CN114106610A - Nano photocatalytic marine antifouling anticorrosive paint and preparation method thereof - Google Patents
Nano photocatalytic marine antifouling anticorrosive paint and preparation method thereof Download PDFInfo
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- CN114106610A CN114106610A CN202111539239.2A CN202111539239A CN114106610A CN 114106610 A CN114106610 A CN 114106610A CN 202111539239 A CN202111539239 A CN 202111539239A CN 114106610 A CN114106610 A CN 114106610A
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- titanium dioxide
- anticorrosive paint
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 40
- 239000003973 paint Substances 0.000 title claims abstract description 31
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 13
- 239000013535 sea water Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000003385 bacteriostatic effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000238586 Cirripedia Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
-
- 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
- C09D5/08—Anti-corrosive paints
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a nano photocatalytic marine antifouling anticorrosive paint, which comprises the following steps: mixing titanium dioxide, urea and deionized water in proportion, stirring in a crusher for more than 12 hours at room temperature, and drying at a certain temperature for 24-30 hours; the state of the chemical becomes solid; collecting the solid, heating the solid in a muffle furnace to a calcining temperature, and calcining the solid at the high temperature for 4 to 5 hours; and (3) after calcining in a muffle furnace, changing the color of the titanium dioxide into brown, and ball-milling for 15-25 minutes in a ball mill to obtain the titanium dioxide. The nano photocatalytic marine antifouling anticorrosive paint can effectively perform anticorrosion through photocathode protection. After the electron-hole pairs are formed, electrons can be transferred to the metal substrate, so that the potential of the electrode is reduced, and the anticorrosion effect is achieved; the nanostructured material can act as a filler, stopping Cl‑And Na+Transport of ions to achieve corrosion resistanceThe hydrophobic nature of the surface also contributes to the anti-corrosion function.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a nano photocatalytic marine antifouling anticorrosive coating and a preparation method thereof.
Background
In the marine industry, fouling and corrosion are major problems. Fouling of the hull and propeller can reduce the speed of the marine vessel, resulting in poor fuel efficiency. Corrosion can lead to material failure and shorten the service life of metal parts operating in seawater. In addition, marine infrastructure and facilities, such as seawater cooling systems, face the same problems. Fouling of the hull during marine transport can increase frictional resistance, resulting in low speed and fuel efficiency. There is evidence that fouling results in an additional 30-40% fuel consumption, corresponding to an economic loss of 100 billion dollars per year worldwide.
In the past, toxic tributyltin (TBT) coatings have been used to prevent biofouling growth on ship hulls. While effective, TBT coatings kill other marine organisms and destroy habitats. Therefore, the International Maritime Organization (IMO) and many regional environmental authorities prohibit the use of TBT. Currently, conventional antifouling paints contain mainly copper or zinc as the main biocide to mitigate marine biofouling. Although copper-based and zinc-based coatings are less toxic than TBT, they are still environmentally hazardous. Seawater and sediments around shipyards, aquafarms and marine industrial sites are heavily contaminated with heavy metals. Our recent measurements show that the concentration of heavy metals in the sediment exceeds 60 times the international allowable limit. This degraded ecology can have adverse effects on the food chain and our health. Although various marine antifouling anticorrosive coatings exist on the market, the marine antifouling anticorrosive coatings have the defects of limited effectiveness, environmental pollution, ecological influence and the like.
Currently, conventional antifouling paints contain mainly copper or zinc as the main biocide to mitigate marine biofouling. However, fouling and corrosion problems still exist. In addition, heavy metals are very harmful to the marine environment and ecosystem. Seawater and sediments around shipyards, aquafarms and marine industrial sites are heavily contaminated with heavy metals, causing serious adverse effects on marine ecology and seafood.
Currently, research on marine paints and methods for preparing marine paints, such as CN111100529A, has been conducted, but the cost of the active ingredients used is high, and industrialization is difficult. Chinese invention patent CN110484028A discloses a photocatalytic antibacterial antifouling inorganic anticorrosive coating and a coating method thereof, the coating has good antifouling effect, but the environmental protection performance needs to be improved by adopting fluoride and a semiconductor bacteriostatic agent; therefore, it is necessary to develop a new marine antifouling anticorrosive paint.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a nano photocatalytic marine antifouling anticorrosive paint.
