CN113860734B - Ceramic glaze with antibacterial function and preparation method and application thereof - Google Patents

Ceramic glaze with antibacterial function and preparation method and application thereof Download PDF

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Publication number
CN113860734B
CN113860734B CN202111169027.XA CN202111169027A CN113860734B CN 113860734 B CN113860734 B CN 113860734B CN 202111169027 A CN202111169027 A CN 202111169027A CN 113860734 B CN113860734 B CN 113860734B
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glaze
scandium
ceramic
neodymium
ceramic glaze
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CN113860734A (en
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倪成林
周楚煌
黄继伟
郑敏玲
刘敏銮
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Guangdong Songfa Ceramics Co ltd
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Guangdong Songfa Ceramics Co ltd
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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
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • 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
    • 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
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

Abstract

The invention belongs to the technical field of ceramic materials, and discloses a ceramic glaze with an antibacterial function, and a preparation method and application thereof. The ceramic glaze comprises a basic glaze and a composite antibacterial agent, wherein the composite antibacterial agent comprises a carrier and scandium-and-neodymium-doped zinc oxide, and the scandium-and-neodymium-doped zinc oxide is loaded in the carrier to form a wrapping structure. The preparation method of the ceramic glaze comprises the following steps: adding the carrier into an acid solution and mixing to obtain a suspension solution; mixing an acid solution, an alkali solution and water to obtain a mixed solution; mixing the suspension solution and the mixed solution, adding soluble zinc salt, soluble scandium salt and soluble neodymium salt, mixing and calcining to obtain the composite antibacterial agent; and mixing the basic glaze with the composite antibacterial agent, and grinding to obtain the ceramic glaze. The ceramic glaze material of the invention can still maintain excellent antibacterial performance and glaze surface quality under the firing conditions of the daily ceramic firing temperature of 1280-1350 ℃ and the firing time of 8-10 h.

Description

Ceramic glaze with antibacterial function and preparation method and application thereof
Technical Field
The invention belongs to the technical field of ceramic materials, particularly relates to a functional material for domestic ceramics, and particularly relates to a ceramic glaze material with an antibacterial function, and a preparation method and application thereof.
Background
With the increasing health awareness, people pay more and more attention to the sanitation of appliances used in daily life, and in addition to the easy-to-clean property of the surface, people also pay attention to the antibacterial property of the appliances. At present, the antibacterial daily-use ceramic appliances have also come into the visual field of consumers, and the antibacterial functional ceramic appliances are mainly realized by antibacterial glaze.
Metal ion antibacterial agents such as silver system, zinc system and copper system are widely used in the field of ceramics, but the zinc system antibacterial agent is generally preferred in view of the problems of coloring of glaze and high cost of silver and copper system metal ion antibacterial agents. The zinc system antibacterial agent has small influence on the glaze surface and the zinc oxide is a common component for improving the glaze light transmittance, so the zinc oxide antibacterial agent is more suitable for being used as the antibacterial agent of the ceramic glaze, but the antibacterial property of the zinc oxide antibacterial agent is lower than that of a silver system, so the ceramic glaze generally adopts silver-zinc composite antibacterial agent, such as zirconium phosphate silver-zinc-carrying antibacterial agent, as the antibacterial agent of the ceramic glaze in the high temperature field, but the influence of silver ion coloring on the glaze surface in the later period can not be avoided.
In the firing process of the domestic ceramics, the firing temperature is required to be high (above 1280 ℃), the firing time is required to be long (above 8 hours), the requirement on the decorative performance of the product is very high, and the zirconium phosphate silver-zinc-carrying antibacterial agent is obviously not the best choice. The existing rare earth antibacterial ceramic glaze is prepared by firstly preparing an antibacterial agent by using zinc oxide, rare earth elements lanthanum and cerium as raw materials and then compounding the antibacterial agent and a base glaze according to a proper weight ratio.
Therefore, it is urgently needed to develop a zinc system high-temperature antibacterial glaze material to make up for the defects in the preparation technology of domestic ceramics.
Disclosure of Invention
The invention provides a ceramic glaze with an antibacterial function, a preparation method and application thereof, which are used for solving one or more technical problems in the prior art and providing at least one beneficial choice or creation condition.
In order to overcome the technical problems, the invention provides a ceramic glaze in a first aspect.
