WO2026016263A1 - 一种铬镍共渗涂层及其制备方法、应用 - Google Patents

一种铬镍共渗涂层及其制备方法、应用

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Publication number
WO2026016263A1
WO2026016263A1 PCT/CN2024/114771 CN2024114771W WO2026016263A1 WO 2026016263 A1 WO2026016263 A1 WO 2026016263A1 CN 2024114771 W CN2024114771 W CN 2024114771W WO 2026016263 A1 WO2026016263 A1 WO 2026016263A1
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WIPO (PCT)
Prior art keywords
chromium
nickel
diffusion
coating
preparation
Prior art date
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PCT/CN2024/114771
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English (en)
French (fr)
Inventor
鲁金涛
胡新元
赵文玮
张醒兴
黄锦阳
袁勇
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Xian Thermal Power Research Institute Co Ltd
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Xian Thermal Power Research Institute Co Ltd
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Publication of WO2026016263A1 publication Critical patent/WO2026016263A1/zh
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Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/02—Pretreatment of the material to be coated
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Definitions

  • This disclosure belongs to the field of material surface coating technology, specifically relating to a chromium-nickel co-diffusion coating and its preparation method and application.
  • the most common method for corrosion protection of metal workpieces is to apply a protective layer of metal, non-metal, or metal-non-metal composite film to the metal surface through physical, chemical, or electrochemical surface treatment processes. This prevents or slows down the chemical reaction between the metal and the medium it comes into contact with.
  • Related metal surface treatment technologies include thermal spraying, electroplating, thermal diffusion, surface phosphating, and metal or non-metal coatings. By creating a coating on the workpiece surface, the composition, microstructure, and composition of the material surface are altered, improving surface properties, enhancing the workpiece's corrosion and wear resistance, and extending its service life.
  • Thermal diffusion technology uses heat to diffuse metallic or non-metallic elements into the surface of a metal workpiece, forming a surface alloy layer.
  • Co-diffusion is the most widely used process in thermal diffusion, where multiple elements are simultaneously diffused into the workpiece surface through a single heating diffusion process.
  • Co-diffusion combines the advantages of various single-element diffusion methods, compensating for the shortcomings of single-element diffusion through element combination, resulting in better overall performance of the workpiece surface.
  • co-diffusion methods based on metallic elements, co-diffusion based on non-metallic elements, and rare earth co-diffusion.
  • aluminum-chromium co-diffusion is used on the surface of high-temperature alloy workpieces to form a dense oxide film, utilizing the stable physicochemical properties of the oxides at high temperatures to improve the service life of the workpiece.
  • most current co-diffusion methods for metal workpieces use solid-state methods, requiring multiple metallic elements and catalysts.
  • the first method involves compounding components such as chemical agents, which requires a long co-diffusion time, demanding experimental requirements, and results in coatings with poor adhesion and thinness, necessitating multiple coats to achieve the desired thickness.
  • the second method uses a gaseous approach, employing an aluminum-chromium co-diffusion agent composed of alumina, chromium powder, aluminum powder, and ammonium chloride.
  • the co-diffusion agent and the workpiece are placed in a crucible and heated under an argon atmosphere to obtain an aluminum-chromium coating.
  • the co-diffusion agent is composed of sodium chloride, barium chloride, sodium fluoride, aluminum powder, and chromium powder.
  • the co-diffusion agent is loaded into a crucible, and the crucible containing the salt bath chromium-aluminum co-diffusion agent is placed in an electric resistance furnace and heated. Then, the sample is placed in the prepared chromium-aluminum co-diffusion salt bath, and the main working surface of the sample is kept as perpendicular as possible to the salt bath flow direction.
  • This disclosure aims to at least solve one of the technical problems existing in the prior art, and to provide a chromium-nickel co-diffusion coating, its preparation method, and its application.
  • this disclosure provides a method for preparing a chromium-nickel co-diffusion coating, the method comprising:
  • Shot peening is performed on the pretreated metal workpiece.
  • a chromium-nickel co-diffusion slurry is applied in one step to the surface of a shot-peened metal workpiece, followed by drying, curing, and sintering to obtain a chromium-nickel co-diffusion coating on the metal workpiece surface; wherein...
  • the chromium-nickel co-infiltration slurry comprises a solid phase component and a liquid phase component; the solid phase component comprises chromium powder, nickel powder, alumina and chromium oxide, and the liquid phase component comprises Al( H2PO4 ) 3 , water glass, ammonium iodide, chromium oxide and magnesium oxide.
  • the solid-liquid ratio of the solid phase component to the liquid phase component is 10:(1-5).
  • the solid phase component comprises, by mass percentage:
  • the chromium powder, nickel powder, alumina, and chromium oxide are ball-milled at a speed of 350-400 r/min for 6-24 h to obtain a solid phase component.
  • liquid phase component comprises, by mass percentage:
  • the coating thickness of the chromium-nickel co-diffusion slurry applied to the surface of the metal workpiece is 0.1 to 1.0 mm.
  • the diameter of the shot particles is 0.1-1.0 mm
  • the shot peening pressure is 0.5-2.0 MPa
  • the shot peening time is 10-30 min.
  • the metal workpiece coated with chromium-nickel co-diffusion slurry is subjected to drying, curing, and sintering treatment, including:
  • the metal workpiece coated with chromium-nickel co-diffusion slurry is pre-dried at 60-85°C for 5-30 minutes, then dried at 100-160°C for 30-60 minutes, and finally cured at 250-300°C for 20-60 minutes.
  • the dried and cured metal workpiece is sintered at 500-650°C for 5-30 minutes.
  • a chromium-nickel co-diffusion coating is provided, prepared according to the preparation method described above.
  • Another aspect of this disclosure proposes an application of a chromium-nickel co-diffusion coating, wherein the chromium-nickel co-diffusion coating described above is applied to the surface of metal workpieces made of carbon steel, austenitic steel and high-temperature alloys.
  • This disclosure provides a chromium-nickel co-diffusion coating, its preparation method, and its application.
  • the preparation method includes: pre-treating the surface of a metal workpiece; and shot peening the pre-treated metal workpiece.
  • the process involves applying a chromium-nickel co-diffusion slurry to the surface of a shot-peened metal workpiece in a single coat, followed by drying, curing, and sintering to obtain a chromium-nickel co-diffusion coating.
  • the slurry comprises a solid phase and a liquid phase.
  • the solid phase includes chromium powder, nickel powder, alumina, and chromium oxide, while the liquid phase includes Al( H2PO4 ) 3 , water glass, ammonium iodide, chromium oxide, and magnesium oxide.
  • This coating is suitable for various metal workpieces requiring surface strengthening, including carbon steel, austenitic stainless steel, and high-temperature alloys. It has a wide range of applications and is highly practical. The coating exhibits strong adhesion and can further improve the metal workpiece's resistance to high and low temperature corrosion and steam oxidation.
  • Figure 1 is a flowchart of a method for preparing a chromium-nickel co-diffusion coating according to an embodiment of the present disclosure
  • Figure 2 is an electron microscope image of the chromium-nickel co-diffusion coating prepared in Example 3 of this disclosure.
  • one aspect of this disclosure provides a method S100 for preparing a chromium-nickel co-diffusion coating, specifically including the following steps S110-S130:
  • organic reagents such as alcohol or acetone are used to clean oil stains and dust from the surface of metal workpieces.
  • steel brushes, sandpaper, or polishing can be used to remove oxide scale from the surface of metal workpieces.
  • this embodiment does not specifically limit the material and type of the metal workpiece.
