Current technologies for the marine biofouling control Fani Sakellariadou Prof. in Geochemical Oceanography University of Piraeus, Dept of Maritime Studies fsakelar@unipi.gr ICABE 2013

Biofouling Accumulation of unwanted biological species at an interface of an artificial structure immersed in seawater. ICABE 2013

Degradation of the vessel’s performance: Hydrodynamic drag increases Negative impacts Degradation of the vessel’s performance: Hydrodynamic drag increases Hull friction increases Fuel consumption increases Ship slows down Vessel becomes more sluggish and less manoeuvrable Results → increased use of manpower → increased use of fuel → increased use of material and dry docking time → increased costs for the shipping industry ICABE 2013

Aquaculture Negative impacts Cage deformation and structural fatigue Restriction of water exchange across the net Reduction of water quality Fish health problems Negative impacts ICABE 2013

shipping : 1046 million tonnes CO2 (3.3% of global) 2007: shipping : 1046 million tonnes CO2 (3.3% of global) international shipping: 870 million tonnes CO2 (2.7% of global) No action European Commission Joint Research Centre: GHG from ships will increase by 150-200% by 2050. Hull protection from biofouling to reduce ICABE 2013

Biofouling control records from 700BC. Plutarch (46-120 A.D.), Symposiacs, Book II, Question VII cleaning of ship hulls. Biofouling control records from 700BC. Organometallic paints (Cu, As, Hg oxides) widely used till the early fifties 1960s: organotin paints were commercialised. 1970s: TBT based self polishing copolymer (SPC) paints a new era up to 5 years fouling free performance. ICABE 2013

early 1980s: TBT extremely toxic to aquatic life poisonous substance widespread, unsustainable harm to the marine environment. 1990, MEPC, adoption of a recommendation resolution: Governments adopt measures to reduce the use of TBT paints on non-aluminium hulled vessels < 25 m length eliminate the use of antifouling paints with a leaching rate of > 4 μg TBT/day. 1998, MEPC, approval of a draft Assembly resolution: 2008 deadline for the complete prohibition of organotins as biocides in antifouling systems on ships. 2001, IMO, “The International Convention on the Control of Harmful Antifouling Systems on Ships (ICAFS)”. 17/9/2008: came into force. Ban of organotins use in antifouling paints. ICABE 2013

Sn replacement by Cu and Zn based coatings with a biocide component. ICABE 2013

Biocide-free foul release coatings Biocidal antifouling paints Nowadays Future environmental legislation: Unlikely to be affected. Biocide-free foul release coatings Biocidal antifouling paints Coating inhibits successful attachment of marine biota. Coating releases chemicals inhibiting settlement of marine biota. Physical action Biocide absence Chemical action Biocide release Silicone or fluoropolymer Hydrolyzing silyl acrylate antifouling better resistance to slime ultra smooth, slippery surface ICABE 2013

Energy and Environmental Research Associates, 2011: 9% average reduce of GHGs by fluoropolymer foul release technology. Main manufacturers of biofouling control paints (complying with IMO document AFS/CONF/26) HEMPEL A/S PPG/SIGMA COATINGS CHUGOKU Marine Paints (CMP) S.A INTERNATIONAL PAINT JOTUN MARINE COATINGS. ICABE 2013

Table 1. List of main organotin free antifouling paints (complying with IMO document AFS/CONF/26) and their characteristics. COMPANY PRODUCT Anti Fouling type Mechanism Vessel’s type and operation Sea water Dry-Docking Interval HEMPEL A/S OLYMPIC+ 72950 Self polishing Ion- exchange High speed. High activity. Short idle periods. Not overly aggressive fouling waters Up to 36 months OCEANIC+ 73900 Self polishing SPC Hydrolysis + Low to medium speed. Low to medium activity. Short to medium idle periods. Medium aggressive fouling waters Up to 60 months OCEANIC+ 73950 Self polishing SPC Medium to high speed. GLOBIC 6000 75950 Low friction, self-smoothening SPC nano-capsule acrylates fine tuned interaction with seawater. Medium activity. Medium aggressive fouling waters Up to 60 months GLOBIC 9000 78900 interaction with seawater Aggressive fouling waters Up to 90 months GLOBIC 9000 78950 Low to high speed. Aaggressive fouling waters DYNAMIC 79540 Self- polishing, self- smoothening Hydrolyzing silyl acrylate DYNAMIC 79560 Mediumto high speed. DYNAMIC 79580 Low to medium speed. Coastal trade.

High and medium activity. Deep sea trade. Prolonged periods COMPANY PRODUCT Anti Fouling type Mechanism Vessel’s type and operation Sea water Dry-Docking Interval PPG, SIGMA COATINGS SIGMA ALPHAGEN 230 Self-polishing Cuprous oxide + organic biocides High and medium activity. Deep sea trade. Prolonged periods depending on sailing pattern and routes SIGMA ALPHAGEN 240 SIGMA ALPHAGEN 650 Coastal operation Aggressive fouling waters Long service periods SIGMA ECOFLEET 238A SIGMA ECOFLEET 290 Up to 60 months SIGMA ECOFLEET 530 SIGMA ECOFLEET 690 Coastal, low activity Extreme and aggressive fouling waters SIGMA NEXEON 750 Cu-free Static, low speed. Low activity. Long stationary periods SIGMA SYLADVANCE 700 Self-polishing and self-smoothing Hydrolysing silyl acrylate High and medium activity SIGMA SYLADVANCE 800 Hydrolyzing organosilyl polymer

