CN109988989B - Alkaline iron oxide anticorrosive coating and preparation method thereof - Google Patents
Alkaline iron oxide anticorrosive coating and preparation method thereof Download PDFInfo
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
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Abstract
The invention relates to the technical field of metal material corrosion prevention, and particularly discloses an alkaline iron oxide anticorrosive coating and a preparation method thereof. The anticorrosive coating comprises the following components (in parts by weight): 1-8% of lithium, 50-69% of iron and 30-35% of oxygen. The coating is of a single-layer or multi-layer composite structure, can be used for high and low temperature corrosion protection of iron, iron-based alloy and steel metal materials in water, atmosphere, soil, industrial media and molten salt electrolyte, has wide environmental and temperature application ranges, and particularly can resist Cl‑And F‑Exhibits excellent anti-aging ability.
Description
Technical Field
The invention relates to the technical field of metal corrosion protection, in particular to an alkaline iron oxide anticorrosive coating and a preparation method thereof.
Background
The metal material is widely applied to various fields of the national civilization, and forms the material foundation of human science and technology civilization. The metal material with high chemical potential is easy to be oxidized and corroded, and the corrosion causes great material loss and has great negative effect on production. Research has shown that the total cost of national corrosion in 2014 exceeds 2.1 trillion yuan, accounting for about 3.34% of the GDP in the year. Therefore, the metal corrosion protection has great economic and social benefits.
The anti-corrosion coating can effectively isolate metal materials from corrosive media, thereby improving the corrosion resistance of the metal and prolonging the service life of the metal. The preparation of anticorrosive coatings on the surfaces of metal materials is the most widely used metal corrosion protection method at present. In order to meet the actual use requirements, the anticorrosive coating needs to meet the following requirements: 1) the corrosion medium is stable; 2) the density is higher; 3) the mechanical property is good; 4) the anti-aging performance is excellent; 5) the processing and preparation are easy; 6) the raw materials are cheap and easy to obtain. Although various coatings (e.g., resin, ceramic) currently used in industrial applications can satisfy the above requirements to various degrees, they are poor in corrosion resistance in environments containing corrosive ions such as Cl "and F". Therefore, it is highly desirable to develop a metal anticorrosive coating having more excellent properties and being capable of adapting to corrosive ionic environments and a method for preparing the same.
Disclosure of Invention
The invention aims to overcome the problems in the prior metal corrosion prevention technology and provide an alkaline iron oxide corrosion prevention coating. The coating has good stability, higher density, good mechanical property, easy processing and preparation, cheap and easily obtained raw materials, wide environmental and temperature adaptability and more importantly can resist the corrosion of Cl-and F-. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an alkaline iron oxide anti-corrosion coating comprises the following components in parts by weight: 1-8% of lithium, 50-69% of iron and 30-35% of oxygen. The sum of the contents of the elements is 100 percent, and inevitable impurity elements can be contained.
Further, the alkaline iron oxide anticorrosive coating is attached to the surface of a metal material substrate, the metal material substrate is specifically a plate or a pipe, and the application environment of the metal material substrate comprises various water bodies (such as surface water, tap water and seawater), atmosphere (such as ocean air and land air), soil, industrial media (such as circulating cooling water), molten salt electrolyte and the like in the range from normal temperature to high temperature (1000 ℃).
Further, the thickness of the alkaline iron oxide anticorrosive coating is 1-1000 μm.
Further, the alkaline iron oxide anticorrosive coating is of a single-layer structure.
Furthermore, the alkaline iron oxide anticorrosive coating is of a multilayer composite structure, and the content of each element in each layer is different.
The preparation method of the alkaline iron oxide anticorrosive coating comprises the following steps: and preparing the alkaline iron oxide anticorrosive coating on the surface of the metal material matrix by at least one of a spraying method, a vapor deposition method, a chemical oxidation method and an electrochemical oxidation method.
Further, the electrochemical oxidation method comprises the following specific steps: and electrolyzing the metal material substrate serving as an anode and the nickel electrode serving as a cathode in a lithium-containing electrolyte to finally obtain a uniform alkaline iron oxide anticorrosive coating on the surface of the metal material substrate. The lithium-containing electrolyte is specifically Li2CO3-Na2CO3-K2CO3Or LiOH-NaOH.
Compared with the prior art, the invention has the following beneficial effects: (1) the coating can be used for high and low temperature corrosion protection of metal in water, atmosphere, soil, industrial medium and molten salt electrolyte, has wide environment and temperature application range, can resist corrosion of Cl & lt- & gt and F & lt- & gt, and simultaneously shows excellent ageing resistance; (2) the coating has good stability, higher density, excellent mechanical property, easy processing and preparation, and cheap and easily obtained raw materials.
Drawings
FIG. 1 is an optical photograph of a cross section of an alkaline iron oxide anticorrosive coating prepared in example 1 of the present invention;
FIG. 2 is a graph showing the results of the alkali iron oxide anticorrosive coating coupon experiment prepared in example 4 of the present invention.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following embodiments are further described.
