CN113025094A - Antioxidant red mud doped paint for high-temperature steel billet - Google Patents
Antioxidant red mud doped paint for high-temperature steel billet Download PDFInfo
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- CN113025094A CN113025094A CN202110262936.1A CN202110262936A CN113025094A CN 113025094 A CN113025094 A CN 113025094A CN 202110262936 A CN202110262936 A CN 202110262936A CN 113025094 A CN113025094 A CN 113025094A
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
- C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
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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
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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Abstract
The invention relates to an antioxidant red mud doped paint for high-temperature billets, which consists of red mud, silicon dioxide, carboxymethyl cellulose, aluminum oxide, magnesium oxide, graphite powder, sodium silicate and water. The mixed powder comprises the following main components in percentage by mass: 15-50% of red mud powder, 20-60% of silicon dioxide powder, 15-75% of alumina powder, 1-20% of graphite powder, 1-20% of magnesium oxide powder, 5-15% of high-temperature binder and 0.4-1% of dispersant. The invention of the antioxidant coating improves the utilization value of the red mud, increases the treatment capacity of the red mud waste material, and reduces the pressure of the red mud on the environment; the anti-oxidation coating has low preparation cost and little environmental pollution, does not pulverize or crack under high temperature environment after being brushed, sprayed or dip-coated on the steel billet, forms a layer of compact protective film on the surface of the steel billet, and has good anti-oxidation performance in the heating and heat preservation processes of the steel billet.
Description
Technical Field
The invention relates to the technical field of high-temperature oxidation resistance protection of steel billets, and also relates to the technical field of recycling of metallurgical solid wastes.
Background
Before the processes of die forging, rolling, annealing, quenching, normalizing and the like are completed, metal and alloy materials are heated to a certain temperature in various industrial furnaces and kilns. In the high-temperature heating process, the oxidation burning loss of steel is inevitable, and the heating time is longerLong, the higher the heating temperature, the more severe the oxidation burning loss of the steel. In addition, alloy elements in the steel are easily oxidized in the high-temperature heating process to generate an oxide layer which is difficult to peel off, and the surface defect phenomenon is formed in the steel pressed in the metal rolling or forging process, so that the rolled piece can be scrapped in severe cases. According to statistics, the oxidation and burning loss caused in the heating process of iron and steel products all over the world exceed 10 percent, and huge waste of resources is caused. The reduction of oxidation and burning loss in the heating and heat preservation processes of steel materials has become a hot point of research in various industrial countries around the world. The NALCO84MB264 coating developed by the American NALCO company can reduce the oxidation burning loss of metal materials such as steel and the like by 70 percent on average in the heating process, and when the coating is coated on the surfaces of tool steel and high-carbon steel, the decarburization of the metal surface can be greatly reduced (the decarburized layer is controlled within 0.25 mm) besides the reduction of the metal oxidation in the heating process. The Nippon Nissan iron company develops a series of aluminum high-temperature oxidation resistant coatings for special steel, the coatings are coated on the surface of metal before heating, and the oxidation burning loss of the metal can be reduced by 98% in the heating process; the manganese series high-temperature resistant coating developed aiming at the plain carbon steel has good anti-oxidation effect in the heating process. The high-temperature coating developed by former Soviet Union scientists aiming at X15H5 steel can reduce the oxidation burning loss of the steel by 25-30% in the heating process, and the quality of the metal surface is improved to a certain extent. The vacuum heating method or the protective atmosphere heating method is adopted in advanced countries such as Japan and America, and the oxidation and burning loss of steel materials can be greatly reduced, but the methods have large investment, high cost and low production efficiency, and cannot be applied to the large-scale continuous casting billet heating and soaking process of steel enterprises. The research and development of ordinary metal parts in China on high-temperature anti-oxidation coating also achieve certain performance from the beginning of the century, but most of domestic related patents are SiO2Or Al2O3The aggregate is added with various additives such as high-temperature binder, thickener, high-temperature-resistant oxide and the like to prepare the mixed material. For example, CN2019106740036 discloses a high-temperature-resistant oxidation-resistant coating for nickel-based alloy hot rolling and a preparation method thereof, the high-temperature-resistant oxidation-resistant coating prepared in the invention can effectively obstruct the reaction between the surface of a rolled piece and the environment atmosphere, obviously delay the oxidation and decarburization of the metal surface, and can be used for preparing a high-temperature-resistant oxidation-resistant coating for nickel-based alloy hot rollingThe coating falls off automatically after treatment, the quality of the subsequent hot-rolled nickel-based alloy is not influenced, but the practicability of the coating is greatly limited due to the complicated preparation process; CN2011100605424 discloses a billet oxidation-resistant and decarburization-resistant coating with high absorption rate, which can enable a billet to have good oxidation resistance at a high temperature, but the coating contains chromium element, and the coating after cooling and stripping can generate Cr which seriously pollutes the environment6+In addition, the cost is high, and the popularization and the application are influenced.
