Ceramic fe-ni alloy double-biomimetic multilayer film structure and preparation method thereof

Abstract

The application discloses a preparation method of a ceramic iron-nickel alloy double-biomimetic multilayer film. The preparation steps comprise the following steps: carrying out carburizing treatment on carbon steel; etching a honeycomb framework on the surface after the carburizing treatment; alternately depositing a metal layer with carburide forming capability, a nickel layer, a metal layer with carburide forming capability and an iron layer along the side wall and the bottom surface of the honeycomb framework as a period of a three-dimensional multilayer film, until the three-dimensional multilayer film is flush with the surface of the substrate; and carrying out heat treatment to make carbon, iron and nickel elements diffuse. Finally, the surface structure is composed of the honeycomb structure framework and the annual ring structure ceramic / iron-nickel alloy multilayer film. The multilayer film has a periodic structure and a gradient ceramic grain size, the interlayer interface is irregular and zigzag and has metallurgical bonding. The ceramic / iron-nickel alloy double-biomimetic structure gradient multilayer film prepared by the application significantly improves the strength and toughness of the film layer and the interfacial bonding force, and further improves the comprehensive performance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of metal material surface treatment, and relates to a ceramic iron-nickel alloy double-bionic multilayer film and a preparation method thereof. BACKGROUND

[0002] With the rapid development of science and technology, the requirements for the surface strength, hardness and wear resistance of carbon steel are increasing, and the preparation of ceramic / metal multilayer film on the surface of carbon steel is an effective way to improve the surface strength, and the ceramic / metal multilayer film is a composite material composed of hard ceramic phase and ductile metal phase. The combination of the two different crystal structures and slip systems of ceramic and metal can effectively hinder the movement of dislocations, thereby improving the strength of the film. In addition, the metal layer with good plasticity is alternately inserted into the ceramic layer, and the metal layer can effectively hinder the crack propagation, thereby improving the fracture toughness of the film. At present, domestic and foreign researchers further optimize the mechanical properties by adjusting the modulation period and modulation ratio of the multilayer film, which can improve the hardness and toughness to a certain extent. However, due to the structure characteristics of the multilayer film, there are few adjustable parameters and strengthening and toughening mechanisms, and the improvement of the strength and toughness of the ceramic / metal multilayer film has encountered a new bottleneck.

[0003] Physical vapor deposition (PVD) is the main technology for preparing ceramic / metal multilayer film, which has the advantages of no pollution, low deposition temperature, fast film formation speed, accurate control of film layer parameters, good process stability and the like. However, the ceramic / metal multilayer film prepared by the PVD technology lacks obvious element interdiffusion at the interface between the ceramic layer and the metal layer and at the film base interface, which makes it difficult to realize metallurgical bonding at the interface, thereby resulting in low interface bonding strength and restricting the further improvement of the comprehensive mechanical properties of the surface.

[0004] In summary, from the perspective of structural regulation of the ceramic / metal multilayer film, there are only modulation period and modulation ratio as adjustable structural parameters, and there are few adjustable parameters to improve the strength and toughness. From the perspective of the preparation method of the ceramic / metal multilayer film, the multilayer film prepared by the physical vapor deposition lacks metallurgical bonding at the interface between the layers and at the film base interface, and the interface bonding strength is low, which restricts the further improvement of the strength and toughness of the ceramic / metal multilayer film. SUMMARY

[0005] The application aims to provide a ceramic iron-nickel alloy double-bionic multilayer film, solve the problems of interface bonding strength and toughness of the multilayer film in the prior art, and provide a preparation method of the ceramic iron-nickel alloy double-bionic multilayer film, which solves the problems of poor strength and toughness of the surface film layer and low interface bonding strength of carbon steel in the prior art.

[0006] The application discloses a ceramic iron-nickel alloy double-biomimetic multilayer film.

[0007] The application discloses a ceramic iron-nickel alloy double-biomimetic multilayer film.

