CN115677219B - Antibacterial glaze, ceramic tile with high hardness, smooth glaze and antibacterial function and preparation method thereof - Google Patents
Antibacterial glaze, ceramic tile with high hardness, smooth glaze and antibacterial function and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of preparation of ceramic tiles, and discloses an antibacterial glaze, a ceramic tile with high hardness, smooth glaze and antibacterial function and a preparation method thereof, wherein the antibacterial glaze comprises the following components in parts by weight: 2-10 parts of sodium bismuthate, 2-12 parts of zinc bismuthate and 4-5 parts of zinc oxide. The zinc bismuthate and the sodium bismuthate in the antibacterial glaze form Bi after calcination 2 O 3 ZnO and Na 2 O，Bi 2 O 3 The two oxides of ZnO have stronger bactericidal effect, sodium oxide is a common component in the glaze, and the sodium oxide is used as a flux to reduce the melting temperature of the glaze, so that albite crystals and sodium glass crystalline phases are finally formed; the sodium bismuthate and the zinc bismuthate are used as the compounds to be applied to the glaze, not only can bismuth oxide and zinc oxide with antibacterial effect be formed, but also the glaze is friendly, the problems of devitrification, color change and the like of the glaze can not be caused, and Bi 2 O 3 And ZnO can be stably existing in the glaze, so that the ceramic glaze has stable antibacterial effect for a long time.
Description
Technical Field
The invention relates to the technical field of ceramics, in particular to an antibacterial glaze, a ceramic tile with high hardness, smooth glaze and antibacterial function and a preparation method thereof.
Background
With the development of ceramic tiles, ceramic products are not limited to their decorative functions, and demands for antimicrobial functions of ceramic products are also attracting attention when they are gradually applied to dining tables and tea tables by consumers. The application of the antibacterial agent enables the ceramic product to have an antibacterial function, the antibacterial agent mainly comprises an organic antibacterial agent and an inorganic antibacterial agent, the organic antibacterial agent is applied more in the textile industry, and the ceramic industry has extremely high requirements on the high temperature resistance of the antibacterial agent due to the fact that the ceramic industry needs to be sintered at high temperature. The antibacterial agent commonly used in the ceramics at present mainly comprises silver ions, copper, zinc and titanium dioxide, and mainly exists in the form of compounds or simple substances prepared from the materials, and the antibacterial agent has an antibacterial effect on bacteria surface cells by utilizing metals.
However, in the existing antibacterial agent used for ceramic tiles, silver ions are easy to volatilize in the firing process due to the problem of insufficient high temperature resistance, so that the antibacterial effect of the ceramic tiles is not stable enough. Copper as an antimicrobial agent itself has a yellow hue, and is liable to cause the glaze to have a yellow hue, thereby affecting the beauty. Titanium dioxide is used as an antibacterial agent, and the titanium dioxide has an opacifying effect, so that the devitrification of the glaze is easy to cause, and the penetration feeling is influenced. When zinc oxide is used as a main antibacterial agent, a glaze formula is required to be strictly formulated, because zinc oxide is used as a material for improving the sintering range of the glaze, zinc aluminum tip crystals with higher wear resistance are easily formed by combining with other components, and thus the antibacterial effect of zinc oxide is greatly reduced. The inorganic antibacterial agent used at present is zinc oxide, the application number is 201911241600.6, the ceramic glaze with antibacterial function disclosed in the patent with antibacterial function, the preparation method and the application thereof mainly has the antibacterial effect of zinc oxide, and the dosage of bismuth oxide and silver oxide is very small. Zinc oxide is mainly used as an antibacterial agent, and a glaze surface needs to be polished to have an antibacterial function; and the publication states that when bismuth oxide reaches more than 5%, the consumption is too low, the melting temperature of the glaze is too low, the gas is difficult to discharge in the firing process of the green body, the condition of large-area pinholes on the glaze is caused, the flatness of the glaze becomes rough, the adhesion of bacteria on the glaze is increased, meanwhile, bismuth ions stay in a glass phase, the antibacterial effect is not achieved, the antibacterial effect is seriously affected, and the antibacterial mechanism greatly limits the glaze effect of a product.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide an antibacterial glaze, a ceramic tile with high hardness, smooth glaze and antibacterial function, and aims to solve the problem that the conventional ceramic tile cannot simultaneously maintain antibacterial stability and better hardness and flatness of the glaze.
The technical scheme of the invention is as follows:
an antibacterial glaze, wherein the antibacterial glaze comprises the following components in parts by weight: 2-10 parts of sodium bismuthate, 2-12 parts of zinc bismuthate and 4-5 parts of zinc oxide.