  • it can be a high-temperature alloy metal workpiece, various types of carbon steel metal workpieces, or austenitic steel metal workpieces.
  • metal workpieces can be pipe workpieces, turbine blades in the aerospace field, or other types of workpieces.
  • shot peening particles are sprayed at high speed onto the surface of a metal workpiece, causing plastic deformation of its surface layer and forming a reinforced layer of a certain thickness.
  • the shot peening particles have a diameter of 0.1-1.0 mm, the shot peening pressure is 0.5-2.0 MPa, and the shot peening time is 10-30 min.
  • the physical properties such as adhesion, roughness, and specific surface area, as well as the bonding strength, are improved. This is beneficial to increasing the adhesion of the subsequent penetrating coating, further improving the penetration effect of the subsequent co-penetrating coating, and making the coating thickness thicker.
  • a chromium-nickel co-diffusion slurry is applied to the surface of a metal workpiece after shot peening, followed by drying, curing, and sintering to obtain a chromium-nickel co-diffusion coating on the surface of the metal workpiece.
  • this embodiment does not specifically limit the method of coating the chromium-nickel co-diffusion slurry onto the surface of the metal workpiece.
  • the chromium-nickel co-diffusion slurry can be coated onto the surface of the metal workpiece by spraying or brushing.
  • the currently prepared chromium-aluminum co-diffusion coating is relatively thin, requiring multiple coatings to increase the coating thickness, and has poor stability.
  • this embodiment eliminates the need for multiple coatings; a single coating process is sufficient to achieve the desired thickness, and the coating thickness can be adjusted according to actual needs.
  • the chromium-nickel co-diffusion slurry is applied to a suitable thickness in a single coating process, without the need for multiple layers.
  • the coating thickness of the chromium-nickel co-diffusion slurry is 0.1–1.0 mm.
  • this embodiment applies the chromium-nickel co-diffusion slurry to the surface of the metal workpiece in a single application, forming a chromium-nickel co-diffusion coating with a thickness of 0.1–1.0 mm. Within this thickness range, both the applicability of the metal workpiece and its high-temperature corrosion resistance are ensured.
  • the slurry coating thickness of the chromium-nickel co-diffusion coating is 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, etc.
  • the service life of a coating depends not only on its thickness but also on the material of the coating itself and its adhesion to the substrate.
  • Most current coatings are chromium-aluminum coatings, which involve mixing chromium powder, aluminum powder, and some chloride powders. This requires a complex pretreatment process including grinding, calcination, and cooling to obtain a co-diffusion agent, which is then coated onto the workpiece surface. Because the co-diffusion agent is composed of powder, this method involves a complex processing procedure, and the coating adhesion to the substrate is also a concern. The workpiece has weak adhesion, and the coating is prone to peeling off. To address this, the chromium-nickel co-diffusion slurry of this embodiment includes both solid and liquid phase components to reduce the pretreatment process of the co-diffusion agent.
  • the chromium-nickel co-diffusion slurry includes a solid phase component and a liquid phase component; the solid phase component includes chromium powder, nickel powder, alumina and chromium oxide, and the liquid phase component includes Al( H2PO4 ) 3 , water glass, ammonium iodide, chromium oxide and magnesium oxide.
  • the adhesion between the chromium-nickel co-diffusion slurry and the workpiece is improved, coating peeling is avoided, and there is no need for a complicated pretreatment process for the solid phase component, which simplifies the slurry preparation process.
  • the solid-liquid ratio (g:mL) of the solid phase component to the liquid phase component is 10:(1-5).
  • the liquid phase component comprises, by mass percentage: 10-30% Al( H2PO4 ) 3 ; 15-25% water glass; 5-10% ammonium iodide; 10-40% chromium oxide; and 15-35% magnesium oxide.
  • Al( H2PO4 ) 3 and water glass act as binders, exhibiting high bonding strength with the metal substrate.
  • a single coating process can achieve the required coating thickness.
  • Al( H2PO4 ) 3 and water glass can decompose directly without producing harmful gases, thus preventing the formation of bubbles within the coating and resulting in a dense, pore -free structure within the coating layer.
  • the aforementioned binder components exhibit good high-temperature toughness and are not prone to cracking during the drying process.
  • ammonium iodide acts as a penetration aid, which can form active transition halide gas, thereby accelerating the penetration of active chromium and nickel atoms into the matrix.
  • magnesium oxide acts as a curing agent, causing the acidic phosphate ions in the binder to dehydrate and condense, effectively reducing the curing temperature of the slurry.
  • adding an appropriate amount of chromium oxide can slow down the curing reaction rate between magnesium oxide and the binder, preventing problems such as cracks on the cured coating surface and failure to form a film due to excessively rapid curing.
  • the content of Al( H2PO4 ) 3 is preferably 10%, 15%, 20%, 25%, or 30%
  • the content of water glass is preferably 15%, 20%, or 25%
  • the content of ammonium iodide is preferably 5%, 7%, or 10%
  • the content of chromium oxide is preferably 10%, 15%, 20%, 28%, 35%, or 40%
  • the content of magnesium oxide is preferably 15%, 25%, 30%, or 35%.
  • the solid phase component comprises, by mass percentage: 50-80% chromium powder; 1-10% nickel powder; 10-20% alumina; and 0-20% chromium oxide.
  • alumina and chromium oxide are used as fillers, which can effectively prevent the adhesion between chromium powder and nickel powder and between chromium powder, nickel powder and matrix during the slurry preparation process, resulting in uneven diffusion layer; secondly, adding a small amount of nickel can increase the diffusion rate and reduce the diffusion temperature, thereby reducing the adverse effects of heat treatment on the comprehensive mechanical properties of the matrix while achieving the required diffusion layer thickness.
  • chromium and nickel elements are diffused into the base metal, and the chromium and nickel diffused into the base metal can also form intermetallic compounds with the base metal.
  • the chromium-nickel co-diffusion layer has superior wear resistance and corrosion resistance.
  • the preferred contents of chromium powder are 50%, 60%, 70%, and 80%
  • the preferred contents of nickel powder are 1%, 5%, and 10%
  • the preferred contents of alumina are 10%, 15%, and 20%
  • the preferred contents of chromium oxide are 1%, 5%, 12%, 15%, and 20%.
  • chromium powder, nickel powder, alumina, and chromium oxide are ball-milled in a star-shaped ball mill jar to obtain a solid phase component.
  • the ball milling speed is 350-400 r/min, and the milling time is 6-24 h.
  • the metal workpiece coated with chromium-nickel co-diffusion slurry undergoes drying, curing, and sintering treatment, including the following specific steps:
  • the metal workpiece coated with chromium-nickel co-diffusion slurry is pre-dried at a low temperature of 60-85°C for 5-30 minutes, then dried at a low temperature of 100-160°C for 30-60 minutes, and finally cured at a medium temperature of 250-300°C for 20-60 minutes.
  • the dried and cured metal workpiece is sintered at 500-650°C for 5-30 minutes.
  • the low-temperature pre-drying temperature is preferably 60°C, 70°C, or 80°C, and the time is preferably 5 min, 10 min, 15 min, 20 min, 25 min, or 30 min.
  • the low-temperature drying temperature is preferably 100°C, 120°C, 140°C, 150°C, or 160°C, and the time is preferably 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, or 60 min.
  • the medium-temperature curing temperature is preferably 250°C, 260°C, 270°C, 280°C, 290°C, or 300°C, and the time is preferably 20 min, 30 min, 40 min, 50 min, or 60 min.
  • the sintering temperature is preferably 500°C, 550°C, or 600°C.
