Skip to main content
Log in

Clean hulls without poisons: Devising and testing nontoxic marine coatings

  • Technical Articles
  • Published:
Journal of Coatings Technology

Abstract

Because this paper marks 50 years since the first Mattiello Memorial Lecture, it begins with a remembrance of the man in whose honor we meet and an appreciation of his character and his contributions to the coatings industry. The body of the paper is concerned with the coating used on a hull of a ship to prevent the accumulation of barnacles and other fouling. The most effective antifouling paint now being used contains toxins and will be forbidden by international regulations within eight years. The ideal replacement will be a nontoxic material that resists the attachment of marine life and encourages the organisms to fall off the ship. This paper describes laboratory and field work during the past 18 years on a variety of fluorinated coatings and silicone coatings with these properties and criteria for formulating successful nontoxic coatings. Silicone and fluorinated coatings frustrate fouling by different mechanisms, and thus the criteria for a successful coating are distinct in important ways.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Kienle, R.H., “Physical Chemical Research in the Protective Coatings Industry,”Official Digest,22, No. 300, 11–51 (1950).

    Google Scholar 

  2. Schulenberg, F., “Lest We Forget,”Am. Paint & Coat. J. Convention Daily, November 8, 1989, p. 7.

  3. Greco, W. J., “The History of the NYSCT,” an address to the New York Society for Coatings Technology on its 50th Anniversary, April 1, 1969; available at http://nysct.org/history2.htm.

  4. Schulenberg, F., “The Gallows Birds,”Am. Paint & Coat. J. Convention Daily, November 8, 1989, p. 8, 41.

  5. Payne, H.F., “Philosophy of Coatings,”Official Digest,32, No. 430, 1371–1434 (1960).

    CAS  Google Scholar 

  6. Callow, M., “Ship Fouling: Problems and Solutions,”Chem. & Ind., 123–27 (1990).

  7. Pain, S., “How to Rule the Waves,”New Scientist, 162, No. 2191, 54–55 (June 19, 1999).

    Google Scholar 

  8. IMO News, The Magazine of the International Maritime Organization, 43 Albert Embarkment, London SE1 7SR, United Kingdom, Number 4, pp. 8–10 (1998).

  9. Naldrett, M.J., “The Importance of Sulphur Crosslinks and Hydrophobic Interactions in the Polymerization of Barnacle Cement,”J. Mar. Biol. Assn. U.K., 73, 689–702 (1993).

    Article  CAS  Google Scholar 

  10. Waite, J.H., “Evidence for a Repeating 3,4-Dihydroxyphenylalanine-and Hydroxyproline-Containing Decapeptide in the Adhesive Protein of the Mussel,Mytilus edulis L.,”J. Biol. Chem., 258, 2911–15 (1983)

    PubMed  CAS  Google Scholar 

  11. Waite, J.H., “The Formation of Mussel Byssus,” in Case, S.T. (Ed.),Results and Problems in Cell Differentiation, Springer-Verlag, Berlin, Vol 2, pp. 27–54, 1992

    Google Scholar 

  12. Papov, V.V., Diamond, T.V., Biemann, K., and Waite, J.H., “Hydroxyarginine-Containing Polyphenolic Proteins in the Adhesive Plaques of the Marine MusselMytilus edulis,”J. Biol. Chem., 270, 20183–92 (1995).

    Article  PubMed  CAS  Google Scholar 

  13. Brady, Jr., R.F., “In Search of Nonstick Coatings,”Chem. & Ind., 219–22 (1997).

  14. Brady, R.F. Jr., “Fluorinated Polyurethane Coatings for Unique Defense Applications,”Eur. Coat. J., 31, 267–69 (1995).

    ADS  MathSciNet  Google Scholar 

  15. Brady, R.F., Jr., “Coming to an Unsticky End,”Nature, 368, No. 6466, 16–17 (1994).

    Article  ADS  Google Scholar 

  16. Griffith, J.R. and Brady, R.F., Jr., “Ready for the Market: An Intriguing Class of Coatings,”Chemtech, 19, 370–373 (1989).

    Google Scholar 

  17. Brady, R.F., Jr., Griffith, J.R., Love, K.S., and Field, D.E., “Nontoxic Alternatives to Antifouling Paints,”Journal of Coatings Technology,59, No. 755, 113–19 (1987).

