Recent developments in superhydrophobic surfaces and their relevance to marine fouling: a review

Abstract

In this review, a brief synopsis of superhydrophobicity (i.e. extreme non-wettability) and its implications on marine fouling are presented. A short overview of wettability and recent experimental developments aimed at fabricating superhydrophobic surfaces by tailoring their chemical nature and physical appearance (i.e. substratum texture) are reviewed. The formation of responsive/“smart” surfaces, which adjust their physico-chemical properties to variations in some outside physical stimulus, including light, temperature, electric field, or solvent, is also described. Finally, implications of tailoring the surface chemistry, texture, and responsiveness of surfaces on the design of effective marine fouling coatings are considered and discussed.     

Mini review: Biomimetic models and bioinspired surfaces for fouling control

Nature provides many examples of mechanisms to control fouling. These defences can be copied (biomimetic) or tailored (bioinspired) to solve problems of fouling on manmade structures. With increasing research in this area over the last two decades, it is timely to review this burgeoning subject, in particular as the biofouling field shifts focus towards novel, physical mechanisms to prevent and control fouling. This change is being promoted by advances in nano- and micro-scale patterning as well as in a variety of nano-biotechnologies, which are transforming the translation of natural surfaces into experimental materials. In this article, research on the defence of marine organisms against fouling and the technologies they are defining is reviewed.     

Using textured PDMS to prevent settlement and enhance release of marine fouling organisms

The antifouling efficacy of a series of 18 textured (0.2–1000 μm) and non-textured (0 μm) polydimethylsiloxane surfaces with the profiles of round- and square-wave linear grating was tested by recording the settlement of fouling organisms in the laboratory and in the field by monitoring the recruitment of a multi-species fouling community. In laboratory assays, the diatoms Nitzschia closterium and Amphora sp. were deterred by all surface topographies regardless of texture type. Settlement of propagules of Ulva sp. was lower on texture sizes less than the propagule size, and settlement of larvae of Saccostrea glomerata and Bugula neritina was lower on texture sizes closest to, but less than, the sizes of larvae. After a six month field trial, all textured surfaces lost their deterrent effect; however, the foul-release capabilities of textures were still present. High initial attachment was correlated with most fouling remaining after removal trials, indicating that fouling organisms recruited in higher numbers to surfaces upon which they attached most strongly.     

Surface-grafted, environmentally sensitive polymers for biofilm release

Controlling bacterial biofouling is desirable for almost every human enterprise in which solid surfaces are introduced into nonsterile aqueous environments. One approach that is used to decrease contamination of manufactured devices by microorganisms is using materials that easily slough off accumulated material (i.e., fouling release surfaces). The compounds currently used for this purpose rely on low surface energy to inhibit strong attachment of organisms. In this study, we examined the possible use of environmentally responsive (or "smart") polymers as a new class of fouling release agents; a surface-grafted thermally responsive polymer, poly(N-isopropylacrylamide) (PNIPAAM), was used as a model compound. PNIPAAM is known to have a lower critical solubility temperature of approximately 32 degrees C (i.e., it is insoluble in water at temperatures above 32 degrees C and is soluble at temperatures below 32 degrees C). Under experimental conditions, >90% of cultured microorganisms (Staphylococcus epidermidis, Halomonas marina) and naturally occurring marine microorganisms that attached to grafted PNIPAAM surfaces during 2-, 18-, 36-, and 72-h incubations were removed when the hydration state of the polymer was changed from a wettability that was favorable for attachment to a wettability that was less favorable. Of particular significance is the observation that an organism known to attach in the greatest numbers to hydrophobic substrata (i.e., H. marina) was removed when transition of PNIPAAM to a more hydrated state occurred, whereas an organism that attaches in the greatest numbers to hydrophilic substrata (i.e., S. epidermidis) was removed when the opposite transition occurred. Neither solvated nor desolvated PNIPAAM exhibited intrinsic fouling release properties, indicating that the phase transition was the important factor in removal of organisms. Based on our observations of the behavior of this model system, we suggest that environmentally responsive polymers represent a new approach for controlling biofouling release.     