[0008] Step 1: carbon steel is taken as a substrate and is subjected to carburizing treatment in a carburizing furnace to obtain carbon steel with a gradient structure of carburized steel on the surface;

[0009] Step 2: the carbon steel treated in step 1 is polished and etched in a honeycomb pattern to form a honeycomb structure skeleton on the surface of the carbon steel;

[0010] Step 3: a thin film preparation process is adopted to deposit along the inner wall of the honeycomb structure skeleton to form a multilayer film with a first metal layer-second metal layer-third metal layer-fourth metal layer as a period until the etching groove is filled up, and carbon steel with a ring-shaped multilayer film formed in the honeycomb skeleton is obtained;

[0011] Step 4: the carbon steel treated in step 3 is placed in a heat treatment furnace for heat treatment, and when all the first metal layer and the third metal layer are converted into carbide ceramic layers and all the second metal layer and the fourth metal layer are converted into alloy layers, the heat treatment is ended and the furnace is cooled, and the ceramic iron-nickel alloy double-biomimetic multilayer film formed on the surface of the carbon steel is completed.

[0012] The application also has the characteristics that the carbon steel in step 1 is one of low-carbon steel, medium-carbon steel and high-carbon steel;

[0013] The carburizing treatment in step 1 is one of solid carburizing, gas carburizing, vacuum carburizing and plasma carburizing, and the temperature range of the carburizing treatment is 800-1000 DEG C;

[0014] The etching method in step 2 is one of wet etching, dry etching and mechanical processing, and the etching depth ranges from 5 μm to 300 μm;

[0015] The first metal layer and the third metal layer in step 3 are metal layers with carbide forming ability, the second metal layer is a nickel layer, and the fourth metal layer is an iron layer;

[0016] The metal layer with carbide forming ability is one of W, Mo, Cr, Ta, Nb, Ti, Zr and V or an alloy with the above-mentioned chemical components as main chemical components, and the thickness of the metal layer with carbide forming ability ranges from 0.3 μm to 3 μm;

[0017] The mass fraction of nickel in the nickel layer ranges from 90% to 99.9999%, and the thickness of the nickel layer deposited along the side wall ranges from 0.3 μm to 3 μm;

[0018] The iron content of the iron layer ranges from 90% to 99.9999%, and the thickness of the iron layer deposited along the sidewall ranges from 0.3 μm to 3 μm.

[0019] The thin film deposition technique in step 3 is one of sputtering, ion plating, or electroplating;

[0020] The temperature range for heat treatment in step 4 is 900℃-1200℃.

[0021] The beneficial effects of the present invention are: (1) The honeycomb regular hexagonal prism structure has excellent geometric and mechanical properties and is known for its excellent compressive strength, bending strength and fracture resistance. The three-dimensional interconnected honeycomb structure matrix skeleton can improve the shear strength; (2) The honeycomb-annual ring three-dimensional configuration of the multilayer film can effectively prevent the crack from propagating along three dimensions, thereby improving the shear strength and reducing the interlayer stress, solving the problem of insufficient strength and toughness caused by the structural characteristics of the multilayer film layered structure arranged in only one direction in the prior art; (3) During the heat treatment process, the carbide ceramic is formed by the in-situ reaction of metal and carbon. The ceramic layer is dense and non-porous, with a high volume fraction of ceramic phase and strong grain boundary bonding force; (4) Iron, nickel and metals with carbide forming ability diffuse with each other under high temperature to form irregular serrations with high roughness. The interface is formed, which leads to the metallurgical bonding between the interlayers of the multilayer structure, improving the bonding strength and toughness of the interlayers of the multilayer film; (5) During the heat treatment process, the diffusion of iron and nickel elements transforms the original iron layer into a body-centered cubic iron-nickel alloy layer with iron as the main component; and transforms the original nickel layer into a face-centered cubic iron-nickel alloy layer with nickel as the main component, so that the multilayer film has a periodically distributed structure, further regulating the plasticity and toughness of the metal layer; (6) Carbon atoms diffuse from the honeycomb skeleton on the surface of the substrate into the multilayer film, so that the grain size of the ceramic layer increases with the distance from the honeycomb skeleton, and there is a grain gradient in the direction perpendicular to the side and bottom of the honeycomb; (7) Due to the carburizing effect, the high carbon steel skeleton with honeycomb structure itself has a gradient structure, which makes the surface both strong and tough. Attached Figure Description

[0022] Figure 1 This is a flowchart of the method for preparing ceramic iron-nickel alloy double biomimetic multilayer film according to the present invention. Detailed Implementation

[0023] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0024] The present invention relates to a ceramic iron-nickel alloy dual biomimetic multilayer film, comprising a honeycomb structure framework on the substrate surface and a multilayer film deposited along the inner wall of the honeycomb framework.