The antibacterial glaze further comprises the following components in parts by weight: 8-15 parts of kaolin, 6-14 parts of calcite, 4-8 parts of wollastonite, 6-12 parts of dolomite, 2-5 parts of alumina, 19.5-29.5 parts of potassium feldspar, 4-8 parts of quartz and 8-16 parts of barium carbonate.
The ceramic tile with the functions of high hardness, smooth glaze and antibiosis comprises a green body layer, a ground glaze layer, a pattern layer and an antibiosis protection glaze layer which are sequentially stacked from bottom to top;
the preparation raw materials of the antibacterial protective glaze layer comprise fine powder antibacterial glaze, wherein the fine powder antibacterial glaze is obtained by crushing the antibacterial glaze after high-temperature calcination, and the particle size of the fine powder antibacterial glaze is 50-80 mu m.
The ceramic tile comprises the following preparation raw materials in parts by weight: 89-92 parts of fine powder antibacterial glaze, 7.5-10.5 parts of ball clay, 0.15-0.2 part of methyl cellulose sodium and 0.35-0.4 part of sodium tripolyphosphate.
The ceramic tile comprises the following chemical components in percentage by mass: 65.10-69.11% of silicon dioxide, 18.69-21.29% of aluminum oxide, 2.11-4.50% of potassium oxide, 1.65-2.85% of sodium oxide, 1.30-2.55% of calcium oxide, 0.82-1.66% of magnesium oxide, 0.55-0.85% of ferric oxide and trace impurities and burning reduction.
The ceramic tile comprises the following chemical components in percentage by mass: 52.23 to 54.85 percent of silicon dioxide, 24.31 to 27.40 percent of aluminum oxide, 2.33 to 3.08 percent of potassium oxide, 2.65 to 3.85 percent of sodium oxide, 2.36 to 3.53 percent of calcium oxide, 1.02 to 2.46 percent of magnesium oxide, 3.26 to 4.86 percent of zinc oxide, 4.22 to 5.84 percent of barium oxide, and the balance of trace impurities and burning.
A preparation method of a ceramic tile with high hardness, smooth glaze and antibacterial function comprises the following steps:
(1) Preparing a green body layer;
(2) Applying a primer layer on the green body layer;
(3) Ink-jet printing a pattern layer on the primer layer;
(4) An antibacterial protective glaze layer is distributed on the pattern layer, and then firing treatment is carried out, so that the ceramic tile with high hardness, smooth glaze and antibacterial function is prepared;
wherein the preparation of the antibacterial protective glaze layer in the step (4) comprises the following steps: weighing raw materials of the antibacterial glaze according to a formula, crushing and mixing to obtain a mixture, calcining the mixture at high temperature to obtain antibacterial frit, and crushing the antibacterial frit to a particle size of 50-80 mu m to obtain the fine powder antibacterial glaze; then weighing all the raw materials according to the formula of the antibacterial protective glaze layer, and performing ball milling treatment to obtain antibacterial protective glaze slurry; and the antibacterial protective glaze slurry is distributed on the pattern layer to form an antibacterial protective glaze layer.
In the preparation method, in the step of calcining the mixture at high temperature to obtain the antibacterial frit, the calcining temperature is 1350-1500 ℃.
The preparation method comprises the steps of distributing the antibacterial protective glaze slurry on the pattern layer to form an antibacterial protective glaze layer, wherein the specific gravity of the antibacterial protective glaze slurry is 1.30-1.35 g/ml, and the glazing amount is 85-90 g/m 2 。
The preparation method comprises the steps of applying an antibacterial protective glaze layer on the pattern layer and then performing firing treatment, wherein the firing temperature is 1185-1200 ℃ and the firing time is 50-60min.
The beneficial effects are that:the antibacterial glaze in the antibacterial protective glaze layer is subjected to calcination treatment in advance, and CaO and K in the antibacterial glaze are subjected to calcination 2 Various oxides such as O, znO and BaO are mixed with Al in an excessive amount 2 O 3 And SiO 2 The formed aluminosilicate combines to form anorthite, celsian and zincate spinel crystals, which not only improves the hardness and the flatness of the glaze surface, but also effectively prevents Bi 2 O 3 With Al 2 O 3 And SiO 2 The aluminosilicate formed combines to form new crystals to give Bi 2 O 3 The antibacterial function is lost, so that the antibacterial stability of the glazed surface of the ceramic tile is ensured.
Drawings
Fig. 1 is a physical XRD phase analysis chart of the ceramic tile prepared in example 1 of the present invention.
Detailed Description
The invention provides an antibacterial glaze, a ceramic tile with high hardness, smooth glaze and antibacterial function and a preparation method thereof, and the invention is further described in detail below for making the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides an antibacterial glaze, which comprises the following components in parts by weight: 2-10 parts of sodium bismuthate, 2-12 parts of zinc bismuthate and 4-5 parts of zinc oxide.
