WO2019029172A1 - Anti-corrosive coating with self-repairing ability, preparation method therefor, and application thereof - Google Patents

Anti-corrosive coating with self-repairing ability, preparation method therefor, and application thereof Download PDF

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Publication number
WO2019029172A1
WO2019029172A1 PCT/CN2018/081736 CN2018081736W WO2019029172A1 WO 2019029172 A1 WO2019029172 A1 WO 2019029172A1 CN 2018081736 W CN2018081736 W CN 2018081736W WO 2019029172 A1 WO2019029172 A1 WO 2019029172A1
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self
inner layer
sodium alginate
corrosion
polyaniline
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PCT/CN2018/081736
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French (fr)
Chinese (zh)
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裴元生
崔骏
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北京师范大学
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Priority to GB1901424.0A priority Critical patent/GB2569462B/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to the field of anti-corrosion materials, in particular to an anti-corrosion coating with self-repairing ability and a preparation method and application thereof.
  • Corrosion of pipelines can cause a range of direct and indirect economic and environmental problems in drinking water networks and circulating water systems.
  • pipeline corrosion can directly reduce the service life of the pipeline, increase the economic cost of the enterprise, and cause the industrial equipment to stop running; the corrosion products generated by the corrosion of the pipeline are easily dissolved in the water under the scouring of the water flow, causing the water quality to deteriorate, resulting in the safety of water being unsafe. Guarantee.
  • the corrosion of the water pipeline is often controlled by adding a corrosion inhibitor and a coating coating technique.
  • corrosion inhibitors often causes deterioration of water quality, such as the addition of phosphorus-based corrosion inhibitors to eutrophication of water bodies (CN 103663746 A); the addition of metal salt corrosion inhibitors enhances the toxicity of water (CN 102583785 A) . Therefore, most countries have strict requirements for the use of corrosion inhibitors, which limits the application of corrosion inhibitors.
  • the coating as an efficient anti-corrosion technology also has obvious defects.
  • the coating is susceptible to cracking due to the surrounding environment.
  • the rate of corrosion at the rupture increases rapidly, and the corrosion range gradually increases near the rupture zone, causing under-film corrosion, which eventually causes large-scale shedding and failure of the coating (CN 103375657 A). Therefore, self-healing coatings have emerged.
  • the commonly used self-healing coating is to encapsulate the corrosion inhibitor in the coating (CN 104927583 A). When the coating is broken, the corrosion inhibitor flows out to form a protective layer on the surface of the pipeline to avoid corrosion of the pipeline.
  • the corrosion inhibitor is usually soluble in water, and under the action of the water flow in the water pipe network, the corrosion inhibitor is not easy to form a protective film at the crack. Therefore, the effect of the self-repair coating on preventing the corrosion of the pipeline of the water pipe network is not satisfactory.
  • the outflow of corrosion inhibitors can cause deterioration of water quality and bring about certain environmental risks. Therefore, the development of environmentally friendly coatings with high efficiency of corrosion protection and self-healing has important practical significance.
  • An object of the present invention is to solve at least one of the above problems, and to provide an anticorrosive coating having self-healing ability, a preparation method and application thereof.
  • the anti-corrosion coating can be attached to the wall of a water pipe of a water pipe network (for example, a carbon steel water pipe) to prevent the water pipe from being corroded by water.
  • an anticorrosive coating having self-healing ability comprising an anticorrosive inner layer and a self-healing top layer, wherein the self-healing top layer material comprises polyaniline coated sodium alginate microcapsules.
  • the polyaniline-coated sodium alginate microcapsule has a particle diameter of 100 nm to 1 ⁇ m.
  • the material of the self-repairing surface layer further comprises an epoxy resin, and the polyaniline-coated sodium alginate microcapsules are dispersed in the epoxy resin, and the volume ratio of the polyaniline-coated sodium alginate microcapsule to the epoxy resin is 1:6. -1:3.
  • the material of the anticorrosive inner layer is mainly composed of graphene oxide modified by boric acid and/or borax.
  • a method of preparing the anticorrosive coating comprising the steps of:
  • the material for preparing the self-repairing surface layer comprises the following steps:
  • the material for preparing the anticorrosive inner layer comprises the following steps:
  • the graphene oxide is mixed with boric acid and/or borax in a deionized water solution; after ultrasonic dispersion, the filter membrane is filtered to obtain a residue; the residue is dispersed in an ethanol solution to form a material for preserving the inner layer.
  • the mass ratio between sodium alginate, polyaniline, epoxy resin and polyamide curing agent is 4-7:3-6:6-12:0.6-4.
  • the mass ratio between the graphene oxide and the borax and/or boric acid as a modification is 1:0.01-0.1.
  • the components of each raw material are subordinate ratios or an equal multiple of the ratio:
  • the components of each of the prepared raw materials are the following ratios or an equal multiple of the ratio:
  • the liquid environment is water having a chloride ion content of 1500 mg/L or less and a calcium ion content of 100 mg/L or more.
  • the invention provides an environment-friendly coating with high-efficiency anti-corrosion ability and self-repairing capability, and has a double-layer structure.
  • the anti-corrosion inner layer is mainly composed of boron oxide-graphene oxide (GO-B) modified by boric acid and/or borax, and the anti-corrosion inner layer has good insulation effect, which can effectively prevent the pipeline and the corrosive water. Electronic transfer.
  • the polyaniline coated sodium alginate (PANI-SA) microcapsules in the outer layer have high self-healing ability in the water pipe network. Under the action of polyaniline, a metal oxide film can be formed between the surface of the pipe and the polyaniline layer, thereby improving the surface resistance of the pipe.
  • sodium alginate can react with calcium ions in the solution to form a calcium alginate precipitate.
  • the mixed precipitate layer of calcium alginate and sodium alginate can effectively prevent the loss of polyaniline and increase the surface resistance of the pipeline. Therefore, in the rupture zone of the coating, a two-layer structure having a polyaniline layer as a base and a mixture of sodium alginate and calcium alginate as a surface layer was formed. In turn, the coating is self-repairing.
  • calcium alginate is insoluble in water, only a very small amount of sodium alginate is released into the water, and sodium alginate is used as an edible material, so that cracking of the coating does not cause water quality safety problems.
  • the anti-corrosion coating provided by the invention has high anti-corrosion ability, can prevent the water pipeline from being corroded by water, and has a rapid self-repairing ability, and can prevent the coating from being broken due to cracking and being unable to be effectively repaired to cause large-scale shedding. Moreover, the anticorrosive coating provided by the present invention releases only a very small amount of edible sodium alginate after rupture, and does not affect the water environment.
  • FIG. 1 is a graph showing changes in polyaniline-coated alginate microcapsules (PANI-SA) over time in the preparation of a self-healing surface layer of an anticorrosive coating according to an embodiment of the present invention
  • FIG. 4 is a three-dimensional fluorescence diagram of water quality before and after dissolution release of an anticorrosive coating according to an embodiment of the present invention.
  • the anti-corrosion coating 1 comprises an anti-corrosion inner layer and a self-repairing surface layer, and the self-repairing surface layer is attached to the surface of the anti-corrosion inner layer, and the self-repairing surface layer material is mainly composed of epoxy resin and sodium alginate microcapsule, and also includes a part Raw material impurities (one or more of polyaniline, N, N-dimethylformamide, amide curing agent and ethanol), sodium alginate microcapsules are uniformly dispersed in epoxy resin, polyaniline coated alginic acid The volume ratio of sodium microcapsules to epoxy resin is 1:6.
  • the material of the anticorrosive inner layer is mainly composed of boron-graphene oxide, and also includes some raw material impurities (ethanol).
  • the GO-B material is sprayed on the inner wall of the water pipeline to form an anticorrosive inner layer having a thickness of 200 nm to 100 ⁇ m, and the epoxy resin material containing the PANI-SA microcapsule is spin-coated on the surface of the anticorrosive inner layer to form a thickness of 500 ⁇ m.
  • the corrosion resistance of the coating was evaluated using a conventional three-electrode system.
  • the composition of the corrosive water is shown in Table 1.
  • Carbon steel electrode (0.15 wt.% C, 0.46 wt.% Mn, 0.28 wt.% Si, ⁇ 0.042 wt.% P, ⁇ 0.049 wt.% S, remainder Fe)) Carbon steel cylinder with a bottom diameter of 1 cm composition.
  • the copper wire was welded to the bottom surface of the carbon steel electrode using an electric welding technique, and the carbon steel electrode was encapsulated with an epoxy resin, leaving only 0.785 cm 2 in contact with corrosive water.
  • the anti-corrosion coating 1 is sprayed or coated on the contact surface. After the treated electrode was immersed in corrosive water for 30 min, the surface impedance was measured. The impedance was measured using an electrochemical workstation Autolab 204 in the range of 0.01 Hz to 100 kHz.
  • the coating was scratched using a blade until it touched the substrate material, and the surface impedance was tested after immersing in the above corrosive water for 10 min, 1 h, 3 h, and 5 h.
