CN112962047A - Method for preparing Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on surface of titanium or titanium alloy - Google Patents

Method for preparing Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on surface of titanium or titanium alloy Download PDF

Info

Publication number
CN112962047A
CN112962047A CN202110262984.0A CN202110262984A CN112962047A CN 112962047 A CN112962047 A CN 112962047A CN 202110262984 A CN202110262984 A CN 202110262984A CN 112962047 A CN112962047 A CN 112962047A
Authority
CN
China
Prior art keywords
titanium
titanium alloy
tial
phase
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110262984.0A
Other languages
Chinese (zh)
Other versions
CN112962047B (en
Inventor
李发国
张家霖
王子涵
齐福刚
谢颖
胡孝愿
尹付成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiangtan University
Original Assignee
Xiangtan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiangtan University filed Critical Xiangtan University
Priority to CN202110262984.0A priority Critical patent/CN112962047B/en
Publication of CN112962047A publication Critical patent/CN112962047A/en
Application granted granted Critical
Publication of CN112962047B publication Critical patent/CN112962047B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/30—Fluxes or coverings on molten baths
    • 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
    • C23C8/06—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 gases
    • C23C8/08—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 gases only one element being applied
    • C23C8/20—Carburising

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention discloses a method for preparing a Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on the surface of titanium or titanium alloy. The method comprises the following steps: firstly, degreasing, cleaning and plating assisting on the surface of titanium or titanium alloy; secondly, forming a Ti-Al system intermediate phase layer and a pure aluminum layer on the surface of the titanium or the titanium alloy by adopting a hot dip aluminum plating technology; thirdly, immersing the hot dipped titanium or titanium alloy into NaOH hot solution to dissolve the pure aluminum layer and expose TiAl3An intermediate phase layer; fourthly, TiAl is exposed3The titanium or titanium alloy of the intermediate phase layer is carburized without hydrogen to finally form Ti-Al systemThe interphase/Ti-Al-C series MAX phase composite coating. The invention adopts a gradual coating method of hot dip aluminum plating and then hydrogen-free carburization to ensure that TiAl with excellent high-temperature oxidation resistance is preferentially formed3Intermediate phase layer, then using TiAl3Reaction with activated carbon atoms in TiAl3the/C interface forms a Ti-Al-C MAX phase layer which is wear-resistant, high-temperature oxidation-resistant and corrosion-resistant. The method is suitable for preparing the Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on the titanium or titanium alloy workpiece with a complex structure, the coating is tightly combined with the substrate, and the preparation method is simple, convenient, low in cost and easy to realize.

