CN107213801B - Super-hydrophilic and underwater super-oleophobic ceramic membrane and preparation method thereof - Google Patents
Super-hydrophilic and underwater super-oleophobic ceramic membrane and preparation method thereof Download PDFInfo
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- 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
- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
- B01D71/02—Inorganic material
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Abstract
The invention provides a super-hydrophilic and underwater super-oleophobic ceramic membrane, which takes a porous ceramic membrane as a substrate, and nano-scale columnar titanium dioxide is arranged on the surface of the substrate to form a titanium dioxide nano array. The ceramic membrane structure has a static contact angle of less than 10 degrees to water, and a contact angle of more than 150 degrees to oil under water, can be used as an oil-water separation membrane, and has excellent oil-water separation effect and anti-fouling effect. The invention also provides a method for preparing the ceramic membrane with super-hydrophilicity and underwater super-oleophobicity, which comprises the steps of firstly preparing a layer of metal titanizing layer on the surface of a porous ceramic membrane as a substrate, and then oxidizing by using an oxidizing solution consisting of hydrogen peroxide, nitric acid and melamine to obtain the ceramic membrane with the titanium dioxide nano array.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a super-hydrophilic and underwater super-oleophobic ceramic membrane and a preparation method thereof.
Background
The membrane separation is a new technology of modern high-efficiency separation, is widely applied to the fields of environmental protection, sewage treatment, biomedicine and the like, and provides a new way for circular economy production. The ceramic membrane is made of ceramic materials sintered at high temperature, and has unique strength and corrosion resistance, so that the ceramic membrane becomes one of the most rapid and most promising varieties in the membrane field as soon as the ceramic membrane enters the market.
With the intensive research of people on special invasive surfaces in nature, preparation methods of the special invasive surfaces are continuously emerging. Most of the reported methods today focus on the separation of oil from water. In the prior art, the ceramic membrane is mainly applied in a water phase system, and when an oil phase is separated, oil stains are often adhered to the surface and pores of the material due to the existing oil-water separation ceramic membrane material, so that the oil stains are difficult to clean, the filtration flux of the membrane is low, the separation efficiency is reduced, the equipment investment cost and the use cost are high, and the marketization is difficult to realize.
Patent CN1336352A discloses a titanium dioxide photocatalysis self-cleaning ceramic and a preparation method thereof, wherein a photocatalysis film and low-temperature glaze which are mainly composed of nano titanium dioxide are tightly compounded on a ceramic body or the glaze of a ceramic finished product, titanium dioxide sol is loaded on the ceramic glaze, and the required titanium dioxide photocatalysis self-cleaning ceramic is prepared by sintering. However, the titanium dioxide in the titanium dioxide photocatalysis self-cleaning ceramic prepared by the method has lower durability, is easy to poison and inactivate, and affects the service life of the titanium dioxide photocatalysis self-cleaning ceramic. In 2015, li and the like prepared TiO on the surface of foam titanium by anodic oxidation 2 The oil-water separation is carried out by the nano tube, but the super-hydrophilicity mentioned by the method has poor stability; at the same time, the nanotube structure is disadvantageous for the construction of superhydrophilic interfaces (j. Mater. Chem. A,2015,3,1279).
Disclosure of Invention
The invention provides a super-hydrophilic and underwater super-oleophobic ceramic membrane structure, which takes a porous ceramic membrane as a substrate, wherein nano-level columnar titanium dioxide is arranged on the surface of the substrate, namely, the titanium dioxide is in a columnar structure, the diameter and the height of the titanium dioxide are in nano-scale, and a titanium dioxide nano array is formed on the surface of the substrate.
In the invention, titanium dioxide is combined on the surface of the porous ceramic substrate, and the titanium dioxide material has the characteristics of super hydrophilicity, good chemical stability, strong corrosion resistance and the like. Experiments prove that the ceramic membrane structure has a static contact angle of less than 10 degrees to water and a contact angle of more than 150 degrees to oil under water, can be used as an oil-water separation membrane, and has excellent oil-water separation effect and anti-fouling effect.
The porous ceramic membrane is not limited and includes porous alumina ceramic membrane and the like.