In the invention, zinc bismuthate and sodium bismuthate in the antibacterial glaze form Bi after calcination 2 O 3 ZnO and Na 2 O，Bi 2 O 3 And ZnO, sodium oxide is a common component in the glaze, and serves as a flux to reduce the melting temperature of the glaze, so that albite crystals and sodium glass crystalline phases are finally formed. The sodium bismuthate and the zinc bismuthate are used as the compounds to be applied to the glaze, not only can bismuth oxide and zinc oxide with antibacterial effect be formed, but also the glaze is friendly, the problems of devitrification, color change and the like of the glaze can not be caused, and Bi 2 O 3 And ZnO can be stably existing in the glaze, so that the ceramic glaze has stable antibacterial effect for a long time.
In some embodiments, the antimicrobial glaze further comprises, in parts by weight: 8-15 parts of kaolin, 6-14 parts of calcite, 4-8 parts of wollastonite, 6-12 parts of dolomite, 2-5 parts of alumina, 19.5-29.5 parts of potassium feldspar, 4-8 parts of quartz and 8-16 parts of barium carbonate.
In this embodiment, the chemical composition of the kaolin comprises: 40.23-44.65% of Al 2 O 3 55.01-58.99% SiO 2 The balance of trace impurities and burning loss; the chemical composition of the calcite comprises 53.40-55.50% of CaO, and the rest is burning; the chemical composition of the wollastonite comprises: 46.35-50.25% CaO,50.75-53.65% SiO 2 The balance of trace impurities and burning loss; the chemical composition of the dolomite comprises: 20.12-23.45% CaO,30.25-35.45% MgO, and the rest is burning off; the chemical composition of the potassium feldspar comprises: 13.52-15.64% of Al 2 O 3 72.56-74.35% of SiO 2 7.55-9.65% of K 2 O,1.02-2.36% Na 2 O, the balance of trace impurities and burning loss; the chemical composition of the quartz comprises 99.0-99.5% of SiO 2 The balance of trace impurities.
In this embodiment, the antimicrobial glaze provides Al 2 O 3 And SiO 2 After firing, aluminosilicate is formed, and CaO, K in the antibacterial glaze 2 Various types of materials such as O, znO, baO, etc. are used for Bi 2 O 3 The oxide with stronger activity can be combined with the aluminosilicate in an excessive mode to form anorthite, celsian and zincate spinel crystals, the anorthite crystals and the zincate spinel crystals enable the glaze to have higher hardness, the wear resistance of the glaze is ensured, the celsian crystals enable the glaze to have smooth hand feeling, and each crystal is filled in a glaze glass phase to enable the glaze to be smoother; in this example, the zinc bismuthate and sodium bismuthate form Bi after calcination 2 O 3 ZnO and Na 2 O，Bi 2 O 3 And ZnO, sodium oxide is a common component in the glaze, and serves as a flux to reduce the melting temperature of the glaze, so that albite crystals and sodium glass crystalline phases are finally formed. The sodium bismuthate and the zinc bismuthate are used as chemical agents The compound is applied to the glaze, not only can form bismuth oxide and zinc oxide with antibacterial effect, but also is friendly to the glaze, can not cause the problems of devitrification, color change and the like of the glaze, and is Bi 2 O 3 And ZnO can be stably existing in the glaze, so that the ceramic glaze has stable antibacterial effect for a long time. In this example, since there are no excessive aluminosilicate ions and Bi 2 O 3 To combine, so the Bi 2 O 3 Can be dispersed in the glaze and the glaze layer in the form of single bismuth oxide. Bi (Bi) 2 O 3 Has a cubic fluorite type structure, 1/4 oxygen ion position in the crystal lattice is vacant, and is easy to combine with water molecules in the air to promote the water molecules to form OH - And H + The positive ions and the negative ions have the function of killing bacterial cells, thereby leading the Bi to be contained 2 O 3 Has antibacterial function, and Bi in the invention 2 O 3 Evenly dispersed in the glaze layer, and has long-lasting stable antibacterial function.
In some embodiments, the invention also provides a ceramic tile with high hardness, smooth glaze and antibacterial function, wherein the ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top; the preparation raw materials of the antibacterial protective glaze layer comprise fine powder antibacterial glaze, wherein the fine powder antibacterial glaze is obtained by crushing the antibacterial glaze after high-temperature calcination, and the particle size of the fine powder antibacterial glaze is 50-80 mu m.
