Carbon fiber toughened ceramic reinforced metal composite material, and preparation method and application thereof

Abstract

The application relates to a carbon fiber toughened ceramic reinforced metal composite material and a preparation method and application thereof, and belongs to the field of metal composite materials. The carbon fiber toughened ceramic reinforced metal composite material is prepared by sealing layers of metal paste in an upper and lower layer, and three layers (the first layer is carbon fiber toughened ceramic particles, the second layer is low-layer high-interval metal paste printing, and the third layer is high-layer low-interval metal paste printing) in a cycle, performing layered printing and drying, and then performing low-temperature liquid-solid two-phase zone sintering. The carbon fiber toughened ceramic reinforced metal composite material has weldable performance, can set the required thickness according to the requirements of equipment parts, serves as a wear-resistant layer, or is printed into various shapes to serve as wear-resistant parts. The low-temperature liquid-solid two-phase zone sintering method makes the metal matrix produce a molten "paste" state to wet the carbon fiber toughened ceramic particles, avoids the movement of the carbon fiber toughened ceramic particles, and solves the problem of uneven distribution of the ceramic particles.

Description

Technical Field

[0001] This invention relates to the field of metal composite materials technology, specifically to a carbon fiber toughened ceramic reinforced metal composite material, its preparation method, and its application. Background Technology

[0002] With the development of modern industry, the requirements for wear-resistant materials are becoming increasingly stringent. Common wear-resistant materials include metals and ceramics. To combine the toughness, plasticity, and impact resistance of metals with the high hardness and excellent wear resistance of ceramics, the preparation of metal-ceramic composites has become a trend. However, a common problem is that high-hardness, high-strength ceramic particles are prone to crack initiation, brittle fracture, and particle detachment under certain impact and wear conditions, failing to achieve the expected ceramic reinforcement effect. Another common problem is that the metal-ceramic materials are not fully mixed, resulting in uneven distribution of the metal and ceramic phases, leading to poor wear resistance. While using binders to improve the compatibility of metals and ceramics can also lead to ceramic detachment and wear resistance failure due to the aging of the binders. Another method involves coating a metal with a layer of ceramic to improve wear resistance; however, this method generates residual thermal stress due to the large coefficients of thermal expansion of both ceramics and metals, resulting in poor joint performance and easy detachment.

[0003] To address the aforementioned issues, some studies are incorporating carbon fibers into materials. This improves the toughness of ceramic particles and modifies the material's wear resistance through the crack-blocking mechanism of carbon fibers. A common method involves grinding carbon fibers and ceramics into powder, then pressing them with metal powder and sintering the mixture. This approach uses carbon fibers as a carbon source, achieving good and efficient carburization during the sintering stage, thus improving wear resistance. While this method enhances wear resistance, it also involves metal carburization and electrochemical corrosion. Furthermore, because carbon fibers have low surface energy and lack chemically active bonds, their bonding ability with metals and other materials is poor, directly impacting the properties of the composite material. Summary of the Invention

[0004] To address the problems existing in the prior art, the purpose of this invention is to provide a carbon fiber toughened ceramic-reinforced metal composite material, its preparation method, and its application, thereby improving the bonding strength between carbon fibers, ceramics, and metals in the carbon fiber toughened ceramic-reinforced metal composite material and enhancing its wear resistance. A novel ceramic-reinforced metal composite material is prepared by first toughening ceramic particles and then further reinforcing the metal material with carbon fiber toughened ceramic particles. The carbon fibers in the carbon fiber toughened ceramic particles remain fibrous. Through fiber layup and 3D layer printing, the position, distribution, and layup ratio of the carbon fiber toughened ceramic particles are ensured. A low-temperature liquid-solid two-phase sintering method is used to create a molten "paste"-like wettability of the carbon fiber toughened ceramic particles in the metal matrix, preventing particle movement and maximally solving the problem of uneven ceramic particle distribution. A dense carbon fiber toughened ceramic-reinforced metal composite material is then prepared under prolonged heat treatment.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] The first aspect of the present invention provides a method for preparing a carbon fiber toughened ceramic reinforced metal composite material, comprising the following steps:

[0007] Carbon fiber toughened ceramic particles and metal paste are printed in layers, with one layer of metal paste sealing layer on the top and bottom, and three layers in the middle forming a cycle. The three middle layers are: the first layer is carbon fiber toughened ceramic particles, the second layer is low-layer high-gap metal paste printing, and the third layer is high-layer low-gap metal paste printing. The first to the third layer is one cycle, and N cycles are performed. The top and bottom layers outside the cycle layers are metal paste sealing layers, resulting in a layered printed metal paste carbon fiber toughened ceramic composite material.

[0008] After drying the layered printed metal slurry carbon fiber toughened ceramic composite material, it is then sintered in a low-temperature liquid-solid two-phase region to obtain a carbon fiber toughened ceramic reinforced metal composite material.

[0009] The N is preferably 1 to 10, and more preferably 2 to 5.

[0010] The raw materials selected for the carbon fiber toughened ceramic particles are carbon fiber and ceramic materials, with a mass ratio of carbon fiber to ceramic material of 1:1 to 10. In the carbon fiber toughened ceramic particles, carbon fiber is the toughening phase. The angle of the carbon fiber is selected from one or more of the following: transverse, longitudinal, and cross. The distribution of carbon fiber and ceramic material is a combination of three methods: long carbon fiber layering, short carbon fiber dispersion, and mixing of carbon fiber powder and ceramic powder.

[0011] The ceramic material is selected from oxide ceramics, carbide ceramics, and nitride ceramics, preferably one or more of alumina, zirconium carbide, and boron nitride, and more preferably Al2O3.

