table 18.
Table 18. Test conditions of the Mebon Prohesion Test.

Cycle description Temperature Airflow Pressure pH

2 hours of dry-off and 4 hours of spray with 0,05 w% NaCl and 0,35 w% (NH4)2SO4 Dry period: 352 C Spray period: 200,5 C 0,8 l/s 1-2 ml/hour pr. 80 cm2 1,4 bar 6,0 6,5

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Inspections of the test panels are normally performed in an interval of 1, 3, 7, 14, 21 and 42 days but the resistance depends on the applied paint system. Shopprimers will usually not last 42 days of exposure. At each inspection, rust and blisters are evaluated according to standardized norms in ASTM D 610-95 and ASTM 714-02. A final evaluation of the paint systems is given with regards to rust creep and adhesion as specified in ASTM D1654.

3.3.5 Cathodic Protection Test

The Cathodic Protection Test is part of the test procedure for ballast tank paint systems and determines the ability of the paint to withstand cathodic protection. The test procedure is described in ISO 15711. The test equipment consists of a rectifier to which a reference electrode of saturated calomel (SCE) and a platinized titanium anode are attached. A test tank and a store tank are used for cooling and circulation of the electrolyte. The electrolyte consists of artificial seawater as specified in ASTM D 1141-98. During exposure the potential is stabilized at -1050 mV vs. SCE by impressed current. Before exposure, the painted steel panels are provided with an 12 mm score placed in the centre of the panel. Inspections of blistering are regularly performed where blister size and density are reported according to ASTM D 714-87. The disbonded area at the bare spot and the adhesion are evaluated when the test is stopped by a knife test.

3.3.6 Immersion Test

Immersion in seawater is part of the test procedure that determines the corrosion resistance of paint systems for ballast tanks. The immersion test is described and fulfils the standardized norms in ISO 20340. The painted steel panels are prepared with a 50 x 2 mm score placed across the panel and are then placed in a test tank consisting of aerated artificial seawater at a temperature of 401 C. The standard recommends an exposure period of 4200 hours or until the paint system is degraded and posseses no anti-corrosive effect. An evaluation according to rust formation, blistering and delamination is reported frequently as specified in ASTM D 714-02 and ASTM D 610-01. Delamination and adhesion are evaluated at the end of the test by a knife test.

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3.3.7 Salt Spray Test

The Salt Spray Test is performed in order to determine the corrosion resistance of painted steel and aluminium panels in the off-shore industry above the waterline. Guidelines and test procedures are described in the international standard ASTM B117. The salt spray test is performed in a special fog chamber where salt fog enters the chamber by nozzles at a constant temperature and pressure. A salt fog with a concentration of 5% NaCl and a pH of 6,5-7,2 is applied and the chamber is kept at a constant temperature at 35 C. Before startup, all the test panels are provided with a 50 x 2 mm score across the panel and placed in a defined angle in the salt spray chamber. The exposure time depends on the corrosion resistance of the painted panels. Each panel is frequently inspected during the test period and is evaluated according to rust formation, blistering and delamination. The same evaluation procedure is performed at the end of the test together with a pull-off test in order to determine the adhesion. Evaluation procedures are performed according to ASTM D 714-02 and ASTM D 610-01.

3.3.8 Cyclic Test

The Cyclic Test is a standardized test designed especially for applications in the paint industry and determines the corrosion resistance of painted steel and aluminium. The test is developed to reflect the harsh environment in off-shore applications above the waterline. Test conditions and procedures are described in standard ISO 20340. Before exposure, each test panel is applied with a 50 x 2 mm score across the panel. The cyclic test consists of an alternating test procedure involving three different types of corrosive conditions. Table 19 describes the test cycle and the coherent conditions.
Table 19. Test description and applied conditions for the cyclic test.

Period Description

Day 1

Day 2

Day 3

Day 4

Day 5

Day 6

Day 7 Low temperature exposure.

Alternating exposure in 4 hours UV-lighting and 4 hours condensation.

Salt spray exposure according to ASTM B 117.

Conditions

UV-light: UVA 340 nm and 603 C Condensation: 503 C

5% NaCl and 35 C

-202 C

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Between salt spray exposure and low-temperature exposure, the test panels must be rinsed with de-ionized water in order to remove most of the salt from the surface. According to the standard, the normal test period is 25 cycles or 4200 hours. The test panels are inspected frequently and are evaluated with regards to rust formation, blistering and delamination according to the standards ASTM D 714-02 and ASTM D 610-01. When the test is finished, a pull-off test is performed in order to determine the adhesion of the painted panels.

3.3.9 Filiform Corrosion Test

The Filiform Corrosion Test determines the resistance of organic coated aluminium to filiform corrosion. Test procedures and conditions are described in standard ISO 4623-2. The painted aluminium panels are provided with 2 scores, with the dimensions 50x1 mm and 50x2 mm. The scores are placed on the panel at least 20 mm apart and perpendicular to each other. In order to accelerate filiform corrosion, the test panels are exposed to concentrated 37% HCl vapour for an hour at room temperature. After exposure in HCl vapour the test panels are placed in a holder for 15-30 min to dry. Finally, the test panels are placed horizontally in a moist chamber at 40 C and 82% relative humidity for about 1000 hours. During exposure in the moist chamber, the test panels are inspected regularly and are evaluated according to filiform corrosion as specified in ISO 4628-10. When the test is finished, a final evaluation of the extension of filiform corrosion is reported and the paint is removed in order to establish hidden corrosion products beneath the paint surface.

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4 RESULTS AND DISCUSSION

This chapter contains a review of the experimental results which are obtained in light of the described experiments in chapter 3. A thorough analyse is made in order to confirm or disprove the hypotheses stated in section 2.4.1, and the efficiency is evaluated in relation to other anti-corrosive paint systems or surface treatments. This chapter is divided in to four sections which deal with the four application areas described in previous sections.

4.1 Shopprimer
The Mebon Prohesion Test and the Natural Weathering Test were used to examine the protection properties of the three different shopprimer systems based on either PVB, zinc phosphate epoxy polyamide or low-zinc ethyl silicate. The two tests were finished after an exposure time of 92 days. Pictures taken after test exposure are presented in appendix A and B.

4.1.1 PVB shopprimers

A conventional PVB-shopprimer from Hempel and a polyaniline containing PVB paint from Ormecon are examined and compared. The two types of PVB paints do not distinguish significantly from each other after exposure in the natural weathering test, and the degradation of the panels is poor. The applied score is corroded but the rest of the panel is more or less intact. Two of the CORRPASSIV panels contain marks of chalking and the film thickness is probably the reason for this difference. Measurements of the dry film thickness showed that panel 1 and 2 only had a film thickness about 12 m. The other panels had a film thickness about 20 m, which are the normal film thickness of shopprimers. The degradation of the two PVB paints is more severe after exposure in the Mebon Prohesion Test. The panels are corroded in the score and on the plain paint surface, but no significant difference is seen between the two PVB paints. The degradation of the plain paint surface starts as blisters, which subsequently burst and cause the underlying steel surface to corrode.

