CN114806234A - Metal high-temperature protection lubricating coating and preparation method, use method and recycling method thereof - Google Patents

Metal high-temperature protection lubricating coating and preparation method, use method and recycling method thereof Download PDF

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CN114806234A
CN114806234A CN202210359658.6A CN202210359658A CN114806234A CN 114806234 A CN114806234 A CN 114806234A CN 202210359658 A CN202210359658 A CN 202210359658A CN 114806234 A CN114806234 A CN 114806234A
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metal
lubricating coating
temperature
oxide powder
coating
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CN114806234B (en
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倪培远
乔亦凡
崔磊
丁玉石
厉英
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Northeastern University China
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Northeastern University China
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0239—Lubricating
    • B21B45/0242—Lubricants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00—Extruding metal; Impact extrusion
    • B21C23/32—Lubrication of metal being extruded or of dies, or the like, e.g. physical state of lubricant, location where lubricant is applied
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
    • B21J3/00—Lubricating during forging or pressing
    • 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
    • C09D7/20—Diluents or solvents
    • 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
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles

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Abstract

A metal high-temperature protective lubricating coating, a preparation method, a use method and a recycling method thereof. The metal high-temperature protection lubricating coating comprises 0-90% of oxide powder A, 0-90% of oxide powder B, 0.2-50% of solid particle additive, 1-50% of solvent and 0-5% of surfactant in percentage by mass, and provides a preparation method thereof, a using method of protection, heating and hot working (rolling, forging, extruding and the like), and a recycling method. The metal high-temperature protection lubricating coating is low in cost, simple in process, environment-friendly, pollution-free, easy to recover and reusable, can realize green and environment-friendly protection of metal from oxidation and nitridation corrosion within a large temperature range from room temperature to 1450 ℃, and can play a lubricating role in a hot working process.

Description

Metal high-temperature protection lubricating coating and preparation method, use method and recycling method thereof
Technical Field
The invention relates to the metal surface protection under the conditions of room temperature to high temperature and the field of hot working such as metal rolling, forging, extrusion and the like, in particular to a metal high-temperature protection lubricating coating, a preparation method, a use method and a recycling method thereof.
Background
The metal rolling, forging and extrusion are usually carried out at high temperature, and the rolling, forging and extrusion temperature can reach 700-1350 ℃, 500-1200 ℃ and 600-1250 ℃ respectively according to different metals and processes. In the process of heating, transporting and hot processing (rolling, forging or extruding and the like) of metal, the metal can react with oxygen and nitrogen in the air to generate oxide skin or nitride, so that metal material waste is caused, the quality of subsequent products is even directly influenced, in addition, temperature drop can be caused in the transporting process, the temperature can be reduced by 100-300 ℃ every time of transporting according to statistics, great difficulty is caused to the subsequent rolling, forging and extruding processes, meanwhile, the temperature of a roller, a forging die and an extruding die is increased due to high heat transfer coefficient of the metal, and in the rolling, forging and extruding processes, when the friction force between the metal and the roller and the die is large, the obvious scratch on the surface of the metal and the abrasion of the die can be caused, and the service life of the die is shortened. In addition, the problems of air oxidation, nitridation and the like are also faced under the high-temperature service working condition of the metal.
In order to reduce oxidation, nitridation and the like of the metal in the hot working process of high-temperature service, heating, transportation and rolling, forging and extrusionUnder the circumstances, various protection technologies have been developed, and inert gas is generally used for protection heating in metal heating. In addition, although many oxidation resistant coatings have been developed, most coatings have application temperatures of less than 1200 ℃, have a small application temperature interval, and have too low an oxidation resistance temperature for most nickel-based alloys; for the problem of temperature drop in the metal transportation process, the general solution is to heat the metal for the second time or raise the temperature of the metal to be heated, which not only consumes a large amount of energy, but also easily exceeds the temperature of the phase change point of the metal, so that the structure of the metal is changed, the performance of the produced product is reduced, and even the product is scrapped; high temperature metal can cause the die temperature to be too high for hot rolling, forging, and extrusion processes, and oxidation, nitridation of the metal and friction of the metal against the die can cause the die life to decrease. The current coatings mainly play a role in oxidation resistance, but the protection temperature range is limited, low-temperature protection is difficult to realize, few coatings have a lubricating effect, and some coatings contain PbTiO 3 And CrO 3 The heavy metal substances have potential environmental pollution problems, and some coatings contain components such as nitrides, and the like, so that nitrogen oxides are easily generated after the metal is nitrided and oxidized.
The hot working such as rolling, forging and extrusion is an important means for metal production, and the hot working processes such as rolling, forging and extrusion involve complex behaviors such as metal heating, deformation, phase change, heat transfer, new surface formation, softening and melting of a metal high-temperature protective lubricating coating, so that the metal high-temperature protective lubricating coating with the lubricating effect is an important functional material in the hot working processes such as rolling, forging and extrusion in order to obtain a high-quality product and reduce waste of metal blanks, die wear and process energy consumption. The development of a novel protective lubricating coating which is suitable for the whole-flow production of hot working such as rolling, forging, extrusion and the like, is environment-friendly, harmless to a metal matrix and capable of being recycled is urgently needed.
Disclosure of Invention
The invention provides a metal high-temperature protection lubricating coating, and a preparation method, a use method and a recycling method thereof, aiming at realizing the whole-process protection of the metal surface in the hot working processes of metal high-temperature service, rolling, forging, extrusion and the like, reducing the temperature drop in the transportation process, enhancing the lubrication and prolonging the service life of a die.
In order to realize the purpose, the technical scheme is as follows:
the metal high-temperature protection lubricating coating comprises the following components in percentage by mass: 0-90 wt.% of oxide powder A (the particle size is 100-700 meshes), 0-90 wt.% of oxide powder B (the particle size is 100-700 meshes), 0.2-50 wt.% of solid particle additive (the particle size is 1 nm-300 mu m), 1-50 wt.% of solvent and 0-5 wt.% of surfactant, wherein the sum of the mass percentages of the components is 100 wt.%;
the oxide powder A comprises the following components in percentage by mass: 1 to 70 wt.% B 2 O 3 、 1～60wt.％P 2 O 5 、0.5～15wt.％Al 2 O 3 、0.1～10wt.％ZnO、0～15wt.％CaO、0～15wt.％SiO 2 、 0.5～25wt.％Na 2 O、0.2～15wt.％MgO、0～10wt.％BaO、0.1～20wt.％K 2 O, less than 2 wt.% of inevitable impurity components, the sum of the mass percentages of the components being 100 wt.%;
the oxide powder B comprises the following components in percentage by mass: 5 to 75 wt.% SiO 2 、1～60wt.％B 2 O 3 、 0～15wt.％K 2 O、5～30wt.％Na 2 O、0.5～15wt.％Al 2 O 3 、0～10wt.％TiO 2 、1～20wt.％CaO、 1～15wt.％MgO、0～5wt.％La 2 O 3 、0～5wt.％CeO 2 、0～10wt.％BaO、0～5wt.％Nd 2 O 3 And less than 2 wt.% impurities, the sum of the mass percentages of the components being 100 wt.%.
The solid particle additive is: TiB 2 、ZrB 2 、B、TiO 2 、ZrO 2 、CeO 2 、Cr 2 O 3 、Al 2 O 3 、Mo 2 NiB 2 、 Mo 2 FeB 2 One or a mixture of more of SiC, MgO and zircon.
The solvent comprises the following components in percentage by mass: 1-5 wt.% of carboxymethyl cellulose, 0.5-20 wt.% of water glass, 0.5-5 wt.% of sodium polyacrylate or polyvinyl alcohol or polyurethane, and the balance of water; the sodium silicate is sodium silicate or potassium silicate, the modulus of the sodium silicate is 0.5-3.5, and the modulus of the potassium silicate is 1-4.
The surfactant is one or a mixture of ethanol, glycol and oleic acid.
