CN110818261A - Antibacterial ceramic glaze and preparation method and application thereof - Google Patents
Antibacterial ceramic glaze and preparation method and application thereof Download PDFInfo
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- CN110818261A CN110818261A CN201911340842.0A CN201911340842A CN110818261A CN 110818261 A CN110818261 A CN 110818261A CN 201911340842 A CN201911340842 A CN 201911340842A CN 110818261 A CN110818261 A CN 110818261A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
Abstract
The invention relates to the technical field of building ceramics, in particular to an antibacterial ceramic glaze and a preparation method and application thereof. An antibacterial ceramic glaze comprises ceramic glaze, an antibacterial agent, a suspending agent and a debonding agent; the antibacterial agent is a mixture of nano silver-loaded zirconium silicate and nano zinc oxide, and the addition amount of the nano silver-loaded zirconium silicate is 2-6% and the addition amount of the nano zinc oxide is 0.05-2% calculated according to the weight percentage of the dry weight of the ceramic glaze; the suspending agent is a mixture of low-viscosity sodium carboxymethyl cellulose and medium-viscosity sodium carboxymethyl cellulose, and the debonder is one of sodium tripolyphosphate or sodium metasilicate. The invention aims to provide an antibacterial ceramic glaze and a preparation method and application thereof, and the prepared ceramic glaze can realize the uniform dispersion of an antibacterial agent in a ceramic tile overglaze, and has high-efficiency sterilization and bacteriostasis effects and stable sustainable sterilization effects.
Description
Technical Field
The invention relates to the technical field of building ceramics, in particular to an antibacterial ceramic glaze and a preparation method and application thereof.
Background
At present, the competition of the building ceramics is intensified day by day, in order to continuously expand the market coverage, the production cost is reduced, the color of the product is improved, meanwhile, the functionality and the technical content of the product are more emphasized, and the added value of the product is greatly improved through the performances, so that the competitiveness of the product is strengthened. At present, with the improvement of living standard of people, people also put forward higher requirements on the living environment, and how to prevent pathogenic bacteria from invading human bodies is urgent. As ceramic tiles commonly applied to living rooms of people, dead corners of pollution and bacteria breeding always exist, bacteria are easy to breed particularly in places such as family kitchens, toilets and the like, fine pinholes which cannot be seen by naked eyes exist on the surfaces of the ceramic tiles, the ceramic tiles are long in service time, bacteria are easy to accumulate and breed and even infect, and the body health is seriously affected. The traditional ceramic tile prepared by directly adding the organic antibacterial agent and the inorganic antibacterial agent to endow the ceramic glaze with an antibacterial function is often poor in antibacterial durability and incapable of achieving an ideal antibacterial effect due to the fact that the antibacterial agent is easy to agglomerate and is unevenly dispersed in the glaze.
Disclosure of Invention
Aiming at the problems in the background art, the invention aims to provide an antibacterial ceramic glaze, wherein an antibacterial agent can be uniformly dispersed in the ceramic glaze, and sufficient silver ions and zinc ions are dissociated from the ceramic glaze, so that the antibacterial effect is effectively achieved, and the antibacterial performance and the durability of the glaze are effectively improved.
The invention also aims to provide the preparation method of the antibacterial ceramic glaze, and the prepared ceramic glaze can realize the uniform dispersion of the antibacterial agent in the ceramic tile overglaze, ensures the coverage of the antibacterial effect of the ceramic glaze, and has high-efficiency sterilization and bacteriostasis effects and stable sustainable sterilization effects.
The invention also aims to provide a preparation method of the ceramic tile using the antibacterial ceramic glaze, and the ceramic tile prepared by using the antibacterial ceramic glaze can reach the indexes of JC/T897-2014 antibacterial ceramic product antibacterial performance, the antibacterial rate is more than or equal to 90 percent, and the antibacterial durability is more than or equal to 85 percent.
In order to achieve the purpose, the invention adopts the following technical scheme:
an antibacterial ceramic glaze comprises ceramic glaze, an antibacterial agent, a suspending agent and a debonding agent;
the antibacterial agent is a mixture of nano silver-loaded zirconium silicate and nano zinc oxide, and the addition amount of the nano silver-loaded zirconium silicate is 2-6% and the addition amount of the nano zinc oxide is 0.05-2% calculated according to the weight percentage of the dry weight of the ceramic glaze;
the suspending agent is a mixture of low-viscosity sodium carboxymethyl cellulose and medium-viscosity sodium carboxymethyl cellulose, and the adding amount of the suspending agent is 0.05-0.15 percent by weight percentage based on the dry weight of the ceramic glaze containing the antibacterial agent, wherein the adding amount of the low-viscosity sodium carboxymethyl cellulose is 0.005-0.05 percent, and the adding amount of the medium-viscosity sodium carboxymethyl cellulose is 0.05-0.14 percent;
the debonder is one of sodium tripolyphosphate or sodium metasilicate, and the addition amount of the debonder is 0.1-0.6% by weight percent based on the dry weight percentage of the ceramic glaze containing the antibacterial agent.
Preferably, the polymerization degree of the low-viscosity sodium carboxymethyl cellulose is 150-300, and the polymerization degree of the medium-viscosity sodium carboxymethyl cellulose is 500-600.
Preferably, the particle diameters of the nano-zirconium silicate silver-carrying and the nano-zinc oxide are respectively 25nm +/-10 nm.
Preferably, the Fe in the mixture of the nano-zirconium silicate silver-carrying nano-zinc oxide is calculated according to the weight percentage of the raw materials203Less than or equal to 0.03 percent and TiO2≤0.03％。
The antibacterial agent is added into the ceramic glaze according to the weight percentage and uniformly mixed, the suspending agent and the debonding agent are added into the ceramic glaze raw material containing the antibacterial agent according to the weight percentage and uniformly mixed, and then water is added for ball milling for 5-12 hours, so that the antibacterial ceramic glaze is prepared, wherein the fineness of ball milling slurry is that the ball milling slurry is sieved by a proportion cup and then sieved by a 325-mesh sieve, the screen residue is 0.5-0.8%, and the flow rate is 30-50 seconds.
Preferably, the pH value of the ball milling slurry is 6.5-9.0, and the ball milling temperature is 40-70 ℃.
The preparation method of the ceramic tile using the antibacterial ceramic glaze comprises the following steps:
(1) preparing a green brick;
(2) pouring base glaze: pouring base glaze on the surface of the green brick, and performing ink-jet printing treatment to obtain a green brick with the surface provided with the ink-jet printing layer;
(3) pouring the antibacterial glaze: spraying the antibacterial ceramic glaze on the surface of the ink-jet printing layer;
(4) and putting into a kiln for sintering to obtain the ceramic tile with the antibacterial function.
