CN113621937B - Method for preparing ceramic multilayer film on metal surface by chemical heat treatment - Google Patents
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Abstract
The invention discloses a method for preparing a ceramic multilayer film on a metal surface by utilizing chemical heat treatment. Firstly, preparing a metal/metal multilayer film with carbide or nitride forming capacity on the surface of a metal matrix needing surface strengthening by using a physical vapor deposition method; then carrying out high-temperature heat treatment on the sample to promote interdiffusion among metal element layers; finally, the sample is carburized or nitrided, and the metal/metal multilayer film is converted into a carbide/carbide nitride/nitride multilayer film as carbon or nitrogen diffuses inward and reacts with the metal. Finally, a ceramic/ceramic multilayer film is formed on the surface of the substrate. Compared with the prior art, the method can promote the mutual diffusion of metal elements at the interlayer interface, form a high-strength interlayer interface with metallurgical bonding and a film-substrate interface, and remarkably improve the comprehensive mechanical property of the film.
Description
Technical Field
The invention belongs to the technical field of metal material surface treatment methods, and particularly relates to a method for preparing a ceramic multilayer film on a metal surface by utilizing chemical heat treatment.
Background
The increasing range of applications for transition metal materials has placed ever increasing demands on their surface strength, hardness and wear resistance. For example, for tungsten-based alloy used for friction stir welding, the improvement of the strength, hardness and wear resistance of the surface of the tungsten-based alloy can not only prolong the service life of equipment parts, but also be beneficial to improving the welding quality. The preparation of ceramic/ceramic multilayer films on the surface of transition metals is one of effective means for improving the surface strength, hardness and wear resistance of the transition metals, namely, two ceramic layers are alternately prepared on the surface of the transition metals, and the strength, hardness and wear resistance are improved by utilizing the high hardness of the two ceramic phases and the layered arrangement of the ceramic layers.
At present, the preparation method of the ceramic/ceramic multilayer film mainly comprises physical vapor deposition and chemical vapor deposition. Physical vapor deposition uses two targets (such as a Ti target and a Cr target) to work alternately to generate deposition particles, and the deposition particles react with the atmosphere to alternately generate ceramic layers (such as TiN layers and CrN layers) corresponding to the two targets on the surface. Chemical vapor deposition is carried out by alternately introducing different gases to react and form a ceramic layer on the metal surface.
However, with the above two methods, since the deposition material is supplied by turns, the phase transition, element diffusion, metallurgical bonding, large interface residual stress, and low interlayer bonding strength exist at the interlayer interface of the ceramic/ceramic multilayer film prepared by vapor deposition. Meanwhile, a sharp interface formed by a ceramic phase and a metal phase exists between the multilayer film and the substrate, the difference of the crystallographic properties of the phases is large, and the bonding strength of the film-substrate interface is low. Therefore, in the using process, the whole surface film layer is easy to fall off under the action of external force. It is seen that the further improvement of the mechanical properties of the ceramic/ceramic multilayer film is restricted by the problem that the film-substrate interface and the interlayer interface are lack of metallurgical bonding.
Disclosure of Invention
The invention provides a method for preparing a ceramic multilayer film on a metal surface by utilizing chemical heat treatment, solves the problems that the interlayer interface and the film-base interface of the existing ceramic/ceramic multilayer film lack element mutual diffusion and are difficult to realize metallurgical bonding, obviously improves the interface bonding strength of the multilayer film, and further improves the comprehensive mechanical property of the multilayer film.
The invention relates to a method for preparing a ceramic multilayer film on a metal surface by utilizing chemical heat treatment, which specifically comprises the following steps:
step 1: pretreating the surface of a metal matrix needing surface strengthening, and preparing a metal/metal multilayer film with carbide or nitride forming capacity by using a physical vapor deposition method;
and 2, step: carrying out high-temperature heat treatment on the sample obtained in the step 1;
and step 3: and (3) carrying out chemical heat treatment on the sample obtained in the step (2) to convert the metal layer and the surface layer of the matrix deposited in the step (1) into a carbide layer or a nitride layer, thereby obtaining the ceramic/ceramic multilayer film.
