An impact-resistant composite ceramic material and a method of making and using the same

Abstract

This invention relates to the field of ceramic materials technology, and discloses an impact-resistant composite ceramic material, its preparation method, and its application. The preparation method of the impact-resistant composite ceramic material includes the following steps: mixing potassium feldspar, quartz, kaolin, wollastonite, bentonite, calcium silicate, talc, alumina, and reduced-treated composite modified zirconium oxide powder to obtain a green body material; mixing potassium feldspar, sodium feldspar, quartz sand, calcite, dolomite, kaolin, talc, fluorapatite, alumina, zinc powder, and silicon carbide whiskers to obtain a mixture, which is then ball-milled and sieved to obtain a glaze slurry; forming the green body material into a ceramic green body matrix; applying the glaze slurry onto the ceramic green body matrix, and sintering in stages to obtain the impact-resistant composite ceramic material. The impact-resistant composite ceramic material of this invention has excellent gloss and aesthetics, and also exhibits excellent impact resistance and thermal shock resistance.

Description

Technical Field

[0001] This invention relates to the field of ceramic materials technology, specifically to an impact-resistant composite ceramic material, its preparation method, and its application. Background Technology

[0002] Ceramic materials refer to a class of inorganic non-metallic materials made from natural or synthetic compounds through shaping and high-temperature sintering. They possess advantages such as high melting point, high hardness, high wear resistance, and oxidation resistance, and are widely used in various applications. With the rapid development of the national economy and the rapid improvement of people's living standards, ceramic handicrafts are becoming increasingly popular. However, ceramic handicrafts themselves have poor impact resistance and are easily broken, affecting their service life. Therefore, improving the impact resistance of ceramic materials is of great significance. Summary of the Invention

[0003] To address the aforementioned technical problems, this invention provides a method for preparing an impact-resistant composite ceramic material, comprising the following steps:

[0004] Step 1: Using zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, and yttrium chloride hexahydrate as raw materials, binary doped zirconium oxide microspheres are obtained through atomization-assisted chemical vapor deposition technology;

[0005] The ternary composite material was mixed with binary doped zirconia microspheres to obtain composite modified zirconia powder; the composite modified zirconia powder was then thermally reduced to obtain reduced composite modified zirconia powder.

[0006] Potassium feldspar, quartz, kaolin, wollastonite, bentonite, calcium silicate, talc, alumina, and reduced-treated composite modified zirconium oxide powder are mixed to obtain the green body material.

[0007] The preparation method of the ternary composite material includes the following steps:

[0008] S1. Graphene oxide and carbon nanotubes are processed separately to obtain aminated graphene oxide and carboxylated carbon nanotubes; the aminated graphene oxide and carboxylated carbon nanotubes are combined to obtain a graphene oxide / carbon nanotube hybrid material.

[0009] S2. Nano-silica is grown in situ on the surface of graphene oxide / carbon nanotube hybrid material to obtain ternary composite material;

[0010] The green body material is made into a ceramic green body matrix;

[0011] Step 2: Mix potassium feldspar, sodium feldspar, quartz sand, calcite, dolomite, kaolin, talc, fluorapatite, alumina, zinc powder, and silicon carbide whiskers to obtain a mixture, then ball mill and sieve to obtain a glaze slurry.

[0012] The glaze slurry is applied to the ceramic body substrate and sintered in stages to obtain an impact-resistant composite ceramic material.

[0013] Preferably, in step one, the method for preparing the reduced-treated composite modified zirconium oxide powder specifically includes:

[0014] Zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, yttrium chloride hexahydrate, and distilled water were mixed in a mass ratio of 15:(1-2):(1.3-1.7):500 and stirred. The solution was then converted into 3-5 μm droplets by ultrasonic atomization. The solution was then heated at 600-900℃ using atomization-assisted chemical vapor deposition (ACVD) while maintaining an atomization rate of 500 mL / h for 80-100 min. The resulting powder was heated to 1300-1600℃ at a rate of 100℃ / min and compacted under a pressure of 50 MPa to obtain binary doped zirconia microspheres with a diameter of 0.4-0.5 μm.

[0015] The ternary composite material was added to deionized water and sonicated. Then, binary doped zirconia microspheres were added and stirred to make the mass ratio of the ternary composite material to the binary doped zirconia microspheres (0.1-0.3):1, thus obtaining composite modified zirconia powder.

[0016] The composite modified zirconia powder was thermally reduced in an argon atmosphere at a heating rate of 8℃ / min to 750-850℃ to obtain the reduced composite modified zirconia powder.

[0017] In the above process, binary doped zirconia microspheres co-doped with gadolinium and yttrium were prepared using zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, and yttrium chloride hexahydrate as raw materials. The co-doping of gadolinium and yttrium can promote the growth of tetragonal zirconia, improve the strength, hardness, and toughness of zirconia ceramics, and thus improve the thermal shock resistance of ceramics. At the same time, the binary doped zirconia microspheres prepared by atomization-assisted chemical vapor deposition technology have a hollow structure. The unique hollow microsphere structure significantly enhances the sintering advantages, alleviates the common problem of nanoparticle agglomeration, and during the sintering process of ceramic materials (especially hot pressing sintering), the collapse of the ordered hollow microsphere structure leads to the generation of smaller nanosheets, which increases the specific surface area and surface energy, promotes the densification of ceramic materials, enhances sintering activity, and reduces sintering temperature.