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Electrochemical measurements are performed in a 3,5w% NaCl solution in order to establish the corrosion potential and corrosion current for each of the PVB paints. The OCP potential and the polarization curves are illustrated in figure 17 and 18.

-50

-100

Potential vs SHE (mV)

-150 Steel CORRPASSIV PVB shopprimer

-200

-250

-300

-350

-400 0 2 4 6 8 10 Time (min) 12 14 16 18 20

Figure 17. OCP potential of PVB based shopprimers in 3,5w% NaCl.

600

400

200 Potential vs SHE (mV)

0 Steel CORRPASSIV -200 PVB shopprimer

-400

-600

-800 0,0000001

0,000001

0,00001

0,0001

0,001

0,01

0,1

10

100

Current density (mA/cm2)

Figure 18. Polarization curves of PVB based shopprimers in 3,5w% NaCl.

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The OCP measurements in figure 17 show an increase in corrosion potential for both PVB paints when compared to uncoated steel after 20 min exposure to 3,5w% NaCl. The conventional PVB primer stabilizes at a potential of -125 mV while CORRPASSIV reach a potential of -200 mV. A greater ennobling is therefore present in the conventional PVB primer when compared to CORRPASSIV. The reason for this difference is to be found in the paint composition of the conventional PVB primer. It emerged that the conventional PVB primer contains additives such as zinc phosphate (Zn3(PO4)2) and iron oxide (Fe2O3), which both contributes to an increase of the potential. The same pigment additives were not found in the CORRPASSIV paint, which indicates that polyaniline also has an ennobling effect on the steel substrate. The polarization curves in figure 18 shows a decrease in the corrosion current of the painted steel specimens when compared to uncoated steel. The corrosion current of the painted specimens is approximately the same, and it is therefore likely that inhibition of the corrosion rate is due to a barrier effect. The corrosion potential of the two PVB paints is in agreement with the OCP measurements while the uncoated steel specimens has a corrosion potential about 100 mV more noble when compared to the OCP potential. This raise in the corrosion potential of steel is possibly caused by formation of noble iron-chloride complexes on the surface. The conclusion is therefore that no significant difference in the anti-corrosive effect is present in the two examined PVB paints. The content of inhibitive additives in the conventional PVB primer complicates a comparison of the two paints, but electrochemical measurements indicate that polyaniline has an ennobling effect of the steel substrate.

4.1.2 Zinc phosphate shopprimers

Two versions of a zinc phosphate pigmented epoxy polyamide shopprimer from Hempel were examined and compared in relation to their anti-corrosive character. The preparation of a polyaniline containing zinc phosphate primer was difficult and caused problems with the homogeneity of the paint blend. The final dry paint film therefore contained non-dispersed polyaniline particles. These difficulties are also stated in the literature and are probably caused by the physical nature of polyaniline. Polyaniline possesses a very high surface tension (69,4 mN/m), which makes it difficult to wet and corporate into a paint blend. [43] The natural weathering test causes no serious damage to the two zinc phosphate shopprimers. Only the applied score is exposed to a slight degree of rusting, while the plain paint surface is intact on both of the shopprimer systems. An interesting observation was however made after about 1 month of exposure on the polyaniline containing zinc phosphate primer. It appeared that

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the surface of the paint film had started some kind of segregation and the dry paint film felt wet. A possible explanation could be that polyaniline is increasing the absorption of water which causes the paint film to segregate. The exposure in the Mebon Prohesion Test was more severe to the painted test panels, and corrosion damages appear both in the score and on the plain panel. As it appears in the pictures in appendix B, the polyaniline containing zinc phosphate primer is exposed to a greater extent of corrosion in comparison to the conventional zinc phosphate primer. Earlier observations showed that the degradation was initiated by small liquid containing blisters on the paint surface. It is unclear if the blistering is accelerated by the presence of polyaniline, but it is possible that the nondispersed polyaniline particles act as small local cathodes. The formation of cathodic reaction products (e.g. OH-) will therefore be concentrated around the polyaniline particles and blisters are formed. Observations related to segregation of the dry paint film were also made in the Mebon Prohesion Test and the polyaniline containing primer turned mat. The conclusion is therefore that no improvement of the corrosion resistance is reached by adding polyaniline to a zinc phosphate shopprimer. A very likely explanation for this is related to the difficulties of creating a fully dispersed polyaniline paint blend.

4.1.3 Zinc silicate shopprimers

Three versions of a low-zinc ethyl silicate shopprimer from Hempel were formulated and examined according to their anti-corrosive character. The aim is to examine the influence of zinc content and polyaniline addition. As it appears on the pictures in appendix A, the panels are exposed to corrosion in the natural weathering test. A corrosive attack is present both in the score and on the plain paint film. The corrosion present on the panel is named pin-point rusting due to the formation of pin holes in the paint film. Pin-point rusting is normally formed if the shopprimer does not entirely cover the profile of the steel surface. In this way, the corrosive attack is concentrated at small peaks on the steel surface. As seen on the pictures, the corrosion is most severe on the paint systems with reduced zinc content, i.e. respectively 30 and 40w% Zn. No significant differences are present between the paint containing Panipol (panel 44) and the pure zinc paint (panel 42). The conclusion is therefore that anti-corrosive effect is determined by the zinc content in these zinc-silicate shopprimers. The observations from the Mebon Prohesion Test are similar to the ones seen in the natural weathering test. The only difference is the degree of corrosion which is higher due to a more

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severe environment. As it appears from the pictures in appendix B, the conventional zinc silicate shopprimer (panel 45) is exposed to white rusting. This corrosion phenomenon is caused by a higher zinc content (i.e. 50w% Zn) and a more effective galvanic contact between zinc and steel. The final conclusion is therefore that the best corrosion resistance is obtained by the conventional zinc silicate shopprimer. The tests also show no improvement of the cathodic protection by addition of polyaniline.

4.2 Paint for ballast tanks

A Cathodic Protection Test and an Immersion test were used to examine the protection properties of three versions of a polyamide-adduct cured epoxy paint system, designed especially for ballast tank protection. The two tests were stopped after 96 days of exposure, and the adhesion was evaluated by a knife test. Pictures taken after the final evaluation are presented in appendix C and D. As seen in figure 19, a cathodic disbonding occurred on the painted steel panels after exposure in the cathodic protection test. This cathodic disbonding is created in continuation of the applied defect in the paint and forms a recognizable circle pattern.