The ceramic glaze comprises a base glaze and a composite antibacterial agent, wherein the composite antibacterial agent comprises a carrier and scandium-and-neodymium-doped zinc oxide, and the scandium-and-neodymium-doped zinc oxide is loaded in the carrier to form a wrapping structure.
The ceramic glaze provided by the invention contains the composite antibacterial agent, the main antibacterial component of the composite antibacterial agent is zinc oxide, the antibacterial performance of the zinc oxide is improved by rare earth scandium and neodymium doped zinc oxide, and meanwhile, the scandium and neodymium doped zinc oxide is loaded in the carrier to form a wrapping structure, so that the overall thermal stability of the composite antibacterial agent can be improved, and the ceramic glaze still has high antibacterial activity after being fired for 8-10 hours at the firing temperature of 1280-1350 ℃.
The composite antibacterial agent belongs to a zinc metal ion type inorganic antibacterial agent, zinc ions mainly form zinc oxide by the zinc ions except for having the function of destroying bacterial cell enzymes, bacteria are killed by utilizing ZnO photocatalysis, the action mechanism process of the composite antibacterial agent can be explained according to the electron transition theory in materials, a large number of hole electron pairs are formed in the electron transition process, the delta G of the reaction of the hole electron pairs and water and oxygen in the air is negative, the hole electron pairs can spontaneously react to generate free radicals without external energy, the free radicals can react with chemical bonds in the enzymes to stop the normal respiratory metabolism function of the bacteria, and intracellular solutes can react with the free radicals again to finally thoroughly decompose bacterial debris into water and carbon dioxide products harmless to the environment, but the wide band gap and the low visible light utilization rate of ZnO limit the antibacterial performance of the ZnO, so rare earth elements scandium and neodymium are doped into ZnO crystal lattices to reduce the bandwidth and improve the electron transition capability, thereby improving the photocatalytic antibacterial activity of the zinc oxide.
Meanwhile, scandium-and-neodymium-doped zinc oxide is loaded in a carrier, and the carrier is mainly used for wrapping zinc oxide crystals, so that partial or even all zinc oxide is prevented from being fused into a glass phase to form an amorphous body in the high-temperature sintering process of the ceramic glaze, and the antibacterial effect of the zinc oxide is reduced.
As a further improvement of the above scheme, in the scandium-and-neodymium-doped zinc oxide, the molar ratio of zinc ions, scandium ions, and neodymium ions is (30-150): (0.1-2.5): 1. specifically, scandium and neodymium are doped in the zinc oxide in a certain proportion, so that the best antibacterial activity of the zinc oxide is favorably exerted.
As a further improvement of the above scheme, the carrier comprises at least one of sepiolite, diatomaceous earth, zeolite, montmorillonite, and calcium phosphate.
Preferably, the carrier is sepiolite. In particular, sepiolite has a large specific surface area (up to 900 m) 2 The/g) and the unique inner pore canal structure are one of the clay minerals with the strongest adsorption capacity, and are beneficial to adsorbing zinc and rare earth ions (scandium ions and neodymium ions) to form a coating structure. Meanwhile, the sepiolite is a silicate mineral and can resist the high temperature of 1500-1700 DEG CThe scandium-neodymium doped zinc oxide is coated by sepiolite, so that the activity of zinc ions is improved, and the reduction of antibacterial performance caused by the fact that zinc and rare earth ions are fused into a glass phase in the high-temperature firing process is avoided.
As a further improvement of the scheme, the fineness of the carrier is 250-400 meshes. Specifically, on one hand, a carrier with certain fineness can provide more adsorption pore channels so as to be beneficial to better loading scandium-and-neodymium-doped zinc oxide; on the other hand, the fineness of the carrier is controlled, the specific surface area of the carrier can be increased, and the sintering activity is improved, so that the influence of overlarge particles on the sintering degree and the glaze quality is avoided.
As a further improvement of the scheme, the weight percentage of the composite antibacterial agent in the ceramic glaze is 6-10%. Specifically, the addition of a certain amount of the composite antibacterial agent can ensure the antibacterial performance of the glaze and simultaneously does not influence the glaze effect of the glaze.
As a further improvement of the above scheme, the basic glaze composition comprises, in parts by weight: 18-20 parts of quartz, 8-10 parts of silica fume, 35-39 parts of potash feldspar, 6-8 parts of Longyan wash mud, 12-14 parts of calcite, 2-5 parts of calcined talc and 3-5 parts of spodumene.
