CN112812671A - Method for preparing flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint - Google Patents
Method for preparing flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint Download PDFInfo
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- CN112812671A CN112812671A CN202011630351.2A CN202011630351A CN112812671A CN 112812671 A CN112812671 A CN 112812671A CN 202011630351 A CN202011630351 A CN 202011630351A CN 112812671 A CN112812671 A CN 112812671A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention relates to a method for preparing flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint, which comprises the steps of preparing a precursor solution of titanium dioxide-based composite photocatalytic particles, and sequentially and mechanically stirring and uniformly mixing the precursor solution and the components of the water-based interior wall paint to obtain a mixed coating; and (3) carrying out microwave reaction synthesis on the mixed coating to obtain the flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint. According to the invention, the titanium dioxide-based composite photocatalytic nanoparticles are dispersed in the water-based interior wall paint in the form of precursor mixed liquid, so that the photocatalytic particles are stable, better in dispersity and free from agglomeration, the attached photocatalytic nanoparticles are uniformly dispersed and coated on the flower-shaped titanium dioxide photocatalytic particles, and the specific surface of the synthesized flower-shaped titanium dioxide-based composite photocatalytic particles can provide more active sites, so that the antibacterial effect of the prepared photocatalytic water-based interior wall paint can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic environment-friendly coatings, and particularly relates to a method for preparing a flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint.
Background
As interior wall decoration materials widely used in aqueous interior wall paints are in contact with human bodies for a long time in living and working, the contents of VOC, APEO and PFOS harmful substances and the contents of free formaldehyde, lead, chromium and other heavy metal ions in the aqueous interior wall paints have attracted much attention to the safety of long-term use thereof. Meanwhile, as the requirement of people on the indoor air quality is higher and higher, especially the continuous influence of air-borne diseases of various closed spaces, the people are forced to put forward higher requirements on the indoor antibacterial decorative material. The existing photocatalytic interior wall paint is basically prepared by simply mechanically stirring ready-made photocatalytic particles, resin emulsion and other additives, and the uniform dispersibility and agglomeration of the photocatalytic particles cannot be guaranteed. In addition, the addition of the single structure or single kind of photocatalytic particles can also cause the poor photocatalytic antibacterial effect of the water-based interior wall paint.
Disclosure of Invention
In conclusion, the invention aims to provide a method for preparing a flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint, so as to solve the problem that the prepared photocatalytic water-based interior wall paint is poor in antibacterial effect due to the fact that photocatalytic particles with a single structure or a single kind are added in the water-based interior wall paint and are easy to agglomerate and uneven in dispersity.
In order to achieve the purpose, the invention provides the following technical scheme:
the method for preparing the flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint comprises the following steps:
step 1, preparing a titanium dioxide-based composite photocatalytic particle precursor solution, specifically comprising
Step 1.1, weighing a titanium dioxide titanium source, dissolving the titanium dioxide titanium source in ultrapure water, adding an ammonia water solution to control a titanium ammonia complex to separate out a precipitate, then performing suction filtration to separate the precipitate, fully cleaning the precipitate by using the ultrapure water and absolute ethyl alcohol, and drying in a constant-temperature drying oven to obtain the titanium ammonia complex precipitate;
step 1.2, adding a solution with 6mg/mL of attached photocatalytic nanoparticles into the titanium-ammonia complex precipitate prepared in the step 1.1, preparing the solution into a precursor solution with the concentration of 2.0-3.0mol/L by ammonia water and ultrapure water, and carrying out ultrasonic oscillation for 30min to fully disperse the precursor solution so as to obtain a titanium dioxide-based composite photocatalytic particle precursor solution;
step 2, sequentially mechanically stirring and uniformly mixing the composite precursor solution obtained in the step 1 and the components of the water-based interior wall paint in a reaction kettle to obtain a mixed coating;
and 3, carrying out microwave reaction synthesis on the mixed coating to obtain the flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint.
