CN111378968A - Anti-corrosion nano coating and plasma preparation method thereof - Google Patents
Anti-corrosion nano coating and plasma preparation method thereof Download PDFInfo
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- CN111378968A CN111378968A CN202010301722.6A CN202010301722A CN111378968A CN 111378968 A CN111378968 A CN 111378968A CN 202010301722 A CN202010301722 A CN 202010301722A CN 111378968 A CN111378968 A CN 111378968A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The invention relates to an anti-corrosion nano coating and a plasma preparation method thereof, wherein the preparation method comprises the following steps: (1) treating the base material at low temperature, then placing the base material in a dielectric barrier discharge plasma generating area, and introducing a first path of gas as discharge gas; (2) introducing a monomer by taking the second path of gas as a carrier gas, and starting plasma discharge in a filament discharge mode; the monomer component at least comprises a liquid compound containing fluorine or organic silicon. The invention overcomes the technical prejudice, utilizes unstable filament discharge plasma to atomize and deposit the monomer on the surface of the substrate, and further enables the nano coating to be dispersed and atomized due to the larger temperature difference between the low temperature of the substrate and the high temperature of the filament discharge, thereby forming the anti-corrosion coating with high haze. The preparation process is green and environment-friendly, no wastewater and waste chemical reagents are generated, and the preparation method is simple and easy to implement.
Description
Technical Field
The invention belongs to the field of surface protection, and particularly relates to an anti-corrosion nano coating and a plasma preparation method thereof.
Background
The material or device is extremely easy to be corroded by acid, alkali, salt and the like in special or extreme environment, and the original performance of the material is damaged. In order to improve the reliability of materials and devices, a nano-coating is often deposited or coated on the surface of the material. In recent years, numerous techniques have been used to achieve corrosion protection of materials. In particular, the preparation of nano-coating by using plasma technology is more importantly developed.
With the rapid development of the electronic information industry, optical base materials, especially polymer-based thin film materials, are widely used. In practice, corrosion protection is also required for such materials. At the same time, such materials need to have high haze while maintaining high light transmission. Chinese patent CN201810445739.1 discloses a liquid organic silicon coating with high light transmittance and high haze and a preparation method thereof, and the components of the coating comprise: methyl vinyl silicone oil, Pt catalyst, inhibitor, nano silicon dioxide, rod-shaped nano material, silane coupling agent and the like. However, such coatings are complex in composition and thick to coat and are not suitable for flexible substrate materials.
In view of the problems of the prior art, if a nano coating having both corrosion resistance and high haze can be prepared by using a plasma technology, a substantial technical progress will be motivated.
Disclosure of Invention
The invention aims to provide a high-haze anti-corrosion nano coating and a plasma preparation method thereof, which can improve the light diffusivity of a transparent base material and ensure the anti-corrosion performance of the transparent base material under the normal pressure condition.
The invention discloses a high-haze plasma anti-corrosion nano coating and a preparation method thereof, which are characterized in that the high-haze plasma anti-corrosion nano coating is deposited on the surface of a base material in a mist form instead of a continuous film formed by plasma chemical vapor deposition under the normal pressure condition by utilizing the filamentous characteristic of plasma discharge.
One aspect of the invention provides a preparation method of an anti-corrosion nano coating, which comprises the following steps:
(1) treating the base material at low temperature, then placing the base material in a dielectric barrier discharge plasma generating area, and introducing a first path of gas as discharge gas;
(2) and (3) taking the gas in the second path as a carrier gas, introducing the liquid monomer, and starting plasma discharge in a filament discharge mode.
In the technical scheme of the invention, the power of the discharge in the step (2) is 500-2000W.
In the technical scheme of the invention, the discharging time in the step (2) is 1min-8min, preferably 2min-5 min.
In the technical scheme of the invention, the temperature of the low-temperature treatment in the step (1) is below 0 ℃. Preferably-5 ℃ or lower, more preferably-10 ℃ or lower.
In the technical scheme of the invention, the structure of the dielectric barrier discharge is selected from a flat plate type and a pipeline type.
In the technical scheme of the invention, the dielectric barrier discharge adopts a high-frequency power supply, preferably a radio-frequency power supply.
In the technical scheme of the invention, the flow of the discharge gas is 1-5 slm.
In the technical scheme of the invention, the flow rate of the liquid monomer is 1-5 mL/min.
In the technical scheme of the invention, the discharge gas is selected from air, oxygen, argon and nitrogen, and is preferably air.
In the technical scheme of the invention, the carrier gas is selected from air, oxygen, argon and nitrogen, and is preferably air.
