Free Association Paint

tttttt
CICCCIC14

-,CCC4 acc Occ(, cccc-c, I

VIIII ,, Cc rr ~ I

C
r-,

Figure 7.5: Biocide (Dispersed in a Resinous Martrix),

(b) Longlife Antifoulings

These are referred to as 'insoluble matrix' paints. The binder is insoluble in seawater and, as only biocides are released, the paint film is left as a porous skeleton. As the porous layer increases, the rate of biocide release reduces. Eventually no more biocides can be released and performance drops dramatically. The layer becomes clogged with fouling, The effective life is up to 24 months and a relative porous surface remains.

Figure 7.6: Ship Panned with Antifouling Paint

Conventional and Longlife paints were once the only antifoulings option. The porous film left after the biocides leach out leaves a weak substrate for subsequent new coatings and a sealer coat is normally required.
Almost the total area has been spot blasted To prepare the Surface for a new coat of A/F

Top coat Bare Steel Antifouling

Figure 7.7: Spot blasted Surface

Not all of the active components in the film are released, wasting both resources and money. Applying coat on coat can cause detachment of the paint film and this accumulation (sandwich coatings) causes very high hull roughness.

41

(c)
Environmental
p r o t e c t i o n

Selfpolishing Antifoulings (containing TBT) Selfpolishing antifoulings were introduced in the 1970s. They developed rapidIy

leading to predictable performance and better control. It became possible to plan material purchases and the sailing intervals between dry-dockings. The new technology, introduced at a time when fuel prices rocketed, made it possible to achieve virtually smooth, clean bottoms providing considerable economic benefits to the shipowner or operator. These antifoulings contain chemically bound organotin, which is released following hydrolysis in seawater. Once this is released the remaining polymer backbone is soluble and is released from the surface. Layer after layer of the antifouling provides the same performance until the total paint film is polished away. Selective erosion occurs because the turbulence on the surface peaks of the paints is greater. These peaks erode at a faster rate than the general paint film and lead to a polishing of the Surface. Roughness is therefore reduced and results in more economic performance.

TBT
TBT

Copolymer System
Copolymer SYSTEM

Figure 7.8: Self-Polishing Copolymer System

(d) Selfpolishing Antifoulings (Tin Free)

With tin-free compositions a different mechanism takes place. Manufacturers use various blends of water soluble and water sensitive binders. Early 'ablative' or physically-deteriorating paints have been refined. The polishing effect is similar to those containing tin but not identical in performance, mainly because of a different reaction with seawater and to the removal of the very efficient organotin compositions as biocides. However, there are many successes using tin-free compositions.

40

Conventional A/C Long life A/F Selfpolishing A/F

30

Minimum release level for fouling protection

Time, years

Figure 7.9: Release rate for Antifoulings Comparison of Release rates of Biocides for Different Antifouling Types.

The Benefits of using Self Polishing Anti Foulings

42

One very important argument for the SPA is the possibility of avoiding "sandwich coating", which is often found when using conventional or long life antifoulings. The advantages of using SPA are that the surface will not become porous and there will be no need for sealer. After hosing down with fresh water to remove hosing

slime and any other contamination, the new antifouling is applied directly on top of the old one.

Anti Fouling Paints

Figure 7.10: Removal of Marine Growth, Salts and Loose Paint by Low Pressure Washing

The intention is to apply the new antifouling at an adequate film thickness, taking into consideration the old, intact antifouling left from the previous dry-docking. In practise, however, the issued procedure when coating dry-docking vessels with SPA has been very difficult to carry out, mainly for two reasons:

Figure 7.11: Spray Application of Antifouling Paint

The vessels are very often spot-blasted on damaged areas and touched up with primers to build up an adequate anticorrosive system. Application, which is always done with an . airless spray, often results in large areas of overlapping on the intact antifouling. This means that most of the surface consists of sandwich coating-exactly what we try to avoid. Because of touch-up done by airless spray resulting in overlapping, the remaining area not covered by sealer is so small that antifouling left from the previous drydocking is not taken into consideration. Consequently, the new antifouling system is applied in full thickness over the entire surface, which also contributes to build-up of too high a film thickness, which after a number of dry-dockings results in cracking or flaking of the anti fouling. All of this can, however, be avoided by the following:
(i)

Do not spot-blast smaller damaged areas or rusty spots. Blast-cleaning only to be used on larger areas. On smaller areas mechanical abrasion should be used.

