CN114573375A - Zirconium silicate-containing high-wear-resistance sanitary ceramic and preparation method thereof - Google Patents
Zirconium silicate-containing high-wear-resistance sanitary ceramic and preparation method thereof Download PDFInfo
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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Abstract
The invention discloses a high wear-resistant sanitary ceramic containing zirconium silicate and a preparation method thereof, wherein during preparation, double-layer glaze is sprayed on the surface of a ceramic blank, copper powder, copper-aluminum alloy powder and basic glaze are mixed and ground to form glaze A, rare earth oxide, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze are mixed and ground to form glaze B, and the glaze A and the glaze B are sprayed on the surface of the ceramic blank in sequence; the sanitary ceramic glaze is flat, and the ceramic has excellent wear resistance and thermal shock resistance, excellent antibacterial performance, easy surface cleaning and high overall practicability.
Description
Technical Field
The invention relates to the technical field of sanitary ceramics, in particular to high-wear-resistance sanitary ceramics containing zirconium silicate and a preparation method thereof.
Background
Sanitary ware is glazed ceramic products used in places such as toilets, kitchens, laboratories and the like, is also called sanitary ware, different materials and performances can be selected according to different use environments when the sanitary ware is actually purchased, along with the continuous improvement and development of living standard, the capacity and yield of the sanitary ware industry in China are continuously increased, the domestic market demand is larger, and meanwhile, the performance requirement on the sanitary ware is higher and higher.
The wear resistance of the sanitary ceramics purchased on the market is poor, and the antibacterial property of the sanitary ceramics is difficult to last along with the longer and longer service time, which brings great influence to the practical application; in order to solve the technical problem, the application discloses a high-wear-resistance sanitary ceramic containing zirconium silicate and a preparation method thereof.
Disclosure of Invention
The invention aims to provide high-wear-resistance sanitary ceramic containing zirconium silicate and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of high-wear-resistance sanitary ceramic containing zirconium silicate comprises the following steps:
(1) taking a ceramic blank, sequentially placing the ceramic blank in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning, drying after cleaning, performing laser treatment on the surface of the ceramic blank to form a plurality of transverse grooves and longitudinal grooves which are arranged periodically, wherein the transverse grooves and the longitudinal grooves are mutually vertically staggered to form a grid structure, and performing ultrasonic cleaning and vacuum drying after laser treatment to obtain a pretreated ceramic blank;
(2) mixing copper powder, copper-aluminum alloy powder and basic glaze, ball-milling for 1-2 h by taking water as a medium, and sieving to remove iron to obtain glaze A with the fineness of 8-12 mu m; mixing rare earth oxide, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze, and ball-milling for 1-2 hours by taking water as a medium to obtain glaze B with the fineness of 6-10 microns;
and glazing the surface of the pretreated ceramic blank, spraying glaze A to form a base glaze, spraying glaze B to form a surface glaze, drying, and firing to obtain the sanitary ceramic.
According to an optimized scheme, the basic glaze comprises the following components in percentage by weight: 22-25 parts of potash feldspar, 25-30 parts of quartz powder, 2-3 parts of zinc oxide, 2-5 parts of alumina, 4-6 parts of kaolin, 8-9 parts of zirconium silicate, 3-4 parts of serpentine, 3-5 parts of 809 frit, 3-5 parts of corundum, 2-5 parts of calcined talc, 6-8 parts of calcite, 3-6 parts of dolomite, 10-12 parts of wollastonite and 0.5-1 part of magnesium oxide.
According to an optimized scheme, in the glaze A, the copper powder accounts for 20-25 wt% of the glaze A; the copper-aluminum alloy powder accounts for 15-20 wt% of the glaze A.
According to an optimized scheme, in the glaze B, the rare earth oxide accounts for 1-1.5 wt% of the glaze B; the titanium dioxide is 5-7 wt% of the glaze B; the calcium carbonate whiskers account for 3-5 wt% of the glaze B, and the calcium sulfate whiskers account for 3-5 wt% of the glaze B;
the rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, the total mass of the yttrium oxide and the neodymium oxide is M1, and the mass of the lanthanum oxide is M2, so that M1 is more than or equal to 0.5M2 and more than M2.
According to an optimized scheme, in the step (2), the titanium dioxide is surface modified titanium dioxide, and the specific preparation steps are as follows:
s1: mixing zirconium nitrate and thiourea, and adjusting the pH value to 2-3 by using dilute nitric acid to obtain a material A; mixing absolute ethyl alcohol and tetrabutyl titanate, stirring for 10-15 min, adding the material A, stirring for 10-15 min, performing hydrothermal reaction for 2-3 h at 150-155 ℃, filtering and collecting a product, drying and grinding, and transferring to 600-620 ℃ for calcining for 2-3 h to obtain doped titanium dioxide;
s2: mixing ethyl orthosilicate and ethanol, hydrolyzing for 30-40 min, adding doped titanium dioxide, stirring for 30-40 min, adding zirconium oxychloride and sodium fluoride, standing for 20-30 min, adjusting the pH to 8-9 with ammonia water, reacting for 4-6 h under the hydrothermal condition of 170-180 ℃, filtering and drying.
In the optimized scheme, in the step (1), the distance between every two adjacent transverse grooves and the distance between every two adjacent longitudinal grooves are both 0.1 mm; the depth of the transverse grooves and the depth of the longitudinal grooves are both 30-40 mu m.
According to an optimized scheme, in the step (2), the thickness of the ground glaze is 0.8-1 mm, the thickness of the overglaze is 0.2-0.3 mm, the glaze firing temperature is 1200-1250 ℃, and the glaze firing time is 15-18 h.
According to an optimized scheme, the magnesium oxide is doped magnesium oxide, and the preparation method comprises the following specific steps: taking magnesium oxide, grinding and crushing, then ball-milling for 1-2 h, sieving, adding ferrous chloride and magnesium chloride, mixing, grinding for 1-2 h, transferring the mixed material to an air atmosphere for calcining, heating to 1000-1100 ℃ at the heating rate of 4-5 ℃/min, and preserving heat for 1.5-2 h to obtain the doped magnesium oxide.
