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MODULE 14 Basic Paint Technology

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MODULE 14 BASIC PAINT TECHNOLOGY


CONTENTS Study Guide Section 1 Section 2 Section 3 Section 4 Why Paint? Paint Types Basic Paint Formulation Paint Performance PAGE 3 4-29 30-38 39-45 46-75 76-77 78

ITQ Answers and Comments Case Study 1

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STUDY GUIDE
This module has been designed to provide an introduction into why ships are painted, a basic introduction to the nature of paint, and details of how paint is tested prior to introduction into the market. The key subject areas covered are: Corrosion Fouling Paint Composition and Formulation Basic Marine Paints Paint Performance Testing

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SECTION 1 WHY PAINT? OBJECTIVES


When you have completed Section 1, you should be able to:1. 2. 3. 4. Give 5 reasons for painting ships. Be aware of the basic principles of corrosion, factors affecting corrosion rates and methods to prevent it. Understand the principles involved in fouling prevention. Understand the different properties that a paint scheme must provide depending upon vessel area.

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SECTION 1 WHY PAINT?


1.1 INTRODUCTION Mild steel is the most widely used material of construction for new ships, principally due to the ease of workability, good mechanical properties and relatively low cost. New ships are expensive to build, typical costs in Q2-2000 for ocean going cargocarrying vessels are: Tankers

VLCC Suezmax Aframax Handysize Bulkers

300,000 dwt* 150,000 dwt 110,000 dwt 47,000 dwt

$70m $42m $33m $26m

Capesize Panamax Handymax

170,000 dwt 75,000 dwt 51,000 dwt

$35m $22m $20m

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Container Ships

Capacity

3,500 TEU** 1,100 TEU

$56m $17m

Gas Carriers

Capacity

LPG LNG

78,000m3 125,000m3

$56m $165m

* dwt = Deadweight Tonnage - weight of cargo, stores, fuel, etc. on a ship when loaded to its maximum summer loadline. ** TEU = Twenty foot equivalent unit - a standard freight container is 20 x 8 x 8 = 1 TEU Prices for more specialised vessels are: Offshore Supply Vessel Jumbocat Fast Ferry Passenger/Vehicle Ferry Cruise Liner 3,000 dwt 60m (length) 4,000 dwt 1800 passenger $13m $23m $130m $400m

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1.2 REASONS FOR PAINTING Ships are painted for the following reasons: Corrosion Prevention Fouling Prevention Aesthetics Cargo Carriage Crew Safety Special Function, e.g. LSA (Low Solar Absorption)

The above can be summarised as: Asset Protection Maximisation of Revenue Earning Capability

1.2.1 CORROSION The single most important reason to paint a ship is to prevent corrosion. 1.2.1.1 CORROSION MECHANISM Corrosion can be defined as the deterioration of a substance due to a reaction with its environment; most commonly the term is applied to attack on metals. The most widespread type of corrosion arises due to electrochemical reactions. It is important to understand the mechanisms by which steel corrodes in order to develop effective preventative measures. All steels are alloys of iron, carbon, and other metals. The susceptibility to corrosion is dependent upon the steel composition and the method of manufacture. The nature of steel manufacture leads to materials which are not uniform in nature, this in turn increases the likelihood of electrochemical corrosion. The non-uniform composition of steel leads to the presence of both anodic and cathodic sites on the steel surface, in the presence of oxygen and water, iron will dissolve from the anodic sites. The basic electrochemical reactions taking place are: Anode 4Fe 4Fe++ +8eCathode 2O2 + 4H2O + 8e8OH-

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The ferrous and hydroxyl ions formed react to form ferrous hydroxide, which is then oxidised to hydrated ferric oxide (rust): 4Fe++ +8OH4Fe(OH)2+O2 i.e. 4Fe(OH)2 2Fe2O3.H2O + 2H2O 2Fe2O3.H2O

4Fe + 3O2 + 2H2O

1.2.1.2 CORROSION RATES The rate of corrosion in seawater is dependant upon many factors: Oxygen Concentration As the concentration of dissolved oxygen increases the rate of corrosion increases. Beyond about 10-12ml/l of dissolved oxygen the corrosion rate slows down due to different reactions taking place at the cathode resulting in polarisation occurring. At higher concentrations, more oxygen reaches the metal surface than can be reduced by the corrosion reaction (depolarisation) at a cathode. The excess oxygen oxidises the ferrous ions to ferric ions as they are formed. Ferric hydroxide is less soluble than ferrous hydroxide and hence forms a barrier over the anodic sites, the iron is said to be passivated. The critical concentration of oxygen is dependent upon several conditions, for example temperature and water depth. ITQ 1 At which point on the steel surface will the corrosion rate be the highest? Answer

pH At around pH10 the critical oxygen concentration reaches that for saturated water, which is 6ml O2/litre, this results in iron being passivated against corrosion above pH10.

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Corrosio n Rate

14 Temperature

10

pH

The solubility of oxygen in water decreases as the temperature increases so that in an open system where oxygen can escape the rate of corrosion will go through a maximum before decreasing; in a closed system the rate of corrosion will increase with temperature Closed System e.g. ballast tank Corrosion Rate Open System e.g. underwater hull 80C Dissolved Salts The rate of corrosion is dependent upon the conductivity of the water in which it is immersed; the presence of soluble salts increases the conductivity. It is believed that the presence of salts leads to a reduction in oxygen solubility hence beyond a critical level corrosion rates fall. Corrosion Rate Temperature

NaCl %

The rate of corrosion in a marine environment is dependent upon the presence of chlorides, sulphates and sulphites and other airborne
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contaminants. Corrosivity generally decreases with increasing height above sea level. 1.2.1.3 POTENTIAL CAUSES OF CORROSION RATES Exposed Steel Exposed steel, which is not electrochemically protected, will corrode. When steel has been coated, areas may be exposed by: a) Holidays or pinholes remaining in the application. b) Mechanical damage to the coating. c) Cracking of the coating. Soluble Salts If soluble salts remain on the steel surface prior to coating, their presence can lead to blistering of the coating and subsequent corrosion. Millscale In addition to the factors presented earlier, one of the principal causes of steel corrosion is the presence of millscale. The steel plate used in shipbuilding is made by hot-rolling, leaving the rolled material to cool from 800-900C. During the cooling process in air a blueblack shiny scale, made up of several layers of various oxides of iron (magnetite), forms at the steel surface - this is known as millscale. The thickness of millscale varies between 5-60 microns. A potential difference of around 0.3 volt exists between steel and millscale; this results in the millscale becoming cathodic to the anodic steel surface. The consequence of this is that any breaks in the millscale surface will act as corrosion sites and duly concentrate corrosive activity. Millscale is brittle by nature and hence is prone to cracking, this leads to more corrosion sites and, if painted over, future surface coating detachment problems. The following diagram shows the corrosion reactions taking place on a piece of millscaled steel in seawater: coating following

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It is essential that millscale is removed prior to coating steel. Bacterial Corrosion Also referred to as micro-biological corrosion or anaerobic (without air), this type of corrosion may occur due to local environments and conditions being compatible with bacterial activity. Attack can occur in oil tanks, ballast tanks, cargo pipework and similar areas. The following list summarises the principal requirements to foster bacterial corrosion: stagnant (anaerobic) water hydrocarbon food source e.g. oil, coatings presence of sulphates temperature between 20-40C presence of bacteria

1.2.2 CORROSION PREVENTION Corrosion prevention may be affected by one, or a combination of three, basic mechanisms: Chemical (Inhibition/Passivation) Electrical (Cathodic Protection) Coatings (Barrier)

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1.2.2.1 CHEMICAL - INHIBITION/PASSIVATION Inhibitors suppress corrosion by several means. One class of inhibitors which suppress corrosion by retarding the anodic reaction are called passivators. Section 1.2.1.2 Corrosion Rates describes the mechanism of passivation and shows that passivation will occur in the pH range above 10. However this is not a practical proposition as the levels of oxygen required are far in excess of those actually present in water in equilibrium with the atmosphere. However it has been shown that a wide range of oxidising agents will reduce corrosion rates by passivating steel surfaces, typically chromate, nitrite, molybdate, plumbate and tungstate salts. The mechanism of passivation by salts is analogous to that of oxygen, above a certain concentration the corrosion rate decreases probably due to the formation and deposition at the steel surface of mixed ferric/metal oxides. This oxide layer acts as a barrier to prevent further corrosion. Non-oxidising salts, such as the alkali metal salts of boric, phosphoric and benzoic acids, are known to act as passivating agents. The mechanism of action is not as well understood as that of the oxidising agents but it is believed to be due to either the deposition of insoluble salts on cathodic areas or from the highly alkaline solutions produced lowering the critical oxygen concentration required for passivation. 1.2.2.2 ELECTRICAL - CATHODIC PROTECTION The principle behind cathodic protection is to make a ships hull cathodic to an external anode thereby preventing corrosion, as in:

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There are two mechanisms in use practically to cathodically protect steel in seawater from corrosion: Direct (Impressed) Current Systems

Essentially electrolysis of water takes place in preference to corrosion of steel. Impressed current cathodic protection systems are expensive to run efficiently, a lower cost option is the use of sacrificial anodes. Sacrificial Anodes

The sacrificial anode corrodes preferentially to steel; the choice of anode material is based upon the Electrochemical Series:

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Magnesium, zinc and aluminium are higher in the series than steel; these metals are used to protect steel from corrosion. Blocks of these metals are placed around a ships underwater hull in electrical contact, on immersion the blocks corrode. Replacement is required as blocks are depleted. ITQ 2 Why is it more common to find zinc anodes used on a mild steel ship in preference to magnesium? What would be the results if copper were attached to the hull of the ship? Answer

Another example of the use of cathodic protection is the galvanising of steel by coating steel with a thin layer of metallic zinc. The use of tinplating to prevent corrosion is not an example of cathodic protection. When tin and iron are in electrical contact the tin acts as the cathode and the iron corrodes at a faster rate, this is clearly obvious if the cut edges of opened tins are examined. The tin coating is acting as a highly efficient barrier to oxygen and water. 1.2.2.3 COATINGS The effectiveness of coatings in preventing corrosion depends upon many factors, for example, environment, end use, composition, damage and many more. There have been many theories to explain the mechanics of corrosion protection by coatings.

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INTACT COATINGS Until about 30 years ago it was assumed that coatings were acting as simple barriers to oxygen and water. At around this time research into water and oxygen permeability of coatings lead to the conclusion that the amounts of water and oxygen permeating to the steel surface were in excess of that needed to promote corrosion. In essence, this research means that the barrier effect theory may not give the full story. It was hypothesised that the controlling effect must be the electrical conductivity of the coating, the assumption being that coatings with low conductivity would offer the best protection. However, the improvement in corrosion resistance brought about by inclusion of aluminium in paint, casts doubt on this hypothesis and supports the barrier theory. Current theories are based on the work of Funke who proposes that water permeating through a coating to steel could displace a coating from the steel to such a degree that the presence of water and oxygen would then cause the onset of corrosion. It is now believed that WET ADHESION is the single most important aspect of corrosion control in intact coatings. Perfect wet adhesion is practically not achievable; this inevitably leads to sites on the steel surface being more susceptible to corrosion by attack from oxygen and water. In such areas the permeability characteristics of the coatings used are very important. Hence a combination of good wet adhesion, low oxygen/water permeability and inclusion of barrier pigments such as aluminium will delay the onset of corrosion. If these are well balanced, long-term protection can be achieved. In summary, the Funke model for corrosion protection by intact coatings involves: a) b) Good wet adhesion, promoted by coatings being absorbed onto the steel surface. Low permeability to oxygen and water.

The following notes discuss mechanisms by which adhesion may be improved and water/oxygen permeability reduced. ADHESION Adhesion may be regarded in relation to the force required to remove a coating from a substrate.
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Steel surfaces to be coated must be clean to promote adhesion that is free of oil, rust, salts and other contaminants. Surface roughness leads to greater surface area, this can increase adhesion, and the most usual means to achieve this is by abrasive blasting techniques. However depending upon the nature of the coating this is not always the case. If the coating does not penetrate into all of the pores/crevices on the steel surface there will be areas of coating not in contact with steel. In such cases oxygen and water can more easily contact the steel resulting in corrosion and coating detachment.
H2O/O2 H2O/O2 Coating

good penetration good adhesion

Steel poor penetration poor adhesion corrosion / detachment

Penetration of coatings into the surface roughness can be improved by: reducing surface tension of coating in relation to surface tension of steel reduce viscosity of the coating use slower evaporating solvents use slower cross-linking mechanisms increase application temperature The surface of clean steel is not free iron, a complex mix of oxides and hydrates exist with the presence of oxygen and hydroxyl groups bonded to the steel. Adhesion can be enhanced by polar interaction and hydrogen bonding between the coating and steel. Hydrogen bonds between the coating and steel may be displaced by water, it is suggested (Funke) that this rate of water displacement can be reduced by having a sufficient number of polar groups on the polymer molecules in the coating. Evidence shows that the presence of amine groups on coating polymers will improve wet adhesion and this is thought to be due to the very strong hydrogen bonds formed between the amine and the oxides on the steel surfaces.