  • the optimal sintering time is 5 min, 10 min, 15 min, 20 min, 25 min, or 30 min at 650°C.
  • the surface quality problems of the co-infiltrating slurry will not be caused by local stress during the curing process.
  • the chromium-nickel co-diffusion coating preparation method of this embodiment is simple, does not require vacuum conditions, has high production efficiency, and produces little pollution during the production process.
  • the chromium-nickel co-diffusion coating formed based on the above components has good adhesion to the substrate, effectively preventing the coating from peeling off during use, thereby extending the coating life.
  • this chromium-nickel co-diffusion coating has a wide range of applications and is highly practical. It is not only suitable for high-temperature alloys, but also for various carbon steels and other metal workpieces such as austenitic steels.
  • a chromium-nickel co-diffusion coating is provided, prepared according to the preparation method described above.
  • the thickness of the chromium-nickel co-diffusion coating formed on various metal workpieces is 5-50 ⁇ m.
  • the coating with this thickness has good adhesion to the surface of the metal workpiece and also has excellent resistance to high and low temperature corrosion and steam oxidation.
  • Another aspect of this disclosure proposes an application of a chromium-nickel co-diffusion coating, wherein the chromium-nickel co-diffusion coating described above is applied to the surface of metal workpieces made of carbon steel, austenitic steel and high-temperature alloys.
  • This example uses a large boiler pipe made of carbon steel as the metal workpiece to be processed.
  • the pipe has an outer diameter of 55mm, a wall thickness of 8mm, and a length of 4000mm.
  • the surface treatment of this metal workpiece is chromium-nickel diffusion, which includes the following steps:
  • Alcohol/acetone is used to clean the surface of the pipe workpiece to remove oil stains, dust, etc., while steel brushes are used to remove the surface oxide scale.
  • the cleaned pipe workpiece was shot peened with a shot particle diameter of 0.3 mm, a shot peening pressure of 0.5 MPa, and a shot peening time of 10 min.
  • the chromium-nickel co-diffusion slurry is applied in one go by spraying (or brushing, etc.).
  • the thickness should be 0.5mm, and multiple layers of coating are not allowed.
  • the preparation method of the chromium-nickel co-diffusion slurry is as follows: Based on the mass percentage of the solid phase components, weigh 70% chromium powder, 5% nickel powder, 15% alumina, and 10% chromium oxide, respectively. Ball mill the mixed metal powder at 350 r /min for 8 hours to obtain the final solid phase component. Based on the mass percentage of the liquid phase components, weigh 25% Al( H2PO4 ) 3 , 18% water glass, 7% ammonium iodide, 15% chromium oxide, and 35% magnesium oxide, and mix them to obtain the liquid phase component. Mix the solid and liquid phase components at a solid-liquid (g:ml) ratio of 10:2 to obtain the final metal powder coating raw material.
  • the metal pipe workpiece was subjected to rapid sintering diffusion chromium infiltration by rapid heating, followed by air cooling to room temperature; the heating rate was set to 1000°C/min, the holding temperature was 500°C, and the holding time was 30min, resulting in a chromium-nickel co-infiltration coating on the metal pipe workpiece.
  • Example 1 the wear resistance of the obtained chromium-nickel co-diffusion coating was tested, as follows: Under test conditions of 10g load and 10s holding time, the microhardness of the prepared chromium-nickel co-diffusion coating was approximately 412 HV, while the microhardness of the carbon steel substrate was approximately 320 HV, representing an increase in hardness of about 1.3 times. Secondly, in Example 1, following the national standard GB/T 12444-2006 "Metallic Materials - Test Methods for Wear Resistance", the wear resistance of the carbon steel and the coating was tested. Under the same test conditions, the friction wear of the coated sample decreased by approximately 21.7%, and the coefficient of friction decreased by approximately 6.8%.
  • This example uses a large boiler pipe made of austenitic steel as the metal workpiece to be processed.
  • the pipe has an outer diameter of 55mm, a wall thickness of 8mm, and a length of 4000mm.
  • the surface of the part is treated with chromium-nickel diffusion, including the following steps:
  • Alcohol/acetone is used to clean the surface of the pipe workpiece to remove oil stains, dust, etc., while steel brushes are used to remove the surface oxide scale.
  • the chromium-nickel co-diffusion slurry should be applied in one go to a thickness of 0.5 mm using spraying (or brushing, etc.). Multiple layers of application are not allowed.
  • the preparation method of the chromium-nickel co-diffusion slurry is as follows: Based on the mass percentage of the solid phase components, weigh 75% chromium powder, 3% nickel powder, 10% alumina, and 12% chromium oxide, respectively. Ball mill the mixed metal powder at 350 r /min for 10 h to obtain the final solid phase component. Based on the mass percentage of the liquid phase components, weigh 30% Al( H2PO4 ) 3 , 25% water glass, 10% ammonium iodide, 20% chromium oxide, and 15% magnesium oxide, and mix them to obtain the liquid phase component. Mix the solid and liquid phase components at a solid-liquid (g:ml) ratio of 10:3 to obtain the final metal powder coating raw material.
  • a segmented gradient curing process is adopted, in which the metal pipe workpiece coated with chromium-nickel infiltration material is pre-dried at 85°C for 5 minutes, then dried at 160°C for 55 minutes, and finally cured at 300°C for 30 minutes.
  • the metal pipe workpiece was subjected to rapid sintering diffusion chromium infiltration by rapid heating, followed by air cooling to room temperature; the heating rate was set to 1000°C/min, the holding temperature was 550°C, and the holding time was 30min, resulting in a chromium-nickel co-infiltration coating on the metal pipe workpiece.
  • Example 2 the obtained chromium-nickel co-diffusion coating was subjected to an oxidation resistance test, as follows: After cyclic oxidation at 650°C for 100 hours, the oxidation weight gain of the prepared chromium-nickel co-diffusion coating sample was 0.000078 mg/ mm2 , and the oxidation weight gain of the stainless steel substrate was 0.0047 mg/ mm2 , with the oxidation rate decreasing by 98.3%.
  • Example 2 the wear resistance test was conducted on the obtained chromium-nickel co-diffusion coating, as detailed below: Under test conditions of 10g load and 10s holding time, the microhardness of the prepared chromium-nickel co-diffusion coating was approximately 400 HV, while the microhardness of the austenitic steel substrate was approximately 190 HV, representing an increase in hardness of about 2.1 times. Secondly, in Example 2, following the national standard GB/T 12444-2006 "Metallic Materials - Test Methods for Wear and Tear," the wear resistance of the austenitic steel and the coating was tested. Under the same test conditions, the friction and wear of the coated sample decreased by approximately 39%, and the coefficient of friction decreased by approximately 13%.
  • This example uses a large boiler pipe made of high-temperature alloy as the metal workpiece to be processed.
  • the pipe has an outer diameter of 55mm, a wall thickness of 8mm, and a length of 4000mm.
  • the surface chromium-nickel diffusion treatment is performed on this metal pipe workpiece, including the following steps:
  • Alcohol/acetone is used to clean the surface of the pipe workpiece to remove oil stains, dust, etc., while steel brushes are used to remove the surface oxide scale.
  • the cleaned pipe workpiece was shot peened with a shot particle diameter of 0.5 mm, a shot peening pressure of 1.5 MPa, and a shot peening time of 15 min.
  • the chromium-nickel co-diffusion slurry should be applied in one go to a thickness of 1.0 mm using spraying (or brushing, etc.). Multiple layers of coating are not allowed.
