CN112933999A - Preparation method of self-cleaning membrane material for capping of sewage station - Google Patents

Preparation method of self-cleaning membrane material for capping of sewage station Download PDF

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CN112933999A
CN112933999A CN202110214479.9A CN202110214479A CN112933999A CN 112933999 A CN112933999 A CN 112933999A CN 202110214479 A CN202110214479 A CN 202110214479A CN 112933999 A CN112933999 A CN 112933999A
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zro
ptfe
film
self
cleaning
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CN112933999B (en
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陆朝阳
张纪文
张以飞
徐遵主
李明
蒋海涛
金小贤
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Nanjing University Environmental Planning And Design Institute Group Co Ltd
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Nanjing University Environmental Planning And Design Institute Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores

Abstract

The invention provides a preparation method of a self-cleaning membrane material for capping a sewage station, which comprises the steps of pretreatment of a PTFE fluorocarbon fiber membrane and ZrO2Preparation of precursor sol and PTFE-ZrO2Preparation of film, Bi2O3Preparation of precursor gel and PTFE-ZrO2‑Bi2O3And preparing the self-cleaning film. The invention firstly prepares a layer of ZrO on a Polytetrafluoroethylene (PTFE) fluorocarbon fiber membrane by a dip-coating method2Film on PTFE-ZrO by sol-gel method2Preparing a layer of Bi on the film2O3Photocatalyst film, PTFE-ZrO produced2‑Bi2O3The self-cleaning film can prevent the damage of ultraviolet rays and strong free radicals of photocatalytic products to a film material on one hand, and on the other hand, the self-cleaning film in sunlightThe ultra-hydrophilic ultraviolet light source can be in a super-hydrophilic state under the action of ultraviolet rays, so that the self-cleaning function is realized, the maximum reaction temperature is not more than 300 ℃, the operation is simple, the cost is low, the practicability is high, and the popularization is suitable.

Description

Preparation method of self-cleaning membrane material for capping of sewage station
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a preparation method of a self-cleaning membrane material for capping a sewage station.
Background
The fluorocarbon fiber membrane has the advantages of corrosion resistance, high strength, light weight and the like, and is widely applied to the capping and sealing engineering of sewage treatment plants to prevent waste gas from overflowing and scattering in the sewage treatment process. Common sealing forms are inflatable membrane capping and reverse hanging membrane capping. The commonly used fluorocarbon fiber membranes mainly include Polytetrafluoroethylene (PTFE) membrane, ethylene-tetrafluoroethylene (ETFE) membrane, polyvinylidene fluoride (PVDF) and polyvinyl chloride (PVC) membrane. The fluorocarbon fiber membrane material generally takes high-strength glass fiber or high-strength polyester fiber as a base material, and PTFE, ETFE, PVDF or PVC polymer coatings are coated on the upper and lower parts of the base material.
The fluorocarbon fiber film is aged under the action of ultraviolet rays in sunlight in the long-term use process, and the color of the fluorocarbon fiber film becomes dark yellow; various pollutants in the environmental air of the sewage plant, such as oily smoke, particulate matters and various pollutants, can also adhere to the surface of the fluorocarbon fiber film; in addition, the sewage station has a humid environment and more microbial nutrients, and a great amount of microbes are bred on the surface of the fluorocarbon fiber film. On the whole, the fluorocarbon fiber membrane is in a severe use environment of the sewage station, and the aesthetic degree is gradually deteriorated in the use process, so that the fluorocarbon fiber membrane becomes a problem to be paid much attention.
The common super-hydrophilic self-cleaning material at present generally takes ceramic, glass or metal as a substrate, and then generates a photocatalyst coating on the substrate. The conventional solid phase method, the chemical vapor deposition method and the sol-gel method in the liquid phase method all require high temperature conditions, and the fluorocarbon fiber membrane is generally not high temperature resistant, so that the method is not suitable for preparing the super-hydrophilic self-cleaning material. In addition, if the photocatalyst coating is directly contacted with the PTFE, ETFE, PVDF or PVC polymer coating on the surface of the fluorocarbon fiber membrane, under the action of ultraviolet rays, a photocatalytic reaction can generate free radicals with strong reaction activity, so that the free radicals can attack the polymer coating, and the aging and decomposition of the polymer coating are accelerated under the action of the ultraviolet rays.
