CN110655068A - Preparation method of super-hydrophilic reduction-graphene oxide coating and product thereof - Google Patents
Preparation method of super-hydrophilic reduction-graphene oxide coating and product thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a super-hydrophilic reduction-graphene oxide coating, which comprises the steps of taking water dispersion of graphene oxide as a raw material, adding a proper amount of carboxymethyl cellulose aqueous solution to form mixed liquid serving as coating slurry, coating the mixed liquid on a heat-resistant carrier, and carrying out heat treatment to obtain the super-hydrophilic reduction-graphene oxide coating. In addition, a coating product prepared by the preparation method of the super-hydrophilic reduction-graphene oxide coating is also disclosed. The invention breaks through the bottleneck problem of poor hydrophilicity of the existing reduction-oxidation graphene material, greatly improves the hydrophilicity of the reduction-oxidation graphene coating, and has the advantages of simple and convenient process, low cost, excellent product performance and the like, thereby having wide market prospect.
Description
Technical Field
The invention relates to the technical field of coating material preparation, in particular to a preparation method of a super-hydrophilic reduction-graphene oxide coating and a product thereof.
Background
Rest with waterSurfaces with a contact angle of less than 5 ° are generally defined as superhydrophilic surfaces, which have strong interaction with water and on which a drop of water can spread out rapidly and completely. The surface has multiple unique and excellent functions of self-cleaning, atomization prevention and the like, so the surface has wide application prospect and has been widely researched and applied in various fields. At present, the material for preparing the super-hydrophilic surface is mainly TiO2、SiO2And graphene oxide, and the like, and the preparation method mainly comprises a vapor deposition method, an etching method, a layer-by-layer self-assembly method, a sol-gel method, a liquid phase deposition method and the like. However, the existing preparation process of the super-hydrophilic coating generally has the defects of complex operation, high cost and the like, so that the application of the super-hydrophilic coating is severely restricted.
Therefore, aiming at the technical defects of the super-hydrophilic materials in the prior art, the preparation technology of the novel super-hydrophilic coating with simple and convenient process, low cost and excellent product performance and related products are researched and developed in time, and become important requirements and important trends in the development of the super-hydrophilic industry at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a super-hydrophilic reduction-graphene oxide coating, which is simple and convenient in process, low in cost and excellent in product performance. Another object of the present invention is to provide a coated product obtained by the above preparation method.
The purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a super-hydrophilic reduction-graphene oxide coating, which comprises the following steps:
(1) preparing graphene oxide by using a Hummers method, cleaning a reaction product to be neutral, and dispersing the reaction product in water to form a graphene oxide aqueous solution;
(2) carrying out ultrasonic stripping and centrifugal separation treatment on the graphene oxide aqueous solution to obtain 0.2-2 mg/ml graphene oxide aqueous dispersion;
(3) adding a carboxymethyl cellulose aqueous solution with the concentration of 0.1-0.3% into the graphene oxide aqueous dispersion, wherein the addition amount of the carboxymethyl cellulose aqueous solution is 5-10V/V% of the graphene oxide aqueous dispersion, and preparing a uniform mixed solution;
(4) coating the mixed solution on a carrier, such as a spin coating method, a dripping coating method or a spraying method, to obtain the carrier with a coating layer;
(5) and carrying out heat treatment on the carrier with the coating layer, and naturally cooling to obtain the super-hydrophilic reduced-oxidized graphene coating.
Further, the ultrasonic stripping process in the step (2) of the invention comprises the following steps: the ultrasonic power is 700-900W, and the ultrasonic time is 10-20 minutes; the centrifugal separation process comprises the following steps: the centrifugal speed is 5000-8000 rpm, and the centrifugal time is 20-30 minutes. The thickness of the coating layer in the step (4) is 200-500 nanometers.
Further, the heat treatment in step (5) of the present invention is performed in stages, wherein the first stage is: preserving the heat for 10-20 minutes at the temperature of 90-110 ℃; and a second stage: preserving the heat for 10-20 minutes at the temperature of 190-210 ℃; and a third stage: preserving the heat for 10-20 minutes at 290-310 ℃; a fourth stage: and preserving the heat for 10 to 20 minutes at the temperature of 340 to 360 ℃.
