Anti Fouling | Paint | Materials

An Update on the Current Antifouling Paint Technology Shailesh Rajan

Boat India’08 15th Dec 2008

Agenda • Marine Fouling • Antifouling Coatings – A brief history • Different Antifouling Coating Technologies available Today • Controlled Depletion Polymer • Hybrid • Acrylate – Self Polishing Copolymer • Non Biocidal – Fluoro Polymer • The impact of your choice

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Marine Fouling

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Marine Fouling
 Without antifouling measures the fuel consumption of the world shipping fleets would increase by 40%, equivalent to an extra 120 mio tonnes of fuel annually.  Control of fouling of water intakes, piping systems and heat exchangers in desalinization and power plants, costs over $ 15 billion per year.  Control of fouling on membranes used in wastewater and desalination systems costs over Euro 1 billion per year.  Fouling of aquaculture systems in fish farms costs an average of Euro 100,000 per year.  The total global market for antifouling coatings for ship and pleasure crafts is approx $ 700 M per annum.  Environmental Cost

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What is Fouling?
“Micro-fouling” = Slime “Macro-fouling” = Weed + Animal

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Bio Fouling Formation

Figure 1: (A) A light micrograph of a cypris larva, (B) a cyprid antennule, (C) a settled cyprid, attached underwater by secretion of permanent cement, (D) and metamorphose juvenile barnacle, still attached by the permanent cement. Images C and D were captured using fluorescence microscopy after staining the organisms using an amine dye.

The ultra structure and morphology of the cyprid temporary adhesive system taken under atomic force microscopy.

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Effect of fouling

Enteromorpha (“Marine Grass”)

Slime Fouling: 1~2 % increase in drag

Weed Fouling: Up to 10% increase in drag

Shell Fouling: Up to 40% increase in drag

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Various Antifouling Systems
 Surface Based Technologies - Materials with specific surface properties can be used to prevent settlement of organisms .  Nano Fibre Wall – Makes a “wall - of -death”  Photo catalytic Surfaces - Prevents fouling through the generation of reactive oxygen species very close to a surface.  Nanostructured Surfaces – Ability to trap air at the solid/water interface producing a barrier to fouling.  Chloropac Systems – Sodium Hypochorite generating systems  Electrochemical Prevention – Disinfection due to the direct electrochemical oxidation of cells.  Antifouling Coatings – CDP/SPC/Foul Release

Interprime 198

Multiprime

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Foul Control Technique - Antifouling Coatings History
Time
Ancient

Ship Material Antifouling used
Wood •Coal tar, Oil & wax coating •Wooden and metallic (lead & Copper) sheating

1850 – 1900

Wood & Iron

•Copper Sheeting •Galvanic action for Iron •“Patent paints” •“Italian Moravian” hot plastic paint

1900 – 1950

Iron

•Antifouling paints (various binders & Copper Oxide) •Hot plastic paint followed by cold plastic paint

1950 – present

Iron

•Insoluble or soluble matrix used, containing copper oxide and mercuric oxide as toxics - organotin and copper oxide combinations •- organotin polymer antifoulant (self-polishing co-polymer)

Present - Future

•low and non toxic paint •electrolysis technology of seawater by electro-conductive coating system •use of copper alloy etc. •Low surface-energy paint

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IMO AFS Convention

 From the late 1980’s concerns over the effect the tributyl tin was having on the environment were starting to be raised.  In October 2001, the text for a treaty on antifouling paints was agreed by the 76 countries present at an IMO Diplomatic Conference, held in London: “International Convention on the Control of Harmful Anti-Fouling Systems on Ships” (IMO-AFS Convention).  This bans the application of TBT paints from 1/1/2003, and the use (presence) of TBT paints on ships from 1/1/2008.

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IMO AFS Convention
- Marine antifoulings are classed as Biocidal Products - Biocidal products are (becoming) regulated like pesticides

Biocide on paint surface Biocide in water column Biocide in sediments 3 Key environmental issues: degradation degradation

Rate of biocide degradation Toxicity to non-target organisms Potential for bio-accumulation
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Antifouling Coatings –TBT Free Technology Options

Biocidal Rosin-based Hybrid SPC Non Biocidal/Foul Release Silicone Fluoropolymer SPC

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Antifouling Coatings – TBT Free Technology Options: Performance vs Price

TBT Based

Acrylate SPC

Hybrid

E CNA MR OF REP

Rosin Based

PRICE

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Antifouling Coatings – TBT Free Technology Options – Rosin Based
 Rosin comes from trees, and has been used for over 100 years in antifouling paints because it is slightly soluble in seawater, enabling the biocides to be released by diffusion.

