CN112956494A - Nano composite antibacterial powder and application thereof in ceramic tea set - Google Patents
Nano composite antibacterial powder and application thereof in ceramic tea set Download PDFInfo
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- CN112956494A CN112956494A CN202110190241.7A CN202110190241A CN112956494A CN 112956494 A CN112956494 A CN 112956494A CN 202110190241 A CN202110190241 A CN 202110190241A CN 112956494 A CN112956494 A CN 112956494A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
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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
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
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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
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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
- C03C2204/00—Glasses, glazes or enamels with special properties
- C03C2204/02—Antibacterial glass, glaze or enamel
Abstract
The invention provides a nano composite antibacterial powder and an application thereof in ceramic tea sets. The invention also provides an antibacterial and antiviral glaze, an antibacterial and antiviral tea set and a preparation method thereof. The nano composite antibacterial powder has good antibacterial and antiviral properties through the synergistic effect among the nano metal oxide, the silver-doped nano bismuth tungstate and the silver-loaded antibacterial agent; the antibacterial tea set is added into ceramic glaze, and blank glaze with antibacterial and antiviral effects can be formed on the surface of the tea set after spraying and calcining, so that the whole antibacterial tea set is realized, the antibacterial time is long, and the strength, the wear resistance and the appearance of the tea set are not influenced; the preparation method of the antibacterial and antiviral tea set is simple and efficient, energy-saving and environment-friendly, no additional treatment process is needed, and the application value is very high.
Description
Technical Field
The invention belongs to the technical field of daily ceramics, and particularly relates to nano composite antibacterial powder and application thereof in a ceramic tea set.
Background
China is the hometown of tea, and at least thousands of years of history exist from the discovery and drinking of tea to the present, and tea culture is gradually formed. The tea set can be divided into a pottery clay tea set, a porcelain tea set, a lacquer tea set, a glass tea set, a bamboo tea set and the like according to the material, wherein the ceramic tea set is widely used in daily life. The ceramic tea set is a special appliance for making and drinking tea leaves, which is made by firing kaolin and purple clay serving as raw materials, and comprises a ceramic teapot, a ceramic cover bowl, a ceramic teacup, a ceramic tea tray, a ceramic saucer, a ceramic tea washing and the like.
As an appliance directly contacting with drinks, people increasingly have demands on the functionality and safety of tea sets. Various bacteria and viruses in the air are easily attached to the tea set along with the flowing of the airflow, and breed and propagate on the tea set, thereby bringing great threat to the health of users; a large amount of water stains and tea stains exist on the tea set which is not cleaned and dried in time, conditions are created for the growth and propagation of pathogenic microorganisms, and the tea set is not beneficial to the health of people. However, the common tea set sold in the market has single function and does not have corresponding antibacterial and antiviral effects.
Currently, there are related studies on antibacterial tea sets. CN110078485A discloses a novel antibacterial ceramic tea set and a manufacturing method thereof, which comprises the steps of collecting diatomite, clay, calcium oxide and alumina, crushing and ball-milling the diatomite, preparing slurry, pressing the slurry into porcelain clay by a mud press, forming, firing at high temperature to prepare the antibacterial ceramic tea set with strong water absorption, then attaching a layer of nano titanium dioxide silver ion solution on the surface layer of the ceramic tea set, and baking at 200-300 ℃ to obtain the antibacterial ceramic tea set with strong water absorption. The antibacterial tea set can solve the problems of bacterial breeding, odor and mildew of ceramic tea set caused by water accumulation, decay, moisture and residual moisture through the antibacterial and water-absorbing functions of the antibacterial tea set. However, the preparation process of the tea set is complex, the energy consumption is high, the antibacterial coating is easily affected by external environment, human factors and the like, the adhesive force is poor, and the antibacterial performance is not durable.
CN111517828A discloses a nano antibacterial tea set and its manufacturing process, which achieves antibacterial effect by applying a common glaze layer and a nano antibacterial glaze layer on a biscuit, but the nano antibacterial glaze layer is only arranged on the inner walls of a ceramic teapot and a ceramic teacup, which does not achieve the overall antibacterial effect, and applying glaze twice has complex process, difficult operation, complex overall structure of the tea set, and increased production cost by means of a special production instrument.
