CN111792913A - Wear-resistant antibacterial ceramic and processing method thereof - Google Patents
Wear-resistant antibacterial ceramic and processing method thereof Download PDFInfo
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Abstract
The invention relates to a wear-resistant antibacterial ceramic and a processing method thereof, wherein a green body is formed by firing a green body material for the first time, then glaze layers are formed on two surfaces of the green body by glazing with glaze respectively, and the green body material is obtained by firing for the second time, wherein the green body material is prepared from sodium bentonite, flint clay, pyrophyllite, dolomite and other raw materials; the glaze is prepared from raw materials such as silicon dioxide, potassium fluoroaluminate, boron oxide, barium oxide, yttrium oxide, titanium silicon co-doped graphene, large ball mud and the like; the second firing comprises three-stage heating and heat preservation and three-stage cooling, wherein the heating and heat preservation is sequentially carried out under the air atmosphere, the nitrogen atmosphere and the hydrogen atmosphere at each time, and the three-stage cooling is natural cooling, rapid cooling and natural cooling. The obtained ceramic product has excellent antibacterial performance and wear resistance, and meets the high-quality requirement of ceramics.
Description
Technical Field
The invention belongs to the technical field of ceramic processing, and relates to wear-resistant antibacterial ceramic and a processing method thereof.
Background
The ceramic is a general term of pottery and porcelain, is also an industrial art in China, and is wild and simple ancient painted pottery and black pottery in China in the age of the stone novelties. Ceramics have different textures and properties. Pottery is made of clay with high viscosity and high plasticity as main material, and has opaque, fine pores and weak hydroscopicity. The porcelain is made of clay, feldspar and quartz, is semitransparent, does not absorb water, is corrosion resistant, has hard and compact matrix, and is crisp when being knocked. The traditional ceramic handicraft in China is high in quality, beautiful in shape, high in artistic value and famous in the world.
The traditional ceramics are generated along with the requirements of people on daily life, such as tableware, tea sets, coffee sets, wine sets, vase containers used in life and the like. However, with the improvement of living standard and the expansion of ceramic application field, people put higher requirements on the quality of ceramics, such as wear resistance and antibacterial property.
Poor wear resistance directly affects the aesthetic property of the ceramic, and for ceramic products in special fields (such as ceramic knives) also directly affects the service performance, so that improvement of wear resistance is very necessary. In addition, the inner wall and the outer wall of the ceramic often have a large number of tiny micropores, the micropores are exposed outside, bacteria are easily stored, and the micropores multiply with the passage of time, which is very unfavorable for the human health contacting the ceramic, so that the improvement of the bacteriostatic performance of the ceramic is also very necessary.
In order to improve the wear resistance and bacteriostatic properties of ceramics, coating the surface of ceramics has been attempted, but this affects the indexes such as whiteness of ceramics, and the aesthetic property is deteriorated, and the coating comes off to different degrees with the extension of the storage or use time of ceramics, and even the falling off of a small area causes the wear resistance and bacteriostatic properties of ceramics to be greatly deteriorated.
Patent application CN110451924A discloses an antibacterial Dehua glutinous rice embryo white porcelain with a cavity and a manufacturing method thereof, which is prepared by taking kaolin, Longyan soil, calcined kaolin, bone meal, feldspar, dolomite, nano titanium dioxide, Dehua quartz, nano aluminum oxide, fused quartz, lithium porcelain stone, an antibacterial additive and the like as raw materials and simply mixing and firing the raw materials, wherein the compatibility among the components is poor, the strength of the obtained product is not good, the aesthetic property and the antibacterial property are also poor, and the wear resistance is poor.
Disclosure of Invention
In view of the above, the invention aims to provide a wear-resistant antibacterial ceramic and a processing method thereof, which have excellent antibacterial performance and wear resistance, good aesthetic property and good strength, and meet the high-quality requirements of ceramics.
In order to achieve the purpose, the invention provides the following technical scheme:
a processing method of wear-resistant antibacterial ceramic comprises the steps of firstly firing a blank material into a blank body by using a blank material for the first time, then glazing on two surfaces of the blank body by adopting glaze materials to form glaze layers, and carrying out secondary firing; the tire material is prepared from the following raw materials in parts by weight: 100 parts of sodium bentonite, 30-40 parts of flint clay, 12-15 parts of pyrophyllite and 5-8 parts of dolomite; the glaze is prepared from the following raw materials in parts by weight: 100 parts of silicon dioxide, 20-25 parts of potassium fluoroaluminate, 8-10 parts of boron oxide, 5-7 parts of barium oxide, 4-6 parts of yttrium oxide, 1-2 parts of titanium-silicon co-doped graphene and 0.2-0.5 part of large ball mud; the second firing comprises three-stage heating and heat preservation and three-stage cooling, wherein the heating and heat preservation is sequentially carried out under the air atmosphere, the nitrogen atmosphere and the hydrogen atmosphere at each time, and the three-stage cooling is natural cooling, rapid cooling and natural cooling.
Preferably, the preparation method of the vegetarian fetus comprises the following steps: the raw materials of the green body are respectively crushed, mixed according to the formula ratio and transferred to a ball mill, water is added to the mixture to be uniformly mixed to prepare a pug, the pug is sealed and placed for 30-35 hours, pugging is carried out to prepare blank mud, the blank mud is formed and dried, and the blank mud is put into a kiln to be fired for the first time, so that the green body is obtained.
