A ZrB2 ultra-high temperature ceramic material and its preparation method and device

Abstract

The technical field of ceramic materials of the present invention particularly relates to a ZrB2 ultra-high temperature ceramic material and a preparation method and device thereof. The present invention obtains a mixture of ZrB2 powder and a binder with good rheology, good uniformity and good formability during printing by setting a specific ratio of ZrB2 powder and a binder, the composition, ratio and addition order of the binder; at the same time, the present invention combines the pre-printing mode of a 3D printer to circumvent the problems existing in printing through pre-printing, thereby obtaining a high-precision, structurally stable ZrB2 ultra-high temperature ceramic material. The preparation method of the present invention realizes geometric shapes that cannot be achieved by traditional manufacturing processes by combining PEP technology; the cost is reduced by 90%, the efficiency is increased by 10 to 100 times, and the manufacturing cycle is shortened; the product performance is consistent and excellent; the material can be recycled; batch sintering treatment can be carried out for large-scale manufacturing.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic materials, and in particular to a ZrB 2 Ultra-high temperature ceramic material and preparation method and device thereof. Background Art

[0002] Ultra-high temperature ceramics refer to a class of non-oxide ceramic materials with a melting point of more than 3000°C, mainly including carbides, nitrides and borides of early transition metals. Carbides and nitrides have a series of unique properties, including high density, chemical thermal stability, corrosion resistance and extremely high melting point, making them ideal candidate material systems for ultra-high temperature thermal structures and thermal protection systems.

[0003] Borides of early transition metals such as ZrB 2 , ZrB 2 Can be used as an antioxidant for refractory materials; ZrB 2 The resistivity is very low, and the conductive mechanism is electronic conduction. It is suitable for electric shock materials and electrode materials. It can be used in the electrodes of metal thermocouples and high-temperature heating elements. ZrB 2 It has extremely high hardness and is a very good wear-resistant material, and is widely used in knives and cutting tools. 2 Ceramic materials are excellent special refractory materials and can be used as high-temperature thermocouple protection sleeves, metallurgical metal crucibles, casting molds, etc.

[0004] ZGar 2 The powder is mainly produced by boriding zirconium or zirconium oxide. 2 The powder synthesis method is to realize the oxide carbon thermal reduction process in a high-temperature induction furnace or a resistance furnace. This method has a simple process, but the temperature is generally high (about 1800°C), the synthesized powder has low purity, a relatively large average particle size, and poor sintering activity.

[0005] Existing ZrB 2 The sintering methods of ceramic materials include hot pressing sintering and pressureless sintering, but both have technical defects. Hot pressing sintering has a high sintering temperature, a long time, and a high cost; pressureless sintering has a high sintering temperature and significant grain growth. ZrB 2 Ceramic materials are mostly sintered by hot pressing, which is a process of simultaneous forming and sintering, but only ZrB with simple shapes can be obtained. 2 Ceramic products.

[0006] For the existing ZrB 2 There are problems in the preparation of ceramic materials. It is necessary to develop a new type of ZrB 2 Preparation method of ultra-high temperature ceramic material. Summary of the invention

[0007] The main purpose of the present invention is to provide a ZrB 2 Ultra-high temperature ceramic material and preparation method and device thereof are intended to solve the existing ZrB 2 The ultra-high temperature ceramic material preparation technology has the following shortcomings: low purity of powder raw materials, large average particle size, poor sintering activity, high cost, and difficulty in preparing complex / special-shaped structural parts. This paper provides a ZrB 2 Ceramic powder raw material, low cost, simple preparation, various shapes of ZrB 2 Preparation method of ultra-high temperature ceramic material.

[0008] The present invention adopts a specific ZrB 2 The ratio of powder to binder, the composition, ratio and addition order of the binder were set to obtain ZrB with good rheology, good uniformity and good formability during printing. 2 The present invention combines the pre-printing mode of the 3D printer to avoid the problems existing in printing through pre-printing, thereby obtaining high-precision and structurally stable ZrB 2 Ultra-high temperature ceramic materials.

