CN108554745B - Surface treatment method of DLC film layer - Google Patents
Surface treatment method of DLC film layer Download PDFInfo
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- CN108554745B CN108554745B CN201810260992.XA CN201810260992A CN108554745B CN 108554745 B CN108554745 B CN 108554745B CN 201810260992 A CN201810260992 A CN 201810260992A CN 108554745 B CN108554745 B CN 108554745B
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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
- B05D1/62—Plasma-deposition of organic layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/22—Esters containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/52—Polymerisation initiated by wave energy or particle radiation by electric discharge, e.g. voltolisation
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Abstract
The invention discloses a surface treatment method of a DLC film, which adopts a plasma polymerization deposition technology, wherein a gasified acrylate monomer is introduced into a plasma polymerization reaction cavity, chemical bonds of the monomer are broken under the action of glow discharge to form active groups to generate plasma polymerization reaction on the surface of the DLC film, and a corrosion-resistant micron or nanometer hole sealing film is formed on the surface of the DLC film by cohesion and deposition in micropores in the DLC film, so that the defects of the DLC film are overcome, and the corrosion resistance of the DLC film is improved.
Description
Technical Field
The invention relates to the technical field of functional film layer modification, in particular to a surface treatment method of a DLC film layer.
Background
Mixed sp contained in DLC film2And sp3The bond is amorphous, has the property similar to a diamond film, has high hardness, low friction coefficient, wear resistance, good chemical stability, thermal conductivity, electrical insulation, light transmittance, biocompatibility and the like, and has wide application prospect in the fields of machinery, electronics, optics, acoustics, computers, aerospace, biomedicine and the like.
Although the DLC film layer has certain corrosion resistance, the DLC film layer prepared usually has a plurality of pinhole-shaped micropores, and corrosive media easily enter a substrate through the micropores to corrode the substrate, so that the performance of the film layer is greatly reduced. In addition, in order to increase the bonding force of the DLC film layer to the substrate, the substrate is usually subjected to a cleaning treatment before depositing the DLC film layer on the substrate surface, but the treatment may damage the oxide film on the substrate surface, thereby reducing the corrosion resistance of the substrate.
Therefore, a method capable of sealing micropores in the DLC film layer without affecting the excellent properties of the DLC film layer is urgently required to improve the corrosion resistance of the DLC film layer.
Disclosure of Invention
Aiming at the technical current situation, after a large number of experiments and researches, the inventor discovers that a plasma polymerization deposition technology is adopted, gasified acrylate monomers are introduced into a plasma polymerization reaction cavity, plasma polymerization reaction is carried out on the surface of a DLC film layer, a hole-sealing film layer can be deposited on the surface of the DLC film layer, and therefore the performance of the DLC film layer is improved, and particularly the corrosion resistance of the DLC film layer is greatly improved.
Namely, the technical scheme of the invention is as follows: a surface treatment method of DLC film layer adopts plasma polymerization deposition technology, and gasified acrylate monomers are introduced into a plasma polymerization reaction cavity to generate plasma polymerization reaction on the surface of the DLC film layer.
The method for gasifying the acrylate monomer comprises the following steps: the acrylic ester monomer is put into a feeding tank which is communicated with a heating system, so that the acrylic ester monomer is changed into a gaseous state at the temperature of 90-150 ℃.
The acrylic ester monomer is preferably a fluorine-containing acrylic ester monomer.
As one implementation mode, the plasma polymerization deposition process is as follows: placing a DLC film layer in a plasma polymerization reaction cavity, firstly vacuumizing the cavity, then introducing a gasified acrylate monomer, controlling the gas flow, and breaking the chemical bonds of the monomer under the action of glow discharge to form active groups to perform plasma polymerization reaction on the surface of the DLC film layer.
Preferably, the base pressure of the vacuum chamber is 15 to 25mTorr, more preferably 20 to 25 mTorr.
Preferably, the gaseous monomer is carried into the vacuum chamber using nitrogen gas pressure.
Preferably, the flow rate of the acrylate monomer is 5sccm to 9sccm, more preferably 5sccm to 7 sccm.
