CN108554745A - A kind of surface treatment method of DLC film layer - Google Patents
A kind of surface treatment method of DLC film layer Download PDFInfo
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- CN108554745A CN108554745A CN201810260992.XA CN201810260992A CN108554745A CN 108554745 A CN108554745 A CN 108554745A CN 201810260992 A CN201810260992 A CN 201810260992A CN 108554745 A CN108554745 A CN 108554745A
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- film layer
- dlc film
- treatment method
- surface treatment
- monomer
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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
-
- 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
-
- 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
Abstract
The present invention discloses a kind of surface treatment method of DLC film layer, using plasma aggregation deposition technology, the acrylic ester monomer of gasification is passed through plasma polymerization intracavitary, so that monomer chemistries key is broken to form active group under glow discharge effect and plasma polymerization occurs in DLC film layer surface, in DLC film layer surface, the micropore cohesion being included therein merges deposition and forms one layer of micron with corrosion resistance or nano level sealing of hole film, to compensate for the defect of DLC film layer, the corrosion resistance of DLC film layer is improved.
Description
Technical field
The present invention relates to functional film layer technical field of modification, and in particular to a kind of surface treatment method of DLC film layer.
Background technology
Contain mixed sp in DLC film2And sp3Key, and be unsetting, property is similar to diamond thin, has
Hardness is high, friction coefficient is low, wearability and has both good chemical stability, thermal conductivity, electrical insulating property, translucency and biology
Compatibility etc. makes it have in fields such as machinery, electronics, optics, acoustics, computer, aerospace and biomedicines extensive
Application prospect.
Although DLC film layer has certain corrosion resistance, there are some Pinhole-shapeds for DLC film layer usually obtained
Micropore, Korrosionsmedium easily enter substrate to cause to corrode to substrate by micropore, the performance of film layer are made to substantially reduce.Separately
Outside, in order to increase the binding force of DLC film layer and substrate, usually substrate is carried out before substrate surface DLC films deposited layer clear
Processing is washed, but the processing can destroy the oxidation film of substrate surface, to reduce the corrosion resistance of substrate.
Therefore, it is badly in need of a kind of excellent properties that can not influence DLC film layer and the side that micropore in DLC film layer can be closed
Method, to improve the corrosion resistance of DLC film layer.
Invention content
Present situation in view of the above technology, the present inventor have found after many experiments are explored, using plasma aggregation deposition
The acrylic ester monomer of gasification is passed through plasma polymerization intracavitary by technology, and plasma occurs in DLC film layer surface
Polymerisation, can DLC film layer surface deposit can sealing of hole film layer especially make its anti-corruption to improve the performance of DLC film layer
Corrosion can greatly improve.
That is, the technical scheme is that：A kind of surface treatment method of DLC film layer, using plasma aggregation deposition
The acrylic ester monomer of gasification is passed through plasma polymerization intracavitary by technology, and plasma occurs in DLC film layer surface
Polymerisation.
The gasification process of the acrylic ester monomer is：Acrylic ester monomer is put into head tank, head tank connects
Logical heating system, makes acrylic ester monomer become gaseous state at 90 DEG C -150 DEG C.
The acrylic ester monomer is preferably fluorine-containing acrylate monomer.
As a kind of realization method, the plasma polymerization deposition process is：Plasma polymerization intracavitary is put
DLC film layer is set, cavity is vacuumized first, then passes to the acrylic ester monomer of gasification, gas flow is controlled, in brightness
So that monomer chemistries key is broken to form active group under light discharge process and plasma polymerization occurs in DLC film layer surface.
Preferably, the basic air pressure of vacuum cavity is 15-25mTorr, more preferably 20-25mTorr.
Preferably, bringing gaseous monomer into vacuum cavity using nitrogen pressure.
Preferably, the acrylic ester monomer flow is 5sccm-9sccm, more preferably 5sccm-7sccm.
Preferably, being passed through after monomer vacuum reaction intracavitary air pressure adjustment to 30mTorr-40mTorr.