Preferably, the thickness of the antibacterial glaze layer sprayed in the step (3) is 0.1 mm-0.4 mm.
Preferably, in the step (4), the firing temperature is 1150-1210 ℃, the firing time is 50-90 min, and the water absorption rate of the finished ceramic tile is less than or equal to 0.2%.
Preferably, the kiln firing process further comprises one or more steps of edging, polishing, grading and antifouling treatment.
Compared with the prior art, the invention has the following beneficial effects:
the antibacterial ceramic glaze is prepared by adding nano silver-loaded zirconium silicate and nano zinc oxide into a conventional ceramic glaze as antibacterial agents, firing at high temperature, and then solidifying the antibacterial agents in the glaze, wherein when microorganisms such as bacteria contact with the surface of a brick, the silver ions and the zinc ions released by the nano silver-loaded zirconium silicate and the nano zinc oxide in the antibacterial ceramic glaze are killed under the combined action. Meanwhile, the requirements of the particle size and the impurity content of the antibacterial agent are controlled, so that sufficient silver ions and zinc ions are dissociated from the antibacterial glaze on the surface of the ceramic tile coated with the antibacterial glaze, and the antibacterial ceramic tile has high-efficiency sterilization and bacteriostasis effects and stable sustainable sterilization effects. In addition, the suspending agent and the degumming agent are added into the antibacterial ceramic glaze, the addition amount of the suspending agent and the degumming agent in the antibacterial glaze is controlled, the polymerization degree of the suspending agent is controlled, so that the suspending effect on the nano-scale antibacterial agent with small density and particle size is ensured, the viscosity of the glaze is controlled, the antibacterial agent can be uniformly distributed in the antibacterial glaze, the coverage of the antibacterial effect of the ceramic glaze on the surface of the ceramic tile is ensured, and the antibacterial function is better exerted on the surface of the ceramic tile.
Detailed Description
An antibacterial ceramic glaze comprises ceramic glaze, an antibacterial agent, a suspending agent and a debonding agent;
the antibacterial agent is a mixture of nano silver-loaded zirconium silicate and nano zinc oxide, and the addition amount of the nano silver-loaded zirconium silicate is 2-6% and the addition amount of the nano zinc oxide is 0.05-2% calculated according to the weight percentage of the dry weight of the ceramic glaze;
the suspending agent is a mixture of low-viscosity sodium carboxymethyl cellulose and medium-viscosity sodium carboxymethyl cellulose, and the adding amount of the suspending agent is 0.05-0.15 percent by weight percentage based on the dry weight of the ceramic glaze containing the antibacterial agent, wherein the adding amount of the low-viscosity sodium carboxymethyl cellulose is 0.005-0.05 percent, and the adding amount of the medium-viscosity sodium carboxymethyl cellulose is 0.05-0.14 percent;
the debonder is one of sodium tripolyphosphate or sodium metasilicate, and the addition amount of the debonder is 0.1-0.6% by weight percent based on the dry weight percentage of the ceramic glaze containing the antibacterial agent.
The sum of the weight percentages of the raw materials contained in the antibacterial ceramic glaze provided by the application is 100%.
Zn2+And Ag+Can directly act with bacteria because of Zn2+And Ag+Can destroy the activity of active enzyme of bacterial cell membrane or cell protoplasm at very low concentration, damage the three-dimensional structure (denaturation), and cause dysfunction in a short time, so that Zn2+And Ag+Is toxic to microorganisms (bacteria, molds, viruses also broadly include algae and protozoa), strongly attracts enzyme proteins in bacteria, rapidly binds to the enzyme which is an essential group, inactivates the enzyme, and causes the bacteria to die, and when the bacteria are killed, Zn is added2+And Ag+And the bacterial colonies dissociate and contact with other bacterial colonies to play a new round of antibacterial action, and the process is repeated.
The antibacterial ceramic glaze is obtained by adding an antibacterial agent, a suspending agent and a degumming agent into a conventional ceramic glaze, wherein nano-zirconium silicate silver-carrying and nano-zinc oxide are added as the antibacterial agent, a brick blank coated with the antibacterial ceramic glaze is fired at high temperature, the antibacterial agent is solidified in the antibacterial ceramic glaze, and when microorganisms such as bacteria contact with the brick surface, silver ions released by the nano-zirconium silicate silver-carrying and zinc ions released by the nano-zinc oxide in the antibacterial ceramic glaze are killed under the combined action.
According to the invention, sodium carboxymethylcellulose is added as a suspending agent, so that the stability of the glaze can be improved in the ceramic glaze, the components in the glaze are uniformly dispersed, and the smoothness of the glaze is improved to avoid bubbles formed after glazing. The antibacterial agent used in the invention is a nano-scale antibacterial agent, the density and the particle size of the antibacterial agent are small, so that the low-viscosity and medium-viscosity sodium carboxymethylcellulose is adopted to be matched, the dosage of the low-viscosity sodium carboxymethylcellulose is limited, the polymerization degree of the low-viscosity sodium carboxymethylcellulose is small, the molecular chain is short, and the antibacterial agent with the lower suspension density and the smaller particle size can be suspended.
In addition, sodium tripolyphosphate or sodium metasilicate is added as a debonding agent, electrons are increased in a glaze system along with the addition of the debonding agent, particles in the glaze are gradually changed into a surface structure from the edge and side structures, the glaze is diluted, the viscosity is reduced, the particles in the glaze system can move freely and can be suspended by being combined with a suspending agent, meanwhile, the slurry is low in viscosity and flow velocity, the slurry leveling performance is good, the prepared glaze is smooth and flat, and the inside and the outside are uniform. The addition amount of the debonder is limited within the range, because the viscosity of the glaze slip is reduced in a parabolic manner with the addition of the debonder, the viscosity is reduced with the addition of a small amount of the debonder, the trend becomes gradually slow, and the viscosity is gradually increased with the addition amount of the debonder when the addition amount is too large. Therefore, the addition amounts of the suspending agent and the debonder are controlled in the antibacterial glaze, so that the antibacterial agent can be uniformly distributed in the antibacterial glaze, and the antibacterial function can be better exerted on the surface of the ceramic tile.
Preferably, the polymerization degree of the low-viscosity sodium carboxymethyl cellulose is 150-300, and the polymerization degree of the medium-viscosity sodium carboxymethyl cellulose is 500-600.
