CN112626454B - Composite coating with three-dimensional layered structure with self-diffusion characteristic and preparation method thereof - Google Patents

Composite coating with three-dimensional layered structure with self-diffusion characteristic and preparation method thereof Download PDF

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CN112626454B
CN112626454B CN202011486110.5A CN202011486110A CN112626454B CN 112626454 B CN112626454 B CN 112626454B CN 202011486110 A CN202011486110 A CN 202011486110A CN 112626454 B CN112626454 B CN 112626454B
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composite coating
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CN112626454A (en
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崔秀芳
刘昌昊
金国
苏文男
杨雨云
关亚杰
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Harbin Engineering University
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • C23C14/081Oxides of aluminium, magnesium or beryllium
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0688Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58After-treatment
    • C23C14/5846Reactive treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58After-treatment
    • C23C14/5846Reactive treatment
    • C23C14/586Nitriding
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C8/00Solid 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

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  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
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Abstract

The invention discloses a composite coating with a self-diffusion characteristic and a preparation method thereof, belongs to the technical field of surface engineering, and aims to solve the problem that a shell part is easy to crack under the action of airflow and wake flow in the service process. The composite coating with the self-diffusion characteristic and the three-dimensional layered structure is characterized in that an inner layer and an outer layer are sequentially deposited on the surface of a substrate, the inner layer is a porous hard layer and a tough layer which are alternately deposited by high-energy beams, wherein the porous hard layer takes metal oxide or ceramic as a main phase and is doped with a pore-forming agent; wherein the toughness layer takes metal oxide or ceramic as a main phase and is doped with low-melting-point metal or organic compound; the outer layer is obtained by adopting a laser nitriding or carbonizing process. The alternating structure of the porous hard layer and the toughness layer of the inner layer in the composite coating can increase the deflection orientation of cracks, relieve the stress impact effect of external load and increase the service time from the initiation of microcracks to the appearance of macrocracks.

Description

Composite coating with three-dimensional layered structure with self-diffusion characteristic and preparation method thereof
Technical Field
The invention belongs to the technical field of surface engineering, and particularly relates to a composite coating with a laminated structure and a preparation method thereof.
Background
When parts such as automobile shells, spacecrafts and the like are subjected to airflow and wake flow in the service process, certain pressure is generated on the parts, the parts can generate cracks when the service time is too long or the pressure is suddenly increased, and the parts can fail along with the expansion of the cracks.
The surface coating technology is one of important means for protecting components, and the hard particles generated on the surface are better combined than the particles added outside, so that the component can be better protected. For example, the hard nitride can be formed on the surface of the component by adopting a laser nitriding process, and the hard nitride has stronger hardness and abrasion resistance.
Disclosure of Invention
The invention aims to provide a composite coating with a three-dimensional layered structure and a preparation method thereof, which has a self-diffusion characteristic and aims to solve the problem that the service life of cracks is low easily caused by the action of airflow and wake flow during the service process of a shell part.
The composite coating with the self-diffusion characteristic and the three-dimensional layered structure is obtained by sequentially depositing an inner layer and an outer layer on the surface of a substrate, wherein the inner layer is a porous hard layer and a tough layer which are alternately deposited, the porous hard layer takes metal oxide or ceramic as a main phase and is doped with a pore-forming agent by adopting a high-energy beam deposition process; wherein the toughness layer is obtained by using a high-energy beam deposition process by taking metal oxide or ceramic as a main phase and doping low-melting-point metal or organic matter;
the outer layer is obtained by adopting a laser nitriding or carburizing process.
The preparation method of the composite coating with the self-diffusion characteristic and the three-dimensional layered structure is realized according to the following steps:
1. depositing a porous hard layer on the surface of the substrate by adopting high-energy beams, wherein the porous hard layer takes metal oxide or ceramic as a main phase and is doped with a pore-forming agent to obtain the substrate with the porous hard layer;
2. depositing a toughness layer on the surface of the substrate with the porous hard layer by adopting high-energy beams, wherein the toughness layer takes metal oxide or ceramic as a main phase and is doped with low-melting-point metal or organic matter to obtain the substrate with the hard layer-toughness layer;
3. sequentially repeating the high-energy beam deposition process of the first step and the second step;
4. carrying out heat treatment on the substrate with the inner layer at 800-1500 ℃ to obtain the substrate with the inner layer;
5. and processing the substrate with the inner layer by adopting a laser nitriding or carburizing process to obtain the composite coating with the self-diffusion characteristic and the three-dimensional layered structure.