    CAS  Google Scholar 

  18. Zisman, W.A., “Surface Energetics of Wetting, Spreading, and Adhesion,”Journal of Coatings Technology,44, No. 564, 41–57 (1972).

    CAS  Google Scholar 

  19. O’Rear, J.G., Griffith, J.R., and Reines, S.A., “Some New Fluorinated Epoxies and Polymeric Derivatives,”Journal of Paint Technology,43, No. 552, 113 (1971)

    Google Scholar 

  20. Reines, S.A., Griffith, J.R., and O’Rear, J.G., “Substitutent Effects in the Reaction Rates of 2-Arylhexafluoroisopropyl Glycidyl Ethers with Dibutylamine,”J. Org. Chem., 36, 1209–13 (1971)

    Article  CAS  Google Scholar 

  21. Griffith, J. R., O’Rear, J. G., and Reines, S. A., “Fluorinated Epoxy Resins,”Chemtech, 311–16 (1972)

  22. Reardon, J.P., O’Rear, J.G., and Griffith, J.R., “Preparation and Wetting Characteristics of Some Poly(Fluorinated Aromatic Glycidyl Ethers),”Ind. Eng. Chem. Prod. Res. & Dev., 11, 365 (1972)

    Article  CAS  Google Scholar 

  23. Griffith, J.R. and O’Rear, J.G., “3,3-Bis(Trifluoromethyl)Oxiranes,”Ind. Eng. Chem. Prod. Res. & Dev., 13, 148 (1974)

    Article  CAS  Google Scholar 

  24. Griffith, J.R. and O’Rear, J.G., “Synthesis of 1,3-Bis[2-Hydroxyhexafluoro-2-Propyl]-5-Perfluoroalkyl Benzenes,”Synthesis, 7, 493 (1974).

    Article  Google Scholar 

  25. O’Rear, J.G. and Griffith, J.R. (to the Secretary of the Navy), “Bis(Trifluoromethyl) Epoxides,” U.S. Patent 3,849,450 (November 19, 1974)

  26. O’Rear, J.G. and Griffith, J.R. (to the Secretary of the Navy), “Highly Fluorinated Diglycidyl Ethers,” U.S. Patent 3,993,631 (July 9, 1975)

  27. O’Rear, J.G. and Griffith, J.R. (to the Secretary of the Navy), “Fluoroanhydride Curing Agents and Precursors Thereof for Fluorinated Epoxy Resins,” U.S. Patent 4,045,408 (August 30, 1977)

  28. Griffith. J.R. and O’Rear, J.G. (to the Secretary of the Navy), “Cis-Trans Fluoropolyol Polyacrylate,” U.S. Patent 4, 284,747 (August 18, 1981).

  29. Field, D.E. and Griffith, J.R., “Cross-Linked Fluoropolymer Coatings,”Ind. Eng. Chem. Prod. Res. & Dev, 14, 52–54 (1975)

    Article  CAS  Google Scholar 

  30. Field, D.E., “Fluorinated Polyepoxy and Polyurethane Coatings,”Journal of Coatings Technology,48, No. 615, 43–7 (1976)

    CAS  Google Scholar 

  31. Field, D.E. and Griffith, J.R. (to the Secretary of the Navy), “Fluorinated Network Polymers,” U.S. Patent 4,157,358, June 5, 1979.

  32. Bultman, J.D. and Griffith, J.R., “Fluorinated Naval Coatings,”Ind. Eng. Chem. Prod. Res. & Dev., 17, 8–9 (1978)

    Article  Google Scholar 

  33. Griffith, J.R. and Bultman, J.D., “Fouling Release Coatings,”Naval Engineers J., 92, 129–132 (1980).

    Article  Google Scholar 

  34. Moniz, W.B., Griffith, J.R., Brady, Jr., R.F., and Thompson, C.M., “Fluorinated Organic Polymers for Diverse Applications,”NRL Memorandum Report 5517, March 6, 1985.

  35. 21st Century Coatings, Inc., 1439 N. Great Neck Road, Virginia Beach, VA 23454; 757-496-9008; fax 757-496-9050.

  36. Brady, R.F., Jr., “Formulations and Field Performance of Fluorinated Polyurethane Coatings,” inOrganic Coatings for Corrosion Control, Bierwagen, G. P. (Ed.), ACS Symposium Series 689, American Chemical Society, Washington, D.C., Chap. 22, pp. 282–91, 1998.