Based on the above, the invention provides a preparation method of a self-cleaning membrane material for capping a sewage station, so as to solve the above problems.
Disclosure of Invention
The invention aims to provide a preparation method of a self-cleaning membrane material for capping a sewage station, aiming at overcoming the defects of the prior art, so as to avoid the damage of ultraviolet rays and strong free radicals of photocatalysis products to the membrane material, improve the tolerance temperature of a PTFE fluorocarbon fiber membrane and realize the self-cleaning function.
The invention adopts the following technical scheme:
a preparation method of a self-cleaning membrane material for capping a sewage station comprises the following steps:
s1, pretreatment of the PTFE fluorocarbon fiber membrane:
respectively ultrasonically cleaning a PTFE fluorocarbon fiber membrane by using absolute ethyl alcohol and deionized water, and then drying; placing the dried fluorocarbon fiber film into a low-temperature plasma instrument for treatment for later use;
S2、ZrO2preparing precursor sol:
mixing acetone, water or hydrogen peroxide, adding ZrO2Formation of ZrO2Precursor sol;
S3、PTFE- ZrO2preparation of the film:
taking a proper amount of ZrO prepared from S22Precursor sol, soaking the PTFE fluorocarbon fiber film pretreated by S1 in the ZrO by adopting a dipping and pulling method2Dipping the precursor sol for 10-60min, and drying in an oven at 150 ℃ and 200 ℃ for 1-2 h; repeating the steps of dipping, pulling and drying for 1-5 times to obtain PTFE-ZrO2A film;
S4、Bi2O3preparation of precursor gel:
mixing acetone, ethylene glycol and nitric acid, and stirring at 40-50 deg.C for 20-60 min; adding five waterMixing bismuth nitrate, stirring at 40-50 deg.C until light yellow Bi is formed2O3Precursor gel;
S5、PTFE- ZrO2- Bi2O3preparing a self-cleaning film:
PTFE-ZrO prepared from S3 by adopting dip-coating method2Film dipping into Bi prepared in S42O3Soaking the precursor gel for 10-60min, drying, and drying to obtain PTFE-ZrO2- Bi2O3And (5) self-cleaning the membrane.
Further, in S1, the PTFE fluorocarbon fiber film substrate is glass fiber, the thickness is more than or equal to 0.8mm, and the tensile strength is more than or equal to 4000N.
Further, in S1, after the dried fluorocarbon fiber film is placed in a low-temperature plasma instrument, introducing oxygen into the low-temperature plasma instrument and vacuumizing to 20-80Pa by using a vacuum pump, wherein the discharge power is 100-; the fluorocarbon fiber film is treated in a low-temperature plasma instrument for 10-60 min.
Further, in S1, ultrasonically cleaning the PTFE fluorocarbon fiber membrane for 30-60min by using absolute ethyl alcohol and deionized water respectively, and cleaning for 1-3 times; the drying temperature is 80-100 ℃, and the drying time is 1-2 h.
Further, in S2, the volume ratio of the acetone to the water or the hydrogen peroxide is 1:1-1: 10; added ZrO2The molar mass ratio of the water to the water is 1:10-1: 30.
Further, in S4, the volume ratio of acetone, glycol and nitric acid is 2:2: 1; the molar mass ratio of the added pentahydrate bismuth nitrate to the acetone is 1:20-1: 60.
Further, in S5, the drying process includes: drying in an oven at 80 deg.C for 0.5-2h, and then heating to 300 deg.C for 1-4h to obtain PTFE-ZrO2- Bi2O3And (5) self-cleaning the membrane.