Further, the titanium dioxide-based composite photocatalytic particles include titanium dioxide photocatalytic particles and attached photocatalytic nanoparticles.
Further, the titanium dioxide titanium source in step 1.2 is one or more of titanium tetrachloride, tetrabutyl titanate, titanyl sulfate, titanium isopropoxide, titanium sulfate and titanium difluorooxide.
Further, the attached photocatalytic nanoparticles in step 1.2 are one or more of silver nanowires, graphene oxide, reduced graphene oxide, or graphene quantum dots.
Further, in the step 2, the titanium dioxide-based composite photocatalytic particles and the water-based interior wall paint comprise, by mass, 13-15 wt% of the titanium dioxide-based composite photocatalytic particles, 47-65 wt% of single-component water-based resin, 14-20 wt% of pigment and filler, 2-3 wt% of a dispersant, 2-3 wt% of a defoaming agent, 1-2 wt% of a thickening agent and 17-20 wt% of water.
Further, the method for mixing the composite precursor solution and the components of the water-based interior wall paint in the step 2 is that the single-component water-based resin is added into the composite precursor solution and fully stirred for 30min at the stirring speed of 850r/min, and then the mixture of the pigment, the dispersant, the defoamer and the thickener is added and fully stirred for 1h at the stirring speed of 1600 + 1900 r/min.
Further, in the step 3, the heating temperature of the microwave reaction is 75-105 ℃, and the reaction time is 2-4 min.
Further, the single-component water-based resin is one or more of water-based alkyd resin, water-based acrylic resin and water-based polyurethane resin.
Furthermore, the pigment and filler is one or more of calcium carbonate, calcined kaolin and titanium dioxide.
The flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint synthesized by microwave is observed under a scanning electron microscope, and the diameter of the obtained flower-shaped titanium dioxide-based composite photocatalytic particles is concentrated between 2 and 3 mu m.
The invention has the beneficial effects that:
1. according to the invention, the titanium dioxide-based composite photocatalytic nanoparticles are dispersed in the water-based interior wall paint in the form of precursor mixed liquid, so that the stability of the photocatalytic particles is better, the titanium dioxide-based composite photocatalytic particles have better dispersibility in the water-based interior wall paint, and the particles are not easy to agglomerate, so that the prepared water-based interior wall paint has more excellent photocatalytic antibacterial performance;
2. the flower-shaped titanium-based composite photocatalytic particles are synthesized in the water-based interior wall paint through a microwave rapid reaction, compared with the traditional photocatalytic particles, the attached photocatalytic nanoparticles are uniformly dispersed and coated on the flower-shaped titanium dioxide photocatalytic particles, the specific surface area of the synthesized flower-shaped titanium dioxide-based composite photocatalytic particles is larger, more active site numbers are provided, the antibacterial and bactericidal effects of the prepared composite water-based interior wall paint can be effectively improved, and finally, the photocatalytic antibacterial inactivation of escherichia coli and staphylococcus aureus in the composite water-based interior wall paint under the condition of visible light can be realized in a short time;
3. according to the invention, through different adding sequences and adding processes of the titanium dioxide-based composite photocatalytic particle precursor mixed liquid and various water-based interior wall paint raw materials, on one hand, the resin in the water-based interior wall paint has the advantages of good mechanical property, machining property, good film forming property, strong adhesive force, high drying speed and the like, and the defects of insufficient mechanical property of direct mixing of the photocatalytic particles and the various water-based interior wall paint raw materials are solved. On the other hand, the flower-shaped titanium dioxide-based composite photocatalytic particles are more tightly combined with the water-based interior wall paint, the photocatalytic particles are not easy to fall off and agglomerate in the construction and long-term use processes, and the problems that the photocatalytic particles with single structures or single components are not tightly combined with the water-based interior wall paint, and the photocatalytic particles are easy to fall off or agglomerate are solved;
4. the titanium dioxide-based composite photocatalytic particles can enable the water-based interior wall paint to generate hydroxyl radicals with strong oxidizing property under the irradiation of visible light; meanwhile, the flower-shaped titanium dioxide-based composite photocatalytic particles can also provide more active sites, and the antibacterial effect of the prepared photocatalytic water-based interior wall paint can be effectively improved.
