Selective Metal Coordination in Antifouling Coatings

<p>Marine biofouling is the accumulation of biological material (e.g. microorganisms, soft- and hard-fouling organisms) on the surface of an object submerged in seawater, and it remains a worldwide problem for shipping industries. The fouling of ship hulls results in a reduction of speed and manoeuvrability due to frictional drag, as well as increased fuel consumption and accelerated corrosion, and the exorbitant expenses and losses of efficiency attributed to biofouling have prompted the development of antifouling coatings. Current antifouling paints use copper as a biocidal agent, but copper-based paints are increasingly being banned due to environmental concerns about the non-target effects of leached copper. This project aims to circumvent these concerns and tightening regulations via a revolutionary concept: the development of marine antifouling paints that incorporate Cu(II)-selective ligands to draw the biocidal ingredient (i.e. Cu(II)) from seawater. A multistage strategy emerged for the development of this technology. First, criteria were established for the project’s ideal ligand, and ligands were synthesised or selected based on these criteria. Second, the ligands were incorporated in coatings through covalent modification of the paint binder or additives. Third, methodology was developed and implemented to test each coating’s ability to coordinate and retain Cu(II), as well as its subsequent ability to prevent microfouling by marine bacteria. The suitability of two ligand classes was assessed: acylhydrazones and tetraaza macrocycles, specifically cyclen. Unlike the acylhydrazones, cyclen met the established criteria and was initially evaluated as a curing agent and/or surface-modifier in a two-pack epoxy system with resin Epikote™ 235. However, the Cu(II)-loading by these coatings was relatively low, being at most ~0.05% w/w, and the modification of silica, a common paint additive, with cyclen was explored as an alternative formulation route. The method for the functionalisation of silica with cyclen was optimised, and the maximum Cu(II)-loading achieved by the product was 2.60% w/w. The cyclen-functionalised silica was incorporated on the surface of an epoxy coating, and a bacterial adherence assay was developed to assess the cellular attachment of marine bacterium Vibrio harveyi to this coating, which was found to be undeterred. Yet, the development of the strategy and testing methodology by which the project’s goals may be achieved provides a solid foundation for future work.</p>

Selective Metal Coordination in Antifouling Coatings

<p>Marine biofouling is the accumulation of biological material (e.g. microorganisms, soft- and hard-fouling organisms) on the surface of an object submerged in seawater, and it remains a worldwide problem for shipping industries. The fouling of ship hulls results in a reduction of speed and manoeuvrability due to frictional drag, as well as increased fuel consumption and accelerated corrosion, and the exorbitant expenses and losses of efficiency attributed to biofouling have prompted the development of antifouling coatings. Current antifouling paints use copper as a biocidal agent, but copper-based paints are increasingly being banned due to environmental concerns about the non-target effects of leached copper. This project aims to circumvent these concerns and tightening regulations via a revolutionary concept: the development of marine antifouling paints that incorporate Cu(II)-selective ligands to draw the biocidal ingredient (i.e. Cu(II)) from seawater. A multistage strategy emerged for the development of this technology. First, criteria were established for the project’s ideal ligand, and ligands were synthesised or selected based on these criteria. Second, the ligands were incorporated in coatings through covalent modification of the paint binder or additives. Third, methodology was developed and implemented to test each coating’s ability to coordinate and retain Cu(II), as well as its subsequent ability to prevent microfouling by marine bacteria. The suitability of two ligand classes was assessed: acylhydrazones and tetraaza macrocycles, specifically cyclen. Unlike the acylhydrazones, cyclen met the established criteria and was initially evaluated as a curing agent and/or surface-modifier in a two-pack epoxy system with resin Epikote™ 235. However, the Cu(II)-loading by these coatings was relatively low, being at most ~0.05% w/w, and the modification of silica, a common paint additive, with cyclen was explored as an alternative formulation route. The method for the functionalisation of silica with cyclen was optimised, and the maximum Cu(II)-loading achieved by the product was 2.60% w/w. The cyclen-functionalised silica was incorporated on the surface of an epoxy coating, and a bacterial adherence assay was developed to assess the cellular attachment of marine bacterium Vibrio harveyi to this coating, which was found to be undeterred. Yet, the development of the strategy and testing methodology by which the project’s goals may be achieved provides a solid foundation for future work.</p>

Design and Preparation of PU/EP Blend Resin Grafted by Hydrophilic Molecular Segments

Film-forming resins, as carriers of antifouling coatings, play an essential role in the functional performance of coatings. With the gradual promotion of coatings in the field of marine antifouling, the preparation of film-forming resins containing hydrophilic chain segments is urgently needed to give full play to the functional and time-sensitive performance of antifouling coatings. In this paper, the single-ended isocyanate group (NCO) polyurethane (PU) prepolymer with hydrophilic chain segments was prepared and grafted onto an epoxy resin (EP) molecular chain to obtain the PU/EP grafted blend. Successful preparation of the PU/EP grafted blends was confirmed by infrared spectrum analysis. Simultaneously, the grafted blend was cured, and its hydrophilicity and mechanical properties were also tested. The results demonstrate that the grafted method can effectively improve the hydrophilicity of the film-forming resin while maintaining its mechanical properties. It can be concluded from the hydrophilic and mechanical properties of the materials that the comprehensive properties of PU/EP grafted blends are the best when the PU content is between 40% and 50%. The hanging plate test showed that the antifouling effect of the antifouling coating prepared by hydrophilic modified PU/EP film-forming resin was better than that of the traditional antifouling coating under the experimental conditions.