Preferably, the process conditions of the first firing are as follows: firing at 850-890 ℃ for 8-10 hours.
Preferably, the thickness of the glaze layer is 0.2-0.4 mm.
Preferably, the preparation method of the glaze layer is as follows:
(A) weighing the raw materials according to the formula ratio, uniformly mixing, grinding, and sieving by a 60-80-mesh sieve to obtain a mixture;
(B) then smelting the mixture at 850-950 ℃ for 1-1.5 hours, then smelting at 1200-1400 ℃ for 1-2 hours, and then water quenching to obtain a block glaze;
(C) and finally, ball-milling the massive glaze material by a wet method, sieving to remove impurities to obtain glaze slip, uniformly applying the glaze slip to the inner surface and the outer surface of the biscuit, and drying until the moisture in the glaze slip is less than 1% to form a glaze layer.
Further preferably, the smelting is carried out in a box-type silicon carbide rod resistance furnace; the concentration of the glaze slip is 1.4-2.0 g/mL; the drying is drying at 60-80 ℃ or naturally airing.
Preferably, the preparation method of the titanium-silicon co-doped graphene comprises the following steps: firstly, adding titanium nitrate and heat-treated liquid polyacrylonitrile into a solvent, and uniformly stirring to obtain liquid polyacrylonitrile-coated titanium particles; then adding nano silicon powder, uniformly oscillating by ultrasonic waves, and drying at 180-220 ℃ for 5-6 hours until the solvent is completely evaporated to obtain a precursor; and finally calcining for 5-8 hours at 1800-2000 ℃ under the protection of inert atmosphere to obtain the titanium-silicon co-doped graphene.
Further preferably, the liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, and the monomer ratio is 1: 1; the relative molecular weight of the liquid polyacrylonitrile is 10000-15000.
Further preferably, the heat treatment method of the liquid polyacrylonitrile comprises the following steps: stirring liquid polyacrylonitrile at 220-230 ℃ for 15-18 hours to partially cyclize the polyacrylonitrile, then heating to 280-300 ℃, stirring for 5-6 hours to thermally oxidize the polyacrylonitrile.
Preferably, the amount of the solvent is 2-3 times of the volume of the liquid polyacrylonitrile; the solvent is a mixture of methanol, n-hexanol and deionized water, and the volume ratio of the methanol to the n-hexanol to the deionized water is 0.3-0.4: 0.1-0.2: 1.
preferably, the inert atmosphere is helium or argon, and the gas flow is 340-350 mL/min.
Preferably, the specific method of three-stage temperature rise and preservation in the second firing is as follows: firstly, heating to 900-950 ℃ at a heating rate of 20-30 ℃/min in an air atmosphere, and preserving heat for 2-3 hours; then, under the nitrogen atmosphere, heating to 1000-1100 ℃ at the heating rate of 5-8 ℃/min, and preserving heat for 30-40 min; and then heating to 1200-1220 ℃ at the heating rate of 12-14 ℃/min under the hydrogen atmosphere, and preserving the heat for 40-50 min.
Preferably, during the second firing, the three-stage cooling method comprises the following steps: stopping heating, naturally cooling to 900-1000 ℃, opening the kiln door, rapidly cooling to 600-650 ℃, closing the kiln door, and continuously naturally cooling to room temperature (25 ℃).
The wear-resistant antibacterial ceramic is obtained by the processing method.
The invention has the beneficial effects that:
the invention firstly uses the matrix material to be fired into a plain matrix for the first time, then glaze is respectively applied to the two sides of the plain matrix by adopting glaze to form a glaze layer, and the second firing is carried out, wherein the matrix material is prepared by sodium bentonite, flint clay, pyrophyllite, dolomite and other raw materials; the glaze is prepared from raw materials such as silicon dioxide, potassium fluoroaluminate, boron oxide, barium oxide, yttrium oxide, titanium silicon co-doped graphene, large ball mud and the like; the second firing comprises three-stage heating and heat preservation and three-stage cooling, wherein the heating and heat preservation is sequentially carried out under the air atmosphere, the nitrogen atmosphere and the hydrogen atmosphere at each time, and the three-stage cooling is natural cooling, rapid cooling and natural cooling. The obtained ceramic product has excellent antibacterial performance and wear resistance, and meets the high-quality requirement of ceramics.
In the raw materials of the base material, the sodium bentonite has good plasticity, exquisite porcelain quality, soft color, good transmittance, collision resistance and certain mechanical strength; the flint clay is hard and compact in structure; the pyrophyllite is low in aluminum and high in silicon, has small expansion characteristic, and is beneficial to densification of ceramics; dolomite has a fluxing action to further promote densification. The raw materials are combined in a soft and hard mode to form a mullite phase with proper composition, so that the mechanical property is improved, the raw material is more compact, the surface is compact and exquisite, the uniform coating of a glaze layer is facilitated, and the glossiness of the glaze surface is improved.
