Ceramic skeleton multilayer film with three-dimensional multi-interface structure on metal surface and preparation method of ceramic skeleton multilayer film

Abstract

The ceramic skeleton multilayer film with the metal surface three-dimensional multi-interface structure comprises a metal material, a three-dimensional ceramic skeleton and a W / Mo metal multilayer film are grown on the surface of the metal material in a mixed mode, the three-dimensional ceramic skeleton is composed of a / ceramic multilayer film and a MeC ceramic layer, the / ceramic multilayer film is of a vertically-through porous structure, and the MeC ceramic layer is of a porous structure. Pores of the porous structure are filled with W / Mo metal multilayer films, MeC / Me interfaces of the multilayer films are located in an initial metal material, the interface bonding strength is high, and stripping is not prone to occurring; the invention also provides a preparation method of the multilayer film. The preparation method comprises the following steps: step 1, preparing a W / Mo metal multilayer film on the surface of a metal material; 2, tungsten carbide particles are adopted for imprinting on the surface of the high-carbon steel; step 3, carrying out hot pressing treatment on the impressed high-carbon steel and the metal material with the W / Mo metal multilayer film to form a ceramic skeleton multilayer film with a three-dimensional multi-interface structure; and 4, the high-carbon steel on the surface of the multilayer film is removed through an etchant solution. The method is simple in process and wide in application range.

Description

Technical Field

[0001] The present invention belongs to the technical field of material surface modification, and specifically relates to a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface, and also relates to a method for preparing the ceramic skeleton multilayer film with the three-dimensional multi-interface structure on a metal surface. Background Art

[0002] Currently, the preparation of metal / ceramic multilayer films on the surface of metal materials is a method for strengthening their surfaces. This multilayer film is a composite reinforced surface layer obtained by alternating the deposition of a metal phase with excellent plasticity and toughness and a ceramic phase with high hardness. The multilayer film contains periodic interlayer interfaces, which can effectively hinder the long-range movement of dislocations, induce crack deflection, and give it excellent strength and toughness matching. However, ceramic multilayer films have the following problems: First, from the perspective of material system design, the physical separation effect of the metal layer on the ceramic layer in the ceramic / metal multilayer film. This interlayer isolation makes the material prone to interfacial slip when subjected to stress and has poor shear resistance; second, at the preparation process level, the interlayer interface and the membrane-base interface lack diffusion bonding, which makes the multilayer film easy to peel off. The above factors restrict the improvement of the mechanical properties of metal / ceramic multilayer films. Summary of the Invention

[0003] The first purpose of the present invention is to provide a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface, which effectively solves the problem of poor shear resistance caused by the metal layer isolating the ceramic layer in the ceramic / metal multilayer film in the prior art.

[0004] The second object of the present invention is to provide a method for preparing the ceramic skeleton multilayer film with the above-mentioned three-dimensional multi-interface structure on the metal surface.

[0005] The first technical solution adopted by the present invention is: Ceramic skeleton multilayer film with three-dimensional multi-interface structure on metal surface, including metal materials , metal materials The surface is mixed with a three-dimensional ceramic skeleton and a W / Mo metal multilayer film. The three-dimensional ceramic skeleton is composed of / Ceramic multilayer and C ceramic layer together constitutes, / The ceramic multilayer film presents a porous structure that penetrates from top to bottom, and the pores of the porous structure are filled with W / Mo metal multilayer films.

[0006] The present invention is also characterized in that: / Ceramic multilayer film is located in C ceramic layer surface, / Ceramic multilayer film Layer and Layers are stacked alternately to form C ceramic layer is made of metal material Several areas of the surface are formed by carbonization.

[0007] W / Mo metal multilayers grown on metal materials On the surface, the W / Mo metal multilayer film is formed by alternately depositing W layers and Mo layers through thin film preparation technology.

[0008] / The thickness of the ceramic multilayer film is the same as that of the W / Mo metal multilayer film; The total thickness range of the W / Mo metal multilayer film is 3 μm to 30 μm, and the modulation period range is 1 μm to 5 μm.

[0009] Metal materials Any one of an alloy and a pure metal is selected, the pure metal is composed of any one of Ti, Zr, Nb, Ta, W, Cr, and Mo, the main chemical component of the alloy is any one of Ti, Zr, Nb, Ta, W, Cr, and Mo, and the mass percentage of the main chemical component in the alloy is greater than 90%.

[0010] The thin film preparation technology is any one of ion plating, sputtering plating, vacuum evaporation and chemical vapor deposition.

[0011] The second technical solution adopted by the present invention is: a method for preparing the ceramic skeleton multilayer film with the above-mentioned three-dimensional multi-interface structure on the metal surface, specifically comprising the following steps: Step 1: First, the metal material Surface pretreatment is performed, and then thin film preparation technology is used on metal materials Prepare W / Mo metal multilayer film on the surface to obtain a metal material with W / Mo metal multilayer film on the surface ; Step 2: pre-treating the surface of the high carbon steel, and then imprinting the surface of the high carbon steel with tungsten carbide particles to obtain a high carbon steel with hemispherical pits on the surface; Step 3: The high carbon steel with hemispherical pits on the surface in step 2 and the metal material with W / Mo metal multilayer film on the surface in step 1 are mixed. Hot pressing treatment, in metal materials A ceramic skeleton multilayer film with a three-dimensional multi-interface structure formed on the surface; Step 4: Use a corrosive solution to remove the high carbon steel on the surface of the ceramic skeleton multilayer film with a three-dimensional multi-interface structure.