The components adopted by the metal high-temperature protection lubricating coating do not contain fluoride, lead oxide, heavy chromium oxide and other components which have potential harm to the environment, and the metal high-temperature protection lubricating coating belongs to an environment-friendly coating material; in addition, the components adopted by the metal high-temperature protection lubricating coating do not contain substances such as nitride which have potential nitriding on metal materials. Among the components adopted by the metal high-temperature protective lubricating coating, the organic components in solvents such as carboxymethyl cellulose, polyvinyl alcohol or polyurethane and the like can play a role in protecting a metal matrix at a low temperature of below 400 ℃. The oxide powder A is a phosphorus borate low-melting-point system, the softening and melting temperature of the oxide powder A is lower than 400 ℃, the oxide powder A can be melted and wetted on a metal matrix at a low temperature, and meanwhile, the oxide powder A plays a role in bonding unmelted powder; the oxide powder B is a silicate or silicon borate system and mainly plays a role in protection at a higher temperature. The solid particle additive mainly comprises boride and partial high-melting point oxide, and TiB 2 The boride reacts with oxygen at high temperature to generate oxide components such as boron oxide and titanium dioxide, so that the boron oxide volatilized at high temperature can be effectively supplemented, and meanwhile, the generated substances such as titanium dioxide and the like can play a role in thickening the melt at high temperature, so that the high-temperature stability of the coating melt is improved. In addition, the oxidation reaction can further reduce the oxygen activity of the melt, consume oxygen, nitrogen and the like diffused to the metal through the coating, and better protect the metal matrix. By the method, the protection of the metal material from room temperature to 1450 ℃ in a large temperature range is realized, and in addition,the coating material of the invention can also have a lubricating effect in hot working. After the coating falls off, the coating can be recycled through simple recovery, and the resource is saved.
The invention relates to a preparation method of a metal high-temperature protection lubricating coating, which comprises the following steps:
step 1: respectively preparing a raw material of a component corresponding to the oxide powder A, a raw material of a component corresponding to the oxide powder B, a solid particle additive, a raw material of a component corresponding to the solvent and a surfactant according to the proportion of each component in the prepared metal high-temperature protection lubricating coating;
step 2: uniformly mixing the raw materials of the corresponding components of the oxide powder A to obtain a mixed raw material of the oxide powder A;
putting the mixed raw material of the oxide powder A into a high-temperature smelting furnace at 1200-1500 ℃ for smelting; then quenching the smelted material, and crushing to obtain oxide powder A;
uniformly mixing the raw materials of the corresponding components of the oxide powder B to obtain a mixed raw material of the oxide powder B;
putting the mixed raw material of the oxide powder B into a high-temperature smelting furnace at 1200-1500 ℃ for smelting; then quenching the smelted materials, and crushing to obtain oxide powder B;
and step 3: carrying out ball milling and mixing on the solid particle additive, the oxide powder A and the oxide powder B obtained in the step 2, and 5-30 wt.% and 0-5 wt.% of surfactant of water in the solvent in the step 1, and carrying out ball milling for 1-24 h to obtain a primary product of the metal high-temperature protective lubricating coating;
and 4, step 4: preparing the solvent raw materials in the step 1 in proportion, heating water with 5-30 wt.% being deducted from the solvent to 80-100 ℃, then adding 1-5 wt.% of carboxymethyl cellulose, 0.5-20 wt.% of sodium water glass (modulus 0.5-3.5) or potassium water glass (modulus 1-4), 0.5-5 wt.% of sodium polyacrylate or polyvinyl alcohol or polyurethane, stirring uniformly, and cooling to room temperature to obtain the solvent;
and 5: and (4) uniformly mixing the primary product of the metal high-temperature protection lubricating coating obtained in the step (3) with the solvent obtained in the step (4) to obtain the metal high-temperature protection lubricating coating slurry.
The invention relates to a method for using a metal high-temperature protection lubricating coating, which comprises the following steps:
the method comprises the following steps: metal surface overlay coating
Spraying, dipping or brushing the metal high-temperature protection lubricating coating slurry on the surface of the metal at room temperature, and naturally drying or drying at a low temperature of more than 200 ℃ to obtain the metal with the metal high-temperature protection lubricating coating; wherein the thickness of the high-temperature protection lubricating coating is 0.1-1.0 mm;
step two: heating of
Heating the metal with the metal high-temperature protective lubricating coating in the step I to a specified temperature according to the characteristics of the metal and the process, and then conveying the metal to corresponding equipment for rolling, forging or extruding; the specified temperature range is from room temperature to 1450 ℃; and discharging the metal from the furnace after the temperature of the metal is uniform to obtain the hot metal, and blowing, spreading or rolling dry powder or not blowing, spreading or rolling the dry powder onto the hot metal, wherein the thickness of the coating is further increased by the blowing, spreading or rolling the dry powder, so that lubrication and protection are better realized, and the heated metal is obtained. In the heating process, the glaze of the coating on the metal surface is good, and the temperature drop in the transportation process is 30-60 ℃. In general, compared with the lubricating coating without metal high-temperature protection, the anti-oxidation and anti-nitridation capability is improved, and no obvious surface oxidation is found in the metal protected by the coating. Meanwhile, the temperature drop in the transportation process is effectively inhibited, the energy consumption is saved, and the benefit is increased in the actual production.
Step three: hot working or high-temperature service
The metal heated in the step two is served at high temperature, the serving temperature is between room temperature and 1450 ℃, air cooling or water cooling is carried out to the room temperature, and the automatically-falling metal high-temperature protection lubricating coating is recovered;
the hot working is one of rolling, forging or extruding:
(1) rolling: rolling the metal heated in the step two, wherein the rolling temperature is as follows: air cooling or water cooling to room temperature after rolling at 700-1450 ℃, and recovering the automatically-falling metal high-temperature protective lubricating coating;
(2) forging: forging the metal heated in the step two, wherein the forging temperature is as follows: the forging method comprises the following steps of (1) carrying out air cooling or salt bath on a forged blank at 650-1350 ℃, and then recovering a metal high-temperature protective lubricating coating which automatically falls off;
(3) extruding: extruding the metal heated in the step two, wherein the extrusion temperature is as follows: and (3) cooling the extruded blank in air at 500-1250 ℃, and then washing the extruded blank with high-pressure water to remove the metal high-temperature protective lubricating coating on the surface.
In the rolling, forging and extrusion hot processing processes, the friction force between metal and a die is effectively reduced, and due to the characteristics of the metal high-temperature protective lubricating coating, the heat conductivity coefficient between a metal blank and the die is effectively reduced, and is reduced from 15-240W/(m.K) to 1-5W/(m.K); the service life of the die is effectively prolonged; and the temperature drop in the rolling, forging and extrusion hot working processes is 25-40 ℃, and no obvious oxidation phenomenon is found on the surface of the metal blank after rolling, forging and extrusion hot working.
In the second step, the dry powder is as follows: the oxide powder A, the oxide powder B and the solid particle additive mixture comprise the following components in percentage by mass: 1-90 wt% of oxide powder A, 1-90 wt% of oxide powder B and 0.2-50 wt% of solid particle additive, wherein the sum of the mass percentages of the components is 100%.
According to another object of the invention, the recycling method of the metal high-temperature protection lubricating coating comprises the following steps:
step (1): grinding and crushing the recovered metal high-temperature protection lubricating coating to 20-700 meshes to obtain a crushed coating;
step (2): mixing the crushed coating with a solid particle additive, adding water and a surfactant, and performing ball milling for further mixing to obtain powder slurry; wherein, the crushed coating is as follows according to the mass ratio: solid particulate additive: water: surfactant ═ (60-100): (0.1-20): (5-30): (0-5);
and (3): preparing a solvent according to the following mixture ratio;
the solvent comprises the following components in percentage by mass: 1-5 wt.% of carboxymethyl cellulose, 0.5-20 wt.% of water glass, 0.5-5 wt.% of sodium polyacrylate or polyvinyl alcohol or polyurethane, and the balance of water; the sodium silicate is sodium silicate or potassium silicate, the modulus of the sodium silicate is 0.5-3.5, and the modulus of the potassium silicate is 1-4;
wherein, the solvent is prepared according to the proportion of water with 5-30wt percent being deducted;
and (4): and adding the mixed powder slurry into a solvent, and further stirring and mixing uniformly to obtain the recycled metal high-temperature protective lubricating coating.
The metal high-temperature protection lubricating coating can be recycled for 5 to 30 times.
Compared with the prior art, the metal high-temperature protection lubricating coating, the preparation method, the use method and the recycling method thereof have the beneficial effects that:
1. the coating has a lubricating effect and low heat transfer coefficient, so that the processed high-temperature metal has good surface quality and few defects, the metal oxidation is light, the service life of the die is effectively prolonged, the defects of scratches and the like on the metal surface are reduced, and the product quality is improved.
2. The rolling, forging and extruding hot processing method for metal high temperature protection can effectively recycle the fallen coating, realize the cyclic utilization of resources, save time and process and save cost.
Drawings
FIG. 1 is a surface topography of TA2 titanium metal before and after application of a coating according to an embodiment of the present invention, wherein (a) before application and (b) after application;
fig. 2 is a surface topography of TA2 titanium metal after being coated with a coating layer and subjected to high temperature heating, wherein (a) the surface topography is obtained after being heated at high temperature, and (b) the surface topography is obtained after the coating layer is peeled off.