The power is preferably 20W-35W, more preferably 20W-30W.
The polymerization reaction time is preferably 60s-2400s, more preferably 300s-1200s.
The DLC film layer structure is unlimited, including single layer structure and multilayered structure.The DLC film layer material includes pure
DLC materials, and the DLC materials etc. containing doped chemical.
The preparation method of the DLC film layer is unlimited, including magnetron sputtering technique etc..
The DLC film layer is normally at matrix surface, and basis material is unlimited, including stainless steel etc..
Compared with prior art, the present invention has the advantages that：
(1) using plasma aggregation deposition technology, plasma polymerization deposition technology are a kind of simple for process, convenient fast
Prompt, clean surface treatment method is by radio frequency low pressure glow discharge, and the energy of generation is about 5eV, can cause molecule covalent
The fracture of key (4eV) is made using electronics, particle, free radical and other excited state molecule isoreactivity particles in plasma
Monomer polymerization.
(2) acrylic ester monomer is used, plasma is generated by glow discharge after being gasified, makes the change of gaseous monomer
It learns key fracture and generates active group, for active group in DLC film layer surface, the micropore cohesion merging deposition being included therein forms one
Layer has the micron of corrosion resistance or nano level sealing of hole film, to make up the defect of DLC film layer, improves DLC film layer
Corrosion resistance；
(3) operating process of the present invention is easy, timeliness is high, energy consumption is small, and film layer is thin, original various not influencing DLC film layer
The corrosion resistance of DLC film layer is improved under conditions of excellent properties, corrosion resistance improves an order of magnitude.
Description of the drawings
Fig. 1 is that DLC film layer is arrived through confocal laser scanning microscope before plasma polymerization processing in the embodiment of the present invention 1
Surface topography；
Fig. 2 is that DLC film layer confocal laser scanning microscope after plasma polymerization is handled arrives in the embodiment of the present invention 1
Surface topography；
Fig. 3 is that DLC film layer carries out electrochemistry in 3.5%NaCl before and after the processing through plasma polymerization in the embodiment of the present invention 1
The polarization curve of corrosion test；
Fig. 4 is that DLC film layer carries out electrochemistry in 3.5%NaCl before and after the processing through plasma polymerization in the embodiment of the present invention 1
The impedance diagram of corrosion test.
Specific implementation mode
With reference to embodiment, present invention is further described in detail, it should be pointed out that embodiment described below purport
Convenient for the understanding of the present invention, and any restriction effect is not played to it.
Embodiment 1：
Fluorine-containing acrylate monomer is put into head tank, and head tank connection heating system is heated, and acrylate is made
Unit heating extremely gasifies.
DLC film is placed in the working cavity of plasma polymerization system, and is placed on the objective table in working cavity；It is first
First, 20mTorr is evacuated to working cavity, then uses helium that the acrylate monomer of gasification is passed through working chamber as carrier gas
In body, flow of monomer setting is in 9sccm, and work cavity pressure is set as 40mTorr, discharge power 35W, in DLC film layer table
Plasma polymerization, aggregation deposition 2400s occur for face.
Fig. 1,2 be the DLC film that is arrived using confocal laser scanning microscope through above-mentioned plasma polymerization before and after the processing
Surface topography, there are the micropores of a large amount of Pinhole-shapeds for DLC film layer surface before display processing, after the processing of above-mentioned plasma polymerization significantly
Reduce film surface micropore number.
Fig. 3,4 are that the DLC film carries out electrochemical corrosion test in 3.5%NaCl before and after the processing through above-mentioned plasma polymerization
Polarization curve and impedance curve, there it can be seen that after plasma polymerization is handled, the corrosion electric current density of DLC film layer drops
Low, corrosion electric current density is down to 8.124 × 10-10A/cm2, nearly two orders of magnitude are reduced than uncoated substrate, are shown
The corrosion resistance of film layer greatly improves after the processing of above-mentioned plasma polymerization.