In the invention, the fine powder antibacterial glaze provides Al 2 O 3 And SiO 2 After firing, aluminosilicate is formed, and CaO, K in the fine powder antibacterial glaze 2 Various oxides with stronger activity such as O, znO, baO and the like are compared with Bi 2 O 3 In other words, anorthite, celsian and zincate spinel crystals can be formed by combining with the aluminosilicate in an excessive mode preferentially, the anorthite crystals and the zincate spinel crystals enable the glaze to have higher hardness, the wear resistance of the glaze is ensured, the celsian crystals enable the glaze to have smooth hand feeling, and each crystal is filled in a glaze glass phase, so that the glaze is smoother; in the present invention,the zinc bismuthate and the sodium bismuthate form Bi after calcination 2 O 3 ZnO and Na 2 O，Bi 2 O 3 And ZnO, sodium oxide is a common component in the glaze, and serves as a flux to reduce the melting temperature of the glaze, so that albite crystals and sodium glass crystalline phases are finally formed. The sodium bismuthate and the zinc bismuthate are used as the compounds to be applied to the glaze, not only can bismuth oxide and zinc oxide with antibacterial effect be formed, but also the glaze is friendly, the problems of devitrification, color change and the like of the glaze can not be caused, and Bi 2 O 3 And ZnO can be stably existing in the glaze, so that the ceramic glaze has stable antibacterial effect for a long time. In the invention, since the silicon aluminate ions are not excessive and Bi is contained 2 O 3 To combine, so the Bi 2 O 3 Can be dispersed in the glaze and the glaze layer in the form of single bismuth oxide. Bi (Bi) 2 O 3 Has a cubic fluorite type structure, 1/4 oxygen ion position in the crystal lattice is vacant, and is easy to combine with water molecules in the air to promote the water molecules to form OH - And H + The positive ions and the negative ions have the function of killing bacterial cells, thereby leading the Bi to be contained 2 O 3 Has antibacterial function, and Bi in the invention 2 O 3 Evenly dispersed in the glaze layer, and has long-lasting stable antibacterial function.
The ceramic tile provided by the invention has the main antibacterial effect of Bi 2 O 3 Contains Bi 2 O 3 The ceramic tile is prepared by combining various oxides, has lasting and efficient antibacterial function, does not need polishing, has smooth and fine glaze without being limited by antibacterial agents, has higher hardness, and can not reduce the antibacterial function due to abrasion of the glaze in the use process.
In the invention, the particle size of the fine powder antibacterial glaze is 50-80 mu m. The grain diameter of the existing fine powder antibacterial glaze is difficult to achieve below 50 mu m due to process limitation, and if the grain diameter of the fine powder antibacterial glaze is larger than 80 mu m, the fact that the antibacterial glaze is not completely calcined can lead to uneven glaze surface and affect the quality of ceramic tiles.
In some embodiments, the ceramic tile with high hardness, smooth glaze and antibacterial function, wherein the chemical composition of the green body layer comprises, in mass percent: 65.10-69.11% of silicon dioxide, 18.69-21.29% of aluminum oxide, 2.11-4.50% of potassium oxide, 1.65-2.85% of sodium oxide, 1.30-2.55% of calcium oxide, 0.82-1.66% of magnesium oxide, 0.55-0.85% of ferric oxide and trace impurities and burning reduction.
In some embodiments, the ceramic tile with high hardness, smooth glaze and antibacterial function, wherein the chemical composition of the primer layer comprises, in mass percent: 52.23 to 54.85 percent of silicon dioxide, 24.31 to 27.40 percent of aluminum oxide, 2.33 to 3.08 percent of potassium oxide, 2.65 to 3.85 percent of sodium oxide, 2.36 to 3.53 percent of calcium oxide, 1.02 to 2.46 percent of magnesium oxide, 3.26 to 4.86 percent of zinc oxide, 4.22 to 5.84 percent of barium oxide, and the balance of trace impurities and burning.
In some embodiments, there is also provided a method for preparing a ceramic tile having high hardness, smooth glaze and antimicrobial function, comprising the steps of:
(1) Preparing a green body layer;
(2) Applying a primer layer on the green body layer;
(3) Ink-jet printing a pattern layer on the primer layer;
(4) An antibacterial protective glaze layer is distributed on the pattern layer, and then firing treatment is carried out, so that the ceramic tile with high hardness, smooth glaze and antibacterial function is prepared;
wherein the preparation of the glaze layer in the step (4) comprises the following steps: weighing raw materials of the antibacterial glaze according to a formula, crushing and mixing to obtain a mixture, calcining the mixture at high temperature to obtain antibacterial frit, and crushing the antibacterial frit to a particle size of 50-80 mu m to obtain the fine powder antibacterial glaze; then weighing all the raw materials according to the formula of the antibacterial protective glaze layer, and performing ball milling treatment to obtain antibacterial protective glaze slurry; and the antibacterial protective glaze slurry is distributed on the pattern layer to form an antibacterial protective glaze layer.