Detailed Description
To further clarify the operation of the present invention, the following description will be made with reference to specific examples. .
In the following examples, SiO 2 The raw material is chemical pure silicon dioxide and/or quartz sand, B 2 O 3 The raw material is one or the combination of a plurality of chemical pure boron trioxide, boric acid and borax, P 2 O 5 The raw materials are chemically pure phosphorus pentoxide, calcium phosphate, potassium pyrophosphate, sodium hexametaphosphate, magnesium phosphate, aluminum phosphate and/or phosphate ore and the like, Al 2 O 3 The raw material of the catalyst is one or a combination of more of chemical pure aluminum oxide, pyrophyllite, kaolin and bauxite, and TiO 2 The raw material of the titanium dioxide-rutile titanium dioxide composite is one or a combination of more of chemically pure titanium dioxide, titanium dioxide and rutile, and Na 2 The raw material of O is one or the combination of more of chemical pure sodium oxide, chemical pure sodium carbonate, soda ash and feldspar, and K 2 The raw material of O is one or a combination of more of chemically pure potassium oxide, potassium carbonate and feldspar, the raw material of CaO is one or a combination of more of chemically pure calcium oxide, chemically pure calcium carbonate, limestone and calcite, the raw material of MgO is one or a combination of more of chemically pure magnesium oxide, chemically pure magnesium hydroxide or magnesium carbonate, dolomite and magnesite, the raw material of BaO is one or a combination of more of chemically pure barium oxide, barium carbonate and witherite, the raw material of ZnO is one or a combination of more of chemically pure zinc oxide, calamine and zinc ash, La 2 O 3 、 CeO 2 、Nd 2 O 3 The raw material is chemically pure oxide or rare earth mineral, TiB 2 、ZrB 2 、B、TiO 2 、ZrO 2 、CeO 2 、 Cr 2 O 3 、Al 2 O 3 、Mo 2 NiB 2 、Mo 2 FeB 2 The raw materials of SiC and zircon are powder materials of corresponding materials.
Example 1
A metal high-temperature protection lubricating coating and a preparation method, a use method and a recycling method thereof comprise the following steps:
the metal used in this example was TA2 titanium metal.
(1) According to the proportion of 35 wt.% of oxide powder A, 30 wt.% of oxide powder B and 18 wt.% of TiO 2 (solid particulate additive), 15 wt.% solvent and 2 wt.% ethanol (surfactant) to make a metal high temperature protective lubricating coating; wherein the solvent is weighed as raw materials by 1.5 wt.% of carboxymethyl cellulose, 5 wt.% of sodium water glass, 1.5 wt.% of polyvinyl alcohol and 92 wt.% of water.
(2) 60 wt.% B 2 O 3 、11wt.％P 2 O 5 、6.5wt.％Al 2 O 3 、10wt.％Na 2 O、2.5wt.％K 2 O, 0.5 wt.% of MgO, 7.5 wt.% of CaO and 2 wt.% of ZnO, uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for fully melting, pouring out, water quenching, drying and crushing, and taking oxide powder A which is sieved by a 300-mesh sieve for later use;
59.2 wt.% SiO 2 、3.5wt.％B 2 O 3 、、3wt.％Al 2 O 3 、4wt.％.TiO 2 、3.5wt.％K 2 O、10wt.％Na 2 O、 5wt.％CaO、8.3wt.％MgO、0.8wt.％La 2 O 3 2 wt.% BaO and 0.7 wt.% Nd 2 O 3 Uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out water quenching, drying and crushing, and taking oxide powder B which is sieved by a 300-mesh sieve for later use;
(3) mixing the prepared oxide powder A and oxide powder B with 1 μm solid particle additive TiO 2 Mixing, adding 15 wt.% of water and 2 wt.% of ethanol in the solvent, and performing ball milling for 15 hours to obtain a primary product of the metal high-temperature protective lubricating coating.
(4) According to the weighing raw materials of the solvent in the step (1), dissolving 1.5 wt.% of carboxymethyl cellulose in 77 wt.% of water and stirring for 2h, adding 5 wt.% of sodium water glass and stirring for 1h, adding 1.5 wt.% of polyvinyl alcohol, and stirring for 30min again to obtain a uniform solvent;
(4) pouring the prepared primary product of the metal high-temperature protection lubricating coating into a solvent, and fully mixing to obtain metal high-temperature protection lubricating coating slurry;
(5) spraying, dipping or brushing the metal high-temperature protection lubricating coating slurry on the surface of a TA2 titanium billet, and naturally drying to obtain a TA2 titanium billet with a metal high-temperature protection lubricating coating, wherein the thickness of the metal high-temperature protection lubricating coating is 0.3 mm; wherein, the surface topography before and after coating is shown in figure 1, which shows that the coating effect is good.
(6) The TA2 titanium billet with the metal high-temperature protection lubricating coating is placed in an induction furnace and heated to 900 ℃, the metal billet is discharged after the temperature of the metal billet is uniform, a hot metal billet is obtained, dry powder is sprayed on the hot metal billet, the thickness of the coating is further increased, lubrication and protection are better realized, the heated metal billet is obtained, the surface topography graph after high-temperature heating is shown in figure 2(a), the anti-oxidation effect is good, and then the metal billet is transported to a device corresponding to extrusion for extrusion, and the extrusion temperature is as follows: 850 ℃. The temperature drop in the process of transporting the TA2 titanium billet is 50 ℃, wherein the dry powder comprises the following components in percentage by mass: 90 wt.% of oxide powder A, 1 wt.% of oxide powder B and 9 wt.% of solid particle additive, wherein the components of the oxide powder A and the oxide powder B are the same as those in the step (2).
(7) After extrusion, the TA2 titanium billet is cooled in air, and most of the metal high-temperature protective lubricating coating falls off automatically as shown in figure 2(b), which shows that the falling-off performance is good, so that the extruded TA2 product is obtained, and meanwhile, the fallen metal high-temperature protective lubricating coating is recovered. No obvious oxidation is found on the surface of the extruded titanium billet; the extrusion die wears less.
(8) Grinding and crushing the recovered metal high-temperature protection lubricating coating to 400 meshes, mixing the crushed coating with a micron solid particle additive MgO, adding water and ethanol, performing ball milling for 10 hours, and uniformly mixing to obtain powder slurry; and (2) crushing the coating according to the mass ratio: solid particulate additive: water: ethanol is 100:5:10: 2;
(9) weighing raw materials according to 2 wt.% of carboxymethyl cellulose, 5 wt.% of sodium water glass, 1 wt.% of sodium polyacrylate and 92 wt.% of water, deducting the water added in the step (8), heating the rest water to 80 ℃, dissolving the carboxymethyl cellulose in the water, stirring for 2 hours, adding the sodium water glass, stirring for 1 hour, adding the sodium polyacrylate, and stirring for 30 minutes to obtain a uniform solvent;
(10) and (4) pouring the powder slurry mixed in the step (9) into a solvent, and uniformly stirring to prepare the recycled metal high-temperature protective lubricating coating. The prepared recycled metal high-temperature protective lubricating coating can be recycled for 10 times.
Example 2
A metal high-temperature protection lubricating coating and a preparation method, a use method and a recycling method thereof comprise the following steps:
the metal used in this example is TC4 titanium alloy.
Preparing a metal high-temperature protective lubricating coating by using 40 wt.% of oxide powder A, 30 wt.% of oxide powder B, 15 wt.% of zircon (solid particle additive), 12 wt.% of solvent and 3 wt.% of oleic acid (surfactant) according to the proportion; wherein, the solvent is used for weighing raw materials according to 1.5 wt.% of carboxymethyl cellulose, 7.5 wt.% of sodium water glass, 0.5 wt.% of sodium polyacrylate and 90.5 wt.% of water;
(2) 56 wt.% B 2 O 3 、10wt.％P 2 O 5 、6.5wt.％Al 2 O 3 、6wt.％Na 2 O、1wt.％K 2 O, 12.5 wt.% CaO, 5 wt.% MgO and 3 wt.% ZnO, uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out, water quenching, drying and crushing, and taking oxide powder A which is sieved by a 400-mesh sieve for later use;
65 wt.% SiO 2 、2.5wt.％Al 2 O 3 、5wt.％B 2 O 3 、3wt.％K 2 O、12wt.％Na 2 O、5wt.％CaO、 2.5wt.％MgO、4wt.％BaO、0.5wt.％La 2 O 3 And 0.5 wt.% Nd 2 O 3 Uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out water quenching, drying and crushing, and taking oxide powder B which is sieved by a 400-mesh sieve for later use;
(3) mixing the prepared oxide powder A and oxide powder B with a micron solid particle additive, namely zircon, adding 12 wt.% of water and 3 wt.% of oleic acid in a solvent, carrying out ball milling for 20 hours, and uniformly mixing to obtain a primary product of the metal high-temperature protective lubricating coating.