Figure 19. Cathodic disbonding after exposure in CPT. Panel 106: Standard ballast tank paint; Panel 116: Ballast tank paint w. Panipol; Panel 126: CORRPASSIV primer + ballast tank paint w. Panipol.

The cathodic disbonding is stated as an average of the distance from the defect to the point where the adhesion is intact. Table 20 lists the measured values of the cathodic disbonding for each of the three paint systems. The reference panels are not cathodic protected by an impressed current.

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Table 20. Measurements of the cathodic disbonding after the cathodic protection test.

Panel nr. 105 (ref.) 106 107 115 (ref.) 116 117 125 (ref.) 126 127 (ref.)

Paint system Standard ballast tank paint

Cathodic disbonding (cm) 1,0 1,8 1,8 1,2 1,3 0,8 2,4 1,8

Comments Bad adhesion in the area with cathodic disbonding.

Standard ballast tank paint w. Panipol

The paint is softer and the adhesion in the area with cathodic disbonding is lower than panel 105 to 107. Very bad adhesion in the area with cathodic disbonding and the steel surface shows signs of rusting.

CORRPASSIV primer paint w. Panipol

+ standard ballast tank 2,7

As indicated in table 20, the best resistance to cathodic disbonding is seen in panels 115 to 117. These panels are painted with a standard ballast tank paint containing Panipol (red. polyaniline) in the first layer. The second best performance is seen in panels 105 to 107, which contain the conventional ballast tank paint from Hempel. Both of these two paint systems keep the requirement, i.e. less than 20 mm disbondment. The final paint system stated as panels 125 to 127 in table 20 is painted with a CORRPASSIV primer and a paint system similar to panel 115 to 117 on top. This paint system shows very bad adhesion properties and a high degree of disbonding. The results therefore show that the addition of Panipol provides an inhibition of the cathodic disbonding, but the type of binder is also important. The CORRPASSIV primer which is based on a PVB binder is not a suitable paint for ballast tank application. The lower degree of cathodic disbonding is in agreement with the results provided by Holness [31]. Therefore, the assumption is made that polyaniline inhibits the disbonding by absorbing OH- and reacts to form the nonconductive emeraldine base form. Figure 20 shows a section of the same three paint systems after seawater immersion at 40 C. The paint systems are presented in the same order as figure 19.

4 RESULTS AND DISCUSSSION

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Figure 20. Cathodic disbonding after seawater immersion. Panel 109: Standard ballast tank paint; Panel 118: Ballast tank paint w. Panipol; Panel 130: CORRPASSIV primer + ballast tank paint w. Panipol.

As illustrated in figure 20, the best resistance to cathodic disbonding is seen in panel 118. This is similar to the results obtained in the cathodic protection test. The width of the area with cathodic disbonding is measured and listed in table 21 for each of the three paint systems.

Table 21. Measurements of the cathodic disbonding after the immersion test.

Panel nr. 108 109 110 118 119 120 128 129 130

Paint system Standard ballast tank paint

Cathodic disbonding (cm) 3,3 3,2 3,3 2,8 2,7 3,1 3,7 5,0 5,0

Comments Low adhesion in the area with cathodic disbonding.

Standard ballast tank paint w. Panipol

Low adhesion in the area with cathodic disbonding. Small blisters on the panel. Very bad adhesion in the area with cathodic disbonding. Rust formation at the steel surface around the score.

CORRPASSIV primer + standard ballast tank paint w. Panipol

Some differences are observed between the immersion test and the cathodic protection test. Despite the good resistance to cathodic disbondment, the paint films in panels 118 to 120 show small blisters about 1 cm from the score and in the splash zone. Both areas are exposed to a high degree of oxygen which increases the risk of cathodic blistering. The formation of cathodic blisters is properly accelerated by a higher exposure temperature and by the presence of non-dispersed

4 RESULTS AND DISCUSSSION

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polyaniline particles in the paint film. If the particles act as local cathodes at the steel surface, the cathodic reactions are concentrated in these spots and cathodic blisters form more easily. An interesting discovery was made in the case of the last paint system which contained the CORRPASSIV primer. The primer had changed colour from green to blue after the exposure to seawater, but only in the area with cathodic disbonding. This observations states that a chemical reaction is taking place between the primer and hydroxide ions. A small experiment was performed in order to confirm this statement. A dry film of CORRPASSIV was exposed to ammonium hydroxide (NH4OH) and the same colour change was observed. Exposing the blue paint film to hydrochloride acid (HCl) forced the opposite colour change. The primer is therefore reacting to pH changes in the surrounding environment. As recalled in figure 3, the emeraldine salt form is green while the emeraldine base form is blue. Without further analysis, the assumption is made that polyaniline reacts with OH- to form the blue emeraldine base form. The conclusion is therefore that polyaniline has an inhibiting effect on the cathodic disbonding. This is due to absorption of hydroxide ions, but the efficiency is strongly dependant on the type of binder and the homogeneity of dry paint film.

4.3 Paint for off-shore environments

A Salt Spray Test and a Cyclic Test were used to examine the protective properties of paint systems for application in off-shore environment above the waterline. The examination was performed on a solvent based paint system and a water based paint system. Pictures taken after test exposure are presented in appendix E and F.

4.3.1 Solvent based paint system

The solvent based paint system is a conventional anti-corrosive paint system from Hempel composed of three coatings: A zinc-rich epoxy primer, an epoxy polyamide barrier coating and an acrylic polyurethane topcoat. Two versions of the paint systems are prepared, and deviate from each other by the addition of Panipol F in the primer. The two tests were finished after an exposure period of 90 days. The salt spray exposure causes no serious degradation on either of the paint systems. Only the applied score is corroded, while the plain paint surface remains intact and free of blistering. A final evaluation is performed in order to examine the adhesion and the degree of undercutting

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54

corrosion. The undercutting corrosion is insignificant and there is no difference between the two paint systems. The adhesion is determined by a pull-off test and the results are listed in table 22.
Table 22. Measurements of adhesion by pull-off test after the salt spray test.

Panel nr.