The influence of natural surface microtopographies on fouling

Multiple antifouling strategies of marine organisms may consist of combinations of physical, chemical and mechanical mechanisms. In this study, the role of surface microtopography (< 500 microns) of different marine organisms, such as Cancer pagurus, Mytilus edulis, Ophiura texturata and the eggcase of Scyliorhinus canicula, has been investigated as a possible component of their defence systems. High resolution resin replicates of these natural surface structures were exposed to natural fouling in field experiments. Abundances of recruits were determined and compared to those on untextured, but otherwise identical, control surfaces to quantify the influence of the different microtopographies on fouling rates. Antifouling effects of microtopographies varied with type of microtopography and coloniser species. The surface microtopography of C. pagurus significantly rejected macrofoulers. The surface structures of the eggcase and O. texturata had repellent effects on microfoulers. Barnacle settlement was temporarily reduced on surface microtopographies of M. edulis and the eggcase. These results emphasise the promising nontoxic antifouling properties of microtextured surfaces.     

Mechanical factors favoring release from fouling release coatings

For some twenty years the marine coatings industry has been intrigued by polymer surfaces with low adhesion to other materials, especially to the biological glues used by marine organisms. Polymers with fouling release surfaces have been made from sundry materials, and their resistance to marine fouling in both static and dynamic tests has been evaluated in the world's oceans. Although the polymer surface property most frequently correlated with bioadhesion is its critical surface tension (γ(?)), resistance to fouling is also influenced by other bulk and surface properties of the polymer. This paper reviews the types of bonding associated with polymeric materials used in fouling resistant coatings, describes the removal process in terms of fracture mechanics, and discusses the importance of surface energy, elastic modulus and coating thickness in the release of biofoulants.     

The biology of biofouling diatoms and their role in the development of microbial slimes

Diatoms are a major component of microbial slimes that develop on man-made surfaces placed in the marine environment. Toxic antifouling paints, as well as environmentally friendly, fouling-release coatings, tend to be effective against most fouling organisms, yet fail badly to diatom slimes. Biofouling diatoms have been found to tenaciously adhere to and colonise even the most resistant of artificial surfaces. This review covers the basic biology of fouling marine diatoms, their mechanisms of adhesion and the nature of their adhesives, as well as documenting the various approaches that have been utilised to understand the formation and maintenance of diatom biofouling layers.     

The biology of biofouling diatoms and their role in the development of microbial slimes

Diatoms are a major component of microbial slimes that develop on man-made surfaces placed in the marine environment. Toxic antifouling paints, as well as environmentally friendly, fouling-release coatings, tend to be effective against most fouling organisms, yet fail badly to diatom slimes. Biofouling diatoms have been found to tenaciously adhere to and colonise even the most resistant of artificial surfaces. This review covers the basic biology of fouling marine diatoms, their mechanisms of adhesion and the nature of their adhesives, as well as documenting the various approaches that have been utilised to understand the formation and maintenance of diatom biofouling layers.     

Analysis of behavioural rejection of micro-textured surfaces and implications for recruitment by the barnacle Balanus improvisus

Experiments performed in the field and in the laboratory show that the barnacle, Balanus improvisus, preferentially settles on smooth surfaces. Settlement and recruitment of B. improvisus was evaluated on micro-textured surfaces with scales of surface texture ranging from 1 to 100 μm in profile heights. Surface texture with profile heights within a topographic range of 30-45 μm reduced settlement and recruitment by 92% as compared to smooth surfaces. The reduction in recruitment on micro-textured surfaces is best explained by behavioural responses to surface topography. Behavioural experiments show that cyprids have a higher propensity for smooth surfaces than for micro-textured surfaces. Cyprids spend more time exploring smooth surfaces and more time swimming when exposed to micro-textured surfaces. Micro-textured surfaces are more often rejected by cyprids after exploration than smooth surfaces. It is suggested that some scales of surface texture could be exploited to improve future anti-fouling techniques in geographical areas where Balanus improvisus is a severe fouling problem.     