At present, the existing antibacterial tea set often has the problems that the whole antibacterial effect cannot be realized and the preparation process is complex. How to provide a ceramic tea set with an overall structure, antibacterial and antiviral capabilities, excellent performance, simple preparation method and low production cost becomes a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects and actual requirements of the prior art, the invention provides the nano composite antibacterial powder and the application thereof in the ceramic tea set, the nano composite antibacterial powder has good antibacterial and antiviral properties through the mutual matching of the nano metal oxide, the silver-doped nano bismuth tungstate and the silver-loaded antibacterial agent, and the ceramic glaze prepared by adding the nano composite antibacterial powder into the raw materials of the ceramic glaze has antibacterial and antiviral effects.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a nano-composite antibacterial powder, which comprises a nano metal oxide, silver-doped nano bismuth tungstate and a silver-loaded antibacterial agent.
In the invention, the metal oxide can release metal ions to react with proteins on bacterial proteins to influence the functions of the proteins, so that the antibacterial effect is generated, and after the metal oxide is prepared into nano particles, the size is small, the affinity with pathogens is enhanced, and the antibacterial efficiency is higher; the nano bismuth tungstate can form peroxide ions and hydroxide ions under illumination, and can generate strong oxidation reaction after contacting with bacteria and viruses so as to play a bactericidal effect, and the silver-doped nano bismuth tungstate enhances the synthesis capability of oxidizing ions in the nano bismuth tungstate and has stronger killing capability on pathogenic microorganisms; the silver-carrying antibacterial agent can continuously release silver ions, and kill bacteria and inhibit the proliferation of the bacteria through electrostatic adsorption contact action. The three substances are matched with each other, so that a synergistic effect can be generated, the antibacterial and antiviral capabilities are stronger, the substance stability is higher, long-acting antibacterial and antiviral effects can be realized, and the application value is higher.
In the invention, the silver-doped nano bismuth tungstate is prepared by the following method:
adding sodium oleate and bismuth nitrate into deionized water, stirring for 1-3 h, wherein the stirring time can be 1h, 1.5h, 2h, 2.5h or 3h, adding silver nitrate, stirring for 1-3 h by magnetic force, the magnetic stirring time can be 1h, 1.5h, 2h, 2.5h or 3h, adding sodium tungstate, and mixing for 1-3 h, wherein the mixing time can be 1h, 1.5h, 2h, 2.5h or 3h, and finally the molar ratio of the sodium oleate to the bismuth nitrate to the silver nitrate to the sodium tungstate is 4:1:0.1: 1;
adding the obtained mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 190-210 ℃ for 22-26 h, wherein the reaction temperature can be 190 ℃, 191 ℃, 192 ℃, 193 ℃, 194 ℃, 195 ℃, 196 ℃, 197 ℃, 198 ℃, 199 ℃, 200 ℃, 201 ℃, 202 ℃, 203 ℃, 204 ℃, 205 ℃, 206 ℃, 207 ℃, 208 ℃, 209 ℃ or 210 ℃, and the reaction time can be 22h, 22.5h, 23h, 23.5h, 24h, 24.5h, 25h, 25.5h or 26 h;
cooling to 20-30 ℃, wherein the cooling temperature can be 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, the precipitate is washed 3 times by normal hexane and ethanol respectively, and dried for 8-12 hours at 75-85 ℃, wherein the drying temperature can be 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃ or 85 ℃, and the drying time can be 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours or 12 hours, so as to obtain the silver-doped nano bismuth tungstate.
Preferably, the nano metal oxide comprises any one or a combination of at least two of nano aluminum oxide, nano zinc oxide, nano titanium dioxide, nano zirconium oxide or nano iron oxide, and can be nano aluminum oxide or a combination of nano titanium dioxide and nano zirconium oxide.
Preferably, the silver-loaded antimicrobial agent comprises any one of or a combination of at least two of silver-loaded hydroxyapatite, silver-loaded zirconium phosphate, silver-loaded calcium phosphate, silver-loaded titanium phosphate, silver-loaded clay mineral, silver-loaded silicate or silver-loaded zeolite, and may be, for example, silver-loaded hydroxyapatite or a combination of silver-loaded zirconium phosphate and silver-loaded calcium phosphate.