When the glaze layer is prepared, the used raw materials mainly comprise silicon dioxide, fluorine in potassium fluoroaluminate forms a silicon-fluorine bond with silicate in the matrix material in the firing process, so that the composite strength of the matrix material and the glaze material is improved, and the wear resistance is improved; the boron oxide and the barium oxide have strong fluxing property, and the combination of the boron oxide and the barium oxide greatly reduces the viscosity of the system, is beneficial to the refinement of glaze and improves the wear resistance of the product; the yttrium oxide has special refractive power to light, and is beneficial to improving the glossiness of a glaze surface; in addition, barium, yttrium and titanium contained in the barium oxide, yttrium oxide and titanium silicon co-doped graphene can deform protein, so that bacteria lose activity in a replication process, and a sterilization effect is achieved. The raw materials of the glaze also contain large ball clay which is pure white, has few impurities, has the content of alumina more than 35 percent and the content of silica more than 41 percent, further improves the glossiness of the glaze surface and is beneficial to improving the wear resistance of the product.
The second firing comprises three-stage heating and heat preservation and three-stage cooling, wherein the heating and heat preservation is sequentially carried out in air atmosphere, nitrogen atmosphere and hydrogen atmosphere each time, so that the raw materials in the glaze are uniformly combined, and the glossiness and the wear resistance of the glaze are improved; and the atmosphere is air at first, which is beneficial to the full bonding of the glaze layer and the plain tire, then the atmosphere is changed into nitrogen, the formation of nitrides such as boron nitride is promoted, the wear resistance of the product is improved, and finally the atmosphere is hydrogen, and the reducing atmosphere can avoid the formation of colored oxides, so that the whiteness and the glossiness of the product are ensured. The three-section type cooling is natural cooling, rapid cooling and natural cooling, further improves the evenness of the glaze layer, and is beneficial to further improving the glossiness and the wear resistance of the glaze surface.
Detailed Description
The preferred embodiments of the present invention will be described in detail below.
Example 1:
a processing method of wear-resistant antibacterial ceramic comprises the steps of firstly firing a blank material into a blank body by using a blank material for the first time, then glazing on two surfaces of the blank body by adopting glaze materials to form glaze layers, and carrying out secondary firing; the tire material is prepared from the following raw materials in parts by weight: 100 parts of sodium bentonite, 30 parts of flint clay, 15 parts of pyrophyllite and 5 parts of dolomite; the glaze is prepared from the following raw materials in parts by weight: 100 parts of silicon dioxide, 25 parts of potassium fluoroaluminate, 8 parts of boron oxide, 7 parts of barium oxide, 4 parts of yttrium oxide, 2 parts of titanium-silicon co-doped graphene and 0.2 part of large ball mud; the second firing comprises three-stage heating and heat preservation and three-stage cooling, wherein the heating and heat preservation is sequentially carried out under the air atmosphere, the nitrogen atmosphere and the hydrogen atmosphere at each time, and the three-stage cooling is natural cooling, rapid cooling and natural cooling.
The preparation method of the plain embryo comprises the following steps: respectively crushing the raw materials of the green body, mixing according to the formula ratio, transferring to a ball mill, adding water, uniformly mixing to prepare a pug, sealing, standing for 35 hours, pugging to prepare a blank mud, forming, drying, and putting into a kiln for primary firing to obtain the green body.
The process conditions for the first firing are as follows: firing at 850 ℃ for 10 hours.
The thickness of the glaze layer is 0.2 mm.
The preparation method of the glaze layer comprises the following steps:
(A) weighing the raw materials according to the formula ratio, uniformly mixing, grinding, and sieving with a 80-mesh sieve to obtain a mixture;
(B) then smelting the mixture for 1.5 hours at 850 ℃, then smelting for 2 hours at 1200 ℃, and then quenching with water to obtain a massive glaze;
(C) and finally, ball-milling the massive glaze material by a wet method, sieving to remove impurities to obtain glaze slip, uniformly applying the glaze slip to the inner surface and the outer surface of the biscuit, and drying until the moisture in the glaze slip is less than 1% to form a glaze layer.
The smelting is carried out in a box-type silicon carbide rod resistance furnace; the concentration of the glaze slip is 1.4 g/mL; the drying is drying at 80 ℃ or naturally airing.
The preparation method of the titanium-silicon co-doped graphene comprises the following steps: firstly, adding titanium nitrate and heat-treated liquid polyacrylonitrile into a solvent, and uniformly stirring to obtain liquid polyacrylonitrile-coated titanium particles; then adding nano silicon powder, uniformly oscillating by ultrasonic waves, and drying at 180 ℃ for 6 hours until the solvent is completely evaporated to obtain a precursor; and finally calcining for 8 hours at 1800 ℃ under the protection of inert atmosphere to obtain the titanium-silicon co-doped graphene.
The liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, and the monomer ratio is 1: 1; the liquid polyacrylonitrile has a relative molecular weight of 10000.
The heat treatment method of the liquid polyacrylonitrile comprises the following steps: the liquid polyacrylonitrile was stirred at 230 ℃ for 15 hours to partially cyclize it, then heated to 300 ℃ and stirred for 5 hours to thermally oxidize it.
The dosage of the solvent is 3 times of the volume of the liquid polyacrylonitrile; the solvent is a mixture of methanol, n-hexanol and deionized water, and the volume ratio of the methanol to the n-hexanol to the deionized water is 0.3: 0.2: 1.
the inert atmosphere was helium and the gas flow was 340 mL/min.
During the second firing, the specific method of three-stage temperature rise and preservation is as follows: firstly, heating to 900 ℃ at the heating rate of 30 ℃/min in the air atmosphere, and preserving heat for 3 hours; then heating to 1100 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, and preserving the heat for 30 minutes; then, the temperature is raised to 1200 ℃ at a heating rate of 14 ℃/min under a hydrogen atmosphere, and the temperature is maintained for 50 min.
