CN107673629B - Titanium oxide composite membrane with antibacterial performance and preparation method thereof - Google Patents
Titanium oxide composite membrane with antibacterial performance and preparation method thereof Download PDFInfo
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- CN107673629B CN107673629B CN201710908180.7A CN201710908180A CN107673629B CN 107673629 B CN107673629 B CN 107673629B CN 201710908180 A CN201710908180 A CN 201710908180A CN 107673629 B CN107673629 B CN 107673629B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading
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Abstract
The invention relates to an antibacterial composite membrane, in particular to a titanium oxide composite membrane with antibacterial performance and a preparation method thereof. The composite film sequentially comprises a bottom layer, a transition layer and an antibacterial layer; the glaze layer is used as a bottom layer, the glass layer is used as a transition layer, and the anatase titanium dioxide layer is used as an antibacterial layer. The invention can be applied to ceramic products and the like, and the prepared ceramic has smooth and beautiful surface and is silvery white. The antibacterial test shows that the surface of the ceramic tile has stronger antibacterial activity. Can be used for making floor and wall tiles of kitchens and bathrooms, daily sanitary ceramic products, handicraft articles and the like.
Description
Technical Field
The invention relates to an antibacterial composite membrane, in particular to a titanium oxide composite membrane with antibacterial performance and a preparation method thereof.
Background
Titanium oxide, especially anatase titanium dioxide, has photocatalytic properties. When the photon energy irradiated on the titanium oxide is larger than the forbidden bandwidth, a photogenerated electron is generated in the conduction band, and a photogenerated hole is generated in the valence band, so that a photogenerated electron-hole pair is formed. The oxidizing reactant contacts with electrons transferred from a conduction band to the surface of the titanium oxide to generate a reduction reaction; the reducing reactant is combined with the hole transferred from the valence band to the titanium oxide surface, and an oxidation reaction occurs. In addition, the electrons and holes may be recombined in the titanium oxide or the inner surface to be annihilated, and the energy is emitted by radiation. The photo-generated holes transport the adsorbate in the gas or water phase contacting the semiconductor surface, thereby generating a photocatalytic reaction. TiO 22The photo-generated holes on the surface have strong electron gaining capability and can absorb OH adsorbed on the surface-And H2The O molecule is oxidized into hydroxyl radical OH, which has strong oxidizing power and can oxidize a plurality of organic pollutants and inorganic matters. To TiO2The photo-generated electrons on the surface have strong reducing capability and can be adsorbed on TiO2The oxygen molecules on the surface are subjected to reduction reaction to generate peroxide free radicals O2 -.、HO2 -Etc., are finally converted to O2 -And OH.free radical, allHas strong chemical activity, and can directly attack bacterial cells, destroy unsaturated bonds, and decompose protein and lipid of bacteria, thereby killing bacteria.
The application of titanium dioxide photocatalytic materials generally adopts a hot-melt method, a binder mixing method, a solgel method and the like to prepare semiconductor films, and the problem is that the bonding force of some films is not strong.
Disclosure of Invention
The invention aims to provide a titanium oxide composite film with antibacterial performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
a titanium oxide composite membrane with antibacterial property is provided, the composite membrane comprises a bottom layer, a transition layer and an antibacterial layer in sequence; the glaze layer is used as a bottom layer, the glass layer is used as a transition layer, and the anatase titanium dioxide layer is used as an antibacterial layer.
The thickness of the bottom layer is 0.1mm-0.5 mm; the glaze layer is an oxide solid solution obtained by high-temperature firing at 700-3000 ℃.
The thickness of the glass transition layer is 100nm-20000nm, the glass transition layer is formed by firing dispersion liquid prepared by mixing deionized water, polyvinyl alcohol solution and glass powder, and the melting point is 400-700 ℃.
The antibacterial layer is 15-200 nm thick and is formed by firing a dispersion prepared by mixing deionized water, a polyvinyl alcohol solution and nano titanium dioxide, and the average particle size is 5-30 nm.
