CN116949516A - Inert anode with high-entropy alloy coating and preparation method thereof - Google Patents
Inert anode with high-entropy alloy coating and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
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- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
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- 239000003795 chemical substances by application Substances 0.000 claims description 6
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- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 4
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- 239000010963 304 stainless steel Substances 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- 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
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/106—Coating with metal alloys or metal elements only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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Abstract
The invention discloses an inert anode with a high-entropy alloy coating and a preparation method thereof, and belongs to the technical field of electrolytic aluminum electrodes. The inert anode comprises a metal matrix and a FeCoCrNiMnMo high-entropy alloy coating on the surface of the metal matrix, has good conductivity, toughness and corrosion resistance and excellent high-temperature stability, and solves the problem that carbon body electrode participates in reaction to generate CO 2 The gas and the existing inert electrode have the technical problems of poor conductivity and large brittleness. The invention also provides a preparation method of the inert anode, which has simple process and low cost, is suitable for preparing anode materials with larger size, and has good forming quality, high bonding strength and good application prospect.
Description
Technical Field
The invention relates to the technical field of electrolytic aluminum electrodes, in particular to an inert anode with a high-entropy alloy coating and a preparation method thereof.
Background
Aluminum and its alloys yields are ranked first two in metal materials, next to steel. The industrial production of aluminum metal mainly adopts cryolite-alumina fusion electrolysis method (also called Hall-Elluter fused salt electrolysis method), the fused cryolite is solvent, alumina is used as solute, carbon body is used as anode, aluminium liquid is used as cathode, strong direct current is introduced, and electrochemical reaction is carried out on two poles in the electrolytic tank at 950-970 ℃ to obtain pure aluminum. However, in this process, the carbon anode generates a large amount of CO due to the participation in the reaction 2 The gas causes a severe production environment and pollutes the natural environment.
Compared with the traditional carbon anode, the inert anode has some remarkable advantages: on the one hand, the inert anode is not consumed or consumed very little in the aluminum electrolysis engineering, so that frequent replacement is not needed, and the cost can be saved. In addition, in the electrolysis process using inert cations, no toxic and harmful gas is generated, and the pollution to the environment is avoided. While the search for inert anode materials that replace carbon anodes has focused mainly on ceramic materials, metal alloy materials, and the like. Among them, the ceramic material is the best inert but relatively poor in conductivity, and is extremely brittle, and is easily damaged during use. The metal alloy inert anode has the characteristics of high toughness, good conductivity, excellent processability and the like, and has higher research and application values.
The invention discloses an inert anode for preparing an oxidation-resistant corrosion-resistant oxide film on the surface of a NiFeCoCrAl high-entropy alloy, which is disclosed in the patent with the application number of 202211681679.6, and the high-entropy alloy is used as an inert anode material, and is subjected to preoxidation to obtain an oxide film with a multiple structure on the surface, so that the oxide film has good cryolite molten salt corrosion resistance and high-temperature oxidation resistance, and good conductivity. But the inert anode is prepared by using high-entropy alloy, the material is expensive, and the cost is high. The invention relates to an inert anode with an oxidation-resistant corrosion-resistant coating on the surface of a nichrome, which is prepared by using an alloy containing high Cr and Ni as an inert anode in the patent with the application number of 202011287965.5, and forming the oxidation-resistant corrosion-resistant coating on the surface of the alloy through electroplating and pre-oxidation.
Disclosure of Invention
In view of the foregoing drawbacks of the prior art, in a first aspect of the present invention, an inert anode is provided that has good conductivity, toughness and corrosion resistance, and excellent high temperature stability, the inert anode comprising a metal substrate and a protective coating on the surface thereof, the protective coating being a FeCoCrNiMnMo high entropy alloy coating.
In the inert anode, cr and Mo elements can form a protective oxide film in the subsequent corrosion process, ni can promote the stability of a metal oxide film and improve the thermodynamic stability, and in addition, the FeCoCrNiMnMo high-entropy alloy and the oxide film formed by the alloy have good conductivity, so that the use requirement of the inert electrode is met.
Preferably, the FeCoCrNiMnMo high-entropy alloy coating comprises the following components in percentage by mass: 18.7 to 19.3 percent of Fe, 19.7 to 20.3 percent of Co, 17.3 to 17.9 percent of Cr, 19.6 to 20.2 percent of Ni, 18.3 to 18.9 percent of Mn and 4.8 to 6.4 percent of Mo.