Paint system Zinc-rich epoxy

POT measured (MPa) 5,7 7,2 5,6 5,2 5,8 5,4

Description of fracture 35% adhesive break, 25% cohesive break, 40% break in glue 50% adhesive break, 50% cohesive break 90% cohesive break, 10% break in glue 20% adhesive break, 80% cohesive break 25% adhesive break, 40% cohesive break, 35% break in glue 90% cohesive break, 10% break in glue 90% cohesive break, 10% break in glue 45% adhesive break, 55% cohesive break 100% cohesive break 95% cohesive break, 5% break in glue 98% cohesive break, 2% break in glue 15% adhesive break, 70% cohesive break, 15% break in glue

52

primer + epoxy polyamide barrier coat + acrylic

53

polyurethane topcoat

Zinc-rich epoxy 62 primer w. Panipol F + epoxy polyamide barrier coat 63 + acrylic polyurethane topcoat

5,8 4,8 6,2 5,9 5,0 5,5

As indicated in table 22, the adhesion is very low and the requirement of at least 5MPa is barely obtained. The most important reason for these low POT values is the panel thickness which is less than 5 mm. This causes the panel to deform and a lower POT value is measured. The fracture is based on three types of break in the paint: 1) an adhesive break between the steel surface and the primer 2) a cohesive break in the topcoat and 3) a break in the glue. As described in table 22, the break is primarily concentrated in the topcoat in both of the paint system. An incomplete curing of the topcoat could explain this phenomenon. The cyclic test contains a very aggressive test environment which causes a more severe degradation of the paint film. Each of the test panels are exposed to score rusting and blistering around the score. The degree of blistering is most severe on the panels coated with a paint system containing Panipol in the primer. In the final evaluation, the paint was removed from the steel panel and the

4 RESULTS AND DISCUSSSION

55

degree of undercutting corrosion was determined. Figure 21 shows the undercutting corrosion in four of the test panels. Panel 54 and 56 are coated with the conventional anti-corrosive paint system from Hempel while panel 64 and 66 are coated with the version that contains Panipol in the primer.

Figure 21. Undercutting corrosion. Panel 54 + 56: Normal anti-corrosive paint system; Panel 64 + 66: Anti-corrosive paint system with addition of Panipol in primer.

The degree of undercutting corrosion is measured at 9 points along the score. The final value of undercutting corrosion (M) is calculated by means of equation 4.1, where C is the average of the 9 measurements.

M =

(C 2) 2

(4.1)

The M-value is determined for each of the panels illustrated at figure 21, and the results are listed in table 23.

4 RESULTS AND DISCUSSSION

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Table 23. Measurements of undercutting corrosion after the cyclic test.

Panel 54 M (mm) 2,9

Panel 56 4,3

Panel 64
(w. Panipol)

Panel 66
(w. Panipol)

4,7

4,9

As seen in table 23, the best resistance to undercutting corrosion is provided by the conventional anti-corrosive paint system from Hempel (panel 56), but the results has a low reproducibility. The addition of Panipol in the primer does not seem to be a suitable inhibitor against undercutting corrosion. It is possible that the anti-corrosive effect of polyaniline is not functional in an offshore environment in which undercutting corrosion and blistering are dominant. Blistering and undercutting corrosion both produce an acidic environment beneath the paint film. Polyaniline is possibly an efficient inhibitor in an alkaline environment (cf. ballast tank application), while an acidic environment has the opposite effect. The adhesion was finally determined by a pull-off test. Table 24 lists the measured POT values and a description of the belonging fracture in the coating.
Table 24. Measurements of the adhesion by pull-off test after the cyclic test.

Panel nr.

Paint system Zinc-rich epoxy

POT measured (MPa) 10,5 9,5 13,9 12,3 12,1 14,2 10,9 13,1 18,8 15,0 13,7 10,0

Description of fracture 100% cohesive break 5% adhesive break, 95% cohesive break 45% cohesive break, 55% break in glue 100% cohesive break 40% adhesive break, 60% cohesive break 20% adhesive break, 80% cohesive break 20% adhesive break, 80% cohesive break 100% cohesive break 100% cohesive break 40% adhesive break, 60% cohesive break 40% adhesive break, 60% cohesive break 100% cohesive break

54

primer + epoxy polyamide barrier coat

56

+ acrylic polyurethane topcoat Zinc-rich epoxy

64

primer w. Panipol F + epoxy polyamide barrier coat

66

+ acrylic polyurethane topcoat

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57

In comparison to the measured POT values after the salt spray test are the POT values in table 23 considerable higher and satisfactorily in relation to the requirements. However, no significant difference is seen between the adhesion of the two paint systems, and the fracture is mainly concentrated as a cohesive break in the topcoat. The conclusion is therefore that no improvement of the corrosion resistance is reached by adding polyaniline to a conventional anti-corrosive paint system from Hempel. The results indicate that the anti-corrosive effect of polyaniline is inhibited by the acidic environment formed by blistering and undercutting corrosion.

4.3.2 Water based paint system

Four versions of a water based zinc rich epoxy primer from Hempel were prepared and examined according to their corrosion resistance. The primer was covered with a polyamide cured epoxy barrier coating. The four paint systems were exposed to a salt spray test and a cyclic test for 60 days. The panels to be tested by salt spray exposure were only applied with a 70m primer coating and contained no barrier coating. The barrier coating was excluded in order to examine the protective character of the primer. Early inspections of the panels showed that white rusting was present to a higher extent on the panels coated with a primer containing polythiophene. The white rust was especially formed near the score, but no visual difference was present between primers with high and low zinc content. White rust is formed when zinc corrodes due to the galvanic coupling with steel. It is therefore clear that the content of polythiophene has an effect on the galvanic coupling between zinc and steel. A final evaluation was performed after 60 days of exposure. This evaluation indicated that the low-loaded zinc primer (60w% Zn) provided a better corrosion protection than the high-loaded zinc primer (85w% Zn). This is a surprising discovery and no explanation was to be found. Electrochemical measurements were performed in order to understand the mechanisms of the four different zinc primers. Measurements of the OCP potential and the polarization curves are illustrated at figure 22, 23 and 24.

4 RESULTS AND DISCUSSSION

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200

100

0 Potential vs SHE (mV)

-100

85% Zn 85% Zn, BAYTRON 60% Zn 60% Zn, BAYTRON

-200

Steel

-300

-400

-500 0 2 4 6 8 10 Time (min) 12 14 16 18 20

Figure 22. OCP measurements of water based paint in 3,5w% NaCl.

600

400

200

Potential vs SHE (mV)

Steel 85% Zn 85% Zn, BAYTRON

-200

-400

-600

-800 0,00000001 0,0000001 0,000001 0,00001 0,0001 0,001 0,01 0,1 1 10 100 Current density (mA/cm2)

Figure 23. Polarization curves of water based paint with 85w% Zn in 3,5w% NaCl.

4 RESULTS AND DISCUSSSION

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600

400

200 Potential vs SHE (mV)

Steel 60% Zn
-200

60% Zn, BAYTRON

-400

-600

-800 1E-09 1E-08 1E-07 0,000001 0,00001 0,0001 0,001 0,01 0,1 1 10 100 Current density (mA/cm2)

Figure 24. Polarization curves of water based paint with 60w% Zn in 3,5w% NaCl.