According to an optimized scheme, the sanitary ceramic is prepared by the preparation method of the high-wear-resistance sanitary ceramic containing zirconium silicate.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a high wear-resistant sanitary ceramic containing zirconium silicate and a preparation method thereof, wherein during preparation, double-layer glaze is sprayed on the surface of a ceramic blank, copper powder, copper-aluminum alloy powder and basic glaze are mixed and ground to form glaze A, rare earth oxide, titanium dioxide, calcium carbonate whisker, calcium sulfate whisker and basic glaze are mixed and ground to form glaze B, the glaze A and the glaze B are sprayed on the surface of the ceramic blank in sequence, and the sanitary ceramic containing the double-layer glaze is formed after glaze firing; the sanitary ceramic glaze is flat, and the ceramic has excellent wear resistance and thermal shock resistance, excellent antibacterial performance, easy surface cleaning and high overall practicability.
The application limits that the inner layer ceramic is 'basic glaze + copper powder + copper aluminum alloy powder', and limits the content of the copper powder and the copper aluminum alloy powder in the inner layer, and the purpose of the step is as follows: copper powder and copper-aluminum alloy powder are added into the glaze surface of the bottom layer, the hardness of the finally formed bottom glaze is lower than that of the outer-layer glaze, the inner-layer bottom glaze can be used as a buffer layer, so that a hierarchical structure with soft inside and hard outside is formed on the surface of the ceramic blank, and the design of the hierarchical structure can effectively improve the wear resistance and the thermal shock resistance of the sanitary ceramic.
On the basis of the hierarchical structure, reinforcing materials such as rare earth oxides, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and the like are introduced into the glaze B, and the introduction of the rare earth oxides can refine grains and improve the compactness of a cover glaze layer, so that the wear resistance of the sanitary ceramic is further improved; the introduction of calcium carbonate whiskers and calcium sulfate whiskers can be used as a reinforcing phase to improve the surface hardness and wear resistance of the overglaze layer and ensure the formation of an outer-layer hard structure; the introduction of titanium dioxide can improve the antibacterial performance of the sanitary ceramic, and the titanium dioxide can destroy the cell membrane structure of bacteria under the photocatalysis effect so as to realize the effects of sterilizing and inhibiting the growth of the bacteria.
On the basis of the scheme, the method is further improved, before the glaze surface is sprayed on the surface of the ceramic blank body, laser processing is carried out on the surface of the ceramic blank body to form a grid structure which is vertically staggered transversely and longitudinally, wherein a plurality of transverse grooves are periodically arranged in the vertical direction, and the distance between the transverse grooves is 0.1 mm; the plurality of longitudinal grooves are arranged periodically along the horizontal direction, the distance between the longitudinal grooves is 0.1mm, and the longitudinal grooves are mutually staggered to form a grid structure; the purpose of this step is: the grooves are formed on the surface of the ceramic through laser processing, the surface roughness of the ceramic body can be improved, so that the adhesive force between the ground glaze and the ceramic body is improved, on the other hand, the microstructure formed through laser processing can also support the glaze surface, the ground glaze and the surface glaze are sprayed after the laser processing, and the wear resistance and the thermal shock resistance of the sanitary ceramic are further improved.
On the basis of the scheme, the application further improves the scheme: when titanium dioxide is added, sulfur and zirconium doping is firstly carried out on the titanium dioxide so as to improve the photocatalytic activity of the titanium dioxide; meanwhile, the porous zirconium silicate is added into silica sol, zirconium oxychloride and sodium fluoride are added, the zirconium silicate is formed after hydrothermal reaction, and at the moment, the porous zirconium silicate is distributed around titanium dioxide and is coated, and the zirconium silicate is stable during subsequent glaze firing, so that the diffusion of glaze to the titanium dioxide can be inhibited, the influence of the glaze on the activity of the titanium dioxide is reduced, and the titanium dioxide still has excellent photocatalytic performance; on the other hand, the existence of the porous zirconium silicate can improve the adhesion property between the titanium dioxide and the glaze, the titanium dioxide is not easy to fall off, and the overall antibacterial lasting property is more excellent; the self-cleaning performance of the sanitary ceramic surface is improved, and oil stains attached to the surface of the sanitary ceramic can be effectively decomposed and removed.
Further, the magnesium oxide is subjected to iron and magnesium doping modification, the magnesium oxide is ground and crushed, then ball-milled and sieved, ferrous chloride and magnesium chloride are added, grinding and calcining are carried out, the doped magnesium oxide is added into the basic glaze, the doped magnesium oxide is added into the ground glaze and the overglaze of the ceramic body, and when the overglaze layer of the ceramic body is damaged, the magnesium oxide in the ground glaze can still ensure the antibacterial performance of the sanitary ceramic.
The invention discloses a high wear-resistant sanitary ceramic containing zirconium silicate and a preparation method thereof, the structural design is reasonable, a double-layer glaze surface is sprayed on the surface of the ceramic blank, and the sanitary ceramic containing the double-layer glaze surface is formed after glaze firing; the sanitary ceramic glaze is flat, and the ceramic has excellent wear resistance and thermal shock resistance, excellent antibacterial performance, easy surface cleaning and high overall practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the doped magnesium oxide was prepared by the following steps: taking magnesium oxide, grinding and crushing the magnesium oxide, then carrying out ball milling for 2h, sieving, adding ferrous chloride and magnesium chloride, mixing and grinding for 1.5h, transferring the mixed material to the air atmosphere for calcining, heating to 1000 ℃ at the heating rate of 5 ℃/min, and carrying out heat preservation for 2h to obtain the doped magnesium oxide.
The formula of the ceramic body is as follows: 70 wt% of aluminum oxide, 18 wt% of silicon dioxide, 0.5 wt% of calcium oxide, 0.5 wt% of magnesium oxide, 5 wt% of Suzhou kaolin, 5 wt% of calcined kaolin and 1 wt% of titanium dioxide. The blank body is prepared into a wafer ceramic blank body with the thickness of 10mm and the diameter of 70mm by adopting a dry pressing forming method.
The copper-aluminum alloy powder is Cu-0.2% Al alloy powder.
Example 1:
a preparation method of high-wear-resistance sanitary ceramic containing zirconium silicate comprises the following steps:
(1) taking a ceramic blank, sequentially placing the ceramic blank in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min, drying after cleaning, performing laser treatment on the surface of the ceramic blank to form a plurality of periodically arranged transverse grooves and longitudinal grooves, wherein the transverse grooves and the longitudinal grooves are mutually vertically staggered to form a grid structure, performing ultrasonic cleaning after laser treatment, and performing vacuum drying to obtain a pretreated ceramic blank; the distance between every two adjacent transverse grooves and the distance between every two adjacent longitudinal grooves are both 0.1 mm; the depth of the transverse grooves and the depth of the longitudinal grooves are both 30 mu m.
