Environment-friendly ceramic and preparation method thereof

Abstract

The application discloses an environment-friendly ceramic and a preparation method thereof, and belongs to the field of ceramics. The method comprises the following steps: dissolving zinc nitrate, zirconium nitrate and iron nitrate in a solvent and stirring and mixing to obtain a mixed solution; grinding and mixing kaolin, illite, magnesium oxide, iron titanate, calcium titanate, titanium, silicon powder, carbon powder and aluminum oxide, and adding into the mixed solution to mix to obtain a first slurry; taking the first slurry, adding zinc oxide and iron oxide into the taken first slurry to mix to obtain a second slurry; adding kaolin, zirconium oxide, boron carbide, carbon powder, boron oxide, aluminum, boron, titanium, silicon and titanium dioxide into a dispersing solvent to mix to obtain a third slurry; and performing sintering treatment on the prepared embryo to obtain the ceramic. The ceramic has high mechanical strength, good corrosion resistance, good antibacterial property, is not prone to cracking or damage when the external temperature changes rapidly, has stable overall performance, and has high durability.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ceramics, and particularly relates to an environment-friendly ceramic and a preparation method thereof. BACKGROUND

[0002] Ceramics are prepared by using different clays as raw materials and other components, and the preparation process mainly includes processes such as batching, forming, drying and baking. Ceramics were previously mainly used as appliances in life. With the development of ceramic manufacturing technology, the performance of ceramics is getting better and better. Ceramics are applied to more and more fields due to excellent performances such as high strength, high temperature resistance, good insulation and corrosion resistance. For example, ceramics need to have good strength and antibacterial properties in the field of life, ceramics need to have good wear resistance and high strength performance in the field of building, and ceramics need to have good insulation and mechanical strength in the field of industry. With the increasing application environment of ceramics, the performance requirements for ceramics are getting higher and higher. The corrosion resistance of ceramics is still difficult to meet the requirements, and ceramics with better corrosion resistance need to be researched. SUMMARY

[0003] The purpose of the embodiment of the application is to provide an environment-friendly ceramic and a preparation method thereof, so as to solve the problem of poor corrosion resistance of ceramics.

[0004] The embodiment of the application provides a preparation method of an environment-friendly ceramic, which comprises the following steps:

[0005] Zinc nitrate, zirconium nitrate and iron nitrate are dissolved in a solvent and stirred and mixed to obtain a mixed solution;

[0006] Kaolin, illite, magnesium oxide, iron titanate, calcium titanate, titanium, silicon powder, carbon powder and aluminum oxide are ground and mixed, and then added to the mixed solution and stirred and mixed to obtain a first slurry;

[0007] Part of the first slurry is taken, and zinc oxide and iron oxide are added to the taken first slurry and stirred and mixed to obtain a second slurry;

[0008] Kaolin, zirconium oxide, boron carbide, carbon powder, boron oxide, aluminum, boron, titanium, silicon and titanium dioxide are added to a dispersion solvent and stirred and mixed to obtain a third slurry;

[0009] A first embryo is prepared by using the first slurry, and then the second slurry is coated on the surface of the first embryo to obtain a second embryo;

[0010] The second embryo is placed in a sintering furnace and dried in a vacuum environment at 160-220 DEG C for 1-2.5 h;

[0011] Then the sintering furnace is heated to 580-730 DEG C for sintering treatment for 0.5-2 h;

[0012] After the second body is taken out from the sintering furnace, it is cooled, and then is treated in an acid solution for 0.5-1.5 hours, and is washed with deionized water;

[0013] The second body is immersed in a third slurry for 0.5-2 hours;

[0014] The second body is then placed in a sintering furnace and heated to 850-970°C and treated in a vacuum environment for 1-3.5 hours;

[0015] The sintering furnace is then heated to 1050-1260°C and treated in a first treatment environment for 2-4.5 hours;

[0016] The temperature is then increased to 1330-1550°C and treated in a second treatment environment for 1-3 hours;

[0017] The second body is then treated in nitrogen at 1100-1220°C for 0.5-2 hours;

[0018] The first treatment environment is vacuum or inert, and the second treatment environment is vacuum or inert.

[0019] Optionally, the components in the first slurry have the following amounts:

[0020] Zinc nitrate 0.7-2.2 parts by weight;

[0021] Zirconium nitrate 0.5-1.5 parts by weight;

[0022] Iron nitrate 0.4-1 parts by weight;

[0023] Kaolin 28-40 parts by weight;

[0024] Illite 7-15 parts by weight;

[0025] Magnesium oxide 0.3-0.8 parts by weight;

[0026] Iron titanate 0.8-1.5 parts by weight;

[0027] Calcium titanate 0.3-0.8 parts by weight;

[0028] Titanium 0.4-0.9 parts by weight;

[0029] Silicon powder 0.5-1.2 parts by weight;

[0030] Carbon powder 1.5-2.8 parts by weight;

[0031] Aluminum oxide 1.5-2.3 parts by weight.

[0032] Optionally, the components in the second slurry have the following amounts:

[0033] zinc oxide is 3.3-5.5% by mass of the second slurry;

[0034] iron oxide is 2.5-4% by mass of the second slurry.

[0035] Optionally, the component content in the third slurry is:

[0036] kaolin 10-17 parts by weight;

[0037] zirconium oxide 0.3-0.9 parts by weight;

[0038] boron carbide 0.5-1.2 parts by weight;

[0039] carbon powder 1.2-2.5 parts by weight;

[0040] boron oxide 0.8-1.4 parts by weight

[0041] aluminum 0.3-0.7 parts by weight;

[0042] boron 0.3-0.5 parts by weight;

[0043] titanium 0.2-0.5 parts by weight;

[0044] silicon 0.3-0.6 parts by weight;

[0045] titanium dioxide 0.4-0.8 parts by weight.

[0046] Optionally, the first processing environment further comprises:

[0047] methane, nitrogen and argon.

[0048] Optionally, the second processing environment further comprises:

[0049] silane, nitrogen and argon.