5. Compared with titanium dioxide composite photocatalytic particles with other shapes, such as particles, rods and the like, the flower-shaped titanium dioxide composite photocatalytic particles have larger specific surface area, more photocatalytic nanoparticles can be supported and attached on the surfaces, and the supported space direction and active sites are more abundant, so that the degradability and the bactericidal property of the flower-shaped titanium dioxide-based composite photocatalytic particle antibacterial water-based interior wall paint under visible light are higher under the same photocatalytic particle loading.
Drawings
FIG. 1 is a 7000 times magnified microscopic structure diagram of the flower-like titanium dioxide-based composite photocatalytic antibacterial aqueous interior wall paint prepared in example 3 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will become apparent to those skilled in the art after reading the present invention, as defined in the appended claims.
Example 1
The method for preparing the flower-shaped titanium dioxide-based composite photocatalytic particle antibacterial water-based interior wall paint comprises the following steps:
step 1, preparing a titanium dioxide-based composite photocatalytic particle precursor solution: weighing titanium dioxide titanium source titanium tetrachloride, dissolving the titanium dioxide titanium source titanium tetrachloride in ultrapure water, adding an ammonia water solution to control the titanium ammonia complex to separate out a precipitate, then performing suction filtration to separate the precipitate, fully cleaning the precipitate by using the ultrapure water and absolute ethyl alcohol, and drying in a constant-temperature drying oven to obtain the titanium ammonia complex precipitate. And then adding a solution of 6mg/mL attached photocatalytic nanoparticle graphene and reduced graphene oxide into the prepared titanium-ammonia complex precipitate, configuring the solution into a precursor solution of 2mol/L by ammonia water and ultrapure water, and performing ultrasonic oscillation for 30min to obtain the uniformly dispersed titanium dioxide-based composite photocatalytic particle precursor solution. And 2, selecting 30 wt% of the composite precursor solution prepared in the step 1 and 51 wt% of waterborne polyurethane resin, fully stirring for 30min in a reaction kettle at a stirring speed of 750r/min, then adding a mixture of 14 wt% of pigment and filler, 2 wt% of dispersing agent, 2 wt% of defoaming agent and 1 wt% of thickening agent, and fully stirring for 1h in the reaction kettle at a stirring speed of 1700r/min, wherein the pigment and filler comprises 33 wt% of calcium carbonate, 11 wt% of calcined kaolin and 56 wt% of titanium dioxide. And 3, putting the mixed coating prepared in the step 2 into a microwave rapid reaction synthesizer to react for 2min at 75 ℃. The photocatalytic degradation performance of the finally prepared flower-shaped titanium dioxide-based composite photocatalytic particle antibacterial water-based interior wall paint reaches 94% of 10mg/L rhodamine B solution degraded within 45min under the visible light condition, 100% of escherichia coli and staphylococcus aureus are killed within 55min under the visible light condition, the VOC content is 0, the alkali resistance is not abnormal (24h), and the drying time is 30min (surface drying).
