CN1234465C - Method for preparing nano grain film biphobic coating by normal pressure medium barrier discharge polymerization - Google Patents
Method for preparing nano grain film biphobic coating by normal pressure medium barrier discharge polymerization Download PDFInfo
- Publication number
- CN1234465C CN1234465C CN 03115252 CN03115252A CN1234465C CN 1234465 C CN1234465 C CN 1234465C CN 03115252 CN03115252 CN 03115252 CN 03115252 A CN03115252 A CN 03115252A CN 1234465 C CN1234465 C CN 1234465C
- Authority
- CN
- China
- Prior art keywords
- barrier discharge
- coating
- dielectric barrier
- fabric
- normal pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to a method for preparing a coating layer by blocking discharge polymerization with normal pressure media. The method can be used for tidying rejected water and oil on other base substances of fabrics, fibers, plastic films, glass, ceramics, etc. The present invention is characterized in that fluorocarbon and carbon gas monomers excite monomer polymerization by the mode of blocking discharge by media under normal pressure and room temperature. A layer of thin hydrophobic and oleophobic film with a nanometer particle membrane structure is coated on the surface of a base material to make the contact angles between water (or glycerol) on the surface of cotton fabrics and alpha-bromonaphthalene respectively 130 DEG and 120 DEG more or less. Static beads on the surface can be retained until the beads are naturally and completely volatilized. GB/T4745 moistening tests reach average two-grade; the mechanical performance and hand feeling comfort of lossless fabrics are enhanced. The present invention is a new method with low cost, serialization, large area and no pollution for tidying hydrophobic and oleophobic coating layers.
Description
Technical field
The present invention relates to the polymer coated method of plasma discharge, specifically relate under the normal pressure polymerization of plasma dielectric barrier discharge and prepare the two open coat methods of nano-particular film.
Background technology
The two thin fabrics of water and oil repellant are important contents that functional fabric is studied, and not only can satisfy the needs of each type games kimonos frilled organ material, and to reducing the environmental pollution that brings because of cleaning, washing crucial meaning are arranged also.Immersion coating, physics coating, plasma coating etc. are roughly arranged in coating process at present.Utilize immersion coating can obtain compound functions films such as some fluorides, silicide, polyurethane.But the normal conventional chemical finishing technique that pads-bake that adopts of immersion coating method is grafted to fiber surface with water repellent under the effect of high temperature and additive.Because treatment temperature height (general＞120 ℃), time is long, the energy consumption height, efficient is low, pollutes greatly the synthetic fibers lower to glass transition temperature (as terylene, nylon etc.), above-mentioned chemical finishing method Yin Wendu too high (surpassing glass transition temperature), bad phenomenon such as fiber retraction, orientation texture destruction, mechanical property damage to occur, the drapability and the flexibility that obtain fabric are too poor, and also bigger to the contaminative of environment; It is too high to utilize the physics coating surface to modify the bionical coating apparatus cost of preparation, thus can not popularization and application in production.And the plasma coating method can be divided into vacuum coating and normal pressure coating again.Can prepare and have field emission effect, photoluminescence property, vapour lock effect, refuse oil and refuse water characteristic film etc., but vacuum coating method in-house facility cost height commonly used at present, and be unfavorable for that industrial serialization large tracts of land produces.And that the coating under normal device has is simple in structure, characteristics such as equipment and operating cost are low, and the polymer coated method of atmospheric plasma to have dry state, serialization, room temperature film-forming, environmental pollution little, can obtain advantages such as types of functionality film.If it can be developed into a kind of serialization, large area functional top finish new method, to the model change of these traditional industries of weaving, promote the application of nano material, have crucial application prospect and innovative significance.But have not yet to see the research report that is applied to textile or other host materials.
Summary of the invention
Purpose of the present invention provides the polymerization of a kind of atmospheric plasma dielectric barrier discharge to prepare the two open coat methods of nano-particular film at the deficiencies in the prior art, can be applicable to two open coat arrangements of fabric, fiber or other matrix.Be characterized under the atmospheric pressure at room dry state, utilizing the plasma medium barrier discharge, make fluorine carbon gaseous monomer excite polymerization, apply the film of one deck nano particle membrane structure in fabric, fiber or other stromal surface, carrying out the top finish of hydrophobic oleophobic functional membrane, is a kind of serialization, large tracts of land, pollution-free, low consumption, little to fabric damage, and can improve the method for sorting of the water and oil repellant of its comfortable feel.