[0012] The present invention is also characterized in that: The specific process of step 1 is as follows: Step 1.1: Select the metal material The surface is pretreated. The specific pretreatment process is: use sandpaper to clean the metal material The surface is ground and polished, and then ultrasonically cleaned with alcohol until the surface oil and oxides are removed; Step 1.2: Use thin film preparation technology to prepare the metal material after pretreatment W layers and Mo layers are alternately deposited on the surface to obtain a metal material with a W / Mo metal multilayer film on the surface .

[0013] The specific process of step 2 is as follows: Step 2.1. Select high carbon steel and perform surface pretreatment on it. The specific pretreatment method is: grind and polish the surface of the high carbon steel with sandpaper, and then use alcohol ultrasonic cleaning to remove surface oil and oxides; Step 2.2: Apply one side of a PET double-sided tape to the surface of high-carbon steel. Attach a layer of spherical tungsten carbide particles to the other side of the PET double-sided tape. Then, press the steel using a tablet press. Finally, use alcohol to clean the tungsten carbide particles and the PET double-sided tape from the surface to obtain high-carbon steel with hemispherical pits on the surface.

[0014] The thickness of the PET double-sided tape in step 2.2 is 10-15 μm; the average diameter of the hemispherical pits ranges from 50 μm to 200 μm, the average center distance between two adjacent hemispherical pits ranges from 200 μm to 400 μm, the pressure load range of the tablet press is 30-60 MPa, and the imprinting time is 10 min to 15 min.

[0015] The specific process of step 3 is as follows: The surface of the W / Mo metal multilayer film was brought into contact with a high-carbon steel surface having hemispherical pits, and then placed in a hot pressing furnace for hot pressing. During hot pressing, a uniaxial longitudinal pressure of 6 to 22 MPa was applied in the normal direction. The hot pressing temperature was 900°C to 1200°C. By controlling the holding time, the W / Mo metal multilayer film below the non-hemispherical pit area was carbonized to / Ceramic multilayer film, metal materials The surface carbonization C ceramic layer, The thickness of the C ceramic layer ranges from 3 to 8 μm, and finally on the metal material A ceramic skeleton multilayer film with a three-dimensional multi-interface structure is formed on the surface.

[0016] In step 4, the corrosion solution adopts a composite system of hydrochloric acid and sulfuric acid as the corrosion medium, wherein the mass fraction of hydrochloric acid is 18% to 28%, and the mass fraction of sulfuric acid is 45% to 60%.

[0017] The beneficial effects of the present invention are: The first technical solution provided by the present invention is a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface. In the multilayer film, there is inter-diffusion of elements between the Mo2C / W2C ceramic multilayer film and the W / Mo metal multilayer film, and the interlayer interface bonding strength is high; at the same time, the multilayer film C / The interface is located at the initial metal material Internally, the interface has a higher interfacial bonding strength, and the prepared multilayer film is not easy to peel off, which effectively solves the problem of poor shear resistance caused by the metal layer isolating the ceramic layer in the existing ceramic / metal multilayer film; The invention provides a method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface. The method can obtain a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal material surface. The process is simple and has a wide range of applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a process flow chart of the method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface according to the present invention; Figure 2 It is a schematic diagram of a W / Mo metal multilayer film in the method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface; Figure 3 This is a schematic diagram of the surface of tungsten carbide particles after being embossed on a high-carbon steel surface in the method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface of the present invention; Figure 4 It is a schematic diagram of the cross-sectional structure of high carbon steel after tungsten carbide particles are imprinted in the method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface of the present invention; Figure 5 It is a schematic diagram of hot pressing treatment of a metal multilayer film and high-carbon steel with pits in the method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface of the present invention; Figure 6 It is a schematic diagram of the cross-sectional structure of a three-dimensional ceramic skeleton in the method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface of the present invention; Figure 7 Schematic diagram of a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a ZOY surface in the method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface of the present invention; Figure 8 It is a schematic diagram of a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a ZOX surface in the method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface of the present invention. DETAILED DESCRIPTION

[0019] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0020] The first technical solution provided by the present invention is a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface, comprising a metal material M e , metal materials The surface is mixed with a three-dimensional ceramic skeleton and a W / Mo metal multilayer film. The three-dimensional ceramic skeleton is composed of / Ceramic multilayer and C ceramic layer together constitutes, / The ceramic multilayer film presents a porous structure that penetrates from top to bottom, and the pores of the porous structure are filled with W / Mo metal multilayer films.

[0021] / Ceramic multilayer film is located in C ceramic layer surface, / Ceramic multilayer film Layer and Layers are stacked alternately to form C ceramic layer is made of metal material Several areas of the surface layer are formed by carbonization; W / Mo metal multilayers grown on metal materials On the surface, the W / Mo metal multilayer film is formed by alternating deposition of W and Mo layers; / The thickness of ceramic multilayer film is the same as that of W / Mo metal multilayer film. The total thickness range of W / Mo metal multilayer film is 3μm~30μm, modulation period (the sum of the thickness of two adjacent metal layers) Range: 1μm~5μm.