The invention is also characterized in that:
the chemical heat treatment comprises nitriding treatment and carburizing treatment; in the carburizing process, the carburizing depth is required to exceed the total thickness of the metal/metal multilayer film prepared in the step 1, so that the interface of the ceramic layer/metal layer is positioned on the surface layer of the metal matrix;
the temperature of the carburizing treatment or the nitriding treatment needs to be higher than 900 ℃ and lower than the melting points of the metal/metal multilayer film and the metal matrix; the carburizing treatment or nitriding treatment time depends on the carburizing temperature and the thickness of the multilayer film, and the thickness of the ceramic layer should be finally made larger than that of the metal/metal multilayer film deposited in step 1, i.e. the film-substrate interface is located within the surface of the metal substrate.
The physical vapor deposition method includes any physical vapor deposition method that can deposit a metal having carbide-forming ability, such as vacuum evaporation, sputtering, ion plating, and the like. The metal matrix needing surface strengthening in the step 1 comprises pure metal formed by one element of Ti, Zr, Nb, Ta, Mo, W and Cr or alloy taking the pure metal as a main chemical component.
The metal with carbide forming ability in the step 1 comprises pure metal formed by one element of Ti, Zr, V, Nb, Ta, Mo, W, Cr and Hf or alloy with the pure metal as a main chemical component; the metal with nitride forming ability is pure metal formed by any one element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W or alloy with the pure metal as the main chemical component.
The surface pretreatment in the step 1 is to grind and polish by using sand paper, and then respectively clean by using acetone, alcohol and ultrasonic waves to remove surface pollutants, reduce the surface roughness and ensure the quality of a deposited film.
The metal/metal multilayer film described in step 1 is a multilayer film formed of two different metals, one of which may be the same as the metal base material, the number of layers of the metal/metal multilayer film being in the range of 2 to 30 layers, and the total thickness being in the range of 5 to 30 μm.
The purpose of the heat treatment in the step 2 is to promote the mutual diffusion of metal elements at the interface between the metal/metal multilayer film layers; the heat treatment temperature range is 900-2000 ℃, the heat treatment time is 0.5-48h, and the sample after heat treatment is cooled to room temperature along with the furnace.
The carburizing treatment in the step 3 comprises solid carburizing, gas carburizing and interstitial atom carburizing; the nitriding treatment can be selected from solid nitriding, gas nitriding and ion nitriding; the oxidation can be prevented by vacuumizing or introducing inert gas during the carburizing or nitriding process.
The carburizing method selects interstitial atom carburizing, and comprises the following specific steps:
firstly, selecting high carbon steel or cast iron with carbon content ranging from 1.0 to 4.0wt.% as a solid carbon source; grinding and polishing one surface of the solid carbon source; then, a solid carbon source is placed on the metal substrate of which the multilayer film is prepared, the surface of the multilayer film is contacted with the polished surface of the solid carbon source, the multilayer film is placed in a hot pressing furnace, then the pressure which is vertical to the surface of the multilayer film is applied to 2-30MPa, the multilayer film is heated to 900-fold-temperature 1150 ℃ in a vacuum or inert gas environment, and then the multilayer film is insulated, and finally the multilayer film is cooled to room temperature.
The invention has the beneficial effects that:
(1) the invention firstly prepares the metal/metal multilayer film, and promotes the mutual diffusion of elements between metal layers by utilizing high-temperature heat treatment, so that the metallurgical bonding of the interlayer interfaces is realized, and the bonding strength and the comprehensive mechanical property of the multilayer film interface are obviously improved.