The OCP measurements in figure 22 clearly show that the addition of polythiophene increases the corrosion potential by 100-200 mV independently of the zinc content. The OCP measurements also state that a cathodic protection of the steel surface is not present in any of the four paint systems. Is this possible or are the results incorrect? The polarization curves on figure 23 and 24 can maybe lead to an answer. Figure 23 illustrates the polarization curves of the high-loaded zinc primers and no remarkable differences in the corrosion potential and current are present between the two primers. The appearance of the two curves shows that it is difficult for a current to travel through the paint film. Only when a small defect is introduced to the paint film can a transport of electrons take place. The polarization curves of the low-loaded zinc primers are illustrated in figure 24 and show a significant difference between the two primers. The pure zinc primer is able to suppress the corrosion potential of steel and establish a cathodic protection, while the primer containing polythiophene has a corrosion potential about 200 mV higher and similar to steel. The lowest corrosion current is also provided by the pure zinc primer. The polarization curves therefore confirm that the low-loaded zinc primer provides the best corrosion protection, as observed in the salt spray test. These observations change the basic idea of the protective mechanism of a zinc-rich primer. Maybe the amount of zinc powder in the primer is not crucial for the efficiency of corrosion protection, and is it possible that the cathodic protection only provides a small part of the corrosion protection? These questions are interesting hypotheses but remain out of the scope of this project.

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The cyclic test was performed on the same four zinc primers covered with a polyamide cured epoxy barrier coating. Earlier inspections indicated that the best cathodic protection was provided by the paint system with high zinc content and no addition of BAYTRON. Only a slight degree of rusting was present at the applied score which indicates that cathodic protection had occurred. No significant difference was present at the other three paint systems on which the score was fully corroded. The final evaluation was performed after 60 days of exposure and a difference was noted between the paint systems with and without BAYTRON. A greater extent of blistering around the score was present at the panels coated with a paint system without BAYTRON. A great extent of blistering around the score is normally equal to a high degree of undercutting corrosion, and the paint was therefore removed from the steel surface. Figure 25 shows pictures of the undercutting corrosion on the four different paint systems.

Figure 25. Undercutting corrosion. Panel 73: 85w% Zn (in primer); Panel 77: 85w% Zn + BAYTRON; Panel 83: 60w% Zn + BAYTRON; Panel 88: 60w% Zn.

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The degree of undercutting corrosion is calculated from 9 points along the score. Table 25 lists the calculated M-value for the panels illustrated at figure 25.
Table 25. Measurements of undercutting corrosion after the cyclic test.

Panel 73
(85% Zn)

Panel 77
(85% Zn + BAYTRON)

Panel 83
(60% Zn + BAYTRON)

Panel 88
(60% Zn)

M (mm)

2,4

1,7

2,1

3,4

The results in table 25 indicate that the addition of polythiophene when combined with a high zinc content provides the best resistance to undercutting corrosion (cf. panel 77). These results are in contrast to the observations of the solvent based paint systems. A reasonable explanation could be that a better dispersion of the conducting polymer occurred within these water based paint systems. A SEM analysis was performed in order to examine the corrosion behaviour of the four water based paint systems. The aim was to examine whether any differences in topography and composition were present between the paint systems after 60 days of exposure in the cyclic test. The SEM analyse revealed no significant differences between the four paint systems exposed in the cyclic test, but a general model of the degradation of zinc particles was established. Figure 26 illustrates an example of the corrosive behaviour of the zinc particles which are distributed in the primer. The picture on the left is produced by ejection of secondary electrons and shows the topography of the primer. The picture on the right is produced by backscattered electrons and indicates the composition of the primer. The light components in the primer appear dark in the backscattered picture, while heavy components appear light.

Figure 26. SEM pictures of a zinc primer in secondary signal (left) and backscattered signal (right).

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The SEM pictures in figure 26 indicate that a big part of the heavy zinc particles, which are in contact to the steel surface, are degraded to lighter corrosion products. Analysis of the composition shows that these corrosion products mainly contain zinc, iron, chloride and oxygen. A mapping of the composition shows that chloride and oxygen is evenly distributed within the primer. The mapping also indicates increased iron content and reduced zinc content up to 10 m away from the steel surface. Therefore, the suggestion is made that iron ions diffuse into the primer and form a complex with zinc which are thermodynamic stable at a high potential range. It is proposed that this complex contributes to the protective mechanisms of zinc paint. This could explain why the low-loaded zinc paint provides the best performance in the salt spray test. Maybe the formation of a protective iron/zinc complex is more important than the galvanic contact between steel and zinc? The conclusion is therefore that the addition of polythiophene provides some kind of positive effect on the protective behaviour of water based zinc paints, but only if the primer is coated with a barrier paint. Without the barrier coating, polythiophene seems to accelerate the degradation of zinc within the primer.

4.4 Paint for aluminium substrates

Salt Spray Test, Cyclic Test and Filiform Corrosion Test were used to examine the protective properties of four different coating systems designed for protection of aluminium. The four different coating systems were painted with the same barrier coating and topcoat, but deviate from one another in the application of a primer or a preceding surface treatment. The test panels were exposed to a salt spray test and a cyclic test for a period of 96 days. The only sign of degradation of the paint film was due to adhesion problems. A qualitative analyse of the adhesion was performed by a knife test in the final evaluation. Tables 26 and 27 on the following page list the results.

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Table 26. Evaluation of the adhesion after the salt spray test.

Surface treatment Anodizing Chromatizing Altizizing

Adhesion evaluation by knife test

Comments Disbonding about 1,5 cm from the score. Nothing to note! Disbonding about 1,0 cm from the score. The adhesion is good but not to be compared with the anodized aluminium panels.

Corrpassiv 4001 Very bad Very good Bad Good

Table 27. Evaluation of the adhesion after the cyclic test.

Surface treatment Anodizing Chromatizing Altizizing

Adhesion evaluation by knife test

Comments Improved adhesion compared to the salt spray test. Nothing to note! Disbonding about 0,5 cm from the score. The adhesion was really bad and the paint was pealing of.

Corrpassiv 4001 Good Very good Bad Very bad

As described in tables 26 and 27, the adhesion of the test panels coated with the CORRPASSIV primer is dependant on the test conditions. The assumption is made that epoxy resins in the primer are cured when exposed to UV light at 60 C in the cyclic test. As described earlier, the CORRPASSIV primer is a PVB based paint but small amount of epoxy was also discovered by chemical analysis. A colour change similar to the one observed in the immersion test was also present in the primer after the salt spray test and cyclic test. It is therefore proven that polyaniline is reduced to its non-conductive base form due to the formation of an alkaline environment beneath the primer. The opposite adhesion property is current at the altizized aluminium panels. No adhesion problems are observed in the salt spray test while the cyclic test causes the paint to peal of in large areas. It was especially the exposure to heat and condensation in the cyclic process that caused serious adhesion problems. The chromatizing process is surprisingly not a suitable surface treatment, as a low degree of adhesion is found in both tests. No remarks are made regarding the anodized aluminium panels, which had a superior adhesion to the paint. An analysis of the surface

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topography was performed by SEM in order to explain some of the adhesive behaviour of the applied coatings. SEM-pictures of an altizized aluminium panel and an anodized aluminium panel are shown in figure 27.