In a second aspect of the invention, a method for preparing an inert anode with simple process and low cost is provided, comprising the following steps:
(1) Ball milling the metal raw material powder to an alloying state to obtain alloy powder;
(2) Pretreating a metal matrix at a certain temperature to obtain a pre-deposited matrix; pretreating the alloy powder at a certain temperature to obtain pre-deposited powder;
(3) In a protective gas atmosphere, adopting a plasma cladding process to enable the pre-cladding powder to be welded on the surface of the pre-cladding substrate to form a cladding layer, so as to obtain a high-entropy alloy plasma cladding layer;
(4) The high-entropy alloy plasma cladding layer is subjected to cryogenic treatment to prepare the inert anode.
The subzero treatment can lead to compressive stress of crystal grains in the alloy, increase micro-slip in the material, thereby increasing dislocation and stacking fault density and improving the strength of metal; the FeCoCrNiMn high-entropy alloy can generate twin crystals and nanocrystalline in a low-temperature environment, so that the lattice distortion is enhanced, and the toughness of the material is also enhanced.
Preferably, the specific method of the step (1) is as follows: mixing the metal raw material powder with grinding balls and a control agent, performing ball milling in a protective gas atmosphere, and drying and sieving after ball milling is finished to obtain alloy powder.
Further preferably, the control agent is absolute ethyl alcohol, and the dosage ratio of the grinding balls to the control agent is 1: 30-60 kg/mL.
Further preferably, the grinding ball comprises three diameters of 20mm, 10mm and 3 mm; the grinding ball comprises 2 to 3 grinding balls with the diameter of 20mm, and the mass ratio of the rest grinding balls to the grinding balls with the diameters of 10mm and 3mm is 3 to 5:1 are matched.
Preferably, in the step (1), the ball-milling ball-material ratio is 8-10: 1, the ball milling time is 3-7 h.
Preferably, in the step (1), the standard mesh number of the alloy powder is 100 to 300 mesh.
Preferably, in the step (2), the pretreatment temperature of the metal substrate is 400-600 ℃ and the treatment time is 4-6 h.
By preprocessing the metal matrix, the temperature difference between the alloy layer and the matrix in the subsequent plasma cladding process can be ensured to be smaller, and defects such as cracks, air holes and the like can not be generated.
Preferably, in the step (2), the pretreatment temperature of the alloy powder is 70-80 ℃ and the treatment time is 3-7 h.
Preferably, in the step (3), the working current of the plasma welding is 170-190A, the working voltage is 29-30V, the flow rate of the shielding gas is 400-500L/h, the flow rate of the ion gas is 300-350L/h, the flow rate of the powder feeding gas is 300-400L/h, the plasma welding is carried out multi-pass lap welding from top to bottom on the surface of the pre-welding substrate, the distance between the nozzle and the surface of the pre-welding substrate is 8-10 mm, and the scanning speed is 220-250 mm/min.
According to the invention, the technological parameters adopted in the plasma cladding are selected and the optimal technological parameters for preparing the cladding layer are determined by analyzing the matrix and the cladding material in advance according to the used pre-cladding powder components and the requirement difference of the cladding layer performance. In the FeCoCrNiMnMo high-entropy alloy, the melting point of Mo is highest, and the Mn is lowest, so that the proportion among the components also meets the original components of the powder while ensuring that the components are fully mixed in the deposition process, and the working current needs to be kept in a proper range; fe and Co in the alloy can easily absorb oxygen and moisture in the air, and the protective gas can prevent oxidation or water vapor from entering the coating, so that the coating preparation quality is poor, but excessive gas flow can cause the coating to generate air holes in the cooling process, and the powder feeding flow is matched with deposition current, so that the powder can be fully melted to form a melting layer, and the waste of resources can not be caused.
Preferably, in the step (4), the cryogenic treatment is performed in two stages, the high-entropy alloy plasma deposited layer at room temperature is firstly placed at-80 to-100 ℃ for 3-5 hours, then the temperature is reduced to-180 to-190 ℃ for continuous treatment for 5-6 hours, and after the treatment is finished, the high-entropy alloy plasma deposited layer is preserved in water at room temperature and is recovered until the high-entropy alloy plasma deposited layer returns to the room temperature.
