CN115044862B - Nickel-based alloy surface hardening method - Google Patents

Nickel-based alloy surface hardening method Download PDF

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CN115044862B
CN115044862B CN202210690722.9A CN202210690722A CN115044862B CN 115044862 B CN115044862 B CN 115044862B CN 202210690722 A CN202210690722 A CN 202210690722A CN 115044862 B CN115044862 B CN 115044862B
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CN115044862A (en
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彭宇清
彭智虎
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CHANGSHA TOPWELLWEAR METAL MATERIAL SCIENCE CO LTD
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/028—Borodising,, i.e. borides formed electrochemically
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32

Abstract

The invention relates to the technical field of metal surface treatment, in particular to a nickel-based alloy surface hardening method, which comprises the following steps of carrying out surface treatment on a nickel-based alloy; pouring the first boronizing agent into a container, burying the nickel-based alloy, placing the container in a heating furnace, keeping the temperature for 4-8h at 900-950 ℃, cooling to 600-620 ℃, keeping the temperature for 1-3h, cooling the furnace to room temperature, and taking out the nickel-based alloy; under the protection of argon, putting the second boronizing agent into a graphite crucible, putting the graphite crucible into a stainless steel sleeve, heating to the temperature, preserving heat for 2-4h, inserting the nickel-based alloy as a cathode, immersing the nickel-based alloy into the second boronizing agent, taking the graphite crucible as an anode, respectively connecting the anode and the cathode with a pulse electroplating power supply, electrolyzing, taking out the nickel-based alloy after the electrolysis is finished, washing and drying the nickel-based alloy.

Description

Nickel-based alloy surface hardening method
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to a nickel-based alloy surface hardening method.
Background
The alloy formed by adding other elements into the nickel base is called nickel alloy. Nickel has good mechanical, physical and chemical properties, and the oxidation resistance, corrosion resistance and high-temperature strength of the nickel can be improved and certain physical properties can be improved by adding proper elements. The nickel alloy can be used as materials for electronic tubes, precision alloys (magnetic alloys, precision resistance alloys, electrothermal alloys, etc.), nickel-based high-temperature alloys, nickel-based corrosion-resistant alloys, shape memory alloys, etc. The nickel alloy has wide application in energy development, chemical engineering, electronics, navigation, aviation, aerospace and other departments.
Metal surface treatment techniques have been developed rapidly after the 19 th century, particularly in the last few decades. At present, various covering layers are mainly applied and surface modification technology is adopted to improve the environmental resistance of the metal and endow a certain functional characteristic on the surface of a part, and surface hardening refers to hardening the surface layer of the metal by a proper method while the core part still has toughness. The wear resistance and fatigue resistance of metal can be improved by the treatment, and the surface hardness, wear resistance, corrosion resistance and other properties of the metal can be greatly improved by using the boronizing as a surface strengthening method which is effective for various metal materials, but the effect of performing surface hardening treatment on the nickel-based alloy by using the boronizing technology is not ideal at present.
Disclosure of Invention
The invention aims to: aiming at the technical problem, the invention provides a nickel-based alloy surface hardening method.
The adopted technical scheme is as follows:
a method of hardfacing a nickel-base alloy comprising the steps of:
s1: performing surface treatment on the nickel-based alloy;
s2: pouring the first boronizing agent into a container, burying the nickel-based alloy, placing the container in a heating furnace, keeping the temperature for 4-8h at 900-950 ℃, cooling to 600-620 ℃, keeping the temperature for 1-3h, cooling the furnace to room temperature, and taking out the nickel-based alloy;
s3: and under the protection of argon, putting the second boronizing agent into a graphite crucible, putting the graphite crucible into a stainless steel sleeve, heating to the temperature, preserving the heat for 2-4h, inserting the nickel-based alloy as a cathode, immersing the nickel-based alloy into the second boronizing agent, taking the graphite crucible as an anode, respectively connecting the anode and the cathode with a pulse electroplating power supply, electrolyzing, taking out the nickel-based alloy after the electrolysis is finished, washing the nickel-based alloy in boiling water, sequentially washing the nickel-based alloy with water and ethanol, and drying the nickel-based alloy at the temperature of 60-80 ℃ for 8-10 h.