Preferably, the weight part of the nano metal oxide in the nano composite antibacterial powder is 17 to 43 parts, and may be 17 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or 43 parts, for example.
Preferably, the weight part of the silver-doped nano bismuth tungstate in the nano composite antibacterial powder is 10-15 parts, such as 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts.
Preferably, the silver-loaded antibacterial agent is 70 to 85 parts by weight in the nano composite antibacterial powder, and may be, for example, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts or 85 parts.
Preferably, the nano composite antibacterial powder comprises, by weight, 17-43 parts of nano metal oxide, 10-15 parts of silver-doped nano bismuth tungstate and 70-85 parts of silver-loaded antibacterial agent.
In a second aspect, the invention provides an antibacterial and antiviral glaze, which comprises the nano composite antibacterial powder in the first aspect.
According to the invention, the nano composite antibacterial powder is added into the basic glaze, so that the prepared product has antibacterial and antiviral effects and can be used for preparing porcelain with pathogenic microorganism resistance; the nano composite antibacterial powder has good stability and can realize the lasting antibiosis of porcelain.
Preferably, the antibacterial and antiviral glaze further comprises a dispersant, a coupling agent and a base glaze.
Preferably, the dispersant comprises any one or a combination of at least two of carboxymethyl cellulose, sodium hexametaphosphate, sodium pyrophosphate, sodium polyacrylate or sodium polycarboxylate, and may be, for example, carboxymethyl cellulose or a combination of sodium hexametaphosphate and sodium pyrophosphate.
Preferably, the coupling agent comprises any one of or a combination of at least two of vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β -methoxyethoxy) silane, aminopropyltrimethoxysilane or glycidoxypropyltrimethoxysilane, which may be, for example, vinyltrichlorosilane, vinyltriethoxysilane or a combination of aminopropyltrimethoxysilane and glycidoxypropyltrimethoxysilane.
Preferably, the weight part of the nano composite antibacterial powder in the antibacterial and antiviral glaze is 3-13 parts, for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts or 13 parts.
Preferably, the weight part of the dispersant in the antibacterial and antiviral glaze is 1-2 parts, for example, 1 part, 1.5 parts or 2 parts.
Preferably, the coupling agent is present in the antibacterial and antiviral glaze in an amount of 1 to 3 parts by weight, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, or 3 parts.
Preferably, the weight part of the base glaze in the antibacterial and antiviral glaze is 82-95 parts, for example, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts or 95 parts.
Preferably, the antibacterial and antiviral glaze comprises, by weight, 3-13 parts of nano composite antibacterial powder, 1-2 parts of a dispersing agent, 1-3 parts of a coupling agent and 82-95 parts of a basic glaze.
In a third aspect, the present invention provides the use of a nanocomposite antibacterial powder according to the first aspect and/or an antibacterial and antiviral glaze according to the second aspect for the preparation of ceramic articles.
According to the invention, the nano composite antibacterial powder has a strong antibacterial effect through the mutual cooperation of the three substances, and can generate antibacterial and antiviral effects on the basis of not influencing the original functions of the glaze when being added into the basic glaze raw material; the preparation method is simple and efficient, and has a wider application range.
In a fourth aspect, the invention provides an antibacterial and antiviral tea set, which comprises a blank body and a blank glaze sprayed outside the blank body, wherein the raw material for preparing the blank glaze comprises the antibacterial and antiviral glaze material in the second aspect.
According to the invention, the antibacterial and antiviral glaze is sprayed on the green body, so that the green glaze with antibacterial and antiviral effects is formed on the surface of the green body, the overall antibacterial and antiviral effects of the tea set are achieved, the efficacy of resisting pathogenic microorganisms is more durable, and the tea set has a wide application prospect.
In a fifth aspect, the invention provides a method for preparing the antibacterial and antiviral tea set according to the fourth aspect, wherein the preparation method comprises the steps of preparing a green body, spraying the antibacterial and antiviral glaze material according to the second aspect on the green body, drying and calcining to obtain the antibacterial and antiviral tea set.
