Journal of Materials Engineering and Performance

, Volume 27, Issue 11, pp 5947–5963 | Cite as

Antifouling Properties and Release of Dissolved Copper of Cold Spray Cu/Cu2O Coatings for Ships and Steel Structures in Marine Environment

  • Rui DingEmail author
  • Xiangbo Li
  • Jia Wang
  • Weihua Li
  • Xiao Wang
  • Taijiang Gui


At the submarine screen doors of ships, the flow of water was fast and organic coatings were easy to peel off. To solve the problems of biofouling, the Cu/Cu2O coatings were prepared by cold spray technology. In this paper, the release mechanism of effective antifouling components of the coatings was studied by micro-domain electrochemical potential scanning technique. Cuprous oxide in the coatings and the surrounding copper constituted micro-cells which accelerated the local electrochemical dissolution of copper. Cuprous oxide acted as the cathode, and the surrounding copper acted as the anode. Meanwhile, under the action of current, chloride ions were transferred from cathode to the anode and promoted local electrochemical dissolution of copper. Experiments show that the higher the Cu2O content in the coatings, the greater the release rate of dissolved copper and inhibitory effect on diatoms. In the environments varied in dissolved oxygen, salinity, temperature and flow rate, the coatings maintained sufficient release rate of dissolved copper, unless the salinity was very low. Most of the dissolved copper was provided by the electrochemical dissolution process of copper. Whether in the indoor test or marine environment experiments, 30% Cu2O coatings show the best performance. After insulating layer was sprayed, the effect of antifouling was improved evidently and the coatings were applied to the submarine screen doors of ships.


antifouling cold spray copper corrosion galvanic cuprous oxide 



The project was achieved with the China Postdoctoral Science Fund, Grand No. 2018M632726, Qingdao Independent Innovation Special Project, Grant No. 16-7-1-2-ZDZXX, National Science Fund for Distinguished Young Scholars, Grand No. 51525903, AoShan talents cultivation program supported by Qingdao National Laboratory for Marine Science and Technology, Grant No. 2017ASTCP-OS09.


