Study On Construction And Performance Of Bionic Antifouling Coatings

Biofouling or biological fouling is the accumulation of microorganisms, plants,or animals on wetted surfaces, such as the ships, submarines, drilling equipment,instruments and meters, breeding mesh. It is a worldwide problem in marine systems,caused a great economic waste, and restricts the Marine defense and Marine affairs inour country. However, traditional antifouling paints are gradually withdraw from thestage of history for their high toxicity. Thus now, the development of new, efficient,and non-toxic anti-fouling paints material is imminent. Further research anddevelopment of bionic antifouling coatings will provide the technical experience andsupport for biofouling protection, which will reduce energy consumption, improveequipment reliability and durability, enhance the capacity of ships maneuverability ofour country’s ships and Marine facilities, and will have the profound strategicsignificance and great economic benefits, and will produce profound influencepositively, simultaneously.Frist, this article analyzes the harm of fouling organisms and the adhesionmechanism of fouling organisms and its influencing factors and control methods offouling organisms, review analyzes the development history and present situation ofantifouling coating, and emphatically analyses the principle and method of biologicalantifouling in nature. And then, the nature antifouling ways were investigated, and thelow surface energy type, bionic microstructure type, mucus effusion type, antifoulingagent release type, and enzymes load type, five types of antifouling paints were builtbasing on the perspective of bionics, mainly from the perspective of the surfacemicrostructure, antifouling agent release, and mucus effusion. Finally, the Physicaland chemical properties of all antifouling paints were investigated by Contact anglemeasurements，Mechanical testing，Chemical reagents immersion testing，and so on.And the antifouling performance of the antifouling coatings were explored by thelaboratory simulation of microbial adhesion experiments and the real sea peg boardtesting.And the following work was completed in this paper.Ⅰ.Fluorine-containing polyacrylate (named as FPA) and organic siliconmodified polyurethane (named as SPU) were synthesized, and the low surface energycoating, named FPA-SPU was obtained by the curing reaction of FPA and SPU in thispaper. Therein, FPA was obtained by the polymerization of butyl acrylate, styrene,methyl methacrylate, isobornyl acrylate, methyl methacrylate, hydroxyethylmethacrylate and1H,1H,7H-Perfluoroheptyl methacrylate， and phenylethylene, butyl acetate, and1-Methoxy-2-propyl acetate were mixed as solvent, AIBN asinitiator. The reaction temperature, reaction time, feeding methods, monomerdropping, and initiator, hydroxyethyl methacrylate and1H,1H,7H-Perfluoroheptylmethacrylate dosage were detailedly discussed, and then optimal synthesis is obtained.SPU was synthesized by the addition reaction of Using isophorone diisocyanate and astraight-chain dihydroxyl-terminated polyether modified silicone(SF-739).Thereaction temperature, the monomer dropping, initiator dosage, and the molecularweight of SF-739were adjusted to get the best SPU. In the curing reaction, thematerial ratio of FPA and SPU was studied carefully to improve the coatingperformance.Ⅱ.Ring(proline-alanine)(named as RPA),Capsaicin(named as Cap),1,2-benzo-isothiazolin-3-ketone(named as BIT),Protease from Bacilus licheniformis(named asProtease or Pro), Dextranase from chaetomium erraticum(named as Dextranase orDex), Lysozyme(named as Lys), and Horseradish Peroxidase(named as HRP) wereselected as antifouling agent by literature analysis and expert investigation. Naviculapinna adhesion experiments and barnacle larvae culture were carried out to obtain the50%inhibitory concentration and lethal concentration values, respectively.1,2-benzo-isothiazolin-3-ketone and capsaicin chitosan microspheres(named asBIT-CSM or Cap-CSM, respectively) were Successfully prepared by dispersionpolymerization, therein liquid paraffin as dispersant, and glutaraldehyde ascrosslinking agents. The BIT-CSM or Cap-CSM properties