(2) The invention modifies the metal/metal multilayer film into the ceramic/ceramic multilayer film through carburizing treatment or nitriding treatment, so that the ceramic phase is precipitated in situ. In the process, no pores are generated, and the grain boundary binding force is high. And the ceramic phase has larger interface roughness when being separated out in the interdiffusion area of the interlayer interface, even forming a two-phase mixing area. Compared with the method of directly preparing the ceramic/ceramic multilayer film by adopting a physical vapor deposition method, the method solves the problem of low interlayer interface bonding strength caused by phase mutation and component mutation.
(3) The invention requires that the infiltrated layer exceeds the thickness of the metal/metal multilayer film, namely the ceramic layer grows inwards to the surface layer of the metal matrix. The film-substrate interface (ceramic/metal interface) is within the metal substrate surface layer and not the original surface of the metal substrate. Therefore, the film-based interface is not affected by the physical vapor deposition process and the degree of interdiffusion of the interlayer elements. The interface of the film base is composed of base metal and carbide or nitride ceramics thereof, and the bonding strength of the interface of the film base is high.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a ceramic multilayer film on a metal surface by chemical heat treatment.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to the following embodiments.
The method for preparing the ceramic multilayer film on the metal surface by using the chemical heat treatment is shown in figure 1, wherein M represents a base metal, and M1 and M2 represent two metals deposited in the step 1. MC, M 1 C、M 2 C is metal M, M 1 And M 2 Carbide of (2), MN, M 1 N、 M 2 N is metal M, M 1 And M 2 Of (2) is preferably a nitride of (2).
The method specifically comprises the following steps:
step 1: pretreating the surface of a metal matrix needing surface strengthening, and preparing a metal/metal multilayer film with carbide or nitride forming capacity by using a physical vapor deposition method;
step 1.1: aiming at the metal which has the capability of forming the carbide (nitride) and needs surface strengthening, the surface of the metal is ground and polished by abrasive paper, and then is respectively cleaned by acetone, alcohol and ultrasonic waves so as to ensure the quality of the deposited film;
preferably, the metal requiring surface strengthening comprises a pure metal formed by one element of Ti, Zr, Nb, Ta, Mo, W and Cr or an alloy (such as Ti6Al4V, 93W-Ni and the like) taking the pure metal as a main chemical component;
step 1.2: and depositing two metal layers alternately on the substrate by utilizing physical vapor deposition coating and controlling process parameters to form the metal/metal multilayer film. The metal which can be deposited comprises pure metal formed by one element of Ti, Zr, V, Nb, Ta, Mo, W, Cr and Hf or alloy taking the pure metal as main chemical composition.
Preferably, the physical vapor deposition adopts magnetron sputtering and cathode arc ion plating.
Step 2: and (3) carrying out high-temperature heat treatment on the sample with the prepared multilayer film, wherein the heat treatment temperature range is 900-2000 ℃, and cooling the sample to room temperature along with the furnace after the heat treatment.
Preferably, the heat treatment time is 0.5 to 48 hours.
And 3, step 3: subjecting it to a carburizing or nitriding treatment, modifying the metal/metal multilayer film into a carbide (or nitride)/carbide (or nitride) multilayer film as carbon (or nitrogen) atoms diffuse inward and react with the metal to form carbide (or nitride). The carburizing or carburizing temperature should be above 900 degrees celsius and below the melting point of the multilayer film metal and metal matrix. Carburizing treatment or nitriding treatment the carburizing treatment or nitriding treatment time depends on the carburizing temperature and the thickness of the multilayer film, and the thickness of the ceramic layer should be finally made larger than that of the metal/metal multilayer film deposited in step 1, i.e. the film-substrate interface is positioned within the surface of the metal substrate. And (3) cooling the carburized or nitrided material to room temperature along with a furnace.
Preferably, the carburizing method selects solid carburizing and gas carburizing, and the nitriding method selects solid nitriding and gas nitriding. The temperature range of the carburizing treatment or nitriding treatment is 1000 ℃ to 2000 ℃.