A preparation method of a titanium oxide composite membrane with antibacterial performance comprises the following steps:
1) placing the unsintered glaze at 1300-1500 ℃ for firing for 4-6 hours to obtain a smooth glaze layer;
2) mixing 200 parts by mass of deionized water, 10-20 parts by mass of a polyvinyl alcohol solution and 4-8 parts by mass of glass powder with a melting point range of 400-700 ℃ to prepare a dispersion, brushing the dispersion on the surface of the glaze surface in the step 1), and firing at 1200 ℃ for 2-4 hours to form a transition layer;
3) 200 portions of deionized water, 10 to 20 portions of polyvinyl alcohol solution and 0.5 to 2 portions of TiO are used according to the weight portion2Mixing to prepare dispersion liquid, then coating the dispersion liquid on the surface of the transition layer in the step 2), and performing high temperature treatment at 900-1100 DEG CFiring for 2-4 hours, and cooling the surface to obtain the titanium oxide composite membrane with antibacterial performance.
An application of a titanium oxide composite film with antibacterial performance, wherein the titanium oxide composite film is applied as an antibacterial film in ceramics of kitchens and bathrooms and daily hygiene.
The titanium oxide composite membrane with antibacterial performance comprises a suspension liquid of glass powder, the suspension liquid is dispersed on the surface of glaze through methods of brushing, spraying, dipping, lifting and the like and is fired, a glass powder transition layer is formed on the glaze layer, then a layer of titanium dioxide suspension liquid is added on the glass powder transition layer, and the titanium oxide composite membrane with antibacterial performance is obtained after firing.
The invention has the advantages that: the titanium oxide composite membrane with the antibacterial performance has the titanium oxide composite membrane with good associativity, overcomes the defect of poor association between the traditional titanium oxide antibacterial membrane and a glaze layer, can be applied to ceramic products and the like, and is applied to ceramics prepared from ceramics with smooth and beautiful surfaces and silvery white surfaces. Antibacterial tests show that the surface of the ceramic tile has strong antibacterial activity to escherichia coli and staphylococcus aureus. Can be used for making floor and wall tiles of kitchens and bathrooms, daily sanitary ceramic products, handicraft articles and the like.
Drawings
FIG. 1 is an SEM photograph of the surface of an uncoated glazed ceramic tile with a temperature set at about 1500 ℃ and a heating time of 5 hours in example 1 of the present invention, with a magnification of 400 times;
FIG. 2 is an SEM photograph of the surface of a tile coated with glass powder at an initial temperature setting of 1200 ℃ at a magnification of 400 times, wherein 200ml of deionized water, 15g of a polyvinyl alcohol solution and 6g of glass powder provided in example 1 of the present invention are mixed to prepare a dispersion, the dispersion is brushed on the surface of the tile;
FIG. 3 is an SEM photograph of the surface of a glass powder coated tile of example 1 at 4000 Xmagnification.
Detailed Description
The method comprises the steps of firstly preparing a turbid liquid of glass powder, dispersing the turbid liquid on the surface of glaze by methods such as brushing, spraying, dipping, lifting and the like, firing, then adding a layer of turbid liquid of titanium dioxide on a glass powder transition layer, and firing to obtain the titanium oxide composite membrane with antibacterial performance.
Example 1:
preparing a glaze layer: placing the unsintered glazed ceramic in a high-temperature resistance furnace, setting the initial temperature to be about 1500 ℃ by using a temperature controller, and firing at a constant temperature for 5 hours to obtain the ceramic with the smooth glazed layer, wherein an SEM photo under a mirror of the glazed layer is shown in figure 1. Analyzing the surface effect: on SEM pictures, the surface of the ceramic tile presents a high smoothness degree, particularly the part on the left side of the middle is almost completely smooth and flat; the plurality of concave points on the right side are caused by impurities contained in the glaze surface before firing; the defective portion in the upper right corner is located the incision department that the ceramic tile was cut, because the influence of uneven temperature and glaze surface tension when glaze and ceramic tile substrate combine infirm and heating for the glaze has the phenomenon of part perk. It can be seen that under the determined experimental conditions, the unsintered glazed tile (raw tile) is fired to a smooth tile (finished tile) having a high degree of smoothness by heating firing in a high temperature box-type resistance furnace.