The invention has the beneficial effects that:
(1) the invention prepares a layer of ZrO on a Polytetrafluoroethylene (PTFE) fluorocarbon fiber membrane by a sol-gel method2The film can avoid the damage of ultraviolet rays and strong free radicals of photocatalysis products to a film material, and simultaneously improve the temperature resistance of the PTFE fluorocarbon fiber filmDegree;
(2) the invention adopts a sol-gel method to prepare PTFE-ZrO2Preparing a layer of Bi on the film2O3Photocatalyst film due to production of PTFE-ZrO2The drying temperature is lower than 200 ℃ when the film is formed, and ZrO in the film layer is removed2In addition, a certain amount of Zr (OH) is present4By using Bi2O3The photocatalytic effect of (3) may be Zr (OH)4Further conversion to ZrO2Improvement of ZrO2Obtaining yield;
(3) PTFE-ZrO prepared by the invention2-Bi2O3The composite photocatalyst film can present a super-hydrophilic state under the action of ultraviolet rays in sunlight, so that the self-cleaning function is realized;
(4) the method of the invention has the highest reaction temperature not exceeding 300 ℃, and solves the problems that the conventional process is complex in preparation, high in cost and incapable of effectively generating the zirconia and bismuth oxide photocatalytic film on the fluorocarbon fiber film substrate.
Description of the drawings:
FIG. 1 shows the contact angle of PTFE fluorocarbon fiber membrane with water according to the embodiment of the present invention;
FIG. 2 shows PTFE-ZrO according to an example of the present invention2The contact angle of the film with water;
FIG. 3 shows PTFE-ZrO according to an example of the present invention2- Bi2O3Contact angle of the film with water.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
A preparation method of a self-cleaning membrane material for capping a sewage station comprises the following steps:
s1, pretreatment of the PTFE fluorocarbon fiber membrane:
ultrasonically cleaning a commercial PTFE fluorocarbon fiber membrane (substrate glass fiber, thickness of 0.8mm and tensile strength of 4000N) with absolute ethyl alcohol and deionized water for 30-60min respectively, cleaning for 1-3 times, and drying at 80-100 ℃ for 1-2 h; placing the dried fluorocarbon fiber membrane into a low-temperature plasma instrument for treatment for 10-60min, introducing oxygen before treatment, and vacuumizing the low-temperature plasma instrument to 20-80Pa by using a vacuum pump, wherein the discharge power is 100-; finishing the pretreatment;
S2、ZrO2preparing precursor sol:
mixing acetone, water or hydrogen peroxide, adding ZrO2Formation of ZrO2Precursor sol; the volume ratio of the acetone to the water or the hydrogen peroxide is 1:1-1: 10; added ZrO2The molar mass ratio of the water to the water is 1:10-1: 30.
S3、PTFE- ZrO2Preparation of the film:
taking a proper amount of ZrO prepared from S22Precursor sol, soaking the PTFE fluorocarbon fiber film pretreated by S1 in the ZrO by adopting a dipping and pulling method2Dipping the precursor sol for 10-60min, and drying in an oven at 150 ℃ and 200 ℃ for 1-2 h; repeating the steps of dipping, pulling and drying for 1-5 times to obtain PTFE-ZrO2A film;
S4、Bi2O3preparation of precursor gel:
mixing acetone, ethylene glycol and nitric acid according to the volume ratio of 2:2:1, and stirring at 40-50 ℃ for 20-60 min; adding a proper amount of bismuth nitrate pentahydrate, wherein the molar mass ratio of the added bismuth nitrate pentahydrate to the acetone is 1:20-1:60, and continuously stirring the solution at the temperature of 40-50 ℃ until light yellow Bi is formed2O3Precursor gel;
S5、PTFE- ZrO2- Bi2O3preparing a self-cleaning film:
PTFE-ZrO prepared from S3 by adopting dip-coating method2Film dipping into Bi prepared in S42O3Soaking in the precursor gel for 10-60min, oven drying in an oven at 80 deg.C for 0.5-2h, and oven drying at 300 deg.C for 1-4h to obtain PTFE-ZrO2- Bi2O3And (5) self-cleaning the membrane.