The oil is not limited in kind and includes vegetable oil, mineral oil or organic solvent such as toluene emulsified oil, chloroform emulsified oil, emulsified edible peanut oil, etc.
The invention also provides a method for preparing the super-hydrophilic and underwater super-oleophobic ceramic membrane, which comprises the following steps:
(1) Preparing a metal titanizing layer on the surface of the cleaned substrate by taking the porous ceramic film as the substrate to obtain a titanized ceramic film;
the method for cleaning the substrate is not limited, and as an implementation manner, the substrate is sequentially put into deionized water and absolute ethyl alcohol for ultrasonic cleaning;
the method for preparing the metallic titanizing layer on the substrate surface is not limited and includes using chemical deposition or physical deposition such as magnetron sputtering technique and the like.
(2) Placing the titanized ceramic film into an oxidation solution for oxidation, then washing with deionized water, and then drying;
the oxidation solution comprises hydrogen peroxide, nitric acid and melamine in percentage by mass, wherein the volume ratio of the concentrated nitric acid to the hydrogen peroxide is (1-5): (50-100), the mass volume ratio of melamine to hydrogen peroxide is (50-100): (1-5) mg/ml. Wherein, the hydrogen peroxide is used for oxidizing titanium into titanium dioxide; the concentrated nitric acid can oxidize titanium on one hand, and can reduce the pH value of the solution and stabilize titanium dioxide sol on the other hand, so as to reduce the nucleation of the sol in the solution, thereby promoting the growth of nano columnar titanium dioxide; the ammonia ions generated by the hydrolysis of melamine under acidic conditions can promote the selective absorption of titanium dioxide by the nano-array.
Preferably, the mass percentage concentration of the hydrogen peroxide is 30%.
Preferably, the mass percentage concentration of the concentrated nitric acid is 60% -98%.
Preferably, the oxidation time is 2 to 4 hours.
The preparation method of the oxidizing solution is not limited, and comprises the steps of stirring and mixing hydrogen peroxide, concentrated nitric acid and melamine until the melamine is completely dissolved. The mixing temperature is preferably 80 ℃.
In conclusion, the titanium dioxide nano-array grows on the porous ceramic matrix, and the underwater oleophobicity of the matrix is improved due to the super-hydrophilicity of the titanium dioxide. Wherein, a titanium layer is plated on the porous ceramic membrane by adopting the magnetron sputtering technology,
compared with the prior art, the invention has the following advantages:
(1) The ceramic membrane provided by the invention is nontoxic and pollution-free, has super-hydrophilic and underwater super-oleophobic properties, can prevent ceramic micropores from being blocked during oil-water separation, and is convenient to use; the material used for separating the emulsified oil is safe, economical and environment-friendly, has high efficiency for separating the emulsified oil, and has the characteristics of high mechanical strength, high repeated use rate, stable performance, small water surface resistance and the like;
(2) The preparation method provided by the invention can be used for preparing the ceramic film with the nano-scale columnar titanium dioxide on the surface in a large area, has simple process and rich raw materials, and is easy for mass production.
Drawings
FIG. 1 is an SEM image of a ceramic membrane prepared according to example 1;
FIG. 2 is an enlarged view of FIG. 1;
FIG. 3 is the underwater chloroform contact angle of the ceramic film prepared in example 1;
FIG. 4 is an SEM image of a ceramic membrane prepared according to example 3;
FIG. 5 is the underwater chloroform contact angle of the ceramic film prepared in example 3;
FIG. 6 is an SEM image of a ceramic membrane prepared according to example 5;
FIG. 7 is the underwater chloroform contact angle of the ceramic film prepared in example 5;
FIG. 8 is the contact angle of peanut oil in water for a ceramic film prepared in example 11;
fig. 9 is an SEM image of the ceramic membrane prepared in comparative example 1.
Detailed Description
The technical scheme of the invention is further described below with reference to a plurality of embodiments and drawings. It should be noted that the following examples and terms are intended to facilitate understanding of the present invention, and are not intended to be limiting in any way.
Example 1:
in this embodiment, the ceramic membrane uses a porous alumina ceramic sheet as a substrate, nano-scale columnar titanium dioxide is arranged on the surface of the substrate, and a titanium dioxide nano array is formed on the surface of the substrate.
