CN101376968A - Normal atmosphere plasma strip steel film coating process - Google Patents
Normal atmosphere plasma strip steel film coating process Download PDFInfo
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- CN101376968A CN101376968A CNA2007100452850A CN200710045285A CN101376968A CN 101376968 A CN101376968 A CN 101376968A CN A2007100452850 A CNA2007100452850 A CN A2007100452850A CN 200710045285 A CN200710045285 A CN 200710045285A CN 101376968 A CN101376968 A CN 101376968A
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- film coating
- coating process
- strip steel
- normal atmosphere
- atmosphere plasma
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Abstract
The invention discloses a normal pressure plasma strip steel film coating process; a base plate coil is decoiled and enters into a normal pressure plasma film coating unit; two electrodes are adopted, wherein, a high-voltage electrode is arranged above a steel sheet and covered by a barrier layer; a running base plate is arranged below the high-voltage electrode, grounded or arranged above a grounding electrode, and separated by an insulating substance; AC or DC with the frequency between 200Hz to 20KHz is fed between the two electrodes by feeding an organic precursor and carrier gas thereof with the flow more than 0.01sccm as well as reactant gas with the flow more than 1sccm; a dielectric layer or an insulating layer obstructs the current and produces dielectric discharge; medium obstructs the discharge and generates plasma; the steel sheet is coated with film when passing the plasma area. The whole process is environment protective, can realize a plurality of film coated products, and has simpler process and low investment compared with strip steel vacuum film coating.
Description
Technical field
The present invention relates to the belt steel surface treatment technology, particularly a kind of normal atmosphere plasma strip steel film coating process.
Background technology
Steel plate with excellent surface performance is the critical material of automobile, building and household electric appliances.
Existing band steel coating technique mainly comprises coating process such as pot galvanize, electro-galvanizing, eleetrotinplate, color coating.Usually also comprise pre-process and post-process operations such as chemical pre-treatment and phosphatization, passivation, the plated film of anti-the fingerprint.
In the last few years, market constantly increased the demand with better surface property steel plate, and simultaneously, the user also gets over Gao Yuegao to the performance requriements of coated layer product.The user wishes that the coated layer product can not only satisfy corrosion-resistant, environmental protection consistency, good workability and surface optical performance, can also have performances such as ornamental, anti-scribbling property, fingerprint easy to clean, wear-resistant, anti-, sound insulation, anti-zoned trace; The customer requirements coated layer is more and more thinner, and over-all properties is become better and better.
Vacuum plating has obtained using widely in industries such as electronics, glass, plastics as surface modification and coating process.The vacuum coating technology major advantage is its environmental protection, good film performance and the diversity that can plate material.Environmental protection, multifunction craft as band steel plated film have carried out a lot of research and development.But these technologies all need be carried out in certain vacuum plating.In order to reach required vacuum tightness,, need 7-8 grades multi-stage sealed device, equipment complexity, one-time investment expense height, production maintenance cost costliness especially for the used air to air mode of coil of strip scale operation.Therefore, the next developing direction after the band steel vacuum coating technology is the atmospheric plasma coating technique.
Along with the raising of pressure, the mean free path of electronics shortens, and the quality of film has been subjected to influence.However, the atmospheric plasma coating technique is to the very promising technology of the extensive plated film production of steel industry, compares with traditional hot dip, plating simultaneously, and its film quality also can reach gratifying degree.
Summary of the invention
The object of the present invention is to provide the technology of plasma strip steel film coating under a kind of normal pressure, whole technological process environmental protection can realize multiple plated film product; Compare with the vacuum plating of band steel, technological process is simple, invests low.
For achieving the above object, technical scheme of the present invention is,
A kind of normal atmosphere plasma strip steel film coating process, substrate enter the atmospheric plasma film coating unit after winding off volume; Adopt two electrodes, wherein high voltage electrode is positioned at the top of steel plate, covers with the blocking layer; The substrate of operation is positioned at high voltage electrode below, and substrate ground connection or be positioned at the top of ground-electrode intercepts by megohmite; Feed organic precursor by carrier gas, gas flow is greater than 0.01sccm; And reactant gas, flow adds alternating-current or direct current greater than 1sccm between two electrodes, frequency is between 200Hz-20KHz; Dielectric layer or insulating layer blocks electric current, produce dielectric discharge; Dielectric barrier discharge produces plasma, and steel plate carries out plated film by plasma area the time; The substrate operating rate is between 2～200 meters/minute.