The technical scheme of the invention is as follows:
a preparation method of a nano photocatalytic marine antifouling anticorrosive paint comprises the following steps:
step A: mixing titanium dioxide, urea and deionized water in proportion, stirring in a crusher for more than 12 hours at room temperature, and drying at a certain temperature for 24-30 hours; the state of the chemical becomes solid;
and B: collecting the solid, heating the solid in a muffle furnace to a calcining temperature, and calcining the solid at the high temperature for 4 to 5 hours;
and C: and (3) after calcining in a muffle furnace, changing the color of the titanium dioxide into brown, and ball-milling for 15-25 minutes in a ball mill to obtain the titanium dioxide.
Preferably, in the step a, the ratio of titanium dioxide, urea and deionized water is (0.5-2) g: (0.8-1.5) g: 20 ml.
Further preferably, in the step a, the ratio of the titanium dioxide, the urea and the deionized water is 1 g: 1 g: 20 ml.
Preferably, in the step A, the drying temperature is 50-70 ℃.
Preferably, in the step B, the calcination temperature is 350-.
The invention also claims the nano photocatalytic marine antifouling anticorrosive paint prepared by the method.
The invention has the advantages that:
1. photocatalysis is a promising method for solving the problem of marine pollution. When the photocatalyst is activated by light, strong Reactive Oxygen Species (ROS) are generated. Photocatalytic oxidation and superhydrophobicity are attributes that contribute to the antifouling effect. The nano photocatalytic marine antifouling/anticorrosive paint adopts solar photocatalysis to prevent barnacles, tuba worms, mussels and the like from growing on the ship body.
2. The photocatalyst has no adverse effect on marine ecology. Our ongoing research into nano-photocatalytic antifouling paints using modified visible light-activated photocatalysts has successfully demonstrated that photocatalyst additives can reduce the use of copper in antifouling paints. The results of the study further reveal the potential of photocatalysis in the development of copper-free antifouling paints.
3. In the past, we have succeeded in developing an effective photocatalytic material comprising an anion-doped titanium dioxide for enhancing solar photocatalysis. At present, materials are further modified through anion/metal co-doping so as to enhance the antifouling effect and provide an additional anticorrosion function for steel, iron and aluminum ships.
4. The product is named as nano photocatalytic marine antifouling/anticorrosive paint. It can be effectively preserved by photocathode protection. After the electron-hole pairs are formed, electrons can be transferred to the metal substrate, so that the potential of the electrode is reduced, and the anticorrosion effect is achieved. Another corrosion protection mechanism is that the nanostructured material can act as a filler, stopping Cl-And Na+Transport of ions to achieve corrosion resistance. The hydrophobic nature of the surface also contributes to the corrosion protection function.
Detailed Description
The reagents used in the following examples, unless otherwise specified, were purchased from conventional biochemical reagent stores. The quantitative data in the following examples were set up in triplicate and the results averaged.
Example 1
A preparation method of a nano photocatalytic marine antifouling anticorrosive paint comprises the following steps:
step A: titanium dioxide, urea and deionized water were mixed in a ratio of 1 g: 1 g: 20ml of the mixture is mixed, stirred in a crusher for 16 hours at room temperature, and dried for 24 hours at the temperature of 60 ℃; the state of the chemical becomes solid;
and B: collecting the solid, heating to 350 ℃ at the speed of 5 ℃/min in a muffle furnace, and then calcining for 4.5 hours at the high temperature;
and C: and (3) after calcining in a muffle furnace, changing the color of the titanium dioxide into brown, and performing ball milling in a ball mill for 20 minutes to obtain the titanium dioxide.
