High-strength ceramic-based composite material as well as preparation method and application thereof

Abstract

The invention provides a high-strength ceramic-based composite material as well as a preparation method and application thereof. The high-strength ceramic-based composite material comprises the following components in percentage by weight: 65% of aluminum oxide ceramic; 15%-20% of a carbon fiber reinforced phase; 18% to 20% of a SiO2-CaO-Na2O binding phase; 1% of a dispersant; in this way, the tensile strength and fracture toughness of the composite material are improved, the technical problem that a traditional ceramic pull-up type 3D printing piece is prone to brittle fracture is solved, the geometric accuracy in the pull-up type 3D printing process is ensured, it is ensured that the composite material has good fluidity and forming quality in the pull-up type 3D printing process, and the quality of the composite material is improved. Deformation and breakage caused by gravity are avoided, the service life of the 3D printing product is prolonged, the working reliability of the 3D printing product is improved, and a high-quality solution is provided for rapid manufacturing of the high-strength and high-precision 3D printing product.

Description

Technical Field

[0001] The present invention relates to the technical field of top-pull 3D printing, and in particular to a high-strength ceramic-based composite material and a preparation method and application thereof. Background Art

[0002] With the rapid development of modern science and technology, especially the growing demand for high-performance and lightweight materials in aerospace, automobile manufacturing, biomedicine and other fields, ceramic-based composites have gradually become one of the hot spots in materials science research due to their unique physical, chemical and mechanical properties, such as high hardness, high wear resistance, excellent corrosion resistance and good thermal stability. However, the traditional ceramic materials are limited in their wide application in complex structural parts due to their brittleness and processing difficulties.

[0003] In recent years, the rise of 3D printing technology (also known as additive manufacturing technology) has provided a new idea for the preparation of ceramic-based composites. 3D printing technology can accurately control the layer-by-layer stacking of materials and realize the integrated molding of complex shapes and structures, which greatly broadens the application scope of ceramic-based composites. In particular, the top-pull 3D printing technology, with its unique bottom-up construction method, further improves the printing efficiency and material utilization rate, and has become an emerging means of preparing high-performance ceramic-based composites. At present, there are the following technical problems in the top-pull 3D printing process:

[0004] The inherent high hardness and brittleness of traditional ceramic materials make them prone to brittle fracture when subjected to external forces and difficult to adapt to large deformations or impact loads, which is particularly evident in the top-down 3D printing process. Due to the accumulation of layers under the action of gravity, especially when building tall and slender structures, significant stress concentration and deformation are easily generated inside the material, thereby increasing the risk of composite material fracture during and after printing.

[0005] The ratio of traditional ceramic powder to binder directly affects the fluidity and molding quality during the printing process. If the ratio is not appropriate, it may cause problems such as inconsistent shrinkage, cracking or deformation of the printed parts during the sintering process, thus affecting the geometric accuracy.

[0006] Traditional ceramic materials usually have a high melting point, and the melting and solidification process is complex, requiring precise control of temperature and cooling. This high melting point makes it difficult for traditional ceramic materials to melt quickly and flow evenly during top-pull 3D printing, thus affecting the fluidity and molding accuracy during top-pull 3D printing.

[0007] The disclosure of the above background technology content is only used to assist in understanding the inventive concept and technical solution of the present invention. It does not necessarily belong to the prior art of the present invention application, nor does it necessarily provide technical guidance. In the absence of clear evidence that the above content has been disclosed before the filing date of the present invention application, the above background technology should not be used to evaluate the novelty and creativity of the present application. Summary of the invention

[0008] In order to solve the technical problems that traditional ceramic 3D printed parts are prone to brittle fracture, the geometric accuracy cannot be ensured in the top-pull 3D printing process, and the fluidity and molding accuracy in the top-pull 3D printing process are poor, the present invention proposes a high-strength ceramic-based composite material and a preparation method and application thereof, which improves the tensile strength and fracture toughness of the composite material, solves the technical problem that traditional ceramic top-pull 3D printed parts are prone to brittle fracture, ensures the geometric accuracy in the top-pull 3D printing process, ensures that the composite material has good fluidity and molding quality in the top-pull printing process, avoids deformation and fracture caused by gravity, improves the service life and working reliability of 3D printed parts, and provides a high-quality solution for the rapid manufacturing of high-strength and high-precision parts.

[0009] In order to achieve the above object, the technical solution of the present invention is as follows:

[0010] In one aspect, the present invention provides a high-strength ceramic matrix composite material, comprising the following components in weight percentage: 65% alumina ceramic; 15% to 20% carbon fiber reinforcement phase; SiO 2 -CaO-Na 2 O Binder phase 18%~20%; dispersant 1%.

[0011] The present invention proposes a high-strength ceramic-based composite material and a preparation method and application thereof, which improves the tensile strength and fracture toughness of the composite material, solves the technical problem that traditional ceramic pull-up 3D printed parts are prone to brittle fracture, ensures the geometric accuracy during the pull-up 3D printing process, ensures that the composite material has good fluidity and molding quality during the pull-up 3D printing process, avoids deformation and fracture caused by gravity, improves the service life and working reliability of 3D printed products, and provides a high-quality solution for the rapid manufacturing of high-strength and high-precision 3D printed products.

[0012] As a preferred technical solution, active groups are introduced on the surface of the carbon fiber to form a carbon fiber reinforcement phase, and the active groups include: carboxyl active groups and hydroxyl active groups.

[0013] As a preferred technical solution, the following components are also included in weight percentage: 0.8-1% plasticizer.

