Properties and antifouling performance of fabricated polymers containing copper thiocyanate

Krishnamurthy Prasad; Richard F. Piola; Jitraporn Vongsvivut; Hareem Khan; Paul J. Molino; Dominic J. Hare; Nisa V. Salim; Nishar Hameed

doi:10.1071/CH24162

RESEARCH ARTICLE (Open Access)

Properties and antifouling performance of fabricated polymers containing copper thiocyanate

Krishnamurthy Prasad ^A , Richard F. Piola ^B , Jitraporn Vongsvivut ^C , Hareem Khan ^D , Paul J. Molino ^D , Dominic J. Hare

^D , Nisa V. Salim ^A and Nishar Hameed ^A ^D ^*

+ Author Affiliations

- Author Affiliations

^A School of Engineering, Swinburne University of Technology, John Street, Hawthorn, Vic. 3122, Australia.

^B Australian Submarine Agency, Fishermans Bend, Vic., Australia.

^C Infrared Microspectroscopy Beamline, ANSTO‒Australian Synchrotron, Clayton, Vic., Australia.

^D Defence Science and Technology Group, Fishermans Bend, Vic., Australia.

^* Correspondence to: nisharhameed@swin.edu.au

Handling Editor: John Wade

Australian Journal of Chemistry 78, CH24162 https://doi.org/10.1071/CH24162

Submitted: 7 November 2024 Accepted: 20 December 2024 Published online: 31 January 2025

© 2025 The Author(s) (or their employer(s)). Published by CSIRO Publishing. This is an open access article distributed under the Creative Commons Attribution-NonCommercial-No Derivatives 4.0 International License (CC BY-NC-ND)

Abstract

Fouling of subsurface structures by micro and macro-organisms is a centuries-old problem that can be better managed by the use of multi-functional materials and modern fabrication techniques. Copper(I) thiocyanate, or CuTC, is a common coordination polymer that reduces the adherence and growth of marine organisms on underwater surfaces used as a paint additive. Test samples of polymers that contained up to 20% (w/w) CuTC were fabricated using two methods: a two-part epoxy system, cast into moulds and cured at room temperature; and stereolithography, a 3-D printing technique that uses UV light to set designs additively manufactured from a single part urethane resin. Fabricated materials were extensively characterised by advanced X-ray diffraction (XRD), scanning electron microscopy (SEM) and polarised synchrotron Fourier transform infrared (S-FTIR) microspectroscopy, which together revealed distinct molecular networking structures within the added chemical biocide that depended on the manufacturing method used. Performance was tested over a 3-month deployment, which showed marked differences in the effectiveness of the fabricated material types in resisting fouling by aquatic organisms in a static estuarine environment. These differences are attributable to distinct physical and chemical properties of the test materials imparted upon them by the fabrication method, all of which are areas for further investigation in the development of manufactured fouling-resistant polymers for use in marine environments.

Keywords: antifouling, antimicrobial, composite materials, copper thiocyanate, fouling-resistant materials, marine fouling, metal–organic frameworks, stereolithography, synchrotron Fourier transform infrared microspectroscopy.

References

1 Garibay-Valdez E, Martínez-Córdova LR, Vargas-Albores F, Emerenciano MGC, Miranda-Baeza A, Cortés-Jacinto E, Ortiz-Estrada ÁM, Cicala F, Martínez-Porchas M. The biofouling process: the science behind a valuable phenomenon for aquaculture. Rev Aquac 2023; 15: 976-990.
| Crossref | Google Scholar |

2 Dürr S, Thomason JC. Biofouling. Blackwell Publishing Ltd; 2010. 10.1002/9781444315462

3 Amara I, Miled W, Slama RB, Ladhari N. Antifouling processes and toxicity effects of antifouling paints on marine environment. A review. Environ Toxicol Pharmacol 2018; 57: 115-130.
| Crossref | Google Scholar | PubMed |