Because the polymerization degree of the sodium carboxymethyl cellulose is an important factor influencing the viscosity of the sodium carboxymethyl cellulose, the higher the polymerization degree is, the more chain segments are contained by a molecular chain, the higher the viscosity is, the polymerization degree of the low-viscosity sodium carboxymethyl cellulose and the medium-viscosity sodium carboxymethyl cellulose is limited, if the polymerization degree of the medium-viscosity sodium carboxymethyl cellulose is overlarge, the more chain segments are contained by the molecular chain, overlong molecular chains are interwoven together, the viscosity of the obtained antibacterial ceramic glaze is overlarge, the fluidity is poor, if the polymerization degree of the low-viscosity sodium carboxymethyl cellulose is overlarge, the suspension of an antibacterial agent with smaller density and particle size cannot be realized, if the polymerization degree of the medium-viscosity sodium carboxymethyl cellulose is overlow, the suspension effect on solid particles with large density and particle size in the ceramic glaze cannot be realized, the suspension effect is reduced, and the antibacterial ceramic glaze is easily dispersed unevenly so as to be layered, the antibacterial effect of the ceramic glaze is affected.
Preferably, the particle diameters of the nano-zirconium silicate silver-carrying and the nano-zinc oxide are respectively 25nm +/-10 nm.
The particle size ranges of the nano silver-loaded zirconium silicate and the nano zinc oxide are limited, the particle size level of the antibacterial agent is nano level, when the particle sizes of the nano silver-loaded zirconium silicate and the nano zinc oxide are smaller and are 25nm +/-10 nm, the specific surface area of the antibacterial agent is large, the antibacterial agent has high replaceability and adsorbability, can be better adsorbed on the surface of a bacterial colony and plays an antibacterial role, and can be more quickly dissociated after the antibacterial role is played to play a new round of antibacterial effect, and the antibacterial effect is better than that of the antibacterial agent with the particle size of micron-grade or even larger. When the particle size is too large, the specific surface area is too large, the antibacterial effect and the antibacterial effect are deteriorated, and when the particle size is too small, agglomeration easily occurs, and the antibacterial effect of the antibacterial agent in the glaze is restricted.
Preferably, the Fe in the mixture of the nano-zirconium silicate silver-carrying nano-zinc oxide is calculated according to the weight percentage of the raw materials203Less than or equal to 0.03 percent and TiO2≤0.03％。
Because some enzyme proteins can loosely bind organic substances with small molecular weight (cofactors of the enzyme), such as metal ions and some organic compounds with small molecular weight, if Fe is contained in the antibacterial ceramic glaze203And TiO2If the content of (b) is too high, iron ions and titanium ions released by the nano antibacterial agent are easy to combine with enzyme protein, so that Zn in the nano antibacterial agent is influenced2+、Ag+The combination with enzyme influences the antibacterial effect of the nano antibacterial agent, so that the introduction of Fe is avoided in the preparation and material selection of the nano silver-zirconium silicate and the nano zinc oxide203And TiO2Impurities to ensure Fe in the nano antibacterial agent203And TiO2Preferably contains no Fe203And TiO2Impurities.
The antibacterial agent is added into the ceramic glaze according to the weight percentage and uniformly mixed, the suspending agent and the debonding agent are added into the ceramic glaze raw material containing the antibacterial agent according to the weight percentage and uniformly mixed, and then water is added for ball milling for 5-12 hours, so that the antibacterial ceramic glaze is prepared, wherein the fineness of ball milling slurry is that the ball milling slurry is sieved by a proportion cup and then sieved by a 325-mesh sieve, the screen residue is 0.5-0.8%, and the flow rate is 30-50 seconds.
After the antibacterial agent is added and uniformly mixed with the conventional ceramic glaze, the suspending agent and the dispergator are added, the mixing uniformity of the slurry is improved, the effect of improving the dispersion uniformity of the antibacterial agent is better exerted by the suspending agent and the dispergator, the fineness and the flow rate of the ball-milled slurry are limited, and the final antibacterial performance is influenced by the excessively fine fineness or the excessively coarse fineness; if the flow rate is too large, the glazing is easy to be uneven and skinning is easy to occur, if the flow rate is too small, the glaze curtain is easily influenced by the outside world to cause uneven glaze pouring, and the production efficiency is low, so the fineness and the flow rate of the slurry ball milling are limited within the range.
Preferably, the pH value of the ball milling slurry is 6.5-9.0, and the ball milling temperature is 40-70 ℃.
Preferably, the ball milling slurry has a pH of 7.0 and a ball milling temperature of 50 ℃.
When the pH value of the slurry containing the medium-viscosity sodium carboxymethyl cellulose and the low-viscosity sodium carboxymethyl cellulose is too small or too large, the viscosity of the slurry can be obviously reduced, uneven glazing is easily caused, and when the pH value is too small, the medium-viscosity sodium carboxymethyl cellulose and the low-viscosity sodium carboxymethyl cellulose are easy to precipitate, so that the antibacterial performance is influenced.
The preparation method of the ceramic tile using the antibacterial ceramic glaze comprises the following steps:
(1) preparing a green brick;
(2) pouring base glaze: pouring base glaze on the surface of the green brick, and performing ink-jet printing treatment to obtain a green brick with the surface provided with the ink-jet printing layer;
(3) pouring the antibacterial glaze: spraying the antibacterial ceramic glaze on the surface of the ink-jet printing layer;
(4) and putting into a kiln for sintering to obtain the ceramic tile with the antibacterial function.
The antibacterial ceramic glaze is poured after the inkjet printing treatment to serve as the overglaze, the overglaze can be in direct contact with air, when bacteria in the air are adsorbed on the surface of the ceramic tile, the antibacterial agent which is uniformly dispersed in the antibacterial ceramic glaze can play a role in destroying the activity of cell membranes or cell protoplasm active enzymes of the bacteria, and the antibacterial ceramic glaze plays a role in resisting bacteria and sterilizing.
Preferably, the thickness of the antibacterial glaze layer sprayed in the step (3) is 0.1 mm-0.4 mm.
The glaze layer of the antibacterial ceramic glaze is too thin, antibacterial ions of antibacterial agents in the glaze layer are too few, and the too thin glaze layer easily influences the uniformity of the glaze layer after glaze spraying, so that the antibacterial effect is influenced, the antibacterial effect on the surface of the ceramic tile is weakened, and when the glaze layer is too thick, the mechanical property of the ceramic tile is easily reduced, and the overall use effect is influenced.