  1. 1.
    I. Davidson, C. Scianni, C. Hewitt, R. Everett, E. Holm, M. Tamburri, and G. Ruiz, Mini-Review: Assessing the Drivers of Ship Biofouling Management—Aligning Industry and Biosecurity Goals, Biofouling, 2016, 32(4), p 411–428CrossRefGoogle Scholar
  2. 2.
    Y.K. Demirel, D. Uzun, Y. Zhang, H.-C. Fang, A.H. Day, and O. Turan, Effect of Barnacle Fouling on Ship Resistance and Powering, Biofouling, 2017, 33, p 1–16CrossRefGoogle Scholar
  3. 3.
    J. Monty, E. Dogan, R. Hanson, A. Scardino, B. Ganapathisubramani, and N. Hutchins, An Assessment of the Ship Drag Penalty Arising from Light Calcareous Tubeworm Fouling, Biofouling, 2016, 32(4), p 451–464CrossRefGoogle Scholar
  4. 4.
    X. Li, G. Zhu, L. Dong, C. Ni, X. Yan, and L. Yu, Synthesis, Crystal Structure, and Theoretical Calculation of the Cu(II) Complex With 1,2-Benzisothiazolin-3-One, Synth. React. Inorg. Met. Org. Chem., 2016, 46(5), p 659–664CrossRefGoogle Scholar
  5. 5.
    G. Zhu, L. Yu, X. Li, S. Xia, and X. Yan, Synthesis, Crystal Structure, and Theoretical Calculation of the Cu (II) Complex with 2-Furoic Acid, Synth. React. Inorg. Met. Org. Chem., 2014, 44(7), p 1054–1058CrossRefGoogle Scholar
  6. 6.
    Y. Liu, X. Suo, Z. Wang, Y. Gong, X. Wang, and H. Li, Developing Polyimide-Copper Antifouling Coatings with Capsule Structures for Sustainable Release of Copper, Mater. Des., 2017, 130, p 285–293CrossRefGoogle Scholar
  7. 7.
    Y. Xiong, G. Wang, Z. Xie, Y. Li, A. Wang, and H. Jiang, Synthesis of Cu2O Hollow Microspheres and Its Application in Antifouling Materials, Paint Ind., 2017, 47(4), p 55–65Google Scholar
  8. 8.
    H. Gao, L. Yu, J. Zhao, and J. Sui, Preparation of Nanometer Cuprous Oxide and Its Application in Antifouling Coatings, Shanghai Coat., 2008, 46(12), p 30–33Google Scholar
  9. 9.
    J. Sui, Study on Preparation of Ultrafine Cuprous Oxide and Its Modification, Ocean University of China, Qingdao Shi, 2005Google Scholar
  10. 10.
    V. Champagne and D. Helfritch, The Unique Abilities of Cold Spray Deposition, Int. Mater. Rev., 2016, 61(7), p 437–455CrossRefGoogle Scholar
  11. 11.
    M. Rokni, S. Nutt, C. Widener, V. Champagne, and R. Hrabe, Review of Relationship Between Particle Deformation, Coating Microstructure, and Properties in High-Pressure Cold Spray, J. Therm. Spray Technol., 2017, 26(6), p 1308–1355CrossRefGoogle Scholar
  12. 12.
    A. Sova, R. Maestracci, M. Jeandin, P. Bertrand, and I. Smurov, Kinetics of Composite Coating Formation Process in Cold Spray: Modelling And Experimental Validation, Surf. Coat. Technol., 2017, 318, p 309–314CrossRefGoogle Scholar
  13. 13.
    D. Rui, L. Xiangbo, W. Jia, and X. Likun, Electrochemical Corrosion and Mathematical Model of Cold Spray Cu-Cu2O Coating in NaCl Solution—Part I: Tafel Polarization Region Model, Int. J. Electrochem. Sci., 2013, 8, p 5902–5924Google Scholar
  14. 14.
    D. Rui, H. Yu, and X. Li, Electrochemical Corrosion and Mathematical Model of Cold Spray Copper Composite Coating—Part II: Limiting Current Region, Int. J. Electrochem. Sci., 2017, 12(2), p 1232–1246CrossRefGoogle Scholar
  15. 15.
    C. Stenson, K.A. Mcdonnell, S. Yin, B. Aldwell, M. Meyer, D.P. Dowling, and R. Lupoi, Cold Spray Deposition to Prevent Fouling of Polymer Surfaces, Surf. Eng., 2016, 1, p 1–11Google Scholar
  16. 16.
    R. Lupoi, C. Stenson, K.A. Mcdonnell, D.P. Dowling, and E. Ahearne, Antifouling Coatings Made with Cold Spray onto Polymers: Process Characterization, CIRP Ann. Manuf. Technol., 2016, 65(1), p 545–548CrossRefGoogle Scholar
  17. 17.
    R. Ding, Study on Preparation, Anticorrosion and Antifouling Properties of Copper Composite Coatings Prepared by Cold Spray Technology, Ocean University of China, Qingdao Shi, 2014Google Scholar
  18. 18.