(4) According to the weighing raw materials of the solvent in the step (1), dissolving 1.5 wt.% of carboxymethyl cellulose in 78.5 wt.% of water and stirring for 2 hours, adding 7.5 wt.% of sodium water glass and stirring for 1 hour, adding 0.5 wt.% of sodium polyacrylate and stirring for 30 minutes to obtain a uniform solvent;
(5) pouring the prepared metal high-temperature protection lubricating coating primary product into a solvent, and fully mixing to obtain metal high-temperature protection lubricating coating slurry;
(6) spraying, dipping or brushing the metal high-temperature protection lubricating coating slurry on the surface of a TC4 titanium alloy billet, and drying at a low temperature of 100 ℃ to obtain the TC4 titanium alloy billet with the metal high-temperature protection lubricating coating, wherein the thickness of the metal high-temperature protection lubricating coating is 0.35 mm;
(7) putting a TC4 titanium alloy billet with a metal high-temperature protection lubricating coating into a heating furnace to be heated to 1000 ℃, discharging the metal billet after the temperature of the metal billet is uniform to obtain a hot metal billet, spraying dry powder onto the hot metal billet, further increasing the thickness of the coating, better realizing lubrication and protection, obtaining the heated metal billet, then transporting the metal billet to a corresponding rolling device to be rolled, wherein the rolling temperature is as follows: 950 ℃. The temperature drop in the process of transporting the TC4 titanium alloy billet is 50 ℃, wherein the dry powder comprises the following components in percentage by mass: 1 wt.% of oxide powder A, 90 wt.% of oxide powder B and 9 wt.% of solid particle additive, wherein the components of the oxide powder A and the oxide powder B are the same as those in the step (2).
(8) And after rolling, carrying out water cooling on the TC4 titanium alloy billet, enabling the metal high-temperature protective lubricating coating to fall off by self to obtain a rolled product, and recovering the fallen metal high-temperature protective lubricating coating. No significant oxidation was observed on the surface of the rolled titanium ingot.
(9) Grinding the recovered metal high-temperature protective lubricating coating to 500 meshes, mixing the crushed coating with a micron solid particle additive zircon, adding water and oleic acid, and performing ball milling and uniform mixing to obtain powder slurry; and (2) crushing the coating according to the mass ratio: solid particulate additive: water: oleic acid 100:5:12: 3;
(10) weighing raw materials according to 1.8 wt.% of carboxymethyl cellulose, 5 wt.% of sodium water glass, 1.2 wt.% of sodium polyacrylate and 92 wt.% of water, deducting the water added in the step (9), heating the rest water to 85 ℃, dissolving the carboxymethyl cellulose in the water and stirring for 2 hours, adding the sodium water glass and stirring for 1 hour, adding the sodium polyacrylate and stirring for 30 minutes to obtain a uniform solvent;
(11) and (4) pouring the powder slurry mixed in the step (9) into a solvent, and uniformly stirring to prepare the recycled metal high-temperature protective lubricating coating. The prepared recycled metal high-temperature protective lubricating coating can be recycled for 15 times.
Example 3
A metal high-temperature protection lubricating coating and a preparation method, a use method and a recycling method thereof comprise the following steps:
the metal used in this example is TC11 titanium alloy.
(1) According to the proportion of 45 wt.% of oxide powder A, 35 wt.% of oxide powder B and 10 wt.% of ZrB 2 (solid particulate additive), 3 wt.% ethanol (surfactant) and 7 wt.% solvent make metal high temperature protective lubricating coating; wherein, the solvent is weighed by 3 wt.% of carboxymethyl cellulose, 4.5 wt.% of sodium water glass, 1.2 wt.% of polyurethane and 91.3 wt.% of water;
(2) 55 wt.% of B 2 O 3 、12wt.％P 2 O 5 、15wt.％Al 2 O 3 、7wt.％Na 2 O、2wt.％K 2 O, 2.1 wt.% CaO, 5 wt.% MgO and 1.9 wt.% ZnO, uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out water quenching, drying and crushing, and taking oxide powder A which is sieved by a 700-mesh sieve for later use;
66 wt.% SiO 2 、2.5wt.％Al 2 O 3 、7.8wt.％B 2 O 3 、2wt.％K 2 O、9wt.％Na 2 O、9wt.％CaO、 1.5wt.％MgO、1.5wt.％BaO、0.5wt.％La 2 O 3 And 0.2 wt.% Nd 2 O 3 Mixing uniformly to obtain a mixture, and putting the mixture into a high-temperature furnaceAfter the materials are fully melted, pouring out water quenching, drying and crushing, and taking oxide powder B which is sieved by a 700-mesh sieve for later use;
(3) mixing the prepared oxide powder A and oxide powder B with solid particle additive ZrB 2 Mixing, adding 15 wt.% of water and 3 wt.% of ethanol in a solvent, and performing ball milling for 20 hours to obtain a primary product of the metal high-temperature protective lubricating coating.
(4) According to the weighing raw materials of the solvent in the step (1), dissolving 3 wt.% of carboxymethyl cellulose in 76.3 wt.% of water and stirring for 2h, adding 4.5 wt.% of sodium water glass and stirring for 1h, adding 1.2 wt.% of polyurethane, and stirring for 30min again to obtain a uniform solvent;
(5) pouring the prepared primary product of the metal high-temperature protection lubricating coating into a solvent, fully mixing, and standing for 12 hours to obtain metal high-temperature protection lubricating coating slurry;
(6) brushing the metal high-temperature protection lubricating coating slurry on the surface of a TC11 titanium alloy billet, and drying at a low temperature of 50 ℃ to obtain a TC11 titanium alloy billet with a metal high-temperature protection lubricating coating, wherein the thickness of the metal high-temperature protection lubricating coating is 0.55 mm;
(7) putting the TC11 titanium alloy billet with the metal high-temperature protection lubricating coating into an electromagnetic induction furnace, heating to 1020 ℃, preserving heat for 2h, discharging the metal billet after the temperature of the metal billet is uniform to obtain a hot metal billet, blowing dry powder onto the hot metal billet, further increasing the thickness of the coating, better realizing lubrication and protection, obtaining the heated metal billet, then transporting to corresponding forging equipment for forging, and forging temperature: 975 deg.C. The temperature drop in the process of transporting the TC11 titanium alloy billet is 45 ℃, wherein the dry powder comprises the following components in percentage by mass: 25 wt.% of oxide powder A, 25 wt.% of oxide powder B and 50 wt.% of solid particle additive, wherein the components of the oxide powder A and the oxide powder B are the same as those in the step (2).
(8) And after forging, carrying out water cooling on the TC11 titanium alloy billet, and enabling the metal high-temperature protective lubricating coating to fall off by self to obtain the forged TC11 titanium alloy, and meanwhile, recovering the fallen metal high-temperature protective lubricating coating. No significant oxidation was observed on the surface of the forged titanium ingot.
(9) Grinding and crushing the recovered metal high-temperature protective lubricating coating to 700 meshes, and mixing the crushed coating with a micron solid particle additive ZrB 2 Mixing, adding water and ethanol, ball-milling for 10h, and mixing to obtain powder slurry; and (2) crushing the coating according to the mass ratio: solid particulate additive: water: ethanol-100: 5:15: 3;
(10) weighing 2.6 wt.% of carboxymethyl cellulose, 5 wt.% of sodium water glass, 1.1 wt.% of polyurethane and 91.3 wt.% of water, subtracting the water added in the step (9), heating the rest water to boil, dissolving the carboxymethyl cellulose in the water, stirring for 2 hours, adding the sodium water glass, stirring for 1 hour, adding sodium polyacrylate, and stirring for 30 minutes to obtain a uniform solvent;
(11) and (5) pouring the powder slurry mixed in the step (9) into a solvent, and uniformly stirring to prepare the recycled metal high-temperature protective lubricating coating. The prepared recycled metal high-temperature protective lubricating coating can be recycled for 20 times.
Example 4
A metal high-temperature protection lubricating coating and a preparation method, a use method and a recycling method thereof comprise the following steps:
the metal used in this example is 441 ferritic stainless steel.