The preparation method of the antibacterial and antiviral tea set is simple and efficient, and the antibacterial and antiviral tea set has antibacterial and antiviral effects on the premise of not increasing the original production steps and has the potential of batch production; the antibacterial functional components are calcined in the glaze, so that the long-term antibacterial effect can be achieved, and the appearance, strength and wear resistance of the ceramic tea set are not affected; the preparation process has no harmful components, no environmental pollution, energy saving, environmental protection, no harm to human body and high application value.
Preferably, the step of preparing the antibacterial and antiviral glaze is also included before spraying.
Preferably, the preparation method of the antibacterial and antiviral glaze comprises the steps of mixing the nano composite antibacterial powder, the dispersing agent, the coupling agent and the basic glaze, and stirring after dispersing to obtain the antibacterial and antiviral glaze.
Preferably, the dispersing time is 15-20 min, such as 15min, 16min, 17min, 18min, 19min or 20 min.
Preferably, the stirring time is 30-40 min, such as 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, 39min or 40 min.
Preferably, the temperature of the drying is 95-105 ℃, for example, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃ or 105 ℃, preferably 100 ℃.
Preferably, the drying time is 1-2 h, for example, 1h, 1.5h or 2h, preferably 1.5 h.
Preferably, the calcination is carried out in a high-temperature muffle furnace, and the temperature rise rate of the high-temperature muffle furnace is 2-5 ℃/min; for example, it may be 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min or 5 ℃/min.
Preferably, the calcination temperature is 1180-1280 ℃, for example 1180 ℃, 1190 ℃, 1200 ℃, 1210 ℃, 1220 ℃, 1230 ℃, 1240 ℃, 1250 ℃, 1260 ℃, 1270 ℃ or 1280 ℃.
Preferably, the calcination time is 10-30 min, for example, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min or 30 min.
As a preferred technical scheme, the preparation method of the antibacterial and antiviral tea set specifically comprises the following steps:
firing ceramic raw materials into a blank;
mixing the nano composite antibacterial powder, the dispersing agent, the coupling agent and the basic glaze, dispersing for 15-20 min, and stirring for 30-40 min to obtain an antibacterial and antiviral glaze;
and spraying the obtained antibacterial and antiviral glaze on the blank, drying at 95-105 ℃ for 1-2 h, heating to 1180-1280 ℃ at 2-5 ℃/min in a high-temperature muffle furnace, and calcining for 10-30 min to obtain the antibacterial and antiviral tea set.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nano composite antibacterial powder enhances the performance of resisting pathogenic microorganisms by the mutual cooperation of the nano metal oxide, the silver-doped nano bismuth tungstate and the silver-loaded antibacterial agent, has higher antibacterial and antiviral efficiency and longer time, has the antibacterial rate on staphylococcus aureus of not less than 98.88 percent, the antibacterial rate on escherichia coli of not less than 98.72 percent, the antibacterial rate on candida albicans of not less than 98.43 percent, the activity rate on H1N1 of not less than 99.01 percent and the mildew-proof grade of 0; through reasonable proportioning of the raw materials, the antibacterial and antiviral performances are better, the antibacterial rate to staphylococcus aureus is not lower than 99.89%, the antibacterial rate to escherichia coli is not lower than 99.75%, the antibacterial rate to candida albicans is not lower than 98.53%, and the activity rate to H1N1 is not lower than 99.12%; after the antibacterial and antiviral glaze is formed together with the basic glaze, the dispersing agent and the coupling agent, a layer of blank glaze with antibacterial and antiviral functions is directly formed on the surface of the blank, so that the production process flow of the product is ensured to be unchanged, the integral antibacterial effect of the tea set is realized, and the antibacterial effect is better; the functional components are calcined in the glaze, so that the effect is more durable, and the appearance, the strength, the wear resistance and the like of the tea set are not influenced;
(2) the preparation method of the antibacterial and antiviral tea set is simple and efficient, energy-saving and environment-friendly, does not need to increase preparation steps, does not generate harmful substances in the preparation process, is easy to operate and low in cost, and promotes the use and popularization of the product.
