CN114453213A - Method for preparing hydrophobic film by plasma vapor deposition - Google Patents
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- CN114453213A CN114453213A CN202111629022.0A CN202111629022A CN114453213A CN 114453213 A CN114453213 A CN 114453213A CN 202111629022 A CN202111629022 A CN 202111629022A CN 114453213 A CN114453213 A CN 114453213A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 3
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 claims description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 3
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
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- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention discloses a method for preparing a hydrophobic film by plasma vapor deposition. The method comprises the following steps: activating the base material; vaporizing the coating material; the coating material has a symmetrical structure and contains silicon element; and introducing the vaporized coating material into the reaction cavity, starting a radio frequency power supply, and setting radio frequency power and vacuum degree so as to deposit the coating material on the surface of the substrate to form a hydrophobic film. The method generates the environment-friendly hydrophobic film with the thickness reaching the nanometer level on the surface of the base material through plasma chemical vapor deposition under the condition of not influencing the property of the base material.
Description
Technical Field
The invention relates to a method for preparing a hydrophobic film by plasma vapor deposition, belonging to the field of preparation of hydrophobic materials.
Background
In the middle of the 60 s of the 20 th century, researchers discovered the structure of the lotus leaf surface by using an electron microscope, thereby releasing the secret of the lotus leaf being hydrophobic. During the last decades, hydrophobic materials have become a focus of interest for researchers. The hydrophobic property of the material has a certain relation with the surface structure, the material composition and the wettability. The hydrophobic purpose can be achieved by two means of increasing the roughness of the surface of the material and reducing the surface energy of the material. Layer-by-layer assembly, solution soaking and electrochemical methods are common hydrophobic membrane preparation methods, but the methods have the problems of complex process, unsuitability for mass production and the like. The plasma vapor deposition technology is a new and developing technology, has simple process, is easy to master, is suitable for large-scale production, can adopt compounds with different structures to prepare multifunctional hydrophobic materials, and has wide application prospect in the aspect of coating.
Due to the unique wettability of the hydrophobic surface, water drops are difficult to stay on the hydrophobic surface, so that the hydrophobic material has wide application prospects in various fields, such as antifogging and waterproof glass, waterproof fabrics, self-cleaning clothes, sewage treatment and the like. At present, the hydrophobic material is usually a fluorine-containing material, has potential harm to human bodies and the environment, particularly, the fluoride has strong stimulation and corrosion to eyes, nose and skin, inflammation is easily caused after high-concentration fluoride is inhaled, and the fluoride released into the environment can also cause harm to the environment. For example, the air pollution and the soil water pollution caused by fluoride can threaten the planting industry and the animal husbandry, and the long-term drinking of water with high fluorine content can cause harm to human teeth and bones and cause chronic poisoning. In view of this, it is very important to develop an environment-friendly hydrophobic membrane preparation method by plasma vapor deposition.
Disclosure of Invention
Aiming at the problems that the preparation process of the hydrophobic film is complex and fluorine-containing substances are easy to cause harm to the environment and human bodies, the invention provides the method for preparing the hydrophobic film by plasma vapor deposition.
In a first aspect, the present invention provides a method for preparing a hydrophobic film by plasma vapor deposition. The method comprises the following steps:
activating the base material;
vaporizing the coating material; the coating material has a symmetrical structure and contains silicon element;
and introducing the vaporized coating material into the reaction cavity, starting a radio frequency power supply, and setting radio frequency power and vacuum degree so as to deposit the coating material on the surface of the substrate to form a hydrophobic film.
Preferably, the coating material is at least one of hexamethyldisiloxane, hexamethyldisilane, dimethyldimethoxysilane and octamethylcyclotetrasiloxane.
Preferably, the deposition of the coating material is carried out in a pulse wave mode; in the deposition process, a power supply for providing plasma is a radio frequency power supply, the power supply power is 200-300W, the temperature of the reaction cavity is controlled at 40-60 ℃, and the vacuum degree is kept between 0.01-0.2 mbar.
