Self-polishing emulsion platforms: Eco-friendly surface engineering of coatings toward water borne marine antifouling

https://doi.org/10.1016/j.porgcoat.2020.105945Get rights and content

Highlights

  • Water borne self-polishing marine antifouling coating was fabricated.

  • Attractive antifouling performance was obtained via interface self-refresh.

  • Lower abrasion rate of film but effective release behavior of antifoulant could be guaranteed.

  • This method was simple and facile to scale-up preparation, showing great potential application.

Abstract

Biofouling has been a great challenge for the exploitation of marine resources and could be generally avoided by decorating with protective coatings on the ships or equipment, while the process will produce a great amount of volatile organic compounds (VOC) and lead to or even aggravate environmental hazards. A high-performance water borne antifouling coating (WBAC) composed of self-polishing emulsion and bioactive ingredient was prepared, in which triisopropylsilyl ester acted as the self-polishing matrix and zwitterionic complex with cupric ion was used as the main antifoulant. The surface wettability, self-polishing rate, essential mechanical properties and the broad-spectrum antifouling capability were characterized in the lab. The experimental results indicated that the designed fully solvent free coating was capable of adjustable polishing rate and possessed robust stability and excellent antifouling performance for the settlement of green algae, red algae and diatom. Moreover, the long-term but robust performance of the engineered WBACs has been proved in the marine field test. Considering its solvent-free character and excellent antifouling behavior, this research would provide insights into the design of the next-generation of the eco-friendly and sustainable marine antifouling coating.

Introduction

Marine antifouling has great and long-standing significance for the exploitation of ocean resources, especially for the industries closely related to the national economy [1,2], because the unexpected biofouling would aggravate the corrosion and damage to the ground or underwater equipment, such as the various types of underwater vehicle. Besides, they will also increase both the resistance of vessels and naval ships movement and the maintenance cost, which are serious in marine field [[3], [4], [5]]. Ocean situation is complex generally, including the varied composition of seawater and a great deal of fauna and flora [6,7], hence it is very challenging to make up a prescription with broad-spectrum antifouling properties. At present, researchers have proposed varieties of effective antifouling methods containing the dynamic surface antifouling [[8], [9], [10]], coating based on releasing antifoulants [[11], [12], [13]] and the nature-inspired surface modification strategies. Among that, self-polishing coatings (SPCs) have attracted great attention because of high efficiency, enduring antifouling performance and facile processing.

SPCs generally possess polymer backbone or side chains that can be hydrolyzed in alkaline medium to achieve antifouling, which means the surface layer with a certain thickness will be peeled off unremittingly and a fresh surface will be exposed. Especially, functional compounds incorporating esters and metal salt (tin acrylate, zinc acrylate, etc.) have been studied [[14], [15], [16]]. This kind of coating undoubtedly has a strong self-renewal ability and also overcomes the defects that the soluble matrix and controlled depletion polymer coatings accelerate their own failure with the dissolution of the coating matrix [17,18]. Although SPCs have been studied for many decades and can maintain antifouling performances for 4∼5 years, they always adopt bulk of organic solvents as diluent [19,20]. Unfortunately, almost all diluents are volatile organic compounds (VOCs) which are generally toxic and carcinogenic. Besides, they can lead to photochemical smog and aggravate the greenhouse effect as well [21]. Therefore, considering the coating industry is an important route involved a great deal of VOCs, it is significant to reduce or avoid the usage the organic solvents alleviating the discharge of VOCs in the atmosphere [[22], [23], [24]].