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.     

Development of the initial diatom microfouling layer on antifouling and fouling-release surfaces in temperate and tropical Australia

Diatoms are a major component of the slime layers that form on artificial surfaces in marine environments. In this article, the role played by diatoms during the pioneering stages of colonization of three marine antifouling (AF) coatings, viz Intersmooth 360®, Super Yacht 800® and a fouling-release (FR) coating Intersleek 700®, was investigated. The study was conducted over three distinct seasons in two very different marine environments in Australia, ie temperate Williamstown, Victoria and tropical Cairns, Queensland. Diatom fouling occurred more rapidly on the FR coating Intersleek 700, compared to both biocidal AF paints. However, colonization by diatoms on all three coatings was generally slow during the 16-day study. Benthic diatoms do not subsist by floating around in the water column, rather they only gain the opportunity to colonize new surfaces when they either voluntarily release or are displaced from their benthic habitat, thereafter entering the water column where the opportunity to adhere to a new surface presents itself. However, once settled, fouling diatoms grow exponentially from the site of attachment, spreading out until they populate large areas of the surface. This mode of surface colonization correlates more with an ‘infection’ type, epidemiology model, a mechanism that accounts for the colonization of significant regions of the coating surface from a single fouling diatom cell, forming ‘clonal patches’. This is in comparison to the bacterial colonization of the surface, which exhibits far more rapid recruitment and growth of cells on the substratum surface. Therefore, it is hypothesized that fouling diatoms may be characterized more by their ability to adhere and grow on surfaces already modified by bacterial biofilms, rather than on their strength of adhesion. Cell morphology and the ability to avoid shear may also be an important factor.     

The potential for translocation of marine species via small-scale disruptions to antifouling surfaces

Vessel hull fouling is a major vector for the translocation of nonindigenous species (NIS). Antifouling (AF) paints are the primary method for preventing the establishment and translocation of fouling species. However, factors such as paint age, condition and method of application can all reduce the effectiveness of these coatings. Areas of hull that escape AF treatment (through limited application or damage) constitute key areas that may be expected to receive high levels of fouling. The investigation focused on whether small-scale (mm(2) to cm(2)) areas of unprotected surface or experimental 'scrapes' provided sufficient area for the formation of fouling assemblages within otherwise undamaged AF surfaces. Recruitment of fouling taxa such as algae, spirorbids and hydroids was recorded on scrapes as narrow as 0.5 cm wide. The abundance and species richness of fouling assemblages developing on scrapes > or =1 cm often equalled or surpassed levels observed in reference assemblages totally unprotected by AF coatings. Experiments were conducted at three sites within the highly protected and isolated marine park surrounding Lady Elliott Island at the southernmost tip of the Great Barrier Reef, Australia. Several NIS were recorded on scrapes of AF coated surfaces at this location, with 1-cm scrapes showing the greatest species richness and abundance of NIS relative to all other treatments (including controls) at two of the three sites investigated. Slight disruptions to newly antifouled surfaces may be all that is necessary for the establishment of fouling organisms and the translocation of a wide range of invasive taxa to otherwise highly protected marine areas.     