(2) Mixing copper powder, copper-aluminum alloy powder and basic glaze, ball-milling for 1h by taking water as a medium, and sieving to remove iron to obtain glaze A with the fineness of 10 mu m; in the glaze A, the copper powder accounts for 20 wt% of the glaze A; the copper-aluminum alloy powder accounts for 15 wt% of the glaze A.
Mixing rare earth oxide, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze, and ball-milling for 1h by taking water as a medium to obtain glaze B with the fineness of 8 mu m; the rare earth oxide accounts for 1.5 wt% of the glaze B; the titanium dioxide is 6 wt% of the glaze B; the calcium carbonate whiskers account for 5 wt% of the glaze B, and the calcium sulfate whiskers account for 5 wt% of the glaze B; the rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, wherein the total mass of the yttrium oxide and the neodymium oxide is M1, the mass of the lanthanum oxide is M2, and M1 is 0.5M 2.
And glazing the surface of the pretreated ceramic blank, spraying glaze A to form a base glaze, spraying glaze B to form a surface glaze, drying, and firing to obtain the sanitary ceramic. The thickness of the ground glaze is 1mm, the thickness of the overglaze is 0.3mm, the glaze firing temperature is 1200 ℃, and the glaze firing time is 18 h.
The basic glaze comprises the following components in percentage by weight: by weight, 22 parts of potash feldspar, 25 parts of quartz powder, 2 parts of zinc oxide, 2 parts of alumina, 4 parts of kaolin, 8 parts of zirconium silicate, 3 parts of serpentine, 3 parts of 809 fusion cake, 3 parts of corundum, 2 parts of calcined talc, 6 parts of calcite, 3 parts of dolomite, 10 parts of wollastonite and 0.5 part of magnesium oxide.
Example 2:
a preparation method of high-wear-resistance sanitary ceramic containing zirconium silicate comprises the following steps:
(1) taking a ceramic blank, sequentially placing the ceramic blank in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min, drying after cleaning, performing laser treatment on the surface of the ceramic blank to form a plurality of periodically arranged transverse grooves and longitudinal grooves, wherein the transverse grooves and the longitudinal grooves are mutually vertically staggered to form a grid structure, performing ultrasonic cleaning after laser treatment, and performing vacuum drying to obtain a pretreated ceramic blank; the space between every two adjacent transverse grooves and the space between every two adjacent longitudinal grooves are both 0.1 mm; the depth of the transverse grooves and the depth of the longitudinal grooves are both 30 mu m.
(2) Mixing copper powder, copper-aluminum alloy powder and basic glaze, ball-milling for 2 hours by taking water as a medium, and sieving to remove iron to obtain glaze A with the fineness of 10 mu m; in the glaze A, the copper powder accounts for 20 wt% of the glaze A; the copper-aluminum alloy powder is 15 wt% of the glaze A.
Mixing rare earth oxide, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze, and ball-milling for 2 hours by taking water as a medium to obtain glaze B with the fineness of 8 mu m; the rare earth oxide accounts for 1.5 wt% of the glaze B; the titanium dioxide is 6 wt% of the glaze B; the calcium carbonate whiskers account for 5 wt% of the glaze B, and the calcium sulfate whiskers account for 5 wt% of the glaze B; the rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, wherein the total mass of the yttrium oxide and the neodymium oxide is M1, the mass of the lanthanum oxide is M2, and M1 is 0.5M 2.
And glazing the surface of the pretreated ceramic blank, spraying glaze A to form a base glaze, spraying glaze B to form a surface glaze, drying, and firing to obtain the sanitary ceramic. The thickness of the ground glaze is 1mm, the thickness of the overglaze is 0.3mm, the glaze firing temperature is 1220 ℃, and the glaze firing time is 16 h.
The basic glaze comprises the following components in percentage by weight: 23 parts of potash feldspar, 28 parts of quartz powder, 2.5 parts of zinc oxide, 4 parts of alumina, 5 parts of kaolin, 8.5 parts of zirconium silicate, 3.5 parts of serpentine, 4 parts of 809 fusion cake, 4 parts of corundum, 4 parts of calcined talc, 7 parts of calcite, 5 parts of dolomite, 11 parts of wollastonite and 0.8 part of magnesium oxide.
Example 3:
a preparation method of high-wear-resistance sanitary ceramic containing zirconium silicate comprises the following steps:
(1) taking a ceramic blank, sequentially placing the ceramic blank in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min, drying after cleaning, performing laser treatment on the surface of the ceramic blank to form a plurality of transverse grooves and longitudinal grooves which are arranged periodically, wherein the transverse grooves and the longitudinal grooves are mutually vertically staggered to form a grid structure, and performing ultrasonic cleaning and vacuum drying after laser treatment to obtain a pretreated ceramic blank; the distance between every two adjacent transverse grooves and the distance between every two adjacent longitudinal grooves are both 0.1 mm; the depth of the transverse grooves and the depth of the longitudinal grooves are both 30 mu m.
(2) Mixing copper powder, copper-aluminum alloy powder and basic glaze, ball-milling for 2 hours by taking water as a medium, and sieving to remove iron to obtain glaze A with the fineness of 10 mu m; in the glaze A, the copper powder accounts for 20 wt% of the glaze A; the copper-aluminum alloy powder accounts for 15 wt% of the glaze A.
Mixing rare earth oxide, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze, and ball-milling for 2 hours by taking water as a medium to obtain glaze B with the fineness of 8 mu m; the rare earth oxide accounts for 1.5 wt% of the glaze B; the titanium dioxide accounts for 6 wt% of the glaze B; the calcium carbonate whiskers account for 5 wt% of the glaze B, and the calcium sulfate whiskers account for 5 wt% of the glaze B; the rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, wherein the total mass of the yttrium oxide and the neodymium oxide is M1, the mass of the lanthanum oxide is M2, and M1 is 0.5M 2.
And glazing the surface of the pretreated ceramic blank, spraying glaze A to form ground glaze, spraying glaze B to form overglaze, drying, and firing to obtain the sanitary ceramic. The thickness of the ground glaze is 1mm, the thickness of the surface glaze is 0.3mm, the glaze firing temperature is 1250 ℃, and the glaze firing time is 15 h.
