Insights into the composition, morphology, and formation of the calcareous shell of the serpulid Hydroides dianthus.

To date, the calcareous tubes of serpulid marine worms have not been studied extensively in a biomineralization context. The structure and composition of the tube shell and adhesive cement of the marine tubeworm Hydroides dianthus were studied using a variety of characterization techniques, including powder XRD, FTIR, SEM, EDX, and AFM. The tube and cement were determined to be inorganic-organic composite materials, consisting of inorganic aragonite (CaCO(3)) and Mg-calcite ((Ca(0.8)Mg(0.2))CO(3)) crystals, and both soluble and insoluble organic matrices (SOM and IOM). SEM imaging revealed a variety of crystal morphologies. AFM nanoindentation of the inorganic components yielded Young's moduli of approximately 20GPa in the wet state, and approximately 50GPa in the dry state. Amino acid analysis of the SOM indicated substantial amounts of acidic and non-polar neutral amino acids. Part of the insoluble organic tube lining was identified as being composed of collagen-containing fibres aligned in a criss-crossed structure. The SOM and organic tube lining were found to contain carboxylated and sulphated polysaccharides. In an artificial seawater solution, the SOM and the organic tube lining mediated CaCO(3) mineralization in vitro.

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.

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.

Surface elastic modulus of barnacle adhesive and release characteristics from silicone surfaces.

The properties of barnacle adhesive on silicone surfaces were studied by AFM indentation, imaging, and other tests and compared to the barnacle shear adhesion strength. A multilayered structure of barnacle adhesive plaque is proposed based on layered modulus regions measured by AFM indentation. The fracture of barnacles from PDMS surfaces was found to include both interfacial and cohesive failure of barnacle adhesive plaque, as determined by protein staining of the substratum after forced barnacle release from the substrate. Data for freshly released barnacles showed that there was a strong correlation between the mean Young's modulus of the outermost (softest) adhesive layer (E<0.3 MPa) and the shear strength of adhesion, but no correlation for other higher modulus regions. Linear, quadratic, and Griffith's failure criterion (based on rough estimate of crack length) regressions were used in the fit, and showed significance.

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.