Figure 27. Surface topography of altizized (left) and anodized (right) aluminium panels.

It is clear from figure 27 that the anodized surface is much more porous than the altizized surface. This can be a possible explanation for the observed differences in the adhesive properties. It is easier for the paint to stick on a porous surface than a smooth. The resistance to filiform corrosion was examined for each of the four coating systems after an exposure of 50 days. Pictures taken after test exposure are illustrated in appendix G. The best resistance to filiform corrosion is seen on the anodized and the altizized aluminium panels, which contain no sign of filiform corrosion. The chromatized panel and the CORRPASSIV painted panel are both attacked by filiform corrosion and about 3 mm filaments are formed beneath the paint film. Finally, electrochemical measurements were performed in order to understand the protective mechanisms of each of the four coating systems. The panels to be analysed were only provided with a surface treatment or a primer. Measurements of the OCP potential and the polarization curves are illustrated in figures 28 and 29.

4 RESULTS AND DISCUSSSION

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-350

-400

-450 Potential vs SHE (mV) Ano Al Chrom Al MnO2 Al CORRPASSIV Uncoated Al

-500

-550

-600

-650 0 2 4 6 8 10 Time (min) 12 14 16 18 20

Figure 28. OCP potential of aluminium specimens in 3,5w% NaCl.

100 0 -100 -200 -300 -400 -500 -600 -700 -800 -900 -1000 1,0E-08 Ano Al Chrom Al MnO2 Al CORRPASSIV Uncoated Al

Potential vs SHE (mV)

1,0E-07

1,0E-06

1,0E-05

1,0E-04

1,0E-03

1,0E-02

1,0E-01

1,0E+00

1,0E+01

1,0E+02

Current density (mA/cm2)

Figure 29. Polarization curves of aluminium specimens in 3,5w% NaCl.

As illustrated in figure 28, the corrosion potential of each of the three different surface treatments is more or less similar to the corrosion potential of uncoated aluminium, while the CORRPASSIV coated aluminium specimen exhibits a much lower potential. These observations are in contrast to

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the theory which claims that an ennobling of the aluminium surface should take place for each of the applied coatings. The corrosion potential is also determined by the polarization curves illustrated in figure 29. These curves show an increase of the corrosion potential for the chromatized and anodized aluminium panels, while the corrosion potential of the altizized and CORRPASSIV coated panels is similar to pure aluminium. A decrease of the corrosion current is observed at anodized and CORRPASSIV painted specimens. This decrease is attributed to a barrier effect due to a higher coating thickness. The conclusion is therefore that no satisfactory corrosion protection is provided by the CORRPASSIV primer, and an ennobling process is also not registered. The best adhesive properties and the highest resistance to filiform corrosion are still provided by a conventional anodizing surface treatment.

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5 CONCLUSION
Anti-corrosive paint systems based on conducting polymers have been formulated and tested in four different application areas. The aim was to establish if polyaniline and polythiophene are effective corrosion inhibitors and evaluate the protective mechanisms behind. For shopprimer application, the conclusion is made, that addition of polyaniline has no positive effect on the corrosion resistance. In some of the applied shopprimers, polyaniline seems to accelerate the degradation of the paint film instead. It is suggested that a low dispersibility of polyaniline is an important issue and plays the crucial part of the protective behaviour of these shopprimer systems. In the case of ballast tank paints, addition of polyaniline seems to improve the resistance to cathodic disbonding. The assumption is made, that polyaniline possess an amphoteric nature and therefore reacts with the hydroxide ions produced in the cathodic reaction. In this reaction, polyaniline is reduced to its non-conductive emeraldine base form. The applied paint systems for protection in off-shore environments show no significant anticorrosive improvements by the addition of polyaniline to a zinc-rich primer. The hypothesis that polyaniline acts as a conductive additive and improves the cathodic effect of the zinc particles is therefore not true. Some positive effect is registered in the water based paint systems with the addition of polythiophene. It is possible that a better degree of dispersibility is the main explanation for this observation. Finally, different coating systems for aluminium protection have been tested, and the efficiency has been evaluated. The results show that the polyaniline containing primer is not suitable for protection of aluminium due to bad adhesion and low resistance to filiform corrosion. A conventional coating system with an anodizing pre-treatment provides the best corrosion protection of aluminium substrates.

6 PERSPECTIVE

68

6 PERSPECTIVE
The development of an anti-corrosive paint system based on conducting polymers in this project has been difficult, and the results show no significant improvement of the corrosion resistance when compared to conventional paint systems from Hempel. Some suggestions are therefore presented in this chapter in order to create a more effective paint system based on conducting polymers The formulation of a homogeneous paint film is vital in order to achieve an effective corrosion protection. The preparation of a polyaniline containing paint was very difficult, and some of the dry paint films therefore contained non-dispersed particles of polyaniline. Similar dispersion problems have been described in the literature and the explanation seems to be related to the high surface tension of polyaniline. Due to a very high surface tension, it becomes very difficult to wet these polyaniline particles which tend to agglomerate instead. Some scientists have tried to change the physical properties of polyaniline by preparing a double stranded polyaniline compound in which polyaniline is grafted to another polymer chain. Yang [44] have described a way to adjust the solubility parameter of polyaniline by the synthesis of complex between polyaniline and poly(acrylic) acid. This complex has a more stable conductivity and can be dispersed in water. According to Yang, it is possible to adjust the compatibility with the binder resins by changing the choice of the second strand. This is a very interesting discovery, and a further examination of the anti-corrosive behaviour of these double-stranded polyaniline compounds is therefore recommended. Another approach for the preparation of an effective anti-corrosive paint system is to examine the influence of varying polyaniline content. As described in the previous theory section, a better corrosion protection is present in paints with a low load of polyaniline. This connection between the corrosion resistance and the polyaniline content is also explained in relation to the compatibility aspect. A high content of polyaniline creates a more porous paint film with higher permeability and lower corrosion resistance. The author therefore recommends an examination that determines the optimum polyaniline content. In the case of paint for ballast tank protection, the results in this report indicate that polyaniline improves the resistance to cathodic protection. The assumption is made that polyaniline acts as an amphoteric substance and absorbs the hydroxide ions produced in the cathodic reaction. An amphoteric substance is characterized by the ability to react as either acid or base. Other materials,

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69

such as aluminium hydroxide, also possess this amphoteric nature. It could be interesting to see if these materials also improve the resistance to cathodic disbonding in ballast tank application. Finally, the author recommends a further examination of the protective mechanisms of zinc-rich paint systems. This project has revealed some surprising results in relation to the protective behaviour of zinc paints with varying zinc content. According to theory, the best cathodic protection is established in paints with a high load of zinc (i.e. 85w% Zn), but this project indicates that en effective corrosion protection is also present in paints with a low zinc content (i.e. 60w% Zn). A SEM analysis has revealed that a complex between iron and zinc is formed near the steel surface. It is assumed that this complex contributes to the protective mechanisms of zinc paints. An examination of the protective behaviour of this complex is therefore to be recommended in the future.