[0012] The preparation method of the carbon fiber toughened ceramic particles is as follows: carbon fibers are arranged at a selected angle, ceramic materials and carbon fibers are mixed, and carbon fiber toughened ceramic composite material is obtained by hot pressing sintering. The carbon fiber toughened ceramic composite material is crushed to obtain carbon fiber toughened ceramic particles with a particle size of 50-100 mesh.

[0013] In the hot pressing sintering method described above, the sintering pressure is 35-45 MPa and the sintering temperature is 1850-2100℃.

[0014] The low-layer high-pitch metal paste printing, high-layer low-pitch metal paste printing, and metal paste sealing layer all use metal paste as the printing material. The metal paste includes metal powder, C powder, and binder solution. By mass ratio, the metal matrix (metal powder + C powder): binder solution = 1:(2~5); the mass percentage of C powder in the metal matrix is ​​0.5~1.0%.

[0015] The metal matrix is ​​selected from Cr steel metal matrix and / or Mn steel metal matrix, and the mesh size of the metal matrix is ​​200 mesh;

[0016] The binder solution is an aqueous solution of PVA powder, and the density of the PVA powder aqueous solution is 1.0–1.5 g / cm³. 3 The viscosity is 3600-3750 MPa.

[0017] The first layer of carbon fiber toughened ceramic particles is a single layer of carbon fiber toughened ceramic particles. The single layer of carbon fiber toughened ceramic particles is placed on the surface of the corundum sheet using a mold. The mold has multiple holes arranged in a matrix. After the mold holes are filled, the mold is vertically moved away, allowing the carbon fiber toughened ceramic particles to remain on the corundum surface according to the mold's design. The surface area occupied by the carbon fiber toughened ceramic particles on the mold surface, the shape of the holes on the mold surface, and the height of the holes on the mold surface can all be designed according to actual needs. The surface area of ​​the single layer of carbon fiber toughened ceramic particles accounts for 20% to 60% of the surface area of ​​the corundum sheet.

[0018] The low-layer, high-spacing metal paste printing is characterized by: the diameter of the paste ejected from the printing nozzle being 4-6 mm, i.e., the printing height being 4-6 mm; and the spacing between paste passes being 8-12 mm.

[0019] The high-level low-gap metal paste printing refers to the paste diameter of the printing nozzle being 10-15mm, i.e., the printing height being 10-15mm; the spacing between paste passes is 12-18mm.

[0020] The printing lines between the upper and lower layers of the low-layer high-spacing metal paste and the high-layer low-spacing metal paste are vertically distributed.

[0021] The metal paste sealing layer is a printed sealing metal paste with a sealing degree of 90-100% and a sealing height of 10-20mm.

[0022] The layered printed metal slurry carbon fiber toughened ceramic composite material is dried in the oven for 24 to 48 hours; then it is dried at 60 to 80°C for 10 to 24 hours.

[0023] The aforementioned low-temperature liquid-solid two-phase sintering is a three-stage heating sintering process, including the following sintering steps:

[0024] (1) Low temperature heating stage: The dried layered printed metal slurry carbon fiber toughened ceramic composite material is heated to 200-280℃ at room temperature at a heating rate of 3-5℃ / min; after reaching 200-280℃, the temperature is further increased to 400-450℃ at a heating rate of 3-4℃ / min, and then held at 400-450℃ for 2-3 hours. This stage is the PVA decomposition zone.

[0025] (2) Medium temperature heating stage: The temperature is raised from 400-450℃ to 800-850℃ at a rate of 4-6℃ / min, and held for 2-3 hours. This stage is the metal powder gas emission zone.

[0026] (3) Heating stage in the liquid-solid two-phase region: Heating from 800 to 850℃ to 1050℃ to 1100℃ at a rate of 4 to 7℃ / min, and holding for 5 to 10 hours. This stage is the sintering of the liquid-solid two-phase region, resulting in carbon fiber toughened ceramic reinforced metal composite material.

[0027] During the heating stage in the liquid-solid two-phase region, the carbon fiber toughened ceramic particles were kept in a relatively stable position. By impregnating the carbon fiber toughened ceramic particles with 30-40% metal slurry for a long time, the carbon fiber toughened ceramic particles were evenly distributed in the metal slurry, resulting in a carbon fiber toughened ceramic reinforced metal composite material.

[0028] The percentage of liquid and solid phases was obtained through simulation using J-Matpro software, which in turn controlled the liquid-solid two-phase sintering process of carbon fiber toughened ceramic reinforced metal composites.

[0029] A second aspect of the present invention provides a carbon fiber toughened ceramic reinforced metal composite material, prepared by the above-described preparation method, wherein the carbon fiber toughened ceramic is uniformly distributed.

[0030] The carbon fiber toughened ceramic reinforced metal composite material has weldability.

[0031] A third aspect of the present invention provides an application of a carbon fiber toughened ceramic reinforced metal composite material, which is set to the required thickness according to the requirements of equipment components, as a wear-resistant layer, or printed into various shapes as wear-resistant parts.

[0032] The carbon fiber toughened ceramic reinforced metal composite material of the present invention, its preparation method and application, have the following advantages compared with the prior art:

[0033] 1. This invention uses carbon fiber-reinforced ceramics as the reinforcing phase. Currently, in existing technologies, the reinforcing ceramics used for metals are all carbide ceramics, oxide ceramics, or nitride ceramics. These ceramics have low plasticity and poor toughness, making them prone to catastrophic fracture failure during use. Under strong wear and impact conditions, ceramic particles often crack, fracture, and detach. Therefore, this invention toughens the ceramic particles using carbon fiber as the toughening material. Carbon fiber is a high-strength, high-modulus fiber with a carbon content of over 90%. It has a fibrous, soft, and low-density appearance, with its internal graphite microcrystalline structure preferentially oriented along the fiber axis. Using carbon fiber-reinforced ceramics and applying it to the preparation of composite materials has high application value. Furthermore, the carbon fiber toughening method incorporates designed carbon fiber angles and fiber distribution patterns, ensuring optimal performance of the ceramic phase in the composite material.