[0050] Optionally, the kaolin is a modified kaolin, and the preparation method of the modified kaolin is:

[0051] the kaolin is pickled in an acidic solution, then washed with water and dried;

[0052] the kaolin is ground and mixed with zirconium to obtain a first mixture;

[0053] the first mixture is placed in an impregnation solution containing barium nitrate and zirconium chloride, and then sodium hydroxide solution is added to the impregnation solution to obtain an impregnation mixture, and the impregnation mixture is placed in a reaction container and heated to 110-170℃ for hydrothermal treatment for 0.5-1.5h;

[0054] After filtration, dry to obtain a dry substance, mix the dry substance with aluminum and boron oxide, and then immerse in a glucose aqueous solution to obtain a second mixture;

[0055] Then, the second mixture is treated in vacuum at 450-550 DEG C for 1-2 hours.

[0056] Then, the second mixture is treated in inert gas at 1260-1350 DEG C for 1-3 hours, and then grinded after cooling to obtain the modified kaolin.

[0057] Optionally, in the first mixture, the mass of zirconium is 1.2-3.5% of the mass of kaolin, the concentration of barium nitrate in the immersion solution is 0.3-0.8 mol / L, and the concentration of zirconium chloride in the immersion solution is 0.3-0.8 mol / L.

[0058] Optionally, in the second mixture, the mass of aluminum is 0.6-1.7% of the mass of kaolin, the mass of boron oxide is 1.5-2.8% of the mass of kaolin, and the mass concentration of the glucose solution is 25-50%.

[0059] The embodiment of the present application provides an environment-friendly ceramic prepared by the preparation method in the above embodiment.

[0060] The preparation method of the environment-friendly ceramic provided by the embodiment of the present application comprises the following steps: dissolving zinc nitrate, zirconium nitrate and iron nitrate in a solvent to obtain a mixed solution; grinding and mixing kaolin, illite, magnesium oxide, iron titanate, calcium titanate, titanium, silicon powder, carbon powder and aluminum oxide, and then adding into the mixed solution to obtain a first slurry; taking part of the first slurry, and then adding zinc oxide and iron oxide into the taken first slurry to obtain a second slurry; grinding and mixing kaolin, zirconium oxide, boron carbide, carbon powder, boron oxide, aluminum, boron, titanium, silicon and titanium dioxide in a dispersing solvent to obtain a third slurry; preparing a first embryo by using the first slurry; coating the second slurry on the surface of the first embryo to obtain a second embryo; placing the second embryo in a sintering furnace for sintering treatment and then cooling; treating the second embryo in an acidic solution; and immersing the second embryo in the third slurry for treatment, and then sintering the second embryo in the sintering furnace to obtain the ceramic. DETAILED DESCRIPTION

[0061] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all the other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0062] The preparation method of the environment-friendly ceramic according to the embodiment of the application comprises the following steps:

[0063] Dissolve zinc nitrate, zirconium nitrate and iron nitrate in a solvent to obtain a mixed solution; the solvent can be water, a solution of water and ethanol, etc.

[0064] Grind and mix kaolin, illite, magnesium oxide, iron titanate, calcium titanate, titanium, silicon powder, carbon powder and aluminum oxide, and add them to the mixed solution to obtain a first slurry by stirring and mixing;

[0065] Take part of the first slurry and add zinc oxide and iron oxide to the taken first slurry to obtain a second slurry by stirring and mixing; the addition of zinc oxide and iron oxide to the first slurry by stirring and mixing can make the content of zinc oxide and iron oxide in the second slurry higher, and the zinc oxide and iron oxide can be easily combined with the first slurry;

[0066] Add kaolin, zirconium oxide, boron carbide, carbon powder, boron oxide, aluminum, boron, titanium, silicon and titanium dioxide to a dispersion solvent to obtain a third slurry by stirring and mixing;

[0067] Prepare a first body using the first slurry, and then coat the second slurry on the surface of the first body to obtain a second body;

[0068] Place the second body in a sintering furnace, heat it to 160-220℃, and dry it in a vacuum environment for 1-2.5h;

[0069] Then heat the sintering furnace to 580-730℃, and perform sintering treatment on the second body for 0.5-2h;

[0070] After taking the second body out of the sintering furnace, cool it, then place it in an acidic solution for 0.5-1.5h, and clean it with deionized water; the treatment in the acidic solution can remove components such as zinc oxide and iron oxide which are easily removed by the acidic solution, and form pores on the surface of the body, which is easy to be impregnated and combined with other component layers;

[0071] Place the second body in the third slurry to perform impregnation treatment for 0.5-2h;

[0072] Then place the second body in the sintering furnace, heat it to 850-970℃, and treat it in a vacuum environment for 1-3.5h;

[0073] Then heat the sintering furnace to 1050-1260℃, and treat the second body in a first treatment environment for 2-4.5h;

[0074] Continue to heat it to 1330-1550℃, and treat it in a second treatment environment for 1-3h;

[0075] The second body is then treated in nitrogen at 1100-1220°C for 0.5-2h;

[0076] The first processing environment is vacuum or inert, and the second processing environment is vacuum or inert.

[0077] In some embodiments, the component content in the first slurry can be:

[0078] Zinc nitrate 0.7-2.2 parts by weight;

[0079] Zirconium nitrate 0.5-1.5 parts by weight;

[0080] Iron nitrate 0.4-1 parts by weight;

[0081] Kaolin 28-40 parts by weight;

[0082] Illite 7-15 parts by weight;

[0083] Magnesium oxide 0.3-0.8 parts by weight;

[0084] Iron titanate 0.8-1.5 parts by weight;

[0085] Calcium titanate 0.3-0.8 parts by weight;

[0086] Titanium 0.4-0.9 parts by weight;

[0087] Silicon powder 0.5-1.2 parts by weight;

[0088] Carbon powder 1.5-2.8 parts by weight;

[0089] Alumina 1.5-2.3 parts by weight.

[0090] In other embodiments, the component content in the second slurry can be:

[0091] Zinc oxide is 3.3-5.5% by mass of the second slurry;

[0092] Iron oxide is 2.5-4% by mass of the second slurry.