Surface microtopographies of tropical sea stars: lack of an efficient physical defence mechanism against fouling

The role of surface topography as a defence against fouling in tropical sea stars was investigated. The sea stars Linckia laevigata, Fromia indica, Cryptasterina pentagona and Archaster typicus are not fouled and have paxillae (modified ossicles with a median vertical pillar) on their aboral surfaces, which varied in diameter, height and distance depending on species and position on the aboral surface, providing unique and complex surface microtopographies for each species. The surfaces of the sea stars L. laevigata, F. indica and A. typicus were moderately wettable, with their mean seawater contact angles, calculated from captive bubble measurements, being 60.1 degrees, 70.3 degrees and 57.3 degrees, respectively. The seawater contact angle of C. pentagona could not be measured. To evaluate the effectiveness of the surface microtopographies in deterring the settlement of fouling organisms, field experiments with resin replicas of the four sea star species were conducted at three sites around Townsville, Australia, for 8 weeks during the dry and wet seasons. The fouling community and total fouling cover did not differ significantly between replicas of L. laevigata, F. indica, C. pentagona, A. typicus and control surfaces at any site during the dry season. Significant differences between fouling communities on the replicas of the sea stars and control surfaces were detected at two sites during the wet season. However, these differences were transitory, and the total fouling cover did not differ significantly between replicas of sea stars and control surfaces at two of the three sites. In contrast to recent literature on the effects of biofouling control by natural surfaces in the marine environment, the surface microtopographies of tropical sea stars alone were not effective in deterring the settlement and growth of fouling organisms.     

The potential for translocation of marine species via small-scale disruptions to antifouling surfaces

Vessel hull fouling is a major vector for the translocation of nonindigenous species (NIS). Antifouling (AF) paints are the primary method for preventing the establishment and translocation of fouling species. However, factors such as paint age, condition and method of application can all reduce the effectiveness of these coatings. Areas of hull that escape AF treatment (through limited application or damage) constitute key areas that may be expected to receive high levels of fouling. The investigation focused on whether small-scale (mm² to cm²) areas of unprotected surface or experimental ‘scrapes’ provided sufficient area for the formation of fouling assemblages within otherwise undamaged AF surfaces. Recruitment of fouling taxa such as algae, spirorbids and hydroids was recorded on scrapes as narrow as 0.5 cm wide. The abundance and species richness of fouling assemblages developing on scrapes ≥1 cm often equalled or surpassed levels observed in reference assemblages totally unprotected by AF coatings. Experiments were conducted at three sites within the highly protected and isolated marine park surrounding Lady Elliott Island at the southernmost tip of the Great Barrier Reef, Australia. Several NIS were recorded on scrapes of AF coated surfaces at this location, with 1-cm scrapes showing the greatest species richness and abundance of NIS relative to all other treatments (including controls) at two of the three sites investigated. Slight disruptions to newly antifouled surfaces may be all that is necessary for the establishment of fouling organisms and the translocation of a wide range of invasive taxa to otherwise highly protected marine areas.     

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.     

Effects of surface texture and interrelated properties on marine biofouling: a systematic review

This systematic review examines effects of surface texture on marine biofouling and characterizes key research methodologies. Seventy-five published articles met selection criteria for qualitative analysis; experimental data from 36 underwent quantitative meta-analysis. Most studies investigated fouling mechanisms and antifouling performance only in laboratory assays with one to several test species. Textures were almost exclusively a single layer of regularly arranged geometric features rather than complex hierarchical or irregular designs. Textures in general had no effect or an inconclusive effect on fouling in 46% of cases. However, effective textures more often decreased (35%) rather than increased (19%) fouling. Complex designs were more effective against fouling (51%) than were regular geometric features (32%). Ratios of feature height, width, or pitch to organism body length were significant influences. The authors recommend further research on promising complex and hierarchical texture designs with more test species, as well as field studies to ground-truth laboratory results.     

Barnacle cyprid motility and distribution in the water column as an indicator of the settlement-inhibiting potential of nontoxic antifouling chemistries

Testing of new coatings to control fouling frequently involves single-species laboratory bioassays. Barnacle cyprids are among the most widely used model organisms in marine biofouling research, and surfaces that inhibit their settlement are considered to be promising candidates for new coating concepts. An analysis of motility parameters (mean velocity and swimming area coefficient) and distribution of cyprids of Balanus amphitrite in different swimming regions in the vicinity of model surfaces (self-assembled monolayers) is presented. The data are correlated with the settlement preferences of cyprids on these surfaces. Cyprids were predominantly found in interfacial regions and the transition frequencies between swimming regions of different depths were determined.     

