Impact-resistant composite ceramic material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of ceramic materials, and discloses an impact-resistant composite ceramic material as well as a preparation method and application thereof. The preparation method of the impact-resistant composite ceramic material comprises the following steps: mixing potassium feldspar, quartz, kaolin, wollastonite, bentonite, calcium silicate, talc, aluminum oxide and reduced composite modified zirconium oxide powder to obtain a green body material; mixing potassium feldspar, albite, quartz sand, calcite, dolomite, kaolin, talc, fluorapatite, aluminum oxide, zinc powder and silicon carbide whiskers to obtain a mixture, and performing ball milling and sieving to obtain glaze slurry; preparing the green body material into a ceramic green body base body; and applying the glaze slurry to a ceramic green body matrix, and sintering step by step to obtain the impact-resistant composite ceramic material. The impact-resistant composite ceramic material provided by the invention has good glossiness and aesthetic degree, and has excellent impact resistance and thermal shock resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic materials, in particular to an impact-resistant composite ceramic material and a preparation method and application thereof. Background Art

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

[0003] In order to solve the above technical problems, the present 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 zirconia microspheres are obtained by atomization-assisted chemical vapor deposition technology;

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

[0006] Potassium feldspar, quartz, kaolin, wollastonite, bentonite, calcium silicate, talc, aluminum oxide, and reduced composite modified zirconium oxide powder are mixed to obtain a green body material;

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

[0008] S1. treating graphene oxide and carbon nanotubes respectively to obtain amino-treated graphene oxide and carboxylated carbon nanotubes; combining the amino-treated graphene oxide and carboxylated carbon nanotubes to obtain a graphene oxide / carbon nanotube hybrid material;

[0009] S2, in situ growing nano-silicon dioxide on the surface of the graphene oxide / carbon nanotube hybrid material to obtain a ternary composite material;

[0010] forming a green body material into a ceramic green body matrix;

[0011] Step 2: mixing potassium feldspar, sodium feldspar, quartz sand, calcite, dolomite, kaolin, talc, fluorapatite, aluminum oxide, zinc powder, and silicon carbide whiskers to obtain a mixture, and then ball milling and sieving to obtain a glaze slurry;

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

[0013] Preferably, in step 1, the method for preparing the reduction-treated composite modified zirconia powder specifically comprises:

[0014] Zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, yttrium chloride hexahydrate, and distilled water are mixed in a mass ratio of 15:(1-2):(1.3-1.7):500, stirred, and then converted into 3-5 μm droplets by ultrasonic atomization. The mixture is then heated at 600-900°C by atomization-assisted chemical vapor deposition technique, and an atomization rate of 500 mL / h is maintained. The reaction is maintained for 80-100 minutes. The resulting 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.

[0015] The ternary composite material is added to deionized water, ultrasonicated, and then binary doped zirconia microspheres are added and stirred to make the mass ratio of the ternary composite material to the binary doped zirconia microspheres be (0.1-0.3):1, to obtain a composite modified zirconia powder;

[0016] The composite modified zirconia powder is heated to 750-850° C. at a heating rate of 8° C. / min in an argon atmosphere to perform thermal reduction, thereby obtaining a reduced composite modified zirconia powder;

[0017] In the above process, gadolinium-yttrium co-doped binary zirconia microspheres 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 the 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 advantage and alleviates the common problem of nanoparticle agglomeration. In addition, during the sintering process of the ceramic material (especially hot pressing sintering), the ordered hollow microsphere structure collapses, resulting in smaller nanosheets, which increases the specific surface area and surface energy, promotes the densification of the ceramic material, enhances the sintering activity, and reduces the sintering temperature.

[0018] Furthermore, the ternary composite material is mixed with the binary doped zirconia microspheres. The hydrophilic groups (hydroxyl, carboxyl, amino) on the surface of the ternary composite material enable it to combine with the binary doped zirconia microspheres. After reduction treatment, the graphene oxide in the ternary composite material is converted into reduced graphene oxide. During the sintering process, Zr-OC chemical bonds are formed between the reduced graphene oxide and the binary doped zirconia microspheres. Due to the strong interface effect of the layered structure of the reduced graphene oxide, the binary doped zirconia microspheres can be better dispersed in the green body material. The ternary composite material contains reduced graphene oxide. Graphene, multi-walled carbon nanotubes, reduced graphene oxide, and multi-walled carbon nanotubes have excellent thermal conductivity and can promote grain refinement and growth. Reduced graphene oxide and multi-walled carbon nanotubes also exhibit the effects of grain boundary fixation, bending, pull-out, bridging, and promoting crack propagation, which have a positive impact on the mechanical properties and thermal shock resistance of zirconia ceramics. In addition, nano-silica in the ternary composite material contributes to the formation and stabilization of tetragonal zirconia, and forms covalent Si-O-Zr bonds with zirconia, which makes the ternary composite material and the binary doped zirconia microspheres have better interface compatibility.