[0018] Furthermore, the ternary composite material was mixed with binary doped zirconia microspheres. The hydrophilic groups (hydroxyl, carboxyl, and amino groups) on the surface of the ternary composite material allowed it to bond with the binary doped zirconia microspheres. After reduction treatment, the graphene oxide in the ternary composite material was converted into reduced graphene oxide. During sintering, Zr-OC chemical bonds were formed between the reduced graphene oxide and the binary doped zirconia microspheres. Due to the strong interfacial effect of the sheet structure of the reduced graphene oxide, it can help the binary doped zirconia microspheres to be better dispersed in the preform material. The ternary composite material contains reduced graphene oxide... Graphene and multi-walled carbon nanotubes, especially reduced graphene oxide and multi-walled carbon nanotubes, possess excellent thermal conductivity, which can promote grain refinement and growth. Reduced graphene oxide and multi-walled carbon nanotubes also exhibit effects such as grain boundary fixation, bending, pull-out, bridging, and crack propagation, which have a positive impact on the mechanical properties and thermal shock resistance of zirconia ceramics. In addition, nano-silica in ternary composite materials helps to form and stabilize tetragonal zirconia, and forms covalent Si-O-Zr bonds with zirconia, resulting in better interfacial compatibility between ternary composite materials and binary doped zirconia microspheres.

[0019] Preferably, in step one, the components in the blank material, by weight, are: 35-40 parts potassium feldspar, 25-30 parts quartz, 10-15 parts kaolin, 10-15 parts wollastonite, 8-12 parts bentonite, 7-10 parts calcium silicate, 6-8 parts talc, 5-8 parts alumina, and 12-20 parts reduced-treated composite modified zirconium oxide powder.

[0020] In the above process, potassium feldspar, quartz, and kaolin are used as the main aggregates for the green body material, which have good adhesion. Wollastonite is also added, which can lower the firing temperature, fill gaps, and improve the uniformity and density of the green body. Bentonite has water absorption and expansion properties and also has adhesion. Together with other components, it lowers the sintering temperature and improves the mechanical properties of the ceramic material. In addition, it is well known that zirconium oxide can give ceramic materials high toughness, high flexural strength, and high wear resistance. Compared with zirconium oxide, the composite modified zirconium oxide powder treated by reduction further improves the performance of the ceramic material due to the presence of graphene oxide, nano-silica, and multi-walled carbon nanotubes.

[0021] Furthermore, in step one, the preparation method of the ternary composite material specifically includes the following steps:

[0022] S1. Mix multi-walled carbon nanotubes, concentrated sulfuric acid, and concentrated nitric acid, reflux and sonicate for 5-6 hours, add deionized water, and purify to obtain carboxylated carbon nanotubes; wherein, the ratio of multi-walled carbon nanotubes, concentrated sulfuric acid, concentrated nitric acid, and deionized water is (2.5-5) g:(75-150) mL:(25-50) mL:(200-400) mL;

[0023] Graphene oxide was added to deionized water and sonicated. Then, sodium hydroxide aqueous solution was added and sonicated again. The sodium hydroxide was neutralized with hydrochloric acid aqueous solution, centrifuged and rinsed. Then, ultrapure water and ethylenediamine were added and sonicated. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added, centrifuged, and dialyzed to obtain aminated graphene oxide. The mass ratio of graphene oxide to ethylenediamine was (0.04-0.08):(0.4-0.8).

[0024] A dispersant was obtained by mixing polyvinylpyrrolidone and ethanol in an equal mass ratio. Aminated graphene oxide and carboxylated carbon nanotubes were added to the dispersant to obtain a suspension of aminated graphene oxide with a mass fraction of 0.2-1.2% and a suspension of carboxylated carbon nanotubes with a mass fraction of 0.2-1.2%. The aminated graphene oxide suspension and the carboxylated carbon nanotube suspension were mixed at a volume ratio of 1:2, ultrasonicated for 20-30 min, centrifuged, washed, and dried to obtain a graphene oxide / carbon nanotube hybrid material.

[0025] In the above process, multi-walled carbon nanotubes are treated with concentrated sulfuric acid and concentrated nitric acid, which introduces abundant carboxyl groups on their surface to obtain carboxylated carbon nanotubes; amino groups in graphene oxide are combined with ethylenediamine through an amidation reaction to obtain aminated graphene oxide; aminated graphene oxide and carboxylated carbon nanotubes are combined through electrostatic interactions and hydrogen bonds between amino and carboxyl groups, and the carboxylated carbon nanotubes are intercalated into the sheet structure of graphene oxide to obtain graphene oxide / carbon nanotube hybrid materials;

[0026] S2. Disperse the graphene oxide / carbon nanotube hybrid material in an 80% (v / v) aqueous ethanol solution and sonicate to obtain a mixed solution A with a concentration of 1 mg / mL.

[0027] Ethyl silicate and an 80% (v / v) aqueous ethanol solution were mixed to obtain an ethyl silicate dispersion with a concentration of 0.1-0.15 mol / L. The pH was adjusted to 4 to obtain mixture B. Mixture A and mixture B were mixed at a volume ratio of 1:(3.8-4.2) under stirring conditions. The pH was adjusted to 9 with an aqueous sodium hydroxide solution. The mixture was then stirred at 63-67℃ and 40-60 r / min for 50-70 min. After purification, a ternary composite material was obtained.

[0028] In the above process, ethyl silicate hydrolyzes into orthosilicic acid. The hydrolysis rate is accelerated in the presence of acetic acid. The hydroxyl groups of orthosilicic acid combine with the hydroxyl groups and amino groups on the graphene oxide in the graphene oxide / carbon nanotube hybrid material, thereby adsorbing the orthosilicic acid onto the graphene oxide / carbon nanotube hybrid material. Then, through condensation interaction, it forms stable covalent bonds with the graphene oxide / carbon nanotube hybrid material, thus realizing the in-situ growth of nano-silica on the surface of the graphene oxide / carbon nanotube hybrid material.