In the technical scheme of the invention, the liquid monomer at least comprises a fluorine-containing or organosilicon liquid compound,
preferably, the organosilicon is a liquid organosilicon monomer with a double bond, Si-Cl, Si-O-C, Si-N-Si, Si-O-Si structure or a ring structure,
preferably, the organosilicon is tetramethoxysiloxane, tetraethoxysiloxane, hexamethyldisiloxane, tetraethoxysilane, tetramethoxysilane, hexamethyldisilazane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethyldisiloxane, n-octyltriethoxysilane, vinyltriethoxysilane, trimethoxyhydrosiloxane, phenyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, triethylvinylsilane, hexaethylcyclotrisiloxane, 3- (methacryloyloxy) propyltrimethoxysilane, phenyltris (trimethylsiloxy) silane, diphenyldiethoxysilane, dodecyltrimethoxysilane, hexamethyldisilazane, and the like, N-octyltriethoxysilane, dimethoxysilane, 3-chloropropyltrimethoxysilane, triphenylchlorosilane, methylvinyldichlorosilane, trifluoropropyltrichlorosilane, trifluoropropylmethyldichlorosilane, dimethylphenylchlorosilane, tributylchlorosilane, benzyldimethylchlorosilane, hexamethyldisilazane, hexamethylcyclotrisilylamino, hexamethyldisilazane, hexamethyldisiloxane.
Preferably, the fluorine-containing liquid compound is a fluorosilane compound or a fluorine-containing acrylate monomer.
More preferred are dodecafluoroheptylpropyltrimethoxysilane, dodecafluoroheptylpropylmethyldimethoxysilane, tridecafluoroctyltrimethoxysilane, 4-methyl- (perfluorohexylethyl) propyltrimethoxysilane, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluoroctyl acrylate and tridecafluoroctyl methacrylate.
In the technical scheme of the invention, the substrate is selected from inorganic substrates or organic substrates, and is preferably an organic high molecular polymer film.
In another aspect, the invention provides an anti-corrosion nano coating prepared by the method.
In the technical scheme of the invention, the thickness of the nano coating is less than 800nm, preferably 200-500 nm.
In the technical scheme of the invention, the haze is higher than 50%, preferably, higher than 70%, and more preferably, 70% -90%
In another aspect of the invention, a substrate having a corrosion-inhibiting nanocoating obtained by the method of the invention is provided.
The method of the invention adopts a plasma wire-shaped discharge method for the first time to realize the formation of the high-haze nano coating on the surface of the substrate, although the scheme of carrying out surface nano coating deposition preparation by using a plasma technology exists in the prior art, the wire-shaped discharge is generally considered to be unstable, the prepared nano coating is not uniform, and the wire-shaped discharge mode is avoided. However, the present invention has surprisingly found that the mist deposition of the nano-coating can be realized by utilizing the unstable state of the nano-coating in the filament discharge treatment, so that the preparation of the high-haze coating can be realized on the surface of the optical material such as the high molecular film material. Meanwhile, the base material is subjected to low-temperature treatment before plasma treatment, so that the temperature difference is increased, and the dispersion atomization effect of the nano coating is further enhanced. More importantly, the increase of the haze can obviously improve the corrosion prevention effect of the coating.
Has the advantages that:
the invention overcomes the technical prejudice, utilizes unstable filament discharge plasma to atomize and deposit the liquid monomer on the surface of the matrix, and further leads the nano coating to be dispersed and atomized due to the larger temperature difference between the low temperature of the matrix and the high temperature of the filament discharge, thereby forming the anti-corrosion coating with high haze. The preparation process is green and environment-friendly, no wastewater and waste chemical reagents are generated, and the preparation method is simple and easy to implement.
The method is novel, unique, simple and efficient, and the preparation of the high-haze anti-corrosion nano coating is realized by designing the plasma discharge and the nano coating preparation process.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below, but the present invention is not to be construed as being limited to the implementable range thereof.
Example 1
Selecting a polycarbonate film as a substrate, storing the substrate in an environment with the temperature of-10 ℃ for 30min, then placing the substrate in a flat-plate type dielectric barrier discharge plasma region, introducing air at the flow rate of 1slm, introducing tetramethoxysilane at the flow rate of 2mL/min, turning on a radio frequency power supply, adjusting the discharge power to be 1000W, and discharging for 2min to obtain the nano coating with the thickness of 300 nm. The haze of the film is 80.5% and the salt corrosion resistance is 70 h.
Example 2
Selecting a polyester film as a base material, storing the base material in an environment with the temperature of-15 ℃ for 20min, then placing the base material in a pipeline type dielectric barrier discharge plasma region, introducing air at the flow rate of 2slm, introducing tetraethoxysilane at the flow rate of 5mL/min, turning on a radio frequency power supply, adjusting the discharge power to 1200W, and discharging for 3min to obtain the nano coating with the thickness of 600 nm. The haze of the film is 90.6% and the film is resistant to acid corrosion for 12 h.
Example 3
Selecting a polymethyl methacrylate film as a base material, placing the base material in an environment with the temperature of-20 ℃ for storage for 12min, then placing the base material in a dielectric barrier discharge plasma jet region, introducing air at the flow rate of 3slm, introducing tetramethoxysilane at the flow rate of 5mL/min, turning on a radio frequency power supply, adjusting the discharge power to 800W, and discharging for 5min to obtain the nano coating with the thickness of 500 nm. The haze of the film is 88.2% and the film is resistant to alkali corrosion for 15 h.