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WATER/OXYGEN PERMEABILITY Water and oxygen will permeate to some degree through any polymer with no obvious imperfections (cracks/pores). The rate at which this happens is dependent upon the Tg (Glass Transition Temperature - the temperature at which a polymer changes character from brittleness to flexibility) of the polymer, the higher the ambient temperature is above the Tg then the greater will be the degree of permeation. Hence coatings should be designed with a Tg above the temperature at which corrosion protection is to be effected. Extremely highly cross-linked systems are likely to have lower permeability characteristics. Pigmentation can have a significant effect on water and oxygen permeability. Permeability decreases as a function of pigment volume in the film up to a critical pigment volume over which voids will exist in the film and permeability will increase. Pigment shape also has an important part to play in reducing permeability, thin/flat particles being preferred. As solvent evaporates the film shrinks, this has the effect of aligning lamellar pigments parallel to the surface. coating Steel Solvent evaporation Steel

This increases the pathlength for water and oxygen to penetrate to the steel surface. To get the greatest benefit from pigment alignment, low solids coatings are preferable. Film thickness can affect permeability. In general, thicker films delay (but do not stop) the arrival of oxygen and water at the steel surface. However there is evidence to show that, in air drying heavy duty coating systems, film thickness in excess of 400m provides a more than proportional level of corrosion protection. In all coating films microscopic defects are present which penetrate to the steel surface and act as conduits for oxygen and moisture. At high film thickness it is believed that such defects do not penetrate to the steel and hence a greater degree of corrosion protection is achieved. This is far more likely to be true in multi-coat systems:-

v 1 x Thick Film
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4 x Thin Films

To summarise the above, the optimum corrosion protection from coatings can be achieved by the application of several coats of a low solids/low viscosity, lamellar pigmented coating with a polymer Tg above the ambient temperature of application. NON-INTACT COATINGS Coatings will be damaged due to mechanical failure and it is important to maintain corrosion protection despite the damage.
Anodic/cathodic sites f established

during damage, corrosion will occur

stee

It is essential to have good wet adhesion to prevent undercutting at the damaged area, and also to use coatings which are resistant to the hydroxyl ions produced during the corrosion reaction. There are two other mechanisms used to prevent corrosion at damaged areas. i) Use of passivating salts as pigments. Passivation is described in 1.2.2.1. Typically zinc chromate, strontium chromate, calcium metaborate, zinc phosphate. ii) Use of metallic zinc as a sacrificial pigment, see 1.2.2.2 Cathodic Protection. Neither is suitable for coatings subject to immersion service. 1.2.3 FOULING CONTROL 1.2.3.1 INTRODUCTION Fouling is the term used to describe the settlement and growth of marine plants and animals on man made structures in the sea, typically ship hulls, piers, piling and oil rigs, but also including the internals of pipes used to carry seawater as coolant to industrial plants. The presence of fouling on a structure can have serious consequences. On a ships hull for example, fouling will increase the roughness and hence drag of the vessel resulting in an increased fuel demand to maintain operating efficiency. To meet the challenge it is essential to understand why fouling occurs.

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It is estimated that there are in excess of 5000 species involved, although only a small number of these are of major concern to ship owners. Many of these species live their entire lives either swimming or floating and never have a requirement to settle on a surface, on the other hand there are a large number of species which require a surface on which to settle in order to develop into adult animals or plants (typically sea shore weeds, mussels, barnacles). Many shore dwelling and bottom living organisms are unable to move or have limited mobility as adults. An animal or plant attached to the seabed has difficulty in reproducing or in colonising new locations. Sedentary organisms spawn by releasing sperm and eggs into the ocean, plants release spores. Fertilisation is essentially accidental, although it can be enhanced by seasonal factors. For many species fertilisation results in the formation of a larva, which is free floating and/or capable of swimming. This has two advantages for the species: - competition for food decreases - new territories may be colonised Due to the cyclical nature of the reproductive process there is usually a vast abundance of marine larvae in the sea. At metamorphosis the larvae compete for space to settle and grow into mature adults, this is why any man made structure is seen as a suitable candidate for colonisation and which will, in time, be encrusted with marine animal and plant growth. It is important to understand that adult mussels and barnacles are not floating around looking for a suitable surface on which to settle - it is their larvae which do so at particular times of the year in different places around the globe. In other words fouling attack is seasonal. The larvae of mussels and barnacles are microscopic and in this phase are temporary members of the plankton community. As such they drift around the oceans dependent upon currents, tides and waves. At a suitable time in their life cycle comes the time for settlement and metamorphosis - this is when the larva will look for a suitable surface. The same happens when plant spores arrive, once settled they will grow into seaweeds.

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Plankton is the basis of the marine food chain and as such has a direct impact upon the severity of the potential fouling attack. The food chain depends upon plants converting the energy of sunlight into sugars, starches and proteins on which animals can live. Marine plants are predominantly microscopic and depend for their nutrients on the salt and minerals in seawater; the sea is particularly rich in nutrients in springtime following winter storms. This, with the increasing hours of daylight, causes dramatic increase in the abundance of marine planktonic plants, known as phytoplankton, which in turn creates an increase in other planktonic forms which feed on the phytoplankton. This means that fouling organisms (spores and larvae) will be more abundant when seasonal spawning, light, heat and seaborne minerals permit and vice versa. 1.2.3.2 FOULING ORGANISMS Fouling is classified in two broad groups: i) Macrofouling - includes plants and animals ii) Microfouling - includes bacteria and diatoms (also referred to as slime) Macrofouling and microfouling may be subdivided: ANIMAL Barnacles Hydroids Molluscs Polyzoa Tube Worms Tunicates a) MACROFOULING PLANT Brown Algae (Ectocarpus) Green Algae (Enteromorpha) Red Algae (Rhodophycea) MICROFOULING SLIME Bacteria Diatoms (plants)

ANIMAL FOULING Animal fouling is caused by the settlement of the larval stage. Usually 2-3 days is required for the larva to settle and for metamorphosis to the adult to take place. The change in shipping patterns (less stationary periods) has resulted in the fouling problem switching from animal domination to plant domination, however if a ship is subject to lengthy stationary periods it will be vulnerable to animal fouling.

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ACORN BARNACLES The most commonly encountered fouling animal. Barnacle larvae are selective in their site for settlement and appear to recognise other barnacles. This results in barnacles settling close to other members of the species, which aids in cross fertilisation. Barnacles live within hard calcareous shells, which are difficult to remove. Removal by underwater scrubbing or scraping results in a residue of shells being left behind. This promotes further colonisation thereby increasing the fouling problem.

GOOSENECK BARNACLES These animals are especially adapted for planktonic life attached to floating objects. Gooseneck barnacles are the exception in that they are not a shoreline based source of fouling problems. Depending upon conditions they can settle on a ships hull in the open ocean.

HYDROIDS Plant-like in appearance, hydroids are relations of sea anemones. Hydroids have a battery of stinging cells, which are used to paralyse planktonic food. Hydroids live in colonies and are often found on the flat bottom of vessels where they are often thought to be algae. However due to the low light levels in flat bottom areas it is a good assumption to make that all filamental growth in this area are types of hydroid.

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MOLLUSC Animals with paired shells such as mussels and oysters. These animals have hard shells but are attached to structures by relatively weak threads. This tends to limit settlement to stationary structures; the attachments are usually not strong enough to survive on a ship in service.

POLYZOA Animals composed of many cells, which have a calcareous skeleton. Form varies from flat, encrusting species to erect, branching species.

TUBEWORMS Live in easily recognisable calcareous tubes, which protect the soft bodies. Larvae can recognise their own species, resulting in large colonies being established. Tends to settle on the more stationary objects or vessels which spend long periods in port, such as cruise liners.

a)

PLANT FOULING The most regularly encountered plant fouling is the brown algae Ectocarpus and the green algae Enteromorpha, often referred to as grass due to the similar appearance.

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Algae are simple organisms taking nutrients from seawater; root structures do not absorb nutrients and are used simply to anchor the plants. Algal fouling is caused by the settlement of microscopic spores, which settle in seconds and establish within hours. Algae require light for growth and are not usually found on the flat bottoms of vessels.

Ectocarpus

Enteromorph

1.2.3.3 FOULING ENVIRONMENT By looking at season and geography it is possible to split the oceans in terms of their fouling environment: i) Polar Zone - short period of active fouling before and after midsummer, few species. ii) Temperate Zone - active period from spring to early summer. iii) Tropical Zone - year round fouling, many species. iv) Severe Zone - year round fouling in tropical/subtropical coastal regions. Pictorially this is represented as:

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In summary: i) ii) iii) iv) Animal larvae and plant spores are the root cause of fouling. Risk of fouling is dependant upon location and season. Plant fouling requires sunlight to flourish and occurs principally around the waterline. Animal fouling affects all parts of the underwater hull.

ITQ 2 What is the main reason that ship operators wish to reduce fouling? Answer

1.2.3.4 CONSEQUENCES OF FOULING Fouling can seriously impair the operational efficiency of a ship, if left uncontrolled, by increasing the friction between the hull and the water. The basic frictional resistance of a vessel is governed by the initial design; this cannot be altered once the ship is built. The frictional resistance varies within limits due to the roughness of the ships hull. Hull roughness is composed of two main categories:i) Permanent - due to weld seams, valve openings, plate deformities ii) Temporary - due to corrosion, detaching old paint, porous paint, badly applied paint, mechanical damage and fouling. Temporary roughness can be minimised by good maintenance practices. The presence of fouling on a vessel increases the Hull Roughness and thereby increases the friction between the hull and the water. This either slows the ship down or increases the fuel consumption necessary to maintain service speed. In certain cases of severe fouling it may be impossible to maintain service speed. The economic consequences to the ship operator can be dramatic for even a small loss of speed or increase in fuel consumption. On offshore structures the presence of fouling can considerably increase the surface area of the supporting framework, this leads to increases in the forces acting on the structure due to tidal flow and wave action. This factor added to the basic increase in weight due to the presence of fouling has major influences on the initial design of the structure and can have substantial safety and financial consequences.
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The above examples show that the presence of fouling on marine structures can give rise to serious economic and safety concerns. Fouling build up is usually prevented by the use of anti-fouling paints. 1.2.3.5 FOULING PREVENTION BY COATINGS There are two basic mechanisms employed in coatings to prevent fouling settlement: a) b) a) Production of a surface which is toxic to organisms - Toxic Antifouling Production of a surface to which the organisms cannot adhere and therefore not settle - Foul Release Coating TOXIC ANTIFOULING The prevention of fouling by a surface coating requires the maintenance, in the water in contact with the coating, of a concentration of toxin that is lethal to all of the target organisms. Presently, the most commonly used toxin is copper and its compounds. Experiments have shown that a coating needs to release around 10g/cm/day of copper to maintain a lethal concentration to most organisms, up to 20g/cm/day is required to prevent microscopic algal settlement. Copper is a good all-purpose toxin but is often used in combination with other more specific biocides at lower levels to provide a more universal toxic cocktail to the target organisms. The key issue for the paint manufacturer is to provide a system which continually delivers sufficient toxic material for the expected in-service period of the coating, at the right cost. Toxic antifouling paints have traditionally been classified according to the delivery mechanism of the toxin (biocide): i) Conventional Also known as soluble matrix with rosin as the main binder. This is a natural material, which slowly dissolves in seawater due to the presence of carboxylic acid groups. Biocides dispersed within the rosin system are released on contact with water, biocide release is uncontrolled and usually there is an initial flood of release, which rapidly slows down. Such systems can only be formulated with short, effective, life times. As the rosin system is soluble there is some dissolution of the coating leading to a reduction in surface roughness.
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ii) Long Life Antifouling Also known as insoluble matrix. Biocides are insoluble in water. As biocide is released the coating becomes porous, release is exponential. As above, formulations do not have long, effective lifetimes. iii) Self Polishing Conventional and Long Life systems were for many years the only choices for fouling protection. There were many disadvantages associated with such systems: short life time build up of porous/weak layers increase in overall hull roughness