[0029] Preferably, in step one, the method for preparing the ceramic body matrix specifically includes: mixing the body material with water, ball milling with alumina balls as the ball milling medium for 15-25 hours, ball milling speed of 200-250 r / min, and the weight ratio of body material, alumina balls and water being 1:(1.8-2):(0.6-0.7). The ball-milled slurry is passed through a 200-mesh sieve, and after iron removal, it is pressed and filtered into mud cakes. After the mud cakes are processed into the required shapes, they are shaped, trimmed, and dried. After drying, they are placed in a kiln and heated to 500-600℃ at a rate of 5-10℃ / min and held for 2-4 hours. Then, the temperature is increased to 700-800℃ at a rate of 10-15℃ / min and sintered for 6-8 hours. The temperature is then reduced to 600-650℃ and held for 1-2 hours. After sintering, the temperature is naturally cooled to 40-50℃ before being removed from the kiln to obtain the ceramic body matrix.

[0030] Preferably, in step two, the method for preparing the glaze slurry specifically includes: taking 15-20 parts by weight of potassium feldspar, 5-10 parts by weight of sodium feldspar, 35-55 parts by weight of quartz sand, 2-5 parts by weight of calcite, 2-5 parts by weight of dolomite, 2-5 parts by weight of kaolin, 2-5 parts by weight of talc, 2-5 parts by weight of fluorapatite, 2-4 parts by weight of alumina, 2-10 parts by weight of zinc powder, and 1-2 parts by weight of silicon carbide whiskers to obtain a mixture; mixing the mixture with water at a mass ratio of 5:(2-3) and then ball milling at a ball milling speed of 1000-1500 r / min for 25-35 min; and then passing the mixture through a 200-400 mesh sieve to obtain the glaze slurry.

[0031] In the above process, the components of the glaze work together to give the ceramic material a jade-like texture and luster, thus improving its aesthetics; while the added silicon carbide whiskers can improve the strength and toughness of the ceramic material.

[0032] Preferably, in step two, the application conditions of the glaze slurry include: glaze specific gravity 1.7-1.9 g / m³. 3 Glaze weight 600-800g / m 2 .

[0033] Preferably, in step two, the stepwise sintering includes: first heating to 1150-1180℃ at a heating rate of 1.5-2℃ / min, holding at that temperature for 2-3 hours, then heating to 1180-1200℃, holding at that temperature for 7.5-8.5 hours, and finally heating to 1250-1300℃ and hot-pressing sintering under a constant pressure of 20-50MPa, holding at that temperature for 1.5-2.5 hours;

[0034] In the above process, a step-by-step sintering method is adopted during sintering, with hot pressing sintering in the middle. During the hot pressing sintering process, the collapse of the ordered hollow microsphere structure leads to the generation of smaller nanosheets, which increases the specific surface area and surface energy, promotes the densification of ceramic materials, and thus improves the performance of ceramic materials.

[0035] The impact-resistant composite ceramic material is prepared by the aforementioned method.

[0036] The impact-resistant composite ceramic material is used in ceramic handicrafts.

[0037] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0038] 1. This invention incorporates reduced-treated composite modified zirconia powder into the green body material of an impact-resistant composite ceramic material. The reduced-treated composite modified zirconia powder is obtained by combining a ternary composite material with binary doped zirconia microspheres and then undergoing reduction treatment. The binary doped zirconia microspheres can improve the strength, hardness, and toughness of the ceramic material, thereby giving the ceramic material excellent impact resistance and thermal shock resistance. Furthermore, the zirconia microspheres can also lower the sintering temperature of the ceramic material. The reduced graphene oxide, multi-walled carbon nanotubes, and nano-silica in the ternary composite material work together, and the ternary composite material and the binary doped zirconia microspheres are chemically bonded, resulting in good interfacial compatibility and a positive impact on the mechanical properties and thermal shock resistance of zirconia ceramics. In addition, the ternary composite material also promotes the dispersion of binary doped zirconia microspheres in the green body material of the impact-resistant composite ceramic material, thereby giving the ceramic material better impact resistance.

[0039] 2. The present invention coats the surface of the impact-resistant composite ceramic material with glaze, giving the ceramic material a good gloss and appearance. The added silicon carbide whiskers can improve the strength and toughness of the ceramic material, thereby giving the ceramic material excellent impact resistance.

[0040] 3. In the sintering process, the impact-resistant composite ceramic material of the present invention adopts a stepwise sintering method. The hot pressing sintering in this method promotes the collapse of the green body material, resulting in smaller nanosheets, which increases the specific surface area and surface energy, promotes the densification of the ceramic material, and thus improves the impact resistance of the ceramic material. Attached Figure Description

[0041] Figure 1 This is a comparison chart of the hardness tests of the impact-resistant composite ceramic materials prepared in Examples 2-4 and Comparative Examples 4-7 of the present invention.

[0042] Figure 2 This is a comparison chart of the fracture toughness tests of the impact-resistant composite ceramic materials prepared in Examples 2-4 and Comparative Examples 4-7 of the present invention. Detailed Implementation

[0043] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0044] Example 1

[0045] This embodiment discloses a method for preparing a ternary composite material, including the following steps:

[0046] S1. Mix 3.8g of multi-walled carbon nanotubes, 125mL of 92.5% concentrated sulfuric acid and 37.5mL of 68% concentrated nitric acid, reflux and sonicate for 5.5h, add 300mL of deionized water, filter, wash with deionized water and acetone until neutral, dry to obtain carboxylated carbon nanotubes.