[0019] Preferably, in the step 1, the contents of the components in the green body material, in parts by weight, are: 35-40 parts of potassium feldspar, 25-30 parts of quartz, 10-15 parts of kaolin, 10-15 parts of wollastonite, 8-12 parts of bentonite, 7-10 parts of calcium silicate, 6-8 parts of talc, 5-8 parts of aluminum oxide, and 12-20 parts of reduced composite modified zirconium oxide powder;

[0020] In the above process, the green body material uses potassium feldspar, quartz, and kaolin as the main aggregates, which have good viscosity. At the same time, wollastonite is added, which can reduce the firing temperature, fill gaps, and improve the uniformity and density of the green body; bentonite has water absorption and expansion properties and is viscous, and works together with other components to reduce the sintering temperature and improve the mechanical properties of the ceramic material; in addition, it is well known that zirconium oxide can make ceramic materials have high toughness, high flexural strength and high wear resistance, and compared with zirconium oxide, the composite modified zirconium oxide powder treated with reduction has the presence of graphene oxide, nano-silica, and multi-walled carbon nanotubes, which further improves the performance of the ceramic material.

[0021] Furthermore, in step 1, the method for preparing the ternary composite material specifically comprises the following steps:

[0022] S1. Mix multi-walled carbon nanotubes, concentrated sulfuric acid, and concentrated nitric acid, condense and reflux, and ultrasonicate for 5-6 hours, then add deionized water and purify to obtain carboxylated carbon nanotubes; wherein the amount 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] Adding graphene oxide to deionized water, sonicating, then adding a sodium hydroxide aqueous solution thereto, sonicating, neutralizing the sodium hydroxide with a hydrochloric acid aqueous solution, centrifuging and rinsing, then adding ultrapure water and ethylenediamine, sonicating, adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, centrifuging, and dialysis to obtain amino-modified graphene oxide; wherein the mass ratio of graphene oxide to ethylenediamine is (0.04-0.08):(0.4-0.8);

[0024] Polyvinyl pyrrolidone and ethanol are mixed in equal mass ratios to obtain a dispersant; amino-modified graphene oxide and carboxylated carbon nanotubes are added to the dispersant to obtain an amino-modified graphene oxide suspension with a mass fraction of 0.2-1.2% and a carboxylated carbon nanotube suspension with a mass fraction of 0.2-1.2%; the amino-modified graphene oxide suspension and the carboxylated carbon nanotube suspension are mixed in a volume ratio of 1:2, ultrasonically treated for 20-30 minutes, 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 to introduce abundant carboxyl groups on their surfaces, thereby obtaining carboxylated carbon nanotubes; amino groups in graphene oxide are combined with ethylenediamine through an amidation reaction to obtain amino-containing graphene oxide; the amino-containing graphene oxide and carboxylated carbon nanotubes are combined through electrostatic interaction and hydrogen bonding between amino and carboxyl groups, and the carboxylated carbon nanotubes are intercalated into the sheet structure of graphene oxide to obtain a graphene oxide / carbon nanotube hybrid material;

[0026] S2, dispersing the graphene oxide / carbon nanotube hybrid material in an 80% by volume ethanol aqueous solution, and sonicating to obtain a mixed solution A with a concentration of 1 mg / mL;

[0027] Ethyl silicate and an 80% by volume aqueous ethanol solution are mixed to obtain an ethyl silicate dispersion having a concentration of 0.1-0.15 mol / L, and the pH is adjusted to 4 to obtain a mixed solution B; mixed solution A and mixed solution B are mixed at a volume ratio of 1:(3.8-4.2) under stirring, the pH is adjusted to 9 with an aqueous sodium hydroxide solution, and then stirred at 63-67° C. and 40-60 r / min for 50-70 minutes, and purified to obtain a ternary composite material;

[0028] In the above process, ethyl silicate is hydrolyzed into orthosilicic acid. The presence of acetic acid can promote the hydrolysis rate. The hydroxyl groups of the orthosilicic acid combine with the hydroxyl groups and amino groups on the graphene oxide in the graphene oxide / carbon nanotube hybrid material, so that the orthosilicic acid is adsorbed on the graphene oxide / carbon nanotube hybrid material. Then, through condensation interaction, a stable covalent bond is formed with the graphene oxide / carbon nanotube hybrid material, thereby realizing the in situ growth of nano-silicon dioxide on the surface of the graphene oxide / carbon nanotube hybrid material.