The preparation method of the ceramic membrane comprises the following steps:
(1) Step 1: soaking the porous alumina ceramic wafer in a solvent for ultrasonic cleaning to remove stains and grease on the surface of the ceramic wafer, and then drying;
(2) Step 2: fixing the cleaned ceramic sheet on magnetron sputtering equipment, taking metallic titanium as a target material, and controlling sputtering time for 2 hours to obtain a ceramic sheet with the surface plated with titanium;
(3) Step 3: preparing an oxidizing solution, specifically: 3ml of 63% concentrated nitric acid, 70ml of 30% hydrogen peroxide and 80mg of melamine are stirred at the temperature of 80 ℃ until the melamine is completely dissolved;
(4) Step 4: putting the titanium-plated ceramic sheet obtained in the step 2 into the oxidation solution prepared in the step 3, and preserving the temperature at 80 ℃ for 2 hours to enable Ti metal plated on the surface of the ceramic sheet to be completely oxidized into TiO 2 A nano array.
(5) Step 5: and (3) cleaning the ceramic sheet obtained in the step (4), and drying in a drying oven to obtain the ceramic film with the titanium dioxide array on the surface.
An SEM image of the ceramic film prepared above is shown in fig. 1, and an enlarged image is shown in fig. 2, showing that nano-scale titanium dioxide is arranged on the surface of the substrate to form a titanium dioxide nano array.
The ceramic membrane prepared above was subjected to water contact angle in air, chloroform contact angle under water test, and oil-water separation efficiency test.
The oil-water separation efficiency testing method comprises the following steps: and (3) loading a certain volume of toluene-in-water emulsified oil into an oil-water separation device, adding 0.02Mpa external pressure to separate the emulsified oil, taking a raw emulsified oil sample and a filtrate sample, and measuring ultraviolet absorbance before and after emulsion separation, wherein the oil-water separation efficiency (%) = (1-filtrate concentration/raw emulsion concentration) ×100.
The underwater oleophobic testing method comprises the following steps: the ceramic film prepared above was immersed in a container filled with water, chloroform was dropped, and the size of the underwater oil contact angle was measured.
The test results according to the test method are as follows: the contact angle of chloroform under water is 153.7 degrees, the contact angle of water in air is 2 degrees, and the oil-water separation efficiency is 99.2 percent as shown in figure 3.
Example 2:
in this embodiment, the ceramic membrane structure is similar to that of embodiment 1, in which a porous alumina ceramic plate is used as a substrate, nano-scale columnar titanium dioxide is arranged on the surface of the substrate, and a titanium dioxide nano-array is formed on the surface of the substrate.
The preparation method of the ceramic membrane was substantially the same as that in example 1, except that in the preparation of the oxidizing solution in step 3, the addition amount of 63% concentrated nitric acid was 1ml.
The SEM image of the ceramic film prepared above is similar to that shown in fig. 1, and shows that nano-scale titanium dioxide is arranged on the surface of the substrate to form a titanium dioxide nano array.
The ceramic membrane prepared above was subjected to water contact angle in air, chloroform contact angle under water test, and oil-water separation efficiency test. The test method was the same as in example 1.
The test results according to the test method are as follows: the contact angle of the chloroform under water is 151 degrees+/-3 degrees, the contact angle of the water in air is 3 degrees, and the oil-water separation efficiency is 97.6 percent.
Example 3:
in this embodiment, the ceramic membrane structure is similar to that of embodiment 1, in which a porous alumina ceramic plate is used as a substrate, nano-scale columnar titanium dioxide is arranged on the surface of the substrate, and a titanium dioxide nano-array is formed on the surface of the substrate.
The preparation method of the ceramic membrane was substantially the same as that in example 1, except that the addition amount of 63% concentrated nitric acid in the preparation of the oxidizing solution in step 3 was 5ml.
The SEM image of the ceramic film prepared above is shown in fig. 4, which shows that nano-scale titanium dioxide is arranged on the surface of the substrate to form a titanium dioxide nano array.
The ceramic membrane prepared above was subjected to water contact angle in air, chloroform contact angle under water test, and oil-water separation efficiency test. The test method was the same as in example 1.