More preferably, the carburizing method is interstitial carburizing. Firstly, high carbon steel or cast iron with carbon content ranging from 1.0 to 4.0wt.% is selected as the solid carbon source. One surface of the solid carbon source is ground and polished. Then, the solid carbon source is placed on the metal substrate on which the multilayer film is prepared, the surface of the multilayer film is contacted with the polished surface of the solid carbon source, the multilayer film is placed in a hot pressing furnace, then the pressure which is vertical to the surface of the multilayer film is applied to be 2-30MPa, the multilayer film is heated to a certain temperature of 900-1150 ℃ in a vacuum or inert gas environment such as argon, and then the multilayer film is insulated, and finally the multilayer film is cooled to room temperature.
Example 1:
this example includes the following steps:
step 1: the surface of a metal tungsten (W) matrix needing surface strengthening is pretreated, and a multilayer film containing niobium (Nb)/tantalum (Ta) is prepared by a magnetron sputtering method.
Step 1.1: a metal tungsten (W) plate having a purity of 99.9 wt.% was prepared, subjected to surface treatment, ground and polished with sandpaper, and then washed with acetone and alcohol, respectively, in ultrasonic waves.
Step 1.2: and (3) alternately depositing niobium (Nb) and tantalum (Ta) metal layers on the metal tungsten substrate by using a magnetron sputtering method to form a Nb/Ta multilayer film with 30 layers in total and a total thickness of 30 microns.
Step 2: and (3) carrying out high-temperature heat treatment on the sample with the prepared multilayer film, wherein the heat treatment temperature is 2000 ℃, the heat treatment heat preservation time is 0.5 hour, and the sample after heat treatment is cooled to room temperature along with the furnace.
And step 3: the sample was carburized by solid carburization, and the sample was buried in a carburizing agent (90 wt% carbon black powder and 10 wt% sodium carbonate powder) and placed in a carburizing pot and argon gas was introduced, and then the carburizing pot was sealed and placed in a high-temperature heat treatment furnace. With the temperature rise, carbon atoms diffuse inwards and react with the metal tantalum and niobium to form an NbC layer, a TaC layer and the Nb/Ta multilayer film is modified into a TaC/NbC multilayer film. The carburizing temperature was 2000 ℃. The carburizing time depends on the carburizing temperature and the thickness of the multilayer film, and finally the thickness of the carburized layer is 35 microns (which is 30 microns larger than that of the Ta/Nb multilayer film), namely, the film-substrate interface is positioned in the surface of the metal tungsten substrate to form a WC/W film-substrate interface. And cooling the carburized sample to room temperature along with the furnace.
The multilayer film obtained by the method has the following specific characteristics: 1) each ceramic layer is compact and non-porous; 2) the volume fraction of carbide is high (80-95%); 3) the surface hardness can reach 2500 HV; 4) The interlayer interface bonding force of the multilayer film is more than 50N; 5) the bonding force between the multilayer film and the metal matrix is more than 100N; 6) greatly improves the surface wear resistance of the tungsten matrix (which is improved by more than 50 times compared with the wear resistance of the matrix).
Example 2:
this example includes the following steps:
step 1: the surface of a titanium alloy (Ti6Al4V) plate which needs surface strengthening is pretreated, and a tungsten (W)/tantalum (Ta) multilayer film is prepared by utilizing a cathode arc ion plating method.
Step 1.1: a titanium alloy (Ti6Al4V) plate is prepared, the surface of the titanium alloy plate is treated, ground and polished by sand paper, and then cleaned by ultrasonic waves respectively by acetone and alcohol.
Step 1.2: tungsten (W) and tantalum (Ta) metal layers are alternately deposited on the titanium alloy substrate by using a cathodic arc ion plating method to form a W/Ta multilayer film with 2 layers in total and 5 microns of total thickness.
Step 2: and (3) carrying out high-temperature heat treatment on the sample with the prepared multilayer film, wherein the heat treatment temperature is 900 ℃, the heat treatment heat preservation time is 48 hours, and the sample after heat treatment is cooled to room temperature along with the furnace.