(1) The proportion of oxide powder A is 35 wt.%, oxide powder B is 47 wt.%, and Cr is 10 wt.% 2 O 3 (solid particulate additive), 1.5 wt.% ethylene glycol (surfactant) and 6.5 wt.% solvent make metal high temperature protective lubricant coating; wherein the solvent is used for weighing 3.5 wt.% of carboxymethyl cellulose, 4 wt.% of sodium water glass, 1.4 wt.% of sodium polyacrylate and 91.1 wt.% of water;
(2) 53 wt.% B 2 O 3 、14wt.％P 2 O 5 、12wt.％Al 2 O 3 、9wt.％Na 2 O、5wt.％K 2 O, 3.3 wt.% CaO, 3 wt.% MgO and 0.7 wt.% ZnO, uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out, water quenching, drying and crushing, and taking oxide powder A which is sieved by a 600-mesh sieve for later use;
60 wt.% SiO 2 、8.5wt.％Al 2 O 3 、7.8wt.％B 2 O 3 、4wt.％K 2 O、7wt.％Na 2 O、7.5wt.％CaO、 3wt.％MgO、0.5wt.％BaO、1.5wt.％La 2 O 3 And 0.2 wt.% Nd 2 O 3 Uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out water quenching, drying and crushing, and taking oxide powder B which is sieved by a 700-mesh sieve for later use;
(3) mixing the prepared oxide powder A and oxide powder B with solid particle additive Cr 2 O 3 Mixing, adding 19 wt.% of water and 1.5 wt.% of glycol in a solvent, and performing ball milling for 18h to obtain a primary product of the metal high-temperature protective lubricating coating.
(4) According to the weighing raw materials of the solvent in the step (1), 3.5 wt.% of carboxymethyl cellulose is dissolved in 72.1 wt.% of water and stirred for 2 hours, 4 wt.% of sodium silicate is added and stirred for 1 hour, 1.4 wt.% of sodium polyacrylate is added and stirred for 30 minutes to obtain a uniform solvent;
(5) pouring the prepared primary product of the metal high-temperature protection lubricating coating into a solvent, fully mixing, and standing for 12 hours to obtain metal high-temperature protection lubricating coating slurry;
(6) brushing the metal high-temperature protection lubricating coating slurry on the surface of the 441 ferritic stainless steel, and naturally drying to obtain a 441 ferritic stainless steel billet with a metal high-temperature protection lubricating coating, wherein the thickness of the metal high-temperature protection lubricating coating is 0.45 mm;
(7) the 441 ferritic stainless steel connectors with metallic high temperature protective lubricating coatings may be in service at 600 c for fuel cell operation.
(8) In the repeated heating and cooling process, the metal high-temperature protection lubricating coating can fall off, the falling part can be repaired after cooling, and the fallen metal high-temperature protection lubricating coating is recovered.
(9) Grinding and crushing the recovered metal high-temperature protective lubricating coating to 700 meshes, and mixing the crushed coating with a micron solid particle additive Cr 2 O 3 Mixing, adding water and BBall-milling the diol for 10 hours and uniformly mixing to obtain powder slurry; and (2) crushing the coating according to the mass ratio: solid particulate additive: water: ethylene glycol 100:4.2:19: 1.5;
(10) weighing 2.8 wt.% of carboxymethyl cellulose, 5 wt.% of sodium water glass, 1.3 wt.% of sodium polyacrylate and 90.9 wt.% of water, subtracting the water added in the step (9), heating the rest water to 90 ℃, dissolving the carboxymethyl cellulose in the water and stirring for 2 hours, adding the sodium water glass and stirring for 1 hour, adding the sodium polyacrylate and stirring for 30 minutes to obtain a uniform solvent;
(11) and (4) pouring the powder slurry mixed in the step (9) into a solvent, and uniformly stirring to prepare the recycled metal high-temperature protective lubricating coating. The prepared recycled metal high-temperature protective lubricating coating can be recycled for 15 times.
Example 5
A metal high-temperature protection lubricating coating and a preparation method, a use method and a recycling method thereof comprise the following steps: the metal used in this example is 304 stainless steel.
(1) According to the proportion of 30 wt.% of oxide powder A, 45 wt.% of oxide powder B and 8 wt.% of TiO 2 (solid particulate additive), 2 wt.% oleic acid (surfactant) and 15 wt.% solvent make metal high temperature protective lubricating coatings; wherein the solvent is weighed by 4.5 wt.% of carboxymethyl cellulose, 5 wt.% of potassium water glass, 1.5 wt.% of polyurethane and 89 wt.% of water;
(2) 50 wt.% B 2 O 3 、12wt.％P 2 O 5 、8wt.％SiO 2 、8wt.％Al 2 O 3 、8wt.％Na 2 O、4wt.％K 2 O, 6.3 wt.% CaO, 2 wt.% MgO and 1.7 wt.% ZnO, uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out water quenching, drying and crushing, and taking oxide powder A which is sieved by a 500-mesh sieve for later use;
mixing 55 wt.% SiO 2 、15wt.％Al 2 O 3 、5.5wt.％B 2 O 3 、3wt.％K 2 O、10wt.％Na 2 O、5.3wt.％CaO、 4wt.％MgO、0.7wt.％BaO、1.2wt.％La 2 O 3 And 0.3 wt.% Nd 2 O 3 Uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out water quenching, drying and crushing, and taking oxide powder B which is sieved by a 600-mesh sieve for later use;
(3) mixing the prepared oxide powder A and oxide powder B with solid particle additive TiO 2 Mixing, adding 15 wt.% of water and 2 wt.% of oleic acid in a solvent, and performing ball milling for 20 hours to obtain a primary product of the metal high-temperature protective lubricating coating.
(4) According to the weighing raw materials of the solvent in the step (1), 4.5 wt.% of carboxymethyl cellulose is dissolved in 74 wt.% of water and stirred for 2h, 5 wt.% of potassium water glass is added and stirred for 1h, 1.5 wt.% of polyurethane is added and stirred for 30min, and a uniform solvent is obtained;
(5) pouring the prepared primary product of the metal high-temperature protection lubricating coating into a solvent, fully mixing, and standing for 12 hours to obtain metal high-temperature protection lubricating coating slurry;
(6) brushing the metal high-temperature protection lubricating coating slurry on the surface of a 304 stainless steel billet ingot, and naturally drying to obtain the 304 stainless steel billet ingot with the metal high-temperature protection lubricating coating, wherein the thickness of the metal high-temperature protection lubricating coating is 0.5 mm;
(7) the 304 stainless steel billet ingot connectors with the metal high temperature protective lubricating coating can be in service at the 650 ℃ temperature of the fuel cell operation.
(8) In the repeated heating and cooling process, the metal high-temperature protection lubricating coating can fall off, the falling part can be repaired after cooling, and the fallen metal high-temperature protection lubricating coating is recovered.
(9) Grinding and crushing the recovered metal high-temperature protective lubricating coating to 600 meshes, and mixing the crushed coating with a micron solid particle additive TiO 2 Mixing, adding water and oleic acid, performing ball milling for 12 hours, and uniformly mixing to obtain powder slurry; and (2) crushing the coating according to the mass ratio: solid particulate additive: water: oleic acid 100:4.5:15: 2;
(10) weighing the raw materials according to 3 wt.% of carboxymethyl cellulose, 5 wt.% of potassium water glass, 1.5 wt.% of polyurethane and 90.5 wt.% of water, deducting the water added in the step (9), heating the rest water to 95 ℃, dissolving the carboxymethyl cellulose in the water and stirring for 2 hours, adding the potassium water glass and stirring for 1 hour, adding sodium polyacrylate and stirring for 30 minutes to obtain a uniform solvent;
(11) and (4) pouring the powder slurry mixed in the step (9) into a solvent, and uniformly stirring to prepare the recycled metal high-temperature protective lubricating coating. The prepared recycled metal high-temperature protective lubricating coating can be recycled for 18 times.
Example 6
A metal high-temperature protection lubricating coating and a preparation method, a use method and a recycling method thereof comprise the following steps:
the metal used in this example is 316L stainless steel.
(1) Preparing a metal high-temperature protective lubricating coating by using 40 wt.% of oxide powder A, 40 wt.% of oxide powder B, 7 wt.% of B (solid particle additive), 1.2 wt.% of ethanol (surfactant) and 11.8 wt.% of solvent according to the proportion; wherein the solvent is weighed by 3 wt.% of carboxymethyl cellulose, 4.5 wt.% of sodium water glass, 1.5 wt.% of polyethylene and 91 wt.% of water;
(2) will 58 wt.% B 2 O 3 、15wt.％P 2 O 5 、12wt.％Al 2 O 3 、8wt.％Na 2 O、4wt.％K 2 O, 0.8 wt.% CaO, 1.5 wt.% MgO and 0.7 wt.% ZnO, uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for fully melting, pouring out, water quenching, drying and crushing, and taking oxide powder A which is sieved by a 500-mesh sieve for later use;
65 wt.% SiO 2 、7.5wt.％Al 2 O 3 、5wt.％B 2 O 3 、3.8wt.％K 2 O、6wt.％Na 2 O、6.5wt.％CaO、 3.7wt.％MgO、0.7wt.％BaO、1.3wt.％La 2 O 3 And 0.5 wt.% Nd 2 O 3 Uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out water quenching, drying and crushing, and taking oxide powder B which is sieved by a 600-mesh sieve for later use;
(3) mixing the prepared oxide powder A and oxide powder B with a solid particle additive B, adding 11.8 wt.% of water and 1.2 wt.% of ethanol in a solvent, and carrying out ball milling for 20 hours to obtain a primary product of the metal high-temperature protective lubricating coating.
