Judith Stein

Nonwetting of impinging droplets on textured surfaces

This paper studies the impinging droplets on superhydrophobic textured surfaces and proposes a design guideline for nonwetting surfaces under droplet impingement. A new wetting pressure, the effective water hammer pressure, is introduced in the study to clearly define wetting states for the impinging droplets. This approach establishes the design criteria for nonwetting surfaces to impinging droplets. For impingement speed higher than raindrop speed, the surfaces need to have sub-100-nm features to generate a large enough antiwetting pressure for the droplets to take a nonwetting state after impingement.

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.

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.

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.

The chemistry of fumarate and maleate inhibitors with platinum hydrosilylation catalysts

Abstract Pt(MviMvi)x (MviMvi = 1.3-divinyltetramethyl disiloxane), 1, was reacted with dimethyl fumarate to give 2. Compound 2 was investigated by 1H and 13C NMR spectroscopy which showed it to be a mono-nuclear platinum compound containing one dimethyl fumarate and one chelating MviMvi ligand. The reaction of 1 with dimethyl maleate gave 3 which was analogous in structure to the fumarate product as shown by 1H and 13C NMR spectroscopy and extended X-ray absorption fine structure spectroscopy (EXAFS). The EXAFS analysis showed the presence of Pt-C bonds and a through space close contact between Pt and the O from the carbonyl. The NMR assignments were confirmed by comparing the NMR spectra of 2 and 3 with that of (PPh3)Pt(MviMvi), 4. Reaction of 2 or 3 with an excess of an SiH-containing compound (either MDHDHM (MDHDHM = 1,3-bis(trimethylsiloxy)-1,3-dimethylsiloxane) or Et3SiH) gave 5 in all cases. Compound 5 contains an alkyl succinate ligand. Hydrogenation of the fumarate ligand (of 2) or of the maleate ligand (of 3) occurs by reaction with SiH; 5 appears to be an intermediate in the hydrogenation process. The reaction between 4, dimethylmaleate, and MDHDHM also gives dimethyl succinate. Differential scanning calorimetry was used to compare the effectiveness of the inhibitors in a curable formulation composed of vinyl-stopped-polydimethyl siloxane, polydimethylsiloxanemethylhydrogen-copolymer, a platinum catalyst and either a maleate or fumarate inhibitor.

A silane functionalized styrene monomer and its polymerization

Synthetic methodology for a new monomer, (4-vinylphenyl)tris(dimethylsiloxy) silane (3), which can be polymerized to give either hyperbranched polymers or linear polymers has been developed. Hyperbranched polymers can be prepared from the monomer via hydrosilation. Monomer3 can undergo free radical polymerization, which yields a linear homopolymer. Copolymers with styrene have also been prepared. The resulting polymers, which contain pendant silicon hydride functionality, can be functionalized with a variety of reagents. The glass transition temperature was found to depend strongly on the amount of silicon incorporated into the polymers.