  • the water sample was subjected to three-dimensional fluorescence and total boron concentration measurement after being immersed in the above-mentioned corrosive water having a water flow rotation speed of 100 r/min and a temperature of 30 ° C for 48 hours.
  • the particle size of the produced microcapsules increases with time, and the particle diameter is in the range of 100 nm to 500 nm.
  • the anti-corrosion coating 2 comprises an anti-corrosion inner layer and a self-repairing surface layer, and the self-repairing surface layer is attached to the surface of the anti-corrosion inner layer, and the self-repairing surface layer material is mainly composed of epoxy resin and sodium alginate microcapsule, and also includes a part Raw material impurities (one or more of polyaniline, N, N-dimethylformamide, amide curing agent and ethanol), sodium alginate microcapsules are uniformly dispersed in epoxy resin, polyaniline coated alginic acid The volume ratio of sodium microcapsules to epoxy resin is 1:5.
  • the material of the anticorrosive inner layer is mainly composed of boron-graphene oxide, and also contains some raw material impurities (ethanol).
  • the GO-B material is sprayed on the inner wall of the water pipeline to form an anticorrosive inner layer having a thickness of 200 nm to 100 ⁇ m, and the epoxy resin material containing the PANI-SA microcapsule is spin-coated on the surface of the anticorrosive inner layer to form a thickness of 500 ⁇ m. – 10mm self-healing outer layer to form an anti-corrosion coating 2 .
  • test method is the same as in the first embodiment.
  • the particle size of the produced microcapsules increases with time, and the particle diameter is within the range of 300 nm to 1 ⁇ m.
  • the anti-corrosion coating 3 comprises an anti-corrosion inner layer and a self-repairing surface layer, and the self-repairing surface layer is attached to the surface of the anti-corrosion inner layer, and the self-repairing surface layer material is mainly composed of epoxy resin and sodium alginate microcapsule, and also includes a part Raw material impurities (one or more of polyaniline, N, N-dimethylformamide, amide curing agent and ethanol), sodium alginate microcapsules are uniformly dispersed in epoxy resin, polyaniline coated alginic acid The volume ratio of sodium microcapsules to epoxy resin is 1:4.
  • the material of the anticorrosive inner layer is mainly composed of boron-graphene oxide, and also contains some raw material impurities (ethanol).
  • a mixture of 9.6 g of graphene oxide and 0.528 g of borax and boric acid was mixed in a deionized aqueous solution, ultrasonically dispersed for 2.5 h, passed through a 0.45 ⁇ m filter, and the residue was washed three times with deionized water.
  • the residue was dispersed in a 90 mL ethanol solution, stirred at 50-80 ° C for 3 h, and then ultrasonically dispersed for 1.5 h to obtain a GO-B inner layer material.
  • the GO-B material is spin-coated on the inner wall of the water pipeline to form an anti-corrosion inner layer having a thickness of 200 nm to 100 ⁇ m, and the epoxy resin material containing the PANI-SA microcapsule is poured on the surface of the anticorrosive inner layer to form a thickness of 500 ⁇ m.
  • test method is the same as in the first embodiment.
  • the particle size of the produced microcapsules increases with time, and the particle diameter is in the range of 100 nm to 1 ⁇ m.
  • the surface resistance of the test article to which the anticorrosive coating 3 was added was significantly improved as compared with the sample without the added coating. It was calculated that the surface resistance of the test article with the anti-corrosion coating 3 increased by 16143 times and the corrosion inhibition efficiency reached 99.9986%.
  • the anti-corrosion coating 4 comprises an anti-corrosion inner layer and a self-repairing surface layer, and the self-repairing surface layer is attached to the surface of the anti-corrosion inner layer, and the self-repairing surface layer material is mainly composed of an epoxy resin and a sodium alginate microcapsule, and also includes a part Raw material impurities (one or more of polyaniline, N, N-dimethylformamide, amide curing agent and ethanol), sodium alginate microcapsules are uniformly dispersed in epoxy resin, polyaniline coated alginic acid The volume ratio of sodium microcapsules to epoxy resin is 1:3.
  • the material of the anticorrosive inner layer is mainly composed of boron-graphene oxide, and also contains some raw material impurities (ethanol).
  • the GO-B material is dip coated on the inner wall of the water pipeline to form an anticorrosive inner layer having a thickness of 200 nm to 100 ⁇ m, and the epoxy resin material containing the PANI-SA microcapsule is poured on the surface of the anticorrosive inner layer to form a thickness of 500 ⁇ m.
  • a self-repairing outer layer of -10 mm forms an anticorrosive coating 4.
  • test method is the same as in the first embodiment.
  • the particle size of the produced microcapsules increases with time, and the particle diameter is in the range of 200 nm to 1 ⁇ m.
  • the anti-corrosion coating 5 comprises an anti-corrosion inner layer and a self-repairing surface layer, and the self-repairing surface layer is attached to the surface of the anti-corrosion inner layer, and the self-repairing surface layer material is mainly composed of epoxy resin and sodium alginate microcapsule, and also includes a part Raw material impurities (one or more of polyaniline, N, N-dimethylformamide, amide curing agent and ethanol), sodium alginate microcapsules are uniformly dispersed in epoxy resin, polyaniline coated alginic acid The volume ratio of sodium microcapsules to epoxy resin is 1:6.
  • the material of the anticorrosive inner layer is mainly composed of boron-graphene oxide, and also contains some raw material impurities (ethanol).
  • the material of the self-repairing outer layer was prepared by dissolving 4.75 g of sodium alginate in 37.5 mL of deionized water and stirring at 8000 r/min for 22.5 minutes to obtain an sodium alginate emulsion; and fully dissolving 3.75 g of polyaniline 37.5 mL of N,N-dimethylformamide.
  • the polyaniline-containing solution was slowly added to the sodium alginate emulsion and stirred at 8000 r/min for 22.5 min. At this time, the mixed solution was passed through a 0.45 ⁇ m fiber membrane, and the residue was washed three times with deionized water. The residue was dissolved in 75 mL of ethanol and sonicated for 15 min.
  • E-44 epoxy resin 7.5 g was added, and stirred at 5000 r/min for 15 min, and then 0.6-4 g of a polyamide curing agent was added, and stirred at 2000 r/min for 15 min. That is, an epoxy resin material containing PANI-SA microcapsules (having a particle diameter of 100 nm to 1 ⁇ m) was obtained.
  • the GO-B material is poured on the inner wall of the water pipeline to form an anticorrosive inner layer having a thickness of 200 nm to 100 ⁇ m, and the epoxy resin material containing the PANI-SA microcapsule is sprayed on the surface of the anticorrosive inner layer to form a thickness of 500 ⁇ m- A self-repairing outer layer of 10 mm forms an anticorrosive coating 5.
  • test method is the same as in the first embodiment.
  • the particle size of the produced microcapsules increases with time, and the particle diameter is in the range of 100 nm to 1 ⁇ m.
  • microcapsules prepared by the present invention increase in particle size with time due to agglomeration, and are in the range of 100 nm to 1 ⁇ m.
  • the coating provided by the invention has a surface resistance of 10,000 times, a corrosion inhibition efficiency of over 98%, and a strong anticorrosive effect.
  • the coating provided by the present invention can recover and enhance the surface resistance in a short time after being scratched, and has a strong self-repairing ability.
  • the coating provided by the present invention has high anticorrosive and self-repairing properties and is an environmentally friendly coating material.

Abstract

An anti-corrosive coating with self-repairing ability, comprising an anti-corrosive inner layer and a self-repairing surface layer. The material of the self-repairing surface layer mainly consists of polyaniline coated sodium alginate microcapsules and an epoxy resin, and the material of the anti-corrosive inner layer mainly consists of graphene oxide modified with boric acid and/or borax. A preparation method therefor comprises: preparing a material of an anti-corrosive inner layer, and coating the material of the anti-corrosive inner layer on a substrate to form the anti-corrosive inner layer; preparing a material of a self-repairing surface layer, and coating the material of the self-repairing surface layer on the anti-corrosive inner layer, to form the self-repairing surface layer; and forming an anti-corrosive coating. The anti-corrosive coating can prevent water pipelines from being corroded by liquid environments, and has a rapid self-repairing ability.

Description

具备自修复能力的防腐涂层及其制备方法和应用Anti-corrosion coating with self-repairing ability and preparation method and application thereof 技术领域Technical field
本发明涉及防腐蚀材料领域，特别涉及具备自修复能力的防腐涂层及其制备方法和应用。The invention relates to the field of anti-corrosion materials, in particular to an anti-corrosion coating with self-repairing ability and a preparation method and application thereof.