[0022] Metal materials Any one of alloys and pure metals is selected. The pure metal is composed of any one of Ti (titanium), Zr (zirconium), Nb (niobium), Ta (tantalum), W (tungsten), Cr (chromium), and Mo (molybdenum). The main chemical components of the alloy are any one of Ti, Zr, Nb, Ta, W, Cr, and Mo. The mass percentage of the main chemical components in the alloy is greater than 90%.

[0023] Among them, the three-dimensional ceramic skeleton includes / Ceramic multilayer and C ceramic layer, this multi-interface structure has the function of inducing crack deflection, maintaining the high strength of the material while improving the toughness and shear resistance of the material; at the same time, the W / Mo metal multilayer film exists between the ceramic skeleton, which further improves the strength and toughness of the material; the three-dimensional ceramic skeleton and the metal multilayer film between them have a multi-interface structure in the three-dimensional direction, which can induce crack deflection and achieve three-dimensional toughening.

[0024] / Both ceramic multilayer films and W / Mo metal multilayer films have inter-layer element diffusion and high interlayer interface bonding strength; metal materials The surface is carbonized C ceramic layer, ceramic skeleton / metal material interface ( C / interface) located at the initial metal material Internally, the interface has a higher interface bonding strength, so the ceramic skeleton multilayer film with a three-dimensional multi-interface structure is not easy to peel off.

[0025] The iron element in high carbon steel is solid-solution doped in the ceramic layer, causing lattice distortion, increasing defect density and promoting the diffusion of interstitial carbon atoms, and the ceramic layer growth rate is faster; in addition, the doping of iron element plays a role of solid solution strengthening, improving / Strength of ceramic multilayer films.

[0026] The second technical solution provided by the present invention is a method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface, such as Figure 1 The specific steps are as follows: Step 1: First, the metal material Surface pretreatment is performed and then thin film preparation technology is used on metal materials Prepare W (tungsten) / Mo (molybdenum) metal multilayer film on the surface to obtain a metal material with W / Mo metal multilayer film on the surface The specific process is as follows: Step 1.1: Select the metal material Surface pretreatment to remove metal materials Surface oil and oxides, etc., reduce the surface roughness. The specific pretreatment process is: use sandpaper to sand the metal material M e The surface is ground and polished, and then ultrasonically cleaned with alcohol until the surface oil and oxides are removed; Step 1.2: Use thin film preparation technology to prepare the metal material after pretreatment W layers and Mo layers are deposited alternately on the surface, such as Figure 2 As shown, a metal material with a W / Mo metal multilayer film on the surface is obtained. .

[0027] The thin film preparation technology is any one of ion plating, sputtering, vacuum evaporation and chemical vapor deposition; Step 2: Pre-treat the surface of high carbon steel, and then use tungsten carbide particles to imprint on the surface of high carbon steel, such as Figure 3 As shown, a high carbon steel with hemispherical pits on the surface is obtained. The specific process is as follows: Step 2.1. Select high carbon steel and perform surface pretreatment on it. The specific pretreatment method is: grind and polish the surface of the high carbon steel with sandpaper, and then use alcohol ultrasonic cleaning to remove surface oil and oxides; Step 2.2: Apply one side of a PET double-sided tape to the surface of high-carbon steel. Attach a layer of spherical tungsten carbide particles to the other side of the PET double-sided tape. Then, press the steel using a tablet press. Finally, use alcohol to clean the tungsten carbide particles and the PET double-sided tape from the surface to obtain high-carbon steel with hemispherical pits on the surface.

[0028] Among them, taking advantage of the high hardness of tungsten carbide spherical particles, a single layer of particles is attached to the surface of high carbon steel using PET double-sided tape, and hemispherical pits are formed on the surface of the high carbon steel under the action of pressure load, preparing for subsequent selective carbonization.

[0029] The role of high carbon steel is to provide carbon atoms that can diffuse into the W / Mo metal multilayer film, that is, to make the high carbon steel and the W / Mo metal multilayer film reach atomic-scale contact under hot pressing conditions, and the interstitial carbon atoms in the high carbon steel will move to the W / Mo metal multilayer film and the metal material under the action of the carbon concentration gradient. diffuses in the W / Mo metal multilayer film and reacts with the metal atoms in the W / Mo metal multilayer film to precipitate carbides, and finally obtains a dense structure with inward growth. / Ceramic multilayer film.

[0030] The thickness of PET double-sided tape is 10μm ~ 15μm; hemispherical pits such as Figure 4 As shown, Figure 4 This is a schematic diagram of the cross-sectional structure of high-carbon steel after tungsten carbide particles are imprinted. The average diameter d of the hemispherical pits ranges from 50 μm to 200 μm, the average center distance L between two adjacent hemispherical pits ranges from 200 μm to 400 μm, the pressure load range of the tablet press is 30 MPa to 60 MPa, and the imprinting time is 10 min to 15 min.