The preparation method of the ceramic tile provided by the invention is simple and easy to operate, and because of CaO and K in the fine powder antibacterial glaze 2 The various oxides such as O, znO and BaO can be combined with Al in an excessive amount 2 O 3 And SiO 2 The formed aluminosilicate combines to form anorthite, celsian and zincate spinel crystals, which not only improves the hardness and the flatness of the glaze surface, but also effectively prevents Bi 2 O 3 To combine with the aluminosilicate to form new crystals to form Bi 2 O 3 The loss of the antibacterial function, that is, bi as described in the present invention 2 O 3 Can be stably and evenly dispersed in the glaze layer, thereby ensuring that the ceramic tile has a continuous and long-term stable antibacterial function.
In some embodiments, the step of applying an antimicrobial protective glaze layer over the pattern layer comprises: crushing and mixing 8-15 parts of kaolin, 6-14 parts of calcite, 4-8 parts of wollastonite, 6-12 parts of dolomite, 2-5 parts of aluminum oxide, 19.5-29.5 parts of potassium feldspar, 4-8 parts of quartz, 2-10 parts of sodium bismuthate, 2-12 parts of zinc bismuthate, 4-5 parts of zinc oxide and 8-16 parts of barium carbonate according to parts by weight to obtain a mixed material; calcining the mixed material to obtain an antibacterial frit; crushing the antibacterial frit to a particle size of 50-80 mu m to obtain a fine powder antibacterial glaze; 89-92 parts of fine powder antibacterial glaze, 7.5-10.5 parts of ball clay, 0.15-0.2 part of methyl cellulose and 0.35-0.4 part of sodium tripolyphosphate are subjected to ball milling treatment according to parts by weight to prepare antibacterial protective glaze slurry; and the antibacterial protective glaze slurry is distributed on the pattern layer to form an antibacterial protective glaze layer.
In this example, sodium bismuthate and zinc bismuthate in the mixture are calcined to form Bi 2 O 3 ZnO and Na 2 O，Bi 2 O 3 And ZnO, sodium oxide is a common component in the glaze, and serves as a flux to reduce the melting temperature of the glaze, so that albite crystals and sodium glass crystalline phases are finally formed. Al in the mixture 2 O 3 And SiO 2 Silicon aluminum formation during calcinationAn acid salt of said aluminosilicate and excess CaO, K in said mixture 2 The anorthite crystal and the gazelle spinel crystal enable the glaze to have higher hardness, so that the wear resistance of the glaze is ensured, the anorthite crystal enables the glaze to have smooth hand feeling, and each crystal is filled in the glaze glass phase to enable the glaze to be smoother; the Bi extracted from the zinc bismuthate and the sodium bismuthate 2 O 3 Since it is relatively stable and no excessive aluminosilicate ions are bound thereto, this results in Bi 2 O 3 The bismuth oxide can be dispersed in the glaze surface and the glaze layer in a single bismuth oxide form, so that the bismuth oxide has a durable stable antibacterial function.
In this example, after the antibacterial frit is produced, the antibacterial frit is continuously crushed to form a fine powder antibacterial frit having a particle size of 50-80 μm. The grain diameter of the existing fine powder antibacterial glaze is difficult to achieve below 50 mu m due to process limitation, and if the grain diameter of the fine powder antibacterial glaze is larger than 80 mu m, the fact that the antibacterial glaze is not completely calcined can lead to uneven glaze surface and affect the quality of ceramic tiles. In this example, in the step of calcining the mixture, the calcining temperature was 1350-1500 ℃.
In some embodiments, in the step of applying the antibacterial protective glaze slurry on the pattern layer to form an antibacterial protective glaze layer, the specific gravity of the antibacterial protective glaze slurry is 1.30-1.35g/ml, and the glazing amount is 85-90g/m 2 . In the embodiment, if the specific gravity of the antibacterial protective glaze slurry is smaller than 1.30g/ml, the glaze is thinner, the thickness of the glaze layer is affected, and when the glazing quantity is increased, excessive water is compensated for during glazing, so that damage defects are caused; if the specific gravity of the antibacterial protective glaze slip is greater than 1.35g/ml, the glaze is difficult to atomize, and uneven glaze spraying is caused. When the glaze amount is less than 85g/m 2 When the thickness of the glaze layer is thinner, the corresponding antibacterial components are also less, the antibacterial effect and the smoothness of the glaze surface are affected, and when the thickness is more than 90g/m 2 When the thickness of the glaze surface is increased, the cost is increased.
In some embodiments, in the step of firing after applying the antimicrobial protective glaze layer on the pattern layer, the firing temperature is 1185-1200 ℃ and the firing time is 50-60min. In this embodiment, if the firing temperature is lower than 1185, the glaze surface does not reach the mature temperature, and is in a green state, so that the effect is poor, and if the firing temperature is higher than 1200, the glaze surface is too small, more pinholes are generated, and the product is easy to absorb dirt. If the firing time is less than 50 minutes, the glaze is not sufficiently melted, has raw firing components, causes dirt absorption and uneven glaze surface, and if the firing time is more than 60 minutes, the glaze is too long, so that the overfiring of the glaze surface is caused, more defects appear, and the antibacterial effect is reduced.