The basic glaze comprises the following components in percentage by weight: by weight, 25 parts of potash feldspar, 30 parts of quartz powder, 3 parts of zinc oxide, 5 parts of alumina, 6 parts of kaolin, 9 parts of zirconium silicate, 4 parts of serpentine, 5 parts of 809 fusion cake, 5 parts of corundum, 5 parts of calcined talc, 8 parts of calcite, 6 parts of dolomite, 12 parts of wollastonite and 1 part of magnesium oxide.
Example 4: on the basis of example 3, the preparation method of the magnesium oxide is improved and replaced by the doped magnesium oxide, and the molar amount of the magnesium oxide, the ferrous chloride and the magnesium chloride in the doped magnesium oxide is 3: 1: 2.
a preparation method of high-wear-resistance sanitary ceramic containing zirconium silicate comprises the following steps:
(1) taking a ceramic blank, sequentially placing the ceramic blank in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min, drying after cleaning, performing laser treatment on the surface of the ceramic blank to form a plurality of transverse grooves and longitudinal grooves which are arranged periodically, wherein the transverse grooves and the longitudinal grooves are mutually vertically staggered to form a grid structure, and performing ultrasonic cleaning and vacuum drying after laser treatment to obtain a pretreated ceramic blank; the distance between every two adjacent transverse grooves and the distance between every two adjacent longitudinal grooves are both 0.1 mm; the depth of the transverse grooves and the depth of the longitudinal grooves are both 30 mu m.
(2) Mixing copper powder, copper-aluminum alloy powder and basic glaze, ball-milling for 2 hours by taking water as a medium, and sieving to remove iron to obtain glaze A with the fineness of 10 mu m; in the glaze A, the copper powder accounts for 20 wt% of the glaze A; the copper-aluminum alloy powder accounts for 15 wt% of the glaze A.
Mixing rare earth oxide, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze, and ball-milling for 2 hours by taking water as a medium to obtain glaze B with the fineness of 8 mu m; the rare earth oxide accounts for 1.5 wt% of the glaze B; the titanium dioxide is 6 wt% of the glaze B; the calcium carbonate whiskers account for 5 wt% of the glaze B, and the calcium sulfate whiskers account for 5 wt% of the glaze B; the rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, wherein the total mass of the yttrium oxide and the neodymium oxide is M1, the mass of the lanthanum oxide is M2, and M1 is 0.5M 2.
And glazing the surface of the pretreated ceramic blank, spraying glaze A to form a base glaze, spraying glaze B to form a surface glaze, drying, and firing to obtain the sanitary ceramic. The thickness of the ground glaze is 1mm, the thickness of the surface glaze is 0.3mm, the glaze firing temperature is 1250 ℃, and the glaze firing time is 15 h.
The basic glaze comprises the following components in percentage by weight: by weight, 25 parts of potash feldspar, 30 parts of quartz powder, 3 parts of zinc oxide, 5 parts of alumina, 6 parts of kaolin, 9 parts of zirconium silicate, 4 parts of serpentine, 5 parts of 809 fusion cake, 5 parts of corundum, 5 parts of calcined talc, 8 parts of calcite, 6 parts of dolomite, 12 parts of wollastonite and 1 part of doped magnesia.
Example 5: on the basis of example 4, the preparation process of titanium dioxide was modified and replaced by doped titanium dioxide.
A preparation method of high-wear-resistance sanitary ceramic containing zirconium silicate comprises the following steps:
(1) taking a ceramic blank, sequentially placing the ceramic blank in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min, drying after cleaning, performing laser treatment on the surface of the ceramic blank to form a plurality of transverse grooves and longitudinal grooves which are arranged periodically, wherein the transverse grooves and the longitudinal grooves are mutually vertically staggered to form a grid structure, and performing ultrasonic cleaning and vacuum drying after laser treatment to obtain a pretreated ceramic blank; the distance between every two adjacent transverse grooves and the distance between every two adjacent longitudinal grooves are both 0.1 mm; the depth of the transverse grooves and the depth of the longitudinal grooves are both 30 mu m.
(2) The titanium dioxide is doped titanium dioxide, and the specific preparation steps are as follows:
mixing zirconium nitrate and thiourea, and adjusting the pH value to 3 by using dilute nitric acid to obtain a material A; mixing absolute ethyl alcohol and tetrabutyl titanate, stirring for 15min, adding the material A, stirring for 15min, performing hydrothermal reaction for 3h at 150 ℃, filtering and collecting a product, drying and grinding, transferring to 600 ℃ for calcining for 2.5h to obtain doped titanium dioxide; the volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 6: 1; the zirconium nitrate is 0.1 percent of the molar weight of tetrabutyl titanate; the thiourea is 0.15 percent of the molar weight of tetrabutyl titanate.
(3) Mixing copper powder, copper-aluminum alloy powder and basic glaze, ball-milling for 2 hours by taking water as a medium, and sieving to remove iron to obtain glaze A with the fineness of 10 mu m; in the glaze A, the copper powder accounts for 20 wt% of the glaze A; the copper-aluminum alloy powder accounts for 15 wt% of the glaze A.
Mixing rare earth oxide, doped titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze, and ball-milling for 2 hours by taking water as a medium to obtain glaze B with the fineness of 8 mu m; the rare earth oxide accounts for 1.5 wt% of the glaze B; the doped titanium dioxide accounts for 6 wt% of the glaze B; the calcium carbonate whiskers account for 5 wt% of the glaze B, and the calcium sulfate whiskers account for 5 wt% of the glaze B; the rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, wherein the total mass of the yttrium oxide and the neodymium oxide is M1, the mass of the lanthanum oxide is M2, and M1 is 0.5M 2.
And glazing the surface of the pretreated ceramic blank, spraying glaze A to form a base glaze, spraying glaze B to form a surface glaze, drying, and firing to obtain the sanitary ceramic. The thickness of the ground glaze is 1mm, the thickness of the surface glaze is 0.3mm, the glaze firing temperature is 1250 ℃, and the glaze firing time is 15 h.
The basic glaze comprises the following components in percentage by weight: by weight, 25 parts of potash feldspar, 30 parts of quartz powder, 3 parts of zinc oxide, 5 parts of alumina, 6 parts of kaolin, 9 parts of zirconium silicate, 4 parts of serpentine, 5 parts of 809 fusion cake, 5 parts of corundum, 5 parts of calcined talc, 8 parts of calcite, 6 parts of dolomite, 12 parts of wollastonite and 1 part of doped magnesia.