The adoption of two-stage cryogenic treatment can prevent sudden shrinkage of materials caused by chilling and deformation or cracking of the materials caused by sudden increase of internal stress, and finally, water with proper heat conduction performance is adopted for room temperature heat preservation recovery, so that the deformation of the materials caused by sudden change of temperature can be prevented.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides an inert anode with a high-entropy alloy coating, the surface of the inert anode is a protective coating formed by FeCoCrNiMnMo high-entropy alloy, the conductivity, the toughness and the corrosion resistance are good, the high-temperature stability is excellent, and the problem that carbon body electrodes participate in the reaction to generate CO is solved 2 The gas and the existing inert electrode have the technical problems of poor conductivity and large brittleness.
The invention provides a preparation method of an inert anode, which has simple process and low cost, is suitable for preparing anode materials with larger size, and has good forming quality, high bonding strength and good application prospect.
Drawings
FIG. 1 is a schematic diagram of a plasma cladding process;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the weld line region of the FeCoCrNiMnMo high entropy alloy coating of the inert anode of example 1, where 1 represents the FeCoCrNiMnMo high entropy alloy coating, 2 represents the Q235 matrix, and 3 represents the weld line.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples:
the metal matrix is Q235 alloy steel; the grinding ball is a 304 stainless steel ball; argon gas with purity of 99.99%.
Example 1
The preparation method of the inert anode comprises the following steps:
(1) According to the composition ratio of the high-entropy alloy coating, 18.9wt.% Fe, 20.0wt.% Co, 17.6wt.% Cr, 19.9wt.% Ni, 18.6wt.% Mn, 5wt.% Mo metal raw material powder is prepared, 500g of grinding balls and the metal raw material powder (ball-to-material ratio 10:1) are placed in a ball milling tank, the grinding balls comprise 2 grinding balls with the diameter of 20mm, and the rest grinding balls are formed by stainless steel balls with the diameters of 10mm and 3mm according to the mass ratio of 5:1, matching uniformly; then adding 15ml of absolute ethyl alcohol into a ball milling tank as well as filling argon, ball milling for 3 hours, placing the obtained powder into a drying oven at 80 ℃ for drying for 8 hours, and then screening by using a stainless steel screen to leave alloy powder with 200 meshes;
(2) Polishing rust and an oxide layer on the surface of a Q235 alloy steel substrate by an angle grinder, removing impurities and greasy dirt on the surface of the substrate by acetone, drying in a drying oven at 70 ℃ for 5 hours, and then pre-treating the Q235 alloy steel substrate at 400 ℃ for 4 hours to obtain a pre-deposited substrate; sieving alloy powder for the second time to keep the granularity of 200 meshes, then drying the alloy powder in a drying oven at 80 ℃, loading the dried alloy powder into a disc, uniformly spreading the alloy powder at the temperature for 5 hours, turning the powder during the drying process, and finishing pretreatment to obtain pre-deposited powder;
(3) Argon is introduced into plasma cladding equipment, the argon is used as protective gas and working gas, the working current of plasma cladding is set to be 170A, the working voltage is 30V, the flow rate of the protective gas is 400L/h, the flow rate of the ion gas is 300L/h, the flow rate of powder feeding gas is 300L/h, the distance between a nozzle and the surface of a base material is 10mm, multi-pass lap cladding is carried out on the base plate from top to bottom, the scanning speed is 220mm/min, and the pre-cladding powder is deposited on the surface of a pre-cladding base body to form a cladding layer, so that a high-entropy alloy plasma cladding layer is obtained;
(4) Naturally cooling the obtained high-entropy alloy plasma cladding layer to room temperature, then carrying out cryogenic treatment on the high-entropy alloy plasma cladding layer, carrying out cryogenic treatment in two stages, firstly immersing the high-entropy alloy plasma cladding layer in liquid nitrogen at the temperature of minus 90 ℃ for 3 hours, then placing the high-entropy alloy plasma cladding layer in liquid nitrogen at the temperature of minus 190 ℃ for 5 hours, and placing the high-entropy alloy plasma cladding layer in purified water at room temperature for heat preservation and recovery after the cryogenic treatment is completed until the high-entropy alloy plasma cladding layer returns to the room temperature, thus obtaining the inert anode.
