船舶低表面能防污涂料研究进展

本文论述了低表面能防污涂料的机理和研究进展,展望了仿生技术在低表面能防污涂料研究中的应用前景。     

Dissolution rate measurements of sea water soluble pigments for antifouling paints: ZnO

The dissolution of soluble pigments from both tin-based and tin-free chemically active antifouling (AF) paints is a key process influencing their polishing and biocide leaching rates. In this context, a low time- and resources-consuming method capable of screening the pigment behaviour in the search for the most promising materials or mixtures is of great interest. A preliminary attempt to develop such a method is presented in this paper based on the widely used ZnO pigments.

While highly pure, nano-polished, monocrystalline ZnO substrates yielded very low dissolution rates in the order of 17.3 ± 3.7 μg Zn²⁺ cm⁻² day⁻¹, pellets prepared by compacting and sintering technical grade ZnO pigments dissolved about three times faster according to inductively-coupled plasma mass spectrometry (ICP-MS) measurements. The rougher and more porous surface exposed, together with the larger number of defects in the lattice structure, are hypothesised to be responsible for the faster sea water attack of the pellets compared to the ZnO crystals. In any case, the ZnO dissolution rates reported in this paper are markedly lower than those associated with the sea water dissolution of cuprous oxide (Cu₂O) particles which are also used in AF paints. Experimental performance testing of model antifouling paints formulated with ZnO and/or Cu₂O demonstrates that the binder/pigment interaction should not be disregarded if the leaching of sea water soluble pigments from paint systems is to be determined.     

Development of hybrid antifouling paints

The objectives of this study are to measure the efficiency of a hybrid system for antifouling paint and to observe the influence of the physico-chemical properties of the binder on the antifouling activity. Poly(ɛ-caprolactone) (PCL) and poly(dimethylsiloxane) (PDMS) homopolymers are already used as binder for different antifouling strategies. The use of the block copolymer should allow to mix the properties of erosion and hydrophobicity to obtain a more efficient paint with a reduced environmental impact.Paints containing triblock copolymer were immersed in seawater in Lorient harbour to evaluate their antifouling activities. The water absorption, the degradation and the surface properties of the copolymer were measured in distilled water to understand the influence of the binder characteristics in the resulting antifouling properties.The hybrid paints have shown efficiency close to a commercial paint during their immersion in situ in spite of inadequate static conditions of test.     

Prevention of biofouling on aquaculture nets with eco‐friendly antifouling paint formulation

Aquaculture, which is an important part of food supply, is usually carried out in cage nets made of textile materials. Fouling organisms settle on the cage nets over time, close the mesh openings, and cause unwanted weight gain. In order to prevent fouling, aquaculture nets are generally treated with antifouling paints. In this paper, warp knitted cage nets made from various raw materials were treated with three different antifouling paints. Econea was used as a biocide to prepare an eco‐friendly antifouling paint formulation, and two copper‐based commercial antifouling paints were supplied for comparison. Antifouling paint‐treated and untreated net samples were immersed in a marine ecosystem next to an aquaculture zone for 6 months. Settlement of fouling organisms on nets was observed by taking underwater photographs at periodic intervals. Following the field study, changes in the structure of the nets and antifouling performance of the paints were evaluated considering the results of underwater photographs, biomass growth, variation in mass and strength tests. Colour fastness of the antifouling paints to sea water was also measured to learn about biocide release and surface hydrophobicity. The results show that copper‐free eco‐friendly antifouling paint is just as effective against the fouling mechanism for all types of nets as copper‐based commercial antifouling paints. The novel eco‐friendly formulation has promising results, which provides an alternative for producers when considering the selection of raw materials.     