Example 6: on the basis of example 5, the preparation process of titanium dioxide was continued to be improved and replaced by surface-coated doped titanium dioxide.
A preparation method of high-wear-resistance sanitary ceramic containing zirconium silicate comprises the following steps:
(1) taking a ceramic blank, sequentially placing the ceramic blank in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min, drying after cleaning, performing laser treatment on the surface of the ceramic blank to form a plurality of transverse grooves and longitudinal grooves which are arranged periodically, wherein the transverse grooves and the longitudinal grooves are mutually vertically staggered to form a grid structure, and performing ultrasonic cleaning and vacuum drying after laser treatment to obtain a pretreated ceramic blank; the distance between every two adjacent transverse grooves and the distance between every two adjacent longitudinal grooves are both 0.1 mm; the depth of the transverse grooves and the depth of the longitudinal grooves are both 30 mu m.
(2) The titanium dioxide is doped titanium dioxide with a coated surface, and the preparation method comprises the following specific steps:
s1: mixing zirconium nitrate and thiourea, and adjusting the pH value to 3 by using dilute nitric acid to obtain a material A; mixing absolute ethyl alcohol and tetrabutyl titanate, stirring for 15min, adding the material A, stirring for 15min, performing hydrothermal reaction for 3h at 150 ℃, filtering and collecting a product, drying and grinding, transferring to 600 ℃ for calcining for 2.5h to obtain doped titanium dioxide; the volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 6: 1; the zirconium nitrate is 0.1 percent of the molar weight of tetrabutyl titanate; the thiourea is 0.15 percent of the molar weight of tetrabutyl titanate.
S2: mixing ethyl orthosilicate and ethanol, hydrolyzing for 35min, adding doped titanium dioxide, stirring for 35min, adding zirconium oxychloride and sodium fluoride, standing for 25min, adjusting pH to 8 with ammonia water, reacting for 5h under the hydrothermal condition of 180 ℃, filtering and drying. The mass ratio of the doped titanium dioxide to the tetraethoxysilane is 3: 1, the volume ratio of the ethyl orthosilicate to the ethanol is 1: 10; the molar ratio of the zirconium oxychloride to the sodium fluoride to the tetraethoxysilane is 1: 1: 1.
(3) mixing copper powder, copper-aluminum alloy powder and basic glaze, ball-milling for 2 hours by taking water as a medium, and sieving to remove iron to obtain glaze A with the fineness of 10 mu m; in the glaze A, the copper powder accounts for 20 wt% of the glaze A; the copper-aluminum alloy powder accounts for 15 wt% of the glaze A.
Mixing rare earth oxide, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze, and ball-milling for 2 hours by taking water as a medium to obtain glaze B with the fineness of 8 mu m; the rare earth oxide accounts for 1.5 wt% of the glaze B; the titanium dioxide accounts for 6 wt% of the glaze B; the calcium carbonate whiskers account for 5 wt% of the glaze B, and the calcium sulfate whiskers account for 5 wt% of the glaze B; the rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, wherein the total mass of the yttrium oxide and the neodymium oxide is M1, the mass of the lanthanum oxide is M2, and M1 is 0.5M 2.
And glazing the surface of the pretreated ceramic blank, spraying glaze A to form a base glaze, spraying glaze B to form a surface glaze, drying, and firing to obtain the sanitary ceramic. The thickness of the ground glaze is 1mm, the thickness of the surface glaze is 0.3mm, the temperature is raised to 900 ℃ during glaze firing, the temperature is kept for 0.5h, the temperature is raised to 1250 ℃ again, and the glaze firing is carried out for 15 h.
The basic glaze comprises the following components in percentage by weight: by weight, 25 parts of potash feldspar, 30 parts of quartz powder, 3 parts of zinc oxide, 5 parts of alumina, 6 parts of kaolin, 9 parts of zirconium silicate, 4 parts of serpentine, 5 parts of 809 fusion cake, 5 parts of corundum, 5 parts of calcined talc, 8 parts of calcite, 6 parts of dolomite, 12 parts of wollastonite and 1 part of doped magnesia.
Comparative example 1: comparative example 1, which is based on example 4, adjusts the molar amount of magnesium oxide, ferrous chloride and magnesium chloride in the doped magnesium oxide to 3: 2: 1.
a preparation method of high-wear-resistance sanitary ceramic containing zirconium silicate comprises the following steps:
(1) taking a ceramic blank, sequentially placing the ceramic blank in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min, drying after cleaning, performing laser treatment on the surface of the ceramic blank to form a plurality of transverse grooves and longitudinal grooves which are arranged periodically, wherein the transverse grooves and the longitudinal grooves are mutually vertically staggered to form a grid structure, and performing ultrasonic cleaning and vacuum drying after laser treatment to obtain a pretreated ceramic blank; the distance between every two adjacent transverse grooves and the distance between every two adjacent longitudinal grooves are both 0.1 mm; the depth of the transverse grooves and the depth of the longitudinal grooves are both 30 mu m.
(2) Mixing copper powder, copper-aluminum alloy powder and basic glaze, ball-milling for 2 hours by taking water as a medium, and sieving to remove iron to obtain glaze A with the fineness of 10 mu m; in the glaze A, the copper powder accounts for 20 wt% of the glaze A; the copper-aluminum alloy powder accounts for 15 wt% of the glaze A.
Mixing rare earth oxide, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze, and ball-milling for 2 hours by taking water as a medium to obtain glaze B with the fineness of 8 mu m; the rare earth oxide accounts for 1.5 wt% of the glaze B; the titanium dioxide accounts for 6 wt% of the glaze B; the calcium carbonate whiskers account for 5 wt% of the glaze B, and the calcium sulfate whiskers account for 5 wt% of the glaze B; the rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, wherein the total mass of the yttrium oxide and the neodymium oxide is M1, the mass of the lanthanum oxide is M2, and M1 is 0.5M 2.
And glazing the surface of the pretreated ceramic blank, spraying glaze A to form a base glaze, spraying glaze B to form a surface glaze, drying, and firing to obtain the sanitary ceramic. The thickness of the ground glaze is 1mm, the thickness of the surface glaze is 0.3mm, the glaze firing temperature is 1250 ℃, and the glaze firing time is 15 h.