Detailed Description
To further illustrate the technical means and effects of the present invention, the present invention is further described with reference to the following examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or apparatus used are conventional products commercially available from normal sources, not indicated by the manufacturer.
Raw materials:
the silver-doped nano bismuth tungstate is prepared by a self-made method as follows:
adding sodium oleate and bismuth nitrate into deionized water, stirring for 2h, adding silver nitrate, magnetically stirring for 2h, adding sodium tungstate, and mixing for 2h to obtain a mixture, wherein the molar ratio of sodium oleate to bismuth nitrate to silver nitrate to sodium tungstate is 4:1:0.1: 1;
and adding the obtained mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 24h at 200 ℃, cooling to 25 ℃, washing the precipitate for 3 times by using n-hexane and ethanol respectively, and drying for 10h at 80 ℃ to obtain the silver-doped nano bismuth tungstate.
Nano alumina was purchased from shanghai mclin biochemical technologies, ltd;
the nano zinc oxide is purchased from Shanghai Merlin Biotechnology, Inc.;
the silver-carrying calcium phosphate is purchased from Mingkai of Huizhou city, antimildew and antibacterial science and technology Limited;
sodium polyacrylate was purchased from Shanghai Michelin Biochemical technology, Inc.;
vinyltriethoxysilane is available from Shanghai Merlin Biotech, Inc.;
the nano titanium dioxide is purchased from Shanghai Merlin Biotechnology, Inc.;
silver-loaded zirconium phosphate was purchased from Mingkai mildew-proof antibacterial science and technology Limited, Huizhou;
the basic glaze is purchased from Jiangsu Gaochun ceramics GmbH;
escherichia coli was purchased from ATCC company under No. e.coli ATCC 25922;
staphylococcus aureus, purchased from ATCC, inc, No. s.aureus ATCC 25923;
candida albicans purchased from ATCC company under the designation c.albicans ATCC 10213;
the H1N1 influenza A virus is taken from diseased local chickens.
Example 1
The embodiment provides a nano composite antibacterial powder which comprises, by weight, 6 parts of nano aluminum oxide, 30 parts of nano zinc oxide, 13 parts of silver-doped nano bismuth tungstate and 80 parts of silver-loaded calcium phosphate.
The embodiment also provides an antibacterial and antiviral tea set which comprises a blank body and a blank glaze sprayed outside the blank body, wherein the raw materials for preparing the blank glaze comprise, by weight, 10 parts of nano-composite antibacterial powder, 1.5 parts of sodium polyacrylate, 2 parts of vinyl triethoxysilane and 90 parts of basic glaze.
The preparation method of the antibacterial and antiviral tea set comprises the following steps:
firing ceramic raw materials into a blank;
mixing the nano composite antibacterial powder, sodium polyacrylate, vinyl triethoxysilane and base glaze, dispersing for 18min, and stirring for 35min to obtain antibacterial and antiviral glaze;
and spraying the obtained antibacterial and antiviral glaze on the green body, drying at 100 ℃ for 1.5h, heating to 1200 ℃ at a speed of 3 ℃/min in a high-temperature muffle furnace, and calcining for 20min to obtain the antibacterial and antiviral tea set.
Example 2
The embodiment provides a nano composite antibacterial powder which comprises, by weight, 2 parts of nano aluminum oxide, 15 parts of nano titanium dioxide, 15 parts of silver-doped nano bismuth tungstate and 85 parts of silver-loaded calcium phosphate.
The embodiment also provides an antibacterial and antiviral tea set which comprises a blank body and a blank glaze sprayed outside the blank body, wherein the preparation raw materials of the blank glaze comprise, by weight, 13 parts of nano-composite antibacterial powder, 2 parts of sodium polyacrylate, 3 parts of vinyl triethoxysilane and 95 parts of basic glaze.
The preparation method of the antibacterial and antiviral tea set comprises the following steps:
firing ceramic raw materials into a blank;
mixing the nano composite antibacterial powder, sodium polyacrylate, vinyl triethoxysilane and base glaze, dispersing for 20min, and stirring for 40min to obtain antibacterial and antiviral glaze;
and spraying the obtained antibacterial and antiviral glaze on the green body, drying at 105 ℃ for 1h, heating to 1280 ℃ at 5 ℃/min in a high-temperature muffle furnace, and calcining for 10min to obtain the antibacterial and antiviral tea set.