Coating process of the present invention may further comprise the steps:
(1) preparation of reacting gas
The employing fluorocarbons is a reaction monomers, and the chemical structural formula of monomer is C
xF
y(x=1-8, y=1-18, the ratio of x and y is 1: 1-4), for example helium, neon or argon gas are carrier gas to adopt inert gas during discharge polymerization, the volume ratio of inert gas and monomer is 0-500: 1, inert gas and monomer are fully mixed in gas mixer, be made into a certain proportion of reacting gas, and be 0.1-1.30SLM (standard liter/min) by flowmeter control flow rate of reactive gas.
(2) polymerization of plasma medium barrier discharge prepares the nano particle membrane coat
Fiber, fabric or other host material sample are cleaned up, place the dielectric barrier discharge reactor.Other matrix can be glass, plank, pottery, plastic sheeting etc.Reaction electrode in the dielectric barrier discharge reactor adopts spiral electrode, and perhaps the parallel dielectric the inside that is embedded in of positive and negative electrode forms surface-discharge.Dielectric adopts aluminium oxide, quartz glass or tetrafluoroethene etc.Power supply adopts commercially available high-voltage ac power, input voltage: 220V, input floating voltage peak value: 15000V, frequency: 10-100KHz.The discharge of unlatching high-voltage ac power, be 30 seconds-10 minutes discharge time.Entire reaction course is to carry out in the reactor of semi open model at normal temperatures and pressures, and sample is back to back from import and export, and the discharge reactor remainder is an enclosed construction.Monomer is excited polymerization by high voltage source, fiber, fabric or other matrix are taken out after placing electrode reaction district certain hour, or control transfer rate, making fabric is 30 seconds-10 minutes in the total time of conversion zone process, as under 4 electrode situations, transfer rate can be 1 rev/min-100 rev/mins, passes through continuously from reaction zone, two the dredging that promptly applies one deck nano particle (particle diameter 20-200nm) membrane structure at sample surfaces filmed, and forms coating.Need not to carry out again other processing after the coating.
Fabric fibre after the arrangement and glass properties test result
1. measurement of contact angle
Adopt quiet contact angle measurement of JC2000A to carry out the test of contact angle, the result shows, under the normal pressure plasma dielectric barrier discharge coating bafta can obtain with commercial Scotchgard waterproofing agent arrangement after fabric and the suitable contact angle of vacuum plasma coating bafta.With about 130 ° of the contact angle average out to of polarizable medium water, with about 120 ° of the contact angle average out to (seeing Table 1) of apolar medium α-bromonaphthalene.
2. fabric moisture transmission property testing
Fabric bedding after handling on the evaporating dish of certain area, under the constant temperature and humidity, by the variation of the weight of water in the different time evaporating dish, thereby is calculated the saturating wet speed and the saturating wet index of this fabric.Saturating wet index is that coating is handled the ratio that the saturating wet speed of fabric and coating are not handled the saturating wet speed of fabric.The result shows (seeing Table 1), atmospheric plasma dielectric barrier discharge coating handles the water vapour permeability of back fabric and coated fabric is not than almost changing, and wet thoroughly speed and saturating wet index increase than the vacuum plasma coating or with Scotchgard waterproofing agent arrangement coated fabric.
3. test gets wet
Undertaken by GB GB/T4745, tested the surperficial moisture resistance (experiment gets wet) of coated fabric.Experimental result shows that atmospheric plasma dielectric barrier discharge coating surface of cotton fabric moisture resistance can reach 2 grades.
4. comfortable feel property testing
Adopt FAST (Fabric Style instrument) to carry out, the result shows, the sample after the processing, and warp, weft direction stretch rate change little, 37.7% and 71.8% (the seeing Table 2) but the bending stiffness of sample warp, broadwise has descended respectively illustrates the flexibility of fabric is made moderate progress.
5. Electronic Speculum test
By JSM-5600LV digitlization low vacuum scanning electron microscopic observation, find the atmospheric plasma dielectric barrier discharge polymer coated be the nano particle accumulating film of 20-200nm, film has loose structure and (sees Fig. 1-Fig. 4).The nano particle accumulating film of this loose structure provides the surface of certain roughness, helps raising hydrophobic, oleophobic property.
Atmospheric dielectric barrier discharge of the present invention polymerization prepares the two open coat methods of nano-particular film, has broken through the limitation of vacuum plasma treatment, has overcome immersion coating and has put seriously polluted reaching weakness such as the original performance impact of fabric are bigger in order.Not only can on bafta, can also carry out the two thin functional coats of water and oil repellant on surfaces such as glass, plank, pottery, sealed polyethylene plastics and handle the following advantage of having compared with traditional chemical finishing method:
1. efficient, low energy consumption can be finished whole coating processing procedure in several minutes.
2. be reflected under the atmospheric pressure at room and carry out, the performance undamaged evil of matrix sample itself.