The basic glaze comprises the following components in percentage by weight: by weight, 25 parts of potash feldspar, 30 parts of quartz powder, 3 parts of zinc oxide, 5 parts of alumina, 6 parts of kaolin, 9 parts of zirconium silicate, 4 parts of serpentine, 5 parts of 809 fusion cake, 5 parts of corundum, 5 parts of calcined talc, 8 parts of calcite, 6 parts of dolomite, 12 parts of wollastonite and 1 part of doped magnesia.
Comparative example 2: in comparison with example 6, comparative example 2 was not laser-treated.
A preparation method of high-wear-resistance sanitary ceramic containing zirconium silicate comprises the following steps:
(1) taking a ceramic blank, sequentially placing the ceramic blank in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min, and drying after cleaning to obtain a pretreated ceramic blank;
(2) the titanium dioxide is doped titanium dioxide with a coated surface, and the preparation method comprises the following specific steps:
s1: mixing zirconium nitrate and thiourea, and adjusting the pH value to 3 by using dilute nitric acid to obtain a material A; mixing absolute ethyl alcohol and tetrabutyl titanate, stirring for 15min, adding the material A, stirring for 15min, performing hydrothermal reaction for 3h at 150 ℃, filtering and collecting a product, drying and grinding, transferring to 600 ℃ for calcining for 2.5h to obtain doped titanium dioxide; the volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 6: 1; the zirconium nitrate is 0.1 percent of the molar weight of tetrabutyl titanate; the thiourea is 0.15 percent of the molar weight of tetrabutyl titanate.
S2: mixing ethyl orthosilicate and ethanol, hydrolyzing for 35min, adding doped titanium dioxide, stirring for 35min, adding zirconium oxychloride and sodium fluoride, standing for 25min, adjusting pH to 8 with ammonia water, reacting for 5h under the hydrothermal condition of 180 ℃, filtering and drying. The mass ratio of the doped titanium dioxide to the tetraethoxysilane is 3: 1, the volume ratio of the ethyl orthosilicate to the ethanol is 1: 10; the molar ratio of zirconium oxychloride to sodium fluoride to tetraethoxysilane is 1: 1: 1.
(3) mixing copper powder, copper-aluminum alloy powder and basic glaze, ball-milling for 2 hours by taking water as a medium, and sieving to remove iron to obtain glaze A with the fineness of 10 mu m; in the glaze A, the copper powder accounts for 20 wt% of the glaze A; the copper-aluminum alloy powder accounts for 15 wt% of the glaze A.
Mixing rare earth oxide, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze, and performing ball milling for 2 hours by taking water as a medium to obtain glaze B with the fineness of 8 microns; the rare earth oxide accounts for 1.5 wt% of the glaze B; the titanium dioxide accounts for 6 wt% of the glaze B; the calcium carbonate whiskers account for 5 wt% of the glaze B, and the calcium sulfate whiskers account for 5 wt% of the glaze B; the rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, wherein the total mass of the yttrium oxide and the neodymium oxide is M1, the mass of the lanthanum oxide is M2, and M1 is 0.5M 2.
And glazing the surface of the pretreated ceramic blank, spraying glaze A to form a base glaze, spraying glaze B to form a surface glaze, drying, and firing to obtain the sanitary ceramic. The thickness of the ground glaze is 1mm, the thickness of the surface glaze is 0.3mm, the temperature is raised to 900 ℃ during glaze firing, the temperature is kept for 0.5h, the temperature is raised to 1250 ℃ again, and the glaze firing is carried out for 15 h.
The basic glaze comprises the following components in percentage by weight: by weight, 25 parts of potash feldspar, 30 parts of quartz powder, 3 parts of zinc oxide, 5 parts of alumina, 6 parts of kaolin, 9 parts of zirconium silicate, 4 parts of serpentine, 5 parts of 809 fusion cake, 5 parts of corundum, 5 parts of calcined talc, 8 parts of calcite, 6 parts of dolomite, 12 parts of wollastonite and 1 part of doped magnesia.
Comparative example 3: in contrast to example 6, the doped titania of comparative example 3 was prepared without the addition of zirconium nitrate.
A preparation method of high-wear-resistance sanitary ceramic containing zirconium silicate comprises the following steps:
(1) taking a ceramic blank, sequentially placing the ceramic blank in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min, drying after cleaning, performing laser treatment on the surface of the ceramic blank to form a plurality of transverse grooves and longitudinal grooves which are arranged periodically, wherein the transverse grooves and the longitudinal grooves are mutually vertically staggered to form a grid structure, and performing ultrasonic cleaning and vacuum drying after laser treatment to obtain a pretreated ceramic blank; the distance between every two adjacent transverse grooves and the distance between every two adjacent longitudinal grooves are both 0.1 mm; the depth of the transverse grooves and the depth of the longitudinal grooves are both 30 mu m.
(2) The titanium dioxide is doped titanium dioxide with a coated surface, and the preparation method comprises the following specific steps:
s1: mixing thiourea and dilute nitric acid, and adjusting the pH value to 3 to obtain a material A; mixing absolute ethyl alcohol and tetrabutyl titanate, stirring for 15min, adding the material A, stirring for 15min, performing hydrothermal reaction for 3h at 150 ℃, filtering and collecting a product, drying and grinding, transferring to 600 ℃ for calcining for 2.5h to obtain doped titanium dioxide; the volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 6: 1; the thiourea is 0.25% of the molar weight of tetrabutyl titanate.
S2: mixing ethyl orthosilicate and ethanol, hydrolyzing for 35min, adding doped titanium dioxide, stirring for 35min, adding zirconium oxychloride and sodium fluoride, standing for 25min, adjusting pH to 8 with ammonia water, reacting for 5h under the hydrothermal condition of 180 ℃, filtering and drying. The mass ratio of the doped titanium dioxide to the tetraethoxysilane is 3: 1, the volume ratio of the ethyl orthosilicate to the ethanol is 1: 10; the molar ratio of the zirconium oxychloride to the sodium fluoride to the tetraethoxysilane is 1: 1: 1.
(3) mixing copper powder, copper-aluminum alloy powder and basic glaze, ball-milling for 2 hours by taking water as a medium, and sieving to remove iron to obtain glaze A with the fineness of 10 mu m; in the glaze A, the copper powder accounts for 20 wt% of the glaze A; the copper-aluminum alloy powder accounts for 15 wt% of the glaze A.