Description

Method for preparing Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on surface of titanium or titanium alloy
Technical Field
The invention relates to the technical field of titanium or titanium alloy surface treatment, in particular to a method for preparing a Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on the surface of titanium or titanium alloy.
Background
Titanium and its alloy have light weight, specific strength is big, heat resistance is strong, corrosion-resistant etc. excellent comprehensive properties, are known as "future metal", are a kind of novel structural material with development prospect. Titanium alloys have been widely used in various departments of the national economy. It is an indispensable material in rockets, missiles and space shuttles. Nowadays, the method is also widely applied to various industrial departments such as ships, chemical industry, power generation and the like.
The titanium alloy has the advantages of high strength, high hardness, small density, good corrosion resistance and heat resistance, and the like. The high-temperature titanium alloy is widely applied to advanced aircraft engines at present, the dosage of the high-temperature titanium alloy accounts for 25% -40% of the total weight of the engine, and although titanium and the titanium alloy have many excellent properties and are widely applied in various fields, the titanium and the titanium alloy also have some defects. The general disadvantages of titanium and titanium alloys are low surface hardness (the hardness of pure titanium is about 150-200HV, and titanium alloys usually do not exceed 350 HV), large friction coefficient, and poor wear resistance. Titanium alloys present a "thermal barrier" temperature at 600 ℃. That is, when the service temperature of the titanium alloy is higher than 600 ℃, the high temperature oxidation resistance of the titanium alloy is sharply reduced, which is one of the important reasons for limiting the development of the titanium alloy. In order to improve the high temperature oxidation resistance of titanium alloy, various methods are adopted to modify the surface of the titanium alloy, and an aluminum-plated coating is initially formed on the surface of the titanium alloy, so that compact TiAl is expected to be obtained3Phase layer, TiAl3Is one relative volume of all Ti-Al series intermediate compoundsThe titanium-aluminum compound of the Ti-Al-C series MAX phase coating can be easily obtained by carburization.
The MAX phase is a novel ternary layered compound composed of M, A and X, and its chemical formula is expressed as MN+1AXN(wherein, M is an early transition metal, A is a group A element, X is carbon or nitrogen, N =1, 2, 3 …), and has the excellent performances of metal materials (excellent electric and thermal conductivity, machinability, thermal shock resistance and the like) and ceramic materials (high modulus, high temperature resistance, oxidation resistance, corrosion resistance and the like). The MAX phase material is a novel machinable ceramic material, and has the characteristics of self-lubrication and high toughness due to the unique nano-layered crystal structure.
Ti2AlC and Ti3AlC2Is the most typical compound in MAX phase, and combines the properties of metal and ceramic: not only has high conductivity and high fracture toughness of metal, but also has high strength and excellent high temperature oxidation resistance of ceramic, and simultaneously has good processability, so that Ti2AlC and Ti3AlC2Has very wide application prospect. The special material is applied to titanium and titanium alloy, so that the damage of coating cracking and the like can be greatly reduced, and the high-temperature corrosion resistance and wear resistance of the coating can be improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on the surface of titanium or titanium alloy aiming at the defects of the prior art. The method adopts a step-by-step coating method of hot dip aluminum plating and hydrogen-free carburization to ensure that TiAl with excellent high-temperature oxidation resistance is preferentially formed3Intermediate phase layer, then proceeding non-hydrogen carburization to utilize TiAl3Reaction with activated carbon atoms in TiAl3the/C interface forms a Ti-Al-C MAX phase layer which is wear-resistant, high-temperature oxidation-resistant and corrosion-resistant. The method is suitable for preparing the Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on the titanium or titanium alloy workpiece with a complex structure, and solves the problem of unmatched performance between the coating and the substrate. The coating has good thermal stability, high compactness and excellent resistanceHigh-temperature oxidation performance, and the method also has the advantages of easy realization, low cost and the like.