 Rosin does enable higher solids paints to be made (55~60% Volume Solids content). Biocides

Sea Water

Leached Layer

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TBT-Free Technology Options – Rosin Based

Non-Polishing Reference

Amount dissolved

Anticorrosive Leached Layer ~ 55 µm

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TBT-Free Technology Options – Rosin Based

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TBT-Free Technology Options – Rosin Based The Effect of Fouling on Fuel Consumption: Ship Comparison
CDP 8 % Increase in Fuel Consumption 6 4 2 0 -2 0 10 20 30 months 40 50 60 SPC

On-set of weed fouling on CDP
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Antifouling Coatings – TBT Free Technology Options – Rosin Based
Rosin has some disadvantages: it is a brittle material, and can cause cracking and detachment. it reacts with oxygen and has to be immersed relatively quickly. It does not prevent water going into the antifouling paint film.

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TBT-Free Technology Options

Biocidal Rosin-based Hybrid SPC SPC

Non Biocidal Silicone Fluoropolymer

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TBT-Free Technology Options – SPC Acrylate Based

Attempts to mimic the TBT SPC seawater reaction have been underway for many years, by all Marine paint companies.

 To date, only three TBT-Free SPC technologies have been commercialised: Copper Acrylate Zinc Acrylate Silyl Acrylate (Polymer --- COO --- Cu --- R) (Polymer --- COO --- Zn --- R) (Polymer --- COO --- Si --- R3)

 New boosting biocides have been incorporated to “off-set” the loss of the TBT, together with Copper.

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TBT-Free Technology Options – SPC Acrylate Based
 The unique Copper Acrylate polymer mirrors the chemical reaction of TBT SPC in sea water.  This means that it has the same features as TBT SPC systems have: § Predictable polishing rates § Controlled Release of biocides § Easy re-coat properties § No build-up of thick leached layers § Excellent mechanical properties § Compatibility with the new building process (long exposure prior to immersion)

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TBT-Free Technology Options – SPC Acrylate Based

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TBT-Free Technology Options – SPC Acrylate Based

Non-Polishing Reference Amount polished off

100 µm Intersmooth

Anticorrosive

Leached Layer ~ 10 µm

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TBT-Free Technology Options – SPC Acrylate Based
The graph below shows the number of satisfactory ships (ie with Fouling Rating < 10) at each drydocking interval:

SPC % ships with FR < 10 100 90 80 70 60 50 0-12 13-18 19-24

CDP

25-30

31-36

37-42

43-60

M onths In-Service

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TBT-Free Technology Options – SPC Acrylate Based

Seahorse Standard, 60 months, before washing
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TBT-Free Technology Options – SPC Acrylate Based

Trader, 36 months, before washing
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TBT-Free Technology Options – SPC Acrylate Based

CDP (Rosin)

Intersmooth 360 SPC

Intersmooth 460 SPC

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TBT-Free Technology Options – SPC Acrylate Based “European Navigator” August 1998 (Ro-Ro, 12 mo)
CDP

Intersmooth 360 SPC
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TBT-Free Technology Options – SPC Acrylate Based “Bremen” May 2001 (Frigate, 36 mo.)
TBT SPC

TBT Free SPC
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TBT-Free Technology Options

Biocidal Rosin-based Hybrid SPC SPC

Non Biocidal Silicone Fluoropolymer

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TBT-Free Technology Options: Performance vs Price

TBT Based

Acrylate SPC

Hybrid

E CNA MR OF REP

Rosin Based

PRICE

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TBT Free Technology Options - Hybrid SPC/CDP
CDP (Rosin) • • High volume solids content Surface tolerant
SPC • • • • • Good film properties Polishing control Thin leached layer Control of biocide release Best a/f performance

• • • • • • •

Hybrid SPC/CDP High volume solids content Polishing control Surface tolerant Good film properties Control of biocide release Control of leached layer size Good a/f performance

Interswift Hybrid

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TBT Free Technology Options - Hybrid SPC/CDP
Interspeed 340 Interswift 655 Interspeed 340 Interswift 655

Interswift 655: “Charles Darwin” Test Patches (22 mo.)
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TBT Free Technology Options - Hybrid SPC/CDP

“Ibone” (Bulker), Jan 2005, 23 mo.
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TBT-Free Technology Options

B R

io c id a l S P C / C D P S P C

o s i n - b a s eH d y b r i d C D P o lu b le

( S

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Interspeed 340

Interswift 655

Intersmooth SPC

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TBT-Free Technology Options – How to tell the Difference?
 Rosin based or “Controlled Depletion Polymers” “Hydration”, “Ablative”, “Eroding”, “Polishing”, “Ion Exchange”, “Self Polishing Types” or “Colophony”  Hybrid A mixture of Rosin and Acrylate (Copper, Silyl or Zinc) How much of each - ideally 50:50 blend  True Self Polishing, Self Smoothing Copolymers Can only be 100% pure Acrylate, be it Copper, Silyl or Zinc  How much Cuprous Oxide?  What and how much booster biocide?

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TBT-Free Technology Options

Biocidal Rosin-based Hybrid SPC SPC

Non Biocidal Silicone Fluoropolymer

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TBT-Free Technology Options – Non Biocidal

 What is Non Biocidal?