[0034] 2. Most current ceramic-reinforced metal composites use iron-based materials, while this invention uses steel-based materials, which can improve the impact resistance of the metal matrix and ensure wear resistance. Cr steel matrix is ​​suitable for working environments with strong wear but no impact. Mn steel matrix is ​​suitable for conditions with wear and impact.

[0035] The innovative point of this invention is:

[0036] 1. By combining carbon fiber-reinforced ceramics and metals, the overall performance of the composite material is improved.

[0037] 2. This invention provides a method for preparing composite materials using 3D layered printing, achieving a uniform distribution of carbon fiber, ceramics, and metals. The 3D printing method of this invention pre-lays carbon fiber-reinforced ceramic particles between the layers of the composite material, ensuring the position, distribution, and placement ratio of the particles. Based on the subsequent sintering mechanism of the metal matrix, the placement height is precisely to cover one to 1.5 layers of ceramic particles. In other traditional methods, the ceramics are in powder form, not granular; traditional techniques involve mixing ceramic powder with the matrix before 3D printing. The main reason for using 3D printing in this invention is to achieve uniform distribution and fixation of the ceramic particles.

[0038] 3. This invention solves the incompatibility problem between carbon fiber, ceramics, and metals through low-temperature liquid-solid two-phase sintering, thus improving the wear resistance of the composite material. Traditional methods, such as liquid-phase sintering, powder metallurgy, and sol-gel methods, result in uncontrollable ceramic particle distribution. This invention utilizes 3D printing to pre-lay the ceramic particles, followed by drying and low-temperature liquid-solid two-phase sintering. This method primarily produces a molten "paste"-like substance in the metal matrix, but without forming a liquid. Under prolonged heat treatment, the paste-like molten metal wets the ceramic particles, forming an effective interface layer. Simultaneously, it allows the matrix to become a dense matrix material under prolonged heat treatment. This method avoids ceramic particle movement and largely solves the problem of uneven ceramic particle distribution. The "paste" region metal is calculated using phase diagrams and simulated using J-Matpro software to obtain paste regions with different liquid-solid two-phase ratios.

[0039] 4. Using the carbon fiber toughened ceramic-reinforced metal composite material prepared according to this invention as a wear-resistant layer effectively reduces equipment costs. It can be printed in different shapes, exhibits good conformal application to the wear-resistant working surfaces of parts, and the thickness of the wear-resistant zone is controllable. The carbon fiber toughened ceramic-reinforced composite material has a superior ceramic reinforcement effect compared to other patents. Attached Figure Description

[0040] Figure 1 This is a schematic diagram of the 3D printing method of the carbon fiber toughened ceramic reinforced metal composite material of the present invention; in the figure, 1-1 is a schematic diagram of 3D printing; 1-2 is a cross-sectional view of the first layer; 1-3 is a cross-sectional view of the second layer; 1-4 is a cross-sectional view of the third layer; 1-5 is a cross-sectional view of the fourth layer; and 1-6 is a cross-sectional view of the top layer.

[0041] Figure 2 This is a schematic diagram of the ceramic particle filling mold of the present invention; in the figure, 2-1 is a three-dimensional view of the mold; 2-2 is a top view of the mold. Detailed Implementation

[0042] The present invention will be further described in detail below with reference to the embodiments.

[0043] Example 1: Preparation of Wear-Resistant Composite Liner

[0044] A method for preparing carbon fiber toughened ceramic reinforced metal composite material:

[0045] Step 1: Selection and preparation of carbon fiber toughened ceramic materials

[0046] The selected ceramic particles are oxide ceramics: Al2O3, and the toughening phase is carbon fiber toughening.

[0047] Preparation method: Al2O3 ceramic powder was pre-laid in a preparation mold. Long carbon fibers were distributed transversely within each layer of ceramic powder, with a mass ratio of ceramic powder to carbon fibers of 1:1. The mixed carbon fiber ceramic composite material was dried, and the monolithic carbon fiber toughened ceramic composite material was prepared by hot pressing sintering. The sintering pressure was 35 MPa, and the sintering temperature was 1850℃. After hot pressing sintering, the carbon fiber toughened ceramic composite material was crushed to obtain carbon fiber toughened ceramic particles. After screening, the particle size of the carbon fiber toughened ceramic particles was selected to be 50 mesh.

[0048] Step 2: Selection of Metal Substrate

[0049] The selected metal matrix is ​​a Cr steel matrix with a particle size of 200 mesh.

[0050] Step 3: Prefabrication of composite materials using 3D printing

[0051] Crushed carbon fiber-reinforced ceramic particles are placed onto the surface of a corundum sheet using a mold. The mold has multiple holes arranged in a matrix, as shown in the schematic diagram. Figure 2 As shown. The placement method is single-layer placement. After the carbon fiber toughened ceramic particles fill the mold hole, the mold is moved vertically to keep the carbon fiber toughened ceramic particles on the corundum surface according to the mold setting. The surface area of ​​the single-layer particles accounts for 20% of the surface area of ​​the corundum sheet;

[0052] Particle Placement Uniformity: To ensure uniform particle placement, a prefabricated mold is used, filled with carbon fiber-reinforced ceramic particles. The prefabricated mold is as follows: Figure 2 As shown; 2-1 Mold perspective view; 2-2 Mold top view.

