A nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material and its preparation process

Abstract

The present invention discloses a nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material and a preparation process, relating to the field of silicon carbide composite ceramic materials. The 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 parts of polyethylene glycol, and 25-30 parts of water. The synthesized nano-nickel-titanium-based resin binder is a polyacrylate binder obtained by polymerization of a double bond product containing a terminal carbon-carbon double bond, nano-cerium oxide, nano-nickel-titanium alloy, and an epoxy group. The binder has the effects of promoting sintering, corrosion resistance, and mechanical strength, achieving the goal of multi-purpose use with one dose, and is worthy of promotion and use.

Description

Technical Field

[0001] The present 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 it, 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 alloys have strong high-temperature resistance and corrosion resistance. However, due to their poor compatibility with organic binders in ceramic materials, nano-nickel-titanium alloys are not conducive to uniform mixing with other raw materials, which limits their 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 properties of silicon carbide ceramic materials. However, due to the disadvantages of nano-cerium oxide's small specific surface area, it is easy to agglomerate and has poor compatibility with organic binders in ceramic materials. Directly adding it to silicon carbide composite ceramic materials cannot produce 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:

[0008] 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;

[0009] Furthermore, 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;

[0010] The nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material is prepared by the following steps:

[0011] 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 1.5-2 MPa 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 adjusted to a heating rate of 50-60° C. to heat to 1000-1200° C., kept warm for 5-6 hours, and cooled in the furnace after sintering to obtain a nickel-titanium alloy reinforced nano silicon carbide composite ceramic material;

[0012] The preparation of the nano nickel-titanium based resin binder comprises the following steps:

[0013] Step A1: adding nano nickel-titanium alloy powder to a sodium hydroxide solution and stirring at 75-85° C. for 1-1.5 hours to obtain a surface-treated nano nickel-titanium alloy; adding an epoxy silane coupling agent to anhydrous ethanol, ultrasonically dispersing at 60-70° C. for 4-5 hours, adding the surface-treated nano nickel-titanium alloy, heating to 90-95° C., and reflux stirring for 12-13 hours to obtain a modified nano nickel-titanium alloy;

[0014] Furthermore, the dosage ratio of the nano nickel-titanium alloy powder and the sodium hydroxide solution is 1-2 g: 80-90 mL, and the concentration of the sodium hydroxide solution is 1-2 mol / L; the dosage ratio of the epoxy silane coupling agent, anhydrous ethanol, and the 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;

[0015] During the reaction process of step A1, the surface of the nano nickel-titanium alloy powder is pre-oxidized after being heated in a sodium hydroxide solution to form oxygen-containing groups such as hydroxyl groups; the silanols after the hydrolysis of the epoxy silane coupling agent react with the nano nickel-titanium alloy with the pre-oxidized surface to obtain a modified nano nickel-titanium alloy with epoxy groups on the surface;

[0016] Step A2: An aminosilane coupling agent and anhydrous ethanol are mixed and ultrasonically dispersed at 60-65° C. for 3-4 hours, and then nano-cerium oxide is added. The temperature is raised to 80-85° C., and the mixture is refluxed with stirring for 8-9 hours to obtain NH2-nano-cerium oxide; NH2-nano-cerium oxide and modified nano-nickel-titanium alloy are added to dimethyl sulfoxide, stirred at 60-65° C. for 24-25 hours, and filtered and dried to obtain an alcoholic hydroxyl product;

[0017] Furthermore, 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;

[0018] During the reaction process of step A2, the aminosilane coupling agent modifies the surface of the nano-cerium oxide to obtain nano-cerium oxide containing amino groups on the surface, i.e., NH2-nano-cerium oxide; the amino groups of the NH2-nano-cerium oxide react with the epoxy groups of the modified nano-nickel-titanium alloy to obtain an alcoholic hydroxyl product containing nano-cerium oxide and nano-nickel-titanium alloy;