 It is a foul release system that contains no biocides or poisons  Works by producing a surface that fouling organisms cannot stick to  Produces an extremely low coating roughness or Average Hull Roughness (AHR)

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Surface Profiles

Silicone foul release coating - freshly sprayed

SPC antifouling - freshly sprayed

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Foul Release Coatings

Flouro Chemistry represents the latest developments in foul release coatings

• It is established that the marine fouling secrete an adhesive protein or glycoprotein which is either hydrophilic or hydrophobic • Having a coating surface which is ambiphilic reduces the adhesion of fouling to the surface

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Foul Release Coatings Fluoropolymer chemistry represents the very latest advances in foul release technology, significantly improving upon the performance of silicone based systems. A fluoropolymer provides an amphiphilic surface, both hydrophobic and hydrophilic. It has been established that marine fouling organisms secrete an adhesive protein or glycoprotein, either of a hydrophobic or hydrophilic nature. By having a balanced amphiphilic surface we can minimise the chemical and electrostatic interactions between the surface and the adhesive secreted from a wide range of fouling organisms.
Fluoropolymer
Hydrophilic terminus Hydrophobic main chain Hydrophilic terminus

Nanotechnology!
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Foul Release Coatings

Hydrophobic adhesive protein

Species 1

Species 2

Hydrophilic adhesive protein

hydrophobic surface

hydrophilic surface

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Foul Release Coatings

Hydrophobic adhesive protein

Species 1

Species 2

Hydrophilic adhesive protein

hydrophobic surface

hydrophilic surface

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Foul Release Coatings
Hydrophobic adhesive protein Hydrophilic adhesive protein

Species 1

Species 2

hydrophobic surface (I all silicone foul-release)

hydrophilic surface

Fluoropolymer
Amphiphilic surface (both hydrophilic and hydrophobic properties)

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Foul Release Coatings

Species 1

Species 2

hydrophobic surface (all silicone foul-release)
Species 1

hydrophilic surface Hydrophobic adhesive protein Hydrophilic adhesive protein

Species 2

Fluoropolymer
Amphiphilic surface (both hydrophilic and hydrophobic properties)

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Foul Release Coatings
s1 cie pe S
Sp ec

ies

2

Hydrophobic adhesive protein

Hydrophilic adhesive protein

Fluoropolymer
Amphiphilic surface (both hydrophilic and hydrophobic properties

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TBT-Free Technology Options – Non Biocidal

 Military (1990)
• • • • • • • • • • • • • • Flexible dry dock intervals Overcome High Speed and Cavitation problems Environmental image and Metal Free Copper free for Aluminium hulls Overcome High Speed and Cavitation problems Environmental image Flexible dry dock intervals Ultra-smooth and Slippery Hulls to reduce Fuel consumption Ultra-smooth and Slippery Hulls to increase ships speed Environmental image and Metal Free Improved performance over Intersleek 700 Suitable for vessels 25% active and 10 knots Ultra-smooth and Slippery Hulls to increase ships speed Environmental image and Metal Free

 High Speed Catamarans (1995)

 Deep Sea (1997)

 Intersleek 900 launched (2006)

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Non Biocidal Foul Release Coatings

 In comparison to normal antifouling, Intersleek® has • Reduced hull roughness • Lower coefficient of friction (reduced drag) • Improved foul release properties / static performance • Reduced slime build up • Resulting in fuel savings And as a further result reduced stack emissions – Save money and gain competitive advantage

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TBT-Free Technology Options – Non Biocidal

Before Cleaning

“Tropic Lure” Feb 2003 Ro-Ro, 2563 dwt, 117 months

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TBT-Free Technology Options – Non Biocidal

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Environmental Footprint
Down by 6% for Intersleek® 900 Stack emissions Down by 6% for Intersleek® 900 Bunker consumption Reduced life-time Paint consumption

No biocides registed

Raw material consumption Hazardous Materials (Green Passport)

General waste Oily Water Ballast water (invasive species) Biofouling (invasive species) No animal or weed transit Biocidal release from antifoulings No biocides released -During application -In-service -Removal

100% reduction
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TBT-Free Technology Options – Non Biocidal
Potential fuel savings and less emissions Environmental Image Durable & Long lasting

Low VOC

Foul Release system

Less weight

Antifouling Performance

Less paint initially

Lower M&R costs

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Impact -Selection of Antifouling Systems

• • • • • •

There are a range of fouling-control technologies now on the market which can be very confusing to the vessel owners or operators. Degree of Fouling Recoating intervals and the price vs performance criteria Fuel is an important cost when operating a vessel, and this is directly affected by the roughness of the outer hull. Choosing the correct fouling control system can save considerable costs, and also help the environment. Foul Release coatings are the most effective and preferred method..

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THANK YOU FOR YOUR ATTENTION

Boat India‘08, Cochin 15th Dec 2008

SHAILESH

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