Water borne coating has been one of the most promising strategies for this problem since it has a small amount VOCs (less than 50 g/L). In recent years, some research concerning water borne antifouling coating was conducted, in which F and Si segment were employed to control the surface property [[25], [26], [27]]. Meanwhile, water-borne polyurethane also has attracted great attention due to its robust mechanical properties, flexible designability of structure and composition [[28], [29], [30]], while their more practical implementation was usually hindered by the complicated processing in large scale production and poor performance. Generally, the water-based paint is consisted of suspension of polymer particles, pigment, coalescent and rheological additives [31]. While for solvent-based formation, the polymer is completely swelled in organic solvent, and the high entanglement between polymer chains makes them easily prepare high gloss and high-quality coatings. However, the film of water-based coatings is complex progress in which the polymer particle chains first diffused, squeezed, deformed with the water evaporation and finally formed a coherent film [32]. If the circumstance temperature is too low or the glass transition temperature of the polymer is too high when the film is formed, the polymer particle chain cannot be diffused well in water, which will lead to the poor performance of the coating and even the emergence of chalking [33]. In addition, the ocean was a typical corrosive and fouling circumstance due to the fluctuation of temperature, salinity, pH and oxygen content. At present, there are still no references mentioning the water borne coatings in this harsh marine circumstances, especially no promising research for marine antifouling applications. Meanwhile, it is still a large challenge for water borne coating under harsh condition because the film-forming process often leads to defects in the coating [21].

Apparently, an ideal excellent antifouling coating should inherit the advantages of traditional SPCs but avoid its shortcomings. Therefore, an eco-friendly performance was integrated with the durability by adopting the fascination of common SPCs in this paper. A complete solvent free antifouling concept was proposed using water borne functionalized latex, both the high film-forming capability and the excellent antifouling property were guaranteed by adjusting the self-polishing latex and antifoulants. As a result, combining the unique properties of traditional SPCs with the water borne concept enables the designed coating technique is capable of eco-friendly character and shows great application prospects in the field of marine antifouling.

Section snippets

Materials

Isobornyl methacrylate (IBOMA, AR grade), acrylic acid (AC, AR grade), triisopropylsilyl methacrylate (TIPSMA, AR grade), styrene (St, AR grade), methyl methacrylate (MMA, AR grade), n-Butyl acrylate (BA, AR grade), butyl methacrylate (BMA, AR grade), copper(I) oxide (Cu2O), iron(III) oxide (Fe2O3), sodium bicarbonate (NaHCO3), ammonia water solution (25 % m/m), 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate (SBMA, AR grade), bis (1-hydroxy-1H-pyridine-2-thionato-O,

Physicochemical characterization of WBACs

The micelle size of AFL was tested by dynamic light scattering (DLS) (Zeta sizer Nano ZS, Malvern Instruments, UK) at 25 °C, the AFL was diluted with ethanol (v (latex): v (water) = 3:1), the sample was tested three times at least; The microscope images of AFL were obtained on a JSM-6701 F field emission scanning electron microscope (FE-SEM) at 5−10 kV; The chemical compositions of the resulted AFL were characterized by Fourier transform infrared (FT-IR) spectroscopy (Nicolet iS10, Thermo

Results and discussion

Using seed emulsion polymerization, the aqueous emulsion with low dispersity was prepared. As shown in Fig. 1, the compliance, thermal properties, mechanical stability and self-polishing capability of the latex can be manipulated by adjusting the molar ratio of the various acrylic monomers and some specialized components [37]. For example, increasing the amount of MMA could change the thermal properties and glass transition temperature of the copolymer, the result was shown in Fig. S1.

Conclusion

In summary, water borne functionalized latex with low dispersity and ideal film-forming properties was prepared by emulsion polymerization, in which SBMA with antifouling activity and silyl ester TIPSMA as functional self-polishing composition was incorporated. A complete solvent free antifouling strategy was established through integrating the functionalized latex with the water borne slurry. Some pivotal parameters, including the wetting behavior, the release capability of the antifoulant,

Declaration of Competing Interest

The authors reported no declarations of interest.

Acknowledgment

The authors acknowledge the financial support from NSFC (51905519, 21773274), Dr Wufang Yang also thanks the project of Western Young Scholar "B" of Chinese Academy of Sciences and the financial support provided by Opening Foundation of Research and Development Center of Transport Industry of Technologies, Materials and Equipments of Highway Construction and Maintenance. (Gansu Road & Bridge Construction Group, No. GLKF201815).

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