  • the preparation method of the chromium-nickel co-diffusion slurry is as follows: Based on the mass percentage of the solid phase components, weigh 60% chromium powder, 5% nickel powder, 20% alumina, and 15% chromium oxide, respectively. Ball mill the mixed metal powder at 350 r /min for 12 h to obtain the final solid phase component. Based on the mass percentage of the liquid phase components, weigh 25% Al( H2PO4 ) 3 , 20% water glass, 5% ammonium iodide, 35% chromium oxide, and 15% magnesium oxide, and mix them to obtain the liquid phase component. Mix the solid and liquid phase components at a solid-liquid (g:ml) ratio of 10:5 to obtain the final metal powder coating raw material.
  • a segmented gradient curing process is adopted, in which the metal pipe workpiece coated with chromium-nickel infiltration material is pre-dried at 80°C for 10 min, then dried at 150°C for 30 min, and finally cured at 300°C for 20 min.
  • the metal pipe workpiece was subjected to rapid sintering diffusion chromium infiltration by rapid heating, followed by air cooling to room temperature; the heating rate was set to 1000°C/min, the holding temperature was 650°C, and the holding time was 20min, resulting in a chromium-nickel co-infiltration coating on the metal pipe workpiece.
  • Example 3 the oxidation resistance of the obtained chromium-nickel co-diffusion coating was tested, as follows: After cyclic oxidation at 1000°C for 100h, the oxidation weight gain of the prepared chromium-nickel co-diffusion coating sample was 0.012mg/ mm2 , and the oxidation weight gain of the high-temperature alloy substrate was 0.108mg/ mm2 , with the oxidation rate decreasing by 88.9%.
  • Example 3 the wear resistance of the obtained chromium-nickel co-diffusion coating was tested, and the results are as follows: the microhardness of the prepared chromium-nickel co-diffusion coating is approximately 437 HV, while the microhardness of the high-temperature alloy substrate is approximately 300 HV, representing an increase in hardness of about 1.5 times. Furthermore, Example 3 also followed the national standard GB/T 12444-2006 "Metallic Materials - Test Methods for Wear" to test the wear resistance of the high-temperature alloy and the coating. Under the same test conditions, the frictional wear of the coated sample decreased by approximately 20.3%, and the coefficient of friction decreased by approximately 6.8%.
  • the thickness of the chromium-nickel co-diffusion coating obtained in Example 3 is about 31 ⁇ m, with an average chromium content of 35 wt.% and a nickel content of 6 wt.%.
  • the co-diffusion coating has a uniform and dense structure, no obvious internal defects, and good metallurgical bonding with the substrate.
  • This example uses a large boiler pipe made of high-temperature alloy as the metal workpiece to be processed.
  • the pipe has an outer diameter of 55mm, a wall thickness of 8mm, and a length of 4000mm.
  • the surface chromium-nickel diffusion treatment is performed on this metal pipe workpiece, including the following steps:
  • Alcohol/acetone is used to clean the surface of the pipe workpiece to remove oil stains, dust, etc., while steel brushes are used to remove the surface oxide scale.
  • the cleaned pipe workpiece was shot peened with a shot particle diameter of 0.1 mm, a shot peening pressure of 1.0 MPa, and a shot peening time of 20 min.
  • the chromium-nickel co-diffusion slurry is applied in one go by spraying (or brushing, etc.).
  • the thickness should be 0.8mm, and multiple layers of coating are not allowed.
  • the preparation method of the chromium-nickel co-diffusion slurry is as follows: Based on the mass percentage of the solid phase components, weigh 70% chromium powder, 5% nickel powder, 10% alumina, and 15% chromium oxide, respectively. Ball mill the mixed metal powder at 400 r /min for 24 h to obtain the final solid phase component. Based on the mass percentage of the liquid phase components, weigh 20% Al( H2PO4 ) 3 , 15% water glass, 7% ammonium iodide, 28% chromium oxide, and 30% magnesium oxide, and mix them to obtain the liquid phase component. Mix the solid and liquid phase components at a solid-liquid (g:ml) ratio of 10:5 to obtain the final metal powder coating raw material.
  • a segmented gradient curing process is adopted, in which the metal pipe workpiece coated with chromium-nickel infiltration material is pre-dried at 60°C for 5 minutes, then dried at 100°C for 55 minutes, and finally cured at 250°C for 30 minutes.
  • the metal pipe workpiece was subjected to rapid sintering diffusion chromium infiltration by rapid heating, followed by air cooling to room temperature; the heating rate was set to 1000°C/min, the holding temperature was 500°C, and the holding time was 30min, resulting in a chromium-nickel co-infiltration coating on the metal pipe workpiece.
  • Example 4 the oxidation resistance of the obtained chromium-nickel co-diffusion coating was tested, as follows: After cyclic oxidation at 1000°C for 100h, the oxidation weight gain of the prepared chromium-nickel co-diffusion coating sample was 0.033mg/ mm2 , and the oxidation weight gain of the high-temperature alloy substrate was 0.108mg/ mm2 , with the oxidation rate decreasing by 69.4%.
  • This disclosure presents a chromium-nickel co-diffusion coating, its preparation method, and its application, which have the following advantages compared to the prior art:
  • the chromium-nickel high-temperature corrosion-resistant coating and its preparation method disclosed herein do not require vacuum conditions, the preparation process is simple, and the chromium-nickel co-diffusion coating preparation is highly efficient, produces little pollution, and has a achievable thickness. It has good ductility and wear resistance, and especially excellent resistance to high and low temperature corrosion and steam oxidation.
  • the metal powder raw materials described in this disclosure are suitable for various metal workpieces that require surface strengthening, including carbon steel, austenitic stainless steel and high-temperature alloys, and have a wide range of applications and are extremely practical.
  • this disclosure further enhances the surface coating strength and corrosion resistance by subjecting the workpiece to shot peening before co-infiltration coating, thereby increasing the specific surface area of the metal workpiece, improving the penetration of metal elements and the adhesion of the coating.

