CN109536880B - Method for nitriding or carbonitriding stainless steel surface by molten salt electrochemical method - Google Patents
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- CN109536880B CN109536880B CN201910085005.1A CN201910085005A CN109536880B CN 109536880 B CN109536880 B CN 109536880B CN 201910085005 A CN201910085005 A CN 201910085005A CN 109536880 B CN109536880 B CN 109536880B
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- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
- C23C8/52—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions more than one element being applied in one step
- C23C8/54—Carbo-nitriding
- C23C8/56—Carbo-nitriding of ferrous surfaces
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- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
- C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
- C23C8/48—Nitriding
- C23C8/50—Nitriding of ferrous surfaces
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- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
A method for nitriding or carbonitriding the surface of stainless steel by a molten salt electrochemical method belongs to the technical field of stainless steel surface repair. The method comprises the following steps: taking stainless steel to be repaired as a stainless steel cathode, taking nitrate containing N or mixed salt of nitrate containing N and C and carbonate as a reaction medium and electrolyte, taking a graphite rod as a graphite anode, applying voltage between the stainless steel cathode and the graphite anode at the temperature of 200-450 ℃ to perform electrolytic reaction, after the electrolytic reaction is finished, extracting the stainless steel cathode from molten salt, cooling, washing the molten salt on the surface of the cathode with deionized water, and storing after vacuum drying. According to the method, nitriding or carbonitriding can be regulated and controlled by controlling the components of the molten salt, and the temperature can be controlled below 480 ℃ to prevent CrN from being generated.
Description
Technical Field
The invention relates to a surface repairing technology of stainless steel applied to the fields of building, petroleum, aviation and the like, in particular to a method for nitriding or carbonitriding the surface of stainless steel by a molten salt electrochemical method.
Background
Because stainless steel has the advantages of good hardness, corrosion resistance, toughness and the like, the stainless steel is widely applied to the fields of buildings, petrochemical industry, nuclear industry, aerospace and the like, but in practical application, the problems of serious surface abrasion, insufficient strength, short service life and the like still occur, and the reliability of the stainless steel is seriously influenced. Therefore, various strengthening measures are needed to improve the properties of developed stainless steel grades, further exert the advantages of various stainless steels and expand the application range of the stainless steels. The surface modification treatment technology of stainless steel is one of the methods for effectively improving the surface hardness, wear resistance and fatigue resistance of materials, and the main surface modification methods comprise nitriding, carburizing, carbonitriding, film deposition and the like. However, the carburizing process is not only high in operating temperature (the gas carburizing requires 800-. The traditional nitriding method comprises gas nitriding, ion nitriding, plasma low-temperature nitriding and the like, but the conventional nitriding methods have defects of different degrees, such as CrN can be generated when the gas nitriding temperature is too high (higher than 480 ℃), so that chromium is poor in a stainless steel matrix, and the corrosion resistance of the stainless steel matrix is damaged; when the plasma is nitrided at low temperature, "expanded" martensite/austenite is generated, which causes the toughness to be reduced, the thermal stability to be low and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for nitriding or carbonitriding the surface of stainless steel by a molten salt electrochemical method. The method comprises the steps of firstly, taking stainless steel to be repaired as a stainless steel cathode, taking nitrate containing N or mixed salt of nitrate containing N and C and carbonate as a reaction medium and electrolyte, taking a graphite rod as a graphite anode, and applying voltage between the stainless steel cathode and the graphite anode at the temperature of 200-450 ℃ (the specific temperature is determined according to the composition of molten salt). After the electrolytic reaction is carried out for a period of time, the stainless steel cathode is lifted away from the molten salt and cooled, the molten salt on the surface of the cathode is washed by deionized water, and the molten salt is stored after vacuum drying. According to the method, nitriding or carbonitriding can be regulated and controlled by controlling the components of the molten salt, and the temperature can be controlled below 480 ℃ to prevent CrN from being generated.