[0009] The present invention adopts the metal-ceramic indirect 3D printing technology that combines "3D printing + powder metallurgy" - powder extrusion printing technology. 2 Ceramic powder is mixed with a binder and granulated into a green body, which is then 3D printed and degreased and sintered to obtain the finished product. Powders of any shape can be used in the powder configuration process, and the requirements for powders in the molding process are reduced, thus solving the problems of low powder purity and large average particle size. Direct extrusion is used in the printing process to solve the problems of high cost and difficulty in preparing complex structural parts; by taking advantage of powder extrusion and layer-by-layer stacking, models of any complex shape can be designed through the design of 3D modeling software such as Solidworks, and then ZrB 2 Complex structural parts made of ultra-high temperature ceramic materials have high precision and structural stability, which greatly expands the application of ZrB 2 Application of ultra-high temperature ceramic materials. At the same time, the 3D printer equipment used in the present invention has low cost, simple process, low manufacturing cost, and effectively solves the problem of ZrB 2 The problem of high preparation cost of ultra-high temperature ceramic materials.

[0010] To achieve the above object, the present invention provides a ZrB 2 The method for preparing ultra-high temperature ceramic material comprises the following steps:

[0011] ZrB 2The powder and binder are mixed and granulated, and the obtained particles are used to prepare ZrB 2 Ultra-high temperature ceramic green body, ZrB 2 Ultra-high temperature ceramic green body is degreased to remove the binder and then sintered to produce ZrB 2 Ultra-high temperature ceramic materials.

[0012] Preferably, the ZrB 2 The mass ratio of powder to binder is 55-65:35-45.

[0013] Further preferably, the ZrB 2 The mass ratio of powder to binder is 60-65:35-40.

[0014] Further preferably, the ZrB 2 The mass ratio of powder to binder is 60:40.

[0015] Preferably, the binder comprises polypropylene (PP), polyethylene glycol (PEG), paraffin, peanut oil and stearic acid (SA).

[0016] Preferably, the ZrB 2 The powder is mixed with a binder, specifically ZrB 2 The powder was mixed with paraffin, peanut oil, polypropylene (PP), polyethylene glycol (PEG), and stearic acid (SA) in sequence.

[0017] Preferably, the binder comprises, by weight, 4 to 24 parts of polypropylene (PP); 30 to 35 parts of polyethylene glycol (PEG); 40 to 50 parts of paraffin; 5 to 8 parts of peanut oil; and 1 to 3 parts of stearic acid (SA).

[0018] Further preferably, the binder comprises, by weight, 4 to 14 parts of polypropylene (PP); 33 to 35 parts of polyethylene glycol (PEG); 40 to 45 parts of paraffin; 6 to 8 parts of peanut oil; and 2 to 3 parts of stearic acid (SA).

[0019] Further preferably, the binder comprises, by weight, 14 parts of polypropylene (PP); 33 parts of polyethylene glycol (PEG); 45 parts of paraffin; 6 parts of peanut oil; and 2 parts of stearic acid (SA).

[0020] Preferably, the ZrB 2 The powder particles are spherical, square or irregular.

[0021] Preferably, the ZrB 2 Powder is micron ZrB 2 powder.

[0022] Preferably, the ZrB 2The particle size of the powder is 0.1 μm to 50 μm.

[0023] Preferably, the 3D printing comprises: melting the mixture, extruding the molten mixture using a 3D printer nozzle, and stacking the mixture layer by layer according to the modeling model to print out ZrB 2 Ultra-high temperature ceramic green body.

[0024] Preferably, the printing parameters of the 3D printer are a speed of 30 to 150 mm / s and a layer thickness of 10 to 500 μm.

[0025] Preferably, the printing parameters of the 3D printer are a speed of 30 to 60 mm / s and a layer thickness of 50 to 500 μm.

[0026] Further preferably, the printing parameters of the 3D printer are a speed of 60 mm / s and a layer thickness of 50 μm.

[0027] Preferably, the melting temperature is 190°C to 210°C.

[0028] More preferably, the melting temperature is 200°C.

