Nickel-titanium alloy reinforced nano silicon carbide composite ceramic material and preparation process thereof

Abstract

The invention discloses a nickel-titanium alloy reinforced nano silicon carbide composite ceramic material and a preparation process, and relates to the field of silicon carbide composite ceramic materials, the nickel-titanium alloy reinforced nano silicon carbide composite ceramic material comprises the following raw materials by weight: 75-85 parts of silicon carbide powder, 2.3-2.5 parts of carbon nanotubes, 0.8-1.2 parts of boron carbide, 10-12 parts of a nano nickel-titanium-based resin binder, 0.08-0.1 part of polyethylene glycol, and 25-30 parts of water. The synthesized nano nickel-titanium-based resin binder is a polyacrylate binder obtained by carrying out polymerization reaction on a double-bond product containing terminal carbon-carbon double bonds, nano cerium oxide, nano nickel-titanium alloy and epoxy groups, has the effects of promoting sinterability, corrosion resistance and enhancing mechanical strength, achieves the purpose of one agent with multiple purposes, and is worthy of popularization and application.

Description

Technical Field

[0001] The invention relates to the field of silicon carbide composite ceramic materials, and in particular to a nickel-titanium alloy reinforced nano silicon carbide composite ceramic material and a preparation process thereof. Background Art

[0002] Silicon carbide ceramic materials are widely used in industrial fields such as petroleum, chemical industry, microelectronics, machinery, automobile, aerospace, papermaking, laser, steel, nuclear energy and processing. They have excellent high-temperature oxidation resistance, high hardness, high thermal conductivity and other characteristics.

[0003] However, the high covalent properties of silicon carbide and its extremely low diffusion coefficient make it difficult to sinter and densify, and the high porosity of silicon carbide ceramics makes its bending strength low, affecting the high-temperature load-bearing performance of silicon carbide composite ceramic materials. With the rapid development of science and technology today, higher requirements are placed on the mechanical properties of silicon carbide composite ceramic materials.

[0004] Nano nickel-titanium alloy has strong high temperature resistance and corrosion resistance. However, due to its poor compatibility with organic binders in ceramic materials, nano nickel-titanium alloy is not conducive to uniform mixing with other raw materials, which limits its use in silicon carbide composite ceramic materials. In addition, rare earth oxides such as nano cerium oxide and yttrium oxide are often used to improve the sintering performance of silicon carbide ceramic materials. However, due to the small specific surface area, nano cerium oxide is easy to agglomerate and has poor compatibility with organic binders in ceramic materials. Directly adding it cannot obtain a more uniform silicon carbide composite ceramic material.

[0005] Therefore, a suitable modification method is needed to apply nano-nickel-titanium alloy and nano-cerium oxide with improved compatibility with organic binders in ceramic materials to the preparation process of silicon carbide composite ceramic materials, while improving the cracking phenomenon caused by rapid evaporation of water during the sintering process, so as to obtain silicon carbide composite ceramic materials with better mechanical strength, corrosion resistance and density. Summary of the invention

[0006] In order to solve the above technical problems, the present invention provides a nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material and a preparation process.

