UV emitting glass: A promising strategy for biofilm inhibition on transparent surfaces.

Marine biofouling causes serious environmental problems and has adverse impacts on the maritime industry. Biofouling on windows and optical equipment reduces surface transparency, limiting their application for on-site monitoring or continuous measurement. This work illustrates that UV emitting glasses (UEGs) can prevent the establishment and growth of biofilm on the illuminated surfaces. Specifically, this paper describes how UEGs are enabled by innovatively modifying the surfaces of the glass with light scattering particles. Modification of glass surface with silica nanoparticles at a concentration 26.5 µg/cm2 resulted in over ten-fold increase in UV irradiance, while maintaining satisfactory visible and IR transparency metrics of over 99 %. The UEG reduced visible biological growth by 98 % and resulted in a decrease of 1.79 log in detected colony forming units when compared to the control during a 20 day submersion at Port Canaveral, Florida, United States. These findings serve as strong evidence that UV emitting glass should be explored as a promising approach for biofilm inhibition on transparent surfaces.

Measuring the recruitment and growth of biofouling communities using clear recruitment panels.

Ecological monitoring has been recognized as a key tool for guiding biofouling management practices. A two-year study was designed to collect comprehensive data on the biofouling community progression at Port Canaveral, Florida, using clear recruitment panels and a scanner to directly observe organisms attached to the surface. This method allowed for minimal disruption to the natural community development and aided the collection of a suite of metrics to explore environmental relationships. Seasonal changes in community composition and biofouling pressure, especially at earlier stages, were related to abiotic conditions. Interannual variation within seasonal communities was also observed. The type of dominant organism present impacted the rate at which surfaces were covered (e.g. fastest cover with tunicates) and the overall biomass accumulation (e.g. highest rate with tubeworms). Results highlight that understanding the influence of the time of year and the dominant organism identity is ecologically vital for improving biofouling management.

Investigating the Impacts of UVC Radiation on Natural and Cultured Biofilms: An assessment of Cell Viability.

Biofilms are conglomerates of cells, water, and extracellular polymeric substances which can lead to various functional and financial setbacks. As a result, there has been a drive towards more environmentally friendly antifouling methods, such as the use of ultraviolet C (UVC) radiation. When applying UVC radiation, it is important to understand how frequency, and thus dose, can influence an established biofilm. This study compares the impacts of varying doses of UVC radiation on both a monocultured biofilm consisting of Navicula incerta and field-developed biofilms. Both biofilms were exposed to doses of UVC radiation ranging from 1626.2 mJ/cm2 to 9757.2 mJ/cm2 and then treated with a live/dead assay. When exposed to UVC radiation, the N. incerta biofilms demonstrated a significant reduction in cell viability compared to the non-exposed samples, but all doses had similar viability results. The field biofilms were highly diverse, containing not only benthic diatoms but also planktonic species which may have led to inconsistencies. Although they are different from each other, these results provide beneficial data. Cultured biofilms provide insight into how diatom cells react to varying doses of UVC radiation, whereas the real-world heterogeneity of field biofilms is useful for determining the dosage needed to effectively prevent a biofilm. Both concepts are important when developing UVC radiation management plans that target established biofilms.

Semantic segmentation for fully automated macrofouling analysis on coatings after field exposure.

Biofouling is a major challenge for sustainable shipping, filter membranes, heat exchangers, and medical devices. The development of fouling-resistant coatings requires the evaluation of their effectiveness. Such an evaluation is usually based on the assessment of fouling progression after different exposure times to the target medium (e.g. salt water). The manual assessment of macrofouling requires expert knowledge about local fouling communities due to high variances in phenotypical appearance, has single-image sampling inaccuracies for certain species, and lacks spatial information. Here an approach for automatic image-based macrofouling analysis was presented. A dataset with dense labels prepared from field panel images was made and a convolutional network (adapted U-Net) for the semantic segmentation of different macrofouling classes was proposed. The establishment of macrofouling localization allows for the generation of a successional model which enables the determination of direct surface attachment and in-depth epibiotic studies.

On the mechanism of marine fouling-prevention performance of oil-containing silicone elastomers.