[0029] Preferably, the degreasing method is thermal degreasing or catalytic degreasing to remove most of the polymer binder.

[0030] Preferably, the catalytic degreasing is wax-based degreasing or water-based degreasing.

[0031] Preferably, the sintering is vacuum sintering, the sintering temperature is 1900° C. to 2100° C., and the sintering time is 2 to 5 h.

[0032] More preferably, the sintering temperature is 2000° C. and the sintering time is 3 h.

[0033] In a specific embodiment, the present invention uses a sublimation 3D UPS250 printing device to make ZrB 2 The ultra-high temperature ceramic green body is printed out layer by layer and formed by utilizing the viscosity of the polymer binder. The printing equipment has a hot air chamber constant temperature system and a vacuum adsorption platform, which can effectively prevent warping. At the same time, the software can simulate and simulate. Printing is simulated in the software first to avoid problems in the printing process, which can effectively improve accuracy and structural stability.

[0034] To achieve the above object, the present invention provides ZrB prepared by the preparation method 2 Ultra-high temperature ceramic materials.

[0035] To achieve the above object, the present invention provides the ZrB 2 A preparation device for ultra-high temperature ceramic materials comprises a mixing and granulating module, a 3D printing module, a degreasing module and a sintering module.

[0036] The 3D printing module includes a computer, through which the printing model is input and the printing is controlled. The printing model is designed using three-dimensional modeling software such as Solidworks, and the model can be of any complex shape.

[0037] The present invention utilizes PEP technology, breaking the traditional manufacturing model, and can shape metal materials without a mold, and then combine degreasing sintering and other processes for post-processing, so that the consistency of product performance can be ensured through low-temperature forming and high-temperature forming, thereby obtaining a product that meets the needs of practical applications. The preparation method of the present invention does not require mold opening, is simple to operate, and is agilely formed; it is designed and optimized for product functions to achieve geometric shapes that cannot be achieved by traditional manufacturing processes; the cost is reduced by 90%, the efficiency is increased by 10 to 100 times, and the manufacturing cycle is greatly reduced; 3D printing forming + powder metallurgy sintering, to obtain consistent and excellent product performance; materials can be recycled; powder injection molding, mature, stable technology and material system can be used to meet the needs of industrial production; batch sintering treatment, can be scaled manufacturing. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The metal / ceramic product (ZrB 2 Flow chart of the preparation method of ultra-high temperature ceramic materials).

[0039] Figure 2 ZrB 2 Schematic diagram of the preparation device for ultra-high temperature ceramic materials. DETAILED DESCRIPTION

[0040] The following examples are only used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0041] The experimental methods in the following examples, unless otherwise specified, are all conventional experimental methods in the art. The experimental materials used in the following examples, unless otherwise specified, are all conventional experimental materials.

[0042] The present invention is a ZrB 2 Ultra-high temperature ceramic material and preparation method and device thereof are intended to solve the existing ZrB 2 The ultra-high temperature ceramic material preparation technology has the following shortcomings: low purity of powder raw materials, large average particle size, poor sintering activity, high cost, and difficulty in preparing complex / special-shaped structural parts. This paper provides a ZrB 2 Ceramic powder raw material, low cost, simple preparation, various shapes of ZrB 2 Preparation method of ultra-high temperature ceramic material.

[0043] The present invention provides a ZrB2 The method for preparing ultra-high temperature ceramic material comprises the following steps:

[0044] ZrB 2 The powder and binder are mixed and granulated, and the obtained particles are used to prepare ZrB 2 Ultra-high temperature ceramic green body, ZrB 2 Ultra-high temperature ceramic green body is degreased to remove the binder and then sintered to produce ZrB 2 Ultra-high temperature ceramic materials.

[0045] In one embodiment, the metal / ceramic product (ZrB 2 The preparation method flow chart of ultra-high temperature ceramic material is as follows Figure 1 As shown, the specific steps are:

[0046] Metal / ceramic powder (ZrB 2 The powder) is mixed with a binder, kneaded and granulated to obtain metal / ceramic particles, the metal / ceramic particles are printed layer by layer through heating and screw extrusion to obtain a green body, the green body is degreased to obtain a brown body, and the brown body is sintered to obtain a metal / ceramic product.