[0014] As a preferred technical solution, the SiO2 -CaO-Na 2 The average particle size of the O bonding phase is 12-18 μm, and the particle size of the alumina ceramic is 10-15 μm.

[0015] In another aspect, the present invention provides a method for preparing a high-strength ceramic-based composite material, wherein the method comprises the following steps:

[0016] S1 pre-treats alumina ceramic powder, carbon fiber and silicate glass to obtain alumina ceramic, carbon fiber reinforced phase and SiO 2 -CaO-Na 2 O bonding phase;

[0017] S2 is alumina ceramics, carbon fiber reinforced phase, SiO 2 -CaO-Na 2 The binder phase and the dispersant are fully mixed and stirred to obtain a mixture;

[0018] S3 extrudes and granulates the mixture to obtain a high-strength ceramic-based composite material.

[0019] As a preferred technical solution, the alumina ceramic powder is pretreated in step S1, specifically comprising the following steps:

[0020] The alumina ceramic powder is ball-milled, and the average particle size of the pre-treated alumina ceramic is controlled to be 10 to 15 μm.

[0021] As a preferred technical solution, the carbon fiber is pretreated in step S1, specifically comprising the following steps:

[0022] The carbon fiber is subjected to electrochemical anodizing treatment. In a 10% sulfuric acid solution, carboxyl active groups and hydroxyl active groups are introduced into the surface of the carbon fiber to obtain a pretreated carbon fiber reinforced phase. The voltage of the electrochemical anodizing treatment is 14 to 18 V, and the time of the electrochemical anodizing treatment is 28 to 35 minutes.

[0023] As a preferred technical solution, the silicate glass is pretreated in step S1, specifically comprising the following steps:

[0024] The silicate glass is melted at 1400-1500℃, cooled and crushed to an average particle size of 12-18μm to obtain the pre-treated SiO 2 -CaO-Na 2 O bonding phase.

[0025] As a preferred technical solution, the following step is also included between step S2 and step S3: adding a plasticizer to the mixture and fully mixing and stirring for 12 to 15 minutes to obtain a uniformly mixed powder.

[0026] On the other hand, the use of the high-strength ceramic-based composite material according to any one of the above items in preparing a top-pull 3D printed part comprises the following steps:

[0027] Printing the high-strength ceramic-based composite material includes the following steps: putting the high-strength ceramic-based composite material into a top-pull 3D printer for printing to obtain a top-pull 3D printed preform, wherein the wavelength of the light source is 300 to 400 nm, printing is performed layer by layer, the thickness of each layer is 20 to 50 μm, and the printing speed is greater than 100 layers / h;

[0028] Degreasing the top-pull 3D printed preform, including the following steps: heating from room temperature to 200°C, holding time for 2 hours, heating rate of 0.5°C / min; heating from 200°C to 400°C, holding time for 3 hours, heating rate of 0.3°C / min; heating from 400°C to 600°C, holding time for 2 hours, heating rate of 0.5°C / min, cooling to room temperature, and obtaining a degreased top-pull 3D printed preform;

[0029] The degreased top-pull 3D printed preform is sintered, which includes the following steps: sintering at a temperature of 1200-1300° C. for 2-3 hours to obtain a top-pull 3D printed part.

[0030] The present invention provides a high-strength ceramic-based composite material and a preparation method and application thereof, which have the following beneficial effects:

[0031] 1) The tensile strength and fracture toughness of the composite material are improved, the technical problem of brittle fracture of traditional ceramic pull-up 3D printed parts is solved, the geometric accuracy in the pull-up 3D printing process is ensured, and the composite material has good fluidity and molding quality in the pull-up 3D printing process, which avoids deformation and fracture caused by gravity, improves the service life and working reliability of 3D printed products, and provides a high-quality solution for the rapid manufacturing of high-strength and high-precision 3D printed products.

[0032] 2) Adding 15% to 20% carbon fiber as a reinforcement phase greatly improves the tensile strength (≥310MPa) and fracture toughness (≥5.6MPa·m1 / 2) of the composite material, solving the technical problem of brittle fracture of traditional ceramic 3D printed parts;

[0033] Add 18% to 20% SiO 2 -CaO-Na 2O acts as a bonding phase, forming a chemical bond with the alumina ceramic matrix, effectively improving the dimensional stability of the composite material, making the dimensional change rate ≤ 0.3%, ensuring the geometric accuracy during the pull-up 3D printing process;

[0034] Dispersants improve the dispersion and fluidity of raw material powders, ensuring good molding during 3D printing;

[0035] The optimized formula of high-strength ceramic-based composite materials shows good fluidity and molding quality during the top-down 3D printing process, and the degree of deformation is significantly lower than that of traditional ceramic materials;

[0036] This innovative high-performance ceramic-based composite material can be widely used in top-pull 3D printing technology, providing a high-quality solution for the rapid manufacturing of high-strength and high-precision 3D printed products.

[0037] 3) Alumina ceramics are a typical high-strength, high-temperature resistant ceramic material with excellent mechanical properties and thermal stability. By controlling the particle size to 10-15 μm through pretreatment, good fluidity and molding quality can be ensured during 3D printing;

[0038] Carbon fiber is electrochemically oxidized to obtain a carbon fiber reinforcement phase, and active groups such as carboxyl and hydroxyl groups are introduced on the surface of the carbon fiber to form a strong interface bond with the alumina ceramic matrix; this greatly improves the tensile strength and fracture toughness of the composite material, solving the problem of brittle fracture of traditional ceramic 3D printed parts;

[0039] Silicate glass is melted at 1400-1500℃ and crushed after cooling. By controlling the average particle size to 12-18μm, it can form a chemical bond with the alumina ceramic matrix, which is conducive to ensuring the geometric accuracy during the top-down 3D printing process and further improving the mechanical properties and dimensional stability of the composite material.