(ii) Touch up these smaller spots with brush, roller or by airless spray gun, the nozzle of which has an acute angle (20 o - 30 o).

43

Environmental Protection

It is important to avoid an excessive thickness of the antifouling film, which may lead to cracks or detachment. In certain cases it pays to do without a new coat of antifouling. However, such decisions can only be made when they actually arise. Sailing Periods with Tin Bearing and Tin Free sailing period between dry-dockings from 30 to 60 months is economically beneficial to an owner or charterer. Whilst today's best tin bearing antifioulings can provide such protection, experience from practise has shown that tin freer antifoulings may not yet fully achieve. it. However, although tin free antifoulings may not yet be fully up to the standard of tin bearing types, supplementary underwater cleaning should be a viable option for owners specifying tin free antifoulings and extended dry-docking periods. Underwater cleaning once or twice at a few thousand dollars and taking only a few hours must be beneficial compared with 5-7 days dock hire, off-hire. lost income, gas freeing, etc.
To extend the

Figure 7.12: Vessel in dry-dock

7.5 THE ENVIRONMENTAL IMPACT

The Environmental Consequences In the old days of wooden sailing ships, antifouling methods include use of arsenic, lime and mercurial compounds to prevent shipworms and barnacles from destroying the hull. Although organotin compounds were synthesized almost 150 years ago, it was not until the 1960's when tributyl tin (TBT) first appeared in marine paint formulations. By the 1970's, most ships were coated with some form of antifouling paint containing tin and copper. The shipping industry relies heavily on the use ref TBT impregnated marine coatings that disperse into the sea at damaging rates. Such marine paints are cheap, very effective and preferred by the industry.Biofouling organisms are killed upon contact with such painted surfaces, thereby preventing fouling for periods ranging from 6 months to 5 years depending upon the composition of the paint and the amount of heavy metals present. Heavy metals are responsible for environmental damage to both terrestrial and marine life. In the marine environment, the continuous leaching of heavy metals has been responsible for the destruction of shellfish populations, sex changes in invertebrates and possible genetic defects in other marine animals. In the early 1980s it became clear that organotin (TBT) not only killed fouling organisms, but its slow release into the water had toxic effects at concentrations of parts per billion on a wide range of other marine species, particularly molluscs such as whelks and oysters. In marine harbours that were contaminated with the TBT, whelks were starting to show sex-changing disorders, and oysters developed abnormally thick shells. Within a few years, some whelk species had disappeared from many harbours and marinas along the North Sea.
44

Environmental concerns grew as poisoning of marine organisms including fi sh had risen to alarming levels. The effects have also been detected in the vicinity of maintenance and repair drydocks where repair TAT contaminated washdown water is released untreated into the marine environment.

Anti Fouling Paints

7.6 IMO REGULATIONS FOR ANTI FOULING PAINT TO 2003/2008

International Maritime Organization (IMO) Adopts Convention to Prohibit Organotins in Anti-Fouling Paints The International Maritime Organization (IMO), an Agency of the United Nations, acted on the increasing reports of toxicity to non-target organisms by adop ing a resolution in 1990 recommending measures to eliminate antifouling paints containing TBT. It took eight more years (1998) before a resolution was passed for a global I robibition on the application of organotin compounds which function as biocides in antifouling marine paints. The International Maritime Organization (IMO) adopted the International Convention Convention on the Control of Harmful Anti-Fouling Systems on October 5, 2001. This Convention will prohibit the use of harmful organotins in anti-fouling paints used on ships. It will also establish a mechanism to prevent the potential future use of other harmful substances in anti-fouling systems. The new Convention will require parties to the Convention to prohibit and/or restrict the use of harmful anti-fouling systems on: ships flying their flag, ships that are not entitled to fly their flag but which operate under their authority, and all ships of a Party that enter a port, shipyard or offshore terminal.

Ships of 400 gross tonnage and above engaged in international voyages (excluding fixed or floating platforms, FSUs and FPSOs) will be required to undergo an initial g survey before the ship is put into service, or before the International Anti-fouling System Certificate is issued for the first time. An additional survey will be required when the anti-fouling systems are changed or replaced. Ships of 24 meters or more in length but less than 400 gross tonnage engaged in international voyages (excluding fixed or floating platforms, FSUs and FPSOs) will have to carry a Declaration on Anti-fouling Systems, signed by the owner or authorized agent. Appropriate documentation, such as a paint receipt or contractor invoice, must accompany the declaration. All Ships: by January 1, 2003 shall not apply or re-apply organotins compounds that act as biocides in anti-fouling systems. by January 1, 2008 including fixed and floating platforms, floating storage units (FSUs), and Floating Production Storage and Offtake units (FPSOs) must either: not have organotin compounds on their hulls or external parts or surfaces; or

have a barrier coating on top of non-compliant anti-fouling systems coating so that they cannot leach into the environment.