[0025] The method for preparing a ceramic iron-nickel alloy double biomimetic multilayer film of the present invention, as follows:Figure 1 As shown, the method is implemented according to the following steps:

[0026] Step 1: carbonizing the carbon steel substrate to convert the surface layer into a gradient structure of carburized steel;

[0027] The carbon steel includes one of low-carbon steel, medium-carbon steel, and high-carbon steel; the carburizing treatment includes one of solid carburizing, gas carburizing, vacuum carburizing, and plasma carburizing; the carburizing temperature ranges from 800°C to 1000°C.

[0028] Step 2: polishing and polishing the gradient structure surface of carburized steel obtained in step 1, and etching a honeycomb pattern thereon to form a high-carbon steel honeycomb structure skeleton on the surface of the carbon steel; the honeycomb hexagon of the honeycomb pattern has a side length ranging from 10μm to 300μm, and the honeycomb wall thickness ranges from 5μm to 200μm; the etching method includes one of wet etching, dry etching, and mechanical processing; the etching depth ranges from 5μm to 300μm;

[0029] Step 3: using a thin film preparation process to deposit a three-dimensional periodic multilayer film with a period of metal layer with carbide forming ability-nickel layer-metal layer with carbide forming ability-iron layer on the side wall and bottom surface of the high-carbon steel honeycomb structure skeleton obtained in step 2, until the etching groove is filled, forming an annual ring-shaped multilayer film; the thin film deposition technology uses one of sputtering plating, ion plating, and electroplating; the metal with carbide forming ability is one of W, Mo, Cr, Ta, Nb, Ti, Zr, and V, and an alloy with one of these elements as the main component. The thickness of the metal layer with carbide forming ability ranges from 0.3μm to 3μm;

[0030] The nickel layer is a metal layer, and the mass fraction of nickel element ranges from 90% to 99.9999%, and the thickness of the nickel layer deposited along the side wall ranges from 0.3μm to 3μm; the iron layer is a metal layer, and the mass fraction of iron element ranges from 90% to 99.9999%, and the thickness of the iron layer deposited along the side wall ranges from 0.3μm to 3μm;

[0031] Step 4: heat treating the annual ring-shaped multilayer film until the metal layer with carbide forming ability deposited in step 3 is converted into a carbide ceramic layer, and the nickel layer and the iron layer are converted into an iron-nickel alloy layer, and then cooling in the furnace after the heat treatment is completed, finally obtaining a ceramic / iron-nickel alloy double-biomimetic multilayer film on the surface of the carbon steel; the temperature of the heat treatment in step 4 ranges from 900°C to 1200°C.

[0032] In the method for preparing the bionic structure gradient multilayer film of ceramic / iron-nickel alloy on the surface of carbon steel in the application: the role of step 1 is to provide the carbon source for self-carburizing in the heat treatment process of step 4, and to increase the carbon content of the carbon steel with low carbon content by carburizing treatment, so that the self-carburizing process in step 4 can be carried out smoothly, and the surface of the steel is carburized to obtain a gradient structure, so that the steel has good hardness, wear resistance and toughness.

[0033] In the method for preparing the bionic structure gradient multilayer film of ceramic / iron-nickel alloy on the surface of carbon steel in the application: the role of step 4 is that, in this process, the interstitial carbon atoms in the carbon steel with a honeycomb skeleton diffuse into the multilayer film prepared in step 2 to realize self-carburizing, and the nickel atoms in the nickel layer diffuse into the adjacent non-nickel metal layer, and the iron atoms in the iron layer diffuse into the adjacent non-iron layer, wherein the carbon, iron and nickel diffused into the metal layer with carbide forming ability convert the metal layer with carbide forming ability into a carbide ceramic layer with dissolved iron and nickel atoms, and the ceramic grain size increases with the increase of the distance to the honeycomb skeleton, showing a grain size gradient; the element interdiffusion of the iron layer and the nickel layer converts the nickel layer into an iron-nickel alloy layer with face-centered cubic structure and mainly composed of nickel elements, and converts the iron layer into an iron-nickel alloy layer with body-centered cubic structure and mainly composed of iron elements, and due to the periodic distribution of the nickel layer and the iron layer in the deposited multilayer film, the multilayer film shows a periodic structure in the direction perpendicular to the side wall and the bottom surface of the honeycomb structure; the interdiffusion of iron, nickel and carbon elements also makes the interlayer interface of the multilayer film irregular and jagged, and has metallurgical bonding, and finally the surface of the carbon steel is composed of a honeycomb structure high carbon steel skeleton and a ring-shaped three-dimensional structure multilayer film of ceramic layer and iron-nickel alloy layer arranged alternately along the honeycomb skeleton.