[0040] Dispersants improve the dispersion and fluidity of raw material powders, ensuring good molding during 3D printing;

[0041] Plasticizers can improve the toughness of composite materials during high-temperature 3D printing and reduce the risk of deformation;

[0042] Furthermore, the raw material particle size, formula ratio and process parameters are optimized, and the alumina ceramic, carbon fiber reinforced phase, SiO 2 -CaO-Na 2 The synergistic combination of the binder phase, dispersant and plasticizer makes the composite material exhibit excellent performance in mechanical properties, geometric accuracy, fluidity and molding accuracy.

[0043] 4) Optimize 3D printing process parameters to ensure that the composite material has good fluidity and molding quality during the pull-up printing process, further avoid deformation and fracture caused by gravity, and improve the strength of the product. DETAILED DESCRIPTION

[0044] The preferred embodiments of the present invention are described in detail below with reference to the embodiments.

[0045] The present invention provides a high-strength ceramic-based composite material, comprising the following components in weight percentage: 65% alumina ceramic; 15% to 20% carbon fiber reinforcement phase; SiO 2 -CaO-Na 2 O Binder phase 18%~20%; dispersant 1%.

[0046] The present invention provides a high-strength ceramic-based composite material, which improves the tensile strength and fracture toughness of the composite material, solves the technical problem that traditional ceramic pull-up 3D printed parts are prone to brittle fracture, ensures the geometric accuracy during the pull-up 3D printing process, ensures that the composite material has good fluidity and molding quality during the pull-up 3D printing process, avoids deformation and fracture caused by gravity, improves the service life and working reliability of 3D printed products, and provides a high-quality solution for the rapid manufacturing of high-strength and high-precision 3D printed products.

[0047] Preferably, active groups are introduced on the surface of the carbon fiber to form a carbon fiber reinforcement phase, and the active groups include: carboxyl active groups and hydroxyl active groups.

[0048] Preferably, the following components are further included in weight percentage: 0.8-1% of plasticizer.

[0049] Preferably, the SiO 2 -CaO-Na 2 The average particle size of the O bonding phase is 12-18 μm, and the particle size of the alumina ceramic is 10-15 μm.

[0050] The present invention provides a method for preparing a high-strength ceramic-based composite material, and the method comprises the following steps:

[0051] S1 pre-treats alumina ceramic powder, carbon fiber and silicate glass to obtain alumina ceramic, carbon fiber reinforced phase and SiO 2 -CaO-Na 2 O bonding phase;

[0052] In step S1, the alumina ceramic powder is pretreated, which specifically includes the following steps:

[0053] The alumina ceramic powder is ball-milled to control the average particle size of the pre-treated alumina ceramic to 10 to 15 μm;

[0054] In step S1, the carbon fiber is pretreated, which specifically comprises the following steps:

[0055] The carbon fiber is subjected to electrochemical anodizing treatment. In a 10% sulfuric acid solution, carboxyl active groups and hydroxyl active groups are introduced into the surface of the carbon fiber to obtain a pretreated carbon fiber reinforced phase. The voltage of the electrochemical anodizing treatment is 14 to 18 V, and the time of the electrochemical anodizing treatment is 28 to 35 minutes.

[0056] In step S1, silicate glass is pretreated, which specifically includes the following steps:

[0057] The silicate glass is melted at 1400-1500℃, cooled and crushed to an average particle size of 12-18μm to obtain the pre-treated SiO 2 -CaO-Na 2 O bonding phase;

[0058] S2 is alumina ceramics, carbon fiber reinforced phase, SiO 2 -CaO-Na 2 The binder phase and the dispersant are fully mixed and stirred to obtain a mixture;

[0059] S3 extrudes and granulates the mixture to obtain a high-strength ceramic-based composite material.

[0060] Preferably, the following step is further included between step S2 and step S3: adding a plasticizer to the mixture and fully mixing and stirring for 12 to 15 minutes to obtain a uniformly mixed powder.

[0061] The use of the high-strength ceramic-based composite material according to any one of the above items in preparing a top-pull 3D printed part comprises the following steps:

[0062] Printing the high-strength ceramic-based composite material includes the following steps: putting the high-strength ceramic-based composite material into a top-pull 3D printer for printing to obtain a top-pull 3D printed preform, wherein the wavelength of the light source is 300 to 400 nm, printing is performed layer by layer, the thickness of each layer is 20 to 50 μm, and the printing speed is greater than 100 layers / h;

[0063] Degreasing the top-pull 3D printed preform, including the following steps: heating from room temperature to 200°C, holding time for 2 hours, heating rate of 0.5°C / min; heating from 200°C to 400°C, holding time for 3 hours, heating rate of 0.3°C / min; heating from 400°C to 600°C, holding time for 2 hours, heating rate of 0.5°C / min, cooling to room temperature, and obtaining a degreased top-pull 3D printed preform;

[0064] The degreased top-pull 3D printed preform is sintered, which includes the following steps: sintering at a temperature of 1200-1300° C. for 2-3 hours to obtain a top-pull 3D printed part.