A major breakthrough came with the development of systems where biocides were chemically bound to the film-forming medium. The biocide is released following hydrolysis with water. Once this stage is complete the residual polymeric backbone becomes water soluble due to the formation of sodium and potassium salts. This layer dissolves away to expose a fresh layer of biocidal polymer and so on. This self polishing system has two major advantages: allows for constant release of biocide reduces overall hull roughness

The consequence is predictable performance over a long period of time. The following graph represents the three types of toxic antifouling paint in terms of biocide release and expected lifetime. (Cu2O) Biocide 40 Release (gm/day) 30 20 10 1 2 3 4 5 Years

Conventional Long Life Self Polishing

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b)

FOUL RELEASE COATINGS Marine fouling organisms settle and attach to submerged structures by secretion of adhesive materials. Foul release coatings have a surface with very low surface energy, which dramatically reduces the efficiency of the attachment process, i.e. a non-stick surface is presented to the organism. Experience has shown that organisms either cannot settle and adhere to a structure or that the adhesive bonds formed on settlement are so weak that simple wave action or vessel movement can remove them. ITQ 4 Give 3 advantages of SPC antifouling over conventional or long-life antifoulings. Answer

1.2.4 AESTHETICS Aesthetics is concerned with the presentation and maintenance of a cosmetically acceptable appearance. Vessel appearance is particularly important to the operators of cruise liners and to those ship operators wishing to convey the image of a high quality operation. Specially formulated cosmetic coatings are used in all areas on ships, except the underwater hull. Of particular concern are those used on the boottop, topsides and external deck areas due to the severe environments faced. The principle requirements from a cosmetic coating are: to have good initial gloss to maintain gloss level over the in service period of the coating system to maintain colour by resisting atmospheric degradation

Secondary to the above, cosmetic coatings for use on externally exposed areas on ships must be able to resist one or more of the following: CW/10979R/DS Rev. 1

exposure to seawater (spray, pooling) abrasion and impact from on deck activities chemical spillage from loading/offloading activities
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Cosmetic coating systems must also be easy to clean and to maintain.

1.2.5 CARGO CARRIAGE The principle cargoes carried on the worlds oceans are: dry bulk solids bulk liquids liquefied gas freight containers

The cargo carrying spaces are the revenue earning spaces on cargo ships. It is vital that they are in good condition to maximise the earning potential of the vessel. 1.2.5.1 CARGO HOLDS Coatings are used principally to prevent corrosion in these spaces. To achieve this the coatings used must have good adhesion to steel and be particularly resistant to impact and abrasion damage caused during the loading and offloading of dry bulk cargoes, such as coal and iron ore. On some vessels the cargo holds are used as auxiliary ballast spaces. In such cases only the highest performing anticorrosive coating systems should be used. As well as protecting the steel of the ship it is important that the coating used does not contaminate the cargo, either by exudation of substances within the coating or by coating detachment (flaking). This is particularly important in the carriage of foodstuffs such as grain. 1.2.5.2 CARGO TANKS Corrosion protection is paramount in coatings used to coat cargo tanks. The range of materials carried in tanks on board ships is extensive:

Fuel Tanks - fuel oil, diesel oil, gas turbine fuel Drinking Water Tanks Grey Water Tanks - waste from kitchen, laundry activities Crude Oil Tanks Product Tanks - refined oils, lubricating oils, fuels Solvent Tanks - ketones, etc. Chemical Tanks organic (methanol, MTBE, xylene etc.), inorganic (phosphoric acid, caustic soda solution etc.), vegetable oils & animal fats. Gas Tanks - liquefied gas Consumer Goods Tanks - edible oil, wines

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It is essential that the coatings resist attack from the cargo to prevent damage to the ships structure. If coating breakdown occurs in these areas the vessel cannot trade until repairs are made. It is equally important that the coating does not contaminate the cargo either by exudation or flaking. However probably more important is that coatings should not absorb cargoes, as this absorbed material may subsequently become a threat to future cargoes. It is essential that well established cargo resistance lists are developed and agreed with the vessel owner. 1.2.6 CREW SAFETY In this module only two requirements of coatings are mentioned specifically with regard to providing crew safety. The coatings used must:provide non-slip surfaces in appropriate areas. Non-slip aggregates are usually added to standard coatings to provide good surfaces on walkways and in other similar areas. in areas subject to the potential outbreak of fire, for example engine rooms, comply with the SOLAS (Safety of Life at Sea) regulations. This requires that the coatings meet certain defined performance criteria with regard to how they burn and the substances emitted from them during burning. This is an extremely heavily legislated area, the scope of which lies outside of the brief of this paper.

1.2.7 WORKING ENVIRONMENT Ensuring an acceptable working environment whilst operating in hot climates can put a great deal of stress on a vessels air conditioning system and lead to high operating and maintenance costs. Low Solar Absorption (LSA) coatings reflect infrared radiation (heat) from the sun, allowing a lower surface temperature to be maintained on areas such as topsides, external decks and superstructure. In comparison with typical non-LSA coatings, internal areas remain cooler, (typically 4 8C (8 15F) cooler) with minimised energy requirements and operating coasts.

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SECTION 2 PAINT TYPES OBJECTIVES


When you have completed Section 2, you should be able to:5. 6. 7. 8. Describe the 6 main constituents of paint and understand why they are used. Understand the difference between convertible and non-convertible coatings, provide examples of each and be aware of their advantages and disadvantages. Understand the principles involved in the 3 main mechanisms of drying. Compare coating types in terms of the properties they provide.

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SECTION 2 PAINT TYPES


2.1 WHAT IS PAINT? Paint, surface coating, lacquer and varnish are terms which have become somewhat synonymous and confused. ISO 4618/1 gives the following definitions: Paint - a product, liquid or in powder form, containing pigment(s), which, when applied to a substrate, forms an opaque film having protective, decorative or specific technical properties. Varnish - a product which, when applied to a substrate forms a solid, transparent film having protective, decorative or specific technical properties. Coating materials have been used for over 15,000 years; the Stone Age cave paintings of Southern France being the first known example. The first materials which resemble modern coatings were the lacquers developed by the Chinese in around 2,000BC. These materials were based on the sap of the Chinese Lacquer Tree (Rhus Vernicifera). In the 16th century AD lacquered articles were increasingly being imported into Europe. This lead to a demand for lacquers to be developed on indigenous European raw materials. Combinations of vegetable oils and tree resins were used to develop coating materials. Coatings were used at this time purely for decoration and the development of the paints was usually done by the artists and painters themselves. It is really only since the middle of the 19th century that coatings have been used for protection. Nowadays this is the primary function of surface coatings. The need for protective surface coatings highlighted the performance failings of the traditional vegetable based coating. Cellulose nitrate, synthetic phenolic and alkyd resins were developed early in the 20th century and are considered to be the first synthetic resins used by the coatings industry. Nowadays there is a wide range of raw materials available to the paint chemist supplied by the global chemical industry. 2.2 COMPOSITION OF PAINT Modern coatings are composed of many different raw materials grouped as:

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Volatile

Non Volatile

Solvents Coalescing Agents Film Formers Resins Plasticisers Additives Dyes Pigments Extenders

Binder

Varnish Paint

FILM FORMERS Film formers are either macromolecular products (e.g. chlorinated rubber) or low molecular mass products, which combine to form macromolecular structures (e.g. epoxy/amine). The molecular mass obtained has a critical bearing on the final paint as it influences mechanical properties and application properties inversely, the right blend is crucial for optimum overall performance. Most film formers are known as resins. RESINS Resins are correctly defined as vitreous - amorphous solids, which do not have defined melting points. Nowadays the term is used to denote that group of synthetic or natural film formers with resinous consistency. The essence of a resin is that it can be applied to a substrate and can be made to form a continuous adherent film over the substrate. The nature of the resin employed has a major bearing on the ultimate decorative/protective/mechanical properties of the paint developed. PLASTICISERS Plasticisers are organic liquids of oily consistency and low volatility. They are used to modify the film characteristics of the resin being used, for example by improving flow and increasing flexibility. Plasticisers do not generally react with the resin. In chemically curing coatings, it may be desirable to reduce the viscosity of the paint to improve application characteristics, aid flow and aid wet adhesion. Addition of a plasticiser which does not react with the resin however, would lead to a film with lower cross-link density and poorer chemical resistance and hardness, as well as longer drying times. In such coatings therefore, a Reactive Diluent may be used. An example of a reactive diluent is a mono-functional glycidyl ether in epoxy coatings. These materials have lower viscosity than epoxy resins, but contain functional groups, which react with amine groups in the curing-agent. Film formers, resin, plasticiser combinations are referred to as the Binder of the paint system.
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PIGMENTS Pigments provide colour, hiding power and, in special cases, specific properties (e.g. passivation, antifouling). Pigments are finely ground, crystalline solids dispersed in the paint. Metals, inorganic, organic, organometallic compounds are used as pigments. Pigments are expensive and are used as sparingly as possible. EXTENDERS Extenders are naturally occurring or synthetic materials which have little hiding power or effect on colour. Extenders are used to impart specific properties to the paint (e.g. gloss control, abrasion resistance, reinforcement) and to reduce the cost of the finished product. Typical extenders are barytes, talc, mica, and dolomite. SOLVENTS Solvents are volatile fluids used to assist in dissolving solid resins and to aid the application of paint. Solvents evaporate from the coating during drying and essentially play no part in the final coating performance. ADDITIVES Additives are a wide range of materials used in paint at low levels, to significantly improve the finished product. For example: Driers - catalyse the reaction between atmospheric oxygen and alkyd resin to produce hard/dry films. Anti-Skin Agents - antioxidants used to prevent alkyd paints skinning in the can. During film formation they evaporate and have no effect on product drying time. Thixotropes - used to aid film formation/build properties by importing anti-sag properties and to improve in can stability by reducing pigment settlement on storage. Wetting/Anti Float/Anti Flood - surfactants used to counteract the tendencies of pigments to flocculate/separate and other potential pigment - binder interface problems. 2.3 CLASSIFICATION OF PAINTS One of the most common, and useful ways in which paints are classified is by their drying/curing mechanism. Basically these are: i) Physically drying (solvent loss) - Non Convertible ii) Chemically drying - Convertible The following diagram shows the various types of convertible and non convertible coating types commonly met in the marine coatings business.
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Paints

Physically (solvent) drying

Chemically drying

Chlorinated rubber

Vinyl/ Vinyl tar

Bituminous

Acrylic

Air drying

Stoving paints

Moisture curing

Two-pack

Oxidatively drying

Zinc silicate

Moisture curing polyurethane

Polyester

Polyurethane

Epoxy

Alkyd

Oil-based

Epoxy ester

NON-CONVERTIBLE COATINGS Such coatings dry by simple solvent evaporation. No chemical reaction takes place. Binders are usually long chain polymers, which can interlock to form continuous films without chemical reaction. These polymers tend to have high viscosity and, to apply a film, it is necessary to dissolve the polymers in appropriate solvents. This means that any usable paint will have a low solids content. The current legislative position with regard to the use of volatile organic compounds is having a major impact on the use of low solids (high solvent) coatings. Physically drying paints can be redissolved in appropriate solvents as no chemical changes have taken place. This has advantages and disadvantages to the end user. The most important advantage is effectively an indefinite overcoating period with subsequent good intercoat adhesion. Solvents, in a freshly applied coat of the material will penetrate into the underlying paint film and on drying the layers will have become interlocked. Another key feature of such systems is the ability to dry at essentially all temperatures, the only variation will be a change in drying time due to a change in the solvent evaporation rate. Regardless of temperature of application, physically drying systems will ultimately yield a film of the same properties. There are two principal disadvantages associated with non-convertible coatings, the most important being low solids levels. The use of high molecular weight polymers as film formers with their inherently high viscosity results in low solids coatings in order to achieve efficient application to the substrate. This in turn leads to low film build resulting in the need to apply several low film thickness coats to achieve the film thickness necessary for the level of protection required. This adds extra time and costs to coatings projects. Further disadvantages of non-convertible systems are: The polymers used have low Tg values, leading to the paint film being susceptible to softening by heat - known as thermoplasticity. This precludes their use on certain vessel areas and in certain climatic conditions.
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CW/10979R/DS Rev. 1

Poor chemical/solvent resistance, including poor resistance to spillages on decks etc.