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Abstract

本公开提供一种铬镍共渗涂层及其制备方法、应用。其中，制备方法包括：对金属工件进行表面预处理；对预处理后的金属工件进行喷丸处理；将铬镍共渗料浆一次涂覆在喷丸处理后的金属工件表面，经烘干固化、烧结处理，在金属工件表面得到铬镍共渗涂层；其中，所述铬镍共渗料浆包括固相组分和液相组分；所述固相组分包括铬粉、镍粉、氧化铝以及氧化铬，所述液相组分包括Al(H2PO4)3、水玻璃、碘化铵、氧化铬以及氧化镁。该涂层适用于各类表面需要强化的金属工件，包括碳钢、奥氏体不锈钢以及高温合金等工件，应用范围广、实用性极强，并且涂层具有很强的附着性，可提高金属工件的抗高低温腐蚀性和抗蒸汽氧化性。

Description

一种铬镍共渗涂层及其制备方法、应用
相关申请的交叉引用
本申请要求在2024年7月19日提交中国专利局、申请号为202410975833.3、发明名称为“铬镍共渗涂层及其制备方法、应用”的中国专利申请的优先权，其全部内容通过引用的方式并入本文中。
技术领域
本公开属于材料表面涂层技术领域，具体涉及一种铬镍共渗涂层及其制备方法、应用。
背景技术
金属工件最常用的防腐方法是通过物理、化学或电化学的金属表面处理工艺在金属表面覆盖上金属、非金属或金属-非金属复合膜作为保护层，以阻止或减缓金属与所接触介质之间的化学反应。相关的金属表面处理技术包括热喷涂、电镀、热扩渗、表面磷化处理、金属或非金属涂层等，通过在工件表面构建涂层以使材料表面的成分、组织、结构发生变化，提高表面性能，提高工件的耐腐蚀与耐磨损性能，延长工件使用寿命。
其中，热扩渗技术是用加热扩散的方式使欲渗金属或非金属元素渗入金属工件的表面，从而形成表面合金层的工艺。共渗是热扩渗技术应用最广泛的一种处理工艺，通过一次加热扩散，使多种元素同时渗入工件表层。共渗的出现，吸收了各种单元渗的优点，通过元素的配合弥补了单元渗的不足之处，使工件表面可以获得更好的综合性能。
目前，已有金属元素为主的共渗、非金属元素为主的共渗和稀土共渗等，例如，在高温合金工件表面铝铬共渗，形成致密氧化膜的元素涂层，利用其氧化物在高温条件下稳定的物化特性，提高工件的使用寿命，但当前大部分金属工件共渗采用的是固体法，需要多种金属元素以及催 化剂等组分复配，共渗时间长，实验要求高，且形成的涂层附着力较差，厚度小，需要多次涂覆才能达到所需厚度，适用范围较窄，尤其对于高碳钢及高合金钢等金属工件来，在元素扩散过程中，由于Cr或Al、Fe扩散速度不相同，存在原子扩散的柯肯达尔效应，在Cr或Al扩散的同时伴随着空洞的出现，导致涂层内有大量孔隙，涂层不致密，脆性增大，甚至还会引起涂层脱落，严重影响使用性能。其次，也有采用气体法，将氧化铝、铬粉、铝粉以及氯化铵组成铝铬共渗剂，将铬铝共渗剂与零件放入至坩埚中，在氩气气氛下加热，以得到含有铝铬涂层的零件，这种方法需要在真空环境下进行，且需要严格控制制备过程。此外，也有采用中性盐浴铬铝共渗，由氯化钠、氯化钡、氟化钠、铝粉、铬粉组成共渗剂，将共渗剂装入坩埚中，并将装有盐浴铬铝共渗剂的坩埚放入电阻炉中加热，之后将试样放入配备好的铬铝共渗盐浴内使试样的主要工作面尽量保持与盐浴流动方向垂直，保温4h后取出油淬，即在镍基高温合金表面制得铬铝共渗层，这种方法保温时间较长，对试样的放置位置要求较高，形成的涂层厚度较薄，仅为20μm左右，耐蚀耐磨效果较差。
发明内容
本公开旨在至少解决现有技术中存在的技术问题之一，提供一种铬镍共渗涂层及其制备方法、应用。
本公开的一方面，提供一种铬镍共渗涂层的制备方法，所述制备方法包括：
对金属工件进行表面预处理；
对预处理后的金属工件进行喷丸处理；
将铬镍共渗料浆一次涂覆在喷丸处理后的金属工件表面，经烘干固化、烧结处理，在金属工件表面得到铬镍共渗涂层；其中，
所述铬镍共渗料浆包括固相组分和液相组分；所述固相组分包括铬粉、镍粉、氧化铝以及氧化铬，所述液相组分包括Al(H2PO4)3、水玻璃、碘化铵、氧化铬以及氧化镁。
可选地，所述固相组分与所述液相组分的固液比为10:(1-5)。
可选地，按照质量百分比计，所述固相组分包括：
50-80％的铬粉；
1-10％的镍粉；
10-20％的氧化铝；
0-20％的氧化铬；
以上各固相组分的质量百分比之和为100％。
可选地，所述铬粉、镍粉、氧化铝以及氧化铬在转速为350-400r/min的条件下，球磨6-24h，得到固相组分。
可选地，按照质量百分比计，所述液相组分包括：
10-30％的Al(H2PO4)3；
15-25％的水玻璃；
5-10％的碘化铵；
10-40％氧化铬；
15-35％的氧化镁；
以上各液相组分的质量百分比之和为100％。
可选地，在金属工件表面涂覆的铬镍共渗料浆的涂覆厚度为0.1～1.0mm。
可选地，在喷丸处理中，喷丸颗粒直径为0.1-1.0mm，喷丸压力为0.5-2.0MPa，喷丸时间为10-30min。
可选地，对涂覆有铬镍共渗料浆的金属工件经烘干固化、烧结处理，包括：
将涂覆有铬镍共渗料浆的金属工件在60～85℃下预烘干5～30min，然后在100～160℃下烘干30～60min，最后在250～300℃下中温固化20～60min；
将烘干固化后的金属工件在500-650℃下烧结处理5～30min。
本公开的另一方面，提出一种铬镍共渗涂层，根据前文记载的所述制备方法制得。
本公开的另一方面，提出一种铬镍共渗涂层的应用，采用前文记载的铬镍共渗涂层应用在碳钢、奥氏体钢及高温合金的金属工件表面。
本公开提供一种铬镍共渗涂层及其制备方法、应用。其中，制备方法包括：对金属工件进行表面预处理；对预处理后的金属工件进行喷丸 处理；将铬镍共渗料浆一次涂覆在喷丸处理后的金属工件表面，经烘干固化、烧结处理，在金属工件表面得到铬镍共渗涂层；其中，所述铬镍共渗料浆包括固相组分和液相组分；所述固相组分包括铬粉、镍粉、氧化铝以及氧化铬，所述液相组分包括Al(H2PO4)3、水玻璃、碘化铵、氧化铬以及氧化镁。该涂层适用于各类表面需要强化的金属工件，包括碳钢、奥氏体不锈钢以及高温合金等工件，应用范围广、实用性极强，该涂层具有很强的附着性，可进一步提高金属工件的抗高低温腐蚀性和抗蒸汽氧化性。
附图说明
图1为本公开一实施例的铬镍共渗涂层的制备方法的流程框图；
图2为本公开实施例3中所制备铬镍共渗涂层的电镜图。
具体实施方式
为使本领域技术人员更好地理解本公开的技术方案，下面结合附图和具体实施方式对本公开作进一步详细描述。显然，所描述的实施例是本公开的一部分实施例，而不是全部的实施例。基于所描述的本公开的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本公开保护范围。
如图1所示，本公开的一方面，提供一种铬镍共渗涂层的制备方法S100，具体包括以下步骤S110-S130：
S110、对金属工件进行表面预处理。
具体地，采用酒精或丙酮等有机试剂对金属工件的表面油渍、灰尘进行清洁，同时还可利用钢刷、砂纸或抛光等方式去除金属工件表面氧化皮。