[0047] Optionally, the ZrB 2 The mass ratio of powder to binder is 55-65:35-45.

[0048] Optionally, the ZrB 2 The mass ratio of powder to binder is 60-65:35-40.

[0049] Optionally, the ZrB 2 The mass ratio of powder to binder is 60:40.

[0050] Optionally, the binder includes polypropylene (PP), polyethylene glycol (PEG), paraffin, peanut oil and stearic acid (SA).

[0051] Optionally, the ZrB 2 The powder is mixed with a binder, specifically ZrB 2 The powder was mixed with paraffin, peanut oil, polypropylene (PP), polyethylene glycol (PEG), and stearic acid (SA) in sequence.

[0052] Optionally, the binder includes, by weight, 4 to 24 parts of polypropylene (PP); 30 to 35 parts of polyethylene glycol (PEG); 40 to 50 parts of paraffin; 5 to 8 parts of peanut oil; and 1 to 3 parts of stearic acid (SA).

[0053] Optionally, the binder includes, by weight, 4 to 14 parts of polypropylene (PP); 33 to 35 parts of polyethylene glycol (PEG); 40 to 45 parts of paraffin; 6 to 8 parts of peanut oil; and 2 to 3 parts of stearic acid (SA).

[0054] Optionally, the binder includes, by weight, 14 parts of polypropylene (PP); 33 parts of polyethylene glycol (PEG); 45 parts of paraffin; 6 parts of peanut oil; and 2 parts of stearic acid (SA).

[0055] Optionally, the ZrB 2 The powder particles are spherical, square or irregular.

[0056] Optionally, the ZrB 2 Powder is micron ZrB 2 powder.

[0057] Optionally, the ZrB 2 The particle size of the powder is 0.1 μm to 50 μm.

[0058] Optionally, the 3D printing includes: melting the mixture, extruding the molten mixture using a 3D printer nozzle, and stacking the mixture layer by layer according to the modeling model to print out ZrB 2 Ultra-high temperature ceramic green body.

[0059] Optionally, the printing parameters of the 3D printer are a speed of 30 to 150 mm / s and a layer thickness of 10 to 500 μm.

[0060] Optionally, the printing parameters of the 3D printer are a speed of 30 to 60 mm / s and a layer thickness of 50 to 500 μm.

[0061] Optionally, the printing parameters of the 3D printer are a speed of 60 mm / s and a layer thickness of 50 μm.

[0062] Optionally, the melting temperature is 190°C to 210°C.

[0063] Optionally, the melting temperature is 200°C.

[0064] Optionally, the degreasing method is thermal degreasing or catalytic degreasing to remove most of the polymer binder.

[0065] Optionally, the catalytic degreasing is wax-based degreasing or water-based degreasing.

[0066] Optionally, the sintering is vacuum sintering, the sintering temperature is 1900° C. to 2100° C., and the sintering time is 2 to 5 h.

[0067] Optionally, the sintering temperature is 2000° C. and the sintering time is 3 h.

[0068] The present invention adopts a specific ZrB 2 The ratio of powder to binder, the composition of the binder and the setting of the ratio have resulted in ZrB with good rheology, good uniformity and good formability during printing. 2 A mixture of powder and binder; at the same time, the present invention combines the pre-printing mode of the 3D printer to avoid the problems existing in printing through pre-printing, thereby obtaining a high-precision, structurally stable ZrB 2 Ultra-high temperature ceramic materials.