[0007] The purpose of the present invention can be achieved through the following technical solutions: A nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material, comprising the following raw materials in parts by weight: 75-85 parts of silicon carbide powder, 2.3-2.5 parts of carbon nanotubes, 0.8-1.2 parts of boron carbide, 10-12 parts of nano-nickel-titanium based resin binder, 0.08-0.1 parts of polyethylene glycol, and 25-30 parts of water; Further, the average particle size of α-silicon carbide in the silicon carbide powder is 200-500 nm, the average particle size of β-silicon carbide is 50-100 nm, and the mass ratio of α-silicon carbide to β-silicon carbide is 10-12:1.3-1.5; The preparation of the nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material comprises the following steps: Mix silicon carbide powder, carbon nanotubes, boron carbide, nano nickel-titanium based resin binder, polyethylene glycol and water and stir for 2-2.5 h to obtain a mixed slurry; then dry the mixed slurry in a spray drying tower at 500-510 °C for 20-30 min to obtain powder; then press the powder into a blank at 1.5-2 MPa, and dry the blank at 100-110 °C for 2.5-3 h to obtain a dried blank; then heat the dried blank at a heating rate of 15-25 °C to 500-600 °C, keep it warm for 2-3 h, then adjust the heating rate to 50-60 °C and heat it to 1000-1200 °C, keep it warm for 5-6 h, and then cool it with the furnace after sintering to obtain the nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material; The preparation of the nano nickel-titanium based resin binder comprises the following steps: Step A1: Add nano nickel-titanium alloy powder to sodium hydroxide solution, stir at 75-85 °C for 1-1.5 h to obtain surface-treated nano nickel-titanium alloy; add epoxy group silane coupling agent to absolute ethanol, ultrasonically disperse at 60-70 °C for 4-5 h, then add the surface-treated nano nickel-titanium alloy, and raise the temperature to 90-95 °C, and reflux and stir for 12-13 h to obtain modified nano nickel-titanium alloy; Further, the dosage ratio of nano nickel-titanium alloy powder to sodium hydroxide solution is 1-2 g:80-90 mL, and the concentration of sodium hydroxide solution is 1-2 mol / L; the dosage ratio of epoxy group silane coupling agent, absolute ethanol and surface-treated nano nickel-titanium alloy is 5-6 g:200-220 mL:9-10 g, and the epoxy group silane coupling agent is 5,6-epoxyhexyltriethoxysilane; During the reaction process of step A1, the surface of the nano nickel-titanium alloy powder is pre-oxidized after being heated by sodium hydroxide solution to form oxygen-containing groups such as hydroxyl groups; the silanol after hydrolysis of the epoxy group silane coupling agent reacts with the surface-pre-oxidized nano nickel-titanium alloy to obtain a modified nano nickel-titanium alloy with epoxy groups on the surface; Step A2: Mix amino silane coupling agent and absolute ethanol and ultrasonically disperse at 60-65 °C for 3-4 h, then add nano cerium oxide, raise the temperature to 80-85 °C, and reflux and stir for 8-9 h to obtain NH2-nano cerium oxide; add NH2-nano cerium oxide and modified nano nickel-titanium alloy to dimethyl sulfoxide, stir and react at 60-65 °C for 24-25 h, filter and dry to obtain an alcohol hydroxyl product; Further, the dosage ratio of the aminosilane coupling agent, absolute ethanol, and nano-ceria is 6.5 - 7.5 g : 230 - 250 mL : 3.5 - 4.5 g, and the aminosilane coupling agent is KH550; the dosage ratio of NH2-nano-ceria, modified nano-nickel titanium alloy, and dimethyl sulfoxide is 7 - 8 g : 14 - 15 g : 300 - 350 mL; During the reaction process of step A2, the surface of nano-ceria is modified by the aminosilane coupling agent to obtain nano-ceria with amino groups on the surface, namely NH2-nano-ceria; the amino group of NH2-nano-ceria reacts with the epoxy group of the modified nano-nickel titanium alloy to obtain an alcohol hydroxyl product containing nano-ceria and nano-nickel titanium alloy; Step A3: Add 3-acetyl-5-nitrobenzoic acid to DMF, add thionyl chloride under stirring, and reflux and stir at 40 - 45 °C for 10 - 11 h to obtain an acyl chloride product; stir and mix the alcohol hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide to obtain mixture 1; add the acyl chloride product to dimethyl sulfoxide to obtain mixture 2, and in an ice-water bath, add mixture 2 dropwise to mixture 1. After the addition is complete, raise the temperature to 40 - 45 °C and stir at a constant temperature for 11 - 12 h, then perform vacuum distillation to obtain the nitro product; Further, the dosage ratio of 3-acetyl-5-nitrobenzoic acid, DMF, and thionyl chloride is 20 - 22 g : 70 - 80 mL : 12 - 13 g; the dosage ratio of the alcohol hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide in mixture 1 is 10 - 11 g : 0.8 - 0.9 g : 5 - 6 g : 160 - 170 mL; the dosage ratio of the acyl chloride product and dimethyl sulfoxide in mixture 2 is 22 - 23 g : 50 - 55 mL; the dosage ratio of mixture 1 and mixture 2 is 18 - 20 mL : 7.5 - 8.5 mL; During the reaction process of step A3, 3-acetyl-5-nitrobenzoic acid reacts with thionyl chloride to obtain an acyl chloride product; the acyl chloride product reacts with the alcohol hydroxyl product to obtain a nitro product containing a ketone carbonyl group, nano-ceria, and nano-nickel titanium alloy; Step A4: Mix the nitro product, ethanol, concentrated hydrochloric acid, and stannous dichloride, and stir and react at 50 - 55 °C for 5 - 5.5 h, then filter, wash, and dry to obtain an amino product; add epichlorohydrin, the amino product, and tetrabutylammonium bromide to toluene, reflux and stir at 110 - 115 °C for 6 - 7 h, cool to room temperature, then add sodium hydroxide solution and stir for 5 - 6 h to obtain the epoxy product; Further, the dosage ratio of the nitro product, ethanol, concentrated hydrochloric acid, and stannous dichloride is 2 - 3 g : 100 - 110 mL : 5 - 6 mL : 5.3 - 5.5 g; the dosage ratio of epichlorohydrin, amino product, tetrabutylammonium bromide, toluene, and sodium hydroxide solution is 12 - 13 g : 7 - 8 g : 2 - 2.5 g : 140 - 150 mL : 10 - 15 mL; the mass fraction of the sodium hydroxide solution is 40 - 50%; During the reaction in step A4, the nitro group of the nitro product is reduced to an amino group to obtain an amino product; the amino group of the amino product undergoes ring-opening and then ring-closing with epichlorohydrin to obtain an epoxy product containing a ketone carbonyl group, nano-ceria, and nano-nickel-titanium alloy; Step A5: In an atmosphere of protective gas, add the epoxy product and methylenetriphenylphosphine to anhydrous tetrahydrofuran, and reflux and stir at 50 - 55 °C for 8 - 9 h to obtain a double-bond product; mix methyl methacrylate, butyl acrylate, acrylic acid, double-bond product, benzoyl peroxide, xylene, and butyl acetate, and react at 100 - 105 °C for 10 - 11 h to obtain a nano-nickel-titanium-based resin binder; Further, the dosage ratio of the epoxy product, methylenetriphenylphosphine, and anhydrous tetrahydrofuran is 10 - 11 g : 6 - 7 g : 130 - 140 mL; the dosage ratio of methyl methacrylate, butyl acrylate, acrylic acid, double-bond product, benzoyl peroxide, xylene, and butyl acetate is 40 - 45 g : 35 - 40 g : 5 - 6 g : 5 - 6 g : 1 - 1.5 g : 150 - 160 mL : 100 - 110 mL; During the reaction in step A5, the ketone carbonyl group of the epoxy product undergoes a Wittig reaction with methylenetriphenylphosphine to generate a double-bond product containing a terminal carbon-carbon double bond, nano-ceria, nano-nickel-titanium alloy, and epoxy group; under the initiation of benzoyl peroxide, the double-bond product polymerizes with methyl methacrylate, butyl acrylate, and acrylic acid to obtain a polyacrylate containing nano-ceria, nano-nickel-titanium alloy, and epoxy group, that is, a nano-nickel-titanium-based resin binder.