Examples of film formers used in non-convertible coatings are chlorinated rubbers, vinyls and acrylics. CONVERTIBLE COATINGS Such coatings dry by chemical reaction. That is, they are converted from their original state into a new state. Once they are fully dried they cannot be redissolved in the original carrier solvent, unlike non-convertible coatings. The film forming substances are usually relatively low molecular weight materials which react together to form large cross linked molecules. In the marine coatings industries three main reactive mechanisms are used: reaction with atmosphere oxygen reaction with water reaction with chemicals (curing agents) - Oxidative Drying e.g. Alkyds - Moisture Curing e.g. Moisture cured urethanes - Multi Pack Products e.g. Epoxies, Polyurethanes

OXIDATIVE DRYING Early paints were based on natural oils, such as linseed oil. These are generally long chain aliphatic systems containing reactive CH2 groups between C=C double bonds e.g. -CH2-CH=CH-CH2-CH=CH-CH2The reactive CH2 reacts with oxygen free radicals in the atmosphere thereby enabling crosslinked systems to be built up. Reactivity is dependent upon the number of double bonds in the oil molecule. Oil molecules are fairly small hence drying to produce a dense film takes a long time. To reduce the drying time it is possible to modify the original oil to create larger basic molecules. The most common form of modification are the Alkyd resins. These are based on natural oils but can be modified to give a range of materials with very specific proportions. Full dry/cure of these systems requires penetration of oxygen right through the film, hence applied film thickness tends to be low to prevent surface drying (skinning) only.

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TWO PACK Chemically curing materials, which require the mixing of two components for film formation to occur, are known as two-pack. Individually neither component is capable of producing an acceptable paint film. Once mixed the two components react chemically. This process is irreversible leading to one of the major disadvantages of such systems. Once mixed, two pack materials have a finite usable lifetime during which application is practical. This can vary from seconds to days. This is termed the pot life of the product. There are many ways of handling pot life issues, which will be discussed later in this training module. There are a huge variety of possibilities for two pack systems resulting in a range of products with broad or specific properties for example, UV resistance, wear resistance, chemical resistance, flexibility, etc. The nature of the films produced (hard/solvent resistant) can lead to adhesion problems on overcoating, often resulting in very limited overcoating windows or the need to carry out surface preparation, such as abrading, prior to overcoating. The most commonly found two-pack systems in the marine business are the Epoxies. MOISTURE CURING These are coating systems which cure by reacting with atmospheric moisture. There are two main systems used in the marine business. The reaction between isocyanate and moisture to create urethane linkages -N=C=O + -OH -NH-C-OII O Urethane The toxic and respiratory sensitisation problems associated with isocyanates tends to restrict their use. The main use of moisture cure in the marine business is with Zinc Ethyl Silicates. The binder is an alkyl silicate, which reacts with moisture to form a hard cross-linked matrix. If blended with metallic zinc (sacrificial pigment) systems can be developed which are extremely effective in preventing corrosion.

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ITQ 5 Give simple definitions of convertible and non-convertible coatings. Provide two commonly used examples of each. Answer

2.4 FILM FORMATION Liquid paint should be considered as an intermediate product, which is only of real value after it has been applied to an object and formed a continuous solid surface coating. This process is called film formation. A useful definition of a solid film is that it is a material which does not flow significantly under the forces or conditions to which it is usually subject. Hence it is possible to define whether or not a material is solid under a set of conditions by stating the maximum viscosity at which flow would be observed. A paint film is termed dry or solid when it develops certain properties or passes certain tests, again this can be related to viscosity. At application, paint viscosity is typically in the region of 0.5 - 10 poise. It has been reported that at the touch dry stage viscosity will be greater than 104 poise and that if blocking* is to be resisted under normal pressure a viscosity of 108 poise is required. There are two basic mechanisms by which film formation is effected - physical drying and chemical drying. Two broad classes of resin (polymer) are used in coatings, thermoplastic and thermoset. For thermoplastic materials, the final polymer is formulated into the coating and applied to the substrate. With thermoset materials, low molecular weight polymers are formulated into the coating, the coating is applied and chemical reaction takes place to produce the final polymer. The two mechanisms described give rise to the terminology: NON-CONVERTIBLE COATINGS - physically drying, thermoplastic CONVERTIBLE COATINGS - chemically drying (curing), thermoset *blocking - ability of two coated surfaces to resist sticking together 2.5 TYPICAL MARINE COATING PROPERTIES The table on the following page compares the properties of the coating systems most commonly used in the marine business.

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TYPICAL MARINE COATING PROPERTIES


PAINT TYPE DRYING MECHANISM MECHANICAL PROPERTIES COSMETIC PROPERTIES OVERCOATABILITY WATER Acrylic Alkyd Bituminous Chlorinated Rubber Epoxy Epoxy-Ester Epoxy-Tar EpoxyPhenolic Polyurethane Polyurethane -Tar Vinyl Vinyl-Tar Zinc Silicate Physical Oxidative Physical Physical Chemical Cure Oxidative Chemical Cure Chemical Cure Chemical Cure Chemical Cure Physical Physical Moisture Cure Moderate Moderate Poor Moderate Very Good Moderate Good Very Good Very Good Good Good Moderate Very Good Very Good Good N/A Moderate Poor Moderate N/A N/A Very Good N/A Good N/A N/A Good Good Very Good Very Good Poor Good Moderate Poor Moderate Moderate Very Good Very Good Very Poor - Self to Self Good - with epoxies Moderate Moderate Very Good Good Good Moderate Very Good Good Good Very Good Good Very Good Very Good RESISTANCE TO: ACID Good Poor Good Good Very Good Poor Good Excellent Very Good Good Good Good Very Poor ALKALI Good Poor Good Good Very Good Poor Good Excellent Very Good Good Good Good Very Poor SOLVENTS Poor Moderate Very Poor Poor Very Good Moderate Moderate Excellent Very Good Moderate Moderate Poor Excellent ---------------------------UNDER WATER (antifouling) ---AREA OF USE: ABOVE WATER CARGO HOLDS -CARGO TANKS -----BALLAST TANKS ---

N/A = Not applicable


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SECTION 3 PAINT FORMULATION OBJECTIVES


When you have completed Section 3, you should be able to:9. Understand the concepts of mass solids, volume solids and volatile organic content.

10. Understand the importance of pigment loading and the effect of pigment volume concentration (PVC) on paint properties. 11. Give examples of properties affected by PVC. 12. Understand the concept of mix ratio in multi-pack products. 13. Calculate the spreading rate of paints, given the volume solids and required dry film thickness.

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SECTION 3 PAINT FORMULATION


In section 2 we looked at the constituents that are combined in a paint formulation to produce a coating which will provide the required properties to perform a particular function. In this section, we will examine the factors which need to be considered during formulation and introduce terms commonly used. 3.1 SOLIDS CONTENT The solids content of a paint determines the dry film thickness which will remain following solvent loss from the wet film thickness applied. Within a formulation, a balance must be achieved between sufficient volatile component (i.e. solvent), to facilitate manufacture, application and flow/levelling, and non-volatile (solid) component to provide the paint properties. The quantity of solvent released from an applied paint must also be considered from an environmental perspective. 3.1.1 MASS SOLIDS The mass solids is mainly only of concern during paint manufacture, when it may be used as a quality control tool. It can be defined as the ratio of the mass of the solid components to the total mass, and is expressed as a percentage: MS% = MP + MR x 100% MP + MR + MS where MP = Mass of pigments MR = Mass of resins MS = Mass of solvent 3.1.2 VOLUME SOLIDS The concept of volume solids is essential when considering the dry film thickness expected from an applied wet paint film. Volume solids is the ratio of the volume of the solid components to the total volume, and is expressed as a percentage: VS% = VP + VR x 100% VP + VR + VS where VP = Volume of pigments, extenders, etc. VR = Volume of resins VS = Volume of solvent Practically measured volume solids are usually higher than the theoretical figure derived from the formulation by calculation.
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This is due to a number of factors including: solvent entrapment voids in the dry film chemical curing, whereby volatile components are reacted into the coating resin system before volatilization.

A practically determined figure is used on product data sheets. 3.1.3 V.O.C. Volatile Organic Compounds (VOC) are released to the air as the paint is applied and then dries/cures. The amount of such material released is the subject of environmental legislation, which varies around the world. In Europe, a solvent emissions directive (SED) exists, whereby it is assumed that all solvent will ultimately escape from the film. The VOC content is calculated from the paint formulation and is expressed as grams of VOC per kilogram of wet paint. In the rest of the world, VOC content is normally expressed as the weight of VOC in grams (or pounds in the USA) contained in one litre (or gallon in the USA) of wet paint. This is a practically determined figure, which is temperature dependent. Calculated VOC is usually different to that which is practically achieved, for similar reasons to volume solids in 3.1.2. For use on product data sheets a practically determined figure is normally required, with the exception of calculated European SED figures. ITQ 6 Although high solids coatings are desirable in terms of reduced solvent emissions, give 3 disadvantages of increasing solids. Answer

3.2 PIGMENT LOADING The quantity of pigment, in this case meaning both pigment and extenders, contained in a paint formulation can have a major effect on the final properties of the coating. These effects are not only aesthetic, e.g. colour, gloss or opacity, but also can determine performance.

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3.2.1 P.V.C. Pigment Volume concentration (PVC) is the ratio of the volume of pigment to the volume of all solid components, and is expressed as a percentage: PVC% = VP x 100% VP + VR where VP = Volume of pigments, extenders, etc. VR = Volume of resin

The above relationship is somewhat simplistic, as it does not consider particle shape, size or packing factors, or the oil absorption of the pigments used. Many fundamental coating properties are dependant upon the PVC and CPVC. 3.2.2 C.P.V.C. Critical Pigment Volume Concentration (CPVC) is that particular Pigment Volume Concentration (PVC) at which there is just sufficient resin in the dry film to give a completely adsorbed layer on all pigment surfaces and to fill all of the gaps between the particles when they are randomly loose packed. This is expressed in percentage terms as: CPVC% = VP VP + VRC x 100% where VP = Volume of pigments, extenders, etc. VRC = Critical volume of resin Above the CPVC voids are present in the paint film. Below the CPVC the pigment particles are separated. This change in configuration at the CPVC brings marked changes to the properties and behaviour of paint films. Many physical, permeability and optical properties of coatings change more or less abruptly at the CPVC: Density - The density of the dry paint film reaches a peak at CPVC. Tensile Strength - The strength of a paint film reaches a maximum at CPVC, but reduces dramatically once the CPVC is exceeded. Porosity - A paint film becomes porous at the CPVC. This can lead to a large increase in penetration by liquids and gases. Rusting Porosity in paint films will promote the onset of rusting. This will be manifest by rust spots on the film surface. The shift from no corrosion to severe corrosion is centred around a narrow PVC band around the CPVC.

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Blistering - Blister resistance is a measure of the paint films ability to resist the action of moisture without raising blisters. Porous films allow underfilm moisture to escape without blister formation. If the paint film is impermeable, trapped moisture will form blisters. The change from severe blistering to no blistering occurs within a narrow PVC band around the CPVC. Hiding Power - Beyond the CPVC air is included into the paint film. This will improve the hiding power (or opacity) of the paint. Gloss Gloss is reduced as the PVC rises and approaches zero at the CPVC. ITQ 7 Would you expect the following coatings to have low, medium or high PVC? a) An alkyd cosmetic finish b) A zinc silicate shop primer c) An abrasion resistant epoxy anticorrosive Answer

3.3 RATIOS IN MULTI-PACK PAINTS Paints which cure by chemical reaction between components are supplied in separate containers to prevent reaction prior to mixing and application. There are usually two components, but three-component paints, such as Intersleek 757 are also encountered. In order to control the reaction, and the resultant paint film properties, it is necessary to combine the components in specific ratios. 3.3.1 STOICHIOMETRY Stoichiometric is defined in the dictionary as: concerned with, involving or having the exact proportion for a chemical reaction. In simple terms, the stoichiometry is a measure of how fully the two components of a two-pack paint react during cure. If the components were to fully react, for example if all the epoxy groups in the base component of a two-pack epoxy/amine paint reacted will all of the amine groups in the curing agent, the stoichiometry would be 100%. However, stoichiometry is largely theoretical in that several factors, such as steric hindrance, prevent total chemical reaction. Some unreacted components will remain. At 100% stoichiometry however, the cured paint film can be very brittle and the high level of reaction can reduce overcoatability. For these reasons, two-pack paints are normally formulated below 100% stoichiometry, and the precise ratio used is usually determined by experimentation/performance testing.
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3.3.2 MIX RATIO Once the stoichiometry of a multi-pack paint has been optimised, other, non-reactive, components such as pigment, extenders, additives and solvents are added. Often, pigments and extenders are only added to one component, but in some paints, both are pigmented. The result is a ratio in which the components must be mixed in order to achieve the required stoichiometry. This is the mix ratio. As the molecular weight of resins differ, and hence the functionality, the mix ratios of different paints will differ. It is usual to attempt to achieve a whole number mix ratio, e.g. 3:1 or 4:1, to simplify pack sizes. For example, a 3:1 mix ratio would give 15 litres in a 20-litre tin to be mixed with 5 litres in a 5-litre tin. 3.4 SPECIFIC GRAVITY The specific gravity (s.g.) is an expression of the mass of a certain volume of paint. Mass = Volume x Density (s.g.) Hence, if an antifouling has an s.g. of 1.85g/cm, then 20 litres will weigh 20 x 1.85 = 37Kg. 3.4.1 SPREADING RATE The spreading rate, or theoretical coverage as used on International Paint product data sheets, is the coverage per unit volume (or weight) to give a specified dry film thickness. Spreading rate can be expressed in many units, for example: SR (m/litre) = %Volume solids x 10, dft SR (m/kilogram) = %Volume solids x 10, dft x SG SR (kilogram/m) = SR (litre/m) = dft x SG %Volume solids x 10 dft %Volume solids x 10 where dft = dry film thickness in microns where SG = Specific Gravity of paint

However, spreading rate is usually expressed as m/litre, for example 1 litre of paint with volume solids of 100% applied to give a dry film thickness of 1000m will cover 1 square metre.