[0047] 0.06 g of graphene oxide was added to 15 g of deionized water and ultrasonically dispersed for 1.5 h. Then, 15 mL of 3 mol / L sodium hydroxide aqueous solution was added and ultrasonically treated for 3 h. The sodium hydroxide was neutralized with 1 mol / L hydrochloric acid aqueous solution, centrifuged and rinsed. Then, 90 g of ultrapure water and 0.6 g of ethylenediamine were added and ultrasonically treated for 8 min. Then, 0.08 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added and ultrasonically treated for 30 min. Then, 2.1 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added, centrifuged and dialyzed to obtain aminated graphene oxide.

[0048] A dispersant was obtained by mixing polyvinylpyrrolidone and ethanol in an equal mass ratio. Aminated graphene oxide and carboxylated carbon nanotubes were added to the dispersant to obtain a suspension of aminated graphene oxide with a mass fraction of 0.7% and a suspension of carboxylated carbon nanotubes with a mass fraction of 0.7%. The aminated graphene oxide suspension and the carboxylated carbon nanotube suspension were mixed at a volume ratio of 1:2, ultrasonicated for 25 min, centrifuged, washed, and dried to obtain a graphene oxide / carbon nanotube hybrid material.

[0049] S2. Disperse the graphene oxide / carbon nanotube hybrid material in an 80% (v / v) aqueous ethanol solution and sonicate for 45 min to obtain a mixed solution A with a concentration of 1 mg / mL.

[0050] Ethyl silicate and an 80% (v / v) aqueous ethanol solution were mixed to obtain an ethyl silicate dispersion with a concentration of 0.12 mol / L. The pH of the ethyl silicate dispersion was adjusted to 4 with acetic acid to obtain mixture B. Mixture A and mixture B were mixed at a volume ratio of 1:4 under stirring conditions. The pH was adjusted to 9 with a 0.1 mol / L aqueous sodium hydroxide solution. The mixture was then stirred at 50 r / min for 60 min at 65 °C. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain the ternary composite material.

[0051] Example 2

[0052] This embodiment discloses a method for preparing an impact-resistant composite ceramic material, including the following steps:

[0053] Step 1: Zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, yttrium chloride hexahydrate, and distilled water were mixed in a mass ratio of 15:1:1.3:500 and stirred for 2 hours. The solution was then converted into 3 μm droplets by ultrasonic atomization. The solution was then heated at 600 °C using atomization-assisted chemical vapor deposition (ACVD) while maintaining an atomization rate of 500 mL / h for 100 min. The resulting powder was heated to 1300 °C at a rate of 100 °C / min and compacted under a pressure of 50 MPa to obtain binary doped zirconia microspheres with a diameter of 0.4 μm.

[0054] The ternary composite material was added to deionized water and ultrasonically treated for 1 hour. Then, binary doped zirconia microspheres were added and stirred for 20 minutes to make the mass ratio of the ternary composite material to the binary doped zirconia microspheres 0.1:1. After centrifugation, washing and drying, composite modified zirconia powder was obtained.

[0055] The composite modified zirconia powder was thermally reduced to 750℃ in an argon atmosphere at a heating rate of 8℃ / min to obtain the reduced composite modified zirconia powder.

[0056] By weight, 35 parts of potassium feldspar, 25 parts of quartz, 10 parts of kaolin, 10 parts of wollastonite, 8 parts of bentonite, 7 parts of calcium silicate, 6 parts of talc, 5 parts of alumina, and 12 parts of reduced-treated composite modified zirconium oxide powder are mixed to obtain the green body material.

[0057] The green body material was mixed with water and ball-milled using alumina balls as the milling medium for 15 hours at a speed of 200 r / min. The weight ratio of green body material, alumina balls, and water was 1:1.8:0.6. The slurry after ball milling was passed through a 200-mesh sieve, and after iron removal by a magnetic separator, it was pressed into a mud cake by a hydraulic mud press. The mud cake was processed into the required shape, shaped, trimmed, and dried. After drying, it was put into a kiln and heated to 500℃ at a rate of 5℃ / min and held for 4 hours. Then, it was heated to 700℃ at a rate of 10℃ / min and sintered for 8 hours. Then, it was cooled to 600℃ and held for 2 hours. After sintering, it was naturally cooled to 40℃ before being removed from the kiln to obtain the ceramic green body matrix.

[0058] Step 2: By weight, take 15 parts potassium feldspar, 5 parts sodium feldspar, 35 parts quartz sand, 2 parts calcite, 2 parts dolomite, 2 parts kaolin, 2 parts talc, 2 parts fluorapatite, 2 parts alumina, 2 parts zinc powder, and 1 part silicon carbide whiskers to obtain a mixture. Mix the mixture with water at a mass ratio of 5:2 and ball mill at a speed of 1000 r / min for 25 min. Then pass the mixture through a 200 mesh sieve to obtain a glaze slurry.

[0059] The glaze slurry is evenly applied to the ceramic body substrate, with a glaze specific gravity of 1.7 g / m³. 3 Glaze weight 600g / m 2 After drying, the material is first heated to 1150℃ at a heating rate of 1.5℃ / min and held for 3 hours. Then it is heated to 1180℃ and held for 8.5 hours. Finally, it is heated to 1250℃ and hot-pressed under a constant pressure of 20MPa for 2.5 hours to obtain an impact-resistant composite ceramic material.

[0060] Example 3

[0061] This embodiment discloses a method for preparing an impact-resistant composite ceramic material, including the following steps:

[0062] Step 1: Zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, yttrium chloride hexahydrate, and distilled water were mixed in a mass ratio of 15:2:1.7:500 and stirred for 3 hours. The solution was then converted into 5 μm droplets by ultrasonic atomization. The solution was then heated at 900 °C using atomization-assisted chemical vapor deposition (ACVD) while maintaining an atomization rate of 500 mL / h for 100 minutes. The resulting powder was heated to 1600 °C at a rate of 100 °C / min and compacted under a pressure of 50 MPa to obtain binary doped zirconia microspheres with a diameter of 0.5 μm.