The invention relates to a method for nitriding or carbonitriding stainless steel surface by a molten salt electrochemical method, which comprises the following steps:
(1) preparation of
Connecting the stainless steel to be treated as a stainless steel cathode to a first molybdenum rod by using a fine molybdenum wire;
connecting a graphite rod serving as a graphite anode with a second molybdenum rod;
drying the raw materials of the molten salt system to remove moisture, placing the raw materials in a crucible, and placing the crucible in a molten salt electrochemical reactor;
suspending a stainless steel cathode and a graphite anode on the surface of a molten salt system, sealing a molten salt electrochemical reactor, and introducing argon into the molten salt electrochemical reactor to form an argon atmosphere;
(2) electrolysis
Heating the raw materials of a molten salt system to a melting temperature to form molten salt, continuously introducing argon, and taking moisture in the heating process out of the molten salt electrochemical reactor;
inserting a stainless steel cathode and a graphite anode into the molten salt to form a two-electrode system, electrolyzing, extracting the electrolyzed cathode from the molten salt, and cooling; wherein, a constant bath pressure of 1.0-3.0V is applied between the cathode and the anode during electrolysis, and the electrolysis time is 30 min-3 h;
(3) and cleaning the cooled stainless steel cathode by using deionized water to remove attached molten salt, and then carrying out vacuum drying to obtain the stainless steel with the surface nitrided or carbonitrided.
In the step (1), the molten salt system is a nitrate containing N or a mixed salt thereof when nitriding, is a mixed salt of a nitrate containing N and C and a carbonate containing N and C when carbonitriding, and has a salt purity of analytical purity or more; the nitrate containing N or its mixed salt is preferably NaNO3Molten salt system, KNO3Molten salt system, KNO3-NaNO3Molten salt systems, CsNO3-KNO3Molten salt system, KNO3-RbNO3One of a molten salt system; the mixed salt of nitrate and carbonate containing N and C is preferably Na2CO3-NaNO3Molten salt system, K2CO3-KNO3One of a molten salt system;
the KNO3-NaNO3Molten salt system, according to mol ratio: KNO3：NaNO3＝0.51:0.49；
The CsNO3-KNO3Molten salt system, according to mol ratio: CsNO3：KNO3＝0.40:0.60；
The KNO3-RbNO3Molten salt system, according to mol ratio: KNO3：RbNO3＝0.32:0.68；
Said Na2CO3-NaNO3Molten salt system, according to mol ratio: na (Na)2CO3：NaNO3＝0.02:0.98；
Said K2CO3-KNO3Molten salt system, according to mol ratio: k2CO3：KNO3＝0.037:0.963。
In the step (1), the molten salt electrochemical reactor is a stainless steel reactor.
In the step (1), the graphite rod is a high-purity graphite rod, the diameter of the graphite rod is 10 +/-0.1 mm-15 +/-0.1 mm, and the purity of the graphite rod is more than or equal to 99.999 wt.%.
In the step (1), the diameter of the fine molybdenum wire is 0.1 +/-0.01 mm, the diameter of the first molybdenum rod is 0.5 +/-0.01-1.5 +/-0.01 mm, and the diameter of the second molybdenum rod is 0.5 +/-0.01-1.5 +/-0.01 mm.
In the step (1), the raw materials of the molten salt system are dried to remove moisture, and the adopted process comprises the following steps: and (3) putting the raw materials of the molten salt system into a vacuum drying machine at 100-200 ℃ for 10-15 h.
In the step (1), the stainless steel is suitable for nitriding, and specifically one of 38CrMoAlA, 35CrAl, 40CrNiMoA, 20CrMoTi and 4Cr10Si2Mo is selected.
In the step (2), after the electrolyzed cathode is lifted away from the molten salt, another cathode to be treated is inserted into the molten salt, voltage is applied, and electrolysis is continued.
In the step (2), the melting temperature is determined according to the components of the molten salt, and is preferably 200 +/-5-450 +/-5 ℃.
In the step (2), the molten salt is heated to the melting temperature, and the molten salt electrochemical reactor is placed in a resistance furnace wire for heating.
In the step (2), the distance between the horizontal electrodes of the cathode and the anode is 10-20 mm.
The method for nitriding or carbonitriding the surface of the stainless steel by the molten salt electrochemical method has the beneficial effects that:
1. the invention utilizes a molten salt electrochemical method to carry out nitriding or carbonitriding, and constant groove pressure is applied between a stainless steel cathode and a graphite anode to carry out electrochemical deoxidation-nitriding or deoxidation-carbonitriding processes. The molten salt can provide an anhydrous and oxygen-free environment, and the stainless steel cathode can be subjected to electrochemical polarization in the molten salt to rapidly remove an oxide layer on the surface of the stainless steel cathode, so that the surface of the stainless steel can keep a high-activity state, and the penetration of N or C, N is promoted.
