CN115677219A - Antibacterial glaze, ceramic tile with high hardness, smooth glaze surface and antibacterial function and preparation method of ceramic tile - Google Patents
Antibacterial glaze, ceramic tile with high hardness, smooth glaze surface and antibacterial function and preparation method of ceramic tile Download PDFInfo
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Abstract
The invention relates to the technical field of ceramic tile preparation, and discloses an antibacterial glaze material, a ceramic tile with high hardness, a smooth glaze surface and an antibacterial function and a preparation method thereof, wherein the antibacterial glaze material 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 material form Bi after being calcined 2 O 3 ZnO and Na 2 O，Bi 2 O 3 The oxides of the components and ZnO have stronger bactericidal action, and sodium oxide is a commonly used component in the glaze and used as a flux to reduce the melting temperature of the glaze, so that albite crystals and sodium glass crystal phases are finally formed; what is needed isThe sodium bismuthate and the zinc bismuthate are used as compounds to be applied to glaze, so that the antibacterial bismuth oxide and zinc oxide can be formed, the glaze is friendly, the problems of glaze devitrification, color change and the like can not be caused, and the Bi is 2 O 3 And ZnO can stably exist 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 material, a ceramic tile with high hardness, a smooth glaze surface and an antibacterial function and a preparation method thereof.
Background
With the development of ceramic wall and floor tiles, ceramic products are not limited to their decoration functions, and when the ceramic products are gradually applied to areas such as dining tables and tea tables by consumers, the requirements for the antibacterial function of the ceramic products are also concerned. The antibacterial agent is mainly composed of an organic antibacterial agent and an inorganic antibacterial agent, the organic antibacterial agent is widely applied 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 fired at high temperature. The commonly used antibacterial agents of the existing ceramics mainly comprise silver ions, copper, zinc and titanium dioxide, and mainly exist in the form of compounds or simple substances prepared from the materials, and the metal is utilized to kill and kill bacteria surface layer cells to play an antibacterial role.
However, in the current antibacterial agents 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 antibacterial agent has yellow color tone, and the glaze surface is easily caused to have yellow color tone, thereby affecting the appearance. Titanium dioxide is used as an antibacterial agent, and has the function of opacification, so that the glaze surface is easy to lose transparency, and the transparency is influenced. When the zinc oxide is used as a main antibacterial agent, a glaze formula needs to be strictly established, and as the zinc oxide is used as a material for generally improving the sintering range of the glaze, the zinc oxide is easily combined with other components to form a zinc-aluminum sharp crystal with higher wear resistance, so that the antibacterial effect of the zinc oxide is greatly reduced. The currently used relatively mature inorganic antibacterial agent is zinc oxide, and the antibacterial ceramic glaze disclosed in the patent with the application number of 201911241600.6, namely ceramic glaze with antibacterial function, preparation method and application thereof, mainly has the antibacterial effect of zinc oxide, and the dosage of bismuth oxide and silver oxide is very small. The method mainly depends on zinc oxide as an antibacterial agent, and the glaze surface is required to be polished to have an antibacterial function; moreover, the patent discloses that when the bismuth oxide reaches more than 5%, the melting temperature of the glaze is too low due to excessive use amount, gas is difficult to discharge in the firing process of a blank body, the glaze surface has large-area pinholes, the smoothness of the glaze surface becomes rough, the adhesion of bacteria on the glaze surface is increased, meanwhile, bismuth ions stay in a glass phase, the antibacterial effect cannot be achieved, the antibacterial effect is seriously influenced, and the glaze surface effect of a product is greatly limited by the antibacterial mechanism.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an antibacterial glaze material, a ceramic tile with high hardness, a smooth glaze surface and an antibacterial function, and aims to solve the problems that the existing ceramic tile cannot simultaneously maintain the stability of antibacterial performance and the better hardness and the better flatness of the glaze surface.
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.
A ceramic tile with high hardness, flat glaze and antibacterial function comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top;
the raw materials for preparing the antibacterial protective glaze layer comprise fine powder antibacterial glaze, 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 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 sodium methyl cellulose and 0.35-0.4 part of sodium tripolyphosphate.
The ceramic tile, wherein the chemical composition of the green body layer comprises, in mass percent: 65.10 to 8978 percent of silicon dioxide, 18.69 to 21.29 percent of aluminum oxide, 2.11 to 4.50 percent of potassium oxide, 1.65 to 2.85 percent of sodium oxide, 1.30 to 2.55 percent of calcium oxide, 0.82 to 1.66 percent of magnesium oxide, 0.55 to 0.85 percent of ferric oxide, and the balance of trace impurities and ignition loss.