[0019] Step A3, adding 3-acetyl-5-nitrobenzoic acid to DMF, adding dichlorothionyl with stirring, and refluxing with stirring at 40-45° C. for 10-11 hours to obtain an acyl chloride product; stirring and mixing the alcoholic hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide to obtain a mixed solution 1; adding the acyl chloride product to dimethyl sulfoxide to obtain a mixed solution 2, and adding the mixed solution 2 dropwise to the mixed solution 1 in an ice-water bath. After the addition is complete, the temperature is raised to 40-45° C., the mixture is stirred at a constant temperature for 11-12 hours, and distilled under reduced pressure to obtain a nitro product;

[0020] Furthermore, the amount ratio of 3-acetyl-5-nitrobenzoic acid, DMF, and dichlorothionyl is 20-22 g: 70-80 mL: 12-13 g; the amount ratio of the alcohol hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide in the mixed solution 1 is 10-11 g: 0.8-0.9 g: 5-6 g: 160-170 mL; the amount ratio of the acyl chloride product and dimethyl sulfoxide in the mixed solution 2 is 22-23 g: 50-55 mL; the amount ratio of the mixed solution 1 to the mixed solution 2 is 18-20 mL: 7.5-8.5 mL;

[0021] During the reaction of step A3, 3-acetyl-5-nitrobenzoic acid reacts with thionyl chloride to obtain an acyl chloride product; the acyl chloride product reacts with an alcoholic hydroxyl product to obtain a nitro product containing a ketocarbonyl group, nano-cerium oxide, and nano-nickel-titanium alloy;

[0022] Step A4: Mix the nitro product, ethanol, concentrated hydrochloric acid, and stannous dichloride, stir and react at 50-55° C. for 5-5.5 hours, filter, wash, and dry to obtain the amino product; add epichlorohydrin, the amino product, and tetrabutylammonium bromide to toluene, reflux and stir at 110-115° C. for 6-7 hours, cool to room temperature, add sodium hydroxide solution, and stir for 5-6 hours to obtain the epoxy product;

[0023] Furthermore, the usage 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 usage 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%.

[0024] During the reaction of 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 is subjected to ring opening and then ring closing with epichlorohydrin to obtain an epoxy product containing a ketocarbonyl group, nano-cerium oxide, and nano-nickel-titanium alloy;

[0025] Step A5: In a protective gas atmosphere, the epoxy product and methylenetriphenylphosphine are added to anhydrous tetrahydrofuran, and the mixture is stirred under reflux at 50-55° C. for 8-9 hours 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 the mixture is reacted at 100-105° C. for 10-11 hours to obtain a nano-nickel-titanium-based resin binder;

[0026] Furthermore, 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;

[0027] During the reaction process of step A5, the ketone carbonyl of the epoxy product undergoes a ylide reaction with methylenetriphenylphosphine to generate a double bond product containing a terminal carbon-carbon double bond, nano-cerium oxide, nano-nickel-titanium alloy, and an epoxy group; the double bond product is polymerized with methyl methacrylate, butyl acrylate, and acrylic acid under the initiation of benzoyl peroxide to obtain a polyacrylate containing nano-cerium oxide, nano-nickel-titanium alloy, and an epoxy group, i.e., a nano-nickel-titanium-based resin binder.

[0028] Beneficial effects of the invention: The invention discloses a nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material, comprising the following raw materials: silicon carbide powder, carbon nanotubes, boron carbide, nano-nickel-titanium based resin binder, polyethylene glycol and water.

[0029] The synthesized nano nickel-titanium based resin binder is a polyacrylate binder obtained by the polymerization reaction of a double bond product containing a terminal carbon-carbon double bond, nano cerium oxide, nano nickel-titanium alloy, and an epoxy group; the nano nickel-titanium alloy is surface oxidized and treated with a silane coupling agent, and then participates in a 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, and the nano nickel-titanium alloy powder particles can play a bridging role in the crack propagation process, preventing 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 a polymerization reaction to be grafted into the polyacrylate binder. 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 the cracking of the green body due to excessive evaporation of water during the calcination process, 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 properties, corrosion resistance, sintering promotion and mechanical strength enhancement, achieving the goal of multiple uses with one dose.

[0030] Therefore, the silicon carbide composite ceramic material of the present invention has excellent mechanical strength, corrosion resistance and density, and is worthy of promotion and use.