[0093] Optionally, the component content in the third slurry can be:

[0094] Kaolin 10-17 parts by weight;

[0095] Zirconia 0.3-0.9 parts by weight;

[0096] Boron carbide 0.5-1.2 parts by weight;

[0097] Carbon powder 1.2-2.5 parts by weight;

[0098] boron oxide 0.8-1.4 parts by weight;

[0099] aluminum 0.3-0.7 parts by weight;

[0100] boron 0.3-0.5 parts by weight;

[0101] titanium 0.2-0.5 parts by weight;

[0102] silicon 0.3-0.6 parts by weight;

[0103] titanium dioxide 0.4-0.8 parts by weight.

[0104] Further, the first processing environment can further comprise:

[0105] methane, nitrogen and argon. The first processing environment can be a mixed gas of methane, nitrogen and argon, the volume of methane accounting for 10-16% of the volume of the mixed gas, and the volume of nitrogen accounting for 17-22% of the volume of the mixed gas;

[0106] Further, the second processing environment can further comprise:

[0107] silane, nitrogen and argon. The second processing environment can be a mixed gas of silane, nitrogen and argon, the volume of silane accounting for 7-12% of the volume of the mixed gas, and the volume of nitrogen accounting for 15-28% of the volume of the mixed gas.

[0108] In some embodiments of the present application, the kaolin is modified kaolin, and the preparation method of the modified kaolin can be:

[0109] acid washing the kaolin in an acidic solution, then washing with water and drying;

[0110] grinding and mixing the kaolin with zirconium to obtain a first mixture;

[0111] placing the first mixture in an impregnation solution containing barium nitrate and zirconium chloride, then adding a sodium hydroxide solution to the impregnation solution to obtain an impregnation mixture, and placing the impregnation mixture in a reaction container and heating to 110-170°C for hydrothermal treatment for 0.5-1.5h;

[0112] drying to obtain a dry product, mixing the dry product with aluminum and boron oxide, and then placing it in an aqueous glucose solution for impregnation, and filtering to obtain a second mixture;

[0113] then placing the second mixture in a vacuum and treating at 450-550°C for 1-2h;

[0114] The second mixture is treated in an inert gas at 1260-1350 DEG C for 1-3 hours, and then ground after cooling to obtain the modified kaolin. The inert gas can be at least one of nitrogen and argon, for example, nitrogen.

[0115] In some embodiments, the mass of zirconium in the first mixture is 1.2-3.5% of the mass of kaolin, the concentration of barium nitrate in the impregnation solution is 0.3-0.8 mol / L, and the concentration of zirconium chloride in the impregnation solution is 0.3-0.8 mol / L. For example, the mass of zirconium in the first mixture is 3.5% of the mass of kaolin, the concentration of barium nitrate in the impregnation solution is 0.5 mol / L, and the concentration of zirconium chloride in the impregnation solution is 0.6 mol / L.

[0116] In some embodiments of the present application, in the second mixture, the mass of aluminum is 0.6-1.7% of the mass of kaolin, the mass of boron oxide is 1.5-2.8% of the mass of kaolin, and the mass concentration of the glucose solution is 25-50%. For example, in the second mixture, the mass of aluminum is 0.9% of the mass of kaolin, the mass of boron oxide is 1.8% of the mass of kaolin, and the mass concentration of the glucose solution is 35%.

[0117] The environmentally friendly ceramic of the embodiments of the present application is prepared by the preparation method described in the above embodiments.

[0118] The present application is further described below by some embodiments. Embodiment 1

[0119] The preparation process of the environmentally friendly ceramic is as follows:

[0120] Zinc nitrate, zirconium nitrate, and iron nitrate are dissolved in a solvent to obtain a mixed solution by stirring; the solvent is a mixed solvent of water and ethanol, and the volume ratio of water to ethanol in the mixed solvent is 4:1;

[0121] Kaolin, illite, magnesium oxide, iron titanate, calcium titanate, titanium, silicon powder, carbon powder, and aluminum oxide are ground and mixed, and then added to the mixed solution to obtain a first slurry by stirring;

[0122] Part of the first slurry is taken, and zinc oxide and iron oxide are added to the taken first slurry to obtain a second slurry by stirring;

[0123] Kaolin, zirconium oxide, boron carbide, carbon powder, boron oxide, aluminum, boron, titanium, silicon, and titanium dioxide are added to water to obtain a third slurry by stirring;

[0124] A first embryo is prepared by using the first slurry, and then the second slurry is coated on the surface of the first embryo to obtain a second embryo;

[0125] The second embryo is placed in a sintering furnace and heated to 160℃ and dried in a vacuum environment for 2.5h;

[0126] The sintering furnace is then heated to 730℃ and sintering treatment is performed for 0.5h;

[0127] After the second embryo is taken out of the sintering furnace and cooled, the second embryo is placed in an acid solution for 0.5h and cleaned with deionized water; the acid solution is a 0.3mol / L nitric acid solution;

[0128] The second embryo is placed in a third slurry for ultrasonic immersion treatment for 2h;

[0129] The second embryo is then placed in a sintering furnace and heated to 850℃ and treated in a vacuum environment for 3.5h;

[0130] The sintering furnace is then heated to 1260℃ and treated in a first treatment environment for 2h;

[0131] Continued heating to 1330℃ and treated in a second treatment environment for 3h;

[0132] The second embryo is then treated in nitrogen at 1100℃ for 2h;

[0133] The first treatment environment is vacuum and the second treatment environment is vacuum;

[0134] The component content in the first slurry is:

[0135] Zinc nitrate 0.7 parts by weight; zirconium nitrate 0.5 parts by weight; iron nitrate 1 part by weight;

[0136] Kaolin 28 parts by weight; illite 15 parts by weight; magnesium oxide 0.3 parts by weight;

[0137] Iron titanate 0.8 parts by weight; calcium titanate 0.8 parts by weight; titanium 0.4 parts by weight;

[0138] Silicon powder 0.5 parts by weight; carbon powder 1.5 parts by weight; aluminum oxide 2.3 parts by weight; solvent 75 parts by weight;

[0139] The component content in the second slurry is:

[0140] Zinc oxide is 3.3% of the mass of the second slurry; iron oxide is 2.5% of the mass of the second slurry;

[0141] The component content in the third slurry is:

[0142] Kaolin 10 parts by weight; zirconium oxide 0.3 parts by weight; boron carbide 0.5 parts by weight;

[0143] Carbon powder 1.2 parts by weight; boron oxide 0.8 parts by weight; aluminum 0.3 parts by weight;

[0144] Boron 0.5 parts by weight; titanium 0.2 parts by weight; silicon 0.3 parts by weight;

[0145] Titanium dioxide 0.8 parts by weight; water 22 parts by weight. Example 2

[0146] The preparation process of the environmentally friendly ceramic is as follows:

[0147] Dissolve zinc nitrate, zirconium nitrate and iron nitrate in a solvent to obtain a mixed solution; the solvent is a mixed solvent of water and ethanol, and the volume ratio of water to ethanol in the mixed solvent is 4:1;

[0148] Grind and mix kaolin, illite, magnesium oxide, iron titanate, calcium titanate, titanium, silicon powder, carbon powder and aluminum oxide, and add them to the mixed solution to stir and mix to obtain a first slurry;

[0149] Take part of the first slurry and add zinc oxide and iron oxide to the taken first slurry to stir and mix to obtain a second slurry;

[0150] Add kaolin, zirconium oxide, boron carbide, carbon powder, boron oxide, aluminum, boron, titanium, silicon and titanium dioxide to water to stir and mix to obtain a third slurry;

[0151] Use the first slurry to prepare a first embryo, and then coat the second slurry on the surface of the first embryo to obtain a second embryo;

[0152] Place the second embryo in a sintering furnace and heat it to 220℃ for drying in a vacuum environment for 1h;

[0153] Then heat the sintering furnace to 580℃ for sintering treatment for 2h;

[0154] After taking the second embryo out of the sintering furnace, cool it down, and then place it in an acid solution for treatment for 1.5h, and clean it with deionized water; the acid solution is a 0.3mol / L nitric acid solution;

[0155] Place the second embryo in the third slurry for ultrasonic immersion treatment for 0.5h;

[0156] Then place the second embryo in the sintering furnace and heat it to 970℃ for treatment in a vacuum environment for 1h;

[0157] Then heat the sintering furnace to 1050℃ for treatment in a first treatment environment for 4.5h;

[0158] Continue to heat to 1550℃ for treatment in a second treatment environment for 1h;

[0159] Then the second embryo is placed in nitrogen at 1220℃ for 0.5h;

[0160] The first processing environment is vacuum, and the second processing environment is vacuum;

[0161] The component content in the first slurry is:

[0162] Zinc nitrate 2.2 parts by weight; zirconium nitrate 1.5 parts by weight; iron nitrate 0.4 parts by weight;

[0163] Kaolin 40 parts by weight; illite 7 parts by weight; magnesium oxide 0.8 parts by weight;

[0164] Iron titanate 1.5 parts by weight; calcium titanate 0.3 parts by weight; titanium 0.9 parts by weight;

[0165] Silicon powder 1.2 parts by weight; carbon powder 2.8 parts by weight; aluminum oxide 1.5 parts by weight; solvent 93 parts by weight;

[0166] The component content in the second slurry is:

[0167] Zinc oxide is 5.5% of the mass of the second slurry; iron oxide is 4% of the mass of the second slurry;

[0168] The component content in the third slurry is:

[0169] Kaolin 17 parts by weight; zirconium oxide 0.9 parts by weight; boron carbide 1.2 parts by weight;

[0170] Carbon powder 2.5 parts by weight; boron oxide 1.4 parts by weight; aluminum 0.7 parts by weight;

[0171] Boron 0.3 parts by weight; titanium 0.5 parts by weight; silicon 0.6 parts by weight;

[0172] Titanium dioxide 0.4 parts by weight; water 45 parts by weight.

[0173] Example 3

[0174] The preparation process of the environmental protection ceramic is:

[0175] Dissolve zinc nitrate, zirconium nitrate, and iron nitrate in a solvent and stir to mix to obtain a mixed solution; the solvent is a mixed solvent of water and ethanol, and the volume ratio of water to ethanol in the mixed solvent is 4:1;

[0176] Grind and mix kaolin, illite, magnesium oxide, iron titanate, calcium titanate, titanium, silicon powder, carbon powder, and aluminum oxide, and add them to the mixed solution and stir to mix to obtain a first slurry;

[0177] Take part of the first slurry and add zinc oxide, iron oxide to the taken first slurry to stir and mix to obtain a second slurry;

[0178] Add kaolin, zirconium oxide, boron carbide, carbon powder, boron oxide, aluminum, boron, titanium, silicon, titanium dioxide to water to stir and mix to obtain a third slurry;

[0179] Use the first slurry to prepare a first embryo, and then coat the second slurry on the surface of the first embryo to obtain a second embryo;

[0180] Place the second embryo in a sintering furnace and heat to 190℃ to dry in a vacuum environment for 1.5h;

[0181] Then heat the sintering furnace to 670℃ to perform sintering treatment for 1h;

[0182] After taking out the second embryo from the sintering furnace, cool it down, and then place it in an acidic solution for 1h, and clean it with deionized water; the acidic solution is a 0.3mol / L nitric acid solution;

[0183] Place the second embryo in the third slurry to perform ultrasonic immersion treatment for 1h;

[0184] Then place the second embryo in a sintering furnace and heat to 900℃ to treat in a vacuum environment for 2.5h;

[0185] Then heat the sintering furnace to 1150℃ to treat in a first treatment environment for 3h;

[0186] Continue to heat to 1450℃ to treat in a second treatment environment for 2h;

[0187] Then place the second embryo in nitrogen at 1160℃ for 1.5h;

[0188] The first treatment environment is vacuum, and the second treatment environment is vacuum;

[0189] The component content in the first slurry is:

[0190] Zinc nitrate 1.6 parts by weight; zirconium nitrate 0.9 parts by weight; iron nitrate 0.7 parts by weight;