For many decades, silicone elastomers with oil incorporated have served as fouling-release coating for marine applications. In a comprehensive study involving a series of laboratory-based marine fouling assays and extensive global field studies of up to 2-year duration, we compare polydimethylsiloxane (PDMS) coatings of the same composition loaded with oil via two different methods. One method used a traditional, one-pot pre-cure oil addition approach (o-PDMS) and another method used a newer post-cure infusion approach (i-PDMS). The latter displays a substantial improvement in biofouling prevention performance that exceeds established commercial silicone-based fouling-release coating standards. We interpret the differences in performance between one-pot and infused PDMS by developing a mechanistic model based on the Flory-Rehner theory of swollen polymer networks. Using this model, we propose that the chemical potential of the incorporated oil is a key consideration for the design of future fouling-release coatings, as the improved performance is driven by the formation and stabilization of an anti-adhesion oil overlayer on the polymer surface.

Grooming of fouling-release coatings to control marine fouling and determining how grooming affects the surface.

Grooming may be an effective technique to control marine biofouling without damaging the coating or discharging active ingredients into the environment. This study assessed the grooming performance of three experimental biocide-free siloxane polyurethane (SiPU) fouling-release coatings. Coatings were statically immersed in Port Canaveral, Florida, and groomed every two weeks for five months using three different brush types. The ungroomed panels became heavily fouled with biofilm, tubeworms, barnacles, and bryozoans. Two of the brushes were able to control the fouling with a coverage of <5%. The commercial silicone elastomer coating was damaged from grooming procedures, while the SiPU coatings were not. Laboratory biological assays were carried out and mirrored the grooming results. Through surface characterization techniques, it was concluded that the coatings were unaffected by the grooming procedures. This study shows that marine fouling on durable SiPU fouling-release coatings can be controlled via grooming without damage or changing the surface properties.

Reduction of biofilm accumulation by constant and alternating potentials in static and dynamic field experiments.

The application of electric fields to conductive coatings is an environmentally friendly way to reduce biofilm formation. In particular alternating potentials (APs) have received increasing attention in recent studies. Here, an electrochemical rotating disk setup for dynamic field exposure experiments was developed to study how APs alter the attachment of fouling organisms in a multispecies ocean environment. A specific focus of the device design was proper integration of the potentiostat in the strongly corroding saltwater environment. The effect of APs on the accumulation of fouling organisms in short term field exposures was studied. Potentials on conductive gold surfaces were periodically switched between -0.3 V and 0.3 V or between -0.8 V and 0.6 V at a frequency of 0.5 Hz. APs were capable of significantly reducing the attachment of marine fouling organisms compared with the conductive samples immersed at open circuit potentials.

Low Fouling Polysulfobetaines with Variable Hydrophobic Content.

Amphiphilic polymer coatings combining hydrophilic elements, in particular zwitterionic groups, and hydrophobic elements comprise a promising strategy to decrease biofouling. However, the influence of the content of the hydrophobic component in zwitterionic coatings on the interfacial molecular reorganization dynamics and the anti-fouling performance is not well understood. Therefore, coatings of amphiphilic copolymers of sulfobetaine methacrylate 3-[N-2'-(methacryloyloxy)ethyl-N,N-dimethyl]-ammonio propane-1-sulfonate (SPE) are prepared which contain increasing amounts of hydrophobic n-butyl methacrylate (BMA). Their fouling resistance is compared to that of their homopolymers PSPE and PBMA. The photo-crosslinked coatings form hydrogel films with a hydrophilic surface. Fouling by the proteins fibrinogen and lysozyme as well as by the diatom Navicula perminuta and the green algae Ulva linza is assessed in laboratory assays. While biofouling is strongly reduced by all zwitterionic coatings, the best fouling resistance is obtained for the amphiphilic copolymers. Also in preliminary field tests, the anti-fouling performance of the amphiphilic copolymer films is superior to that of both homopolymers. When the coatings are exposed to a marine environment, the reduced susceptibility to silt incorporation, in particular compared to the most hydrophilic polyzwitterion PSPE, likely contributes to the improved fouling resistance.

Amphiphilic Zwitterionic Acrylate/Methacrylate Copolymers for Marine Fouling-Release Coatings.