Red mud is also called red mud, which is the solid waste left after alumina is leached from bauxite by strong alkali, 1.5-2.5 tons of red mud are additionally generated per one ton of alumina, and the global red mud yield is about 1.2 hundred million tons every year; according to the data of the national statistical bureau, the alumina yield of China is increased year by year, the red mud discharge amount is rapidly increased, and hundreds of millions of tons are accumulated at present; the red mud is piled up in large quantity, which causes waste of land resources and environmental pollution. Comprehensive utilization of red mud is very important in China, and the general statement in "industrial green development planning (2016-2020)", issued by the Ministry of industry and communications specifically indicates that: greatly promotes the comprehensive utilization of industrial solid wastes and continuously promotes the cycle development. At present, the comprehensive utilization rate of the red mud mainly stays in a test stage, the scale application is less than 10%, the comprehensive utilization rate is mainly concentrated in the building fields of damming, concrete, cement, road paving and the like, and large-scale industrial treatment is still a worldwide problem.
In summary, Al is used2O3Or SiO2The high-temperature oxidation resistant protective coating for the aggregate can improve the high-temperature oxidation resistance of the steel material, but the use of the coating is greatly limited because the steps for preparing the coating are too complicated or because the coating contains chromium to cause environmental pollution. The red mud is used as high-alkalinity waste slag generated in the alumina industry, has huge production amount and storage amount, is comprehensively utilized, and has great economic value and social value. The red mud as a coating has good compactness, can isolate external gas and protect a matrix, and has good stability at high temperature; the red mud is used as aggregate to develop a high-temperature anti-oxidation coating which is simply brushed, sprayed or dip-coated on the surface of a steel billetThen, the coating performs antioxidant protection on the steel billet through three different mechanisms of mutual melting reaction, consumption reaction and inert molten film shielding, and has the characteristics of low investment, low cost, strong adaptability and the like, and the popularization and application values of the coating are huge.
Disclosure of Invention
In view of the use of Al2O3Or SiO2The technical problems that the preparation process of the high-temperature antioxidant protective coating of the aggregate is complicated, the cost is relatively high, and the waste residue of the chromium-containing antioxidant coating after cooling and stripping can cause serious environmental pollution are solved by the invention, which comprises the following steps: the high-temperature antioxidant coating has the advantages of simple preparation process, low cost, wide applicability, strong antioxidant capacity of the steel material coating in the heating process and no chromium element polluting the environment.
In order to achieve the technical purpose, the technical scheme provided by the invention is as follows:
(1) the invention relates to an antioxidant red mud doped coating, which comprises the following raw materials in percentage by mass: 15-50% of red mud powder, 20-60% of silicon dioxide powder, 15-75% of alumina powder, 1-20% of graphite powder, 1-20% of magnesium oxide powder, 5-15% of high-temperature binder and 0.4-1% of dispersant.
(2) The main components of the red mud powder are silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, sodium oxide and the like; SiO modified by red mud powder2The mass fraction range of (A) is 10-65%, the mass fraction range of Al2O3 is 15-50%, the mass fraction range of CaO is 15-50%, the mass fraction range of MgO is 1-10%, and Na2The mass fraction of O is 3-15%. The aggregate of the doped coating is modified red mud powder and alumina powder, the high-temperature binder is sodium silicate, the dispersant is carboxymethyl cellulose, the average particle size of the modified red mud powder is 100-1000 um, and the viscosity of the carboxymethyl cellulose is 2000-4500 mPa.s.
(3) The preparation method of the high-temperature oxidation-resistant red mud doped coating comprises the following steps:
the method comprises the following steps: preparing modified red mud powder. Respectively weighing 20g of raw red mud powder and 2g of alumina powder, wherein the granularity of the alumina is 50-150 mu m, uniformly mixing the raw red mud powder and the alumina powder in a beaker, then putting the mixture into a ball milling tank, and carrying out dry milling by using a high-energy ball mill. Ball milling parameters: the ball-material ratio is 4:1, the ball mill operates in a single row, and the ball milling time is 90-120 min.