    Y. Hou, L. Xu, C. Shen, and X. Li, Electrochemical Characterization for Corrosion Resistance of Plasma-Sprayed Cr2O3 Coating with Sealing, J. Chin. Soc. Corros. Prot., 2012, 32(6), p 473–477Google Scholar
  19. 19.
    O. Andrews, E. Buitenhuis, C. Le Quéré, and P. Suntharalingam, Biogeochemical Modelling of Dissolved Oxygen in a Changing Ocean, Philos. Trans. R. Soc. A, 2017, 375(2102), p 20160328CrossRefGoogle Scholar
  20. 20.
    A. Hameau, F. Joos, J. Mignot, K. Keller, Variability of dissolved oxygen over the last millennium and the 21st century in CESM, in EGU General Assembly Conference Abstracts (2017), p. 14031Google Scholar
  21. 21.
    L. Stramma, S. Schmidtko, M. Visbeck, Deoxygenation of the ocean, in Goldschmidt Conference (2017), p 13–18Google Scholar
  22. 22.
    M. Benallal, H. Moussa, F. Touratier, C. Goyet, and A. Poisson, Ocean Salinity from Satellite-Derived Temperature in the Antarctic Ocean, Antarct. Sci., 2016, 28(2), p 127–134CrossRefGoogle Scholar
  23. 23.
    M. Munnich, A. Haumann, S. Eberenz, N. Gruber, Modeling the Influence of Land and Sea Ice on Southern Ocean Salinity and its Recent Trends, AGU Fall Meeting Abstracts (2016)Google Scholar
  24. 24.
    J. Scott, T. Meissner, F. Wentz, Ocean Surface Salinity from the SMAP Sensor, American Geophysical Union, Ocean Sciences Meeting 2016, abstract# PO44E-3212 (2016)Google Scholar
  25. 25.
    B. Bereiter, J. Severinghaus, S. Shackleton, D. Baggenstos, K. Kawamura, Mean ocean temperature change over the last glacial transition based on heavy noble gases in the atmosphere, in EGU General Assembly Conference Abstracts (2017), p. 5247Google Scholar
  26. 26.
    S.A. Keith, J.A. Maynard, A.J. Edwards, J.R. Guest, A.G. Bauman, R. Van Hooidonk, S.F. Heron, M.L. Berumen, J. Bouwmeester, S. Piromvaragorn, Coral mass spawning predicted by rapid seasonal rise in ocean temperature, in Proceedings of Royal Society B. The Royal Society (2016), p. 20160011Google Scholar
  27. 27.
    G.C. Hays, Ocean Currents and Marine Life, Curr. Biol., 2017, 27(11), p R470–R473CrossRefGoogle Scholar
  28. 28.
    E. Wolbrecht, J. Osborn, S. Qualls, R. Ross, J. Canning, M. Anderson, D. Edwards, Estimating and compensating for water currents: field testing, in OCEANS 2016 MTS/IEEE Monterey (IEEE, 2016), pp. 1–5Google Scholar
  29. 29.
    H. Yanfeng, X. Likun, S. Chengjin, and L. Xiangbo, Electrochemical Characterization for Corrosion Resistance of Plasma-Sprayed Cr2O3 Coating with Sealing, J. Chin. Soc. Corros. Prot., 2012, 32(6), p 473–477Google Scholar
  30. 30.
    Inspection and Quarantine of PRC. General administration of quality supervision, Standardization administration of the People’s Republic of China, “Method for Testing Antifouling Panels in Shallow Submergence,” GB/T 5370-2007, Standardization administration of the People’s Republic of China (2007)Google Scholar
  31. 31.
    Inspection and Quarantine of PRC. General administration of quality supervision, Standardization administration of the People’s Republic of China, “Determination for release rate of cupper ions for antifouling paints on ship bottoms,” GB/T 6824-2008, Standardization administration of the People’s Republic of China (2008)Google Scholar
  32. 32.
    A. Lotz, Marine Coatings: Making Sense of US, State, and Local Mandates of Copper-Based Antifouling Regulations, JCT CoatingsTech, 2016, 13(9), p 50–54Google Scholar
  33. 33.
    M. Tribou and G. Swain, The Effects of Grooming on a Copper Ablative Coating: A Six Year Study, Biofouling, 2017, 33(6), p 494–504CrossRefGoogle Scholar
  34. 34.
    A. Moridi, S. Hassani-Gangaraj, M. Guagliano, and M. Dao, Cold Spray Coating: Review of Material Systems and Future Perspectives, Surf. Eng., 2014, 30(6), p 369–395CrossRefGoogle Scholar