The composite coating with the three-dimensional layered structure and the self-diffusion characteristic provided by the invention has the advantages that the deflection orientation of cracks can be increased by the alternating structure of the porous hard layer and the toughness layer of the inner layer, the stress impact effect of external load is relieved, and the service time from the initiation of microcracks to the appearance of macrocracks is prolonged. The protective coating can be cooperated with the protective action of the enhanced surface of the outer layer to realize toughness and toughness integration, and the problem that the toughness and the strength are incompatible is solved. The preparation method of the coating is reliable in process, can realize integrated rapid and accurate manufacturing of the coating structure, is high in efficiency, and can ensure that the coating structure and the size are stable and controllable. The compression-resistant component with the coating prepared on the surface can meet the service requirement.
The composite coating with the three-dimensional laminated structure with the self-diffusion characteristic can be prepared on the surface of a pressure-resistant part, such as the surface of an automobile shell and the surface of a spacecraft fuselage.
The composite coating with the three-dimensional layered structure and the self-diffusion characteristic provided by the invention has the advantages that the inner layer has the porous continuous layered structure, the porous continuous layered structure uses the 'brick-mud structure' of the shell as a reference, the hard phase is used as the 'brick', the tough phase is used as mud, the self-diffusion capability of the structure is enhanced, the toughness is better, the outer layer has the reinforced phase, and the strength and the hardness are better. The two materials cooperate to overcome the difficulty that the toughness of the coating cannot be compatible, the toughness is integrated, the coating and the matrix are metallurgically combined, and the comprehensive corrosion-resistant protection capability is obviously improved.
Drawings
FIG. 1 is a schematic view of the overall structure of a three-dimensional layered composite coating with self-diffusion characteristics according to the present invention;
FIG. 2 is a sectional electron microscope image of the composite coating with a three-dimensional layered structure having a self-diffusion characteristic obtained in the example.
Detailed Description
The first specific implementation way is as follows: the composite coating with the self-diffusion characteristic and the three-dimensional layered structure is obtained by sequentially depositing an inner layer and an outer layer on the surface of a substrate, wherein the inner layer is a porous hard layer and a tough layer which are alternately deposited, the porous hard layer is prepared by taking metal oxide or ceramic as a main phase and doping pore-forming agent, and a high-energy beam deposition process is adopted; wherein the toughness layer is obtained by doping low-melting-point metal or organic compound with metal oxide or ceramic as a main phase and adopting a high-energy beam deposition process;
the outer layer is obtained by adopting a laser nitriding or carburizing process.
In this embodiment, the hard layer and the tough layer are composed of a main phase and a doped phase (auxiliary phase), and the content of the raw material of the auxiliary phase is 0.5 to 5wt% of the main phase. The main phase is used for adjusting the matching degree of the toughness layer and the hard layer, and the auxiliary phase is mainly used for regulating the melting point of the toughness layer and increasing the toughness of the toughness layer. When the content of the auxiliary phase exceeds 5wt%, the melting point of the toughness phase layer and the matching degree of the toughness phase layer and the hard phase layer can be influenced by too much auxiliary phase, the toughness and the melting point required by the toughness layer can not be reached by too little auxiliary phase, the matching degree and the melting point can not be influenced within the range of 0.5-5wt%, and a better effect is achieved.
The outer layer includes a nitride or carbide self-forming reinforcing phase. The raw materials of the toughness phase and the hard phase are powder with the grain diameter of 50-150 mu m, and the powder has good fluidity and higher deposition quality in the grain diameter range.
The hard layer in the composite coating with the self-diffusion characteristic and the three-dimensional layered structure contains artificial through holes, and the existence of the holes mainly provides a bonding space for a toughness phase and provides deflection orientation of cracks; furthermore, the volume proportion of the holes is 30-50%, and the proportion in the range is proper, so that the hardness of the hard layer is not lower or the matching degree of the hard layer and the toughness layer is not reduced.
The second embodiment is as follows: the present embodiment is different from the first embodiment in that the metal oxide is Al 2 O 3 The ceramic is SiC.