Example 2
A preparation method of a nano photocatalytic marine antifouling anticorrosive paint comprises the following steps:
step A: titanium dioxide, urea and deionized water were mixed in a ratio of 2 g: 0.8 g: 20ml, stirring in a crusher for 12.5 hours at room temperature, and drying at 70 ℃ for 28 hours; the state of the chemical becomes solid;
and B: collecting the solid, heating to 520 ℃ in a muffle furnace at the speed of 5 ℃/min, and then calcining for 4 hours at the high temperature;
and C: and (3) after calcining in a muffle furnace, converting the color of the titanium dioxide into brown, and ball-milling for 25 minutes in a ball mill.
Example 3
A preparation method of a nano photocatalytic marine antifouling anticorrosive paint comprises the following steps:
step A: titanium dioxide, urea and deionized water were mixed in an amount of 0.5 g: 1.5 g: mixing at a ratio of 20ml, stirring in a crusher for 15 hours at room temperature, and drying at 50 ℃ for 30 hours; the state of the chemical becomes solid;
and B: collecting the solid, heating to 400 ℃ at a speed of 5 ℃/min in a muffle furnace, and calcining for 5 hours at the high temperature;
and C: and (3) after calcining in a muffle furnace, changing the color of the titanium dioxide into brown, and performing ball milling for 15 minutes in a ball mill to obtain the titanium dioxide.
Example 4
A preparation method of a nano photocatalytic marine antifouling anticorrosive paint comprises the following steps:
step A: titanium dioxide, urea and deionized water were mixed in a ratio of 1.2 g: 1 g: mixing at a ratio of 20ml, stirring in a crusher for 15 hours at room temperature, and drying at 60 ℃ for 28 hours; the state of the chemical becomes solid;
and B: collecting the solid, heating to 520 ℃ in a muffle furnace at the speed of 5 ℃/min, and then calcining for 4 hours at the high temperature;
and C: and (3) after calcining in a muffle furnace, changing the color of the titanium dioxide into brown, and performing ball milling in a ball mill for 20 minutes to obtain the titanium dioxide.
Example 5
A preparation method of a nano photocatalytic marine antifouling anticorrosive paint comprises the following steps:
step A: titanium dioxide, urea and deionized water were mixed in a ratio of 1 g: 1.5 g: 20ml of the mixture is mixed, stirred in a crusher for 15 hours at room temperature, and dried for 24 hours at 70 ℃; the state of the chemical becomes solid;
and B: collecting the solid, heating to 400 ℃ at a speed of 5 ℃/min in a muffle furnace, and calcining for 5 hours at the high temperature;
and C: and (3) after calcining in a muffle furnace, converting the color of the titanium dioxide into brown, and ball-milling for 25 minutes in a ball mill.
The coatings of examples 1-5 of the present invention, example 1 of CN111100529A and example 1 of CN110484028A were selected as comparative examples 1-2, and uncoated samples were tested for their bacteriostatic and antifouling properties. The test method refers to the national standard GB/T5370-2007 shallow sea immersion test method for antifouling paint sample plate and GB/T6822-2014-Hull antifouling and antirust paint system. The substrate used was a low carbon steel plate 3mm thick and 350mm x 250mm in size. The shallow sea soaking period was set at 4 months and 8 months, and the test results were as follows.
Table 1: results of the bacteriostatic antifouling performance test (4 months);
table 2: results of the bacteriostatic antifouling performance test (8 months);
the seawater corrosion resistance of the samples of comparative examples 1-2, which were prepared by using the coatings of examples 1-5 of the present invention, example 1 of CN111100529A, and example 1 of CN110484028A, and uncoated samples were tested. The test method is carried out according to the standard GB/T6458-86 neutral salt spray test (NSS) for metal coatings. The test temperature is 35 +/-2 ℃, and the used corrosion solution is 5% sodium chloride solution. After 3500 hours of etching, the test results are as follows.
Table 3: test results of seawater corrosion resistance (3500 hours);
the test data show that the nano photocatalytic marine antifouling anticorrosive paint has very good antifouling and seawater-resistant anticorrosive performances.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. A preparation method of a nano photocatalytic marine antifouling anticorrosive paint is characterized by comprising the following steps:
step A: mixing titanium dioxide, urea and deionized water in proportion, stirring in a crusher for more than 12 hours at room temperature, and drying at a certain temperature for 24-30 hours; the state of the chemical becomes solid;
and B: collecting the solid, heating the solid in a muffle furnace to a calcining temperature, and calcining the solid at the high temperature for 4 to 5 hours;
and C: and (3) after calcining in a muffle furnace, changing the color of the titanium dioxide into brown, and ball-milling for 15-25 minutes in a ball mill to obtain the titanium dioxide.