Described substrate is cold-rolled steel coils, galvanized coil, stainless-steel roll or organic precoated coil of strip.
Again, the frequency of the voltage of alternating current of electrode employing is adjustable in 200Hz arrives the 20kHz scope.
Described blocking layer can be selected quartz, Al for use
2O
3Or stupalith.
Described dielectric barrier discharge is for being in glow discharge, Townsend avalanche or three kinds of states of low-temperature plasma; Preferably, dielectric barrier discharge remains in the Townsend avalanche scope.
Described reactant gas adopts helium, nitrogen, argon gas or oxygen.Wherein the feeding amount of reactant gas suppresses metastable ability decision by this gas.
Described organic precursor is HMDSO, HMDS, SiH
4In a kind of.
Again, organic precursor of the present invention is transported to coating system by preheating through carrier gas, reacts.
In the technology of the present invention behind the plated film, heat or cool off.
Under the normal pressure, cold body discharge is made up of at the micro discharges of 100 micron levels a lot of radiuses usually, is easy to into arc.Current density is limited in the certain limit, could produce plasma.Dielectrically impeded discharge is the isoionic method of the easiest realization under the normal pressure, and its discharge characteristics can make forms such as glow discharge, Townsend avalanche, plasma discharge.Usually realize by two interelectrode gas blanket and intermediary solid dielectric layer thereof.Solid dielectric can be taken as the electric capacity that gas gap connects.
Can prevent to produce under the normal pressure micro discharges by adopting two kinds of methods: 1) gas pre-arcing, allow to take place simultaneously very great snowslide, cause forming the big area electrical discharge zone.2) Townsend avalanche that causes of the negative electrode secondary discharge that forms of ion and metastable atom, molecule bombardment.Have only Townsend avalanche can produce glow discharge.
The method and the condition that form uniform large-area dielectric barrier discharge (DBD discharge, Dielectric barrier discharge) are more clearly, are easy to extension simultaneously.Under given conditions, DBD can cover several meters width of steel plate, continuously operation.
Under normal pressure, reactant gas feeds plasma ambient by main carrier gas, forms film.These gases can be helium, argon gas or nitrogen, are used for guaranteeing uniform discharge.The Different Effects of gas discharge physics, especially even DBD discharge physics.Rare gas element is used in normal pressure glow discharge (APGD) usually, uses nitrogen to realize Townsend avalanche (APTD).The electrode of APGD and APTD is identical, but the maximum ion rate is obviously different, and the former is 10
-8, the latter is 10
-11Simultaneously, at argon gas (10
13/ cm
3) or nitrogen 10
13/ cm
3) in the time that continues of discharge pulse and the density of metastable atom or molecule also inequality, therefore the electric energy that distributes depends on and is used for the carrier gas of stable discharging.When frequency was 10kHz, the average power that distributes in the helium was 0.1W/cm2, was 5W/cm2 in the nitrogen.In helium, can improve plasma ratio in the discharge by increasing operating frequency, but compare with helium, the cost of nitrogen is much lower.
By selecting different carrier gas, can realizing different DBD discharges; By selecting different presomas for use, can realize different plated films.
The present invention proposes to adopt atmospheric plasma technology to be with the steel plated film.Baseplate material can be cold-rolled steel coils, galvanized coil, stainless-steel roll, reach organic precoated coil of strip etc.
Enter the atmospheric plasma film coating unit after the coil of strip uncoiling; By carrier and organic precursor, produce plasma by dielectric barrier discharge, steel plate carries out plated film by plasma area the time; Be implemented on carbon steel (comprising galvanized sheet) volume, stainless-steel roll, the organosilicon prepolymer coating coil of strip and realize environmental protection, multifunctional film-coating.
The DBD dielectric barrier discharge adds alternating-current between two electrodes, dielectric layer or insulating layer blocks electric current, will produce dielectric discharge.In order to improve plated film speed, can adopt multi-group electrode, every group of two electrodes.Wherein high voltage electrode is positioned at the top of steel plate, covers with the blocking layer; The band steel of operation is positioned at the high voltage electrode below, can adjust, optimize with the spacing of high voltage electrode; Band steel ground connection, the while also can be positioned at the top of ground-electrode, intercepts by megohmite.