45

Environmental Protection

Article 12 of the Convention states that a ship shall be entitled to compensation if it is unduly detained or delayed while undergoing inspection for possible violations of the Convention. Article 6 on Process for Proposing Amendments to controls on anti-fouling systems explains how to evaluate an anti-fouling system. A technical group will review proposals for other prohibited or restricted substances that are used in anti-fouling systems. Enforcement: 12 months after 25 States representing 25% of the world's merchant shipping tonnage ratify it.

7.7 ALTERNATE ANTI FOULING SYSTEMS

A wide variety of new TBT-free products have been introduced over recent years in order to replace the TBT-SPCs effectively. In general, two main generic routes have been followed: A biocidal route, based principally on the use of copper and boosting biocides, and A non-biocidal route, using foul-release technology

(A) BIOCIDAL ROUTE

Copper-Based Antifouling Paints When seeking a biocidal route to replace TBT-SPCs, most formulators have developed antifoulings based on copper, which has been used since the late 1700s for fouling control on ships. "Two main technology routes have been followed for these copperbased antifoulings: (i) Upgrading conventional "soluble matrix" technology, using modern reinforcing resins. This is referred to as "Controlled Depletion Polymer" (CDP) technology. Synthesis of completely new acrylic polymers which react with seawater in the same way as the TBT co-polymers. This is referred to as "TBT-free SPC" technology.

(ii)

Both these technologies achieve their overall antifouling effectiveness by including boosting biocides to work alongside the copper compounds used. These boosting biocides have been selected to have minimal environmental impact, in particular by having shorter half-lives in seawater than TBT".

tf

Contr

Figure 7.13: Biocide Dispersed in Resinous Matrix(i

46

"Controlled Depletion Polymer (CDP) antifoulings are derived from traditional or conventional "soluble matrix" antifoulings, and are formulated using a substance obtained from trees: Rosin. This material has been used for well over a century by antifouling paint chemists, and is used because it is slightly soluble in sea-water. This

enables the paint film to slowly dissolve or "solubilise" and thus release the biocides contained in the coating matrix. Rosin is a cheap renewable resource, but it does have some drawbacks. It is a brittle material, and if too much is used in the coating it can cause cracking and detachment. In order to overcome this, CDP systems include modern reinforcing polymer resins, such as acrylics, vinyls, polyesters or polyamides. Care has to be taken not to include these polymers at too high a level since they are water insoluble, and addition of too much would retard the solubilisation process and so prevent biocide release. Another drawback of Rosin arises from the fact that, unlike the TBT SPC polymers, it cannot prevent seawater penetration into the depth of the coating. As the seawater penetrates further and further into the bulk of the CDP film, a large leached layer can develop, slowing down biocide release, which eventually leads to the attachment of fouling. In CDP systems, this is most commonly seen as green weed on the vertical sides. Prior to the advent of TBT SPC systems, it was well known that the leached Layer was the ratecontrolling and lifetime limiting step in all antifouling formulation work. Once it is formed, the only way to remove it is either by in-water scribbling, or by high pressure fresh water washing in dry dock. If it is not removed prior to over coating, it can lead to detachment and increased roughness at subsequent dockings. Given the above disadvantages inherent to Rosin, CDP systems based on it cannot match the longevity and fouling control performance of TBT SPC systems. (ii) TBT-Free SPCs "The main developments in TBT-free SPC antifoulings have been pioneered by Japanese paint companies, in response to the TBT application ban which was introduced in Japan in the early 1990s. A series of new acrylic polymers have been synthesized which attempt to mimic the chemistry of TBT in seawater. There are three main types:
copper Acrylate Silyl Acrylate Zinc Acrylate