were investigated by FTIR,SEM, XRD, TG/DTA and other technical means. And the release trajectory was testedin PBS Solution.SBA-15and MCM-41mesoporous materials were synthesized by the hydrolysisreaction of TEOS in the presence of P123or CTMAB as template, respectively. Andthen SBA-15and MCM-41were modified by APTES or AAPTS to gain the aminatedmesoporous materials, and then modified by succinic anhydride to obtain carboxylmesoporous materials. All the mesoporous materials’ properties were investigated byFTIR, TEM, SAXS, TG/DTA and N2adsorption–desorption.At last, All themesoporous materials were used to immobilized Protease from Bacilus licheniformis,Dextranase from chaetomium erraticum, Lysozyme, and Horseradish Peroxidase. Thethermal stability, pH stability and operating stability of the immobilized enzyme weredetailedly investigated. Ⅲ. The low surface energy type, bionic microstructure type, mucus effusion type,antifouling agent release type, and enzymes load type, five types and twenty kinds ofantifouling paints were built basing on the perspective of bionics but all withFPA-SPU as substrate material. Among them, the low surface energy type was builtonly with FPA and SPU, three kinds of the bionic microstructure type was built byadding different weight nano-SiO2hybrid, Seven kinds of the mucus effusion type andone kind of SPC was constructed by adding different kinds and different viscositysilicone oil, four kinds of the antifouling agent release type by adding BIT-CSM,Cap-CSM or pure1,2-benzo-isothiazolin-3-ketone, or capsaicin, and four kinds of theenzymes load type was obtained by adding immobilized enzymes to FPA and SPUsystem.And then the basic physical and chemical properties of antifouling coatings wasstudied in detail by SEM, Contact angle measurements，Mechanical testing，Chemicalreagents immersion testing，and other technical means. The release trajectory of themucus effusion type and the antifouling agent release type was tested in PBS Solution.In addition, the dispersion, and shape and the size of the seepage in the coatings of themucus effusion type were detailedly investigated, too.Ⅳ. Laboratory simulation of microbial adhesion experiments and real sea pegboard testing were implemented to investigate the antifouling performance of theantifouling coatings in this paper. Microbial adhesion inhibition rates were obtainedby Navicula pinna adhesion experiments, Navicula pinna stripping experiment, andbarnacle larvae adhesion experiments. The results showed: the navicula pinnaadhesion inhibition rates of some mucus effusion type by lower viscosity methylsilicone oil or phenyl silicone oil is the least, then followed is Lysozyme load type,Horseradish Peroxidaseload type, and the bionic microstructure type. While thenavicula pinna which on the surface of some mucus effusion type by lower viscositymethyl silicone oil was easier than others to leave, then followed Protease load typeand one kind of the bionic microstructure type SiO2-3.The barnacle larvae adhesion inhibition rates of all mucus effusion type by lowerviscosity phenyl silicone oil is the least, then followed is the antifouling agent releasetype by adding BIT-CSM or pure1,2-benzo-isothiazolin-3-ketone, and then one kindof mucus effusion type by adding methyl silicone oil201-100, Lysozyme load type,he antifouling agent release type by adding Cap-CSM. The results of the real sea peg board testing showed that among all the mucuseffusion type, antifouling properties of phenyl silicone oil is the best, then hydroxysilicone oil, and the methyl silicone oil is the least, but still better than the FPA-SPU,named low surface energy type. Among one kind of silicone oil, lower viscosity isbeneficial for antifouling. Among the low surface energy type, bionic microstructuretype, antifouling agent release type, and enzymes load type, four types and twelvekinds of antifouling paints, antifouling properties of antifouling agent release type isthe best, then is enzymes load type, bionic microstructure type, low surface energytype. In addition, It is worth mentioning that all kinds of antifouling paints built in thispaper is better than the fluorocarbon resin cand polydimethylsiloxane resin.