Seawater-soluble pigments and their potential use in self-polishing antifouling paints: simulation-based screening tool

This work concerns the on-going development of efficient and environmentally friendly antifouling paints for biofouling control on large ocean-going ships. It is illustrated how a detailed mathematical model for a self-polishing antifouling paint exposed to seawater can be used as a product engineering tool to obtain a quick estimate of the paint behaviour that a given seawater-soluble pigment will provide. In the present context, “pigment” refers to relevant particulate solids of organic-, inorganic-, or biological nature. Simulations performed at 15 and 30 °C suggest that pigment solubility and seawater diffusivity of dissolved pigment species have a significant influence on the polishing and leaching behaviour of a typical self-polishing paint system. The pigment size distribution, on the other hand, only has a minor influence on the paint–seawater interaction. Simulations also indicate that only compounds which are effective against biofouling at very low seawater concentrations are useful as active antifouling paint ingredients. The need for model verification and exploration of practical issues, subsequent a given pigment has been found of interest, is discussed. The model approach is of relevance in the search for novel antifouling paints and for the development of accelerated test methods.     

铝壳舰船用防污涂层的性能评价

分析了铝壳艇水下防污的现状,介绍了国内外不同生产厂家铝合金配套防污涂层在厦门、三亚和青岛海域实海浸泡和厦门海域动态模拟试验的结果。结果表明:低表面能类防污涂料,在厦门海域可以保持9个月的防污效果;硫氰酸亚铜类防污涂料,不同的厂家防污效果有所不同,其防污效果可以达到6～12个月;无毒环保类防污涂料,防污效果较差,一般均在6个月以下。同时比较了各种防污涂料配套体系的耐冲刷性能和对铝合金基体的保护作用,结果显示,所选防污涂料配套体系均有良好的耐冲刷性能;对铝合金也有良好的保护作用。     

自抛光防污涂层及评价技术的发展

介绍了自抛光防污涂料的防污机理和防污特点,概括了有机锡自抛光防污涂料和无锡自抛光涂料的防污机理和发展状况,阐述了几种不同无锡自抛光涂料的防污原理,对自抛光防污涂料通过测定防污涂层的有效成分渗出率间接反映防污性能的评价方法和实海挂板直接评价防污涂层的防污性能的传统评价方法进行了总结。详细介绍了几种自抛光防污涂料室内动态模拟性能评价方法和生物性能评价方法,并对自抛光防污涂料的发展方向进行了展望。     

Antifouling activity of marine paints: Study of erosion

It is generally agreed that the prevention of marine fouling can be achieved by coatings from which a controlled release of toxic molecules prevents the growth of adhered organisms (bacteria, algae, molluscs). Since the end of 1990s, antifouling paints have been made by the blending of polyacrylic resins with biocides. The aim of this study was to use new polymers in order to obtain biodegradable antifouling paints with controlled release of biocide.     

High-build soluble matrix antifouling paints tested on raft and ship''s bottom

The characteristics and properties of some experimental high-build soluble matrix antifouling paints have been studied. Thixotropic samples were formulated with WW rosin and Grade 10 chlorinated rubber as a binder, using red cuprous oxide as the main toxicant and zinc oxide as the reinforcing toxicant. Non-thixotropic reference samples having the same composition but prepared with Grade 20 chlorinated rubber in the formulation were also used. Rheological additives at 2.0 and 1.0% concentrations were employed for the high-build and conventional formulations, respectively.

The paints were tested by means of raft and ship trials to determine their bioactivity. Films of 50–60 and 100–120 μm thickness were evaluated to establish the influence of this variable on the antifouling characteristics of the prepared products.

Good antifouling protection extending to 14, 26 and 36 months was obtained with some of the samples tested on raft panels and up to 25 months for the paints applied on the ship hull.     

Differentiation of the drying time of paints by dynamic speckle interferometry

This work is part of studies of drying of paints using dynamic speckle interferometry (DSI), a technique based on the use of laser light. DSI is a non-invasive method that does not disturb the drying process. The sample is illuminated by a laser light from a source and the images corresponding to a phenomenon of interference called speckle are registered. If the surface shows activity, the interference pattern changes in time. Following this evolution, we can analyze the drying process by means of an image-processing algorithms. Therefore, it is possible to determine the temporal evolution of surfaces with different drying times. In this work the application of DSI to follow the drying process of paints with different drying times and drying velocities is presented. Different types of paints applied in different thicknesses of wet film and aerosol spray were analyzed. Quantitative measurements were obtained by analysis of the inertia moment of the co-occurrence matrix. Also, qualitative measurements were obtained by sample activity. A new approach for monitoring simultaneously zones with different drying times is discussed and applied. As in previous work, results were compared with those from conventional techniques such as gravimetric analysis providing a good correlation between both techniques.     