    Chapter  Google Scholar 

  37. Bonafede, S.J. and Brady, R.F., Jr., “Compositional Effects on the Fouling Resistance of Fluorourethane Coatings,”Sur. Coat. Int., 81 (4), 181–185 (1998).

    Article  CAS  Google Scholar 

  38. Moore, G., Zhu, D.-W., Clark, G., Pellerite, M., Burton, C., Schmidt, D.L., and Coburn, C.E., “Water-Borne Crosslinkable Fluorochemical Coatings,Sur. Coat. Int., 79, 377 (1995)

    Google Scholar 

  39. Schmidt, D.L., DeKoven, B.M., Coburn, C.E., Potter, G.E., Meyers, G.F., and Fisher, D.A., “Characterization of a New Family of Non-Wettable, Non-Stick Surfaces,”Langmuir, 12, 518 (1996)

    Article  CAS  Google Scholar 

  40. Lin, J., Zhu, J., Swanson, D.R., and Milco, L., “Cross-Linking and Physical Characteristics of a Water-Based Nonstick Hydrophobic Coating,”Langmuir, 12, 6676–80 (1996).

    Article  CAS  Google Scholar 

  41. Brady, Jr., R.F., Bonafede, S.J., and Schmidt, D.L., “Self-Assembled Waterborne Fluoropolymer Coatings for Marine Fouling Resistance,”Sur. Coat. Int., in press (1999).

  42. Saroyan, J.R., Lindler, E., Dooley, C.A., and Bleile, H.R., “Barnacle Cement—Key to Second-Generation Antifouling Coatings,”Ind. Eng. Chem. Prod. Res. & Dev., 9, 123–28 (1970).

    Google Scholar 

  43. Bonafede, S.J., Pawlikowski, G.T., and Brady, R.F., Jr., “Macrofouling of Hydrocarbon Polymers which Contain Variable Proportions of Crystallinity,”Biofouling, 14, 1–14 (1999).

    Article  CAS  Google Scholar 

  44. Brady, Jr., R.F. and Pawlikowski, G.T. (to the Secretary of the Navy), “Robust Nontoxic Antifouling Polymers,” U.S. Patent 5,652,027 (July 29, 1997).

  45. Anon., “Surface Preparation Specification No. 10, Near-White Blast Cleaning,”Steel Structures Painting Manual, Keane, J.D. (Ed.), Steel Structures Painting Council, Pittsburgh, Vol. 2, pp. 47–48, 1982.

  46. Bullock, S., Johnston, E.E., Wilson, T., Gatenholm, P., and Wynne, K.J., “Surface Science of a Filled Polydimethylsiloxane-Based Alkoxysilane-Cured Elastomer: RTV-11,”J. Colloid Interfac. Sci., 210, 18–36 (1999).

    Article  CAS  Google Scholar 

  47. Adkins, J.D., Mera, A.E., Roe-Short, M.A., Pawlikowski, G.T., and Brady, R.F., Jr., “Novel Nontoxic Coatings Designed to Resist Marine Fouling,”Prog. Org. Coat., 29, 1–5 (1996).

    Article  CAS  Google Scholar 

  48. Brady, Jr., R.F. and Adkins, J.D., “Antifouling and Nonfouling Coatings for Sonar Dome Rubber Windows (SDRWs) and Sonar Rubber Domes (SRDs); Progress Report,” NRL Letter Report 6120–260, August 30, 1993.

  49. Lewis, J.A., Foster, T., and Brady, Jr., R.F., “Environmentally Acceptable Flexible Fouling Release or Prevention Coatings,”Final Report, TTCP MAT Group Assignment MAT-TP-6-O9, June 1997.

  50. Jones-Meehan, J., Cella, J., Montemarano, J.A., Swain, G.W., Wiebe, D., Meyer, A. and Baier, R.E., “Advanced Nontoxic Fouling Release Coatings,” Naval Research Laboratory Report NRL/PU/6110-99-388, July 27, 1999.

  51. Milne, A. and Callow, M.E., “Non-Biocidal Antifouling Processes,” in Smith, R. (Ed.), “Polymers in a Marine Environment,” London,Trans. Inst. Marine Eng. (C), 97, Conference 2, Paper 37, 229–33 (1985).