Preferably, in the step (4), the firing temperature is 1150-1210 ℃, the firing time is 50-90 min, and the water absorption rate of the finished ceramic tile is less than or equal to 0.2%.
The ceramic tile of the antibacterial ceramic glaze obtained after high-temperature sintering has good antibacterial performance, sufficient silver ions and zinc ions in the ceramic glaze can be dissociated out to play an effective antibacterial role, the water absorption rate of the finished product of the prepared ceramic tile is less than or equal to 0.2 percent, the density of the ceramic tile is high, bacterial colonies are prevented from invading into a blank body, the bacterial colonies are killed under the action of the antibacterial ceramic glaze of the glaze surface, and the prepared ceramic tile can reach the indexes of JC/T897 ion ceramic antibacterial performance.
Preferably, the kiln firing process further comprises one or more steps of edging, polishing, grading and antifouling treatment.
Preferably, the antifouling treatment is surface waxing or surface treatment with a surface antifouling treatment agent for polished glazed tiles.
The ceramic tile using the antibacterial ceramic glaze is subjected to edging, polishing, grading and antifouling treatment to obtain the antifouling glazed brick with the antibacterial function, so that the antibacterial performance and the antifouling performance of the glazed brick are effectively improved, and a strong practical effect is achieved while an attractive effect is achieved.
The technical solution of the present invention is further explained by the following embodiments.
And (3) performance testing:
1. and (3) determination of antibacterial rate: the antibacterial rate is determined according to the test method of JC/T897-2014 antibacterial ceramic product antibacterial performance.
2. And (3) antibacterial durability measurement: the antibacterial durability is determined according to the test method of JC/T897-2014 antibacterial ceramic product antibacterial performance.
Example 1
A ceramic tile using the antibacterial ceramic glaze is prepared by the following steps:
(1) according to the weight percentage of the dry weight of the ceramic glaze, 2 percent of nano-zirconium silicate silver and 0.1 percent of nano-zinc oxide (the grain diameter of the nano-zirconium silicate silver and the nano-zinc oxide is 25nm +/-2 nm, and Fe in the mixture of the raw material of the nano-zirconium silicate silver and the nano-zinc oxide is added into the conventional ceramic glaze203≤0.01％，TiO2Not more than 0.02 percent) and evenly mixing to prepare the ceramic glaze containing the antibacterial agent, wherein 0.1 percent of medium viscosity sodium carboxymethyl cellulose (the polymerization degree is 600), 0.01 percent of low viscosity sodium carboxymethyl cellulose (the polymerization degree is 150) and 0.5 percent of sodium metasilicate are added into the ceramic glaze containing the antibacterial agent according to the weight percentage of the dry weight of the ceramic glaze containing the antibacterial agent and evenly mixed, water is added for ball milling for 6 hours, the pH of ball milling slurry is 7.0, the ball milling temperature is 50 ℃, the fineness of the ball milling slurry is that a proportion cup passes through a 325-mesh sieve, the screen residue is 0.6 percent, and the flow rate is 40 seconds, so that the antibacterial ceramic glaze is prepared for later use.
(2) Mixing known ceramic powder, adding water, ball-milling for 9 hours, and then spraying and granulating the obtained slurry through a spray tower;
(3) pressing the powder obtained by spray granulation into a green brick and then drying;
(4) spraying known ceramic base glaze on the green brick, and then carrying out ink-jet printing treatment on the surface of the green brick;
(5) spraying the antibacterial ceramic glaze prepared in the step (1) on the surface of the ink-jet printing layer, wherein the glazing thickness is 0.3 mm;
(6) and (3) firing for 80min at the firing temperature of 1165 ℃, wherein the water absorption rate of the finished product is less than or equal to 0.1%, and obtaining the ceramic tile with the antibacterial function.
Example 2
A ceramic tile using the antibacterial ceramic glaze is prepared by the following steps:
(1) according to the weight percentage of the dry weight of the ceramic glaze, 5 percent of nano-zirconium silicate silver and 1 percent of nano-zinc oxide (the particle diameter of the nano-zirconium silicate silver and the nano-zinc oxide is 25nm +/-5 nm, and Fe in the mixture of the raw material of the nano-zirconium silicate silver and the nano-zinc oxide is added into the conventional ceramic glaze203≤0.01％，TiO2Not more than 0.03 percent) and uniformly mixing to obtain the ceramic glaze containing the antibacterial agent, adding 0.12 percent of medium viscosity sodium carboxymethyl cellulose (the polymerization degree is 550), 0.02 percent of low viscosity sodium carboxymethyl cellulose (the polymerization degree is 200) and 0.3 percent of sodium metasilicate into the ceramic glaze containing the antibacterial agent according to the weight percentage of the dry weight of the ceramic glaze containing the antibacterial agent, uniformly mixing, adding water and ball milling for 6 hours, wherein the ball milling slurry has the pH value of 7.0, the ball milling temperature is 50 ℃, the fineness of the ball milling slurry is that a specific gravity cup passes through a 325-mesh sieve, the screen residue is 0.5 percent, and the flow rate is 35 seconds, thus obtaining the antibacterial ceramic glaze for later use.
(2) Mixing known ceramic powder, adding water, ball-milling for 9 hours, and then spraying and granulating the obtained slurry through a spray tower;
(3) pressing the powder obtained by spray granulation into a green brick and then drying;
(4) spraying known ceramic base glaze on the green brick, and then carrying out ink-jet printing treatment on the surface of the green brick;
(5) spraying the antibacterial ceramic glaze prepared in the step (1) on the surface of the ink-jet printing layer, wherein the glazing thickness is 0.4 mm;
(6) and (3) firing at 1185 ℃ for 75min to obtain the ceramic tile with the antibacterial function, wherein the water absorption of the finished product is less than or equal to 0.1%.
Example 3
A ceramic tile using antibacterial ceramic glaze is prepared by the following steps:
(1) according to the weight percentage of the dry weight of the ceramic glaze, 1.5 percent of nano-silver-supported zirconium silicate and 0.03 percent of nano-zinc oxide (the grain diameter of the nano-silver-supported zirconium silicate and the nano-zinc oxide is 25nm +/-2 nm, and Fe in the mixture of the nano-silver-supported zirconium silicate and the nano-zinc oxide is added into the conventional ceramic glaze203≤0.01％，TiO2Not more than 0.02 percent) and evenly mixing to prepare the ceramic glaze containing the antibacterial agent, wherein 0.1 percent of medium viscosity sodium carboxymethyl cellulose (with the polymerization degree of 550), 0.01 percent of low viscosity sodium carboxymethyl cellulose (with the polymerization degree of 200) and 0.5 percent of sodium metasilicate are added into the ceramic glaze containing the antibacterial agent according to the weight percentage of the dry weight of the ceramic glaze containing the antibacterial agent, and after the mixture is evenly mixed, water is added for ball milling for 6 hours, the pH of ball milling slurry is 8.0, the ball milling temperature is 45 ℃, the fineness of the ball milling slurry is that a specific gravity cup passes through a 325-mesh sieve, the screen residue is 0.6 percent, and the flow rate is 40 seconds, so that the antibacterial ceramic.