Bioactivity of antifouling paints based on organotin toxicants

This paper discusses the bioactivity of antifouling paints based on organotin toxicants, such as tributyltin fluoride (TBTF) and triphenyltin fluoride (TPTF). These compounds were used alone or mixed as the main toxicant in formulations. The use of TPTF or mixtures of TPTF and TBTF, with vinyl binders, led to paints with satisfactory bioactivity during a 24 months immersion period. With the same binders, TBTF alone provided only 12 months of antifouling protection. The correlation coefficients calculated from the fouling attachment values and the rosin content in the binder showed that the bioactivity of the tested formulations depended on the solubility of the toxicant in sea water and on the composition and solubility of the binders.     

High-build soluble matrix antifouling paints based on vinyl resin

The aim of this work was to formulate and evaluate high-build, soluble matrix antifouling paints showing reduced solvent retention in the film and sufficient bioactivity to protect structures submerged in sea water for long immersion periods.

The variables analyzed were binder composition, pigment content, toxicant type and thixotropic agent content.

Binder dissolution in sea water was achieved by employing WW rosin or calcium resinate; the control of the binder dissolution rate was achieved by using a vinyl resin as a cobinder. The paints were formulated with pigment volume concentrations of 40 and 45%; red cuprous oxide and triphenyl tin fluoride were used as the main toxicants. The rheological additive employed was hydrogenated castor oil at levels of 2.0 and 2.5 wt.% in the paint.

The bioactivity of the antifouling paints was determined in the natural environment (30 month immersion in sea water).     

High-build antifouling paints based on rosin and chlorinated rubber

The fundamental objective of this work was to formulate antifouling paints giving a high thickness film with a reduced number of coats and having suitable physico-chemical properties and biocidal characteristics for the protection of ships' hulls. Formulation variables studied were WW rosin (gum rosin)/chlorinated rubber (grade 10) ratio, which defines the binder dissolution rate, and the rheological agent content (castor oil), which influences the paints' thixotropic behaviour. Red cuprous oxide, zinc oxide and natural calcium carbonate were used as pigments. Tests were made in the laboratory for evaluating abrasion resistance, adhesion and elongation. Binder dissolution rate of the different paints in artificial sea water and also some rheological parameters of the samples were determined. Service tests were performed on ships' hulls (a destroyer, two light destroyers and an aircraft carrier), showing some paints retaining good antifouling characteristics after 25 months' immersion.     

机能性涂料与摩擦学

介绍了机能性涂料的定义、分类并通过摩擦学时机能化表面技术进行了分析。     

Cupric tannate: A low copper content antifouling pigment

Fouling organisms attached to man-made surfaces submerged in seawater constitute a major worldwide technical and economical problem. Protection against biofouling is essential for efficient service of boats and ships. Due to recent and imminent restrictions of the use of traditional toxic antifouling paints, there is a growing need for new alternative compounds that ensure a good performance without polluting the marine ecosystem.

The aim of this work is to develop a new antifouling formulation using compounds of natural origin, i.e. tannates, in combination with a minimum concentration of a known bioactive pigment, i.e. copper.

Laboratory assays have shown that cupric tannate has a narcotic effect on biofouling larvae. In the field, after 12 months of immersion in Mar del Plata harbor (Argentine), none of the tested painted panels showed macrofouling organisms. This result was obtained with a large decrease in copper content in the order of 40 times relative to conventional cuprous oxide based paints.

Because copper tannate is not lethal at low concentrations, this pigment has an excellent potential as an antifouling agent.     