2. The method for preparing nano photocatalytic marine antifouling anticorrosive paint according to claim 1, wherein in the step A, the ratio of titanium dioxide, urea and deionized water is (0.5-2) g: (0.8-1.5) g: 20 ml.
3. The method for preparing nano photocatalytic marine antifouling anticorrosive paint according to claim 1, wherein in the step A, the ratio of titanium dioxide, urea and deionized water is 1 g: 1 g: 20 ml.
4. The method for preparing nano photocatalytic marine antifouling anticorrosive paint according to claim 1, wherein in the step A, the drying temperature is 50-70 ℃.
5. The method for preparing the nano photocatalytic marine antifouling anticorrosive paint as claimed in claim 1, wherein in the step B, the calcination temperature is 250 ℃ and 280 ℃, and the temperature rise of a muffle furnace is set to be 5 ℃/min.
6. The nano photocatalytic marine antifouling anticorrosive paint prepared by the method of any one of claims 1 to 5.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111539239.2A CN114106610A (en) | 2021-12-15 | 2021-12-15 | Nano photocatalytic marine antifouling anticorrosive paint and preparation method thereof |
| PCT/CN2021/142517 WO2023108824A1 (en) | 2021-12-15 | 2021-12-29 | Nano photocatalytic marine antifouling and anticorrosive coating and preparation method therefor |
| TW111106104A TW202325400A (en) | 2021-12-15 | 2022-02-18 | A preparation method of a nano-photocatalytic marine anti-fouling and anti-corrosion coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111539239.2A CN114106610A (en) | 2021-12-15 | 2021-12-15 | Nano photocatalytic marine antifouling anticorrosive paint and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN114106610A true CN114106610A (en) | 2022-03-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202111539239.2A Pending CN114106610A (en) | 2021-12-15 | 2021-12-15 | Nano photocatalytic marine antifouling anticorrosive paint and preparation method thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN114106610A (en) |
| TW (1) | TW202325400A (en) |
| WO (1) | WO2023108824A1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1392079B1 (en) * | 2008-12-05 | 2012-02-09 | Italcementi Spa | METHOD FOR THE PREPARATION OF A TITANIUM DIOXIDE WITH PHOTOCATALYTIC ACTIVITY FOR IRRADIATION WITH VISIBLE LIGHT |
| CN102302943A (en) * | 2011-06-01 | 2012-01-04 | 重庆工商大学 | Method for synthesizing nitrogen doped nano-titanium dioxide by utilizing industrial titanium dioxide |
| EP2650335B1 (en) * | 2012-04-13 | 2018-05-30 | Tata Consultancy Services Ltd. | A process for synthesis of doped titania nanoparticles having photocatalytic activity in sunlight |
| CN109179497B (en) * | 2018-09-26 | 2020-11-06 | 青岛滨海学院 | Preparation method of spherical titanium dioxide and application of spherical titanium dioxide in self-cleaning coating |
| CN110420630A (en) * | 2019-09-02 | 2019-11-08 | 上海市农业科学院 | A kind of black titanium dioxide photochemical catalyst and the preparation method and application thereof |
| CN110922792A (en) * | 2019-12-02 | 2020-03-27 | 湖南太子化工涂料有限公司 | Mildew-proof nano coating with antibacterial property |
-
2021
- 2021-12-15 CN CN202111539239.2A patent/CN114106610A/en active Pending
- 2021-12-29 WO PCT/CN2021/142517 patent/WO2023108824A1/en unknown
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2022
- 2022-02-18 TW TW111106104A patent/TW202325400A/en unknown
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| Publication number | Publication date |
|---|---|
| TW202325400A (en) | 2023-07-01 |
| WO2023108824A1 (en) | 2023-06-22 |
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