3. be a kind of course of reaction of dry state, need not chemical reagent is carried out operations such as any separation, cleaning, oven dry before and after the reaction, help environmental protection.
4. the hydrophobic of prepared sample is effective, and the mechanical property of fabric is not had influence, to the also raising to some extent of comfortable feel of fabric.
5. equipment manufacturing cost is low, and small investment helps industrial serialization large-scale production.
Description of drawings
Fig. 1 is that monomer is CF among the embodiment 2
4The time, the electron microscopic observation figure of dielectric barrier discharge coating institute's film forming on sheet glass.
Fig. 2 is that monomer is C among the embodiment 2
2F
6The time, the electron microscopic observation figure of dielectric barrier discharge coating institute's film forming on sheet glass.
Fig. 3 is the electron microscopic observation figures of embodiment 3 dielectric barrier discharge coatings in fabric face institute film forming.
Fig. 4 is the electron microscopic observation figures of embodiment 3 dielectric barrier discharge coatings in fiber surface institute film forming.
Fig. 5 be embodiment 4 dielectric barrier discharge coatings on surface of cotton fabric institute film forming, form leave standstill globule photo.
Fig. 6 be embodiment 4 dielectric barrier discharge coatings on glass surface institute film forming, form leave standstill globule photo.
Fig. 7 is the schematic diagram of continuous media barrier discharge reactor.
The specific embodiment
Embodiment 1
The bafta sample is cleaned up, place the electrode discharge reaction zone of medium (aluminium oxide) barrier discharge reactor.Argon gas and monomer CF
4Mixing ratio is 300: 1, mixes to be made into reacting gas, and reaction gas flow is 0.32SLM, and power is 11kw, carries out discharge process under atmospheric pressure at room, and the processing time is 1 minute.Contact angle, fabric moisture-penetrability and the comfortable feel comparative result of the fabric that the commercial water-proof aagent of gained atmospheric plasma coating and vacuum coating and Scotchgard is handled on bafta sees Table 1 and table 2.
The contact angle of table 1, fabric, fabric moisture transmission speed and wet thoroughly index are relatively
| The coating classification | Contact angle (degree) | Saturating wet speed (g/min.cm 2) | Saturating wet index | ||
| Water | Glycerine | α-bromonaphthalene | |||
| Atmospheric plasma | 132.96 | 131.28 | 124.19 | 4.456×10 -5 | 0.9997 |
| Vacuum plasma | 137.06 | 134.47 | 4.413×10 -5 | 0.990 | |
| The Scothgard coating | 128.72 | 134.88 | 121.92 | 4.323×10 -5 | 0.970 |
Table 2, fabric constant load be elongation performance, fabric Bending Stiffness Analysis test result down
| Load (gf) | Percentage elongation (%) | Bending stiffness (mgf.cm) | ||||
| Radially | Broadwise | Oblique | Warp-wise | Broadwise | ||
| Be untreated | 5 | 0.1 | 0.1 | 0.5 | 156.6 | 172.2 |
| 20 | 0.3 | 0.1 | ||||
| 100 | 0.8 | 0.7 | ||||
| After the processing | 5 | 0.1 | 0 | 0.7 | 113.7 | 48.7 |
| 20 | 0.3 | 0.2 | ||||
| 100 | 1.8 | 0.9 | ||||
Embodiment 2
Glass sheet sample is cleaned up, place the electrode discharge reaction zone of medium (tetrafluoroethene) barrier discharge reactor, helium and monomer mixing ratio are 200: 1, adopt monomer CF
4(or C
2F
6), mixing the reaction gas flow that is made into is 0.05SLM, power is 8kw, carry out discharge process under atmospheric pressure at room, the processing time is 4 minutes, the electron microscopic observation figure of the coating of different monomers on sheet glass, see Fig. 1 and Fig. 2, show that coating is the nano particle accumulating film of loose structure,, help the raising of hydrophobic oleophobic for the surface provides certain roughness.
Embodiment 3:
Fabric and fiber sample are cleaned up, place the electrode discharge reaction zone of medium (aluminium oxide) barrier discharge reactor, neon and monomer C
6F
6Mixing ratio is 500: 1, mixing the reaction gas flow that is made into is 0.2SLM, power 10kw, under atmospheric pressure at room, carry out discharge process, processing time is that 6 minutes the fabric and the electron microscopic observation figure of fiber see Fig. 3 and Fig. 4, show that coating is the nano particle accumulating film of loose structure,, help the raising of hydrophobic oleophobic for the surface provides certain roughness.