The third concrete implementation mode: the present embodiment is different from the first or second embodiment in that the low-melting-point metal is Al, and the organic compound is graphene.
The fourth concrete implementation mode: this embodiment differs from one of the first to third embodiments in that the inner layer has 4 to 8 layers in total.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is that the ratio of the thickness of the inner layer to the thickness of the outer layer is 2:0.5 to 1.
Under the condition that the thickness of the inner layer and the thickness of the outer layer are in the range, the bionic layered coating can have better strength and toughness.
The sixth specific implementation mode: this embodiment is different from the first to the fifth embodiments in that the pore-forming agent is ammonium bicarbonate or urea.
The seventh embodiment: the preparation method of the composite coating with the three-dimensional layered structure and the self-diffusion characteristic is implemented according to the following steps:
1. depositing a porous hard layer on the surface of the substrate by adopting high-energy beams, wherein the porous hard layer takes metal oxide or ceramic as a main phase and is doped with a pore-forming agent to obtain the substrate with the porous hard layer;
2. depositing a toughness layer on the surface of the substrate with the porous hard layer by adopting high-energy beams, wherein the toughness layer takes metal oxide or ceramic as a main phase and is doped with low-melting-point metal or organic matter to obtain the substrate with the hard layer-toughness layer;
3. sequentially repeating the high-energy beam deposition process of the first step and the second step;
4. carrying out heat treatment on the substrate with the inner layer at 800-1500 ℃ to obtain the substrate with the inner layer;
5. and processing the substrate with the inner layer by adopting a laser nitriding or carburizing process to obtain the composite coating with the self-diffusion characteristic and the three-dimensional layered structure.
The preparation method of the composite coating with the self-diffusion characteristic and the three-dimensional layered structure is reliable in process, high in coating preparation precision and stable in performance.
The specific implementation mode eight: the difference between this embodiment and the seventh embodiment is that the process conditions of the high energy beam deposition in the first step and the second step are as follows:
controlling the laser power to be 800-1200W, the scanning speed to be 8-15mm/s, the powder feeding amount to be 3-5g/min, and the protective gas to be inert gas.
The deposition power and the scanning speed directly influence the input energy, the influence on the inner layer forming quality and the tissue formation is large, the inner layer defects obtained by adopting the process parameters after the orthogonal experiment optimization are few, the forming quality is high, and the forming tissue is favorable for ensuring the performance of the inner layer.
In the embodiment, the oxygen content is controlled not to exceed 100ppm, and the horizontal offset of the lance head is 1-2mm.
The specific implementation method nine: the seventh or eighth embodiment is different from the seventh or eighth embodiment in that the time of the heat treatment in the fourth step is 1.5 to 2.5 hours.
The specific implementation mode is ten: the difference between this embodiment and one of the seventh to ninth embodiments is that the process conditions of the laser nitridation in the step five are as follows:
the laser power is controlled to be 1000-1500W, the diameter of a light spot is 2mm, the scanning speed is 10mm/s, and the environment is a nitrogen (nitrogen) filled environment.
The concrete implementation mode eleven: the seventh embodiment is different from the seventh embodiment in that the carburizing process in the fifth embodiment is carburizing for 0.5 to 2.5 hours at a temperature of 500 to 600 ℃.
The detailed implementation mode is twelve: this embodiment differs from one of the seventh to eleventh embodiments in that the thickness of the composite coating layer having a three-dimensional layered structure with a self-diffusion characteristic is 6 to 12mm.