[0191] Kaolin 33 parts by weight; illite 11 parts by weight; magnesium oxide 0.5 parts by weight;

[0192] Iron titanate 1.2 parts by weight; calcium titanate 0.6 parts by weight; titanium 0.6 parts by weight;

[0193] Silicon powder 0.8 parts by weight; carbon powder 2 parts by weight; aluminum oxide 1.8 parts by weight; solvent 75 parts by weight;

[0194] The component content in the second slurry is:

[0195] Zinc oxide is 4.5% by mass of the second slurry; iron oxide is 3.6% by mass of the second slurry;

[0196] In the third slurry, the component content is:

[0197] Kaolin 14 parts by weight; zirconium oxide 0.7 parts by weight; boron carbide 0.8 parts by weight;

[0198] Carbon powder 1.8 parts by weight; boron oxide 1 part by weight; aluminum 0.6 parts by weight;

[0199] Boron 0.4 parts by weight; titanium 0.4 parts by weight; silicon 0.5 parts by weight;

[0200] Titanium dioxide 0.6 parts by weight; water 36 parts by weight.

[0201] Example 4

[0202] The difference between Example 4 and Example 3 is:

[0203] The first processing environment is a mixed gas of methane, nitrogen and argon, and the volume of methane accounts for 16% of the mixed gas, and the volume of nitrogen accounts for 22% of the mixed gas;

[0204] The second processing environment is a mixed gas of silane, nitrogen and argon, and the volume of silane accounts for 12% of the mixed gas, and the volume of nitrogen accounts for 28% of the mixed gas.

[0205] Example 5

[0206] The difference between Example 5 and Example 3 is:

[0207] The first processing environment is a mixed gas of methane, nitrogen and argon, and the volume of methane accounts for 10% of the mixed gas, and the volume of nitrogen accounts for 17% of the mixed gas;

[0208] The second processing environment is a mixed gas of silane, nitrogen and argon, and the volume of silane accounts for 7% of the mixed gas, and the volume of nitrogen accounts for 15% of the mixed gas.

[0209] Example 6

[0210] The difference between Example 6 and Example 3 is:

[0211] The kaolin is modified kaolin, and the preparation method of the modified kaolin is:

[0212] The kaolin is placed in an acid solution for pickling, and then washed with water and dried; the acid solution is a 0.5 mol / L nitric acid solution;

[0213] The kaolin is ground and mixed with zirconium to obtain a first mixture;

[0214] The first mixture is placed in an impregnation solution including barium nitrate and zirconium chloride, and then a sodium hydroxide solution is added to the impregnation solution to obtain an impregnation mixture, and the impregnation mixture is placed in a reaction container and heated to 110°C for hydrothermal treatment for 1.5h;

[0215] After filtration, drying is performed to obtain a dry product, and the dry product is mixed with aluminum and boron oxide and then placed in an aqueous glucose solution for impregnation, and after filtration, a second mixture is obtained;

[0216] Then, the second mixture is placed in a vacuum and treated at 450°C for 2h;

[0217] Then, the second mixture is placed in a vacuum and treated at 450°C for 2h;

[0218] In the first mixture, the mass of zirconium is 1.2% of the mass of kaolin, the concentration of barium nitrate in the impregnation solution is 0.3mol / L, and the concentration of zirconium chloride in the impregnation solution is 0.3mol / L; the concentration of the sodium hydroxide solution is 2mol / L, and the volume of the sodium hydroxide solution is 0.4 times the volume of the impregnation solution;

[0219] In the second mixture, the mass of aluminum is 1.7% of the mass of kaolin, the mass of boron oxide is 1.5% of the mass of kaolin, and the mass concentration of the glucose solution is 25%.

[0220] Example 7

[0221] The difference between Example 7 and Example 3 is:

[0222] The kaolin is modified kaolin, and the preparation method of the modified kaolin is:

[0223] The kaolin is placed in an acidic solution for acid washing, and then washed with water and dried; the acidic solution is a 0.5mol / L nitric acid solution;

[0224] The kaolin is mixed with zirconium by grinding to obtain a first mixture;

[0225] The first mixture is placed in an impregnation solution including barium nitrate and zirconium chloride, and then a sodium hydroxide solution is added to the impregnation solution to obtain an impregnation mixture, and the impregnation mixture is placed in a reaction container and heated to 170°C for hydrothermal treatment for 0.5h;

[0226] After filtration, drying is performed to obtain a dry product, and the dry product is mixed with aluminum and boron oxide and then placed in an aqueous glucose solution for impregnation, and after filtration, a second mixture is obtained;

[0227] Then, the second mixture is placed in a vacuum and treated at 550°C for 1h;

[0228] Then the second mixture is placed in nitrogen at 1260℃ for 3h, and after cooling, grinding is performed to obtain modified kaolin;

[0229] The mass of zirconium in the first mixture is 3.5% of the mass of kaolin, the concentration of barium nitrate in the impregnation solution is 0.8mol / L, the concentration of zirconium chloride in the impregnation solution is 0.8mol / L; the concentration of sodium hydroxide solution is 2mol / L, and the volume of sodium hydroxide solution is 0.7 times the volume of the impregnation solution;

[0230] In the second mixture, the mass of aluminum is 0.6% of the mass of kaolin, the mass of boron oxide is 2.8% of the mass of kaolin, and the mass concentration of the glucose solution is 50%.