[0031] Specific embodiments include

[0032] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0033] Example 1

[0034] A nano nickel-titanium-based resin binder, the preparation of which comprises the following steps:

[0035] Step A1. Add nano nickel-titanium alloy powder (supplier: Ningbo Luofei Nanotechnology Co., Ltd.) to a sodium hydroxide solution and stir at 75° C. for 1 hour to obtain a surface-treated nano nickel-titanium alloy; add an epoxy silane coupling agent to anhydrous ethanol, ultrasonically disperse at 60° C. for 4 hours, add the surface-treated nano nickel-titanium alloy, heat to 90° C., and reflux with stirring to react for 12 hours to obtain a modified nano nickel-titanium alloy; the amount ratio of the nano nickel-titanium alloy powder to the sodium hydroxide solution is 1 g:80 mL, and the concentration of the sodium hydroxide solution is 1 mol / L; the amount ratio of the epoxy silane coupling agent to anhydrous ethanol to the surface-treated nano nickel-titanium alloy is 5 g:200 mL:9 g, and the epoxy silane coupling agent is 5,6-epoxyhexyltriethoxysilane;

[0036] Step A2: An aminosilane coupling agent and anhydrous ethanol were mixed and ultrasonically dispersed at 60°C for 3 hours, and then nano-cerium oxide (supplier: Zibo Xiyan Nanomaterial Co., Ltd.) was added. The temperature was raised to 80°C, and the mixture was refluxed with stirring for 8 hours to obtain NH2-nano-cerium oxide; NH2-nano-cerium oxide and modified nano-nickel-titanium alloy were added to dimethyl sulfoxide, stirred and reacted at 60°C for 24 hours, filtered, and dried to obtain an alcoholic hydroxyl product; the amount ratio of the aminosilane coupling agent, anhydrous ethanol, and nano-cerium oxide was 6.5g:230mL:3.5g, and the aminosilane coupling agent was KH550; the amount ratio of the NH2-nano-cerium oxide, modified nano-nickel-titanium alloy, and dimethyl sulfoxide was 7g:14g:300mL;

[0037] Step A3, 3-acetyl-5-nitrobenzoic acid was added to DMF, and dichlorothionyl was added under stirring, and the mixture was refluxed and stirred at 40 ° C for 10 hours to obtain an acyl chloride product; the alcohol hydroxy product, pyridine, triethylamine and dimethyl sulfoxide were stirred to obtain a mixed solution 1; the acyl chloride product was added to dimethyl sulfoxide to obtain a mixed solution 2, and the mixed solution 2 was added dropwise to the mixed solution 1 in an ice-water bath. After the addition was complete, the temperature was raised to 40 ° C, and the mixture was stirred at constant temperature for 11 hours, and the mixture was reduced. The nitro product was obtained by pressure distillation; the dosage ratio of 3-acetyl-5-nitrobenzoic acid, DMF, and thionyl chloride was 20 g:70 mL:12 g; the dosage ratio of the alcohol hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide in the mixed solution 1 was 10 g:0.8 g:5 g:160 mL; the dosage ratio of the acyl chloride product and dimethyl sulfoxide in the mixed solution 2 was 22 g:50 mL; the dosage ratio of the mixed solution 1 to the mixed solution 2 was 18 mL:7.5 mL;

[0038] Step A4: Mix the nitro product, ethanol, concentrated hydrochloric acid, and stannous dichloride, stir and react at 50° C. for 5 hours, filter, wash, and dry to obtain an amino product; add epichlorohydrin, the amino product, and tetrabutylammonium bromide to toluene, reflux and stir at 110° C. for 6 hours, cool to room temperature, add sodium hydroxide solution, and stir for 5 hours to obtain an epoxy product; the amount ratio of the nitro product, ethanol, concentrated hydrochloric acid, and stannous dichloride is 2 g:100 mL:5 mL:5.3 g; the amount 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%;

[0039] Step A5. In a nitrogen atmosphere, the epoxy product and methylenetriphenylphosphine are added to anhydrous tetrahydrofuran, and the mixture is refluxed with stirring at 50°C for 8 hours 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 the mixture is reacted at 100°C for 10 hours to obtain a nano-nickel-titanium-based resin binder; the amount ratio of the epoxy product, methylenetriphenylphosphine and anhydrous tetrahydrofuran is 10g:6g:130mL; the amount ratio of methyl methacrylate, butyl acrylate, acrylic acid, the double bond product, benzoyl peroxide, xylene and butyl acetate is 40g:35g:5g:5g:1g:150mL:100mL.