  35. 35.
    G. Burstein, H. Bi, and G. Kawaley, The Persistence of Inhibition of Copper Corrosion in Tap Water, Electrochim. Acta, 2016, 191, p 247–255CrossRefGoogle Scholar
  36. 36.
    R.J. Ferguson, Modeling Lead and Copper Corrosion and Solubility in Municipal Water Distribution Systems, CORROSION 2017, 2017, NACE InternationalGoogle Scholar
  37. 37.
    J. Wu, L. Wang, P. Liu, Y. Liu, B. Chen, Z. Tao, W. He, Electrochemical investigation of thiourea as corrosion inhibitor for copper in acidic solution, in AIP Conference Proceedings (AIP Publishing, 2017), p 020047Google Scholar
  38. 38.
    D. Chandran, H.K. Ng, H.L.N. Lau, S. Gan, and Y.M. Choo, Investigation of the Effects of Palm Biodiesel Dissolved Oxygen and Conductivity on Metal Corrosion and Elastomer Degradation Under Novel Immersion Method, Appl. Therm. Eng., 2016, 104, p 294–308CrossRefGoogle Scholar
  39. 39.
    C. Demuth, J. Varonier, V. Jossen, R. Eibl, and D. Eibl, Novel Probes for pH and Dissolved Oxygen Measurements in Cultivations from Millilitre to Benchtop Scale, Appl. Microbiol. Biotechnol., 2016, 100(9), p 3853–3863CrossRefGoogle Scholar
  40. 40.
    H. Bi, G. Burstein, B. Rodriguez, and G. Kawaley, Some Aspects of the Role of Inhibitors in the Corrosion of Copper in Tap Water as Observed by Cyclic Voltammetry, Corros. Sci., 2016, 102, p 510–516CrossRefGoogle Scholar
  41. 41.
    P. Broadbridge, B. Bradshaw-Hajek, D. Triadis, Exact non-classical symmetry solutions of Arrhenius reaction–diffusion, in Proceedings of the Royal Society A (The Royal Society, 2015), p. 20150580Google Scholar
  42. 42.
    G. Hultquist, M. Graham, O. Kodra, S. Moisa, R. Liu, U. Bexell, J. Smialek, Corrosion of copper in distilled water without molecular oxygen and the detection of produced hydrogen. Strålsäkerhetsmyndigheten (2013)Google Scholar
  43. 43.
    G. Hultquist, M. Graham, J. Smialek, O. Kodra et al., Response to Comment by A. Hedin et al. on “Corrosion of Copper in Distilled Water Without Oxygen and the Detection of Produced Hydrogen, Corros. Sci., 2016, 106, p 306–307CrossRefGoogle Scholar
  44. 44.
    J.H. Michel, I. Richardson, C. Powell, B. Phull, Development of Copper Alloys for Seawater Service from Traditional Application to State-of-the Art Engineering, CORROSION 2017 (NACE International, 2017)Google Scholar
  45. 45.
    L. Wu, S. Hahn, C. Yan, Modeling of Evolution Process of Edge Over Erosion in Copper CMP Using Frequency Components Algorithm, in Semiconductor Technology International Conference (CSTIC), 2016 China (IEEE, 2016), pp. 1–3Google Scholar
  46. 46.
    C.H. Hsu and F. Mansfeld, Technical Note: Concerning the Conversion of the Constant Phase Element Parameter Y0 into a Capacitance, Corrosion, 2012, 57(9), p 747–748CrossRefGoogle Scholar
  47. 47.
    S.S. Vaghani, M.M. Patel, and C.S. Satish, Synthesis and Characterization of pH-Sensitive Hydrogel Composed of Carboxymethyl Chitosan for Colon Targeted Delivery of Ornidazole, Carbohyd. Res., 2012, 347(1), p 76CrossRefGoogle Scholar

Copyright information

© ASM International 2018

Authors and Affiliations

  • Rui Ding
    • 1
    • 3
    Email author
  • Xiangbo Li
    • 2
  • Jia Wang
    • 4
  • Weihua Li
    • 5
  • Xiao Wang
    • 6
  • Taijiang Gui
    • 6
  1. 1.College of OceanographyYantai UniversityYantaiChina
  2. 2.Science and Technology on Marine Corrosion and Protection LaboratoryLuoyang Ship Material Research Institute (LSRMI)QingdaoChina
  3. 3.Institute of OceanologyChinese Academy of ScienceQingdaoChina
  4. 4.Ocean University of ChinaQingdaoChina
  5. 5.College of Chemical Engineering and TechnologySun Yat-sen UniversityZhuhaiChina
  6. 6.Marine Chemical Research Institute, State Key Laboratory of Marine CoatingsQingdaoChina

Personalised recommendations