The ceramic tile is characterized in that the chemical composition of the ground glaze layer comprises the following components in percentage by mass: 3238-3262 of silica, 24.31-27.40 of alumina, 2.33-3.08 of potassium oxide, 2.65-3.85 of sodium oxide, 2.36-3.53 of calcium oxide, 1.02-2.46 of magnesium oxide, 3.26-4.86 of zinc oxide, 4.22-5.84 of barium oxide, and the balance of trace impurities and ignition loss.
A preparation method of a ceramic tile with high hardness, flat glaze and antibacterial function comprises the following steps:
(1) Preparing a green body layer;
(2) Applying a ground glaze layer on the blank layer;
(3) Ink-jet printing a pattern layer on the ground coat layer;
(4) After the antibacterial protective glaze layer is distributed on the pattern layer, firing treatment is carried out to prepare the ceramic tile with high hardness, smooth glaze surface and antibacterial function;
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, then calcining the mixture at high temperature to obtain antibacterial frit, crushing the antibacterial frit to the particle size of 50-80 mu m to obtain fine powder antibacterial glaze; then weighing all the raw materials according to the formula of the antibacterial protective glaze layer, and carrying out ball milling treatment to prepare antibacterial protective glaze slurry; and spreading the antibacterial protective glaze slip on the pattern layer to form an antibacterial protective glaze layer.
The preparation method comprises the step of calcining the mixture at high temperature to obtain the antibacterial frit, wherein the calcining temperature is 1350-1500 ℃.
The preparation method comprises the step of forming the antibacterial protective glaze layer by applying the antibacterial protective glaze slip on the pattern layer, wherein the antibacterial protective glaze slip has the specific gravity of 1.30-1.35g/ml and the glazing amount of 85-90g/m 2 。
The preparation method comprises the step of firing after the antibacterial protective glaze layer is coated on the pattern layer, wherein the firing temperature is 1185-1200 ℃, and the firing time is 50-60min.
Has the advantages that: the antibacterial glaze in the antibacterial protective glaze layer is calcined in advance, and CaO and K in the antibacterial glaze are calcined 2 Various oxides such as O, znO and BaO are mixed with Al in excess 2 O 3 And SiO 2 The formed aluminosilicate is combined to form anorthite, celsian and zinc-aluminum spinel crystals, which not only improves the hardness and the flatness of the glaze surface, but also effectively prevents Bi 2 O 3 Same as Al 2 O 3 And SiO 2 The formed aluminosilicate combines to form new crystals to enable Bi 2 O 3 The antibacterial function is lost, thereby ensuring the antibacterial stability of the glaze surface of the ceramic tile.
Drawings
FIG. 1 is a physical XRD phase analysis of the ceramic tile made in example 1 of the present invention.
Detailed Description
The invention provides an antibacterial glaze material, a ceramic tile with high hardness, flat glaze and antibacterial function and a preparation method thereof, and the invention is further detailed below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit 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, the zinc bismuthate and the sodium bismuthate in the antibacterial glaze form Bi after being calcined 2 O 3 ZnO and Na 2 O，Bi 2 O 3 And ZnO have stronger bactericidal action, and sodium oxide is a commonly used component in the glaze and used as a flux to reduce the melting temperature of the glaze, and finally forms albite crystals and sodium glass crystal phases. The sodium bismuthate and the zinc bismuthate are applied to the glaze as compounds, so that the antibacterial bismuth oxide and the antibacterial zinc oxide can be formed, the glaze is friendly, the problems of devitrification, color change and the like of the glaze are avoided, and the Bi is 2 O 3 And ZnO can stably exist 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 example, the chemical composition of the kaolin includes: 40.23-44.65% Al 2 O 3 55.01-58.99% SiO 2 The rest is trace impurities and ignition loss; the chemical composition of the calcite comprises 53.40-55.50% CaO, and the balance is causticization; the chemical composition of the wollastonite comprises: 46.35-50.25% CaO,50.75-53.65% SiO 2 The rest is trace impurities and scorching; the chemical composition of the dolomite comprises: 20.12 to 23.45 percent of CaO,30.25 to 35.45 percent of MgO, and the balance of ignition loss; the chemical composition of the potassium feldspar comprises: 13.52-15.64% of Al 2 O 3 72.56-74.35% SiO 2 7.55-9.65% of K 2 O,1.02-2.36% of Na 2 O, and trace impurities and ignition loss in the rest; the chemical composition of the quartz comprises 99.0-99.5% of SiO 2 And the balance of trace impurities.