[0029] Preferably, in the step one, the preparation method of the ceramic green body matrix specifically includes: mixing the green body material with water, ball milling with alumina balls as the ball milling medium, the ball milling time is 15-25h, the ball milling speed is 200-250r / min, the weight ratio of the green body material, alumina balls and water is 1: (1.8-2): (0.6-0.7), the slurry after ball milling is passed through a 200 mesh sieve, and after iron removal, it is filter-filtered into a mud cake, and after the mud cake is processed into the desired shape, it is shaped, sharpened, and air-dried. After drying, it is put into a kiln, heated to 500-600℃ at a rate of 5-10℃ / min and kept warm for 2-4h, then heated to 700-800℃ at a rate of 10-15℃ / min, and sintered for 6-8h; then cooled to 600-650℃, kept warm for 1-2h, and after sintering, naturally cooled to 40-50℃ and taken out of the kiln to obtain the ceramic green body matrix.

[0030] Preferably, in the step 2, the preparation method of the glaze slurry specifically comprises: taking, by weight, 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 whiskers to obtain a mixture; mixing the mixture with water in 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 through a 200-400 mesh sieve to obtain a glaze slurry;

[0031] In the above process, the various components of the above glaze cooperate with each other. When applied on the ceramic material, it can make the ceramic material have a jade-like texture and gloss, thereby improving the aesthetics of the ceramic material; and the added silicon carbide whiskers can increase the strength and toughness of the ceramic material.

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

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

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

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

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

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] 1. The present invention adds a reduced composite modified zirconia powder to the body material of the impact-resistant composite ceramic material. The reduced composite modified zirconia powder is obtained by combining a ternary composite material with binary doped zirconia microspheres and then subjecting them to a reduction treatment. The binary doped zirconia microspheres can improve the strength, hardness and toughness of the ceramic material, thereby making the ceramic material have excellent impact resistance and thermal shock resistance, and the zirconia microspheres can also reduce the sintering temperature of the ceramic material; and 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 combined in the form of chemical bonds, with good interface compatibility, which has a positive effect on the mechanical properties and thermal shock resistance of the zirconia ceramic. In addition, the ternary composite material also promotes the dispersion of the binary doped zirconia microspheres in the 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, which gives the ceramic material good gloss and aesthetics, and 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. During the sintering process, the impact-resistant composite ceramic material of the present invention adopts a step-by-step sintering method, in which the hot pressing sintering promotes the collapse of the green body material, resulting in the production of smaller nanosheets, increasing the specific surface area and surface energy, and promoting the densification of the ceramic material, thereby improving the impact resistance of the ceramic material. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0042] Figure 2 It is a comparative diagram of the fracture toughness test of the impact-resistant composite ceramic materials prepared in Examples 2-4 of the present invention and Comparative Examples 4-7. DETAILED DESCRIPTION

[0043] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work 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, comprising the following steps:

[0046] S1. 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, condensed and refluxed, and ultrasonicated for 5.5 h. 300 mL of deionized water was added, the mixture was filtered, and the mixture was washed with deionized water and acetone in sequence until neutral, and dried 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. 15 mL of a 3 mol / L sodium hydroxide aqueous solution was added thereto. After ultrasonic treatment for 3 h, the sodium hydroxide was neutralized with a 1 mol / L hydrochloric acid aqueous solution. The mixture was centrifuged and rinsed. 90 g of ultrapure water and 0.6 g of ethylenediamine were added and ultrasonically treated for 8 min. 0.08 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added and ultrasonically treated for 30 min. 2.1 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added. The mixture was centrifuged and dialyzed to obtain amino-modified graphene oxide.