Preferably, the pressure in the vacuum reaction chamber after the introduction of the monomer is adjusted to 30mTorr to 40 mTorr.
The power is preferably 20W-35W, more preferably 20W-30W.
The polymerization time is preferably from 60s to 2400s, more preferably from 300s to 1200 s.
The DLC film layer structure is not limited and comprises a single-layer structure and a multi-layer structure. The DLC film layer material comprises a pure DLC material, a DLC material containing a doping element and the like.
The preparation method of the DLC film layer is not limited and comprises a magnetron sputtering technology and the like.
The DLC film layer is generally positioned on the surface of a substrate, and the substrate is made of an unlimited material and comprises stainless steel and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the plasma polymerization deposition technology is a surface treatment method with simple, convenient and fast process and cleanness, and is characterized in that radio frequency low-pressure glow discharge generates energy of about 5eV, molecular covalent bonds (4eV) are broken, and the monomers are polymerized by utilizing active particles such as electrons, particles, free radicals and other excited-state molecules in the plasma.
(2) The method is characterized in that an acrylate monomer is adopted, and is gasified and then subjected to glow discharge to generate plasma, so that chemical bonds of the gaseous monomer are broken to generate active groups, and the active groups are polymerized and deposited on the surface of the DLC film layer including micropores to form a corrosion-resistant micron-scale or nanometer-scale hole sealing film, so that the defects of the DLC film layer are overcome, and the corrosion resistance of the DLC film layer is improved;
(3) the invention has simple and convenient operation process, high timeliness, low energy consumption and thin film layer, improves the corrosion resistance of the DLC film layer under the condition of not influencing the original various excellent properties of the DLC film layer, and improves the corrosion resistance by one order of magnitude.
Drawings
FIG. 1 shows the surface morphology of a DLC film layer before plasma polymerization in example 1 of the present invention;
FIG. 2 is the surface morphology of the DLC film layer after plasma polymerization observed by a confocal laser microscope in example 1;
FIG. 3 is a polarization curve of an electrochemical corrosion test conducted on a DLC film layer before and after plasma polymerization treatment in example 1 of the present invention at 3.5% NaCl;
FIG. 4 is an impedance diagram of an electrochemical corrosion test conducted on a DLC film layer before and after plasma polymerization treatment in example 1 of the present invention with 3.5% NaCl.
Detailed Description
The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention without limiting it in any way.
Example 1:
and putting the fluorine-containing acrylate monomer into a feeding tank, and heating the feeding tank by communicating with a heating system to heat the acrylate monomer until the acrylate monomer is gasified.
The DLC film is arranged in a working cavity of the plasma polymerization system and is arranged on an object stage in the working cavity; firstly, a working cavity is vacuumized to 20mTorr, then, helium gas is used as carrier gas to introduce gasified acrylate monomer into the working cavity, the monomer flow is set to be 9sccm, the pressure in the working cavity is set to be 40mTorr, the discharge power is 35W, plasma polymerization reaction occurs on the surface of a DLC film layer, and the polymerization deposition lasts 2400 s.
FIGS. 1 and 2 show the surface morphology of the DLC film before and after the plasma polymerization treatment, which was observed by a confocal laser microscope, showing that a large number of pinhole-shaped micropores were present on the surface of the DLC film before the treatment, and the number of micropores on the surface of the DLC film was greatly reduced after the plasma polymerization treatment.
FIGS. 3 and 4 show the polarization curve and impedance curve of the electrochemical corrosion test of the DLC film with 3.5% NaCl before and after the plasma polymerization treatment, from which it can be seen that the corrosion current density of the DLC film layer is reduced to 8.124X 10 after the plasma polymerization treatment-10A/cm2Compared with the substrate without the coating, the corrosion resistance of the film layer after the plasma polymerization treatment is greatly improved by about two orders of magnitude.
Example 2:
and putting the fluorine-containing acrylate monomer into a feeding tank, and heating the feeding tank by communicating with a heating system to heat the acrylate monomer until the acrylate monomer is gasified.