需要说明的是，本实施方式对金属工件的材质及类别不做具体限定，例如，可以为高温合金金属工件，也可以为各类碳钢金属工件，还可以为奥氏体钢金属工件。当然，这类金属工件可以为管道工件，也可以为航空领域的涡轮叶片，还可以为其他类别的工件。
S120、对预处理后的金属工件进行喷丸处理。
具体地，在喷丸处理过程中，通过将喷丸颗粒高速喷射到金属工件表面，使其表层发生塑性变形，形成一定厚度的强化层，其中，喷丸颗粒直径0.1-1.0mm，喷丸压力为0.5-2.0MPa，喷丸时间为10-30min。
在本实施方式中，通过对金属工件表面进行活化处理，提高金属工件表面附着力、粗糙度以及比表面积等物理性能和胶合强度，有利于增加后续渗透涂层的附着性，进一步提高后续共渗涂层的渗透效果，使涂层厚度较厚。
S130、将铬镍共渗料浆一次涂覆在喷丸处理后的金属工件表面，经烘干固化处理与烧结处理，在金属工件表面得到铬镍共渗涂层。
需要说明的是，本实施方式对于铬镍共渗料浆涂覆在金属工件表面上的方式不做具体限定，例如，采用喷涂方式，或者排刷方式等将铬镍共渗料浆涂覆在金属工件表面。
进一步需要说明的是，目前制备的铬铝共渗涂层厚度较薄，需要多次涂覆才能实现增加涂层的厚度，稳定性较差。而本实施方式无需多次涂覆，仅一次涂覆处理即可达到所需的厚度，且该涂层厚度可根据实际需要进行调节。
具体地，本实施方式在涂覆过程中是一次性将铬镍共渗浆料涂覆至合适厚度，无需多次分层涂覆，其中，铬镍共渗浆料的涂覆厚度为0.1～1.0mm。也就是说，本实施方式是将铬镍共渗浆料一次性涂覆在金属工件表面，形成一层铬镍共渗涂层，一层铬镍共渗涂层的厚度为0.1～1.0mm，在上述厚度范围内，既能保证金属工件本身的应用性，还能提高金属工件的高温耐腐蚀性。
在一些可选实施例中，铬镍共渗涂层的料浆涂覆厚度为0.1mm，0.2mm，0.3mm，0.4mm，0.5mm，0.6mm，0.7mm，0.8mm，0.9mm，1.0mm等。
应当理解的是，涂层的使用寿命除了与涂层厚度有关外，还与涂层本身材质以及与基体的结合性有一定的关联性。目前的涂层大多为铬铝涂层，将铬粉、铝粉以及一些氯化物等粉末一起混合，需要经研磨、煅烧、冷却等复杂的预处理过程得到共渗剂，再将其涂覆在工件表面，由于共渗剂均由粉末组成，这种方法对共渗剂的处理过程复杂，且涂层与 工件的结合力弱，涂层易脱落。针对此，本实施方式的铬镍共渗料浆除了包括有固相组分外，还包括有液相组分，以减少对共渗剂的预处理过程。
具体地，铬镍共渗料浆包括固相组分和液相组分；固相组分包括铬粉、镍粉、氧化铝以及氧化铬，液相组分包括Al(H2PO4)3、水玻璃、碘化铵、氧化铬以及氧化镁。
在本实施方式中，通过将液相组分与固相组分混合，提高铬镍共渗料浆与工件的粘结性，避免涂层脱落，且无需对固相组分进行复杂的预处理过程，简化了料浆的制备过程。
在另一些可选实施例中，固相组分与液相组分固液比(g:mL)为10:(1-5)。
在另一些可选实施例中，按照质量百分比计，所述液相组分包括：10-30％的Al(H2PO4)3；15-25％的水玻璃；5-10％的碘化铵；10-40％氧化铬；15-35％的氧化镁。
其中，在液相组分中，Al(H2PO4)3和水玻璃作粘结剂，与金属基体间的粘结强度高，一次涂覆处理即可达到制备涂层所需的涂覆厚度；其次，在对料浆进行烘干处理的过程中，Al(H2PO4)3和水玻璃能直接分解，不产生有害气体，能够避免在涂层内部形成气泡，进而使得涂覆层内结构致密无气孔；并且，上述粘结剂组分高温韧性好，在烘干过程中不易开裂。
进一步地，在液相组分中，碘化铵作助渗剂，能够形成活性过渡卤化物气体，促进活性铬原子、镍原子渗入基体的速度。
更进一步地，在液相组分中，氧化镁作固化剂，使粘结剂中的酸式磷酸根脱水缩聚，能有效降低料浆的固化成膜温度。同时，添加适量的氧化铬能降低氧化镁和粘结剂的固化反应速度，防止因固化速度过快导致固化后涂层表面出现裂纹，无法成膜等问题。
作为可选的方案，Al(H2PO4)3的含量优选10％、15％、20％、25％、30％，水玻璃的含量优选15％、20％、25％，碘化铵优选含量5％、7％、10％，氧化铬的含量优选10％、15％、20％、28％、35％、40％，氧化镁的含量优选15％、25％、30％、35％。
在另一些可选实施例中，按照质量百分比计，固相组分包括：50-80％的铬粉；1-10％的镍粉；10-20％的氧化铝；0-20％的氧化铬。
其中，在固相组分中，氧化铝和氧化铬作填充剂，能有效防止料浆制备过程中铬粉与镍粉之间及铬粉、镍粉与基体之间粘结导致渗层不均匀；其次，添加少量的镍能提高渗铬的速度，降低渗铬温度，在实现所需渗层厚度的前提下减少热处理对基体综合力学性能的不利影响。
值得注意的是，本实施方式的铬、镍元素分别渗入基体金属中，且渗入基体中的铬、镍还能分别与基体形成金属间化合物，相较于单一渗铬涂层，铬镍共渗层具有更加优异的耐磨和耐腐蚀性能。
作为可选的方案，铬粉的含量优选50％、60％、70％、80％，镍粉的含量优选1％、5％、10％，氧化铝的含量优选10％、15％、20％，氧化铬的含量优选1％、5％、12％、15％、20％。
在另一些可选实施例中，铬粉、镍粉、氧化铝以及氧化铬在在星式球磨罐中球磨处理，得到固相组分。其中，球磨处理的转速为350-400r/min，球磨时间为6-24h。通过将混合好的各金属粉末进行球磨，之后再与液相组分混合，有利于各组分混合均匀。
进一步地，对涂覆有铬镍共渗料浆的金属工件经烘干固化、烧结处理，包括下述具体步骤：
将涂覆有铬镍共渗料浆的金属工件在60～85℃下低温预烘干5～30min，然后在100～160℃下低温烘干30～60min，最后在250～300℃下中温固化20～60min；
将烘干固化后的金属工件在500-650℃下烧结处理5～30min。
在一些可选实施例中，低温预烘干温度优选60℃，70℃，80℃，时间优选5min，10min，15min，20min，25min，30min。
在另一些可选实施例中，低温烘干的温度优选100℃，120℃，140℃，150℃，160℃，时间优选30min，35min，40min，45min，50min，55min，60min。
在另一些可选实施例中，中温固化的温度优选250℃，260℃，270℃，280℃，290℃，300℃，时间优选20min，30min，40min，50min，60min。
在另一些可选实施例中，烧结的温度优选500℃，550℃，600℃， 650℃，烧结时间优选5min，10min，15min，20min，25min，30min。
在本实施方式中，通过采用分段式梯度固化工艺，在保证共渗料浆在固化过程中不会因局部应力而产生表面质量问题，同时有利于共渗料浆的附着性增加，提高涂覆效果，缩短固化时间，减少能耗。
本实施方式的铬镍共渗涂层制备方法简单，无需在真空条件下进行，生产效率较高，生产过程中污染小，基于上述组分形成的铬镍共渗涂层与基体之间具有良好的结合性，有效防止涂层在使用过程中的脱落现象，从而达到延长涂层寿命的目的，并且，该铬镍共渗涂层应用范围广，实用性强，不仅适用于高温合金，还可适用于各类碳钢以及奥氏体钢等其他金属工件中。