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ITQ 8 What is the weight of mixed paint for a two-pack coating consisting of 15 litres of base (s.g. 1.41) and 5 litres of curing agent (s.g. 0.98)? If this coating had a volume solids of 72% and was to be applied at 150 microns dry film thickness, what would be the spreading rate in m/litre)? Answer

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SECTION 4 PAINT PERFORMANCE OBJECTIVES


When you have completed Section 4, you should be able to:14. 15. 16. 17. 18. 19. 20. State which properties of paint are important for different vessel areas. Understand the tests required to ensure that a paint is suitable for application to a vessel, prior to becoming a dry coating. State the factors which determine the ultimate mechanical properties of a paint and understand the associated test requirements. Understand the testing involved to ensure chemical and water resistance. Understand the testing involved to ensure resistance to atmospheric exposure. Be aware of specific test requirements for antifoulings and shop primers. Be aware of further testing which may be specified by customers or be required by legislation.

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SECTION 4 PAINT PERFORMANCE


4.1 REQUIREMENTS OF PAINT Paint, for use on a ship, has to satisfy many requirements depending upon the type of vessel and the area of the vessel to which the paint is to be applied. Each product will therefore be required to exhibit a combination of properties.
External superstructure (corrosion, Decks and hatch covers (corrosion, abrasion, impact, cosmetics)

Underwater hull (corrosion, abrasion, antifouling)

Boottop (corrosion, cosmetics)

Topsides (corrosion, cosmetics)

Accommodation (fire resistance)

Cargo tanks (cargo resistance) Cargo holds (corrosion, abrasion, impact, cleanability)

Void spaces and cofferdams (corrosion)

Chain locker (corrosion, abrasion)

Potable water tank (corrosion, potable water approval) Engine room (fire resistance, chemical resistance)

Ballast tanks - including fore and aft peak tanks (corrosion)

Performance can also be split into distinct areas: Mechanical properties - including adhesion, both to substrates and between coats, hardness, flexibility, impact resistance and abrasion resistance. Chemical properties - for the marine industry this essentially means resistance to water, i.e. corrosion resistance, and to liquid cargoes. Additionally, resistances to spillages, e.g. oil, may be required. Resistance to weathering - including gloss retention, chalking resistance, resistance to discoloration and dirt retention.

In addition, certain types of coatings used in the marine industry, e.g. antifoulings and shop primers, require specialised properties.

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International Paint must be confident that a product is both fit for use and "fit for purpose". Our product development laboratories must therefore carry out exhaustive testing of product before they are introduced into the market. This does not mean however that the customer will have the same confidence and he may therefore require additional testing to recognised industry standards, e.g. Norsok anticorrosive testing, US MIL-SPEC testing, DEF-STAN etc. Additional testing may be required to satisfy legislation, e.g. surface spread of flame, potable water, weld fume, carriage of grain etc. 4.2 FITNESS FOR USE In addition to testing a product to ensure that it performs its required functions as a coating, it is also important to ensure that the product is "fit for use". Before becoming a part of a coating scheme on a ship, a paint must be transported, stored and applied and then must dry or cure, i.e. it must be fit for use. In many cases, the first contact a customer will have with a product is during application. It is therefore important that the product: Has good storage properties, i.e. it looks good in the tin and can be easily mixed for application. Has good application properties. Has practical drying / curing times.

4.2.1 STORAGE PROPERTIES In the period between manufacture and application, a product is stored, transported and then stored again. The storage period could be up to 12 months and the temperature during that period could be as low as -5C (23F) or as high as +40C (104F). Testing is therefore carried out to ensure that the paint can be stored, in a container similar to that used in practice, for long periods at extreme conditions. Typical tests, which may be carried out on the stored paint, include: Viscosity - has an unacceptable increase in viscosity taken place? Settlement - has the material settled into distinct phases and can these be easily reincorporated on mixing? Gelling - have any components reacted? Loss of functionality - have any reactive resins been affected by other components (e.g. epoxy resin with alcoholic solvents) causing loss of functionality, affecting drying, hold-up or resistance? Colour change Application properties - when applied, does the product coalesce, hold up etc.? Drying times

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4.2.2 APPLICATION PROPERTIES Marine paints can be applied by several methods: Airless spray Conventional, air-assisted spray Roller Brush Trowel

Although the majority of newbuilding and major refurbishment applications will be by airless spray, on-board maintenance (OBM), carried out by the crew, will often be by roller or brush. It may therefore be necessary to evaluate the application properties of a paint using several methods. (i) Airless spray Properties are examined at suitable temperatures. This is especially important at low temperatures (e.g. -5C, 23F) where the required level of thinning needs to be evaluated and particular attention is paid to fan quality and coalescence. A range of spray tip sizes and fan widths are used, and the air pressure at the pump varied, to arrive at recommendations for practical application. Airless spray trials using long lines, where a significant pressure drop will occur between pump and spray tip, are also carried out. For coatings to be applied by plural feed equipment, heating temperatures and application pressures are determined using equipment similar to that which will be used in practice. Factors considered during airless spray evaluation are: Coalescence - the minimum thickness required to produce a continuous film. Hold-up. Fan quality - no horning, tailing etc.

Even fan
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Fingering

Tailing / horning

Dry spray
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(ii)

Conventional spray Essentially, the procedure is similar to assessment of airless spray properties. Particular attention is paid to the choice of thinner and thinning levels. Testing is carried out such that advice can be given to the end user regarding gun and tip types.

(iii) Roller and Brush It should be noted that it is not only at OBM when rollers or brushes are used. For example, stripe coats in ballast and cargo tanks are usually applied by these methods and therefore it is not only above water primers and finishes which will require evaluation. Factors considered include: Wet edge time - when coating a large area, does the paint present pick-up problems when returning to a recently applied area? Flow - does the paint flow out to provide an even, aesthetically pleasing film? Coverage - how many coats need to be applied to give the specified film thickness? Splattering - does the paint have the correct rheological properties to prevent dripping and splattering of the coating, especially when painting overhead?

(iv) Trowel Some paints, for example high-build deck coatings, may be applied by trowel. Factors considered in this case include flow, air entrapment etc. 4.2.3 OPACITY (HIDING POWER) Opacity is the ability of a paint to obliterate the background over which it is applied. In the case of cosmetic finishes, which are usually applied at low film thickness, over a primer which may be of a different colour, opacity tests are carried out to ensure good cosmetic properties. 4.2.4 POT-LIFE For multiple pack products, whichever method of application is being evaluated, one major consideration is the pot life of the coating, i.e. the time available between mixing and application. After this time, the paint will have risen in viscosity or gelled to an extent where application properties, and possibly subsequent film properties, will be detrimentally affected.

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4.2.5 DRYING The rate and mechanism of drying, or curing in the case of non-convertible coatings, is a very important property of paint and there are many methods used to determine drying times, e.g.: Beck Koller (BK) Dry Track recorder mainly used to compare drying behaviour of similar coatings. Ballotini - after suitable periods, ballotini (small glass spheres) is dropped onto the applied film. Once the ballotini can be easily removed with a soft brush, without damaging the coating, the paint can be said to be touch dry. Manual drying time the applied paint is placed under controlled temperature conditions. At suitable periods the panel is tested, first by touching the surface lightly with the finger. When no tackiness can be detected, and no marks are left on the surface, the film is touch dry. At a later stage, the panel is placed on a flat surface and the thumb pressed firmly down onto the coating and twisted through 180. If no damage to the paint film is observed, the coating is hard dry. Walk-on time - for vessel areas such as ballast tanks and decks, a coating must attain a stage of drying whereby the applicator can walk on the coating in order to apply subsequent coats. A device known as a "mechanical thumb" is available which mimics the forces exerted by a man weighing 70kg walking on a coating. It is preferable however to carry out a practical test whereby the product is applied to a large steel panel under the specified temperature conditions. At specified intervals, a person stands on the coating and immediately twists through 90. If the coating remains undamaged, it is considered to be suitably cured to walk on. In all cases, it is vital that paint is applied at the thickness at which it will be specified in practice. Thicker films will give rise to longer drying times. Humidity may also be a factor affecting the drying rate of paint, particularly in the case of zinc silicates, and therefore a controlled humidity environment would be required. 4.3 FITNESS FOR PURPOSE 4.3.1 MECHANICAL PROPERTIES One function which a coating scheme must perform is protection of the substrate from damage. Depending upon the vessel area, the importance of this function varies, e.g. a ballast tank is an enclosed space which will not be subject to high levels of mechanical damage, however a cargo hold will experience severe abuse during loading, carriage and unloading. Coatings for cargo holds, decks and outer hull undergo mechanical testing as they are subject to the following damage types:

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Abrasion - for example caused by cargo settlement or the "rubbing" of a vessel alongside a fender. Impact - caused by cargo loading and unloading operations, collisions, and the dropping of equipment onto decks. Gouging.

In order to resist these forms of damage, a coating needs to possess a combination of the following properties: Adhesion - both to steel and to underlying coatings. Flexibility - in order to deform on impact and transmit shock forces. Cohesive strength. Tensile strength.

There are many other factors which make a coating scheme resistant to mechanical damage and, often, a balance between these properties is required. For example, a coating may have very high cohesive and tensile strength but may be brittle, with all impact forces being concentrated at an interface and therefore causing detachment. 4.3.1.1 ADHESION & OVERCOATABILITY Overcoatability can be thought of as simply adhesion to an underlying coat. As such, it should be realised that adhesion not only depends upon the coating being applied but also to the surface to which it is being applied. 4.3.1.1.1 Adhesion The mechanism of adhesion is complex and involves a combination of the following: "Wettability" of the substrate Chemical bonding Mechanical keying

Adhesion testing of marine products typically involves evaluation of adhesion of primers to steel substrates and of coatings to each other. Factors involved in adhesion to steel include the following: Level, and type, of surface preparation e.g. various levels of gritblasting, hydroblasting or power tool cleaning. Surface contamination - including salts, loosely adherent rust etc. Dampness - condensation on the steel substrate.

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There are several means of testing adhesion, these essentially being split into two types: a) Quantitative - e.g. pull-off testing where a dolly (a device to enable a force to be applied to the coating scheme) is applied to the surface of a coating scheme by the use of an adhesive and a constant force is applied until detachment occurs. Qualitative - it has been found that a subjective assessment of the force required to remove a coating, either from the substrate or an underlying coating, using a penknife, can provide a reliable measure. It must be stressed however that this method is subjective and requires a skilled operator who has received considerable training. This training also covers several generic types of paint as, depending upon their thickness and cohesive strength, their removal can have a different "feel". In essence, the penknife adhesion test consists of cutting a 'V' shape in the coating scheme, down to the interface in question, the angle of the 'V' being approximately 30. The end of the penknife is then inserted at the point of the 'V' and an attempt is made to lift the coating. The ease with which the coating can be removed is rated on a scale of 0-5, 0 being spontaneous detachment and 5 being perfect adhesion. Other methods of adhesion assessment do exist, such as the cross-cut adhesion test where a series of parallel incisions are made through the coating horizontally and vertically. The action of cutting this "grid" can cause paint to be removed at the intersection of the cuts and the degree of removal is compared to pictorial standards and a rating of adhesion given. Prior to the rating assessment, pressure-sensitive adhesive tape may be applied over the "grid", pressed down, and then removed, taking any loose coating with it. The adhesive strength of the tape used may affect the result. Cross-cut methods can be useful when assessing adhesion of thin coats with relatively low adhesion, e.g. cosmetic finishes. Their use is limited in the area of marine coatings however as high build coatings, especially epoxies, resist the cutting tool and often their adhesive strength is too high for the coating to be removed by this method.

b)

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4.3.1.1.2

Surface Tolerance Many types of coating (e.g. pure epoxy, coal tar epoxy, chlorinated rubber) require a high level of surface preparation, such as gritblasting to ISO 8501-1 Standard Sa2 in order to achieve good adhesion and subsequent performance. This obviously has surface preparation cost implications to the customer. Surface tolerant coatings, such as hydrocarbonmodified epoxies (Interbond 201 for example), allow application over reduced levels of surface preparation, or directly over certain types of aged coatings. Other surface tolerant coatings (such as Interbond 808) have been formulated to enable application over damp surfaces. Evaluation of the surface tolerance of a coating involves preparation of relevant substrates and aged coating schemes. Once overcoated with the product under test, adhesion assessment is carried out, followed by appropriate performance testing (e.g. immersion, atmospheric exposure). Whilst surface tolerant coatings will perform over such surfaces, optimum performance will be achieved over gritblasted steel.