[0040] Example 2

[0041] A nano nickel-titanium-based resin binder, the preparation of which comprises the following steps:

[0042] Step A1. Add nano nickel-titanium alloy powder (supplier: Ningbo Luofei Nanotechnology Co., Ltd.) to a sodium hydroxide solution and stir at 80° C. for 1.3 hours to obtain a surface-treated nano nickel-titanium alloy; add an epoxy silane coupling agent to anhydrous ethanol, ultrasonically disperse at 65° C. for 4.5 hours, add the surface-treated nano nickel-titanium alloy, heat to 93° C., and reflux with stirring for 12.5 hours to obtain a modified nano nickel-titanium alloy; the amount ratio of the nano nickel-titanium alloy powder to the sodium hydroxide solution is 1.5 g:85 mL, and the concentration of the sodium hydroxide solution is 1.5 mol / L; the amount ratio of the epoxy silane coupling agent to anhydrous ethanol to the surface-treated nano nickel-titanium alloy is 5.5 g:210 mL:9.5 g, and the epoxy silane coupling agent is 5,6-epoxyhexyltriethoxysilane;

[0043] Step A2: An aminosilane coupling agent and anhydrous ethanol were mixed and ultrasonically dispersed at 63° C. for 3.5 hours, and then nano-cerium oxide (supplier: Zibo Xiyan Nanomaterial Co., Ltd.) was added. The temperature was raised to 83° C. and the mixture was refluxed with stirring for 8.5 hours to obtain NH2-nano-cerium oxide; NH2-nano-cerium oxide and modified nano-nickel-titanium alloy were added to dimethyl sulfoxide, stirred and reacted at 63° C. for 24.5 hours, filtered, and dried to obtain an alcoholic hydroxyl product; the amount ratio of the aminosilane coupling agent, anhydrous ethanol, and nano-cerium oxide was 7.0 g: 240 mL: 4.0 g, and the aminosilane coupling agent was KH550; the amount ratio of the NH2-nano-cerium oxide, modified nano-nickel-titanium alloy, and dimethyl sulfoxide was 7.5 g: 14.5 g: 330 mL;

[0044] Step A3, 3-acetyl-5-nitrobenzoic acid was added to DMF, and dichlorothionyl was added under stirring, and the mixture was refluxed and stirred at 43 ° C for 10.5 hours to obtain an acyl chloride product; the alcohol hydroxy product, pyridine, triethylamine and dimethyl sulfoxide were stirred and mixed to obtain a mixed solution 1; the acyl chloride product was added to dimethyl sulfoxide to obtain a mixed solution 2, and the mixed solution 2 was added dropwise to the mixed solution 1 in an ice-water bath. After the addition was complete, the temperature was raised to 43 ° C, the mixture was stirred at constant temperature for 11.5 hours, and the mixture was evaporated under reduced pressure. The nitro product was obtained by distillation; the usage ratio of 3-acetyl-5-nitrobenzoic acid, DMF, and thionyl chloride was 21 g:75 mL:12.5 g; the usage ratio of the alcohol hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide in mixed solution 1 was 10.5 g:0.85 g:5.5 g:165 mL; the usage ratio of the acyl chloride product and dimethyl sulfoxide in mixed solution 2 was 22.5 g:53 mL; the usage ratio of mixed solution 1 to mixed solution 2 was 19 mL:8.0 mL;