The invention is further illustrated by the following examples:
example 1
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 6 parts of sodium bismuthate, 7 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 50 mu m;
preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
Spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
As can be seen from FIG. 1, the XRD phase analysis chart of the ceramic tile prepared in this example is shown in FIG. 1, and the surface of the ceramic tile contains potassium feldspar KAlSi 3 O 8 And bismuth trioxide, illustrating Bi in this example 2 O 3 The bismuth trioxide is dispersed in the glaze surface and the glaze layer in a single bismuth trioxide form, so that the ceramic tile has a durable stable antibacterial function.
Example 2
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 2 parts of sodium bismuthate, 7 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 50 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 3
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 6 parts of sodium bismuthate, 2 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 50 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 4
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 2 parts of sodium bismuthate, 2 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 50 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 5
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 10 parts of sodium bismuthate, 7 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 50 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 6
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 6 parts of sodium bismuthate, 12 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 50 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 7
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 10 parts of sodium bismuthate, 12 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 50 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 8
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 6 parts of calcite, 4 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 6 parts of sodium bismuthate, 7 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 50 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 9
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 14 parts of calcite, 8 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 6 parts of sodium bismuthate, 7 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 50 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 10
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 6 parts of sodium bismuthate, 7 parts of zinc bismuthate, 4.5 parts of zinc oxide and 8 parts of barium carbonate are selected, and after being crushed and uniformly mixed, the mixture is calcined at a high temperature of 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with a particle size of 50 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 11
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 6 parts of sodium bismuthate, 7 parts of zinc bismuthate, 4.5 parts of zinc oxide and 16 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 50 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 12
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 6 parts of sodium bismuthate, 7 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 50 mu m;
Preparation of antibacterial protective glaze slurry: 89 parts of the fine powder antibacterial glaze, 10.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for later use;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 13
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 6 parts of sodium bismuthate, 7 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 50 mu m;
Preparation of antibacterial protective glaze slurry: 92 parts of fine powder antibacterial glaze, 7.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 14
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 6 parts of sodium bismuthate, 7 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 60 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 15
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 6 parts of sodium bismuthate, 7 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 70 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 16
The ceramic tile comprises a green body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially laminated from bottom to top, and the preparation steps comprise:
preparing a fine powder antibacterial glaze: 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of aluminum oxide, 25 parts of potassium feldspar, 6 parts of quartz, 6 parts of sodium bismuthate, 7 parts of zinc bismuthate, 4.5 parts of zinc oxide and 12 parts of barium carbonate are selected, crushed and uniformly mixed, and then subjected to high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and the antibacterial frit with larger particles is crushed to form fine powder antibacterial glaze with the particle size of 80 mu m;
Preparation of antibacterial protective glaze slurry: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and antibacterial protective glaze slurry with fineness of 325 meshes, screen residue of 0.5% and specific gravity of 1.80g/ml is obtained through ball milling for standby;
manufacturing an archaized ceramic green brick body, pressing the green brick, drying to remove water, and obtaining a green body layer;
spraying ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the primer layer to obtain a pattern layer;
spraying the antibacterial protective glaze slurry on the surface of the pattern layer, adding water into the antibacterial protective glaze to adjust the specific gravity to 1.30 g/ml, and firing after the antibacterial protective glaze layer is obtained, so as to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Comparative example 1
This comparative example 1 provides a preparation method of ceramic tile, which is similar to the preparation method in example 1, the only difference being that the formulation of the fine powder antibacterial glaze in comparative example 1 contains 1 part of sodium bismuthate and 0 part of zinc bismuthate, and the other formulation compositions and steps are the same as those in example 1.
Comparative example 2
This comparative example 2 provides a preparation method of ceramic tile, which is similar to the preparation method in example 1, the only difference being that zinc bismuthate is 1 part in the formulation of the fine powder antibacterial glaze in comparative example 2, sodium bismuthate is 0 part, and other formulation compositions and steps are the same as in example 1.
Comparative example 3
This comparative example 3 provides a preparation method of ceramic tile, which is similar to the preparation method in example 1, the only difference being that 12 parts of sodium bismuthate and 14 parts of zinc bismuthate are contained in the formulation of the fine powder antimicrobial glaze in comparative example 3, and the other formulation compositions and steps are the same as those in example 1.
Comparative example 4
This comparative example 4 provides a method for producing ceramic tiles, which is similar to the method of example 1, the only difference being that calcite mainly forming anorthite is not used in the formulation of the fine powder antimicrobial glaze of comparative example 4, that is, calcite is 0 parts, and other formulation compositions and steps are the same as those of example 1.