The coating product prepared by the preparation method of the super-hydrophilic reduction-graphene oxide coating has a water static contact angle of less than 5 degrees.
The invention has the following beneficial effects:
according to the invention, the aqueous dispersion of graphene oxide is used as a raw material, a mixed solution formed by adding a proper amount of carboxymethyl cellulose aqueous solution is used as a coating slurry, the coating slurry is coated on a heat-resistant carrier (the heat-resistant temperature is more than 360 ℃), reduced-oxidized graphene with a small amount of oxygen-containing functional groups is obtained after heat treatment, and meanwhile, the formation of a micro-nano structure on the surface structure of the reduced-oxidized graphene coating is conveniently realized by utilizing the pyrolysis reaction of carboxymethyl cellulose under the heat treatment condition, so that the coating has a super-hydrophilic effect. The technology of the invention breaks through the bottleneck problem of poor hydrophilicity of the existing reduction-oxidation graphene material, greatly improves the hydrophilicity of the reduction-oxidation graphene coating, and has the advantages of simple and convenient process, low cost, excellent product performance and the like, and has wide market prospect.
Drawings
The invention will now be described in further detail with reference to the following examples and the accompanying drawings:
fig. 1 is a process flow diagram of a method for preparing a superhydrophilic reduced-graphene oxide coating according to an embodiment of the present invention;
FIG. 2 is a phase analysis diagram of reduced-oxidized graphene in an example of the present invention;
FIG. 3 is a static water contact angle diagram of a super-hydrophilic reduced-graphene oxide coating prepared in an embodiment of the present invention (a: embodiment I; b: embodiment II; c: embodiment III).
In the figure:
Detailed Description
The first embodiment is as follows:
the preparation method of the super-hydrophilic reduction-graphene oxide coating according to the embodiment is shown in fig. 1, and includes the following steps:
(1) preparing graphene oxide by using a Hummers method, cleaning a reaction product to be neutral, and dispersing the reaction product in water to form a graphene oxide aqueous solution;
(2) ultrasonically stripping the graphene oxide aqueous solution for 10 minutes at 900W, centrifuging for 20 minutes at the centrifugal rotation speed of 8000 rpm, discarding centrifugal precipitation, and reserving the upper-layer solution to obtain 0.2mg/ml graphene oxide aqueous dispersion;
(3) adding 0.5 ml of carboxymethyl cellulose aqueous solution with the concentration of 0.3% into 10 ml of the graphene oxide aqueous dispersion to prepare uniform mixed solution;
(4) coating the mixed solution on a glass substrate in a spraying manner to obtain the glass substrate with a coating layer, wherein the thickness of the coating layer is 300 nanometers;
(5) putting the glass substrate with the coating layer into a muffle furnace for staged heat treatment, wherein in the first stage: keeping the temperature at 90 ℃ for 20 minutes; and a second stage: keeping the temperature at 210 ℃ for 10 minutes; and a third stage: keeping the temperature at 290 ℃ for 20 minutes; a fourth stage: preserving the heat for 20 minutes at the temperature of 340 ℃, and naturally cooling to obtain the super-hydrophilic reduced-oxidized graphene coating (see figure 2).
The coating product of this example had a static contact angle of water of 4.1 ° (see fig. 3 a).
Example two:
the preparation method of the super-hydrophilic reduction-graphene oxide coating according to the embodiment is shown in fig. 1, and includes the following steps:
(1) preparing graphene oxide by using a Hummers method, cleaning a reaction product to be neutral, and dispersing the reaction product in water to form a graphene oxide aqueous solution;
(2) ultrasonically stripping the graphene oxide aqueous solution for 20 minutes at 700W, centrifuging for 30 minutes at a centrifugal rotation speed of 5000 rpm, discarding centrifugal precipitation, and reserving an upper layer solution to obtain a 2mg/ml graphene oxide aqueous dispersion;
(3) adding 2 ml of carboxymethyl cellulose aqueous solution with the concentration of 0.1% into 20 ml of the graphene oxide aqueous dispersion to prepare uniform mixed solution;
(4) coating the mixed solution on an alumina ceramic matrix in a dripping coating mode to obtain the alumina ceramic matrix with a coating layer, wherein the thickness of the coating layer is 500 nanometers;
(5) putting the alumina ceramic substrate with the coating layer into a muffle furnace for staged heat treatment, wherein in the first stage: keeping the temperature at 100 ℃ for 15 minutes; and a second stage: keeping the temperature at 200 ℃ for 15 minutes; and a third stage: keeping the temperature at 300 ℃ for 15 minutes; a fourth stage: and (3) preserving the heat for 15 minutes at the temperature of 350 ℃, and naturally cooling to obtain the super-hydrophilic reduced-oxidized graphene coating (see figure 2).