[0063] The ternary composite material was added to deionized water and ultrasonically treated for 2 hours. Then, binary doped zirconia microspheres were added and stirred for 40 minutes to make the mass ratio of the ternary composite material to the binary doped zirconia microspheres 0.3:1. After centrifugation, washing and drying, composite modified zirconia powder was obtained.

[0064] The composite modified zirconia powder was thermally reduced to 850℃ in an argon atmosphere at a heating rate of 8℃ / min to obtain the reduced composite modified zirconia powder.

[0065] By weight, 40 parts of potassium feldspar, 30 parts of quartz, 15 parts of kaolin, 15 parts of wollastonite, 12 parts of bentonite, 10 parts of calcium silicate, 8 parts of talc, 8 parts of alumina, and 20 parts of reduced-treated composite modified zirconium oxide powder are mixed to obtain the green body material.

[0066] The green body material was mixed with water and ball-milled using alumina balls as the milling medium for 25 hours at a speed of 200 r / min. The weight ratio of green body material, alumina balls, and water was 1:2:0.7. The slurry after ball milling was passed through a 200-mesh sieve, and after iron removal by a magnetic separator, it was pressed into a mud cake by a hydraulic mud press. The mud cake was processed into the required shape, shaped, trimmed, and dried. After drying, it was put into a kiln and heated to 600℃ at a rate of 10℃ / min and held for 2 hours. Then, it was heated to 800℃ at a rate of 15℃ / min and sintered for 6 hours. Then, it was cooled to 650℃ and held for 1 hour. After sintering, it was naturally cooled to 50℃ and then removed from the kiln to obtain the ceramic green body matrix.

[0067] Step 2: By weight, take 20 parts potassium feldspar, 10 parts sodium feldspar, 55 parts quartz sand, 5 parts calcite, 5 parts dolomite, 5 parts kaolin, 5 parts talc, 5 parts fluorapatite, 4 parts alumina, 10 parts zinc powder, and 2 parts silicon carbide whiskers to obtain a mixture. Mix the mixture with water at a mass ratio of 5:3 and ball mill at a speed of 1500 r / min for 25 min. Then pass the mixture through a 400 mesh sieve to obtain a glaze slurry.

[0068] The glaze slurry is evenly applied to the ceramic body substrate, with a glaze specific gravity of 1.9 g / m³. 3 Glaze weight 800g / m 2 After drying, the material is first heated to 1180℃ at a heating rate of 2℃ / min and held for 2 hours. Then it is heated to 1200℃ and held for 7.5 hours. Finally, it is heated to 1300℃ and hot-pressed under a constant pressure of 50MPa for 1.5 hours to obtain an impact-resistant composite ceramic material.

[0069] Example 4

[0070] This embodiment discloses a method for preparing an impact-resistant composite ceramic material, including the following steps:

[0071] Step 1: Zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, and yttrium chloride hexahydrate distilled water were mixed in a mass ratio of 15:1.5:1.5:500 and stirred for 2.5 h. The solution was then converted into 4 μm droplets by ultrasonic atomization. The solution was then heated at 750 °C using atomization-assisted chemical vapor deposition (ACVD) while maintaining an atomization rate of 500 mL / h for 90 min. The resulting powder was heated to 1450 °C at a rate of 100 °C / min and compacted under a pressure of 50 MPa to obtain binary doped zirconia microspheres with a diameter of 0.45 μm.

[0072] The ternary composite material was added to deionized water and ultrasonically treated for 1.5 h. Then, binary doped zirconia microspheres were added and stirred for 30 min to make the mass ratio of ternary composite material to binary doped zirconia microspheres 0.2:1. After centrifugation, washing and drying, composite modified zirconia powder was obtained.

[0073] The composite modified zirconia powder was thermally reduced to 800℃ in an argon atmosphere at a heating rate of 8℃ / min to obtain the reduced composite modified zirconia powder.

[0074] By weight, 37.5 parts of potassium feldspar, 27.5 parts of quartz, 12.5 parts of kaolin, 12.5 parts of wollastonite, 10 parts of bentonite, 8.5 parts of calcium silicate, 7 parts of talc, 5-8 parts of alumina, and 16 parts of reduced-treated composite modified zirconium oxide powder are mixed to obtain the green body material.

[0075] The green body material was mixed with water and ball-milled using alumina balls as the milling medium for 30 hours at a speed of 230 r / min. The weight ratio of green body material, alumina balls, and water was 1:1.9:0.65. The slurry after ball milling was passed through a 200-mesh sieve, and after iron removal by a magnetic separator, it was pressed into a mud cake by a hydraulic mud press. The mud cake was processed into the required shape, shaped, trimmed, and dried. After drying, it was put into a kiln and heated to 550℃ at a rate of 7.5℃ / min and held for 3 hours. Then, the temperature was increased to 750℃ at a rate of 12.5℃ / min and sintered for 7 hours. The temperature was then reduced to 625℃ and held for 1.5 hours. After sintering, it was naturally cooled to 45℃ before being removed from the kiln to obtain the ceramic green body matrix.

[0076] Step 2: By weight, take 17.5 parts potassium feldspar, 7.5 parts sodium feldspar, 45 parts quartz sand, 3.5 parts calcite, 3.5 parts dolomite, 3.5 parts kaolin, 3.5 parts talc, 3.5 parts fluorapatite, 3 parts alumina, 6 parts zinc powder, and 1.5 parts silicon carbide whiskers to obtain a mixture. Mix the mixture with water at a mass ratio of 5:2.5 and ball mill at a speed of 1300 r / min for 30 min. Then pass the mixture through a 300 mesh sieve to obtain a glaze slurry.