The first embodiment is as follows: the preparation method of the composite coating with the three-dimensional layered structure with the self-diffusion characteristic is implemented according to the following steps:
1. ultrasonic cleaning titanium alloy plate substrate with acetone, depositing porous hard layer on the surface of the substrate with high energy beam, wherein the porous hard layer is metal oxide Al 2 O 3 The main phase is doped with pore-forming agent (5 wt% ammonium bicarbonate) to obtain a matrix with a porous hard layer, and the volume of the artificial pores accounts for about 40%;
2. depositing a toughness layer on the surface of a substrate with a porous hard layer by using a high-energy beam, wherein the toughness layer is Al 2 O 3 Spherical powder is used as a main phase and is doped with 1wt% of low-melting-point pure metal Al nano powderUniformly mixing the powder by using a planetary ball mill and then drying to obtain a matrix with a hard layer-toughness layer;
3. sequentially repeating the high-energy beam deposition process of the first step and the second step, and co-depositing three hard layers and three tough layers;
4. carrying out heat treatment on the substrate with the inner layer at 1000 ℃ for 2h, so that the pure metal part of the toughness layer is melted into the artificial holes of the hard layer and well combined, the toughness of the inner layer is improved as much as possible, and the deflection orientation of cracks is increased, thereby obtaining the substrate with the inner layer;
5. the method comprises the following steps of treating a substrate with an inner layer by adopting a laser nitriding process, wherein the process conditions are as follows: the power is 1200W, the diameter of a light spot is 2mm, the scanning speed is 12mm/s, and the environment is a nitrogen-filled environment, so that the composite coating with the self-diffusion characteristic and the three-dimensional layered structure is obtained.
The composite coating with the three-dimensional layered structure and the self-diffusion characteristic prepared in the embodiment has the overall thickness of 9.0mm, the inner layer and the outer layer of the composite coating are respectively 6.0mm and 3.0mm, wherein the inner layer is composed of reinforcing layers and toughness layers in an alternating mode, six layers are counted, and each layer is 1.0mm.
Metal oxide Al of the present example 2 O 3 The particle size of the starting material was about 90 μm.
In the first step of this embodiment, the laser deposition conditions are as follows: argon is adopted in a laser deposition equipment bin for protection, the oxygen content in the bin is controlled to be 80ppm, the substrate is preheated at 350 ℃ before laser deposition, the laser power is 1000W, the scanning speed is 10mm/s, and the powder feeding amount is 4.0g/min;
the laser deposition conditions in the second step are as follows: the laser power was 800W, the scanning speed was 9mm/s, and the powder feed amount was 4.0g/min.
The structural member prepared in the embodiment is subjected to tissue characterization and performance test, the test standard refers to GB/T6383-009 and GB/T4340-2009, and the result shows that: the microhardness of the high-pressure structure coating reaches 720HV, and under the application of continuous pressure, the service life of the part protected by the coating is prolonged by 40%, and the tensile strength is improved by 30%.
Comparative example one: the difference between the first embodiment and the second embodiment is that the high energy beam deposition process of the first step and the second step is sequentially repeated in the third embodiment, and five hard layers and five tough layers are co-deposited.
Comparative example two: the difference between this example and the first example is that the particle size of the metal oxide powder used was 20 μm.
Comparative example three: the difference between this example and the first example is that the metal oxide powder having a particle size of 200 μm was used.
Comparative example four: the difference between the present embodiment and the first embodiment is that the ductile layer is Al 2 O 3 The spherical powder is a main phase and is doped with 5wt% of low-melting-point pure metal Al nano powder.
Comparative example five: the difference between this embodiment and the first embodiment is that the proportion of the artificial pores in the hard layer is increased to 70%.
The biomimetic layered coatings obtained from comparative examples one-fifth were subjected to tissue characterization and performance testing according to the test criteria in example 1, and the results are shown. In the first comparative example, the number of the layers of the coating is too large, so that the alternate deposition effect of the tough phase layer and the hard phase layer is poor, the bonding performance is poor, the internal deflection of cracks cannot be realized, and the compressive capacity is poor. In the second comparative example, the powder of the coating is too fine, the powder is agglomerated, so that the deposition effect is very poor, a large number of defects such as cavities and cracks exist in the coating, and the test performance of the final coating is lower than that of a common component. In the third comparative example, the coating has extremely poor laser deposition effect due to the fact that the powder is too coarse, a large amount of unfused powder exists, and then a large amount of defects such as cavities and cracks appear in the coating, and the test performance of the final coating is lower than that of a common component. In the fourth comparative example, excessive doping of the auxiliary phase Al reduces the matching degree of the tough phase layer and the hard phase layer, and affects the formation of the hard phase in the forming process, so that the distribution is not uniform, stress concentration is easily generated, and the test performance of the coating is poor. In the fifth comparative example, the voids account for too much, which results in too loose structure, and although the combination effect of the tough layer and the hard layer is better, the compressive property of the inner layer is too poor, which further results in poor test performance of the coating.
