Amphiphilic hydrolyzable polydimethylsiloxane-b-poly(ethyleneglycol methacrylate-co-trialkylsilyl methacrylate) block copolymers for marine coatings. II. Antifouling laboratory tests and field trials

Abstract

Poly(dimethylsiloxane) (PDMS) elastomer coatings containing an amphiphilic hydrolyzable diblock copolymer additive were prepared and their potential as marine antifouling and antiadhesion materials was tested. The block copolymer additive consisted of a PDMS first block and a random poly(trialkylsilyl methacrylate (TRSiMA, R?=?butyl, isopropyl)-co-poly(ethyleneglycol) methacrylate (PEGMA) copolymer second block. PDMS-b-TRSiMA block copolymer additives without PEGMA units were also used as additives. The amphiphilic character of the coating surface was assessed in water using the captive air bubble technique for measurements of static and dynamic contact angles. The attachment of macro- and microorganisms on the coatings was evaluated by field tests and by performing adhesion tests to the barnacle Amphibalanus amphitrite and the green alga Ulva rigida. All the additive-based PDMS coatings showed better antiadhesion properties to A. amphitrite larvae than to U. rigida spores. Field tests provided meaningful information on the antifouling and fouling release activity of coatings over an immersion period of 23?months.     

Evaluation of the performance enhancement of silicone biofouling-release coatings by oil incorporation

In response to increased evidence of ecosystem damage by toxic antifouling paints, many researchers have developed nontoxic silicone fouling release coatings. The fouling release capability of these Systems may be improved by adding nonbonding silicone oils to the coating matrix. This idea has been tested by comparing the adhesion strength of hard- and soft-fouling organisms on a cured polydimethylsilicone (PDMS) network to that of the same network containing free polydi-methyldiphenylsilicone (PDMDPS) oil at five exposure sites in North America and Hawaii. Fouling coverage is discussed, together with the bioadhesion data, to emphasize that although these coatings foul the fouling is easily removed. The partitioning of the incorporated oil upon exposure of the coatings to a simulated marine environment containing sediment was determined. Less than 1.1 wt% of the incorporated oil was lost from the coating over one year, and the toxicity of these coatings was shown to be minimal to shrimp and fish. Brush abrasion wear was greater for coatings containing free oil, but the modulus of elasticity was not appreciably decreased by the addition of 10wt% free oil.     

Poly(dimethyl siloxane) (PDMS) network blends of amphiphilic acrylic copolymers with poly(ethylene glycol)-fluoroalkyl side chains for fouling-release coatings. II. Laboratory assays and field immersion trials

Amphiphilic copolymers containing different amounts of poly(ethylene glycol)-fluoroalkyl acrylate and polysiloxane methacrylate units were blended with a poly(dimethyl siloxane) (PDMS) matrix in different proportions to investigate the effect of both copolymer composition and loading on the biological performance of the coatings. Laboratory bioassays revealed optimal compositions for the release of sporelings of Ulva linza, and the settlement of cypris larvae of Balanus amphitrite. The best-performing coatings were subjected to field immersion tests. Experimental coatings containing copolymer showed significantly reduced levels of hard fouling compared to the control coatings (PDMS without copolymer), their performance being equivalent to a coating based on Intersleek 700?. XPS analysis showed that only small amounts of fluorine at the coating surface were sufficient for good antifouling/fouling-release properties. AFM analyses of coatings under immersion showed that the presence of a regular surface structure with nanosized domains correlated with biological performance.     

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

Abstract

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.     

化学生态学在海洋污损生物防除中的应用

在海洋环境中,许多海洋生物都能产生对环境无危害的、具有防污活性的次生代谢产物以保护自身的洁净,利于自身的生存.用化学生态学的方法从海洋生物中提取天然防除物质成为近年来解决海洋污损生物问题的新思路,其目标是寻找高效无毒的防污材料取代原有的对海洋环境有严重危害的化学合成防污材料.虽然目前对提取生物的次生代谢产物的防污机理还所知甚少,但不少从海洋生物中获得的天然产物已显示出良好的防污活性.要解决污损生物防污问题,还需对天然产物的作用机制、生态学效应、天然产物与涂料的结合、控制和释放及野外实验进行更加深入的研究与探讨.     