Mixing rare earth oxide, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze, and performing ball milling for 2 hours by taking water as a medium to obtain glaze B with the fineness of 8 microns; the rare earth oxide accounts for 1.5 wt% of the glaze B; the titanium dioxide accounts for 6 wt% of the glaze B; the calcium carbonate whiskers account for 5 wt% of the glaze B, and the calcium sulfate whiskers account for 5 wt% of the glaze B; the rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, wherein the total mass of the yttrium oxide and the neodymium oxide is M1, the mass of the lanthanum oxide is M2, and M1 is 0.5M 2.
And glazing the surface of the pretreated ceramic blank, spraying glaze A to form a base glaze, spraying glaze B to form a surface glaze, drying, and firing to obtain the sanitary ceramic. The thickness of the ground glaze is 1mm, the thickness of the surface glaze is 0.3mm, the temperature is raised to 900 ℃ during glaze firing, the temperature is kept for 0.5h, the temperature is raised to 1250 ℃ again, and the glaze firing is carried out for 15 h.
The basic glaze comprises the following components in percentage by weight: by weight, 25 parts of potash feldspar, 30 parts of quartz powder, 3 parts of zinc oxide, 5 parts of alumina, 6 parts of kaolin, 9 parts of zirconium silicate, 4 parts of serpentine, 5 parts of 809 fusion cake, 5 parts of corundum, 5 parts of calcined talc, 8 parts of calcite, 6 parts of dolomite, 12 parts of wollastonite and 1 part of doped magnesia.
Comparative example 4: in comparison with example 6, comparative example 4 does not have glaze a sprayed on.
A preparation method of high-wear-resistance sanitary ceramic containing zirconium silicate comprises the following steps:
(1) taking a ceramic blank, sequentially placing the ceramic blank in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min, drying after cleaning, performing laser treatment on the surface of the ceramic blank to form a plurality of transverse grooves and longitudinal grooves which are arranged periodically, wherein the transverse grooves and the longitudinal grooves are mutually vertically staggered to form a grid structure, and performing ultrasonic cleaning and vacuum drying after laser treatment to obtain a pretreated ceramic blank; the distance between every two adjacent transverse grooves and the distance between every two adjacent longitudinal grooves are both 0.1 mm; the depth of the transverse grooves and the depth of the longitudinal grooves are both 30 mu m.
(2) The titanium dioxide is doped titanium dioxide with a coated surface, and the preparation method comprises the following specific steps:
s1: mixing zirconium nitrate and thiourea, and adjusting the pH value to 3 by using dilute nitric acid to obtain a material A; mixing absolute ethyl alcohol and tetrabutyl titanate, stirring for 15min, adding the material A, stirring for 15min, performing hydrothermal reaction for 3h at 150 ℃, filtering and collecting a product, drying and grinding, transferring to 600 ℃ for calcining for 2.5h to obtain doped titanium dioxide; the volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 6: 1; the zirconium nitrate is 0.1 percent of the molar weight of tetrabutyl titanate; the thiourea is 0.15 percent of the molar weight of tetrabutyl titanate.
S2: mixing ethyl orthosilicate and ethanol, hydrolyzing for 35min, adding doped titanium dioxide, stirring for 35min, adding zirconium oxychloride and sodium fluoride, standing for 25min, adjusting pH to 8 with ammonia water, reacting for 5h under the hydrothermal condition of 180 ℃, filtering and drying. The mass ratio of the doped titanium dioxide to the tetraethoxysilane is 3: 1, wherein the volume ratio of the tetraethoxysilane to the ethanol is 1: 10; the molar ratio of zirconium oxychloride to sodium fluoride to tetraethoxysilane is 1: 1: 1.
(3) mixing rare earth oxide, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze, and ball-milling for 2 hours by taking water as a medium to obtain the glaze with the fineness of 8 mu m; the rare earth oxide accounts for 1.5 wt% of the glaze; the titanium dioxide accounts for 6 wt% of the glaze; the calcium carbonate whiskers account for 5 wt% of the glaze, and the calcium sulfate whiskers account for 5 wt% of the glaze; the rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, wherein the total mass of the yttrium oxide and the neodymium oxide is M1, the mass of the lanthanum oxide is M2, and M1 is 0.5M 2.
And glazing the surface of the pretreated ceramic blank, spraying glaze to form surface glaze, drying, and firing to obtain the sanitary ceramic. The thickness of the overglaze is 1.3mm, the temperature is raised to 900 ℃ during glaze firing, the temperature is preserved for 0.5h, the temperature is raised to 1250 ℃ again, and the glaze firing is carried out for 15 h.
The basic glaze comprises the following components in percentage by weight: by weight, 25 parts of potash feldspar, 30 parts of quartz powder, 3 parts of zinc oxide, 5 parts of alumina, 6 parts of kaolin, 9 parts of zirconium silicate, 4 parts of serpentine, 5 parts of 809 fusion cake, 5 parts of corundum, 5 parts of calcined talc, 8 parts of calcite, 6 parts of dolomite, 12 parts of wollastonite and 1 part of doped magnesia.
Comparative example 5: in comparative example 5, M1 was adjusted to 0.8M2, based on the control of example 6.
The rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, wherein the total mass of the yttrium oxide and the neodymium oxide is M1, the mass of the lanthanum oxide is M2, and M1 is 0.8M 2.
Comparative example 6: based on the comparison of example 6, in comparative example 6, M1 is adjusted to 1.2M 2.
The rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, wherein the total mass of the yttrium oxide and the neodymium oxide is M1, the mass of the lanthanum oxide is M2, and M1 is 1.2M 2.
Detection experiment:
the following performance tests were performed on the wafer ceramic green body samples prepared in examples 1 to 6 and comparative examples 1 to 6:
1. and (3) antibacterial property: detecting the antibacterial property of a sample according to GB15979-2002 hygienic Standard for Disposable sanitary articles, wherein a detection strain is escherichia coli, the sample is cleaned during detection, bacterial liquid is dropwise added on the glaze surface of the sample after drying, and the test time is 24 hours; antibacterial durability was determined according to the test method disclosed in JC/T897-2014 antibacterial ceramic article antibacterial Performance.
2. Wear resistance: the wear resistance of the surface of the sample was tested according to the standard published in GB/T3810.7-2016 and the amount of wear was measured and recorded.