[0034] Example 1:

[0035] In this example, a bionic multilayer film of WC / iron-nickel alloy is prepared on the surface of Q235 steel, which includes the following steps:

[0036] Step 1: The Q235 steel plate (low carbon steel) is subjected to carburizing treatment, and the carburizing is carried out by gas carburizing at a temperature of 800℃ for 20h;

[0037] Step 2: The gradient structure surface of the carburized steel obtained in step 1 is polished and polished, and a honeycomb pattern is etched by plasma etching (a kind of dry etching) to form a high carbon steel honeycomb structure skeleton on the surface of the Q235 steel, the honeycomb hexagonal side length is 10μm, the honeycomb wall thickness is 5μm, and the etching depth is 5μm;

[0038] Step 3: A three-dimensional periodic multilayer film with a period of tungsten layer-nickel layer-tungsten layer-iron layer is deposited on the side wall and bottom surface of the high carbon steel honeycomb structure skeleton obtained in Step 2 by using a magnetron sputtering technique until the etching groove is filled up, forming a ring-shaped multilayer film. In the film, each tungsten layer has a thickness of 0.3 μm, each nickel layer contains 90% of nickel by mass, each nickel layer deposited on the side wall has a thickness of 0.3 μm, each iron layer contains 90% of iron by mass, and each iron layer deposited on the side wall has a thickness of 0.3 μm;

[0039] Step 4: The ring-shaped multilayer film obtained in Step 3 is subjected to heat treatment at 900 °C until the tungsten layer deposited in Step 3 is converted into a tungsten carbide ceramic layer and the nickel layer and the iron layer are converted into an iron-nickel alloy layer, and then the heat treatment is finished and the film is cooled in the furnace. Finally, a ceramic / iron-nickel alloy double biomimetic multilayer film is obtained on the surface of the Q235 steel.

[0040] By the above method, the ceramic / iron-nickel alloy double biomimetic multilayer film obtained on the surface of the Q235 steel substrate has the following characteristics: 1) The honeycomb skeleton makes the layered arrangement of the multilayer film three-dimensional, and the multilayer film appears ring-shaped from the surface, and the film layers are not easy to peel off as a whole. 2) The WC ceramic layer is dense and pore-free, and the WC volume fraction in the ceramic layer is as high as 98%; 3) The iron-nickel alloy layer formed from the original iron layer is mainly composed of iron and has a body-centered cubic structure, and the iron-nickel alloy layer formed from the original nickel layer is mainly composed of nickel and has a face-centered cubic structure; 4) The WC grain size increases with the distance from the honeycomb skeleton, showing a grain size gradient, and the gradient direction is perpendicular to the side wall and the bottom surface of the honeycomb; 5) The surface of the Q235 steel after carburizing treatment is a high carbon steel gradient carburizing structure; 6) Iron and nickel elements are solid-solved in each layer; 7) The interface between the multilayer film layers is irregularly jagged, has metallurgical bonding, and the hardness of the film layer is 2600 HV, and the fracture toughness is 18.5 MPa.m 1 / 2 , and the surface wear resistance is about 70 times higher than that of the substrate.