Anti Fouling Paints

The first of these to be introduced was the copper acrylate system, launched in 1990 under the brand name "Ecoloflex SPC, by Nippon Paint Marine Coatings. The copper acrylate polymer reacts with seawater in exactly the same way as the TBT SPC co.polymer, producing a soluble micro-layer at the paint surface, resulting in the gradual "polishing away" of the coating. This mechanism ensures that there is no leached layer build up over time, and that the biocides in the system are released in a controlled way, to give long-term fouling protection, and with lifetime proportional to the thickness applied. The biocides in the Ecoloflex SPC products are copper oxide and zinc pyrithione. Copper itself is safe to man and the environment when used in antifouling paints for ships, and is registered for use as an antifouling biocide in products for commercial vessels with government authorities around the world. It is clearly accepted that its use in antifouling paints is much safer to the environment than TBT. Zinc pyrithione is degraded and becomes non-toxic quickly after release from the coating. It is not persistent and will result in minimal impact on the marine environment. The other major use of zinc pyrithione is as an antidandruff agent in shampoos. As many thousands of tonnes of this substance is applied to human flair each morning and subsequently discharged into the environment via sewage treatment works without incident, its safety to humans and the environment is proven.
47

Environmental Protection

Ecoloflex SPC products have been applied to the complete underwater hull of over 1,350 commercial vessels greater than 4,000 dwt. At present there are more than a dozen ships currently in-service with five year Ecoloflex SPC systems applied to the entire underwater hull. One of these has now completed 53 months in-service and a recent underwater inspection showed that performance was good. The Royal Australian Navy has also been carrying out long-term testing of Ecoloflex SPC on Patrol Boats, and after 64 months Ecoloflex SPC showed exactly equivalent performance to the standard TBT-SPC product used. This was far superior to the other tin-free products tested, which were all of the CDP type.

(B) NON-BIOCIDNL
Foul-Release Systems

*'From an environmental perspective the most desirable approach to fouling control is one which does not rely on the release of biocides to achieve its effect. One of the first patents in this area was filed in January 1975, which was less than a year after the launch, of the first TBT SPC system (April 1974). This patent describes a biocide-free fouling control coating which is based on silicone elastomer technology, and which works on a "non-stick" principle. This technology was largely dormant for the years 1975 to 1990, during which time the TBT SPC systems came to dominate the antifouling market. It has only been since 1990, as the environmental problems associated with TBT SPC have arisen, that the technology has reemerged in the marine market. There are now silicone-based foul release products available for both high speed specialist vessels (such as fast ferries, trading at over 30 knots) and for high activity deep sea scheduled ships, which operate at speeds between 15 and 30 knots (<10% of the world fleet by dwt)" These foul-release coatings rely partly on their smoothness and partly on their low surface energy for their efficacy. Fouling organisms have difficulty adhering to the smooth, hydrophobic surfaces, and so either move away to find another, more favourable, site for settlement, or they are removed by the action of the seawater over the hull during voyaging. A force of less than 0.7MPa is required to remove most types of fouling off these surfaces. The only type of fouling that can adhere, even at speeds in excess of 35 knots, is slime fouling. The effect of this slime fouling has not been fully evaluated. Operators, who have compared fuel consumption and speed before and after full ship applications of a commercial foul release system, report that little difference can be seen between the previously used TBT systems and the foul-release (even with slime). It would appear that, although the foul-release is initially smoother and has less drag, this is then off-set by the slime fouling that inevitably occurs. resulting in an overall drag which is similar to that of the previous TBT SPC system, which was less smooth originally. When compared to CDP systems on the other hand, there have been reports of significant speed increases and fuel savings achieved. On one 36m high speed catamaran the operating crew reported an increase in speed of 3 knots after the anti fouling was first installed, and with an overall fuel consumption reduction of 12%. Given their very attractive environmental profile, it can be anticipated that even without any speed or fuel saving benefits, foul release systems will become increasingly important in the 21st century for control of marine fouling. At present, their use is restricted to a small sector of the marine market where the vessels are fast and active enough.