Preferably, the deposition time is 20-40 min.
Preferably, the coating material is vaporized in a heating cup, and the heating temperature of the heating cup is 50-100 ℃.
Preferably, while depositing the coating material, simultaneously introducing an auxiliary gas into the reaction chamber as a carrier gas, wherein the carrier gas comprises at least one of hydrogen, oxygen and argon, and the flow rate of the carrier gas is 50-400 sccm.
Preferably, the method further comprises vacuum breaking and constant-temperature constant-humidity post-treatment; the constant temperature and humidity post-treatment is to place the substrate with the deposited coating material in a constant temperature and humidity environment with the temperature of 25-60 ℃ and the humidity of 2-10% for 2-48 h.
Preferably, the thickness of the hydrophobic film is 200-400 nm.
Preferably, the dripping flow rate of the coating material in the heating cup is 0.5-5 ul/s.
Preferably, the hydrophobic membrane has a water contact angle of 90-165 °, preferably greater than 120 °.
Drawings
Fig. 1 shows a hydrophobic angle measurement diagram of the hydrophobic membrane prepared in example 1.
Fig. 2 shows a film thickness test chart of the hydrophobic film prepared in example 1;
FIG. 3 shows a hydrophobic angle measurement plot of the hydrophobic membrane prepared in comparative example 1;
fig. 4 shows a film thickness test chart of the hydrophobic film prepared in comparative example 1;
FIG. 5 shows a hydrophobic angle measurement of the hydrophobic membrane prepared in example 2;
fig. 6 shows a film thickness test chart of the hydrophobic film prepared in example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. Unless otherwise specified, each percentage means a mass percentage.
The following is an exemplary illustration of the method of preparing hydrophobic films by plasma vapor deposition according to the present invention.
And (5) activating the base material. And placing the base material in a reaction chamber, introducing activated gas, starting plasma discharge, and activating the base material to increase the roughness of the surface of the base material so that the coating material is easy to bond on the surface of the base material. The activation treatment is performed under vacuum conditions. The vacuum can be 0.02-0.1 mbar. The activating gas may be at least one of helium, argon, nitrogen, and oxygen. The flow rate of the activating gas is 60-200 sccm. The power source for the plasma discharge may be a radio frequency power source. The power of the power supply is 200-300W. The activating treatment time is 1-5 min.
The material of the substrate includes, but is not limited to, metal, dust-free cloth, glass, silicon wafer, etc. The method of the present invention is not particularly limited to the substrate, i.e., the universality of the substrate is one of the important features of the present invention.
The substrate may be cleaned prior to the activation process. For example, wiping the surface of the substrate with alcohol for 2-3 times, then cleaning with deionized water for 2-3 times, putting into an oven, and drying at constant temperature of 30-40 ℃ until the moisture is dried.
The coating material is vaporized. The coating material has a symmetrical structure and contains silicon. The coating material comprises at least one of hexamethyldisiloxane, hexamethyldisilane, dimethyldimethoxysilane and octamethylcyclotetrasiloxane.
As an example, hexamethyldisilazane (may also be referred to as "hexamethyldisilazane" or "hexamethyldisilazane") is used as the plating material. The structural formula of hexamethyldisilazane is as follows:
it can be seen from this formula that hexamethyldisilazane is a fluorine-free compound. The fluorine-free hexamethyldisilazane is environment-friendly to alkane, does not pollute the environment, and can also avoid the irritation to eyes, nose and mouth of an operator or the corrosion of a mucous membrane system of a respiratory tract caused by a fluorine-containing material in the plasma vapor deposition process. Based on the method, operators can prepare the hexamethyldisilazane hydrophobic film in a safe working environment.