The Influence of Natural Surface Microtopographies on Fouling

Multiple antifouling strategies of marine organisms may consist of combinations of physical, chemical and mechanical mechanisms. In this study, the role of surface microtopography (?<?500?μm) of different marine organisms, such as Cancer pagurus, Mytilus edulis, Ophiura texturata and the eggcase of Scyliorhinus canicula, has been investigated as a possible component of their defence systems. High resolution resin replicates of these natural surface structures were exposed to natural fouling in field experiments. Abundances of recruits were determined and compared to those on untextured, but otherwise identical, control surfaces to quantify the influence of the different microtopographies on fouling rates. Antifouling effects of microtopographies varied with type of microtopography and coloniser species. The surface microtopography of C. pagurus significantly rejected macrofoulers. The surface structures of the eggcase and O. texturata had repellent effects on microfoulers. Barnacle settlement was temporarily reduced on surface microtopographies of M. edulis and the eggcase. These results emphasise the promising non-toxic antifouling properties of microtextured surfaces.     

Observations on the mechanisms of attachment of some marine fouling blue-green algae

Using scanning electron microscopy (SEM), differential interference contrast microscopy (DICM) and cytochemical staining techniques, preliminary observations have been made on the mechanisms of attachment of some common, marine, benthic fouling blue-green algae ("cyanobacteria") isolated into culture from various toxic and non-toxic surfaces in Langstone Harbour, south coast of England. Blue-green algae investigated included species of Calothrix, Dermocarpa, Plectonema, Phormidium and Xenococcus. The blue-green algae are rapid colonisers and can make an important contribution to the pioneering communities on both toxic and non-toxic surfaces. A characteristic feature of the colonization process is the production of variable quantities of extracellular polymeric substances (EPS) which appear to function as adhesives. Cytochemical staining revealed the EPS to be an acidic polysaccharide and, therefore, chemically similar to the EPS produced by sessile diatoms. It is suggested that the EPS additionally assists in cell motility, acts as an antidesiccant and may influence the fouling process by combining with antifouling paint toxins and modifying the surface energy of substrata.     

Surface microtopographies of tropical sea stars: lack of an efficient physical defence mechanism against fouling

Abstract

The role of surface topography as a defence against fouling in tropical sea stars was investigated. The sea stars Linckia laevigata, Fromia indica, Cryptasterina pentagona and Archaster typicus are not fouled and have paxillae (modified ossicles with a median vertical pillar) on their aboral surfaces, which varied in diameter, height and distance depending on species and position on the aboral surface, providing unique and complex surface microtopographies for each species. The surfaces of the sea stars L. laevigata, F. indica and A. typicus were moderately wettable, with their mean seawater contact angles, calculated from captive bubble measurements, being 60.1°, 70.3° and 57.3°, respectively. The seawater contact angle of C. pentagona could not be measured. To evaluate the effectiveness of the surface microtopographies in deterring the settlement of fouling organisms, field experiments with resin replicas of the four sea star species were conducted at three sites around Townsville, Australia, for 8 weeks during the dry and wet seasons. The fouling community and total fouling cover did not differ significantly between replicas of L. laevigata, F. indica, C. pentagona, A. typicus and control surfaces at any site during the dry season. Significant differences between fouling communities on the replicas of the sea stars and control surfaces were detected at two sites during the wet season. However, these differences were transitory, and the total fouling cover did not differ significantly between replicas of sea stars and control surfaces at two of the three sites. In contrast to recent literature on the effects of biofouling control by natural surfaces in the marine environment, the surface microtopographies of tropical sea stars alone were not effective in deterring the settlement and growth of fouling organisms.