[0008] The beneficial effects of the present invention: The present invention discloses a nickel-titanium alloy-reinforced nano-silicon carbide composite ceramic material, which includes the following raw materials: silicon carbide powder, carbon nanotubes, boron carbide, nano-nickel-titanium-based resin binder, polyethylene glycol, and water.

[0009] The synthesized nano nickel-titanium-based resin binder is a polyacrylate binder obtained by polymerization reaction of double bond products containing terminal carbon-carbon double bonds, nano cerium oxide, nano nickel-titanium alloy, and epoxy groups; the nano nickel-titanium alloy is surface oxidized and treated with a silane coupling agent, and then participates in the polymerization reaction to be grafted into the polyacrylate binder. With the bonding effect of the binder, it forms a more uniform whole with the resin binder and other raw materials, which will be more conducive to improving the corrosion resistance of the composite ceramic material. In addition, the nano nickel-titanium alloy powder particles can play a bridging role in the crack propagation process to prevent the crack from developing, thereby being more conducive to improving the mechanical strength of the composite ceramic material; the nano cerium oxide is treated with a silane coupling agent and participates in the polymerization reaction to be grafted into the polyacrylate binder. With the bonding effect of the binder, the nano nickel-titanium alloy forms a more uniform whole with the resin binder and other raw materials, which will be more conducive to improving the corrosion resistance of the composite ceramic material. With the bonding effect of the binder, it forms a more uniform whole with other raw materials such as resin binder and boron carbide. During the sintering process, CeB6 is generated in situ with boron carbide and B series products are enriched, which increases the sintering driving force, promotes sintering densification, and makes the interior of the composite ceramic material tighter, which is beneficial to the improvement of mechanical strength; the epoxy group helps to enhance the bonding performance of the resin binder, and has a certain water retention capacity, which not only promotes the bonding of the binder with other raw materials to form a uniform whole, but also avoids cracking of the green body due to excessive evaporation of water during calcination, which is beneficial to the improvement of the mechanical strength of the composite ceramic material; therefore, the nano nickel-titanium-based resin binder has bonding, corrosion resistance, sintering promotion and mechanical strength enhancement, achieving the goal of one dose for multiple uses.

[0010] Therefore, the silicon carbide composite ceramic material of the present invention has excellent mechanical strength, corrosion resistance and density, and is worthy of popularization and use.