Example 3
The embodiment provides a nano composite antibacterial powder which comprises, by weight, 8 parts of nano aluminum oxide, 35 parts of nano titanium dioxide, 10 parts of silver-doped nano bismuth tungstate and 70 parts of silver-loaded zirconium phosphate.
The embodiment also provides an antibacterial and antiviral tea set which comprises a blank body and a blank glaze sprayed outside the blank body, wherein the raw materials for preparing the blank glaze comprise, by weight, 3 parts of nano-composite antibacterial powder, 1 part of sodium polyacrylate, 1 part of vinyl triethoxysilane and 82 parts of basic glaze.
The preparation method of the antibacterial and antiviral tea set comprises the following steps:
firing ceramic raw materials into a blank;
mixing the nano composite antibacterial powder, sodium polyacrylate, vinyl triethoxysilane and base glaze, dispersing for 15min, and stirring for 30min to obtain antibacterial and antiviral glaze;
and spraying the obtained antibacterial and antiviral glaze on the green body, drying at 95 ℃ for 2h, heating to 1180 ℃ at 2 ℃/min in a high-temperature muffle furnace, and calcining for 30min to obtain the antibacterial and antiviral tea set.
Example 4
The difference from example 1 is that the amount of the nano composite antibacterial powder added to the raw materials for preparing the glaze blank in this example is 15 parts, and the rest of the raw materials and the preparation method are the same as those of example 1.
Example 5
The difference from the example 1 is only that the addition amount of the nano composite antibacterial powder in the raw materials for preparing the blank glaze in the example is 2 parts, the missing parts by weight are supplemented with 0.1 part of sodium polyacrylate, 0.2 part of vinyl triethoxysilane and 7.7 parts of base glaze, and the rest raw materials and the preparation method are the same as the example 1.
Example 6
The difference from the example 1 is only that the nano composite antibacterial powder in the example comprises 1 part of nano aluminum oxide, 10 parts of nano zinc oxide, 18 parts of silver-doped nano bismuth tungstate and 100 parts of silver-loaded calcium phosphate, and the rest of the raw materials and the preparation method are the same as the example 1.
Comparative example 1
The difference from the example 1 is that in the comparative example, nano aluminum dioxide and nano zinc oxide are not added, 5 parts of silver-doped nano bismuth tungstate and 31 parts of silver-loaded calcium phosphate are supplemented in the lacking parts by weight, and the rest of raw materials and the preparation method are the same as the example 1.
Comparative example 2
The difference from the example 1 is that in the comparative example, silver-doped nano bismuth tungstate is not added, 0.7 part of nano aluminum dioxide, 3.3 parts of nano zinc oxide and 9 parts of silver-loaded calcium phosphate are added, and the rest raw materials and the preparation method are the same as the example 1.
Comparative example 3
The difference from the example 1 is that in the comparative example, silver-loaded calcium phosphate is not added, 9.8 parts of nano aluminum dioxide, 49 parts of nano zinc oxide and 21.2 parts of silver-doped nano bismuth tungstate are supplemented in the lacking parts by weight, and the rest of raw materials and the preparation method are the same as the example 1.
Comparative example 4
The difference from the example 1 is that the raw materials for preparing the glaze blank in the comparative example do not add the nano composite antibacterial powder, 0.2 part of sodium polyacrylate, 0.2 part of vinyl triethoxysilane and 9.6 parts of base glaze are supplemented in parts by weight, and the rest raw materials and the preparation method are the same as the example 1.
Evaluation of antibacterial Properties
The antibacterial performance of the products prepared in the examples and the comparative examples of the invention is tested according to JC/T897-2002 antibacterial ceramic product antibacterial performance.
Evaluation of antiviral Properties
The antiviral performance of the products prepared in the examples and the comparative examples is tested according to the NASBA test method in GB/T19440-2004.
Evaluation of mold resistance
The products prepared in the examples and the comparative examples of the invention are tested for mildew resistance according to GB/T24128-2009.