The invention forms ZrO by surface treatment of fluorocarbon fiber film2The film can avoid the damage of ultraviolet rays and strong free radicals of photocatalysis products to a film material, and simultaneously improves the tolerance temperature of the PTFE fluorocarbon fiber film. The sintering temperature of zirconium oxide prepared by conventionally adopting tetrabutyl zirconate needs to reach more than 500 ℃, the fluorocarbon fiber film cannot tolerate the high temperature, the preparation temperature of the process does not exceed 200 ℃, and the preparation process is simple; then at ZrO2Formation of Bi on thin films2O3A photocatalytic film. Bi on the surface of the fluorocarbon fiber film material under the action of ultraviolet rays in sunlight2O3The photocatalysis film can present super hydrophilic state, is difficult for adsorbing the pollutant on the one hand, even adnexed pollutant on the other hand also can follow fluorocarbon fiber surface layer desorption under the effect of dead weight, water film and outside wind power to realize from clean function. Furthermore, since PTFE-ZrO is produced2The drying temperature is lower than 200 ℃ when the film is formed, and ZrO in the film layer is removed2In addition, a certain amount of Zr (OH) is present4By using Bi2O3The photocatalytic effect of (3) may be Zr (OH)4Further conversion to ZrO2Improvement of ZrO2And (4) obtaining the yield.
The fluorocarbon fiber film substrate selected by the invention is high-strength glass fiber, the polymer coating is a PTFE coating, and the fluorocarbon fiber film has high strength, good durability, fire resistance and flame retardance, and can be used for a long time at 280 ℃. Formation of dense ZrO on fluorocarbon fiber films2The thin film further increases the endurance temperature of the fluorocarbon fiber film material to 320 ℃, and simultaneously improves the aging resistance of the fluorocarbon fiber film material. Continuation of ZrO on fluorocarbon fiber membrane by sol-gel method2Formation of Bi on the thin film layer2O3The film is photo-catalyzed, thereby realizing the self-cleaning function of the fluorocarbon fiber film.
Example 1
The embodiment of the invention provides a self-cleaning membrane material for capping a sewage station and a preparation method thereof, and the self-cleaning membrane material specifically comprises the following steps:
s1, pretreatment of the PTFE fluorocarbon fiber membrane:
cutting the PTFE fluorocarbon fiber membrane into strips of 5 multiplied by 5cm, immersing the strips in absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic cleaning for 3 times, each time for 30min, and then drying for 2h at 80 ℃ for later use; placing the dried PTFE fluorocarbon fiber membrane into a low-temperature plasma instrument for treatment for 60min, introducing oxygen before treatment, vacuumizing the low-temperature plasma instrument to 40Pa by using a vacuum pump, and finishing the pretreatment, wherein the discharge power is 1000 w;
S2、ZrO2preparing precursor sol:
500ml of water is added into 500ml of acetone to be mixed evenly, and then 0.1mol of ZrO is added into the mixed solution2Stirring for 60min to form ZrO2And (5) precursor sol.
S3、PTFE- ZrO2Preparation of the film:
taking a proper amount of ZrO prepared from S22Precursor sol, soaking the PTFE fluorocarbon fiber film pretreated by S1 in the ZrO by adopting a dipping and pulling method2Soaking the precursor sol for 30min, and drying in an oven at 200 ℃ for 1 h; repeating the steps of dipping, pulling and drying for 3 times to obtain the PTFE-ZrO2A film;
S4、Bi2O3preparation of precursor gel:
mixing 200ml of acetone, 200ml of ethylene glycol and 100ml of nitric acid, and stirring at 50 ℃ for 30 min; 0.1mol of pentahydrated bismuth nitrate is added, and the solution is stirred at 50 ℃ until pale yellow Bi is formed2O3Precursor gel;
S5、PTFE- ZrO2- Bi2O3preparing a self-cleaning film:
PTFE-ZrO prepared from S3 by adopting dip-coating method2Film dipping into Bi prepared in S42O3Soaking the precursor gel for 30min, drying in an oven at 80 deg.C for 1h, and heating to 300 deg.C for 4h to obtain PTFE-ZrO2- Bi2O3And (5) self-cleaning the membrane.