[0045] Step A4: After mixing the nitro product, ethanol, concentrated hydrochloric acid and stannous dichloride, stirring and reacting at 53° C. for 5.3 hours, filtering, washing and drying to obtain an amino product; adding epichlorohydrin, amino product and tetrabutylammonium bromide to toluene, stirring and reacting at 113° C. for 6.5 hours, cooling to room temperature, adding sodium hydroxide solution and stirring for 5.5 hours to obtain an epoxy product; the amount 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 amount ratio of epichlorohydrin, 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%;

[0046] Step A5. In a nitrogen atmosphere, the epoxy product and methylenetriphenylphosphine are added to anhydrous tetrahydrofuran, and the mixture is refluxed with stirring at 53°C for 8.5 hours 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 the mixture is reacted at 103°C for 10.5 hours to obtain a nano-nickel-titanium-based resin binder; the amount ratio of the epoxy product, methylenetriphenylphosphine and anhydrous tetrahydrofuran is 10.5g:6.5g:135mL; the amount ratio of methyl methacrylate, butyl acrylate, acrylic acid, the double bond product, benzoyl peroxide, xylene and butyl acetate is 43g:37g:5.5g:5.5g:1.3g:155mL:105mL.

[0047] Example 3

[0048] A nano nickel-titanium-based resin binder, the preparation of which comprises the following steps:

[0049] Step A1. Add nano nickel-titanium alloy powder (supplier: Ningbo Luofei Nanotechnology Co., Ltd.) to a sodium hydroxide solution and stir at 85° C. for 1.5 hours to obtain a surface-treated nano nickel-titanium alloy; add an epoxy silane coupling agent to anhydrous ethanol, ultrasonically disperse at 70° C. for 5 hours, add the surface-treated nano nickel-titanium alloy, heat to 95° C., and reflux with stirring for 13 hours to obtain a modified nano nickel-titanium alloy; the amount ratio of the nano nickel-titanium alloy powder to the sodium hydroxide solution is 2 g:90 mL, and the concentration of the sodium hydroxide solution is 2 mol / L; the amount ratio of the epoxy silane coupling agent, anhydrous ethanol, and the surface-treated nano nickel-titanium alloy is 6 g:220 mL:10 g, and the epoxy silane coupling agent is 5,6-epoxyhexyltriethoxysilane;

[0050] Step A2: An aminosilane coupling agent and anhydrous ethanol were mixed and ultrasonically dispersed at 65°C for 4 hours, and then nano-cerium oxide (supplier: Zibo Xiyan Nanomaterial Co., Ltd.) was added. The temperature was raised to 85°C, and the mixture was refluxed with stirring for 9 hours to obtain NH2-nano-cerium oxide; NH2-nano-cerium oxide and modified nano-nickel-titanium alloy were added to dimethyl sulfoxide, stirred and reacted at 65°C for 25 hours, filtered, and dried to obtain an alcoholic hydroxyl product; the amount ratio of the aminosilane coupling agent, anhydrous ethanol, and nano-cerium oxide was 7.5g:250mL:4.5g, and the aminosilane coupling agent was KH550; the amount ratio of the NH2-nano-cerium oxide, modified nano-nickel-titanium alloy, and dimethyl sulfoxide was 8g:15g:350mL;

[0051] Step A3, 3-acetyl-5-nitrobenzoic acid was added to DMF, and dichlorothionyl was added under stirring, and the mixture was refluxed and stirred at 45 ° C for 11 hours to obtain an acyl chloride product; the alcohol hydroxy product, pyridine, triethylamine and dimethyl sulfoxide were stirred to obtain a mixed solution 1; the acyl chloride product was added to dimethyl sulfoxide to obtain a mixed solution 2, and the mixed solution 2 was added dropwise to the mixed solution 1 in an ice-water bath. After the addition was complete, the temperature was raised to 45 ° C, and the mixture was stirred at constant temperature for 12 hours, and the mixture was reduced. The nitro product was obtained by pressure distillation; the dosage ratio of 3-acetyl-5-nitrobenzoic acid, DMF, and dichlorothionyl was 22 g: 80 mL: 13 g; the dosage ratio of the alcohol hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide in the mixed solution 1 was 11 g: 0.9 g: 6 g: 170 mL; the dosage ratio of the acyl chloride product and dimethyl sulfoxide in the mixed solution 2 was 23 g: 55 mL; the dosage ratio of the mixed solution 1 to the mixed solution 2 was 20 mL: 8.5 mL;