[0053] The 3D printing matrix powder consists of a Cr steel matrix and 1% (mass fraction) C powder; the binder solution is PVA powder plus deionized water, resulting in a PVA aqueous solution with a density of 1 g / cm³. 3 The viscosity is 3600 MPa. The mass ratio of metal powder to PVA solution is set to 1:2.

[0054] 3D printing uses a layered metal paste printing technique, with the following layering method (starting from the bottom layer 1 to the top layer, with N=10 cycles): Layer 1: A single layer of densely packed metal paste with a sealing degree of 90%-95% and a sealing height of 10-15mm; Layer 2: Carbon fiber-reinforced ceramic particles with a particle density of 30%-50% (surface percentage); Layer 3: Low-layer, high-spacing metal paste printing with a printing height of 4-8mm; the spacing between paste passes is 8-16mm; Layer 4: High-layer, low-spacing metal paste printing with a printing height of 10-15mm; the spacing between paste passes is 12mm. -18mm; 5 layers of carbon fiber toughened ceramic particles, with a particle density of 30% (surface percentage); 6 layers: low-layer high-spacing metal paste printing; 7 layers: high-layer low-spacing metal paste printing; 8 layers: carbon fiber toughened ceramic particles, with 2, 3, and 4 layers forming a cycle, for a total of 10 cycles... 31 layers: high-layer low-spacing metal paste printing, with the top layer of metal paste printing serving as a metal paste sealing layer, achieving a 90% sealing degree and a sealing height of 10mm, resulting in a layered printed slurry metal carbon fiber toughened ceramic composite material; a schematic diagram of its layered printing is shown below. Figure 1 In the diagram, 1-1 is a schematic diagram of 3D printing; 1-2 is a cross-sectional view of the first layer; 1-3 is a cross-sectional view of the second layer; 1-4 is a cross-sectional view of the third layer; 1-5 is a cross-sectional view of the fourth layer; and 1-6 is a cross-sectional view of the top layer.

[0055] Step 4: Composite Material Pre-drying Technology

[0056] 1. The printed slurry metal carbon fiber toughened ceramic composite material was air-dried in a corundum crucible for 24 hours.

[0057] 2. Place the air-dried composite slurry metal-ceramic composite material into a drying oven and dry it at 60℃ for 10 hours.

[0058] Step 5: Low-temperature liquid-solid two-phase sintering technology for composite materials

[0059] By using J-Matpro software simulation to determine the percentage of liquid and solid phases, the liquid-solid two-phase sintering process of the composite material can be controlled. The sintering process used in Example 1 is as follows:

[0060] 1. Low-temperature heating zone: from room temperature to 200℃, the heating rate is 3℃ / min; continue heating to 400℃, the heating rate is 3℃ / min, and hold for 2 hours. This stage is the PVA decomposition zone.

[0061] 2. Medium-temperature heating zone: 400℃ to 800℃, heating rate of 4℃ / min, holding for 2 hours. This stage is the metal powder gas emission zone.

[0062] 3. Liquid-solid two-phase heating zone: 800℃ to 1050℃, heating rate of 4℃ / min, holding for 5 hours. This stage is liquid-solid two-phase sintering, that is, maintaining the carbon fiber toughened ceramic particles in a relatively stable position, and obtaining a composite material with uniformly distributed carbon fiber toughened ceramic particles by long-term impregnation of the carbon fiber toughened ceramic particles with 30% metal liquid phase.

[0063] Step 6. Application of composite materials

[0064] The prepared composite material can be printed into conventional plate shapes for use on the surface of wear-resistant composite lining plates; the composite material is weldable, making it suitable for repair work after surface wear; the prepared composite material is designed according to the actual working layer thickness of the lining plate, significantly reducing the additional cost of equipment.

[0065] Example 2: Preparation of Jaw Crusher Tooth Plates

[0066] A method for preparing carbon fiber toughened ceramic reinforced metal composite material:

[0067] Step 1: Selection and preparation of carbon fiber toughened ceramic materials

[0068] The selected ceramic particles are oxide ceramics: Al2O3 and ZrO2, and the toughening phase is carbon fiber toughening.

[0069] Preparation method: Al2O3 ceramic powder and ZrO2 ceramic powder were pre-laid in a preparation mold (by mass ratio, Al2O3 ceramic powder: ZrO2 ceramic powder = 1:4). Long carbon fibers were distributed longitudinally at an angle within each layer of ceramic powder, with a mass ratio of ceramic powder to carbon fibers of 1:10. The mixed carbon fiber ceramic composite material was dried, and the integral carbon fiber toughened ceramic composite material was prepared by hot pressing sintering. The sintering pressure was 40 MPa, and the sintering temperature was 1900℃. After hot pressing sintering, the composite material was crushed to obtain carbon fiber toughened ceramic particles, which were then screened to a particle size of 100 mesh.

[0070] Step 2: Selection of Metal Substrate

[0071] The selected metal matrix is ​​Mn steel matrix, C powder accounts for 0.5% (mass fraction) of the matrix, and the particle size of the matrix material is 200 mesh.

[0072] Step 3: Prefabrication of composite materials using 3D printing

[0073] Crushed carbon fiber toughened ceramic particles were placed on the surface of a corundum sheet in a single layer, with the surface area of ​​the single layer of particles accounting for 60% of the surface area of ​​the corundum sheet.