2. The method regulates and controls nitriding or carbonitriding by controlling the components of the molten salt, and can control the temperature to be below 480 ℃ to prevent the generation of CrN.
3. The invention relates to a stainless steel surface modification method related to nitriding/carbonitriding, which has low cost, high efficiency, short flow and environmental friendliness.
Detailed Description
The present invention will be described in further detail with reference to examples.
In the embodiment of the invention, the adopted fine molybdenum wire is a commercial product.
In the embodiment of the invention, the graphite rod is a commercially available product.
In the embodiment of the invention, the raw material of the adopted molten salt is pure salt, and the salt purity is analytically pure.
In the embodiment of the invention, the diameter of the adopted graphite rod is 10 +/-0.1 mm-15 +/-0.1 mm, the purity of the graphite rod is high-purity graphite rod, and the purity is more than or equal to 99.999 wt.%.
In the embodiment of the invention, the diameter of the adopted molybdenum rod is 0.5 +/-0.01-1.5 +/-0.01 mm, and the purity is 99.99%.
In the embodiment of the invention, the temperature of the molten salt is controlled to be 200 +/-5-450 +/-5 ℃.
In the embodiment of the invention, the low voltage applied between the two electrodes is 1.0-3.0V.
In the embodiment of the invention, the adopted power supply is a direct-current stabilized power supply, and the type is as follows: NEWARE 5V-6A.
In the embodiment of the invention, the gas outlet of the molten salt electrochemical reactor extends to the lower part of the liquid level of the safety bottle outside the molten salt electrochemical reactor through the pipeline, and bubbles emerge when argon gas continuously circulates.
In the embodiment of the invention, the molten salt raw material is dried to remove water, and is placed in a vacuum resistance furnace, and is dried for 12 hours at the temperature of 200 ℃ to remove adsorbed water and part of crystal water.
In the embodiment of the invention, the step of heating the materials in the molten salt electrochemical reactor is to place the molten salt electrochemical reactor in a resistance wire furnace for heating.
Example 1
A method for nitriding stainless steel surface by a molten salt electrochemical method comprises the following steps:
1. connecting a 35CrAl stainless steel sheet serving as a stainless steel cathode with a first molybdenum rod current collector with the diameter of 0.5 +/-0.01-1.5 +/-0.01 mm and the purity of 99.99%;
taking graphite with the diameter of 10 +/-0.1 mm as a graphite anode, and connecting the graphite anode with a second molybdenum rod current collector with the diameter of 0.5 +/-0.01-1.5 +/-0.01 mm and the purity of 99.99%;
placing 500g of dehydrated analytically pure sodium nitrate into an alumina crucible with the diameter of 100 +/-0.01 mm, and then placing the crucible into a molten salt electrochemical reactor;
suspending a stainless steel cathode and a graphite anode on a molten salt system, sealing the molten salt electrochemical reactor, and continuously introducing argon into the molten salt electrochemical reactor through an air inlet and an air outlet on the molten salt electrochemical reactor to form an argon atmosphere in the molten salt electrochemical reactor;
2. heating sodium nitrate to 350 +/-5 ℃ for melting, and taking away moisture generated in the heating process by argon;
simultaneously inserting a stainless steel cathode and a graphite anode into molten salt to form a two-electrode system, keeping the electrode spacing at 15 +/-5 mm, and applying a 2.0V tank pressure between the two electrodes for electrolysis for 30 min; extracting the stainless steel cathode from the molten salt, and cooling the stainless steel cathode above the molten salt electrochemical reactor to obtain a cooled stainless steel cathode; meanwhile, inserting another stainless steel cathode to apply the same voltage to continue the electrolysis experiment;
3. and putting the cooled stainless steel cathode into deionized water with the pH value of 7, washing off molten salt on the stainless steel cathode, and drying in vacuum to prepare the stainless steel with nitrided surface.
Example 2
The method for nitriding the surface of the stainless steel by the molten salt electrochemical method is different from the method in example 1 in that:
(1) 2.3V is applied between the two electrodes in the step 2;
the other ways are the same.
Example 3
The method for nitriding the surface of the stainless steel by the molten salt electrochemical method is different from the method in example 1 in that:
(1) 2.5V is applied between the two electrodes in the step 2;
the other ways are the same.
Example 4
The method for nitriding the surface of the stainless steel by the molten salt electrochemical method is different from the method in example 1 in that:
(1) the electrolysis time in the step 1 is 1 h;
(2) the 35CrAl was replaced with 40CrNiMoA, otherwise the same.