ABBREVIATIONS
DFT: EB: ECP: ECT: EIS: ES: ESCA: FTIR: OCP: LE: PANI: PEDOT/PSS: PMMA: POT: PVB: RH: SCE: SECM: SEM: SHE: St-BuA: Dry Film Thickness Emeraldine Base Electrically Conducting Polymer Eddy Current Test Electrochemical Impedance Spectroscopy Emeraldine Salt Electron Spectroscopy Chemical Analysis Fourier Transform Infrared Open Circuit Potential Leucoemeraldine Polyaniline Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) Polymethylmethacrylate Pull-Off Test Polyvinyl butyral Relative Humidity Standard Calomel Electrode Scanning Electrochemical Microscopy Scanning Electron Microscopy Standard Hydrogen Electrode Styrene-butyl acrylate

ii

BIBLIOGRAPHY
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Cameron, C.G. 2004, Enhanced Rates of Electron Transport in Conjugated-Redox Polymer Hybrids, online thesis, 23-02-06 http://mmrc.caltech.edu/colin/science/past/PhD/html-thesis/thesis.html

[13]

Bredas, J.L. et al 1985, Polarons, bipolarons and solitons in conducting polymers, Acc. Chem. Res., 1985, pp. 309-315.

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Fahlman, M. 2005, Electrical conducting polymers: An introduction, New polymer material with electrical conducting polymers, Mller, P. (ed.), CD-rom from conference hold at Danish Technical University, 01-06-2005.

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vi

LIST OF APPENDIX
Pictures:
Appendix A: Appendix B: Appendix C: Appendix D: Appendix E: Appendix F: Appendix G: Pictures from the Natural Weathering Test. Pictures from the Mebon Prohesion Test. Pictures from the Cathodic Protection Test. Pictures from the Immersion Test. Pictures from the Salt Spray Test Pictures from the Cyclic Test. Pictures from the Filiform Corrosion Test.

Data sheets:
Appendix H: Appendix I: Appendix J: Appendix K: Appendix L: Appendix M: Appendix N: Appendix O: Appendix P: Appendix Q: Appendix R: Data sheet of CORRPASSIV 4000 Data sheet of CORRPASSIV 4001 Data sheet of PVB shopprimer from Hempel* Data sheet of zinc phosphate shopprimer from Hempel* Data sheet of zinc-silicate shopprimer from Hempel* Data sheet of zinc epoxy primer from Hempel* Data sheet of polyamide/epoxy ballast tank paint from Hempel* Data sheet of water-borne epoxy barrier paint from Hempel* Data sheet of water-borne zinc epoxy primer from Hempel* Data sheet of polyamide/epoxy barrier paint from Hempel* Datasheet of acrylic polyurethane topcoat from Hempel*

* Confidential information material

vii

Appendix A
Test: Application area: Time of exposure:
Panel nr. 1 3 12 21 23 32 41 43 PVB/polyaniline primer (CORRPASSIV 4000) PVB/polyaniline primer (CORRPASSIV 4000) PVB shopprimer Zinc phosphate shopprimer Zinc phosphate shopprimer Zinc phosphate shopprimer w. Panipol Zinc silicate shopprimer w. 50% Zn Zinc silicate shopprimer w. 40% Zn and Panipol * DFT = dry film thickness 30,6 44 21,3 42 20,6 39,8 51,6 45,3 13 22 31 33 PVB shopprimer Zinc phosphate shopprimer Zinc phosphate shopprimer w. Panipol Zinc phosphate shopprimer w. Panipol Zinc silicate shopprimer w. 30% Zn Zinc silicate shopprimer w. 30% Zn and Panipol 28,7 25,2 39,1 19,8 40,7 44,3 17,9 11 Paint system

Natural Weathering Test Shopprimer 92 days

DFT* (m) 11,1 Panel nr. 2 PVB/polyaniline primer (CORRPASSIV 4000) PVB shopprimer 21,4 Paint system DFT* (m) 12,2

Panel 1

Panel 2

viii

Panel 3

Panel 11

Panel 12

Panel 13

Panel 21

Panel 22

ix

Panel 23

Panel 31

Panel 32

Panel 33

Panel 41

Panel 42

Panel 43

Panel 44

xi

Appendix B
Test: Application area: Time of exposure:
Panel nr. 4 6 15 24 34 45 47 PVB/polyaniline primer (CORRPASSIV 4000) PVB/polyaniline primer (CORRPASSIV 4000) PVB shopprimer Zinc phosphate shopprimer Zinc phosphate shopprimer w. Panipol Zinc silicate shopprimer w. 50% Zn Zinc silicate shopprimer w. 30% Zn and Panipol * DFT = dry film thickness 28,7 21,3 46 19,2 50,4 47,9 16 25 35 PVB shopprimer Zinc phosphate shopprimer Zinc phosphate shopprimer w. Panipol Zinc silicate shopprimer w. 40% Zn and Panipol 30,6 21,1 56,6 47,6 18,2 14 Paint system

Mebon Prohesion Test Shopprimer 92 days

DFT* (m) 16,5 Panel nr. 5 PVB/polyaniline primer (CORRPASSIV 4000) PVB shopprimer 16,4 Paint system DFT* (m) 17,9

Panel 4

Panel 5

xii

Panel 6

Panel 14

Panel 15

Panel 16

Panel 24

Panel 25

xiii

Panel 34

Panel 35

Panel 45 (OBS: 66 days of exposure)

Panel 46 (OBS: 66 days of exposure)

Panel 47 (OBS: 66 days of exposure)

xiv

Appendix C
Test: Application area: Time of exposure: Cathodic Protection Test Ballast tank 96 days

Panel nr. 105

Paint system (2 x) Polyamide/epoxy ballast tank paint

DFT* (m) 245,4

Panel nr. 106

Paint system (2 x) Polyamide/epoxy ballast tank paint

DFT* (m) 255,5

107

(2 x) Polyamide/epoxy ballast tank paint

254,5

115

Polyamide/epoxy ballast tank paint w. Panipol + Polyamide/epoxy ballast tank paint

286,0

116

Polyamide/epoxy ballast tank paint w. Panipol + Polyamide/epoxy ballast tank paint

260,5

117

Polyamide/epoxy ballast tank paint w. Panipol + Polyamide/epoxy ballast tank paint

257,0

125

CORRPASSIV 4000 + Polyamide/epoxy ballast tank paint w. Panipol + Polyamide/epoxy ballast tank paint