In this embodiment, the antibacterial glaze provides Al 2 O 3 And SiO 2 Forming aluminosilicate after firing, and CaO, K in antibacterial glaze 2 O, znO, baO, etc. in a plurality of proportions relative to Bi 2 O 3 The more active oxide can be combined with the aluminosilicate to form anorthite, celsian and zinc-aluminum spinel crystals in an excessive manner preferentiallyThe feldspar crystal and the zinc-aluminum spinel crystal enable the glaze to have higher hardness, the wear resistance of the glaze is guaranteed, the barium feldspar crystal enables the glaze to have smooth hand feeling, and the crystals are filled in the glass phase of the glaze, so that the glaze is smoother; in this example, 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 have stronger bactericidal action, and sodium oxide is a commonly used component in the glaze and used as a flux to reduce the melting temperature of the glaze, and finally forms albite crystals and sodium glass crystal phases. The sodium bismuthate and the zinc bismuthate are applied to the glaze as compounds, so that the antibacterial bismuth oxide and the antibacterial zinc oxide can be formed, the glaze is friendly, the problems of devitrification, color change and the like of the glaze are avoided, and the Bi is 2 O 3 And ZnO can stably exist in the glaze, so that the ceramic glaze has stable antibacterial effect for a long time. In this example, since there is no excessive aluminosilicate ion and Bi 2 O 3 Are combined, so that said Bi 2 O 3 Can be dispersed in the glaze surface and the glaze layer in the form of single bismuth oxide. Bi 2 O 3 Has a cubic fluorite structure, has 1/4 oxygen ion positions in crystal lattices which are vacant, is easily combined with water molecules in the air, and promotes the water molecules to form OH - And H + The positive ions and the negative ions have a bactericidal effect on bacterial cells, so that Bi is contained 2 O 3 The glaze material has an antibacterial function, and the Bi in the invention 2 O 3 Uniformly dispersed in the glaze layer, and has lasting and long-term stable antibacterial function.
In some embodiments, the invention also provides a ceramic tile with high hardness, flat glaze and antibacterial function, wherein the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top; the raw materials for preparing the antibacterial protective glaze layer comprise fine powder antibacterial glaze, wherein the fine powder antibacterial glaze is obtained by calcining the antibacterial glaze at high temperature and then crushing, and the particle size of the fine powder antibacterial glaze is 50-80 mu m.
In the present invention, the fine powder is resistant toAl provided by bacterial glaze 2 O 3 And SiO 2 Forming aluminosilicate after firing, and fine powder of CaO, K in antibacterial glaze 2 More active oxides such as O, znO and BaO relative to Bi 2 O 3 In other words, the crystal can be preferentially combined with the aluminosilicate in an excessive way to form anorthite, celsian and zinc-aluminum spinel crystals, the anorthite crystal and the zinc-aluminum spinel crystal enable the glaze to have higher hardness and ensure the wear resistance of the glaze, the celsian crystal enables the glaze to have smooth hand feeling, and the crystals are filled in a glaze glass phase to enable the glaze to be smoother; in the 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 have stronger bactericidal action, and sodium oxide is a commonly used component in the glaze and used as a flux to reduce the melting temperature of the glaze, and finally forms albite crystals and sodium glass crystal phases. The sodium bismuthate and the zinc bismuthate are applied to the glaze as compounds, can form bismuth oxide and zinc oxide with antibacterial effect, is friendly to the glaze, and can not cause the problems of devitrification, discoloration and the like of the glaze, and the Bi is 2 O 3 And ZnO can stably exist in the glaze, so that the ceramic glaze has stable antibacterial effect for a long time. In the invention, since there is not too much aluminosilicate ion and Bi 2 O 3 Are combined, so that said Bi 2 O 3 Can be dispersed in the glaze surface and the glaze layer in the form of single bismuth oxide. Bi 2 O 3 Has a cubic fluorite structure, has 1/4 oxygen ion positions in crystal lattices which are vacant, is easily combined with water molecules in the air, and promotes the water molecules to form OH - And H + The positive ions and the negative ions have a bactericidal effect on bacterial cells, so that Bi is contained 2 O 3 The glaze of (3) has an antibacterial function, and Bi in the invention 2 O 3 Uniformly dispersed in the glaze layer, and has lasting and long-term stable antibacterial function.
The ceramic tile provided by the invention has the main antibacterial effect that Bi plays a role 2 O 3 Containing Bi 2 O 3 Enamel layer of (A) for Escherichia coli and Staphylococcus aureusThe ceramic tile is prepared by combining various oxides, has lasting and efficient antibacterial function, has the same antibacterial function as a ceramic glaze surface without polishing, is smooth and fine, is not limited by an antibacterial agent, has higher hardness, and does not reduce the antibacterial function due to abrasion of the glaze surface in the using process.
In the present invention, the particle size of the fine powder antibacterial glaze is 50-80 μm. The particle size of the existing fine powder antibacterial glaze is difficult to realize below 50 mu m due to process limitation, and if the particle size of the fine powder antibacterial glaze is more than 80 mu m, the condition that the calcination of the antibacterial glaze is incomplete causes the unsmooth glaze surface and influences the quality of ceramic tiles is shown.