Embodiment 2：
Fluorine-containing acrylate monomer is put into head tank, and head tank connection heating system is heated, and acrylate is made
Unit heating extremely gasifies.
DLC film is placed in the working cavity of plasma polymerization system, and is placed on the objective table in working cavity；It is first
First, 25mTorr is evacuated to working cavity, then uses helium that the acrylate monomer of gasification is passed through working chamber as carrier gas
In body, flow of monomer setting is in 8sccm, and work cavity pressure is set as 35mTorr, discharge power 35W, in DLC film layer table
Plasma polymerization, aggregation deposition 1200s occur for face.
Surface shape of the DLC film arrived using confocal laser scanning microscope through above-mentioned plasma polymerization before and after the processing
Looks, the as a result comparing result in similar embodiment 1, there are the micropores of a large amount of Pinhole-shapeds for DLC film layer surface before display processing, through upper
Film surface micropore number is greatly reduced after stating plasma polymerization processing.
The polarization that the DLC film carries out electrochemical corrosion test through above-mentioned plasma polymerization in 3.5%NaCl before and after the processing is bent
Line comparison and the comparing result in impedance curve comparing result embodiment 1, show after plasma polymerization is handled, DLC film layer
Corrosion electric current density reduce, corrosion resistance greatly improves.
Embodiment 3：
Fluorine-containing acrylate monomer is put into head tank, and head tank connection heating system is heated, and acrylate is made
Unit heating extremely gasifies.
DLC film is placed in the working cavity of plasma polymerization system, and is placed on the objective table in working cavity；It is first
First, 25mTorr is evacuated to working cavity, then uses helium that the acrylate monomer of gasification is passed through working chamber as carrier gas
In body, flow of monomer setting is in 7sccm, and work cavity pressure is set as 30mTorr, discharge power 25W, in DLC film layer table
Plasma polymerization, aggregation deposition 600s occur for face.
Surface shape of the DLC film arrived using confocal laser scanning microscope through above-mentioned plasma polymerization before and after the processing
Looks, the as a result comparing result in similar embodiment 1, there are the micropores of a large amount of Pinhole-shapeds for DLC film layer surface before display processing, through upper
Film surface micropore number is greatly reduced after stating plasma polymerization processing.
The polarization that the DLC film carries out electrochemical corrosion test through above-mentioned plasma polymerization in 3.5%NaCl before and after the processing is bent
Line comparison and the comparing result in impedance curve comparing result embodiment 1, show after plasma polymerization is handled, DLC film layer
Corrosion electric current density reduce, corrosion resistance greatly improves.
Embodiment 4：
Fluorine-containing acrylate monomer is put into head tank, and head tank connection heating system is heated, and acrylate is made
Unit heating extremely gasifies.
DLC film is placed in the working cavity of plasma polymerization system, and is placed on the objective table in working cavity；It is first
First, 25mTorr is evacuated to working cavity, then uses helium that the acrylate monomer of gasification is passed through working chamber as carrier gas
In body, flow of monomer setting is in 7sccm, and work cavity pressure is set as 30mTorr, discharge power 20W, in DLC film layer table
Plasma polymerization, aggregation deposition 120s occur for face.
Surface shape of the DLC film arrived using confocal laser scanning microscope through above-mentioned plasma polymerization before and after the processing
Looks, the as a result comparing result in similar embodiment 1, there are the micropores of a large amount of Pinhole-shapeds for DLC film layer surface before display processing, through upper
Film surface micropore number is greatly reduced after stating plasma polymerization processing.
The polarization that the DLC film carries out electrochemical corrosion test through above-mentioned plasma polymerization in 3.5%NaCl before and after the processing is bent
Line comparison and the comparing result in impedance curve comparing result embodiment 1, show after plasma polymerization is handled, DLC film layer
Corrosion electric current density reduce, corrosion resistance greatly improves.
Embodiment 5：
Fluorine-containing acrylate monomer is put into head tank, and head tank connection heating system is heated, and acrylate is made
Unit heating extremely gasifies.