And step 3: the alloy is carburized by interstitial atom carburization. First, cast iron having a carbon content of 4.0wt.% was selected as the solid carbon source. One surface of the solid carbon source is ground and polished. Then, cast iron is placed on the titanium alloy with the W/Ta multilayer film, the surface of the multilayer film is in contact with the polished surface of the cast iron, the cast iron is placed in a hot pressing furnace, pressure (30MPa) perpendicular to the surface of the multilayer film is applied, the temperature is kept after the cast iron is heated to 900 ℃ in an argon environment, the tungsten layer and the tantalum layer are converted into carbide ceramic layers, and a titanium carbide/titanium alloy film-base interface is formed on the surface layer of the titanium alloy. The sample was then cooled to room temperature.
The multilayer film obtained by the above method has the following specific characteristics: 1) each ceramic layer is compact and non-porous; 2) high carbide volume fraction (about 100%); 3) the surface hardness can reach 1800 HV; 4) The interlayer interface bonding force of the multilayer film is more than 40N; 5) the bonding force between the multilayer film and the metal matrix is more than 100N; 6) the surface wear resistance of the Ti6Al4V metal matrix is greatly improved (the wear resistance is improved by more than 30 times compared with that of the matrix).
Example 3:
this example includes the following steps:
step 1: the surface of a metal molybdenum (Mo) matrix needing surface strengthening is pretreated, and a molybdenum (Mo)/zirconium (Zr) multilayer film is prepared by utilizing a cathode arc ion plating method.
Step 1.1: preparing a molybdenum (Mo) plate, performing surface treatment on the molybdenum plate, grinding and polishing the molybdenum plate by using sand paper, and then respectively cleaning the molybdenum plate by using acetone and alcohol in ultrasonic waves.
Step 1.2: molybdenum (Mo) and zirconium (Zr) metal layers were alternately deposited on a molybdenum substrate by means of cathodic arc ion plating to form a Mo/Zr multilayer film having 15 layers in total and a total thickness of 15 μm.
Step 2: and (3) carrying out high-temperature heat treatment on the sample with the prepared multilayer film, wherein the heat treatment temperature is 1500 ℃, the heat treatment heat preservation time is 24 hours, and the sample after heat treatment is cooled to room temperature along with the furnace.
And step 3: the alloy is carburized by interstitial atom carburization. First, a high carbon steel having a carbon content of 1.0 wt.% was selected as a solid carbon source. And grinding and polishing one surface of the high-carbon steel. Then, high-carbon steel is placed on a molybdenum substrate of which the Mo/Zr multilayer film is prepared, the surface of the multilayer film is contacted with the polished surface of the high-carbon steel, the high-carbon steel is placed in a hot pressing furnace, then pressure (2MPa) vertical to the surface of the multilayer film is applied, the multilayer film is heated to 1150 ℃ in an argon environment and then is insulated, and the molybdenum layer and the zirconium layer are respectively converted into Mo 2 C and ZrC ceramic layers, and Mo is formed on the surface layer of the molybdenum substrate 2 C/Mo film-based interface. The sample was then cooled to room temperature.
The multilayer film obtained by the above method has the following specific characteristics: 1) each ceramic layer is compact and non-porous; 2) the volume fraction of carbide is close to 100%; 3) the surface hardness can reach 2400 HV; 4) the interlayer interface bonding force of the multilayer film is more than 40N; 5) the bonding force between the multilayer film and the metal substrate is more than 120N; 6) greatly improves the surface wear resistance of the molybdenum metal matrix (the wear resistance of the molybdenum metal matrix is improved by more than 60 times).
Example 4:
this example includes the following steps:
step 1: the surface of a metal tantalum (Ta) substrate needing surface strengthening is pretreated, and a titanium (Ti)/vanadium (V) multilayer film is prepared by utilizing a magnetron sputtering ion plating method.