Another object of the present invention is to provide a method for preparing a Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating layer without hydrogen carburization after hot dip aluminizing of titanium or a titanium alloy, the method comprising the steps of:
step one, adopting a metal cleaning agent to remove oil on the surface of titanium or titanium alloy and then soaking the titanium or titanium alloy into saturated K heated in a water bath kettle at the temperature of 92 DEG C2ZrF6Taking out the plating assistant agent for 2 minutes, and putting the plating assistant agent in a drying oven for drying;
step two, immersing the titanium or the titanium alloy covered with the plating assistant agent on the surface in the step one into pure aluminum liquid protected by covering agent KCl, NaCl, NaF =4:3:1 (molar ratio), preserving the heat for a certain time, and then rapidly extracting for water quenching;
step three, immersing the titanium or the titanium alloy subjected to the hot dipping in the step two into 10wt.% NaOH hot solution heated in water bath at the temperature of 75 ℃, dissolving the pure aluminum layer, and exposing TiAl3An intermediate phase layer;
step four, exposing TiAl in step three3Placing the titanium or titanium alloy of the intermediate phase layer in a hydrogen-free carburizing furnace for hydrogen-free carburizing treatment, and setting TiAl on the surface3the/C reaction generates a Ti-Al-C series MAX phase layer, and finally a Ti-Al series intermediate phase/Ti-Al-C series MAX phase composite coating is formed.
A process for preparing the Ti-Al system intermediate phase/Ti-Al-C MAX system composite coating without hydrogen carburization after hot dip aluminizing of Ti or Ti alloy includes hot dip aluminizing on Ti alloy to form compact TiAl on its surface3Intermediate phase layer, then proceeding non-hydrogen carburization to utilize TiAl3Reacting with activated carbon atoms to TiAl3the/C interface forms a Ti-Al-C MAX phase layer which is wear-resistant, high-temperature oxidation-resistant and corrosion-resistant. The preparation scheme of the Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating which is subjected to non-hydrogen carburization after the titanium or titanium alloy is subjected to hot dip aluminum plating combines the advantages of a hot dip plating method and the advantages of a non-hydrogen carburization method, and TiAl is controlled to be generated by controlling the hot dip plating temperature and the hot dip plating time3The thickness of the phase and the thickness of the Ti-Al compound intermediate phase layer, thereby forming a layer of compact TiAl on the surface of the titanium alloy3Phase, active carbon atoms are infiltrated into TiAl by using hydrogen-free carburization technology3The intermediate phase generates diffusion reaction to form a dense Ti-Al-C series MAX phase layer on the outermost layer of the titanium or titanium alloy coating, thereby forming the Ti-Al series intermediate phase/Ti-Al-C series MAX phase composite coating. The high-temperature oxidation resistance of the coating can be greatly improved, the coating has good thermal stability, simple preparation process and low cost, and the service temperature and the service life of a high-temperature titanium alloy workpiece can be greatly improved.
The method can also control the aluminum concentration gradient and the thickness of the Ti-Al compound phase layer in the titanium-aluminum alloy liquid by controlling the hot dip plating temperature and the hot dip plating time according to the actual use requirement. The thickness and physical properties of the synthetic MAX phase layer can also be controlled by controlling the time and temperature of the hydrogen-free carburization. Therefore, the Ti-Al-C series MAX phase layer formed by the non-hydrogen carburization after the hot dip aluminum plating has controllability.
The method for preparing the Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on the surface of the titanium or the titanium alloy is characterized in that the TiAl in the step two3The thickness of the phase layer is 50-150 microns. The thickness range can ensure that the activated carbon atoms can be fully infiltrated into TiAl in the subsequent carburization treatment3The phase layer has diffusion reaction with the TiAl to meet the requirement of carburizing TiAl3The requirement of raw materials. The Ti-Al-C MAX phase layer with uniform components is guaranteed to be formed, the performance of the Ti-Al-C MAX phase coating is favorably exerted, and the waste of raw materials is avoided.