Since the plasma cladding temperature is very high, and the process is usually carried out at room temperature and the substrate temperature is relatively low, a large temperature gradient is generated along the direction perpendicular to the cladding in the cladding process, and serious mismatching values exist on two sides of the interface, so that the welding line becomes a high-energy movable interface, strain energy is generated due to the temperature gradient, component fluctuation and different metal lattice parameters on two sides of the welding line, the welding boundary moves into the cladding layer under the driving of the strain energy, and when the temperature is continuously reduced, the welding boundary stops at a short distance from the welding line to form the boundary. Observing the fusion line area of the FeCoCrNiMnMo high entropy alloy coating of the inert anode by adopting a Scanning Electron Microscope (SEM), wherein the boundary in the drawing does not have obvious deformation and fluctuation, and the boundary shows that the fusion layer and the substrate are well combined; in addition, no obvious problems such as cracks and defects are observed in the graph, the thickness of the whole coating is uniform, the average thickness is about 2mm, and the coating shows uniform contrast and has a dendrite structure.
Compared with the protective coating of the inert anode which is not subjected to cryogenic treatment under the same condition, the cryogenic treatment enables crystal grains in the alloy to generate compressive stress, and micro-slippage in the material is increased, so that dislocation and stacking fault density are increased, and the strength of metal is improved; the FeCoCrNiMn high-entropy alloy can generate twin crystals and nanocrystalline in a low-temperature environment, so that the lattice distortion is enhanced, and the toughness of the material is also enhanced; in combination with fig. 2, no deformation or cracking of the material is observed, and the material is prevented from suddenly shrinking due to chilling and suddenly shrinking due to internal stress, and is prevented from deforming due to sudden change of temperature by adopting water with proper heat conduction property for room temperature heat preservation and recovery.
Example 2
The preparation method of the inert anode comprises the following steps:
(1) According to the composition ratio of the high-entropy alloy coating, a metal raw material powder of 18.7wt.% Fe, 19.7wt.% Co, 17.3wt.% Cr, 19.6wt.% Ni, 18.3wt.% Mn, 6.4wt.% Mo was prepared, 500g of grinding balls containing 2 grinding balls of 20mm diameter and the remaining grinding balls consisting of stainless steel balls of 10mm and 3mm diameter in a mass ratio of 5:1, matching uniformly; then adding 15ml of absolute ethyl alcohol into a ball milling tank as well as filling argon, ball milling for 3 hours, placing the obtained powder into a drying oven at 80 ℃ for drying for 8 hours, and then screening by using a stainless steel screen to leave alloy powder with 200 meshes;
(2) Polishing rust and an oxide layer on the surface of a Q235 alloy steel substrate by an angle grinder, removing impurities and greasy dirt on the surface of the substrate by acetone, drying in a drying oven at 70 ℃ for 5 hours, and then pre-treating the Q235 alloy steel substrate at 400 ℃ for 4 hours to obtain a pre-deposited substrate; sieving alloy powder for the second time to keep the granularity of 200 meshes, then drying the alloy powder in a drying oven at 80 ℃, loading the dried alloy powder into a disc, uniformly spreading the alloy powder at the temperature for 5 hours, turning the powder during the drying process, and finishing pretreatment to obtain pre-deposited powder;
(3) Argon is introduced into plasma cladding equipment, the argon is used as protective gas and working gas, the working current of plasma cladding is set to be 170A, the working voltage is 30V, the flow rate of the protective gas is 400L/h, the flow rate of the ion gas is 300L/h, the flow rate of powder feeding gas is 300L/h, the distance between a nozzle and the surface of a base material is 10mm, multi-pass lap cladding is carried out on the base plate from top to bottom, the scanning speed is 220mm/min, and the pre-cladding powder is deposited on the surface of a pre-cladding base body to form a cladding layer, so that a high-entropy alloy plasma cladding layer is obtained;
(4) Naturally cooling the obtained high-entropy alloy plasma cladding layer to room temperature, then carrying out cryogenic treatment on the high-entropy alloy plasma cladding layer, carrying out cryogenic treatment in two stages, firstly immersing the high-entropy alloy plasma cladding layer in liquid nitrogen at the temperature of minus 90 ℃ for 3 hours, then placing the high-entropy alloy plasma cladding layer in liquid nitrogen at the temperature of minus 190 ℃ for 5 hours, and placing the high-entropy alloy plasma cladding layer in purified water at room temperature for heat preservation and recovery after the cryogenic treatment is completed until the high-entropy alloy plasma cladding layer returns to the room temperature, thus obtaining the inert anode.