The blocking layer can be selected quartz, Al for use
2O
3Or stupalith.
The frequency of the voltage of alternating current that electrode adopts is adjustable in 200Hz arrives the 20kHz scope.DBD can be in glow discharge, Townsend avalanche or three kinds of states of low-temperature plasma.Its discharge is remained in the Townsend avalanche scope.
Discharge gas can adopt helium and nitrogen, preferably nitrogen; Simultaneously all right aerating oxygen isoreactivity gas, wherein the feeding amount of reactant gas suppresses metastable ability decision by this gas.In order to realize plated film, need to feed some presomas, HMDSO, HMDS, SiH
4Deng; These presomas can pass through preheating unit, are transported to coating system through carrier gas, react.
The average gas temperature rise of substrate is particularly useful for handling some thermally sensitive substrates in this technology implementation procedure between the several years.By the control process processing parameter, realize even, high speed surface coating.
Be further to improve the performance of plated film, can be after film coating unit, heat or cool off.
The operating rate of substrate (volume) is between 2 to 200 meters/minute.
Beneficial effect of the present invention
The present invention can realize the production technique of environmental protection, does not have the discharging of waste water, spent acid, salkali waste in the whole process of production; Sliver can be realized the SiO that vacuum plating can realize
2, TiO
2Deng the plated film product, but do not need vacuum unit, investment, running cost are low.
Related products of the present invention can comprise TiOx, SiOx etc., can be used as the alternative techniques of independent plated film product or phosphatization, passivation.The application of these products mainly contains industries such as automobile, household electrical appliances, building, photovoltaic, chemistry.
Description of drawings
Fig. 1 is the synoptic diagram of one embodiment of the invention;
Fig. 2 is the synoptic diagram of another embodiment of the present invention.
Embodiment
Referring to Fig. 1, an embodiment of normal atmosphere plasma strip steel film coating process of the present invention is used for coating single side and handles.
Enter atmospheric plasma film coating unit 2 after the coil of strip uncoiling; Adopt multi-group electrode 3, every group of two electrodes; Wherein high voltage electrode 31 is positioned at the top of band steel 1, covers with dielectric barrier layer 4; The band steel 1 of operation is positioned at high voltage electrode 31 belows; Band steel 1 is positioned at the top of ground-electrode 32, intercepts by megohmite 6; Add between two electrodes and submit (directly) stream electricity, dielectric layer has stopped electric current, produces dielectric discharge; Feed organic precursor and reactant gas 5 by carrier gas, nitrogen or argon gas or helium or oxygen, flow add alternating-current or direct current greater than 1sccm between two electrodes, and frequency is between 200Hz-20KHz; Dielectric layer or insulating layer blocks electric current, produce dielectric discharge; Dielectric barrier discharge produces plasma, and steel plate carries out plated film by plasma area the time.
See also Fig. 2 again, it is second embodiment of technology of the present invention, and it is used for double-sided coating and handles.
Enter atmospheric plasma film coating unit 2 after the coil of strip uncoiling; Adopt multi-group electrode 3, every group of two electrodes; Wherein high voltage electrode 31 is positioned at the top of band steel 1, covers with dielectric barrier layer 4; The band steel 1 of operation is positioned at high voltage electrode 31 belows; Add between two electrodes and submit (directly) stream electricity, dielectric layer has stopped electric current, produces dielectric discharge; Feed organic precursor and reactant gas 5 by carrier gas, produce plasma by dielectric barrier discharge, band steel 1 carries out plated film by plasma area the time.
Embodiment 1
Produce Townsend avalanche as carrier gas, HMDSO as presoma with nitrogen and realize band steel plating SiO
2
In the present embodiment, select for use nitrogen as carrier gas, DBD produces Townsend avalanche, to cold-rolled steel coils plating SiO
2Film.
In the DBD section, under normal pressure, feed 20sccm nitrogen, the content of HMDSO guarantees [N at 20ppm
2O]/ratio of [HMDSO] is about 24, to realize SiO
2Film.