[0011] Specific implementation method includes The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0012] Example 1 A nano nickel-titanium-based resin binder, the preparation of which comprises the following steps: Step A1: Add nano nickel-titanium alloy powder (supplier: Ningbo Luofei Nano Technology Co., Ltd.) to sodium hydroxide solution, stir at 75°C for 1 h to obtain surface-treated nano nickel-titanium alloy; add epoxy group silane coupling agent to absolute ethanol, ultrasonically disperse at 60°C for 4 h, then add the surface-treated nano nickel-titanium alloy, heat up to 90°C, and reflux and stir for 12 h to obtain modified nano nickel-titanium alloy; the dosage ratio of nano nickel-titanium alloy powder to sodium hydroxide solution is 1 g:80 mL, and the concentration of sodium hydroxide solution is 1 mol / L; the dosage ratio of epoxy group silane coupling agent, absolute ethanol, and surface-treated nano nickel-titanium alloy is 5 g:200 mL:9 g, and the epoxy group silane coupling agent is 5,6-epoxyhexyltriethoxysilane; Step A2: Mix amino silane coupling agent and absolute ethanol, ultrasonically disperse at 60°C for 3 h, then add nano cerium oxide (supplier: Zibo Xiyan Nano Materials Co., Ltd.), heat up to 80°C, and reflux and stir for 8 h to obtain NH2-nano cerium oxide; add NH2-nano cerium oxide and modified nano nickel-titanium alloy to dimethyl sulfoxide, stir and react at 60°C for 24 h, filter and dry to obtain alcohol hydroxyl product; the dosage ratio of amino silane coupling agent, absolute ethanol, and nano cerium oxide is 6.5 g:230 mL:3.5 g, and the amino silane coupling agent is KH550; the dosage ratio of NH2-nano cerium oxide, modified nano nickel-titanium alloy, and dimethyl sulfoxide is 7 g:14 g:300 mL; Step A3: Add 3-acetyl-5-nitrobenzoic acid to DMF, add thionyl chloride under stirring, reflux and stir at 40°C for 10 h to obtain acyl chloride product; stir and mix alcohol hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide to obtain mixture 1; add the acyl chloride product to dimethyl sulfoxide to obtain mixture 2, in an ice-water bath, dropwise add mixture 2 to mixture 1, after dropping, heat up to 40°C, keep stirring at a constant temperature for 11 h, and perform reduced pressure distillation to obtain nitro product; the dosage ratio of 3-acetyl-5-nitrobenzoic acid, DMF, and thionyl chloride is 20 g:70 mL:12 g; the dosage ratio of alcohol hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide in mixture 1 is 10 g:0.8 g:5 g:160 mL; the dosage ratio of acyl chloride product and dimethyl sulfoxide in mixture 2 is 22 g:50 mL; the dosage ratio of mixture 1 to mixture 2 is 18 mL:7.5 mL; Step A4: Mix the nitro product, ethanol, concentrated hydrochloric acid, and stannous dichloride, and stir and react at 50 °C for 5 h. Filter, wash, and dry to obtain the amino product. Add epichlorohydrin, the amino product, and tetrabutylammonium bromide to toluene, reflux and stir and react at 110 °C for 6 h. After cooling to room temperature, add sodium hydroxide solution and stir for 5 h to obtain the epoxy product. The dosage ratio of the nitro product, ethanol, concentrated hydrochloric acid, and stannous dichloride is 2 g: 100 mL: 5 mL: 5.3 g. The dosage ratio of epichlorohydrin, the amino product, tetrabutylammonium bromide, toluene, and sodium hydroxide solution is 12 g: 7 g: 2 g: 140 mL: 10 mL. The mass fraction of the sodium hydroxide solution is 40%. Step A5: In a nitrogen atmosphere, add the epoxy product and methylenetriphenylphosphine to anhydrous tetrahydrofuran, and reflux and stir and react at 50 °C for 8 h to obtain the double bond product. Mix methyl methacrylate, butyl acrylate, acrylic acid, the double bond product, benzoyl peroxide, xylene, and butyl acetate, and react at 100 °C for 10 h to obtain the nano nickel-titanium-based resin binder. The dosage ratio of the epoxy product, methylenetriphenylphosphine, and anhydrous tetrahydrofuran is 10 g: 6 g: 130 mL. The dosage ratio of methyl methacrylate, butyl acrylate, acrylic acid, the double bond product, benzoyl peroxide, xylene, and butyl acetate is 40 g: 35 g: 5 g: 5 g: 1 g: 150 mL: 100 mL.