Step 1.1: a tantalum (Ta) plate was prepared with a purity of 99.9 wt.%, and the tantalum plate was surface-treated, ground and polished with sandpaper, and then washed with acetone and alcohol, respectively, in ultrasonic waves.
Step 1.2: and (3) alternately depositing titanium (Ti) and vanadium (V) metal layers on the metal tungsten substrate by using a magnetron sputtering ion plating method to form a Ti/V multilayer film with 20 layers in total and the total thickness of 10 microns.
Step 2: and (3) carrying out high-temperature heat treatment on the sample with the prepared multilayer film, wherein the heat treatment temperature is 1200 ℃, the heat treatment heat preservation time is 12 hours, and the sample after heat treatment is cooled to room temperature along with the furnace.
And step 3: carburizing the carbon steel by adopting gas carburization, introducing methane gas into a carburizing furnace, and setting the carburizing temperature to be 1000 ℃. Carburizing makes the Ti/V multilayer film transform into TiC/VC ceramic multilayer film, and finally makes the carburized layer thickness 12 microns (greater than the thickness of the multilayer film (10 microns)), namely the film-substrate interface is located in the metal tantalum substrate surface, forms TaC/Ta film-substrate interface. And cooling the carburized sample to room temperature along with the furnace.
The multilayer film obtained by the above method has the following specific characteristics: 1) each ceramic layer is compact and non-porous; 2) the volume fraction of carbide is high (85-95%); 3) the surface hardness can reach 2300 HV; 4) The interlayer interface bonding force of the multilayer film is more than 60N; 5) the bonding force between the multilayer film and the metal substrate is more than 120N; 6) greatly improves the surface wear resistance of the tantalum metal matrix (which is improved by more than 60 times compared with the wear resistance of the matrix).
Example 5:
this example includes the following steps:
step 1: the surface of a metal zirconium (Zr) matrix needing surface strengthening is pretreated, and a titanium (Ti)/molybdenum (Mo) multilayer film is prepared by utilizing a magnetron sputtering ion plating method.
Step 1.1: a zirconium (Zr) plate having a purity of 99.9 wt.% was prepared, surface-treated, ground and polished with sand paper, and then washed with acetone and alcohol, respectively, in ultrasonic waves.
Step 1.2: titanium (Ti) and molybdenum (Mo) metal layers are alternately deposited on a metal tungsten substrate by a magnetron sputtering ion plating method to form a Ti/Mo multilayer film with 10 layers in total and the total thickness of 20 microns.
And 3, step 3: and (3) carrying out high-temperature heat treatment on the sample with the prepared multilayer film, wherein the heat treatment temperature is 1800 ℃, the heat treatment heat preservation time is 15 hours, and the sample after heat treatment is cooled to room temperature along with the furnace.
And 4, step 4: and nitriding the steel by adopting gas nitriding, introducing ammonia gas into a nitriding furnace, and setting the nitriding temperature to be 1100 ℃. Nitriding converts the Ti/Mo multilayer film into a TiN/MoN ceramic multilayer film, and finally makes the thickness of the nitriding layer be 24 micrometers (larger than the thickness (20 micrometers) of the multilayer film), namely, the film-substrate interface is positioned in the surface of the metal Zr matrix, so that the ZrN/Zr film-substrate interface is formed. And cooling the carburized sample to room temperature along with the furnace.
The multilayer film obtained by the method has the following specific characteristics: 1) each ceramic layer is compact and non-porous; 2) high nitride volume fraction (80% -100%); 3) the surface hardness can reach 2400 HV; 4) The interlayer interface bonding force of the multilayer film is more than 70N; 5) the bonding force between the multilayer film and the metal substrate is more than 130N; 6) greatly improves the surface wear resistance of the zirconium metal matrix (which is improved by more than 50 times compared with the wear resistance of the matrix).