背景技术Background technique
在饮用水管网和循环水***中，管道的腐蚀可引发一系列直接和间接的经济和环境问题。例如，管道腐蚀可直接降低管道使用寿命，增加企业经济成本，导致工业设备停止运行；因管道腐蚀产生的腐蚀产物，在水流的冲刷下易溶解在水中，造成水质恶化，导致用水安全得不到保障。目前常采用投加缓蚀剂和涂覆涂层的技术手段控制输水管道腐蚀。然而，投加缓蚀剂常会引起水质的恶化，如投加磷系缓蚀剂可引发水体富营养化(CN 103663746 A)；投加金属盐类缓蚀剂增强水的毒性(CN 102583785 A)。因此，大部分国家对缓蚀剂的使用有严格要求，从而限制了缓蚀剂的应用。Corrosion of pipelines can cause a range of direct and indirect economic and environmental problems in drinking water networks and circulating water systems. For example, pipeline corrosion can directly reduce the service life of the pipeline, increase the economic cost of the enterprise, and cause the industrial equipment to stop running; the corrosion products generated by the corrosion of the pipeline are easily dissolved in the water under the scouring of the water flow, causing the water quality to deteriorate, resulting in the safety of water being unsafe. Guarantee. At present, the corrosion of the water pipeline is often controlled by adding a corrosion inhibitor and a coating coating technique. However, the addition of corrosion inhibitors often causes deterioration of water quality, such as the addition of phosphorus-based corrosion inhibitors to eutrophication of water bodies (CN 103663746 A); the addition of metal salt corrosion inhibitors enhances the toxicity of water (CN 102583785 A) . Therefore, most countries have strict requirements for the use of corrosion inhibitors, which limits the application of corrosion inhibitors.
在输水管网的防腐过程中，涂层作为一种高效的防腐技术，也存在着明显的缺陷。涂层易受周围环境的影响发生破裂。当涂层破裂后，在破裂处的腐蚀速率迅速增加，并在破裂区附近腐蚀范围逐渐扩大，发生膜下腐蚀现象，最终造成涂层大面积脱落及失效(CN 103375657 A)。因此，自修复涂层应运而生。目前常用的自修复涂层是将缓蚀剂包裹在涂层中(CN 104927583 A)，当涂层破裂后，缓蚀剂流出，在管道表面形成保护层，从而避免管道的腐蚀。然而，缓蚀剂通常易溶于水，并在输水管网中水流的冲刷作用下，缓蚀剂不易在破裂处形成保护膜。因此目前自修复涂层在防止输水管网管道腐蚀的效果不理想。此外，缓蚀剂的流出可造成水质恶化，带来一定的环境风险。因此，研发具有高效防腐能力和自修复能力的环境友好型涂层具有重要的现实意义。In the anti-corrosion process of the water pipe network, the coating as an efficient anti-corrosion technology also has obvious defects. The coating is susceptible to cracking due to the surrounding environment. When the coating ruptures, the rate of corrosion at the rupture increases rapidly, and the corrosion range gradually increases near the rupture zone, causing under-film corrosion, which eventually causes large-scale shedding and failure of the coating (CN 103375657 A). Therefore, self-healing coatings have emerged. At present, the commonly used self-healing coating is to encapsulate the corrosion inhibitor in the coating (CN 104927583 A). When the coating is broken, the corrosion inhibitor flows out to form a protective layer on the surface of the pipeline to avoid corrosion of the pipeline. However, the corrosion inhibitor is usually soluble in water, and under the action of the water flow in the water pipe network, the corrosion inhibitor is not easy to form a protective film at the crack. Therefore, the effect of the self-repair coating on preventing the corrosion of the pipeline of the water pipe network is not satisfactory. In addition, the outflow of corrosion inhibitors can cause deterioration of water quality and bring about certain environmental risks. Therefore, the development of environmentally friendly coatings with high efficiency of corrosion protection and self-healing has important practical significance.
发明内容Summary of the invention
本发明的目的是为解决以上问题的至少一个，本发明提供一种具备自修复能力的防腐涂层及其制备方法和应用。该防腐涂层可附着于输水管网的输水管 道(例如碳钢输水管道)壁上，用于防止输水管道被水腐蚀。An object of the present invention is to solve at least one of the above problems, and to provide an anticorrosive coating having self-healing ability, a preparation method and application thereof. The anti-corrosion coating can be attached to the wall of a water pipe of a water pipe network (for example, a carbon steel water pipe) to prevent the water pipe from being corroded by water.
根据本发明的一个方面，提供一种具备自修复能力的防腐涂层，包括防腐内层和自修复面层，其中，自修复面层的材料中含有聚苯胺包覆海藻酸钠微胶囊。According to an aspect of the invention, there is provided an anticorrosive coating having self-healing ability, comprising an anticorrosive inner layer and a self-healing top layer, wherein the self-healing top layer material comprises polyaniline coated sodium alginate microcapsules.
其中，聚苯胺包覆海藻酸钠微胶囊的粒径为100nm-1μm。The polyaniline-coated sodium alginate microcapsule has a particle diameter of 100 nm to 1 μm.
其中，自修复面层的材料还含有环氧树脂，聚苯胺包覆海藻酸钠微胶囊分散于环氧树脂中，聚苯胺包覆海藻酸钠微胶囊与环氧树脂的体积比为1:6-1:3。The material of the self-repairing surface layer further comprises an epoxy resin, and the polyaniline-coated sodium alginate microcapsules are dispersed in the epoxy resin, and the volume ratio of the polyaniline-coated sodium alginate microcapsule to the epoxy resin is 1:6. -1:3.
其中，防腐内层的材料主要由经硼酸和/或硼砂修饰的氧化石墨烯组成。Among them, the material of the anticorrosive inner layer is mainly composed of graphene oxide modified by boric acid and/or borax.
根据本发明的第二个方面，提供该防腐涂层的制备方法，该制备方法包括以下步骤：According to a second aspect of the present invention, there is provided a method of preparing the anticorrosive coating, the method comprising the steps of:
制备防腐内层的材料；将防腐内层的材料涂布在基体上，形成防腐内层；制备自修复面层的材料；将自修复面层的材料涂布在防腐内层上，形成自修复面层；形成防腐涂层。Preparing the material of the anti-corrosion inner layer; coating the anti-corrosion inner layer material on the substrate to form an anti-corrosion inner layer; preparing the self-repairing surface layer material; coating the self-repairing surface layer material on the anti-corrosion inner layer to form self-repairing a surface layer; an anti-corrosion coating is formed.
其中，制备自修复面层的材料包括以下步骤：Wherein, the material for preparing the self-repairing surface layer comprises the following steps:
使用海藻酸钠和去离子水制备海藻酸钠乳化液；将聚苯胺充分溶于N,N-二甲基甲酰胺，得到聚苯胺溶液；将聚苯胺溶液加入至海藻酸钠乳化液中，搅拌得混合液；将混合液过滤膜，得到聚苯胺包覆海藻酸钠微胶囊；将聚苯胺包覆海藻酸钠微胶囊分散至环氧树脂中，得到分散液；在分散液中加入聚酰胺固化剂对分散液进行固化，得到自修复面层的材料。Preparing sodium alginate emulsion by using sodium alginate and deionized water; fully dissolving polyaniline in N,N-dimethylformamide to obtain polyaniline solution; adding polyaniline solution to sodium alginate emulsion, stirring Obtaining a mixed solution; filtering the mixture to obtain a polyaniline-coated sodium alginate microcapsule; dispersing the polyaniline-coated sodium alginate microcapsule into an epoxy resin to obtain a dispersion; and adding a polyamide to the dispersion The agent solidifies the dispersion to obtain a self-healing surface layer material.
其中，制备防腐内层的材料包括以下步骤:Wherein, the material for preparing the anticorrosive inner layer comprises the following steps:
将氧化石墨烯连同硼酸和/或硼砂在去离子水溶液中混合；超声分散后过滤膜滤得残渣；将残渣分散在乙醇溶液中，生成防腐内层的材料。The graphene oxide is mixed with boric acid and/or borax in a deionized water solution; after ultrasonic dispersion, the filter membrane is filtered to obtain a residue; the residue is dispersed in an ethanol solution to form a material for preserving the inner layer.
其中，制备自修复面层的材料的步骤中：海藻酸钠、聚苯胺、环氧树脂与聚酰胺固化剂之间的质量比为4-7:3-6:6-12:0.6-4。Wherein, in the step of preparing the self-repairing surface material, the mass ratio between sodium alginate, polyaniline, epoxy resin and polyamide curing agent is 4-7:3-6:6-12:0.6-4.
制备防腐内层的材料的步骤中：氧化石墨烯与作为修饰物的硼砂和/或硼酸之间的质量比为1:0.01-0.1。In the step of preparing the material of the anticorrosive inner layer, the mass ratio between the graphene oxide and the borax and/or boric acid as a modification is 1:0.01-0.1.
其中，制备自修复面层的材料的步骤中，各原料的组分为下属比例或该比例的同等倍数：Wherein, in the step of preparing the material of the self-repairing surface layer, the components of each raw material are subordinate ratios or an equal multiple of the ratio:
海藻酸钠：4-7g；聚苯胺:3-6g；N,N-二甲基甲酰胺：30-60mL；环氧树脂： 6-12g；聚酰胺固化剂：0.6-4g；乙醇：60-120mL。Sodium alginate: 4-7 g; polyaniline: 3-6 g; N,N-dimethylformamide: 30-60 mL; epoxy resin: 6-12 g; polyamide curing agent: 0.6-4 g; ethanol: 60- 120mL.