The interaction between water molecules and the surface of different solid materials is different. At the intersection point of three phases of water (liquid phase), material (solid phase) and air (gas phase), an included angle theta formed by a tangent line along the surface of the water drop and a contact surface of the water and the material is called a contact angle, and the contact angle is hydrophilic when being less than 90 degrees; when the contact angle is 0 degrees, the material is completely wetted and is in a super-hydrophilic state; contact angle >90 ° is hydrophobic; when the contact angle is 180 degrees, the film is completely non-wetting and shows a super-hydrophobic state. The water can form gathered water drops on the super-hydrophobic material (such as lotus leaves) spontaneously, and dust particles attached to the surface can be taken away spontaneously when the water drops roll; water can spread into the very thin water film of the very big thickness of area voluntarily on super hydrophilic surface, hinders particulate matter such as grease and dust and surface direct contact, can take away surface adhesion material when treating its evaporation. The contact angle is less than 10 degrees or more than 150 degrees, the super-hydrophilicity and the super-hydrophobicity are provided, and the self-cleaning function is provided, and the self-cleaning performance is poorer when the contact angle deviates from the range.
The PTFE fluorocarbon fiber film, PTFE-ZrO of example 1 of the present invention2Membrane and PTFE-ZrO2- Bi2O3The results of the hydrophilicity test of the membrane are shown in FIGS. 1 to 3. Under the irradiation of a high-pressure mercury lamp with a wavelength of 365nm (simulating an ultraviolet light wave band in sunlight), the PTFE fluorocarbon fiber membrane which is not treated is in a hydrophobic state, the contact angle with water is 126 degrees, and the self-cleaning effect is poor as shown in figure 1. ZrO generated on the surface of PTFE fluorocarbon fiber film2Then, under the irradiation of a high-pressure mercury lamp with a wavelength of 365nm, PTFE-ZrO2The surface changed from hydrophilic to hydrophobic and the contact angle with water was changed to 25 °. ZrO on surface of PTFE fluorocarbon fiber membrane2Further generation of Bi on the protective layer2O3Then, under the irradiation of a high-pressure mercury lamp with a wavelength of 365nm, PTFE-ZrO2- Bi2O3The contact angle between the surface and water is changed to be close to 0 degree, and the super-hydrophilic property is presented at the time, so that the self-cleaning function is realized.
The invention prepares a layer of ZrO on a Polytetrafluoroethylene (PTFE) fluorocarbon fiber film by a dip-coating method2The film can avoid the damage of ultraviolet rays and strong free radicals of photocatalysis products to a film material, and simultaneously improves the tolerance temperature of the PTFE fluorocarbon fiber film; in the presence of PTFE-ZrO2Preparing a layer of Bi on the film2O3The photocatalyst film can present a super-hydrophilic state under the action of ultraviolet rays in sunlight, so that the self-cleaning function is realized; the invention adopts a sol-gel method, and the maximum reaction temperature is not more than 300 ℃, thereby solving the problem of the conventional methodComplex process preparation, high cost and incapability of effectively generating the photocatalytic film on the fluorocarbon fiber film substrate. The invention has reasonable design and convenient operation, and the prepared PTFE-ZrO2- Bi2O3The self-cleaning film can effectively reduce damage on one hand, and can realize self-cleaning function on the other hand, so that the self-cleaning film is high in practicability and suitable for popularization.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention, it should be noted that, for those skilled in the art, several modifications and decorations without departing from the principle of the present invention should be regarded as the protection scope of the present invention.