(2) Mixing known ceramic powder, adding water, ball-milling for 9 hours, and then spraying and granulating the obtained slurry through a spray tower;
(3) pressing the powder obtained by spray granulation into a green brick and then drying;
(4) spraying known ceramic base glaze on the green brick, and then carrying out ink-jet printing treatment on the surface of the green brick;
(5) spraying the antibacterial ceramic glaze prepared in the step (1) on the surface of the ink-jet printing layer, wherein the glazing thickness is 0.3 mm;
(6) and (3) firing for 80min at the firing temperature of 1165 ℃, wherein the water absorption rate of the finished product is less than or equal to 0.1%, and obtaining the ceramic tile with the antibacterial function.
Example 4
A ceramic tile using antibacterial ceramic glaze is prepared by the following steps:
(1) according to the weight percentage of the dry weight of the ceramic glaze, 2 percent of nano-zirconium silicate silver and 0.1 percent of nano-zinc oxide (the grain diameter of the nano-zirconium silicate silver and the nano-zinc oxide is 25nm +/-2 nm, and Fe in the mixture of the raw material of the nano-zirconium silicate silver and the nano-zinc oxide is added into the conventional ceramic glaze203≤0.01％，TiO2Not more than 0.02 percent) and evenly mixed to prepare the ceramic containing the antibacterial agentThe glaze is prepared by adding 0.03 percent of medium viscosity sodium carboxymethyl cellulose (with the polymerization degree of 400), 0.01 percent of low viscosity sodium carboxymethyl cellulose (with the polymerization degree of 200) and 0.2 percent of sodium metasilicate into the ceramic glaze containing the antibacterial agent according to the weight percentage of the dry weight of the ceramic glaze containing the antibacterial agent, uniformly mixing, adding water, and carrying out ball milling for 6 hours, wherein the pH of ball milling slurry is 9.0, the ball milling temperature is 55 ℃, the fineness of the ball milling slurry is that a specific gravity cup passes through a 325-mesh sieve, the screen residue is 0.6 percent, and the flow rate is 45 seconds.
(2) Mixing known ceramic powder, adding water, ball-milling for 9 hours, and then spraying and granulating the obtained slurry through a spray tower;
(3) pressing the powder obtained by spray granulation into a green brick and then drying;
(4) spraying known ceramic base glaze on the green brick, and then carrying out ink-jet printing treatment on the surface of the green brick;
(5) spraying the antibacterial ceramic glaze prepared in the step (1) on the surface of the ink-jet printing layer, wherein the glazing thickness is 0.3 mm;
(6) and (3) firing for 80min at the firing temperature of 1160 ℃, wherein the water absorption rate of the finished product is less than or equal to 0.1%, and obtaining the ceramic tile with the antibacterial function.
Example 5
A ceramic tile using antibacterial ceramic glaze is prepared by the following steps:
(1) according to the weight percentage of the dry weight of the ceramic glaze, 2 percent of nano-zirconium silicate silver and 0.1 percent of nano-zinc oxide (the grain diameter of the nano-zirconium silicate silver and the nano-zinc oxide is 25nm +/-2 nm, and Fe in the mixture of the raw material of the nano-zirconium silicate silver and the nano-zinc oxide is added into the conventional ceramic glaze203≤0.01％，TiO2Not more than 0.02 percent) and evenly mixed to prepare the ceramic glaze containing the antibacterial agent, according to the weight percentage of the dry weight of the ceramic glaze containing the antibacterial agent, 0.25 percent of medium viscosity sodium carboxymethyl cellulose (with the polymerization degree of 700), 0.03 percent of low viscosity sodium carboxymethyl cellulose (with the polymerization degree of 200) and 0.8 percent of sodium metasilicate are added into the ceramic glaze containing the antibacterial agent and evenly mixed, water is added for ball milling for 6 hours, the pH of ball milling slurry is 8.5, the ball milling temperature is 50 ℃, the fineness of the ball milling slurry is that a specific gravity cup passes through a 325-mesh sieve, the residue is 0.6 percent, and the mixture flows and is milled forThe speed is 50 seconds, and the antibacterial ceramic glaze is prepared for later use.
(2) Mixing known ceramic powder, adding water, ball-milling for 9 hours, and then spraying and granulating the obtained slurry through a spray tower;
(3) pressing the powder obtained by spray granulation into a green brick and then drying;
(4) spraying known ceramic base glaze on the green brick, and then carrying out ink-jet printing treatment on the surface of the green brick;
(5) spraying the antibacterial ceramic glaze prepared in the step (1) on the surface of the ink-jet printing layer, wherein the glazing thickness is 0.3 mm;
(6) and (3) firing for 80min at the firing temperature of 1160 ℃, wherein the water absorption rate of the finished product is less than or equal to 0.1%, and obtaining the ceramic tile with the antibacterial function.
Example 6
A ceramic tile using the antibacterial ceramic glaze is prepared by the following steps:
(1) according to the weight percentage of the dry weight of the ceramic glaze, 2 percent of nano-zirconium silicate silver and 0.1 percent of nano-zinc oxide (the grain diameter of the nano-zirconium silicate silver and the nano-zinc oxide is 25nm +/-2 nm, and Fe in the mixture of the raw material of the nano-zirconium silicate silver and the nano-zinc oxide is added into the conventional ceramic glaze203≤0.01％，TiO2Not more than 0.02 percent) and evenly mixing to prepare the ceramic glaze containing the antibacterial agent, wherein 0.1 percent of medium viscosity sodium carboxymethyl cellulose (with the polymerization degree of 600), 0.01 percent of low viscosity sodium carboxymethyl cellulose (with the polymerization degree of 350) and 0.5 percent of sodium metasilicate are added into the ceramic glaze containing the antibacterial agent according to the weight percentage of the dry weight of the ceramic glaze containing the antibacterial agent, and after the mixture is evenly mixed, water is added for ball milling for 6 hours, the pH of ball milling slurry is 7.0, the ball milling temperature is 55 ℃, the fineness of the ball milling slurry is that a specific gravity cup passes through a 325-mesh sieve, the screen residue is 0.6 percent, and the flow rate is 40 seconds, so that the antibacterial ceramic.