The coating material is vaporized in a heating cup. The dripping flow (adding amount) of the coating material in the heating cup is 0.5-5 ul/s. The specific flow rate can be adjusted according to the target film thickness. The coating material of the structure of the present invention is liable to cause incomplete atomization if the parameters (dropping flow rate) are improperly controlled, and therefore, it is necessary to maintain a proper dropping flow rate. The dripping flow of the coating material in the heating cup is lower than 0.5ul/s, which can cause low dripping amount, the target thickness of the film layer can not be reached and the structure of the film layer is not uniform; the dripping flow of the coating material in the heating cup is higher than 5ul/s, which can cause incomplete atomization and affect the quality of the coating. The heating temperature of the heating cup is 50-100 ℃.
And introducing the vaporized coating material into the reaction cavity, starting a radio frequency power supply, and setting radio frequency power and vacuum degree so as to deposit the coating material on the surface of the substrate to form a hydrophobic film. Plasma wire discharge is characterized in that high voltage is applied to a wire electrode to generate corona discharge, and the high voltage ionizes surrounding gas to form plasma. Since the filament discharge is unstable, the structure of the nanomembrane plated by the filament discharge is not uniform. In order to prepare a hard hydrophobic film with large area, good uniformity and high purity, the invention preferably adopts Microwave Plasma Chemical Vapor Deposition (MPCVD). The discharge mode adopted by the invention is dielectric barrier discharge, vaporized coating materials are filled between two flat electrodes, and when voltage is applied to the two electrodes, the vaporized coating materials are ionized into a plasma form, namely free radical-NH2Or the ions and the surface of the base material generate crosslinking reaction to form a compact crosslinking layer.
In the process, the vaporized coating material is collided to generate high pressureCan generate electrons and active particles, and form free radicals on the surface of the substrate. The surface of the substrate is changed under the action of the plasma. Specifically, plasma polymerization of a substrate surface is divided into three stages: in the first stage, under the action of radio frequency, a large number of electrons obtain energy from an electric field and collide with molecules of a coating material vaporized in a space, and the collided coating material absorbs energy to generate active excited particles; in the second stage, the excited coating material is unstable and decomposed into-H and-CH3The radicals consume the absorbed energy and may dissociate into hydrogen ions or retain energy and stay in a metastable state. Thus, the plasma reacts with-H and-CH3And the like react to form a modified layer and/or the free radicals or ions react on the surface of the substrate to form a dense cross-linked layer. In the process, the coating material with the hydrophobic effect is introduced to the surface of the base material, so that the prepared hydrophobic material has a good hydrophobic effect.
The power supply for providing the plasma is a radio frequency power supply. The power of the power supply is 200-300W. The deposition may be performed by means of pulsed waves. In the deposition process, the temperature of the reaction chamber is controlled at 40-60 ℃, and the vacuum degree is kept between 0.01-0.2mbar, so that the coating material can be completely vaporized in the vacuum state.
The deposition time is 20-40 min. The purpose of controlling the deposition time within the above range is to ensure sufficient radical formation. Ions and free radicals are generated between electrons and the coating material through bombardment collision in the vapor deposition process, sufficient deposition time is favorable for ensuring sufficient bombardment collision times, and further, the formation of a large number of free radicals for promoting coating deposition is ensured.
In some embodiments, the vaporized coating material enters the reaction chamber at a gas inlet section and is drawn out in a vacuum manner from the other end opposite to the gas inlet section. In the process of depositing the coating material, the vaporized coating material is continuously introduced into the reaction cavity, and gas in the reaction cavity is continuously discharged.
And simultaneously introducing auxiliary gas into the reaction chamber as carrier gas while depositing the coating material. The carrier gas includes, but is not limited to, at least one of hydrogen, oxygen, argon. The function of introducing the carrier gas is to open a channel in the plasma and carry and convey the coating material into the plasma device. The flow rate of the carrier gas is 50-400 sccm.
After deposition is completed, vacuum is slowly broken. The vacuum breaking time is 1-5 min. This enables efficient deposition of energetic electrons and active particles on the surface of the substrate.