In some embodiments, the ceramic tile with high hardness, smooth glaze and antibacterial function, wherein the chemical composition of the green body layer comprises, by mass percent: 65.10 to 8978 percent of silicon dioxide, 18.69 to 21.29 percent of aluminum oxide, 2.11 to 4.50 percent of potassium oxide, 1.65 to 2.85 percent of sodium oxide, 1.30 to 2.55 percent of calcium oxide, 0.82 to 1.66 percent of magnesium oxide, 0.55 to 0.85 percent of ferric oxide, and the balance of trace impurities and ignition loss.
In some embodiments, the ceramic tile with high hardness, smooth glaze and antibacterial function, wherein the chemical composition of the ground glaze layer comprises the following components in percentage by mass: 3238-3262 of silica, 24.31-27.40 of alumina, 2.33-3.08 of potassium oxide, 2.65-3.85 of sodium oxide, 2.36-3.53 of calcium oxide, 1.02-2.46 of magnesium oxide, 3.26-4.86 of zinc oxide, 4.22-5.84 of barium oxide, and the balance of trace impurities and ignition loss.
In some embodiments, there is also provided a method for preparing a ceramic tile having high hardness, a smooth glaze surface, and an antibacterial function, comprising the steps of:
(1) Preparing a green body layer;
(2) Applying a ground glaze layer on the blank layer;
(3) Ink-jet printing a pattern layer on the ground coat layer;
(4) After the antibacterial protective glaze layer is distributed on the pattern layer, firing treatment is carried out to prepare the ceramic tile with high hardness, smooth glaze surface and antibacterial function;
wherein the preparation of the 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, then calcining the mixture at high temperature to obtain antibacterial frit, crushing the antibacterial frit to the particle size of 50-80 mu m to obtain fine powder antibacterial glaze; then weighing all the raw materials according to the formula of the antibacterial protective glaze layer, and carrying out ball milling treatment to prepare antibacterial protective glaze slurry; and spreading the antibacterial protective glaze slip 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 the CaO and K in the fine powder antibacterial glaze are 2 Various oxides such as O, znO and BaO may be used in excess with Al 2 O 3 And SiO 2 The formed aluminosilicate is combined to form anorthite, celsian and zinc-aluminum spinel crystals, which not only improves the hardness and the flatness of the glaze surface, but also effectively prevents Bi 2 O 3 Bi is combined with the aluminosilicate to form new crystals 2 O 3 Lose the antibacterial function, that is, bi described in the present invention 2 O 3 Can be stably and uniformly dispersed in the glaze layer, thereby ensuring that the ceramic tile has a lasting and long-term stable antibacterial function.
In some embodiments, the step of applying an antimicrobial protective glaze layer on 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 alumina, 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 the particle size of 50-80 mu m to obtain fine powder antibacterial glaze; performing ball milling treatment on 89-92 parts by weight of fine powder antibacterial glaze, 7.5-10.5 parts by weight of ball clay, 0.15-0.2 part by weight of sodium methylcellulose and 0.35-0.4 part by weight of sodium tripolyphosphate to prepare antibacterial protective glaze slurry; and spreading the antibacterial protective glaze slip on the pattern layer to form an antibacterial protective glaze layer.
In this example, sodium bismuthate and zinc bismuthate in the mixture were calcined to form Bi 2 O 3 ZnO and Na 2 O，Bi 2 O 3 And ZnO have stronger bactericidal action, and sodium oxide is a commonly used component in the glaze and used as a flux to reduce the melting temperature of the glaze, and finally forms albite crystals and soda glass crystal phases. Al in the mixture 2 O 3 And SiO 2 Forming aluminosilicates during calcination, said aluminosilicates having excess CaO, K in said combined material 2 Various oxides such as O, znO, baO and the like are combined to form anorthite, celsian and zinc-aluminum spinel crystals, the anorthite and zinc-aluminum spinel crystals enable the glaze to have higher hardness and ensure the wear resistance of the glaze, the celsian crystals enable the glaze to have smooth hand feeling, and the crystals are filled in a glaze glass phase to enable the glaze to be smoother; bi extracted from the zinc bismuthate and the sodium bismuthate 2 O 3 This makes Bi stable and does not have excessive aluminosilicate ions bound to it 2 O 3 Can be dispersed in the glaze surface and the glaze layer in a single bismuth oxide form, thereby having lasting and long-lasting stable antibacterial function.