Product/method 48

Advantages/disadvantages

Copper-based anti-fouling paints Tin-free antifouling paints

Already exist and less toxic than TB I in aquatic environment. Onlyeffective against marine fauna -- to combat weed growth, herbicides are added which may pose new threats to environment. Have proved adequate on passenger ferries in North Sea. Work best on vessels that go to dry dock every three and a half years or more frequently because some fouling does occur. Works on special purpose vessels such as tugs, pilot boats, lifeboats, research vessels if these are used at least 100 days per year and go into dry dock at least every three years. When use is not as frequent they run more risk of fouling and will need dry dock every year. Contain no biocide but have extremely slippery surface preventing fouling occurring and making it easier to clean when it does. Most suitable for vessels with minimum speed of 30 knots. Damage to coating difficult to repair. Light fouling occurs but easily removed with high-pressure hose in annual dry dock visits. Periodic cleaning of hull is most appropriate for ships operating in both sea and fresh water and in areas where few organisms attach to hull. Cleaning of merchant ships involved divers using rotating brushes or high-pressure hoses. Substance produced in nat ire which prevent fouling or hinder fouling process - based on capacity of marine organisms such as corals and sponges to remain free of fouling. Research on use of natural compounds is in early stages, but active metabolites (for example ceratinamine and mauritiamine) have been identified and new biocides have been synthesised. Enzymes can break the sticking of bacteria (the first phase of fouling's growth) to the hull; while the concept of hydrophilic coating has been in spired by the preference of fouling to stick to hydrophobic surfaces, such as rocks and vessels. the organisms have no grip on hydrophilic 'wettish' surfaces. Paint and research institutes are involved in Camellia project (running 1996-2000), 0 bsidised by EU, to research use ofnatural compounds. Creating a difference in electrical charge between the hull and sea water unleashes chemical process which prevents fouling. This technology shown to be more effective than tin-free paint in preventing fouling, but system is easily damaged and expensive. Also creates increased corrosion risk and higher energy consumption. Includes coatings with microscopic prickles. Effectiveness depends on length and distribution of prickles, but have been shown to prevent attachment of barnacles and algae with no harm to environment. However, prickles could increase water resistance of vessel. Use of prickly surfaces on static objects such as buoys and cooling water inlets seen as realistic option in near future.

Anti Fouling Paints

Non-stick coatings

Cleaning

Natural resistance, natural biocides

Electricity

Prickly coatings

7.8 FUTURE OF ANTI-FOULING PAINTS

There have been a number of new developments in antifouling paint through technological innovations originating in the paint industry. However, these 'eco-friendly' paints that are tinfree contain, instead, very high concentrations of copper, pine or combinations of these with other toxic biocides. Moreover. these new paints are two to three times more expensive than TBT based paints. The toxic chemicals copper and zinc will eventually be phased out because of environmental problems and many companies view the future of antifouling in non-toxic chemicals which employ a repellent action rather than a toxic mechanism. Typical biocides now in use are nonspecific, this means they will kill other organisms which come into contact with the material. Repellents, on the oth er hand, will prevent attachment because the animal perceives the surface to be unpleasant and moves away without any cellular damage. Tests currently being performed on ships hulls comparing TBT vs. non-TBT antifouling paints. Regulations do not yet restrict untested TBT-free antifouling paints. SAQ I
(a) (h)

What are Anti-fouling paints? How do Anti-fouling paints protect a ships hull? What are the effects of fouling? What are the various types of AT paints available? What is the impact of A/F paints on the marine species?

(c) (d) (e)

Environmental Protection

(t) (g) (h) (i)

What are the regulations enacted by IMO with regard to AT paints? What are the new developments in PA paints? What are the advantages of using self polishing A/F paints? Briefly describe the new biocidal method to be used for anti-fouling paints. Briefly describe the new non-biocidal method to be used for anti-fouling paints.

7.9 SUMMARY
Fouling is the term used to describe the growth of marine plants and animals on man made structure in the sea. Antifouling paint was developed to reduce drag on ship hulls by preventing the buildup of barnacles and other organism, consequently making ships faster and more fuel efficient. The type of organism and growth intensity varies with temperature salinity and light intensity in the sea. The shipping industry relies heavily on the use of TBT impregnated marine coating that disperse into the sea at damaging rates. In the marine environment, the continuous leaching of heavy metals from anti-fouling paints has been responsible for the destruction of shellfish populations, sex change in invertebrates and possible genetic defects in other marine animals. The IMO adopted the International Convention on the control of harmful anti-fouling system that prohibits the use of harmful organization in anti-fouling paints used on ships. When seeking a biocidal route to replace TBT-SPCs, most formulators have developed anti-fouling paints based on copper. Many view the future of antifouling in non-toxic chemicals which employ a repellent action rather than a toxic mechanism, that will prevent attachment because the animal perceives the surface to be unpleasant and moves away.

Note: Some of the pictures/images used in this Unit have been sourced from the internet. We wish to thank the creators/publishers for the usage of their material.

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