The preparation method also comprises constant temperature and humidity post-treatment. The specific operation of the constant temperature and humidity post-treatment is to place the substrate with the deposited coating material in a constant temperature and humidity environment for 2-48h at the temperature of 25-60 ℃ and the humidity of 2-10%. The purpose of the post-treatment is to ensure that the sample is isolated from oxygen and moisture in the air, to avoid contamination of the membrane layer, and to further stabilize the hydrophobic membrane by the post-treatment.
The thickness of the hydrophobic film obtained is preferably 200-400 nm. Too thin a film affects the hydrophobicity of the sample, and too thick a film affects the appearance of the sample and increases the cost.
The invention adjusts the performance of the hydrophobic film by optimizing the coating material and adjusting the plasma chemical vapor deposition parameters, and is beneficial to obtaining a coating film with high quality and uniform thickness. For example, controlling the dropping rate can increase the deposition rate of the film on the substrate, and adjusting the temperature of the heating cup can affect the vaporization rate of the coating material, which can affect the thickness and performance of the film.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The method for preparing the hydrophobic film by plasma vapor deposition comprises the following steps:
and (5) activating the base material. And placing the base material in a reaction chamber, introducing activated gas, starting plasma discharge, and activating the base material to increase the roughness of the surface of the base material so that the coating material is easy to bond on the surface of the base material. The activation treatment is performed under vacuum conditions. The vacuum was 0.08 mbar. The activating gas is at least one of helium, argon, nitrogen and oxygen. The flow rate of the activating gas was 100 sccm. The power source for the plasma discharge may be a radio frequency power source. The power of the power supply is 200-300W. The activating treatment time is 1-5 min.
The coating material is vaporized. The coating material is hexamethyl disilazane (amine) alkane. The heating temperature of the heating cup is 50-100 ℃; the dripping flow of the coating material in the heating cup is 3 ul/s.
And introducing the vaporized coating material into the reaction cavity, starting a radio frequency power supply, and setting radio frequency power and vacuum degree so as to deposit the coating material on the surface of the substrate to form a hydrophobic film. The power supply for providing the plasma is a radio frequency power supply. The power supply power is 230W. The deposition is carried out by means of pulsed waves. During the deposition process, the temperature of the reaction chamber is controlled at 40-60 deg.C, and the vacuum degree is maintained at 0.01-0.2 mbar. The deposition time was 30 min.
And simultaneously introducing auxiliary gas into the reaction chamber as carrier gas while depositing the coating material. The carrier gas is at least one of hydrogen, oxygen and argon. The flow rate of the carrier gas was 200 sccm. Under the condition of radio frequency power supply, the carrier gas and the vaporized coating material generate collision reaction to generate high-energy electrons and active particles and form free radicals on the surface of the substrate.
Slowly breaking vacuum for 1-5 min.
And taking out the sample after vacuum breaking, sealing and packaging the sample by using a self-sealing bag, and placing the sample for 24 hours in a constant-temperature and constant-humidity environment with the temperature of 45 ℃ and the humidity of 5% to obtain the hydrophobic film with the film thickness of 307.38 nm.
Fig. 1 shows a hydrophobic angle measurement of the hydrophobic membrane of example 1, the hydrophobic angle of the hydrophobic membrane being 147.277 °.
Fig. 2 shows a film thickness test chart of the water-repellent film of example 1, and the film thickness was uniform.
Comparative example 1
The method for preparing the hydrophobic film by plasma vapor deposition comprises the following steps:
and (5) activating the base material. And placing the base material in a reaction chamber, introducing activated gas, starting plasma discharge, and activating the base material to increase the roughness of the surface of the base material so that the coating material is easy to bond on the surface of the base material. The activation treatment is performed under vacuum conditions. The vacuum was 0.08 mbar. The activating gas is at least one of helium, argon, nitrogen and oxygen. The flow rate of the activating gas was 100 sccm. The power source for the plasma discharge may be a radio frequency power source. The power of the power supply is 200-300W. The activating treatment time is 1-5 min.
