The effects of silicone fluid additives and silicone elastomer matrices on barnacle adhesion strength

Barnacle adhesion strength was used to screen seventy-seven polydimethylsiloxane elastomeric coatings for fouling-release properties. The test coatings were designed to investigate the effect on barnacle adhesion strength of silicone fluid additive type, additive location, additive molecular weight, additive loading level, mixtures of additives, coating matrix type and coating fillers. The type of silicone fluid additive was the primary controlling factor in barnacle fouling-release. The type of silicone matrix in which the fluid resided was found to alter the effect on fouling-release. Two PDMS fluids, DMSC15 and DBE224, significantly reduced the adhesion strength of barnacles compared to unmodified elastomers. Optimum fouling-release performance was dependent on the interaction of fluid type and elastomeric matrix.     

Incorporation of silicone oil into elastomers enhances barnacle detachment by active surface strain

Silicone-oil additives are often used in fouling-release silicone coatings to reduce the adhesion strength of barnacles and other biofouling organisms. This study follows on from a recently reported active approach to detach barnacles, which was based on the surface strain of elastomeric materials, by investigating a new, dual-action approach to barnacle detachment using Ecoflex®-based elastomers incorporated with poly(dimethylsiloxane)-based oil additives. The experimental results support the hypothesis that silicone-oil additives reduce the amount of substratum strain required to detach barnacles. The study also de-coupled the two effects of silicone oils (ie surface-activity and alteration of the bulk modulus) and examined their contributions in reducing barnacle adhesion strength. Further, a finite element model based on fracture mechanics was employed to qualitatively understand the effects of surface strain and substratum modulus on barnacle adhesion strength. The study demonstrates that dynamic substratum deformation of elastomers with silicone-oil additives provides a bifunctional approach towards management of biofouling by barnacles.     

The effect of surface colour on the adhesion strength of Elminius modestus Darwin on a commercial non-biocidal antifouling coating at two locations in the UK

A number of factors affect the adhesion strength of organisms to fouling-release coatings, and except for a few studies focussing on black or white surfaces none have dealt specifically with the effect of coating colour. The aim was to test the effect of colour on the adhesion strength of the barnacle Elminius modestus. Panels coated in six commercial colours of Intersleek 700® were submerged at two field sites and barnacles were pushed-off using a standard assay procedure. The strength of adhesion (SOA) varied between and within sites for colour and by barnacle basal area, SOA per unit area being higher for smaller barnacles. Higher SOA with a small basal area may be because of size-specific predation, differential hydrodynamic effects or adhesive failure with age. The complex effect of colour on barnacle adhesion may be because of physico-chemical surface characteristics varying with pigments, and their interactions with local environmental conditions, as well as interactions with the settling barnacle larvae.     

Interspecific variation in patterns of adhesion of marine fouling to silicone surfaces

The adhesion of six fouling organisms: the barnacle Balanus eburneus, the gastropod mollusc Crepidulafornicata, the bivalve molluscs Crassostrea virginica and Ostrea/Dendrostrea spp., and the serpulid tubeworms Hydroides dianthus and H. elegans, to 12 silicone fouling-release surfaces was examined. Removal stress (adhesion strength) varied among the fouling species and among the surfaces. Principal component analysis of the removal stress data revealed that the fouling species fell into two distinct groups, one comprising the bivalve molluscs and tubeworms, and the other the barnacle and the gastropod mollusc. None of the silicone materials generated a minimum in removal stress for all the organisms tested, although several surfaces produced low adhesion strengths for both groups of species. These results suggest that fouling-release materials do not rank (in terms of adhesion strength) identically for all fouling organisms, and thus development of a globally-effective hull coating will continue to require testing against a diversity of encrusting species.     