其中，制备防腐内层的材料的步骤中，各制备原料的组分为下述比例或该比例的同等倍数：Wherein, in the step of preparing the material of the anticorrosive inner layer, the components of each of the prepared raw materials are the following ratios or an equal multiple of the ratio:
氧化石墨烯：9.6g；硼砂或/或硼酸：0.096-0.96g；乙醇：60-120mL。Graphene oxide: 9.6 g; borax or/or boric acid: 0.096-0.96 g; ethanol: 60-120 mL.
根据本发明的第三个方面，提供该防腐涂层在防止输水管道被液体环境腐蚀方面的应用。According to a third aspect of the invention, there is provided the use of the anticorrosive coating for preventing corrosion of a water conduit by a liquid environment.
其中，液体环境为氯离子的含量小于等于1500mg/L、钙离子的含量大于等于100mg/L的水。The liquid environment is water having a chloride ion content of 1500 mg/L or less and a calcium ion content of 100 mg/L or more.
本发明提供的具有高效防腐能力和自修复能力的环境友好型涂层，具有双层结构。其中防腐内层主要由经硼酸和/或硼砂修饰的氧化石墨烯即硼-氧化石墨烯(GO-B)组成，防腐内层起到良好的绝缘效果，可有效阻止管道和腐蚀性水间的电子转移。而外层中的聚苯胺包覆海藻酸钠(PANI-SA)微胶囊在输水管网中具有高效的自修复能力。在聚苯胺的作用下，金属氧化物薄膜可在管道表面和聚苯胺层之间生成，从而提高管道表面阻抗。此外，海藻酸钠可与溶液中的钙离子反应，生成海藻酸钙沉淀，该海藻酸钙和海藻酸钠的混合沉淀层可有效阻止聚苯胺的流失并增加管道表面阻抗。因此，在涂层破裂区，形成了具有以聚苯胺层为底，以海藻酸钠和海藻酸钙混合物为表层的双层结构。进而达到涂层自修复的目的。此外，由于海藻酸钙不溶于水，因此只有极少量海藻酸钠释放到水中，而海藻酸钠作为一种可食用材料，因此涂层的破裂不会引发水质安全问题。The invention provides an environment-friendly coating with high-efficiency anti-corrosion ability and self-repairing capability, and has a double-layer structure. The anti-corrosion inner layer is mainly composed of boron oxide-graphene oxide (GO-B) modified by boric acid and/or borax, and the anti-corrosion inner layer has good insulation effect, which can effectively prevent the pipeline and the corrosive water. Electronic transfer. The polyaniline coated sodium alginate (PANI-SA) microcapsules in the outer layer have high self-healing ability in the water pipe network. Under the action of polyaniline, a metal oxide film can be formed between the surface of the pipe and the polyaniline layer, thereby improving the surface resistance of the pipe. In addition, sodium alginate can react with calcium ions in the solution to form a calcium alginate precipitate. The mixed precipitate layer of calcium alginate and sodium alginate can effectively prevent the loss of polyaniline and increase the surface resistance of the pipeline. Therefore, in the rupture zone of the coating, a two-layer structure having a polyaniline layer as a base and a mixture of sodium alginate and calcium alginate as a surface layer was formed. In turn, the coating is self-repairing. In addition, since calcium alginate is insoluble in water, only a very small amount of sodium alginate is released into the water, and sodium alginate is used as an edible material, so that cracking of the coating does not cause water quality safety problems.
本发明具有以下有益效果：The invention has the following beneficial effects:
本发明提供的防腐涂料，具有高效的防腐能力，能够防止输水管道被水腐蚀，同时具有快速的自修复能力，能够避免涂层因破裂且得不到有效修复进而产生大规模脱落。并且，本发明提供的防腐涂层在破裂后仅释放出极少量可食用的海藻酸钠，对水环境不造成影响。The anti-corrosion coating provided by the invention has high anti-corrosion ability, can prevent the water pipeline from being corroded by water, and has a rapid self-repairing ability, and can prevent the coating from being broken due to cracking and being unable to be effectively repaired to cause large-scale shedding. Moreover, the anticorrosive coating provided by the present invention releases only a very small amount of edible sodium alginate after rupture, and does not affect the water environment.
附图说明DRAWINGS
通过阅读下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并 不认为是对本发明的限制。而且在整个附图中，用相同的参考符号表示相同的部件。在附图中：Various other advantages and benefits will become apparent to those skilled in the art from a The drawings are only for the purpose of illustrating the preferred embodiments and are not to be construed as limiting. Throughout the drawings, the same reference numerals are used to refer to the same parts. In the drawing:
图1示出了根据本发明实施方式的防腐涂层的自修复面层的材料的制备过程中聚苯胺包覆海藻酸钠微胶囊(PANI-SA)随时间的变化图；1 is a graph showing changes in polyaniline-coated alginate microcapsules (PANI-SA) over time in the preparation of a self-healing surface layer of an anticorrosive coating according to an embodiment of the present invention;
图2示出了根据本发明实施方式的防腐涂层的防腐效果评价图(Nyquist)；2 shows an anticorrosion effect evaluation diagram (Nyquist) of an anticorrosive coating according to an embodiment of the present invention;
图3示出了根据本发明实施方式的防腐涂层的自修复能力评价图(Nyquist)；3 shows a self-healing ability evaluation chart (Nyquist) of an anticorrosive coating according to an embodiment of the present invention;
图4示出了根据本发明实施方式的防腐涂层的溶解释放前后水质三维荧光图。4 is a three-dimensional fluorescence diagram of water quality before and after dissolution release of an anticorrosive coating according to an embodiment of the present invention.
具体实施方式Detailed ways
下面将参照附图更详细地描述本公开的示例性实施方式。虽然附图中显示了本公开的示例性实施方式，然而应当理解，可以以各种形式实现本公开而不应被这里阐述的实施方式所限制。相反，提供这些实施方式是为了能够更透彻地理解本公开，并且能够将本公开的范围完整的传达给本领域的技术人员。Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While the exemplary embodiments of the present disclosure are shown in the drawings, it is understood that the invention may be embodied in various forms and not limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be more fully understood, and the scope of the disclosure can be fully conveyed to those skilled in the art.
实验例1：Experimental Example 1:
防腐涂层1，包括防腐内层和自修复面层，自修复面层附着于防腐内层的表面上，自修复面层的材料主要由环氧树脂和海藻酸钠微胶囊组成，还包括部分原料杂质(聚苯胺、N,N-二甲基甲酰胺、酰胺固化剂和乙醇中的一种或多种)，海藻酸钠微胶囊均匀地分散于环氧树脂中，聚苯胺包覆海藻酸钠微胶囊与环氧树脂的体积比为1:6。防腐内层的材料主要由硼-氧化石墨烯组成，还包括部分原料杂质(乙醇)。The anti-corrosion coating 1 comprises an anti-corrosion inner layer and a self-repairing surface layer, and the self-repairing surface layer is attached to the surface of the anti-corrosion inner layer, and the self-repairing surface layer material is mainly composed of epoxy resin and sodium alginate microcapsule, and also includes a part Raw material impurities (one or more of polyaniline, N, N-dimethylformamide, amide curing agent and ethanol), sodium alginate microcapsules are uniformly dispersed in epoxy resin, polyaniline coated alginic acid The volume ratio of sodium microcapsules to epoxy resin is 1:6. The material of the anticorrosive inner layer is mainly composed of boron-graphene oxide, and also includes some raw material impurities (ethanol).
防腐涂层1的制备方法：Preparation method of anticorrosive coating 1:
将9.6g氧化石墨烯和0.096硼砂在去离子水溶液中混合，超声分散1h，过0.45μm滤膜，残渣用去离子水洗涤三遍。再将残渣分散在60乙醇溶液中，在50℃的条件下搅拌2h，之后超声分散1h，即得到GO-B材料。9.6 g of graphene oxide and 0.096 borax were mixed in a deionized aqueous solution, ultrasonically dispersed for 1 h, passed through a 0.45 μm filter, and the residue was washed three times with deionized water. The residue was further dispersed in a 60-ethanol solution and stirred at 50 ° C for 2 h, followed by ultrasonic dispersion for 1 h to obtain a GO-B material.
将4g海藻酸钠充分溶于30mL去离子水中，在8000r/min的条件下搅拌10min，得到海藻酸钠乳化液；将3g聚苯胺充分溶于30mL N,N-二甲基甲酰胺。再将含聚苯胺的溶液缓慢加入到海藻酸钠乳化液中，并在8000r/min的条 件下搅拌10min。此时混合液通过0.45μm纤维膜，残渣用去离子水洗涤3次。将残渣溶于60mL乙醇中，超声分散10min。此时加入6g E-44环氧树脂，并在5000r/min的条件下搅拌10min，再加入0.6g聚酰胺固化剂，在2000r/min的条件下搅拌10min，即得到含PANI-SA微胶囊的环氧树脂材料。4 g of sodium alginate was sufficiently dissolved in 30 mL of deionized water, and stirred at 8000 r/min for 10 min to obtain an sodium alginate emulsion; 3 g of polyaniline was sufficiently dissolved in 30 mL of N,N-dimethylformamide. The polyaniline-containing solution was slowly added to the sodium alginate emulsion and stirred at 8000 r/min for 10 min. At this time, the mixed solution was passed through a 0.45 μm fiber membrane, and the residue was washed three times with deionized water. The residue was dissolved in 60 mL of ethanol and dispersed by ultrasonic for 10 min. At this time, 6g E-44 epoxy resin was added, and stirred at 5000r/min for 10min, and then 0.6g of polyamide curing agent was added, and stirred at 2000r/min for 10min to obtain PANI-SA microcapsules. Epoxy resin material.