Methacrylate and acrylate monomers are popular building blocks for antifouling (AF) and fouling-release (FR) coatings to counteract marine biofouling. They are used in various combinations and often combined into amphiphilic materials. This study investigated the FR properties of amphiphilic ethylene glycol dicyclopentenyl ether acrylate (DCPEA) and the corresponding methacrylate (DCPEMA) blended with 5 wt % zwitterionic carboxybetaine acrylate (CBA) and the corresponding methacrylate (CBMA). A series of (co)polymers with different acrylate/methacrylate compositions were synthesized and tested against the attachment of the diatom Navicula perminuta and in short-term dynamic field exposure experiments. The more hydrophobic methacrylate DCPEMA homopolymer outperformed its acrylate counterpart DCPEA. Incorporated zwitterionic functionality of both CBMA and CBA imparted ultralow fouling capability in the amphiphilic polymers toward diatom attachment, whereas in the real ocean environment, only the employment of CBMA reduced marine biofouling. Moreover, it was observed that CBA-containing coatings showed different surface morphologies and roughnesses compared to the CBMA analogues. Particularly, a high impact was found when acrylic CBA was mixed with methacrylic DCPEMA. While the wettability of the coatings was comparable, investigated methacrylates in general exhibited superior fouling resistance compared to the acrylates.

Synthesis and Characterization of Dendritic and Linear Glycol Methacrylates and Their Performance as Marine Antifouling Coatings.

Dendritic polyglycerol (PG) was covalently coupled to 2-hydroxyethyl methacrylate (HEMA) by an anionically catalyzed ring-opening polymerization generating a dendritic PG-HEMA with four PG repetition units (PG4MA). Coatings of the methacrylate monomer were prepared by grafting-through and compared against commercially available hydrophilic monomers of HEMA, poly(ethylene) glycol methacrylate (PEGMA), and poly(propylene) glycol methacrylate (PPGMA). The obtained coatings were characterized by modern surface analytical techniques, including water contact angle goniometry (sessile and captive bubble), attenuated total internal reflection Fourier transform infrared spectroscopy, and atomic force microscopy. The antifouling (AF) and fouling-release (FR) properties of the coatings were tested against the model organisms Cobetia marina and Navicula perminuta in laboratory-scale dynamic accumulation assays as well as in a dynamic short-term field exposure (DSFE) in the marine environment. In addition, the hydration of the coatings and their susceptibility toward silt uptake were evaluated, revealing a strong correlation between water uptake, silt incorporation, and field assay performance. While all glycol derivatives showed good resistance in laboratory settlement experiments, PPGMA turned out to be less susceptible to silt incorporation and outperformed PEGMA and PG4MA in the DSFE assay.

Sol-Gel-Based Hybrid Materials as Antifouling and Fouling-Release Coatings for Marine Applications.

Hybrid materials (HMs) offer unique properties as they combine inorganic and organic components into a single material. Here, we developed HM coatings for marine antifouling applications using sol-gel chemistry and naturally occurring polysaccharides. The coatings were characterized by spectroscopic ellipsometry, contact angle goniometry, AFM, and ATR-FTIR, and their stability was tested in saline media. Marine antifouling and fouling-release properties were tested in laboratory assays against the settlement of larvae of the barnacle Balanus improvisus and against the settlement and removal of the diatom Navicula incerta. Furthermore, laboratory data were confirmed in short-term dynamic field assays in Florida, USA. All hybrid coatings revealed a superior performance in the assays compared to a hydrophobic reference. Within the hybrids, those with the highest degree of hydrophilicity and negative net charge across the surface performed best. Alginate and heparin showed good performance, making these hybrid materials promising building blocks for fouling-resistant coatings.

Effects of crosslink density in zwitterionic hydrogel coatings on their antifouling performance and susceptibility to silt uptake.

Hydrogel coatings effectively reduce the attachment of proteins and organisms in laboratory assays, in particular when made from zwitterionic monomers. In field experiments with multiple species and non-living material, such coatings suffer from adsorption of particulate matter. In this study, the zwitterionic monomer 3-[N-(2-methacryloyloxyethyl)-N,N-dimethylammonio] propanesulfonate (SPE) was copolymerized with increasing amounts of the photo-crosslinker benzophenon-4-yloxyethyl methacrylate (BPEMA) to systematically alter the density of crosslinks between the polymer chains. The effect of increasing crosslink density on the antifouling (AF) performance of the coatings was investigated in laboratory assays and fields tests. In both cases, the AF performance was improved by increasing the crosslinker content. The coatings reduced protein, diatom, and barnacle accumulation, and showed better resistance to biomass accumulation. The findings underline that the marine AF performance of hydrogel coatings does not only depend on the specific chemical structure of the polymers, but also on their physico-chemical properties such as rigidity and swelling.