[0074] Particle Placement Uniformity: To ensure uniform particle placement, a prefabricated mold is used, filled with carbon fiber-reinforced ceramic particles. The prefabricated mold is as follows: Figure 2 As shown.

[0075] The matrix powder for 3D printing is prepared using Mn steel matrix and C powder; the binder solution is PVA powder plus deionized water, resulting in a PVA aqueous solution with a density of 1.5 g / cm³. 3 The viscosity is 3700 MPa. The mass ratio of metal powder to PVA solution is set to 1:5.

[0076] 3D printing involves layered metal slurry printing. The layering technique is as follows (from bottom layer 1 to top layer, N=5 cycles): Layer 1: Single-layer densely packed metal slurry with a sealing degree of 95% and a sealing height of 15mm; Layer 2: Carbon fiber toughened ceramic particles with a particle density of 50% (surface percentage); Layer 3: Low-layer high-spacing metal slurry printing with a printing height of 8mm and a spacing of 16mm between slurry passes; Layer 4: High-layer low-spacing metal slurry printing with a printing height of 15mm and a spacing of 18mm between slurry passes; Layer 5: Carbon fiber toughened ceramic particles with a particle density of 50% (surface percentage); Layer 6: Low-layer high-spacing metal slurry printing; Layer 7: High-layer low-spacing metal slurry printing; Layer 8: Carbon fiber toughened ceramic particles... Layer 16: High-layer low-spacing metal slurry printing. The top layer of metal slurry is a sealing metal slurry with a sealing degree of 95% and a sealing height of 15mm, resulting in a layered printed slurry-metal carbon fiber toughened ceramic composite material.

[0077] Step 4: Composite Material Pre-drying Technology

[0078] 1. The printed slurry metal carbon fiber toughened ceramic composite material was air-dried in a corundum crucible for 48 hours.

[0079] 2. Place the air-dried composite slurry metal-ceramic composite material into a drying oven and dry it at 80℃ for 24 hours.

[0080] Step 5: Low-temperature liquid-solid two-phase sintering technology for composite materials

[0081] By using J-Matpro software simulation to determine the percentage of liquid and solid phases, the liquid-solid two-phase sintering process of the composite material can be controlled. The sintering process used in Example 2 is as follows:

[0082] 1. Low-temperature heating zone: from room temperature to 280℃, the heating rate is 5℃ / min; continue heating to 450℃, the heating rate is 4℃ / min, and hold for 3 hours. This stage is the PVA decomposition zone.

[0083] 2. Medium-temperature heating zone: 450℃ to 850℃, heating rate is 6℃ / min, hold for 3 hours. This stage is the metal powder gas emission zone.

[0084] 3. Liquid-solid two-phase heating zone: 850℃ to 1100℃, heating rate of 7℃ / min, holding for 10 hours. This stage is liquid-solid two-phase sintering, that is, maintaining the carbon fiber toughened ceramic particles in a relatively stable position, and obtaining a composite material with uniformly distributed carbon fiber toughened ceramic particles by long-term impregnation of the carbon fiber toughened ceramic particles with 40% metal liquid phase.

[0085] Step 6. Application of composite materials

[0086] The prepared composite material can be printed into trapezoidal jaw teeth for use on the surface of jaw crusher teeth; the composite material is weldable, making it suitable for surface wear repair; the prepared composite material is designed according to the actual working layer thickness of the tooth height, significantly reducing the additional cost of the equipment.

[0087] Example 3: Preparation of Hot-Rolled Coil Side Guide Plate

[0088] A method for preparing carbon fiber toughened ceramic reinforced metal composite material:

[0089] Step 1: Selection and preparation of carbon fiber toughened ceramic materials

[0090] The selected ceramic particles are oxide ceramics: B2O3, and the toughening phase is carbon fiber toughening.

[0091] Preparation method: B2O3 ceramic powder was pre-laid in a preparation mold. Long carbon fibers were distributed in each layer of ceramic powder using a combination of cross-fiber angles and short fiber dispersion. The mass ratio of ceramic powder to carbon fibers was 1:3. The mixed carbon fiber toughened ceramic composite material was dried and then prepared as a monolithic carbon fiber toughened ceramic composite material by hot pressing sintering. The sintering pressure was 45 MPa and the sintering temperature was 2000℃. After hot pressing sintering, the carbon fiber toughened ceramic composite material was crushed to obtain carbon fiber toughened ceramic particles. After screening, the particle size of the carbon fiber toughened ceramic particles was selected to be 100 mesh.

[0092] Step 2: Selection of Metal Substrate

[0093] The selected metal matrix is ​​Mn steel matrix, C powder accounts for 0.8% (mass fraction) of the matrix, and the particle size of the matrix material is 200 mesh.

[0094] Step 3: Prefabrication of composite materials using 3D printing

[0095] Crushed carbon fiber toughened ceramic particles were placed on the surface of a corundum sheet in a single layer, with the surface area of ​​the single layer of particles accounting for 50% of the surface area of ​​the corundum sheet.

[0096] Particle Placement Uniformity: To ensure uniform particle placement, a prefabricated mold is used, filled with carbon fiber-reinforced ceramic particles. The prefabricated mold is as follows: Figure 2 As shown.

[0097] The matrix powder for 3D printing is prepared using Mn steel matrix and C powder; the binder solution is PVA powder plus deionized water, resulting in a PVA aqueous solution with a density of 1.2 g / cm³. 3 The viscosity is 3750 MPa. The mass ratio of the metal matrix to the PVA solution is set to 1:3.