Step two: and (4) preparing raw materials. Respectively weighing the powder, wherein the mass percentages of the components are as follows: 15-50% of red mud powder (the granularity is 100-1000 mu m), 20-60% of silicon dioxide powder (the granularity is 75-300 mu m), 15-75% of aluminum oxide powder (the granularity is 50-150 mu m), 1-20% of graphite powder (the granularity is 50-100 mu m), 1-20% of magnesium oxide powder (the granularity is 50-100 mu m), 5-15% of high-temperature binder and 0.4-1% of dispersant (the granularity is 100-400 mu m).
Step three: and (4) uniformly mixing. And (3) putting the mixed powder weighed in the step one into an edge runner mill, uniformly stirring and mixing the dry powder, adding water accounting for 50-80% of the total weight of the mixed slurry into the edge runner mill in batches, and stirring until the slurry is uniformly mixed.
(4) The application method of the antioxidant coating produced by the invention used in the heating and heat preservation processes of steel materials comprises the following steps:
after removing oil stains on the surface of a steel billet, uniformly coating a high-temperature oxidation-resistant coating on the surface of the steel billet to be processed in a brushing, spraying or dip-coating mode, naturally drying the steel billet in air, and then heating the steel billet in a furnace, or uniformly coating the high-temperature oxidation-resistant coating on the surface of the steel billet with the temperature of 700-900 ℃ on a continuous casting roller way in a spraying mode, and then feeding the steel billet into a steel rolling heating furnace.
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
the modified red mud powder in the mixed powder contains SiO2、Al2O3And Na2And O, which can be softened and melted at a lower temperature (below 800 ℃) to form a low-melting-point and viscous vitreous body film, and the vitreous body film can uniformly and firmly cover the surface of the matrix to prevent the high-temperature furnace gas from contacting the steel matrix to generate mutual melting reaction, thereby playing a role in protection. The modified red mud powder in the mixed powder contains Fe3O4Powder of Fe3O4Can be melted on the surface of the substrate to form inertia at high temperatureA protective film for enhancing the antioxidant protection of the coating, and Na2O and Fe3O4Can also be used as a fluxing agent of the coating, and can reduce the sintering temperature of the coating.
The mixed powder contains MgO, so that the coating material can generate MgAl under the high-temperature condition0.6Fel.4O4And MgFe2O4The spinel structure is equal, so that the compactness of an oxide layer is enhanced, the thickness of the oxide layer is reduced, the diffusion rate of high-temperature Fe element in the oxide layer is effectively inhibited, and the oxidation burning loss is reduced; in addition, the MgO has higher thermal conductivity and melting point, the influence of the coating on the high-temperature heating speed of the matrix can be improved, the melting temperature of the coating is increased, and the coating is automatically peeled off when the temperature of the coating is sharply reduced.
The graphite powder in the mixed powder can play a role in deoxidation, so that the oxygen content in the coating is obviously reduced, and the oxidation and surface decarburization of the billet (or steel part) are reduced. As the heating of the billet (or steel piece) proceeds and the temperature rises, graphite and oxygen in the atmosphere form an extremely thin gas layer, called a high-temperature gas film, which continuously diffuses to the outside or reacts with oxides in the coating inside, but the gas generation is also continuous because the wrapping of the graphite by the melt reduces the oxidation rate of the graphite; whether CO or CO is produced2The oxygen-containing composite material can form certain obstruction to the invasion of external oxygen, dilute the oxygen concentration or directly react with the oxygen to consume partial oxygen, and alleviate the oxidation of the oxygen to a matrix. But the difference with the carbon powder is that the graphite has a layered structure, has the characteristics of high temperature resistance, small thermal expansion coefficient and good thermal shock resistance, and can reduce the generation of cracks.
The red mud powder in the mixed powder contains CaO, and the fusible substances are softened faster than the refractory substances during high-temperature heating, so that the refractory substances can be bonded, and the compactness of the coating is improved. In addition, the fusible material can react with the substance on the surface of the billet (steel piece) at high temperature by virtue of high chemical activity to form a transition layer between the coating and the substrate, so that the coating is better adhered to the surface of the substrate. The coating has low content of fusible substances and is difficult to corrode the surface of a substrate; in addition, because of the different thermal expansion coefficients of the substances, the steel sample after cooling is helpful to strip the scale on the bonding surface from the surface of the substrate. The addition of CaO can promote the sintering densification of the powder, improve the fluidity and the wettability of the glass phase liquid at high temperature and enable the coating to uniformly cover the surface of the workpiece.