Preferably, the chemical composition of the micro silicon powder is as follows by weight percent: siO 2 2 92-97％，Al 2 O 3 0.3-0.5％，Fe 2 O 3 0.02-0.06％，CaO 0.3-0.6％，MgO 0.8-1.2％，K 2 O 4-5％，Na 2 O 0.2-4％。
Preferably, the fineness of the micro silicon powder is 300-400 meshes.
Specifically, the micro silicon powder is a tailing material produced by metal silicon powder, is mainly applied to the concrete industry as an active material at present, and has low utilization value. The invention applies the silicon micro-powder to ceramic glaze, because of SiO in the silicon micro-powder 2 The content of the silicon dioxide reaches 92-97 percent, and the silicon dioxide can be used as SiO 2 Principal source of component, and Fe 2 O 3 The content is lower than 0.06 percent, and the requirement of the whiteness of the glaze surface is fully ensured. Meanwhile, ultrafine powder with the fineness of tailing micro silicon powder more than 300-400 meshes is selected, and compared with the method of adding common quartz to introduce SiO 2 The component is not only micro silicon powderThe glaze quality is improved, the firing temperature is reduced, the grading and the resource maximum utilization of the tailing micro silicon powder can be promoted, and the utilization value of the tailing micro silicon powder is further improved.
The second aspect of the invention provides a preparation method of the ceramic glaze.
Specifically, the preparation method of the ceramic glaze comprises the following steps:
adding the carrier into an acid solution and mixing to obtain a suspension solution;
mixing an acid solution, an alkali solution and water to obtain a mixed solution;
mixing the suspension solution with the mixed solution, adding soluble zinc salt, soluble scandium salt and soluble neodymium salt, mixing and calcining to obtain the composite antibacterial agent;
and mixing the basic glaze with the composite antibacterial agent, and grinding to obtain the ceramic glaze.
Preferably, the acid solution comprises acetic acid.
Preferably, the alkali solution comprises ammonia.
Preferably, the soluble zinc salt comprises zinc nitrate and/or zinc acetate.
Preferably, the soluble scandium salt comprises scandium nitrate and/or scandium acetate.
Preferably, the soluble neodymium salt comprises neodymium nitrate and/or neodymium acetate.
Preferably, the temperature of the calcination is 480-520 ℃, and the time of the calcination is 10-15 minutes.
Preferably, a method for preparing a ceramic glaze comprises the following steps:
adding 5-10g of sepiolite powder and 100-120mL of acetic acid into a reactor, and stirring for 10-20 minutes to obtain a suspension solution;
adding 200-250mL of acetic acid, 15-20mL of ammonia water and 5-8mL of water into another reactor, and stirring for 10-20 minutes to obtain a mixed solution;
and mixing the suspension solution and the mixed solution, adding 50-100mL (0.9 mol/L) of zinc nitrate solution, 20-50mL (3 mmol/L) of scandium nitrate solution and 20-50mL (3 mmol/L) of neodymium nitrate solution, stirring for 10-20 minutes, standing for reaction for 4-6 hours, then performing centrifugal separation, and finally calcining at 480-520 ℃ for 10-15 minutes to obtain the composite antibacterial agent.
And mixing the basic glaze with the composite antibacterial agent, adding water, and ball-milling for 20-30 minutes to obtain the ceramic glaze.
Specifically, acid-base neutralization and complexation mainly occur in the mixing process of the solutions, acetic acid is added into the sepiolite to further erode to form more sepiolite pore structures, and redundant acetic acid in the pore structures reacts with the mixed solution of zinc-ammonia complex ions such as zinc, scandium, neodymium, ammonia water and the like to promote the zinc ions, scandium ions and neodymium ions to be adsorbed on the pore walls of the sepiolite to form a wrapped structure. Meanwhile, the purpose of calcination can further enable zinc ions to form zinc oxide, and volatilize and remove excessive organic matters decomposed by acid, alkali and nitrate, so that the influence on the glaze quality is avoided.
The third aspect of the invention provides a ceramic glaze.
The domestic ceramic appliance comprises a green body layer and an antibacterial glaze layer, wherein the antibacterial glaze layer is formed by firing the ceramic glaze.
Preferably, the firing temperature of the ceramic glaze is 1280-1350 ℃.
Preferably, the firing time of the ceramic frit is 8 to 10 hours.