(4) According to the weighing raw materials of the solvent in the step (1), 3 wt.% of carboxymethyl cellulose is dissolved in 79.2 wt.% of water and stirred for 2 hours, 4.5 wt.% of sodium silicate is added and stirred for 1 hour, 1.5 wt.% of polyethylene is added and stirred for 30 minutes to obtain a uniform solvent;
(5) pouring the prepared primary product of the metal high-temperature protection lubricating coating into a solvent, fully mixing, and standing for 12 hours to obtain metal high-temperature protection lubricating coating slurry;
(6) brushing the metal high-temperature protection lubricating coating slurry on the surface of a 316L stainless steel billet ingot, and naturally drying to obtain the 316L stainless steel billet ingot with the metal high-temperature protection lubricating coating, wherein the thickness of the metal high-temperature protection lubricating coating is 0.5 mm;
(7) the 316L stainless steel connector with the metal high temperature protective lubricating coating can be in service at the 650 ℃ temperature of the fuel cell operation.
(8) In the repeated heating and cooling process, the metal high-temperature protection lubricating coating can fall off, the falling part can be repaired after cooling, and the fallen metal high-temperature protection lubricating coating is recovered.
(9) Grinding and crushing the recovered metal high-temperature protection lubricating coating to 600 meshes, mixing the crushed coating with a micron solid particle additive B, adding water and ethanol, performing ball milling for 10 hours, and uniformly mixing to obtain powder slurry; and (2) crushing the coating according to the mass ratio: solid particulate additive: water: ethanol-100: 4.5:11.8: 1.2;
(10) weighing 3.5 wt.% of carboxymethyl cellulose, 5.5 wt.% of sodium water glass, 1.5 wt.% of polyethylene and 89.5 wt.% of water, subtracting the water added in the step (9), heating the rest water to boil, dissolving the carboxymethyl cellulose in the water and stirring for 2h, adding the sodium water glass and stirring for 1h, adding sodium polyacrylate, and stirring for 30min to obtain a uniform solvent;
(11) and (4) pouring the powder slurry mixed in the step (9) into a solvent, and uniformly stirring to prepare the recycled metal high-temperature protective lubricating coating. The prepared recycled metal high-temperature protective lubricating coating can be recycled for 18 times.
Example 7
A metal high-temperature protection lubricating coating and a preparation method, a use method and a recycling method thereof comprise the following steps:
the metal used in this example is GH93 nickel base wrought superalloy.
(1) Preparing a metal high-temperature protective lubricating coating by using 30 wt.% of oxide powder A, 45 wt.% of oxide powder B, 15 wt.% of MgO (solid particle additive), 3 wt.% of glycol (surfactant) and 7 wt.% of solvent according to the proportion; wherein the solvent is weighed as raw materials by 4.5 wt.% of carboxymethyl cellulose, 5 wt.% of sodium water glass, 1.5 wt.% of sodium polyacrylate and 89 wt.% of water;
(2) 50 wt.% B 2 O 3 、17wt.％P 2 O 5 、12wt.％Al 2 O 3 、10.6wt.％Na 2 O、7wt.％K 2 O, 2 wt.% CaO, 0.8 wt.% MgO and 0.6 wt.% ZnO, uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out water quenching, drying and crushing, and taking oxide powder A which is sieved by a 700-mesh sieve for later use;
58 wt.% SiO 2 、8.5wt.％Al 2 O 3 、9.8wt.％B 2 O 3 、4wt.％K 2 O、7wt.％Na 2 O、6wt.％CaO、 4.5wt.％MgO、1wt.％BaO、1wt.％La 2 O 3 And 0.2 wt.% Nd 2 O 3 Uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out water quenching, drying and crushing, and taking oxide powder B which is sieved by a 700-mesh sieve for later use;
(3) mixing the prepared oxide powder A and oxide powder B with a solid particle additive MgO, adding 7 wt.% of water and 3 wt.% of glycol in a solvent, and carrying out ball milling for 20h to obtain a primary product of the metal high-temperature protective lubricating coating.
(4) According to the weighing raw materials of the solvent in the step (1), 4.5 wt.% of carboxymethyl cellulose is dissolved in 82 wt.% of water and stirred for 2 hours, 5 wt.% of sodium silicate is added and stirred for 1 hour, 1.5 wt.% of sodium polyacrylate is added and stirred for 30 minutes to obtain a uniform solvent;
(5) pouring the prepared primary product of the metal high-temperature protection lubricating coating into a solvent, fully mixing, and standing for 12 hours to obtain metal high-temperature protection lubricating coating slurry;
(6) brushing the metal high-temperature protective lubricating coating slurry on the surface of a GH93 nickel-based wrought superalloy billet, and naturally drying to obtain a GH93 nickel-based wrought superalloy billet with a metal high-temperature protective lubricating coating, wherein the thickness of the metal high-temperature protective lubricating coating is 0.55 mm;
(7) GH93 nickel base deformation superalloy billet with metal high temperature protection lubricating coating is put into vacuum induction furnace and is heated to 1250 ℃, keeps warm for 4h, and the metal billet is discharged after the temperature is even to obtain hot metal billet, blows dry powder toward hot metal billet, further increases coating thickness, better realization lubrication and protection, obtains the metal billet after the heating, then transports to the equipment that forges corresponding and forges, and the forging temperature: 1150 ℃. The temperature drop in the process of transporting the GH93 nickel-based wrought superalloy billet is 970 ℃, and the air cooling is carried out for 4 hours, wherein the dry powder comprises the following components in percentage by mass: 89.8 wt.% of oxide powder A, 10 wt.% of oxide powder B and 0.2 wt.% of solid particle additive, wherein the components of the oxide powder A and the oxide powder B are the same as those in the step (2).
(8) In the repeated heating and cooling process, the metal high-temperature protection lubricating coating can fall off, the falling part can be repaired after cooling, and the fallen metal high-temperature protection lubricating coating is recovered.
(9) Grinding and crushing the recovered metal high-temperature protection lubricating coating to 700 meshes, mixing the crushed coating with a micron solid particle additive MgO, adding water and ethylene glycol, performing ball milling for 10 hours, and uniformly mixing to obtain powder slurry; and (2) crushing the coating according to the mass ratio: solid particulate additive: water: ethylene glycol-100: 4:7: 3;
(10) weighing the raw materials according to 3 wt.% of carboxymethyl cellulose, 5 wt.% of sodium water glass, 1.7 wt.% of sodium polyacrylate and 90.3 wt.% of water, deducting the water added in the step (9), heating the rest water to 96 ℃, dissolving the carboxymethyl cellulose in the water and stirring for 2 hours, adding the sodium water glass and stirring for 1 hour, adding the sodium polyacrylate and stirring for 30 minutes to obtain a uniform solvent;
(11) and (4) pouring the powder slurry mixed in the step (9) into a solvent, and uniformly stirring to prepare the recycled metal high-temperature protective lubricating coating. The prepared recycled metal high-temperature protective lubricating coating can be recycled for 20 times.
Example 8
A metal high-temperature protection lubricating coating and a preparation method, a use method and a recycling method thereof comprise the following steps:
the metal used in this example is GH90 nickel base wrought superalloy.