The coating product of this example had a static contact angle of water of 3.2 ° (see fig. 3 b).
Example three:
the preparation method of the super-hydrophilic reduction-graphene oxide coating according to the embodiment is shown in fig. 1, and includes the following steps:
(1) preparing graphene oxide by using a Hummers method, cleaning a reaction product to be neutral, and dispersing the reaction product in water to form a graphene oxide aqueous solution;
(2) ultrasonically stripping the graphene oxide aqueous solution for 15 minutes at 800W, centrifuging for 25 minutes at the centrifugal rotation speed of 7000 r/min, discarding centrifugal precipitation, and reserving the upper-layer solution to obtain 1mg/ml graphene oxide aqueous dispersion;
(3) adding 1 ml of carboxymethyl cellulose aqueous solution with the concentration of 0.2% into 10 ml of the graphene oxide aqueous dispersion to prepare uniform mixed solution;
(4) coating the mixed solution on a stainless steel substrate in a spin coating manner to obtain the stainless steel substrate with a coating layer, wherein the thickness of the coating layer is 200 nanometers;
(5) putting the stainless steel substrate with the coating layer into a muffle furnace for staged heat treatment, wherein in the first stage: keeping the temperature at 110 ℃ for 10 minutes; and a second stage: keeping the temperature at 190 ℃ for 20 minutes; and a third stage: keeping the temperature at 310 ℃ for 10 minutes; a fourth stage: preserving the heat for 10 minutes at the temperature of 360 ℃, and naturally cooling to obtain the super-hydrophilic reduced-oxidized graphene coating (see figure 2).
The coating product of this example had a static contact angle of water of 2.8 ° (see fig. 3 c).
Claims (6)
1. A preparation method of a super-hydrophilic reduction-graphene oxide coating is characterized by comprising the following steps:
(1) preparing graphene oxide by using a Hummers method, cleaning a reaction product to be neutral, and dispersing the reaction product in water to form a graphene oxide aqueous solution;
(2) carrying out ultrasonic stripping and centrifugal separation treatment on the graphene oxide aqueous solution to obtain 0.2-2 mg/ml graphene oxide aqueous dispersion;
(3) adding a carboxymethyl cellulose aqueous solution with the concentration of 0.1-0.3% into the graphene oxide aqueous dispersion, wherein the addition amount of the carboxymethyl cellulose aqueous solution is 5-10V/V% of the graphene oxide aqueous dispersion, and preparing a uniform mixed solution;
(4) coating the mixed solution on a carrier to obtain the carrier with a coating layer;
(5) and carrying out heat treatment on the carrier with the coating layer, and naturally cooling to obtain the super-hydrophilic reduced-oxidized graphene coating.
2. The method for preparing a superhydrophilic reduced-graphene oxide coating according to claim 1, wherein: the ultrasonic stripping process in the step (2) comprises the following steps: the ultrasonic power is 700-900W, and the ultrasonic time is 10-20 minutes; the centrifugal separation process comprises the following steps: the centrifugal speed is 5000-8000 rpm, and the centrifugal time is 20-30 minutes.
3. The method for preparing a superhydrophilic reduced-graphene oxide coating according to claim 1, wherein: the thickness of the coating layer in the step (4) is 200-500 nanometers.