Further, the nickel-based alloy comprises the following elements in weight percent:
c:0.03-0.1%, si:0.8-1.2%, mn:1.5-1.8%, P: less than or equal to 0.004%, S: less than or equal to 0.002%, cr:17-25%, mo:2.2-4%, zr:1.2-1.5%, fe:10-12%, cu:1-1.4%, ta:0.3 to 0.6 percent, and the balance of nickel and other inevitable impurities.
Further, the nickel-based alloy comprises the following elements in percentage by weight:
c:0.08%, si:1.2%, mn:1.55%, P: less than or equal to 0.004%, S: less than or equal to 0.002%, cr:22.4%, mo:4%, zr:1.5%, fe:11.6%, cu:1.4%, ta:0.6%, the balance being nickel and the balance being unavoidable impurities.
Further, the method of surface treatment is as follows:
cleaning the nickel-based alloy with water and ethanol in sequence, drying, and then performing sand blasting treatment, wherein the sand grains are carborundum with the diameter of 50-100 mu m, the sand blasting pressure is 0.3-0.5MPa, the sand blasting treatment time is 1-2min, and the nozzle is vertical to the surface of the nickel-based alloy and has the distance of 50-100mm.
Further, the first boronizing agent comprises borax, boron carbide and a slowly-permeating agent, and the mass ratio of the borax to the boron carbide to the slowly-permeating agent is 1-3:1-3:6-8.
Further, the permeation-retarding agent is silicon dioxide-nickel microspheres.
Further, the preparation method of the silica-nickel microspheres comprises the following steps:
adding tetraethoxysilane and nickel chloride hexahydrate into water, stirring and mixing uniformly, then adding urea, stirring for 0.5-1h, transferring the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, sealing, reacting for 12-15h at 200-210 ℃, cooling to room temperature, collecting a solid product, washing with water, drying for 12-15h at 70-80 ℃, and then roasting for 3-5h at 500-530 ℃ in a hydrogen atmosphere.
Further, the molar ratio of the ethyl orthosilicate to the nickel chloride hexahydrate is 1-1.1:1.
further, the second boronizing agent comprises sodium chloride, potassium chloride, sodium fluoride and sodium tetraborate, and the mass ratio of the sodium chloride to the potassium chloride to the sodium fluoride to the sodium tetraborate is 12-15:15-20:4-5:1.
further, the current density during electrolysis is 60-80mA/cm 2 The electrolysis temperature is 800-840 ℃, the time is 60-80min, the pulse width is 200-400 mus, and the pulse interval is 800-1000 mus.
The invention has the beneficial effects that:
the invention provides a nickel-based alloy surface hardening method, which adopts a molten salt-electrolysis composite boronizing technology to obtain a stable boronizing layer structure, wherein a first boronizing agent takes borax as a base salt, a boron donor agent boron carbide with high boron potential is added to ensure that a salt bath has a sufficient boron source, and simultaneously, a permeability-retarding agent silicon dioxide-nickel microsphere is added to effectively reduce the formation of brittle iron boride (FeB), so that the stability of the boron potential of the molten salt is ensured, the brittleness of the boronizing layer is effectively reduced, and the boronizing layer can be strengthened by electrolyzing a second boronizing agent to ensure that the boronizing layer structure is more compact and smooth.
Drawings
Fig. 1 is a cross-sectional view of a nickel-based alloy after a surface hardening treatment in example 1 of the present invention.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
a surface hardening method of a nickel-based alloy comprises the following steps:
the nickel-based alloy is cleaned by water and ethanol in sequence, dried and then subjected to sand blasting treatment, wherein sand grains are carborundum with the diameter of 50-100 mu m, the sand blasting pressure is 0.4MPa, the sand blasting treatment time is 2min, a nozzle is perpendicular to the surface of the nickel-based alloy and has the distance of 50mm, and the nickel-based alloy comprises the following elements in percentage by weight: c:0.08%, si:1.2%, mn:1.55%, P: less than or equal to 0.004%, S: less than or equal to 0.002%, cr:22.4%, mo:4%, zr:1.5%, fe:11.6%, cu:1.4%, ta:0.6 percent of nickel and the balance of inevitable impurities, and mixing borax, boron carbide and silicon dioxide-nickel microspheres in a mass ratio of 2:2:6, burying the nickel-based alloy, placing the container in a heating furnace for heat preservation at 930 ℃ for 6 hours, cooling to 620 ℃ for heat preservation for 2 hours, cooling the furnace to room temperature, and taking out the nickel-based alloy, wherein the preparation method of the silicon dioxide-nickel microspheres comprises the following steps: adding 442g of tetraethoxysilane and 504.3g of nickel chloride hexahydrate into 64L of water, stirring and mixing uniformly, then adding 800g of urea, stirring for 0.5h, transferring the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, sealing, reacting for 13h at 210 ℃, cooling to room temperature, collecting a solid product, washing with water, drying for 14h at 80 ℃, placing in a hydrogen atmosphere, roasting for 4h at 520 ℃, and under the protection of argon, adding sodium chloride, potassium chloride, sodium fluoride and sodium tetraborate in a mass ratio of 14:16:4:1 into a graphite crucible, heating the graphite crucible in a stainless steel sleeve, keeping the temperature for 4h, inserting the nickel-based alloy as a cathode into the second boronizing agent, taking the graphite crucible as an anode, connecting the anode and the cathode with a pulse plating power supply respectively, and feedingThe current density during the electrolysis is 60mA/cm 2 The electrolysis temperature is 820 ℃, the time is 60min, the pulse width is 400 mu s, the pulse interval is 800 mu s, the nickel-based alloy is taken out after the electrolysis is finished, the nickel-based alloy is placed in boiling water for washing, then is washed by water and ethanol in sequence, and is dried for 10h at 80 ℃.