Further preferably, the firing system of the ceramic glaze is as follows: burning at 0-600 deg.C for 180min; burning at 601-860 deg.C for 60min; calcining at 861-1025 deg.C for 60min; burning at 1026-1090 deg.C for 60min; baking at 1091-1320 deg.C for 60min; keeping the temperature at 1320-1320 ℃ for 120min, then naturally cooling, cooling to 750 ℃ and then quenching.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
according to the invention, rare earth elements scandium and neodymium are doped with zinc oxide, so that the rare earth elements scandium and neodymium are doped into ZnO crystal lattices, the forbidden bandwidth is reduced, and the electron transition capability is improved, thereby improving the photocatalytic antibacterial activity of the zinc oxide. Meanwhile, scandium-and-neodymium-doped zinc oxide is loaded in the carrier, so that the activity of zinc ions is improved, the thermal stability of the composite antibacterial agent is improved, and the phenomenon that zinc and rare earth ions are fused into a glass phase in the high-temperature firing process to reduce the antibacterial performance is avoided.
The tailing micro silicon powder produced by adding metal silicon powder into the basic glaze is used as SiO in the glaze 2 The main source of the silica fume is not only beneficial to improving the glaze quality and reducing the firing temperature, but also can promote the grading and the resource maximum utilization of the silica fume, further improve the utilization value of the silica fume and provide a green development way for the recycling of the silica fume.
The ceramic glaze material with the antibacterial function can still maintain excellent antibacterial performance and glaze surface quality under the firing conditions that the firing temperature of the domestic ceramic is 1280-1350 ℃ and the firing time is 8-10 hours.
Detailed Description
The present invention is described in detail below by way of examples to facilitate understanding of the present invention by those skilled in the art, and it is to be specifically noted that the examples are provided only for the purpose of further illustrating the present invention and are not to be construed as limiting the scope of the present invention.
Example 1
A ceramic glaze contains a composite antibacterial agent and a basic glaze, wherein: the composite antibacterial agent comprises sepiolite and scandium-neodymium doped zinc oxide, wherein the scandium-neodymium doped zinc oxide is loaded in the sepiolite to form a wrapping structure.
In the ceramic glaze, the weight percentage of the composite antibacterial agent is 10 percent; the fineness of the sepiolite is 300 meshes; in the scandium-neodymium doped zinc oxide, the molar ratio of zinc ions to scandium ions to neodymium ions is 75:1:1; the basic glaze comprises the following components in parts by weight: 18 parts of quartz, 10 parts of silica fume, 37 parts of potash feldspar and 7 parts of Longyan washing mud12 parts of calcite, 2 parts of calcined talc and 4 parts of spodumene. Wherein: the chemical composition of the micro silicon powder comprises the following components in percentage by weight: siO 2 2 92％，Al 2 O 3 0.3％，Fe 2 O 3 0.02％，CaO 0.6％，MgO 1.2％，K 2 O 5％，Na 2 0.88 percent of O; the fineness of the micro silicon powder is 400 meshes.
A preparation method of ceramic glaze comprises the following steps:
adding 5g of sepiolite powder and 100mL of acetic acid into a reactor, and stirring for 15 minutes to obtain a suspension solution;
adding 200mL of acetic acid, 15mL of ammonia water and 5mL of water into another reactor, and stirring for 15 minutes to obtain a mixed solution;
and mixing the suspension solution and the mixed solution, adding 50mL (0.9 mol/L) of zinc nitrate solution, 20mL (3 mmol/L) of scandium nitrate solution and 20mL (3 mmol/L) of neodymium nitrate solution, stirring for 15 minutes, standing for reaction for 5 hours, then performing centrifugal separation, and finally calcining at the temperature of 500 ℃ for 10 minutes to obtain the composite antibacterial agent.
And mixing the basic glaze and the composite antibacterial agent, adding water, and ball-milling for 20 minutes to obtain the ceramic glaze.
The domestic ceramic utensil includes one green body layer and one antiseptic glaze layer, and the green body layer is produced with common domestic ceramic green body and through applying the glaze material to the green body layer and firing.
Wherein: the firing temperature of the ceramic glaze is 1300 ℃, and the firing time of the ceramic glaze is 9 hours. The specific firing system is as follows: burning at 0-600 deg.C for 180min; burning at 601-860 deg.C for 60min; calcining at 861-1025 deg.C for 60min; burning at 1026-1090 deg.C for 60min; heating at 1091-1300 deg.C for 60min; preserving the heat at 1300-1300 ℃ for 120min, then naturally cooling, cooling to 750 ℃ and then quenching.