Nanoparticles in marine antifouling coatings: a case study

The problem of fouling of hydraulic structures, marine structures, ships and vessels has been acute since the beginning of the era of navigation. The formation of a biofilm of fouling reduces the speed of the vessel, worsens its controllability, increases fuel consumption, shortens the service life of hydraulic structures and increases the load on them. Many methods have been proposed to control fouling. One of the most promising coatings is considered to be based on the use of nanoparticles of biologically active metals and their oxides. The paper discusses various strategies for using nanoparticles to combat biofouling. The paper also presents preliminary results of a study of the antifouling efficiency of coatings modified with nanoparticles of metal oxides Fe-ZnO, ZnO, CuO. The study was carried out by exposing plates with experimental compositions at the sea test site in the Sevastopol Bay for a year, starting from August 2020. The species composition of a separate group of microperiphyton - microalgae - on plates with experimental coatings in the first two months of exposure, as well as the result of photographic fixation of the state of the surface of the plates from the point of view of macro-fouling, was investigated.

A Review of Biofouling of Ships’ Internal Seawater Systems

Internal seawater systems (ISS) are critical to the proper functioning of maritime vessels. Sea water is pumped on board ships for a broad array of uses, primarily for temperature control (e.g., engine and electrical systems), cooling capacity (e.g., air conditioners and refrigeration), and water provision (e.g., drinking, firefighting, steam, and ballast). Although sea water may spend only a brief period within ISS of a vessel, it can carry microorganisms and larval stages of macroorganisms throughout the system leading to biofouling accumulation that can impair system function or integrity. ISS can also act as a sub-vector of species translocations, potentially facilitating biological invasions. This review describes ships’ ISS with a focus on operational impacts of biofouling and current drivers and barriers associated with ISS biofouling management. As ISS internal components are difficult to access, reports and studies of ISS biofouling are uncommon and much of the dedicated literature is decades old. The impact of biofouling on ISS and vessel operations is based on increased surface roughness of pipework and equipment, restricted water flow, corrosion and subsequent component impingement, reduced surface functional efficiency, and potential contamination by pathogens that can affect human and aquatic animal health. Biofouling management is primarily achieved using antifouling coatings and marine growth prevention systems, but independent and accessible data on their efficacy in ISS remain limited. Further research is required to resolve the extent to which biofouling occurs in ISS of the modern commercial fleet and the efficacy of preventive systems. Such information can ultimately inform decisions to improve operational efficiency for vessel operators and ensure any biosecurity risks are appropriately managed.

Amphiphilic Polyphosphonate Copolymers as New Additives for PDMS-Based Antifouling Coatings

Poly(ethyl ethylene phosphonate)-based methacrylic copolymers containing polysiloxane methacrylate (SiMA) co-units are proposed as surface-active additives as alternative solutions to the more investigated polyzwitterionic and polyethylene glycol counterparts for the fabrication of novel PDMS-based coatings for marine antifouling applications. In particular, the same hydrophobic SiMA macromonomer was copolymerized with a methacrylate carrying a poly(ethyl ethylene phosphonate) (PEtEPMA), a phosphorylcholine (MPC), and a poly(ethylene glycol) (PEGMA) side chain to obtain non-water soluble copolymers with similar mole content of the different hydrophilic units. The hydrolysis of poly(ethyl ethylene phosphonate)-based polymers was also studied in conditions similar to those of the marine environment to investigate their potential as erodible films. Copolymers of the three classes were blended into a condensation cure PDMS matrix in two different loadings (10 and 20 wt%) to prepare the top-coat of three-layer films to be subjected to wettability analysis and bioassays with marine model organisms. Water contact angle measurements showed that all of the films underwent surface reconstruction upon prolonged immersion in water, becoming much more hydrophilic. Interestingly, the extent of surface modification appeared to be affected by the type of hydrophilic units, showing a tendency to increase according to the order PEGMA < MPC < PEtEPMA. Biological tests showed that Ficopomatus enigmaticus release was maximized on the most hydrophilic film containing 10 wt% of the PEtEP-based copolymer. Moreover, coatings with a 10 wt% loading of the copolymer performed better than those containing 20 wt% for the removal of both Ficopomatus and Navicula, independent from the copolymer nature.