10 years of CERENA Prof. J. Bordado

Transcription

1 10 years of CERENA Prof. J. Bordado

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3 INDEX 1. The Problem to Solve 2. Different Types of Fouling 3. Marine Biofouling 4. Biocide linking with covalent bond 5. Biocidal activity 6. Biocides pre-selection 7. Non-leaching antifouling coatings 8. Derivatised antifouling agents 9. Non- Adhesion Improvement 10. Sea exposure test 11. Conclusions

4 Seventh Frammework Programme EU Total Budget IST Budget PARTNERS WITH DIFFERENT COMPETENCES AND COMPLEMENTARITY TO ACOOMPLISH THE OBJECTIVES IST Team Prof. João Bordado Denise Afonso Drª. Elisabete Silva Tânia Pinto Olga Ferreira WEBSITE: FOUL-X-SPEL

5 Partnership Instituto Superior Técnico/Centro de Recursos Naturais e Ambiente Instituto Superior Técnico (IST) is a school of engineering. Founded in 1911, is the largest and most prestigious school of engineering in Portugal. Estaleiros Navais de Peniche, S.A ENP is the new shipyard reference in the Portuguese West Coast Instituto de Soldadura e Qualidade Founded in 1965, ISQ is a private and independent company providing inspection, testing, training and technical consultancy.

6 Partnership HEMPEL A/S Hempel is a world-leading coatings supplier for the decorative, protective, marine, container and yacht markets. Fundacion Tekniker TEKNIKER is a centre of mechatronics, manufacturing technologies and microtechnologies, in areas as different as designing industrial products and consumer goods, troubleshooting in fields like friction, wear and lubrication University of Strathclyde University of Strathclyde is a leading international technological University located in the heart of Glasgow, Scotland's biggest city.

7 Partnership CARNIVAL & PLC Carnival Corporation & plc ("Carnival") is an American-British cruise company and the world's largest travel leisure company, with a combined fleet of over 100 vessels across 10 cruise line brands. LLOYD S REGISTER EMEA Lloyd s Register (LR) is a global engineering, technical and business services organisation wholly owned by the Lloyd s Register Foundation, a UK charity dedicated to research and education in science and engineering. Founded in 1760 as a marine classification society, LR now operates across many industry sectors, with over 9,000 employees based in 78 countries.

8 Partnership University of Southampton Is a research-intensive university and a founding member of the prestigious Russel Group. National Technical University of Athens The National Technical University (NTUA) is the oldest and most prestigious educational institution of Greece in the field of technology, and has contributed unceasingly to the country's scientific, technical and economic development since its foundation in 1836.

9 1. The problem to solve

10 1. The problem to solve

11 1. the problem to solve The antifoulings in use Limited Eficiency (3 to 4 years) High cost of Dry Dock Leaching the toxic component (Usually Tributyltin) Irreversible environmental Damage in Ports Fuel consumption up to 40% More Higher operating Costs

12 2. DIFFERENT TYPES OF FOULING

13 2. Different types of fouling

14 3. MARINE BIOFOULING Microorganisms in marine environmental tend to adhere on submerged surfaces forming the so-called biofilms. Fouling organisms, from seaweeds, algae to hard foulers, will attach over time, creating then, the macrofouling.

15 3. MARINE BIOFOULING This marine biofouling, causes serious retrofitting consequences for marine transport.

16 Metallic Plate ESSENTIAL to inhibit the formation of EPS or its Adhesion 3.1 MARINE BIOFOULING FORMATION Coating Incipient formation of biofilm (first hours of exposure) Seawater Adsorbed organics Microorganism Extracellular Polymeric Substances (EPS)

17 3.1 MARINE BIOFOULING FORMATION The Exopolymeric substances (EPS) are the initial tacky film, and these substances are mostly produced inside the cells and excreted to the surface. The EPS promotes the adhesion of Macrofouling. ALTERNATIVES: PREVENT EPS FORMATION INDUCE NON- ADHESION of EPS Layer.

18 3.1 BIOFOULING FORMATION EXAMPLES OF DIFFERENT STAGES OF FOULING FORMATION

19 NEW APPROACH in this Project Anti- Fouling Agents linked by covalent Bonds to the Structure of the Coating Contact Biocides and Contact Anti-Vegetatives

20 4. BIOCIDE LINKING WITH COVALENT BOND Functional groups Functional groups ~ ~

21 5. BIOCIDAL ACTIVITY Biocidal Activity may be affected by the new linkage: 1. By additional steric hindrance in this area of the molecule; 2. Other mechanism.

22 5. BIOCIDAL ACTIVITY Stages of attachment of marine organisms on surfaces immersed in sea water Processes involved Attached organisms Nature of film formed Approximate initiation time Stage 1 Essentially physical forced Adhesion of organic molecules Conditioner few minutes Stage 2 Reversible adsorption of species weakly adsorbed Bacteria and diatoms Microbial biofilm 1-24 hours

23 5. BIOCIDAL ACTIVITY Processes involved Attached organisms Nature of film formed Approximate initiation time Stage 3 See weed or other Algae Algae Macrofilm of Algae few weeks Stage 4 Barnacles Tube worms Macroorganisms Attached Macrofilm few months

24 6. BIOCIDES PRE-SELECTION Range of potency for antifouling purpose, as well as recognized effectiveness; The ones which after bonding to the base resin will follow a nonreleasing biocide mechanism: Contact Biocides

25 6. BIOCIDES PRE-SELECTION Feasibility to be immobilised successfully by covalent binding (e.g. NH and OH groups); Stability (chemical, photo stability,.); Biocides that have never been bonded to the structure of the resin (NEW APPROACH); Conformity with BPD (Biocidal Products Directive/Regulations) registering.