[0065] Example 1

[0066] The present invention provides a method for preparing a top-pull 3D printed part, comprising the following preparation steps:

[0067] Pre-treating the alumina ceramic powder, subjecting 65% by weight of the alumina ceramic powder to ball milling, controlling the average particle size of the pre-treated alumina ceramic to 15 μm, and obtaining the alumina ceramic;

[0068] Pre-treating the carbon fiber, introducing 15% by weight of carboxyl active groups and hydroxyl active groups on the surface of the carbon fiber in a 10% sulfuric acid solution to obtain a carbon fiber reinforced phase, wherein the voltage of the electrochemical anodizing treatment is 18V, and the time of the electrochemical anodizing treatment is 28min;

[0069] The silicate glass was pretreated, 18% by weight of silicate glass was melted at 1500°C, and then pulverized to an average particle size of 18 μm to obtain SiO 2 -CaO-Na 2 O bonding phase;

[0070] Alumina ceramics, carbon fiber reinforcement, SiO 2 -CaO-Na 2 The O binding phase and 1% by weight of a dispersant are fully mixed and stirred to obtain a mixture;

[0071] Add 0.8% by weight of a plasticizer to the mixture and stir thoroughly for 15 minutes to obtain a uniformly mixed powder;

[0072] The uniformly mixed powder is extruded and granulated to obtain a high-strength ceramic-based composite material;

[0073] Printing the high-strength ceramic-based composite material includes the following steps: putting the high-strength ceramic-based composite material into a top-pull 3D printer for printing to obtain a top-pull 3D printed preform, wherein the wavelength of the light source is 400nm, printing is performed layer by layer, the thickness of each layer is 50μm, and the printing speed is 110 layers / h;

[0074] Degreasing the top-pull 3D printed preform, including the following steps: heating from room temperature to 200°C, holding time for 2 hours, heating rate of 0.5°C / min; heating from 200°C to 400°C, holding time for 3 hours, heating rate of 0.3°C / min; heating from 400°C to 600°C, holding time for 2 hours, heating rate of 0.5°C / min, cooling to room temperature, and obtaining a degreased top-pull 3D printed preform;

[0075] The degreased top-pull 3D printed preform is sintered, including the following steps: sintering at a temperature of 1300° C. for 2 hours to obtain a top-pull 3D printed part.

[0076] The present invention also provides a top-pull 3D printed part, which is prepared according to the above-mentioned method for preparing the top-pull 3D printed part.

[0077] Comparative Example 1

[0078] Comparative Example 1 provides pure alumina ceramic powder;

[0079] Printing pure alumina ceramic powder includes the following steps: putting the pure alumina ceramic powder into a top-pull 3D printer for printing to obtain a top-pull 3D printed preform, wherein the wavelength of the light source is 400nm, printing is performed layer by layer, the thickness of each layer is 50μm, and the printing speed is 110 layers / h;

[0080] Degreasing the top-pull 3D printed preform, including the following steps: heating from room temperature to 200°C, holding time for 2 hours, heating rate of 0.5°C / min; heating from 200°C to 400°C, holding time for 3 hours, heating rate of 0.3°C / min; heating from 400°C to 600°C, holding time for 2 hours, heating rate of 0.5°C / min, cooling to room temperature, and obtaining a degreased top-pull 3D printed preform;

[0081] The degreased top-pull 3D printed preform is sintered, including the following steps: sintering at a temperature of 1300° C. for 2 hours to obtain a top-pull 3D printed part.

[0082] Comparative Example 1 also provides a top-pull 3D printed part, which is prepared according to the above-mentioned method for preparing the top-pull 3D printed part.

[0083] Comparative Example 2

[0084] Comparative Example 2 The present invention provides a method for preparing a top-pull 3D printed part, comprising the following preparation steps:

[0085] Pre-treating the alumina ceramic powder, subjecting 65% by weight of the alumina ceramic powder to ball milling, controlling the average particle size of the pre-treated alumina ceramic to 15 μm, and obtaining the alumina ceramic;

[0086] Pre-treating the carbon fiber, introducing carboxyl active groups and hydroxyl active groups into the surface of 10% by weight of the carbon fiber in a 10% sulfuric acid solution, to obtain a pre-treated carbon fiber reinforced phase, wherein the voltage of the electrochemical anodizing treatment is 18V, and the time of the electrochemical anodizing treatment is 28min, to obtain a carbon fiber reinforced phase;

[0087] The silicate glass was pretreated, 18% by weight of silicate glass was melted at 1500°C, and then crushed to an average particle size of 18 μm to obtain SiO 2 -CaO-Na 2 O bonding phase;

[0088] Alumina ceramics, carbon fiber reinforcement, SiO 2 -CaO-Na 2 The O binding phase and 1% by weight of a dispersant are fully mixed and stirred to obtain a mixture;

[0089] Add 0.8% by weight of a plasticizer to the mixture and stir thoroughly for 15 minutes to obtain a uniformly mixed powder;

[0090] The uniformly mixed powder is extruded and granulated to obtain a high-strength ceramic-based composite material;

[0091] Printing the high-strength ceramic-based composite material includes the following steps: putting the high-strength ceramic-based composite material into a top-pull 3D printer for printing to obtain a top-pull 3D printed preform, wherein the wavelength of the light source is 400nm, printing is performed layer by layer, the thickness of each layer is 50μm, and the printing speed is 110 layers / h;

[0092] Degreasing the top-pull 3D printed preform, including the following steps: heating from room temperature to 200°C, holding time for 2 hours, heating rate of 0.5°C / min; heating from 200°C to 400°C, holding time for 3 hours, heating rate of 0.3°C / min; heating from 400°C to 600°C, holding time for 2 hours, heating rate of 0.5°C / min, cooling to room temperature, and obtaining a degreased top-pull 3D printed preform;

[0093] The degreased top-pull 3D printed preform is sintered, including the following steps: sintering at a temperature of 1300° C. for 2 hours to obtain a top-pull 3D printed part.