Molecular approaches to nontoxic antifouling

Summary

A consequence of environmental and human health concerns arising from the use of toxic metals in marine antifouling coatings has been to recognise the need for a nontoxic alternative to fouling control. Recent research has focused on two approaches to this problem: the development of (a) foul-release coatings that work on the principle of either low surface free energy or coating ablation, and (b) coatings that incorporate a compound(s) that is nontoxic, or at least environmentally benign, that will deter fouling. Here we discuss the nature of the fouling problem and a new technology that is emerging to address it. The use of natural marine products and of analogues to these compounds holds considerable promise and is an area of intense research. It is recognized, however, that a melding of the technologies of foul-release and foul-deterrence may be required to develop broad spectrum, nontoxic antifouling coatings. This approach may more closely reflect antifouling strategies adopted by marine organisms that maintain a foul-free surface.     

Dynamic surface deformation of silicone elastomers for management of marine biofouling: laboratory and field studies using pneumatic actuation

Many strategies have been developed to improve the fouling release (FR) performance of silicone coatings. However, biofilms inevitably build on these surfaces over time. Previous studies have shown that intentional deformation of silicone elastomers can be employed to detach biofouling species. In this study, inspired by the methods used in soft-robotic systems, controlled deformation of silicone elastomers via pneumatic actuation was employed to detach adherent biofilms. Using programmed surface deformation, it was possible to release > 90% of biofilm from surfaces in both laboratory and field environments. A higher substratum strain was required to remove biofilms accumulated in the field environment as compared with laboratory-grown biofilms. Further, the study indicated that substratum modulus influences the strain needed to de-bond biofilms. Surface deformation-based approaches have potential for use in the management of biofouling in a number of technological areas, including in niche applications where pneumatic actuation of surface deformation is feasible.     

Poly(dimethyl siloxane) (PDMS) network blends of amphiphilic acrylic copolymers with poly(ethylene glycol)-fluoroalkyl side chains for fouling-release coatings. II. Laboratory assays and field immersion trials

Amphiphilic copolymers containing different amounts of poly(ethylene glycol)-fluoroalkyl acrylate and polysiloxane methacrylate units were blended with a poly(dimethyl siloxane) (PDMS) matrix in different proportions to investigate the effect of both copolymer composition and loading on the biological performance of the coatings. Laboratory bioassays revealed optimal compositions for the release of sporelings of Ulva linza, and the settlement of cypris larvae of Balanus amphitrite. The best-performing coatings were subjected to field immersion tests. Experimental coatings containing copolymer showed significantly reduced levels of hard fouling compared to the control coatings (PDMS without copolymer), their performance being equivalent to a coating based on Intersleek 700?. XPS analysis showed that only small amounts of fluorine at the coating surface were sufficient for good antifouling/fouling-release properties. AFM analyses of coatings under immersion showed that the presence of a regular surface structure with nanosized domains correlated with biological performance.     

Antifouling potential of Subtilisin A immobilized onto maleic anhydride copolymer thin films

The proteinaceous nature of the adhesives used by most fouling organisms to attach to surfaces suggests that coatings incorporating proteolytic enzymes may provide a technology for the control of biofouling. In the present article, the antifouling (AF) and fouling release potential of model coatings incorporating the surface-immobilized protease, Subtilisin A, have been investigated. The enzyme was covalently attached to maleic anhydride copolymer thin films; the characteristics of the bioactive coatings obtained were adjusted through variation of the type of copolymer and the concentration of the enzyme solution used for immobilization. The bioactive coatings were tested for their effect on the settlement and adhesion strength of two major fouling species: the green alga Ulva linza and the diatom Navicula perminuta. The results show that the immobilized enzyme effectively reduced the settlement and adhesion strength of zoospores of Ulva and the adhesion strength of Navicula cells. The AF efficacy of the bioactive coatings increased with increasing enzyme surface concentration and activity, and was found to be superior to the equivalent amount of enzyme in solution. The results provide a rigorous analysis of one approach to the use of immobilized proteases to reduce the adhesion of marine fouling organisms and are of interest to those investigating enzyme-containing coating technologies for practical biofouling control.     