[0048] Polyvinyl pyrrolidone and ethanol are mixed in equal mass ratios to obtain a dispersant; amino-modified graphene oxide and carboxylated carbon nanotubes are added to the dispersant to obtain a 0.7% amino-modified graphene oxide suspension and a 0.7% carboxylated carbon nanotube suspension; the amino-modified graphene oxide suspension and the carboxylated carbon nanotube suspension are mixed in a volume ratio of 1:2, ultrasonically treated for 25 minutes, centrifuged, washed, and dried to obtain a graphene oxide / carbon nanotube hybrid material;

[0049] S2, dispersing the graphene oxide / carbon nanotube hybrid material in an 80% by volume ethanol aqueous solution, and ultrasonically treating for 45 minutes to obtain a mixed solution A with a concentration of 1 mg / mL;

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

[0051] Example 2

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

[0053] Step 1: zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, yttrium chloride hexahydrate, and distilled water are mixed in a mass ratio of 15:1:1.3:500, stirred for 2 hours, and then converted into 3 μm droplets by ultrasonic atomization. The solution is then heated at 600 ° C by atomization-assisted chemical vapor deposition technology, and the atomization rate is maintained at 500 mL / h. The reaction is maintained for 100 minutes. The resulting powder is 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, and then binary doped zirconia microspheres were added and stirred for 20 minutes to adjust the mass ratio of the ternary composite material to the binary doped zirconia microspheres to 0.1:1. The mixture was centrifuged, washed, and dried to obtain a composite modified zirconia powder;

[0055] The composite modified zirconia powder was heated to 750°C in an argon atmosphere at a heating rate of 8°C / min to perform thermal reduction, thereby obtaining a reduced composite modified zirconia powder;

[0056] In parts 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 aluminum oxide, and 12 parts of reduced composite modified zirconium oxide powder were mixed to obtain a green body material;

[0057] The green body material is mixed with water and ball milled with alumina balls as the ball milling medium. The ball milling time is 15 hours, the ball milling speed is 200 r / min, and the weight ratio of the green body material, alumina balls and water is 1:1.8:0.6. The slurry after ball milling is passed through a 200-mesh sieve, deironed by a magnetic separator, and then filtered into a mud cake by a hydraulic mud press. After the mud cake is processed into the desired shape, it is shaped, sharpened, and aired. After drying, it is put into a kiln, heated to 500°C at a rate of 5°C / min and kept warm for 4 hours, then heated to 700°C at a rate of 10°C / min, and sintered for 8 hours; then cooled to 600°C and kept warm for 2 hours. After sintering, it is naturally cooled to 40°C and taken out of the kiln to obtain a ceramic green body matrix.

[0058] Step 2: Take 15 parts of potassium feldspar, 5 parts of sodium feldspar, 35 parts of quartz sand, 2 parts of calcite, 2 parts of dolomite, 2 parts of kaolin, 2 parts of talc, 2 parts of fluorapatite, 2 parts of aluminum oxide, 2 parts of zinc powder, and 1 part of silicon carbide whisker by weight to obtain a mixture, mix the mixture with water in a mass ratio of 5:2, and then ball mill at a ball milling speed of 1000 r / min for 25 min, and then pass through a 200 mesh sieve to obtain a glaze slurry;

[0059] Apply the glaze slurry evenly on the ceramic body substrate, the glaze specific gravity is 1.7g / m 3 , glaze weight 600g / m 2 After drying, it was first heated to 1150°C at a heating rate of 1.5°C / min, kept warm for 3 hours, then heated to 1180°C, kept warm for 8.5 hours, and finally heated to 1250°C. It was hot-pressed and sintered at a constant pressure of 20 MPa and kept warm 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, comprising the following steps:

[0062] Step 1: zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, yttrium chloride hexahydrate, and distilled water are mixed in a mass ratio of 15:2:1.7:500, stirred for 3 hours, and then converted into 5 μm droplets by ultrasonic atomization. The solution is then heated at 900 ° C by atomization-assisted chemical vapor deposition technology, and the atomization rate is maintained at 500 mL / h. The reaction is maintained for 100 minutes. The resulting powder is 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, and then binary doped zirconia microspheres were added and stirred for 40 minutes to adjust the mass ratio of the ternary composite material to the binary doped zirconia microspheres to 0.3:1. The mixture was centrifuged, washed, and dried to obtain a composite modified zirconia powder;

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

[0065] In parts 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 aluminum oxide, and 20 parts of reduced composite modified zirconium oxide powder were mixed to obtain a green body material;