Amphiphilic Dicyclopentenyl/Carboxybetaine-Containing Copolymers for Marine Fouling-Release Applications.

Zwitterionic materials received great attention in recent studies due to their high antifouling potential, though their application in practical coatings is still challenging. Amphiphilic polymers have been proven to be an effective method to combat fouling in the marine environment. This study reports the incorporation of small amounts of zwitterionic carboxybetaine methacrylate (CBMA) into hydrophobic ethylene glycol dicyclopentenyl ether acrylate (DCPEA). A new set of copolymers with varying amphiphilicities was synthesized and coated on chemically modified glass substrates. The antifouling capabilities were assessed against the diatom Navicula perminuta and multiple species in the field. Unsurprisingly, high diatom densities were observed on the hydrophobic control coatings. The integration of small zwitterionic contents of only ∼5 wt % was already sufficient to rapidly form a hydrophilic interface that led to a strong reduction of fouling. Ultralow fouling was also observed for the pure zwitterionic coatings in laboratory experiments, but it failed when tested in the real ocean environment. We noticed that the ability to absorb large amounts of water and the diffuse nature of the interphase correlate with the adsorption of silt, which can mask the hydrophilic chemistries and facilitate the settlement of organisms. The amphiphilic coatings showed low fouling in dynamic short-term field exposures, which could be explained by the reduced tendency of the coatings for sediment adsorption.

Adhesion of acorn barnacles on surface-active borate glasses.

Concerns about the bioaccumulation of toxic antifouling compounds have necessitated the search for alternative strategies to combat marine biofouling. Because many biologically essential minerals have deleterious effects on organisms at high concentration, one approach to preventing the settlement of marine foulers is increasing the local concentration of ions that are naturally present in seawater. Here, we used surface-active borate glasses as a platform to directly deliver ions (Na+, Mg2+ and BO43-) to the adhesive interface under acorn barnacles (Amphibalanus (=Balanus) amphitrite). Additionally, surface-active glasses formed reaction layers at the glass-water interface, presenting another challenge to fouling organisms. Proteomics analysis showed that cement deposited on the gelatinous reaction layers is more soluble than cement deposited on insoluble glasses, indicating the reaction layer and/or released ions disrupted adhesion processes. Laboratory experiments showed that the majority (greater than 79%) of adult barnacles re-attached to silica-free borate glasses for 14 days could be released and, more importantly, barnacle larvae did not settle on the glasses. The formation of microbial biofilms in field tests diminished the performance of the materials. While periodic water jetting (120 psi) did not prevent the formation of biofilms, weekly cleaning did dramatically reduce macrofouling on magnesium aluminoborate glass to levels below a commercial foul-release coating. This article is part of the theme issue 'Transdisciplinary approaches to the study of adhesion and adhesives in biological systems'.

Using ultraviolet light for improved antifouling performance on ship hull coatings.

A two-part study was designed to investigate the efficacy of using UVC to prevent biofouling in the context of ship hull coatings. The first study determined the frequency of UVC required for a coating that does not have any additives (epoxy). It was found that 1 min/day was effective at preventing hard fouling but not biofilm development. The second study addressed several variables: coating type (epoxy, copper, fouling release), frequency of UVC (no exposure, continuous exposure, 1min/6h, 1 min/day), and distance from the lamp (25 and 50 mm). Continuous UVC exposure resulted in no biofouling settlement but it did damage the copper coating. Intermittent UVC exposure was effective at preventing biofouling recruitment to both the copper and the fouling release coatings. Variations were observed with regards to the fouling composition, especially biofilms, sedimentary tubeworms and barnacles, suggesting tolerances within the community.

Sediment challenge to promising ultra-low fouling hydrophilic surfaces in the marine environment.