[0013] Example 2 A nano nickel-titanium-based resin binder, the preparation thereof comprising the following steps: Step A1: Add nano nickel-titanium alloy powder (supplier: Ningbo Luofei Nano Technology Co., Ltd.) to sodium hydroxide solution, and stir at 80 °C for 1.3 h to obtain surface-treated nano nickel-titanium alloy. Add epoxy group silane coupling agent to anhydrous ethanol, ultrasonically disperse at 65 °C for 4.5 h, then add the surface-treated nano nickel-titanium alloy, raise the temperature to 93 °C, and reflux and stir and react for 12.5 h to obtain modified nano nickel-titanium alloy. The dosage ratio of nano nickel-titanium alloy powder and sodium hydroxide solution is 1.5 g: 85 mL, and the concentration of the sodium hydroxide solution is 1.5 mol / L. The dosage ratio of epoxy group silane coupling agent, anhydrous ethanol, and surface-treated nano nickel-titanium alloy is 5.5 g: 210 mL: 9.5 g, and the epoxy group silane coupling agent is 5,6-epoxyhexyltriethoxysilane; Step A2: Mix the amino-silane coupling agent and absolute ethanol, and ultrasonically disperse them at 63°C for 3.5 h. Then add nano-ceria (supplier: Zibo Xiyan Nano Materials Co., Ltd.), heat up to 83°C, and reflux and stir for reaction for 8.5 h to obtain NH2-nano-ceria. Add NH2-nano-ceria and the modified nano-nickel-titanium alloy to dimethyl sulfoxide, and stir and react at 63°C for 24.5 h. Filter and dry to obtain the alcohol hydroxyl product. The dosage ratio of the amino-silane coupling agent, absolute ethanol, and nano-ceria is 7.0 g: 240 mL: 4.0 g, and the amino-silane coupling agent is KH550. The dosage ratio of NH2-nano-ceria, the modified nano-nickel-titanium alloy, and dimethyl sulfoxide is 7.5 g: 14.5 g: 330 mL; Step A3: Add 3-acetyl-5-nitrobenzoic acid to DMF, add thionyl chloride under stirring, and reflux and stir at 43°C for reaction for 10.5 h to obtain the acyl chloride product. Stir and mix the alcohol hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide to obtain mixture 1. Add the acyl chloride product to dimethyl sulfoxide to obtain mixture 2. In an ice-water bath, add mixture 2 dropwise to mixture 1. After the addition is complete, heat up to 43°C and stir at a constant temperature for reaction for 11.5 h, and then perform reduced pressure distillation to obtain the nitro product. The dosage ratio of 3-acetyl-5-nitrobenzoic acid, DMF, and thionyl chloride is 21 g: 75 mL: 12.5 g. The dosage ratio of the alcohol hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide in mixture 1 is 10.5 g: 0.85 g: 5.5 g: 165 mL. The dosage ratio of the acyl chloride product and dimethyl sulfoxide in mixture 2 is 22.5 g: 53 mL. The dosage ratio of mixture 1 and mixture 2 is 19 mL: 8.0 mL; Step A4: Mix the nitro product, ethanol, concentrated hydrochloric acid, and stannous dichloride, and stir and react at 53°C for 5.3 h. Filter, wash, and dry to obtain the amino product. Add epichlorohydrin, the amino product, and tetrabutylammonium bromide to toluene, reflux and stir at 113°C for reaction for 6.5 h. After cooling to room temperature, add sodium hydroxide solution and stir for 5.5 h to obtain the epoxy product. The dosage ratio of the nitro product, ethanol, concentrated hydrochloric acid, and stannous dichloride is 2.5 g: 105 mL: 5.5 mL: 5.4 g. The dosage ratio of epichlorohydrin, the amino product, tetrabutylammonium bromide, toluene, and sodium hydroxide solution is 12.5 g: 7.5 g: 2.3 g: 145 mL: 13 mL. The mass fraction of the sodium hydroxide solution is 45%; Step A5: In a nitrogen atmosphere, add the epoxy product and methylenetriphenylphosphine to anhydrous tetrahydrofuran, reflux and stir at 53 °C for 8.5 h to obtain a double bond product; mix methyl methacrylate, butyl acrylate, acrylic acid, the double bond product, benzoyl peroxide, xylene, and butyl acetate, and react at 103 °C for 10.5 h to obtain a nano nickel-titanium-based resin binder; the dosage ratio of the epoxy product, methylenetriphenylphosphine, and anhydrous tetrahydrofuran is 10.5 g: 6.5 g: 135 mL; the dosage ratio of methyl methacrylate, butyl acrylate, acrylic acid, the double bond product, benzoyl peroxide, xylene, and butyl acetate is 43 g: 37 g: 5.5 g: 5.5 g: 1.3 g: 155 mL: 105 mL.

[0014] Example 3 A nano nickel-titanium-based resin binder, the preparation of which comprises the following steps: Step A1: Add nano nickel-titanium alloy powder (supplier: Ningbo Luofei Nano Technology Co., Ltd.) to sodium hydroxide solution, stir at 85 °C for 1.5 h to obtain surface-treated nano nickel-titanium alloy; add epoxy group silane coupling agent to anhydrous ethanol, ultrasonically disperse at 70 °C for 5 h, then add the surface-treated nano nickel-titanium alloy, heat up to 95 °C, and reflux and stir for 13 h to obtain modified nano nickel-titanium alloy; the dosage ratio of nano nickel-titanium alloy powder and sodium hydroxide solution is 2 g: 90 mL, and the concentration of sodium hydroxide solution is 2 mol / L; the dosage ratio of epoxy group silane coupling agent, anhydrous ethanol, and surface-treated nano nickel-titanium alloy is 6 g: 220 mL: 10 g, and the epoxy group silane coupling agent is 5,6-epoxyhexyltriethoxysilane; Step A2: Mix the amino silane coupling agent and anhydrous ethanol, ultrasonically disperse at 65 °C for 4 h, then add nano cerium oxide (supplier: Zibo Xiyan Nano Materials Co., Ltd.), heat up to 85 °C, and reflux and stir for 9 h to obtain NH2-nano cerium oxide; add NH2-nano cerium oxide and modified nano nickel-titanium alloy to dimethyl sulfoxide, stir and react at 65 °C for 25 h, filter and dry to obtain an alcohol hydroxyl product; the dosage ratio of amino silane coupling agent, anhydrous ethanol, and nano cerium oxide is 7.5 g: 250 mL: 4.5 g, and the amino silane coupling agent is KH550; the dosage ratio of NH2-nano cerium oxide, modified nano nickel-titanium alloy, and dimethyl sulfoxide is 8 g: 15 g: 350 mL; Step A3: Add 3-acetyl-5-nitrobenzoic acid to DMF, add thionyl chloride under stirring, reflux and stir the reaction at 45 °C for 11 h to obtain an acyl chloride product; stir and mix the alcohol hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide to obtain mixture 1; add the acyl chloride product to dimethyl sulfoxide to obtain mixture 2. In an ice-water bath, add mixture 2 dropwise to mixture 1. After the addition is complete, raise the temperature to 45 °C and stir the reaction at a constant temperature for 12 h, then perform reduced-pressure distillation to obtain the nitro product; the dosage ratio of 3-acetyl-5-nitrobenzoic acid, DMF, and thionyl chloride is 22 g: 80 mL: 13 g; the dosage ratio of the alcohol hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide in mixture 1 is 11 g: 0.9 g: 6 g: 170 mL; the dosage ratio of the acyl chloride product and dimethyl sulfoxide in mixture 2 is 23 g: 55 mL; the dosage ratio of mixture 1 to mixture 2 is 20 mL: 8.5 mL; Step A4: Mix the nitro product, ethanol, concentrated hydrochloric acid and stannous dichloride, and stir the reaction at 55 °C for 5.5 h, then filter, wash and dry to obtain the amino product; add epichlorohydrin, the amino product and tetrabutylammonium bromide to toluene, reflux and stir the reaction at 115 °C for 7 h, cool to room temperature, then add sodium hydroxide solution and stir for 6 h to obtain the epoxy product; the dosage ratio of the nitro product, ethanol, concentrated hydrochloric acid and stannous dichloride is 3 g: 110 mL: 6 mL: 5.5 g; the dosage ratio of epichlorohydrin, the amino product, tetrabutylammonium bromide, toluene and sodium hydroxide solution is 13 g: 8 g: 2.5 g: 150 mL: 15 mL; the mass fraction of the sodium hydroxide solution is 50%; Step A5: In a nitrogen atmosphere, add the epoxy product and methylenetriphenylphosphine to anhydrous tetrahydrofuran, reflux and stir the reaction at 55 °C for 9 h to obtain a double bond product; mix methyl methacrylate, butyl acrylate, acrylic acid, the double bond product, benzoyl peroxide, xylene and butyl acetate, and react at 105 °C for 11 h to obtain a nano-nickel-titanium-based resin binder; the dosage ratio of the epoxy product, methylenetriphenylphosphine and anhydrous tetrahydrofuran is 11 g: 7 g: 140 mL; the dosage ratio of methyl methacrylate, butyl acrylate, acrylic acid, the double bond product, benzoyl peroxide, xylene and butyl acetate is 45 g: 40 g: 6 g: 6 g: 1.5 g: 160 mL: 110 mL.