The method for preparing the Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on the surface of the titanium or the titanium alloy is characterized in that the hot dip aluminum plating temperature in the step two is 700-800 ℃, and the hot dip plating time is 10-30 minutes. The temperature range can ensure that a target product TiAl is generated after immersion plating3Meanwhile, the problem of uneven Al distribution caused by rapid infiltration of aluminum due to overhigh temperature is avoided. The hot dip coating time range can control TiAl3The thickness of the phase layer is 50-150 microns3And (4) phase layer.
The method for preparing the Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on the surface of the titanium or the titanium alloy is characterized in that the thickness of the Ti-Al-C system MAX phase layer in the fourth step is 10-30 microns.
The method for preparing the Ti-Al series intermediate phase/Ti-Al-C series MAX phase composite coating on the surface of the titanium or the titanium alloy is characterized in that the hydrogen-free carburizing temperature in the fourth step is 800-900 ℃, and the hydrogen-free carburizing time is 2-4 hours. The carburization temperature ensures the integrity of the matrix, prevents the temperature exceeding the phase change point from damaging the original structure of the matrix, seriously reduces the mechanical property of the material, and simultaneously can ensure that the carburized layer can obtain higher hardness. The carburizing time avoids the phenomenon that the burning loss of the surface layer of the material is serious due to overlong carburizing time, and the condition that the carbon atoms are not fully infiltrated and the MAX phase layer is not generated due to insufficient carburizing time can not occur. The carburizing time ensures the full generation of the Ti-Al-C MAX phase coating.
Compared with the patent of CN201811455613.9 patent of preparation method of Ti-Al-C series MAX phase coating on the surface of titanium or titanium alloy, the Ti-Al series intermediate phase/Ti-Al-C series MAX phase composite coating and the preparation method thereof have the following advantages:
1. the invention firstly carries out hot-dip coating of an aluminum layer on titanium or titanium alloy, and TiAl is generated firstly after the titanium and the aluminum fully react3Intermediate phase, then for the exposed TiAl3The intermediate phase layer is carburized, and the bonding degree between the Ti-Al-C series MAX phase layer and the titanium or titanium alloy substrate is improved by adopting a method for gradually preparing the coating, so that the excellent performance of the Ti-Al-C series MAX phase layer is ensured. The phenomena of cracking, falling off and the like of the coating when in use are prevented. Meanwhile, the method of firstly dipping and then carburizing greatly reduces the cost of raw materials, and is closer to industrial production application in economic applicability.
2. The invention is realized by the TiAl3The control of the layer thickness ensures that the active carbon atoms fully infiltrate into TiAl3The full diffusion reaction occurs in the layer, the uniformity of each component in the Ti-Al-C MAX phase coating is further improved, the performance of the Ti-Al-C MAX phase coating is ensured, and the waste of raw materials and energy consumption is avoided.
3. The method is simple and easy to realize, and can be effectively popularized and applied to the fields with high requirements on the comprehensive properties of wear resistance, corrosion resistance, high-temperature hot corrosion resistance and the like of titanium or titanium alloy.
4. The technical method is suitable for preparing the Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on the titanium or titanium alloy workpiece with the complex structure, and solves the problem of limitation of inapplicability of the complex workpiece.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic view of the technical principle of the method for preparing the Ti-Al system intermediate phase/Ti-Al-C system MAX phase coating on the surface of titanium or titanium alloy.
Detailed Description
The Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating phase structure of the non-hydrogen carburization after the hot dip aluminizing of the titanium alloy can be variously designed according to the actual use requirement, and the generated titanium-aluminum alloy intermediate phase TiAl is controlled by controlling the hot dip aluminizing temperature and the hot dip aluminizing time3The thickness of the layer. The Ti-Al-C series MAX coating phase and the thickness thereof can also be controlled by controlling the carburizing temperature and the carburizing time. Thus, the passage is in TiAl3The Ti-Al-C series MAX phase coating generated by the non-hydrogen carburization on the phase layer has good controllability.
Example 1