  52. Milne, A. (to The International Paint Company, Ltd.), “Anti-Fouling Marine Compositions,” U.S. Patent 4,025,693 (May 24, 1977)

  53. McLearie, J., Finnie, A.A., Andrews, A.F., Millichamp, I.S., and Milne, A. (to The International Paint Company, Ltd.), “Anti-Fouling Coating Compositions,” U.S. Patent 5,302,192 (April 12, 1994).

  54. Ghanem, N.A., El-Awady, N.I., El-Hamouly, W.S. and El-Awady, M.M., “New Approaches to Non-Toxic Antifouling Coatings for Ship-Hull Protection,”Journal of Coatings Technology,54, No. 684, 83–88 (1982).

    CAS  Google Scholar 

  55. Griffith, A.A., “The Phenomena of Rupture and Flow in Solids,”Philosophical Transactions of the Royal Society (London), A221, 163–198 (1921).

    Article  ADS  Google Scholar 

  56. Kinloch, A.J. and Young, R.J.,Fracture Behaviour of Polymers, Applied Science Publishers, London, 1983.

    Google Scholar 

  57. Kendall, K., “The Adhesion and Surface Energy of Elastic Solids,”J. Physics D: Appl. Phys., 4, 1186–1195 (1971).

    Article  ADS  Google Scholar 

  58. Brady, Jr., R.F. and Singer, I.L., “Mechanical Factors Favoring Release from Fouling Release Coatings,”Biofouling, in press (1999).

  59. Zisman, W.A., “Relation of the Equilibrium Contact Angle to Liquid and Solid Constitution,” in Gould, R.F. (Ed.),Contact Angle: Wettability and Adhesion, American Chemical Society, Washington, D.C.,Adv. Chem. Ser. 43, pp. 1–51 (1964).

    Google Scholar 

  60. Baier, R.E. and DePalma, V.A., “The Relation of the Internal Surface of Grafts to Thrombosis,” in Dale, W.A. (Ed.),Management of Occlusive Arterial Disease, Yearbook Medical Publishers, Chicago, pp. 147–163, 1971.

    Google Scholar 

  61. Brady, R.F., Jr., “Properties Which Influence Marine Fouling Resistance in Polymers Containing Silicon and Fluorine.”Prog. Org. Coat., 35, 31–35 (1999).

    Article  ADS  CAS  Google Scholar 

  62. Roland, C.M. and Ngai, K.L., “Segmental Relaxation in Poly(dimethylsiloxane),”Macromolecules, 29, 5747–50 (1996).

    Article  ADS  CAS  Google Scholar 

  63. Zhang Newby, B.-M., Chaudhury, M.K., and Brown, H.R., “Macroscopic Evidence of the Effect of Interfacial Slippage on Adhesion,”Science, 269, 1407–1409 (1995)

    Article  ADS  CAS  Google Scholar 

  64. Zhang Newby, B.-M. and Chaudhury, M.K., “Effect of Interfacial Slippage on Viscoelastic Adhesion,”Langmuir, 13, 1805–1809 (1997).

    Article  CAS  Google Scholar 

  65. Brady, R.F., Jr., “Fluoropolymers,”Chemistry in Britain, 26, 427–430 (1990).

    CAS  Google Scholar 

  66. Kohl, J.G. and Singer, I.L., “Pull-Off Behavior of Epoxy Bonded to Silicone Duplex Coatings,”Prog. Org. Coat., 36, 15–20 (1999).

    Article  CAS  Google Scholar 

  67. Swain, G.W., Schultz, M.P., Griffith, J.R. and Snyder, S., “The Relationship Between Barnacle and Pseudo-Barnacle Adhesion Measurements: A Method to Predict the Foul Release Properties of Silicones,” in Brady, R.F. Jr., and Park, Y. (Eds.),Proceedings, Workshop on Emerging Nonmetallic Materials for the Marine Environment, Office of Naval Research, Arlington, pp. 1–60 to 1–69 (1997).

    Google Scholar 

  68. Swain, G.W., Griffith, J.R., Bultman, J.D., and Vincent, H.L., “The Use of Barnacle Adhesion Measurements for the Field Evaluation of Non-Toxic Foul Release Surfaces,”Biofouling, 6, 105–114 (1992).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Additional information

Chemistry Div., Washington, D.C. 20375-5342.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Brady, R.F. Clean hulls without poisons: Devising and testing nontoxic marine coatings. Journal of Coatings Technology 72, 45–56 (2000). https://doi.org/10.1007/BF02698394

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02698394

Keywords

Navigation