[0094] Comparative Example 2 also provides a top-pull 3D printed part, which is prepared according to the above-mentioned method for preparing the top-pull 3D printed part.

[0095] Comparative Example 3

[0096] Comparative Example 3 provides a method for preparing a top-pull 3D printed part, comprising the following preparation steps:

[0097] Pre-treating the alumina ceramic powder, subjecting 65% by weight of the alumina ceramic powder to ball milling, controlling the average particle size of the pre-treated alumina ceramic to 15 μm, and obtaining the alumina ceramic;

[0098] Pre-treating the carbon fiber, introducing carboxyl active groups and hydroxyl active groups into the surface of 20% by weight of the carbon fiber in a 10% sulfuric acid solution to obtain a carbon fiber reinforced phase, wherein the voltage of the electrochemical anodizing treatment is 18V, and the time of the electrochemical anodizing treatment is 28min;

[0099] The silicate glass was pretreated, 18% by weight of silicate glass was melted at 1500°C, and then pulverized to an average particle size of 18 μm to obtain SiO 2 -CaO-Na 2 O bonding phase;

[0100] Alumina ceramics, carbon fiber reinforcement, SiO 2 -CaO-Na 2 The O binding phase and 1% by weight of a dispersant are fully mixed and stirred to obtain a mixture;

[0101] Add 0.8% by weight of a plasticizer to the mixture and stir thoroughly for 15 minutes to obtain a uniformly mixed powder;

[0102] The uniformly mixed powder is extruded and granulated to obtain a high-strength ceramic-based composite material;

[0103] Printing the high-strength ceramic-based composite material includes the following steps: putting the high-strength ceramic-based composite material into a top-pull 3D printer for printing to obtain a top-pull 3D printed preform, wherein the wavelength of the light source is 400nm, printing is performed layer by layer, the thickness of each layer is 50μm, and the printing speed is 110 layers / h;

[0104] Degreasing the top-pull 3D printed preform, including the following steps: heating from room temperature to 200°C, holding time for 2 hours, heating rate of 0.5°C / min; heating from 200°C to 400°C, holding time for 3 hours, heating rate of 0.3°C / min; heating from 400°C to 600°C, holding time for 2 hours, heating rate of 0.5°C / min, cooling to room temperature, and obtaining a degreased top-pull 3D printed preform;

[0105] The degreased top-pull 3D printed preform is sintered, including the following steps: sintering at a temperature of 1300° C. for 2 hours to obtain a top-pull 3D printed part.

[0106] Comparative Example 3 also provides a top-pull 3D printed part, which is prepared according to the above-mentioned method for preparing the top-pull 3D printed part.

[0107] Comparative Example 4

[0108] Comparative Example 4 provides a method for preparing a top-pull 3D printed part, comprising the following preparation steps:

[0109] Pre-treating the alumina ceramics, subjecting 65% by weight of alumina ceramic powder to ball milling, controlling the average particle size of the pre-treated alumina ceramics to 15 μm, and obtaining alumina ceramics;

[0110] Pre-treating the carbon fiber, introducing carboxyl active groups and hydroxyl active groups into the surface of 15% by weight of the carbon fiber in a 10% sulfuric acid solution, to obtain a pre-treated carbon fiber reinforced phase, wherein the voltage of the electrochemical anodizing treatment is 18V, and the time of the electrochemical anodizing treatment is 28min;

[0111] Alumina ceramics, carbon fiber reinforcement phase and 1% by weight of a dispersant are fully mixed and stirred to obtain a mixture;

[0112] Add 0.8% by weight of a plasticizer to the mixture and stir thoroughly for 15 minutes to obtain a uniformly mixed powder;

[0113] The uniformly mixed powder is extruded and granulated to obtain a high-strength ceramic-based composite material;

[0114] Printing the high-strength ceramic-based composite material includes the following steps: putting the high-strength ceramic-based composite material into a top-pull 3D printer for printing to obtain a top-pull 3D printed preform, wherein the wavelength of the light source is 400nm, printing is performed layer by layer, the thickness of each layer is 50μm, and the printing speed is 110 layers / h;

[0115] Degreasing the top-pull 3D printed preform, including the following steps: heating from room temperature to 200°C, holding time for 2 hours, heating rate of 0.5°C / min; heating from 200°C to 400°C, holding time for 3 hours, heating rate of 0.3°C / min; heating from 400°C to 600°C, holding time for 2 hours, heating rate of 0.5°C / min, cooling to room temperature, and obtaining a degreased top-pull 3D printed preform;

[0116] The degreased top-pull 3D printed preform is sintered, including the following steps: sintering at a temperature of 1300° C. for 2 hours to obtain a top-pull 3D printed part.

[0117] Comparative Example 4 also provides a top-pull 3D printed part, which is prepared according to the above-mentioned method for preparing the top-pull 3D printed part.