To sum up, the laminated structure of inlayer can alleviate the stress impact effect of external load in the bionical lamellar coating that this application provided, increases crackle extension orientation, increases the consumption of percussion power, and the high hard reinforced surface layer in surface can promote shock-resistant and wear-resisting antifriction performance simultaneously, is favorable to making this bionical lamellar coating break away from the tough incompatible difficult problem of current coating, realizes that the coating is tough integrative. After the bionic layered coating is metallurgically combined with the substrate, the wear-resistant comprehensive protection capability can be obviously improved. The preparation method of the bionic layered coating is reliable in process, can realize integrated rapid and accurate manufacturing of the coating structure, is high in efficiency, and can ensure that the coating structure and the size are stable and controllable. The flow passage component with the surface provided with the coating with the layered structure can meet the protection requirements of airflow scouring, long-time low-pressure service, high-pressure impact and the like.

Claims (8)

1. The composite coating with the three-dimensional layered structure with the self-diffusion characteristic is characterized in that an inner layer and an outer layer are sequentially deposited on the surface of a substrate, the inner layer is a porous hard layer and a tough layer which are alternately deposited, the number of the inner layers is 4-8, the porous hard layer takes metal oxide or ceramic as a main phase and is doped with a pore-forming agent, and the composite coating is obtained by adopting a high-energy beam deposition process; wherein the toughness layer takes metal oxide or ceramic as a main phase and is doped with low-melting-point metal, the low-melting-point metal is Al, the low-melting-point metal is obtained by adopting a high-energy beam deposition process, then the substrate with the inner layer is subjected to heat treatment at 800-1500 ℃, and the raw materials of the porous hard layer and the toughness layer are powder with the particle size of 50-150 mu m;
the outer layer is obtained by adopting a laser nitriding or carburizing process.
2. The composite coating layer having a three-dimensional layered structure with self-diffusion characteristic according to claim 1, wherein the metal oxide is Al 2 O 3 The ceramic is SiC.
3. The composite coating of claim 1, characterized by a thickness ratio of the inner layer to the outer layer of 2:0.5 to 1.
4. The composite coating with the three-dimensional layered structure having the self-diffusion characteristic of claim 1, wherein the pore-forming agent is ammonium bicarbonate or urea.
5. The method for preparing a composite coating having a three-dimensional layered structure with self-diffusion characteristics as claimed in claim 1, wherein the preparation method is carried out according to the following steps:
1. depositing a porous hard layer on the surface of the substrate by adopting high-energy beams, wherein the porous hard layer takes metal oxide or ceramic as a main phase and is doped with a pore-forming agent to obtain the substrate with the porous hard layer;
2. depositing a toughness layer on the surface of the substrate with the porous hard layer by adopting high-energy beams, wherein the toughness layer takes metal oxide or ceramic as a main phase and is doped with low-melting-point metal to obtain the substrate with the hard layer-toughness layer;
3. sequentially repeating the high-energy beam deposition process of the first step and the second step;
4. carrying out heat treatment on the substrate with the inner layer at 800-1500 ℃ to obtain the substrate with the inner layer;
5. processing the substrate with the inner layer by adopting a laser nitriding or carburizing process to obtain a composite coating with a three-dimensional layered structure with self-diffusion characteristics;
wherein the low-melting-point metal in the second step is Al; the inner layer has 4-8 layers.
6. The method for preparing a composite coating with a three-dimensional layered structure having a self-diffusion characteristic as claimed in claim 5, wherein the process conditions of the high energy beam deposition in the first and second steps are as follows:
the laser power is controlled to be 800-1200W, the scanning speed is 8-15mm/s, the powder feeding amount is 3-5g/min, and the protective gas is inert gas.
7. The method for preparing a composite coating with a three-dimensional layered structure having a self-diffusion characteristic according to claim 5, wherein the process conditions of the laser nitridation in the step five are as follows:
the laser power is controlled to be 1000-1500W, the diameter of a light spot is 2mm, the scanning speed is 10mm/s, and the environment is a nitrogen-filled environment.
8. The method for preparing a three-dimensional layered structure composite coating with self-diffusion characteristics as claimed in claim 5, wherein the carburizing process in the fifth step is to carburize 0.5-2.5h at a temperature of 500-600 ℃.
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