The results of the tests of the antibacterial, antiviral and antifungal properties of the tea sets prepared in examples 1 to 6 and comparative examples 1 to 4 are shown in table 1.
TABLE 1
As can be seen from table 1, the antibacterial and antiviral tea sets prepared in examples 1 to 6 have good performance, the antibacterial rate to staphylococcus aureus is not lower than 98.88%, the antibacterial rate to escherichia coli is not lower than 98.72%, the antibacterial rate to candida albicans is not lower than 98.43%, the activity rate to H1N1 is not lower than 99.01%, and the mildew-proof grades are all 0;
compared with the examples 1 to 6, the antibacterial, antiviral and mildewproof performances of the products prepared in the comparative examples 1 to 4 are poor, wherein the nano aluminum dioxide and the nano zinc oxide are not added in the comparative example 1, the silver-doped nano bismuth tungstate is not added in the comparative example 2, the silver-loaded calcium phosphate is not added in the comparative example 3, and the capability of resisting pathogenic microorganisms is influenced to a certain extent, which shows that the nano metal oxide, the silver-doped nano bismuth tungstate and the silver-loaded antibacterial agent have a synergistic effect, and the optimal effect can be achieved only by adding the three substances simultaneously; the nano composite antibacterial powder is not added in the comparative example 4, so that the product does not have corresponding functions;
comparing examples 1 to 3 with example 6, it can be seen that the antibacterial and antiviral tea sets prepared in examples 1 to 3 have better performance, the antibacterial rate to staphylococcus aureus is not lower than 99.89%, the antibacterial rate to escherichia coli is not lower than 99.75%, the antibacterial rate to candida albicans is not lower than 98.53%, and the activity rate to H1N1 is not lower than 99.12%; the addition amount of each component in the nano composite antibacterial powder in the embodiment 6 is not in a better range, and the antibacterial and antiviral effects of the product are influenced, which shows that when the addition amount of the nano metal oxide in the nano composite antibacterial powder is 17-43 parts, the addition amount of the silver-doped nano bismuth tungstate is 10-15 parts, and the addition amount of the silver-loaded antibacterial agent is 70-85 parts, a better antibacterial effect can be generated;
compared with the embodiments 1 to 3 and 4 to 5, the nano composite antibacterial powder in the embodiment 4 has more addition amount, the antibacterial performance of the product is not obviously improved, and the production cost is improved; in the embodiment 5, the addition amount of the nano composite antibacterial powder is less, and the antibacterial performance is slightly poor, which shows that when the addition amount of the nano composite antibacterial powder in the antibacterial and antiviral glaze is 3-13 parts, a better antibacterial, antiviral and mildewproof effect can be achieved, the production cost is lower, and the application value is wider.
In conclusion, the invention provides the nano composite antibacterial powder which has good antibacterial and antiviral properties; the antibacterial and antiviral ceramic glaze is added into the ceramic glaze, and blank glaze with antibacterial and antiviral functions is formed on the surface of the tea set after spraying and calcining, so that the overall antibacterial property of the tea set is realized; the long-acting and lasting antibiosis of the tea set can be realized by calcining the antibacterial functional component in the glaze; the preparation method is energy-saving and efficient, is easy to operate, does not need to add extra processing steps, and does not influence the original performance and appearance of the tea set; no polluting substances are generated in the preparation process, no harm is caused to the environment, and the application range is wide.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The nano composite antibacterial powder is characterized by comprising nano metal oxide, silver-doped nano bismuth tungstate and a silver-loaded antibacterial agent.
2. The nano-composite antibacterial powder according to claim 1, wherein the nano metal oxide comprises any one or a combination of at least two of nano aluminum oxide, nano zinc oxide, nano titanium dioxide, nano zirconium oxide or nano iron oxide;
preferably, the silver-loaded antibacterial agent comprises any one or a combination of at least two of silver-loaded hydroxyapatite, silver-loaded zirconium phosphate, silver-loaded calcium phosphate, silver-loaded titanium phosphate, silver-loaded clay mineral, silver-loaded silicate or silver-loaded zeolite;
preferably, the weight part of the nano metal oxide in the nano composite antibacterial powder is 17-43 parts;
preferably, the weight part of the silver-doped nano bismuth tungstate in the nano composite antibacterial powder is 10-15 parts;
preferably, the silver-loaded antibacterial agent accounts for 70-85 parts by weight of the nano-composite antibacterial powder;
preferably, the nano composite antibacterial powder comprises, by weight, 17-43 parts of nano metal oxide, 10-15 parts of silver-doped nano bismuth tungstate and 70-85 parts of silver-loaded antibacterial agent.