Example 5
The method for nitriding the surface of the stainless steel by the molten salt electrochemical method is different from the method in example 1 in that:
(1) the electrolysis time in the step 2 is 2 hours;
the other ways are the same.
Example 6
A molten salt electrochemical method for carbonitriding the surface of stainless steel, which is the same as the embodiment 1, and is characterized in that:
(1) changing the molten salt in the step 1 to K2CO3-KNO3(ii) a Wherein, the molar ratio is as follows: k2CO3：KNO3＝0.037:0.963；
The other modes are the same; the surface carbonitrided stainless steel was obtained.
Example 7
A molten salt electrochemical method for carbonitriding the surface of stainless steel, which is similar to example 6, and is characterized in that:
(1) 2.3V is applied between the two electrodes in the step 2;
(2) replacing 35CrAl with 4Cr10Si2Mo in the same way; the surface carbonitrided stainless steel was obtained.
Example 8
A molten salt electrochemical method for carbonitriding the surface of stainless steel, which is similar to example 6, and is characterized in that:
(1) the electrolysis time of the step 2 is 1 h;
(2) replacing 35CrAl with 20CrMoTi in the same way; the surface carbonitrided stainless steel was obtained.
Example 9
A molten salt electrochemical method for carbonitriding the surface of stainless steel, which is similar to example 6, and is characterized in that:
(1) the electrolysis time of the step 2 is 2 hours;
(2) the molten salt adopts Na2CO3-NaNO3Molten salt system, according to mol ratio: na (Na)2CO3：NaNO3＝0.02:0.98；
The other modes are the same; the surface carbonitrided stainless steel was obtained.
Example 10
A method for nitriding stainless steel surface by a molten salt electrochemical method comprises the following steps:
1. connecting a 38CrMoAlA stainless steel sheet serving as a stainless steel cathode with a first molybdenum rod current collector with the diameter of 0.5 +/-0.01-1.5 +/-0.01 mm and the purity of 99.99%;
taking a graphite rod with the diameter of 10 +/-0.1 mm as a graphite anode, and connecting the graphite anode with a second molybdenum rod current collector with the diameter of 0.5 +/-0.01-1.5 +/-0.01 mm and the purity of 99.99%;
analytically pure KNO after water removal3-NaNO3500g of mixed salt is placed in an alumina crucible with the diameter of 100 +/-0.01 mm, and then the crucible is placed in a molten salt electrochemical reactor; wherein, the molar ratio is as follows: KNO3-NaNO3＝0.51:0.49；
Suspending a stainless steel cathode and a graphite anode on a molten salt system, sealing the molten salt electrochemical reactor, and continuously introducing argon into the molten salt electrochemical reactor through an air inlet and an air outlet on the molten salt electrochemical reactor to form an argon atmosphere in the molten salt electrochemical reactor;
2. heating the mixed salt of sodium nitrate and potassium nitrate to 300 +/-5 ℃ for melting, and taking away moisture generated in the heating process by argon;
simultaneously inserting a stainless steel cathode and a graphite anode into molten salt to form a two-electrode system, keeping the electrode spacing at 15 +/-5 mm, applying 1.0V tank pressure between the two electrodes, and electrolyzing for 3 hours; extracting the stainless steel cathode from the molten salt, and cooling the stainless steel cathode above the molten salt electrochemical reactor to obtain a cooled stainless steel cathode; meanwhile, inserting another stainless steel cathode to apply the same voltage to continue the electrolysis experiment;
3. and putting the cooled stainless steel cathode into deionized water with the pH value of 7, washing off molten salt on the stainless steel cathode, and drying in vacuum to prepare the stainless steel with nitrided surface.
Example 11
A method for nitriding stainless steel surface by molten salt electrochemical method, which is different from the method in example 10 in that:
(1) the molten salt is CsNO3-KNO3Molten salt system, according to mol ratio: CsNO3：KNO3＝0.40:0.60；
(2) Applying constant bath pressure of 3.0V, and electrolyzing for 40 min;
(3) changing the temperature of the molten salt to 260 ℃;
the other ways are the same.
Example 12
A method for nitriding stainless steel surface by molten salt electrochemical method, which is different from the method in example 10 in that:
(1) the molten salt is KNO3-RbNO3Molten salt system, according to mol ratio: KNO3：RbNO3＝0.32:0.68；
(2) Replacing 38CrMoAlA with 4Cr10Si2 Mo;
(3) the temperature of the molten salt is changed to 320 ℃;
the other ways are the same.