In this example, the antibacterial frit was produced and then crushed to form a fine powder antibacterial frit having a particle size of 50 to 80 μm. The particle size of the existing fine powder antibacterial glaze is difficult to realize below 50 mu m due to process limitation, and if the particle size of the fine powder antibacterial glaze is more than 80 mu m, the sintering of the antibacterial glaze is incomplete, so that the glaze surface is unsmooth, and the quality of the ceramic tile is influenced. In this example, in the step of subjecting the mixed material to calcination treatment, the calcination temperature was 1350 to 1500 ℃.
In some embodiments, in the step of applying the antibacterial protective glaze slip on the pattern layer to form the antibacterial protective glaze layer, the antibacterial protective glaze slip has a specific gravity of 1.30-1.35g/ml and a glazing amount of 85-90g/m 2 . In this embodiment, if the specific gravity of the antibacterial protective glaze slip is less than 1.30g/ml, the glaze material is thin and affects the glazeThe thickness of the layer is increased, and the defect of damage caused by excessive moisture during glazing is compensated by increasing the glazing amount; if the specific gravity of the antibacterial protective glaze slip is more than 1.35g/ml, the glaze is difficult to atomize, and the glaze spraying is not uniform. When the glaze amount is less than 85g/m 2 When the thickness of the glaze layer is smaller, the corresponding antibacterial components are less, the antibacterial effect and the glaze surface flatness are influenced, and when the thickness is more than 90g/m 2 The thickness of the glaze is increased, and the cost is increased.
In some embodiments, in the step of performing the firing treatment after the antibacterial protective glaze layer is applied 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 does not reach the mature temperature and is in a raw firing state, and the effect is poor, and if the firing temperature is higher than 1200, the glaze is too little, and many pinholes are generated, so that the product is easy to absorb dirt. If the firing time is less than 50 minutes, the glaze material 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 material firing time is too long, causes overburning of the glaze surface, has more defects, and causes the reduction of antibacterial effect.
The invention is further illustrated by the following specific examples:
example 1
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 mu m;
preparing antibacterial protection glaze slurry: selecting 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying the glaze with the glazing amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
The physical XRD phase analysis pattern of the ceramic tile prepared in this example is shown in FIG. 1, and it can be seen from FIG. 1 that the surface of the ceramic tile contains potassium feldspar KAlSi 3 O 8 And bismuth trioxide, which illustrates Bi in this example 2 O 3 Is dispersed in the glaze surface and the glaze layer in a single bismuth trioxide mode, thereby ensuring that the ceramic tile has lasting and long-lasting stable antibacterial function.
Example 2
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, then calcining at the high temperature of 1500 ℃ to form antibacterial clinker with an antibacterial function, and crushing the antibacterial clinker with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 microns;
preparing antibacterial protective glaze slip: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and the antibacterial protection glaze slurry with the fineness of 325 meshes and the residual weight of 0.5 percent and the specific gravity of 1.80g/ml is obtained by ball milling for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the layer containing the ground coat to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying glaze in an amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 3
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 mu m;
preparing antibacterial protective glaze slip: selecting 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the layer containing the ground coat to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying the glaze with the glazing amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 4
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 mu m;
preparing antibacterial protective glaze slip: 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methyl cellulose and 0.35 part of sodium tripolyphosphate are selected, and the antibacterial protection glaze slurry with the fineness of 325 meshes and the residual weight of 0.5 percent and the specific gravity of 1.80g/ml is obtained by ball milling for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying the glaze with the glazing amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 5
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, then calcining at the high temperature of 1500 ℃ to form antibacterial clinker with an antibacterial function, and crushing the antibacterial clinker with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 microns;
preparing antibacterial protective glaze slip: selecting 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying glaze in an amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 6
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 mu m;
preparing antibacterial protective glaze slip: selecting 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing water to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying the glaze with the glazing amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 7
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 mu m;
preparing antibacterial protection glaze slurry: selecting 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying the glaze with the glazing amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 8
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 6 parts of calcite, 4 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, then calcining at the high temperature of 1500 ℃ to form antibacterial clinker with an antibacterial function, and crushing the antibacterial clinker with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 microns;
preparing antibacterial protective glaze slip: selecting 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying the glaze with the glazing amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 9
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 14 parts of calcite, 8 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 mu m;
preparing antibacterial protective glaze slip: selecting 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying the glaze with the glazing amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 10
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 mu m;