[0077] The glaze slurry is evenly applied to the ceramic body substrate, with a glaze specific gravity of 1.8 g / m³. 3 Glaze weight 700g / m 2 After drying, the material is first heated to 1165℃ at a heating rate of 1.8℃ / min and held for 2.5 hours. Then it is heated to 1190℃ and held for 8 hours. Finally, it is heated to 1275℃ and hot-pressed under a constant pressure of 35MPa for 2 hours to obtain an impact-resistant composite ceramic material.

[0078] The ternary composite materials in Examples 2-4 above are the ternary composite materials prepared in Example 1.

[0079] Comparative Example 1

[0080] This comparative example discloses a method for preparing a binary composite material, including the following steps:

[0081] S1. Mix 3.8g of multi-walled carbon nanotubes, 125mL of 92.5% concentrated sulfuric acid and 37.5mL of 68% concentrated nitric acid, reflux and sonicate for 5.5h, add 300mL of deionized water, filter, wash with deionized water and acetone until neutral, dry to obtain carboxylated carbon nanotubes.

[0082] S2. Disperse carboxylated carbon nanotubes in an 80% (v / v) aqueous ethanol solution and sonicate for 45 min to obtain a mixed solution A with a concentration of 1 mg / mL.

[0083] Ethyl silicate and an 80% (v / v) aqueous ethanol solution were mixed to obtain an ethyl silicate dispersion with a concentration of 0.12 mol / L. The pH of the ethyl silicate dispersion was adjusted to 4 with acetic acid to obtain mixture B. Mixture A and mixture B were mixed at a volume ratio of 1:4 under stirring conditions. The pH was adjusted to 9 with a 0.1 mol / L aqueous sodium hydroxide solution. The mixture was then stirred at 65 °C and 50 r / min for 60 min. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain the binary composite material.

[0084] Comparative Example 2

[0085] This comparative example discloses a method for preparing a binary composite material, including the following steps:

[0086] S1. Add 0.06g of graphene oxide to 15g of deionized water and sonicate for 1.5h. Then add 15mL of 3mol / L sodium hydroxide aqueous solution and sonicate for 3h. Neutralize the sodium hydroxide with 1mol / L hydrochloric acid aqueous solution, centrifuge and rinse. Then add 90g of ultrapure water and 0.6g of ethylenediamine and sonicate for 8min. Add 0.08g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and sonicate for 30min. Then add 2.1g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, centrifuge and dialyze to obtain aminated graphene oxide.

[0087] S2. Aminated graphene oxide is dispersed in an 80% (v / v) aqueous ethanol solution and ultrasonically treated for 45 min to obtain a mixed solution A with a concentration of 1 mg / mL.

[0088] Ethyl silicate and an 80% (v / v) aqueous ethanol solution were mixed to obtain an ethyl silicate dispersion with a concentration of 0.12 mol / L. The pH of the ethyl silicate dispersion was adjusted to 4 with acetic acid to obtain mixture B. Mixture A and mixture B were mixed at a volume ratio of 1:4 under stirring conditions. The pH was adjusted to 9 with a 0.1 mol / L aqueous sodium hydroxide solution. The mixture was then stirred at 65 °C and 50 r / min for 60 min. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain the binary composite material.

[0089] Comparative Example 3

[0090] This comparative example discloses a method for preparing a binary composite material, including the following steps:

[0091] 3.8 g of multi-walled carbon nanotubes, 125 mL of 92.5% concentrated sulfuric acid and 37.5 mL of 68% concentrated nitric acid were mixed, refluxed and sonicated for 5.5 h. 300 mL of deionized water was added, filtered, and washed with deionized water and acetone until neutral. The mixture was then dried to obtain carboxylated carbon nanotubes.

[0092] 0.06 g of graphene oxide was added to 15 g of deionized water and ultrasonically dispersed for 1.5 h. Then, 15 mL of 3 mol / L sodium hydroxide aqueous solution was added and ultrasonically treated for 3 h. The sodium hydroxide was neutralized with 1 mol / L hydrochloric acid aqueous solution, centrifuged and rinsed. Then, 90 g of ultrapure water and 0.6 g of ethylenediamine were added and ultrasonically treated for 8 min. Then, 0.08 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added and ultrasonically treated for 30 min. Then, 2.1 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added, centrifuged and dialyzed to obtain aminated graphene oxide.

[0093] A dispersant was obtained by mixing polyvinylpyrrolidone and ethanol in an equal mass ratio. Aminated graphene oxide and carboxylated carbon nanotubes were added to the dispersant to obtain aminated graphene oxide suspension and carboxylated carbon nanotube suspension, each with a mass fraction of 0.7%. The aminated graphene oxide suspension and carboxylated carbon nanotube suspension were mixed at a volume ratio of 1:2, ultrasonicated for 25 min, centrifuged, washed, and dried to obtain graphene oxide / carbon nanotube hybrid material, i.e., binary composite material.

[0094] Comparative Example 4

[0095] Compared with Example 4, Comparative Example 4 used the binary composite material prepared in Comparative Example 1 in the process of preparing composite modified zirconia powder, while keeping other conditions unchanged.

[0096] Comparative Example 5

[0097] Compared with Example 4, Comparative Example 5 used the binary composite material prepared in Comparative Example 2 in the process of preparing composite modified zirconia powder, while keeping other conditions unchanged.

[0098] Comparative Example 6

[0099] Compared with Example 4, Comparative Example 6 used the binary composite material prepared in Comparative Example 3 in the process of preparing composite modified zirconia powder, while keeping other conditions unchanged.

[0100] Comparative Example 7

[0101] Compared with Example 4, Comparative Example 7 used zirconia powder with an average particle size of 450 nm instead of the binary doped zirconia microspheres in Example 4 during the preparation of composite modified zirconia powder, while keeping other conditions unchanged.