Example 2
The method for preparing the flower-shaped titanium dioxide-based composite photocatalytic particle antibacterial water-based interior wall paint comprises the following steps:
step 1, preparing a titanium dioxide-based composite photocatalytic particle precursor solution: weighing titanium dioxide titanium source titanium tetrachloride, dissolving the titanium dioxide titanium source titanium tetrachloride in ultrapure water, adding an ammonia water solution to control the titanium ammonia complex to separate out a precipitate, then performing suction filtration to separate the precipitate, fully cleaning the precipitate by using the ultrapure water and absolute ethyl alcohol, and drying in a constant-temperature drying oven to obtain the titanium ammonia complex precipitate. And then adding a solution of 6mg/mL attached photocatalytic nanoparticle graphene and reduced graphene oxide into the prepared titanium-ammonia complex precipitate, configuring the solution into a precursor solution of 2.5mol/L by ammonia water and ultrapure water, and performing ultrasonic oscillation for 30min to obtain the uniformly dispersed titanium dioxide-based composite photocatalytic particle precursor solution. And 2, selecting 31 wt% of the composite precursor solution prepared in the step 1 and 50 wt% of waterborne polyurethane resin, fully stirring for 30min at a stirring speed of 800r/min in a reaction kettle, then adding a mixture of 14 wt% of pigment and filler, 2 wt% of dispersing agent, 2 wt% of defoaming agent and 1 wt% of thickening agent, and fully stirring for 1h at a stirring speed of 1800r/min in the reaction kettle, wherein the pigment and filler comprises 33 wt% of calcium carbonate, 11 wt% of calcined kaolin and 56 wt% of titanium dioxide. And 3, putting the mixed coating prepared in the step 2 into a microwave rapid reaction synthesizer to react for 3min at 90 ℃. The photocatalytic degradation performance of the finally prepared flower-shaped titanium dioxide-based composite photocatalytic particle antibacterial water-based interior wall paint reaches that 95% of 10mg/L rhodamine B solution is degraded in 35min under the visible light condition, 100% of escherichia coli and staphylococcus aureus are killed in 40min under the visible light condition, the VOC content is 0, the alkali resistance is not abnormal (24h), and the drying time is 30min (surface drying).
Example 3
The method for preparing the flower-shaped titanium dioxide-based composite photocatalytic particle antibacterial water-based interior wall paint comprises the following steps:
step 1, preparing a titanium dioxide-based composite photocatalytic particle precursor solution: weighing titanium dioxide titanium source titanium tetrachloride, dissolving the titanium dioxide titanium source titanium tetrachloride in ultrapure water, adding an ammonia water solution to control the titanium ammonia complex to separate out a precipitate, then performing suction filtration to separate the precipitate, fully cleaning the precipitate by using the ultrapure water and absolute ethyl alcohol, and drying in a constant-temperature drying oven to obtain the titanium ammonia complex precipitate. And then adding a solution of 6mg/mL attached photocatalytic nanoparticle graphene and reduced graphene oxide into the prepared titanium-ammonia complex precipitate, configuring the solution into a precursor solution of 3mol/L by ammonia water and ultrapure water, and performing ultrasonic oscillation for 30min to obtain the uniformly dispersed titanium dioxide-based composite photocatalytic particle precursor solution. And 2, selecting 34 wt% of the composite precursor solution prepared in the step 1 and 47 wt% of waterborne polyurethane resin, fully stirring for 30min in a reaction kettle at a stirring speed of 850r/min, then adding a mixture of 14 wt% of pigment and filler, 2 wt% of dispersing agent, 2 wt% of defoaming agent and 1 wt% of thickening agent, and fully stirring for 1h in the reaction kettle at a stirring speed of 1900r/min, wherein the pigment and filler comprises 33 wt% of calcium carbonate, 11 wt% of calcined kaolin and 56 wt% of titanium dioxide. And 3, putting the mixed coating prepared in the step 2 into a microwave rapid reaction synthesizer to react for 4min at 105 ℃. The photocatalytic degradation performance of the finally prepared flower-shaped titanium dioxide-based composite photocatalytic particle antibacterial water-based interior wall paint reaches 97% of 10mg/L rhodamine B solution degraded within 25min under the visible light condition, 100% of escherichia coli and staphylococcus aureus are killed within 30min under the visible light condition, the VOC content is 0, the alkali resistance is not abnormal (24h), and the drying time is 30min (surface drying).
