Christina Darkangelo Wood

Silicone Foul Release Coatings: Effect of the Interaction of Oil and Coating Functionalities on the Magnitude of Macrofouling Attachment Strengths

Silicone biofouling release coatings have been shown to be an effective method of combating fouling. Nearly all silicone foul release coatings are augmented with an oil additive to decrease macrofouling attachment strength. This paper addresses the effect of the type of oil that is incorporated into the silicone coating and the type of silicone coating itself (silica vs calcium carbonate filled) on macrofouling adhesion strengths to the coating. It was found that not only are the main effects of oil type and silicone coating type important in determining the magnitude of the attachment strength of the organism, but the interaction term (oil type crossed with coating type) is highly significant for all organisms studied, except oysters at the University of Hawaii test site (Oahu, Hawaii) which has a significance level of f =0.1. Each of the organisms exhibited a unique response to the various silicone fouling release coatings. Thus, in order to predict the effectives of foul release coatings, the composition variables of the coatings and the type of target organisms must be considered.

Structure-Property Relationships of Silicone Biofouling-Release Coatings: Effect of Silicone Network Architecture on Pseudobarnacle Attachment Strengths

Model silicone foul-release coatings with controlled molecular architecture were evaluated to determine the effect of compositional variables such as filler loading and crosslink density on pseudobarnacle attachment strength. Pseudobarnacle adhesion values correlated with filler loadings in both condensation and hydrosilylation-cured silicones. Variation of crosslink density of hydrosilylation-cured silicones had an insignificant effect on attachment strength. X-ray photoelectron spectroscopy (XPS) indicated that the mode of failure upon detachment of the pseudobarnacle was dependent upon the crosslink density; samples with high crosslink density failed cohesively within the silicone.

Variation in adhesion strength of Balanus eburneus, crassostrea virginica and hydroides dianthus to fouling‐release coatings

This study compared the shear adhesion strength of barnacles, oysters and tubeworms on eight RTV 11‐based silicone fouling‐release coatings containing different silicone oil additives. It was found that adhesion strength differed among species and coating types. In most cases, oysters and tubeworms had higher adhesion strengths than barnacles. Barnacle adhesion strength was reduced on all coatings containing oil additives; however, this was not generally true for oysters and tubeworms. The difference in the adhesion strength among the three organisms tested in this study emphasizes the importance of understanding the fundamental interaction between marine invertebrate adhesives and the substratum.

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.

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.

Contact angle anomalies indicate that surface-active eluates from silicone coatings inhibit the adhesive mechanisms of fouling organisms.

Abstract Silicone coatings with critical surface tensions (CST) between 20 and 30 mN m−1 more easily release diverse types of biofouling than do materials of higher and lower CST. Oils added to these coatings selectively further diminish the attachment strengths of different marine fouling organisms, without significantly modifying the initial CST. In a search for the mechanisms of this improved biofouling resistance, the interfacial instabilities of four silicone coatings were characterised by comprehensive contact angle analyses, using up to 12 different diagnostic fluids selected to mimic the side chain chemistries of the common amino acids of bioadhesive proteins. The surfaces of painted steel test panels were characterised both before and after exposure to freshwater, brackish water, and seawater over periods ranging from 9 months to nearly 4 years. Contact angle measurements demonstrated significant surface activity of the oil-amended coatings both before and after long-term underwater exposure. The surface activity of the control (coating without oil) increased as a result of underwater exposure, consistent with mild surface chain scission and hydrolysis imparting a self-surfactancy to the coating and providing a weak boundary layer promoting continuing easy release of attaching foulants. Coatings with additives that most effectively reduced biofouling showed both initial and persistent contact angle anomalies for the test liquid, thiodiglycol, suggesting lower-shear biofouling release mechanisms based upon diminished bioadhesive crosslinking by interfering with hydrogen- and sulfhydryl bonds. Swelling of the silicone elastomeric coatings by hydrocarbon fluids was observed for all four coatings, before and after immersion.

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.