[0041] Example 2:

[0042] In this example, a Mo2C / iron-nickel alloy double biomimetic multilayer film is prepared on the surface of a 45 steel, which comprises the following steps:

[0043] Step 1: The prepared 45 steel (medium carbon steel) is subjected to carburizing treatment, and solid carburizing is used for carburizing at a temperature of 1000 °C for 1 h;

[0044] Step 2: The carburized steel gradient structure surface obtained in Step 1 is polished and polished, and a honeycomb pattern is etched by mechanical processing to form a high carbon steel honeycomb structure skeleton on the surface of the 45 steel. The honeycomb hexagonal side length is 300 μm, the honeycomb wall thickness is 200 μm, and the etching depth is 300 μm;

[0045] Step 3: depositing a three-dimensional periodic multilayer film with a period of molybdenum layer-nickel layer-molybdenum layer-iron layer on the side wall and bottom surface of the high-carbon steel honeycomb structure skeleton obtained in Step 2 by cathodic arc ion plating until the etching grooves are filled up, forming a ring-shaped multilayer film, wherein each molybdenum layer has a thickness of 3 μm, the mass fraction of nickel element in each nickel layer is 99.9999%, each nickel layer deposited on the side wall has a thickness of 3 μm, the mass fraction of iron element in each iron layer is 99.9999%, and each iron layer deposited on the side wall has a thickness of 3 μm;

[0046] Step 4: performing heat treatment on the ring-shaped multilayer film obtained in Step 3 at 1200°C until the molybdenum layer deposited in Step 3 is converted into a Mo2C ceramic layer and the nickel layer and the iron layer are converted into an iron-nickel alloy layer, and then cooling down in the furnace after the heat treatment is completed, finally obtaining a ceramic / iron-nickel alloy double-biomimetic multilayer film on the surface of the 45 steel.

[0047] By the above method, the ceramic / iron-nickel alloy double-biomimetic multilayer film obtained on the surface of the 45 steel substrate has the following characteristics: 1) the honeycomb skeleton makes the layered arrangement direction of the multilayer film three-dimensional, and the multilayer film appears ring-shaped from the surface, and the film layer is not easy to peel off as a whole; 2) the Mo2C ceramic layer is dense and pore-free, and the volume fraction of carbide in the ceramic layer is as high as 99%; 3) the iron-nickel alloy layer generated from the original iron layer is mainly composed of iron and has a body-centered cubic structure, and the iron-nickel alloy layer generated from the original nickel layer is mainly composed of nickel and has a face-centered cubic structure; 4) the Mo2C grain size increases with the increase of the distance from the honeycomb skeleton, showing a grain size gradient, and the gradient direction is perpendicular to the side wall and the bottom surface of the honeycomb; 5) the surface of the 45 steel after carburizing treatment is a high-carbon steel gradient carburizing structure; 6) iron and nickel elements are solid-solved in each layer; 7) the interface between the multilayer film layers is irregularly jagged, has metallurgical bonding, and finally the hardness of the film layer is 2200 HV, and the fracture toughness is 27.5 MPa.m 1 / 2 , and the surface wear resistance is about 50 times higher than that of the substrate.

[0048] Example 3:

[0049] In this example, a TiC / iron-nickel alloy double-biomimetic multilayer film is prepared on the surface of 45 steel, including the following steps:

[0050] Step 1: preparing a 45 steel (medium-carbon steel) and performing carburizing treatment on it, wherein the carburizing is performed by plasma carburizing, the carburizing temperature is 900°C, and the carburizing time is 10 h;

[0051] Step 2: polishing and polishing the gradient structure surface of the carburized steel obtained in Step 1, and performing honeycomb pattern etching on it by using a hydrochloric acid solution (a kind of wet etching), thereby forming a high-carbon steel honeycomb structure skeleton on the surface of the 45 steel, wherein the length of the hexagonal side of the honeycomb is 200 μm, the honeycomb wall thickness is 100 μm, and the etching depth is 200 μm;

[0052] Step 3: A three-dimensional periodic multilayer film with a period of titanium layer-nickel layer-titanium layer-iron layer is deposited on the side wall and bottom surface of the high carbon steel honeycomb structure skeleton obtained in Step 2 by electroplating until the etching groove is filled and a ring-shaped multilayer film is formed, wherein the thickness of each titanium layer is 3 μm, the mass fraction of nickel element in each nickel layer is 95%, the thickness of each nickel layer deposited along the side wall is 1 μm, the mass fraction of iron element in each iron layer is 95%, and the thickness of each iron layer deposited along the side wall is 1 μm;

[0053] Step 4: The ring-shaped multilayer film obtained in Step 3 is subjected to heat treatment at 1100°C until the titanium layer deposited in Step 3 is converted into a TiC ceramic layer and the nickel layer and the iron layer are converted into an iron-nickel alloy layer, and the heat treatment is completed by cooling in the furnace, and finally a ceramic / iron-nickel alloy double biomimetic multilayer film is obtained on the surface of the 45 steel.