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (9)
1. The method for preparing the flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint is characterized by comprising the following steps of:
step 1, preparing a titanium dioxide-based composite photocatalytic particle precursor solution, specifically comprising
Step 1.1, weighing a titanium dioxide titanium source, dissolving the titanium dioxide titanium source in ultrapure water, adding an ammonia water solution to control a titanium ammonia complex to separate out a precipitate, then performing suction filtration to separate the precipitate, fully cleaning the precipitate by using the ultrapure water and absolute ethyl alcohol, and drying in a constant-temperature drying oven to obtain the titanium ammonia complex precipitate;
step 1.2, adding a solution with 6mg/mL of attached photocatalytic nanoparticles into the titanium-ammonia complex precipitate prepared in the step 1.1, preparing the solution into a precursor solution with the concentration of 2.0-3.0mol/L by ammonia water and ultrapure water, and carrying out ultrasonic oscillation for 30min to fully disperse the precursor solution so as to obtain a titanium dioxide-based composite photocatalytic particle precursor solution;
step 2, sequentially mechanically stirring and uniformly mixing the composite precursor solution obtained in the step 1 and the components of the water-based interior wall paint in a reaction kettle to obtain a mixed coating;
and 3, carrying out microwave reaction synthesis on the mixed coating to obtain the flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint.
2. The method for preparing the flower-like titanium dioxide-based composite photocatalytic antibacterial aqueous interior wall paint according to claim 1, wherein the titanium dioxide-based composite photocatalytic particles comprise titanium dioxide photocatalytic particles and attached photocatalytic nanoparticles.
3. The method for preparing the flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint according to claim 1, wherein the titanium dioxide titanium source in the step 1.2 is one or more of titanium tetrachloride, tetrabutyl titanate, titanyl sulfate, titanium isopropoxide, titanium sulfate and titanyl difluoride.
4. The method for preparing the flower-like titanium dioxide-based composite photocatalytic antibacterial aqueous interior wall paint according to claim 1, wherein the attached photocatalytic nanoparticles in the step 1.2 are one or more of silver nanowires, graphene oxide, reduced graphene oxide or graphene quantum dots.
5. The method for preparing the flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint as claimed in claim 1, wherein the titanium dioxide-based composite photocatalytic particle and the water-based interior wall paint in step 2 comprise, by mass, 13-15% of the titanium dioxide-based composite photocatalytic particle, 47-65% of the single-component water-based resin, 14-20% of the pigment and filler, 2-3% of the dispersant, 2-3% of the defoaming agent, 1-2% of the thickener and 17-20% of water.
6. The method for preparing the flower-like titanium dioxide-based composite photocatalytic antibacterial aqueous interior wall paint as claimed in claim 1, wherein the step 2 of mixing the composite precursor solution and the aqueous interior wall paint comprises the steps of adding single-component aqueous resin into the composite precursor solution, fully stirring for 30min at the stirring speed of 550-1900 r/min, and then adding a mixture of pigment, filler, dispersant, defoamer and thickener, fully stirring for 1h at the stirring speed of 1600-1900 r/min.
7. The method for preparing the flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint as claimed in claim 1, wherein the microwave reaction heating temperature in step 3 is 75-105 ℃, and the reaction time is 2-4 min.
8. The method for preparing the flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint as claimed in claim 5, wherein the single-component water-based resin is one or more of water-based alkyd resin, water-based acrylic resin and water-based polyurethane resin.
9. The method for preparing the flower-shaped titanium dioxide-based composite photocatalytic antibacterial water-based interior wall paint as claimed in claim 5, wherein the pigment and filler is one or more of calcium carbonate, calcined kaolin and titanium dioxide.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113736330A (en) * | 2021-09-29 | 2021-12-03 | 哈尔滨工程大学 | Flower-like TiO2Photocatalytic self-polishing resin-based composite coating and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736330A (en) * | 2021-09-29 | 2021-12-03 | 哈尔滨工程大学 | Flower-like TiO2Photocatalytic self-polishing resin-based composite coating and preparation method thereof |
| CN113736330B (en) * | 2021-09-29 | 2022-09-27 | 哈尔滨工程大学 | Flower-like TiO 2 Photocatalytic self-polishing resin-based composite coating and preparation method thereof |
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