The frequency of voltage is 6kHz, and its discharge density is at 0.1～2W/cm
2Between.
Cold-reduced sheet passes through with 20 meters/minute, can realize 50～100nm SiO
2The plated film product.
The width of cold-reduced sheet is in the 300mm scope time, and film thickness fluctuates in 3%.Its membrane structure as shown in Figure 1, as seen its deposit for SiO
2Film.
With nitrogen as carrier gas, SiH
4Produce Townsend avalanche as presoma and realize band steel plating SiO
2
In the present embodiment, select for use nitrogen as carrier gas, DBD produces Townsend avalanche, to cold-rolled steel coils plating SiO
2Film.
In the DBD section, under normal pressure, with the speed feeding nitrogen of 5sccm, SiH
4Content remain on 5ppm, O
2Content remain on 15ppm.
The frequency of voltage is selected in 1～10kHz scope, and its discharge density is at 3.4W/cm
2Between.Scope apart from steel plate is adjustable in 1～2mm scope.
Cold-reduced sheet passes through with 10 meters/minute, can realize 50～100nm SiO
2The plated film product.
The width of cold-reduced sheet is in the 300mm scope time, and film thickness fluctuates in 5%.Its surface, XPS analysis result surface is SiO
2Structure, specific refraction is in 1.15～1.4 scopes.Along with the minimizing of steel plate speed, its SiO
2Purity improving constantly, be up to 98%.
With nitrogen as carrier gas, TiO[CH
3COCH=C (O-) CH
3]
2Produce Townsend avalanche as presoma and realize stainless-steel roll plating TiO
2
In the present embodiment, select for use nitrogen as carrier gas, TiO[CH
3COCH=C (O-) CH
3]
2Produce Townsend avalanche as presoma, to stainless-steel roll plating TiO
2Film.
In the DBD section, under normal pressure, with the speed feeding nitrogen of 5sccm, the content of oxygen is 20%, TiO[CH
3COCH=C (O-) CH
3]
2Flow remain between 0.02～1mol/l.
The frequency of voltage is selected 100kHz, is 1mm apart from the scope of steel plate.
If stainless steel plate is preheating to 200～300 degree, pass through with 10 meters/minute, can realize 20～50nmTiO
2The plated film product.The content of oxygen element is directly proportional with the content of oxygen in the feeding gas in the plated film.Along with the rising of preheating temperature, the content of the Ti-OH in the coating reduces gradually.If adopt the annealing aftertreatment can make sedimentary TiO
2Structure is to anatase structured conversion.
Claims (11)
1. normal atmosphere plasma strip steel film coating process, substrate enters the atmospheric plasma film coating unit after winding off volume; Adopt two electrodes, wherein high voltage electrode is positioned at the top of steel plate, covers with the blocking layer; The substrate of operation is positioned at high voltage electrode below, and substrate ground connection or be positioned at the top of ground-electrode intercepts by megohmite; Feed organic precursor by carrier gas, gas flow is greater than 0.01sccm; And reactant gas, flow is greater than 1sccm; Add alternating-current or direct current between two electrodes, frequency is between 200Hz-20KHz; Dielectric layer or insulating layer blocks electric current, produce dielectric discharge; Dielectric barrier discharge produces plasma, and substrate carries out plated film by plasma area the time, and the substrate operating rate is between 2～200 meters/minute.
2. normal atmosphere plasma strip steel film coating process as claimed in claim 1 is characterized in that, described substrate is cold-rolled steel coils, galvanized coil, stainless-steel roll or organic precoated coil of strip.
3. normal atmosphere plasma strip steel film coating process as claimed in claim 1 is characterized in that, adopts multi-group electrode, every group of two electrodes.
4. normal atmosphere plasma strip steel film coating process as claimed in claim 1 is characterized in that, the frequency of the voltage of alternating current that electrode adopts is adjustable in 200Hz arrives the 20kHz scope.
5. normal atmosphere plasma strip steel film coating process as claimed in claim 1 is characterized in that described blocking layer is selected quartz or Al for use
2O
3Or stupalith.
6. normal atmosphere plasma strip steel film coating process as claimed in claim 1 is characterized in that, described dielectric barrier discharge is for being in glow discharge, Townsend avalanche or three kinds of states of low-temperature plasma.