[0098] 3D printing is a layered metal paste printing process. The layering technique is as follows (from bottom layer 1 to top layer, number of cycles N=1): Layer 1: Single layer of densely packed metal paste with a sealing degree of 90% and a sealing height of 12mm; Layer 2: Carbon fiber toughened ceramic particles with a particle density of 45% (surface percentage); Layer 3: Low-layer high-spacing metal paste printing with a printing height of 6mm and a spacing of 12mm between paste passes; Layer 4: High-layer low-spacing metal paste printing with a printing height of 10mm and a spacing of 15mm between paste passes; The top layer of metal paste sealing layer is printed as a sealing metal paste with a sealing degree of 90% and a sealing height of 12mm, resulting in a layered printed slurry metal carbon fiber toughened ceramic composite material.

[0099] Step 4: Composite Material Pre-drying Technology

[0100] 1. The printed slurry metal carbon fiber toughened ceramic composite material was air-dried in a corundum crucible for 40 hours.

[0101] 2. Place the air-dried composite slurry metal-ceramic composite material into a drying oven and dry it at 70℃ for 24 hours.

[0102] Step 5: Low-temperature liquid-solid two-phase sintering technology for composite materials

[0103] The percentage of liquid and solid phases in the composite material was determined through J-Matpro software simulation, thus controlling the liquid-solid two-phase sintering process. The sintering process used in Example 3 is as follows:

[0104] 1. Low-temperature heating zone: from room temperature to 260℃, the heating rate is 4℃ / min; continue heating to 420℃, the heating rate is 3.5℃ / min, and hold for 2.5 hours. This stage is the PVA decomposition zone.

[0105] 2. Medium-temperature heating zone: 420℃ to 820℃, heating rate of 5℃ / min, holding for 2.5 hours. This stage is the metal powder gas emission zone.

[0106] 3. Liquid-solid two-phase heating zone: 820℃ to 1100℃, heating rate of 6℃ / min, holding for 8 hours. This stage is liquid-solid two-phase sintering, that is, maintaining the carbon fiber toughened ceramic particles in a relatively stable position, and obtaining a composite material with uniformly distributed carbon fiber toughened ceramic particles by long-term impregnation of the carbon fiber toughened ceramic particles with 35% metal liquid phase.

[0107] Step 6. Application of composite materials

[0108] The prepared composite material can be printed into irregularly shaped hot-rolled coiled side guide plate surface inlay components for use on the side guide plate surface; the composite material has weldability, making it suitable for surface wear repair work; the prepared composite material is designed according to the actual scratch depth of the wear part of the side guide plate, which greatly reduces the additional cost of equipment.

[0109] Example 4: Preparation of Wear-Resistant Hammerhead

[0110] A method for preparing carbon fiber toughened ceramic reinforced metal composite material:

[0111] Step 1: Selection and preparation of carbon fiber toughened ceramic materials

[0112] The selected ceramic particles are oxide ceramics: Al2O3, and the toughening phase is carbon fiber toughening.

[0113] Preparation method: Al2O3 ceramic powder and carbon fiber powder were mixed uniformly at a ratio of 1:2 (volume percentage). The mixed carbon fiber ceramic composite material was dried, and the monolithic carbon fiber toughened ceramic composite material was prepared by hot pressing sintering. The sintering pressure was 40 MPa, and the sintering temperature was 2100℃. After hot pressing sintering, the carbon fiber toughened ceramic composite material was crushed to obtain carbon fiber toughened ceramic particles. After screening, the particle size of the carbon fiber toughened ceramic particles was selected to be 100 mesh.

[0114] Step 2: Selection of Metal Substrate

[0115] The selected metal matrix is ​​a Cr steel matrix, with C powder accounting for 0.7% (mass fraction) of the metal matrix, and the particle size of the matrix material is 200 mesh.

[0116] Step 3: Prefabrication of composite materials using 3D printing

[0117] Crushed carbon fiber toughened ceramic particles were placed on the surface of a corundum sheet in a single layer, with the surface area of ​​the single layer of particles accounting for 50% of the surface area of ​​the corundum sheet.

[0118] Particle Placement Uniformity: To ensure uniform particle placement, a prefabricated mold is used, filled with carbon fiber-reinforced ceramic particles. The prefabricated mold is as follows: Figure 2 As shown.

[0119] The matrix powder for 3D printing is composed of Cr steel matrix and C powder; the binder solution is PVA powder plus deionized water, resulting in a PVA aqueous solution with a density of 1.3 g / cm³. 3 The viscosity is 3700 MPa. The mass ratio of the metal matrix to the PVA solution is set to 1:4.

[0120] 3D printing is a layered metal paste printing process. The layering technique is as follows (from bottom layer 1 to top layer, N=2 cycles): Layer 1: Single layer of densely packed metal paste with a sealing degree of 95% and a sealing height of 15mm; Layer 2: Carbon fiber toughened ceramic particles with a particle density of 45% (surface percentage); Layer 3: Low-layer high-spacing metal paste printing with a printing height of 7mm and a spacing of 14mm between paste passes; Layer 4: High-layer low-spacing metal paste printing with a printing height of 12mm and a spacing of 16mm between paste passes; Layer 5: Carbon fiber toughened ceramic particles with a particle density of 45% (surface percentage); Layer 6: Low-layer high-spacing metal paste printing; Layer 7: High-layer low-spacing metal paste printing; The top layer of metal paste is a sealing metal paste with a sealing degree of 95% and a sealing height of 15mm, resulting in a layered printed slurry metal carbon fiber toughened ceramic composite material.

[0121] Step 4: Composite Material Pre-drying Technology

[0122] 1. The printed slurry metal carbon fiber toughened ceramic composite material was air-dried in a corundum crucible for 42 hours;

[0123] 2. Place the air-dried composite slurry metal-ceramic composite material into a drying oven and dry it at 75℃ for 20 hours.