Preparing a glass layer: the fired glaze ceramics are respectively processed as follows: firstly, 200ml of deionized water, 15g of polyvinyl alcohol solution and 6g of glass powder are used for preparing suspension of the glass powder, the suspension is dispersed on a ceramic glaze surface by methods of brushing, spraying, dipping, lifting and the like, the firing is carried out at 1200 ℃, and the firing is carried out in a high-temperature box-shaped resistance furnace for 3 hours. FIG. 2 is an SEM photograph of the surface of a fired glass powder coated tile at 400 times magnification, and its effective surface index (used to characterize the smoothness of the tile surface and nano TiO coating after firing)2The powder is divided into 10 grades with 1-10, 10 being the most uniform and smooth surface distribution, and 1 vice versa) being 8. Analyzing the surface effect: most of the glass powder particles fused into the glaze layer present dark spots and a relatively uniform distribution over the whole tile surface (especially on the left side). In addition, the surface of the ceramic tile has white bright spots, which are only a small part of glass powder particles blended into the glazed layer of the ceramic tile. FIG. 3 is an SEM photograph of the surface of a glass powder coated ceramic tile at a magnification of 4000 times, and the upper dark block in the middle of the pictureThe glass powder particles embedded into the glaze layer are enlarged, and it can be seen that the glass powder with small particle size is fused into the glaze layer to a greater extent in the heating and firing process, and the particles with large particle size are effectively fused with the glaze layer. It can be seen from the above two pictures that, under the determined experimental conditions, the ceramic tile with the mixed liquid coating fired by heating the high-temperature box-type resistance furnace forms a relatively uniform glass powder layer on the surface of the glazed ceramic tile, and can be used as a transition layer for brushing a titanium dioxide layer below the glazed ceramic tile.
Preparing an antibacterial layer: 200ml of deionized water, 15g of polyvinyl alcohol solution and nano TiO21 g of suspension of nano titanium dioxide powder is prepared, dispersed on the surface of the ceramic with the glass powder transition layer by a brush coating method and fired for 3 hours at 1000 ℃. And cooling to obtain the composite film with the surface effect index of 8.
The nano titanium dioxide powder is purchased from Naoshan Mingri nano material Co., Ltd, a crystal type substance anatase phase and a product code HR3, and is white loose powder with the purity of 99.5% (silicon-containing), the average particle size of 15nm, the specific surface area of 160 +/-20 m2/g and the apparent density of 0.04-0.06g/cm 3.
Glass powder: the used glass powder is 7070 type purchased from Nanjing Jianxin glass Co., Ltd, the corresponding parameters are as follows,
relevant performance parameters of the glass powder
And (3) testing antibacterial performance: test points are respectively set on the obtained titanium oxide composite membrane, escherichia coli and staphylococcus aureus are respectively dripped around the two test points of the ceramic tile and are sent into a constant temperature box at 37 ℃ for overnight (the time is about 24 hours), the ceramic tile is taken out and then the growth condition of bacteria on the surface of the ceramic tile is observed, and the evidence that bacteria on the surface do not grow continuously is found, so that the antibacterial ceramic tile fired by the method has good antibacterial performance.
Example 2: the quality of the polyvinyl alcohol solution in the preparation of the glass layer in the example 1 is adjusted to 20 g, other treatments are the same as the example 1, the surface effect index is 6, and the antibacterial performance test shows that the polyvinyl alcohol solution has good antibacterial performance.
Example 3: the quality of the glass powder in the preparation of the glass layer in the example 1 is adjusted to 4 g, other treatments are the same as the example 1, the surface effect index is 5, and the antibacterial performance test shows that the antibacterial performance is good.
Example 4: the mass of the polyvinyl alcohol solution in the preparation of the antibacterial layer in example 1 was adjusted to 10 g, and the other treatments were the same as in example 1, the surface effect index was 6, and the antibacterial performance test showed good antibacterial performance.
Example 5: the mass of the polyvinyl alcohol solution in the preparation of the antibacterial layer in example 1 was adjusted to 20 g, and the other treatments were the same as in example 1, the surface effect index was 7, and the antibacterial performance test showed good antibacterial performance.
Example 6: the mass of titanium dioxide in the preparation of the antibacterial layer in the example 1 is adjusted to 0.5 g, the surface effect index is 5 in the same way as that in the example 1, and the antibacterial performance test shows that the titanium dioxide has good antibacterial performance.