[0066] The green body material is mixed with water and ball milled with alumina balls as the ball milling medium. The ball milling time is 25 hours, the ball milling speed is 200 r / min, and the weight ratio of the green body material, alumina balls and water is 1:2:0.7. The slurry after ball milling is passed through a 200-mesh sieve, deironed by a magnetic separator, and then filtered into a mud cake by a hydraulic mud press. After the mud cake is processed into the desired shape, it is shaped, sharpened, and aired. After drying, it is put into a kiln, heated to 600°C at a rate of 10°C / min and kept warm for 2 hours, then heated to 800°C at a rate of 15°C / min, and sintered for 6 hours; then cooled to 650°C and kept warm for 1 hour. After sintering, it is naturally cooled to 50°C and taken out of the kiln to obtain a ceramic green body matrix.

[0067] Step 2: Take 20 parts of potassium feldspar, 10 parts of sodium feldspar, 55 parts of quartz sand, 5 parts of calcite, 5 parts of dolomite, 5 parts of kaolin, 5 parts of talc, 5 parts of fluorapatite, 4 parts of aluminum oxide, 10 parts of zinc powder, and 2 parts of silicon carbide whiskers by weight to obtain a mixture, mix the mixture with water in a mass ratio of 5:3, and then ball mill at a ball milling speed of 1500 r / min for 25 min, and then pass through a 400 mesh sieve to obtain a glaze slurry;

[0068] Apply the glaze slurry evenly on the ceramic body substrate, the glaze specific gravity is 1.9g / m 3 , glaze weight 800g / m 2 After drying, it was first heated to 1180°C at a heating rate of 2°C / min, kept warm for 2 hours, then heated to 1200°C, kept warm for 7.5 hours, and finally heated to 1300°C. It was hot-pressed and sintered at a constant pressure of 50 MPa and kept warm 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, comprising the following steps:

[0071] Step 1: zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, and yttrium chloride hexahydrate distilled water are mixed in a mass ratio of 15:1.5:1.5:500, stirred for 2.5 hours, and then converted into 4 μm droplets by ultrasonic atomization. The mixture is then heated at 750 ° C by atomization-assisted chemical vapor deposition technology, and the atomization rate is maintained at 500 mL / h. The reaction is maintained for 90 minutes. The resulting powder is 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 hours, and then binary doped zirconia microspheres were added and stirred for 30 minutes to adjust the mass ratio of the ternary composite material to the binary doped zirconia microspheres to 0.2:1. The mixture was centrifuged, washed, and dried to obtain a composite modified zirconia powder;

[0073] The composite modified zirconia powder was heated to 800°C in an argon atmosphere at a heating rate of 8°C / min to perform thermal reduction, thereby obtaining a reduced composite modified zirconia powder;

[0074] In parts 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 aluminum oxide, and 16 parts of reduced composite modified zirconium oxide powder were mixed to obtain a green body material;

[0075] The green body material is mixed with water and ball milled with alumina balls as the ball milling medium. The ball milling time is 30 hours, the ball milling speed is 230r / min, and the weight ratio of the green body material, alumina balls and water is 1:1.9:0.65. The slurry after ball milling is passed through a 200-mesh sieve, deironed by a magnetic separator, and then filtered into a mud cake by a hydraulic mud press. After the mud cake is processed into the desired shape, it is shaped, sharpened, and aired. After drying, it is put into a kiln, heated to 550°C at a rate of 7.5°C / min and kept warm for 3 hours, then heated to 750°C at a rate of 12.5°C / min, and sintered for 7 hours; then cooled to 625°C and kept warm for 1.5 hours. After sintering, it is naturally cooled to 45°C and taken out of the kiln to obtain a ceramic green body matrix.

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

[0077] Apply the glaze slurry evenly on the ceramic body substrate, the glaze specific gravity is 1.8g / m 3 , glaze weight 700g / m 2 After drying, it was first heated to 1165°C at a heating rate of 1.8°C / min, kept warm for 2.5 hours, then heated to 1190°C, kept warm for 8 hours, and finally heated to 1275°C, hot-pressed and sintered at a constant pressure of 35 MPa, and kept warm for 2 hours to obtain an impact-resistant composite ceramic material.