Barnacle reattachment: a tool for studying barnacle adhesion

Standard approaches for measuring adhesion strength of fouling organisms use barnacles, tubeworms or oysters settled and grown in the field or laboratory, to a measurable size. These approaches suffer from the vagaries of larval supply, settlement behavior, predation, disturbance and environmental stress. Procedures for reattaching barnacles to experimental surfaces are reported. When procedures are followed, adhesion strength measurements on silicone substrata after 2 weeks are comparable to those obtained using standard methods. Hydrophilic surfaces require reattachment for 2-4 weeks. The adhesion strength of barnacles in reattachment assays was positively correlated to results obtained from field testing a series of experimental polysiloxane fouling-release coatings (r = 0.89). The reattachment method allows for precise barnacle orientation, enabling the use of small surfaces and the potential for automation. The method enables down-selection of coatings from combinatorial approaches to manageable levels for definitive field testing. Reattachment can be used with coatings that combine antifouling and fouling-release technologies.     

Combinatorial materials research applied to the development of new surface coatings V. Application of a spinning water-jet for the semi-high throughput assessment of the attachment strength of marine fouling algae

In order to facilitate a semi-high throughput approach to the evaluation of novel fouling-release coatings, a 'spinjet' apparatus has been constructed. The apparatus delivers a jet of water of controlled, variable pressure into the wells of 24-well plates in order to facilitate measurement of the strength of adhesion of algae growing on the base of the wells. Two algae, namely, sporelings (young plants) of the green macroalga Ulva and a diatom (Navicula), were selected as test organisms because of their opposing responses to silicone fouling-release coatings. The percentage removal of algal biofilm was positively correlated with the impact pressure for both organisms growing on all the coating types. Ulva sporelings were removed from silicone elastomers at low impact pressures in contrast to Navicula cells which were strongly attached to this type of coating. The data obtained for the 24-well plates correlated with those obtained for the same coatings applied to microscope slides. The data show that the 24-well plate format is suitable for semi-high throughput screening of the adhesion strength of algae.     

Combinatorial materials research applied to the development of new surface coatings IV. A high-throughput bacterial biofilm retention and retraction assay for screening fouling-release performance of coatings

A high-throughput bacterial biofilm retention screening method has been augmented to facilitate the rapid analysis and down-selection of fouling-release coatings for identification of promising candidates. Coatings were cast in modified 24-well tissue culture plates and inoculated with the marine bacterium Cytophaga lytica for attachment and biofilm growth. Biofilms retained after rinsing with deionised water were dried at ambient laboratory conditions. During the drying process, retained biofilms retracted through a surface de-wetting phenomenon on the hydrophobic silicone surfaces. The retracted biofilms were stained with crystal violet, imaged, and analysed for percentage coverage. Two sets of experimental fouling-release coatings were analysed with the high-throughput biofilm retention and retraction assay (HTBRRA). The first set consisted of a series of model polysiloxane coatings that were systematically varied with respect to ratios of low and high MW silanol-terminated PDMS, level of cross-linker, and amount of silicone oil. The second set consisted of cross-linked PDMS-polyurethane coatings varied with respect to the MW of the PDMS and end group functionality. For the model polysiloxane coatings, HTBRRA results were compared to data obtained from field immersion testing at the Indian River Lagoon at the Florida Institute of Technology. The percentage coverage calculations of retracted biofilms correlated well to barnacle adhesion strength in the field (R(2)=0.82) and accurately identified the best and poorest performing coating compositions. For the cross-linked PDMS-polyurethane coatings, the HTBRRA results were compared to combinatorial pseudobarnacle pull-off adhesion data and good agreement in performance was observed. Details of the developed assay and its implications in the rapid discovery of new fouling-release coatings are discussed.     

Phenotypic variation for adhesive tenacity in the barnacle Balanus amphitrite

Silicone fouling-release coatings represent a non-toxic alternative to biocide-containing ship hull paints. These coatings allow fouling organisms to attach to the hull surface, but prevent firm adhesion. Adhesive tenacity to fouling-release materials varies both among and within species. We quantified broad-sense genetic and environmental sources of intraspecific variation in tenacity to two silicone substrata, for the barnacle Balanus amphitrite. For both materials tenacity varied over an order of magnitude; however, the partitioning of this variation differed between the substrata. For International Veridian, a commercially-available fouling-release coating, removal stress varied significantly among maternal families and replicate barnacle cultures. Variation among the maternal families was associated with previously observed differences among these families in the condition of the adhesive plaque. Additional experiments suggested that variation among the replicate cultures arose from heterogeneity between replicate coatings in properties that affect tenacity. We could not attribute variation in removal stress for Dow Corning Silastic T-2, a silicone rubber used for mold-making, to any of the genetic or environmental sources tested. Instead, variation may have been due to measurement error or heterogeneity within replicate coatings in properties affecting tenacity. Differences among maternal families in removal stress may stem from variation in the interaction between the adhesive and the substratum, or in the viscoelastic properties of the adhesive plaque.     