26 CRITERIA FOR PRE-SELECTION OF ACTIVE SUBSTANCES Mechanism of Action: CONTACT! Effectiveness: Potency Immobilization Feasibility Stability Accessibility Shelf life and Duration of Action Several Suppliers/Comodity Registration as Antifouling

27 6. BIOCIDES PRE-SELECTION For the bridging tests a final biocides list of 41 biocides was proposed Extraction in progress For the first five columns Not feasible Not feasible for some criteria BPD Column Not allowed in EU based on BPD Existing biocides under review in BPD Potential biocide New biocide under evaluation in BPD May be feasible Lack of information to be taken any decision at this stage Nº Biocide 1 Irgarol 9 Polyethylenimine 10 QAS 11 DACO group 14 Momilactone A or B 15 kalihinol A Isocyanosesquiterpen 16/17 e alcohol or furanosesquiterpene 23 Medetomidine 24 Econea 27 Zineb 28 Mancozeb 29 Capsaicin 30 HMMBBA 31 BHMBBA 32 HBDMBA 33 HMBBA Mechanism of action Potency Immobilisation feasibility Stability Accessibility Original material to be registered in BPD two biocides were selected, Irgarol and Econea for first tests

28 6.1 BIOCIDES SELECTION Irgarol (herbicide): Mainly toxic for Algae species. Accessibility, Potency and Immobilization Feasibility, despite no reported evidence of a contact biocide when immobilized.

29 6.1 BIOCIDES SELECTION Econea (Molluscicide): Mainly toxic for different barnacles species. High potency, but is also recognized as a newly boost biocide, thus a lack of data concerning it mechanism of action was found.

30 7. NON-LEACHING ANTIFOULING COATINGS Approach: non-leaching antifouling polymeric coating Model system for test: Two component polyurethane (PU) or silicone based system + + Isocyanate Polyol Derivatised Antifouling Agent Additives for a + paint formulation: catalysts, antifoaming agents, stabilizers, etc. Resin system

31 8. DERIVATISED ANTIFOULING AGENTS Linked Econea Isocyanate Content* (wt. % F group) Samples* Calculated Experimental IRGAROL-1F IRGAROL-2F 11.1 ECONEA-F Linked Irgarol

32 % T % T 8. DERIVATISED ANTIFOULING AGENTS Irgarol-MDI FTIR analysis proved the functionalization structure maintenance; Irgarol Econea-F 40 F peak Wavenumber (cm -1 ) 1660 FTIR spectra of Irgarol/Irgarol-F Econea Wavenumber (cm -1 ) FTIR spectra of Econea/Econea-F Conversions as high as 95±5% both biocides; were achieved for

33 8. DERIVATISED ANTIFOULING AGENTS Tests for Bacteriological Activity Bacteriological action has not been affected after Irgarol and Econea functionalization. Samples Bacteriological analysis E. Coli (MPN/g) Staphylococcus aureus (CFU/g) Pseudomonas pyocyanea (CFU/g) ECONEA Not detected 0 0 ECONEA-F Not detected 0 0 IRGAROL Not detected 0 0 IRGAROL-F Not detected 0 0 E. Coli-COLILERT, HPA w18, ISO ; S. aureus -NP 4343:1998; P. pyocyanea -ISO 6266

34 9. NON-ADHESION IMPROVEMENT Base coating: Silicone Resin Two component Polyurethane Modification of the Macromolecules structure to promote Non-Adhesion.

35 9. NON-ADHESION IMPROVEMENT Approach: Replacement of polyalkyleneglycol by saturated hydrocarbon with aliphatic rings. Increase of the hydrophobic character.

36 10. SEA EXPOSURE TEST Average test conditions: Static test some turbulence in the winter; Temperature: ºC Density(Kg/m 3 ): 1027 Salinity: Deep: 4 meters

37 10. SEA EXPOSURE TEST Main variables to be consider for field tests: 1.Biocides content; combination of biocides; 2.Different locations for testing the effect of different seawater conditions. Prototype 7 with the best behaviour, followed by Prototype 9. Both Prototypes has Econea-F and Irgarol-F in their constitution.

38 10. SEA EXPOSURE TEST Main variables to be consider for field tests: 1.Biocides content; combination of biocides; 2.Different locations for testing the effect of different seawater conditions. Several potential formulations containing immobilised Econea and Irgarol with good behaviours Field test need to continued to provide the best ones for longer immersion time (a year!)

39 11. CONCLUSIONS Commercial biocides, such as ECONEA and Irgarol, have been successfully derivatised using a functionalization approach. Modification of the Coating: With a linked contact biocide Modification of the resin structure.

40 11. CONCLUSIONS Field sea immersion tests evidenced promising antifouling effect. The binding of the derivatised biocides into the PU and silicone based resin (paint) evidenced good stability, pot life and homogeneity

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42 CERENA s 10th Anniversary Happy Anniversary!!