The cost associated with preventing the attachment of marine organisms to underwater surfaces (biofouling) is billions of dollars annually impacting numerous sectors including shipping, aquaculture, offshore drilling, and offshore tidal and wind power. Invariably the most effective biofouling control methods are ones that are biocidal in nature whereby a coating is impregnated with a toxin that leaches out over time. However, persistence and bioaccumulation of heavy metal-based and organic biocides, creates environmental and health problems that have resulted in their regulation. Vigorous hull cleaning, aimed at periodically removing biofouling organisms, disperses fine biocide-impregnated coating particles and this significantly increases biocide persistence in sediments where they are ingested by a variety of marine organisms and bioaccumulate.

Coatings that peel off under conditions of high shear, so called foul-release coatings, are another approach but such coatings are easily damaged, not amenable to grooming and ineffective against microfouling. Further, the most effective foul-release coatings are silicon-based and it is becoming increasing apparent that leaching of toxic silicon oils from the coating matrix plays a role in their superior antifouling performance. Other approaches have been to develop durable coatings with little antifouling activity but that can withstand repeated intense grooming. One of our long term objectives is to identify coating materials with surface properties discouraging the settlement of biofouling organisms but also durable enough to withstand cleaning.

Here we report on the discovery of a transparent, conformal, pin-hole free, and plasma-polymerizable polymer coating made from an inexpensive monomer material that drastically reduces (>90%) algae (Ulva) sporeling settlement and biomass accumulation without any observable toxicity towards Ulva or a non-target brine shrimp species (Artemia). Further the unpolymerized monomer has no antifouling effect indicating that potential leaching of monomer from coated surfaces does not account for the observed antifouling activity. Rather the antifouling effect is believed to rely on the presence of a specific chemical moiety because chemical modification of that moiety abolishes antifouling activity. Testing of other marine antifouling species such as microfouling bacteria (Cellulophaga) and macrofouling mussels (Ischadium) suggests that the antifouling properties of the polymer surface are selective for algae. Potential unique applications for this technology include the coating of algae bioreactor walls or light fixtures allowing for maximal illumination and easy cleaning.

Marine surfaces are known to accumulate fouling material through the starting point of adhesion and settlement of proteins and cells. This effect can be manipulated through the modification and control of the substrate properties via surface functionalization. This approach has led to successful anti-fouling coatings based on biocidal agents containing copper or zinc compounds^[1,2]. The environmental toxicity of these latter materials, however, has increased the demand for less adverse coatings. The use of ultra-thin films consisting of polymer brushes has been considered a promising alternative and many studies have been published in this field^[3,4]. None, however, has focused on developing a protocol that allows a reliable comparison between the efficiency of different well-known anti-fouling polymers. This is one of the aims of this work and has been achieved by using a common, azide-terminated monolayer to which different non-fouling polymers, such as PEG, PEOXA, PVP and PVA, have been covalently bound. The different materials were compared by characterizing the structure-property relationship of the formed polymeric brushes. Also investigated was the role of the solvent used in the anti-fouling polymer solution as a key element to better control the surface homogeneity. A thorough analysis of the influence of this parameter on the conformation of the final polymer brush was based on ellipsometry, XPS and imaging ToF-SIMS. Finally, the anti-fouling surfaces were subjected to a comparative biological study by exposure to complex proteins solution and Ulva zoospores, in order to validate the developed protocol.

References:

^[1] Magin, C.M.; Cooper, S.P.; Brennan, A.B., Materials Today, 2010, 13, 36-44.

^[2] Chambers, L.D.; Stokes, K.R.; Walsh, F.C.; Wood, R.J.K., Surface & Coatings Technology, 2006, 201, 3642-3652.

^[3] Banerjee, I.; Pangule, R.C.; Kane, R.S., Advanced Materials, 2011, 23, 690-718.

^[4] Krishnan, S.; Weinman, C.J.; Ober, C.K.; Journal of Materials Chemistry, 2008, 18, 3405-3413.

Since materials interact with their surroundings via their surfaces, controlling the surface properties of a material are of critical importance. For materials to be used to mitigate biofouling, having the correct surface properties means the difference between a useful material and one that is unsuitable for the application. In many cases, the material properties of compositions which yield useful surface properties are not suitable for the bulk properties of the material. Thus, being able to decouple the surface and bulk properties is of interest in many areas.

Combining polydimethysiloxane (PDMS) with other polymer systems generally results in materials covered with PDMS due to its low surface energy and incompatibility with other polymers. However, if the PDMS is not chemically bound into the system, it can be easily removed from the surface. Thus, forming a copolymer of the PDMS with the other polymer is required for a durable system. Since polyurethanes are known as tough polymers due to extensive internal hydrogen bonding, combining PDMS with a polyurethane could lead to a material which is tough, but has a low surface energy surface provided by the PDMS. Thus, we have found that incorporating a reactive PDMS into a crosslinked polyurethane system can result in a material which has a low surface energy which is stable when immersed in water. High throughput screening has been used to aid in the identification and optimization of PDMS molecular weight, composition of end groups, and the amount of PDMS in the coating. A unique coating was also identified having discrete domains of PDMS on the surface. Coatings having good fouling-release properties have been prepared and tested in ocean immersion testing.

Due to the significant economic burden posed by high operational and maintenance costs of biofouled ships, the design of environmentally benign, antifouling marine coatings has been a significant interest for many researchers since the ban on traditional coatings was enacted. Current approaches for developing new marine coating materials have primarily focused on the preparation of low surface energy materials, such as modified polydimethylsiloxane (PDMS) and fluorinated polymers. These materials have shown great promise for reducing the adhesion strength of various fouling organisms, thus allowing hydrodynamic forces to release the foulants as the ship moves through water. Unfortunately, no existing material has been shown to eliminate adhesion of all of the numerous different fouling organisms, including zoospores, microalgae and diatomaceous species. As such, the development of marine coatings with multiple mechanisms of fouling prevention may be an important avenue of antifouling materials research. Poly(silyl urethanes) coatings have been developed via the reaction of various quaternary ammonium modified orthosilicates with polyisocyantes. Material properties including glass transition temperature, surface energy, and thermal stability have been investigated as a function of orthosilicate and polyisocyanate composition as well the inclusion or omission of low surface energy soft segments. The low surface energy of these materials should provide excellent fouling release properties, as has been seen with other PDMS-like materials, while the inclusion of bound quaternary ammonium biocides should further reduce the adhesion and propagation of fouling organisms at the material interface. Finally, the hydrolysable silyl ether crosslinking may prove to enhance the antifouling capabilities of these materials by allowing any fouled portions of the coating to slough away over time, generating a new active biocidal interface.