The solvent in the invention is selected from water, and the solvent can be obtained by common water, so that the source is rich, and the preparation cost of the coating is reduced;
the high-temperature anti-oxidation red mud coating does not contain high-pollution chromium, and has small pollution to the environment;
the high-temperature anti-oxidation red mud coating has the advantages of low component cost, simple process, high applicability, wide application range and convenient popularization and use.
Drawings
FIG. 1: the oxidation weight loss ratio per unit area of each sample, wherein a is example 1, B is comparative example 1, C is comparative example 2, D is comparative example 3, and E is comparative example 4;
FIG. 2: the coating surface micro-topography of example 1;
FIG. 3: coating cross-sectional morphology of example 1;
FIG. 4: coating Cross-sectional morphology of example 1
FIG. 5: spectral image of example 1
Detailed Description
For a further understanding of the present invention, reference will now be made to the following examples:
example 1
The high-temperature oxidation-resistant red mud coating of the embodiment is composed of mixed powder, a binder and a dispersant solvent. Wherein the mixed powder comprises the following components in percentage by mass: 16.8 percent of red mud powder, 50 percent of silicon dioxide powder, 16.8 percent of alumina powder, 8.3 percent of graphite powder, 1.7 percent of magnesium oxide powder, 6 percent of high-temperature binder and 0.4 percent of dispersant. The main components of the red mud powder in the mixed powder are silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, sodium oxide and ferric oxide. The high-temperature binder in the high-temperature oxidation-resistant red mud coating is sodium silicate, the dispersant is carboxymethyl cellulose, and the solvent is water which accounts for 50% of the total mass.
The preparation method of the high-temperature oxidation-resistant red mud doped coating comprises the following steps:
the method comprises the following steps: preparing modified red mud powder. Respectively weighing 20g of raw red mud powder and 2g of alumina powder, wherein the granularity of the alumina is 50-150 mu m, uniformly mixing the raw red mud powder and the alumina powder in a beaker, then putting the mixture into a ball milling tank, and carrying out dry milling by using a high-energy ball mill. Ball milling parameters: the ball-material ratio is 4:1, the ball mill operates in a single row, and the ball milling time is 90-120 min.
Step two: and (4) preparing raw materials. Respectively weighing the powder, wherein the mass percentages of the components are as follows: 15-50% of red mud powder (the granularity is 100-1000 mu m), 20-60% of silicon dioxide powder (the granularity is 75-300 mu m), 15-75% of aluminum oxide powder (the granularity is 50-150 mu m), 1-20% of graphite powder (the granularity is 50-100 mu m), 1-20% of magnesium oxide powder (the granularity is 50-100 mu m), 5-15% of high-temperature binder and 0.4-1% of dispersant (the granularity is 100-400 mu m).
Step three: and (4) uniformly mixing. And (3) putting the mixed powder weighed in the step one into an edge runner mill, adding water accounting for 50-80% of the total mass of the mixed slurry into the edge runner mill, and stirring until the slurry is uniformly mixed.
The use method of the antioxidant coating produced by the embodiment as a steel material in the heating and heat preservation process comprises the following steps:
after removing oil stains on the surface of the steel billet, uniformly coating a high-temperature oxidation-resistant coating on the surface of the steel billet to be processed by adopting a brushing and spraying mode, naturally drying the steel billet in the air, then heating the steel billet in a furnace to 1000 ℃, and preserving the heat for 60 minutes, wherein the oxidation weight loss rate in unit area of each square centimeter of the surface of the steel material is measured to be 0.0392% after the heating is finished.
Comparative example 1
In this comparative example, as a reference experiment, a steel slab without any coating was heated in a heating furnace to 1000 ℃ and kept at the temperature for 60 minutes, and when the heating was completed, the oxidation weight loss rate per unit area of the surface of the steel slab was measured to be 0.255%.
Comparative example 2
The components in the mixed powder material in the comparative example consist of the following components in percentage by mass: 70% of red mud powder, 5% of silicon dioxide powder, 5% of alumina powder, 5% of graphite powder, 5% of magnesium oxide powder, 9% of high-temperature binder and 1% of dispersant, wherein the preparation method and application of the high-temperature oxidation-resistant red mud coating in the comparative example are the same as those in example 1, a billet coated with the coating is placed in a heating furnace to be heated to 1000 ℃, and after the temperature is kept for 60 minutes, the oxidation weight loss rate in unit area of the surface of the billet is measured to be 0.219%.