The test results according to the test method are as follows: the contact angle of chloroform under water is 155 degrees + -2 degrees, the contact angle of water in air is 2 degrees, and the oil-water separation efficiency is 96.6 percent as shown in figure 5.
Example 4:
in this embodiment, the ceramic membrane structure is similar to that of embodiment 1, in which a porous alumina ceramic plate is used as a substrate, nano-scale columnar titanium dioxide is arranged on the surface of the substrate, and a titanium dioxide nano-array is formed on the surface of the substrate.
The preparation method of the ceramic membrane is basically the same as that of example 1, except that in the process of preparing the oxidizing solution in step 3, the addition amount of 30% hydrogen peroxide is 50ml.
The SEM image of the ceramic film prepared above is similar to that shown in fig. 1, and shows that nano-scale titanium dioxide is arranged on the surface of the substrate to form a titanium dioxide nano array.
The ceramic membrane prepared above was subjected to water contact angle in air, chloroform contact angle under water test, and oil-water separation efficiency test. The test method was the same as in example 1.
The test results according to the test method are as follows: the contact angle of the chloroform under water is 152 degrees+/-1 degrees, the contact angle of the water in air is 3 degrees, and the oil-water separation efficiency is 98.6 percent.
Example 5:
in this embodiment, the ceramic membrane structure is similar to that of embodiment 1, in which a porous alumina ceramic plate is used as a substrate, nano-scale columnar titanium dioxide is arranged on the surface of the substrate, and a titanium dioxide nano-array is formed on the surface of the substrate.
The preparation method of the ceramic membrane is basically the same as that in example 1, except that the addition amount of 30% hydrogen peroxide is 100ml in the process of preparing the oxidizing solution in step 3.
An SEM image of the ceramic film prepared above is shown in fig. 6, which shows that nano-scale titanium dioxide is arranged on the surface of the substrate to form a titanium dioxide nano array.
The ceramic membrane prepared above was subjected to water contact angle in air, chloroform contact angle under water test, and oil-water separation efficiency test. The test method was the same as in example 1.
The test results according to the test method are as follows: the contact angle of chloroform under water is shown in figure 7 and is 155 degrees plus or minus 2 degrees, the contact angle of water in air is 2 degrees, and the oil-water separation efficiency is 98.8 percent.
Example 6:
in this embodiment, the ceramic membrane structure is similar to that of embodiment 1, in which a porous alumina ceramic plate is used as a substrate, nano-scale columnar titanium dioxide is arranged on the surface of the substrate, and a titanium dioxide nano-array is formed on the surface of the substrate.
The preparation method of the ceramic film was substantially the same as that in example 1 except that melamine was added in an amount of 50mg during the preparation of the oxidizing solution in step 3.
The SEM image of the ceramic film prepared above is similar to that shown in fig. 1, and shows that nano-scale titanium dioxide is arranged on the surface of the substrate to form a titanium dioxide nano array.
The ceramic membrane prepared above was subjected to water contact angle in air, chloroform contact angle under water test, and oil-water separation efficiency test. The test method was the same as in example 1.
The test results according to the test method are as follows: the contact angle of the chloroform under water is 156 degrees+/-1 degrees, the contact angle of the water in air is 2 degrees, and the oil-water separation efficiency is 99.1 percent.
Example 7:
in this embodiment, the ceramic membrane structure is similar to that of embodiment 1, in which a porous alumina ceramic plate is used as a substrate, nano-scale columnar titanium dioxide is arranged on the surface of the substrate, and a titanium dioxide nano-array is formed on the surface of the substrate.
The preparation method of the ceramic film was substantially the same as that in example 1 except that melamine was added in an amount of 100mg in the preparation of the oxidizing solution in step 3.
The SEM image of the ceramic film prepared above is similar to that shown in fig. 1, and shows that nano-scale titanium dioxide is arranged on the surface of the substrate to form a titanium dioxide nano array.
The ceramic membrane prepared above was subjected to water contact angle in air, chloroform contact angle under water test, and oil-water separation efficiency test. The test method was the same as in example 1.