As shown in fig. 1, the preparation method of this example includes the following steps:
step one, adopting a metal cleaning agent to remove oil on the surface of a TC4 titanium alloy round bar and cleaning the surface, and then soaking the round bar into saturated K heated by a water bath kettle at the temperature of 92 DEG C2ZrF6Taking out the plating assistant agent for 2 minutes, and putting the plating assistant agent in a drying oven for drying;
and step two, immersing the TC4 titanium alloy round bar covered with the plating assistant agent on the surface in the step one into pure aluminum liquid protected by covering agent KCl, NaCl, NaF =4, 3 and 1 (molar ratio), controlling the hot dipping temperature to be 700 ℃, preserving the heat for 10 minutes, and rapidly extracting out water quenching. Formation of TiAl as required above3The thickness of the phase layer was 50 microns;
step three, immersing the TC4 titanium alloy round bar subjected to hot dipping in the step two into 10wt.% NaOH hot solution heated in water bath at the temperature of 75 ℃, dissolving out the pure aluminum layer, and exposingTiAl production3An intermediate phase layer;
step four, exposing TiAl in step three3Placing the TC4 titanium alloy round bar of the intermediate phase layer in a hydrogen-free carburizing furnace for hydrogen-free carburizing treatment, wherein the surface TiAl3the/C reaction generates a Ti-Al-C series MAX phase layer to finally form TiAl3the/Ti-Al-C series MAX phase composite coating. The temperature of the carburizing diffusion reaction is 800 ℃, and the time is 2 h.
Example 2
As shown in fig. 1, the preparation method of this example includes the following steps:
step one, adopting a metal cleaning agent to remove oil on the surface of a TC4 titanium alloy round bar and cleaning the surface, and then soaking the round bar into saturated K heated by a water bath kettle at the temperature of 92 DEG C2ZrF6Taking out the plating assistant agent for 2 minutes, and putting the plating assistant agent in a drying oven for drying;
and step two, immersing the TC4 titanium alloy round bar covered with the plating assistant agent on the surface in the step one into pure aluminum liquid protected by covering agent KCl, NaCl, NaF =4, 3 and 1 (molar ratio), controlling the hot dipping temperature to be 750 ℃, preserving the heat for 20 minutes, and rapidly extracting water quenching. Formation of TiAl as required above3The thickness of the phase layer was 100 microns;
step three, immersing the TC4 titanium alloy round bar subjected to hot dipping in the step two into 10wt.% NaOH hot solution heated in water bath at the temperature of 75 ℃, dissolving the pure aluminum layer, and exposing TiAl3An intermediate phase layer;
step four, exposing TiAl in step three3Placing the TC4 titanium alloy round bar of the intermediate phase layer in a hydrogen-free carburizing furnace for hydrogen-free carburizing treatment, wherein the surface TiAl3the/C reaction generates a Ti-Al-C series MAX phase layer to finally form TiAl2/TiAl3the/Ti-Al-C series MAX phase composite coating. The temperature of the carburizing diffusion reaction is 850 ℃, and the time is 3 h.
Example 3
As shown in fig. 1, the preparation method of this example includes the following steps:
step one, adopting a metal cleaning agent to remove oil on the surface of a TC4 titanium alloy round bar and cleaning the surface, and then soaking the round bar into saturated K heated by a water bath kettle at the temperature of 92 DEG C2ZrF6Taking out the plating assistant agent for 2 minutes, and putting the plating assistant agent in a drying oven for drying;
step two, the step oneImmersing the TC4 titanium alloy round bar with the middle surface covered with the plating assistant agent into pure aluminum liquid protected by the covering agent KCl, NaCl, NaF =4, 3 and 1 (molar ratio), controlling the hot dipping temperature to be 800 ℃, preserving the heat for 30 minutes, and rapidly extracting for water quenching. Formation of TiAl as required above3The thickness of the phase layer was 150 microns;
step three, immersing the TC4 titanium alloy round bar subjected to hot dipping in the step two into 10wt.% NaOH hot solution heated in water bath at the temperature of 75 ℃, dissolving the pure aluminum layer, and exposing TiAl3An intermediate phase layer;
step four, exposing TiAl in step three3Placing the TC4 titanium alloy round bar of the intermediate phase layer in a hydrogen-free carburizing furnace for hydrogen-free carburizing treatment, wherein the surface TiAl3the/C reaction generates a Ti-Al-C series MAX phase layer to finally form TiAl/TiAl2/TiAl3the/Ti-Al-C series MAX phase composite coating. The temperature of the carburizing diffusion reaction is 900 ℃, and the time is 4 h.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (5)