(2) Mixing known ceramic powder, adding water, ball-milling for 9 hours, and then spraying and granulating the obtained slurry through a spray tower;
(3) pressing the powder obtained by spray granulation into a green brick and then drying;
(4) spraying known ceramic base glaze on the green brick, and then carrying out ink-jet printing treatment on the surface of the green brick;
(5) spraying the antibacterial ceramic glaze prepared in the step (1) on the surface of the ink-jet printing layer, wherein the glazing thickness is 0.3 mm;
(6) and (3) firing for 80min at the firing temperature of 1165 ℃, wherein the water absorption rate of the finished product is less than or equal to 0.1%, and obtaining the ceramic tile with the antibacterial function.
Example 7
A ceramic tile using antibacterial ceramic glaze is prepared by the following steps:
(1) according to the weight percentage of the dry weight of the ceramic glaze, 2 percent of nano-zirconium silicate silver and 0.1 percent of nano-zinc oxide (the grain diameter of the nano-zirconium silicate silver and the nano-zinc oxide is 13nm +/-2 nm, and Fe in the mixture of the raw material of the nano-zirconium silicate silver and the nano-zinc oxide is added into the conventional ceramic glaze203≤0.01％，TiO2Not more than 0.02 percent) and evenly mixing to prepare the ceramic glaze containing the antibacterial agent, wherein 0.1 percent of medium viscosity sodium carboxymethyl cellulose (with the polymerization degree of 550), 0.01 percent of low viscosity sodium carboxymethyl cellulose (with the polymerization degree of 200) and 0.5 percent of sodium metasilicate are added into the ceramic glaze containing the antibacterial agent according to the weight percentage of the dry weight of the ceramic glaze containing the antibacterial agent, and after the mixture is evenly mixed, water is added for ball milling for 6 hours, the pH of ball milling slurry is 7.0, the ball milling temperature is 60 ℃, the fineness of the ball milling slurry is that a specific gravity cup passes through a 325-mesh sieve, the screen residue is 0.6 percent, and the flow rate is 40 seconds, so that the antibacterial ceramic.
(2) Mixing known ceramic powder, adding water, ball-milling for 9 hours, and then spraying and granulating the obtained slurry through a spray tower;
(3) pressing the powder obtained by spray granulation into a green brick and then drying;
(4) spraying known ceramic base glaze on the green brick, and then carrying out ink-jet printing treatment on the surface of the green brick;
(5) spraying the antibacterial ceramic glaze prepared in the step (1) on the surface of the ink-jet printing layer, wherein the glazing thickness is 0.3 mm;
(6) and (3) firing for 80min at the firing temperature of 1160 ℃, wherein the water absorption rate of the finished product is less than or equal to 0.1%, and obtaining the ceramic tile with the antibacterial function.
Example 8
A ceramic tile using antibacterial ceramic glaze is prepared by the following steps:
(1) according to the weight percentage of the dry weight of the ceramic glaze, 2 percent of nano-zirconium silicate silver and 0.1 percent of nano-zinc oxide (the grain diameter of the nano-zirconium silicate silver and the nano-zinc oxide is 13nm +/-2 nm, and Fe in the mixture of the raw material of the nano-zirconium silicate silver and the nano-zinc oxide is added into the conventional ceramic glaze203≤0.55％，TiO2Not more than 0.32 percent) and evenly mixing to prepare the ceramic glaze containing the antibacterial agent, wherein 0.1 percent of medium viscosity sodium carboxymethyl cellulose (with the polymerization degree of 550), 0.01 percent of low viscosity sodium carboxymethyl cellulose (with the polymerization degree of 200) and 0.5 percent of sodium metasilicate are added into the ceramic glaze containing the antibacterial agent according to the weight percentage of the dry weight of the ceramic glaze containing the antibacterial agent, and after even mixing, water is added for ball milling for 6 hours, the pH of ball milling slurry is 8.0, the ball milling temperature is 40 ℃, the fineness of the ball milling slurry is that a specific gravity cup passes through a 325-mesh sieve, the screen residue is 0.6 percent, and the flow rate is 40 seconds, so that the antibacterial ceramic glaze is prepared.
(2) Mixing known ceramic powder, adding water, ball-milling for 9 hours, and then spraying and granulating the obtained slurry through a spray tower;
(3) pressing the powder obtained by spray granulation into a green brick and then drying;
(4) spraying known ceramic base glaze on the green brick, and then carrying out ink-jet printing treatment on the surface of the green brick;
(5) spraying the antibacterial ceramic glaze prepared in the step (1) on the surface of the ink-jet printing layer, wherein the glazing thickness is 0.3 mm;
(6) and (3) firing for 80min at the firing temperature of 1160 ℃, wherein the water absorption rate of the finished product is less than or equal to 0.1%, and obtaining the ceramic tile with the antibacterial function.
Table 1-examples 1-8 performance testing
As is clear from the above test results, the antibacterial agents obtained in examples 1-2 were obtainedThe functional ceramic tile has good antibacterial performance, can reach the indexes of JC/T897-2014 antibacterial ceramic product antibacterial performance, has the antibacterial rate of more than or equal to 90 percent and the antibacterial durability of more than or equal to 85 percent; from the examples 1-2, when the antibacterial agent, the suspending agent and the debonding agent in the formula range are added into the conventional ceramic glaze, and the particle size, the impurity content, the glazing amount and the sintering temperature of the antibacterial agent are in the above ranges, the ceramic glaze with a good antibacterial effect can be obtained, the antibacterial agent is solidified in the antibacterial ceramic glaze, when microorganisms such as bacteria contact with the brick surface, the antibacterial effect is realized by the combined action of silver ions released by the silver-loaded nano zirconium silicate in the antibacterial ceramic glaze and zinc ions released by the nano zinc oxide, wherein the antibacterial agent can be uniformly distributed in the antibacterial glaze by controlling the adding amount and the polymerization degree of the medium-viscosity sodium carboxymethyl cellulose and the low-viscosity sodium carboxymethyl cellulose and matching with the debonding agent, so that the antibacterial agent can better exert the antibacterial function on the surface of the ceramic brick. As can be seen from examples 1-3, the ceramic tile prepared in example 3 has low antibacterial rate and antibacterial durability, and the amount of the nano silver-zirconium silicate and nano zinc oxide antibacterial agent added in example 3 is too small, so that Zn is released2+And Ag+The concentration of the antibacterial agent in the ceramic glaze is too low, so that the antibacterial performance is poor and the antibacterial efficiency is low.