4. The method for preparing a superhydrophilic reduced-graphene oxide coating according to claim 1, wherein: the heat treatment in the step (5) is carried out in stages, wherein the first stage comprises the following steps: preserving the heat for 10-20 minutes at the temperature of 90-110 ℃; and a second stage: preserving the heat for 10-20 minutes at the temperature of 190-210 ℃; and a third stage: preserving the heat for 10-20 minutes at 290-310 ℃; a fourth stage: and preserving the heat for 10 to 20 minutes at the temperature of 340 to 360 ℃.
5. A coated product obtained by the method for preparing a superhydrophilic reduced-graphene oxide coating according to any one of claims 1 to 4.
6. The coated product prepared by the preparation method of the super-hydrophilic reduced-graphene oxide coating according to claim 5, is characterized in that: the coated product has a static contact angle of water of less than 5 °.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231684A (en) * | 2014-09-24 | 2014-12-24 | 景德镇陶瓷学院 | Super-hydrophilic anti-fogging oxidized graphene coating, preparation method and application thereof |
| KR20150094241A (en) * | 2014-02-11 | 2015-08-19 | 인하대학교 산학협력단 | Manufacturing method of graphene oxide paper |
| WO2016162518A1 (en) * | 2015-04-08 | 2016-10-13 | Norwegian University Of Science And Technology (Ntnu) | Composite membrane |
| CN106185908A (en) * | 2016-07-19 | 2016-12-07 | 四川大学 | A kind of graphene aerogel microsphere and preparation method thereof |
| CN106187269A (en) * | 2016-07-19 | 2016-12-07 | 青岛科技大学 | A kind of controlled amphiphilic graphene aerogel of intensity and preparation method thereof |
| CN106256768A (en) * | 2016-04-11 | 2016-12-28 | 南京大学 | A kind of polylayer forest and its production and use |
| CN107572626A (en) * | 2017-10-19 | 2018-01-12 | 青岛大学 | It is a kind of to have hydrophily and black composite and preparation method and application from flotation property concurrently |
| CN108159889A (en) * | 2017-12-18 | 2018-06-15 | 江苏大学 | A kind of super hydrophilic-superoleophobic redox graphene filter membrane and purposes |
-
2019
- 2019-10-29 CN CN201911034583.9A patent/CN110655068B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150094241A (en) * | 2014-02-11 | 2015-08-19 | 인하대학교 산학협력단 | Manufacturing method of graphene oxide paper |
| CN104231684A (en) * | 2014-09-24 | 2014-12-24 | 景德镇陶瓷学院 | Super-hydrophilic anti-fogging oxidized graphene coating, preparation method and application thereof |
| WO2016162518A1 (en) * | 2015-04-08 | 2016-10-13 | Norwegian University Of Science And Technology (Ntnu) | Composite membrane |
| CN106256768A (en) * | 2016-04-11 | 2016-12-28 | 南京大学 | A kind of polylayer forest and its production and use |
| CN106185908A (en) * | 2016-07-19 | 2016-12-07 | 四川大学 | A kind of graphene aerogel microsphere and preparation method thereof |
| CN106187269A (en) * | 2016-07-19 | 2016-12-07 | 青岛科技大学 | A kind of controlled amphiphilic graphene aerogel of intensity and preparation method thereof |
| CN107572626A (en) * | 2017-10-19 | 2018-01-12 | 青岛大学 | It is a kind of to have hydrophily and black composite and preparation method and application from flotation property concurrently |
| CN108159889A (en) * | 2017-12-18 | 2018-06-15 | 江苏大学 | A kind of super hydrophilic-superoleophobic redox graphene filter membrane and purposes |
Non-Patent Citations (3)
| Title |
|---|
| CHENG XIANG ET AL: "Synthesis of carboxymethyl cellulose-reduced graphene oxide aerogel for efficient removal of organic liquids and dyes", 《J.MATER.SCI》 * |
| YUN-SHENG YE ET AL: "Biocompatible reduced graphene oxide sheets with superior water dispersibility stabilized by cellulose nanocrystals and their polyethylene oxide composites", 《GREEN CHEMISTRY》 * |
| 吴波等: "纳米纤维素/还原氧化石墨烯透明导电薄膜的制备及表征", 《林业工程学报》 * |
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