3. Thermal shock resistance: heating the sample to 800 ℃ at the speed of 5 ℃/min, preserving heat for 1h, then placing the sample into flowing water at room temperature for quenching, observing whether cracks exist on the surface of the sample, repeating the step until cracks appear on the surface of the sample, and recording the times.
And (4) conclusion: the ceramic glaze prepared by the invention is flat, has no pinholes, can be easily erased after the surface is marked by an oil pen, has excellent wear resistance and thermal shock resistance, excellent antibacterial property, easy surface cleaning and high overall practicability.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of high wear-resistant sanitary ceramic containing zirconium silicate is characterized by comprising the following steps: the method comprises the following steps:
(1) taking a ceramic blank, sequentially placing the ceramic blank in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning, drying after cleaning, performing laser treatment on the surface of the ceramic blank to form a plurality of transverse grooves and longitudinal grooves which are arranged periodically, wherein the transverse grooves and the longitudinal grooves are mutually vertically staggered to form a grid structure, and performing ultrasonic cleaning and vacuum drying after laser treatment to obtain a pretreated ceramic blank;
(2) mixing copper powder, copper-aluminum alloy powder and basic glaze, ball-milling for 1-2 h by taking water as a medium, and sieving to remove iron to obtain glaze A with the fineness of 8-12 mu m; mixing rare earth oxide, titanium dioxide, calcium carbonate whiskers, calcium sulfate whiskers and basic glaze, and ball-milling for 1-2 hours by taking water as a medium to obtain glaze B with the fineness of 6-10 microns;
and glazing the surface of the pretreated ceramic blank, spraying glaze A to form a base glaze, spraying glaze B to form a surface glaze, drying, and firing to obtain the sanitary ceramic.
2. The method for preparing high wear-resistant sanitary ceramic containing zirconium silicate according to claim 1, wherein the method comprises the following steps: the basic glaze comprises the following components in percentage by weight: by weight, 22-25 parts of potash feldspar, 25-30 parts of quartz powder, 2-3 parts of zinc oxide, 2-5 parts of alumina, 4-6 parts of kaolin, 8-9 parts of zirconium silicate, 3-4 parts of serpentine, 3-5 parts of 809 frit, 3-5 parts of corundum, 2-5 parts of calcined talc, 6-8 parts of calcite, 3-6 parts of dolomite, 10-12 parts of wollastonite and 0.5-1 part of magnesium oxide.
3. The method for preparing high wear-resistant sanitary ceramic containing zirconium silicate according to claim 1, wherein the method comprises the following steps: in the glaze A, the copper powder accounts for 20-25 wt% of the glaze A; the copper-aluminum alloy powder accounts for 15-20 wt% of the glaze A.
4. The method for preparing high wear-resistant sanitary ceramic containing zirconium silicate according to claim 1, wherein the method comprises the following steps: in the glaze B, the rare earth oxide accounts for 1-1.5 wt% of the glaze B; the titanium dioxide is 5-7 wt% of the glaze B; the calcium carbonate whiskers account for 3-5 wt% of the glaze B, and the calcium sulfate whiskers account for 3-5 wt% of the glaze B;
the rare earth oxide comprises lanthanum oxide, yttrium oxide and neodymium oxide, the total mass of the yttrium oxide and the neodymium oxide is M1, and the mass of the lanthanum oxide is M2, so that the rare earth oxide is 0.5M2 which is more than or equal to M1 which is more than M2.
5. The method for preparing high wear-resistant sanitary ceramic containing zirconium silicate according to claim 1, wherein the method comprises the following steps: in the step (2), the titanium dioxide is surface modified titanium dioxide, and the specific preparation steps are as follows:
s1: mixing zirconium nitrate and thiourea, and adjusting the pH value to 2-3 by using dilute nitric acid to obtain a material A; mixing absolute ethyl alcohol and tetrabutyl titanate, stirring for 10-15 min, adding the material A, stirring for 10-15 min, performing hydrothermal reaction for 2-3 h at 150-155 ℃, filtering and collecting a product, drying and grinding, and transferring to 600-620 ℃ for calcining for 2-3 h to obtain doped titanium dioxide;
s2: mixing ethyl orthosilicate and ethanol, hydrolyzing for 30-40 min, adding doped titanium dioxide, stirring for 30-40 min, adding zirconium oxychloride and sodium fluoride, standing for 20-30 min, adjusting the pH to 8-9 with ammonia water, reacting for 4-6 h under the hydrothermal condition of 170-180 ℃, filtering and drying.
6. The method for preparing high wear-resistant sanitary ceramic containing zirconium silicate according to claim 1, wherein the method comprises the following steps: in the step (1), the distance between every two adjacent transverse grooves and the distance between every two adjacent longitudinal grooves are both 0.1 mm; the depth of the transverse grooves and the depth of the longitudinal grooves are both 30-40 mu m.
7. The method for preparing high wear-resistant sanitary ceramic containing zirconium silicate according to claim 1, wherein the method comprises the following steps: in the step (2), the thickness of the ground glaze is 0.8-1 mm, the thickness of the overglaze is 0.2-0.3 mm, the glaze firing temperature is 1200-1250 ℃, and the glaze firing time is 15-18 h.
8. The method for preparing high wear-resistant sanitary ceramic containing zirconium silicate according to claim 2, wherein: the magnesium oxide is doped magnesium oxide, and the specific preparation steps are as follows: taking magnesium oxide, grinding and crushing, then ball-milling for 1-2 h, sieving, adding ferrous chloride and magnesium chloride, mixing, then grinding for 1-2 h, transferring the mixed material to an air atmosphere for calcining, heating to 1000-1100 ℃ at a heating rate of 4-5 ℃/min, and preserving heat for 1.5-2 h to obtain doped magnesium oxide.
9. The sanitary ceramic prepared by the preparation method of the high-wear-resistance sanitary ceramic containing zirconium silicate according to any one of claims 1 to 8.
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| CN115893839A (en) * | 2022-12-20 | 2023-04-04 | 箭牌家居集团股份有限公司 | Composite glaze as well as preparation method and application thereof |
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| CN117088672B (en) * | 2023-07-26 | 2024-06-04 | 桂阳县舂陵江镇柏贵陶业有限公司 | Highlight ecological glaze porcelain and preparation method thereof |
| CN117586044A (en) * | 2023-11-17 | 2024-02-23 | 潮州市欧博瓷业有限公司 | Wear-resistant antibacterial ceramic glaze and preparation method thereof |
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