将GO-B材料喷涂在输水管道的内壁，形成厚度为200nm-100μm的防腐内层，再将含PANI-SA微胶囊的环氧树脂材料旋涂在防腐内层的表面，形成厚度为500μm-10mm的自修复外层，进而形成防腐涂层1。The GO-B material is sprayed on the inner wall of the water pipeline to form an anticorrosive inner layer having a thickness of 200 nm to 100 μm, and the epoxy resin material containing the PANI-SA microcapsule is spin-coated on the surface of the anticorrosive inner layer to form a thickness of 500 μm. A self-repairing outer layer of -10 mm to form an anticorrosive coating 1.
1.防腐能力测试：1. Anti-corrosion test:
采用传统的三电极体系对涂层的防腐效果进行评价，腐蚀性水的组成如表1所示。碳钢电极(0.15 wt.％C、0.46 wt.％Mn、0.28 wt.％Si、<0.042 wt.％P、<0.049 wt.％S，剩余为Fe))由底面直径为1cm的碳钢圆柱组成。使用电焊技术将铜导线焊接在碳钢电极底面，并使用环氧树脂将碳钢电极包封上，仅留下0.785cm 2与腐蚀性水接触。在接触面上喷涂或涂覆上防腐涂层1。将处理好的电极浸泡在腐蚀性水中30min后，对其进行表面阻抗的测定。阻抗采用电化学工作站Autolab 204在0.01Hz-100KHz的范围内进行测定。 The corrosion resistance of the coating was evaluated using a conventional three-electrode system. The composition of the corrosive water is shown in Table 1. Carbon steel electrode (0.15 wt.% C, 0.46 wt.% Mn, 0.28 wt.% Si, <0.042 wt.% P, <0.049 wt.% S, remainder Fe)) Carbon steel cylinder with a bottom diameter of 1 cm composition. The copper wire was welded to the bottom surface of the carbon steel electrode using an electric welding technique, and the carbon steel electrode was encapsulated with an epoxy resin, leaving only 0.785 cm 2 in contact with corrosive water. The anti-corrosion coating 1 is sprayed or coated on the contact surface. After the treated electrode was immersed in corrosive water for 30 min, the surface impedance was measured. The impedance was measured using an electrochemical workstation Autolab 204 in the range of 0.01 Hz to 100 kHz.
表1腐蚀性水的离子组成(mg L -1) Table 1 Ionic composition of corrosive water (mg L -1 )
Figure PCTCN2018081736-appb-000001
Figure PCTCN2018081736-appb-000001
2.自修复能力测试：2. Self-repair ability test:
使用刀片将涂层划伤直至触碰到基底材料，在上述腐蚀性水中浸泡10min、1h、3h和5h后进行表面阻抗的测试。The coating was scratched using a blade until it touched the substrate material, and the surface impedance was tested after immersing in the above corrosive water for 10 min, 1 h, 3 h, and 5 h.
3.环境影响测试：3. Environmental impact test:
使用刀片将涂层划伤后，在水流旋转速度为100r/min，温度为30℃的上述腐蚀性水中浸泡48h后，对水样进行三维荧光和总硼浓度的测定。After the coating was scratched with a blade, the water sample was subjected to three-dimensional fluorescence and total boron concentration measurement after being immersed in the above-mentioned corrosive water having a water flow rotation speed of 100 r/min and a temperature of 30 ° C for 48 hours.
测试结果：Test Results:
1.防腐涂层1的自修复外层的材料的制备过程中，产生的微胶囊粒径随着时间增加而增加，粒径在100nm-500nm内。1. During the preparation of the material of the self-repairing outer layer of the anti-corrosion coating 1, the particle size of the produced microcapsules increases with time, and the particle diameter is in the range of 100 nm to 500 nm.
2.与添加涂层的样品相比，添加了防腐涂层1的测试品的表面阻抗提升了15978倍，缓蚀效率达到98.7746％。2. Compared with the sample added with the coating, the surface resistance of the test article with the anti-corrosion coating 1 increased by 15978 times and the corrosion inhibition efficiency reached 98.7746%.
3.在涂层被划伤后的50分钟内，表面阻抗恢复到未划伤水平，并在4.5h后表面阻抗提升到原来的4倍。3. Within 50 minutes after the coating was scratched, the surface resistance returned to the unscratched level, and the surface impedance increased to 4 times after 4.5 hours.
4.48h后，作为浸泡液的腐蚀性水溶液中检测出少量的类蛋白物质，并未检测出硼。After 4.48 h, a small amount of protein-like substance was detected in the corrosive aqueous solution as the soaking solution, and boron was not detected.
实验例2：Experimental Example 2:
防腐涂层2，包括防腐内层和自修复面层，自修复面层附着于防腐内层的表面上，自修复面层的材料主要由环氧树脂和海藻酸钠微胶囊组成，还包括部分原料杂质(聚苯胺、N,N-二甲基甲酰胺、酰胺固化剂和乙醇中的一种或多种)，海藻酸钠微胶囊均匀地分散于环氧树脂中，聚苯胺包覆海藻酸钠微胶囊与环氧树脂的体积比为1:5。防腐内层的材料主要由硼-氧化石墨烯组成，还包含部分原料杂质(乙醇)。The anti-corrosion coating 2 comprises an anti-corrosion inner layer and a self-repairing surface layer, and the self-repairing surface layer is attached to the surface of the anti-corrosion inner layer, and the self-repairing surface layer material is mainly composed of epoxy resin and sodium alginate microcapsule, and also includes a part Raw material impurities (one or more of polyaniline, N, N-dimethylformamide, amide curing agent and ethanol), sodium alginate microcapsules are uniformly dispersed in epoxy resin, polyaniline coated alginic acid The volume ratio of sodium microcapsules to epoxy resin is 1:5. The material of the anticorrosive inner layer is mainly composed of boron-graphene oxide, and also contains some raw material impurities (ethanol).
防腐涂层2的制备方法：Preparation method of anticorrosive coating 2:
将9.6g氧化石墨烯和0.96g硼酸在去离子水溶液中混合，超声分散4h，过0.45μm滤膜，残渣用去离子水洗涤三遍。再将残渣分散在120mL乙醇溶液中，在80℃的条件下搅拌4h，之后超声分散2h，即得到GO-B材料。9.6 g of graphene oxide and 0.96 g of boric acid were mixed in a deionized aqueous solution, ultrasonically dispersed for 4 hours, passed through a 0.45 μm filter, and the residue was washed three times with deionized water. The residue was dispersed in a 120 mL ethanol solution, stirred at 80 ° C for 4 h, and then ultrasonically dispersed for 2 h to obtain a GO-B material.
将7g海藻酸钠充分溶于60mL去离子水中，在8000r/min的条件下搅拌60min，得到海藻酸钠乳化液；将3-6g聚苯胺充分溶于60mL N,N-二甲基甲酰胺。再将含聚苯胺的溶液缓慢加入到海藻酸钠乳化液中，并在8000r/min的条件下搅拌60min。此时混合液通过0.45μm纤维膜，残渣用去离子水洗涤3次。将残渣溶于120mL乙醇中，超声分散10-30min。此时加入12g E-44环氧树脂，并在5000r/min的条件下搅拌30min，再加入0.6-4g聚酰胺固化剂，在2000r/min的条件下搅拌30min。即得到含有PANI-SA微胶囊的环氧树脂材料。7 g of sodium alginate was sufficiently dissolved in 60 mL of deionized water and stirred at 8000 r/min for 60 min to obtain an sodium alginate emulsion; 3-6 g of polyaniline was sufficiently dissolved in 60 mL of N,N-dimethylformamide. The polyaniline-containing solution was slowly added to the sodium alginate emulsion and stirred at 8000 r/min for 60 min. At this time, the mixed solution was passed through a 0.45 μm fiber membrane, and the residue was washed three times with deionized water. The residue was dissolved in 120 mL of ethanol and dispersed by ultrasonic for 10-30 min. At this time, 12 g of E-44 epoxy resin was added, and stirred at 5000 r/min for 30 min, and then 0.6-4 g of a polyamide curing agent was added, and stirred at 2000 r/min for 30 min. That is, an epoxy resin material containing PANI-SA microcapsules was obtained.