[0231] Example 8

[0232] The difference between Example 8 and Example 5 is:

[0233] The kaolin is modified kaolin, and the preparation method of the modified kaolin is:

[0234] The kaolin is placed in an acidic solution for pickling, and then washed with water and dried; the acidic solution is a 0.5mol / L nitric acid solution;

[0235] The kaolin is ground and mixed with zirconium to obtain a first mixture;

[0236] The first mixture is placed in an impregnation solution containing barium nitrate and zirconium chloride, and then sodium hydroxide solution is added to the impregnation solution to obtain an impregnation mixture. The impregnation mixture is placed in a reaction container and heated to 110℃ for hydrothermal treatment for 1.5h;

[0237] After filtration and drying, a dry material is obtained. The dry material is mixed with aluminum and boron oxide and then placed in a glucose aqueous solution for impregnation. After filtration, a second mixture is obtained;

[0238] Then the second mixture is placed in a vacuum at 450℃ for 2h;

[0239] Then the second mixture is placed in nitrogen at 1350℃ for 1h, and after cooling, grinding is performed to obtain modified kaolin;

[0240] The mass of zirconium in the first mixture is 1.2% of the mass of kaolin, the concentration of barium nitrate in the impregnation solution is 0.3mol / L, the concentration of zirconium chloride in the impregnation solution is 0.3mol / L; the concentration of sodium hydroxide solution is 2mol / L, and the volume of sodium hydroxide solution is 0.4 times the volume of the impregnation solution;

[0241] In the second mixture, the mass of aluminum is 1.7% of the mass of kaolin, the mass of boron oxide is 1.5% of the mass of kaolin, and the mass concentration of the glucose solution is 25%. Example 9

[0242] The difference between Example 9 and Example 5 is:

[0243] The kaolin is modified kaolin, and the preparation method of the modified kaolin is:

[0244] The kaolin is placed in an acidic solution for pickling, then washed with water and dried; the acidic solution is a 0.5 mol / L nitric acid solution.

[0245] The kaolin is ground and mixed with zirconium to obtain a first mixture.

[0246] The first mixture is placed in an impregnation solution containing barium nitrate and zirconium chloride, and then sodium hydroxide solution is added to the impregnation solution to obtain an impregnation mixture. The impregnation mixture is placed in a reaction container and heated to 170℃ for hydrothermal treatment for 0.5h.

[0247] After filtration and drying, a dry material is obtained. The dry material is mixed with aluminum and boron oxide and then placed in a glucose aqueous solution for impregnation. After filtration, a second mixture is obtained.

[0248] Then the second mixture is placed in a vacuum and treated at 550℃ for 1h.

[0249] The second mixture is then placed in nitrogen and treated at 1260℃ for 3h. After cooling, grinding is performed to obtain modified kaolin.

[0250] In the first mixture, the mass of zirconium is 3.5% of the mass of kaolin. The concentration of barium nitrate in the impregnation solution is 0.8 mol / L, and the concentration of zirconium chloride in the impregnation solution is 0.8 mol / L. The concentration of sodium hydroxide solution is 2 mol / L, and the volume of sodium hydroxide solution is 0.7 times the volume of the impregnation solution.

[0251] In the second mixture, the mass of aluminum is 0.6% of the mass of kaolin, the mass of boron oxide is 2.8% of the mass of kaolin, and the mass concentration of the glucose solution is 50%.

[0252] Comparative Example 1

[0253] The difference between Comparative Example 1 and Example 3 is:

[0254] In Comparative Example 1, the acidic solution in the step "after taking the second body out of the sintering furnace, cooling, and then placing the second body in the acidic solution for 1h and washing with deionized water" is replaced with deionized water.

[0255] Comparative Example 2

[0256] The difference between Comparative Example 2 and Example 3 is that:

[0257] In Comparative Example 2, the component content in the second slurry is:

[0258] The mass of zinc oxide is 0% of the mass of the second slurry; the mass of iron oxide is 0% of the mass of the second slurry;

[0259] Comparative Example 3

[0260] The preparation process of the environmentally friendly ceramic is:

[0261] Dissolve zinc nitrate, zirconium nitrate, and iron nitrate in a solvent to obtain a mixed solution; the solvent is a mixed solvent of water and ethanol, and the volume ratio of water to ethanol in the mixed solvent is 4:1;

[0262] Grind and mix kaolin, illite, magnesium oxide, iron titanate, calcium titanate, titanium, silicon powder, carbon powder, and aluminum oxide, and add them to the mixed solution to obtain a first slurry by stirring and mixing;

[0263] Use the first slurry to prepare a green body, and place the green body in a sintering furnace to heat to 190°C and dry in a vacuum environment for 1.5h;

[0264] Then heat the sintering furnace to 670°C and perform sintering treatment for 1h;

[0265] Then place the green body in the sintering furnace and heat to 900°C to treat in a vacuum environment for 2.5h;

[0266] Then heat to 1150°C and treat in a first treatment environment for 3h;

[0267] Continue to heat to 1450°C and treat in a second treatment environment for 2h;

[0268] Then place the green body in nitrogen at 1160°C and treat for 1.5h;

[0269] The first treatment environment is vacuum, and the second treatment environment is vacuum;

[0270] The component content in the first slurry is:

[0271] Zinc nitrate 1.6 parts by weight; zirconium nitrate 0.9 parts by weight; iron nitrate 0.7 parts by weight;

[0272] Kaolin 33 parts by weight; illite 11 parts by weight; magnesium oxide 0.5 parts by weight;

[0273] Iron titanate 1.2 parts by weight; calcium titanate 0.6 parts by weight; titanium 0.6 parts by weight;

[0274] Silicon powder 0.8 parts by weight; carbon powder 2 parts by weight; aluminum oxide 1.8 parts by weight; solvent 65 parts by weight.

[0275] (1) The performance of the ceramic prepared in the above example was tested, and the specific test results are shown in Table 1.

[0276] Table 1 Performance test results of the ceramic

[0277] Name Tensile strength / MPa Wear resistance revolution Example 1 408 16560 Example 2 417 16630 Example 3 412 16610 Example 4 425 17120 Example 5 432 17180 Example 6 457 16970 Example 7 463 17090 Example 8 474 17040 Example 9 478 17170 Comparative Example 1 383 16330 Comparative Example 2 391 16350 Comparative Example 3 341 13360

[0278] From Table 1, it can be seen that the ceramic prepared by the method in the above example has high tensile strength, good wear resistance, and high overall structural strength.

[0279] (2) The corrosion resistance of the prepared ceramic was tested, and the test process was as follows:

[0280] Acid resistance test: The prepared ceramic was placed in a 1.5 mol / L hydrochloric acid solution at 25°C for 15 days, then washed with deionized water and dried at 40°C, the ceramic surface was observed, and the weight was measured.