Claims (5)
1. The method for preparing the ceramic multilayer film on the metal surface by utilizing the chemical heat treatment is characterized by comprising the following steps:
step 1: pretreating the surface of a metal matrix needing surface strengthening, and preparing a metal/metal multilayer film with carbide or nitride forming capacity by using a physical vapor deposition method;
step 2: carrying out high-temperature heat treatment on the sample obtained in the step 1;
and 3, step 3: carrying out chemical heat treatment on the sample obtained in the step 2 to convert the metal layer and the surface layer of the matrix deposited in the step 1 into a carbide layer or a nitride layer so as to obtain a ceramic/ceramic multilayer film;
the chemical heat treatment comprises nitriding treatment and carburizing treatment; in the carburizing process, the carburizing depth is required to exceed the total thickness of the metal/metal multilayer film prepared in the step 1, so that the interface of the ceramic layer/metal layer is positioned on the surface layer of the metal matrix;
the temperature of the carburizing treatment or the nitriding treatment needs to be higher than 900 ℃ and lower than the melting points of the metal/metal multilayer film and the metal matrix; the carburizing treatment or nitriding treatment time depends on the carburizing temperature or nitriding temperature and the thickness of the multilayer film, and the thickness of the ceramic layer should be made larger than that of the metal/metal multilayer film deposited in step 1;
the metal with carbide forming capability in the step 1 comprises pure metal formed by one element of Ti, Zr, V, Nb, Ta, Mo, W, Cr and Hf or alloy taking the pure metal as a main chemical component; the metal with nitride forming ability is pure metal formed by any one element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W or alloy with the pure metal as the main chemical component;
the metal/metal multilayer film in the step 1 is a multilayer film formed by two different metals, the number of layers of the metal/metal multilayer film ranges from 2 to 30, and the total thickness ranges from 5 to 30 micrometers;
the purpose of the heat treatment in the step 2 is to promote the mutual diffusion of metal elements at the interface between the metal/metal multilayer film layers; the heat treatment temperature range is 900-2000 ℃, the heat treatment time is 0.5-48h, and the sample after heat treatment is cooled to room temperature along with the furnace.
2. The method of claim 1, wherein the metal matrix to be surface strengthened in step 1 comprises a pure metal or an alloy containing one of Ti, Zr, Nb, Ta, Mo, W and Cr as its main chemical component.
3. The method of claim 1, wherein the surface pretreatment in step 1 is grinding and polishing with sand paper, and then washing with acetone, alcohol and ultrasonic wave respectively to remove surface contaminants and reduce surface roughness, thereby ensuring the quality of the deposited film.
4. The method for preparing a ceramic multilayer film on a metal surface by using chemical heat treatment according to claim 1, wherein the carburizing treatment in step 3 comprises solid carburizing, gas carburizing, and interstitial atom carburizing; the nitriding treatment is selected from solid nitriding, gas nitriding and ion nitriding; and during the carburizing or nitriding process, the oxidation is prevented by vacuumizing or introducing inert gas.
5. The method for preparing the ceramic multilayer film on the metal surface by utilizing the chemical heat treatment as claimed in claim 1, wherein the carburizing method is selected from interstitial atom carburizing, and the interstitial atom carburizing method comprises the following specific steps:
firstly, selecting high carbon steel or cast iron with carbon content ranging from 1.0 to 4.0wt.% as a solid carbon source; grinding and polishing one surface of the solid carbon source; then, a solid carbon source is placed on the metal substrate with the multilayer film prepared, the surface of the multilayer film is contacted with the polished surface of the solid carbon source, the solid carbon source is placed in a hot pressing furnace, then the pressure which is perpendicular to the surface of the multilayer film is applied to be 2-30MPa, the multilayer film is heated to 900-1150 ℃ in a vacuum or inert gas environment, then the temperature is kept, and finally the multilayer film is cooled to room temperature.
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| 镁合金表面闭合场磁控溅射离子镀与渗氮复合改性研究;张丹利;《中国优秀硕士学位论文全文数据库（电子期刊）》;20120515(第5期);第B022-192页 * |
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