(1) According to the proportion of 40 wt.% of oxide powder A, 35 wt.% of oxide powder B and 10 wt.% of Cr 2 O 3 (solid particulate additive), 3 wt.% ethylene glycol (surfactant) and 12 wt.% solvent make metal high temperature protective lubricant coating; wherein, the solvent is weighed by 3.5 wt.% of carboxymethyl cellulose, 4.6 wt.% of sodium water glass, 1.4 wt.% of polyurethane and 90.5 wt.% of water;
(2) 55 wt.% of B 2 O 3 、12wt.％P 2 O 5 、13wt.％Al 2 O 3 、8wt.％Na 2 O、5wt.％K 2 O, 2.5 wt.% CaO, 2 wt.% MgO and 1.5 wt.% ZnO, uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out water quenching, drying and crushing, and taking oxide powder A which is sieved by a 500-mesh sieve for later use;
58 wt.% SiO 2 、14wt.％Al 2 O 3 、7.8wt.％B 2 O 3 、3wt.％K 2 O、6wt.％Na 2 O、5.5wt.％CaO、 3wt.％MgO、1wt.％BaO、1.5wt.％La 2 O 3 And 0.2 wt.% Nd 2 O 3 Uniformly mixing to obtain a mixture, putting the mixture into a high-temperature furnace for full melting, pouring out water quenching, drying and crushing, and taking oxide powder B which is sieved by a 600-mesh sieve for later use;
(3) mixing the prepared oxide powder A and oxide powder B with solid particle additive Cr 2 O 3 Mixing, adding 12 wt.% of water and 3 wt.% of glycol in a solvent, and performing ball milling for 18h to obtain a primary product of the metal high-temperature protective lubricating coating.
(4) According to the weighing raw materials of the solvent in the step (1), 3.5 wt.% of carboxymethyl cellulose is dissolved in 78.5 wt.% of water and stirred for 2 hours, 4.6 wt.% of sodium water glass is added and stirred for 1 hour, 1.4 wt.% of polyurethane is added and stirred for 30 minutes to obtain a uniform solvent;
weighing raw materials according to 3.5 wt.% of carboxymethyl cellulose, 4.6 wt.% of sodium water glass, 1.4 wt.% of polyurethane and 90.5 wt.% of water, dissolving the carboxymethyl cellulose in the water, stirring for 2 hours, adding the sodium water glass, stirring for 1 hour, adding sodium polyacrylate, and stirring for 30min to obtain a uniform solvent;
(5) pouring the prepared primary product of the metal high-temperature protection lubricating coating into a solvent, fully mixing, and standing for 12 hours to obtain metal high-temperature protection lubricating coating slurry;
(6) brushing the metal high-temperature protective lubricating coating slurry on the surface of a GH90 nickel-based wrought superalloy billet, and naturally drying to obtain a GH90 nickel-based wrought superalloy billet with a metal high-temperature protective lubricating coating, wherein the thickness of the metal high-temperature protective lubricating coating is 0.5 mm;
(7) GH90 nickel base deformation superalloy billet with metal high temperature protection lubricating coating is put into vacuum induction furnace and is heated 1170 ℃, keeps warm for 2h, and the metal billet is discharged after the temperature is even to obtain hot metal billet, blows dry powder toward hot metal billet, further increases the coating thickness, better realization lubrication and protection, obtains the metal billet after the heating, then transports to the equipment that forges corresponding and forges, and the forging temperature: 1080 ℃. The temperature drop in the process of transporting the GH93 nickel-based wrought superalloy billet is 750 ℃, and the air cooling is carried out for 4 hours, wherein the dry powder comprises the following components in percentage by mass: 40 wt.% of oxide powder A, 30 wt.% of oxide powder B and 30 wt.% of solid particle additive, wherein the components of the oxide powder A and the oxide powder B are the same as those in the step (2).
(8) In the repeated heating and cooling process, the metal high-temperature protection lubricating coating can fall off, the falling part can be repaired after cooling, and the fallen metal high-temperature protection lubricating coating is recovered.
(9) Grinding and crushing the recovered metal high-temperature protective lubricating coating to 700 meshes, and mixing the crushed coating with a micron solid particle additive Cr 2 O 3 Mixing, then adding water and glycol, performing ball milling for 10 hours, and uniformly mixing to obtain powder slurry; and (2) crushing the coating according to the mass ratio: solid particulate additive: water: ethanol-100: 4.5:12: 3;
(10) weighing the raw materials according to 3.8 wt.% of carboxymethyl cellulose, 5 wt.% of sodium water glass, 1.3 wt.% of polyurethane and 89.9 wt.% of water, subtracting the water added in the step (9), heating the rest water to 80 ℃, dissolving the carboxymethyl cellulose in the water and stirring for 2h, adding the sodium water glass and stirring for 1h, adding sodium polyacrylate and stirring for 30min to obtain a uniform solvent;
(11) and (4) pouring the powder slurry mixed in the step (9) into a solvent, and uniformly stirring to prepare the recycled metal high-temperature protective lubricating coating. The prepared recycled metal high-temperature protective lubricating coating can be recycled for 20 times.
Example 9
A metal high-temperature protection lubricating coating and a preparation method, a use method and a recycling method thereof comprise the following steps:
the metal used in this example was TA2 titanium metal.
(1) In a proportion of 50 wt.% Mo 2 NiB 2 (solid particle additive) and 50 wt.% of solvent are used for preparing a metal high-temperature protective lubricating coating; wherein, the solvent is weighed by 5 wt.% of carboxymethyl cellulose, 20 wt.% of sodium water glass, 5 wt.% of polyvinyl alcohol and 70 wt.% of water.
(2) Adding 200 μm of Mo as solid additive 2 NiB 2 And mixing, adding 5 wt.% of water, and performing ball milling for 10 hours to obtain a primary product of the metal high-temperature protective lubricating coating.
(3) According to the weighing raw materials of the solvent in the step (1), 65 wt.% of water is heated to be boiled, 5 wt.% of carboxymethyl cellulose is dissolved in the water and stirred for 2 hours, 20 wt.% of sodium silicate is added and stirred for 1 hour, 5 wt.% of polyvinyl alcohol is added and stirred for 30 minutes to obtain a uniform solvent;
(4) and pouring the prepared primary product of the metal high-temperature protection lubricating coating into a solvent, and fully mixing to obtain the metal high-temperature protection lubricating coating slurry.
The procedure for use and recycling was the same as in example 1.
Comparative example 1
A TC11 high-temperature protective lubricating coating, a preparation method, a use method and a recycling method thereof, which are the same as the embodiment 3, and only differ in that: the oxide powder A had an initial raw material percentage of 45 wt.% B 2 O 3 、7wt.％P 2 O 5 、10wt.％Al 2 O 3 、20wt.％SiO 2 、 7wt.％Na 2 O、2wt.％K 2 O, 2.1 wt.% CaO, 5 wt.% MgO, and 1.9 wt.% ZnO; the components and the mass percentage of the oxide powder B, the solvent, the solid particle additive and the surfactant are the same as those in the embodiment 3;
proved by verification, the coating on the surface of the metal blank can be caused to fall off, the large-area oxidation of the rolled metal blank is caused, and the oxidation degree is more than 2.4 percent.
Comparative example 2
A TC11 high-temperature protective lubricating coating, its making method, use method and recycling method, which is the same as example 3 except that: oxide powder A, oxide powder B, surfactant and solvent are 35:45:3:17 without adding solid particle additives.
The verification proves that the coating on the surface of the metal blank can fall off, the large-area oxidation of the rolled metal blank is caused, and the oxidation degree is more than 1.4-3.9%.
Comparative example 3
A TC11 high-temperature protective lubricating coating, a preparation method, a use method and a recycling method thereof, which are the same as the embodiment 3, and only differ in that: mixing the prepared oxide powder A and oxide powder B with solid particle additive ZrB 2 Mixing, adding 15 wt.% of water and 3 wt.% of ethanol, ball-milling for 20h, drying, and mixingObtaining a primary product of the metal high-temperature protective lubricating coating; the obtained primary product is then mixed with the solvent in step (1) of example 3 for use.
The verification proves that the coating on the surface of the metal blank can fall off, the large-area oxidation of the rolled metal blank is caused, and the oxidation degree is more than 0.5-1.3%.
Comparative example 4
A metal high-temperature protective lubricating coating, a preparation method, a use method and a recycling method thereof, which are the same as the embodiment 1, and have the difference that the mesh number of the adopted oxide powder A is 1000 meshes; proved by verification, the coating on the surface of the metal blank can be caused to fall off, the large-area oxidation of the rolled metal blank is caused, and the oxidation degree is more than 1.2 percent.
Comparative example 5
A metal high temperature protective lubricating coating and its preparation method, use and recovery reuse method, 1, the difference lies in, the grain size of the solid particle additive used is 600 μm; proved by verification, the coating on the surface of the metal blank can be caused to fall off, the large-area oxidation of the rolled metal blank is caused, and the oxidation degree is more than 1.2 percent.
It should be noted that: the ingredients and raw material ratios listed in the above examples are only used to illustrate the specific implementation process of the present invention, and are not limited thereto.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions and scope of the present invention as defined in the appended claims.

Claims (10)

1. A metal high temperature protection lubricating coating is characterized in that: the metal high-temperature protection lubricating coating comprises the following components in percentage by mass: 0-90% of oxide powder A, 0-90% of oxide powder B, 0.2-50% of solid particle additive, 1-50% of solvent and 0-5% of surfactant, wherein the sum of the mass percentages of the components is 100%;
wherein the particle size of the oxide powder A is 100-700 meshes, the particle size of the oxide powder B is 100-700 meshes, and the particle size of the solid particle additive is 1 nm-300 mu m.