4.3.1.1.3

Overcoatability With any marine product, the issue of overcoatability is an important one. Most coatings, with the exception of shop primers, will need to be applied over another coating, even if that is only itself. Additionally, almost all coatings will be overcoated at some stage in their lifetime. It is impossible to accurately predict overcoating properties of a product. Additionally, it is very difficult to formulate for good overcoatability and therefore extensive testing is a necessity. Factors involved in the assessment of overcoatability include: Generic nature of the underlying coat. Generic nature of the coat being applied. Roughness of the underlying coat. Age of the underlying coat - often, coatings may show good overcoating properties for a period of time. After this period, intercoat adhesion becomes poor but may subsequently improve due to factors such as degradation of the underlying coat. This is particularly evident with epoxy coatings, which chalk on UV exposure. Contamination. Conditions to which the underlying coat has been subjected temperature, relative humidity, UV exposure, ventilation conditions etc.
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Overcoatability testing is carried out not only to determine the maximum interval within which one coat may be applied over another, if indeed the coating will adhere at all, but also the minimum interval which will result in good adhesion but without detriment to performance. ITQ 9 What may be the consequences over overcoating at an interval shorter than the minimum stated on the product data sheet? Answer

4.3.1.2 HARDNESS Hardness is more of a concept than an actual property when applied to the relatively thin paint films applied in the marine environment. Many hardness tests are affected by the nature of the substrate and therefore it is possible that a result is more a measurement of the hardness of steel than that of the coating scheme. Methods used for the determination of hardness include: Scratch hardness - the most commonly used test for marine coatings in this category is pencil hardness. This involves scratching the coating with a range of pencils of calibrated hardness (usually 6B - 9H, (9H being the hardest). The hardest pencil which does not scratch the surface is quoted. Pendulum / Rocker hardness - several items of equipment are available, (e.g. Konig pendulum, Sward rocker) whereby a ball or rocker rests on the coating and an attached frame is allowed to rock back and forth. A measure of the hardness is obtained from the damping effect of the coating on the oscillations. Indentation hardness - again, several methods are available, (e.g. Knoop hardness, Buchholz hardness). A loaded indentor presses into the coating giving a measure of hardness. This type of test is most likely to be affected by the hardness of the substrate.

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4.3.1.2 FLEXIBILITY The flexibility of a coating can have a bearing on several properties, including adhesion, resistance to impact, and resistance to cracking due to deformation of the substrate. Despite this, the flexibility of marine coatings is not commonly tested, possibly as most, epoxies for example, are brittle in nature. Several test methods are available, however most are affected by the adhesion of the coating to the substrate as well as flexibility. The most common test is the mandrel bend test, of which there are two main types: Cylindrical mandrel - a coating is applied to a thin metallic substrate which, once the paint is dry, is bent around a cylinder of known diameter. A range of mandrels, differing in diameter, is available. The coating is then visually assessed for cracking and the smallest mandrel diameter which produces no cracking is reported. Conical mandrel - the principle is the same except that one mandrel, tapering in diameter from one end to the other, is used. The point along the mandrel where no cracking occurs is quoted as the result.

Drawbar (to bend panel over mandrel)

Conical mandrel Coated panel 4.3.1.4 IMPACT Impact resistance is important with regard to coating schemes applied to cargo holds, decks and outer shell. Impact may result from cargo loading and unloading operations, collisions, and the dropping of equipment onto decks. Two main types of impact can occur, i.e. direct impact to the coating and reverse impact, where the ship's plate to which the scheme is applied is impacted from the rear. Reverse impacts can result in detachment of ballast tank coatings.

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The reaction of a coating scheme to impact depends upon several properties, i.e. adhesion, hardness, cohesive strength, brittleness and the rate of impact. The result is that a coating which is very hard and cohesively strong may resist a high level of impact but, once disrupted by the impact, may detach from the substrate over a large area. Conversely, a coating which is cohesively weak may be damaged by small impact forces but may simply "crumble", producing a small detached area. In addition, once the coating has been damaged, its resistance to corrosion by undercutting or creep will play an important role in how that damage is manifested. To summarise, the end result of the impact is at least as important as the force required to damage the coating. The main piece of equipment used to test impact resistance is the Gardner Impact Tester. In this test, a known weight is allowed to fall from various heights to produce a range of impact forces on a hemispherical indentor placed upon a coated panel. Once the impact has taken place, the coating is visually assessed for cracking and detachment from the substrate and a penknife is then used to assess the diameter of the detached area. For reverse impact, the indentor is placed on the reverse of the panel.
Graduated guide tube Falling weight

Hemispherical indentor Test panel Schematic diagram of Gardner Impact apparatus

4.3.1.5 ABRASION RESISTANCE Abrasion resistance is an important property for coatings applied to cargo holds and the underwater hull. Customers often require a quantitative comparison of abrasion resistance of coatings. The nature of the abrasion to which coatings are subjected varies and therefore several test methods are available. Historically, International Paint have relied on two test methods and, although flawed, these are still used:

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Taber index - a coated panel is mounted on a turntable and rotated. Calibrated abrasive wheels are pressed onto the coating surface by a known weight whilst the turntable rotates, causing wear of the coating. After a specified number of cycles, typically 1000, the test is interrupted and the panel weighed. This operation is repeated and the weight loss averaged to give weight loss per 1000 cycles. Cargo chute - to mimic conditions encountered during cargo loading, a coated panel is held at 45 under a 6 metre (19.5 foot) long pipe. Cargo, typically in the form of stone chippings, is dropped down the pipe and causes coating to be removed from the panel. The damage caused is not purely abrasion, but also consists of impact and gouging forces. By weighing the coated panel before and after test, weight loss per weight of cargo dropped can be calculated. Again, this test has poor reproducibility. It is also important to standardise the cargo used in the test, as results will vary.

Due to the poor reproducibility of these tests, and to the fact that they do not accurately predict the performance, or indeed the ranking, of cargo hold coatings, a new test was devised in the late 1990's. This test is known as the Cargo Drag test and uses equipment known as a Shear Box. Cargo drag test - a coated panel is placed into a test rig and covered with coal under a known pressure. The coal cargo is then "dragged" across the panel causing damage to the coating scheme. Coal is typically used as it is known to be an "aggressive" cargo, which can cause major damage to a coating as it settles in a cargo hold. The damage is evaluated and a figure for total damage, as a percentage, is quoted. Results suggest that this test may be more reproducible than those discussed above and also ranks coatings in an order which reflects performance in practice.

Coated panel after cargo drag testing

4.3.2 CHEMICAL RESISTANCE In this section of the module, we will consider the resistance of coating schemes to liquids. This will also include resistance to water, i.e. corrosion resistance, as this is also a chemical process.
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4.3.2.1 RESISTANCE TO WATER Coating schemes used in a marine environment will obviously be required to resist corrosion. Depending upon the vessel area to which they are applied, the degree of corrosion resistance required will differ and therefore the degree of testing required also differs. SALT FOG Resistance to salt spray, or "fog", is not extensively tested with marine coatings, being used more frequently in the protective coatings area. This type of test is of little relevance to coating schemes which are to spend most, or all, of their in-service period immersed, but may be used for schemes applied to topsides, superstructure or decks, where "pooling" or exposure to sea-water spray will take place. A test duration of 1000 hours (6 weeks) is typical, with the coating being examined for spot corrosion, underfilm corrosion, and creep from a scribe mark at the end of this period. CONDENSATION Continuous condensation testing forms part of the Norsok M-501 test procedure for ballast tank coatings and is always carried out on products intended for this vessel area, as well as being useful for underwater hull coatings. Subjecting a coating scheme to continuous condensation reflects the conditions in a partially filled ballast tank, particularly if these tanks are adjacent to heated cargo tanks. The test is of 6 months duration and consists of coating a steel panel, on one side only, and using this panel, along with others, to form the lid of a test tank. The tank contains a reservoir of water at 40C and, as the tank is contained in an environment controlled at 23C, a temperature gradient is set up across the panel, causing condensation to continuously form on the surface of the coating.
Room temperature (23C)

Test panels 100% R H Water @ 40C

Condensation Chamber

Panels are assessed for blistering, wrinkling and corrosion.


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IMMERSION TESTING Coatings applied to many vessel areas are subject to permanent, or intermittent, immersion in water: Underwater hull Ballast tanks Fresh water tanks Boottop Ballast holds Decks (pooling of water)

For this reason, all products intended for application to these areas undergo some form of immersion testing. Many variations of test are available, these primarily differing in: Nature of the immersion medium Test temperature Test duration Presence and nature of an artificially introduced defect (holiday)

The effects of variables in test conditions are as follows: Temperature - Increasing the temperature of the water has the effect of accelerating the corrosion process and hence shortening the test duration. An increase in temperature of 10C effectively doubles the rate of corrosion of steel. Waterline - The oxygen content of water is higher at, or near, the waterline and this has the effect of increasing the rate of the corrosion process. Holiday - Both the shape and size of an artificially introduced holiday can affect the results of an immersion test. Nature of the immersion medium - It is possible to use several immersion media (e.g. natural sea water, artificial sea water, sodium chloride solution, fresh water). Observations made when evaluating coating schemes placed on immersion tests include:
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Blistering (size, density and location). Corrosion (both spot corrosion visible on the coating surface and underfilm corrosion) Creep from holiday Adhesion to steel
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CATHODIC PROTECTION (C.P.) Applying paint to steel is not the only way to protect a ship from corrosion. Steel can also be protected electrochemically by either: Applying a current through the steel - referred to as Impressed Current. Connecting anodes, made from a metal higher than steel in the electrochemical series, to the steel - referred to as Sacrificial Anodes.

Impressed current systems are used extensively on offshore structures, but by far the most common method of protecting ships is by bolting sacrificial anodes to the steel. Zinc anodes are most commonly used, but other metals, such as magnesium, may also be used. It is common to find sacrificial anodes used on the outer hull and in the ballast tanks of a ship. The steel surrounding the anodes becomes cathodic, and coatings applied to these areas must therefore be able to resist disbonding in the environment created. Such disbonding can occur where there are discontinuities in the coating, caused by accidental damage, imperfect application, or excessive permeability of the coating. Testing consists of coating a steel panel with the scheme under test, attaching a zinc anode, introducing an artificial holiday through the coating to steel and immersing in sea water. At the end of the test period, the coating is examined for blistering and creep (loss of adhesion and underfilm corrosion) from the substrate. CYCLING Vessel areas such as ballast tanks and the boottop are subject to forms of cycling, whereby the coating is subjected to periods of immersion followed by periods of drying out. Antifouling systems can be greatly affected by cycling but this is discussed later. For this reason, boottop schemes are tested in a cyclic manner, whereby they are immersed for a set period and then allowed to dry out on atmospheric exposure. These cycles are repeated, up to 12 times and, in addition to the normal observations made during long-term immersion testing, are evaluated for resistance to cracking and loss of adhesion. A "Ballast simulation" test is carried out in an attempt to mimic the conditions found in ballast tanks. In this test, welded girder test pieces are coated and immersed in a specially designed tank for 6 months. The immersion water temperature is controlled at 35C (95F), and the water level is cycled such that the test pieces spend 2 days on full immersion followed by 2 days on half-immersion. This creates a humid environment on the top half of the girders during the "dry" period. A test piece protected by a zinc sacrificial anode is also included in this test.
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Ballast tank coatings can also experience another form of cycling when the ballast tank is adjacent to cargo tanks, which can carry liquid cargoes at elevated temperatures. When the cargo tanks are full, the adjacent ballast tank is typically empty, or only partially full, and the coating is subject to hot, "dry" conditions. When the cargo is discharged, the ballast tanks will be filled and the coating becomes subject to immersed conditions at normal temperature. A further test is therefore carried out, whereby the coating scheme is applied to a girder test piece and cycled between wet (25C, 77F) and hot (60C, 140F and 100C, 212F) dry conditions. During evaluation, particular attention is paid to cracking of the coating on the welds. 4.3.2.2 RESISTANCE TO CARGOES The carriage of liquid cargoes presents a major challenge for coating schemes. Ships carry a vast number of liquid cargoes, these can be generally categorised into: Chemical feedstocks / alcohols - e.g. MTBE, methanol, ethanol, acetone, fatty alcohols, ethylene glycol Ketones - e.g. MIBK, MIAK, MEK, cyclohexanone Esters - e.g. Butyl acetate, ethyl acetate Refined vegetable & animal oils and fatty acids - e.g. Tung oil, Castor oils, Safflower oil, Linseed oil Aromatic and chlorinated hydrocarbons - e.g. xylene, styrene monomer, toluene, benzene Aliphatic hydrocarbons / white oils - e.g. crude oil, diesel oil, mineral oils, gasolines, white spirit Aqueous products - e.g. caustic soda, ballast water, molasses

The coating of cargo tanks is an area of huge potential liability for the coatings manufacturer, with performance guarantees being given to ship owners. For this reason, it is essential that all cargo tank coatings are extensively tested. Two types of test are used: a) Simple resistance tests Coated panels are immersed, to 80% of the panel depth, in a single cargo for a period of 84 days. The coating is then allowed to dry out for 24 hours before being immersed in sea water for a further 14 days. At the end of each period, the coating is assessed for softening, discoloration and blistering. At the end of the test, adhesion is also assessed.