[0054] By the above method, the ceramic / iron-nickel alloy double biomimetic multilayer film obtained on the surface of the 45 steel substrate has the following characteristics: 1) The honeycomb skeleton makes the layered arrangement of the multilayer film three-dimensional, and the multilayer film appears ring-shaped from the surface, and the film layer is not easy to peel off as a whole; 2) The TiC ceramic layer is dense and pore-free, and the volume fraction of carbide in the ceramic layer is as high as 98%; 3) The iron-nickel alloy layer generated from the original iron layer is mainly composed of iron and has a body-centered cubic structure, and the iron-nickel alloy layer generated from the original nickel layer is mainly composed of nickel and has a face-centered cubic structure; 4) The TiC grain size increases with the distance from the honeycomb skeleton, showing a grain size gradient, and the gradient direction is perpendicular to the side wall and the bottom surface of the honeycomb; 5) The surface of the 45 steel after carburizing treatment is a high carbon steel gradient carburizing structure; 6) Iron and nickel elements are solid-solved in each layer; 7) The interface between the multilayer film layers is irregularly jagged, has metallurgical bonding, and the hardness of the final film layer is 2500 HV, and the fracture toughness is 20.6 MPa.m 1 / 2 The surface wear resistance is about 60 times higher than that of the substrate.

[0055] Example 4:

[0056] In this example, a TiC / iron-nickel alloy double biomimetic multilayer film is prepared on the surface of T8 steel, which includes the following steps:

[0057] Step 1: The prepared T8 steel (high carbon steel) is subjected to carburizing treatment, and the carburizing is carried out by vacuum carburizing at a temperature of 950°C for 5h;

[0058] Step 2: The carburized steel gradient structure surface obtained in Step 1 is polished and polished, and a honeycomb pattern is etched thereon by plasma etching to form a high carbon steel honeycomb structure skeleton on the surface of the T8 steel, wherein the length of the honeycomb hexagon is 50 μm, the honeycomb wall thickness is 20 μm, and the etching depth is 40 μm;

[0059] Step 3: A three-dimensional periodic multilayer film with a period of titanium layer-nickel layer-titanium layer-iron layer is deposited on the side wall and bottom surface of the high carbon steel honeycomb structure skeleton obtained in Step 2 by using multi-arc ion plating until the etching groove is filled and a ring-shaped multilayer film is formed, wherein the thickness of each titanium layer is 2 μm, the mass fraction of nickel element in each nickel layer is 99.9%, the thickness of each nickel layer deposited along the side wall is 1 μm, the mass fraction of iron element in each iron layer is 99.9%, and the thickness of each iron layer deposited along the side wall is 0.5 μm;

[0060] Step 4: The ring-shaped multilayer film obtained in Step 3 is subjected to heat treatment at 1150°C until the titanium layer deposited in Step 3 is converted into a TiC ceramic layer and the nickel layer and the iron layer are converted into an iron-nickel alloy layer, and the heat treatment is completed after cooling in the furnace, and finally a ceramic / iron-nickel alloy double biomimetic multilayer film is obtained on the surface of the T8 steel.

[0061] By the above method, the ceramic / iron-nickel alloy double biomimetic multilayer film obtained on the surface of the T8 steel substrate has the following characteristics: 1) The honeycomb skeleton makes the layered arrangement direction of the multilayer film three-dimensional, and the multilayer film appears ring-shaped from the surface, and the film layer is not easy to peel off as a whole; 2) The TiC ceramic layer is dense and pore-free, and the volume fraction of carbide in the ceramic layer is as high as 98%; 3) The iron-nickel alloy layer generated from the original iron layer is mainly composed of iron and has a body-centered cubic structure, and the iron-nickel alloy layer generated from the original nickel layer is mainly composed of nickel and has a face-centered cubic structure; 4) The TiC grain size increases with the distance from the honeycomb skeleton, showing a grain size gradient, and the gradient direction is perpendicular to the side wall and the bottom surface of the honeycomb; 5) The surface of the T8 steel after heat treatment is a high carbon steel gradient carburized structure; 6) Iron and nickel elements are solid-solved in each layer; 7) The interface between the multilayer film layers is irregularly jagged, has metallurgical bonding, and the hardness of the final film layer is 2500 HV, and the fracture toughness is 20.6 MPa.m 1 / 2 The surface wear resistance is about 60 times higher than that of the substrate.