Combinatorial materials research applied to the development of new surface coatings IV. A high-throughput bacterial biofilm retention and retraction assay for screening fouling-release performance of coatings

Abstract

A high-throughput bacterial biofilm retention screening method has been augmented to facilitate the rapid analysis and down-selection of fouling-release coatings for identification of promising candidates. Coatings were cast in modified 24-well tissue culture plates and inoculated with the marine bacterium Cytophaga lytica for attachment and biofilm growth. Biofilms retained after rinsing with deionised water were dried at ambient laboratory conditions. During the drying process, retained biofilms retracted through a surface de-wetting phenomenon on the hydrophobic silicone surfaces. The retracted biofilms were stained with crystal violet, imaged, and analysed for percentage coverage. Two sets of experimental fouling-release coatings were analysed with the high-throughput biofilm retention and retraction assay (HTBRRA). The first set consisted of a series of model polysiloxane coatings that were systematically varied with respect to ratios of low and high MW silanol-terminated PDMS, level of cross-linker, and amount of silicone oil. The second set consisted of cross-linked PDMS-polyurethane coatings varied with respect to the MW of the PDMS and end group functionality. For the model polysiloxane coatings, HTBRRA results were compared to data obtained from field immersion testing at the Indian River Lagoon at the Florida Institute of Technology. The percentage coverage calculations of retracted biofilms correlated well to barnacle adhesion strength in the field (R² = 0.82) and accurately identified the best and poorest performing coating compositions. For the cross-linked PDMS-polyurethane coatings, the HTBRRA results were compared to combinatorial pseudobarnacle pull-off adhesion data and good agreement in performance was observed. Details of the developed assay and its implications in the rapid discovery of new fouling-release coatings are discussed.     

Interspecific variation in patterns of adhesion of marine fouling to silicone surfaces

Abstract

The adhesion of six fouling organisms: the barnacle Balanus eburneus, the gastropod mollusc Crepidula fornicata, the bivalve molluscs Crassostrea virginica and Ostrea/Dendrostrea spp., and the serpulid tubeworms Hydroides dianthus and H. elegans, to 12 silicone fouling-release surfaces was examined. Removal stress (adhesion strength) varied among the fouling species and among the surfaces. Principal component analysis of the removal stress data revealed that the fouling species fell into two distinct groups, one comprising the bivalve molluscs and tubeworms, and the other the barnacle and the gastropod mollusc. None of the silicone materials generated a minimum in removal stress for all the organisms tested, although several surfaces produced low adhesion strengths for both groups of species. These results suggest that fouling-release materials do not rank (in terms of adhesion strength) identically for all fouling organisms, and thus development of a globally-effective hull coating will continue to require testing against a diversity of encrusting species.     

Mini-review: Barnacle adhesives and adhesion

Barnacles are intriguing, not only with respect to their importance as fouling organisms, but also in terms of the mechanism of underwater adhesion, which provides a platform for biomimetic and bioinspired research. These aspects have prompted questions regarding how adult barnacles attach to surfaces under water. The multidisciplinary and interdisciplinary nature of the studies makes an overview covering all aspects challenging. This mini-review, therefore, attempts to bring together aspects of the adhesion of adult barnacles by looking at the achievements of research focused on both fouling and adhesion. Biological and biochemical studies, which have been motivated mainly by understanding the nature of the adhesion, indicate that the molecular characteristics of barnacle adhesive are unique. However, it is apparent from recent advances in molecular techniques that much remains undiscovered regarding the complex event of underwater attachment. Barnacles attached to silicone-based elastomeric coatings have been studied widely, particularly with respect to fouling-release technology. The fact that barnacles fail to attach tenaciously to silicone coatings, combined with the fact that the mode of attachment to these substrata is different to that for most other materials, indicates that knowledge about the natural mechanism of barnacle attachment is still incomplete. Further research on barnacles will enable a more comprehensive understanding of both the process of attachment and the adhesives used. Results from such studies will have a strong impact on technology aimed at fouling prevention as well as adhesion science and engineering.     

