CN116553909A - Preparation method of health-care deodorant ceramic tile - Google Patents

Preparation method of health-care deodorant ceramic tile Download PDF

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CN116553909A
CN116553909A CN202310332990.8A CN202310332990A CN116553909A CN 116553909 A CN116553909 A CN 116553909A CN 202310332990 A CN202310332990 A CN 202310332990A CN 116553909 A CN116553909 A CN 116553909A
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ceramic tile
mass ratio
solution
mass
modified resin
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沈龙妹
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • 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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    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/04—Clay; Kaolin
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    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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    • 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
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1245—Inorganic substrates other than metallic
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/665—Local sintering, e.g. laser sintering
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    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract

The invention discloses a preparation method of a health-care deodorant ceramic tile, and relates to the technical field of ceramic tiles. The invention carries out pretreatment on the ceramic tile blank body to enhance the surface adhesiveness; then spinning by taking silver nitrate as an external phase solution and taking polystyrene microspheres as an internal phase solution, and calcining at high temperature to form a porous hollow structure nano-film; then forming a nano zinc oxide seed crystal layer by pulse laser deposition, then continuously growing in a zinc-copper source mixed solution to form a deodorizing layer, generating an electron transfer chain, generating active oxygen, choking bacteria to prevent metabolism of the bacteria, and then sequentially coating an enamel layer and a modified resin layer, wherein the modified resin layer is prepared from 6, 7-dihydroxyl-4-heteroheptylamine, epoxy resin, 2, 6-dihydroxyl-5-chloro-4-pyrimidine methyl formate and perfluoroalkyl ethyl bromide, so as to form a hydrophobic dendritic compound. The health-care deodorant ceramic tile prepared by the invention has deodorant and anti-fouling effects.

Description

Preparation method of health-care deodorant ceramic tile
Technical Field
The invention relates to the technical field of ceramic tiles, in particular to a preparation method of a health-care deodorant ceramic tile.
Background
Along with the progress of science and technology and the development of society, people pay more attention to the quality of life and other problems, so that the health-care ceramic tile has the problems of visual field of people, the traditional ceramic tile with health-care function, such as ceramic tile capable of applying anions and the like, does not achieve the effect of propaganda in the practical use process, because the functional additives in the ceramic tile are generally added into green bricks, and the surface of the ceramic tile is required to be subjected to glaze sealing treatment, the ceramic tile is difficult to exert efficacy, and therefore, the ceramic tile mixes far infrared radiation materials with face paste and adds the far infrared radiation materials into enamel layers.
In addition, the health-care ceramic tile has weaker waterproof performance, is exposed in the air throughout the year, and has the surface subjected to water body scouring, dust or pollution adhesion of other suspended particles, so that the wall body is damped and mildewed, the internal ponding is serious, a large amount of bacteria are easy to grow, odor is generated, the attractive appearance and the use impression of a building are greatly destroyed, and a large amount of manpower and material resources are required to be used for cleaning and repairing each year.
Disclosure of Invention
The invention aims to provide a health-care deodorant ceramic tile and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: a health-care deodorant ceramic tile comprises a modified resin coating, an enamel layer, a deodorant layer and a ceramic tile blank body from top to bottom; the ceramic tile blank comprises, by weight, 50-70 parts of clay, 30-40 parts of kaolin, 10-20 parts of tourmaline, 15-30 parts of quartz, 1-5 parts of magnesium oxide and 1-3 parts of carboxymethyl cellulose.
The deodorizing layer is prepared by the following steps of firstly carrying out plasma pulse bombardment pretreatment on a ceramic blank, and then spinning and calcining at high temperature by taking a silver nitrate solution as an external phase solution and a polystyrene microsphere solution as an internal phase solution to obtain a fiber membrane ceramic tile blank; then depositing by pulse laser to obtain a nano zinc oxide seed crystal layer, and then placing the nano zinc oxide seed crystal layer in a zinc-copper source mixed solution to obtain the deodorizing layer.
Further, the enamel layer is prepared by sintering a facial slurry; the flour paste comprises, by weight, 30-40 parts of silica ore, 6-15 parts of light calcium carbonate, 50-60 parts of white mud, 30-50 parts of quartz sand, 1-5 parts of magnesium oxide, 1-3 parts of carboxymethyl cellulose, 30-40 parts of far infrared radiation material and 50-60 parts of distilled water.
Further, the far infrared radiation material is one or a mixture of more of aluminum oxide, titanium dioxide, magnesium oxide, zirconium dioxide or silicon dioxide.
Further, the modified resin coating is prepared from 6, 7-dihydroxyl-4-heteroheptylamine, epoxy resin, 2, 6-dihydroxyl-5-chloro-4-pyrimidine methyl formate and perfluoroalkyl ethyl bromide.
Further, the preparation method of the health-care deodorant ceramic tile comprises the following preparation steps:
(1) Placing the ceramic tile blank under a plasma gun, and vacuumizing to 1×10 -3 ～5×10 -3 Pa, pulsing 3-7 times to obtain a pretreated ceramic tile blank; taking silver nitrate spinning solution as an external phase solution, taking polystyrene microsphere spinning solution as an internal phase solution, spinning the pretreated ceramic tile blank 15-20 cm away until the thickness of a film layer is 20-40 mu m, heating to 500-550 ℃ at 2-5 ℃/min, and calcining for 2-5 h to obtain a fiber membrane ceramic tile blank;
(2) Placing the fiber membrane tile blank in a molecular laser, and vacuumizing to 1×10 -4 ～5×10 -4 Heating to 300-350 ℃ under Pa, adopting a high-purity zinc target, introducing oxygen at a distance of 5-10 cm and 30-70 sccm to a pressure of 2-6 Pa, and depositing for 5-11 min to obtain a seed crystal layer ceramic tile blank; soaking the seed crystal layer ceramic tile blank in a zinc-copper source mixed solution with the mass of 4-12 times of that of the seed crystal layer ceramic tile blank, standing for 2-5 hours at 70-90 ℃, fishing out, washing with deionized water for 5-10 times, drying at 70-80 ℃ for 30-42 min, and calcining at 200-250 ℃ for 3-6 hours to obtain a deodorizing layer;
(3) Pouring the surface slurry to the deodorizing layer until the thickness is 1-4 mm, drying for 10-20 min at 80-100 ℃, and calcining for 4-9 h at 1100-1300 ℃ to obtain a ceramic tile substrate;
(4) Mixing E-51 epoxy resin, ethylene glycol monobutyl ether and absolute ethyl alcohol according to the mass ratio of 1:0.1:0.1-1:0.4:0.3, heating to 65-75 ℃ under the protection of nitrogen, stirring until the mixture is dissolved, adding 6, 7-dihydroxyl-4-heteroheptylamine with the mass of 0.5-0.9 times of the E-51 epoxy resin, reacting for 8-14 h, adding an ethanol aqueous solution with the mass of 1-4 times of the E-51 epoxy resin, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 0.25:1, and standing for 18-34 min to obtain a modified resin matrix;
(5) Mixing a modified resin matrix, methyl 2, 6-dihydroxyl-5-chloro-4-pyrimidinecarboxylate, potassium carbonate and N, N-dimethylformamide according to the mass ratio of 1:1.1:0.5:35-1:2.4:1.0:43, heating to 70-82 ℃ under argon atmosphere, stirring for 8-14 h at 100-200 rpm, heating to 150-160 ℃, preserving heat for 1-3 h, adding dichloromethane with the mass 60-80 times of the modified resin matrix, washing for 6-13 min sequentially with deionized water and saturated sodium chloride solution, drying for 2-4 h at 38-52 ℃, and repeating the steps for 2-5 times to obtain a dendrimer;
(6) Mixing a dendrimer and methylene dichloride according to the mass ratio of 1:18-1:26 under ice water bath, adding perfluoroalkyl ethyl bromide with the mass of 0.7-1.5 times of the dendrimer, stirring for 20-40 min at 100-200 rpm, adding N, N-dimethylformamide with the mass of 0.07-0.10 times of the dendrimer, removing the ice water bath, reacting for 10-15 h at room temperature, adding sodium sulfite solution with the mass of 3-5 times of the dendrimer and deionized water with the mass of 4-7 times of the dendrimer, wherein the mass ratio of sodium sulfite to deionized water in the sodium sulfite solution is 1:9, separating liquid, extracting, washing for 5-10 times by using deionized water and saturated sodium chloride in sequence, and steaming for 2-4 h at the temperature of 300-400 rpm and 40-50 ℃ to obtain modified resin;
(7) Mixing modified resin, aminoethylpiperazine, polydimethylsiloxane, n-butanol and xylene according to a mass ratio of 1:0.08:0.02:0.6:0.6-1:0.2:0.05:0.9:0.9 to obtain a modified resin coating; spraying modified resin paint with the mass of 0.1-0.3 times of the ceramic tile substrate to the ceramic tile substrate, and drying for 60-80 min at 80-100 ℃ to obtain the health-care deodorant ceramic tile.
Further, the silver nitrate spinning solution in the step (1): mixing polyvinylpyrrolidone, silver nitrate, deionized water and N, N-dimethylformamide according to a mass ratio of l of 1:13:20-1:5:25:33, and stirring at 40-50 ℃ for 2-5 hours at 50-100 rpm to obtain silver nitrate spinning solution; the polystyrene microsphere spinning solution comprises: the polystyrene microsphere with the grain diameter of 400-600 nm and distilled water are mixed according to the mass ratio of 1:5-1:9.
Further, the plasma gun of step (1): pulse width of 50-70 mu s, electron density of plasma of 10 14 ～10 16 cm -3 A power density of 10 5 ～10 7 W/cm 2 The ion velocity is 50 to 70kms -1 The method comprises the steps of carrying out a first treatment on the surface of the The spinning: the spinning voltage is 15-20 kV, the internal phase diameter is 0.5mm, the flow rate is 0.1mL/h, the external phase diameter is 1.2mm, and the flow rate is 0.1-0.3 mL/h.
Further, the molecular laser of step (2): the wavelength is 248nm, the pulse width is 20-40 ns, the pulse repetition frequency is 5-10 Hz, and the pulse energy is 300-400 mJ.
Further, the zinc-copper source mixed solution in step (2): zinc nitrate, hexamethylenetetramine, copper nitrate and ethylene glycol are mixed according to the mass ratio of 1:0.5:0.3:80-1:0.8:0.5:95, and sodium carbonate is added until the pH value of the solution is 7-10.
Compared with the prior art, the invention has the following beneficial effects:
the invention forms a porous deodorization layer on the ceramic tile blank, the surface slurry flows into the through holes and the flow channels of the deodorization layer, is combined with the ceramic tile blank into a whole after sintering, firmly fixes the deodorization layer between the two layers, and the surface slurry contains far infrared radiation materials to form an enamel layer with health care effect, and then is sprayed with a modified resin coating to realize the functions of deodorization and anti-fouling.
Firstly, plasma pulse bombardment pretreatment is carried out on a ceramic tile blank body to form a staggered groove structure, intermolecular crosslinking is generated to strengthen a surface layer, surface adhesiveness is enhanced, and deposition of a deodorizing layer is facilitated; then, silver nitrate and polyvinylpyrrolidone are used as an external phase solution, polystyrene microspheres are used as an internal phase solution, a fiber membrane is prepared by spinning, and under high-temperature calcination, the silver nitrate and carbonyl of the polyvinylpyrrolidone undergo a coordination reaction to generate nano silver, and the polystyrene microspheres are removed to form a porous hollow structure; then forming a nano zinc oxide seed layer by pulse laser deposition, then continuously growing in a zinc-copper source mixed solution to form a zinc oxide nano rod vertical to the surface of a fiber film, and forming nano copper oxide particles on the surface to obtain a deodorizing layer, wherein charge transfer can occur in the structure of the deodorizing layer to generate an electron transfer chain, when the deodorizing layer contacts bacterial cells, active oxygen such as hydroxyl free radicals, superoxide anion free radicals, malondialdehyde and the like is generated, an oxidation stress state is activated, bacteria can be catalytically adsorbed, the bacteria can be choked to prevent bacterial metabolism, the nano silver fiber film can store more charges, and a plurality of zinc oxide and copper oxide nanostructures modify the nano silver fiber film, so that the charge transfer efficiency is improved, and the charge transfer between silver, zinc oxide and copper oxide can be enhanced; in addition, deodorant layer surface energy is lower, can play hydrophobic effect, reduces the inside ponding of ceramic tile, prevents inside bacterium and breeds, reaches deodorant effect.
Secondly, reacting 6, 7-dihydroxyl-4-heteroheptylamine with epoxy groups of epoxy resin, grafting the epoxy resin into a molecular chain, and replacing hydroxyl groups of the 6, 7-dihydroxyl-4-heteroheptylamine with chloride ions of 2, 6-dihydroxyl-5-chloro-4-pyrimidinecarboxylic acid methyl ester, so that tree-shaped molecules are formed repeatedly, and blocking the epoxy resin by using perfluoroalkyl ethyl bromide, so that the epoxy resin is subjected to hydrophobic modification, and pollutants such as dust are taken away by water drops well, so that the ceramic tile has anti-fouling capability; in addition, 6, 7-dihydroxyl-4-heteroheptylamine, 2, 6-dihydroxyl-5-chloro-4-pyrimidine methyl formate and perfluoroalkyl ethyl bromide spontaneously gather on the surface of the epoxy resin, so that the surface energy is reduced, the stability and hydrophobicity of a coating are improved, the antifouling effect of the ceramic tile is improved, the ceramic tile is effectively adsorbed on the surface of the ceramic tile under the action of an adhesive, and the antifouling service life of the ceramic tile is prolonged.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the method for testing each index of the health-care deodorant ceramic tile manufactured in the following examples is as follows:
odor-resistant: the antibacterial effect test is carried out by taking the examples with the same mass and size as the comparative examples.
Stain resistance: the hydrophobic effect test was performed by taking the examples and the comparative examples having the same mass.
Example 1
The preparation method of the health-care deodorant ceramic tile mainly comprises the following preparation steps:
(1) Placing the ceramic tile blank under a plasma gun, and vacuumizing to 1×10 -3 Pa, pulsing 3 times to obtain a pretreated ceramic tile blank; mixing polyvinylpyrrolidone, silver nitrate, deionized water and N, N-dimethylformamide according to a mass ratio of 1:13:20, and stirring at 40 ℃ for 5 hours at 50rpm to obtain silver nitrate spinning solution; mixing polystyrene microspheres with the particle size of 400nm with distilled water according to the mass ratio of 1:5 to obtain a polystyrene microsphere spinning solution; taking silver nitrate spinning solution as an external phase solution, taking polystyrene microsphere spinning solution as an internal phase solution, spinning 15cm away from a pretreated ceramic tile blank until the thickness of a film layer is 20 mu m, heating to 500 ℃ at 2 ℃/min, and calcining for 5 hours to obtain a fiber membrane ceramic tile blank; the plasma gun: pulse width 50. Mu.s, electron density of plasma 10 14 cm -3 A power density of 10 5 W/cm 2 Ion velocity of 50kms -1 The method comprises the steps of carrying out a first treatment on the surface of the The spinning: the spinning voltage is 15kV, the internal phase diameter is 0.5mm, the flow rate is 0.1mL/h, the external phase diameter is 1.2mm, and the flow rate is 0.1mL/h;
(2) Placing the fiber membrane tile blank in a molecular laser, and vacuumizing to 1×10 -4 Heating to 300 ℃ under Pa, adopting a high-purity zinc target, introducing oxygen at a distance of 5cm from a fiber membrane ceramic tile blank to the high-purity zinc target, and depositing for 11min after oxygen is introduced at a pressure of 2Pa at 30sccm to obtain a seed crystal layer ceramic tile blank; mixing zinc nitrate, hexamethylenetetramine, copper nitrate and ethylene glycol according to the mass ratio of 1:0.5:0.3:80, and adding sodium carbonate until the pH value of the solution is the same7, obtaining a zinc-copper source mixed solution; soaking the seed crystal layer ceramic tile blank in a zinc-copper source mixed solution with the mass of 4 times of that of the seed crystal layer ceramic tile blank, standing at 70 ℃ for 5 hours, fishing out, washing with deionized water for 5 times, drying at 70 ℃ for 42 minutes, and calcining at 200 ℃ for 6 hours to obtain a deodorizing layer; the molecular laser: the wavelength is 248nm, the pulse width is 20ns, the pulse repetition frequency is 5Hz, and the pulse energy is 300mJ;
(3) Pouring the surface slurry to the deodorizing layer until the thickness is 1mm, drying for 20min at 80 ℃, and calcining for 9h at 1100 ℃ to obtain a ceramic tile substrate;
(4) Mixing E-51 epoxy resin, ethylene glycol monobutyl ether and absolute ethyl alcohol according to the mass ratio of 1:0.1:0.1, heating to 65 ℃ under the protection of nitrogen, stirring until the mixture is dissolved, adding 6, 7-dihydroxyl-4-heteroheptylamine with the mass of 0.5 times of the E-51 epoxy resin, reacting for 14 hours, adding an ethanol aqueous solution with the mass of 1 time of the E-51 epoxy resin, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 0.25:1, and standing for 18 minutes to obtain a modified resin matrix;
(5) Mixing a modified resin matrix, 2, 6-dihydroxyl-5-chloro-4-pyrimidine methyl formate, potassium carbonate and N, N-dimethylformamide according to a mass ratio of 1:1.1:0.5:35, heating to 70 ℃ under argon atmosphere, stirring at 100rpm for 14h, heating to 150 ℃, preserving heat for 3h, adding dichloromethane with the mass 60 times that of the modified resin matrix, washing with deionized water and saturated sodium chloride solution for 6min in sequence, drying at 38 ℃ for 4h, and repeating the steps for 2 times to obtain a dendrimer;
(6) Mixing a dendrimer and methylene dichloride according to the mass ratio of 1:18 in ice water bath, adding perfluoroalkyl ethyl bromide with the mass of 0.7 times of the dendrimer, stirring for 40min at 100rpm, adding N, N-dimethylformamide with the mass of 0.07 times of the dendrimer, removing ice water bath, reacting for 10h at room temperature, adding sodium sulfite solution with the mass of 3 times of the dendrimer and deionized water with the mass ratio of 4 times of the dendrimer, wherein the mass ratio of sodium sulfite to deionized water in the sodium sulfite solution is 1:9, separating liquid, extracting, washing for 5 times by using deionized water and saturated sodium chloride, and steaming for 4h at the temperature of 40 ℃ at 300rpm to obtain modified resin;
(7) Mixing modified resin, aminoethylpiperazine, polydimethylsiloxane, n-butanol and xylene according to a mass ratio of 1:0.08:0.02:0.6:0.6 to obtain modified resin coating; spraying a modified resin coating with the mass of 0.1 times of that of the ceramic tile substrate on the ceramic tile substrate, and drying at 80 ℃ for 80min to obtain the health-care deodorant ceramic tile.
Example 2
The preparation method of the health-care deodorant ceramic tile mainly comprises the following preparation steps:
(1) Placing the ceramic tile blank under a plasma gun, and vacuumizing to 3×10 -3 Pa, pulsing 5 times to obtain a pretreated ceramic tile blank; mixing polyvinylpyrrolidone, silver nitrate, deionized water and N, N-dimethylformamide according to a mass ratio of l of 3:19:26.5, and stirring at 45 ℃ for 3.5 hours to obtain silver nitrate spinning solution; mixing polystyrene microspheres with the particle size of 500nm with distilled water according to the mass ratio of 1:7 to obtain a polystyrene microsphere spinning solution; taking silver nitrate spinning solution as an external phase solution, taking polystyrene microsphere spinning solution as an internal phase solution, spinning the pretreated ceramic tile blank 18cm away until the thickness of a film layer is 30 mu m, heating to 525 ℃ at 3 ℃/min, and calcining for 3.5h to obtain a fiber membrane ceramic tile blank; the plasma gun: pulse width of 60. Mu.s, electron density of 10 15 cm -3 A power density of 10 6 W/cm 2 Ion velocity of 60kms -1 The method comprises the steps of carrying out a first treatment on the surface of the The spinning: the spinning voltage is 18kV, the internal phase diameter is 0.5mm, the flow rate is 0.1mL/h, the external phase diameter is 1.2mm, and the flow rate is 0.2mL/h;
(2) Placing the fiber membrane tile blank in a molecular laser, and vacuumizing to 3×10 -4 Heating to 325 ℃ under Pa, adopting a high-purity zinc target, introducing oxygen at a distance of 8cm between the fiber membrane ceramic tile blank and the high-purity zinc target, and depositing for 8min after introducing oxygen at a pressure of 50sccm to 4Pa to obtain a seed crystal layer ceramic tile blank; mixing zinc nitrate, hexamethylenetetramine, copper nitrate and ethylene glycol according to a mass ratio of 1:0.65:0.4:87.5, and adding sodium carbonate until the pH value of the solution is 8.5 to obtain a zinc-copper source mixed solution; soaking the seed crystal layer ceramic tile blank in a zinc-copper source mixed solution with the mass of 8 times of that of the seed crystal layer ceramic tile blank, standing at 80 ℃ for 3.5 hours, fishing out, washing with deionized water for 7 times, drying at 75 ℃ for 36 minutes, and calcining at 225 ℃ for 4.5 hours to obtain a deodorizing layer; the molecular laser: the wavelength is 248nm, the pulse width is 30ns, and the pulse is repeatedThe frequency is 7Hz, and the pulse energy is 350mJ;
(3) Pouring the surface slurry to the deodorizing layer until the thickness is 2.5mm, drying for 15min at 90 ℃, and calcining for 6.5h at 1200 ℃ to obtain a ceramic tile substrate;
(4) Mixing E-51 epoxy resin, ethylene glycol monobutyl ether and absolute ethyl alcohol according to the mass ratio of 1:0.25:0.2, heating to 70 ℃ under the protection of nitrogen, stirring until the mixture is dissolved, adding 6, 7-dihydroxyl-4-heteroheptylamine with the mass of 0.7 times of the E-51 epoxy resin, reacting for 11 hours, adding an ethanol aqueous solution with the mass ratio of 1-4 times of the E-51 epoxy resin, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 0.25:1, and standing for 26 minutes to obtain a modified resin matrix;
(5) Mixing a modified resin matrix, 2, 6-dihydroxyl-5-chloro-4-pyrimidine methyl formate, potassium carbonate and N, N-dimethylformamide according to a mass ratio of 1:1.75:0.75:39, heating to 76 ℃ under argon atmosphere, stirring at 150rpm for 11 hours, heating to 155 ℃, preserving heat for 2 hours, adding dichloromethane with the mass 70 times that of the modified resin matrix, washing with deionized water and saturated sodium chloride solution in sequence for 10 minutes, drying at 40 ℃ for 3 hours, and repeating the steps for 3 times to obtain a dendrimer;
(6) Mixing a dendrimer and methylene dichloride according to the mass ratio of 1:22 under ice water bath, adding perfluoroalkyl ethyl bromide with the mass of 1.1 times of the dendrimer, stirring for 30min at 150rpm, adding N, N-dimethylformamide with the mass of 0.08 times of the dendrimer, removing the ice water bath, reacting for 12.5h at room temperature, adding sodium sulfite solution with the mass of 4 times of the dendrimer and deionized water with the mass ratio of 5.5 times of the dendrimer, wherein the mass ratio of sodium sulfite to deionized water in the sodium sulfite solution is 1:9, separating liquid, extracting, washing with deionized water and saturated sodium chloride for 7 times, and steaming at 350rpm and 45 ℃ for 3h to obtain modified resin;
(7) Mixing modified resin, aminoethylpiperazine, polydimethylsiloxane, n-butanol and xylene according to a mass ratio of 1:0.14:0.035:0.75:0.75 to obtain a modified resin coating; spraying a modified resin coating with the mass of 0.2 times of that of the ceramic tile substrate on the ceramic tile substrate, and drying at 90 ℃ for 70min to obtain the health-care deodorant ceramic tile.
Example 3
The preparation method of the health-care deodorant ceramic tile mainly comprises the following preparation steps:
(1) Placing the ceramic tile blank under a plasma gun, and vacuumizing to 5×10 -3 Pa, pulsing 7 times to obtain a pretreated ceramic tile blank; mixing polyvinylpyrrolidone, silver nitrate, deionized water and N, N-dimethylformamide according to a mass ratio of 1:5:25:33, and stirring at 50 ℃ for 2 hours to obtain silver nitrate spinning solution; mixing polystyrene microspheres with the particle size of 600nm with distilled water according to the mass ratio of 1:9 to obtain a polystyrene microsphere spinning solution; taking silver nitrate spinning solution as an external phase solution, taking polystyrene microsphere spinning solution as an internal phase solution, spinning the pretreated ceramic tile blank 20cm away until the thickness of a film layer is 40 mu m, heating to 550 ℃ at 5 ℃/min, and calcining for 2 hours to obtain a fiber membrane ceramic tile blank; the plasma gun: the pulse width was 70. Mu.s, and the electron density of the plasma was 10 16 cm -3 A power density of 10 7 W/cm 2 Ion velocity of 70kms -1 The method comprises the steps of carrying out a first treatment on the surface of the The spinning: the spinning voltage is 20kV, the internal phase diameter is 0.5mm, the flow rate is 0.1mL/h, the external phase diameter is 1.2mm, and the flow rate is 0.3mL/h;
(2) Placing the fiber membrane tile blank in a molecular laser, and vacuumizing to 5×10 -4 Heating to 350 ℃ under Pa, adopting a high-purity zinc target, wherein the distance between the fiber film ceramic tile blank and the high-purity zinc target is 10cm, introducing oxygen at 70sccm to a pressure of 6Pa, and depositing for 5min to obtain a seed crystal layer ceramic tile blank; mixing zinc nitrate, hexamethylenetetramine, copper nitrate and ethylene glycol according to a mass ratio of 1:0.8:0.5:95, and adding sodium carbonate until the pH value of the solution is 10 to obtain a zinc-copper source mixed solution; soaking the seed crystal layer ceramic tile blank in a zinc-copper source mixed solution with the mass of 12 times of that of the seed crystal layer ceramic tile blank, standing at 90 ℃ for 2 hours, fishing out, washing with deionized water for 10 times, drying at 80 ℃ for 30 minutes, and calcining at 250 ℃ for 3 hours to obtain a deodorizing layer; the molecular laser: the wavelength is 248nm, the pulse width is 40ns, the pulse repetition frequency is 10Hz, and the pulse energy is 400mJ;
(3) Pouring the surface slurry to the deodorizing layer until the thickness is 4mm, drying for 10min at 100 ℃, and calcining for 4h at 1300 ℃ to obtain a ceramic tile substrate;
(4) Mixing E-51 epoxy resin, ethylene glycol monobutyl ether and absolute ethyl alcohol according to the mass ratio of 1:0.4:0.3, heating to 75 ℃ under the protection of nitrogen, stirring until the mixture is dissolved, adding 6, 7-dihydroxyl-4-heteroheptylamine with the mass of 0.9 times of the E-51 epoxy resin, reacting for 14 hours, adding an ethanol aqueous solution with the mass ratio of 4 times of the E-51 epoxy resin, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 0.25:1, and standing for 34 minutes to obtain a modified resin matrix;
(5) Mixing a modified resin matrix, 2, 6-dihydroxyl-5-chloro-4-pyrimidine methyl formate, potassium carbonate and N, N-dimethylformamide according to a mass ratio of 1:2.4:1.0:43, heating to 82 ℃ under argon atmosphere, stirring for 8 hours at 200rpm, heating to 160 ℃, preserving heat for 1 hour, adding dichloromethane with the mass 80 times that of the modified resin matrix, washing with deionized water and saturated sodium chloride solution in sequence for 13 minutes, drying at 52 ℃ for 2 hours, and repeating the steps for 5 times to obtain a dendrimer;
(6) Mixing a dendrimer and methylene dichloride according to the mass ratio of 1:26 under ice water bath, adding perfluoroalkyl ethyl bromide with the mass of 1.5 times of the dendrimer, stirring for 20min at 200rpm, adding N, N-dimethylformamide with the mass of 0.10 times of the dendrimer, removing the ice water bath, reacting for 15h at room temperature, adding sodium sulfite solution with the mass of 5 times of the dendrimer and deionized water with the mass ratio of 7 times of the dendrimer, wherein the mass ratio of sodium sulfite to deionized water in the sodium sulfite solution is 1:9, separating liquid, extracting, washing for 10 times sequentially with deionized water and saturated sodium chloride, and steaming for 2h at 50 ℃ at 400rpm to obtain modified resin;
(7) Mixing modified resin, aminoethylpiperazine, polydimethylsiloxane, n-butanol and xylene according to a mass ratio of 1:0.2:0.05:0.9:0.9 to obtain a modified resin coating; spraying modified resin coating with the mass of 0.3 times of that of the ceramic tile substrate on the ceramic tile substrate, and drying at 100 ℃ for 60min to obtain the health-care deodorant ceramic tile.
Comparative example 1
Comparative example 1 differs from example 2 only in the difference of step (1), the step (1) was changed to: mixing polyvinylpyrrolidone, silver nitrate, deionized water and N, N-dimethylformamide according to a mass ratio of l of 3:19:26.5, and stirring at 45 ℃ for 3.5 hours to obtain silver nitrate spinning solution; mixing polystyrene microspheres with the particle size of 500nm with distilled water according to the mass ratio of 1:7 to obtain a polystyrene microsphere spinning solution; silver nitrate spinning solution as external phaseTaking polystyrene microsphere spinning solution as an internal phase solution, spinning the solution 18cm away from a ceramic tile blank until the thickness of a film layer is 30 mu m, heating to 525 ℃ at 3 ℃/min, and calcining for 3.5h to obtain a fiber film ceramic tile blank; the plasma gun: pulse width of 60. Mu.s, electron density of 10 15 cm -3 A power density of 10 6 W/cm 2 Ion velocity of 60kms -1 The method comprises the steps of carrying out a first treatment on the surface of the The spinning: the spinning voltage was 18kV, the internal phase diameter was 0.5mm, the flow rate was 0.1mL/h, the external phase diameter was 1.2mm, and the flow rate was 0.2mL/h. The rest of the procedure is the same as in example 2.
Comparative example 2
The preparation method of the health-care deodorant ceramic tile mainly comprises the following preparation steps:
(1) Placing the ceramic tile blank under a plasma gun, and vacuumizing to 3×10 -3 Pa, pulsing 5 times to obtain a pretreated ceramic tile blank; placing the pretreated ceramic tile blank in a molecular laser, and vacuumizing to 3×10 -4 Heating to 325 ℃ under Pa, adopting a high-purity zinc target, introducing oxygen at a distance of 8cm between the fiber membrane ceramic tile blank and the high-purity zinc target, and depositing for 8min after introducing oxygen at a pressure of 50sccm to 4Pa to obtain a seed crystal layer ceramic tile blank; mixing zinc nitrate, hexamethylenetetramine, copper nitrate and ethylene glycol according to a mass ratio of 1:0.65:0.4:87.5, and adding sodium carbonate until the pH value of the solution is 8.5 to obtain a zinc-copper source mixed solution; soaking the seed crystal layer ceramic tile blank in a zinc-copper source mixed solution with the mass of 8 times of that of the seed crystal layer ceramic tile blank, standing at 80 ℃ for 3.5 hours, fishing out, washing with deionized water for 7 times, drying at 75 ℃ for 36 minutes, and calcining at 225 ℃ for 4.5 hours to obtain a deodorizing layer; the molecular laser: the wavelength is 248nm, the pulse width is 30ns, the pulse repetition frequency is 7Hz, and the pulse energy is 350mJ;
(2) Pouring the surface slurry to the deodorizing layer until the thickness is 2.5mm, drying for 15min at 90 ℃, and calcining for 6.5h at 1200 ℃ to obtain a ceramic tile substrate;
(3) Mixing E-51 epoxy resin, ethylene glycol monobutyl ether and absolute ethyl alcohol according to the mass ratio of 1:0.25:0.2, heating to 70 ℃ under the protection of nitrogen, stirring until the mixture is dissolved, adding 6, 7-dihydroxyl-4-heteroheptylamine with the mass of 0.7 times of the E-51 epoxy resin, reacting for 11 hours, adding an ethanol aqueous solution with the mass ratio of 1-4 times of the E-51 epoxy resin, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 0.25:1, and standing for 26 minutes to obtain a modified resin matrix;
(4) Mixing a modified resin matrix, 2, 6-dihydroxyl-5-chloro-4-pyrimidine methyl formate, potassium carbonate and N, N-dimethylformamide according to a mass ratio of 1:1.75:0.75:39, heating to 76 ℃ under argon atmosphere, stirring at 150rpm for 11 hours, heating to 155 ℃, preserving heat for 2 hours, adding dichloromethane with the mass 70 times that of the modified resin matrix, washing with deionized water and saturated sodium chloride solution in sequence for 10 minutes, drying at 40 ℃ for 3 hours, and repeating the steps for 3 times to obtain a dendrimer;
(5) Mixing a dendrimer and methylene dichloride according to the mass ratio of 1:22 under ice water bath, adding perfluoroalkyl ethyl bromide with the mass of 1.1 times of the dendrimer, stirring for 30min at 150rpm, adding N, N-dimethylformamide with the mass of 0.08 times of the dendrimer, removing the ice water bath, reacting for 12.5h at room temperature, adding sodium sulfite solution with the mass of 4 times of the dendrimer and deionized water with the mass ratio of 5.5 times of the dendrimer, wherein the mass ratio of sodium sulfite to deionized water in the sodium sulfite solution is 1:9, separating liquid, extracting, washing with deionized water and saturated sodium chloride for 7 times, and steaming at 350rpm and 45 ℃ for 3h to obtain modified resin;
(6) Mixing modified resin, aminoethylpiperazine, polydimethylsiloxane, n-butanol and xylene according to a mass ratio of 1:0.14:0.035:0.75:0.75 to obtain a modified resin coating; spraying a modified resin coating with the mass of 0.2 times of that of the ceramic tile substrate on the ceramic tile substrate, and drying at 90 ℃ for 70min to obtain the health-care deodorant ceramic tile.
Comparative example 3
Comparative example 3 differs from example 2 only in the difference of step (2), the step (2) was changed to: mixing zinc nitrate, hexamethylenetetramine, copper nitrate and ethylene glycol according to a mass ratio of 1:0.65:0.4:87.5, and adding sodium carbonate until the pH value of the solution is 8.5 to obtain a zinc-copper source mixed solution; soaking the fiber membrane ceramic tile blank in a zinc-copper source mixed solution with the mass of 8 times of that of the seed crystal layer ceramic tile blank, standing at 80 ℃ for 3.5 hours, fishing out, washing with deionized water for 7 times, drying at 75 ℃ for 36 minutes, and calcining at 225 ℃ for 4.5 hours to obtain a deodorizing layer; the molecular laser: the wavelength was 248nm, the pulse width was 30ns, the pulse repetition frequency was 7Hz, and the pulse energy was 350mJ. The remaining preparation steps were the same as in example 2.
Comparative example 4
Comparative example 4 differs from example 2 only in the difference of step (2), the step (2) was changed to: placing the fiber membrane tile blank in a molecular laser, and vacuumizing to 3×10 -4 Heating to 325 ℃ under Pa, adopting a high-purity zinc target, introducing oxygen at a distance of 8cm between the fiber membrane ceramic tile blank and the high-purity zinc target, and depositing for 8min after oxygen is introduced at a pressure of 4Pa at a speed of 50sccm to obtain a deodorizing layer; the molecular laser: the wavelength was 248nm, the pulse width was 30ns, the pulse repetition frequency was 7Hz, and the pulse energy was 350mJ. The remaining preparation steps were the same as in example 2.
Comparative example 5
Comparative example 5 differs from example 2 in that there is no step (4), step (5) is changed to: mixing E-51 epoxy resin, 2, 6-dihydroxyl-5-chloro-4-pyrimidine methyl formate, potassium carbonate and N, N-dimethylformamide according to the mass ratio of 1:1.75:0.75:39, heating to 76 ℃ under argon atmosphere, stirring for 11 hours at 150rpm, heating to 155 ℃, preserving heat for 2 hours, adding dichloromethane with the mass 70 times that of the E-51 epoxy resin, washing with deionized water and saturated sodium chloride solution in sequence for 10 minutes, drying at 40 ℃ for 3 hours, and repeating the steps for 3 times to obtain the dendrimer. The remaining preparation steps were the same as in example 2.
Comparative example 6
Comparative example 6 differs from example 2 in that there is no step (5), step (6) is changed to: mixing a modified resin matrix and methylene dichloride according to the mass ratio of 1:22 under ice water bath, adding perfluoroalkyl ethyl bromide with the mass of 1.1 times of the modified resin matrix, stirring for 30min at 150rpm, adding N, N-dimethylformamide with the mass of 0.08 times of the modified resin matrix, removing the ice water bath, reacting for 12.5h at room temperature, adding sodium sulfite solution with the mass of 4 times of the modified resin matrix and deionized water with the mass ratio of 5.5 times of the modified resin matrix, wherein the mass ratio of sodium sulfite to deionized water in the sodium sulfite solution is 1:9, separating liquid, extracting, washing with deionized water and saturated sodium chloride for 7 times, and spin-steaming at 350rpm and 45 ℃ for 3h to obtain the modified resin. The rest of the procedure is the same as in example 2.
Comparative example 7
Comparative example 7 differs from example 2 in that there is no step (6), step (7) is changed to: mixing the dendrimer, the aminoethylpiperazine, the polydimethylsiloxane, the n-butanol and the xylene according to the mass ratio of 1:0.14:0.035:0.75:0.75 to obtain the modified resin coating; spraying a modified resin coating with the mass of 0.2 times of that of the ceramic tile substrate on the ceramic tile substrate, and drying at 90 ℃ for 70min to obtain the health-care deodorant ceramic tile. The rest of the procedure is the same as in example 2.
Effect example
The following table 1 gives the results of performance analysis of the health deodorant tiles employing examples 1 to 3 of the present invention and comparative examples 1 to 7.
TABLE 1
Antibacterial efficiency (%) Water contact angle (°)
Example 1 99.7 155.2
Example 2 99.9 156.1
Example 3 99.6 155.8
Comparative example 1 70.3 154.3
Comparative example 2 71.3 154.7
Comparative example 3 72.6 154.6
Comparative example 4 72.8 154.7
Comparative example 5 96.8 90.2
Comparative example 6 96.8 96.3
Comparative example 7 97.0 99.1
As can be found from the comparison of the antibacterial rate experimental data of the embodiment and the comparative example, the invention firstly carries out plasma pulse bombardment pretreatment on the ceramic blank body, which is beneficial to the deposition of the deodorant layer; then, sequentially preparing a porous hollow nano silver fiber membrane, a nano zinc oxide seed crystal layer, a zinc oxide nano rod and nano copper oxide particles to generate an electron transfer chain, and when contacting bacterial cells, generating active oxygen such as hydroxyl free radicals, superoxide anion free radicals, malondialdehyde and the like, activating an oxidative stress state, catalyzing and adsorbing bacteria, and enabling the bacteria to suffocate to prevent metabolism of the bacteria; as can be found from the comparison of the hydrophobic angle experimental data of the examples and the comparative examples, the 6, 7-dihydroxy-4-heteroheptylamine, the 2, 6-dihydroxy-5-chloro-4-pyrimidine methyl formate and the perfluoroalkyl ethyl bromide modified epoxy resin are subjected to hydrophobic modification, and the water drops are well utilized to take away pollutants such as dust and the like, so that the ceramic tile has anti-fouling capability; in addition, 6, 7-dihydroxyl-4-heteroheptylamine, 2, 6-dihydroxyl-5-chloro-4-pyrimidine methyl formate and perfluoroalkyl ethyl bromide spontaneously gather on the surface of the epoxy resin, which is helpful for reducing the surface energy and improving the stability and the hydrophobicity of the coating.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (1)

1. A preparation method of a health-care deodorant ceramic tile is characterized by comprising the following steps: mainly comprises the following preparation steps:
(1) Placing the ceramic tile blank under a plasma gun, and vacuumizing to 3×10 -3 Pa, pulsing 5 times to obtain a pretreated ceramic tile blank; mixing polyvinylpyrrolidone, silver nitrate, deionized water and N, N-dimethylformamide according to a mass ratio of l of 3:19:26.5, and stirring at 45 ℃ for 3.5 hours to obtain silver nitrate spinning solution; mixing polystyrene microspheres with the particle size of 500nm with distilled water according to the mass ratio of 1:7 to obtain a polystyrene microsphere spinning solution; taking silver nitrate spinning solution as an external phase solution, taking polystyrene microsphere spinning solution as an internal phase solution, spinning the pretreated ceramic tile blank 18cm away until the thickness of a film layer is 30 mu m, heating to 525 ℃ at 3 ℃/min, and calcining for 3.5h to obtain a fiber membrane ceramic tile blank; the plasma gun: pulse width of 60. Mu.s, electron density of 10 15 cm -3 A power density of 10 6 W/cm 2 Ion velocity of 60kms -1 The method comprises the steps of carrying out a first treatment on the surface of the The spinning: the spinning voltage is 18kV, the insideThe phase diameter is 0.5mm, the flow rate is 0.1mL/h, the external phase diameter is 1.2mm, and the flow rate is 0.2mL/h;
(2) Placing the fiber membrane tile blank in a molecular laser, and vacuumizing to 3×10 -4 Heating to 325 ℃ under Pa, adopting a high-purity zinc target, introducing oxygen at a distance of 8cm between the fiber membrane ceramic tile blank and the high-purity zinc target, and depositing for 8min after introducing oxygen at a pressure of 50sccm to 4Pa to obtain a seed crystal layer ceramic tile blank; mixing zinc nitrate, hexamethylenetetramine, copper nitrate and ethylene glycol according to a mass ratio of 1:0.65:0.4:87.5, and adding sodium carbonate until the pH value of the solution is 8.5 to obtain a zinc-copper source mixed solution; soaking the seed crystal layer ceramic tile blank in a zinc-copper source mixed solution with the mass of 8 times of that of the seed crystal layer ceramic tile blank, standing at 80 ℃ for 3.5 hours, fishing out, washing with deionized water for 7 times, drying at 75 ℃ for 36 minutes, and calcining at 225 ℃ for 4.5 hours to obtain a deodorizing layer; the molecular laser: the wavelength is 248nm, the pulse width is 30ns, the pulse repetition frequency is 7Hz, and the pulse energy is 350mJ;
(3) Pouring the surface slurry to the deodorizing layer until the thickness is 2.5mm, drying for 15min at 90 ℃, and calcining for 6.5h at 1200 ℃ to obtain a ceramic tile substrate;
(4) Mixing E-51 epoxy resin, ethylene glycol monobutyl ether and absolute ethyl alcohol according to the mass ratio of 1:0.25:0.2, heating to 70 ℃ under the protection of nitrogen, stirring until the mixture is dissolved, adding 6, 7-dihydroxyl-4-heteroheptylamine with the mass of 0.7 times of the E-51 epoxy resin, reacting for 11 hours, adding an ethanol aqueous solution with the mass ratio of 1-4 times of the E-51 epoxy resin, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 0.25:1, and standing for 26 minutes to obtain a modified resin matrix;
(5) Mixing a modified resin matrix, 2, 6-dihydroxyl-5-chloro-4-pyrimidine methyl formate, potassium carbonate and N, N-dimethylformamide according to a mass ratio of 1:1.75:0.75:39, heating to 76 ℃ under argon atmosphere, stirring at 150rpm for 11 hours, heating to 155 ℃, preserving heat for 2 hours, adding dichloromethane with the mass 70 times that of the modified resin matrix, washing with deionized water and saturated sodium chloride solution in sequence for 10 minutes, drying at 40 ℃ for 3 hours, and repeating the steps for 3 times to obtain a dendrimer;
(6) Mixing a dendrimer and methylene dichloride according to the mass ratio of 1:22 under ice water bath, adding perfluoroalkyl ethyl bromide with the mass of 1.1 times of the dendrimer, stirring for 30min at 150rpm, adding N, N-dimethylformamide with the mass of 0.08 times of the dendrimer, removing the ice water bath, reacting for 12.5h at room temperature, adding sodium sulfite solution with the mass of 4 times of the dendrimer and deionized water with the mass ratio of 5.5 times of the dendrimer, wherein the mass ratio of sodium sulfite to deionized water in the sodium sulfite solution is 1:9, separating liquid, extracting, washing with deionized water and saturated sodium chloride for 7 times, and steaming at 350rpm and 45 ℃ for 3h to obtain modified resin;
(7) Mixing modified resin, aminoethylpiperazine, polydimethylsiloxane, n-butanol and xylene according to a mass ratio of 1:0.14:0.035:0.75:0.75 to obtain a modified resin coating; spraying a modified resin coating with the mass of 0.2 times of that of the ceramic tile substrate on the ceramic tile substrate, and drying at 90 ℃ for 70min to obtain the health-care deodorant ceramic tile.
CN202310332990.8A 2022-04-13 2022-04-13 Preparation method of health-care deodorant ceramic tile Pending CN116553909A (en)

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