Example 4
Selecting a polycarbonate film as a substrate, storing the substrate in an environment with the temperature of-10 ℃ for 30min, then placing the substrate in a flat-plate type dielectric barrier discharge plasma region, introducing argon at the flow rate of 1slm, introducing tetramethoxysilane at the flow rate of 2mL/min, turning on a radio frequency power supply, adjusting the discharge power to be 1000W, and discharging for 2min to obtain the nano coating with the thickness of 300 nm. The haze of the film is 65.5% through testing, and the salt corrosion resistance is 60 h.
Example 5
Selecting a polycarbonate film as a substrate, storing the substrate in an environment with the temperature of-10 ℃ for 30min, then placing the substrate in a flat-plate dielectric barrier discharge plasma region, introducing air at the flow rate of 1slm, introducing hexamethyldisiloxane at the flow rate of 2mL/min, turning on a radio frequency power supply, adjusting the discharge power to be 1000W, and discharging for 2min to obtain the nano coating with the thickness of 300 nm. The haze of the film is 82.4% and the salt corrosion resistance is 65 h.
Claims (10)
1. A preparation method of an anti-corrosion nano coating comprises the following steps:
(1) treating the base material at low temperature, then placing the base material in a dielectric barrier discharge plasma generating area, and introducing a first path of gas as discharge gas;
(2) introducing a liquid monomer by taking the second path of gas as a carrier gas, and starting plasma discharge in a filament discharge mode;
the liquid monomer component at least comprises a liquid compound containing fluorine or organic silicon.
2. The process according to claim 1, wherein the temperature of the low-temperature treatment in the step (1) is 0 ℃ or less, preferably-5 ℃ or less.
3. The method of claim 1, wherein the discharge gas is selected from the group consisting of air, oxygen, argon, and nitrogen, preferably at a flow rate of 1 to 5 slm.
4. The method as set forth in claim 1, wherein the flow rate of the liquid monomer is 1000-.
5. The method according to claim 1, wherein the power of the discharge in the step (2) is 500W to 2000W.
6. The method according to claim 1, wherein the dielectric barrier discharge is performed using a high frequency power source, preferably a radio frequency power source.
7. The method according to claim 1, wherein the liquid compound of organosilicon is a liquid organosilicon monomer having a double bond, Si-Cl, Si-O-C, Si-N-Si, Si-O-Si structure or a cyclic structure,
preferably tetramethoxysiloxane, tetraethoxysiloxane, hexamethyldisiloxane, tetraethoxysilane, tetramethoxysilane, hexamethyldisilazane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethyldisiloxane, n-octyltriethoxysilane, vinyltriethoxysilane, trimethoxyhydrosiloxane, phenyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, triethylvinylsilane, hexaethylcyclotrisiloxane, 3- (methacryloyloxy) propyltrimethoxysilane, phenyltris (trimethylsiloxy) silane, diphenyldiethoxysilane, dodecyltrimethoxysilane, n-octyltriethoxysilane, dimethoxysilane, 3-chloropropyltrimethoxysilane, triphenylchlorosilane, methylvinyldichlorosilane, trifluoropropyltrichlorosilane, trifluoropropylmethyldichlorosilane, dimethylphenylchlorosilane, tributylchlorosilane, benzyldimethylchlorosilane, hexamethyldisilazane, hexamethylcyclotrisilylamino, hexamethyldisilazane, hexamethyldisiloxane;
the fluorine-containing liquid compound is a fluorosilane compound and a fluorine-containing acrylate monomer,
preferred are dodecafluoroheptylpropyltrimethoxysilane, dodecafluoroheptylpropylmethyldimethoxysilane, tridecafluoroctyltrimethoxysilane, 4-methyl- (perfluorohexylethyl) propyltrimethoxysilane, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluoroctyl acrylate and tridecafluoroctyl methacrylate.
8. The method according to claim 1, wherein the discharge time in step (2) is 1min to 8min, preferably 2min to 5 min.
9. The anti-corrosion nanocoating produced according to the production method of any one of claims 1 to 7; preferably, the nanolayered coating thickness is 800nm or less, more preferably 200-500 nm.
10. A substrate provided with an anti-corrosion nanocoating obtained by the process according to any one of claims 1-7; preferably, the nanolayered coating thickness is 800nm or less, more preferably 200-500 nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022247633A1 (en) * | 2021-05-26 | 2022-12-01 | 江苏菲沃泰纳米科技股份有限公司 | Plasma polymerisation coating, preparation method, and device |
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| US5660895A (en) * | 1996-04-24 | 1997-08-26 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Low-temperature plasma-enhanced chemical vapor deposition of silicon oxide films and fluorinated silicon oxide films using disilane as a silicon precursor |
| US20130181331A1 (en) * | 2010-09-28 | 2013-07-18 | Ndsu Research Foundation | Atmospheric-pressure plasma-enhanced chemical vapor deposition |
| CN104284997A (en) * | 2012-03-09 | 2015-01-14 | 气体产品与化学公司 | Methods for making silicon containing films on thin film transistor devices |
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| WO2022247633A1 (en) * | 2021-05-26 | 2022-12-01 | 江苏菲沃泰纳米科技股份有限公司 | Plasma polymerisation coating, preparation method, and device |
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