[0052] Step A4: After mixing the nitro product, ethanol, concentrated hydrochloric acid and stannous dichloride, stirring and reacting at 55° C. for 5.5 hours, filtering, washing and drying to obtain an amino product; adding epichlorohydrin, the amino product and tetrabutylammonium bromide to toluene, refluxing and stirring at 115° C. for 7 hours, cooling to room temperature, adding sodium hydroxide solution and stirring for 6 hours to obtain an epoxy product; the amount ratio of the nitro product, ethanol, concentrated hydrochloric acid and stannous dichloride is 3g:110mL:6mL:5.5g; the amount ratio of epichlorohydrin, the amino product, tetrabutylammonium bromide, toluene and sodium hydroxide solution is 13g:8g:2.5g:150mL:15mL; the mass fraction of the sodium hydroxide solution is 50%;

[0053] Step A5. In a nitrogen atmosphere, the epoxy product and methylenetriphenylphosphine are added to anhydrous tetrahydrofuran, and the mixture is refluxed with stirring at 55°C for 9 hours 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 the mixture is reacted at 105°C for 11 hours to obtain a nano-nickel-titanium-based resin binder; the amount ratio of the epoxy product, methylenetriphenylphosphine and anhydrous tetrahydrofuran is 11g:7g:140mL; the amount ratio of methyl methacrylate, butyl acrylate, acrylic acid, the double bond product, benzoyl peroxide, xylene and butyl acetate is 45g:40g:6g:6g:1.5g:160mL:110mL.

[0054] Example 4

[0055] 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 parts of boron carbide, 10 parts of a nano-nickel-titanium-based resin binder, 0.08 parts 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;

[0056] The nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material is prepared by the following steps:

[0057] 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 were mixed and stirred for 2 hours to obtain a mixed slurry; the mixed slurry was then dried in a spray drying tower at 500°C for 20 minutes to obtain a powder; the powder was then molded under 1.5 MPa to obtain a green body, and the green body was dried at 100°C for 2.5 hours to obtain a dried green body; the dried green body was then heated to 500°C at a heating rate of 15°C, kept warm for 2 hours, and then the heating rate was adjusted to 50°C and heated to 1000°C, kept warm for 5 hours, and then cooled in the furnace after sintering to obtain a nickel-titanium alloy reinforced nano silicon carbide composite ceramic material.

[0058] Example 5

[0059] 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 a nano-nickel-titanium-based resin binder, 0.09 parts 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;

[0060] The nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material is prepared by the following steps:

[0061] 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 were mixed and stirred for 2.3 hours to obtain a mixed slurry; the mixed slurry was then dried at 505°C in a spray drying tower for 25 minutes to obtain a powder; the powder was then molded under 1.7 MPa to obtain a green body, and the green body was dried at 105°C for 2.7 hours to obtain a dried green body; the dried green body was then heated to 550°C at a heating rate of 20°C, kept warm for 2.5 hours, and then the heating rate was adjusted to 55°C and heated to 1100°C, kept warm for 5.5 hours, and then cooled in the furnace after sintering to obtain a nickel-titanium alloy reinforced nano silicon carbide composite ceramic material.

[0062] Example 6

[0063] 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 a nano-nickel-titanium-based resin binder, 0.1 parts 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;

[0064] The nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material is prepared by the following steps:

[0065] 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 3, polyethylene glycol and water were mixed and stirred for 2.5 hours to obtain a mixed slurry; the mixed slurry was then dried at 510°C in a spray drying tower for 30 minutes to obtain a powder; the powder was then molded at 2 MPa to obtain a green body, and the green body was dried at 110°C for 3 hours to obtain a dried green body; the dried green body was then heated to 600°C at a heating rate of 25°C, kept warm for 3 hours, and then the heating rate was adjusted to 60°C and heated to 1200°C, kept warm for 6 hours, and then cooled with the furnace after sintering to obtain a nickel-titanium alloy reinforced nano silicon carbide composite ceramic material.