[0069] The present invention adopts the metal-ceramic indirect 3D printing technology that combines "3D printing + powder metallurgy" - powder extrusion printing technology. 2 Ceramic powder is mixed with a binder and granulated into a green body, which is then 3D printed and degreased and sintered to obtain the finished product. Powders of any shape can be used in the powder configuration process, and the requirements for powders in the molding process are reduced, thus solving the problems of low powder purity and large average particle size. Direct extrusion is used in the printing process to solve the problems of high cost and difficulty in preparing complex structural parts; by taking advantage of powder extrusion and layer-by-layer stacking, models of any complex shape can be designed through the design of 3D modeling software such as Solidworks, and then ZrB 2 Complex structural parts made of ultra-high temperature ceramic materials have high precision and structural stability, which greatly expands the application of ZrB 2 Application of ultra-high temperature ceramic materials. At the same time, the 3D printer equipment used in the present invention has low cost, simple process, low manufacturing cost, and effectively solves the problem of ZrB 2 The problem of high preparation cost of ultra-high temperature ceramic materials.

[0070] The present invention also provides ZrB prepared by the preparation method 2 Ultra-high temperature ceramic materials.

[0071] The present invention also provides ZrB 2 Preparation device of ultra-high temperature ceramic material (schematic diagram of the device is as follows Figure 2 As shown in FIG. 1 ), the device includes a mixing and granulating module, a 3D printing module, a degreasing module, and a sintering module. The 3D printing module includes a computer, through which the printing model is input and the printing is controlled. The printing model is designed using three-dimensional modeling software such as Solidworks, and the model can be of any complex shape.

[0072] Example 1 A ZrB 2 Ultra-high temperature ceramic materials

[0073] ZGar 2 The preparation steps of ultra-high temperature ceramic materials are as follows:

[0074] S1. Preparation of metal ceramic particles

[0075] Spherical ZrB with a particle size of 0.1 μm 2 The powder is mixed with a binder, kneaded and granulated to obtain metal ceramic particles; the ZrB 2 The mass ratio of the powder to the binder is 60:40. The binder comprises, by weight, 14 parts of polypropylene (PP); 33 parts of polyethylene glycol (PEG); 45 parts of paraffin; 6 parts of peanut oil; 2 parts of stearic acid (SA); the ZrB 2 The powder is sequentially mixed with paraffin wax, peanut oil, polypropylene (PP), polyethylene glycol (PEG), and stearic acid (SA) in the binder.

[0076] S2、ZrB 2 Preparation of ultra-high temperature ceramic green body

[0077] The metal ceramic particles prepared in step S1 are placed in a screw and heated to melt at a melting temperature of 200°C. The melted paste metal ceramic particles are extruded from a printer nozzle. The printing model is designed according to the Solidworks 3D model software. The 3D sublimation equipment UPS250 is used to make ZrB 2 The ultra-high temperature ceramic green body is printed out layer by layer, stacked layer by layer, with a printing speed of 60mm / s and a layer thickness of 50μm. The viscosity of the binder is used to shape it to obtain ZrB 2 Ultra-high temperature ceramic green body; the printing equipment has a hot air chamber constant temperature system and a vacuum adsorption platform, which can effectively prevent edge warping. The printing software has a simulation mode, which can simulate printing in the software, and effectively improve the accuracy of the printed material and the stability of the structure by avoiding problems in the simulation printing process.

[0078] S3、ZrB 2 Preparation of ultra-high temperature ceramic materials

[0079] The ZrB prepared in step S2 2 The ultra-high temperature ceramic green body was wax-degreased to remove most of the polymer binder, and then sintered at 2000℃ for 3 h in a vacuum environment. During the sintering process, the residual binder was further removed, and the metal ceramic particles (ZrB 2 Ultra-high temperature ceramic particles) are densified to obtain structurally stable ZrB 2 Ultra-high temperature ceramic materials.

[0080] The ZrB prepared in this example 2 Ultra-high temperature ceramic material products have good consistency, no warping, deformation, cracks, holes and other metallurgical defects, high density, high strength, excellent ablation performance, high complexity, and wide application range. Compared with the traditional ZrB 2The preparation of ultra-high temperature ceramic materials has reduced costs by 90% and increased efficiency by 100 times.