Claims (4)
1. A titanium oxide composite film with antibacterial properties, characterized in that: the composite film sequentially comprises a bottom layer, a transition layer and an antibacterial layer; taking a glaze surface as a bottom layer, glass as a transition layer and anatase titanium dioxide as an antibacterial layer;
the thickness of the antibacterial layer is between 15nm and 200nm, the antibacterial layer is formed by firing a dispersion prepared by mixing deionized water, a polyvinyl alcohol solution and nano titanium dioxide, and the average particle size is between 5nm and 30 nm;
the preparation method of the titanium oxide composite membrane with antibacterial performance comprises the following steps:
1) placing the unsintered glaze at 1300-1500 ℃ for firing for 4-6 hours to obtain a smooth glaze layer;
2) mixing 200 parts by mass of deionized water, 10-20 parts by mass of a polyvinyl alcohol solution and 4-8 parts by mass of glass powder with a melting point range of 400-700 ℃ to prepare a dispersion, brushing the dispersion on the surface of the glaze surface in the step 1), and firing at 1200 ℃ for 2-4 hours to form a transition layer;
3) 200 parts of deionized water by weight10-20 parts of polyvinyl alcohol solution and 0.5-2 parts of TiO2Mixing to prepare dispersion liquid, then coating the dispersion liquid on the surface of the transition layer in the step 2), firing at the temperature of 900-1100 ℃ for 2-4 hours, and cooling the surface to obtain the titanium oxide composite membrane with antibacterial performance.
2. The titanium oxide composite membrane having antibacterial properties according to claim 1, characterized in that: the thickness of the bottom layer is 0.1mm-0.5 mm; the glaze layer is an oxide solid solution obtained by high-temperature firing at 700-3000 ℃.
3. A method for preparing the titanium oxide composite membrane having antibacterial properties according to claim 1, characterized in that:
1) placing the unsintered glaze at 1300-1500 ℃ for firing for 4-6 hours to obtain a smooth glaze layer;
2) mixing 200 parts by mass of deionized water, 10-20 parts by mass of a polyvinyl alcohol solution and 4-8 parts by mass of glass powder with a melting point range of 400-700 ℃ to prepare a dispersion, brushing the dispersion on the surface of the glaze surface in the step 1), and firing at 1200 ℃ for 2-4 hours to form a transition layer;
3) 200 portions of deionized water, 10 to 20 portions of polyvinyl alcohol solution and 0.5 to 2 portions of TiO are used according to the weight portion2Mixing to prepare dispersion liquid, then coating the dispersion liquid on the surface of the transition layer in the step 2), firing at the temperature of 900-1100 ℃ for 2-4 hours, and cooling the surface to obtain the titanium oxide composite membrane with antibacterial performance.
4. Use of the titanium oxide composite film having antibacterial properties according to claim 1, characterized in that: the titanium oxide composite film is applied as an antibacterial film in ceramics of kitchens, bathrooms and daily hygiene.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275436A (en) * | 1999-05-27 | 2000-12-06 | Lg电子株式会社 | Optical catalyst filter and manufacturing method thereof, the air purifier formed from same |
| WO2005115614A1 (en) * | 2004-05-26 | 2005-12-08 | Ecology Souzo Kenkyusho Co., Ltd. | Decomposer/purifier using photocatalyst, method for producing same, and decomposing/purifying method using same |
| CN104387119A (en) * | 2014-10-22 | 2015-03-04 | 华文蔚 | Titanium dioxide photocatalytic self-cleaning ceramic and preparation method thereof |
| CN105837253A (en) * | 2015-02-04 | 2016-08-10 | 杜拉维特股份公司 | Ceramic article and method for production the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275436A (en) * | 1999-05-27 | 2000-12-06 | Lg电子株式会社 | Optical catalyst filter and manufacturing method thereof, the air purifier formed from same |
| WO2005115614A1 (en) * | 2004-05-26 | 2005-12-08 | Ecology Souzo Kenkyusho Co., Ltd. | Decomposer/purifier using photocatalyst, method for producing same, and decomposing/purifying method using same |
| CN104387119A (en) * | 2014-10-22 | 2015-03-04 | 华文蔚 | Titanium dioxide photocatalytic self-cleaning ceramic and preparation method thereof |
| CN105837253A (en) * | 2015-02-04 | 2016-08-10 | 杜拉维特股份公司 | Ceramic article and method for production the same |
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