4 Qian P-Y, Cheng A, Wang R, Zhang R. Marine biofilms: diversity, interactions and biofouling. Nat Rev Microbiol 2022; 20: 671-684.
| Crossref | Google Scholar | PubMed |

5 Weber F, Esmaeili N. Marine biofouling and the role of biocidal coatings in balancing environmental impacts. Biofouling 2023; 39: 661-681.
| Crossref | Google Scholar | PubMed |

6 Pistone A, Scolaro C, Visco A. Mechanical properties of protective coatings against marine fouling: a review. Polymers 2021; 13: 173.
| Crossref | Google Scholar | PubMed |

7 Chen L, Duan Y, Cui M, Huang R, Su R, Qi W, He Z. Biomimetic surface coatings for marine antifouling: natural antifoulants, synthetic polymers and surface microtopography. Sci Total Environ 2021; 766: 144469.
| Crossref | Google Scholar | PubMed |

8 Jin H, Tian L, Bing W, Zhao J, Ren L. Toward the application of graphene for combating marine biofouling. Adv Sustain Syst 2021; 5: 2000076.
| Crossref | Google Scholar |

9 Wei T, Tang Z, Yu Q, Chen H. Smart antibacterial surfaces with switchable bacteria-killing and bacteria-releasing capabilities. ACS Appl Mater Interfaces 2017; 9: 37511-37523.
| Crossref | Google Scholar | PubMed |

10 Paz-Villarraga CA, Castro ÍB, Fillmann G. Biocides in antifouling paint formulations currently registered for use. Environ Sci Pollut Res Int 2022; 29: 30090-30101.
| Crossref | Google Scholar | PubMed |

11 Thomas KV, Brooks S. The environmental fate and effects of antifouling paint biocides. Biofouling 2010; 26: 73-88.
| Crossref | Google Scholar | PubMed |

12 Salah I, Parkin IP, Allan E. Copper as an antimicrobial agent: recent advances. RSC Adv 2021; 11: 18179-18186.
| Crossref | Google Scholar | PubMed |

13 Faÿ F, Horel G, Linossier I, Vallée-Réhel K. Effect of biocidal coatings on microfouling: in vitro and in situ results. Prog Org Coat 2018; 114: 162-172.
| Crossref | Google Scholar |

14 Sandberg J, Wallinder IO, Leygraf C, Virta M. Release and chemical speciation of copper from anti-fouling paints with different active copper compounds in artificial seawater. Mater Corros 2007; 58: 165-172.
| Crossref | Google Scholar |

15 Mohammed JS. Applications of 3D printing technologies in oceanography. Methods Oceanog 2016; 17: 97-117.
| Crossref | Google Scholar |

16 Peterson E. Recent innovations in additive manufacturing for marine vessels. Marit Technol Res 2022; 4: 257491.
| Crossref | Google Scholar |

17 Garrido J, Sáez J, Armesto JI, Espada AM, Silva D, Goikoetxea J, Arrillaga A, Lekube B. 3D Printing as an enabling technology to implement maritime plastic circular economy. Procedia Manuf 2020; 51: 635-641.
| Crossref | Google Scholar |

18 Ziółkowski M, Dyl T. Possible applications of additive manufacturing technologies in shipbuilding: a review. Machines 2020; 8: 84.
| Crossref | Google Scholar |

19 Ryley M, Carve M, Piola R, Scardino AJ, Shimeta J. Comparison of biofouling on 3D-printing materials in the marine environment. Int Biodeterior Biodegradation 2021; 164: 105293.
| Crossref | Google Scholar |

20 Vongsvivut J, Pérez-Guaita D, Wood BR, Heraud P, Khambatta K, Hartnell D, Hackett MJ, Tobin MJ. Synchrotron macro ATR-FTIR microspectroscopy for high-resolution chemical mapping of single cells. Analyst 2019; 144: 3226-3238.
| Crossref | Google Scholar | PubMed |