Example 2
A ceramic glaze contains a composite antibacterial agent and a basic glaze, wherein: the composite antibacterial agent comprises sepiolite and scandium-and-neodymium-doped zinc oxide, wherein the scandium-and-neodymium-doped zinc oxide is loaded in the sepiolite to form a wrapping structure.
In the ceramic glaze, the weight of the composite antibacterial agentThe amount percentage is 8%; the fineness of the sepiolite is 350 meshes; in the scandium-neodymium doped zinc oxide, the molar ratio of zinc ions, scandium ions and neodymium ions is 100:1:1; the basic glaze comprises the following components in parts by weight: 19 parts of quartz, 9 parts of silica fume, 35 parts of potassium feldspar, 8 parts of Longyan wash mud, 13 parts of calcite, 3 parts of calcined talc and 5 parts of spodumene. Wherein: the chemical composition of the micro silicon powder is as follows by weight percent: siO 2 2 94％，Al 2 O 3 0.3％，Fe 2 O 3 0.03％，CaO 0.59％，MgO 1％，K 2 O 3％，Na 2 1.08 percent of O; the fineness of the micro silicon powder is 350 meshes.
A preparation method of ceramic glaze comprises the following steps:
adding 8g of sepiolite powder and 100mL of acetic acid into a reactor, and stirring for 15 minutes to obtain a suspension solution;
adding 220mL of acetic acid, 18mL of ammonia water and 6mL of water into another reactor, and stirring for 15 minutes to obtain a mixed solution;
and mixing the suspension solution and the mixed solution, adding 80mL (0.9 mol/L) of zinc nitrate solution, 24mL (3 mmol/L) of scandium nitrate solution and 24mL (3 mmol/L) of neodymium nitrate solution, stirring for 15 minutes, standing for reaction for 5 hours, then performing centrifugal separation, and finally calcining at 480 ℃ for 15 minutes to obtain the composite antibacterial agent.
And mixing the basic glaze and the composite antibacterial agent, adding water, and ball-milling for 25 minutes to obtain the ceramic glaze.
The domestic ceramic utensil includes one green body layer and one antiseptic glaze layer, and the green body layer is produced with common domestic ceramic green body and through applying the glaze material to the green body layer and firing.
Wherein: the firing temperature of the ceramic glaze is 1320 ℃, and the firing time of the ceramic glaze is 9 hours. The specific firing system is as follows: burning at 0-600 deg.C for 180min; burning at 601-860 deg.C for 60min; calcining at 861-1025 deg.C for 60min; burning at 1026-1090 deg.C for 60min; baking at 1091-1320 deg.C for 60min; keeping the temperature at 1320-1320 ℃ for 120min, then naturally cooling, cooling to 750 ℃ and then quenching.
Example 3
A ceramic glaze contains a composite antibacterial agent and a basic glaze, wherein: the composite antibacterial agent comprises sepiolite and scandium-neodymium doped zinc oxide, wherein the scandium-neodymium doped zinc oxide is loaded in the sepiolite to form a wrapping structure.
In the ceramic glaze, the weight percentage of the composite antibacterial agent is 6 percent; the fineness of the sepiolite is 350 meshes; in the scandium-neodymium doped zinc oxide, the molar ratio of zinc ions, scandium ions and neodymium ions is 150:1:1; the basic glaze comprises the following components in parts by weight: 20 parts of quartz, 8 parts of silica fume, 36 parts of potash feldspar, 8 parts of Longyan wash mud, 14 parts of calcite, 5 parts of calcined talc and 3 parts of spodumene. Wherein: the chemical composition of the micro silicon powder comprises the following components in percentage by weight: siO 2 2 94％，Al 2 O 3 0.3％，Fe 2 O 3 0.03％，CaO 0.59％，MgO 1％，K 2 O 3％，Na 2 O1.08%; the fineness of the micro silicon powder is 350 meshes.