[0124] Step 5: Low-temperature liquid-solid two-phase sintering technology for composite materials

[0125] The percentage of liquid and solid phases in the composite material was determined using J-Matpro software simulation, which was then used to control the liquid-solid two-phase sintering process. The sintering process used in Example 4 was as follows:

[0126] 1. Low-temperature heating zone: from room temperature to 240℃, the heating rate is 5℃ / min; continue heating to 430℃, the heating rate is 4℃ / min, and hold for 3 hours. This stage is the PVA decomposition zone.

[0127] 2. Medium-temperature heating zone: 430℃ to 840℃, heating rate is 6℃ / min, hold for 3 hours. This stage is the metal powder gas emission zone.

[0128] 3. Liquid-solid two-phase heating zone: 840℃ to 1100℃, heating rate of 6℃ / min, holding for 8 hours. This stage is liquid-solid two-phase sintering, that is, maintaining the carbon fiber toughened ceramic particles in a relatively stable position, and obtaining a composite material with uniformly distributed carbon fiber toughened ceramic particles by long-term impregnation of the carbon fiber toughened ceramic particles with 38% metal liquid phase.

[0129] Step 6. Application of composite materials

[0130] The prepared composite material can be printed into irregularly shaped hammerhead parts for use on the working surface of the hammerhead; the composite material has weldability, making it suitable for repair work after surface wear; the prepared composite material is designed according to the actual working failure thickness of the hammerhead, which greatly reduces the additional cost of the equipment.

[0131] Comparison Patent 1

[0132] 201810965907.X, A metal-framed toughened ceramic composite material, its preparation method, and its application. The ceramic-reinforced metal matrix is ​​prepared using a programmed temperature-controlled liquid-phase sintering method with a sintering temperature of 1200–1500℃.

[0133] Comparison Patent 2

[0134] Patent No. 201810965885.7, Optimized Particle Size Ceramic Reinforced Metal Matrix Composites and Their Preparation Methods and Applications. This comparative patent describes the preparation and application of ceramic reinforced metal matrix composites, employing a programmed temperature-controlled liquid phase sintering method with a sintering temperature of 1350–1500℃ during the preparation of the ceramic reinforced metal matrix bulk.

[0135] Compared with Comparative Patent 1 and Comparative Patent 2, this invention has two important differences. First, the sintering method used in this invention is liquid-solid two-phase sintering, with the sintering temperature controlled below 1100℃. This means that at the highest sintering temperature, a certain amount of liquid phase encapsulates and wets the ceramic particles and metal powder, preventing large-scale migration of ceramic particles and ensuring a uniform distribution of the ceramic particles. Furthermore, a long-term heat preservation environment allows sufficient time for the liquid phase to metallurgically bond with the ceramic particles, resulting in a dense metal matrix. In contrast, Comparative Patent 1 and Comparative Patent 2 show a significant decrease in the uniformity of ceramic particle distribution compared to this patent. Specifically, in the high-temperature region, low-density ceramic particles float while high-density metal powder sinks, resulting in an accumulation of ceramic particles on the upper part of the sintered block, with fewer or even absent ceramic particles in the lower part.

[0136] Compared to Comparative Patent 1 and Comparative Patent 2, the second important difference is that both comparative patents use a method of uniformly mixing ceramic particles and matrix powder before pressing, or directly performing programmed temperature-controlled liquid phase sintering. The difference in this invention lies in the use of 3D printing to precisely control the distribution of ceramic particles and metal powder in each region during the preparation process, while ensuring the uniform distribution of ceramic particles. In the fabrication process, 3D printing involves layered metal slurry printing. The layering technique consists of a single layer of densely packed metal slurry with a sealing degree of 90%-95%. Layer 2: Carbon fiber toughened ceramic particles, with a particle density of 30%-50% (surface percentage). Layer 3: Low-layer, high-spacing metal slurry printing. Layer 4: High-layer, low-spacing metal slurry printing. Layer 5: Carbon fiber toughened ceramic particles, with a particle density of 30% (surface percentage). Layer 6: Low-layer, high-spacing metal slurry printing. Layer 7: High-layer, low-spacing metal slurry printing. Layer 8: Carbon fiber toughened ceramic particles. This process is repeated 10 times, with layers 2, 3, and 4 forming one cycle. Layer 31: High-layer, low-spacing metal slurry printing. The top layer of metal slurry serves as a sealing layer with a sealing degree of 90% and a sealing height of 10mm, resulting in a layered printed slurry-metal carbon fiber toughened ceramic composite material. The resulting composite material exhibits optimized distribution uniformity, high product quality, and precise control, resulting in a high yield and significantly improved fabrication effect.

[0137] Compared with the comparative patent, the present invention uses carbon fiber-toughened ceramic particles. The composite material prepared by this invention exhibits a superior combination of hardness and toughness in working environments with impact conditions, which greatly improves the overall performance of the composite material and expands the application fields of the composite material.

[0138] Comparative Example 3

[0139] Similar to Example 1, except that the circulating layer consists of two layers: the first layer is carbon fiber toughened ceramic particles, and the second layer is metal slurry, forming a circulating layer.

[0140] Comparative Example 4

[0141] Similar to Example 1, except that the circulation layer consists of three layers: the first layer is carbon fiber toughened ceramic particles, the second layer is a high-layer, low-spacing metal paste, and the third layer is a low-layer, high-spacing metal paste.