When the Mo content is large, a precipitated phase structure with a large amount of Mo and Cr elements is formed with Cr in the metal, and the precipitated phase has high hardness and can improve the mechanical property of the alloy. But may cause the precipitated phase to have a different corrosion resistance from its surrounding structure, thereby causing the oxide film to be unstable and causing localized corrosion to become strong.
Example 3
The preparation method of the inert anode comprises the following steps:
(1) According to the composition ratio of the high-entropy alloy coating, 18.9wt.% Fe, 20.0wt.% Co, 17.6wt.% Cr, 19.9wt.% Ni, 18.6wt.% Mn, 5wt.% Mo metal raw material powder is prepared, 500g of grinding balls and the metal raw material powder (ball-to-material ratio 10:1) are placed in a ball milling tank, the grinding balls comprise 2 grinding balls with the diameter of 20mm, and the rest grinding balls are formed by stainless steel balls with the diameters of 10mm and 3mm according to the mass ratio of 5:1, matching uniformly; then adding 15ml of absolute ethyl alcohol into a ball milling tank as well as filling argon, ball milling for 3 hours, placing the obtained powder into a drying oven at 80 ℃ for drying for 8 hours, and then screening by using a stainless steel screen to leave alloy powder with 200 meshes;
(2) Polishing rust and an oxide layer on the surface of a Q235 alloy steel substrate by an angle grinder, removing impurities and greasy dirt on the surface of the substrate by acetone, drying in a drying oven at 70 ℃ for 5 hours, and then pre-treating the Q235 alloy steel substrate at 400 ℃ for 4 hours to obtain a pre-deposited substrate; sieving alloy powder for the second time to keep the granularity of 200 meshes, then drying the alloy powder in a drying oven at 80 ℃, loading the dried alloy powder into a disc, uniformly spreading the alloy powder at the temperature for 5 hours, turning the powder during the drying process, and finishing pretreatment to obtain pre-deposited powder;
(3) Argon is introduced into plasma cladding equipment, the argon is used as protective gas and working gas, the working current of plasma cladding is set to be 190A, the working voltage is 30V, the flow rate of the protective gas is 400L/h, the flow rate of the ion gas is 300L/h, the flow rate of powder feeding gas is 400L/h, the distance between a nozzle and the surface of a base material is 10mm, multiple lap cladding is carried out on the base plate from top to bottom, the scanning speed is 220mm/min, and the pre-cladding powder is caused to form a cladding layer on the surface of a pre-cladding base material, so that a high-entropy alloy plasma cladding layer is obtained;
(4) Naturally cooling the obtained high-entropy alloy plasma cladding layer to room temperature, then carrying out cryogenic treatment on the high-entropy alloy plasma cladding layer, carrying out cryogenic treatment in two stages, firstly immersing the high-entropy alloy plasma cladding layer in liquid nitrogen at the temperature of minus 90 ℃ for 3 hours, then placing the high-entropy alloy plasma cladding layer in liquid nitrogen at the temperature of minus 190 ℃ for 5 hours, and placing the high-entropy alloy plasma cladding layer in purified water at room temperature for heat preservation and recovery after the cryogenic treatment is completed until the high-entropy alloy plasma cladding layer returns to the room temperature, thus obtaining the inert anode.
When the plasma cladding current is larger, the corresponding powder feeding flow rate is also increased, so that the higher heat caused by the larger current can be ensured to be absorbed by enough powder, and the energy waste can not be caused. At the same time, the powder flow rate was increased, and the thickness of the cladding layer was also increased by 1 to 2mm as compared with example 1. However, higher instantaneous heat input can also cause a greater degree of melting of the substrate during deposition, thereby entering the cladding layer and affecting the alloying elements of the cladding layer to some extent.