[0102] In the above examples and comparative examples, the graphene oxide with a thickness of 0.55-1.2 nm and a diameter of 0.5-3 μm was from Zhongke Leiming (Beijing) Technology Co., Ltd.; the multi-walled carbon nanotubes with a diameter of 10-30 nm and a length of 1-2 μm were from Guangzhou Hongwu Materials Technology Co., Ltd.; the zirconium oxide powder with an average particle size of 450 nm was from Shijiazhuang Jinghuang Technology Co., Ltd.; and the silicon carbide whiskers with an average particle size of 50-100 nm and CAS number 409-21-2 were from Hubei Xinyuhong Biomedical Technology Co., Ltd.

[0103] Experimental Example

[0104] The performance of the impact-resistant composite ceramic materials of Examples 2-4 and Comparative Examples 4-7 was tested.

[0105] I. Hardness Test: The hardness was measured using a Vickers hardness tester (430SVA, Wilson Wolpert Co., Ltd., China) with a load of 10kg.

[0106] II. Fracture toughness test: The test shall be conducted in accordance with the national standard GB / T 23806-2009.

[0107] III. Thermal shock resistance test: The test shall be conducted in accordance with the national standard GB / T 3298-2008.

[0108] The test results are shown in Table 1:

[0109] Table 1

[0110] Hardness / GPa <![CDATA[Fracture toughness / MPa·m 1 / 2 > Thermal shock resistance (180℃-20℃) Example 2 17.9 9.3 No cracks Example 3 18.3 9.8 No cracks Example 4 18.1 9.5 No cracks Comparative Example 4 17.3 8.4 Obvious cracks Comparative Example 5 16.5 8.0 Obvious cracks Comparative Example 6 17.8 9.1 minor cracks Comparative Example 7 15.8 7.6 Obvious cracks

[0111] As shown in Table 1, the impact-resistant composite ceramic materials prepared in Examples 2-4 of this invention exhibit excellent impact resistance and thermal shock resistance. A comparison between Comparative Examples 4-5 and Example 4 reveals that the reduced graphene oxide and multi-walled carbon nanotubes in the ternary composite material possess excellent thermal conductivity, promoting grain refinement and growth. Reduced graphene oxide and multi-walled carbon nanotubes also demonstrate effects such as grain boundary fixation, bending, pull-out, bridging, and crack propagation promotion, positively impacting the mechanical properties and thermal shock resistance of zirconia ceramics. Furthermore, the layered structure of reduced graphene oxide helps improve the dispersion of binary doped zirconia microspheres in the preform material, thereby enhancing the performance of the ceramic material. Comparative Examples 6 and Example 4 show that... As can be seen from the comparison in Example 4, the nano-silica in the ternary composite material helps to form and stabilize the tetragonal phase zirconia, and forms covalent Si-O-Zr bonds with zirconia, which makes the ternary composite material and the binary doped zirconia microspheres have better interfacial compatibility, thereby improving the overall performance of the ceramic. As can be seen from the comparison between Comparative Example 7 and Example 4, compared with zirconia powder of the same particle size, the binary doped zirconia microspheres of the present invention have a significant impact on the overall performance of the ceramic material due to the co-doping of gadolinium and yttrium and the effect of its hollow microsphere structure.

[0112] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method of making an impact-resistant composite ceramic material, characterized in that, It comprises the following steps: Step one, with zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, yttrium chloride hexahydrate as raw material, through the technology of atomization assisted chemical vapor deposition, get the binary doped zirconia microspheres; Mix the ternary composite material with the binary doped zirconia microspheres to obtain the composite modified zirconia powder; The composite modified zirconia powder is heat reduced to obtain the reduced composite modified zirconia powder; Mix the potassium feldspar, quartz, kaolin, wollastonite, bentonite, calcium silicate, talc, alumina, and the reduced composite modified zirconia powder to obtain the green body material; The preparation method of the ternary composite material comprises the following steps: S1, respectively, the graphene oxide, multi-walled carbon nanotube is handled, obtains aminized graphene oxide, carboxylated carbon nanotube;The aminized graphene oxide, carboxylated carbon nanotube is combined, and the graphene oxide / carbon nanotube hybrid material is obtained; S2, in situ growth of nano-silicon dioxide on the surface of graphene oxide / carbon nanotube hybrid material, obtain ternary composite material; The green body material is made into a ceramic green body matrix; Step two, mix the potassium feldspar, sodium feldspar, quartz sand, calcite, dolomite, kaolin, talc, fluorapatite, alumina, zinc powder, silicon carbide whisker to obtain the mixed material, and then ball mill and sieve to obtain the glaze slurry; Apply the glaze slurry to the ceramic green body matrix, and sinter step by step to obtain the impact-resistant composite ceramic material.

2. The method of producing an impact-resistant composite ceramic material according to claim 1, characterized by, In step one, the preparation method of the reduced composite modified zirconia powder specifically comprises: Mix zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, yttrium chloride hexahydrate and distilled water in a mass ratio of 15:(1-2):(1.3-1.7):500, stir, then convert the solution into 3-5 μm droplets by ultrasonic atomization, then heat at 600-900 ℃ by atomization assisted chemical vapor deposition technology, maintain a misting rate of 500 mL / h, maintain the reaction for 80-100 min, the obtained powder is heated to 1300-1600 °C at a rate of 100 °C / min and compacted under a pressure of 50 MPa to obtain binary doped zirconia microspheres with a diameter of 0.4-0.5 μm; Add the ternary composite material to deionized water, ultrasonic, then add the binary doped zirconia microspheres, stir, so that the mass ratio of the ternary composite material and the binary doped zirconia microspheres is (0.1-0.3):1, to obtain the composite modified zirconia powder; Heat reduce the composite modified zirconia powder in an argon atmosphere at a heating rate of 8 °C / min to 750-850 °C to obtain the reduced composite modified zirconia powder.