1. A method for preparing a Ti-Al-C series MAX phase coating on the surface of titanium or titanium alloy is characterized by comprising the following steps: the method comprises the following steps:
step one, adopting a metal cleaning agent to remove oil on the surface of titanium or titanium alloy and then soaking the titanium or titanium alloy into saturated K heated in a water bath kettle at the temperature of 92 DEG C2ZrF6Taking out the plating assistant agent for 2 minutes, and putting the plating assistant agent in a drying oven for drying;
step two, immersing the titanium or the titanium alloy covered with the plating assistant agent on the surface in the step one into pure aluminum liquid protected by covering agent KCl, NaCl, NaF =4:3:1 (molar ratio), preserving the heat for a certain time, and then rapidly extracting for water quenching;
step three, immersing the titanium or the titanium alloy subjected to the hot dipping in the step two into 10wt.% NaOH hot solution heated in water bath at the temperature of 75 ℃, dissolving the pure aluminum layer, and exposing TiAl3An intermediate phase layer;
step four, exposing TiAl in step three3Intermediate (II)Titanium or titanium alloy of the phase layer is placed in a hydrogen-free carburizing furnace for hydrogen-free carburizing treatment, and the surface TiAl3the/C reaction generates a Ti-Al-C series MAX phase layer, and finally a Ti-Al series intermediate phase/Ti-Al-C series MAX phase composite coating is formed.
2. The method for preparing Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on the surface of titanium or titanium alloy according to claim 1, wherein the TiAl in the second step3The thickness of the phase layer is 50-150 microns.
3. The method for preparing the Ti-Al series intermediate phase/Ti-Al-C series MAX phase composite coating on the surface of the titanium or the titanium alloy according to claim 1, wherein the hot dip aluminum plating temperature in the second step is 700-800 ℃, and the hot dip plating time is 10-30 minutes.
4. The method for preparing the Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on the surface of the titanium or the titanium alloy according to the claim 1, wherein the thickness of the Ti-Al-C system MAX phase in the fourth step is 10-30 μm.
5. The method for preparing the Ti-Al series intermediate phase/Ti-Al-C series MAX phase composite coating on the surface of the titanium or the titanium alloy according to the claim 1, wherein the temperature of the hydrogen-free carburization in the fourth step is 800-900 ℃, and the time of the hydrogen-free carburization is 2-4 hours.
CN202110262984.0A 2021-03-11 2021-03-11 Method for preparing Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on surface of titanium or titanium alloy Active CN112962047B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110262984.0A CN112962047B (en) 2021-03-11 2021-03-11 Method for preparing Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on surface of titanium or titanium alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110262984.0A CN112962047B (en) 2021-03-11 2021-03-11 Method for preparing Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on surface of titanium or titanium alloy