Example 2:
a surface hardening method of a nickel-based alloy comprises the following steps:
the nickel-based alloy is cleaned by water and ethanol in sequence, dried and then subjected to sand blasting treatment, wherein sand grains are carborundum with the diameter of 50-100 mu m, the sand blasting pressure is 0.5MPa, the sand blasting treatment time is 2min, a nozzle is vertical to the surface of the nickel-based alloy, the distance is 100mm, and the nickel-based alloy comprises the following elements in percentage by weight: c:0.08%, si:1.2%, mn:1.55%, P: less than or equal to 0.004%, S: less than or equal to 0.002%, cr:22.4%, mo:4%, zr:1.5%, fe:11.6%, cu:1.4%, ta:0.6 percent of nickel and the balance of inevitable impurities, and mixing borax, boron carbide and silicon dioxide-nickel microspheres in a mass ratio of 3:3:8, burying the nickel-based alloy, placing the container in a heating furnace, keeping the temperature of 950 ℃ for 8h, cooling to 620 ℃ and keeping the temperature for 3h, cooling the furnace to room temperature, and taking out the nickel-based alloy, wherein the preparation method of the silicon dioxide-nickel microspheres comprises the following steps: adding 442g of ethyl orthosilicate and 504.3g of nickel chloride hexahydrate into 64L of water, stirring and mixing uniformly, then adding 800g of urea, stirring for 1h, transferring the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, sealing, reacting for 15h at 210 ℃, cooling to room temperature, collecting a solid product, washing with water, drying for 15h at 80 ℃, placing in a hydrogen atmosphere, roasting for 5h at 530 ℃, and under the protection of argon, adding sodium chloride, potassium chloride, sodium fluoride and sodium tetraborate according to the mass ratio of 15:20:5:1 into a graphite crucible, heating the graphite crucible in a stainless steel sleeve, keeping the temperature for 4h, inserting the nickel-based alloy as a cathode into the second boronizing agent, taking the graphite crucible as an anode, connecting the anode and the cathode with a pulse plating power supply respectively, and electrolyzing with the current density of 80mA/cm 2 The electrolysis temperature is 840 ℃, the time is 80min, the pulse width is 400 mu s, and the pulse interval isAnd taking out the nickel-based alloy after the electrolysis is finished every 1000 mu s, washing the nickel-based alloy in boiling water, washing the nickel-based alloy with water and ethanol in sequence, and drying the nickel-based alloy for 10 hours at the temperature of 80 ℃.