Example 4
The preparation method of the inert anode comprises the following steps:
(1) According to the composition ratio of the high-entropy alloy coating, 18.9wt.% Fe, 20.0wt.% Co, 17.6wt.% Cr, 19.9wt.% Ni, 18.6wt.% Mn, 5wt.% Mo metal raw material powder is prepared, 500g of grinding balls and the metal raw material powder (ball-to-material ratio 8:1) are placed in a ball milling tank, the grinding balls comprise 3 grinding balls with the diameter of 20mm, and the rest grinding balls are formed by stainless steel balls with the diameters of 10mm and 3mm according to the mass ratio of 3:1, matching uniformly; then adding 30ml of absolute ethyl alcohol into a ball milling tank as well as filling argon, ball milling for 7 hours, placing the obtained powder into a drying oven at 80 ℃ for drying for 8 hours, and then screening by using a stainless steel screen to leave alloy powder with 200 meshes;
(2) Polishing rust and an oxide layer on the surface of a Q235 alloy steel substrate by an angle grinder, removing impurities and greasy dirt on the surface of the substrate by acetone, drying in a drying oven at 70 ℃ for 5 hours, and then pretreating the Q235 alloy steel substrate at 600 ℃ for 6 hours to obtain a pre-deposited substrate; sieving alloy powder for the second time to keep the granularity of 200 meshes, then placing the alloy powder in a drying oven at 70 ℃ for drying, placing the dried alloy powder in a tray, uniformly spreading the alloy powder at the temperature for 7 hours, turning the powder during the drying process, and finishing pretreatment to obtain pre-deposited powder;
(3) Argon is introduced into plasma cladding equipment, the argon is used as protective gas and working gas, the working current of plasma cladding is set to be 190A, the working voltage is 29V, the flow rate of the protective gas is 500L/h, the flow rate of the ion gas is 350L/h, the flow rate of powder feeding gas is 400L/h, the distance between a nozzle and the surface of a base material is 8mm, multiple lap cladding is carried out on the base plate from top to bottom, the scanning speed is 250mm/min, and the pre-cladding powder is welded on the surface of a pre-cladding matrix to form a cladding layer, so that a high-entropy alloy plasma cladding layer is obtained;
(4) Naturally cooling the obtained high-entropy alloy plasma cladding layer to room temperature, then carrying out cryogenic treatment on the high-entropy alloy plasma cladding layer, carrying out cryogenic treatment in two stages, firstly immersing the high-entropy alloy plasma cladding layer in liquid nitrogen at the temperature of minus 80 ℃ for 5 hours, then placing the high-entropy alloy plasma cladding layer in liquid nitrogen at the temperature of minus 180 ℃ for 6 hours, and placing the high-entropy alloy plasma cladding layer in purified water at room temperature for heat preservation and recovery after the cryogenic treatment is completed until the high-entropy alloy plasma cladding layer returns to the room temperature, thus obtaining the inert anode.
Example 5
The preparation method of the inert anode comprises the following steps:
(1) According to the composition ratio of the high-entropy alloy coating, 18.9wt.% Fe, 20.0wt.% Co, 17.6wt.% Cr, 19.9wt.% Ni, 18.6wt.% Mn, 5wt.% Mo metal raw material powder is prepared, 500g of grinding balls and the metal raw material powder (ball-to-material ratio 10:1) are placed in a ball milling tank, the grinding balls comprise 2 grinding balls with the diameter of 20mm, and the rest grinding balls are formed by stainless steel balls with the diameters of 10mm and 3mm according to the mass ratio of 5:1, matching uniformly; then adding 15ml of absolute ethyl alcohol into a ball milling tank as well as filling argon, ball milling for 3 hours, placing the obtained powder into a drying oven at 80 ℃ for drying for 8 hours, and then screening by using a stainless steel screen to leave alloy powder with 200 meshes;
(2) Polishing rust and an oxide layer on the surface of a Q235 alloy steel substrate by an angle grinder, removing impurities and greasy dirt on the surface of the substrate by acetone, drying in a drying oven at 70 ℃ for 5 hours, and then pre-treating the Q235 alloy steel substrate at 400 ℃ for 4 hours to obtain a pre-deposited substrate; sieving alloy powder for the second time to keep the granularity of 200 meshes, then drying the alloy powder in a drying oven at 80 ℃, loading the dried alloy powder into a disc, uniformly spreading the alloy powder at the temperature for 3 hours, turning the powder during the drying process, and finishing pretreatment to obtain pre-deposited powder;
(3) Argon is introduced into plasma cladding equipment, the argon is used as protective gas and working gas, the working current of plasma cladding is set to be 170A, the working voltage is 30V, the flow rate of the protective gas is 400L/h, the flow rate of the ion gas is 300L/h, the flow rate of powder feeding gas is 300L/h, the distance between a nozzle and the surface of a base material is 10mm, multi-pass lap cladding is carried out on the base plate from top to bottom, the scanning speed is 220mm/min, and the pre-cladding powder is deposited on the surface of a pre-cladding base body to form a cladding layer, so that a high-entropy alloy plasma cladding layer is obtained;
(4) Naturally cooling the obtained high-entropy alloy plasma cladding layer to room temperature, then carrying out cryogenic treatment on the high-entropy alloy plasma cladding layer, carrying out cryogenic treatment in two stages, firstly immersing the high-entropy alloy plasma cladding layer in liquid nitrogen at the temperature of minus 100 ℃ for 3 hours, then placing the high-entropy alloy plasma cladding layer in liquid nitrogen at the temperature of minus 190 ℃ for 5 hours, and placing the high-entropy alloy plasma cladding layer in purified water at room temperature for heat preservation and recovery after the cryogenic treatment is completed until the high-entropy alloy plasma cladding layer returns to the room temperature, thus obtaining the inert anode.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. An inert anode, characterized by: the inert anode comprises a metal matrix and a protective coating on the surface of the metal matrix, wherein the protective coating is a FeCoCrNiMnMo high-entropy alloy coating.