During the second firing, the specific three-stage cooling method is as follows: stopping heating, naturally cooling to 900 deg.C, opening kiln door, rapidly cooling to 650 deg.C, closing kiln door, and continuously naturally cooling to room temperature (25 deg.C).
The wear-resistant antibacterial ceramic is obtained by the processing method.
Example 2:
a processing method of wear-resistant antibacterial ceramic comprises the steps of firstly firing a blank material into a blank body by using a blank material for the first time, then glazing on two surfaces of the blank body by adopting glaze materials to form glaze layers, and carrying out secondary firing; the tire material is prepared from the following raw materials in parts by weight: 100 parts of sodium bentonite, 40 parts of flint clay, 12 parts of pyrophyllite and 8 parts of dolomite; the glaze is prepared from the following raw materials in parts by weight: 100 parts of silicon dioxide, 20 parts of potassium fluoroaluminate, 10 parts of boron oxide, 5 parts of barium oxide, 6 parts of yttrium oxide, 1 part of titanium-silicon co-doped graphene and 0.5 part of large ball mud; the second firing comprises three-stage heating and heat preservation and three-stage cooling, wherein the heating and heat preservation is sequentially carried out under the air atmosphere, the nitrogen atmosphere and the hydrogen atmosphere at each time, and the three-stage cooling is natural cooling, rapid cooling and natural cooling.
The preparation method of the plain embryo comprises the following steps: the raw materials of the green body are respectively crushed, mixed according to the formula ratio and transferred to a ball mill, water is added to the mixture to be uniformly mixed to prepare a pug, the pug is sealed and placed for 30 hours, pugging is carried out to prepare a blank mud, the blank mud is formed and dried, and the blank mud is put into a kiln to be fired for the first time, so that the green body is obtained.
The process conditions for the first firing are as follows: firing at 890 ℃ for 8 hours.
The thickness of the glaze layer is 0.4 mm.
The preparation method of the glaze layer comprises the following steps:
(A) weighing the raw materials according to the formula ratio, uniformly mixing, grinding, and sieving by a 60-mesh sieve to obtain a mixture;
(B) then smelting the mixture for 1 hour at 950 ℃, then smelting for 1 hour at 1400 ℃, and then water quenching to obtain a massive glaze;
(C) and finally, ball-milling the massive glaze material by a wet method, sieving to remove impurities to obtain glaze slip, uniformly applying the glaze slip to the inner surface and the outer surface of the biscuit, and drying until the moisture in the glaze slip is less than 1% to form a glaze layer.
The smelting is carried out in a box-type silicon carbide rod resistance furnace; the concentration of the glaze slip is 2.0 g/mL; the drying is drying at 60 ℃ or naturally airing.
The preparation method of the titanium-silicon co-doped graphene comprises the following steps: firstly, adding titanium nitrate and heat-treated liquid polyacrylonitrile into a solvent, and uniformly stirring to obtain liquid polyacrylonitrile-coated titanium particles; then adding nano silicon powder, uniformly oscillating by ultrasonic waves, and drying at 220 ℃ for 5 hours until the solvent is completely evaporated to obtain a precursor; and finally calcining for 5 hours at 2000 ℃ under the protection of inert atmosphere to obtain the titanium-silicon co-doped graphene.
The liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, and the monomer ratio is 1: 1; the relative molecular weight of the liquid polyacrylonitrile was 15000.
The heat treatment method of the liquid polyacrylonitrile comprises the following steps: the liquid polyacrylonitrile was stirred at 220 ℃ for 18 hours to partially cyclize it, then heated to 280 ℃ and stirred for 6 hours to thermally oxidize it.
The dosage of the solvent is 2 times of the volume of the liquid polyacrylonitrile; the solvent is a mixture of methanol, n-hexanol and deionized water, and the volume ratio of the methanol to the n-hexanol to the deionized water is 0.4: 0.1: 1.
the inert atmosphere was argon and the gas flow was 350 mL/min.
During the second firing, the specific method of three-stage temperature rise and preservation is as follows: firstly, heating to 950 ℃ at the heating rate of 20 ℃/min in the air atmosphere, and preserving heat for 2 hours; then, under the nitrogen atmosphere, heating to 1000 ℃ at the heating rate of 8 ℃/min, and preserving heat for 40 min; then, the temperature is increased to 1220 ℃ at the temperature increasing rate of 12 ℃/min under the hydrogen atmosphere, and the temperature is preserved for 40 min.
During the second firing, the specific three-stage cooling method is as follows: stopping heating, naturally cooling to 1000 deg.C, opening kiln door, rapidly cooling to 600 deg.C, closing kiln door, and continuously naturally cooling to room temperature (25 deg.C).
The wear-resistant antibacterial ceramic is obtained by the processing method.
Example 3:
a processing method of wear-resistant antibacterial ceramic comprises the steps of firstly firing a blank material into a blank body by using a blank material for the first time, then glazing on two surfaces of the blank body by adopting glaze materials to form glaze layers, and carrying out secondary firing; the tire material is prepared from the following raw materials in parts by weight: 100 parts of sodium bentonite, 35 parts of flint clay, 13 parts of pyrophyllite and 6 parts of dolomite; the glaze is prepared from the following raw materials in parts by weight: 100 parts of silicon dioxide, 22 parts of potassium fluoroaluminate, 9 parts of boron oxide, 6 parts of barium oxide, 5 parts of yttrium oxide, 1.5 parts of titanium-silicon co-doped graphene and 0.4 part of large ball mud; the second firing comprises three-stage heating and heat preservation and three-stage cooling, wherein the heating and heat preservation is sequentially carried out under the air atmosphere, the nitrogen atmosphere and the hydrogen atmosphere at each time, and the three-stage cooling is natural cooling, rapid cooling and natural cooling.