The coating material is vaporized. The coating material is 3-aminopropyl triethoxysilane. The heating temperature of the heating cup is 50-100 ℃; the dripping flow of the coating material in the heating cup is 3 ul/s.
And introducing the vaporized coating material into the reaction cavity, starting a radio frequency power supply, and setting radio frequency power and vacuum degree so as to deposit the coating material on the surface of the substrate to form a hydrophobic film. The power supply providing the plasma is a radio frequency power supply. The power supply power is 230W. The deposition is carried out by means of pulsed waves. During the deposition process, the temperature of the reaction chamber is controlled at 40-60 deg.C, and the vacuum degree is maintained at 0.01-0.2 mbar. The deposition time was 30 min.
And simultaneously introducing auxiliary gas into the reaction chamber as carrier gas while depositing the coating material. The carrier gas is at least one of hydrogen, oxygen and argon. The flow rate of the carrier gas was 200 sccm. Under the condition of radio frequency power supply, the carrier gas and the vaporized coating material generate collision reaction to generate high-energy electrons and active particles and form free radicals on the surface of the substrate.
Slowly breaking vacuum for 1-5 min.
And taking out the sample after vacuum breaking, sealing and packaging the sample by using a self-sealing bag, and placing the sample for 24 hours in a constant-temperature and constant-humidity environment with the temperature of 45 ℃ and the humidity of 5% to obtain a hydrophobic film with the film thickness of 113.40 nm.
The film thickness of comparative example 1 is significantly lower than example 1 for the same deposition parameters. This is because 3-aminopropyltriethoxysilane is more difficult to ionize than hexamethyldisilazane and the deposition rate of the ionized coating material on the substrate becomes slow.
Fig. 3 shows a hydrophobic angle measurement of the hydrophobic film of comparative example 1, the hydrophobic angle of the hydrophobic film was 134.7 °, which is lower than that of the plated film sample of example 1.
Fig. 4 shows a film thickness test chart of the water-repellent film of comparative example 1, the film thickness being relatively uniform.
Example 2
The method for preparing the hydrophobic film by plasma vapor deposition comprises the following steps:
and (5) activating the base material. And placing the base material in a reaction chamber, introducing activated gas, starting plasma discharge, and activating the base material to increase the roughness of the surface of the base material so that the coating material is easy to bond on the surface of the base material. The activation treatment is performed under vacuum conditions. The vacuum was 0.08 mbar. The activating gas is at least one of helium, argon, nitrogen and oxygen. The flow rate of the activating gas was 100 sccm. The power source for the plasma discharge may be a radio frequency power source. The power of the power supply is 200-300W. The activating treatment time is 1-5 min.
The coating material is vaporized. The coating material is hexamethyl disilazane (amine) alkane. The heating temperature of the heating cup is 50-100 ℃; the dripping flow of the coating material in the heating cup is 1 ul/s.
And introducing the vaporized coating material into the reaction cavity, starting a radio frequency power supply, and setting radio frequency power and vacuum degree so as to deposit the coating material on the surface of the substrate to form a hydrophobic film. The power supply for providing the plasma is a radio frequency power supply. The power supply power is 230W. The deposition is carried out by means of pulsed waves. During the deposition process, the temperature of the reaction chamber is controlled at 40-60 deg.C, and the vacuum degree is maintained at 0.01-0.2 mbar. The deposition time was 30 min.
And simultaneously introducing auxiliary gas into the reaction chamber as carrier gas while depositing the coating material. The carrier gas is at least one of hydrogen, oxygen and argon. The flow rate of the carrier gas was 200 sccm. Under the condition of radio frequency power supply, the carrier gas and the vaporized coating material generate collision reaction to generate high-energy electrons and active particles and form free radicals on the surface of the substrate.
Slowly breaking vacuum for 1-5 min.
And taking out the sample after vacuum breaking, sealing and packaging the sample by using a self-sealing bag, and placing the sample for 24 hours in a constant-temperature and constant-humidity environment with the temperature of 45 ℃ and the humidity of 5% to obtain the hydrophobic film with the film thickness of 230.11 nm.