本公开的另一方面，提出一种铬镍共渗涂层，根据前文记载的制备方法制得。
在本实施方式中，在各类金属工件上形成的铬镍共渗涂层厚度为5-50μm，该厚度对应的涂层与金属工件表面具有良好的结合力，且还具有优异的抗高低温腐蚀与抗蒸汽氧化性能。
本公开的另一方面，提出一种铬镍共渗涂层的应用，采用前文记载的铬镍共渗涂层应用在碳钢、奥氏体钢及高温合金的金属工件表面。
下面将结合几个具体实施例进一步说明铬镍共渗涂层的制备方法：
实施例1
本示例以碳钢材质的大型锅炉管道作为待处理的金属工件，该管道规格均为外径55mm、壁厚8mm、长度4000mm，在该金属工件上进行表面渗铬镍处理，包括如下步骤：
S1、管道表面清洁：
采用酒精/丙酮清洗管道工件的表面油渍、灰尘等，同时利用钢刷将表面氧化皮去除掉。
S2、表面喷丸处理：
将清洁处理过后的管道工件进行喷丸处理，喷丸颗粒直径0.3mm，喷丸压力为0.5MPa，喷丸时间为10min。
S3、表面料浆涂覆
采用喷涂(也可采用排刷等方式)形式一次性将铬镍共渗浆料涂覆 至厚度为0.5mm，不可多次分层涂覆。
其中，铬镍共渗浆料的的制备方法如下：按照固相组分按质量百分比计，分别称量70％的铬粉、5％的镍粉、15％的氧化铝以及10％的氧化铬，将混合好的金属混合粉末进行球磨，球磨转速为350r/min，球磨时间为8h得到最终的固相组分。液相组分按照质量百分比计，量取25％的Al(H2PO4)3、18％的水玻璃、7％的碘化铵、15％氧化铬以及35％的氧化镁，进行混合搅拌得到液相组分。固相组分与液相组分按照固液(g:ml)比10:2进行混合，得到最终的金属粉末涂层原料。
S4、烘干固化
采用分段式梯度固化工艺，将涂覆有渗铬镍材料的金属管道工件于75℃低温预烘干5min，然后140℃低温烘干55min，最后在250℃下中温固化30min。
S5、快速烧结
采用快速升温的方式对金属管道工件进行快速烧结扩散渗铬，然后空冷至室温；其中升温速率设为1000℃/min，保温温度为500℃，保温时间为30min，得到在金属管道工件上包覆的铬镍共渗涂层。
本实施例1对得到的铬镍共渗涂层进行了抗氧化测试，具体如下：在500℃循环氧化100h后，所制备的铬镍共渗涂层试样的氧化增重为0.15mg/mm2，碳钢基体的氧化增重为1.47mg/mm2，氧化速率降低了89.8％。
本实施例1对得到的铬镍共渗涂层进行了耐磨损测试，具体如下：在载荷10g，保载时间10s的测试条件下，所制备的铬镍共渗涂层的显微硬度约为412HV，碳钢基体的显微硬度硬度约为320HV，其硬度提升了1.3倍左右。其次，本实施例1遵循国标GB/T 12444-2006《金属材料摩损试验方法》，测试了碳钢和涂层的耐磨性能，在相同试验条件下，涂层试样的摩擦磨损量降低了约21.7％，摩擦系数降低了约6.8％。
实施例2
本示例以奥氏体钢材质的大型锅炉管道作为待处理的金属工件，该管道规格均为外径55mm、壁厚8mm、长度4000mm，在该金属管道工 件上进行表面渗铬镍处理，包括如下步骤：
S1、管道表面清洁：
采用酒精/丙酮清洗管道工件的表面油渍、灰尘等，同时利用钢刷将表面氧化皮去除掉。
S2、表面喷丸处理：
将清洁处理过后的管道工件进行喷丸处理，喷丸颗粒直径0.5mm，喷丸压力为1.0MPa，喷丸时间为10min。
S3、表面料浆涂覆
采用喷涂(也可采用排刷等方式)形式一次性将铬镍共渗浆料涂覆至厚度为0.5mm，不可多次分层涂覆。
其中，铬镍共渗浆料的的制备方法如下：按照固相组分按质量百分比计，分别称量75％的铬粉、3％的镍粉、10％的氧化铝以及12％的氧化铬，将混合好的金属混合粉末进行球磨，球磨转速为350r/min，球磨时间为10h得到最终的固相组分。液相组分按照质量百分比计，量取30％的Al(H2PO4)3、25％的水玻璃、10％的碘化铵、20％氧化铬以及15％的氧化镁，进行混合搅拌得到液相组分。固相组分与液相组分按照固液(g:ml)比10:3进行混合，得到最终的金属粉末涂层原料。
S4、烘干固化
采用分段式梯度固化工艺，将涂覆有渗铬镍材料的金属管道工件于85℃低温预烘干5min，然后160℃低温烘干55min，最后在300℃下中温固化30min。
S5、快速烧结
采用快速升温的方式对金属管道工件进行快速烧结扩散渗铬，然后空冷至室温；其中升温速率设为1000℃/min，保温温度为550℃，保温时间为30min，得到在金属管道工件上包覆的铬镍共渗涂层。
本实施例2对得到的铬镍共渗涂层进行了抗氧化测试，具体如下：在650℃循环氧化100h后，所制备的铬镍共渗涂层试样的氧化增重为0.000078mg/mm2，不锈钢基体的氧化增重为0.0047mg/mm2，氧化速率降低了98.3％。
本实施例2对得到的铬镍共渗涂层进行了耐磨损测试，具体如下： 在载荷10g，保载时间10s的测试条件下，所制备的铬镍共渗涂层的显微硬度约为400HV，奥氏体钢基体的显微硬度约为190HV，其硬度提升了2.1倍左右。其次，本实施例2遵循国标GB/T 12444-2006《金属材料摩损试验方法》，测试了奥氏体钢和涂层的耐磨性能，在相同试验条件下，涂层试样的摩擦磨损量降低了约39％，摩擦系数降低了约13％。
实施例3
本示例以高温合金材质的大型锅炉管道作为待处理的金属工件，该管道规格均为外径55mm、壁厚8mm、长度4000mm，在该金属管道工件上进行表面渗铬镍处理，包括如下步骤：
S1、管道表面清洁：
采用酒精/丙酮清洗管道工件的表面油渍、灰尘等，同时利用钢刷将表面氧化皮去除掉。
S2、表面喷丸处理：
将清洁处理过后的管道工件进行喷丸处理，喷丸颗粒直径0.5mm，喷丸压力为1.5MPa，喷丸时间为15min。
S3、表面料浆涂覆
采用喷涂(也可采用排刷等方式)形式一次性将铬镍共渗浆料涂覆至厚度为1.0mm，不可多次分层涂覆。
其中，铬镍共渗浆料的的制备方法如下：按照固相组分按质量百分比计，分别称量60％的铬粉、5％的镍粉、20％的氧化铝以及15％的氧化铬，将混合好的金属混合粉末进行球磨，球磨转速为350r/min，球磨时间为12h得到最终的固相组分。液相组分按照质量百分比计，量取25％的Al(H2PO4)3、20％的水玻璃、5％的碘化铵、35％氧化铬以及15％的氧化镁，进行混合搅拌得到液相组分。固相组分与液相组分按照固液(g:ml)比10:5进行混合，得到最终的金属粉末涂层原料。
S4、烘干固化
采用分段式梯度固化工艺，将涂覆有渗铬镍材料的金属管道工件于80℃低温预烘干10min，然后150℃低温烘干30min，最后在300℃下中温固化20min。
S5、快速烧结
采用快速升温的方式对金属管道工件进行快速烧结扩散渗铬，然后空冷至室温；其中升温速率设为1000℃/min，保温温度为650℃，保温时间为20min，得到在金属管道工件上包覆的铬镍共渗涂层。
本实施例3对得到的铬镍共渗涂层进行了抗氧化测试，具体如下：在1000℃循环氧化100h后，所制备的铬镍共渗涂层试样的氧化增重为0.012mg/mm2，高温合金基体的氧化增重为0.108mg/mm2，氧化速率降低了88.9％。