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.     

Biofouling and barnacle adhesion data for fouling‐release coatings subjected to static immersion at seven marine sites

Little is known about the performance of fouling‐release coatings at different geographical locations. An investigation was designed to measure the differences in biofouling and biofouling adhesion strength on three known silicone formulations and an epoxy control at seven static immersion sites located in California, Florida, Hawaii, Hong Kong, India, Italy and Singapore. The study found that whilst the relative performance of the coatings was similar at each site, there were statistically significant differences in the type and intensity of fouling that developed on the coatings and in barnacle adhesion strength among sites. The results emphasize the importance of evaluating potential coatings at more than one static immersion site.     

Two silicone nontoxic fouling release coatings: Hydrosilation cured PDMS and CaCO3 filled,ethoxysiloxane cured RTV11

Two silicone coatings have been evaluated for barnacle adhesion. One coating is an unfilled hydrosilation cured polydimethylsiloxane (PDMS) network, while the other is a room temperature vulcanized (RTV), filled, ethoxysiloxane cured PDMS elastomer, RTV11^?. The adhesion strength of one species of barnacle, Balanus eburneus, to the hydrosilation coatings is in the range of 0.37–0.60 kg cm^‐2 while the corresponding range for RTV11 is 0.64–0.90 kg cm^‐2. The easier release of B. eburneus from the hydrosilation cured network compared to RTV11 is discussed in relationship to differences in bulk and surface properties. Preliminary results suggest bulk modulus may be the most important parameter in determining barnacle adhesion strength. In light or mechanical property analysis, a re‐evaluation of surface properties and chemical stability is presented.     

Preparation and characterisation of silicone-based coatings filled with carbon nanotubes and natural sepiolite and their application as marine fouling-release coatings

This article reports on the preparation and partial characterisation of silicone-based coatings filled with low levels of either synthetic multiwall carbon nanotubes (MWCNTs) or natural sepiolite (NS). The antifouling and fouling-release properties of these coatings were explored through laboratory assays involving representative soft-fouling (Ulva) and hard-fouling (Balanus) organisms. The bulk mechanical properties of the coatings appeared unchanged by the addition of low amounts of filler, in contrast to the surface properties, which were modified on exposure to water. The release of Ulva sporelings (young plants) was improved by the addition of low amounts of both NS and MWCNTs. The most profound effect recorded was the significant reduction of adhesion strength of adult barnacles growing on a silicone elastomer containing a small amount (0.05%) of MWCNTs. All the data indicate that independent of the bulk properties, the surface properties affect settlement, and more particularly, the fouling-release behaviour, of the filled materials.     

Preparation and characterisation of silicone-based coatings filled with carbon nanotubes and natural sepiolite and their application as marine fouling-release coatings

This article reports on the preparation and partial characterisation of silicone-based coatings filled with low levels of either synthetic multiwall carbon nanotubes (MWCNTs) or natural sepiolite (NS). The antifouling and fouling-release properties of these coatings were explored through laboratory assays involving representative soft-fouling (Ulva) and hard-fouling (Balanus) organisms. The bulk mechanical properties of the coatings appeared unchanged by the addition of low amounts of filler, in contrast to the surface properties, which were modified on exposure to water. The release of Ulva sporelings (young plants) was improved by the addition of low amounts of both NS and MWCNTs. The most profound effect recorded was the significant reduction of adhesion strength of adult barnacles growing on a silicone elastomer containing a small amount (0.05%) of MWCNTs. All the data indicate that independent of the bulk properties, the surface properties affect settlement, and more particularly, the fouling-release behaviour, of the filled materials.     