The preparation method of the plain embryo comprises the following steps: respectively crushing the raw materials of the green body, mixing according to the formula ratio, transferring to a ball mill, adding water, uniformly mixing to prepare a pug, sealing, standing for 33 hours, pugging to prepare a blank mud, forming, drying, and putting into a kiln for primary firing to obtain the green body.
The process conditions for the first firing are as follows: firing at 860 ℃ for 9 hours.
The thickness of the glaze layer is 0.3 mm.
The preparation method of the glaze layer comprises the following steps:
(A) weighing the raw materials according to the formula ratio, uniformly mixing, grinding, and sieving with a 70-mesh sieve to obtain a mixture;
(B) then smelting the mixture for 1.5 hours at 900 ℃, then smelting for 1.5 hours at 1300 ℃, and then water quenching to obtain a massive glaze;
(C) and finally, ball-milling the massive glaze material by a wet method, sieving to remove impurities to obtain glaze slip, uniformly applying the glaze slip to the inner surface and the outer surface of the biscuit, and drying until the moisture in the glaze slip is less than 1% to form a glaze layer.
The smelting is carried out in a box-type silicon carbide rod resistance furnace; the concentration of the glaze slip is 1.8 g/mL; the drying is drying at 70 ℃ or naturally airing.
The preparation method of the titanium-silicon co-doped graphene comprises the following steps: firstly, adding titanium nitrate and heat-treated liquid polyacrylonitrile into a solvent, and uniformly stirring to obtain liquid polyacrylonitrile-coated titanium particles; then adding nano silicon powder, uniformly oscillating by ultrasonic waves, and drying for 5 hours at 200 ℃ until the solvent is completely evaporated to obtain a precursor; and finally calcining for 7 hours at 1900 ℃ under the protection of inert atmosphere to obtain the titanium-silicon co-doped graphene.
The liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, and the monomer ratio is 1: 1; the liquid polyacrylonitrile had a relative molecular weight of 12000.
The heat treatment method of the liquid polyacrylonitrile comprises the following steps: the liquid polyacrylonitrile was stirred at 225 ℃ for 17 hours to partially cyclize it, then heated to 290 ℃ and stirred for 5 hours to thermally oxidize it.
The dosage of the solvent is 3 times of the volume of the liquid polyacrylonitrile; the solvent is a mixture of methanol, n-hexanol and deionized water, and the volume ratio of the methanol to the n-hexanol to the deionized water is 0.35: 0.15: 1.
the inert atmosphere is helium or argon, and the gas flow is 345 mL/min.
During the second firing, the specific method of three-stage temperature rise and preservation is as follows: firstly, heating to 920 ℃ at the heating rate of 25 ℃/min in the air atmosphere, and preserving heat for 2.5 hours; then, under the nitrogen atmosphere, heating to 1050 ℃ at the heating rate of 7 ℃/min, and preserving the heat for 35 min; then, the temperature is raised to 1210 ℃ at the heating rate of 13 ℃/min under the hydrogen atmosphere, and the temperature is kept for 45 min.
During the second firing, the specific three-stage cooling method is as follows: stopping heating, naturally cooling to 950 deg.C, opening kiln door, rapidly cooling to 630 deg.C, closing kiln door, and naturally cooling to room temperature (25 deg.C).
The wear-resistant antibacterial ceramic is obtained by the processing method.
Comparative example 1
A ceramic processing method comprises the steps of firstly firing a green body by using a body material for the first time, then glazing on two surfaces of the green body by adopting glaze to form a glaze layer, and firing for the second time; the tire material is prepared from the following raw materials in parts by weight: 100 parts of sodium bentonite, 30 parts of flint clay and 5 parts of dolomite; the glaze is prepared from the following raw materials in parts by weight: 100 parts of silicon dioxide, 25 parts of potassium fluoroaluminate, 8 parts of boron oxide, 7 parts of barium oxide, 4 parts of yttrium oxide, 2 parts of titanium-silicon co-doped graphene and 0.2 part of large ball mud; the second firing comprises three-stage heating and heat preservation and three-stage cooling, wherein the heating and heat preservation is sequentially carried out under the air atmosphere, the nitrogen atmosphere and the hydrogen atmosphere at each time, and the three-stage cooling is natural cooling, rapid cooling and natural cooling.
The preparation method of the plain embryo comprises the following steps: respectively crushing the raw materials of the green body, mixing according to the formula ratio, transferring to a ball mill, adding water, uniformly mixing to prepare a pug, sealing, standing for 35 hours, pugging to prepare a blank mud, forming, drying, and putting into a kiln for primary firing to obtain the green body.
The process conditions for the first firing are as follows: firing at 850 ℃ for 10 hours.
The thickness of the glaze layer is 0.2 mm.