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b)

Cycling tests Although some ships have cargo tanks dedicated to a particular cargo, more often they will carry a range of cargoes. Although a coating scheme may be resistant to two or more cargoes, this does not necessarily mean that it will be resistant to one cargo followed by another and for this reason, cycling testing is carried out. This test involves the coating scheme being applied to girder test pieces. Once the coating is fully cured, the girders are immersed in containers filled with cargo for a 3-week period. At the end of this period, the coating scheme is allowed to dry out for 24 hours and then immersed in a different cargo. These cycles are repeated, using different cargoes. Evaluation involves the same assessments as simple cargo resistance tests, but particular attention is paid to any cracking of the coating scheme on the welds of the girders.

Girder test pieces showing Girder test piece showing failure resistance to cargo cycling after cargo cycling 4.3.3 WEATHERING Resistance to weathering covers the ability of a coating to withstand: UV light - which can cause degradation of the polymer system Rain and wind Extremes of temperature Environmental pollution

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These conditions may lead to: Chalking (development of a powdery (chalk-like) surface layer). Cracking Corrosion Loss of gloss Discoloration Dirt retention Blushing / Poor resistance to water during curing.

These defects are discussed and illustrated in Technical Service Training Module 5. All coatings applied to vessel areas which are exposed to the atmosphere, in particular, superstructure, topsides and decks, are tested for resistance to weathering. In addition, shop primers, which are applied to steel plates, which are then left outdoors for several months prior to use, are also tested. 4.3.3.1 NATURAL WEATHERING In order to assess the durability of a coating, the full paint scheme is applied to test panels and these panels exposed to the atmosphere. The panels are mounted on specially designed racks, which hold the panel at a 45 angle and face the equator. Natural weathering testing is a time consuming operation and a full test programme takes at least 12 months. In some cases, e.g. for epoxy primer/finishes, this period may be reduced as chalking may result in rapid loss of gloss and early discoloration. 4.3.3.2 ACCELERATED WEATHERING As natural weathering testing takes a considerable period of time, it is of very limited use if it is required to screen formulations for cosmetic properties, or if a minor reformulation is being carried out in a limited time-scale. For these reasons, accelerated weathering tests are very common. As with all accelerated testing, results obtained from a reduced test period are not comparable with results obtained from natural weathering. More than one accelerated weathering apparatus is available, these machines producing controlled conditions of light, heat and moisture. For marine products, the standard apparatus is the Q.U.V. Accelerated Weathering Tester. This equipment utilises those UV wavelengths present in sunlight which are most destructive to polymer bonds, and provides programmable cycles of these UV light and high humidity conditions. Typically, marine products are tested over a period of 1000 hours. For products which show rapid failure, such as epoxies, shorter exposure periods can be used.
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4.3.3.3 EVALUATION Whether testing on natural exposure or using the QUV apparatus, the types of deterioration, and therefore the evaluation methods, are similar: GLOSS AND GLOSS RETENTION Cosmetic finishes, applied to the superstructure and topsides of a ship, are usually required to have a reasonably high gloss and to retain that gloss over a long period. More recently, primer/finishes, usually based on epoxy resins, have become more widely used. The intention is to provide an anticorrosive, and perhaps abrasion resistant, coating, which has a reasonable gloss compared to a standard epoxy primer. One of the main properties to be evaluated during exposure testing therefore, is the level of initial specular gloss and how well the coating retains that gloss. CHALKING AND DISCOLORATION Discoloration will often occur over a period of time during weathering tests. This may take the form of yellowing, or of a change in lightness of a coating. One specific type of discoloration is chalking, typically observed with epoxybased coatings. Chalking may be defined as the appearance of a loosely adherent, fine powder on the surface of a coating, arising from the degradation of one or more of its constituents. Chalking may be quantified by applying adhesive tape to the coating surface, removing the tape, placing on suitable card, and rating the level of chalking. For white, or light coloured, coatings another option is to rub the surface with black velvet and hence quantify chalking. CRACKING AND FLAKING As a coating scheme is exposed to UV light, precipitation (rainfall), and changes in temperature, it is possible that cracking may occur. This is a distinct possibility where coatings of different cohesive strengths and brittleness are contained in the same scheme. Cracking may occur: Within the surface layer of the top-coat Penetrating the top-coat, but with underlying coats unaffected Penetrating the entire scheme

Flaking may also occur, where one, or more, coats "flake" away from underlying coats.
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DIRT RETENTION Coatings applied to decks, topsides and superstructure will come into contact with "dirt" during their service lifetime. This is particularly the case with bulk carriers, which may carry coal or other dusty materials. Depending upon the nature of the coating, such dirt may simply lie on the surface and be easily removed by washing, or it may become ingrained or included within the coating. Thermoplastic coatings such as chlorinated rubbers and acrylics are particularly susceptible to such dirt retention. Tests involve a paint scheme being applied to test panels in various conditions of temperature. Coal, or other specified material, is applied to the surface of the coating scheme and placed under pressure. The degree to which the coal is retained within the coating, after attempts at removal with a soft brush or by washing, is then rated. ANTI-STAIN PROPERTIES Coatings applied to the topsides or superstructure of a ship may be accidentally damaged, resulting in steel being exposed. As this exposed steel corrodes, unsightly staining is produced on the coating below the point of damage. Coatings have been developed which prevent, or reduce, such staining by the presence of an active ingredient which reacts with the rust, forming a colourless compound. In order to evaluate anti-stain, or "rust-hiding", properties, in-house tests have been developed whereby a coating applied to a steel substrate is deliberately damaged, or alternatively a piece of steel is attached through the coating to the substrate. As rusting occurs, this may be artificially accelerated, the degree of staining on the coating below the rust site is evaluated. 4.3.4 ANTIFOULING TESTING Antifoulings are specialised coatings which are essentially designed to fulfil one purpose only, i.e. to prevent fouling from attaching to / settling on the hull of a ship and thereby reducing the efficiency of the vessel. This contrasts with most other marine coatings which are required to fulfil several functions, e.g. as an anticorrosive which also resists damage and provides an easy clean surface. Due to their unique function, International Paint has developed specialised tests over many years of antifouling product development. These tests cover those properties necessary for an antifouling to fulfil its function:
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Antifouling performance - how well a product prevents settlement of fouling Polishing rate - at what rate does an antifouling "polish", and thus release biocide Leaching rate - at what rate are the biocides released Boottop cycling - how well does an antifouling, applied over an anticorrosive scheme, resist cracking Cold flow - how well does a freshly applied antifouling scheme resist shear stress
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ANTIFOULING PERFORMANCE All antifoulings are tested to determine how well they resist the build up of fouling, whether animal or weed. Testing involves the application of antifoulings, over a primer system, onto boards which are placed on static immersion in selected sites around the world. Different sites give rise to different fouling conditions, due to their geographical location, water temperature etc., therefore testing is carried out at several sites: UK - Newton Ferrers (predominantly weed, fouling is seasonal) UK - Burnham (predominantly animal, fouling is seasonal) Singapore - (all fouling types, year round) Brazil - (all fouling types, year round)

When preparing an antifouling board for testing, it is usual to apply several different paints to each board, usually in vertical strips. Fouling varies with water depth and therefore the use of such vertical strips gives a true comparison with other paints applied to the same board. Each board also includes a standard product of known performance. Evaluation of the type and level of fouling on each coating is a complex process which can only be carried out by trained, experienced personnel. Numerical ratings are given to the quantity of each fouling type (slime, weed, barnacles etc.) and these ratings are each multiplied by a factor to produce an overall percentage rating. A completely clean coating would have a rating of 100%.

Antifouling Test Board This type of static antifouling performance testing is very useful as a screening test when developing or modifying formulations. However, actual performance on a moving ship can be quite different and therefore, more than any other type of product, antifoulings are also assessed by application of test patches to ships.
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POLISHING RATE The resin systems of some antifoulings degrade, or "polish", such that the active ingredients, such as copper, are released and hence prevent fouling. The effect of polishing is that the antifouling scheme diminishes in thickness over a period of years, this rate being dependent on vessel speed and on the number of sea-miles it travels. Thus, it is vital to know the polishing rate in order to determine the scheme thickness required for the antifouling to function over its specified lifetime. To properly characterise the polishing behaviour, it is necessary to determine the loss of film thickness, as a function of immersion time, under both static and dynamic conditions. As such, various test methods have been produced to cover: Static versus dynamic behaviour Effect of vessel speed Temperature dependence Effect of underlying priming scheme

In essence, the tests involve applying strips of antifouling paint, around a circular disc with a hole in the centre. Each disc contains strips of a relevant standard product of known performance. The dry film thickness is measured along each strip, using a UBM laser profilometer. The disc is then placed on test, i.e. it is either attached to a rotor shaft and rotated in sea-water (for dynamic measurement), or placed upright in sea-water tanks (for static measurement). After the specified test period, the disc is removed from test and the profilometer used to determine loss of film thickness. For dynamic measurement, different points along each strip represent different vessel speeds, as the disc effectively rotates at a different speed depending upon the distance from the centre. Results are expressed in microns of coating loss per month. LEACHING RATE The leaching rate of a biocide, or other soluble pigment, from an immersed antifouling, is the primary determinant of its effectiveness, in terms of both its level of performance and its service lifetime. Test methods have therefore been produced to determine the release rates of biocides from antifouling paints, under both static and dynamic conditions. These tests can only be carried out by trained personnel in a dedicated test laboratory and also require the use of atomic absorption spectroscopy to detect the leached substances.