[0031] Step 3: The high carbon steel with hemispherical pits on the surface in step 2 and the metal material with W / Mo metal multilayer film on the surface in step 1 are mixed. Heat pressing treatment, such as Figure 5 As shown, in metal materials The ceramic skeleton multilayer film with a three-dimensional multi-interface structure is formed on the surface. The specific process is as follows: The surface of the W / Mo metal multilayer film is placed in contact with a high-carbon steel surface with hemispherical pits, and then placed in a hot pressing furnace for hot pressing. During hot pressing, a uniaxial longitudinal pressure of 6MPa~22MPa is applied in the normal direction, and the hot pressing temperature is 900℃~1200℃. By controlling the holding time, the W / Mo metal multilayer film below the non-hemispherical pit area is carbonized to / Ceramic multilayer film, metal material M e The surface carbonization C ceramic layer, The thickness of the C ceramic layer ranges from 3 to 8 μm, and finally on the metal material A ceramic skeleton multilayer film with a three-dimensional multi-interface structure is formed on the surface.

[0032] During the hot pressing process, the surface of the W / Mo metal multilayer film contacts the surface of the high carbon steel with hemispherical pits to achieve the purpose of selective carburizing, while the area inside the pit of the high carbon steel that is not in contact with the W / Mo metal multilayer film cannot be carburized. Figure 6 As shown, the W / Mo metal multilayer film is still located below the hemispherical pit area.

[0033] The metal multilayer film below the contact area between the W / Mo metal multilayer film surface and the high carbon steel is completely carbonized, and the Mo metal layer and the W metal layer are carbonized to Ceramic layer and Ceramic layer, the iron element in high carbon steel is also solid-solution doped in the ceramic layer, which promotes the diffusion of interstitial carbon atoms, makes the ceramic layer grow faster, and improves the strength of the ceramic multilayer film.

[0034] From an organizational perspective, exist As the carbon atoms diffuse, the adjacent Mo metal layer and W metal layer are carbonized first, and there is a jump layer growth phenomenon, forming a through-hole Layer and its adjacent layer below layer / Grains, most of the ceramic grains in this layer are half , half of The grains penetrate the W-Mo layers; / The size of a single-layer grain in the ceramic multilayer film is consistent with the thickness of two adjacent W / Mo metal multilayer films before carburization. Therefore, the modulation period can be used to control the grain size.

[0035] Ceramic layer C-direction metal materials Internal growth, such as Figure 7 As shown, the membrane-substrate interface is composed of W / The interface changes to C / Interface and W / interface, C / The interface is located at the initial metal material Internally, the interface has a higher interfacial bonding strength.

[0036] Three-dimensional multi-interface structure Three-dimensional multi-interface structure in ceramic skeleton multilayer film, such as Figure 7 and Figure 8 As shown, the interlayer interface of metal multilayer films (Mo / W interface), the interlayer interface of ceramic multilayer films ( / interface) and membrane-substrate interface (W / C interface and parts C / interface) is parallel to the XOY plane, the metal multilayer film (W / Mo metal multilayer film) and the ceramic multilayer film ( / The interface between ceramic multilayers (W / Interface and Mo / interface) is perpendicular to the XOY plane; thus, / Ceramic multilayer and The C ceramic layers together form a three-dimensional ceramic skeleton, and the W / Mo metal multilayer film is filled in between. The ceramic skeleton multilayer film with a three-dimensional multi-interface structure on the surface achieves a synergistic improvement in strength, toughness and shear resistance, effectively solving the problem of poor shear resistance caused by the metal layer isolating the ceramic layer in the ceramic / metal multilayer film in the existing technology.

[0037] Step 4: Use a corrosive solution to remove the high carbon steel on the surface of the ceramic skeleton multilayer film with a three-dimensional multi-interface structure. This method can obtain a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on the surface of a metal material. The process is simple and has a wide range of applications.

[0038] The corrosion solution adopts a composite system of hydrochloric acid and sulfuric acid as the corrosion medium, wherein the mass fraction of hydrochloric acid is 18%~28%, and the mass fraction of sulfuric acid is 45%~60%.

[0039] The method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface of the present invention is described in detail in the following embodiments: Example 1 This embodiment is specifically implemented according to the following steps: Step 1: First, pre-treat the surface of metal Mo, and then use thin film preparation technology to prepare a W / Mo metal multilayer film on the surface of the metal Mo to obtain metal Mo with a W / Mo metal multilayer film on the surface.

[0040] The metal Mo surface in step 1 is pretreated by sanding and polishing with sandpaper, and then ultrasonically cleaning with alcohol until the surface oil and oxides are removed; the thin film preparation technology is sputtering plating, specifically magnetron sputtering technology, the total thickness D1 of the metal multilayer film is 5 μm, and the modulation period D2 is 1 μm.

[0041] Step 2: pre-treat the surface of the high-carbon steel, and then use tungsten carbide particles to imprint the surface of the high-carbon steel to obtain a high-carbon steel with hemispherical pits on the surface.

[0042] Please follow the steps below to implement it: Step 2.1. Select high carbon steel and perform surface pretreatment on it. The specific pretreatment method is: polish it with sandpaper and then use alcohol ultrasonic cleaning to remove surface oil and oxides.

[0043] Step 2.2: Apply one side of a PET double-sided tape to the surface of high-carbon steel, adhere a layer of spherical tungsten carbide particles to the other side of the PET double-sided tape, and then press it on a tablet press. Finally, use alcohol to clean the tungsten carbide particles and PET double-sided tape on the surface to obtain high-carbon steel with hemispherical pits on the surface.

[0044] In step 2.2, the thickness of the PET double-sided tape is about 10 μm, the average diameter d of the hemispherical pits is 50 μm, the average value of the center distance L between adjacent pits is 200 μm, the pressure load of the tablet press is 30 MPa, and the imprinting time is 10 min.