The test results show that the ceramic tiles prepared in the embodiments 4 to 6 have poor antibacterial rate and poor antibacterial durability, because the amount of the medium-viscosity sodium carboxymethyl cellulose added in the embodiment 4 is too small, and the polymerization degree of the medium-viscosity sodium carboxymethyl cellulose is too low, the suspension effect on solid particles with large density and particles in the ceramic glaze is difficult to realize, the dispersion uniformity and stability of the antibacterial agent in the ceramic glaze are difficult to improve, after the overglaze is applied, the antibacterial agent with high density is easy to sink to the bottom of the glaze, the opportunity that the antibacterial agent contacts with microorganisms such as bacteria on the tile surface is reduced, and the prepared ceramic tiles have poor antibacterial rate and antibacterial durability; the amount of the medium-viscosity sodium carboxymethyl cellulose added in the embodiment 5 is too much, the polymerization degree of the medium-viscosity sodium carboxymethyl cellulose is too high, and the addition amount of the sodium metasilicate serving as the debonding agent is too much, so that the glaze slip is thickened and has high thixotropy, the antibacterial performance of the ceramic tile is reduced, pores on the surface are increased, the ceramic tile is more easily polluted by bacteria, and the antibacterial durability is also poor; in example 6, if the polymerization degree of the low-viscosity sodium carboxymethylcellulose is too large and the molecular chain is too long, suspension of the antibacterial agent with a small density and a small particle size cannot be achieved, the suspension effect of the antibacterial agent is reduced, and the antibacterial ceramic glaze is easily dispersed unevenly and thus delaminated, thereby affecting the antibacterial effect of the ceramic glaze.
From the test results, the antibacterial rate and the antibacterial durability of the ceramic tile obtained in example 7 and example 8 are poor, the particle size of the nano silver-loaded zirconium silicate and the nano zinc oxide in example 7 is too small, the specific surface area is too large, the particle surface energy is too large, agglomeration is easy to occur, the antibacterial effect of the antibacterial agent in the ceramic glaze is restricted after the agglomeration of the antibacterial agent, and the antibacterial rate and the antibacterial durability are obviously reduced; in example 8, the Zn in the antibacterial agent is affected by the undersize particle sizes and the oversized impurity contents of the nano-zirconium silicate silver-carrying nano-zinc oxide2+、Ag+And the combination with enzymes in bacteria greatly reduces the antibacterial effect.
Example 9
A stain-resistant glazed brick using antibacterial ceramic glaze is prepared by the following steps:
(1) according to the weight percentage of the dry weight of the ceramic glaze, 2 percent of nano-zirconium silicate silver and 0.1 percent of nano-zinc oxide (the grain diameter of the nano-zirconium silicate silver and the nano-zinc oxide is 25nm +/-2 nm, and Fe in the mixture of the raw material of the nano-zirconium silicate silver and the nano-zinc oxide is added into the conventional ceramic glaze203≤0.01％，TiO2Not more than 0.02 percent) and evenly mixing to prepare the ceramic glaze containing the antibacterial agent, wherein 0.1 percent of medium viscosity sodium carboxymethyl cellulose (with the polymerization degree of 550), 0.01 percent of low viscosity sodium carboxymethyl cellulose (with the polymerization degree of 200) and 0.5 percent of sodium metasilicate are added into the ceramic glaze containing the antibacterial agent according to the weight percentage of the dry weight of the ceramic glaze containing the antibacterial agent, and after the mixture is evenly mixed, water is added for ball milling for 6 hours, the pH of ball milling slurry is 7.0, the ball milling temperature is 50 ℃, the fineness of the ball milling slurry is that a specific gravity cup passes through a 325-mesh sieve, the screen residue is 0.6 percent, and the flow rate is 40 seconds, so that the antibacterial ceramic.
(2) Mixing known ceramic powder, adding water, ball-milling for 9 hours, and then spraying and granulating the obtained slurry through a spray tower;
(3) pressing the powder obtained by spray granulation into a green brick and then drying;
(4) spraying known ceramic base glaze on the green brick, and then carrying out ink-jet printing treatment on the surface of the green brick;
(5) spraying the antibacterial ceramic glaze prepared in the step (1) on the surface of the ink-jet printing layer, wherein the glazing thickness is 0.3 mm;
(6) and (3) firing for 80min at the firing temperature of 1165 ℃, wherein the water absorption rate of the finished ceramic tile product after firing is less than or equal to 0.1%.
(7) And (3) after the ceramic tile is fired in a kiln, carrying out edge grinding, polishing, grading and surface waxing antifouling treatment to prepare the stain-resistant polished glazed tile with the antibacterial function.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (10)
1. An antibacterial ceramic glaze is characterized in that the raw material components comprise a ceramic glaze material, an antibacterial agent, a suspending agent and a degumming agent;
the antibacterial agent is a mixture of nano silver-loaded zirconium silicate and nano zinc oxide, and the addition amount of the nano silver-loaded zirconium silicate is 2-6% and the addition amount of the nano zinc oxide is 0.05-2% calculated according to the weight percentage of the dry weight of the ceramic glaze;
the suspending agent is a mixture of low-viscosity sodium carboxymethyl cellulose and medium-viscosity sodium carboxymethyl cellulose, and the adding amount of the suspending agent is 0.05-0.15 percent by weight percentage based on the dry weight of the ceramic glaze containing the antibacterial agent, wherein the adding amount of the low-viscosity sodium carboxymethyl cellulose is 0.005-0.05 percent, and the adding amount of the medium-viscosity sodium carboxymethyl cellulose is 0.05-0.14 percent;
the debonder is one of sodium tripolyphosphate or sodium metasilicate, and the addition amount of the debonder is 0.1-0.6% by weight percent based on the dry weight percentage of the ceramic glaze containing the antibacterial agent.
2. The antibacterial ceramic glaze according to claim 1, wherein the polymerization degree of the low-viscosity sodium carboxymethyl cellulose is 150-300, and the polymerization degree of the medium-viscosity sodium carboxymethyl cellulose is 500-600.
3. The antibacterial ceramic glaze according to claim 1, wherein the particle sizes of the nano silver silicate and the nano zinc oxide are respectively 25nm +/-10 nm.
