We demonstrate a facile way of cross-linking hydrophobic perfluoropolyethers, PFPEs, with a series of hydrophilic poly(ethylene glycol)s, PEGs, to prepare a range of amphiphilic networks for use as fouling-release coatings. The PFPE matrix of the networks endows the coating with a low surface energy while the PEG is added to weaken fouling adhesion. It is therefore envisioned that the coating surfaces of these optically transparent and mechanically robust films will display hydrophobicity leading to nonfouling and fouling release characteristics. Two kinds of functionalized PEG oligomers have been cross-linked with reactive, dimethacryloxy-functionalized PFPE oligomers to form a range of amphiphilic networks: (i) a monomethacryloxy-functionalized PEG macromonomer (454 g/mol) (PEG454-MA) which was used to yield blends with flexible PEG chains on the surface as well as in bulk and (ii) a dimethacryloxy-functionalized PEG (550 g/mol) (PEG550-DMA) which results in PEG chains that are relatively more restricted in the network blends and serve as an added difunctional cross-linker for the network along with the dimethacryloxy-functionalized PFPE. The PFPE/PEG cross-linked networks coated on a substrate show very low swelling characteristics in water when PEG454-MA comprises not more than 10 wt % of the overall composition or when PEG550-DMA is used and does not comprise more than 30 wt % of the overall composition. The PFPE/PEG454-MA coatings having PEG chains with one untethered chain end were found to display relatively high spore and barnacle release performance in comparison to PFPE/PEG550-DMA coatings which have the PEG chains in a more restricted network topology.

Previous work has shown that organosilica-based xerogels have the potential to control biofouling. In this study, modifications of chemistry were investigated with respect to their resistance to marine slimes and to settlement of barnacle cyprids. Adhesion force measurements of bovine serum albumin (BSA)-coated atomic force microscopy (AFM) tips to xerogel surfaces prepared from aminopropylsilyl-, fluorocarbonsilyl-, and hydrocarbonsilylcontaining precursors, indicated that adhesion was significantly less on the xerogel surfaces in comparison to a poly(dimethylsiloxane) elastomer (PDMSE) standard. The strength of adhesion of BSA on the xerogels was highest on surfaces with the highest and the lowest critical surface tensions, g C and surface energies, g S , and duplicated the 'Baier curve'. The attachment to and removal of cells of the diatom Navicula perminuta from a similar series of xerogel surfaces were examined. Initial attachment of cells was comparable on all of the xerogel surfaces, but the percentage removal of attached cells by hydrodynamic shear stress increased with g C and increased wettability as measured by the static water contact angle, y Ws , of the xerogel surfaces. The percentage removal of cells of Navicula was linearly correlated with both properties (R 2 ¼ 0.74 for percentage removal as a function of y Ws and R 2 ¼ 0.69 for percentage removal as a function of g C ). Several of the aminopropylsilyl-containing xerogels showed significantly greater removal of Navicula compared to a PDMSE standard. Cypris larvae of the barnacle B. amphitrite showed preferred settlement on hydrophilic/higher energy surfaces. Settlement was linearly correlated with y Ws (R 2 ¼ 0.84) and g C (R 2 ¼ 0.84). Hydrophilic xerogels should prove useful as coatings for boats in regions where fouling is dominated by microfouling (protein and diatom slimes).

The facile preparation of amphiphilic network coatings having a hydrophobic dimethacryloxy-functionalized perfluoropolyether (PFPE-DMA; M(w) = 1500 g mol(-1)) crosslinked with hydrophilic monomethacryloxy functionalized poly(ethylene glycol) macromonomers (PEG-MA; M(w) = 300, 475, 1100 g mol(-1)), intended as non-toxic high-performance marine coatings exhibiting antifouling characteristics is demonstrated. The PFPE-DMA was found to be miscible with the PEG-MA. Photo-cured blends of these materials containing 10 wt% of PEG-MA oligomers did not swell significantly in water. PFPE-DMA crosslinked with the highest molecular weight PEG oligomer (ie PEG1100) deterred settlement (attachment) of algal cells and cypris larvae of barnacles compared to a PFPE control coating. Dynamic mechanical analysis of these networks revealed a flexible material. Preferential segregation of the PEG segments at the polymer/air interface resulted in enhanced antifouling performance. The cured amphiphilic PFPE/PEG films showed decreased advancing and receding contact angles with increasing PEG chain length. In particular, the PFPE/PEG1100 network had a much lower advancing contact angle than static contact angle, suggesting that the PEG1100 segments diffuse to the polymer/water interface quickly. The preferential interfacial aggregation of the larger PEG segments enables the coating surface to have a substantially enhanced resistance to settlement of spores of the green seaweed Ulva, cells of the diatom Navicula and cypris larvae of the barnacle Balanus amphitrite as well as low adhesion of sporelings (young plants) of Ulva, adhesion being lower than to a polydimethyl elastomer, Silastic T2.