The DLC film is arranged in a working cavity of the plasma polymerization system and is arranged on an object stage in the working cavity; firstly, a working cavity is vacuumized to 25mTorr, then, helium gas is used as carrier gas to introduce gasified acrylate monomer into the working cavity, the monomer flow is set to be 8sccm, the pressure in the working cavity is set to be 35mTorr, the discharge power is 35W, plasma polymerization reaction occurs on the surface of a DLC film layer, and the polymerization deposition lasts for 1200 s.
The surface morphology of the DLC film before and after the plasma polymerization treatment, as observed by a confocal laser microscope, was similar to the comparison result in example 1, and it was shown that a large number of pin-hole-shaped micropores were present on the surface of the DLC film before the treatment, and the number of micropores on the surface of the DLC film was greatly reduced after the plasma polymerization treatment.
The comparison result of the polarization curve and the impedance curve of the DLC film in the electrochemical corrosion test with 3.5% NaCl before and after the plasma polymerization treatment in example 1 shows that the corrosion current density of the DLC film is reduced and the corrosion resistance is greatly improved after the plasma polymerization treatment.
Example 3:
and putting the fluorine-containing acrylate monomer into a feeding tank, and heating the feeding tank by communicating with a heating system to heat the acrylate monomer until the acrylate monomer is gasified.
The DLC film is arranged in a working cavity of the plasma polymerization system and is arranged on an object stage in the working cavity; firstly, a working cavity is vacuumized to 25mTorr, then, helium gas is used as carrier gas to introduce gasified acrylate monomer into the working cavity, the monomer flow is set to be 7sccm, the pressure in the working cavity is set to be 30mTorr, the discharge power is 25W, plasma polymerization reaction occurs on the surface of a DLC film layer, and the polymerization deposition lasts for 600 s.
The surface morphology of the DLC film before and after the plasma polymerization treatment, as observed by a confocal laser microscope, was similar to the comparison result in example 1, and it was shown that a large number of pin-hole-shaped micropores were present on the surface of the DLC film before the treatment, and the number of micropores on the surface of the DLC film was greatly reduced after the plasma polymerization treatment.
The comparison result of the polarization curve and the impedance curve of the DLC film in the electrochemical corrosion test with 3.5% NaCl before and after the plasma polymerization treatment in example 1 shows that the corrosion current density of the DLC film is reduced and the corrosion resistance is greatly improved after the plasma polymerization treatment.
Example 4:
and putting the fluorine-containing acrylate monomer into a feeding tank, and heating the feeding tank by communicating with a heating system to heat the acrylate monomer until the acrylate monomer is gasified.
The DLC film is arranged in a working cavity of the plasma polymerization system and is arranged on an object stage in the working cavity; firstly, a working cavity is vacuumized to 25mTorr, then helium is used as carrier gas to introduce gasified acrylate monomer into the working cavity, the monomer flow is set to 7sccm, the pressure in the working cavity is set to 30mTorr, the discharge power is 20W, plasma polymerization reaction is carried out on the surface of a DLC film layer, and the polymerization deposition lasts for 120 s.
The surface morphology of the DLC film before and after the plasma polymerization treatment, as observed by a confocal laser microscope, was similar to the comparison result in example 1, and it was shown that a large number of pin-hole-shaped micropores were present on the surface of the DLC film before the treatment, and the number of micropores on the surface of the DLC film was greatly reduced after the plasma polymerization treatment.
The comparison result of the polarization curve and the impedance curve of the DLC film in the electrochemical corrosion test with 3.5% NaCl before and after the plasma polymerization treatment in example 1 shows that the corrosion current density of the DLC film is reduced and the corrosion resistance is greatly improved after the plasma polymerization treatment.
Example 5:
and putting the fluorine-containing acrylate monomer into a feeding tank, and heating the feeding tank by communicating with a heating system to heat the acrylate monomer until the acrylate monomer is gasified.
The DLC film is arranged in a working cavity of the plasma polymerization system and is arranged on an object stage in the working cavity; firstly, a working cavity is vacuumized to 25mTorr, then, helium gas is used as carrier gas to introduce gasified acrylate monomer into the working cavity, the monomer flow is set to be 8sccm, the pressure in the working cavity is set to be 40mTorr, the discharge power is 35W, plasma polymerization reaction occurs on the surface of a DLC film layer, and the polymerization deposition lasts for 60 s.