Example 1
An alkaline iron oxide layer having a thickness of 25 μm was formed on the surface of an a3 steel sheet (metal material substrate) by a plasma spraying method (wherein the mass ratio of lithium to iron to oxygen was 1.7:67.4: 30.9). This is the alkaline iron oxide anti-corrosion coating with single-layer structure, and the physical photograph is shown in fig. 1.
The A3 steel plate with the single-layer alkaline iron oxide anticorrosive coating prepared on the surface is used as a fishing boat body material and is soaked in seawater for 2 years, and meanwhile, the same seawater soaking experiment is carried out by taking the original A3 steel plate (without any anticorrosive coating) of the same batch as a reference. As a result, the A3 steel plate with the alkaline iron oxide anticorrosive coating has no obvious corrosion, the anticorrosive coating is kept intact, and the surface of the original A3 steel plate has severe corrosion. This indicates that the alkaline iron oxide anticorrosive coating has excellent corrosion protection capability against stainless steel materials in a seawater environment.
Example 2
304 stainless steel plate as application material and Li2CO3-Na2CO3-K2CO3(molar ratio Li)2CO3:Na2CO3:K2CO343.5:31.5:25) molten salt as an electrolyte, an anode nickel plate as a cathode, and a basic iron oxide layer (lithium: iron: the mass ratio of oxygen is 7.3:58.9:33.8), and the alkaline iron oxide anticorrosive coating with the single-layer structure is obtained.
The 304 stainless steel plate with the single-layer alkaline iron oxide anticorrosive coating prepared on the surface is used as a structural material of an offshore drilling platform and is exposed in ocean air for 3 years. As a result, it was found that the 304 stainless steel plate having the basic iron oxide anticorrosive coating attached thereto did not undergo significant corrosion, and the anticorrosive coating remained intact. This demonstrates that the alkaline iron oxide corrosion protective coating has excellent corrosion protection against stainless steel in the ocean air.
Example 3
A nodular cast iron pipe is used as an application material, and an alkaline iron oxide layer with the thickness of 20 mu m is prepared on the surface of the nodular cast iron pipe in a chemical vapor deposition mode (the mass ratio of lithium to iron to oxygen is 1.7:67.4:30.9), so that the alkaline iron oxide anti-corrosion coating with a single-layer structure is obtained.
The nodular cast iron pipe with the single-layer alkaline iron oxide anticorrosive coating prepared on the surface is used as a water pipeline and is buried for 4 years in one meter underground soil typical in Wuhan. As a result, it was found that no significant corrosion occurred in the ductile iron pipe. This result indicates that the alkaline iron oxide anticorrosive coating has excellent corrosion protection capability against iron-based materials in the soil environment.
Example 4
An A3 steel plate is used as an application material, and a basic iron oxide layer with the thickness of 2 mu m is prepared on the surface of the steel plate in a chemical oxidation mode (the mass ratio of lithium to iron to oxygen is 7.3:58.9:33.8), so that the basic iron oxide anti-corrosion coating with a single-layer structure is obtained.
The A3 steel plate with the single-layer alkaline iron oxide anticorrosive coating prepared on the surface is placed in Wuhan air, and a hanging experiment with the period of 2 years is carried out. As a result, it was found that the A3 steel sheet did not undergo significant corrosion (see FIG. 2). This indicates that the basic iron oxide anticorrosive coating has excellent corrosion protection capability against stainless steel in an air environment.
Example 5
An A3 steel plate is used as an application material, LiOH-NaOH (molar ratio LiOH: NaOH is 10:90) molten salt is used as electrolyte, the application material is used as an anode nickel plate as a cathode, and a double-layer alkaline iron oxide layer is prepared on the surface of the steel plate in one step in an electrochemical oxidation mode on the premise of controlling oxidation time, so that the double-layer composite alkaline iron oxide anticorrosive coating is obtained. The thickness of the inner layer of the coating was found to be 10 μm by inspection, where lithium: iron: the mass ratio of oxygen is 1.7:67.4: 30.9; the thickness of the outer layer of the coating is 10 μm, wherein the ratio of lithium: iron: the mass ratio of oxygen was 7.3:58.9: 33.8).
The A3 steel plate with the double-layer compound type alkaline iron oxide anticorrosive coating prepared on the surface is used as a wharf supporting material and is soaked in east lake water in Wuhan City for 2 years. As a result, it was found that the A3 steel sheet did not undergo significant corrosion. The composite type alkaline iron oxide anticorrosive coating has excellent corrosion protection capability on stainless steel in the water environment of east lake in Wuhan city.