3. The method of making an impact-resistant composite ceramic material according to claim 1, wherein, In step one, in the green body material, the content of each component in the green body material is potassium feldspar 35-40 parts, quartz 25-30 parts, kaolin 10-15 parts, wollastonite 10-15 parts, bentonite 8-12 parts, calcium silicate 7-10 parts, talc 6-8 parts, alumina 5-8 parts, and reduced composite modified zirconia powder 12-20 parts.

4. The method of making an impact-resistant composite ceramic material according to claim 1, wherein, In step one, the preparation method of the ternary composite material specifically comprises the following steps: S1, mixing multi-walled carbon nanotubes, concentrated sulfuric acid and concentrated nitric acid, condensing and refluxing and ultrasonic treating for 5-6h, adding deionized water, purifying, and obtaining carboxylated carbon nanotubes; wherein the ratio of the amount of multi-walled carbon nanotubes, concentrated sulfuric acid, concentrated nitric acid and deionized water is (2.5-5)g:(75-150)mL:(25-50)mL:(200-400)mL; adding graphene oxide into deionized water and ultrasonic treating, then adding sodium hydroxide aqueous solution into the mixture and ultrasonic treating, neutralizing sodium hydroxide by hydrochloric acid aqueous solution, centrifuging and washing, then adding ultrapure water and ethylenediamine and ultrasonic treating, adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, centrifuging, and dialyzing to obtain aminated graphene oxide; wherein the mass ratio of graphene oxide and ethylenediamine is (0.04-0.08):(0.4-0.8). mixing polyvinylpyrrolidone and ethanol in equal mass ratio to obtain a dispersant; adding aminated graphene oxide and carboxylated carbon nanotubes into the dispersant respectively to obtain aminated graphene oxide suspension with a mass fraction of 0.2-1.2% and carboxylated carbon nanotube suspension with a mass fraction of 0.2-1.2%; mixing the aminated graphene oxide suspension and the carboxylated carbon nanotube suspension in a volume ratio of 1:2, ultrasonic treating for 20-30min, centrifuging, washing, and drying to obtain graphene oxide / carbon nanotube hybrid material. S2, dispersing graphene oxide / carbon nanotube hybrid material in 80% volume fraction ethanol aqueous solution and ultrasonic treating to obtain a mixed solution A with a concentration of 1mg / mL; mixing ethyl silicate and 80% volume fraction ethanol aqueous solution to obtain an ethyl silicate dispersion with a concentration of 0.1-0.15mol / L, adjusting pH to 4 to obtain a mixed solution B; mixing the mixed solution A and the mixed solution B in a volume ratio of 1:(3.8-4.2) under stirring, adjusting pH to 9 by sodium hydroxide aqueous solution, then stirring at a speed of 40-60r / min at 63-67℃ for 50-70min, and purifying to obtain a ternary composite material.

5. The method of making an impact-resistant composite ceramic material according to claim 1, wherein, In the step one, the preparation method of the ceramic body substrate specifically comprises: mixing the body material with water, ball milling with alumina balls as the milling medium, the ball milling time is 15-25h, the ball milling speed is 200-250r / min, the weight ratio of the body material, the alumina balls and the water is 1:(1.8-2):(0.6-0.7), the slurry after ball milling is filtered through a 200 mesh sieve, and the mud cake after iron removal is pressed into a cake, the cake is processed into the required shape, and then shaped, debound, and dried in the air, and then put into the kiln, heated to 500-600℃ at a speed of 5-10℃ / min, kept for 2-4h, then heated to 700-800℃ at a speed of 10-15℃ / min, sintered for 6-8h, then cooled to 600-650℃, kept for 1-2h, and then naturally cooled to 40-50℃ before taken out of the kiln to obtain the ceramic body substrate.

6. The method of making an impact-resistant composite ceramic material according to claim 1, wherein, The preparation method of the glaze slurry in the second step specifically comprises the following steps: taking 15-20 parts of potassium feldspar, 5-10 parts of sodium feldspar, 35-55 parts of quartz sand, 2-5 parts of calcite, 2-5 parts of dolomite, 2-5 parts of kaolin, 2-5 parts of talc, 2-5 parts of fluorapatite, 2-4 parts of aluminum oxide, 2-10 parts of zinc powder and 1-2 parts of silicon carbide whisker by weight to obtain a mixture; and mixing the mixture with water in a mass ratio of 5:(2-3) and ball milling at a speed of 1000-1500 r / min for 25-35 min, and then sieving through a 200-400 mesh sieve to obtain the glaze slurry.

7. The method of making an impact-resistant composite ceramic material according to claim 1, wherein, The application conditions of the glaze slurry in the second step include: glaze specific gravity 1.7-1.9 g / m 3 , glaze amount 600-800 g / m 2 .

8. The method of making an impact-resistant composite ceramic material according to claim 1, wherein, The step-by-step sintering in the second step comprises the following steps: first, heating at a temperature increasing speed of 1.5-2 ℃ / min to 1150-1180 ℃, and keeping the temperature for 2-3 h; then, heating to 1180-1200 ℃, and keeping the temperature for 7.5-8.5 h; and finally, heating to 1250-1300 ℃, and hot-pressing sintering at a constant pressure of 20-50 MPa, and keeping the temperature for 1.5-2.5 h.

9. An impact-resistant composite ceramic material prepared by the method according to any one of claims 1-8.

10. Use of the impact-resistant composite ceramic material according to claim 9 in ceramic artware.

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