将GO-B材料喷涂在输水管道的内壁，形成厚度为200nm-100μm的防腐内层，再将含PANI-SA微胶囊的环氧树脂材料旋涂在防腐内层的表面，形成厚度为500μm–10mm的自修复外层，进而形成防腐涂层2。The GO-B material is sprayed on the inner wall of the water pipeline to form an anticorrosive inner layer having a thickness of 200 nm to 100 μm, and the epoxy resin material containing the PANI-SA microcapsule is spin-coated on the surface of the anticorrosive inner layer to form a thickness of 500 μm. – 10mm self-healing outer layer to form an anti-corrosion coating 2 .
防腐能力测试、自修复能力测试和环境影响测试：Corrosion resistance test, self-repair ability test and environmental impact test:
测试方法与实施例1相同。The test method is the same as in the first embodiment.
测试结果：Test Results:
1.防腐涂层2的自修复外层的材料的制备过程中，产生的微胶囊粒径随着 时间增加而增加，粒径在300nm-1μm内。1. During the preparation of the material of the self-repairing outer layer of the anti-corrosion coating 2, the particle size of the produced microcapsules increases with time, and the particle diameter is within the range of 300 nm to 1 μm.
2.与添加涂层的样品相比，添加了防腐涂层2的测试品的表面阻抗提升了16233倍，缓蚀效率达到98.9562％。2. Compared with the sample added with the coating, the surface resistance of the test article with the anti-corrosion coating 2 increased by 16233 times and the corrosion inhibition efficiency reached 98.9562%.
3.在涂层被划伤后的55分钟内，表面阻抗恢复到未划伤水平，并在4.5h后表面阻抗提升到原来的4倍。3. Within 55 minutes after the coating was scratched, the surface resistance returned to the unscratched level, and the surface impedance increased to 4 times after 4.5 hours.
4.48h后，作为浸泡液的腐蚀性水中检测出少量的类蛋白物质，并未检测出硼。After 4.48 h, a small amount of protein-like substance was detected in the corrosive water as the soaking solution, and boron was not detected.
实验例3：Experimental Example 3:
防腐涂层3，包括防腐内层和自修复面层，自修复面层附着于防腐内层的表面上，自修复面层的材料主要由环氧树脂和海藻酸钠微胶囊组成，还包括部分原料杂质(聚苯胺、N,N-二甲基甲酰胺、酰胺固化剂和乙醇中的一种或多种)，海藻酸钠微胶囊均匀地分散于环氧树脂中，聚苯胺包覆海藻酸钠微胶囊与环氧树脂的体积比为1:4。防腐内层的材料主要由硼-氧化石墨烯组成，还包含部分原料杂质(乙醇)。The anti-corrosion coating 3 comprises an anti-corrosion inner layer and a self-repairing surface layer, and the self-repairing surface layer is attached to the surface of the anti-corrosion inner layer, and the self-repairing surface layer material is mainly composed of epoxy resin and sodium alginate microcapsule, and also includes a part Raw material impurities (one or more of polyaniline, N, N-dimethylformamide, amide curing agent and ethanol), sodium alginate microcapsules are uniformly dispersed in epoxy resin, polyaniline coated alginic acid The volume ratio of sodium microcapsules to epoxy resin is 1:4. The material of the anticorrosive inner layer is mainly composed of boron-graphene oxide, and also contains some raw material impurities (ethanol).
防腐涂层3的制备方法：Preparation method of anticorrosive coating 3:
将9.6g氧化石墨烯和0.528g的硼砂和硼酸的混合物，在去离子水溶液中混合，超声分散2.5h，过0.45μm滤膜，残渣用去离子水洗涤三遍。再将残渣分散在90mL乙醇溶液中，在50-80℃的条件下搅拌3h，之后超声分散1.5h，即得到GO-B内层材料。A mixture of 9.6 g of graphene oxide and 0.528 g of borax and boric acid was mixed in a deionized aqueous solution, ultrasonically dispersed for 2.5 h, passed through a 0.45 μm filter, and the residue was washed three times with deionized water. The residue was dispersed in a 90 mL ethanol solution, stirred at 50-80 ° C for 3 h, and then ultrasonically dispersed for 1.5 h to obtain a GO-B inner layer material.
将5.5g海藻酸钠充分溶于45mL去离子水中，在8000r/min的条件下搅拌10-60min，得到海藻酸钠乳化液；将3-6g聚苯胺充分溶于45mL N,N-二甲基甲酰胺。再将含聚苯胺的溶液缓慢加入到海藻酸钠乳化液中，并在8000r/min的条件下搅拌35min。此时混合液通过0.45μm纤维膜，残渣用去离子水洗涤3次。将残渣溶于90mL乙醇中，超声分散10-30min。此时加入9g E-44环氧树脂，并在5000r/min的条件下搅拌20min，再加入2.3g聚酰胺固化剂，在2000r/min的条件下搅拌20min。即得到含有PANI-SA微胶囊的环氧树脂材料。5.5 g of sodium alginate was dissolved in 45 mL of deionized water, and stirred at 8000 r/min for 10-60 min to obtain an sodium alginate emulsion; 3-6 g of polyaniline was sufficiently dissolved in 45 mL of N,N-dimethyl Formamide. The polyaniline-containing solution was slowly added to the sodium alginate emulsion and stirred at 8000 r/min for 35 min. At this time, the mixed solution was passed through a 0.45 μm fiber membrane, and the residue was washed three times with deionized water. The residue was dissolved in 90 mL of ethanol and dispersed by ultrasonic for 10-30 min. At this time, 9 g of E-44 epoxy resin was added, and stirred at 5000 r/min for 20 min, and then 2.3 g of a polyamide curing agent was added, and stirred at 2000 r/min for 20 min. That is, an epoxy resin material containing PANI-SA microcapsules was obtained.
将GO-B材料旋涂在输水管道的内壁，形成厚度为200nm-100μm的防腐内层，再将含PANI-SA微胶囊的环氧树脂材料浇筑在防腐内层的表面，形成厚度为500μm-10mm的自修复外层，进而形成防腐涂层3。The GO-B material is spin-coated on the inner wall of the water pipeline to form an anti-corrosion inner layer having a thickness of 200 nm to 100 μm, and the epoxy resin material containing the PANI-SA microcapsule is poured on the surface of the anticorrosive inner layer to form a thickness of 500 μm. A self-repairing outer layer of -10 mm to form an anticorrosive coating 3.
防腐能力测试、自修复能力测试和环境影响测试：Corrosion resistance test, self-repair ability test and environmental impact test:
测试方法与实施例1相同。The test method is the same as in the first embodiment.
测试结果：Test Results:
1.如图1所示，防腐涂层3的自修复外层的材料的制备过程中，产生的微胶囊粒径随着时间增加而增加，粒径在100nm-1μm内。1. As shown in FIG. 1, during the preparation of the material of the self-repairing outer layer of the anticorrosive coating 3, the particle size of the produced microcapsules increases with time, and the particle diameter is in the range of 100 nm to 1 μm.
2.如图2所示，与未添加涂层的样品相比，添加了防腐涂层3的测试品的表面阻抗有了明显提升。经计算，添加了防腐涂层3的测试品的表面阻抗提升了16143倍，缓蚀效率达到99.9986％。2. As shown in Fig. 2, the surface resistance of the test article to which the anticorrosive coating 3 was added was significantly improved as compared with the sample without the added coating. It was calculated that the surface resistance of the test article with the anti-corrosion coating 3 increased by 16143 times and the corrosion inhibition efficiency reached 99.9986%.
3.如图3所示，在防腐涂层3被划伤后，防腐涂层表面的阻抗随时间推移逐渐升高。经对比，划伤1h后，表面阻抗恢复到未划伤水平，并在5h后提升到原来的4倍。3. As shown in FIG. 3, after the anticorrosive coating 3 is scratched, the impedance of the surface of the anticorrosive coating gradually increases with time. After comparison, after 1 h of scratching, the surface impedance returned to the unscratched level and increased to 4 times after 5 h.
4.如图4所示，48h后，作为浸泡液的去离子水中检测出少量的类蛋白物质，并未检测出硼。4. As shown in Fig. 4, after 48 hours, a small amount of protein-like substance was detected in the deionized water as the soaking solution, and boron was not detected.
实验例4：Experimental Example 4:
防腐涂层4，包括防腐内层和自修复面层，自修复面层附着于防腐内层的表面上，自修复面层的材料主要由环氧树脂和海藻酸钠微胶囊组成，还包括部分原料杂质(聚苯胺、N,N-二甲基甲酰胺、酰胺固化剂和乙醇中的一种或多种)，海藻酸钠微胶囊均匀地分散于环氧树脂中，聚苯胺包覆海藻酸钠微胶囊与环氧树脂的体积比为1:3。防腐内层的材料主要由,硼-氧化石墨烯组成，还包含部分原料杂质(乙醇)。The anti-corrosion coating 4 comprises an anti-corrosion inner layer and a self-repairing surface layer, and the self-repairing surface layer is attached to the surface of the anti-corrosion inner layer, and the self-repairing surface layer material is mainly composed of an epoxy resin and a sodium alginate microcapsule, and also includes a part Raw material impurities (one or more of polyaniline, N, N-dimethylformamide, amide curing agent and ethanol), sodium alginate microcapsules are uniformly dispersed in epoxy resin, polyaniline coated alginic acid The volume ratio of sodium microcapsules to epoxy resin is 1:3. The material of the anticorrosive inner layer is mainly composed of boron-graphene oxide, and also contains some raw material impurities (ethanol).