Fig. 5 shows a hydrophobic angle measurement of the hydrophobic membrane of example 2, the hydrophobic angle of the hydrophobic membrane being 131.252 °. The hydrophobic angle of example 2 is significantly lower than that of example 1 because the dropping flow rate is reduced, ionized substances are reduced, and the plating material deposited on the surface of the substrate per unit time is reduced, so that the film layer becomes thin and the hydrophobicity is reduced.
Fig. 6 shows a film thickness test chart of the water-repellent film of example 2, and the film thickness was uniform.
Claims (10)
1. A method for preparing a hydrophobic film by plasma vapor deposition, the method comprising the steps of:
activating the base material;
vaporizing the coating material; the coating material has a symmetrical structure and contains silicon element;
and introducing the vaporized coating material into the reaction cavity, starting a radio frequency power supply, and setting radio frequency power and vacuum degree so as to deposit the coating material on the surface of the substrate to form a hydrophobic film.
2. The method of claim 1, wherein the coating material is at least one of hexamethyldisiloxane, hexamethyldisilane, dimethyldimethoxysilane, octamethylcyclotetrasiloxane.
3. The method according to claim 1 or 2, characterized in that the deposition of the coating material is carried out in the form of pulsed waves; in the deposition process, a power supply for providing plasma is a radio frequency power supply, the power supply power is 200-300W, the temperature of the reaction cavity is controlled at 40-60 ℃, and the vacuum degree is kept between 0.01-0.2 mbar.
4. A method according to any of claims 1 to 3, characterized in that the deposition time is 20-40 min.
5. The method as claimed in any one of claims 1 to 4, characterized in that the coating material is vaporized in a heating cup, the heating temperature of which is 50-100 ℃.
6. The method according to any one of claims 1 to 5, wherein an auxiliary gas is introduced into the reaction chamber as a carrier gas while depositing the coating material, the carrier gas comprising at least one of hydrogen, oxygen and argon, and the flow rate of the carrier gas is 50-400 sccm.
7. The method according to any one of claims 1 to 6, further comprising vacuum breaking and constant temperature and humidity post-treatment; the constant temperature and humidity post-treatment is to place the substrate with the deposited coating material in a constant temperature and humidity environment with the temperature of 25-60 ℃ and the humidity of 2-10% for 2-48 h.
8. The method as claimed in any one of claims 1 to 7, wherein the thickness of the hydrophobic membrane is 200-400 nm.
9. The method according to any one of claims 1 to 8, wherein the dropping flow rate of the coating material in the heating cup is 0.5 to 5 ul/s.
10. Method according to any one of claims 1 to 9, characterized in that the hydrophobic membrane has a water contact angle of 90-165 °, preferably more than 120 °.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115569819A (en) * | 2022-08-31 | 2023-01-06 | 宁波大学 | Underwater super-oleophylic surface functional coating and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN214782134U (en) * | 2021-02-01 | 2021-11-19 | 江苏菲沃泰纳米科技股份有限公司 | Plasma coating equipment and radio frequency discharge device |
| CN114833045A (en) * | 2021-02-01 | 2022-08-02 | 江苏菲沃泰纳米科技股份有限公司 | PECVD (plasma enhanced chemical vapor deposition) film coating system and film coating method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN214782134U (en) * | 2021-02-01 | 2021-11-19 | 江苏菲沃泰纳米科技股份有限公司 | Plasma coating equipment and radio frequency discharge device |
| CN114833045A (en) * | 2021-02-01 | 2022-08-02 | 江苏菲沃泰纳米科技股份有限公司 | PECVD (plasma enhanced chemical vapor deposition) film coating system and film coating method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115569819A (en) * | 2022-08-31 | 2023-01-06 | 宁波大学 | Underwater super-oleophylic surface functional coating and preparation method and application thereof |
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