Claims (7)

1. A preparation method of a self-cleaning membrane material for capping a sewage station is characterized by comprising the following steps:
s1, pretreatment of the PTFE fluorocarbon fiber membrane:
respectively ultrasonically cleaning a PTFE fluorocarbon fiber membrane by using absolute ethyl alcohol and deionized water, and then drying; placing the dried fluorocarbon fiber film into a low-temperature plasma instrument for treatment for later use;
S2、ZrO2preparing precursor sol:
mixing acetone, water or hydrogen peroxide, adding ZrO2Formation of ZrO2Precursor sol;
S3、PTFE- ZrO2preparation of the film:
taking a proper amount of ZrO prepared from S22Precursor sol, soaking the PTFE fluorocarbon fiber film pretreated by S1 in the ZrO by adopting a dipping and pulling method2Dipping the precursor sol for 10-60min, and drying in an oven at 150 ℃ and 200 ℃ for 1-2 h; repeating the steps of dipping, pulling and drying for 1-5 times to obtain PTFE-ZrO2A film;
S4、Bi2O3preparation of precursor gel:
mixing acetone, ethylene glycol and nitric acid, and stirring at 40-50 deg.C for 20-60 min; adding bismuth nitrate pentahydrate, and heating the solution at 40-50 deg.CStirring is continued until a pale yellow Bi is formed2O3Precursor gel;
S5、PTFE- ZrO2- Bi2O3preparing a self-cleaning film:
PTFE-ZrO prepared from S3 by adopting dip-coating method2Film dipping into Bi prepared in S42O3Soaking the precursor gel for 10-60min, drying, and drying to obtain PTFE-ZrO2- Bi2O3And (5) self-cleaning the membrane.
2. The method of claim 1, wherein in S1, the PTFE fluorocarbon fiber membrane substrate is glass fiber, has a thickness of 0.8mm or more and a tensile strength of 4000N or more.
3. The method as claimed in claim 1, wherein in step S1, after the dried fluorocarbon fiber membrane is placed in a low temperature plasma instrument, oxygen is introduced into the low temperature plasma instrument and the membrane is evacuated to 20-80Pa by a vacuum pump with a discharge power of 100-; the fluorocarbon fiber film is treated in a low-temperature plasma instrument for 10-60 min.
4. The method for preparing a self-cleaning membrane for capping a sewage station as claimed in claim 1, wherein in S1, the PTFE fluorocarbon fiber membrane is ultrasonically cleaned for 30-60min and 1-3 times respectively with absolute ethanol and deionized water; the drying temperature is 80-100 ℃, and the drying time is 1-2 h.
5. The method for preparing the self-cleaning membrane for capping the sewage station as claimed in claim 1, wherein in S2, the volume ratio of acetone, water or hydrogen peroxide is 1:1-1: 10; added ZrO2The molar mass ratio of the water to the water is 1:10-1: 30.
6. The method for preparing a self-cleaning membrane for capping a sewage station as claimed in claim 1, wherein in S4, the volume ratio of acetone, glycol and nitric acid is 2:2: 1; the molar mass ratio of the added pentahydrate bismuth nitrate to the acetone is 1:20-1: 60.
7. The method of claim 1, wherein the step of drying in step S5 comprises: drying in an oven at 80 deg.C for 0.5-2h, and then heating to 300 deg.C for 1-4h to obtain PTFE-ZrO2- Bi2O3And (5) self-cleaning the membrane.
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CN107626211A (en) * 2017-09-29 2018-01-26 华南理工大学 A kind of film for possessing self-cleaning performance and preparation method thereof
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Publication number Priority date Publication date Assignee Title
CN1209153A (en) * 1995-12-22 1999-02-24 东陶机器株式会社 Photocatalytic process for making surface hydrophilic and composite material having photocatalytically hydrophilic surface
US20160200953A1 (en) * 2014-04-18 2016-07-14 Jason Constantinou Methods and formulations for superhydrophic, self-cleaning, and icephobic polymer coatings and objects having coatings thereon
CN107626211A (en) * 2017-09-29 2018-01-26 华南理工大学 A kind of film for possessing self-cleaning performance and preparation method thereof
CN108285174A (en) * 2018-04-04 2018-07-17 东莞市石鼓污水处理有限公司 A kind of WO3-ZrO2The preparation method of photocatalysis sewage process film

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