[0281] Alkali resistance test: The prepared ceramic was placed in a 1.5 mol / L sodium hydroxide solution at 25°C for 15 days, then washed with deionized water and dried at 40°C, the ceramic surface was observed, and the weight was measured.

[0282] Salt resistance test: Sodium chloride was added to deionized water to prepare a 12% sodium chloride solution, and the prepared ceramic was placed in the salt solution at 25°C for 15 days, then washed with deionized water and dried at 40°C, the ceramic surface was observed, and the weight was measured. The specific test results are shown in Table 2.

[0283] Table 2 Performance test results of the prepared ceramic

[0284] Name Acid resistance test result Alkali resistance test result Salt resistance test result Example 1 No change in surface, no change in quality No change in surface, no change in quality No change in surface, no change in quality Example 2 No change in surface, no change in quality No change in surface, no change in quality No change in surface, no change in quality Example 3 No change in surface, no change in quality No change in surface, no change in quality No change in surface, no change in quality Example 4 No change in surface, no change in quality No change in surface, no change in quality No change in surface, no change in quality Example 5 No change in surface, no change in quality No change in surface, no change in quality No change in surface, no change in quality Example 6 No change in surface, no change in quality No change in surface, no change in quality No change in surface, no change in quality Example 7 No change in surface, no change in quality No change in surface, no change in quality No change in surface, no change in quality Example 8 No change in surface, no change in quality No change in surface, no change in quality No change in surface, no change in quality Example 9 No change in surface, no change in quality No change in surface, no change in quality No change in surface, no change in quality Comparative Example 1 Ceramic edge locally appeared spot-like damage No change in surface, no change in quality No change in surface, no change in quality Comparative Example 2 Ceramic edge locally appeared spot No change in surface, no change in quality No change in surface, no change in quality Comparative Example 3 Surface locally had tiny damage points Surface locally had tiny damage points No change in surface, no change in quality

[0285] From Table 2, it can be seen that the ceramic prepared in the above example has good acid resistance, good alkali resistance, and good salt resistance.

[0286] (3) The ceramic was tested for low temperature resistance, temperature change resistance, and oxidation resistance, and the specific test process was as follows:

[0287] Low temperature resistance test: The prepared ceramic was placed at minus 50°C for 30 days, and then the ceramic surface was observed.

[0288] Temperature change resistance test: The prepared ceramic was placed at minus 50°C for 3 days, then quickly placed in boiling water for 2h, and then the ceramic surface was observed.

[0289] Oxidation resistance test: the prepared ceramic was placed in air at 60°C for 15 days, and the ceramic surface was observed after removal. The specific test results are shown in Table 3.

[0290] Table 3 Performance test results of the prepared ceramic

[0291] Name Low temperature resistance test result Temperature change resistance test result Oxidation resistance test result Example 1 No crack in surface, no change No crack in surface, no change No crack in surface, no change Example 2 No crack in surface, no change No crack in surface, no change No crack in surface, no change Example 3 No crack in surface, no change No crack in surface, no change No crack in surface, no change Example 4 No crack in surface, no change No crack in surface, no change No crack in surface, no change Example 5 No crack in surface, no change No crack in surface, no change No crack in surface, no change Example 6 No crack in surface, no change No crack in surface, no change No crack in surface, no change Example 7 No crack in surface, no change No crack in surface, no change No crack in surface, no change Example 8 No crack in surface, no change No crack in surface, no change No crack in surface, no change Example 9 No crack in surface, no change No crack in surface, no change No crack in surface, no change Comparative Example 1 Ceramic edge locally appeared crack, the rest surface had no crack Ceramic edge locally appeared crack, the rest surface had no crack No crack in surface, ceramic edge locally had tiny spot Comparative Example 2 Ceramic edge locally appeared crack, the rest surface had no crack Ceramic edge locally appeared crack, the rest surface had no crack No crack in surface, no change Comparative Example 3 Ceramic surface had tiny crack Ceramic surface had tiny crack No crack in surface, no change

[0292] As can be seen from Table 3, the ceramic prepared by the above method does not crack and damage in a low temperature environment, does not crack when the temperature changes rapidly, and the surface does not change after being placed in air, and the overall performance of the ceramic is stable.

[0293] (4) The prepared ceramic was tested for antibacterial properties using E. coli. The test method was: Antibacterial Performance of Antibacterial Ceramic Products (JC / T 897-2014).

[0294] Antibacterial property test of ceramic treated by high temperature air: the prepared ceramic was placed in an air environment at 60°C for 15 days, and the ceramic was taken out for antibacterial property test.

[0295] Antibacterial property test of ceramic treated by acid solution: the prepared ceramic was placed in a 1.5 mol / L hydrochloric acid solution at 25°C for 15 days, then washed with deionized water and dried at 40°C, and then the antibacterial property test was performed.

[0296] Antibacterial property test of ceramic treated by alkaline solution: the prepared ceramic was placed in a 1.5 mol / L sodium hydroxide solution at 25°C for 15 days, then washed with deionized water and dried at 40°C, and then the antibacterial property test was performed.

[0297] Antibacterial property test of ceramic treated by salt solution: sodium chloride was added to deionized water to prepare a 12% sodium chloride solution, and the prepared ceramic was placed in the salt solution at 25°C for 15 days, then washed with deionized water and dried at 40°C, and then the antibacterial property test was performed.

[0298] The ceramic treated by the above methods was tested for antibacterial properties, and the specific test results are shown in Table 4.