The test results according to the test method are as follows: the contact angle of the chloroform under water is 154 degrees+/-2 degrees, the contact angle of the water in air is 6 degrees, and the oil-water separation efficiency is 97.8 percent.
Example 8:
in this embodiment, the ceramic membrane structure is similar to that of embodiment 1, in which a porous alumina ceramic plate is used as a substrate, nano-scale columnar titanium dioxide is arranged on the surface of the substrate, and a titanium dioxide nano-array is formed on the surface of the substrate.
The preparation method of the ceramic membrane was substantially the same as that in example 1, except that the oxidation time in step 4 was 4 hours.
The SEM image of the ceramic film prepared above is similar to that shown in fig. 1, and shows that nano-scale titanium dioxide is arranged on the surface of the substrate to form a titanium dioxide nano array.
The ceramic membrane prepared above was subjected to water contact angle in air, chloroform contact angle under water test, and oil-water separation efficiency test. The test method was the same as in example 1.
The test results according to the test method are as follows: the contact angle of the chloroform under water is 153 degrees+/-2 degrees, the contact angle of the water in air is 6 degrees, and the oil-water separation efficiency is 99.3 percent.
Example 9:
in this embodiment, the ceramic membrane structure is similar to that of embodiment 1, in which a porous alumina ceramic plate is used as a substrate, nano-scale columnar titanium dioxide is arranged on the surface of the substrate, and a titanium dioxide nano-array is formed on the surface of the substrate.
The preparation method of the ceramic film was substantially the same as that in example 1, except that the sputtering time in step 2 was 1 hour.
The SEM image of the ceramic film prepared above is similar to that shown in fig. 1, and shows that nano-scale titanium dioxide is arranged on the surface of the substrate to form a titanium dioxide nano array.
The ceramic membrane prepared above was subjected to water contact angle in air, chloroform contact angle under water test, and oil-water separation efficiency test. The test method was the same as in example 1.
The test results according to the test method are as follows: the contact angle of the chloroform under water is 151 degrees+/-2 degrees, the contact angle of the water in air is 5 degrees, and the oil-water separation efficiency is 99.1 percent.
Example 10:
in this embodiment, the ceramic membrane structure is similar to that of embodiment 1, in which a porous alumina ceramic plate is used as a substrate, nano-scale columnar titanium dioxide is arranged on the surface of the substrate, and a titanium dioxide nano-array is formed on the surface of the substrate.
The preparation method of the ceramic film was substantially the same as that in example 1, except that the sputtering time in step 2 was 3 hours.
The SEM image of the ceramic film prepared above is similar to that shown in fig. 1, and shows that nano-scale titanium dioxide is arranged on the surface of the substrate to form a titanium dioxide nano array.
The ceramic membrane prepared above was subjected to water contact angle in air, chloroform contact angle under water test, and oil-water separation efficiency test. The test method was the same as in example 1.
The test results according to the test method are as follows: the contact angle of the chloroform under water is 156 degrees+/-1 degrees, the contact angle of the water in air is 5 degrees, and the oil-water separation efficiency is 98.8 percent.
Example 10:
in this embodiment, the ceramic membrane structure is similar to that of embodiment 1, in which a porous alumina ceramic plate is used as a substrate, nano-scale columnar titanium dioxide is arranged on the surface of the substrate, and a titanium dioxide nano-array is formed on the surface of the substrate.
The preparation method of the ceramic film was the same as in example 1.
The SEM image of the ceramic film prepared above is the same as that of fig. 1, showing that nano-scale titanium dioxide is arranged on the surface of the substrate to form a titanium dioxide nano array.
The ceramic film prepared by the method is subjected to underwater edible peanut oil contact angle test, and the test method comprises the following steps: the ceramic film prepared above was immersed in a container filled with water, and the edible peanut oil was dropped into the container, and the size of the contact angle of the underwater oil was measured, and the result of the test was shown in fig. 8, wherein the contact angle of the underwater edible peanut oil was 151.3±3°.
The oil-water separation efficiency testing method comprises the following steps: the edible peanut oil in water with a certain volume is put into an oil-water separation device, the edible peanut oil is separated by adding external pressure of 0.02Mpa, crude oil aqueous solution and filtrate samples are taken, ultraviolet absorbance before and after emulsion separation is measured, and the oil-water separation efficiency reaches 98.6%.