Hydrophilic coatings exhibit ultra-low fouling properties in numerous laboratory experiments. In stark contrast, the antifouling effect of such coatings in vitro failed when performing field tests in the marine environment. The fouling release performance of nonionic and zwitterionic hydrophilic polymers was substantially reduced compared to the controlled laboratory environment. Microscopy and spectroscopy revealed that a large proportion of the accumulated material in field tests contains inorganic compounds and diatomaceous soil. Diatoms adhered to the accumulated material on the coating, but not to the pristine polymer. Simulating field tests in the laboratory using sediment samples collected from the test sites showed that incorporated sand and diatomaceous earth impairs the fouling release characteristics of the coatings. When exposed to marine sediment from multiple locations, particulate matter accumulated on these coatings and served as attachment points for diatom adhesion and enhanced fouling. Future developments of hydrophilic coatings should consider accumulated sediment and its potential impact on the antifouling performance.

Fouling-Release Properties of Dendritic Polyglycerols against Marine Diatoms.

Dendritic polyglycerols (PGs) were grafted onto surfaces using a ring-opening polymerization reaction, and the fouling-release properties against marine organisms were determined. The coatings were characterized by spectroscopic ellipsometry, contact angle goniometry, ATR-FTIR, and stability tests in different aqueous media. A high resistance toward the attachment of different proteins was found. The PG coatings with three different thicknesses were tested in a laboratory assay against the diatom Navicula incerta and in a field assay using a rotating disk. Under static conditions, the PG coatings did not inhibit the initial attachment of diatoms, but up to 94% of attached diatoms could be removed from the coatings after exposure to a shear stress of 19 Pa. Fouling release was found to be enhanced if the coatings were sufficiently thick. The excellent fouling-release properties were supported in dynamic field-immersion experiments in which the samples were continually exposed to a shear stress of 0.18 Pa.

Dynamic field testing of coating chemistry candidates by a rotating disk system.

Quick and reliable testing is crucial for the development of new fouling release (FR) coatings. Exposure of these coatings to natural multispecies communities is essential in evaluating their efficacy. To this end, we present a rotating disk setup for dynamic field exposure. To achieve a well-defined flow on the surface of the disk, an easy to use sample mounting system was developed that provides a smooth and even surface. We related the angular velocity of the disk to the wall shear stress on the surface with a hydrodynamic model. The wall shear stress was adjusted to values previously found to be suitable to discriminate dynamic diatom attachment on different coating chemistries in the lab. The effect of the dynamic conditions was shown by comparing polystyrene slides under static and dynamic exposure. Using a set of self-assembled monolayers, the discrimination potential of the assay in a multispecies environment was demonstrated.

Biofilm community structure and the associated drag penalties of a groomed fouling release ship hull coating.

Grooming is a proactive method to keep a ship's hull free of fouling. This approach uses a frequent and gentle wiping of the hull surface to prevent the recruitment of fouling organisms. A study was designed to compare the community composition and the drag associated with biofilms formed on a groomed and ungroomed fouling release coating. The groomed biofilms were dominated by members of the Gammaproteobacteria and Alphaproteobacteria as well the diatoms Navicula, Gomphonemopsis, Cocconeis, and Amphora. Ungroomed biofilms were characterized by Phyllobacteriaceae, Xenococcaceae, Rhodobacteraceae, and the pennate diatoms Cyclophora, Cocconeis, and Amphora. The drag forces associated with a groomed biofilm (0.75 ± 0.09 N) were significantly less than the ungroomed biofilm (1.09 ± 0.06 N). Knowledge gained from this study has helped the design of additional testing which will improve grooming tool design, minimizing the growth of biofilms and thus lowering the frictional drag forces associated with groomed surfaces.

Iodine-infused aeration for hull fouling prevention: a vessel-scale study.

Biofouling is a significant economic and ecological problem, causing reduced vessel performance and increases in fuel consumption and emissions. Previous research has shown iodine vapor (I2)-infused aeration to be an environmentally friendly method for deterring the settlement of fouling organisms. An aeration system was deployed on a vessel with hull sections coated with two types of antifoulant coatings, Intersleek® 1100 (fouling-release) and Interspeed® BRA-640 (ablative copper biocide), as well as an inert epoxy barrier coating, to assess the effectiveness of aeration in conjunction with common marine coatings. I2-infused aeration resulted in consistent reductions of 80-90% in hard fouling across all three coatings. Additionally, aeration reduced the soft fouling rate by 45-70% when used in conjunction with both Intersleek® and Interspeed® BRA versus those coatings alone. The results of this study highlight the contribution of I2-infused aeration as a standalone mechanism for fouling prevention or as a complement to traditional antifouling coatings.