CHUGOKU Marine Paints (CMP) S.A SEAFLO NEO Self-polishing COMPANY PRODUCT Anti Fouling type Mechanism Vessel’s type and operation Sea water Dry-Docking Interval CHUGOKU Marine Paints (CMP) S.A SEAFLO NEO Self-polishing Hydrolysing polymer SEAFLO NEO SL Silyl polymer and micro pigmentation Up to 90 months SEA GRANDPRIX 660HS Hydrolysis compounds and hydrophobic polymers Up to 60 months 330R 220HS Up to 36 months period on vertical bottom and 60 months on flat bottom CF-10 Hydrolysis and Zn- polymer Cu free 1000L and silyl acrylate polymer MARK II Silyl/

Super-hydrophilic polymer COMPANY PRODUCT Anti Fouling type Mechanism Vessel’s type and operation Sea water Dry-Docking Interval INTERNATIONAL PAINT Intercept 8000 LPP Linear polishing Super-hydrophilic polymer + Biocide Deep sea Up to 90 months Intersmooth 7465Si Self-polishing Hydrolysing silyl acrylate polymer Intersmooth 7460/7465HS Copper acrylate copolymer Interswift 6800HS Copper acrylate SPC and rosin-based CDP Up to 60 months Interswift 6900Si Hydrolysing silyl acrylate SPC and CDP Interswift 6600 Copper acrylate SPC and CDP technologies Interspped 6400/6200 CDP Up to 36 months Interspeed 6200 Interspeed 6200NA

Self polishing and self smoothing Controlled and linear polishing COMPANY PRODUCT Anti Fouling type Mechanism Vessel’s type and operation Sea water Dry-Docking Interval JOTUN MARINE COATINGS Sea Quantum Ultra S Self polishing and self smoothing Controlled and linear polishing Hydrolysis of silyl acrylate polymer Low activity vessels Up to 90 months Pro Universal trade Up to 90 months (3 coats) Static Static and laid-up 24 months (additional time as a last coat on top of paint system Up to 36 months (low voyage vessels) Plus S High activity Classic S Medium activity Sea Quantum S200 Hydrolysis of silyl methacrylate SeaMate HB66 Controlled and linear polishing Silyl acrylate Biocide Up to 60 months (2 coats) Sea Force 30 Linear and predictable polishing Global trade Up to 36 months Sea Force 60 Selected areas Up to 60 months Sea Force 90 Synthetic polymers

INTERNATIONAL, PROTECTIVE COATINGS Table 2. Fuel savings for selected organotin free antifouling paints. COMPANY PRODUCT Fuel savings PPG, SIGMA COATINGS SIGMA SYLADVANCE 800 3-5% INTERNATIONAL, PROTECTIVE COATINGS Intersmooth 7465Si 4% Intersmooth 7460/7465HS Interswift 6900Si 15% JOTUN MARINE COATINGS Sea Quantum Pro 7% Sea Quantum S200 ICABE 2013

Table 3. List of main biociode-free foul release coatings and their characteristics. COMPANY PRODUCT Mechanism Vessel’s type and operation Paint consumption Lifetime HEMPEL A/S HEMPASIL X3 87500* Hydrogel and Siliocone polymer Speed above 8 knots CHUGOKU Marine Paints (CMP) S.A BIOCLEAN HB Silicone INTERNATIONAL, PROTECTIVE COATINGS Intersleek 425 Silicone based Fast craft Intersleek 700 Deep sea Intersleek 900 Fluoropolymer technology All vessels above 10 knots Intersleek1100SR Intersleek 1100SR Slim release coating All vessels A single full coat every 5 years JOTUN MARINE COATINGS SeaLion repulse Nanorepellent Up to 10 years with a touch up after 5 years. ICABE 2013

Need of total biofouling removal clean it off Biofilm or slime layer development results to a fuel penalty of > 20%. Need of total biofouling removal clean it off drydock Underwater cleaning Complex, expensive, time-consuming activity ports do not permit it. Serious environmental impacts ICABE 2013

Ecospeed product A new environmentally safe approach 2010 Hydrex, “environmentally sound and efficient” TBT-free, Cu-free biocide-free vinyl ester resin base, reinforced with glass platelets underwater cleaning 10 y guaranteed LT 25 y expected LT Mid 2009 - early 2010: Significant fuel consumption reduction Significant reduction of GHGs Limitation/prevention of NIS spread Drydock intervals increase Marine chemical pollution prevention Rotterdam, Antwerp, Copenhagen, Oslo and Barcelona ports (with underwater cleaning ban) decided to permit in case of hulls coated with Ecospeed. ICABE 2013

Comparison of three marine biofouling control products Ecospeed a foul release coating copper based SPC anitifouling paint Ecospeed more expensive initial application than an SPC 10 to 25 years period: Ecospeed (only local touch-ups) significantly lower costs than the other two techniques. IMO, world fleet annual fuel consumption : 310-350 million tonnes. IMO, world fleet annual CO2 output: 850 million - 1.1 billion tonnes. EU LIFE Project ECOTEC-STC: Ecospeed use by 80% of the world fleet instead of biocidal antifoulings corresponds to 28.5 million tonnes of fuels annual save and a drop of 90 million tonnes in annual CO2 output. ICABE 2013

Serious issue tolerating the maritime industry for centuries Marine biofouling Serious issue tolerating the maritime industry for centuries Need for products with an environmentally acceptable antifouling performance allowing a long dry-docking interval corresponding to low costs : Driving forces for the development of successful non-toxic antifouling coatings: rising cost of fuels growing environmental concerns over pollution IMO, regional and local legislation ICABE 2013

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