Factors that influence elastomeric coating performance: the effect of coating thickness on basal plate morphology, growth and critical removal stress of the barnacle Balanus amphitrite

Silicone coatings are currently the most effective non-toxic fouling release surfaces. Understanding the mechanisms that contribute to the performance of silicone coatings is necessary to further improve their design. The objective of this study was to examine the effect of coating thickness on basal plate morphology, growth, and critical removal stress of the barnacle Balanus amphitrite. Barnacles were grown on silicone coatings of three thicknesses (0.2, 0.5 and 2 mm). Atypical ("cupped") basal plate morphology was observed on all surfaces, although there was no relationship between coating thickness and i) the proportion of individuals with the atypical morphology, or ii) the growth rate of individuals. Critical removal stress was inversely proportional to coating thickness. Furthermore, individuals with atypical basal plate morphology had a significantly lower critical removal stress than individuals with the typical ("flat") morphology. The data demonstrate that coating thickness is a fundamental factor governing removal of barnacles from silicone coatings.     

Fluorinated/siloxane copolymer blends for fouling release: chemical characterisation and biological evaluation with algae and barnacles

Fouling-release coatings were prepared from blends of a fluorinated/siloxane copolymer with a poly(dimethyl siloxane) (PDMS) matrix in order to couple the low modulus character of PDMS with the low surface tension typical for fluorinated polymers. The content of the surface-active copolymer was varied in the blend over a broad range (0.15–10 wt % with respect to PDMS). X-ray photoelectron spectroscopy depth profiling analyses were performed on the coatings to establish the distribution of specific chemical constituents throughout the coatings, and proved enrichment in fluorine of the outermost layers of the coating surface. Addition of the fluorinated/siloxane copolymer to the PDMS matrix resulted in a concentration-dependent decrease in settlement of barnacle, Balanus amphitrite, cyprids. The release of young plants of Ulva, a soft fouling species, and young barnacles showed that adhesion strength on the fluorinated/siloxane copolymer was significantly lower than the siloxane control. However, differences in adhesion strength were not directly correlated with the concentration of copolymer in the blends.     

The adhesive strategies of cyprids and development of barnacle-resistant marine coatings

Over the last decade, approaches to the development of surfaces that perturb settlement and/or adhesion by barnacles have diversified substantially. Although, previously, coatings research focussed almost exclusively on biocidal technologies and low modulus, low surface-free-energy ‘fouling-release’ materials, novel strategies to control surface colonisation are now receiving significant attention. It is timely, therefore, to review the current ‘state of knowledge’ regarding fouling-resistant surface characteristics and their mechanisms of action against settling larvae of barnacles. The role of the barnacle in marine fouling is discussed here in the context of its life cycle and the behavioural ecology of its cypris larva. The temporary and permanent adhesion mechanisms of cyprids are covered in detail and an overview of adult barnacle adhesion is presented. Recent legislation has directed academic research firmly towards environmentally inert marine coatings, so the actions of traditional biocides on barnacles are not described here. Instead, the discussion is restricted to those surface modifications that interfere with settlement-site selection and adhesion of barnacle cypris larvae; specifically, textural engineering of surfaces, development of inert ‘non-fouling’ surfaces and the use of enzymes in antifouling.     

Variation among families for characteristics of the adhesive plaque in the barnacle Balanus amphitrite

A quantitative genetics approach was used to examine variation in the characteristics of the adhesive plaque of the barnacle Balanus amphitrite Darwin attached to two silicone substrata. Barnacles settled on silicone polymer films occasionally form thick, soft adhesive plaques, in contrast to the thin, hard plaques characteristic of attachment to other surfaces. The proportion of barnacles producing a thick adhesive plaque was 0.31 for Veridian, a commercially available silicone fouling-release coating, and 0.18 for Silastic T-2, a silicone rubber used for mold-making. For both materials, significant variation among maternal families in the proportion of barnacles producing a thick adhesive plaque was observed, which suggests the presence of genetic variation, or maternal environmental effects, for this plaque characteristic. For the Veridian coating, barnacles expressing the thick adhesive plaque also exhibited significantly reduced tenacity. This represents the first reported case for potential genetic control of intraspecific phenotypic variation in the physical characteristics and tenacity of the adhesive of a fouling invertebrate.