Example 3:
a surface hardening method of a nickel-based alloy comprises the following steps:
the nickel-based alloy is cleaned by water and ethanol in sequence, dried and then subjected to sand blasting treatment, wherein sand grains are carborundum with the diameter of 50-100 mu m, the sand blasting pressure is 0.3MPa, the sand blasting treatment time is 1min, a nozzle is vertical to the surface of the nickel-based alloy, the distance is 50mm, and the nickel-based alloy comprises the following elements in percentage by weight: c:0.08%, si:1.2%, mn:1.55%, P: less than or equal to 0.004%, S: less than or equal to 0.002%, cr:22.4%, mo:4%, zr:1.5%, fe:11.6%, cu:1.4%, ta:0.6 percent of nickel and the balance of inevitable impurities, and mixing borax, boron carbide and silicon dioxide-nickel microspheres in a mass ratio of 1:1:6, burying the nickel-based alloy, placing the container in a heating furnace at 900 ℃ for 4h, cooling to 600 ℃ for 1h, cooling to room temperature, and taking out the nickel-based alloy, wherein the preparation method of the silicon dioxide-nickel microspheres comprises the following steps: adding 442g of tetraethoxysilane and 504.3g of nickel chloride hexahydrate into 64L of water, stirring and mixing uniformly, then adding 800g of urea, stirring for 0.5h, transferring the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, sealing, reacting for 12h at 200 ℃, cooling to room temperature, collecting a solid product, washing with water, drying for 12h at 70 ℃, placing in a hydrogen atmosphere, roasting for 3h at 500 ℃, and under the protection of argon, adding sodium chloride, potassium chloride, sodium fluoride and sodium tetraborate according to the mass ratio of 12:15:4:1 into a graphite crucible, heating the graphite crucible in a stainless steel sleeve, keeping the temperature for 2h, inserting the nickel-based alloy as a cathode into the second boronizing agent, connecting the anode and the cathode with a pulse plating power supply respectively by using the graphite crucible as an anode, and electrolyzing with the current density of 60mA/cm 2 The electrolysis temperature is 800 ℃, the time is 60min, the pulse width is 200 Mus, the pulse interval is 800 Mus, the nickel-based alloy is taken out after the electrolysis is finished, the nickel-based alloy is washed in boiling water, then washed by water and ethanol in sequence, and dried for 8h at 60 ℃ to obtain the nickel-based alloy。
Example 4:
a surface hardening method of a nickel-based alloy comprises the following steps:
the nickel-based alloy is cleaned by water and ethanol in sequence, dried and then subjected to sand blasting treatment, wherein sand grains are carborundum with the diameter of 50-100 mu m, the sand blasting pressure is 0.3MPa, the sand blasting treatment time is 2min, a nozzle is vertical to the surface of the nickel-based alloy, the distance is 50mm, and the nickel-based alloy comprises the following elements in percentage by weight: c:0.08%, si:1.2%, mn:1.55%, P: less than or equal to 0.004%, S: less than or equal to 0.002%, cr:22.4%, mo:4%, zr:1.5%, fe:11.6%, cu:1.4%, ta:0.6 percent of nickel and the balance of inevitable impurities, and mixing borax, boron carbide and silicon dioxide-nickel microspheres in a mass ratio of 1:3:6, burying the nickel-based alloy, placing the container in a heating furnace for heat preservation at 950 ℃ for 4h, cooling to 620 ℃ for heat preservation for 1h, cooling the furnace to room temperature, and taking out the nickel-based alloy, wherein the preparation method of the silicon dioxide-nickel microspheres comprises the following steps: adding 442g of tetraethoxysilane and 504.3g of nickel chloride hexahydrate into 64L of water, stirring and mixing uniformly, then adding 800g of urea, stirring for 1h, transferring the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, sealing, reacting for 15h at 200 ℃, cooling to room temperature, collecting a solid product, washing with water, drying for 15h at 70 ℃, placing in a hydrogen atmosphere, roasting for 5h at 500 ℃, and roasting sodium chloride, potassium chloride, sodium fluoride and sodium tetraborate under the protection of argon according to the mass ratio of 12:20:4:1 into a graphite crucible, heating the graphite crucible in a stainless steel sleeve, keeping the temperature for 4h, inserting the nickel-based alloy as a cathode into the second boronizing agent, taking the graphite crucible as an anode, connecting the anode and the cathode with a pulse plating power supply respectively, and electrolyzing at a current density of 60mA/cm 2 The electrolysis temperature is 840 ℃, the time is 60min, the pulse width is 400 mu s, the pulse interval is 800 mu s, the nickel-based alloy is taken out after the electrolysis is finished, the nickel-based alloy is placed in boiling water for washing, then is washed by water and ethanol in sequence, and is dried for 8h at 80 ℃.