The effects of a serine protease,Alcalase®, on the adhesives of barnacle cyprids (Balanus amphitrite)

Barnacles are a persistent fouling problem in the marine environment, although their effects (eg reduced fuel efficiency, increased corrosion) can be reduced through the application of antifouling or fouling-release coatings to marine structures. However, the developments of fouling-resistant coatings that are cost-effective and that are not deleterious to the marine environment are continually being sought. The incorporation of proteolytic enzymes into coatings has been suggested as one potential option. In this study, the efficacy of a commercially available serine endopeptidase, Alcalase® as an antifoulant is assessed and its mode of action on barnacle cypris larvae investigated. In situ atomic force microscopy (AFM) of barnacle cyprid adhesives during exposure to Alcalase supported the hypothesis that Alcalase reduces the effectiveness of the cyprid adhesives, rather than deterring the organisms from settling. Quantitative behavioural tracking of cyprids, using Ethovision? 3.1, further supported this observation. Alcalase removed cyprid ‘footprint’ deposits from glass surfaces within 26 min, but cyprid permanent cement became resistant to attack by Alcalase within 15 h of expression, acquiring a crystalline appearance in its cured state. It is concluded that Alcalase has antifouling potential on the basis of its effects on cyprid footprints, un-cured permanent cement and its non-toxic mode of action, providing that it can be successfully incorporated into a coating.     

Marine microbial natural products in antifouling coatings

Ecological problems associated with current antifouling technologies have increased interest in the natural strategies that marine organisms use to keep their surfaces clean and free from fouling. Bacteria isolated from living surfaces in the marine environment have been shown to produce chemicals that are potential antifoulants. Active compounds from the cells and culture supernatant of two bacterial strains, FS‐55 and NudMB50–11, isolated from surface of the seaweed, Fucus serratus, and the nudibranch, Archidoris pseudoargus, respectively, were extracted using solid phase extraction. The extracts were combined with acrylic base paint resin and assayed for antifouling activity by measuring their ability to inhibit the growth of fouling bacteria. These formulations were found to be active against fouling bacteria isolated from marine surfaces. The formulation of antifouling paints that incorporate marine microbial natural products is reported here for the first time. This is a significant advance towards the production of an environmentally friendly antifouling paint that utilises a sustainable supply of natural biodegradable compounds.     

Temporal and spatial variations in macrofouling of silicone fouling‐release coatings

Nontoxic, low surface free energy silicone coatings having reduced biofouling adhesion strength have been developed as an alternative to antifouling paints. Silicone coatings permit macrofouling to adhere; however, fouling can be removed easily by water pressure or light scrubbing. One of the current methods used to evaluate the performance of non‐toxic silicone fouling‐release coatings relies heavily on fouling coverage. The organismal community structure as well as total coverage can affect the ease of fouling removal from these coatings. This paper explores fouling coverage and organismal adhesion over time. Long‐term fouling coverage data were collected at four sites (in Massachusetts, Hawaii and Florida) using static immersion panels coated with silicone and oil‐amended silicone systems. Inter‐site differences in fouling coverage and community structure were observed for each coating. Intra‐site variation and temporal change in coverage of fouling was minimal, regardless of coating formulation. The extent of coverage was affected by the duration of immersion and the local environmental conditions; these factors may also have an impact on the foul‐release capability of the silicone coatings. Organismal adhesion data was collected in Hawaii and Florida. These adhesion measurements were used as a tool to discriminate and rank fouling release coatings.     

Thermoplastic,rubber-like marine antifouling coatings with micro-structures via mechanical embossing

Abstract

New processing routes and materials for non-biocidal, antifouling (AF) coatings with an improved performance are currently much sought after for a range of marine applications. Here, the processing, physical properties and marine AF performance of a fluorinated coating based on a thermoplastic (non-crosslinked) fluorinated polymer are reported. It was found that the addition of lubricating oil and hydrodynamic drag reducing microstructures improved the AF properties substantially, i.e. the settlement of a marine biofilm, containing mixed microalgae including diatoms, was reduced to low levels. More importantly, the remaining fouling was removed from the coatings at low hydrodynamic shear rates and promising AF properties were obtained. Moreover, additional potential benefits were revealed originating from the thermoplastic nature of the coating material which might result in significant cost reductions.     