[0045] Step 3: The high-carbon steel with hemispherical pits on the surface of step 2 and the metal Mo with the W / Mo metal multilayer film on the surface of step 1 are hot pressed to form a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on the surface of the metal Mo. The specific process is: the surface of the W / Mo metal multilayer film is brought into contact with the surface of the high-carbon steel with hemispherical pits, and then placed in a hot pressing furnace for hot pressing.

[0046] During hot pressing in step 3, a uniaxial longitudinal pressure of 22 MPa is applied in the normal direction at a temperature of 1200° C., and 3 μm Mo2C is formed on the surface of the metal Mo.

[0047] Step 4: Immerse the workpiece obtained in step 3 in a corrosive solution of a composite system of hydrochloric acid and sulfuric acid until no bubbles emerge, then remove the workpiece. The high-carbon steel on the surface of the multilayer film is completely removed, exposing the multilayer film on the surface, and finally obtain a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on the metal Mo surface.

[0048] In step 4, the mass fraction of hydrochloric acid is 20%, and the mass fraction of sulfuric acid is 45%.

[0049] Example 2 This embodiment is specifically implemented according to the following steps: Step 1: First, pre-treat the surface of metal Ti6Al4V, and then use thin film preparation technology to prepare a W / Mo metal multilayer film on the surface of metal Ti6Al4V to obtain metal Ti6Al4V with a W / Mo metal multilayer film on the surface.

[0050] The metal Ti6Al4V surface in step 1 is pretreated by sanding and polishing with sandpaper, and then ultrasonically cleaning with alcohol until the surface oil and oxides are removed; the thin film preparation technology is chemical vapor deposition, the total thickness D1 of the metal multilayer film is 30μm, and the modulation period (the sum of the thickness of two adjacent metal layers) D2 is 5μm.

[0051] Step 2: pre-treat the surface of the high-carbon steel, and then use tungsten carbide particles to imprint the surface of the high-carbon steel to obtain a high-carbon steel with hemispherical pits on the surface.

[0052] Please follow the steps below to implement it: Step 2.1. Select high carbon steel and perform surface pretreatment on it. The specific treatment method is: polish it with sandpaper and then use alcohol ultrasonic cleaning to remove surface oil and oxides.

[0053] Step 2.2: Apply one side of a PET double-sided tape to the surface of high-carbon steel, adhere a layer of spherical tungsten carbide particles to the other side of the PET double-sided tape, and then press it on a tablet press. Finally, use alcohol to clean the tungsten carbide particles and PET double-sided tape on the surface to obtain high-carbon steel with hemispherical pits on the surface.

[0054] In step 2.2, the thickness of the PET double-sided tape is about 15 μm, the average diameter d of the hemispherical pits is 150 μm, the average value of the center distance L between adjacent pits is 400 μm, the pressure load of the tablet press is 60 MPa, and the imprinting time is 20 min.

[0055] Step 3: The high-carbon steel with hemispherical pits on the surface of step 2 and the Ti6Al4V with a W / Mo metal multilayer film on the surface of step 1 are hot pressed to form a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on the surface of the metal Ti6Al4V. The specific process is: the surface of the W / Mo metal multilayer film is brought into contact with the surface of the high-carbon steel with hemispherical pits, and then placed in a hot pressing furnace for hot pressing.

[0056] During hot pressing in step 3, a uniaxial longitudinal pressure of 15 MPa is applied in the normal direction at a temperature of 1100° C., and 8 μm TiC is formed on the surface of the Ti6Al4V.

[0057] Step 4: Immerse the workpiece obtained in step 3 in a corrosive solution of a composite system of hydrochloric acid and sulfuric acid until no bubbles emerge, then remove the workpiece. The high-carbon steel on the surface of the multilayer film is completely removed, exposing the multilayer film on the surface, and finally obtain a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on the Ti6Al4V surface.

[0058] In step 4, the mass fraction of hydrochloric acid is 25%, and the mass fraction of sulfuric acid is 50%.

[0059] Example 3 This embodiment is specifically implemented according to the following steps: Step 1: First, pre-treat the surface of metal W, and then use thin film preparation technology to prepare a W / Mo metal multilayer film on the surface of the metal W to obtain metal W with a W / Mo metal multilayer film on the surface.

[0060] The surface of the metal W in step 1 is pretreated by sanding and polishing with sandpaper, and then ultrasonically cleaning with alcohol until the surface oil and oxides are removed; the thin film preparation technology is vacuum evaporation technology, the total thickness D1 of the metal multilayer film is 3 μm, and the modulation period (the sum of the thickness of two adjacent metal layers) D2 is 3 μm.

[0061] Step 2: pre-treat the surface of the high-carbon steel, and then use tungsten carbide particles to imprint the surface of the high-carbon steel to obtain a high-carbon steel with hemispherical pits on the surface.

[0062] Please follow the steps below to implement it: Step 2.1. Select high carbon steel and perform surface pretreatment on it. The specific treatment method is: polish it with sandpaper and then use alcohol ultrasonic cleaning to remove surface oil and oxides.

[0063] Step 2.2: Apply one side of a PET double-sided tape to the surface of high-carbon steel, adhere a layer of spherical tungsten carbide particles to the other side of the PET double-sided tape, and then press it on a tablet press. Finally, use alcohol to clean the tungsten carbide particles and PET double-sided tape on the surface to obtain high-carbon steel with hemispherical pits on the surface.