4. The antibacterial ceramic glaze according to claim 1, wherein Fe in the mixture of the nano silver silicate and the nano zinc oxide is calculated according to the weight percentage of the raw materials203Less than or equal to 0.03 percent and TiO2≤0.03％。
5. The preparation method of the antibacterial ceramic glaze according to claim 1, wherein the antibacterial agent is added into the ceramic glaze according to the weight percentage and uniformly mixed, the suspending agent and the dispergator are added into the ceramic glaze raw material containing the antibacterial agent according to the weight percentage and uniformly mixed, and then water is added for ball milling for 5-12 hours to prepare the antibacterial ceramic glaze, wherein the fineness of ball milling slurry is that a specific gravity cup passes through a 325-mesh sieve, the screen residue is 0.5-0.8%, and the flow rate is 30-50 seconds.
6. The preparation method of the antibacterial ceramic glaze according to claim 5, wherein the ball milling slurry has a pH of 6.5-9.0 and a ball milling temperature of 40-70 ℃.
7. The method for preparing ceramic tiles using an antibacterial ceramic glaze according to any one of claims 5 or 6, characterized by comprising the following steps:
(1) preparing a green brick;
(2) pouring base glaze: pouring base glaze on the surface of the green brick, and performing ink-jet printing treatment to obtain a green brick with the surface provided with the ink-jet printing layer;
(3) pouring the antibacterial glaze: spraying the antibacterial ceramic glaze on the surface of the ink-jet printing layer;
(4) and putting into a kiln for sintering to obtain the ceramic tile with the antibacterial function.
8. The method for preparing ceramic tiles using antibacterial ceramic glaze according to claim 7, wherein the thickness of the antibacterial glaze layer sprayed in the step (3) is 0.1mm to 0.4 mm.
9. The preparation method of the ceramic tile using the antibacterial ceramic glaze as claimed in claim 7, wherein the firing temperature in the step (4) is 1150-1210 ℃, the firing time is 50-90 min, and the water absorption rate of the finished ceramic tile is less than or equal to 0.2%.
10. The method for preparing ceramic tiles using antibacterial ceramic glaze according to claim 7, wherein the kiln firing is further followed by one or more steps of edging, polishing, grading and antifouling treatment.
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|---|---|---|---|---|
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4589899A (en) * | 1984-11-05 | 1986-05-20 | Owens-Illinois, Inc. | Sealing glass |
| WO1998022404A1 (en) * | 1996-11-18 | 1998-05-28 | Techneglas, Inc. | Low temperature sealing glass |
| CN103304215A (en) * | 2013-06-08 | 2013-09-18 | 上海御窑艺术品有限公司 | Ultra nanometer silver ion zirconium silicate ceramic artwork and preparation method thereof |
| CN105084867A (en) * | 2015-08-05 | 2015-11-25 | 澧县新鹏陶瓷有限公司 | Antibiosis ceramic product with coal ash as main raw material and preparing method of antibiosis ceramic product |
| CN106396399A (en) * | 2016-08-31 | 2017-02-15 | 广东金意陶陶瓷有限公司 | Mineral crystal fancy glaze with antibacterial effect and ceramic tiles prepared from mineral crystal fancy glaze |
| CN106673633A (en) * | 2016-12-30 | 2017-05-17 | 张海淼 | Antibacterial bathroom ceramic article and preparation method thereof |
| CN106986542A (en) * | 2017-05-15 | 2017-07-28 | 晋大纳米科技（厦门）有限公司 | A kind of far-infrared anti-biotic ceramic glaze and preparation method thereof |
| CN110054413A (en) * | 2019-06-10 | 2019-07-26 | 佛山市玖玖新陶科技有限公司 | It is a kind of to remove simultaneously formaldehyde, except the ceramic glaze of toluene and antibacterial |
| CN110128111A (en) * | 2019-06-03 | 2019-08-16 | 福建省德化县臻晖陶瓷有限公司 | A kind of antibacterial ceramic products and preparation method thereof |
| CN111333325A (en) * | 2020-05-21 | 2020-06-26 | 佛山市东鹏陶瓷发展有限公司 | High-acid-and-alkali-resistance antibacterial ceramic glaze, preparation method thereof and preparation method of ceramic tile |
-
2019
- 2019-12-23 CN CN201911340842.0A patent/CN110818261A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4589899A (en) * | 1984-11-05 | 1986-05-20 | Owens-Illinois, Inc. | Sealing glass |
| WO1998022404A1 (en) * | 1996-11-18 | 1998-05-28 | Techneglas, Inc. | Low temperature sealing glass |
| CN103304215A (en) * | 2013-06-08 | 2013-09-18 | 上海御窑艺术品有限公司 | Ultra nanometer silver ion zirconium silicate ceramic artwork and preparation method thereof |
| CN105084867A (en) * | 2015-08-05 | 2015-11-25 | 澧县新鹏陶瓷有限公司 | Antibiosis ceramic product with coal ash as main raw material and preparing method of antibiosis ceramic product |
| CN106396399A (en) * | 2016-08-31 | 2017-02-15 | 广东金意陶陶瓷有限公司 | Mineral crystal fancy glaze with antibacterial effect and ceramic tiles prepared from mineral crystal fancy glaze |
| CN106673633A (en) * | 2016-12-30 | 2017-05-17 | 张海淼 | Antibacterial bathroom ceramic article and preparation method thereof |
| CN106986542A (en) * | 2017-05-15 | 2017-07-28 | 晋大纳米科技（厦门）有限公司 | A kind of far-infrared anti-biotic ceramic glaze and preparation method thereof |
| CN110128111A (en) * | 2019-06-03 | 2019-08-16 | 福建省德化县臻晖陶瓷有限公司 | A kind of antibacterial ceramic products and preparation method thereof |
| CN110054413A (en) * | 2019-06-10 | 2019-07-26 | 佛山市玖玖新陶科技有限公司 | It is a kind of to remove simultaneously formaldehyde, except the ceramic glaze of toluene and antibacterial |
| CN111333325A (en) * | 2020-05-21 | 2020-06-26 | 佛山市东鹏陶瓷发展有限公司 | High-acid-and-alkali-resistance antibacterial ceramic glaze, preparation method thereof and preparation method of ceramic tile |
Non-Patent Citations (4)
| Title |
|---|
| 任强等: "《绿色硅酸盐材料与清洁生产》", 30 September 2004, 化学工业出版社 * |
| 徐建华等: "《陶瓷花釉与装饰技术》", 30 April 2011, 中国轻工业出版社 * |
| 郑水林等: "《粉体表面改性（第四版）》", 30 June 2019, 中国建材工业出版社 * |
| 陈家威等: "《简明化学辞典》", 31 July 1987, 湖北辞书出版社 * |
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