[0081] Example 2 A ZrB 2 Ultra-high temperature ceramic materials

[0082] ZGar 2 The preparation steps of ultra-high temperature ceramic materials are as follows:

[0083] S1. Preparation of metal ceramic particles

[0084] Spherical ZrB with a particle size of 0.1 μm 2 The powder is mixed with a binder, kneaded and granulated to obtain metal ceramic particles; the ZrB 2 The mass ratio of the powder to the binder is 55:45; the binder, by weight, includes 4 parts of polypropylene (PP); 35 parts of polyethylene glycol (PEG); 50 parts of paraffin; 8 parts of peanut oil; 3 parts of stearic acid (SA); the ZrB 2 The powder is sequentially mixed with paraffin wax, peanut oil, polypropylene (PP), polyethylene glycol (PEG), and stearic acid (SA) in the binder.

[0085] S2、ZrB 2 Preparation of ultra-high temperature ceramic green body

[0086] The metal ceramic particles prepared in step S1 are placed in a screw and heated to melt at a melting temperature of 190°C. The melted paste metal ceramic particles are extruded from a printer nozzle. The printing model is designed according to the Solidworks 3D model software. The 3D sublimation equipment UPS250 is used to make ZrB 2 The ultra-high temperature ceramic green body is printed layer by layer, with a printing speed of 30mm / s and a layer thickness of 500μm. The viscosity of the binder is used to shape it to obtain ZrB 2 Ultra-high temperature ceramic green body; the printing equipment has a hot air chamber constant temperature system and a vacuum adsorption platform, which can effectively prevent edge warping. The printing software has a simulation mode, which can simulate printing in the software, and effectively improve the accuracy of the printed material and the stability of the structure by avoiding problems in the simulation printing process.

[0087] S3、ZrB 2 Preparation of ultra-high temperature ceramic materials

[0088] The ZrB prepared in step S2 2 The ultra-high temperature ceramic green body is wax-degreased to remove most of the polymer binder, and then sintered at 1900℃ for 5h in a vacuum environment. During the sintering process, the residual binder is further removed, and the metal ceramic particles (ZrB 2 Ultra-high temperature ceramic particles) are densified to obtain structurally stable ZrB2 Ultra-high temperature ceramic materials.

[0089] The ZrB prepared in this example 2 Ultra-high temperature ceramic material products have good consistency, without metallurgical defects such as warping, deformation, cracks, holes, etc. The products have high density, high strength, excellent ablation performance, high complexity and wide range of applications.

[0090] Example 3 A ZrB 2 Ultra-high temperature ceramic materials

[0091] ZGar 2 The preparation steps of ultra-high temperature ceramic materials are as follows:

[0092] S1. Preparation of metal ceramic particles

[0093] Spherical ZrB with a particle size of 0.1 μm 2 The powder is mixed with a binder, kneaded and granulated to obtain metal ceramic particles; the ZrB 2 The mass ratio of the powder to the binder is 65:35. The binder comprises, by weight, 24 parts of polypropylene (PP); 30 parts of polyethylene glycol (PEG); 40 parts of paraffin; 5 parts of peanut oil; 1 part of stearic acid (SA); the ZrB 2 The powder is sequentially mixed with paraffin wax, peanut oil, polypropylene (PP), polyethylene glycol (PEG), and stearic acid (SA) in the binder.

[0094] S2、ZrB 2 Preparation of ultra-high temperature ceramic green body

[0095] The metal ceramic particles prepared in step S1 are placed in a screw and heated to melt at a melting temperature of 210°C. The melted paste metal ceramic particles are extruded from a printer nozzle. The printing model is designed according to the Solidworks 3D model software. The 3D sublimation equipment UPS250 is used to make ZrB 2 The ultra-high temperature ceramic green body is printed out layer by layer, with a printing speed of 150mm / s and a layer thickness of 10μm. The viscosity of the binder is used to shape it to obtain ZrB 2 Ultra-high temperature ceramic green body; the printing equipment has a hot air chamber constant temperature system and a vacuum adsorption platform, which can effectively prevent edge warping. The printing software has a simulation mode, which can simulate printing in the software, and effectively improve the accuracy of the printed material and the stability of the structure by avoiding problems in the simulation printing process.