Claims (9)
1. A method for nitriding or carbonitriding the surface of stainless steel by a molten salt electrochemical method is characterized by comprising the following steps:
(1) preparation of
Connecting the stainless steel to be treated as a stainless steel cathode to a first molybdenum rod by using a fine molybdenum wire;
connecting a graphite rod serving as a graphite anode with a second molybdenum rod;
drying the raw materials of the molten salt system to remove moisture, placing the raw materials in a crucible, and placing the crucible in a molten salt electrochemical reactor; the molten salt system is a nitrate containing N or a mixed salt thereof when nitriding, and is a mixed salt of the nitrate containing N and C and a carbonate when carbonitriding;
suspending a stainless steel cathode and a graphite anode on the surface of a molten salt system, sealing a molten salt electrochemical reactor, and introducing argon into the molten salt electrochemical reactor to form an argon atmosphere;
(2) electrolysis
Heating the raw materials of a molten salt system to a melting temperature to form molten salt, continuously introducing argon, and taking moisture in the heating process out of the molten salt electrochemical reactor;
inserting a stainless steel cathode and a graphite anode into the molten salt to form a two-electrode system, electrolyzing, extracting the electrolyzed cathode from the molten salt, and cooling; wherein, a constant bath pressure of 1.0-3.0V is applied between the cathode and the anode during electrolysis, and the electrolysis time is 30 min-3 h;
(3) and cleaning the cooled stainless steel cathode by using deionized water to remove attached molten salt, and then carrying out vacuum drying to obtain the stainless steel with the surface nitrided or carbonitrided.
2. The method for nitriding or carbonitriding stainless steel surface according to claim 1, wherein the nitrate containing N or its mixed salt is NaNO3Molten salt system, KNO3Molten salt system, KNO3-NaNO3Molten salt systems, CsNO3-KNO3Molten salt system, KNO3-RbNO3One of a molten salt system; the mixed salt of nitrate and carbonate containing N and C is Na2CO3-NaNO3Molten salt system, K2CO3-KNO3One of the molten salt systems.
3. The method of molten salt electrochemical nitriding or carbonitriding stainless steel surfaces as claimed in claim 2, wherein said KNO3-NaNO3Molten salt system, according to mol ratio: KNO3：NaNO3=0.51:0.49；
The CsNO3-KNO3Molten salt system, according to mol ratio: CsNO3：KNO3=0.40:0.60；
The KNO3-RbNO3Molten salt system, according to mol ratio: KNO3：RbNO3=0.32:0.68；
Said Na2CO3-NaNO3Molten salt system, according to mol ratio: na (Na)2CO3：NaNO3=0.02:0.98；
Said K2CO3-KNO3Molten salt system, according to mol ratio: k2CO3：KNO3=0.037:0.963。
4. The method for nitriding or carbonitriding the surface of stainless steel by the molten salt electrochemical method according to claim 1, wherein in the step (1), the raw materials of the molten salt system are dried to remove moisture, and the adopted process is as follows: and (3) putting the raw materials of the molten salt system into a vacuum drying machine at 100-200 ℃ for 10-15 h.
5. The method of molten salt electrochemical nitriding or carbonitriding of a stainless steel surface according to claim 1, wherein in step (1), the stainless steel is a stainless steel suitable for nitriding.
6. The method of molten salt electrochemical nitriding or carbonitriding of stainless steel surface according to claim 1 or 5, wherein the stainless steel is selected from one of 38CrMoAlA, 35CrAl, 40CrNiMoA, 20CrMoTi, 4Cr10Si2 Mo.
7. A method of molten salt electrochemical nitriding or carbonitriding stainless steel surface according to claim 1, wherein in step (2), after the electrolyzed cathode is lifted off the molten salt, another cathode to be treated is inserted into the molten salt, and voltage is applied to continue the electrolysis.
8. The method for nitriding or carbonitriding a stainless steel surface by using a molten salt electrochemical method according to claim 1, wherein in the step (2), the melting temperature is 200 ± 5 ℃ to 450 ± 5 ℃ according to the components of the molten salt.
9. The method for nitriding or carbonitriding a stainless steel surface by a molten salt electrochemical method according to claim 1, wherein in the step (2), a horizontal electrode distance between a cathode and an anode is set to be 10-20 mm.
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| CN109536880A (en) | 2019-03-29 |
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