7. normal atmosphere plasma strip steel film coating process as claimed in claim 1 is characterized in that described dielectric barrier discharge remains in the Townsend avalanche scope.
8. normal atmosphere plasma strip steel film coating process as claimed in claim 1 is characterized in that, described reactant gas adopts helium, nitrogen, argon gas or oxygen.
9. normal atmosphere plasma strip steel film coating process as claimed in claim 1 is characterized in that, described organic precursor is HMDSO, HMDS, SiH
4In a kind of.
10. as claim 1 or 9 described normal atmosphere plasma strip steel film coating process, it is characterized in that described organic precursor is transported to coating system by preheating through carrier gas, reacts.
11. normal atmosphere plasma strip steel film coating process as claimed in claim 1 is characterized in that, behind the plated film, heats or cools off.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100452850A CN101376968B (en) | 2007-08-27 | 2007-08-27 | Normal atmosphere plasma strip steel film coating process |
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|---|---|---|---|
| CN2007100452850A CN101376968B (en) | 2007-08-27 | 2007-08-27 | Normal atmosphere plasma strip steel film coating process |
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| Publication Number | Publication Date |
|---|---|
| CN101376968A true CN101376968A (en) | 2009-03-04 |
| CN101376968B CN101376968B (en) | 2011-11-23 |
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ID=40420703
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102080145A (en) * | 2011-01-22 | 2011-06-01 | 中国船舶重工集团公司第七二五研究所 | Method for modifying steel surface of ship body by plasma at normal pressure |
| WO2012079472A1 (en) * | 2010-12-17 | 2012-06-21 | 北京北方微电子基地设备工艺研究中心有限责任公司 | Semiconductor device |
| CN102896115A (en) * | 2011-07-26 | 2013-01-30 | 中国科学院微电子研究所 | Novel normal-pressure medium barrier type active free radical cleaning equipment |
| CN103789749A (en) * | 2012-11-02 | 2014-05-14 | 苏州科技学院 | Corrosion protection method of steel fibers |
| CN105951035A (en) * | 2016-05-28 | 2016-09-21 | 上海大学 | Method of spring steel for bluing under low-temperature plasma |
| CN105951034A (en) * | 2016-05-28 | 2016-09-21 | 上海大学 | Method of spring steel for carburization under low-temperature plasma |
| CN110129771A (en) * | 2019-04-16 | 2019-08-16 | 中国科学院电工研究所 | A kind of film deposition plating system and the method to film progress deposition plating |
| CN113118234A (en) * | 2021-04-16 | 2021-07-16 | 江西富鸿金属有限公司 | Production process of tinned alloy wire for medical equipment |
-
2007
- 2007-08-27 CN CN2007100452850A patent/CN101376968B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012079472A1 (en) * | 2010-12-17 | 2012-06-21 | 北京北方微电子基地设备工艺研究中心有限责任公司 | Semiconductor device |
| CN102080145A (en) * | 2011-01-22 | 2011-06-01 | 中国船舶重工集团公司第七二五研究所 | Method for modifying steel surface of ship body by plasma at normal pressure |
| CN102896115A (en) * | 2011-07-26 | 2013-01-30 | 中国科学院微电子研究所 | Novel normal-pressure medium barrier type active free radical cleaning equipment |
| CN103789749A (en) * | 2012-11-02 | 2014-05-14 | 苏州科技学院 | Corrosion protection method of steel fibers |
| CN105951035A (en) * | 2016-05-28 | 2016-09-21 | 上海大学 | Method of spring steel for bluing under low-temperature plasma |
| CN105951034A (en) * | 2016-05-28 | 2016-09-21 | 上海大学 | Method of spring steel for carburization under low-temperature plasma |
| CN110129771A (en) * | 2019-04-16 | 2019-08-16 | 中国科学院电工研究所 | A kind of film deposition plating system and the method to film progress deposition plating |
| CN113118234A (en) * | 2021-04-16 | 2021-07-16 | 江西富鸿金属有限公司 | Production process of tinned alloy wire for medical equipment |
| CN113118234B (en) * | 2021-04-16 | 2022-09-27 | 江西富鸿金属有限公司 | Production process of tinned alloy wire for medical equipment |
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|---|---|
| CN101376968B (en) | 2011-11-23 |
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