Evaluation of anti-microfouling activity of marine paints by microscopical techniques

The use of two microscopical techniques, SEM and CLSM, was investigated to facilitate the observation of adhered microfouling on antifouling paints. Bacterial and diatom colonisation was quantified on antifouling paints and compared with the standard test, ASTM D 3623. The results indicate that there is a likely correlation between the microscopic study and the antifouling activity. The study revealed the interest of CLSM for the evaluation of antifouling paints and reports on the efficacy of CLSM to study the initial microfouling layer. This method can yield important data relating to biofilm morphology, particularly film thickness and biomass measurements. This non-invasive technique enabled us to obtain qualitative and quantitative data about the biofilm formation during the first weeks of immersion in seawater.     

几种天然产物在海洋防污涂料中的应用研究

将天然产物齐墩果酸、蛇床子素和鱼藤酮作为防污剂,分别制备海洋防污涂料,在厦门海域检验其海区防污效能,并与已报道在厦门海域具防污效能的天然产物喜树碱进行比较,发现蛇床子素和鱼藤酮在海区挂板2个月内显示出一定的防污效能,齐墩果酸没有呈现出防污效能,而喜树碱的海区防污效能明显优于上述3种天然产物。另外,将喜树碱与鱼藤酮进行1∶1复配,并将这2种天然产物与氧化亚铜、N-(2,4,6-三氯苯基)马来酰亚胺(TCPM)和吡啶硫铜锌(ZPT)这3种防污(助)剂分别进行1∶1复配,共获得7种复配防污剂,制备相应的海洋防污涂料以检测其防污效能,发现喜树碱-TCPM、喜树碱-ZPT以及喜树碱-鱼藤酮这3种复配防污剂具良好的防污效能。进一步在上述涂料中选取了防污效能最优的含喜树碱涂料,在福建东山海域和海南陵水海域分别进行了海区挂板试验,结果表明含喜树碱涂料在这2个海域均显示出稳定、优异的防污效能,且期效可达13个月以上。文中研究为推进天然防污产物在海洋防污涂料中的应用进程提供了重要资料。     

大理石花纹漆的配方设计及施工工艺探讨

通过试验,用特殊改性丙烯酸树脂、染料、溶剂等制备大理石花纹漆,探讨了大理石花纹漆各漆层的施工工艺和配方设计,并讨论了树脂、颜料、助剂和有机溶剂等对大理石花纹漆性能和大理石效果的影响。     

Interaction between styrene/butylacrylate latex and water soluble associative thickener for coalescent free wall paints

The effect of water soluble hydrophobically modified ethylene oxide urethane (HEUR) thickener on coalescent free wall paints was studied. Three systems were looked at: latex/thickener blends, model paints (containing no fillers that could have an effect on paint rheology) and satin paints (PVC 30%). The latexes used were a styrene/butylacrylate copolymer, designed for coalescent free wall paints. A full factorial statistical experimental design was employed to study the effect of latex and formulation variables on the viscosity response for the full range of shear rates encountered in paint application. The factors considered in the design were total latex surface area, polymerization surfactant level, thickener type and thickener concentration. The surfactant level was varied between 0.85 and 1.71 parts. The two HEUR thickeners were selected based on the manufacturer's claim that they exhibited good performance at different shear rates. The thickener levels were the extremes recommended by the manufacturer. Measurements were done on Haake, Rheometrics, Brookfield and ICI Cone & Plate rheometers. Total latex surface area and the thickener level are the two significant parameters for latex thickener blends and for model paints at the same significance level, this indicates good correlation between the two systems. The introduction of clay as a filler decreases the effect of all parameters studied.     

海洋防污涂料技术的研究现状及展望

叙述了海洋防污涂料类型与研究现状,介绍了新型环保的低表面能防污涂层技术在海洋方面的应用,介绍了异噻啉酮衍生物（MOP-OCI）对藻类生长的抑制作用,以此化合物为防污剂制备的海洋防污涂料,5个月的实海挂板几乎没有附着海洋污损生物。重点介绍了有机硅涂料、有机氟涂层以及绿色防污涂料的国内外研究进展和应用现状,并介绍了几种防污涂料的防污机理与加速评价方法,展望了海洋防污涂料发展趋势。