[0299] Table 4 Antibacterial property test results of the prepared ceramic

[0300] Name Antibacterial rate of untreated ceramic Antibacterial rate after air treatment Antibacterial rate after acid liquid treatment Antibacterial rate after alkali treatment Antibacterial rate after salt solution treatment Example 1 98.77 98.79 98.75 98.71 98.82 Example 2 98.94 98.91 98.98 98.97 98.95 Example 3 98.93 98.95 98.99 98.89 98.96 Example 4 98.97 98.92 98.96 98.90 99.06 Example 5 98.89 98.85 98.91 98.87 98.93 Example 6 98.93 98.98 98.95 98.89 98.96 Example 7 98.85 98.89 98.79 98.93 98.94 Example 8 98.96 98.90 98.97 98.92 98.93 Example 9 98.94 98.97 98.98 98.90 98.99 Comparative Example 1 98.87 98.90 98.84 98.91 98.89 Comparative Example 2 98.65 98.62 98.73 98.69 98.61 Comparative Example 3 94.31 92.18 91.24 91.08 92.02

[0301] From Table 4, it can be seen that the ceramics prepared in the above examples have good antibacterial properties, and the antibacterial properties of the ceramics treated by the above solution do not change substantially, which indicates that the ceramics can still maintain high antibacterial rates after use in the above environment, and also indicates that the surface of the ceramics does not change substantially after the above solution treatment. The ceramics treated by the above treatment are subjected to tensile strength and wear resistance tests after the antibacterial tests, and the tensile strength and wear resistance revolutions do not change substantially compared with the untreated ceramics.

[0302] The above is described in combination with the embodiments of the present application, but the present application is not limited to the above specific embodiments, and the above specific embodiments are only illustrative but not restrictive. Those skilled in the art can make many forms under the inspiration of the present application without departing from the purpose of the present application and the scope protected by the claims, which all belong to the protection of the present application.

Claims

1. A method for preparing environmentally friendly ceramics, characterized in that: include: Dissolving zinc nitrate, zirconium nitrate and ferric nitrate in a solvent and stirring to obtain a mixed solution; Grind and mix kaolin, illite, magnesium oxide, iron titanate, calcium titanate, titanium, silicon powder, carbon powder, and aluminum oxide, and add the mixture to the mixed solution and stir to obtain a first slurry; Taking a portion of the first slurry and adding zinc oxide and iron oxide to the taken first slurry and stirring and mixing to obtain a second slurry; Adding kaolin, zirconium oxide, boron carbide, carbon powder, boron oxide, aluminum, boron, titanium, silicon, and titanium dioxide into a dispersing solvent and stirring to obtain a third slurry; preparing a first embryonic body using a first slurry, and then coating a second slurry on the surface of the first embryonic body to obtain a second embryonic body; Place the second embryonic body in a sintering furnace, heat it to 160-220°C, and dry it in a vacuum environment for 1-2.5 hours; Then the sintering furnace is heated to 580-730℃ and sintered for 0.5-2h; After removing the second embryo from the sintering furnace, cool it down, then place the second embryo in an acidic solution for 0.5-1.5 hours, and rinse with deionized water; placing the second embryo body in the third slurry for immersion treatment for 0.5-2 hours; Then, the second embryonic body is placed in a sintering furnace and heated to 850-970°C and treated in a vacuum environment for 1-3.5 hours; Then the sintering furnace is heated to 1050-1260℃ and treated in the first treatment environment for 2-4.5h; Continue heating to 1330-1550℃ and treat in the second treatment environment for 1-3 hours; The second embryo body is then treated in nitrogen at 1100-1220° C. for 0.5-2 h; The first processing environment is a vacuum or inert environment, and the second processing environment is a vacuum or inert environment; The kaolin is modified kaolin, and the preparation method of the modified kaolin is: The kaolin is placed in an acid solution for pickling, then washed with water and dried; Grinding and mixing kaolin and zirconium to obtain a first mixture; placing the first mixture in an impregnation solution comprising barium nitrate and zirconium chloride, then adding a sodium hydroxide solution to the impregnation solution to obtain an impregnation mixture, and placing the impregnation mixture in a reaction vessel and heating it to 110-170° C. for hydrothermal treatment for 0.5-1.5 hours; After filtering, drying to obtain a dried product, mixing the dried product with aluminum and boron oxide, and then impregnating the mixture in a glucose aqueous solution, and filtering to obtain a second mixture; The second mixture is then placed in vacuum and treated at 450-550° C. for 1-2 h; The second mixture is then placed in an inert gas and treated at 1260-1350° C. for 1-3 hours, and then ground after cooling to obtain modified kaolin.

2. The preparation method according to claim 1, characterized in that The component contents in the first slurry are: 0.7-2.2 parts by weight of zinc nitrate; 0.5-1.5 parts by weight of zirconium nitrate; 0.4-1 parts by weight of ferric nitrate; 28-40 parts by weight of kaolin; 7-15 parts by weight of illite; 0.3-0.8 parts by weight of magnesium oxide; 0.8-1.5 parts by weight of iron titanate; 0.3-0.8 parts by weight of calcium titanate; Titanium 0.4-0.9 parts by weight; 0.5-1.2 parts by weight of silicon powder; 1.5-2.8 parts by weight of carbon powder; Alumina 1.5-2.3 parts by weight.

3. The preparation method according to claim 1, characterized in that The component contents in the second slurry are: The mass of zinc oxide is 3.3-5.5% of the mass of the second slurry; The mass of iron oxide is 2.5-4% of the mass of the second slurry.

4. The preparation method according to claim 1, characterized in that The component contents in the third slurry are: Kaolin 10-17 parts by weight; 0.3-0.9 parts by weight of zirconium oxide; Boron carbide 0.5-1.2 parts by weight; 1.2-2.5 parts by weight of carbon powder; 0.8-1.4 parts by weight of boron oxide; Aluminum 0.3-0.7 parts by weight; Boron 0.3-0.5 parts by weight; Titanium 0.2-0.5 parts by weight; Silicon 0.3-0.6 parts by weight; 0.4-0.8 parts by weight of titanium dioxide.

5. The preparation method according to claim 1, characterized in that The mass of zirconium in the first mixture is 1.2-3.5% of the mass of kaolin, the concentration of barium nitrate in the impregnation solution is 0.3-0.8 mol / L, and the concentration of zirconium chloride in the impregnation solution is 0.3-0.8 mol / L.

6. The preparation method according to claim 1, characterized in that In the second mixture, the mass of aluminum is 0.6-1.7% of the mass of kaolin, the mass of boron oxide is 1.5-2.8% of the mass of kaolin, and the mass concentration of the glucose solution is 25-50%.

7. An environmentally friendly ceramic, characterized in that: Prepared by the preparation method according to any one of claims 1 to 6.