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

[0079] Comparative Example 1

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

[0081] S1. 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, condensed and refluxed, and ultrasonicated for 5.5 h. 300 mL of deionized water was added, the mixture was filtered, and the mixture was washed with deionized water and acetone in sequence until neutral, and dried to obtain carboxylated carbon nanotubes.

[0082] S2, dispersing the carboxylated carbon nanotubes in an 80% by volume ethanol aqueous solution, and ultrasonically treating for 45 minutes to obtain a mixed solution A with a concentration of 1 mg / mL;

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

[0084] Comparative Example 2

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

[0086] S1, 0.06g of graphene oxide was added to 15g of deionized water, ultrasonically dispersed for 1.5h, and then 15mL of a 3mol / L sodium hydroxide aqueous solution was added thereto. After ultrasonic treatment for 3h, the sodium hydroxide was neutralized by a 1mol / L hydrochloric acid aqueous solution, centrifuged and rinsed, and then 90g of ultrapure water and 0.6g of ethylenediamine were added, ultrasonically treated for 8min, 0.08g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added, ultrasonically treated for 30min, and then 2.1g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added, centrifuged, and dialyzed to obtain amino graphene oxide;

[0087] S2, dispersing the amino-modified graphene oxide in an 80% by volume ethanol aqueous solution, and ultrasonically treating for 45 minutes to obtain a mixed solution A with a concentration of 1 mg / mL;

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

[0089] Comparative Example 3

[0090] This comparative example discloses a method for preparing a binary composite material, comprising 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, condensed and refluxed, and ultrasonicated for 5.5 h. 300 mL of deionized water was added, filtered, and washed with deionized water and acetone in sequence until neutral, and 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. 15 mL of a 3 mol / L sodium hydroxide aqueous solution was added thereto. After ultrasonic treatment for 3 h, the sodium hydroxide was neutralized with a 1 mol / L hydrochloric acid aqueous solution. The mixture was centrifuged and rinsed. 90 g of ultrapure water and 0.6 g of ethylenediamine were added and ultrasonically treated for 8 min. 0.08 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added and ultrasonically treated for 30 min. 2.1 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added. The mixture was centrifuged and dialyzed to obtain amino-modified graphene oxide.

[0093] Polyvinyl pyrrolidone and ethanol are mixed in equal mass ratios to obtain a dispersant; aminated graphene oxide and carboxylated carbon nanotubes are respectively added to the above dispersant to obtain an aminated graphene oxide suspension and a carboxylated carbon nanotube suspension with a mass fraction of 0.7% each; the aminated graphene oxide suspension and the carboxylated carbon nanotube suspension are mixed in a volume ratio of 1:2, ultrasonically treated for 25 minutes, centrifuged, washed, and dried to obtain a graphene oxide / carbon nanotube hybrid material, i.e., a binary composite material.

[0094] Comparative Example 4

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

[0096] Comparative Example 5

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

[0098] Comparative Example 6

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

[0100] Comparative Example 7

[0101] Comparative Example 7 Compared with Example 4, in the process of preparing the composite modified zirconia powder in Comparative Example 7, zirconia powder with an average particle size of 450 nm was used to replace the binary doped zirconia microspheres in Example 4, and other conditions remained unchanged.

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

[0103] Experimental example

[0104] Performance tests were performed on the impact-resistant composite ceramic materials of Examples 2-4 and Comparative Examples 4-7.

[0105] 1. Hardness test: Vickers hardness tester (430SVA, WilsonWolpert Co., Ltd., China) was used for measurement with a load of 10 kg.

[0106] 2. Fracture toughness test: Tested in accordance with national standard GB / T 23806-2009.

[0107] 3. Thermal shock resistance test: Tested in accordance with national standard GBT 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 Slight cracks Comparative Example 7 15.8 7.6 Obvious cracks