[0096] S3、ZrB 2 Preparation of ultra-high temperature ceramic materials

[0097] The ZrB prepared in step S2 2The ultra-high temperature ceramic green body is wax-degreased to remove most of the polymer binder, and then sintered at 2100℃ for 2h in a vacuum environment. During the sintering process, the residual binder is further removed, and the metal ceramic particles (ZrB 2 Ultra-high temperature ceramic particles) are densified to obtain structurally stable ZrB 2 Ultra-high temperature ceramic materials.

[0098] The ZrB prepared in this example 2 Ultra-high temperature ceramic material products have good consistency, without metallurgical defects such as warping, deformation, cracks, holes, etc. The products have high density, high strength, excellent ablation performance, and high complexity.

[0099] Example 4 A ZrB 2 Ultra-high temperature ceramic materials

[0100] ZGar 2 The preparation steps of ultra-high temperature ceramic materials are as follows:

[0101] S1. Preparation of metal ceramic particles

[0102] Spherical ZrB with a particle size of 50 μm 2 The powder is mixed with a binder, kneaded and granulated to obtain metal ceramic particles; the ZrB 2 The mass ratio of the powder to the binder is 60:40. The binder comprises, by weight, 14 parts of polypropylene (PP); 33 parts of polyethylene glycol (PEG); 45 parts of paraffin; 6 parts of peanut oil; 2 parts of stearic acid (SA); the ZrB 2 The powder is sequentially mixed with paraffin wax, peanut oil, polypropylene (PP), polyethylene glycol (PEG), and stearic acid (SA) in the binder.

[0103] S2、ZrB 2 Preparation of ultra-high temperature ceramic green body

[0104] The metal ceramic particles prepared in step S1 are placed in a screw and heated to melt at a melting temperature of 200°C. The melted paste metal ceramic particles are extruded from a printer nozzle. The printing model is designed according to the Solidworks 3D model software. The 3D sublimation equipment UPS250 is used to make ZrB 2 The ultra-high temperature ceramic green body is printed out layer by layer, stacked layer by layer, with a printing speed of 60mm / s and a layer thickness of 50μm. The viscosity of the binder is used to shape it to obtain ZrB 2 Ultra-high temperature ceramic green body; the printing equipment has a hot air chamber constant temperature system and a vacuum adsorption platform, which can effectively prevent edge warping. The printing software has a simulation mode, which can simulate printing in the software, and effectively improve the accuracy of the printed material and the stability of the structure by avoiding problems in the simulation printing process.

[0105] S3、ZrB 2 Preparation of ultra-high temperature ceramic materials

[0106] The ZrB prepared in step S2 2 The ultra-high temperature ceramic green body was wax-degreased to remove most of the polymer binder, and then sintered at 2000℃ for 3 h in a vacuum environment. During the sintering process, the residual binder was further removed, and the metal ceramic particles (ZrB 2 Ultra-high temperature ceramic particles) are densified to obtain structurally stable ZrB 2 Ultra-high temperature ceramic materials.

[0107] The ZrB prepared in this example 2 Ultra-high temperature ceramic material products have good consistency, without metallurgical defects such as warping, deformation, cracks, holes, etc. The products have high density, high strength, excellent ablation performance, and high complexity.

[0108] Compared with the traditional ZrB 2 The preparation cost of ultra-high temperature ceramic materials has been reduced by 90% and the efficiency has been increased by 10 to 100 times.

[0109] Comparative Example 1

[0110] ZGar 2 The preparation steps of ultra-high temperature ceramic materials are as follows:

[0111] S1. Preparation of metal ceramic particles

[0112] Same as Example 1, except that ZrB 2 The mass ratio of powder to binder is 70:30.

[0113] S2、ZrB 2 Preparation of ultra-high temperature ceramic green body

[0114] Same as Example 1.

[0115] S3、ZrB 2 Preparation of ultra-high temperature ceramic materials

[0116] Same as Example 1.

[0117] The ZrB prepared in this comparative example 2 Ultra-high temperature ceramic materials are not dense, product consistency is reduced, cracks and other defects appear, and performance does not meet standards.