本实施例3对得到的铬镍共渗涂层进行了耐磨损测试，具体如下：所制备的铬镍共渗涂层的显微硬度约为437HV，高温合金基体的显微硬度硬度约为300HV，其硬度提升了1.5倍左右。其次，本实施例3还遵循国标GB/T 12444-2006《金属材料摩损试验方法》，测试了高温合金和涂层的耐磨性能，在相同试验条件下，涂层试样的摩擦磨损量降低了约20.3％，摩擦系数降低了约6.8％。
如图2所示，本实施例3得到的铬镍共渗涂层的厚度约31μm，平均铬含量和镍含量分别为35wt.％和6wt.％，共渗涂层组织均匀致密，内部无明显缺陷且与基体冶金结合良好。
实施例4
本示例以高温合金材质的大型锅炉管道作为待处理的金属工件，该管道规格均为外径55mm、壁厚8mm、长度4000mm，在该金属管道工件上进行表面渗铬镍处理，包括如下步骤：
S1、管道表面清洁：
采用酒精/丙酮清洗管道工件的表面油渍、灰尘等，同时利用钢刷将表面氧化皮去除掉。
S2、表面喷丸处理：
将清洁处理过后的管道工件进行喷丸处理，喷丸颗粒直径0.1mm，喷丸压力为1.0MPa，喷丸时间为20min。
S3、表面料浆涂覆
采用喷涂(也可采用排刷等方式)形式一次性将铬镍共渗浆料涂覆 至厚度为0.8mm，不可多次分层涂覆。
其中，铬镍共渗浆料的的制备方法如下：按照固相组分按质量百分比计，分别称量70％的铬粉、5％的镍粉、10％的氧化铝以及15％的氧化铬，将混合好的金属混合粉末进行球磨，球磨转速为400r/min，球磨时间为24h得到最终的固相组分。液相组分按照质量百分比计，量取20％的Al(H2PO4)3、15％的水玻璃、7％的碘化铵、28％氧化铬以及30％的氧化镁，进行混合搅拌得到液相组分。固相组分与液相组分按照固液(g:ml)比10:5进行混合，得到最终的金属粉末涂层原料。
S4、烘干固化
采用分段式梯度固化工艺，将涂覆有渗铬镍材料的金属管道工件于60℃低温预烘干5min，然后100℃低温烘干55min，最后在250℃下中温固化30min。
S5、快速烧结
采用快速升温的方式对金属管道工件进行快速烧结扩散渗铬，然后空冷至室温；其中升温速率设为1000℃/min，保温温度为500℃，保温时间为30min，得到在金属管道工件上包覆的铬镍共渗涂层。
本实施例4对得到的铬镍共渗涂层进行了抗氧化测试，具体如下：在1000℃循环氧化100h后，所制备的铬镍共渗涂层试样的氧化增重为0.033mg/mm2，高温合金基体的氧化增重为0.108mg/mm2，氧化速率降低了69.4％。
本实施例4对得到的铬镍共渗涂层进行了耐磨损测试，具体如下：所制备的铬镍共渗涂层的显微硬度约为419.6HV，高温合金基体的显微硬度硬度约为300HV，其硬度提升了1.4倍左右。其次，本实施例4遵循国标GB/T 12444-2006《金属材料摩损试验方法》，测试了高温合金和涂层的耐磨性能，在相同试验条件下，涂层试样的摩擦磨损量降低了约18.3％，摩擦系数降低了约6.2％。
本公开提出一种铬镍共渗涂层及其制备方法、应用，相对于现有技术而言，具有以下有益效果：
第一、本公开的铬镍高温耐蚀涂层及其制备方法无需在真空条件下进行，制备过程简单，同时铬镍共渗涂层制备效率高、污染小、厚度可 调、耐磨性能好，尤其具有优异的抗高低温腐蚀和抗蒸汽氧化性能；
第二、本公开将固相组分与液相组分混合形成铬镍共渗料浆，该料浆易于包覆在金属工件表面，与工件表面的结合力强。
第三、本公开所述的金属粉末原料适用于各类表面需要强化的金属工件，包括碳钢、奥氏体不锈钢以及高温合金等工件，应用范围广、实用性极强；
第四、本公开在共渗包覆前还经喷丸工艺处理，增加金属工件的比表面积，提高金属元素的渗透和涂层的附着性，从而对表面涂层强度和防腐蚀性能进一步加强。
可以理解的是，以上实施方式仅仅是为了说明本公开的原理而采用的示例性实施方式，然而本公开并不局限于此。对于本领域内的普通技术人员而言，在不脱离本公开的精神和实质的情况下，可以做出各种变型和改进，这些变型和改进也视为本公开的保护范围。

Claims (10)

  1. 一种铬镍共渗涂层的制备方法，其特征在于，所述制备方法包括：
    对金属工件进行表面预处理；
    对预处理后的金属工件进行喷丸处理；
    将铬镍共渗料浆一次涂覆在喷丸处理后的金属工件表面，经烘干固化处理与烧结处理，在金属工件表面得到铬镍共渗涂层；其中，
    所述铬镍共渗料浆包括固相组分和液相组分；所述固相组分包括铬粉、镍粉、氧化铝以及氧化铬，所述液相组分包括Al(H2PO4)3、水玻璃、碘化铵、氧化铬以及氧化镁。
  2. 根据权利要求1所述的制备方法，其特征在于，所述固相组分与所述液相组分的固液比为10:(1-5)。
  3. 根据权利要求1所述的制备方法，其特征在于，按照质量百分比计，所述固相组分包括：
    50-80％的铬粉；
    1-10％的镍粉；
    10-20％的氧化铝；
    0-20％的氧化铬；
    以上各固相组分的质量百分比之和为100％。
  4. 根据权利要求3所述的制备方法，其特征在于，所述铬粉、所述镍粉、所述氧化铝以及所述氧化铬在转速为350-400r/min的条件下，球磨6-24h，得到固相组分。
  5. 根据权利要求1所述的制备方法，其特征在于，按照质量百分比计，所述液相组分包括：
    10-30％的Al(H2PO4)3；
    15-25％的水玻璃；
    5-10％的碘化铵；
    10-40％氧化铬；
    15-35％的氧化镁；
    以上各液相组分的质量百分比之和为100％。
  6. 根据权利要求1至5任一项所述的制备方法，其特征在于，在金属工件表面涂覆的铬镍共渗料浆的涂覆厚度为0.1～1.0mm。
  7. 根据权利要求1至5任一项所述的制备方法，其特征在于，在喷丸处理中，喷丸颗粒直径为0.1-1.0mm，喷丸压力为0.5-2.0MPa，喷丸时间为10-30min。
  8. 根据权利要求1至5任一项所述的制备方法，其特征在于，对涂覆有铬镍共渗料浆的金属工件经烘干固化处理与烧结处理，包括：
    将涂覆有铬镍共渗料浆的金属工件在60～85℃下预烘干5～30min，然后在100～160℃下烘干30～60min，最后在250～300℃下中温固化20～60min；
    将烘干固化后的金属工件在500-650℃下烧结处理5～30min。
  9. 一种铬镍共渗涂层，其特征在于，所述铬镍共渗涂层采用权利要求1至8任一项所述的制备方法制得。
  10. 一种铬镍共渗涂层的应用，其特征在于，采用权利要求9所述的铬镍共渗涂层应用在碳钢、奥氏体钢或高温合金的金属工件表面。
PCT/CN2024/114771 2024-07-19 2024-08-27 一种铬镍共渗涂层及其制备方法、应用 Pending WO2026016263A1 (zh)

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