21 Al-Qatatsheh A, Vongsvivut J, Juodkazis S, Salim NV, Hameed N. Rapidly cured multifunctional epoxy resins with switchable curing temperature and exceptional electrical properties. Adv Mater Technol 2023; 8: 2202028.
| Crossref | Google Scholar |

22 Jahromi FT, Nikzad M, Prasad K, Norén J, Isaksson M, Arian A, Sbarski I. Additive manufacturing of polypropylene micro and nano composites through fused filament fabrication for automotive repair applications. Polym Adv Tech 2023; 34: 1059-1074.
| Crossref | Google Scholar |

23 Bureau of Meteorology. Thursday, 1 June 2023 – monthly climate summary for Greater Melbourne – product code IDCKGC16L0. Canberra, ACT, Australia: Bureau of Meteorology, Australian Government; 2023. Available at http://www.bom.gov.au/climate/current/month/vic/archive/202305.melbourne.shtml

24 Bureau of Meteorology. Saturday, 1 July 2023 – monthly climate summary for Greater Melbourne – product code IDCKGC16L0. Canberra, ACT, Australia: Bureau of Meteorology, Australian Government; 2023. Available at http://www.bom.gov.au/climate/current/month/vic/archive/202306.melbourne.shtml

25 Bureau of Meteorology. Tuesday, 1 August 2023 – monthly climate summary for Greater Melbourne – product code IDCKGC16L0. Canberra, ACT, Australia: Bureau of Meteorology, Australian Government; 2023. Available at http://www.bom.gov.au/climate/current/month/vic/archive/202307.melbourne.shtml

26 Er U, Icli KC, Ozenbas M. Spin-coated copper(I) thiocyanate as a hole transport layer for perovskite solar cells. J Solid State Electrochem 2020; 24: 293-304.
| Crossref | Google Scholar |

27 Yang M, Zhu J-J, Li J-J. Synthesis and characterizations of porous spherical CuSCN nanoparticles. Mater Lett 2005; 59: 842-845.
| Crossref | Google Scholar |

28 Toeniskoetter RH, Solomon S. Infrared spectra of copper thiocyanate complexes. Inorg Chem 1968; 7: 617-620.
| Crossref | Google Scholar |

29 Kabešová M, Dunaj-jurčo M, Serator M, Gažo J, Garaj J. The crystal structure of copper(I) thiocyanate and its relation to the crystal structure of copper(II) diammine dithiocyanate complex. Inorganica Chim Acta 1976; 17: 161-165.
| Crossref | Google Scholar |

30 Vincent M, Duval RE, Hartemann P, Engels-Deutsch M. Contact killing and antimicrobial properties of copper. J Appl Microbiol 2018; 124: 1032-1046.
| Crossref | Google Scholar | PubMed |

31 Miller KM, McCullough SM, Lepekhina EA, Thibau IJ, Pike RD, Li X, Killarney JP, Patterson HH. Copper(I) thiocyanate-amine networks: synthesis, structure, and luminescence behavior. Inorg Chem 2011; 50: 7239-7249.
| Crossref | Google Scholar | PubMed |

32 Iqbal N, Wang X, Yu J, Jabeen N, Ullah H, Ding B. In situ synthesis of carbon nanotube doped metal–organic frameworks for CO₂ capture. RSC Adv 2015; 6: 4382-4386.
| Crossref | Google Scholar |

33 Bowmaker GA, Hanna JV. IR Spectroscopy of two polymorphs of copper(I) thiocyanate and of complexes of copper(I) thiocyanate with thiourea and ethylenethiourea. Z Naturforsch B 2009; 64: 1478-1486.
| Crossref | Google Scholar |

34 Stanila A, Marcu A, Rusu D, Rusu M, David L. Spectroscopic studies of some copper(II) complexes with amino acids. J Molec Struct 2007; 834: 364-368.
| Crossref | Google Scholar |