358,0

126

CORRPASSIV 4000 + Polyamide/epoxy ballast tank paint w. Panipol + Polyamide/epoxy ballast tank paint

341,0

127

CORRPASSIV 4000 + Polyamide/epoxy ballast tank paint w. Panipol + Polyamide/epoxy ballast tank paint

331,0

* DFT = dry film thickness

xv

Panel 105 (reference)

Panel 106

Panel 107

Panel 115 (reference)

Panel 116

Panel 117

xvi

Panel 125 (reference)

Panel 126

Panel 127

xvii

Appendix D
Test: Application area: Time of exposure: Immersion test Ballast tank 96 days

Panel nr. 108

Paint system (2 x) Polyamide/epoxy ballast tank paint

DFT* (m) 268,0

Panel nr. 109

Paint system (2 x) Polyamide/epoxy ballast tank paint

DFT* (m) 280,5

110

(2 x) Polyamide/epoxy ballast tank paint

294,5

118

Polyamide/epoxy ballast tank paint w. Panipol + Polyamide/epoxy paint ballast tank paint

291,5

119

Polyamide/epoxy ballast tank paint w. Panipol + Polyamide/epoxy paint ballast tank paint

313,5

120

Polyamide/epoxy ballast tank paint w. Panipol + Polyamide/epoxy paint ballast tank paint

283,5

128

CORRPASSIV 4000 + Polyamide/epoxy ballast tank paint w. Panipol + Polyamide/epoxy paint ballast tank paint

303,5

129

CORRPASSIV 4000 + Polyamide/epoxy ballast tank paint w. Panipol + Polyamide/epoxy paint ballast tank paint

307,0

130

CORRPASSIV 4000 + Polyamide/epoxy ballast tank paint w. Panipol + Polyamide/epoxy paint ballast tank paint

336,0

* DFT = dry film thickness

xviii

Panel 108

Panel 109

Panel 110

Panel 118

Panel 119

Panel 120

xix

Panel 128

Panel 129

Panel 130

xx

Appendix E
Test: Application area: Time of exposure:
Panel nr. 51 Zinc epoxy primer + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat 53 Zinc epoxy primer + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat 62 Zinc epoxy primer w. Panipol + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat * DFT = dry film thickness 251,5 63 249,5 61 Paint system

Salt Spray Test Off-shore environment 90 days

DFT* (m) 267,0 Panel nr. 52 Zinc epoxy primer + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat Zinc epoxy primer w. Panipol + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat Zinc epoxy primer w. Panipol + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat 251,5 274,0 Paint system DFT* (m) 271,5

Application area: Time of exposure:

Panel nr. 71 75 81 85 Paint system

Off-shore environment (water based paint systems) 60 days

DFT* (m) 83,5 70,0 76,4 84,0 Panel nr. 72 76 82 86 Water-borne zinc epoxy primer w. 85% Zn Water-borne zinc epoxy primer w. 85% Zn and Baytron Water-borne zinc epoxy primer w. 60% Zn and Baytron Water-borne zinc epoxy primer w. 60% Zn 86,0 80,9 68,0 Paint system DFT* (m) 81,7

Water-borne zinc epoxy primer w. 85% Zn Water-borne zinc epoxy primer w. 85% Zn and Baytron Water-borne zinc epoxy primer w. 60% Zn and Baytron Water-borne zinc epoxy primer w. 60% Zn

* DFT = dry film thickness

xxi

Panel 51

Panel 52

Panel 53

Panel 61

Panel 62

Panel 63

xxii

Panel 71

Panel 72

Panel 75

Panel 76

Panel 81

Panel 82

xxiii

Panel 85

Panel 86

xxiv

Appendix F
Test: Application area: Time of exposure:
Panel nr. 54 Zinc epoxy primer + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat 56 Zinc epoxy primer + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat 65 Zinc epoxy primer w. Panipol + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat * DFT = dry film thickness 246,0 66 275,5 64 Paint system

Cyclic Test Off-shore environment 90 days

DFT* (m) 277,0 Panel nr. 55 Zinc epoxy primer + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat Zinc epoxy primer w. Panipol + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat Zinc epoxy primer w. Panipol + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat 244,5 262,5 Paint system DFT* (m) 275,5

Application area: Time of exposure:

Panel nr. 73 77 Paint system

Off-shore environment (waterbased paint systems) 60 days

DFT* (m) 183,4 176,4 Panel nr. 74 78 Water-borne zinc epoxy primer w. 85% Zn + Epoxy barrier paint Water-borne zinc epoxy primer w. 85% Zn and Baytron + Epoxy barrier paint 177,4 84 Water-borne zinc epoxy primer w. 60% Zn and Baytron + Epoxy barrier paint 198,2 88 Water-borne zinc epoxy primer w. 60% Zn + Epoxy barrier paint 205,0 183,0 167,3 Paint system DFT* (m) 193,9

Water-borne zinc epoxy primer w. 85% Zn + Epoxy barrier paint Water-borne zinc epoxy primer w. 85% Zn and Baytron + Epoxy barrier paint

83

Water-borne zinc epoxy primer w. 60% Zn and Baytron + Epoxy barrier paint

87

Water-borne zinc epoxy primer w. 60% Zn + Epoxy barrier paint

* DFT = dry film thickness

xxv

Panel 54

Panel 55

Panel 56

Panel 64

Panel 65

Panel 66

xxvi

Panel 73

Panel 74

Panel 77

Panel 78

Panel 83

Panel 84

xxvii

Panel 87

Panel 88

xxviii

Appendix G
Test: Application area: Time of exposure: Filiform Corrosion Test Aluminium 50 days

Panel nr. 91

Paint system CORRPASSIV 4001 + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat

DFT* (m) 208,0

Panel nr. 92

Paint system CORRPASSIV 4001 + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat

DFT* (m) 210,5

101

Anodized aluminium + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat

193,6

102

Chromatized aluminium + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat

187,3

103

Altizized aluminium + Polyamide/epoxy barrier coat + Acrylic/polyurethane topcoat

183,6

* DFT = dry film thickness

Panel 91 (1mm score)

Panel 91 (2mm score)

xxix

Panel 92 (1mm score)

Panel 92 (2mm score)

Panel 101 (1mm score)

Panel 101 (2mm score)

Panel 102 (1mm score)

Panel 102 (2mm score)

xxx

Panel 103 (1mm score)

Panel 103 (2mm score)

xxxi

Appendix H

xxxii

xxxiii

Appendix I

xxxiv

xxxv

Appendix J

xxxvi

xxxvii

Appendix K

xxxviii

xxxix

Appendix L

xl

xli

Appendix M

xlii

xliii

Appendix N

xliv

xlv

Appendix O

xlvi

xlvii

Appendix P

xlviii

xlix

Appendix Q

li

Appendix R

lii