[0118] Comparative Example 2

[0119] ZGar 2 The preparation steps of ultra-high temperature ceramic materials are as follows:

[0120] S1. Preparation of metal ceramic particles

[0121] Same as Example 1, except that ZrB 2 The mass ratio of powder to binder is 50:50.

[0122] S2、ZrB 2 Preparation of ultra-high temperature ceramic green body

[0123] Same as Example 1.

[0124] S3、ZrB 2 Preparation of ultra-high temperature ceramic materials

[0125] Same as Example 1.

[0126] This comparative example prepares ZrB 2 Ultra-high temperature ceramic materials have low fluidity and are difficult to print.

[0127] Comparative Example 3

[0128] ZGar 2 The preparation steps of ultra-high temperature ceramic materials are as follows:

[0129] S1. Preparation of metal ceramic particles

[0130] Same as Example 1, ZrB 2 The powder was directly mixed with a mixture of binders paraffin wax, peanut oil, polypropylene (PP), polyethylene glycol (PEG), and stearic acid (SA).

[0131] S2、ZrB 2 Preparation of ultra-high temperature ceramic green body

[0132] Same as Example 1.

[0133] S3、ZrB 2 Preparation of ultra-high temperature ceramic materials

[0134] Same as Example 1.

[0135] This comparative example prepares ZrB 2 Ultra-high temperature ceramic materials have uneven mixing, insufficient mutual melting, incomplete bonding, poor sintering performance of the product, and warping and deformation.

[0136] Example 5 A preparation device

[0137] ZGar 2 The preparation device of ultra-high temperature ceramic materials includes a mixing and granulation module, a 3D printing module, a degreasing module, and a sintering module. The 3D printing module includes a computer, through which the printing model is input and the printing is controlled. The printing model is designed using three-dimensional modeling software such as Solidworks, and the model can be of any complex shape. ZrB2 Ultra-high temperature ceramic materials, the specific steps are:

[0138] The metal / ceramic powder (ZrB 2 The powder) is mixed with a binder and placed in a device of a mixing and granulating module. The metal / ceramic particles are obtained by mixing and granulating. The metal / ceramic particles are printed layer by layer through heating and screw extrusion of a printing device of a 3D printing module to obtain a green body. The green body is degreased in the equipment of a degreasing module to obtain a brown body. The brown body is then placed in the equipment of a sintering module for sintering to obtain a metal / ceramic product.

[0139] The above are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing a ZrB2 ultra-high temperature ceramic material, characterized in that: The steps include: The ZrB2 powder is mixed with a binder to form granules, and the obtained granules are used to prepare ZrB2 ultra-high temperature ceramic green bodies by 3D printing, and the ZrB2 ultra-high temperature ceramic green bodies are degreased to remove the binder, and then sintered to obtain ZrB2 ultra-high temperature ceramic materials; The mass ratio of the ZrB2 powder to the binder is 55-65:35-45; The binder includes 4-24 parts of polypropylene; 30-35 parts of polyethylene glycol; 40-50 parts of paraffin; 5-8 parts of peanut oil; and 1-3 parts of stearic acid. The ZrB2 powder is sequentially mixed with paraffin, peanut oil, polypropylene, polyethylene glycol and stearic acid.

2. The preparation method according to claim 1, characterized in that The particles of the ZrB2 powder are spherical, square or irregular.

3. The preparation method according to claim 1, characterized in that: The ZrB2 powder is micron ZrB2 powder.

4. The preparation method according to claim 1, characterized in that: The 3D printing includes: melting the mixture, extruding the molten mixture using a 3D printer nozzle, stacking layer by layer according to the modeling model, and printing out a ZrB2 ultra-high temperature ceramic green body; the printing parameters of the 3D printer are a speed of 30 to 150 mm / s and a layer thickness of 10 to 500 μm.

5. The preparation method according to claim 1, characterized in that: The sintering is vacuum sintering, the sintering temperature is 1900° C. to 2100° C., and the sintering time is 2 to 5 hours.

6. ZrB2 ultra-high temperature ceramic material prepared by the preparation method according to any one of claims 1 to 5.

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