Comparative example 5
This comparative example 5 provides a method for producing ceramic tiles, which is similar to the method of example 1, the only difference being that wollastonite which does not mainly assist in the formation of anorthite in the formulation of the fine powder antimicrobial glaze of comparative example 5, i.e., wollastonite is 0 parts, and other formulation compositions and steps are the same as in example 1.
Comparative example 6
This comparative example 6 provides a method for producing ceramic tiles, which is similar to the method of example 1, except that barium carbonate, which does not mainly form celsian in the formulation of the fine powder antibacterial glaze of comparative example 6, is used, that is, barium carbonate is 0 part, and the other formulation composition and steps are the same as those of example 1.
Comparative example 7
The comparative example 7 provides a method for preparing an antibacterial ceramic tile, which comprises spraying TiO on the surface of ceramic product 2 The antibacterial ceramic tile is obtained by using the antibacterial liquid as the main material.
Comparative example 8
This comparative example 1 provides a method for producing ceramic tiles, which is similar to the production method in example 1, the only difference being that the fine powder antibacterial glaze in comparative example 1 has a particle diameter of 90 μm.
Comparative example 9
This comparative example 1 provides a method for producing ceramic tiles, which is similar to the production method in example 1, the only difference being that the fine powder antibacterial glaze in comparative example 1 has a particle diameter of 100 μm.
Test case
1. The detection of the antibacterial performance is taken as a detection method for mainly detecting whether the ceramic tile has an antibacterial function and antibacterial durability, the detection is carried out in a Guangdong microbiological analysis detection center according to JC/T897-2014, the detection of the antibacterial durability is carried out according to GB/T9266, the washing liquid is sodium hypochlorite disinfectant with the concentration of 5%, the washing times are 500, and then the antibacterial effect is detected according to JC/T897.
According to the detection basis, the detection result evaluation results are as follows:
antibacterial properties: more than or equal to 90 percent
Antibacterial durability: more than or equal to 85 percent
The detection standard is that the data are more than or equal to the data, so that the antibacterial function is realized.
The primary detection is mainly to perform antibacterial detection and antibacterial persistence detection on escherichia coli and staphylococcus aureus.
2. The method for judging the ultra-flat and fine glaze surface comprises the steps of adopting a surface profilometer to test a numerical value, and testing the flatness of the glaze surface, wherein the smaller the numerical value is, the smoother the surface is represented; the 0.5-1.0 μm is generally judged that the glaze is fine and smooth and is more than 1.0 μm, and the larger the value is, the poorer the smoothness of the glaze is.
3. Abrasion resistance: the test was performed using the GB/T3810.7-2016 test standard.
4. The surface hardness test method is as follows: embedding the ore for testing the Mohs hardness on a pen-shaped testing tool on a metal rod, scoring the tested object by using the edge and corner of the ore of a pen point, and judging the hardness of the tested object according to whether the scratch is left or not: if the scratch is left, the hardness of the measured object is lower than that of the hardness pen, and if the scratch is not moved, the hardness of the measured object is higher than that of the hardness pen. The grade corresponding to the test material used for mohs hardness: talc: grade 1, gypsum: grade 2, calcite: grade 3, fluorite: grade 4, apatite: grade 5, feldspar: grade 6, quartz: grade 7, yellow jade: grade 8, diamond: grade 9, diamond: 10 stages.
The results obtained after the above performance tests were carried out on the ceramic tiles prepared in examples 1 to 16 and comparative examples 1 to 9 are shown in Table 1.
Table 1 ceramic tile performance test results
From the test data in Table 1, it can be seen that the antimicrobial agents sodium bismuthate and zinc bismuthate can have stable antimicrobial and antimicrobial durability properties within the scope of the present invention in practice. The formulation ratio of the fine powder antibacterial glaze is changed in comparative examples 1-2, and the antibacterial effect cannot meet the requirement. In comparative example 3, excessive antibacterial effects of sodium bismuthate and zinc bismuthate are selected, but the glaze hardness is poor and the durable antibacterial effect of the glaze is weakened due to excessive clear crystal of the glaze. Comparative example 4 does not use calcite, resulting in low glaze hardness and substandard antibacterial durability. In comparative example 5, wollastonite was not used, which resulted in insufficient glaze reaction and anorthite formation, which resulted in low glaze hardness and poor antimicrobial durability of the glaze. In comparative example 6, barium carbonate was not used, resulting in less celsian crystals, poor flatness of the glaze, uneven glaze, low wear resistance, and low antimicrobial durability of the glaze. The antibacterial agent is coated on the surface of the product in a brushing mode in comparative example 7, and the antibacterial effect is good, but the antibacterial agent has no durability and is easy to reduce in the use process of the product. The fine powder antibacterial glazes in comparative examples 8 and 9 have excessively large particle diameters, resulting in deterioration of the flatness of the glaze, and due to poor dispersibility, the antibacterial property of the ceramic plate is easily lowered relatively, and the antibacterial durability is deteriorated.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (6)
1. The fine-powder antibacterial glaze is characterized by being obtained by crushing an antibacterial glaze after high-temperature calcination at 1350-1500 ℃, wherein the particle size of the fine-powder antibacterial glaze is 50-80 mu m, and the antibacterial glaze comprises the following components in parts by weight: 2-10 parts of sodium bismuthate, 2-12 parts of zinc bismuthate, 4-5 parts of zinc oxide, 8-15 parts of kaolin, 6-14 parts of calcite, 4-8 parts of wollastonite, 6-12 parts of dolomite, 2-5 parts of aluminum oxide, 19.5-29.5 parts of potassium feldspar, 4-8 parts of quartz and 8-16 parts of barium carbonate.