The preparation method of the glaze layer comprises the following steps:
(A) weighing the raw materials according to the formula ratio, uniformly mixing, grinding, and sieving with a 80-mesh sieve to obtain a mixture;
(B) then smelting the mixture for 1.5 hours at 850 ℃, then smelting for 2 hours at 1200 ℃, and then quenching with water to obtain a massive glaze;
(C) and finally, ball-milling the massive glaze material by a wet method, sieving to remove impurities to obtain glaze slip, uniformly applying the glaze slip to the inner surface and the outer surface of the biscuit, and drying until the moisture in the glaze slip is less than 1% to form a glaze layer.
The smelting is carried out in a box-type silicon carbide rod resistance furnace; the concentration of the glaze slip is 1.4 g/mL; the drying is drying at 80 ℃ or naturally airing.
The preparation method of the titanium-silicon co-doped graphene comprises the following steps: firstly, adding titanium nitrate and heat-treated liquid polyacrylonitrile into a solvent, and uniformly stirring to obtain liquid polyacrylonitrile-coated titanium particles; then adding nano silicon powder, uniformly oscillating by ultrasonic waves, and drying at 180 ℃ for 6 hours until the solvent is completely evaporated to obtain a precursor; and finally calcining for 8 hours at 1800 ℃ under the protection of inert atmosphere to obtain the titanium-silicon co-doped graphene.
The liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, and the monomer ratio is 1: 1; the liquid polyacrylonitrile has a relative molecular weight of 10000.
The heat treatment method of the liquid polyacrylonitrile comprises the following steps: the liquid polyacrylonitrile was stirred at 230 ℃ for 15 hours to partially cyclize it, then heated to 300 ℃ and stirred for 5 hours to thermally oxidize it.
The dosage of the solvent is 3 times of the volume of the liquid polyacrylonitrile; the solvent is a mixture of methanol, n-hexanol and deionized water, and the volume ratio of the methanol to the n-hexanol to the deionized water is 0.3: 0.2: 1.
the inert atmosphere was helium and the gas flow was 340 mL/min.
During the second firing, the specific method of three-stage temperature rise and preservation is as follows: firstly, heating to 900 ℃ at the heating rate of 30 ℃/min in the air atmosphere, and preserving heat for 3 hours; then heating to 1100 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, and preserving the heat for 30 minutes; then, the temperature is raised to 1200 ℃ at a heating rate of 14 ℃/min under a hydrogen atmosphere, and the temperature is maintained for 50 min.
During the second firing, the specific three-stage cooling method is as follows: stopping heating, naturally cooling to 900 deg.C, opening kiln door, rapidly cooling to 650 deg.C, closing kiln door, and continuously naturally cooling to room temperature (25 deg.C).
Comparative example 2
A ceramic processing method comprises the steps of firstly firing a green body by using a body material for the first time, then glazing on two surfaces of the green body by adopting glaze to form a glaze layer, and firing for the second time; the tire material is prepared from the following raw materials in parts by weight: 100 parts of sodium bentonite, 30 parts of flint clay, 15 parts of pyrophyllite and 5 parts of dolomite; the glaze is prepared from the following raw materials in parts by weight: 100 parts of silicon dioxide, 25 parts of potassium fluoroaluminate, 8 parts of boron oxide, 7 parts of barium oxide, 4 parts of yttrium oxide, 2 parts of graphene and 0.2 part of large ball mud; the second firing comprises three-stage heating and heat preservation and three-stage cooling, wherein the heating and heat preservation is sequentially carried out under the air atmosphere, the nitrogen atmosphere and the hydrogen atmosphere at each time, and the three-stage cooling is natural cooling, rapid cooling and natural cooling.
The preparation method of the plain embryo comprises the following steps: respectively crushing the raw materials of the green body, mixing according to the formula ratio, transferring to a ball mill, adding water, uniformly mixing to prepare a pug, sealing, standing for 35 hours, pugging to prepare a blank mud, forming, drying, and putting into a kiln for primary firing to obtain the green body.
The process conditions for the first firing are as follows: firing at 850 ℃ for 10 hours.
The thickness of the glaze layer is 0.2 mm.
The preparation method of the glaze layer comprises the following steps:
(A) weighing the raw materials according to the formula ratio, uniformly mixing, grinding, and sieving with a 80-mesh sieve to obtain a mixture;
(B) then smelting the mixture for 1.5 hours at 850 ℃, then smelting for 2 hours at 1200 ℃, and then quenching with water to obtain a massive glaze;
(C) and finally, ball-milling the massive glaze material by a wet method, sieving to remove impurities to obtain glaze slip, uniformly applying the glaze slip to the inner surface and the outer surface of the biscuit, and drying until the moisture in the glaze slip is less than 1% to form a glaze layer.
The smelting is carried out in a box-type silicon carbide rod resistance furnace; the concentration of the glaze slip is 1.4 g/mL; the drying is drying at 80 ℃ or naturally airing.
During the second firing, the specific method of three-stage temperature rise and preservation is as follows: firstly, heating to 900 ℃ at the heating rate of 30 ℃/min in the air atmosphere, and preserving heat for 3 hours; then heating to 1100 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, and preserving the heat for 30 minutes; then, the temperature is raised to 1200 ℃ at a heating rate of 14 ℃/min under a hydrogen atmosphere, and the temperature is maintained for 50 min.
During the second firing, the specific three-stage cooling method is as follows: stopping heating, naturally cooling to 900 deg.C, opening kiln door, rapidly cooling to 650 deg.C, closing kiln door, and continuously naturally cooling to room temperature (25 deg.C).