A new flow-through bioassay for testing low-emission antifouling coatings

Current antifouling (AF) technologies are based on the continuous release of biocides into the water, and consequently discharge into the environment. Major efforts to develop more environmentally friendly coatings require efficient testing in laboratory assays, followed by field studies. Barnacles are important fouling organisms worldwide, increasing hydrodynamic drag on ships and damaging coatings on underwater surfaces, and thus are extensively used as models in AF research, mostly in static, laboratory-based systems. Reliable flow-through test assays for the screening of biocide-containing AF paints, however, are rare. Herein, a flow-through bioassay was developed to screen for diverse low-release biocide paints, and to evaluate their effects on pre- and post-settlement traits in barnacles. The assay distinguishes between the effects from direct surface contact and bulk-water effects, which are crucial when developing low-emission AF coatings. This flow-through bioassay adds a new tool for rapid laboratory-based first-stage screening of candidate compounds and novel AF formulations.     

Biomimetic characterisation of key surface parameters for the development of fouling resistant materials

Material science provides a direct route to developing a new generation of non-toxic, surface effect-based antifouling technologies with applications ranging from biomedical science to marine transport. The surface topography of materials directly affects fouling resistance and fouling removal, the two key mechanisms for antifouling technologies. However, the field is hindered by the lack of quantified surface characteristics to guide the development of new antifouling materials. Using a biomimetic approach, key surface parameters are defined and quantified and correlated with fouling resistance and fouling removal from the shells of marine molluscs. Laser scanning confocal microscopy was used to acquire images for quantitative surface characterisation using three-dimensional surface parameters, and field assays correlated these with fouling resistance and fouling release. Principle component analysis produced a major component (explaining 54% of total variation between shell surfaces) that correlated with fouling resistance. The five surface parameters positively correlated to increased fouling resistance were, in order of importance, low fractal dimension, high skewness of both the roughness and waviness profiles, higher values of isotropy and lower values of mean surface roughness. The second component (accounting for 20% of variation between shells) positively correlated to fouling release, for which higher values of mean waviness almost exclusively dictated this relationship. This study provides quantified surface parameters to guide the development of new materials with surface properties that confer fouling resistance and release.     

Biomimetic characterisation of key surface parameters for the development of fouling resistant materials

Material science provides a direct route to developing a new generation of non-toxic, surface effect-based antifouling technologies with applications ranging from biomedical science to marine transport. The surface topography of materials directly affects fouling resistance and fouling removal, the two key mechanisms for antifouling technologies. However, the field is hindered by the lack of quantified surface characteristics to guide the development of new antifouling materials. Using a biomimetic approach, key surface parameters are defined and quantified and correlated with fouling resistance and fouling removal from the shells of marine molluscs. Laser scanning confocal microscopy was used to acquire images for quantitative surface characterisation using three-dimensional surface parameters, and field assays correlated these with fouling resistance and fouling release. Principle component analysis produced a major component (explaining 54% of total variation between shell surfaces) that correlated with fouling resistance. The five surface parameters positively correlated to increased fouling resistance were, in order of importance, low fractal dimension, high skewness of both the roughness and waviness profiles, higher values of isotropy and lower values of mean surface roughness. The second component (accounting for 20% of variation between shells) positively correlated to fouling release, for which higher values of mean waviness almost exclusively dictated this relationship. This study provides quantified surface parameters to guide the development of new materials with surface properties that confer fouling resistance and release.     

Screening of Marine Algal Extracts for Anti-settlement Activities against Microalgae and Macroalgae

The ban on the use of TBT-based antifouling paints for boats under 25 m in length has lead to a search for new non-toxic antifoulants. One of the most promising alternative technologies to heavy metal based antifouling paint is the development of antifouling coatings whose active ingredients are naturally occurring compounds from marine organisms. This is based on the principle that marine organisms also face the problem of the presence of epibionts on their own surfaces. In this study, the antifouling activity of a series of aqueous, ethanolic and dichloromethane extracts from thirty algae from the North East Atlantic coast was investigated. The extracts were tested in laboratory assays against species representative of two major groups of fouling organisms, viz . macroalgae and microalgae. The activity of several extracts was comparable to that of heavy metals and biocides (such as TBTO and CuSO 4 ) currently used in antifouling paints and their lack of toxicity with respect to the larvae of oysters and sea urchins suggests a potential for novel active ingredients.     