Comparative example 3
The components of the mixed powder in the comparative example consist of the following components in percentage by mass: 60% of red mud powder, 15% of silicon dioxide powder, 10% of alumina powder, 7% of graphite powder, 5% of magnesium oxide powder, 2% of high-temperature binder and 1% of dispersant, and according to the preparation method and application of the high-temperature oxidation-resistant red mud coating in the comparative example, the billet coated with the coating is placed in a heating furnace to be heated to 1000 ℃ and is kept warm for 60 minutes, and then the oxidation weight loss rate in unit area of the billet surface is measured to be 0.246%.
Comparative example 4
The components of the mixed powder in the comparative example consist of the following components in percentage by mass: the preparation method and the application of the high-temperature oxidation-resistant red mud coating in the comparative example are the same as those in example 1, and the oxidation weight loss rate per unit area of the surface of a billet is 0.213 percent after the billet coated with the coating is placed in a heating furnace and heated to 1000 ℃ and is kept warm for 60 minutes.
As can be seen from the oxidation weight loss ratio data of the heated steel billets in the embodiment 1 and the comparative examples 1 to 4, the high-temperature oxidation-resistant red mud coating disclosed by the invention can greatly improve the oxidation resistance of the steel billets in high-temperature heating or heat preservation within the specified range of each component in the coating.
Therefore, the high-temperature oxidation-resistant red mud coating can ensure that the billet has excellent oxidation resistance in the heating process, has simple preparation process, lower cost and wide application range, and does not contain chromium-containing substances polluting the environment; on the other hand, the invention reasonably utilizes the red mud as the raw material, and solves the problem of environmental pollution of the red mud to a certain extent.
TABLE 1 ingredient table of high-temperature antioxidant red mud doped coating in examples and comparative examples
Claims (7)
1. The high-temperature billet oxidation resistant coating is characterized by comprising the following raw materials in percentage by mass: 15-50% of red mud powder, 20-60% of silicon dioxide powder, 15-75% of alumina powder, 1-20% of graphite powder, 1-20% of magnesia powder, 5-15% of high-temperature binder and 0.4-1% of dispersant; wherein, the aggregate of the mixed powder consists of red mud powder, silicon dioxide powder and alumina powder, the high-temperature binder is sodium silicate, and the dispersant is carboxymethyl cellulose.
2. The powder blend of claim 1, wherein: the main components of the red mud powder are silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, sodium oxide and the like.
3. The mixed powder according to claim 1, wherein SiO in the red mud powder2In the range of 10-65% by mass, Al2O3The mass fraction range of (A) is 15-50%, the mass fraction range of CaO is 15-50%, the mass fraction range of MgO is 1-10%, and Na2The mass fraction of O is 3-15%.
4. The mixed powder material as claimed in claim 1, wherein the average particle size of the red mud powder is 100-1000 μm, and the viscosity of the carboxymethyl cellulose dispersant is 2000-4500 mPa.s.
5. Weighing the raw materials according to the mass percentage of claim 1, and then putting the raw materials into an edge runner mill to be uniformly stirred.
6. The high-temperature oxidation-resistant coating as claimed in claim 1, wherein: the selected high-temperature binder is sodium silicate, and the solvent is water.
7. The use of a high-temperature antioxidant coating as claimed in claim 1, wherein the high-temperature antioxidant coating is widely applicable and simple to use, and can be sprayed or brushed on the surface of a continuous casting cold billet or a continuous casting hot billet to be used as an antioxidant coating for a steel billet in a heating furnace of a hot rolling mill, and can also be brushed, sprayed or dip-coated to be used as an antioxidant coating in a steel billet heat treatment process.
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Cited By (3)
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| CN114736002A (en) * | 2022-03-28 | 2022-07-12 | 中电国际新能源海南有限公司 | Preparation method of high-temperature chlorine corrosion resistant ceramic coating for red mud base material of incinerator |
| CN116924790A (en) * | 2023-05-19 | 2023-10-24 | 水利部交通运输部国家能源局南京水利科学研究院 | Red mud-based composite ceramic coating material and preparation method and application thereof |
| CN117736597A (en) * | 2023-12-14 | 2024-03-22 | 常熟理工学院 | High-carbon steel decarburization-preventing coating structure and high-carbon steel decarburization and surface oxidation defect control method |
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Application publication date: 20210625 |