Comparative Toxicity of “Tin Free” Self-Polishing Copolymer Antifouling Paints and Their Inhibitory Effects on Larval Development of a Non-Target Organism

Toxic substances released as a result of leaching from painted surfaces to the aquatic environment affect both fouling organisms and “non-target” biota. Artemia fransiscana nauplii have been considered a useful test system for the examination of toxicity for antifouling paints. In this study, we examined the effect of four “tin free” self-polishing copolymer (SPC) antifouling paints on the larval development of Artemia nauplii. Based on the L(S/V)50 values the order of toxicity of the antifouling paints was: ANTI F > SHARKSKIN > OCEAN T/F > MICRON. Furthermore, the body size of Artemia nauplii was significantly affected at lethal and above lethal L(S/V)5024h values. The body size of 48 h-aged nauplii exposed for the last 24 hours to each of the four SPC antifouling paints was significantly lower than that of the 48 h-aged controls (0.88 ± 0.030 mm). In addition, the body size of 72 h-aged nauplii maintained for the last 24 hours to pure synthetic seawater after exposure for 24 hours to each of the four SPC antifouling paints was significantly lower than that of the 72 h-aged controls (0.96 ±0.027 mm). Overall, the SPCs examined here were substantially toxic to Artemia nauplii, but with different toxicities and modes of action, as a result of the synergistic action of distinct components of the antifouling paints.

Durable self-polishing antifouling Cu-Ti coating by a micron-scale Cu/Ti laminated microstructure design

Marine biofouling is a major issue deteriorating the service performance and lifespan of marine infrastructures.The development of a durable,long-term,and environment-friendly antifouling coating is therefore of significant importance but still a critical challenge in maritime engineering.Herein,we developed a Cu-Ti composite antifouling coating with micron-sized alternating laminated-structure of Cu/Ti by plasma spraying of mechanically mixed Cu/Ti powders.The coating was designed to enable controlled release of Cu ions through galvanic dissolution of Cu laminates from the Cu/Ti micro-galvanic cell in aqueous solution.Results showed that remarkable antifouling efficiency against bacterial survival and adhesion up to~100%was achieved for the Cu-Ti coating.Cu/Ti micro-galvanic cell was in-situ formed within Cu-Ti coating and responsible for its Cu ions release.The successive dissolution of Cu laminates resulted in the formation of micro-channels under Ti laminates near surface,which contributed to controlled slow Cu ions release and self-polishing effect.Thus,environment-friendly antifouling capability and∼200%longer antifouling lifetime than that of the conventional organic antifouling coatings can be achieved for the Cu-Ti coating.On the other hand,as compared to the conventional organic antifouling coatings,the Cu-Ti composite coating presented much higher mechanical durability due to its strong adhesion strength,excellent mechanical properties,and two orders lower wear rate.The present laminated Cu-Ti coating exhibits combination of outstanding antifouling performance and high mechanical durability,which makes this coating very potentially candidates in marine antifouling application.

Research on the Marine Antifouling Ability and Mechanism of Acrylate Copolymers and Marine Coatings Based on a Synergistic Effect

Marine biofouling is an urgent global problem in the process of ocean exploitation and utilization.In our work,a series of zinc-based acrylate copolymers(ACZn-x)were designed and synthesized using benzoic acid,zinc oxide(ZnO)and a random quaternion copolymer consisting of ethyl acrylate(EA),butyl acrylate(BA),acrylic acid(AA)and methacrylic acid(MAA)by free radical polymerization and dehydration condensation.The ACZn-x with a zinc benzoate side chain is able to hydrolyze in natural seawater under static conditions,resulting in the formation of a smooth surface.We investigated and confirmed the antifouling(AF)behavior of ACZn-x in the laboratory and revealed that they have better antibacterial(86%for S.aureus and 72%for E.coli)and anti-algal(≥60.1%for N.closterium and≥67.5%for P.subcordiformis)activities.We also assessed the marine AF properties of ACZn-x and corresponding coatings in Qingdao,China;the ACZn-x exhibited ideal AF properties with little silt and biological mucosa adhered to the ACZn-x surface after 6 months,and corresponding coatings exhibited little biofouling after 16 months in the ocean.Importantly,possible AF mechanisms were further proposed at the cellular level.These results could be helpful for the development and application of effective AF coatings.

Effect of the Side Chain Structure on Hydrolysis Degradation of Zinc Acrylate Copolymers

In this report,zinc acrylate copolymers were synthesized by used different organic acid as the side chain structure.These copolymers were further characterized by GPC,DSC and Water absorption analysis respectively,and then the effects of the chain structure of organic acid on hydrolysis degradation and copper release rate were also discussed.In the meantime,the result shows that the biocide release rate could be controlled by used different chain structure of organic acid.