preparing antibacterial protective glaze slip: selecting 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying the glaze with the glazing amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 11
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 mu m;
preparing antibacterial protective glaze slip: selecting 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the green body layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying the glaze with the glazing amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 12
The utility model provides a pottery brick with high rigidity, level and smooth glaze and antibiotic function, pottery brick includes base coat layer, underglaze layer, pattern layer and the antibiotic protection glaze layer that stacks gradually the setting from bottom to top, and its preparation step includes:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 mu m;
preparing antibacterial protection glaze slurry: selecting 89 parts of the fine powder antibacterial glaze, 10.5 parts of ball clay, 0.15 part of sodium methyl cellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying the glaze with the glazing amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 13
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 50 mu m;
preparing antibacterial protective glaze slip: selecting 92 parts of fine powder antibacterial glaze, 7.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing water to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying glaze in an amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 14
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 60 mu m;
preparing antibacterial protective glaze slip: selecting 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface of the layer containing the ground coat to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying the glaze with the glazing amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 15
The utility model provides a pottery brick with high rigidity, level and smooth glaze and antibiotic function, pottery brick includes base coat layer, underglaze layer, pattern layer and the antibiotic protection glaze layer that stacks gradually the setting from bottom to top, and its preparation step includes:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 70 mu m;
preparing antibacterial protective glaze slip: selecting 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying the glaze with the glazing amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Example 16
The ceramic tile with high hardness, smooth glaze surface and antibacterial function is provided, the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top, and the preparation steps comprise:
preparing fine powder antibacterial glaze: selecting 11.5 parts of kaolin, 10 parts of calcite, 6 parts of wollastonite, 9 parts of dolomite, 3.5 parts of alumina, 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, crushing and uniformly mixing, and then carrying out high-temperature calcination at 1500 ℃ to form antibacterial frit with an antibacterial function, and crushing the antibacterial frit with larger particles to obtain fine powder antibacterial glaze with the particle size of 80 mu m;
preparing antibacterial protective glaze slip: selecting 90 parts of the fine powder antibacterial glaze, 9.5 parts of ball clay, 0.15 part of sodium methylcellulose and 0.35 part of sodium tripolyphosphate, and performing ball milling to obtain antibacterial protective glaze slurry with the fineness of 325-mesh sieve residue of 0.5 percent and the specific gravity of 1.80g/ml for later use;
manufacturing an antique ceramic green body, pressing the green body, drying and removing moisture to obtain a green body layer;
spraying a ground coat on the surface of the blank layer to obtain a ground coat layer;
carrying out ink-jet printing on the surface containing the ground coat layer to obtain a pattern layer;
and spraying the antibacterial protection glaze slip on the surface of the pattern layer, adding water into the antibacterial protection glaze to adjust the specific gravity to 1.30g/ml, and applying glaze in an amount of 85 g/square meter, and firing the obtained antibacterial protection glaze layer to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function.
Comparative example 1
Comparative example 1 provides a method for manufacturing a ceramic tile, which is similar to the method of example 1, except that 1 part of sodium bismuthate and 0 part of zinc bismuthate are used in the formulation of the fine powder antibacterial glaze of comparative example 1, and the other formulation components and steps are the same as those of example 1.
Comparative example 2
The comparative example 2 provides a preparation method of a ceramic tile, which is similar to the preparation method in the example 1, and the only difference is that 1 part of zinc bismuthate and 0 part of sodium bismuthate are contained in the formula of the fine powder antibacterial glaze in the comparative example 2, and the other formula components and steps are the same as those in the example 1.
Comparative example 3
Comparative example 3 provides a method for preparing a ceramic tile, which is similar to the method for preparing the ceramic tile of example 1, the only difference being that 12 parts of sodium bismuthate and 14 parts of zinc bismuthate are used in the formulation of the fine powder antibacterial glaze of comparative example 3, and the other formulation components and steps are the same as those of example 1.
Comparative example 4
Comparative example 4 provides a method for manufacturing ceramic tiles, which is similar to the method for manufacturing ceramic tiles of example 1, with the only difference that the formulation of the fine powder antibacterial glaze of comparative example 4 does not use calcite, which mainly forms anorthite, i.e., 0 part of calcite, and the other formulation composition and procedure are the same as those of example 1.
Comparative example 5
This comparative example 5 provides a process for producing ceramic tiles similar to that of example 1, the only difference being that wollastonite for forming anorthite is not used as a main aid in the formulation of the fine powder antibacterial glaze of comparative example 5, i.e., wollastonite is 0 part, and the other formulation composition and procedure are the same as those of example 1.
Comparative example 6
Comparative example 6 provides a method for manufacturing ceramic tiles similar to that of example 1, except that barium carbonate mainly forming celsian was not used in the formulation of the fine powder antibacterial glaze of comparative example 6, i.e., 0 part of barium carbonate, and the other formulation composition and procedure were the same as those of example 1.
Comparative example 7
Comparative example 7 provides a method for preparing an antibacterial ceramic tile by spraying TiO onto the surface of a ceramic product 2 Mainly using antibacterial liquid to obtain the antibacterial ceramic tile.