Comparative example 1:
this example is a comparative example of example 1.
In this example, the ceramic film was prepared in substantially the same manner as in example 1, except that melamine was not added when preparing the oxidizing solution in step 3. Specifically, the method for preparing the oxidizing solution is as follows:
3ml of 63% concentrated nitric acid and 70ml of 30% hydrogen peroxide are stirred and mixed at the temperature of 80 ℃.
The SEM images of the ceramic films prepared above are completely different from fig. 1, showing the morphology of the ceramic substrate, and no titanium dioxide nanoarrays were formed on the substrate surface as shown in fig. 9 below.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (5)
1. A preparation method of a super-hydrophilic and underwater super-oleophobic ceramic membrane takes a porous ceramic membrane as a substrate and is characterized in that: the surface of the substrate is arranged with nano-level columnar titanium dioxide, and a titanium dioxide nano array is formed on the surface of the substrate; the static contact angle of the ceramic membrane to water is smaller than 10 degrees, and the contact angle of the ceramic membrane to oil under water is larger than 150 degrees;
the nanoscale columnar titanium dioxide is a columnar structure, and the diameter and the height of the columnar titanium dioxide are in nanoscale; the method comprises the following steps:
(1) Preparing a layer of metal titanizing layer on the surface of the cleaned substrate by taking the porous ceramic film as a substrate and utilizing a magnetron sputtering technology to obtain the titanizing ceramic film;
(2) Placing the titanized ceramic film into an oxidation solution for oxidation for 2-4 hours, forming nano-scale columnar titanium dioxide on the surface of a substrate, then washing with deionized water, and then drying;
the oxidation solution comprises hydrogen peroxide, concentrated nitric acid and melamine, wherein the volume ratio of the concentrated nitric acid to the hydrogen peroxide is (1-5): (50-100), the mass volume ratio of melamine to hydrogen peroxide is (50-100): (1-5) mg/ml;
the mass percentage concentration of the hydrogen peroxide is 30%;
the mass percentage concentration of the concentrated nitric acid is 60% -98%.
2. The method for preparing the super-hydrophilic and underwater super-oleophobic ceramic membrane as claimed in claim 1, which is characterized in that: the porous ceramic membrane comprises a porous alumina ceramic membrane.
3. The method for preparing the super-hydrophilic and underwater super-oleophobic ceramic membrane as claimed in claim 1, which is characterized in that: the oil type includes vegetable oil, mineral oil or chloroform.
4. The method for preparing the super-hydrophilic and underwater super-oleophobic ceramic membrane as claimed in claim 1, which is characterized in that: the cleaning treatment method of the substrate comprises the following steps: and sequentially placing the substrate into deionized water and absolute ethyl alcohol for ultrasonic cleaning.
5. Use of the super-hydrophilic and underwater super-oleophobic ceramic membrane prepared by the preparation method as claimed in any one of claims 1 to 4 in oil-water separation.
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| CN109260764B (en) * | 2018-09-18 | 2021-05-25 | 江苏大学 | Preparation method of super-hydrophilic/underwater super-oleophobic self-cleaning tissue fiber membrane |
| CN109569315B (en) * | 2018-10-29 | 2021-06-15 | 绍兴市柯桥区锦策智能科技有限公司 | Preparation and application method of inorganic ceramic membrane for treating oily wastewater |
| CN111153684B (en) * | 2018-11-08 | 2022-06-17 | 中国石油化工股份有限公司 | Ceramic membrane and preparation method and application thereof |
| CN111068525A (en) * | 2019-12-11 | 2020-04-28 | 天津科技大学 | Composite membrane with titanium dioxide nanorod array on surface, and preparation method and application thereof |
| CN112982030B (en) * | 2021-02-04 | 2023-06-23 | 陕西鸿鑫耐斯环保科技有限公司 | Preparation method of super-hydrophilic/underwater super-oleophobic filter paper |
| CN115403357B (en) * | 2022-08-23 | 2023-01-31 | 南京水凝科技有限公司 | Underwater super-oleophobic bionic ceramic substrate and preparation method thereof |
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