[0118] Comparative Example 5

[0119] Comparative Example 5 provides a method for preparing a top-pull 3D printed part, comprising the following preparation steps:

[0120] Pre-treating the alumina ceramics, subjecting 65% by weight of alumina ceramic powder to ball milling, controlling the average particle size of the pre-treated alumina ceramics to 15 μm, and obtaining alumina ceramics;

[0121] Pre-treating the carbon fiber, introducing carboxyl active groups and hydroxyl active groups into the surface of 15% by weight of the carbon fiber in a 10% sulfuric acid solution to obtain a pre-carbon fiber reinforced phase, wherein the voltage of the electrochemical anodizing treatment is 18V, and the time of the electrochemical anodizing treatment is 28min;

[0122] The silicate glass was pretreated, 15% by weight of silicate glass was melted at 1500°C, and then pulverized to an average particle size of 18 μm to obtain SiO 2 -CaO-Na 2 O bonding phase;

[0123] Alumina ceramics, carbon fiber reinforcement, SiO 2 -CaO-Na 2 The O binding phase and 1% by weight of a dispersant are fully mixed and stirred to obtain a mixture;

[0124] Add 0.8% by weight of a plasticizer to the mixture and stir thoroughly for 15 minutes to obtain a uniformly mixed powder;

[0125] The uniformly mixed powder is extruded and granulated to obtain a high-strength ceramic-based composite material;

[0126] Printing the high-strength ceramic-based composite material includes the following steps: putting the high-strength ceramic-based composite material into a top-pull 3D printer for printing to obtain a top-pull 3D printed preform, wherein the wavelength of the light source is 400nm, printing is performed layer by layer, the thickness of each layer is 50μm, and the printing speed is 110 layers / h;

[0127] Degreasing the top-pull 3D printed preform, including the following steps: heating from room temperature to 200°C, holding time for 2 hours, heating rate of 0.5°C / min; heating from 200°C to 400°C, holding time for 3 hours, heating rate of 0.3°C / min; heating from 400°C to 600°C, holding time for 2 hours, heating rate of 0.5°C / min, cooling to room temperature, and obtaining a degreased top-pull 3D printed preform;

[0128] The degreased top-pull 3D printed preform is sintered, including the following steps: sintering at a temperature of 1300° C. for 2 hours to obtain a top-pull 3D printed part.

[0129] The present invention also provides a top-pull 3D printed part, which is prepared according to the above-mentioned method for preparing the top-pull 3D printed part.

[0130] Comparative Example 6

[0131] Comparative Example 6 provides a method for preparing a top-pull 3D printed part, comprising the following preparation steps:

[0132] Pre-treating the alumina ceramics, subjecting 65% by weight of alumina ceramic powder to ball milling, controlling the average particle size of the pre-treated alumina ceramics to 15 μm, and obtaining alumina ceramics;

[0133] Pre-treating the carbon fiber, introducing carboxyl active groups and hydroxyl active groups into the surface of 15% by weight of the carbon fiber in a 10% sulfuric acid solution to obtain a carbon fiber reinforced phase, wherein the voltage of the electrochemical anodizing treatment is 18V, and the time of the electrochemical anodizing treatment is 28min;

[0134] The silicate glass was pretreated, 20% by weight of silicate glass was melted at 1500°C, and then pulverized to an average particle size of 18 μm to obtain SiO 2 -CaO-Na 2 O bonding phase;

[0135] Alumina ceramics, carbon fiber reinforcement, SiO 2 -CaO-Na 2 The O binding phase and 1% by weight of a dispersant are fully mixed and stirred to obtain a mixture;

[0136] Add 0.8% by weight of a plasticizer to the mixture and stir thoroughly for 15 minutes to obtain a uniformly mixed powder;

[0137] The uniformly mixed powder is extruded and granulated to obtain a high-strength ceramic-based composite material;

[0138] Printing the high-strength ceramic-based composite material includes the following steps: putting the high-strength ceramic-based composite material into a top-pull 3D printer for printing to obtain a top-pull 3D printed preform, wherein the wavelength of the light source is 400nm, printing is performed layer by layer, the thickness of each layer is 50μm, and the printing speed is 110 layers / h;

[0139] Degreasing the top-pull 3D printed preform, including the following steps: heating from room temperature to 200°C, holding time for 2 hours, heating rate of 0.5°C / min; heating from 200°C to 400°C, holding time for 3 hours, heating rate of 0.3°C / min; heating from 400°C to 600°C, holding time for 2 hours, heating rate of 0.5°C / min, cooling to room temperature, and obtaining a degreased top-pull 3D printed preform;

[0140] The degreased top-pull 3D printed preform is sintered, including the following steps: sintering at a temperature of 1300° C. for 2 hours to obtain a top-pull 3D printed part.

[0141] The present invention also provides a top-pull 3D printed part, which is prepared according to the above-mentioned method for preparing the top-pull 3D printed part.

[0142] Experimental means of experimental data testing

[0143] The high-strength ceramic-based composite materials and top-pull 3D printed parts prepared in Example 1 and Comparative Examples 1-6 were measured by the following experimental means:

[0144] The tensile strength of ceramic matrix composite materials is tested by direct tensile method, and the test steps are as follows: During the test, the ceramic sample is fixed on the tensile testing machine, and tensile force is applied through the tensile jaws until the sample breaks. By measuring the maximum tensile force at break and combining the cross-sectional area of ​​the sample, the tensile strength of the ceramic material is calculated as shown in Table 1 of the specification.