[0066] Comparative Example 1

[0067] 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 prepare a composite ceramic material.

[0068] Comparative Example 2

[0069] Compared with Example 6, the nano-cerium oxide 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.

[0070] Comparative Example 3

[0071] 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.

[0072] The composite ceramic material prepared by the present invention is further tested for its effects, and the test results are described below.

[0073] Bending strength: Tested according to GB / T6569-2006 "Test method for flexural strength of fine ceramics", and the results are recorded in Table 1;

[0074] Corrosion resistance: The obtained composite ceramic material was placed in a corrosive solution (boiling hydrochloric acid). The surface phenomenon was observed after 48 hours. At the same time, the flexural strength after immersion in the corrosive solution was measured with reference to the above method. The results are recorded in Table 1.

[0075] Bulk density: measured according to GB / T2413-1981 "Measurement method of bulk density of piezoelectric ceramic materials" and the results are recorded in Table 1;

[0076] Table 1: Test results

[0077]

[0078] According to the data in Table 1, the composite ceramic material of the present invention has good mechanical strength, corrosion resistance and density. Comparison of Example 6 with Comparative Example 1 shows 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 the nano nickel powder compared to the nano nickel-titanium alloy is reduced, and the effect of improving the mechanical strength of the composite ceramic material is reduced, resulting in a decrease in the flexural strength of the composite ceramic material and a greater decrease in the flexural strength after immersion in the corrosive solution. Comparison of Example 6 with Comparative Example 2 shows that when the nano cerium oxide in the preparation process of the nano nickel-titanium-based resin binder is replaced with nano silicon carbide, the effect of promoting the sintering of the composite ceramic material is greatly reduced, which is not conducive to improving the density, thereby resulting in a decrease in the volume density and flexural strength of the composite ceramic material. Comparison of Example 6 with Comparative Example 3 shows 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 is reduced, and the water in the composite ceramic material is easily evaporated too quickly due to the reduced water retention during the calcination process, leading to cracking, thereby causing the mechanical strength of the composite ceramic material to decrease, and therefore the flexural strength of the composite ceramic material is reduced.

[0079] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A nickel-titanium alloy reinforced nano-silicon carbide composite ceramic material, characterized by: 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 and 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, and 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, and reflux with stirring to react to obtain NH2-nano-cerium oxide; add NH2-nano-cerium oxide and modified nano-nickel-titanium alloy to dimethyl sulfoxide, and stir to react to obtain an alcohol hydroxyl product; Step A3, adding 3-acetyl-5-nitrobenzoic acid to DMF, adding thionyl chloride with stirring, and reflux stirring to react to obtain an acyl chloride product; The alcoholic hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide are stirred to obtain a mixture 1; the acyl chloride product is added to dimethyl sulfoxide to obtain a mixture 2; the mixture 2 is added dropwise to the mixture 1 in an ice-water bath, and the mixture is stirred to react to obtain a nitro product; Step A4: Mix the nitro product, ethanol, concentrated hydrochloric acid, and stannous dichloride, and stir to react to obtain an amino product; add epichlorohydrin, the amino product, and tetrabutylammonium bromide to toluene, reflux and stir to react, cool to room temperature, add sodium hydroxide solution, and stir to obtain an epoxy product; Step A5: In a protective gas atmosphere, add the epoxy product and methylenetriphenylphosphine to anhydrous tetrahydrofuran, and reflux with stirring to react 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 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 200-500 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.

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 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 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 ratio of 3-acetyl-5-nitrobenzoic acid, DMF, and thionyl chloride is 20-22 g: 70-80 mL: 12-13 g; the ratio of the alcoholic hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide in the 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 ratio of the acyl chloride product and dimethyl sulfoxide in mixed solution 2 is 22-23 g: 50-55 mL; the ratio of mixed solution 1 to 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 usage 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 usage 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 at 500-510°C in a spray drying tower 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 up to 1000-1200°C, kept warm for 5-6 hours, and cooled with the furnace after sintering to obtain a nickel-titanium alloy reinforced nano silicon carbide composite ceramic material.

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