Comparative example 8
This comparative example 1 provides a method of manufacturing a ceramic tile similar to that of example 1, except that the fine powder antibacterial glaze of comparative example 1 has a particle size of 90 μm.
Comparative example 9
This comparative example 1 provides a method of manufacturing a ceramic tile similar to that of example 1, except that the fine powder antibacterial glaze of comparative example 1 has a particle size of 100 μm.
Test example
1. The antibacterial performance detection is used 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 antibacterial durability detection is according to GB/T9266, the washing liquid is 5% sodium hypochlorite disinfectant, the washing times are 500 times, and then the antibacterial effect is detected according to JC/T897.
According to the detection basis, the evaluation results of the detection results are as follows:
antibacterial property: not less than 90%
Antibacterial durability: not less than 85 percent
The detection standard is that the data is more than or equal to the antibacterial function.
The detection is mainly used for carrying out antibacterial detection and antibacterial durability detection on escherichia coli and staphylococcus aureus.
2. The detection method for judging the flatness and fineness of the glaze surface is to test the value by adopting a surface profiler, test the flatness of the glaze surface, and the smaller the value is, the smoother the surface is; the glaze surface is generally judged to be fine and smooth when the thickness is between 0.5 and 1.0 mu m, and is more than 1.0 mu m, and the larger the value is, the poorer the flatness of the glaze surface is.
3. Wear resistance: the test is carried out by using GB/T3810.7-2016 detection standard.
4. The surface hardness was measured as follows: inlay the ore of test mohs' hardness on the pencil testing tool on the metal pole, with the ore edges and corners of nib sculpture testee, then according to whether can leave the mar and judge the hardness of testee: 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. Mohs hardness corresponds to the grade of the test material: talc: grade 1, gypsum: grade 2, calcite: grade 3, fluorite: grade 4, apatite: grade 5, feldspar: grade 6, quartz: grade 7, topaz: grade 8, diamond: grade 9, diamond: and 10 stages.
The results obtained after the above-described property 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
As can be seen from the test data in Table 1, the sodium bismuthate and the zinc bismuthate which are antibacterial agents in the implementation can have stable antibacterial and antibacterial lasting performance within the scope of the invention. In comparative examples 1-2, the formulation ratio of the fine powder antibacterial glaze was changed, and the antibacterial effect was not satisfactory. In the comparative example 3, sodium bismuthate and zinc bismuthate are selected to have excessive antibacterial effect, but the glaze hardness is poor and the lasting antibacterial effect of the glaze is weakened due to excessive clear crystals of the glaze. Comparative example 4 does not use calcite, resulting in low glaze hardness and substandard antibacterial durability. Compared example 5, wollastonite is not used, so that the glaze surface has insufficient reaction, the anorthite formation amount is insufficient, the hardness of the glaze surface is low, and the antibacterial durability of the glaze surface is poor. In comparative example 6, barium carbonate was not used, resulting in a small amount of celsian crystals, poor flatness of the glaze surface, uneven glaze surface, low abrasion resistance, and low durability of antibacterial property of the glaze surface. Comparative example 7 the antibacterial agent is coated on the surface of the product by brushing, but the antibacterial effect is acceptable, but the antibacterial effect is not durable, and the antibacterial effect of the product is easily reduced in the using process. The fine powder antibacterial glaze in comparative example 8 and comparative example 9 has too large particle size, resulting in poor flatness of the glaze surface, and poor dispersibility, easily resulting in relatively reduced antibacterial performance and poor antibacterial durability of the ceramic plate.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. The antibacterial glaze is characterized by comprising 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.
2. The antibacterial glaze according to claim 1, further comprising, 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.
3. A ceramic tile with high hardness, smooth glaze and antibacterial function is characterized in that the ceramic tile comprises a body layer, a ground glaze layer, a pattern layer and an antibacterial protective glaze layer which are sequentially stacked from bottom to top;
the raw materials for preparing the antibacterial protective glaze layer comprise fine powder antibacterial glaze, the fine powder antibacterial glaze is obtained by crushing the antibacterial glaze of claim 1 or 2 after high-temperature calcination, and the particle size of the fine powder antibacterial glaze is 50-80 μm.
4. The ceramic tile as claimed in claim 3, 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 sodium methyl cellulose and 0.35-0.4 part of sodium tripolyphosphate.
5. The ceramic tile as claimed in claim 3, characterized in that the chemical composition of the green body layer comprises, in mass percentages: 65.10 to 8978 percent of silicon dioxide, 18.69 to 21.29 percent of aluminum oxide, 2.11 to 4.50 percent of potassium oxide, 1.65 to 2.85 percent of sodium oxide, 1.30 to 2.55 percent of calcium oxide, 0.82 to 1.66 percent of magnesium oxide, 0.55 to 0.85 percent of ferric oxide, and the balance of trace impurities and ignition loss.