2. The ceramic tile with the functions of high hardness, smooth glaze and antibiosis is characterized by comprising a green body layer, a ground glaze layer, a pattern layer and an antibiosis protection glaze layer which are sequentially stacked from bottom to top;
the antibacterial protective glaze layer is prepared from the fine powder antibacterial glaze material as claimed in claim 1.
3. The ceramic tile with high hardness, smooth glaze and antibacterial function according to claim 2, wherein the antibacterial protective glaze layer is prepared from the following raw materials in parts by weight: 89-92 parts of fine powder antibacterial glaze, 7.5-10.5 parts of ball clay, 0.15-0.2 part of methyl cellulose sodium and 0.35-0.4 part of sodium tripolyphosphate.
4. The ceramic tile with high hardness, smooth glaze and antibacterial function according to claim 2, wherein the chemical composition of the green body layer comprises, in mass percent: 65.10-69.11% of silicon dioxide, 18.69-21.29% of aluminum oxide, 2.11-4.50% of potassium oxide, 1.65-2.85% of sodium oxide, 1.30-2.55% of calcium oxide, 0.82-1.66% of magnesium oxide, 0.55-0.85% of ferric oxide and trace impurities and burning reduction.
5. The ceramic tile with high hardness, smooth glaze and antibacterial function according to claim 2, wherein the chemical composition of the primer layer comprises, in mass percent: 52.23 to 54.85 percent of silicon dioxide, 24.31 to 27.40 percent of aluminum oxide, 2.33 to 3.08 percent of potassium oxide, 2.65 to 3.85 percent of sodium oxide, 2.36 to 3.53 percent of calcium oxide, 1.02 to 2.46 percent of magnesium oxide, 3.26 to 4.86 percent of zinc oxide, 4.22 to 5.84 percent of barium oxide, and the balance of trace impurities and burning.
6. A method for producing a ceramic tile having a high hardness, a smooth glaze and an antibacterial function as claimed in any one of claims 2 to 5, comprising the steps of:
(1) Preparing a green body layer;
(2) Applying a primer layer on the green body layer;
(3) Ink-jet printing a pattern layer on the primer layer;
(4) The pattern layer is coated with an antibacterial protective glaze layer and then is subjected to firing treatment to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function, wherein the firing temperature is 1185-1200 ℃ and the firing time is 50-60min;
wherein the preparation of the antibacterial protective glaze layer in the step (4) comprises the following steps: weighing the raw materials of the antibacterial glaze according to the formula, crushing and mixing to obtain a mixture, calcining the mixture at a high temperature of 1350-1500 ℃ to obtain antibacterial frit, and crushing the antibacterial frit to a particle size of 50-80 mu m to obtain the fine powder antibacterial glaze; then weighing the raw materials according to the formula of the antibacterial protective glaze layer, and performing ball milling treatment to prepareObtaining antibacterial protective glaze slurry; the antibacterial protective glaze slurry is distributed on the pattern layer to form an antibacterial protective glaze layer, the specific gravity of the antibacterial protective glaze slurry is 1.30-1.35g/ml, and the glazing amount is 85-90g/m 2 。
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| CN104529547A (en) * | 2015-01-22 | 2015-04-22 | 南安市荣兴专利技术转移中心有限公司 | Self-cleaning antimicrobial ceramic glaze |
| CN110776257B (en) * | 2019-12-06 | 2021-11-02 | 佛山市东鹏陶瓷有限公司 | Ceramic glaze with antibacterial function and preparation method and application thereof |
| CN110981197B (en) * | 2019-12-20 | 2022-05-24 | 佛山欧神诺陶瓷有限公司 | Preparation method of wet-process dry-grain polished crystal brick and polished crystal brick |
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