[0015] Example 4 A nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material, comprising the following raw materials in parts by weight: 75 parts of silicon carbide powder, 2.3 parts of carbon nanotubes, 0.8 part of boron carbide, 10 parts of nano-nickel-titanium-based resin binder, 0.08 part of polyethylene glycol, and 25 parts of water; the average particle size of α-silicon carbide in the silicon carbide powder is 200 nm, the average particle size of β-silicon carbide is 50 nm, and the mass ratio of α-silicon carbide to β-silicon carbide is 10:1.3; The preparation of the nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material comprises the following steps: Mix silicon carbide powder (supplier: Yumu (Ningbo) New Materials Co., Ltd.), carbon nanotubes (supplier: Jiangsu Tiannai Technology Co., Ltd., FT9000 series powder), boron carbide (supplier: Hubei Xinghengye Technology Co., Ltd.), the nano nickel-titanium-based resin binder obtained in Example 1, polyethylene glycol and water and stir for 2 h to obtain a mixed slurry; then dry the mixed slurry in a spray drying tower at 500 °C for 20 min to obtain a powder; then press the powder into a green body at 1.5 MPa, and dry the green body at 100 °C for 2.5 h to obtain a dried green body; then heat the dried green body at a heating rate of 15 °C to 500 °C, hold for 2 h, then adjust the heating rate to 50 °C and heat to 1000 °C, hold for 5 h, and then cool with the furnace after sintering to obtain the nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material.

[0016] Example 5 A nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material, comprising the following raw materials in parts by weight: 80 parts of silicon carbide powder, 2.4 parts of carbon nanotubes, 1.0 part of boron carbide, 11 parts of nano nickel-titanium-based resin binder, 0.09 part of polyethylene glycol, and 28 parts of water; the average particle size of α-silicon carbide in the silicon carbide powder is 200 nm, the average particle size of β-silicon carbide is 50 nm, and the mass ratio of α-silicon carbide to β-silicon carbide is 11:1.4; The preparation of the nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material comprises the following steps: Mix silicon carbide powder (supplier: Yumu (Ningbo) New Materials Co., Ltd.), carbon nanotubes (supplier: Jiangsu Tiannai Technology Co., Ltd., FT9000 series powder), boron carbide (supplier: Hubei Xinghengye Technology Co., Ltd.), the nano nickel-titanium-based resin binder obtained in Example 2, polyethylene glycol and water and stir for 2.3 h to obtain a mixed slurry; then dry the mixed slurry in a spray drying tower at 505 °C for 25 min to obtain a powder; then press the powder into a green body at 1.7 MPa, and dry the green body at 105 °C for 2.7 h to obtain a dried green body; then heat the dried green body at a heating rate of 20 °C to 550 °C, hold for 2.5 h, then adjust the heating rate to 55 °C and heat to 1100 °C, hold for 5.5 h, and then cool with the furnace after sintering to obtain the nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material.

