Permeability of a Zinc-Methacrylate-Based Self-Polishing Copolymer for Use in Antifouling Coating Materials by Molecular Dynamics Simulations

Molecular dynamics simulations were used to investigate the solubility and permeability of H2O in a self-polishing copolymer (SPC) with two zinc methacrylate (ZMA) contents (Z2: 2 mol% ZMA; Z16: 16 mol% ZMA) and ethyl acrylate, methyl methacrylate, 2-methoxyethyl acrylate, and butyl acrylate as antifouling agents. Water was found to be more soluble in hydrated Z16 than Z2 because ZMA interacts strongly with H2O. In contrast, the diffusion coefficient of H2O in Z16 is lower than that of Z2 because H2O molecules are more constrained in the former due to strong ZMA/H2O interactions. Z16 was found to be significantly more permeable than Z2 over time. The SPC hydrated region in Z2 tends to expand toward the SPC region, while the analogous region in Z16 swelled toward both the SPC and H2O regions to leach SPC owing to the higher permeation of H2O into the SPC. These results reveal that H2O permeability can be controlled by adjusting the ZMA content, which provides insight into antifouling performance.

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.

Nautical Tourism in Marine Protected Areas (MPAs): Evaluating an Impact of Copper Emission from Antifouling Coating

Copper (Cu) has a narrow range between optimal concentrations as a micronutrient critical for phytoplankton growth and concentrations potentially toxic to living organisms. This sensitivity indicates an ecosystem vulnerability that threatens not only nature but also human health due to bioaccumulation. An important source of elevated Cu concentrations in coastal environments are biocides used as antifouling protection on ships. A pilot study conducted in the Marine Protected Area (MPA) of the Krka Estuary (Croatia) over a period of 16 months investigated the relationship between ship traffic and Cu concentrations. The aim was to contribute to more informed environmental management by assessing the associated risks. In the study presented here, Cu concentrations were monitored, analyzed, and correlated with vessel traffic. Observations revealed that the seasonal increase in maritime traffic caused by nautical tourism was associated with an increase in Cu concentrations of more than five times, posing a toxicity risk to the environment. In order to understand the distribution of copper emissions, a mapping of maritime traffic was carried out by counting transits, radar imagery, and drone photography. This approach has proven sufficient to identify the potential risks to the marine environment and human health, thus providing an effective assessment tool for marine stakeholders.

Imparting Strong Antifouling Properties to the Transparent PVB Coating through the Zwitterionic Compound Condensation

Fouling is a ubiquitous and longstanding challenge that causes both economic and environmental problems, especially for underwater detection equipment, as fouling directly limits the normal services and functions of such equipment. Therefore, it is necessary to develop coatings with high transparency and good antifouling performance. Herein, a novel zwitterion compound was synthesized, and an antifouling coating with excellent comprehensive properties was prepared by integrating 3-[[3-(triethoxysilyl)-propyl] amino] propane-1-sulfonic acid (TPAPS) into polyvinyl butyral (PVB) polymer, which possesses excellent mechanical properties and transparency. The physical and chemical, mechanical, and antifouling properties, and the light transmittance of the coating were characterized by the SEM, FT-IR, XPS, UV-VIS. The results show that the coating had good mechanical properties and adhesion to the substrate, and the strong hydration ability of TPAPS endowed the coating with excellent resistance to oil stains and biofouling. More importantly, the structure of the coating was homogenous and its surface roughness was very little, which imparted the coating with high transmittance. This research provides a facile approach for synthesizing high-transparency materials with excellent antifouling and mechanical properties.

The Interfacial Structure and Adhesion Mechanism of N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane and Epoxy Modified Silicone Tie-Coating to Epoxy Primer

The matching application of silicone antifouling coating and epoxy primer is a major problem in engineering. Novel epoxy-modified silicone tie-coating was prepared to tie epoxy primer and silicone antifouling coating. Firstly, N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane was mechanically mixed with bisphenol A epoxy resin to form silylated epoxy resin, then the silylated epoxy resin was uniformly mixed with hydroxy-terminated polydimethylsiloxane and a curing agent and catalyst for coating. An infrared spectrometer, differential scanning calorimeter and tensile tests were used to investigate the chemical structure, phase transition temperature and mechanical properties of the tie-coatings. The interlaminar adhesion of the matching coating system was tested and analyzed by a peel-off test and a shear test. Fracture morphology was observed by scanning using an electron microscope. The results showed that crosslinking density of the tie-coating, the elastic modulus and the tensile strength of the coating increased with an increasing epoxy content, but fracture elongation decreased. The shear strength of the matching coating system is 0.37 MPa, and it shows a good tie performance. The maximum anti-peeling rate of the tie-coating on the epoxy primer reaches 100%.

The Development of Polydimethysiloxane/ZnO–GO Antifouling Coatings

The development of antifouling coating for sensor is desirable because the biofilm can shorten sensor’s life and cause inaccurate reading. In this study, a facile one-pot reaction was used to synthesized ZnO–graphene oxide (GO) (ZnO–GO) nanocomposites. Different amount of ZnO–GO was incorporated in the polydimethylsiloxane (PDMS) matrix respectively though a simple solution mixing method, in order to create PDMS/ZnO–GO nanocomposite (PZGO). The coating was obtained directly by spin coating of PZGO/tetrahydrofuran suspension. The hydrophobicity, surface roughness (Ra), surface free-energy (SFE) and nanoscale structure were investigated as antifouling factors. Antifouling tests were performed using two marine microorganisms, the cyanobacterium Synechococcus sp. Strain PCC 7002 and the diatom Phaeodactylum tricornutum. PZGO0.2 (mass ratio of ZnO–GO to PDMS: 0.2 wt%) displayed excellent antifouling property with 8.5% of Synechococcus sp. Strain PCC 7002 biofilm coverage, while PZGO0.1 (mass ratio of ZnO–GO to PDMS: 0.1 wt%) showed 2.4% P. tricornutum biofilm coverage. The antifouling property of the synthesized PZGO nanocomposite can be attributed to its high Ra and hydrophobicity which was caused by the good dispersion of ZnO–GO in PDMS matrix. This study suggests a potential of PZGO nanocomposite for sensor’s antifouling coating, which could contribute to improve sensor’s durability relating to biofouling in future. Graphic Abstract

Composite Slow-Release Fouling Release Coating Inspired by Synergistic Anti-Fouling Effect of Scaly Fish

Inspired by the antifouling properties of scaly fish, the conventional silicone coating with phenylmethylsilicone oil (PSO/PDMS) composite coating was fabricated and modified with single layer polystyrene (PS) microsphere (PSO/PDMS-PS) arrays. The fish scale like micro-nano structures were fabricated on the surface of bio-inspired coating, which can reduce the contact area with the secreted protein membrane of fouling organisms effectively and prevent further adhesion between fouling organisms and bio-inspired coating. Meanwhile, PSO exuded to the coating surface has the similar function with mucus secreted by fish epidermis, which make the coating surface slithery and will be polished with the fouling organisms in turbulent waters. Compared to PSO/PDMS coating without any structure and conventional silicone coating, PSO/PDMS-PS showed better antiadhesion activity against both marine bacteria and benthic diatom (Navicula sp.). Additionally, the existence of PS microspheres can reduce the release rate of PSO greatly, which will extend the service life of coating. Compared to PSO/PDMS coating, the sustained release efficiency of PSO/PDMS-PS coating can reach 23.2%. This facile method for fabricating the bio-inspired composite slow-release antifouling coating shows a widely fabricating path for the development of synergistic anti-fouling coating.