防腐涂层4的制备方法：Preparation method of anti-corrosion coating 4:
将9.6g氧化石墨烯和0.744g硼酸在去离子水溶液中混合，超声分散3.25h，过0.45μm滤膜，残渣用去离子水洗涤三遍。再将残渣分散在105mL乙醇溶液中，在72.5℃的条件下搅拌3.5h，之后超声分散1.75h，即得到GO-B内层材料。9.6 g of graphene oxide and 0.744 g of boric acid were mixed in a deionized aqueous solution, ultrasonically dispersed for 3.25 h, passed through a 0.45 μm filter, and the residue was washed three times with deionized water. The residue was further dispersed in a 105 mL ethanol solution, stirred at 72.5 ° C for 3.5 h, and then ultrasonically dispersed for 1.75 h to obtain a GO-B inner layer material.
将6.25g海藻酸钠充分溶于52.5mL去离子水中，在8000r/min的条件下搅拌47.5min，得到海藻酸钠乳化液；将5.25g聚苯胺充分溶于52.5mL N,N-二甲基甲酰胺。再将含聚苯胺的溶液缓慢加入到海藻酸钠乳化液中，并在8000r/min的条件下搅拌47.5min。此时混合液通过0.45μm纤维膜，残渣用去离子 水洗涤3次。将残渣溶于105mL乙醇中，超声分散25min。此时加入10.5g E-44环氧树脂，并在5000r/min的条件下搅拌25min，再加入3.15g聚酰胺固化剂，在2000r/min的条件下搅拌25min。即得到含有PANI-SA微胶囊(粒径在100nm-1μm)的环氧树脂材料。6.25 g of sodium alginate was dissolved in 52.5 mL of deionized water, and stirred at 8000 r/min for 47.5 min to obtain an sodium alginate emulsion; 5.25 g of polyaniline was sufficiently dissolved in 52.5 mL of N,N-dimethyl Formamide. The polyaniline-containing solution was slowly added to the sodium alginate emulsion and stirred at 8000 r/min for 47.5 min. At this time, the mixture was passed through a 0.45 μm fiber membrane, and the residue was washed three times with deionized water. The residue was dissolved in 105 mL of ethanol and dispersed by ultrasonic for 25 min. At this time, 10.5 g of E-44 epoxy resin was added, and stirred at 5000 r/min for 25 minutes, and then 3.15 g of a polyamide curing agent was added, and the mixture was stirred at 2000 r/min for 25 minutes. That is, an epoxy resin material containing PANI-SA microcapsules (having a particle diameter of 100 nm to 1 μm) was obtained.
将GO-B材料浸涂在输水管道的内壁，形成厚度为200nm-100μm的防腐内层，再将含PANI-SA微胶囊的环氧树脂材料浇筑在防腐内层的表面，形成厚度为500μm-10mm的自修复外层，进而形成防腐涂层4。The GO-B material is dip coated on the inner wall of the water pipeline to form an anticorrosive inner layer having a thickness of 200 nm to 100 μm, and the epoxy resin material containing the PANI-SA microcapsule is poured on the surface of the anticorrosive inner layer to form a thickness of 500 μm. A self-repairing outer layer of -10 mm forms an anticorrosive coating 4.
防腐能力测试、自修复能力测试和环境影响测试：Corrosion resistance test, self-repair ability test and environmental impact test:
测试方法与实施例1相同。The test method is the same as in the first embodiment.
测试结果：Test Results:
1.防腐涂层4的自修复外层的材料的制备过程中，产生的微胶囊粒径随着时间增加而增加，粒径在200nm-1μm内。1. During the preparation of the material of the self-repairing outer layer of the anti-corrosion coating 4, the particle size of the produced microcapsules increases with time, and the particle diameter is in the range of 200 nm to 1 μm.
2.与添加涂层的样品相比，添加了防腐涂层4的测试品的表面阻抗提升了16121倍，缓蚀效率达到98.6551％。2. Compared with the sample coated with the coating, the surface resistance of the test article with the anti-corrosion coating 4 increased by 16121 times and the corrosion inhibition efficiency reached 98.6551%.
3.在防腐涂层4被划伤后的48分钟内，其表面阻抗恢复到未划伤水平，并在4.3h后提升到原来的4倍。3. Within 48 minutes after the anti-corrosion coating 4 was scratched, the surface resistance returned to the unscratched level and increased to 4 times after 4.3 h.
4.48h后，作为浸泡液的腐蚀性水中检测出少量的类蛋白物质，并未检测出硼。After 4.48 h, a small amount of protein-like substance was detected in the corrosive water as the soaking solution, and boron was not detected.
实验例5：Experimental Example 5:
防腐涂层5，包括防腐内层和自修复面层，自修复面层附着于防腐内层的表面上，自修复面层的材料主要由环氧树脂和海藻酸钠微胶囊组成，还包括部分原料杂质(聚苯胺、N,N-二甲基甲酰胺、酰胺固化剂和乙醇中的一种或多种)，海藻酸钠微胶囊均匀地分散于环氧树脂中，聚苯胺包覆海藻酸钠微胶囊与环氧树脂的体积比为1:6。防腐内层的材料主要由硼-氧化石墨烯组成，还包含部分原料杂质(乙醇)。The anti-corrosion coating 5 comprises an anti-corrosion inner layer and a self-repairing surface layer, and the self-repairing surface layer is attached to the surface of the anti-corrosion inner layer, and the self-repairing surface layer material is mainly composed of epoxy resin and sodium alginate microcapsule, and also includes a part Raw material impurities (one or more of polyaniline, N, N-dimethylformamide, amide curing agent and ethanol), sodium alginate microcapsules are uniformly dispersed in epoxy resin, polyaniline coated alginic acid The volume ratio of sodium microcapsules to epoxy resin is 1:6. The material of the anticorrosive inner layer is mainly composed of boron-graphene oxide, and also contains some raw material impurities (ethanol).
防腐涂层5的制备方法：Preparation method of anticorrosive coating 5:
将9.6g氧化石墨烯和2.472g硼砂在去离子水溶液中混合，超声分散1.75h，过0.45μm滤膜，残渣用去离子水洗涤三遍。再将残渣分散在75mL乙醇溶液中，在57.5℃的条件下搅拌2.5h，之后超声分散1.25h，即得到GO-B内层材 料。9.6 g of graphene oxide and 2.472 g of borax were mixed in a deionized aqueous solution, ultrasonically dispersed for 1.75 h, passed through a 0.45 μm filter, and the residue was washed three times with deionized water. The residue was further dispersed in a 75 mL ethanol solution, stirred at 57.5 ° C for 2.5 h, and then ultrasonically dispersed for 1.25 h to obtain a GO-B inner layer material.
自修复外层的材料的制备是将4.75g海藻酸钠充分溶于37.5mL去离子水中，在8000r/min的条件下搅拌22.5min，得到海藻酸钠乳化液；将3.75g聚苯胺充分溶于37.5mL N,N-二甲基甲酰胺。再将含聚苯胺的溶液缓慢加入到海藻酸钠乳化液中，并在8000r/min的条件下搅拌22.5min。此时混合液通过0.45μm纤维膜，残渣用去离子水洗涤3次。将残渣溶于75mL乙醇中，超声分散15min。此时加入7.5g E-44环氧树脂，并在5000r/min的条件下搅拌15min，再加入0.6-4g聚酰胺固化剂，在2000r/min的条件下搅拌15min。即得到含有PANI-SA微胶囊(粒径在100nm-1μm)的环氧树脂材料。The material of the self-repairing outer layer was prepared by dissolving 4.75 g of sodium alginate in 37.5 mL of deionized water and stirring at 8000 r/min for 22.5 minutes to obtain an sodium alginate emulsion; and fully dissolving 3.75 g of polyaniline 37.5 mL of N,N-dimethylformamide. The polyaniline-containing solution was slowly added to the sodium alginate emulsion and stirred at 8000 r/min for 22.5 min. At this time, the mixed solution was passed through a 0.45 μm fiber membrane, and the residue was washed three times with deionized water. The residue was dissolved in 75 mL of ethanol and sonicated for 15 min. At this time, 7.5 g of E-44 epoxy resin was added, and stirred at 5000 r/min for 15 min, and then 0.6-4 g of a polyamide curing agent was added, and stirred at 2000 r/min for 15 min. That is, an epoxy resin material containing PANI-SA microcapsules (having a particle diameter of 100 nm to 1 μm) was obtained.