[0062] Example 5:

[0063] In this example, a NbC / iron-nickel alloy double biomimetic multilayer film is prepared on the surface of a T10 steel, which includes the following steps:

[0064] Step 1: The prepared T10 steel (high carbon steel) is subjected to carburizing treatment. The carburizing is carried out by gas carburizing at a temperature of 1000°C for 15 hours;

[0065] Step 2: The carburized steel gradient structure surface obtained in Step 1 is polished and polished, and a honeycomb pattern is etched thereon by plasma etching to form a high carbon steel honeycomb structure skeleton on the surface of the T10 steel, wherein the length of the hexagonal side of the honeycomb is 100 μm, the thickness of the honeycomb wall is 30 μm, and the etching depth is 60 μm;

[0066] Step 3: depositing a three-dimensional periodic multilayer film with a period of niobium layer-nickel layer-titanium layer-iron layer on the side wall and bottom surface of the high-carbon steel honeycomb structure skeleton obtained in step 2 by magnetron sputtering until the etching groove is filled up, forming a ring-shaped multilayer film, wherein each niobium layer has a thickness of 2 μm, each titanium layer has a thickness of 3 μm, the mass fraction of nickel in each nickel layer is 98%, the thickness of each nickel layer deposited along the side wall is 0.5 μm, the mass fraction of iron in each iron layer is 99.99%, and the thickness of each iron layer deposited along the side wall is 0.8 μm;

[0067] Step 4: heat treating the ring-shaped multilayer film obtained in step 3 at 1150°C until the niobium layer and titanium layer deposited in step 3 are converted into NbC ceramic layer and TiC ceramic layer respectively, and the nickel layer and iron layer are converted into iron-nickel alloy layer, and then cooling down in the furnace after the heat treatment, finally obtaining a ceramic / iron-nickel alloy double-bionic multilayer film on the surface of T10 steel.

[0068] Through the above method, the ceramic / iron-nickel alloy double-bionic multilayer film obtained on the surface of T10 steel substrate has the following characteristics: 1) the honeycomb skeleton makes the layered arrangement of the multilayer film three-dimensional, and the multilayer film appears ring-shaped from the surface, and the film layer is not easy to peel off as a whole; 2) the NbC ceramic layer and TiC layer are dense and pore-free, and the volume fraction of carbide in the ceramic layer is as high as 98%; 3) the iron-nickel alloy layer generated from the original iron layer is mainly composed of iron and has a body-centered cubic structure, and the iron-nickel alloy layer generated from the original nickel layer is mainly composed of nickel and has a face-centered cubic structure; 4) the grain size of NbC and TiC increases with the increase of the distance from the honeycomb skeleton, showing a grain size gradient, and the gradient direction is perpendicular to the side wall and bottom surface of the honeycomb; 5) the surface of T10 steel after carburizing treatment is a high-carbon steel gradient carburizing structure; 6) iron and nickel elements are solid-solved in each layer; 7) the interface between the multilayer film layers is irregularly jagged, has metallurgical bonding, and finally the hardness of the film layer is 2000HV, and the fracture toughness is 22.3 MPa·m 1 / 2 , and the surface wear resistance is about 65 times higher than that of the substrate.