Example 5:
a surface hardening method of a nickel-based alloy comprises the following steps:
the nickel-based alloy is cleaned by water and ethanol in sequence, dried and then subjected to sand blasting treatment, wherein sand grains are carborundum with the diameter of 50-100 mu m, the sand blasting pressure is 0.5MPa, the sand blasting treatment time is 1min, a nozzle is vertical to the surface of the nickel-based alloy, the distance is 100mm, and the nickel-based alloy comprises the following elements in percentage by weight: c:0.08%, si:1.2%, mn:1.55%, P: less than or equal to 0.004%, S: less than or equal to 0.002%, cr:22.4%, mo:4%, zr:1.5%, fe:11.6%, cu:1.4%, ta:0.6 percent of nickel and the balance of inevitable impurities, and mixing borax, boron carbide and silicon dioxide-nickel microspheres in a mass ratio of 3:1:8, burying the nickel-based alloy, placing the container in a heating furnace at 900 ℃ for 8 hours, cooling to 600 ℃ for 3 hours, cooling the furnace to room temperature, and taking out the nickel-based alloy, wherein the preparation method of the silicon dioxide-nickel microspheres comprises the following steps: adding 442g of tetraethoxysilane and 504.3g of nickel chloride hexahydrate into 64L of water, stirring and mixing uniformly, then adding 800g of urea, stirring for 0.5h, transferring the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, sealing, reacting for 12h at 210 ℃, cooling to room temperature, collecting a solid product, washing with water, drying for 12h at 80 ℃, placing in a hydrogen atmosphere, roasting for 3h at 530 ℃, and under the protection of argon, adding sodium chloride, potassium chloride, sodium fluoride and sodium tetraborate according to the mass ratio of 15:15:5:1 into a graphite crucible, heating the graphite crucible in a stainless steel sleeve, keeping the temperature for 2h, inserting the nickel-based alloy as a cathode into the second boronizing agent, connecting the anode and the cathode with a pulse plating power supply respectively by using the graphite crucible as an anode, and electrolyzing with the current density of 80mA/cm 2 The electrolysis temperature is 800 ℃, the time is 80min, the pulse width is 200 mu s, the pulse interval is 1000 mu s, the nickel-based alloy is taken out after the electrolysis is finished, the nickel-based alloy is placed in boiling water for washing, then is washed by water and ethanol in sequence, and is dried for 10h at 60 ℃.
Comparative example 1:
essentially the same as example 1, except that no silica-nickel microspheres were added.
Comparative example 2:
essentially the same as in example 1, except that commercially available silica was used in place of the silica-nickel microspheres.
Comparative example 3:
substantially the same as in example 1 except that electrolytic boriding was not performed;
a surface hardening method of a nickel-based alloy comprises the following steps:
the nickel-based alloy is cleaned by water and ethanol in sequence, dried and then subjected to sand blasting treatment, wherein sand grains are carborundum with the diameter of 50-100 mu m, the sand blasting pressure is 0.4MPa, the sand blasting treatment time is 2min, a nozzle is perpendicular to the surface of the nickel-based alloy and is at a distance of 50mm, and the nickel-based alloy comprises the following elements in percentage by weight: c:0.08%, si:1.2%, mn:1.55%, P: less than or equal to 0.004%, S: less than or equal to 0.002%, cr:22.4%, mo:4%, zr:1.5%, fe:11.6%, cu:1.4%, ta:0.6 percent of nickel and the balance of inevitable impurities, and mixing borax, boron carbide and silicon dioxide-nickel microspheres in a mass ratio of 2:2:6, burying the nickel-based alloy, placing the container in a heating furnace at 930 ℃ for 6h, cooling to 620 ℃ for 2h, cooling to room temperature, and taking out the nickel-based alloy, wherein the preparation method of the silicon dioxide-nickel microspheres comprises the following steps: adding 442g of tetraethoxysilane and 504.3g of nickel chloride hexahydrate into 64L of water, stirring and mixing uniformly, then adding 800g of urea, stirring for 0.5h, transferring the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, sealing, reacting for 13h at 210 ℃, cooling to room temperature, collecting a solid product, washing with water, drying for 14h at 80 ℃, placing in a hydrogen atmosphere, and roasting for 4h at 520 ℃.
And (3) performance testing:
(1) the Vickers hardness of the nickel-based alloys after the surface hardening treatment in examples 1 to 5 and comparative examples 1 to 3 of the present invention was measured with reference to GB/T7997 to 2014, respectively.
(2) The nickel base alloys after the surface hardening treatment in examples 1 to 5 and comparative examples 1 to 3 of the present invention were subjected to wear resistance tests using a frictional wear tester, wherein the wear load was 196N, the rotation speed was 100 rpm, and the volume of wear after 1000 revolutions was measured, and the smaller the volume of wear, the better the wear resistance.