[0064] In step 2.2, the thickness of the PET double-sided tape is about 12 μm, the average diameter d of the hemispherical pits is 100 μm, the average value of the center distance L between adjacent pits is 200 μm, the pressure load of the tablet press is 45 MPa, and the imprinting time is 13 min.

[0065] Step 3: Hot-press the high-carbon steel with hemispherical pits on its surface obtained in step 2 and the metal W with the W / Mo metal multilayer film on its surface obtained in step 1 to form a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on the surface of the metal W. The specific process is as follows: contact the surface of the W / Mo metal multilayer film with the surface of the high-carbon steel with hemispherical pits, and then place them in a hot pressing furnace for hot pressing.

[0066] During hot pressing in step 3, a uniaxial longitudinal pressure of 6 MPa is applied in the normal direction and the temperature is 900°C. A 3 μm thick layer of metal W is formed on the surface. .

[0067] Step 4: Immerse the workpiece obtained in step 3 in a corrosive solution of a composite system of hydrochloric acid and sulfuric acid until no bubbles emerge, then remove the workpiece. The high-carbon steel on the surface of the multilayer film is completely removed, exposing the multilayer film on the surface, and finally obtain a three-dimensional multi-interface structured ceramic skeleton multilayer film on the surface of the metal W.

[0068] In step 4, the mass fraction of hydrochloric acid is 20%, and the mass fraction of sulfuric acid is 45%.

[0069] Example 4 This embodiment is specifically implemented according to the following steps: Step 1: First, pre-treat the surface of metal Ta, and then use thin film preparation technology to prepare a W / Mo metal multilayer film on the surface of the metal Ta to obtain metal Ta with a W / Mo metal multilayer film on the surface.

[0070] The metal Ta surface in step 1 is pretreated by sanding and polishing with sandpaper, and then ultrasonically cleaning with alcohol until the surface oil and oxides are removed; the thin film preparation technology is ion plating technology, the total thickness D1 of the metal multilayer film is 10μm, and the modulation period (the sum of the thickness of two adjacent metal layers) D2 is 2μm.

[0071] Step 2: pre-treat the surface of the high-carbon steel, and then use tungsten carbide particles to imprint the surface of the high-carbon steel to obtain a high-carbon steel with hemispherical pits on the surface.

[0072] Please follow the steps below to implement it: Step 2.1. Select high carbon steel and perform surface pretreatment on it. The specific treatment method is: polish it with sandpaper and then use alcohol ultrasonic cleaning to remove surface oil and oxides.

[0073] Step 2.2: Apply one side of a PET double-sided tape to the surface of high-carbon steel. Attach a layer of spherical tungsten carbide particles to the other side of the PET double-sided tape. Press the tape under a tablet press. Finally, use alcohol to clean the tungsten carbide particles and PET tape off the surface, resulting in a high-carbon steel with hemispherical pits on the surface.

[0074] In step 2.2, the thickness of the PET double-sided tape is about 14 μm, the average diameter d of the hemispherical pits is 200 μm, the average value of the center distance L between adjacent pits is 400 μm, the pressure load of the tablet press is 60 MPa, and the imprinting time is 12 min.

[0075] Step 3: The high-carbon steel with hemispherical pits on the surface of step 2 and the metal Ta with the W / Mo metal multilayer film on the surface of step 1 are hot pressed to form a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on the surface of the metal Ta. The specific process is: the surface of the W / Mo metal multilayer film is brought into contact with the surface of the high-carbon steel with hemispherical pits, and then placed in a hot pressing furnace for hot pressing.

[0076] During hot pressing in step 3, a uniaxial longitudinal pressure of 20 MPa is applied in the normal direction at a temperature of 1000° C., and 5 μm of TaC is formed on the surface of the metal Ta.

[0077] Step 4: Immerse the workpiece obtained in step 3 in a corrosive solution of a composite system of hydrochloric acid and sulfuric acid until no bubbles emerge, then remove the workpiece. The high-carbon steel on the surface of the multilayer film is completely removed, exposing the multilayer film on the surface, and finally obtain a three-dimensional multi-interface structured ceramic skeleton multilayer film on the metal Ta surface.

[0078] In step 4, the mass fraction of hydrochloric acid is 28%, and the mass fraction of sulfuric acid is 60%.

[0079] Example 5 This embodiment is specifically implemented according to the following steps: Step 1: First, the metal Cr is surface pretreated, and then a W / Mo metal multilayer film is prepared on the surface of the metal Cr using a thin film preparation technology to obtain a metal Cr with a W / Mo metal multilayer film on the surface.

[0080] The metal Cr surface in step 1 is pretreated by sanding and polishing with sandpaper, and then ultrasonically cleaning with alcohol until the surface oil and oxides are removed; the thin film preparation technology is sputtering plating, specifically magnetron sputtering technology, the total thickness D1 of the metal multilayer film is 20μm, and the modulation period (the sum of the thickness of two adjacent metal layers) D2 is 4μm.

[0081] Step 2: pre-treat the surface of the high-carbon steel, and then use tungsten carbide particles to imprint the surface of the high-carbon steel to obtain a high-carbon steel with hemispherical pits on the surface.