DLC film is placed in the working cavity of plasma polymerization system, and is placed on the objective table in working cavity；It is first
First, 25mTorr is evacuated to working cavity, then uses helium that the acrylate monomer of gasification is passed through working chamber as carrier gas
In body, flow of monomer setting is in 8sccm, and work cavity pressure is set as 40mTorr, discharge power 35W, in DLC film layer table
Plasma polymerization, aggregation deposition 60s occur for face.
Surface shape of the DLC film arrived using confocal laser scanning microscope through above-mentioned plasma polymerization before and after the processing
Looks, the as a result comparing result in similar embodiment 1, there are the micropores of a large amount of Pinhole-shapeds for DLC film layer surface before display processing, through upper
Film surface micropore number is greatly reduced after stating plasma polymerization processing.
The polarization that the DLC film carries out electrochemical corrosion test through above-mentioned plasma polymerization in 3.5%NaCl before and after the processing is bent
Line comparison and the comparing result in impedance curve comparing result embodiment 1, show after plasma polymerization is handled, DLC film layer
Corrosion electric current density reduce, corrosion resistance greatly improves.
Technical scheme of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in the spirit of the present invention,
Supplement or similar fashion replacement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of surface treatment method of DLC film layer, it is characterized in that：Using plasma aggregation deposition technology, by the third of gasification
Olefin(e) acid esters monomer is passed through plasma polymerization intracavitary, so that monomer chemistries key is broken to form activity under glow discharge effect
In DLC film layer surface plasma polymerization occurs for group.
2. the surface treatment method of DLC film layer as described in claim 1, it is characterized in that：By acrylic ester monomer be put into
Batch can, head tank are connected to heating system, acrylic ester monomer are made to become gaseous state at 90 DEG C -150 DEG C.
3. the surface treatment method of DLC film layer as described in claim 1, it is characterized in that：The acrylic ester monomer is
Fluorine-containing acrylate monomer.
4. the surface treatment method of DLC film layer as claimed in claim 1,2 or 3, it is characterized in that：Plasma polymerization chamber
Interior placement DLC film layer, first vacuumizes cavity, then passes to the acrylic ester monomer of gasification.
5. the surface treatment method of DLC film layer as claimed in claim 4, it is characterized in that：The basic air pressure of vacuum cavity is 15-
25mTorr, preferably 20-25mTorr.
6. the surface treatment method of DLC film layer as claimed in claim 4, it is characterized in that：Using nitrogen pressure by gaseous list
Body brings vacuum cavity into.
7. the surface treatment method of DLC film layer as claimed in claim 4, it is characterized in that：The acrylic ester monomer stream
Amount is 5sccm-9sccm, preferably 5sccm-7sccm.
8. the surface treatment method of DLC film layer as claimed in claim 4, it is characterized in that：It is passed through vacuum reaction intracavitary after monomer
Air pressure adjustment is to 30mTorr-40mTorr.
9. the surface treatment method of DLC film layer as claimed in claim 4, it is characterized in that：Power is 20W-35W, more preferably
20W-30W。
10. the surface treatment method of DLC film layer as claimed in claim 4, it is characterized in that：Polymerization reaction time is 60s-
2400s, preferably 300s-1200s.
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| CN201810260992.XA CN108554745B (en) | 2018-03-28 | 2018-03-28 | Surface treatment method of DLC film layer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110129700A (en) * | 2019-06-12 | 2019-08-16 | 阳江十八子刀剪制品有限公司 | A kind of preparation method of high-strength high-ductility titanium alloy material cutter |
| 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)
| 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 |
-
2018
- 2018-03-28 CN CN201810260992.XA patent/CN108554745B/en active Active
Patent Citations (4)
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110129700A (en) * | 2019-06-12 | 2019-08-16 | 阳江十八子刀剪制品有限公司 | A kind of preparation method of high-strength high-ductility titanium alloy material cutter |
| 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 |
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| CN108554745B (en) | 2021-09-28 |
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