The test results are shown in table 1:
table 1:
Figure BDA0003699539230000091
from the above table 1, the surface hardening method of the nickel-based alloy provided by the present invention plays a positive role in increasing the surface hardness of the nickel-based alloy and improving the wear resistance of the nickel-based alloy.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; 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 technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (8)

1. A nickel-based alloy surface hardening method is characterized by comprising the following steps:
s1: performing surface treatment on the nickel-based alloy;
s2: pouring the first boronizing agent into a container, burying the nickel-based alloy, placing the container in a heating furnace, keeping the temperature for 4-8h at 900-950 ℃, cooling to 600-620 ℃, keeping the temperature for 1-3h, cooling the furnace to room temperature, and taking out the nickel-based alloy;
s3: under the protection of argon, putting the second boronizing agent into a graphite crucible, putting the graphite crucible into a stainless steel sleeve, heating to a temperature, preserving heat for 2-4h, inserting the nickel-based alloy as a cathode, immersing the nickel-based alloy into the second boronizing agent, taking the graphite crucible as an anode, respectively connecting the anode and the cathode with a pulse electroplating power supply, carrying out electrolysis, taking out the nickel-based alloy after the electrolysis is finished, washing the nickel-based alloy in boiling water, sequentially washing the nickel-based alloy with water and ethanol, and drying the nickel-based alloy at 60-80 ℃ for 8-10 h;
the first boronizing agent comprises borax, boron carbide and a slowly-permeating agent, wherein the mass ratio of the borax to the boron carbide to the slowly-permeating agent is 1-3:1-3:6-8;
the second boronizing agent comprises sodium chloride, potassium chloride, sodium fluoride and sodium tetraborate, and the mass ratio of the sodium chloride to the potassium chloride to the sodium fluoride to the sodium tetraborate is 12-15:15-20:4-5:1.
2. the method for hardfacing a nickel-base alloy of claim 1, wherein the nickel-base alloy comprises, in weight percent:
c:0.03-0.1%, si:0.8-1.2%, mn:1.5-1.8%, P: less than or equal to 0.004%, S: less than or equal to 0.002%, cr:17-25%, mo:2.2-4%, zr:1.2-1.5%, fe:10-12%, cu:1-1.4%, ta:0.3-0.6%, and the balance of nickel and the balance of unavoidable impurities.
3. The method for hardfacing a nickel-base alloy of claim 2, wherein the nickel-base alloy comprises, in weight percent:
c:0.08%, si:1.2%, mn:1.55%, P: less than or equal to 0.004%, S: less than or equal to 0.002%, cr:22.4%, mo:4%, zr:1.5%, fe:11.6%, cu:1.4%, ta:0.6 percent, the balance being nickel and the balance being unavoidable impurities.
4. The method of hardfacing a nickel-base alloy of claim 1, wherein the surface treatment is by the following method:
the nickel-based alloy is cleaned by water and ethanol in sequence, dried and then subjected to sand blasting treatment, wherein the sand grains are carborundum with the diameter of 50-100 mu m, the sand blasting pressure is 0.3-0.5MPa, the sand blasting treatment time is 1-2min, and the nozzle is vertical to the surface of the nickel-based alloy and is 50-100mm away.
5. The method of hardfacing a nickel-base alloy of claim 1, wherein the permeation retarder is silica-nickel microspheres.
6. The method for hardfacing a nickel-base alloy of claim 5, wherein the silica-nickel microspheres are prepared by a method comprising:
adding tetraethoxysilane and nickel chloride hexahydrate into water, stirring and mixing uniformly, then adding urea, stirring for 0.5-1h, transferring the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, sealing, reacting for 12-15h at 200-210 ℃, cooling to room temperature, collecting a solid product, washing with water, drying for 12-15h at 70-80 ℃, and then roasting for 3-5h at 500-530 ℃ in a hydrogen atmosphere.
7. The method for hardfacing a nickel-base alloy of claim 6, wherein the molar ratio of ethyl orthosilicate to nickel chloride hexahydrate is from 1 to 1.1:1.
8. the method of surface hardening of nickel-base alloy according to claim 1, wherein the current density at the time of electrolysis is 60 to 80mA/cm 2 The electrolysis temperature is 800-840 ℃, the time is 60-80min, the pulse width is 200-400 mus, and the pulse interval is 800-1000 mus.
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