[0017] Example 6 A nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material, comprising the following raw materials in parts by weight: 85 parts of silicon carbide powder, 2.5 parts of carbon nanotubes, 1.2 parts of boron carbide, 12 parts of nano-nickel-titanium-based resin binder, 0.1 part of polyethylene glycol, and 30 parts of water; the average particle size of α-silicon carbide in the silicon carbide powder is 200 nm, the average particle size of β-silicon carbide is 50 nm, and the mass ratio of α-silicon carbide to β-silicon carbide is 12:1.5; The preparation of the nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material comprises the following steps: Mix and stir 85 parts of silicon carbide powder (supplier: Yumu (Ningbo) New Materials Co., Ltd.), 2.5 parts of carbon nanotubes (supplier: Jiangsu Tiannai Technology Co., Ltd., FT9000 series powder), 1.2 parts of boron carbide (supplier: Hubei Xinghengye Technology Co., Ltd.), the nano-nickel-titanium-based resin binder obtained in Example 3, 0.1 part of polyethylene glycol and 30 parts of water for 2.5 h to obtain a mixed slurry; then dry the mixed slurry in a spray drying tower at 510 °C for 30 min to obtain a powder; then press the powder into a blank at 2 MPa, and dry the blank at 110 °C for 3 h to obtain a dried blank; then heat the dried blank at a heating rate of 25 °C to 600 °C, hold for 3 h, then adjust the heating rate to 60 °C and heat to 1200 °C, hold for 6 h, and after sintering, cool with the furnace to obtain the nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material.

[0018] Comparative Example 1 Compared with Example 6, the nano-nickel-titanium alloy powder in the preparation process of the nano-nickel-titanium-based resin binder was replaced with nano-nickel powder, and the rest was exactly the same as Example 6 to obtain a composite ceramic material.

[0019] Comparative Example 2 Compared with Example 6, the nano-ceria in the preparation process of the nano-nickel-titanium-based resin binder was replaced with nano-silicon carbide, and the rest was exactly the same as Example 6 to obtain a composite ceramic material.

[0020] Comparative Example 3 Compared with Example 6, the epoxy product in the preparation process of the nano-nickel-titanium-based resin binder was replaced with a nitro product, and the rest was exactly the same as Example 6 to obtain a composite ceramic material.

[0021] The following is a further effect detection of the composite ceramic material prepared by the present invention, and the detection results are as follows.

[0022] Flexural strength: Tested with reference to GB / T6569-2006 "Test Method for Flexural Strength of Fine Ceramics", and the results are recorded in Table 1; Corrosion resistance: Place the obtained composite ceramic material in a corrosion solution (boiling hydrochloric acid), observe the surface phenomenon after 48 h, and at the same time measure the flexural strength after soaking in the corrosion solution with reference to the above method, and the results are recorded in Table 1; Bulk density: It was measured with reference to GB / T 2413-1981 "Method for Measuring Bulk Density of Piezoelectric Ceramic Materials", and the results were recorded in Table 1; Table 1: Test Results

[0023] According to the data in Table 1, the composite ceramic material of the present invention has good mechanical strength, corrosion resistance and density. By comparing Example 6 with Comparative Example 1, it can be seen that when the nano nickel-titanium alloy in the preparation process of the nano nickel-titanium-based resin binder is replaced with nano nickel powder, the corrosion resistance of nano nickel powder is lower than that of nano nickel-titanium alloy, and the promotion effect on the mechanical strength of the composite ceramic material decreases, resulting in a decrease in the flexural strength of the composite ceramic material and a relatively large decrease in the flexural strength after immersion in the corrosion solution. By comparing Example 6 with Comparative Example 2, it can be seen that when nano cerium oxide in the preparation process of the nano nickel-titanium-based resin binder is replaced with nano silicon carbide, the promoting effect on the sintering of the composite ceramic material decreases significantly, which is not conducive to improving the density, resulting in a decrease in the bulk density and flexural strength of the composite ceramic material. By comparing Example 6 with Comparative Example 3, it can be seen that when the epoxy product in the preparation process of the nano nickel-titanium-based resin binder is replaced with a nitro product, that is, no epoxy group is introduced, the bonding performance of the nano nickel-titanium-based resin binder decreases, and the water in the composite ceramic material is prone to evaporate too quickly during calcination due to the decrease in water retention, resulting in cracking, thus leading to a decrease in the mechanical strength of the composite ceramic material. Therefore, the flexural strength of the composite ceramic material decreases.

[0024] The above content is only an example and explanation of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