[0111] From the test results in Table 1, it can be seen that the impact-resistant composite ceramic materials prepared in Examples 2-4 of the present invention have excellent impact resistance and thermal shock resistance. From the comparison between Comparative Examples 4-5 and Example 4, it can be seen that the reduced graphene oxide and multi-walled carbon nanotubes in the ternary composite material have excellent thermal conductivity and can promote grain refinement and growth. The reduced graphene oxide and multi-walled carbon nanotubes also have the effects of grain boundary fixation, bending, pulling out, bridging, and promoting crack propagation, which have a positive effect on the mechanical properties and thermal shock resistance of zirconia ceramics. In addition, the layered structure of reduced graphene oxide helps to improve the dispersion of binary doped zirconia microspheres in the green body material, thereby improving the performance of the ceramic material. From the comparison between Comparative Example 6 and Example 4, it can be seen that the reduced graphene oxide and multi-walled carbon nanotubes in the ternary composite material have excellent thermal conductivity and can promote grain refinement and growth. The reduced graphene oxide and multi-walled carbon nanotubes also have the effects of grain boundary fixation, bending, pulling out, bridging, and promoting crack propagation, which have a positive effect on the mechanical properties and thermal shock resistance of zirconia ceramics. In addition, the layered structure of reduced graphene oxide helps to improve the dispersion of binary doped zirconia microspheres in the green body material, thereby improving the performance of the ceramic material. From the comparison of Example 4, it can be seen that the nano-silica in the ternary composite material contributes to the formation and stabilization of tetragonal zirconia, and forms a covalent Si-O-Zr bond with the zirconia, so that the ternary composite material and the binary doped zirconia microspheres have better interface compatibility, thereby improving the comprehensive performance of the ceramic; from the comparison of Comparative Example 7 and Example 4, it can be seen that the binary doped zirconia microspheres of the present invention have a significant effect on the comprehensive performance of the ceramic material compared with zirconia powder of the same particle size due to the co-doping of gadolinium and yttrium and the effect of its hollow microsphere structure.

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

Claims

1. A method for preparing an impact-resistant composite ceramic material, characterized in that: The following steps are involved: Step 1: Using zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, and yttrium chloride hexahydrate as raw materials, binary doped zirconia microspheres are obtained by atomization-assisted chemical vapor deposition technology; The ternary composite material is mixed with the binary doped zirconia microspheres to obtain composite modified zirconia powder; The composite modified zirconia powder is subjected to thermal reduction to obtain reduced composite modified zirconia powder; Potassium feldspar, quartz, kaolin, wollastonite, bentonite, calcium silicate, talc, aluminum oxide, and reduced composite modified zirconium oxide powder are mixed to obtain a green body material; The preparation method of the ternary composite material comprises the following steps: S1. treating graphene oxide and carbon nanotubes respectively to obtain amino-treated graphene oxide and carboxylated carbon nanotubes; combining the amino-treated graphene oxide and carboxylated carbon nanotubes to obtain a graphene oxide / carbon nanotube hybrid material; S2, in situ growing nano-silicon dioxide on the surface of the graphene oxide / carbon nanotube hybrid material to obtain a ternary composite material; forming a green body material into a ceramic green body matrix; Step 2: mixing potassium feldspar, sodium feldspar, quartz sand, calcite, dolomite, kaolin, talc, fluorapatite, aluminum oxide, zinc powder, and silicon carbide whiskers to obtain a mixture, and then ball milling and sieving to obtain a glaze slurry; The glaze slurry is applied to the ceramic body substrate and sintered in steps to obtain an impact-resistant composite ceramic material.

2. The method for preparing an impact-resistant composite ceramic material according to claim 1, wherein: In the step 1, the method for preparing the composite modified zirconia powder subjected to reduction treatment specifically comprises: Zirconium oxychloride octahydrate, gadolinium chloride hexahydrate, yttrium chloride hexahydrate, and distilled water are mixed in a mass ratio of 15:(1-2):(1.3-1.7):500, stirred, and then converted into 3-5 μm droplets by ultrasonic atomization. The mixture is then heated at 600-900°C by atomization-assisted chemical vapor deposition technique, and an atomization rate of 500 mL / h is maintained. The reaction is maintained for 80-100 minutes. The resulting 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. The ternary composite material is added to deionized water, ultrasonicated, and then binary doped zirconia microspheres are added and stirred to make the mass ratio of the ternary composite material to the binary doped zirconia microspheres be (0.1-0.3):1, to obtain a composite modified zirconia powder; The composite modified zirconia powder is heated to 750-850° C. at a heating rate of 8° C. / min in an argon atmosphere for thermal reduction to obtain a reduced composite modified zirconia powder.

3. The method for preparing the impact-resistant composite ceramic material according to claim 1, characterized in that: In the step 1, the contents of the components in the green body material, in parts by weight, are: 35-40 parts of potassium feldspar, 25-30 parts of quartz, 10-15 parts of kaolin, 10-15 parts of wollastonite, 8-12 parts of bentonite, 7-10 parts of calcium silicate, 6-8 parts of talc, 5-8 parts of aluminum oxide, and 12-20 parts of reduced composite modified zirconium oxide powder.