A preparation method of ceramic glaze comprises the following steps:
adding 10g of sepiolite powder and 120mL of acetic acid into a reactor, and stirring for 15 minutes to obtain a suspension solution;
adding 250mL of acetic acid, 20mL of ammonia water and 8mL of water into another reactor, and stirring for 15 minutes to obtain a mixed solution;
and mixing the suspension solution and the mixed solution, adding 100mL (0.9 mol/L) of zinc nitrate solution, 20mL (3 mmol/L) of scandium nitrate solution and 20mL (3 mmol/L) of neodymium nitrate solution, stirring for 15 minutes, standing for reaction for 6 hours, then performing centrifugal separation, and finally calcining at 520 ℃ for 10 minutes to obtain the composite antibacterial agent.
And mixing the basic glaze and the composite antibacterial agent, adding water, and ball-milling for 30 minutes to obtain the ceramic glaze.
The daily-use ceramic utensil comprises a blank layer and an antibacterial glaze layer, wherein the blank layer is made of a common daily-use ceramic blank, and the ceramic glaze prepared in the embodiment is applied to the blank layer and fired.
Wherein: the firing temperature of the ceramic glaze is 1350 ℃, and the firing time of the ceramic glaze is 10 hours. The specific firing system is as follows: burning at 0-600 deg.C for 180min; burning at 601-860 deg.C for 60min; decocting at 861-1025 deg.C for 60min; burning at 1026-1090 deg.C for 60min; baking at 1091-1350 deg.C for 90min; keeping the temperature at 1350-1350 ℃ for 150min, then naturally cooling, cooling to 750 ℃ and then quenching.
Comparative example 1
A ceramic glaze comprising an antibacterial agent and a base glaze, wherein: the antibacterial agent is scandium-neodymium doped zinc oxide.
In the ceramic glaze, the weight percentage of the antibacterial agent is 10 percent; in the scandium-neodymium doped zinc oxide, the molar ratio of zinc ions, scandium ions and neodymium ions is 75:1:1; the basic glaze comprises the following components in parts by weight: 18 parts of quartz, 10 parts of silica fume, 37 parts of potash feldspar, 7 parts of Longyan wash mud, 12 parts of calcite, 2 parts of calcined talc and 4 parts of spodumene. Wherein: the chemical composition of the micro silicon powder is as follows by weight percent: siO 2 2 92％，Al 2 O 3 0.3％，Fe 2 O 3 0.02％，CaO 0.6％，MgO 1.2％，K 2 O 5％，Na 2 0.88 percent of O; the fineness of the micro silicon powder is 400 meshes.
A preparation method of ceramic glaze comprises the following steps:
100mL (0.9 mol/L) of zinc nitrate solution, 20mL (3 mmol/L) of scandium nitrate solution and 20mL (3 mmol/L) of neodymium nitrate solution were stirred for 15 minutes, left to stand for reaction for 6 hours, centrifuged again, and finally calcined at 520 ℃ for 10 minutes to obtain the antibacterial agent.
And mixing the basic glaze and the antibacterial agent, adding water, and ball-milling for 30 minutes to obtain the ceramic glaze.
A domestic ceramic utensil comprises a body layer and an antibacterial glaze layer, wherein the body layer is made of a common domestic ceramic body, and the ceramic glaze prepared in the comparative example is applied on the body layer to be fired, and the firing system is the same as that in example 1.
The ceramic frit of comparative example 1 differs from example 1 in that: the antibacterial agent does not contain a carrier, namely scandium and neodymium doped zinc oxide is directly added into ceramic glaze, sepiolite is not adopted for coating, and the composition and the addition amount of other raw materials are the same as those in the embodiment 1.
Comparative example 2
A ceramic glaze comprising an antibacterial agent and a base glaze, wherein: the antibacterial agent is a zirconium phosphate silver-loaded antibacterial agent.
In the ceramic glaze, the weight percentage of the antibacterial agent is 10 percent; the basic glaze comprises the following components in parts by weight: 18 parts of quartz, 10 parts of silica fume, 37 parts of potash feldspar, 7 parts of Longyan mud, 12 parts of calcite, 2 parts of calcined talc and 4 parts of spodumene. Wherein: the chemical composition of the micro silicon powder comprises the following components in percentage by weight: siO 2 2 92％，Al 2 O 3 0.3％，Fe 2 O 3 0.02％，CaO 0.6％，MgO 1.2％，K 2 O 5％，Na 2 0.88 percent of O; the fineness of the micro silicon powder is 400 meshes.
A preparation method of ceramic glaze comprises the following steps:
and mixing the basic glaze and the antibacterial agent, adding water, and ball-milling for 30 minutes to obtain the ceramic glaze.