[0145] The fracture toughness test of ceramic matrix composites is based on ISO 14704 (Standard for fracture toughness test methods of advanced ceramics). The test steps are as follows:

[0146] 1) According to the size and shape specified in the standard, the ceramic material is cut, ground and processed to prepare the samples required for the test. The size and shape of the sample must meet the requirements of the test method to ensure the accuracy and repeatability of the test results;

[0147] 2) Polish and clean the sample surface to eliminate the influence of surface defects and contamination on the test results;

[0148] 3) Install the processed sample in the test fixture, ensuring that the sample is correctly aligned and firmly fixed. The test fixture should meet the standard requirements to ensure the stability of the sample during loading.

[0149] 4) Set up the loading system and apply the load according to the loading rate and loading method (such as three-point bending) specified in the standard. The loading system should be able to accurately control the magnitude and speed of the loading force and record relevant data during the loading process;

[0150] 5) Start the loading system and apply load to the sample at the preset loading rate. During the loading process, it is necessary to pay close attention to the deformation and crack propagation of the sample;

[0151] 6) Use the data acquisition system to record the key data such as load value and displacement value during the loading process. These data will be used for subsequent data processing and result analysis;

[0152] 7) Continue loading until the sample breaks. At the moment of fracture, ensure that the data acquisition system can accurately capture the load and displacement values ​​at the time of fracture.

[0153] 8) The recorded data is sorted and analyzed, and the system calculates the fracture toughness value of the sample based on standard mathematical models and formulas.

[0154] The dimensional change rate of the 3D printed parts after sintering was measured by a laser scanner;

[0155] Measurement steps: First, use a high-precision laser scanner to perform a full-scale scan of the 3D printed parts before and after sintering to obtain accurate three-dimensional data; then, use professional three-dimensional processing software to compare the data before and after sintering and calculate the changes in each key dimension.

[0156] Calculation method: Dimension change rate = (size after sintering - size before sintering) / size before sintering × 100%.

[0157] The rheometer is used to measure the fluidity of high-strength ceramic-based composite materials, and the laser interferometer measures the deformation of the surface of 3D printed parts;

[0158] 1. Prepare the sample:

[0159] Take an appropriate amount of the prepared ceramic matrix composite powder and ensure that the sample is dry and uniform;

[0160] The sample size should be sufficient to perform several repeated measurements to ensure the reliability of the data;

[0161] 2. Instrument settings:

[0162] Turn on the Hosokawa PT-X flow tester and perform initialization and calibration;

[0163] Set the measurement mode to Powder Flow Time Test Mode;

[0164] Select appropriate container and flow measurement pipe diameter according to powder characteristics;

[0165] 3. Measurement process:

[0166] Pour the ceramic matrix composite powder into the designated container to ensure there is no agglomeration;

[0167] Regarding the laser interferometer to measure the surface deformation of 3D printed parts, the specific test steps are as follows:

[0168] 1) Before measuring, you need a reference model or design data, which represents the shape and size of the print in an ideal state;

[0169] 2) Comparing the results of laser interferometer measurement with the reference model, the deformation of the printed surface can be intuitively seen;

[0170] 3) Use professional measurement software to analyze the data collected by the laser interferometer to calculate the specific values ​​of deformation, such as deformation amount, deformation direction, deformation distribution, etc.;

[0171] 301) A deformation variable threshold is set according to the application scenario and performance requirements of the printed part. When the measured deformation variable exceeds this threshold, it can be judged as unqualified.

[0172] 302) In addition to the size of the deformation, the distribution of the deformation is also an important basis for judgment. If the deformation is concentrated in a certain area and has little effect on the performance of the product, it may still be acceptable; but if the deformation is widely distributed and affects the overall performance of the product, it needs to be strictly judged as unqualified.

[0173] 303) The final judgment of whether the print is qualified or not also depends on whether it meets the design requirements. Even if the deformation is within the acceptable range, if there is a significant deviation from the design requirements, it should be considered unqualified.

[0174] The experimental data of the high-strength ceramic-based composite materials and the top-pull 3D printed parts prepared in Example 1 and Comparative Examples 1-6 measured by the above experimental means are shown in Table 1 below:

[0175] Table 1 Experimental data

[0176]

[0177] From Table 1, we can observe that the weight percentages of carbon fibers in the high-strength ceramic-based composite materials prepared in Example 1 and Comparative Example 3 are 15% and 20%, respectively. Compared with the pure alumina ceramic powder in Comparative Example 1 containing no carbon fibers and the high-strength ceramic-based composite material provided in Comparative Example 2 having a carbon fiber weight percentage of 10%, the tensile strength of the materials provided in Example 1 and Comparative Example 3 is increased to more than 310 MPa, and the fracture toughness of the materials provided in Example 1 and Comparative Example 3 is increased to more than 20 MPa·m1 / 2, proving that adding 15% to 20% of carbon fibers as a reinforcing phase can significantly improve the tensile strength and fracture toughness of the material, which effectively solves the problem of brittle fracture of traditional ceramic 3D printed parts;

[0178] The high-strength ceramic-based composite materials prepared in Example 1 and Comparative Example 6 contain SiO 2 -CaO-Na 2 The weight percentages of O are 18% and 20% respectively, compared with the high-strength ceramic matrix composite material provided in Comparative Example 4 which does not contain SiO 2 -CaO-Na 2 O and the high-strength ceramic matrix composite material provided in Comparative Example 5 contains Si O 2 -CaO-Na 2 The weight percentage of SiO is 15%, and the dimensional change rate of Example 1 and Comparative Example 6 is reduced to below 0.3%, which proves that adding 18% to 20% SiO 2 -CaO-Na 2 O as a binder phase can significantly improve the dimensional stability of the composite material, which is beneficial to ensure the geometric accuracy during the pull-up 3D printing process;

[0179] In Example 1, the formula of the preferred high-strength ceramic-based composite material is used to prepare the pull-up 3D printed part. Compared with the pull-up 3D printed part prepared by pure alumina ceramic powder in Comparative Example 1, Example 1 shows better fluidity and molding quality in the process of preparing the pull-up 3D printed part, and the degree of deformation is significantly lower than that of pure ceramic. This is mainly due to the following aspects: 1) The addition of carbon fiber as a reinforcing phase improves the toughness of the composite material and reduces the risk of deformation caused by gravity during the pull-up 3D printing process; 2) Silicate glass as a bonding phase can enhance the dimensional stability of the composite material under high-temperature pull-up 3D printing environment; 3) The optimized material formula and particle size distribution ensure that the composite material has good fluidity and molding performance during the printing process.