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BOOTTOP CYCLING The boottop area of a ship is subject to continual variations in exposure to sea-water and atmospheric weathering, depending upon the vessel loading and operating conditions. This has the effect of causing stresses in the coating system as water is absorbed and the coating subsequently dries out. It is therefore essential that antifouling schemes are tested to ensure that cracking or flaking does not occur due to these stresses. A cycling test has been developed whereby an antifouling scheme, applied over a suitable primer scheme, is subjected to cycles of immersion and drying out. Accelerated tests are also available, in which extremes of temperature are used to provide a short-term screening test. The boottop cycling test involves application of the full underwater scheme (primers, tie-coat and antifouling) to steel panels. It may be necessary to test an antifouling system over several anticorrosive schemes if these will be used in practice. The panels are either immersed in sea-water tanks or placed on antifouling test rafts such that part of the coating scheme is above water, for a period of 4 weeks, until the system is saturated. On removal from water, the coating is assessed for cracking as well as colour change, softening, detachment, wrinkling and adhesion. The panels are then subjected to atmospheric exposure for one week and re-assessed. A minimum of 12 of these wet/dry cycles is carried out (subsequent wet cycles lasting only 3 weeks), although a good indication of performance can be obtained after 6 cycles. The boottop cycling test is also used to test film integrity when an antifouling scheme is applied over previously immersed antifoulings. COLD FLOW The antifouling is usually the final coating that is applied to a ship in drydock prior to flooding and departure. Owing to the high cost of drydocking, the time between completion of painting and flooding is kept to a minimum and this can result in solvent being retained in the antifouling, making it subject to viscous flow when a continuous sheer stress is applied, i.e. when the ship sails. If a high thickness of antifouling has been applied, and the thixotrope package has not been optimised, this viscous flow, or "cold flow", can be manifested by an uneven, rippled surface or even by the antifouling "running" off the underlying coating scheme. The results of cold flow are: areas of the underwater hull not being protected by antifouling an increase in hull roughness leading to an increase in fuel consumption

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ITQ 10 Give 4 factors which could result in cold flow. Answer

FOUL RELEASE COATINGS Foul release coatings, based on silicone technology, work on the principle that their low energy, "non-stick", surface prevents attachment of fouling. If fouling does attach, the surface is easily cleaned, either naturally as the vessel moves through the water, or manually in drydock. As this type of product is highly specialised, specific test methods are available, e.g. adhesion assessment and pot life. ITQ 11 Why must great care be taken to avoid contamination of application equipment and adjacent areas of a ship when applying foul release coatings? Answer

4.3.5 SHOP PRIMER TESTING Steel plates are supplied covered in millscale and, as such, are not compatible with modern high-speed welding. Millscale must therefore be removed by blasting in an automatic plant and it is therefore logical that a primer should be applied at the same time. Such a primer must dry at the same rate at which the steel plate can be blasted. As with antifoulings, shop primers are specialised coatings, which require additional testing. A shop primer has several functions:
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To protect steel plates from corrosion during the time between initial surface preparation and fabrication To interfere as little as possible with cutting and welding of the steel plates To present minimal problems when applying subsequent coating schemes
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In order to fulfil these functions, a shop primer requires a balance of properties: Resistance to rust, and to white rust, for a period of 3-6 months Good welding properties, whereby pores are not introduced into the weld, subsequently weakening it. Also not to cause reduction of welding speed Acceptance of subsequent coats of paint with no, or minimal, secondary surface preparation being required

Individually, these properties are not difficult to achieve, however often attaining one property can result in reduction in performance in another. An example of this is the use of zinc, which provides good anticorrosive properties but reduced weldability. For this reason, extensive testing is required, the methods being modifications of test methods for other coating types: Storage properties - additional testing required for the binder component to examine changes in gel time. Pot life - shop primers require long (up to 24 hours) pot life and the end point is difficult to determine. It is therefore necessary to apply the shop primer beyond this time and test subsequent film properties. Application characteristics - includes determination of fan width for use on shop primer lines. Drying time / extent of cure - shop primers are applied at low film thickness and dry within minutes. Extent of cure testing involves solvent resistance and welding tests. Film thickness measurement - as they are applied at a film thickness less that the profile height of blasted steel, smooth plates must be coated for shop primer thickness measurement.

WELDABILITY At newbuilding, shop primed steel plates are welded together to form sections and blocks. These blocks receive initial coats of the specified coating scheme prior to being welded together and receiving the final coats of the scheme. Various welding methods are used, depending upon the yard involved and the type of join required, and shop primers must be tested to ensure that their presence does not reduce the quality of a weld by introduction of porosity. HEAT RESISTANCE Shop primers are subject to intense heat during plate cutting and welding. It is not only necessary that the shop primer can resist this heat, but also that subsequent properties, such as corrosion resistance, are not affected. In order to test the effect of heat on a shop primer, a primed steel plate is heated by electrical induction to temperatures up to 800C (1472F). Any colour change in the shop primer is noted during and after the heating process. The primed plate is then tested for resistance to corrosion and white rust.

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WEATHERING Assessment of anticorrosive performance is essentially the same as for other above water coatings, i.e. by atmospheric exposure. Zinc silicate shop primers are also subject to "white rust", where the zinc has reacted with various substances in the atmosphere and hence becomes depleted. The degree of white rust is therefore also quantified. OVERCOATABILITY Once shop primed plates have been welded together into block sections, the initial coats of the paint scheme are applied. Depending upon the type of product to be applied, and the vessel area involved, it is necessary to carry out some degree of secondary surface preparation. The level of surface preparation may be: Application direct to the shop primer after degreasing. Partial removal of the shop primer by power tool cleaning. Partial removal of the shop primer by grit sweeping. Full removal of the shop primer by gritblasting.

Overcoating zinc silicate shop primers directly can often lead to: Pinholing Blistering on subsequent immersion Loss of adhesion within the coating scheme Splitting within the shop primer

Testing shop primers for acceptability of subsequent coatings involves application of the shop primer to steel panels, followed by a curing period and application of the remaining coating scheme after specified levels of secondary surface preparation. The fully coated panels are then subject to testing, following methods suitable for the scheme involved, e.g.: Schemes for underwater hull, ballast tanks and other immersed areas are tested for overcoatability on immersion. Above water schemes are tested for overcoatability on atmospheric exposure.

4.3.6 USER SPECIFIED TESTS The testing covered in the previous section of this module enables International Paint to have confidence in the performance of a product. Once this testing has been carried out, it is likely that further testing will be required to: a) Satisfy the customer of the performance of a product by testing to either their specification or to a specification laid down by an external body.

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b) Satisfy legal requirements in terms of the safety of the user, the safety of the vessel to which the product is applied, and of the cargo which is being carried. Such testing usually involves submission of paint, or of coated panels, to a recognised test house for external testing. Examples of such tests are: Potable water This test is carried out to ensure that a coating scheme does not taint drinking water carried on a ship. The test is performed by an approved laboratory, e.g. The Water Quality Centre in the UK, to BS 6920. The test involves immersing a coated panel in fresh water for a set period, a sample of this water then being diluted, and a panel of tasters testing the water for odour and taste. The panel is then immersed in a fresh sample of water and the process repeated up to seven times. If, after the final immersion, the water is still tainted, the coating scheme will fail the test. BS6920 also includes additional analytical tests for the level of harmful substances imparted to water by the coating scheme. Carriage of grain Grain is an important cargo shipped worldwide. Any coating applied to cargo holds therefore, must not taint grain. Carriage of grain testing must be carried out by an approved laboratory, e.g. N.O.H.A. in the UK. In the test, a coated panel is fitted into a box, which is filled with wheat grain. At the end of the test period, grain, which has been in contact with the coating, is analysed for toxic constituents. Taste tests may also be carried out. Surface spread of flame and Smoke & Toxicity testing Coating schemes applied to internal accommodation areas of a ship must not, in the event of a fire, cause flame to spread or produce toxic smoke. The International Maritime Organisation (IMO), have issued directives relating to coatings in this regard: IMO Resolution A653 (16) Fire Test Procedures for Surface Flammability of Bulkhead, Ceiling and Deck Finish Materials as amended by Resolution MSC 61(67). IMO Resolution MSC 61(67) Annex 1, Part 2 - Smoke & Toxicity Test

Resolution A653 (16), the surface spread of flame test, involves coated panels being subjected to a flame. Measurements of time to ignition, spread of flame, final extinguishment distance and heat release are taken and compared with limits set by the resolution.
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If the heat released in the A653 (16) test is greater than a specified value, testing according to MSC61(67) must also be carried out to examine the toxicity of smoke produced. Weld quality In order to obtain welding approvals from classification societies such as Lloyds Register, the DVS 0501 test must be carried out on shop primers by an approved test house. It is usual for this testing to be carried out by SLV Duisburg. Weld Fume As shop primers are subjected to intense heat during welding, there is a danger that they could emit toxic fumes. Testing should be carried out, by an approved test house as above, to measure the trace gasses produced during welding. Corrosion control Increasingly, following several major disasters involving break-up of ships due to corrosion, owners and shipyards are requesting assurances that a coating scheme is suitable for use as an anticorrosive, particularly if it is to be used in ballast tanks. This assurance most commonly consists of testing being carried out by an independent test house. Although there is not a test procedure wholly applicable to marine coatings, the industry now places reliance upon Norsok M-501, a procedure consisting of several corrosion resistance tests. Tests include: Cyclic UV / Salt spray test Condensation chamber testing Cathodic disbondment (ASTM G8) Pull-off adhesion

Specification testing Several institutions, often military, require products to be used on their vessels to be tested to their own specifications. Examples are: UK Navy - DEF-STAN tests US Navy - MIL-SPEC tests Petrobras (Brazil)

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4.4 FIELD TRIALS AND TEST PATCHING Field Trials It is important to ascertain the application properties of a paint under yard conditions. Points to consider are: Can the paint be applied using the specified method(s) to large areas? Is an airless-spray applied product suitable for use with long lines? Is a shop primer suited to use on an application line?

In all cases, it is important to seek the opinions of the applicator, who will be familiar with commercially available products, whether supplied by ourselves or our competitors. Test patches Many ship owners or operators are willing to provide areas of their vessels on which a patch of paint can be applied in order to assess or compare its performance. Knowledge of the performance of a product when subjected to in-service conditions is very useful and can also be used during the commercial launch of the finalised product. Test patches are especially useful for: Antifoulings - often, several candidate formulations can be applied alongside each other to compare antifouling performance and polishing. Cosmetic finishes - can be roller applied, as may be the case in practice during on-board maintenance, and later assessed for gloss retention, colour retention, dirt pick-up etc.

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ITQ ANSWERS AND COMMENTS


ITQ 1 The corrosion rate will be at a maximum at the waterline, where the concentration of oxygen in water is at its highest. ITQ 2 Magnesium is significantly more active than zinc and therefore corrodes at a faster rate. Whilst still protecting the steel, magnesium anodes would be used up much more quickly than zinc. Additionally, magnesium anodes are more expensive than those made from zinc. Attaching a metal lower down the electrochemical series than mild steel, e.g. copper, would result in the steel corroding in preference to the copper. ITQ 3 Fouling results in increased hull roughness, increasing drag. This means that more power is required to move at the same speed, increasing fuel usage and engine wear. ITQ 4 SPC antifoulings provide a constant release of biocide, providing effective performance over a longer lifetime. SPC antifoulings also create a smooth surface, reducing hull roughness. As the surface of SPC antifoulings constantly polish away, the weak leached layer produced by conventional and long-life antifoulings is avoided. ITQ 5 Non-convertible coatings dry by simple solvent evaporation and can be re-dissolved in appropriate solvents as no chemical changes have taken place. Convertible coatings dry (cure) by chemical reaction. Once they are fully dried they cannot be re-dissolved in the original carrier solvent. Common non-convertible coatings are acrylics (e.g. Intersheen 579), vinyl (e.g. Intertuf 203) and bituminous (e.g. Intertuf 16). Common convertible coatings are epoxy (e.g. Intershield 300), polyurethane (e.g. Interthane 990) and alkyd (e.g. Interlac 665). ITQ 6 (i) Increasing volume solids can reduce the ability of a paint to wet the substrate, resulting in poorer adhesion. (ii) Increased solids can also make application of paint more difficult due to increased viscosity (iii) The increased viscosity can result in less mobility in the wet applied film, slowing and restricting chemical reaction in two-pack coatings such as epoxies. ITQ 7 a) An alkyd cosmetic finish would have low PVC (around 15%) to aid gloss. b) The main purpose of a zinc silicate shop primer is to protect steel from corrosion prior to fabrication. A high loading of zinc dust, and hence a high PVC (around 45%), is required. Too high a zinc loading would however reduce weldability. c) An abrasion resistant epoxy anticorrosive requires tensile strength, corrosion resistance and blistering resistance, which are aided by increased PVC. However, too high a PVC, above CPVC would reduce tensile strength and increase porosity. Therefore, a medium PVC (25 35%) is ideal.
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ITQ 8 (15 x 1.41) + (5 x 0.98) = 26.05 Kg.


(72 x 10) / 150 = 4.8 m/litre.

ITQ 9 Overcoating at intervals shorter than those stated on the product data sheet could lead to bleed through of components, such as tar, in the underlying coat into the topcoat. Also, solvent may not have the required time to escape from the underlying coat, leading to potential problems with corrosion resistance and blistering. ITQ 10 The following factors could give rise to cold flow: (i) (ii) (iii) (iv) Antifouling is applied at low temperature Antifouling is applied in thick coats. Short overcoating intervals are used between coats Short time to flooding after application of the final coat.

ITQ 11 Foul release coatings are based on silicone resins, which provide a non-stick surface. As such, contamination of application equipment that is to be used to apply other paint types, or surfaces of the ship which require application of other paint types, will lead to problems with paint adhesion and paint defects such as cissing.

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CASE STUDY 1
a) What properties are important for a coating system to be applied to the following vessel areas? (i) (ii) (iii) (iv) (v) b) Underwater hull Ballast tanks Cargo tanks External decks Superstructure

For each of the above vessel areas, suggest a coating type which would provide the necessary properties.

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