[0142] Compared to Comparative Examples 3 and 4, the three-layer circulation system and circulation sequence of this invention enable a more uniform distribution of carbon fiber toughened ceramic particles. Furthermore, a dense carbon fiber toughened ceramic-reinforced metal composite material is prepared under prolonged heat treatment.

Claims

1. A method for preparing a carbon fiber toughened ceramic-reinforced metal composite material, characterized in that, Includes the following steps: Carbon fiber toughened ceramic particles and metal paste are printed in layers, with one layer of metal paste sealing layer on the top and bottom, and three layers in the middle forming a cycle. The three middle layers are: the first layer is carbon fiber toughened ceramic particles, the second layer is low-layer high-gap metal paste printing, and the third layer is high-layer low-gap metal paste printing. The first to the third layer is one cycle, and N cycles are performed. The top and bottom layers outside the cycle layers are metal paste sealing layers, resulting in a layered printed metal paste carbon fiber toughened ceramic composite material. The low-layer high-gap metal paste printing is characterized by a paste diameter of 4-6 mm from the printing nozzle and a paste pass spacing of 8-12 mm. The high-layer low-gap metal paste printing refers to the paste diameter of the printing nozzle being 10~15mm, and the spacing between paste passes being 12~18mm; After drying the layered printed metal slurry carbon fiber toughened ceramic composite material, it is then sintered in a low-temperature liquid-solid two-phase region to obtain a carbon fiber toughened ceramic reinforced metal composite material.

2. The method for preparing carbon fiber toughened ceramic reinforced metal composite material according to claim 1, characterized in that, The N cycles mentioned refer to 1 to 10 cycles.

3. The method for preparing carbon fiber toughened ceramic reinforced metal composite material according to claim 1, characterized in that, The raw materials selected for the carbon fiber toughened ceramic particles are carbon fiber and ceramic materials, with a mass ratio of carbon fiber:ceramic material = 1:1~10; in the carbon fiber toughened ceramic particles, carbon fiber is the toughening phase; the angle of the carbon fiber is selected from one or more of the following: transverse, longitudinal, and cross; the distribution mode of carbon fiber and ceramic material is a combination of three methods: long carbon fiber layering, short carbon fiber dispersion, and carbon fiber powder and ceramic powder mixing; and / or, the ceramic material is selected from oxide ceramics, carbide ceramics, and nitride ceramics.

4. The method for preparing carbon fiber toughened ceramic reinforced metal composite material according to claim 1 or 3, characterized in that, The preparation method of the carbon fiber toughened ceramic particles is as follows: carbon fibers are arranged at a selected angle, ceramic materials and carbon fibers are mixed, and carbon fiber toughened ceramic composite material is obtained by hot pressing sintering. The carbon fiber toughened ceramic composite material is crushed to obtain carbon fiber toughened ceramic particles with a particle size of 50-100 mesh.

5. The method for preparing carbon fiber toughened ceramic reinforced metal composite material according to claim 1, characterized in that, The low-layer high-pitch metal paste printing, high-layer low-pitch metal paste printing, and metal paste sealing layer all use metal paste as the printing material. The metal paste includes metal powder, C powder, and binder solution. By mass ratio, the metal matrix (metal powder + C powder): binder solution = 1:(2~5); the mass percentage of C powder in the metal matrix is ​​0.5~1.0%.

6. The method for preparing carbon fiber toughened ceramic reinforced metal composite material according to claim 1, characterized in that, The first layer of carbon fiber toughened ceramic particles is a single layer of carbon fiber toughened ceramic particles. The single layer of carbon fiber toughened ceramic particles is placed on the surface of the corundum sheet using a mold. The mold is a mold with multiple holes arranged in a matrix. The surface area of ​​the single layer of carbon fiber toughened ceramic particles accounts for 20-60% of the surface area of ​​the corundum sheet.

7. The method for preparing carbon fiber toughened ceramic reinforced metal composite material according to claim 1, characterized in that, The printing lines of the low-layer high-spacing metal paste and the high-layer low-spacing metal paste are vertically distributed between the upper and lower layers. And / or, the metal slurry sealing layer has a sealing degree of 90~100% and a sealing height of 10~20mm.

8. The method for preparing carbon fiber toughened ceramic reinforced metal composite material according to claim 1, characterized in that, The aforementioned low-temperature liquid-solid two-phase sintering is a three-stage heating sintering process, including the following sintering steps: (1) Low temperature heating stage: The dried layered printed metal paste carbon fiber toughened ceramic composite material is heated to 200~280℃ at room temperature at a heating rate of 3~5℃ / min; after reaching 200~280℃, the temperature is further increased to 400~450℃ at a heating rate of 3~4℃ / min, and then held at 400~450℃ for 2~3 hours. This stage is the PVA decomposition zone. (2) Medium temperature heating stage: The temperature is raised from 400~450℃ to 800~850℃ at a rate of 4~6℃ / min, and held for 2~3 hours. This stage is the metal powder gas emission zone. (3) Heating stage in the liquid-solid two-phase region: Heating from 800~850℃ to 1050℃~1100℃ at a rate of 4~7℃ / min, and holding for 5~10 hours. This stage is the sintering of the liquid-solid two-phase region, and carbon fiber toughened ceramic reinforced metal composite material is obtained.

9. A carbon fiber toughened ceramic-reinforced metal composite material, characterized in that, The carbon fiber toughened ceramic is uniformly distributed and prepared by any one of the preparation methods described in claims 1-8; the carbon fiber toughened ceramic reinforced metal composite material has weldability.

10. The application of the carbon fiber toughened ceramic reinforced metal composite material according to claim 9 is to set the required thickness according to the requirements of equipment components, as a wear-resistant layer, or to print it into various shapes as wear-resistant parts.

Images