2. The metal high-temperature protection lubricating coating as claimed in claim 1, wherein the oxide powder A comprises the following components in percentage by mass: 1 to 70% of B 2 O 3 、1～60％P 2 O 5 、0.5～15％Al 2 O 3 、0.1～10％ZnO、0～15％CaO、0～15％SiO 2 、0.5～25％Na 2 O、0.2～15％MgO、0～10％BaO、0.1～20％K 2 O, and inevitable impurity components less than 2 percent, wherein the sum of the mass percentages of the components is 100 percent;
the oxide powder B comprises the following components in percentage by mass: 5 to 75% SiO 2 、1～60％B 2 O 3 、0～15％K 2 O、5～30％Na 2 O、0.5～15％Al 2 O 3 、0～10％TiO 2 、1～20％CaO、1～15％MgO、0～5％La 2 O 3 、0～5％CeO 2 、0～10％BaO、0～5％Nd 2 O 3 And less than 2% of impurities, wherein the sum of the mass percentages of the components is 100%.
3. The metallic high temperature protective lubricating coating of claim 1, wherein the solid particulate additive is: TiB 2 、ZrB 2 、B、TiO 2 、ZrO 2 、CeO 2 、Cr 2 O 3 、MgO、Al 2 O 3 、Mo 2 NiB 2 、Mo 2 FeB 2 One or a mixture of more of SiC and zircon.
4. The metal high-temperature protection lubricating coating as claimed in claim 1, wherein the solvent comprises the following components in percentage by mass: 1-5% of carboxymethyl cellulose, 0.5-20% of water glass, 0.5-5% of sodium polyacrylate or polyvinyl alcohol or polyurethane, and the balance of water; the sodium silicate is sodium silicate or potassium silicate, the modulus of the sodium silicate is 0.5-3.5, and the modulus of the potassium silicate is 1-4;
the surfactant is one or a mixture of ethanol, glycol and oleic acid.
5. The method for preparing the metal high-temperature protective lubricating coating according to any one of claims 1 to 4, characterized by comprising the following steps:
step 1.1: weighing raw materials according to the component proportion of the oxide powder A, melting the raw materials at 1200-1500 ℃, quenching and crushing the raw materials into the oxide powder A;
step 1.2: weighing raw materials according to the component proportion of the oxide powder B, melting the raw materials at 1200-1500 ℃, quenching and crushing the raw materials into oxide powder B;
step 1.3: weighing raw materials according to the components of the metal high-temperature protection lubricating coating, and performing ball milling mixing on the oxide powder A, the oxide powder B, the solid particle additive, 5-30% of water in a solvent and a surfactant according to the proportion to obtain powder slurry;
step 1.4: preparing a solvent according to the proportion of water with 5-30% being deducted;
step 1.5: and stirring and mixing the mixed powder slurry and the solvent uniformly to obtain the metal high-temperature protection lubricating coating.
6. Use of a metallic high temperature protective lubricating coating according to any of claims 1-4, characterised by the steps of:
the method comprises the following steps: spraying, dipping or brushing the metal high-temperature protection lubricating coating on the surface of the metal to be protected to obtain the metal with the metal high-temperature protection lubricating coating;
step two: heating the metal with the metal high-temperature protection lubricating coating to a specified temperature within the range of room temperature to 1450 ℃ to obtain hot metal;
step three: blowing, spreading or roll-coating dry powder or not blowing, spreading or roll-coating the dry powder to the thermal state metal; the dry powder comprises oxide powder A, oxide powder B and solid particle additives to obtain heated metal; the dry powder comprises the following components in percentage by mass: 1-90% of oxide powder A, 1-90% of oxide powder B and 0.2-50% of solid particle additive, wherein the sum of the mass percentages of the components is 100%;
step four: the heated metal is in high-temperature service;
step five: recovering the fallen coating after the metal is subjected to multiple temperature rise and fall service;
step six: and spraying and repairing the place where the metal surface falls off again.
7. The use of the metallic high-temperature protective lubricating coating according to any one of claims 1-4, characterized in that the method is the use of the metallic high-temperature protective lubricating coating in the metal rolling hot working, and specifically comprises the following steps:
step (1): spraying, dipping or brushing the metal high-temperature protection lubricating coating on the metal to be heated to obtain the metal with the metal high-temperature protection lubricating coating;
step (2): heating the metal with the metal high-temperature protection lubricating coating to a specified rolling temperature to obtain hot metal;
and (3): blowing, spreading or roll-coating dry powder or not blowing, spreading or roll-coating the dry powder to the thermal state metal; the dry powder comprises oxide powder A, oxide powder B and solid particle additives to obtain heated metal; the dry powder comprises the following components in percentage by mass: 1-90% of oxide powder A, 1-90% of oxide powder B and 0.2-50% of solid particle additive, wherein the sum of the mass percentages of the components is 100%;
and (4): rolling the heated metal;
and (5): and air cooling or water cooling the rolled metal to room temperature, and recovering the automatically-fallen metal high-temperature protective lubricating coating.
8. The use of the metal high-temperature protective lubricating coating as defined in any one of claims 1-4, wherein the method is used for the metal high-temperature protective lubricating coating in the metal extrusion hot working process, and comprises the following steps:
step 1: spraying, dipping or brushing the metal high-temperature protection lubricating coating on the metal to be heated to obtain the metal with the metal high-temperature protection lubricating coating;
step 2: heating the metal with the metal high-temperature protection lubricating coating to a specified extrusion temperature to obtain hot metal;
and step 3: blowing, spreading or roll-coating dry powder or not blowing, spreading or roll-coating the dry powder to the thermal state metal; the dry powder comprises oxide powder A, oxide powder B and solid particle additives to obtain heated metal; the dry powder comprises the following components in percentage by mass: 1-90% of oxide powder A, 1-90% of oxide powder B and 0.2-50% of solid particle additive, wherein the sum of the mass percentages of the components is 100%;
and 4, step 4: extruding the heated metal;
and 5: and removing the surface coating of the extruded metal after air cooling or high-pressure water washing, and recovering the fallen metal high-temperature protective lubricating coating.
9. Use of a metallic high temperature protective lubricating coating according to any of claims 1-4, characterised in that the method is a use of a metallic high temperature protective lubricating coating in hot working of metal forging, comprising the steps of:
step I: spraying, dipping or brushing the metal high-temperature protection lubricating coating on the metal to be heated to obtain the metal with the metal high-temperature protection lubricating coating;
step II: heating the metal with the metal high-temperature protection lubricating coating to a specified forging temperature to obtain hot metal;
step III: blowing, spreading or roll-coating dry powder or not blowing, spreading or roll-coating the dry powder to the thermal state metal; the dry powder comprises oxide powder A, oxide powder B and solid particle additives to obtain heated metal; the dry powder comprises the following components in percentage by mass: 1-90% of oxide powder A, 1-90% of oxide powder B and 0.2-50% of solid particle additive, wherein the sum of the mass percentages of the components is 100%;
step IV: forging the heated metal;
step V: and cooling the forged metal, and recovering the fallen metal high-temperature protection lubricating coating.
10. The method for recycling the metal high-temperature protective lubricating coating according to any one of claims 1 to 4, characterized by comprising the following steps:
step S1: grinding and crushing the recovered metal high-temperature protection lubricating coating to 20-700 meshes to obtain a crushed coating;
step S2: mixing the crushed coating with a solid particle additive, adding water and a surfactant, and performing ball milling for further mixing to obtain powder slurry; wherein, the crushed coating is as follows according to the mass ratio: solid particulate additive: water: surfactant ═ (60-100): (0.1-20): (5-30): (0-5);
step S3: preparing a solvent according to the following mixture ratio;
the solvent comprises the following components in percentage by mass: 1-5 wt.% of carboxymethyl cellulose, 0.5-20 wt.% of water glass, 0.5-5 wt.% of sodium polyacrylate or polyvinyl alcohol or polyurethane, and the balance of water; the sodium silicate is sodium silicate or potassium silicate, the modulus of the sodium silicate is 0.5-3.5, and the modulus of the potassium silicate is 1-4;
wherein, the solvent is prepared according to the proportion of water with 5-30wt percent being deducted;
step S4: adding the mixed powder slurry into a solvent, and further stirring and mixing uniformly to obtain a recycled metal high-temperature protective lubricating coating; the metal high-temperature protection lubricating coating can be recycled for 5 to 30 times.
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