Comparative example 3
A ceramic processing method comprises the steps of firstly firing a green body by using a body material for the first time, then glazing on two surfaces of the green body by adopting glaze to form a glaze layer, and firing for the second time; the tire material is prepared from the following raw materials in parts by weight: 100 parts of sodium bentonite, 30 parts of flint clay, 15 parts of pyrophyllite and 5 parts of dolomite; the glaze is prepared from the following raw materials in parts by weight: 100 parts of silicon dioxide, 25 parts of potassium fluoroaluminate, 8 parts of boron oxide, 7 parts of barium oxide, 4 parts of yttrium oxide, 2 parts of titanium-silicon co-doped graphene and 0.2 part of large ball mud; the second firing comprises three-stage heating and heat preservation and three-stage cooling, wherein the heating and heat preservation is sequentially carried out under the air atmosphere, the air atmosphere and the hydrogen atmosphere at each time, and the three-stage cooling is natural cooling, rapid cooling and natural cooling.
The preparation method of the plain embryo comprises the following steps: respectively crushing the raw materials of the green body, mixing according to the formula ratio, transferring to a ball mill, adding water, uniformly mixing to prepare a pug, sealing, standing for 35 hours, pugging to prepare a blank mud, forming, drying, and putting into a kiln for primary firing to obtain the green body.
The process conditions for the first firing are as follows: firing at 850 ℃ for 10 hours.
The thickness of the glaze layer is 0.2 mm.
The preparation method of the glaze layer comprises the following steps:
(A) weighing the raw materials according to the formula ratio, uniformly mixing, grinding, and sieving with a 80-mesh sieve to obtain a mixture;
(B) then smelting the mixture for 1.5 hours at 850 ℃, then smelting for 2 hours at 1200 ℃, and then quenching with water to obtain a massive glaze;
(C) and finally, ball-milling the massive glaze material by a wet method, sieving to remove impurities to obtain glaze slip, uniformly applying the glaze slip to the inner surface and the outer surface of the biscuit, and drying until the moisture in the glaze slip is less than 1% to form a glaze layer.
The smelting is carried out in a box-type silicon carbide rod resistance furnace; the concentration of the glaze slip is 1.4 g/mL; the drying is drying at 80 ℃ or naturally airing.
The preparation method of the titanium-silicon co-doped graphene comprises the following steps: firstly, adding titanium nitrate and heat-treated liquid polyacrylonitrile into a solvent, and uniformly stirring to obtain liquid polyacrylonitrile-coated titanium particles; then adding nano silicon powder, uniformly oscillating by ultrasonic waves, and drying at 180 ℃ for 6 hours until the solvent is completely evaporated to obtain a precursor; and finally calcining for 8 hours at 1800 ℃ under the protection of inert atmosphere to obtain the titanium-silicon co-doped graphene.
The liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, and the monomer ratio is 1: 1; the liquid polyacrylonitrile has a relative molecular weight of 10000.
The heat treatment method of the liquid polyacrylonitrile comprises the following steps: the liquid polyacrylonitrile was stirred at 230 ℃ for 15 hours to partially cyclize it, then heated to 300 ℃ and stirred for 5 hours to thermally oxidize it.
The dosage of the solvent is 3 times of the volume of the liquid polyacrylonitrile; the solvent is a mixture of methanol, n-hexanol and deionized water, and the volume ratio of the methanol to the n-hexanol to the deionized water is 0.3: 0.2: 1.
the inert atmosphere was helium and the gas flow was 340 mL/min.
During the second firing, the specific method of three-stage temperature rise and preservation is as follows: firstly, heating to 900 ℃ at the heating rate of 30 ℃/min in the air atmosphere, and preserving heat for 3 hours; then heating to 1100 ℃ at the heating rate of 5 ℃/min in the air atmosphere, and preserving the heat for 30 min; then, the temperature is raised to 1200 ℃ at a heating rate of 14 ℃/min under a hydrogen atmosphere, and the temperature is maintained for 50 min.
During the second firing, the specific three-stage cooling method is as follows: stopping heating, naturally cooling to 900 deg.C, opening kiln door, rapidly cooling to 650 deg.C, closing kiln door, and continuously naturally cooling to room temperature (25 deg.C).
Test examples
The performance of the porcelain obtained in examples 1-3 and comparative examples 1-3 was tested, including antibacterial activity, whiteness, gloss, abrasion resistance, etc., and the results are shown in table 1.
The antibacterial activity is detected by referring to JC/T897-2014, and the whiteness and the glossiness are detected by referring to GB/T3532-2009.
The method for detecting the wear resistance comprises the following steps: the abrasion degree R is used as a medium, a sample of 1cm multiplied by 1cm is placed on a JZ7502 sand wheel wet abrasion tester, a TL80 No. R2A. B250 atmosphere pore tissue green silicon carbide grinding wheel is adopted, the sample is ground by a 300-turn grinding process at a rotating speed of 98R/min under the condition that the load is 40N, the abrasion loss of the sample per unit area is measured, and the abrasion loss is calculated by the following formula: r ═ M1-M2)/S, where M1 is the pre-mill mass (g) of the sample; m2 is the milled mass (g) of the sample; s is the ground area (cm) of the sample2). The test values are expressed as arithmetic mean and variance of several groups of samples.