6. Ceramic tile according to claim 3, characterized in that the chemical composition of the ground glaze layer comprises, in mass percentages: 3238-3262 of silica, 24.31-27.40 of alumina, 2.33-3.08 of potassium oxide, 2.65-3.85 of sodium oxide, 2.36-3.53 of calcium oxide, 1.02-2.46 of magnesium oxide, 3.26-4.86 of zinc oxide, 4.22-5.84 of barium oxide, and the balance of trace impurities and ignition loss.
7. A method for preparing ceramic tile with high hardness, smooth glaze and antibacterial function as claimed in any one of claims 3-6, comprising the steps of:
(1) Preparing a green body layer;
(2) Applying a ground glaze layer on the blank layer;
(3) Ink-jet printing a pattern layer on the ground coat layer;
(4) After the antibacterial protection glaze layer is distributed on the pattern layer, firing treatment is carried out to obtain the ceramic tile with high hardness, smooth glaze surface and antibacterial function;
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 of claim 1 or 2 according to the formula, crushing and mixing to obtain a mixture, then calcining the mixture at high temperature to obtain antibacterial frit, crushing the antibacterial frit to the particle size of 50-80 μm to obtain fine powder antibacterial glaze; then weighing all the raw materials according to the formula of the antibacterial protective glaze layer, and carrying out ball milling treatment to prepare antibacterial protective glaze slurry; and spreading the antibacterial protective glaze slip on the pattern layer to form an antibacterial protective glaze layer.
8. The method according to claim 7, wherein the step of calcining the mixture at a high temperature to obtain the antibacterial frit comprises calcining at a temperature of 1350-1500 ℃.
9. The method according to claim 7, wherein in the step of applying the antibacterial protective glaze slip on the pattern layer to form an antibacterial protective glaze layer, the antibacterial protective glaze slip has a specific gravity of 1.30 to 1.35g/ml and a glaze application amount of 85 to 90g/m 2 。
10. The method as claimed in claim 7, wherein the step of firing after applying the antibacterial cover glaze layer on the pattern layer is performed at 1185-1200 ℃ for 50-60min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116282921A (en) * | 2023-05-22 | 2023-06-23 | 新明珠集团股份有限公司 | Anti-slip protective glaze, anti-slip pollution-resistant ceramic tile and preparation method thereof |
| CN117720366A (en) * | 2024-02-07 | 2024-03-19 | 佛山市三水新明珠建陶工业有限公司 | Ceramic fluorescent glazed tile and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090104459A1 (en) * | 2007-02-20 | 2009-04-23 | Microban Products Company | Ceramic glaze having antimicrobial property |
| 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 |
| CN110776257A (en) * | 2019-12-06 | 2020-02-11 | 佛山市东鹏陶瓷有限公司 | Ceramic glaze with antibacterial function and preparation method and application thereof |
| CN110818261A (en) * | 2019-12-23 | 2020-02-21 | 佛山市东鹏陶瓷有限公司 | Antibacterial ceramic glaze and preparation method and application thereof |
| CN110981197A (en) * | 2019-12-20 | 2020-04-10 | 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 |
-
2022
- 2022-12-28 CN CN202211691567.9A patent/CN115677219B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090104459A1 (en) * | 2007-02-20 | 2009-04-23 | Microban Products Company | Ceramic glaze having antimicrobial property |
| 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 |
| CN110776257A (en) * | 2019-12-06 | 2020-02-11 | 佛山市东鹏陶瓷有限公司 | Ceramic glaze with antibacterial function and preparation method and application thereof |
| CN110981197A (en) * | 2019-12-20 | 2020-04-10 | 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 |
| CN110818261A (en) * | 2019-12-23 | 2020-02-21 | 佛山市东鹏陶瓷有限公司 | Antibacterial ceramic glaze and preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116282921A (en) * | 2023-05-22 | 2023-06-23 | 新明珠集团股份有限公司 | Anti-slip protective glaze, anti-slip pollution-resistant ceramic tile and preparation method thereof |
| CN116282921B (en) * | 2023-05-22 | 2023-09-19 | 新明珠集团股份有限公司 | Anti-slip protective glaze, anti-slip pollution-resistant ceramic tile and preparation method thereof |
| CN117720366A (en) * | 2024-02-07 | 2024-03-19 | 佛山市三水新明珠建陶工业有限公司 | Ceramic fluorescent glazed tile and preparation method thereof |
| CN117720366B (en) * | 2024-02-07 | 2024-04-16 | 佛山市三水新明珠建陶工业有限公司 | Ceramic fluorescent glazed tile and preparation method thereof |
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