The surface morphology of the DLC film before and after the plasma polymerization treatment, as observed by a confocal laser microscope, was similar to the comparison result in example 1, and it was shown that a large number of pin-hole-shaped micropores were present on the surface of the DLC film before the treatment, and the number of micropores on the surface of the DLC film was greatly reduced after the plasma polymerization treatment.
The comparison result of the polarization curve and the impedance curve of the DLC film in the electrochemical corrosion test with 3.5% NaCl before and after the plasma polymerization treatment in example 1 shows that the corrosion current density of the DLC film is reduced and the corrosion resistance is greatly improved after the plasma polymerization treatment.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for reducing micropores on the surface of a DLC film layer is characterized by comprising the following steps: introducing the gasified acrylate monomer into a plasma polymerization reaction cavity by adopting a plasma polymerization deposition technology, and breaking chemical bonds of the monomer under the action of glow discharge to form active groups to generate plasma polymerization reaction on the surface of the DLC film layer;
the flow rate of the acrylate monomer is 5sccm-9 sccm;
after the monomer is introduced, the air pressure in the vacuum reaction cavity is adjusted to 30mTorr-40 mTorr;
the power is 20W-35W; the polymerization reaction time is 60s-2400 s;
the corrosion resistance of the DLC film layer after reaction is improved by one order of magnitude.
2. The method of claim 1, further comprising: the acrylic ester monomer is put into a feeding tank which is communicated with a heating system, so that the acrylic ester monomer is changed into a gaseous state at the temperature of 90-150 ℃.
3. The method of claim 1, further comprising: the acrylic ester monomer is a fluorine-containing acrylic ester monomer.
4. A method as claimed in claim 1, 2 or 3, characterized by: placing a DLC film layer in the plasma polymerization reaction cavity, firstly vacuumizing the cavity, and then introducing a gasified acrylate monomer.
5. The method of claim 4, wherein: the base pressure of the vacuum chamber is 15-25 mTorr.
6. The method of claim 5, wherein: the base pressure of the vacuum chamber is 20-25 mTorr.
7. The method of claim 4, wherein: gaseous monomers were brought into the vacuum chamber using nitrogen gas pressure.
8. The method of claim 4, wherein: the flow rate of the acrylate monomer is 5sccm-7 sccm.
9. The method of claim 4, wherein: the power is 20W-30W.
10. The method of claim 4, wherein: the polymerization reaction time is 300s-1200 s.
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| CN113667976A (en) * | 2021-08-27 | 2021-11-19 | 中国科学院兰州化学物理研究所 | Corrosion-resistant DLC film with hole sealing top layer and preparation method thereof |
Citations (4)
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| CN106868473A (en) * | 2017-01-23 | 2017-06-20 | 无锡荣坚五金工具有限公司 | A kind of preparation method of gradient reduction structure liquid-proof coating |
| CN106906456A (en) * | 2017-01-23 | 2017-06-30 | 无锡荣坚五金工具有限公司 | A kind of preparation method of the controllable coating of the degree of cross linking |
| CN107058981A (en) * | 2017-01-23 | 2017-08-18 | 无锡荣坚五金工具有限公司 | A kind of low adhesion, the preparation method of anti-corrosion coating |
| CN107058980A (en) * | 2017-01-23 | 2017-08-18 | 无锡荣坚五金工具有限公司 | A kind of preparation method on dust-proof surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106868473A (en) * | 2017-01-23 | 2017-06-20 | 无锡荣坚五金工具有限公司 | A kind of preparation method of gradient reduction structure liquid-proof coating |
| CN106906456A (en) * | 2017-01-23 | 2017-06-30 | 无锡荣坚五金工具有限公司 | A kind of preparation method of the controllable coating of the degree of cross linking |
| CN107058981A (en) * | 2017-01-23 | 2017-08-18 | 无锡荣坚五金工具有限公司 | A kind of low adhesion, the preparation method of anti-corrosion coating |
| CN107058980A (en) * | 2017-01-23 | 2017-08-18 | 无锡荣坚五金工具有限公司 | A kind of preparation method on dust-proof surface |
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