TABLE 1 Performance test results
| Whiteness (degree) | Glaze glossiness (%) | Escherichia coli inhibitory rate (%) | Abrasion resistance (g/cm)2) | |
| Example 1 | 94 | 96 | 99.6 | 0.05 |
| Example 2 | 93 | 95 | 99.5 | 0.04 |
| Example 3 | 95 | 97 | 99.6 | 0.03 |
| Comparative example 1 | 90 | 92 | 99.5 | 0.05 |
| Comparative example 2 | 92 | 95 | 97.8 | 0.59 |
| Comparative example 3 | 93 | 94 | 98.9 | 1.02 |
As can be seen from Table 1, the ceramics obtained in the embodiments 1-3 have excellent whiteness and glaze glossiness, high Escherichia coli inhibition rate and good wear resistance, and meet the high-quality requirements of ceramics. In the padding of the comparative example 1, pyrophyllite is omitted, the whiteness and the glossiness of the product are obviously deteriorated, which shows that the whiteness and the glossiness of the product are influenced by the compactness of the padding; the glaze material of the comparative example 2 replaces titanium silicon co-doped graphene with graphene, and the antibacterial property, the wear resistance and the like of the ceramic are obviously deteriorated, which shows that the improvement of the antibacterial effect of the undoped graphene is limited, and the uniform dispersion in a system is influenced, so that various performances such as the wear resistance and the like are influenced; comparative example 3 the nitrogen atmosphere was replaced by an air atmosphere during the second firing, which affected the formation of nitrides and, in turn, the indexes of wear resistance.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (9)
1. The processing method of the wear-resistant antibacterial ceramic is characterized in that a green body is formed by firing a body material for the first time, then glaze layers are formed on two surfaces of the green body by glazing with glaze respectively, and the green body is fired for the second time; the tire material is prepared from the following raw materials in parts by weight: 100 parts of sodium bentonite, 30-40 parts of flint clay, 12-15 parts of pyrophyllite and 5-8 parts of dolomite; the glaze is prepared from the following raw materials in parts by weight: 100 parts of silicon dioxide, 20-25 parts of potassium fluoroaluminate, 8-10 parts of boron oxide, 5-7 parts of barium oxide, 4-6 parts of yttrium oxide, 1-2 parts of titanium-silicon co-doped graphene and 0.2-0.5 part of large ball mud; the second firing comprises three-stage heating and heat preservation and three-stage cooling, wherein the heating and heat preservation is sequentially carried out under the air atmosphere, the nitrogen atmosphere and the hydrogen atmosphere at each time, and the three-stage cooling is natural cooling, rapid cooling and natural cooling.
2. The process according to claim 1, characterized in that the green tyre is prepared as follows: the raw materials of the green body are respectively crushed, mixed according to the formula ratio and transferred to a ball mill, water is added to the mixture to be uniformly mixed to prepare a pug, the pug is sealed and placed for 30-35 hours, pugging is carried out to prepare blank mud, the blank mud is formed and dried, and the blank mud is put into a kiln to be fired for the first time, so that the green body is obtained.
3. The processing method according to claim 1, wherein the process conditions of the first firing are as follows: firing at 850-890 ℃ for 8-10 hours.
4. The method according to claim 1, wherein the glaze layer has a thickness of 0.2 to 0.4 mm.
5. The process according to claim 1, characterized in that said enamel layer is prepared as follows:
(A) weighing the raw materials according to the formula ratio, uniformly mixing, grinding, and sieving by a 60-80-mesh sieve to obtain a mixture;
(B) then smelting the mixture at 850-950 ℃ for 1-1.5 hours, then smelting at 1200-1400 ℃ for 1-2 hours, and then water quenching to obtain a block glaze;
(C) and finally, ball-milling the massive glaze material by a wet method, sieving to remove impurities to obtain glaze slip, uniformly applying the glaze slip to the inner surface and the outer surface of the biscuit, and drying until the moisture in the glaze slip is less than 1% to form a glaze layer.
6. The processing method according to claim 1, wherein the preparation method of the titanium-silicon co-doped graphene is as follows: firstly, adding titanium nitrate and heat-treated liquid polyacrylonitrile into a solvent, and uniformly stirring to obtain liquid polyacrylonitrile-coated titanium particles; then adding nano silicon powder, uniformly oscillating by ultrasonic waves, and drying at 180-220 ℃ for 5-6 hours until the solvent is completely evaporated to obtain a precursor; and finally calcining for 5-8 hours at 1800-2000 ℃ under the protection of inert atmosphere to obtain the titanium-silicon co-doped graphene.
7. The processing method according to claim 1, wherein the specific method of three-stage heating and heat preservation in the second firing is as follows: firstly, heating to 900-950 ℃ at a heating rate of 20-30 ℃/min in an air atmosphere, and preserving heat for 2-3 hours; then, under the nitrogen atmosphere, heating to 1000-1100 ℃ at the heating rate of 5-8 ℃/min, and preserving heat for 30-40 min; and then heating to 1200-1220 ℃ at the heating rate of 12-14 ℃/min under the hydrogen atmosphere, and preserving the heat for 40-50 min.
8. The processing method according to claim 1, wherein the three-stage cooling is performed in the second firing by the following specific method: stopping heating, naturally cooling to 900-1000 ℃, opening the kiln door, rapidly cooling to 600-650 ℃, closing the kiln door, and continuously naturally cooling to room temperature.
9. An abrasion-resistant bacteriostatic ceramic obtained by the processing method of any one of claims 1-8.
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