4. The method for preparing an impact-resistant composite ceramic material according to claim 1, wherein: In the step 1, the preparation method of the ternary composite material specifically comprises the following steps: S1. Mix multi-walled carbon nanotubes, concentrated sulfuric acid, and concentrated nitric acid, condense and reflux, and ultrasonicate for 5-6 hours, then add deionized water and purify to obtain carboxylated carbon nanotubes; wherein the amount 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; Adding graphene oxide to deionized water, sonicating, then adding a sodium hydroxide aqueous solution thereto, sonicating, neutralizing the sodium hydroxide with a hydrochloric acid aqueous solution, centrifuging and rinsing, then adding ultrapure water and ethylenediamine, sonicating, adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, centrifuging, and dialysis to obtain amino-modified graphene oxide; wherein the mass ratio of graphene oxide to ethylenediamine is (0.04-0.08):(0.4-0.8); Polyvinyl pyrrolidone and ethanol are mixed in equal mass ratios to obtain a dispersant; amino-modified graphene oxide and carboxylated carbon nanotubes are added to the dispersant to obtain an amino-modified graphene oxide suspension with a mass fraction of 0.2-1.2% and a carboxylated carbon nanotube suspension with a mass fraction of 0.2-1.2%; the amino-modified graphene oxide suspension and the carboxylated carbon nanotube suspension are mixed in a volume ratio of 1:2, ultrasonically treated for 20-30 minutes, centrifuged, washed, and dried to obtain a graphene oxide / carbon nanotube hybrid material; S2, dispersing the graphene oxide / carbon nanotube hybrid material in an 80% by volume ethanol aqueous solution, and sonicating to obtain a mixed solution A with a concentration of 1 mg / mL; Ethyl silicate and an 80% by volume ethanol aqueous solution are mixed to obtain an ethyl silicate dispersion with a concentration of 0.1-0.15 mol / L, and the pH is adjusted to 4 to obtain a mixed solution B. Under stirring conditions, the mixed solution A and the mixed solution B are mixed in a volume ratio of 1:(3.8-4.2), the pH is adjusted to 9 with a sodium hydroxide aqueous solution, and then the mixture is stirred at 63-67°C and a rotation speed of 40-60 r / min for 50-70 minutes, and purified to obtain a ternary composite material.

5. The method for preparing the impact-resistant composite ceramic material according to claim 1, wherein: In the step 1, the preparation method of the ceramic green body matrix specifically includes: mixing the green body material with water, ball milling with alumina balls as the ball milling medium, the ball milling time is 15-25 hours, the ball milling speed is 200-250r / min, the weight ratio of the green body material, alumina balls and water is 1: (1.8-2): (0.6-0.7), the slurry after ball milling is passed through a 200 mesh sieve, and after iron removal, it is press-filtered into a mud cake, and after the mud cake is processed into the desired shape, it is shaped, sharpened, and air-dried. After drying, it is put into a kiln, heated to 500-600°C at a rate of 5-10°C / min and kept warm for 2-4 hours, then heated to 700-800°C at a rate of 10-15°C / min, and sintered for 6-8 hours; then cooled to 600-650°C, kept warm for 1-2 hours, and after sintering, naturally cooled to 40-50°C before being discharged from the kiln to obtain the ceramic green body matrix.

6. The method for preparing the impact-resistant composite ceramic material according to claim 1, characterized in that: In the step 2, the preparation method of the glaze slurry specifically includes: 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 whiskers by weight to obtain a mixture; mixing the mixture with water in a mass ratio of 5:(2-3) and then ball milling at a ball milling speed of 1000-1500 r / min for a ball milling time of 25-35 min; and then passing through a 200-400 mesh sieve to obtain a glaze slurry.

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

8. The method for preparing an impact-resistant composite ceramic material according to claim 1, wherein: In step 2, the step-by-step sintering includes: first heating to 1150-1180°C at a heating rate of 1.5-2°C / min, keeping warm for 2-3 hours, then heating to 1180-1200°C, keeping warm for 7.5-8.5 hours, and finally heating to 1250-1300°C, hot pressing and sintering at a constant pressure of 20-50 MPa, and keeping warm for 1.5-2.5 hours.

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

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

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