A domestic ceramic utensil comprises a body layer and an antibacterial glaze layer, wherein the body layer is made of a common domestic ceramic body, and the ceramic glaze prepared in the comparative example is applied on the body layer to be fired, and the firing system is the same as that in example 1.
The ceramic frit of comparative example 2 differs from example 1 in that: the antibacterial agent adopts zirconium phosphate silver-carrying antibacterial agent, and the other raw materials and the addition amount are the same as those in the example 1.
Performance test
According to JC/T897-2014 (antibacterial performance of antibacterial ceramic products), the antibacterial rate and antibacterial durability of the daily ceramic appliance samples obtained in the examples and the comparative examples are detected, the glaze quality of the daily ceramic appliance samples is observed, and the test results are shown in Table 1.
TABLE 1 comparison table of product performance test of each example and comparative example
Figure BDA0003290326630000101
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From the results of the product performance tests of the examples and comparative examples in table 1, it can be seen that: the samples corresponding to the embodiments 1, 2 and 3 have good antibacterial effects on escherichia coli and staphylococcus aureus, and the glaze surface of the sample has good quality, no spots and good decoration. In contrast, in comparative example 1, since the antibacterial agent in the ceramic glaze was not coated with sepiolite, part of the zinc oxide was melted into the glass phase during the high-temperature firing, and thus the antibacterial performance was remarkably lowered. Comparative example 2 adopts zirconium phosphate silver-carrying as an antibacterial agent, the glaze surface has brown spots due to the oxidation of silver ions, and the continuous observation shows that the brown spots of the glaze surface are gradually increased in the using process, which affects the use of the domestic ceramics and the health of users.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the present invention.

Claims (7)

1. The ceramic glaze is characterized by comprising a base glaze and a composite antibacterial agent, wherein the composite antibacterial agent comprises a carrier and scandium-neodymium doped zinc oxide, and the scandium-neodymium doped zinc oxide is loaded in the carrier to form a wrapping structure; the carrier is sepiolite;
in the scandium-neodymium doped zinc oxide, the molar ratio of zinc ions, scandium ions and neodymium ions is (30-150): (0.1-2.5): 1;
the ceramic glaze is prepared by a preparation method comprising the following steps of:
adding the carrier into an acid solution, and mixing to obtain a suspension solution;
mixing an acid solution, an alkali solution and water to obtain a mixed solution;
mixing the suspension solution with the mixed solution, adding soluble zinc salt, soluble scandium salt and soluble neodymium salt, mixing and calcining to obtain the composite antibacterial agent;
and mixing the basic glaze with the composite antibacterial agent, and grinding to obtain the ceramic glaze.
2. The ceramic glaze of claim 1 wherein the fineness of the carrier is 250-400 mesh.
3. The ceramic glaze of claim 1 wherein the composite antimicrobial agent is present in the ceramic glaze in an amount of 6 to 10% by weight.
4. The ceramic glaze of claim 1 wherein the base glaze comprises, in parts by weight: 18-20 parts of quartz, 8-10 parts of silica fume, 35-39 parts of potash feldspar, 6-8 parts of Longyan mud, 12-14 parts of calcite, 2-5 parts of calcined talc and 3-5 parts of spodumene.
5. The ceramic glaze according to claim 4, wherein the chemical composition of the micro silicon powder comprises, by weight: siO 2 2 92-97％，Al 2 O 3 0.3-0.5％，Fe 2 O 3 0.02-0.06％，CaO 0.3-0.6％，MgO 0.8-1.2％，K 2 O 4-5％，Na 2 0.2 to 4 percent of O; the fineness of the micro silicon powder is 300-400 meshes.
6. The ceramic glaze of claim 1 wherein the acid solution comprises acetic acid;
the alkali solution comprises ammonia water;
the soluble zinc salt comprises zinc nitrate and/or zinc acetate;
the soluble scandium salt comprises scandium nitrate and/or scandium acetate;
the soluble neodymium salt comprises neodymium nitrate and/or neodymium acetate;
the calcining temperature is 480-520 ℃, and the calcining time is 10-15 minutes.
7. A domestic ceramic appliance comprising a green body layer and an antibacterial glaze layer, wherein the antibacterial glaze layer is formed by firing the ceramic glaze material according to any one of claims 1 to 6.
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