将GO-B材料浇筑在输水管道的内壁，形成厚度为200nm-100μm的防腐内层，再将含PANI-SA微胶囊的环氧树脂材料喷涂在防腐内层的表面，形成厚度为500μm-10mm的自修复外层，进而形成防腐涂层5。The GO-B material is poured on the inner wall of the water pipeline to form an anticorrosive inner layer having a thickness of 200 nm to 100 μm, and the epoxy resin material containing the PANI-SA microcapsule is sprayed on the surface of the anticorrosive inner layer to form a thickness of 500 μm- A self-repairing outer layer of 10 mm forms an anticorrosive coating 5.
防腐能力测试、自修复能力测试和环境影响测试：Corrosion resistance test, self-repair ability test and environmental impact test:
测试方法与实施例1相同。The test method is the same as in the first embodiment.
测试结果：Test Results:
1.防腐涂层5的自修复外层的材料的制备过程中，产生的微胶囊粒径随着时间增加而增加，粒径在100nm-1μm内。1. During the preparation of the material of the self-repairing outer layer of the anti-corrosion coating 5, the particle size of the produced microcapsules increases with time, and the particle diameter is in the range of 100 nm to 1 μm.
2.与添加涂层的样品相比，添加了防腐涂层5的测试品表面阻抗提升了14978倍，缓蚀效率达到98.1331％。2. Compared with the sample added with the coating, the surface resistance of the test article with the anti-corrosion coating 5 increased by 14978 times and the corrosion inhibition efficiency reached 98.1331%.
3.在防腐涂层5被划伤后的70分钟内，其表面阻抗恢复到未划伤水平，并在5.5h后提升到原来的4倍。3. Within 70 minutes after the anti-corrosion coating 5 was scratched, the surface resistance returned to the unscratched level and increased to 4 times after 5.5 h.
4.48h后，作为浸泡液的腐蚀性水中检测出少量的类蛋白物质，并未检测出硼。After 4.48 h, a small amount of protein-like substance was detected in the corrosive water as the soaking solution, and boron was not detected.
结果评价：Evaluation of results:
1.本发明所制备的微胶囊，由于团聚现象，粒径随着时间增加而增加，在100nm-1μm的范围内。1. The microcapsules prepared by the present invention increase in particle size with time due to agglomeration, and are in the range of 100 nm to 1 μm.
2.本发明所提供的涂层，与添加涂层的样品相比，表面阻抗提升万倍，缓蚀效率达到98％以上，防腐效果强。2. Compared with the sample to be coated, the coating provided by the invention has a surface resistance of 10,000 times, a corrosion inhibition efficiency of over 98%, and a strong anticorrosive effect.
3.本发明所提供的涂层，在被划伤后的短时间内，能够恢复并增强表面阻 抗，自修复能力强。3. The coating provided by the present invention can recover and enhance the surface resistance in a short time after being scratched, and has a strong self-repairing ability.
4.本发明所提供的涂层被划伤后，不向浸泡液释放有害物质，对环境友好。4. After the coating provided by the present invention is scratched, it does not release harmful substances to the soaking liquid, and is environmentally friendly.
根据上述实验结果可知，本发明所提供的涂层具有高效防腐和自修复能力，并且属于环境友好型涂层材料。According to the above experimental results, the coating provided by the present invention has high anticorrosive and self-repairing properties and is an environmentally friendly coating material.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。The above is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of changes or within the technical scope disclosed by the present invention. Alternatives are intended to be covered by the scope of the present invention. Therefore, the scope of the invention should be determined by the scope of the appended claims.

Claims (10)

  1. 具备自修复能力的防腐涂层，其特征在于，包括防腐内层和自修复面层，其中，自修复面层的材料中含有聚苯胺包覆海藻酸钠微胶囊。The self-repairing anticorrosive coating is characterized in that it comprises an anticorrosive inner layer and a self-repairing surface layer, wherein the self-repairing surface layer material comprises polyaniline coated sodium alginate microcapsules.
  2. 如权利要求1所述的防腐涂层，其特征在于，The anticorrosive coating according to claim 1, wherein
    聚苯胺包覆海藻酸钠微胶囊的粒径为100nm-1μm。The polyaniline-coated sodium alginate microcapsule has a particle diameter of 100 nm to 1 μm.
  3. 如权利要求1所述的防腐涂层，其特征在于，The anticorrosive coating according to claim 1, wherein
    自修复面层的材料还含有环氧树脂，聚苯胺包覆海藻酸钠微胶囊分散于环氧树脂中，聚苯胺包覆海藻酸钠微胶囊与环氧树脂的体积比为1:6-1:3。The self-healing surface layer material also contains epoxy resin, polyaniline coated sodium alginate microcapsules are dispersed in epoxy resin, and the volume ratio of polyaniline coated sodium alginate microcapsules to epoxy resin is 1:6-1. :3.
  4. 如权利要求1所述的防腐涂层，其特征在于，The anticorrosive coating according to claim 1, wherein
    防腐内层的材料主要由经硼酸和/或硼砂修饰的氧化石墨烯组成。The material of the anticorrosive inner layer is mainly composed of graphene oxide modified with boric acid and/or borax.
  5. 如权利要求1～4中任一所述的防腐涂层的制备方法，其特征在于，所述制备方法包括以下步骤：The method for preparing an anticorrosive coating according to any one of claims 1 to 4, wherein the preparation method comprises the following steps:
    制备防腐内层的材料；将防腐内层的材料涂布在基体上，形成防腐内层；制备自修复面层的材料；将自修复面层的材料涂布在防腐内层上，形成自修复面层；形成防腐涂层；Preparing the material of the anti-corrosion inner layer; coating the anti-corrosion inner layer material on the substrate to form an anti-corrosion inner layer; preparing the self-repairing surface layer material; coating the self-repairing surface layer material on the anti-corrosion inner layer to form self-repairing Surface layer; forming an anti-corrosion coating;
    其中制备自修复面层的材料包括以下步骤：The material for preparing the self-healing surface layer comprises the following steps:
    使用海藻酸钠和去离子水制备海藻酸钠乳化液；将聚苯胺充分溶于N,N-二甲基甲酰胺，得到聚苯胺溶液；将聚苯胺溶液加入至海藻酸钠乳化液中，搅拌得混合液；将混合液过滤膜，滤得聚苯胺包覆海藻酸钠微胶囊；将聚苯胺包覆海藻酸钠微胶囊分散至环氧树脂中，得到分散液；在分散液中加入聚酰胺固化剂对分散液进行固化，得到自修复面层的材料。Preparing sodium alginate emulsion by using sodium alginate and deionized water; fully dissolving polyaniline in N,N-dimethylformamide to obtain polyaniline solution; adding polyaniline solution to sodium alginate emulsion, stirring Obtaining a mixed solution; filtering the mixed solution membrane, filtering the polyaniline coated sodium alginate microcapsule; dispersing the polyaniline coated sodium alginate microcapsule into the epoxy resin to obtain a dispersion; adding the polyamide to the dispersion The curing agent cures the dispersion to obtain a self-healing surface layer material.
  6. 如权利要求5所述的防腐涂层的制备方法，其特征在于，制备防腐内层的材料包括以下步骤：The method of preparing an anticorrosive coating according to claim 5, wherein the material for preparing the anticorrosive inner layer comprises the following steps:
    将氧化石墨烯连同硼酸和/或硼砂在去离子水溶液中混合；超声分散后过滤膜滤得残渣；将残渣分散在乙醇溶液中，生成防腐内层的材料。The graphene oxide is mixed with boric acid and/or borax in a deionized water solution; after ultrasonic dispersion, the filter membrane is filtered to obtain a residue; the residue is dispersed in an ethanol solution to form a material for preserving the inner layer.
  7. 如权利要求5所述的防腐涂层的制备方法，其特征在于，制备自修复面层的材料的步骤中：A method of preparing an anticorrosive coating according to claim 5, wherein in the step of preparing the material of the self-healing surface layer:
    海藻酸钠、聚苯胺、环氧树脂与聚酰胺固化剂之间的质量比为4-7:3-6:6-12:0.6-4。The mass ratio between sodium alginate, polyaniline, epoxy resin and polyamide curing agent is 4-7:3-6:6-12:0.6-4.
  8. 如权利要求6所述的防腐涂层的制备方法，其特征在于，制备防腐内层 的材料的步骤中：A method of preparing an anticorrosive coating according to claim 6, wherein in the step of preparing the material of the anticorrosive inner layer:
    氧化石墨烯与作为修饰物的硼砂和/或硼酸之间的质量比为1:0.01-0.1。The mass ratio between graphene oxide and borax and/or boric acid as a modification is 1:0.01-0.1.
  9. 如权利要求1～4任一所述的防腐涂层在防止输水管道被液体环境腐蚀方面的应用。The anticorrosive coating according to any one of claims 1 to 4 for use in preventing corrosion of a water conduit by a liquid environment.
  10. 如权利要求9所述的防腐涂层的应用，其特征在于，The use of an anticorrosive coating according to claim 9, wherein
    液体环境为氯离子的含量小于等于1500mg/L，钙离子的含量大于等于100mg/L的水。The liquid environment is water having a chloride ion content of 1500 mg/L or less and a calcium ion content of 100 mg/L or more.
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