A comparison of the antifouling/foul-release characteristics of non-biocidal xerogel and commercial coatings toward micro- and macrofouling organisms

Five non-biocidal xerogel coatings were compared to two commercial non-biocidal coatings and a silicone standard with respect to antifouling (AF)/fouling-release (FR) characteristics. The formation and release of biofilm of the marine bacterium Cellulophaga lytica, the attachment and release of the microalga Navicula incerta, and the fraction removal and critical removal stress of reattached adult barnacles of Amphibalanus amphitrite were evaluated in laboratory assays. Correlations of AF/FR performance with surface characteristics such as wettability, surface energy, elastic modulus, and surface roughness were examined. Several of the xerogel coating compositions performed well against both microfouling organisms while the commercial coatings performed less well toward the removal of microalgae. Reattached barnacle adhesion as measured by critical removal stress was significantly lower on the commercial coatings when compared to the xerogel coatings. However, two xerogel compositions showed release of 89-100% of reattached barnacles. These two formulations were also tested in the field and showed similar results.     

Amphiphilic triblock copolymers with PEGylated hydrocarbon structures as environmentally friendly marine antifouling and fouling-release coatings

The ideal marine antifouling (AF)/fouling-release (FR) coating should be non-toxic, while effectively either resisting the attachment of marine organisms (AF) or significantly reducing their strength of attachment (FR). Many recent studies have shown that amphiphilic polymeric materials provide a promising solution to producing such coatings due to their surface dual functionality. In this work, poly(ethylene glycol) (PEG) of different molecular weights (M_w?=?350, 550) was coupled to a saturated difunctional alkyl alcohol to generate amphiphilic surfactants (PEG-hydrocarbon-OH). The resulting macromolecules were then used as side chains to covalently modify a pre-synthesized PS₈?_K-b-P(E/B)₂₅?_K-b-PI₁₀?_K (SEBI or K3) triblock copolymer, and the final polymers were applied to glass substrata through an established multilayer surface coating technique to prepare fouling resistant coatings. The coated surfaces were characterized with AFM, XPS and NEXAFS, and evaluated in laboratory assays with two important fouling algae, Ulva linza (a green macroalga) and Navicula incerta, a biofilm-forming diatom. The results suggest that these polymer-coated surfaces undergo surface reconstruction upon changing the contact medium (polymer/air vs polymer/water), due to the preferential interfacial aggregation of the PEG segment on the surface in water. The amphiphilic polymer-coated surfaces showed promising results as both AF and FR coatings. The sample with longer PEG chain lengths (M_w?=?550?g?mol^?1) exhibited excellent properties against both algae, highlighting the importance of the chemical structures on ultimate biological performance. Besides reporting synthesis and characterization of this new type of amphiphilic surface material, this work also provides insight into the nature of PEG/hydrocarbon amphiphilic coatings, and this understanding may help in the design of future generations of fluorine-free, environmentally friendly AF/FR polymeric coatings.     

A review of surface roughness in antifouling coatings illustrating the importance of cutoff length

Abstract

Surface roughness (SR) can affect the hydrodynamic performance of antifouling (AF) coatings and influence the settlement behaviour of fouling larvae, which makes it an important parameter in the evaluation of novel coatings. This paper reviews the causes and consequences of SR in the shipping industry, the methodology used for measuring it, and the importance of measuring and reporting it correctly. SR is a parameter that originates from marine engineering, but has been used extensively by marine scientists to characterise novel coatings and to investigate microtopographies that might inhibit settlement behaviour. One of the integral components of the SR measurement is the use of a cutoff filter. This is a short-pass filter that lets the high wave-number components through and thus separates the waviness from the roughness. Depending on the length of this filter, roughness at different levels of magnification can be investigated. Much of the published work on SR of AF coatings makes no mention of cutoff length, so that the results cannot be compared. It is suggested that an international standard is needed and that if more researchers were aware of the significance of stating cutoff length when reporting SR, more interdisciplinary work between biologists, engineers and material scientists would be possible in this field.