[0069] The mechanical property test results of the ceramic / iron-nickel alloy double-bionic multilayer film prepared in the above examples 1-5 are as follows:

[0070] Item Fracture toughness Surface hardness Example 1 18.5 MPa-m 1 / 2 ]] 2600 HV Example 2 27.5 MPa-m 1 / 2 ]] 2200 HV Example 3 20.6 MPa-m 1 / 2 ]] 2500 HV Example 4 20.6 MPa-m 1 / 2 ]] 2500 HV Example 5 22.3 MPa-m 1 / 2 ]]> 2000 HV Cr2N / Cu multilayer film <![CDATA[1.3MPa·m 1 / 2 ]]> 1734 HV

[0071] Through the above method, the ceramic / iron-nickel alloy double-bionic multilayer film has a fracture toughness of more than 18.5 MPa·m 1 / 2 , and a surface hardness of more than 2000HV, and has good mechanical properties; the maximum fracture toughness of the Cr2N / Cu multilayer film in the prior art is only 1.3 MPa·m 1 / 2The surface hardness maximum is about 1734HV, so it can be seen that the ceramic iron-nickel alloy double-biomimetic multilayer film of the application forms the irregular jagged interface with higher roughness, further leading to the metallurgical combination of the interface of the multilayer structure, and improving the interfacial bonding strength and toughness of the multilayer film.

Claims

1. A method for preparing a ceramic-iron-nickel alloy double biomimetic multilayer film, characterized in that, The ceramic-iron-nickel alloy dual-biomimetic multilayer film comprises a honeycomb structure framework on the substrate surface and a multilayer film deposited along the inner wall of the honeycomb framework; specifically implemented according to the following steps: Step 1: Carburize carbon steel as the matrix in a carburizing furnace to obtain carbon steel with a gradient structure on the surface. Step 2: Grind and polish the carbon steel treated in Step 1, and etch a honeycomb pattern onto it to form a honeycomb structure skeleton on the surface of the carbon steel. Step 3: A thin film preparation process is used to deposit along the inner wall of the honeycomb structure skeleton to form a multilayer film with a cycle of first metal layer-second metal layer-third metal layer-fourth metal layer until the etched grooves are filled, thus obtaining carbon steel with a ring-like multilayer film formed in the honeycomb skeleton. Step 4: Place the carbon steel treated in Step 3 into a heat treatment furnace for heat treatment. When all the first and third metal layers are transformed into carbide ceramic layers and all the second and fourth metal layers are transformed into alloy layers, the heat treatment ends and the furnace is cooled to complete the formation of a ceramic iron-nickel alloy double biomimetic multilayer film on the surface of the carbon steel. In step 3, the first metal layer and the third metal layer are metal layers with carbide forming ability, the second metal layer is a nickel layer, the fourth metal layer is an iron layer, and the alloy layer is an iron-nickel alloy layer.

2. The method for preparing a ceramic iron-nickel alloy double biomimetic multilayer film according to claim 1, characterized in that, The carbon steel used in step 1 is one of low-carbon steel, medium-carbon steel, or high-carbon steel.

3. The method for preparing a ceramic iron-nickel alloy double biomimetic multilayer film according to claim 1, characterized in that, The carburizing treatment in step 1 is one of solid carburizing, gas carburizing, vacuum carburizing, and plasma carburizing, and the temperature range of the carburizing treatment is 800℃-1000℃.

4. The method for preparing a ceramic iron-nickel alloy double biomimetic multilayer film according to claim 1, characterized in that, The etching method in step 2 is either wet etching or dry etching, and the etching depth ranges from 5μm to 300μm.

5. The method for preparing a ceramic iron-nickel alloy double biomimetic multilayer film according to claim 1, characterized in that, The metal layer with carbide-forming ability is one of W, Mo, Cr, Ta, Nb, Ti, Zr and V or an alloy metal layer with the same as the main chemical component, and its thickness ranges from 0.3 μm to 3 μm.

6. The method for preparing a ceramic iron-nickel alloy double biomimetic multilayer film according to claim 1, characterized in that, The nickel layer has a nickel content ranging from 90% to 99.9999% by mass, and the thickness of the nickel layer deposited along the sidewall ranges from 0.3 μm to 3 μm. The iron layer has an iron content ranging from 90% to 99.9999% by mass, and the thickness of the iron layer deposited along the inner wall of the honeycomb skeleton ranges from 0.3 μm to 3 μm.

7. The method for preparing a ceramic iron-nickel alloy double biomimetic multilayer film according to claim 1, characterized in that, The thin film deposition technique in step 3 is one of sputtering, ion plating, or electroplating.

8. The method for preparing a ceramic iron-nickel alloy double biomimetic multilayer film according to claim 1, characterized in that, The temperature range for heat treatment in step 4 is 900℃-1200℃.

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