3. An antibacterial and antiviral glaze, characterized in that the antibacterial and antiviral glaze comprises the nanocomposite antibacterial powder of claim 1 or 2;
preferably, the antibacterial and antiviral glaze further comprises a dispersant, a coupling agent and a base glaze.
4. The antibacterial and antiviral glaze material according to claim 3, wherein the dispersant comprises any one or a combination of at least two of carboxymethyl cellulose, sodium hexametaphosphate, sodium pyrophosphate, sodium polyacrylate or sodium polycarboxylate;
preferably, the coupling agent comprises any one or a combination of at least two of vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (beta-methoxyethoxy) silane, aminopropyltrimethoxysilane or glycidoxypropyltrimethoxysilane;
preferably, the weight part of the nano composite antibacterial powder in the antibacterial and antiviral glaze is 3-13 parts;
preferably, the weight part of the dispersant in the antibacterial and antiviral glaze is 1-2 parts;
preferably, the weight part of the coupling agent in the antibacterial and antiviral glaze is 1-3 parts;
preferably, the weight part of the base glaze in the antibacterial and antiviral glaze is 82-95 parts;
preferably, the antibacterial and antiviral glaze comprises, by weight, 3-13 parts of nano composite antibacterial powder, 1-2 parts of a dispersing agent, 1-3 parts of a coupling agent and 82-95 parts of a basic glaze.
5. Use of the nanocomposite antibacterial powder according to claim 1 or 2 and/or the antibacterial and antiviral glaze according to claim 3 or 4 for the preparation of ceramic articles.
6. An antibacterial and antiviral tea set, which is characterized by comprising a blank body and a blank glaze sprayed outside the blank body, wherein the raw material for preparing the blank glaze comprises the antibacterial and antiviral glaze material according to claim 3 or 4.
7. The method for preparing the antibacterial and antiviral tea set according to claim 6, wherein the preparation method comprises the steps of preparing a green body, spraying the antibacterial and antiviral glaze material according to claim 3 or 4 on the green body, drying and calcining to obtain the antibacterial and antiviral tea set.
8. The method for preparing the antibacterial and antiviral tea set according to claim 7, characterized by further comprising the step of preparing the antibacterial and antiviral glaze before spraying;
preferably, the preparation method of the antibacterial and antiviral glaze comprises the steps of mixing the nano composite antibacterial powder, the dispersing agent, the coupling agent and the basic glaze, and stirring after dispersing to obtain the antibacterial and antiviral glaze;
preferably, the dispersing time is 15-20 min;
preferably, the stirring time is 30-40 min.
9. The preparation method of the antibacterial and antiviral tea set according to claim 7 or 8, wherein the drying temperature is 95-105 ℃, preferably 100 ℃;
preferably, the drying time is 1-2 h, preferably 1.5 h;
preferably, the calcination is carried out in a high-temperature muffle furnace, and the temperature rise rate of the high-temperature muffle furnace is 2-5 ℃/min;
preferably, the calcining temperature is 1180-1280 ℃;
preferably, the calcining time is 10-30 min.
10. The preparation method of the antibacterial and antiviral tea set according to any one of claims 7 to 9, wherein the preparation method comprises the following steps:
firing ceramic raw materials into a blank;
mixing the nano composite antibacterial powder, the dispersing agent, the coupling agent and the basic glaze, dispersing for 15-20 min, and stirring for 30-40 min to obtain an antibacterial and antiviral glaze;
and spraying the obtained antibacterial and antiviral glaze on the blank, drying at 95-105 ℃ for 1-2 h, heating to 1180-1280 ℃ at 2-5 ℃/min in a high-temperature muffle furnace, and calcining for 10-30 min to obtain the antibacterial and antiviral tea set.
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