[0082] Please follow the steps below to implement it: Step 2.1. Select high carbon steel and perform surface pretreatment on it. The specific treatment method is: polish it with sandpaper and then use alcohol ultrasonic cleaning to remove surface oil and oxides.

[0083] Step 2.2: Apply one side of a PET double-sided tape to the surface of high-carbon steel, adhere a layer of spherical tungsten carbide particles to the other side of the PET double-sided tape, and then press it on a tablet press. Finally, use alcohol to clean the tungsten carbide particles and PET double-sided tape on the surface to obtain high-carbon steel with hemispherical pits on the surface.

[0084] In step 2.2, the thickness of the PET double-sided tape is about 13 μm, the average diameter d of the hemispherical pits is 80 μm, the average value of the center distance L of adjacent pits is 210 μm, the pressure load of the tablet press is 34 MPa, and the printing time is 14 min.

[0085] Step 3: The high-carbon steel with hemispherical pits on the surface of step 2 and the metal Cr with the W / Mo metal multilayer film on the surface of step 1 are hot pressed to form a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on the surface of the metal Cr. The specific process is: the surface of the W / Mo metal multilayer film is brought into contact with the surface of the high-carbon steel with hemispherical pits, and then placed in a hot pressing furnace for hot pressing.

[0086] During hot pressing in step 3, a uniaxial longitudinal pressure of 10 MPa is applied in the normal direction at a temperature of 1200° C., and 8 μm Cr3C2 is formed on the surface of the metal Cr.

[0087] Step 4: Immerse the workpiece obtained in step 3 in a corrosive solution of a composite system of hydrochloric acid and sulfuric acid until no bubbles emerge, then remove the workpiece. The high-carbon steel on the surface of the multilayer film is completely removed, exposing the multilayer film on the surface. Finally, a ceramic skeleton multilayer film with a three-dimensional multi-interface structure is obtained on the metal Cr surface.

[0088] The mass fraction of the hydrochloric acid component in step 4 is 28%, and the mass fraction of the sulfuric acid is 60%.

[0089] Example 6 This embodiment is specifically implemented according to the following steps: Step 1: First, pre-treat the surface of metal Zr, and then use thin film preparation technology to prepare a W / Mo metal multilayer film on the surface of the metal Zr to obtain metal Zr with a W / Mo metal multilayer film on the surface.

[0090] The metal Zr surface in step 1 is pretreated by sanding and polishing with sandpaper, and then ultrasonically cleaning with alcohol until the surface oil and oxides are removed; the thin film preparation technology is ion plating technology, the total thickness D1 of the metal multilayer film is 15μm, and the modulation period (the sum of the thickness of two adjacent metal layers) D2 is 3μm.

[0091] Step 2: pre-treat the surface of the high-carbon steel, and then use tungsten carbide particles to imprint the surface of the high-carbon steel to obtain a high-carbon steel with hemispherical pits on the surface.

[0092] Please follow the steps below to implement it: Step 2.1. Select high carbon steel and perform surface pretreatment on it. The specific treatment method is: polish it with sandpaper and then use alcohol ultrasonic cleaning to remove surface oil and oxides.

[0093] Step 2.2: Apply one side of a PET double-sided tape to the surface of high-carbon steel, adhere a layer of spherical tungsten carbide particles to the other side of the PET double-sided tape, and then press it on a tablet press. Finally, use alcohol to clean the tungsten carbide particles and the PET double-sided tape on the surface to obtain high-carbon steel with hemispherical pits on the surface.

[0094] In step 2.2, the thickness of the PET double-sided tape is about 11 μm, the average diameter d of the hemispherical pits is 170 μm, the average value of the center distance L of adjacent pits is 380 μm, the pressure load of the tablet press is 40 MPa, and the printing time is 11 min.

[0095] Step 3: Hot-press the high-carbon steel with hemispherical pits from Step 2 and the Cr metal with the W / Mo metal multilayer film from Step 1 to form a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on the Zr metal surface. The specific process involves contacting the W / Mo metal multilayer film surface with the high-carbon steel surface with hemispherical pits, followed by hot pressing in a hot press furnace.

[0096] During hot pressing in step 3, a uniaxial longitudinal pressure of 18 MPa is applied in the normal direction at a temperature of 1050° C., and 4 μm ZrC is formed on the surface of the metal Zr.

[0097] Step 4: Immerse the workpiece obtained in step 3 in a corrosive solution of a composite system of hydrochloric acid and sulfuric acid until no bubbles emerge, then remove the workpiece. The high-carbon steel on the surface of the multilayer film is completely removed, exposing the multilayer film on the surface, and finally obtaining a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on the metal Zr surface.

[0098] The mechanical properties of the ceramic skeleton multilayer films with three-dimensional multi-interface structures prepared in Examples 1-6 were tested, and the test results are shown in the following table: Table 1: Mechanical properties test results of ceramic skeleton multilayer films with three-dimensional multi-interface structures of Examples 1-6

[0099] The present invention provides a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on the metal surface, a Mo2C / W2C ceramic multilayer film and a M e The C ceramic layer forms a ceramic skeleton, with the W / Mo metal multilayer film nestled within. Interdiffusion of elements between the ceramic and metal layers results in high interfacial bonding strength. As shown in the table above, the interfacial bonding strength of the multilayer film exceeds 90N, making it less susceptible to single-layer shedding. The film-to-substrate bonding strength is around 130N, making it less susceptible to overall peeling and failure, demonstrating excellent shear resistance.