Publications (2)

Publication Number Publication Date
CN112962047A true CN112962047A (en) 2021-06-15
CN112962047B CN112962047B (en) 2023-03-14

Family

ID=76277208

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110262984.0A Active CN112962047B (en) 2021-03-11 2021-03-11 Method for preparing Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on surface of titanium or titanium alloy

Country Status (1)

Country Link
CN (1) CN112962047B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114259600A (en) * 2021-12-29 2022-04-01 广东省科学院新材料研究所 Material with Zn-Cu-Ti alloy coating and preparation method and application thereof
CN114790547A (en) * 2022-04-28 2022-07-26 湘潭大学 TiAl generated on surface of titanium alloy 3 Dispersed Al 4 C 3 Reinforced Al 2 O 3 Composite coating of layers and method for producing the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4957421A (en) * 1983-10-03 1990-09-18 Alloy Surfaces Company, Inc. Metal treatment
WO1991007242A1 (en) * 1989-11-08 1991-05-30 Alloy Surfaces Company, Inc. Treatment of metals for coating or activation
CN102409282A (en) * 2011-11-15 2012-04-11 中南大学 Low-temperature surface carburization method for titanium-aluminum-based intermetallic compound material
CN109306445A (en) * 2018-11-30 2019-02-05 西北有色金属研究院 The preparation method of titanium or titanium alloy surface Ti-Al-C system MAX phase coating
CN109913796A (en) * 2019-03-29 2019-06-21 长安大学 TiAlN composite coating on surface of titanium alloy and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4957421A (en) * 1983-10-03 1990-09-18 Alloy Surfaces Company, Inc. Metal treatment
WO1991007242A1 (en) * 1989-11-08 1991-05-30 Alloy Surfaces Company, Inc. Treatment of metals for coating or activation
CN102409282A (en) * 2011-11-15 2012-04-11 中南大学 Low-temperature surface carburization method for titanium-aluminum-based intermetallic compound material
CN109306445A (en) * 2018-11-30 2019-02-05 西北有色金属研究院 The preparation method of titanium or titanium alloy surface Ti-Al-C system MAX phase coating
CN109913796A (en) * 2019-03-29 2019-06-21 长安大学 TiAlN composite coating on surface of titanium alloy and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114259600A (en) * 2021-12-29 2022-04-01 广东省科学院新材料研究所 Material with Zn-Cu-Ti alloy coating and preparation method and application thereof
CN114790547A (en) * 2022-04-28 2022-07-26 湘潭大学 TiAl generated on surface of titanium alloy 3 Dispersed Al 4 C 3 Reinforced Al 2 O 3 Composite coating of layers and method for producing the same
CN114790547B (en) * 2022-04-28 2023-10-10 湘潭大学 TiAl is generated on the surface of titanium alloy 3 Dispersion Al 4 C 3 Enhanced Al 2 O 3 Composite coating of layers and method for producing same

Also Published As

Publication number Publication date
CN112962047B (en) 2023-03-14

Similar Documents

Publication Publication Date Title
JP6576832B2 (en) Method for producing a chromium coating on a metal substrate and coated article
JP4762077B2 (en) Hardening method of steel member, hardened steel member and hardened surface protective agent
CN112962047B (en) Method for preparing Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on surface of titanium or titanium alloy
JP7082944B2 (en) Chrome-based coatings, how to produce chrome-based coatings and coated objects
JP2017508879A (en) Method for producing chromium coating and coated object
CN103320745B (en) Aluminized steel and preparation method thereof
CN109306445B (en) Preparation method of Ti-Al-C series MAX phase coating on surface of titanium or titanium alloy
CN101643902A (en) Preparation method of iridium-aluminum high temperature oxidation resistance coating
Yener et al. Wear and oxidation performances of low temperature aluminized IN600
US8065898B2 (en) Method and article for improved adhesion of fatigue-prone components
Hu et al. Thermal shock behaviour and failure mechanism of two-kind Cr coatings on non-planar structure
CN102154617A (en) Cold rolled low-carbon steel surface silicon infiltration alloying method
CN113322464B (en) Method for preparing Ti-Al system intermediate phase/Ti-Al-N system MAX phase composite coating on titanium or titanium alloy surface
CN1255579C (en) Method for in situ growing high-hardness wear resistant ceramic coating layer on titanium alloy surface
CN115491625B (en) Hot-dip Ti-Al-Si coating with surface pre-oxidized and modified titanium and titanium alloy and preparation method thereof
Li et al. Oxidation behavior of niobium aluminide intermetallics protected by aluminide and silicide diffusion coatings
CN108754410B (en) Preparation method of gradient coating for reinforcing surface of blanking die
RU2212473C1 (en) Method for depositing of coatings on alloys
JPH08319557A (en) Method for modifying surface of steel utilizing diffusing dilution of aluminum
CN109735796B (en) Carburizing method for inhibiting net carbide structure of high-chromium and high-cobalt carburizing steel and improving carburizing speed
CN114686800A (en) Method for preparing Ti-Al-Si composite gradient coating on titanium alloy surface by two-step hot-dip aluminizing method
CN116145069A (en) Method for preparing Ti-Al intermediate phase layer/pure aluminum carburized layer composite coating on surface of titanium or titanium alloy
JP4392087B2 (en) Surface treatment method of die casting mold and die
JP5258928B2 (en) Hardening method of steel member, hardened steel member and hardened surface protective agent
JP2012201893A (en) Corrosion-resistant material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant