CN107473770B - Manufacturing process of photocatalyst film composite ceramic - Google Patents
Manufacturing process of photocatalyst film composite ceramic Download PDFInfo
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- CN107473770B CN107473770B CN201710500444.5A CN201710500444A CN107473770B CN 107473770 B CN107473770 B CN 107473770B CN 201710500444 A CN201710500444 A CN 201710500444A CN 107473770 B CN107473770 B CN 107473770B
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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
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G19/00—Table service
- A47G19/02—Plates, dishes or the like
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
- A47K1/00—Wash-stands; Appurtenances therefor
- A47K1/04—Basins; Jugs; Holding devices therefor
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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
- C04B41/5025—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 ceramic materials
- C04B41/5041—Titanium oxide or titanates
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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
- C04B41/52—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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- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
- E03D11/00—Other component parts of water-closets, e.g. noise-reducing means in the flushing system, flushing pipes mounted in the bowl, seals for the bowl outlet, devices preventing overflow of the bowl contents; devices forming a water seal in the bowl after flushing, devices eliminating obstructions in the bowl outlet or preventing backflow of water and excrements from the waterpipe
- E03D11/02—Water-closet bowls ; Bowls with a double odour seal optionally with provisions for a good siphonic action; siphons as part of the bowl
Abstract
The invention provides a manufacturing process of photocatalyst film composite ceramic, belonging to the technical field of ceramic, and adopting the technical scheme that the manufacturing process of photocatalyst film composite ceramic comprises the following steps: preparing an aqueous solution of a peroxotitanium complex system with the concentration of 0.1-5wt.%, and adding a surfactant into the aqueous solution to prepare a spraying liquid; and (3) uniformly coating the spraying liquid on the surface of the clean and dry ceramic, drying the surface, calcining at high temperature, controlling the calcining condition to be 300-900 ℃ for 10-120min, and cooling to room temperature to obtain the photocatalyst film composite ceramic. The beneficial effects are that: the manufacturing process has simple steps, short time consumption of the process flow, high efficiency, low investment and wide application in the flow line of various manufacturers; the product has excellent wear resistance, antibacterial property and formaldehyde degradation property, can efficiently clean air and improve environment, and has the soft and glossy organic gem, high grade and elegant appearance and good aesthetic property.
Description
Technical Field
The invention relates to the technical field of ceramics, in particular to a manufacturing process of photocatalyst film composite ceramics.
Background
Indoor environment is bad due to various factors, and internal decoration pollutants, bacteria and viruses are gathered in dark and humid corners, which are increasingly prominent under the condition of large environment complexity at present. Air pollution caused by indoor furniture, such as formaldehyde, benzene, toluene, xylene, Volatile Organic Compounds (VOC) and the like, is mainly hidden in plates, emulsion paints, wallpaper, adhesives and the like used for indoor decoration. Another serious threat to human health is the accumulation and residue of bacteria and viruses in indoor environment, especially in kitchen and toilet where food is placed, and where humidity and air circulation are poor, odor is easily generated, which is very likely to cause health problems, and is also receiving more and more attention from the residents.
Among various measures for improving the indoor environment, the photocatalyst is deeply favored by consumers due to excellent performances of stable and lasting effect, convenient use and the like. The photocatalyst can generate a photocatalytic reaction similar to photosynthesis under the irradiation of light to generate free hydroxyl and active oxygen with extremely strong oxidizing power, has a very strong photoredox function, can oxidize and decompose various organic compounds and partial inorganic substances, can destroy cell membranes of bacteria and solidify proteins of viruses, can decompose organic pollutants into pollution-free water and carbon dioxide, and has extremely strong functions of sterilization and air purification.
However, the purpose is toThe defects of the front photocatalyst in application are increasingly shown, for example, the photocatalyst spray is sprayed on the wall surface and the furniture surface, but the photocatalyst spray is easy to fall off, even wall cracks, furniture drum leather and the like are caused; on the other hand, the nano titanium dioxide is easy to agglomerate in the placing process, so that the decomposition effect is greatly reduced. The photocatalyst is solidified in daily articles, so that the harmful gas in the air is degraded and the sterilization is a breakthrough progress, but most of the environment-friendly products in the curtain wall market at present adopt organic binders to bond and fix the photocatalyst, and the defects are that the binder is easily decomposed by the photocatalyst to cause the falling of the photocatalyst. In addition, the invention of CN106278244A discloses an antibacterial and mildewproof ceramic of photocatalyst material and a production process thereof, wherein rutile and carbon powder are used as raw materials to prepare TiCl under the conditions of chlorine and high temperature4The ceramic is further mixed with aluminum hydroxide, silicon water glass and water to prepare anatase type nano titanium dioxide photocatalyst aqueous slurry, and finally the anatase type nano titanium dioxide photocatalyst aqueous slurry is mixed into a ceramic glaze material to prepare the antibacterial and mildewproof ceramic; therefore, the research on the application of luminescent catalysts in combination with home decoration products and the products thereof is a technical problem which needs to be solved urgently in the field of improving the environment and ensuring the human health.
Disclosure of Invention
The invention provides a manufacturing process of photocatalyst film composite ceramic, aiming at solving the technical problems of complex production process, unstable product performance and high cost of the existing photocatalyst application, wherein a titanium peroxide complex system aqueous solution added with a surfactant is adopted to control the spraying process parameters to be uniformly sprayed on the surface of the ceramic to form a film, and the film is further calcined at high temperature to obtain the composite ceramic coated with the uniform and compact photocatalyst film, so that the film-coated ceramic surface can be manufactured to have mild and soft pearl luster and infinitely variable organic colors, and the composite ceramic has good performances of resisting bacteria and degrading harmful pollutants and peculiar smell under the conditions of visible light and relative darkness.
The technical scheme adopted by the invention is as follows: the manufacturing process of the photocatalyst film composite ceramic comprises the following steps:
① preparing 0.1-5wt.% aqueous solution of peroxotitanium complex system, adding surfactant into the aqueous solution, and making into spray;
② the spraying pressure is controlled to be 0.5-0.8 MPa, the coating weight is controlled to be 100-2Uniformly coating the spraying liquid on the surface of the clean and dry ceramic, and drying the surface to obtain the film-coated ceramic;
③ calcining the film-coated ceramic at high temperature, controlling the calcining condition at 300-900 ℃ for 10-120min, and cooling to room temperature to obtain the photocatalyst film composite ceramic.
Preferably, the manufacturing process further comprises step ④ of uniformly coating the photocatalyst film composite ceramic surface with Fe3+、Cu2+And drying the soluble salt or complex solution of the rare earth element and/or the noble metal to obtain the micro-loaded photocatalyst film composite ceramic.
Preferably, the peroxo titanium complex system is peroxotitanic acid.
More preferably, the Fe3+、Cu2+Or in soluble salt solutions of noble metals3+、Cu2+Or the concentration of the noble metal is 0.1-1wt%, and the concentration of the soluble salt or complex solution of the rare earth element is 0.1-10 mmol/L.
More preferably, the rare earth element is La3+And/or Ce3+The noble metal is Pt, Au or Ag.
Further, the soluble salt or complex solution coated in the step ④ contains Cu2+And then coating a reducing agent after drying, preserving heat for 1-1.5h at room temperature-100 ℃, reducing, washing with water and drying for the second time to obtain the micro-loaded photocatalyst film composite ceramic.
Preferably, the reducing agent is a mixed solution of sodium hydroxide and glucose in a concentration of 0.5-3wt.%, 0.001-0.1mol/L hydrazine hydrate or 0.001-0.1mol/L sodium borohydride.
Preferably, the surfactant is polyether modified polydimethylsiloxane or acrylate leveling agent, and the addition amount of the surfactant is 0.5-2% of the total mass of the spraying liquid.
Preferably, the high-temperature calcination condition in the step ③ is to place the surface-dried film-coated ceramic in an oven, control the heating rate to 3-10 ℃/min to raise the temperature to 900 ℃ at 300-.
The photocatalyst film composite ceramic is ceramic tableware, a wash basin, a closestool or ceramic tiles.
In the above technical scheme, the steps of the manufacturing process of the photocatalyst film composite ceramic are understood as follows:
① cleaning the pretreated ceramic, wherein the method comprises cleaning with absolute ethanol for 1-3 times to remove oil stain on the surface of the ceramic, cleaning with distilled water for 1-3 times, oven drying to clean and dry the surface of the ceramic, and cleaning to improve the adhesion of the coating on the surface of the ceramic, purchasing peroxotitanium complex system or preparing peroxotitanium complex system with titanium source, diluting and adjusting the concentration of the aqueous solution of peroxotitanium complex system to 0.1-5wt.%, adding surfactant to the aqueous solution to obtain the spray solution, wherein the addition of surfactant can reduce the surface energy of the aqueous solution of peroxotitanium complex system, improve the wettability to the surface of the ceramic, increase the fluidity of the system, facilitate the spray solution to realize self-leveling during the application process, thereby forming uniform, pinhole-free and uniform coating on the surface of the ceramic, and eliminating color unevenness caused by light diffraction interference due to thickness difference.
② the spraying liquid is evenly coated on the clean and dry ceramic surface, when spraying, the spraying pressure is controlled to be 0.5-0.8 MPa, the spraying distance is controlled to be 200-300 mm, and the coating weight is controlled to be 100-2Uniformly coating the spraying liquid on the clean and dry ceramic surface, forming a film of the spraying liquid on the ceramic surface, and obtaining the film-coated ceramic after the surface of the film is dried; in the spraying process, the spraying process parameters are comprehensively controlled to closely influence the spraying quality of the film, the spraying pressure range is controlled to be 0.5-0.8 MPa, the spraying liquid is prevented from splashing to cause loss and coating pinholes, the insufficient atomization and the uneven coating caused by too small pressure are avoided to the maximum extent, and the coating weight is controlled to be 100-2On the one hand, the adhesive force of the spraying liquid on the surface of the ceramic is ensuredOn the other hand, the coating amount of the spraying liquid is controlled, the thickness of the coating is indirectly controlled, and the effects of sterilizing, degrading harmful pollutants and ensuring the glossiness are ensured. The spraying process generally selects a normal temperature environment, the spraying distance is controlled to be 200-300 mm for optimizing the process, and the sputtering of the spraying liquid and the diffusion of the spraying liquid which is not attached are reduced; controlling the spraying speed to be 10-20 cm/s for taking film forming uniformity and process efficiency into consideration; the lapping width 1/3-1/2 is used for reducing the phenomenon of uneven edges, and more strictly, the spraying environment generally requires 30-80% of humidity, no oil and water in the air and 10000 levels of air cleanliness, so that the film forming quality is improved, and the glossiness of a finished product is ensured.
③ calcining the surface-dried film-coated ceramic at high temperature, controlling the calcining condition to 300-900 deg.C, calcining for 10-120min, cooling, such as cooling with furnace or cooling to room temperature, to obtain the photocatalyst film composite ceramic, sintering to form a uniform and compact titanium dioxide photocatalyst film through cross-linking and curing between peroxo titanium molecules, and XRD detecting to find that the titanium dioxide is rutile type, and has high-efficiency sterilization and harmful pollutant degradation properties.
The invention has the beneficial effects that: (1) the manufacturing process has the advantages of simple steps, short time consumption of the process flow, high efficiency, excellent wear resistance, antibacterial property and formaldehyde degradation performance of the produced product, high efficiency of air cleaning and environment improvement; the safety and sanitation of the ceramic product are greatly ensured; (2) the raw materials required by the process are easy to obtain, the operation is simple, the method can be widely applied to the production line of each manufacturer, the investment is low, and the performance is good; (3) the produced product has the soft and lustrous organic gem, high grade and elegant appearance and good aesthetic property.
Detailed Description
The invention provides a manufacturing process of a photocatalyst film composite ceramic, which is characterized in that the implementation method of the process and the performance of the manufactured photocatalyst film composite ceramic are described in detail by specific examples, the operations involved in the examples are all conventional operations unless otherwise specified, and the reagents involved in the examples are all commercially available unless otherwise specified.
Example 1
Cleaning the ceramic with absolute ethyl alcohol for 3 times to remove surface oil stains, then cleaning with distilled water for 3 times, and drying in a drying box to obtain the ceramic with a dry and clean surface for later use; using peroxotitanic acid (manufacturer: Japan spread Co., Ltd.) as a starting material, diluting with distilled water until the concentration of peroxotitanic acid is 0.1wt.%, to obtain peroxotitanic acid aqueous solution, adding polyether modified polydimethylsiloxane into the peroxotitanic acid aqueous solution, wherein the polyether modified polydimethylsiloxane accounts for 0.5% of the total mass of the aqueous solution, and preparing into spraying liquid; the spraying pressure is controlled to be 0.6MPa, the spraying distance from the spray head to the ceramic surface is controlled to be 200mm, the spraying speed is controlled to be 20cm/s, the lap joint width between one spraying path and the previous spraying path is 1/3, and the coating weight is controlled to be 200ml/m2Spraying at room temperature (20 ℃), controlling the humidity of the environment to be 40-50%, keeping no oil and water in the air, enabling the air cleanliness to be 10000 levels, uniformly spraying the spraying liquid on the surface of dry and clean ceramic, measuring to find that the thickness of a wet film is 0.18mm, drying at room temperature for 20min, and drying the surface of the thin film of the spraying liquid to obtain the film-coated ceramic; then the film-covered ceramic is put into a high-temperature furnace with the temperature of 400 ℃ to be calcined for 100min, the furnace is cooled to room temperature, at the moment, the peroxotitanic acid molecules are crosslinked and cured to form a uniform and compact titanium dioxide photocatalyst film, the film has soft and uniform pearl luster and no rainbow color, and the titanium dioxide photocatalyst film is uniform, so that the photocatalyst film composite ceramic is obtained, and more precisely the photocatalyst (titanium dioxide) film composite ceramic.
To facilitate the testing of the properties of the product of this example, the following comparative examples were set up in the same manner and with the same parameters as described above:
comparative example 1-A: selecting the same ceramics as in the embodiment 1, and carrying out pretreatment and cleaning to obtain dry and clean ceramics;
comparative example 1-B: unlike example 1, in this comparative example, the spray coating liquid was not prepared, and the coated ceramic was prepared without spraying the spray coating liquid, but the ceramic having a dry clean surface was directly put into a muffle furnace, and then calcined in a high-temperature furnace at 400 ℃ for 100min, followed by furnace cooling to room temperature.
Comparative example 1-C: unlike example 1, the aqueous solution of peroxotitanic acid contains no surfactant and the rest is the same.
Example 2
Adding 30% hydrogen peroxide (analytically pure) into 1mol/L titanium hydroxide aqueous solution to prepare a titanium peroxide complex system, wherein the volume ratio of the titanium hydroxide aqueous solution to the 30% hydrogen peroxide is 1: adding distilled water with the mass being 10 times that of the titanium peroxide complex system to dilute the titanium peroxide complex system to obtain an aqueous solution of the titanium peroxide complex system, and adding polyether modified polydimethylsiloxane accounting for 0.5wt.% of the total mass into the aqueous solution to prepare a spraying liquid; uniformly spraying the spraying liquid on the dry and clean ceramic surface, controlling the spraying pressure to be 0.8MPa, the spraying distance to be 200mm, the spraying speed to be 20cm/s, the lap joint width to be 1/3 and the coating weight to be 400ml/m2Spraying at the ambient temperature of 15 ℃ and the humidity of 30-40%, wherein the air contains no oil and water, the air cleanliness is 10000 levels, the thickness of a wet film is 0.3mm, drying at room temperature for 30min, and drying the surface of the film of the spraying liquid to obtain the film-coated ceramic; then placing the film-coated ceramic into a muffle furnace, heating to 500 ℃ at a speed of 3 ℃/min, calcining for 80min at a constant temperature of 500 ℃, cooling to room temperature along with the furnace, and crosslinking and curing molecules in a titanium peroxide complex system to form a uniform and compact titanium dioxide photocatalyst film, thereby obtaining the photocatalyst film composite ceramic; further, FeCl of 0.1mol/L is evenly sprayed on the surface of the photocatalyst film composite ceramic3Aqueous solution, spraying amount 400ml/m2Drying at room temperature, Fe3+The Fe micro-loaded photocatalyst film composite ceramic is loaded on a titanium dioxide photocatalyst to form a micro-loaded photocatalyst film, and the micro-loaded photocatalyst film composite ceramic is obtained, in particular to the Fe micro-loaded photocatalyst film composite ceramic, and the product has soft and uniform pearl luster and no rainbow color.
To facilitate the testing of the properties of the product of this example, the following comparative examples were set up in the same manner and with the same parameters as described above:
comparative example 2-A, unlike example 2, in this comparative example, 0.1mol/L FeCl was not sprayed3The step of water solution, namely the comparative example is the photocatalyst film composite ceramic;
comparative example 2-B, unlike example 2, in this comparative example, the spray coating liquid was not prepared, and the coated ceramic was not prepared by spraying the spray coating liquid, but the ceramic having a dry clean surface was directly put into a muffle furnace, heated at 3-10 ℃/min to 500 ℃, and calcined at a constant temperature of 500 ℃ for 80min, cooled to room temperature with the furnace, and sprayed with 0.1mol/L FeCl3Aqueous solution, spraying amount 400ml/m2And drying at room temperature.
Example 3
Cleaning the ceramic disc with absolute ethyl alcohol for 1 time to remove oil stains on the surface, cleaning with distilled water for 3 times, and drying in a drying box to obtain the ceramic disc with a dry and clean surface for later use; using peroxotitanic acid as a starting material, diluting with distilled water until the concentration of the peroxotitanic acid is 5wt.%, to obtain peroxotitanic acid aqueous solution, and adding polyether modified polydimethylsiloxane accounting for 2wt.% of the total mass into the peroxotitanic acid aqueous solution to prepare spraying liquid; uniformly spraying the spraying liquid on the surface of a dry and clean ceramic disc, controlling the spraying pressure to be 0.8MPa, the spraying distance to be 300mm, the spraying speed to be 10cm/s, the lap joint width to be 1/3, and the coating weight to be 100ml/m2Spraying at the ambient temperature of 15 ℃ and the humidity of 30-40%, wherein the air contains no oil and water, the air cleanliness is 10000 levels, the thickness of a wet film is 0.2mm, drying at room temperature for 30min, and drying the surface of the film of the spraying liquid to obtain the film-coated ceramic; then placing the film-coated ceramic into a muffle furnace, heating to 900 ℃ at a speed of 5 ℃/min, calcining for 15min at a constant temperature of 900 ℃, and cooling to room temperature along with the furnace to obtain the photocatalyst film composite ceramic; further, 0.2mol/L CuCl is evenly sprayed on the surface of the photocatalyst film composite ceramic2Aqueous solution, spraying amount 500ml/m2Drying at room temperature, and adding 200ml/m2Spraying a mixed solution of sodium hydroxide with the concentration of 1.25% and glucose with the spraying amount, and keeping the temperature at 90 ℃ for 1h to load Cu2+Reduction to Cu+Slightly rinsing with distilled water, then drying twice, Cu+Loaded on titanium dioxide photocatalyst to form micro-negativeThe micro-load photocatalyst film composite ceramic is obtained by loading the photocatalyst film, more precisely, the Cu micro-load photocatalyst film composite ceramic disc has the advantages of soft and uniform pearl luster and no rainbow color.
To facilitate the testing of the properties of the product of this example, the following comparative examples were set up in the same manner and with the same parameters as described above:
comparative example 3-a, the same ceramic disc as in example 3 was selected, pre-treated and cleaned to obtain a glass disc with a dry clean surface;
comparative example 3-B, unlike example 3, in this comparative example no CuCl spray coating was performed2The step of water solution, namely the comparative example is a photocatalyst film composite ceramic disc;
comparative example 3-C, unlike example 3, in this comparative example, the spray coating liquid was not prepared, and the coated ceramic was not prepared by spraying the spray coating liquid, but the ceramic disk having a dry clean surface was directly placed in a muffle furnace, heated at 5 ℃/min to 900 ℃, and calcined at 900 ℃ for 15min, cooled to room temperature with the furnace, and further 0.2mol/L of CuCl was uniformly sprayed on the surface2Aqueous solution, spraying amount 500ml/m2Drying at room temperature, and adding 200ml/m2Spraying a mixed solution of sodium hydroxide with the concentration of 1.25% and glucose with the spraying amount of 3%, keeping the temperature at 90 ℃ for 1 hour, slightly rinsing with distilled water, and drying for the second time.
Example 4
Cleaning the ceramic closestool blank with absolute ethyl alcohol for 2 times to remove surface oil stains, cleaning with distilled water for 2 times, and drying at room temperature to obtain a ceramic closestool blank with a dry and clean surface for later use; diluting peroxytitanic acid with distilled water to the concentration of 2wt.% to obtain peroxytitanic acid aqueous solution, and adding polyether modified polydimethylsiloxane accounting for 1wt.% of the total mass into the peroxytitanic acid aqueous solution to prepare spraying liquid; uniformly spraying the spraying liquid on the surface of a dry and clean ceramic closestool blank, controlling the spraying pressure to be 0.6MPa, the spraying distance to be 200mm, the spraying speed to be 10cm/s, the lap joint width to be 1/2 and the coating weight to be 400ml/m2Spraying at 20 deg.C and 40-60% humidity, wherein the air contains no oil and water, the air cleanliness is 10000 grade, the wet film thickness is 0.3mm, and drying at room temperature is 30min, drying the surface of the spraying liquid film to obtain a film-coated ceramic closestool blank; then placing the coated ceramic closestool blank into a muffle furnace, heating to 500 ℃ at a speed of 5 ℃/min, calcining at a constant temperature of 500 ℃ for 100min, and cooling to room temperature along with the furnace to obtain the photocatalyst film composite ceramic closestool; further, 0.2mol/L AgCl aqueous solution is uniformly sprayed on the surface of the photocatalyst film composite ceramic closestool, and the spraying amount is 300ml/m2Drying at room temperature to obtain the micro-load photocatalyst film composite ceramic, more precisely, the Ag micro-load photocatalyst film composite ceramic closestool, and the product has soft and uniform pearl luster and no rainbow color.
Example 5
Cleaning the ceramic basin blank with absolute ethyl alcohol for 2 times to remove surface oil stains, cleaning with distilled water for 2 times, and drying at room temperature to obtain a ceramic basin blank with a dry and clean surface for later use; diluting peroxytitanic acid to the concentration of 1wt% by using distilled water to obtain an aqueous solution of peroxytitanic acid, and adding polyether modified polydimethylsiloxane accounting for 1wt% of the total mass into the aqueous solution of peroxytitanic acid to prepare a spraying liquid; uniformly spraying the spraying liquid on the surface of a dry and clean ceramic basin blank, controlling the spraying pressure to be 0.6MPa, the spraying distance to be 200mm, the spraying speed to be 20cm/s, the lap joint width to be 1/2, and the coating weight to be 300ml/m2Spraying at the ambient temperature of 20 ℃ and the humidity of 40-60%, wherein the air contains no oil and water, the air cleanliness is 10000 levels, the thickness of a wet film is 0.3mm by measurement, drying at room temperature for 30min, and drying the surface of the thin film of the spraying liquid to obtain a coated ceramic basin blank; then putting the coated ceramic basin blank into a muffle furnace, heating to 500 ℃ at a speed of 5 ℃/min, calcining at a constant temperature of 500 ℃ for 100min, and cooling to room temperature along with the furnace to obtain a photocatalyst film composite ceramic basin; further, 0.2mol/L of amino acid Schiff base cerium complex aqueous solution is uniformly sprayed on the surface of the photocatalyst film composite ceramic basin, and the spraying amount is 300ml/m2And drying at room temperature to obtain the micro-load photocatalyst film composite ceramic, more precisely, the Ce micro-load photocatalyst film composite ceramic basin, and the product has soft and uniform pearl luster and no rainbow color.
Test of Experimental Properties
The products in the above examples were subjected to performance tests according to the following test methods, and the test results are summarized in table 1.
1. Test of antibacterial Property
Escherichia coli is used as an indicator bacterium, the sterilization rate is detected according to the requirements of GBT 30706-2014 'method and evaluation for testing the antibacterial performance of photocatalytic antibacterial materials and products under visible light irradiation', and the sterilization rate is tested after the irradiation of visible light for 4 hours. The antibacterial performance test under the dark condition comprises the steps of irradiating for 1 hour by visible light, then carrying out dark and dark protection for 3 hours, and then measuring the antibacterial performance.
2. Determination of degradation Rate
Setting a test chamber: the prepared volume for each sample was 1.5m3The experimental chamber of (1.5 m) is prepared3The method comprises the steps of respectively placing the same formaldehyde pollution source which is slowly released into each test chamber, closing the test chambers, simultaneously starting fans of the test chambers to enable pollutants in the chambers to circulate uniformly, sampling the concentrations of the pollutants in the test chambers after 24 hours, analyzing and testing, and calculating the pollutant removal rate, wherein the calculation method refers to the following formula of pollutant removal rate = (pollutant concentration value in a blank control chamber-pollutant concentration value in a sample experiment chamber) ÷ pollutant concentration value in the blank control chamber × 100%.
3. Abrasion resistance test
The production process and parameters of the product in each example are respectively carried out by taking a circular ceramic rod with holes with the diameter of 100mm as a ceramic carrier, the surface of the circular ceramic rod with holes is respectively treated, after the product is prepared by coating, the wear resistance is evaluated according to GB/T1768-2006 rotating rubber grinding wheel method for measuring the wear resistance of colored paint and varnish, and after the sample is rotated for 500 turns, the mass loss (mg) of the sample is measured.
4. Hardness test of coating
The products of the preceding examples were tested for coating hardness according to GB/T6739-2006 "Pencil method for determining paint film hardness".
Table 1 performance testing of the products prepared in examples 1-5
The results show that when the photocatalyst film is sintered on the surface of the ceramic by the manufacturing process, the film has high firmness, excellent wear resistance and high product hardness, and the weight loss is little in the wear resistance test; on the performance of the escherichia coli sterilization rate and the formaldehyde removal rate, the common ceramic and the ceramic which is only subjected to high-temperature treatment have almost no sterilization and formaldehyde degradation effects, and the high-temperature treatment has almost no influence on the sterilization and formaldehyde degradation functions; the sterilization rate of escherichia coli of the photocatalyst (titanium dioxide) film composite ceramic is up to 78%, and the removal rate of formaldehyde is up to 70%; when the spraying liquid without the surfactant is coated, the peroxotitanic acid in a sprayed wet film cannot be uniformly dispersed, so that a sintered photocatalyst (titanium dioxide) film is not uniform, a rainbow phenomenon is generated, on the other hand, the dispersity of the sintered photocatalyst particles is reduced, and the sterilization rate of escherichia coli and the removal rate of formaldehyde are also reduced. In addition, it can be known that, by coating the spraying liquid containing the surfactant and adjusting the thickness of the sprayed wet film, the uniform dispersion of the peroxotitanic acid can be ensured, so that the uniform dispersion of the sintered photocatalyst can be ensured, and the photocatalyst film composite ceramic with infinite color change and color luster can be obtained.
More preferably, the prepared photocatalyst film composite ceramic surface is further sprayed with Fe3+、Cu2+The micro-load photocatalyst film composite ceramic obtained after drying is greatly improved in escherichia coli sterilization rate and formaldehyde removal rate, the escherichia coli sterilization rate reaches more than 95%, the formaldehyde removal rate is 89% and even reaches 95%, compared with photocatalyst film composite ceramic and composite ceramic sprayed with metal ions independently, the effect is greatly enhanced, the effect is higher than the simple addition of two treatment modes, the spectrum response range of the photocatalyst can be increased by the load of the metal ions, electrons and holes can be generated by excitation under visible light, the separation efficiency of carriers can be improved, and the super-strong degradation effect under visible light is shownUsing; in the aspect of antibiosis, metal ions such as Cu, Ag, rare earth ions and the like have an antibacterial function, and the photocatalyst has an excitation effect on electron holes after being irradiated by visible light for 1 hour.
In conclusion, the preparation process provided by the invention has simple and easy operation steps, and the prepared photocatalyst film composite ceramic and the micro-loaded photocatalyst film composite ceramic both have excellent wear resistance, antibacterial and bactericidal performance and formaldehyde degradation performance, and on the other hand, the process is also suitable for recycling and sintering the home decoration ceramic appliance to process the photocatalyst film, so that the product is prevented from being replaced, and the investment of consumers is reduced. More worth saying, the product has the delicate luster similar to organic gems such as pearls and the like, brings a sense of nobility to people, can be widely used for ceramic basins and tiles in home decoration and ceramic tableware and artware in daily life, is safe and sanitary, can improve the indoor environment, and has important significance for human health.
Claims (8)
1. The manufacturing process of the photocatalyst film composite ceramic is characterized by comprising the following steps of:
① preparing 0.1-5wt.% aqueous solution of peroxotitanium complex system, adding surfactant into the aqueous solution, and making into spray;
② the spraying pressure is controlled to be 0.5-0.8 MPa, the coating weight is controlled to be 100-2Uniformly coating the spraying liquid on the surface of the clean and dry ceramic, and drying the surface to obtain the film-coated ceramic;
③ calcining the film-coated ceramic at high temperature, controlling the calcining condition at 300-900 ℃ for 10-120min, cooling to room temperature to obtain the photocatalyst film composite ceramic;
the preparation process also comprises step ④ of uniformly coating the photocatalyst film composite ceramic surface with Fe3+、Cu2+And a soluble salt or complex solution of rare earth elements and/or noble metals, and drying to obtain the micro-loaded photocatalyst film composite ceramic;
coating in said step ④In the solution of soluble salt or complex of (A) containing Cu2+And then coating a reducing agent after drying, preserving heat for 1-1.5h at room temperature-100 ℃, reducing, washing with water and drying for the second time to obtain the micro-loaded photocatalyst film composite ceramic.
2. The process of claim 1, wherein the peroxo-titanium complex system is peroxotitanic acid.
3. The process of claim 1, wherein the Fe is3+、Cu2+Or in soluble salt solutions of noble metals3+、Cu2+Or the concentration of the noble metal is 0.1-1wt%, and the concentration of the soluble salt or complex solution of the rare earth element is 0.1-10 mmol/L.
4. The process according to claim 1, wherein the rare earth element is La3+And/or Ce3+The noble metal is Pt, Au or Ag.
5. The manufacturing process according to claim 1, wherein the reducing agent is a mixed solution of 0.5 to 3wt.% sodium hydroxide and 1 to 5wt.% glucose, 0.001 to 0.1mol/L hydrazine hydrate, or 0.001 to 0.1mol/L sodium borohydride.
6. The manufacturing process according to claim 1, wherein the surfactant is a polyether modified polydimethylsiloxane or acrylate leveling agent, and the addition amount is 0.5-2% of the total mass of the spraying liquid.
7. The manufacturing process as claimed in claim 1, wherein the high temperature calcination in step ③ is performed by placing the surface-dried film-coated ceramic in an oven, heating to 900 ℃ at a heating rate of 3-10 ℃/min, and then calcining at 900 ℃ for 10-120min at 300-.
8. The process of claim 1, wherein the photocatalyst film-coated composite ceramic is ceramic tableware, a wash basin, a toilet, or a tile.
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| CN111732411B (en) * | 2020-08-25 | 2020-11-27 | 广东欧文莱陶瓷有限公司 | Antibacterial ceramic tile containing photocatalyst and preparation method thereof |
| CN113243794B (en) * | 2021-05-12 | 2023-01-03 | 惠州自然道智能家居用品有限公司 | Metal hand washing basin and manufacturing process thereof |
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| CN101554580A (en) * | 2008-12-22 | 2009-10-14 | 天津大学 | Simple preparation method of coating photocatalyst containing titanium dioxide nano-crystal grains |
| CN102426928A (en) * | 2011-12-23 | 2012-04-25 | 彩虹集团公司 | Method for preparing titanium dioxide dense membrane for dye sensitized solar cell |
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