Example 6
A310S stainless steel plate is used as an application material, LiOH-NaOH (molar ratio LiOH: NaOH is 10:90) molten salt is used as electrolyte, the application material is used as an anode nickel plate and is used as a cathode, and an alkaline iron oxide layer with the thickness of 10 mu m is prepared on the surface of the stainless steel in an electrochemical oxidation mode (the mass ratio of lithium to iron to oxygen is 7.3:58.9:33.8), so that the alkaline iron oxide anticorrosive coating with the single-layer structure is obtained.
The 310S stainless steel plate with the single-layer alkaline iron oxide anticorrosive coating prepared on the surface is used as Li2CO3-Na2CO3-K2CO3Molten salt electrolyte (molar ratio Li)2CO3:Na2CO3:K2CO3When the container material was soaked at a temperature of 450 ℃ of 43.5:31.5:25 for 1000 hours, the 310S stainless steel plate was found to be free from significant corrosion. This demonstrates that the alkaline iron oxide corrosion protective coating is resistant to Li at high temperatures of 450 deg.C2CO3-Na2CO3-K2CO3Stainless steel in a molten salt electrolyte use environment has excellent corrosion protection capability.
Example 7
A316L stainless steel pipe is used as an application material, a 1mol/L LiOH aqueous solution is used as an electrolyte, an application material is used as an anode nickel plate and is used as a cathode, and an alkaline iron oxide layer with the thickness of 1 mu m is prepared on the inner wall of the steel pipe in an electrochemical oxidation mode (the mass ratio of lithium to iron to oxygen is 7.3:58.9:33.8), namely the alkaline iron oxide anticorrosive coating with the single-layer structure.
The 316L stainless steel pipe with the single-layer alkaline iron oxide anticorrosive coating on the inner wall is used as a circulating cooling water delivery pipe of a thermal power plant, and after 3 months of use, the 316L stainless steel pipe is found not to be obviously corroded. This shows that the alkaline iron oxide anticorrosive coating has excellent corrosion protection capability for stainless steel pipes in the environment of use of circulating cooling water of a thermal power plant.
Example 8
The medium-silicon nodular cast iron plate is used as an application material, and an alkaline iron oxide layer with the thickness of 10 mu m is prepared on the surface of the medium-silicon nodular cast iron plate in a physical vapor deposition mode (the mass ratio of lithium to iron to oxygen is 7.3:58.9:33.8), namely the alkaline iron oxide anticorrosive coating with the single-layer structure.
The medium-silicon nodular cast iron plate with the single-layer alkaline iron oxide anticorrosive coating prepared on the surface is used as a fire bar of a coal-fired boiler, and after working for 2 years, the medium-silicon nodular cast iron plate is found to be free from obvious oxidation corrosion. This demonstrates that the alkaline iron oxide anti-corrosive coating has excellent corrosion protection capability against nodular cast iron materials under high temperature conditions.
Example 9
A310S stainless steel plate is used as an application material, LiOH-NaOH (molar ratio LiOH: NaOH is 10:90) molten salt is used as electrolyte, the application material is used as an anode nickel plate and is used as a cathode, and an alkaline iron oxide layer with the thickness of 10 mu m is prepared on the surface of the steel plate in an electrochemical oxidation mode (the mass ratio of lithium to iron to oxygen is 7.3:58.9:33.8), so that the alkaline iron oxide anticorrosive coating with the single-layer structure is obtained.
The 310S stainless steel plate with the single-layer alkaline iron oxide anticorrosive coating prepared on the surface is used as a cryolite molten salt electrolyte (the weight ratio of Na to Na)3AlF6：AlF3：CaF2：LiF：Al2O3After soaking the container material at 82.8:6.7:3.0:4.0:3.5 ℃ for 1000h, no significant corrosion of the 310S stainless steel plate occurred. This demonstrates that the basic iron oxide corrosion protective coating has excellent corrosion protection against stainless steel in a cryolite molten salt electrolyte environment.
Claims (3)
1. An alkaline iron oxide anti-corrosion coating, characterized in that the composition of the anti-corrosion coating comprises, in parts by weight: 1% -8% of lithium, 50% -69% of iron and 30% -35% of oxygen; the preparation method of the anticorrosive coating comprises the following steps: electrolyzing a metal material matrix serving as an anode and a nickel electrode serving as a cathode in a lithium-containing electrolyte, and finally forming an alkaline iron oxide anticorrosive coating on the surface of the metal material matrix, wherein the lithium-containing electrolyte is LiOH-NaOH; the anticorrosive coating is of a single-layer structure or a multi-layer composite structure, wherein each layer of the multi-layer composite structure has different element content; the anti-corrosion coating is attached to the surface of a metal material matrix, and the metal material matrix is specifically an iron-based plate or an iron-based pipe.
2. The alkaline iron oxide corrosion protective coating of claim 1, wherein: the application environment of the metal material matrix comprises various water bodies, atmosphere, soil, industrial medium and molten salt electrolyte at different temperatures.
3. The alkaline iron oxide corrosion protective coating of claim 1, wherein: the thickness of the alkaline iron oxide anticorrosive coating is 1-1000 mu m.
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