2. The inert anode according to claim 1, wherein the fecocrymnmo high entropy alloy coating comprises the following components in mass percent: 18.7 to 19.3 percent of Fe, 19.7 to 20.3 percent of Co, 17.3 to 17.9 percent of Cr, 19.6 to 20.2 percent of Ni, 18.3 to 18.9 percent of Mn and 4.8 to 6.4 percent of Mo.
3. A method of preparing an inert anode according to claim 1 or 2, comprising the steps of:
(1) Ball milling the metal raw material powder to an alloying state to obtain alloy powder;
(2) Pretreating a metal matrix at a certain temperature to obtain a pre-deposited matrix; pretreating the alloy powder at a certain temperature to obtain pre-deposited powder;
(3) In a protective gas atmosphere, adopting a plasma cladding process to enable the pre-cladding powder to be welded on the surface of the pre-cladding substrate to form a cladding layer, so as to obtain a high-entropy alloy plasma cladding layer;
(4) The high-entropy alloy plasma cladding layer is subjected to cryogenic treatment to prepare the inert anode.
4. A method according to claim 3, wherein the specific method of step (1) is as follows: mixing the metal raw material powder with grinding balls and a control agent, performing ball milling in a protective gas atmosphere, and drying and sieving after ball milling is finished to obtain alloy powder.
5. The method of manufacturing according to claim 4, wherein: the control agent is absolute ethyl alcohol, and the dosage ratio of the grinding ball to the control agent is 1: 30-60 kg/mL; the grinding ball comprises three diameters of 20mm, 10mm and 3 mm; the grinding ball comprises 2 to 3 grinding balls with the diameter of 20mm, and the mass ratio of the rest grinding balls to the grinding balls with the diameters of 10mm and 3mm is 3 to 5:1 are matched.
6. A method of preparation according to claim 3, characterized in that: in the step (1), the ball-milling ball material ratio is 8-10: 1, the ball milling time is 3-7 h.
7. A method of preparation according to claim 3, characterized in that: in the step (1), the standard mesh number of the alloy powder is 100-300 mesh.
8. A method of preparation according to claim 3, characterized in that: in the step (2), the pretreatment temperature of the metal matrix is 400-600 ℃, and the treatment time is 4-6 h; the pretreatment temperature of the alloy powder is 70-80 ℃, and the treatment time is 3-7 h.
9. A method of preparation according to claim 3, characterized in that: in the step (3), the working current of the plasma cladding is 170-190A, the working voltage is 29-30V, the flow rate of shielding gas is 400-500L/h, the flow rate of ion gas is 300-350L/h, the flow rate of powder feeding gas is 300-400L/h, the plasma cladding is carried out multi-pass lap cladding from top to bottom on the surface of the pre-cladding substrate, the distance between a nozzle and the surface of the pre-cladding substrate is 8-10 mm, and the scanning speed is 220-250 mm/min.
10. A method of preparation according to claim 3, characterized in that: in the step (4), the cryogenic treatment is carried out in two stages, firstly, the high-entropy alloy plasma deposited layer at room temperature is placed at-80 to-100 ℃ for 3 to 5 hours, then the temperature is reduced to-180 to-190 ℃ for continuous treatment for 5 to 6 hours, and after the treatment is finished, the high-entropy alloy plasma deposited layer is preserved in water at room temperature and is recovered until the high-entropy alloy plasma deposited layer returns to the room temperature.
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