[0180] It is to be understood that the present invention is described by some embodiments, and it is known to those skilled in the art that various changes or equivalent substitutions may be made to these features and embodiments without departing from the spirit and scope of the present invention. In addition, under the teachings of the present invention, these features and embodiments may be modified to adapt to specific circumstances and materials without departing from the spirit and scope of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed herein, and all various changes or equivalent substitutions falling within the scope of the claims of the present application are included. In addition, under the teachings of the present invention, these features and embodiments may be modified to adapt to specific circumstances and materials without departing from the spirit and scope of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed herein, and all embodiments falling within the scope of the claims of the present application are within the scope protected by the present invention.

Claims

1. A high-strength ceramic-based composite material, characterized in that: The invention comprises the following components in weight percentage: 65% alumina ceramic; 15% to 20% carbon fiber reinforcement phase; 18% to 20% SiO2-CaO-Na2O bonding phase; and 1% dispersant.

2. The high-strength ceramic matrix composite material according to claim 1, characterized in that: Active groups are introduced on the surface of carbon fibers to form a carbon fiber reinforcement phase, wherein the active groups include carboxyl active groups and hydroxyl active groups.

3. The high-strength ceramic matrix composite material according to claim 1, characterized in that: The invention also comprises the following components in weight percentage: 0.8-1% of plasticizer.

4. The high-strength ceramic matrix composite material according to claim 1, characterized in that: The average particle size of the SiO2-CaO-Na2O bonding phase is 12-18 μm, and the particle size of the alumina ceramic is 10-15 μm.

5. A method for preparing a high-strength ceramic-based composite material, characterized in that: The high-strength ceramic matrix composite material according to any one of claims 1 to 4 is prepared, comprising the following steps: S1 pre-treats alumina ceramic powder, carbon fiber and silicate glass respectively to obtain alumina ceramic, carbon fiber reinforcement phase and SiO2-CaO-Na2O bonding phase; S2: fully mixing and stirring the alumina ceramic, the carbon fiber reinforcement phase, the SiO2-CaO-Na2O binding phase and the dispersant to obtain a mixture; S3 extrudes and granulates the mixture to obtain a high-strength ceramic-based composite material.

6. The method for preparing a high-strength ceramic-based composite material according to claim 5, characterized in that: In step S1, the alumina ceramic powder is pretreated, which specifically includes the following steps: The alumina ceramic powder is ball-milled, and the average particle size of the pre-treated alumina ceramic is controlled to be 10 to 15 μm.

7. The method for preparing a high-strength ceramic-based composite material according to claim 5, characterized in that: In step S1, the carbon fiber is pretreated, which specifically comprises the following steps: The carbon fiber is subjected to electrochemical anodizing treatment. In a 10% sulfuric acid solution, carboxyl active groups and hydroxyl active groups are introduced into the surface of the carbon fiber to obtain a pretreated carbon fiber reinforced phase. The voltage of the electrochemical anodizing treatment is 14 to 18 V, and the time of the electrochemical anodizing treatment is 28 to 35 minutes.

8. The method for preparing a high-strength ceramic-based composite material according to claim 5, characterized in that: In step S1, silicate glass is pretreated, which specifically includes the following steps: The silicate glass is melted at a temperature of 1400-1500°C, and then pulverized to an average particle size of 12-18 μm after cooling to obtain a pre-treated SiO2-CaO-Na2O bonding phase.

9. The method for preparing a high-strength ceramic-based composite material according to claim 5, characterized in that: The following step is also included between step S2 and step S3: adding a plasticizer to the mixture and fully mixing and stirring for 12 to 15 minutes to obtain a uniformly mixed powder.

10. Use of the high-strength ceramic-based composite material according to any one of claims 1 to 4 in preparing a top-pull 3D printed part, characterized in that: The following steps are involved: Printing the high-strength ceramic-based composite material includes the following steps: putting the high-strength ceramic-based composite material into a top-pull 3D printer for printing to obtain a top-pull 3D printed preform, wherein the wavelength of the light source is 300 to 400 nm, printing is performed layer by layer, the thickness of each layer is 20 to 50 μm, and the printing speed is greater than 100 layers / h; Degreasing the top-pull 3D printed preform, including the following steps: heating from room temperature to 200°C, holding time for 2 hours, heating rate of 0.5°C / min; heating from 200°C to 400°C, holding time for 3 hours, heating rate of 0.3°C / min; heating from 400°C to 600°C, holding time for 2 hours, heating rate of 0.5°C / min, cooling to room temperature, and obtaining a degreased top-pull 3D printed preform; The degreased top-pull 3D printed preform is sintered, which includes the following steps: sintering at a temperature of 1200-1300° C. for 2-3 hours to obtain a top-pull 3D printed part.

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