Claims

1. A nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material, characterized in that: The method comprises the following raw materials in parts by weight: 75-85 parts of silicon carbide powder, 2.3-2.5 parts of carbon nanotubes, 0.8-1.2 parts of boron carbide, 10-12 parts of nano nickel-titanium-based resin binder, 0.08-0.1 parts of polyethylene glycol, and 25-30 parts of water; The preparation of the nano nickel-titanium-based resin binder comprises the following steps: Step A1, adding nano nickel-titanium alloy powder to a sodium hydroxide solution, stirring to obtain a surface-treated nano nickel-titanium alloy; adding an epoxy silane coupling agent to anhydrous ethanol, then adding the surface-treated nano nickel-titanium alloy, reflux stirring to react to obtain a modified nano nickel-titanium alloy; Step A2, after mixing an aminosilane coupling agent and anhydrous ethanol, add nano-cerium oxide, reflux and stir to react to obtain NH2-nano-cerium oxide; add NH2-nano-cerium oxide and modified nano-nickel-titanium alloy to dimethyl sulfoxide, stir and react to obtain an alcohol hydroxyl product; Step A3, adding 3-acetyl-5-nitrobenzoic acid to DMF, adding thionyl chloride under stirring, and reacting under reflux and stirring to obtain an acyl chloride product; The alcohol hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide are stirred and mixed to obtain a mixed solution 1; the acyl chloride product is added to dimethyl sulfoxide to obtain a mixed solution 2; the mixed solution 2 is added dropwise to the mixed solution 1 in an ice water bath, and the mixture is stirred and reacted to obtain a nitro product; Step A4, mixing the nitro product, ethanol, concentrated hydrochloric acid and stannous dichloride, stirring and reacting to obtain an amino product; adding epichlorohydrin, the amino product and tetrabutylammonium bromide to toluene, reflux and stir to react, cooling to room temperature, adding sodium hydroxide solution, stirring to obtain an epoxy product; Step A5, in a protective gas atmosphere, adding the epoxy product and methylenetriphenylphosphine to anhydrous tetrahydrofuran, reflux stirring and reacting to obtain a double bond product; methyl methacrylate, butyl acrylate, acrylic acid, the double bond product, benzoyl peroxide, xylene and butyl acetate are mixed, and reacted to obtain a nano nickel-titanium-based resin binder.

2. The nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material according to claim 1, characterized in that: The average particle size of α-silicon carbide in the silicon carbide powder is 200-500nm, the average particle size of β-silicon carbide is 50-100nm, and the mass ratio of α-silicon carbide to β-silicon carbide is 10-12:1.3-1.

5.

3. The nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material according to claim 1, characterized in that: In step A1, the usage ratio of nano nickel-titanium alloy powder and sodium hydroxide solution is 1-2 g: 80-90 mL, and the concentration of the sodium hydroxide solution is 1-2 mol / L.

4. The nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material according to claim 1, characterized in that: In step A1, the usage ratio of epoxy silane coupling agent, anhydrous ethanol and surface treated nano nickel-titanium alloy is 5-6 g: 200-220 mL: 9-10 g, and the epoxy silane coupling agent is 5,6-epoxyhexyltriethoxysilane.

5. The nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material according to claim 1, characterized in that: In step A2, the usage ratio of aminosilane coupling agent, anhydrous ethanol and nano-cerium oxide is 6.5-7.5 g: 230-250 mL: 3.5-4.5 g, and the aminosilane coupling agent is KH550; the usage ratio of NH2-nano-cerium oxide, modified nano-nickel-titanium alloy and dimethyl sulfoxide is 7-8 g: 14-15 g: 300-350 mL.

6. The nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material according to claim 1, characterized in that: In step A3, the usage ratio of 3-acetyl-5-nitrobenzoic acid, DMF and dichlorothionyl is 20-22 g: 70-80 mL: 12-13 g; the usage ratio of alcohol hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide in mixed solution 1 is 10-11 g: 0.8-0.9 g: 5-6 g: 160-170 mL.

7. The nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material according to claim 1, characterized in that: In step A3, the usage ratio of the acyl chloride product and dimethyl sulfoxide in the mixed solution 2 is 22-23 g: 50-55 mL; the usage ratio of the mixed solution 1 and the mixed solution 2 is 18-20 mL: 7.5-8.5 mL.

8. The nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material according to claim 1, characterized in that: In step A4, the dosage ratio of the nitro product, ethanol, concentrated hydrochloric acid and stannous chloride is 2-3 g: 100-110 mL: 5-6 mL: 5.3-5.5 g; the dosage ratio of epichlorohydrin, amino product, tetrabutylammonium bromide, toluene and sodium hydroxide solution is 12-13 g: 7-8 g: 2-2.5 g: 140-150 mL: 10-15 mL, and the mass fraction of the sodium hydroxide solution is 40-50%.

9. The nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material according to claim 1, characterized in that: In step A5, the usage ratio of the epoxy product, methylenetriphenylphosphine and anhydrous tetrahydrofuran is 10-11 g: 6-7 g: 130-140 mL; the usage ratio of methyl methacrylate, butyl acrylate, acrylic acid, double bond product, benzoyl peroxide, xylene and butyl acetate is 40-45 g: 35-40 g: 5-6 g: 5-6 g: 1-1.5 g: 150-160 mL: 100-110 mL.

10. A method for preparing the nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material according to any one of claims 1 to 9, characterized in that: The steps include: Silicon carbide powder, carbon nanotubes, boron carbide, nano nickel-titanium-based resin binder, polyethylene glycol and water are mixed and stirred for 2-2.5 hours to obtain a mixed slurry; the mixed slurry is then dried in a spray drying tower at 500-510°C for 20-30 minutes to obtain a powder; the powder is then molded at 1.5-2MPa to obtain a green body, and the green body is dried at 100-110°C for 2.5-3 hours to obtain a dried green body; the dried green body is then heated to 500-600°C at a heating rate of 15-25°C, kept warm for 2-3 hours, and then the heating rate is adjusted to 50-60°C to heat to 1000-1200°C, kept warm for 5-6 hours, and cooled with the furnace after sintering is completed to obtain a nickel-titanium alloy reinforced nano silicon carbide composite ceramic material.

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