Claims

1. A ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface, characterized in that: Including metal materials , metal materials The surface is mixed with a three-dimensional ceramic skeleton and a W / Mo metal multilayer film. The three-dimensional ceramic skeleton is composed of / Ceramic multilayer and C ceramic layers together constitute the / The ceramic multilayer film presents a porous structure that penetrates from top to bottom, and the pores of the porous structure are filled with W / Mo metal multilayer film.

2. The ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface according to claim 1, characterized in that: described / Ceramic multilayer film is located in C ceramic layer surface, the / Ceramic multilayer film Layer and The layers are alternately stacked to form C ceramic layer is made of metal material Several areas of the surface layer are formed by carbonization; The W / Mo metal multilayer film is grown on the metal material On the surface, the W / Mo metal multilayer film is formed by alternating deposition of W layers and Mo layers; described / The thickness of ceramic multilayer film is the same as that of W / Mo metal multilayer film; The total thickness of the W / Mo metal multilayer film is in the range of 3 μm to 30 μm, and the modulation period is in the range of 1 μm to 5 μm.

3. The ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface according to claim 2, characterized in that: The metal material Any one of an alloy and a pure metal is selected, the pure metal is composed of any one of Ti, Zr, Nb, Ta, W, Cr, and Mo, the main chemical component of the alloy is any one of Ti, Zr, Nb, Ta, W, Cr, and Mo, and the mass percentage of the main chemical component in the alloy is greater than 90%.

4. The method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface according to claim 3, characterized in that: The specific steps include: Step 1: First, the metal material Surface pretreatment is performed, and then thin film preparation technology is used on metal materials Prepare W / Mo metal multilayer film on the surface to obtain a metal material with W / Mo metal multilayer film on the surface ; Step 2: pre-treating the surface of the high carbon steel, and then imprinting the surface of the high carbon steel with tungsten carbide particles to obtain a high carbon steel with hemispherical pits on the surface; Step 3: The high carbon steel with hemispherical pits on the surface in step 2 and the metal material with W / Mo metal multilayer film on the surface in step 1 are mixed. Hot pressing treatment, in metal materials A ceramic skeleton multilayer film with a three-dimensional multi-interface structure formed on the surface; Step 4: Use a corrosive solution to remove the high carbon steel on the surface of the ceramic skeleton multilayer film with a three-dimensional multi-interface structure.

5. The method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface according to claim 4, characterized in that: The specific process of step 1 is as follows: Step 1.1: Select the metal material The surface is pretreated. The specific pretreatment process is: use sandpaper to clean the metal material The surface is ground and polished, and then ultrasonically cleaned with alcohol until the surface oil and oxides are removed; Step 1.2: Use thin film preparation technology to prepare the metal material after pretreatment W layers and Mo layers are alternately deposited on the surface to obtain a metal material with a W / Mo metal multilayer film on the surface .

6. The method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface according to claim 5, characterized in that: The thin film preparation technology described in step 1.2 is selected from any one of ion plating, sputtering, vacuum evaporation, and chemical vapor deposition.

7. The method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface according to claim 6, characterized in that: The specific process of step 2 is as follows: Step 2.

1. Select high carbon steel and perform surface pretreatment on it. The specific pretreatment method is: grind and polish the surface of the high carbon steel with sandpaper, and then use alcohol ultrasonic cleaning to remove surface oil and oxides; Step 2.2: Apply one side of a PET double-sided tape to the surface of high-carbon steel. Attach a layer of spherical tungsten carbide particles to the other side of the PET double-sided tape. Then, press the steel using a tablet press. Finally, use alcohol to clean the tungsten carbide particles and the PET double-sided tape from the surface to obtain high-carbon steel with hemispherical pits on the surface.

8. The method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface according to claim 7, characterized in that: The thickness of the PET double-sided tape in step 2.2 is 10-15 μm; the average diameter range of the hemispherical pits is: 50 μm-200 μm, the average value of the center distance between every two adjacent hemispherical pits is: 200 μm-400 μm, the pressure load range of the tablet press is 30-60 MPa, and the imprinting time is: 10 min-15 min.

9. The method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface according to claim 8, characterized in that: The specific process of step 3 is as follows: The surface of the W / Mo metal multilayer film was brought into contact with a high-carbon steel surface having hemispherical pits, and then placed in a hot pressing furnace for hot pressing. During hot pressing, a uniaxial longitudinal pressure of 6 to 22 MPa was applied in the normal direction. The hot pressing temperature was 900°C to 1200°C. By controlling the holding time, the W / Mo metal multilayer film below the non-hemispherical pit area was carbonized to / Ceramic multilayer film, metal materials The surface carbonization C ceramic layer, The thickness of the C ceramic layer ranges from 3 to 8 μm, and finally on the metal material A ceramic skeleton multilayer film with a three-dimensional multi-interface structure is formed on the surface.

10. The method for preparing a ceramic skeleton multilayer film with a three-dimensional multi-interface structure on a metal surface according to claim 9, characterized in that: The etching solution in step 4 uses a composite system of hydrochloric acid and sulfuric acid as the etching medium, wherein the mass fraction of hydrochloric acid is 18% to 28%, and the mass fraction of sulfuric acid is 45% to 60%.

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