Embodiment 4
Sheet glass and bafta sample are cleaned up, place the electrode discharge reaction zone of medium (quartz glass) barrier discharge reactor, helium and monomer C
8F
18Mixing ratio is 500: 1, mixing the reaction gas flow that is made into is 0.8SLM, power is 10kw, under atmospheric pressure at room, sheet glass and bafta are carried out discharge process, processing time is 30 seconds, the photo that leaves standstill the globule that water forms on sample surfaces is seen Fig. 5 and Fig. 6, and this globule can last till that nature volatilizees fully.
Embodiment 5
As shown in Figure 7, the bafta that cleans up is placed the electrode discharge reaction zone of continuous media (tetrafluoroethene) barrier discharge reactor pass through argon gas and monomer C continuously
2F
6Mixing ratio is 400: 1, and mixing the reaction gas flow that is made into is 1.0SLM, power is 10kw, under atmospheric pressure at room bafta is carried out continuous discharge and handle, the carry-over pinch rolls rotating speed is 5 rev/mins, thereby realizes serialization, large tracts of land, free of contamination pair of open coat arrangement.
Claims (3)
1, the polymerization of a kind of atmospheric dielectric barrier discharge prepares the two open coat methods of nano-particular film, it is characterized in that this method may further comprise the steps:
(1) the preparation reacting gas adopts fluorocarbons C
XF
YBe reaction monomers, x=1-8 wherein, y=1-18, the ratio of x and y are 1: 1-4, monomer and inert gas are 1 by volume: 200-500 is mixed into reacting gas, and reaction gas flow is 0.1-1.30 SLM;
(2) fiber, fabric or glass material are placed the electrode discharge reaction zone of dielectric barrier discharge reactor or pass through continuously from reaction zone, reaction is carried out at normal temperatures and pressures, be 30 seconds-10 minutes discharge time, the monomer polymerization that is excited, apply the two thin film of one deck nano-particular film at material surface, form coating
Wherein: described inert gas is helium, neon or argon gas,
Described medium is aluminium oxide, quartz glass or tetrafluoroethene.
2, as claimed in claim 1 pair of open coat method is characterized in that the electrode in the described dielectric barrier discharge reactor is a spiral electrode, and perhaps the parallel dielectric the inside that is embedded in of positive and negative electrode forms surface-discharge.
3, as claimed in claim 1 pair of open coat method is characterized in that this dielectric barrier discharge reactor is the dielectric barrier discharge reactor that is used to carry out the serialization top finish.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03115252 CN1234465C (en) | 2003-01-29 | 2003-01-29 | Method for preparing nano grain film biphobic coating by normal pressure medium barrier discharge polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03115252 CN1234465C (en) | 2003-01-29 | 2003-01-29 | Method for preparing nano grain film biphobic coating by normal pressure medium barrier discharge polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1433848A CN1433848A (en) | 2003-08-06 |
| CN1234465C true CN1234465C (en) | 2006-01-04 |
Family
ID=27634239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03115252 Expired - Fee Related CN1234465C (en) | 2003-01-29 | 2003-01-29 | Method for preparing nano grain film biphobic coating by normal pressure medium barrier discharge polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1234465C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI121336B (en) * | 2006-03-27 | 2010-10-15 | Beneq Oy | Hydrophobic glass surface |
| CN101045610B (en) * | 2007-03-29 | 2010-10-13 | 刘东平 | Self-clean film material and preparation method |
| CN103127774A (en) * | 2011-11-24 | 2013-06-05 | 辽东学院 | Oil contamination resistant weaving filter cloth and preparation method thereof |
| CN103668939A (en) * | 2013-09-30 | 2014-03-26 | 辽宁天泽产业集团纺织有限公司 | Anti-oil-stain treatment method for textile fiber machine-woven filter cloth |
| CN107740262A (en) * | 2017-11-09 | 2018-02-27 | 青岛大学 | A kind of hydrophobic fabric and preparation method thereof |
| CN113430812B (en) * | 2021-07-08 | 2022-04-12 | 苏州大学 | Preparation method of super-wetting coating |
-
2003
- 2003-01-29 CN CN 03115252 patent/CN1234465C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1433848A (en) | 2003-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101979429B (en) | Surface modification method for polytetrafluoroethylene product | |
| EP2944671A1 (en) | Nanostructured articles and methods to make the same | |
| JP2016145992A (en) | Antireflective articles and methods of making the same | |
| KR101644025B1 (en) | Superhydrophobic Surface Body and Method for Fabricating Superhydrophobic Surface Body Using iCVD | |
| Ai et al. | Biomimetic polymeric superamphiphobic surfaces: their fabrication and applications | |
| CN1234465C (en) | Method for preparing nano grain film biphobic coating by normal pressure medium barrier discharge polymerization | |
| JP2015062077A (en) | Nanostructured articles and method of making nanostructured articles | |
| CN106865493A (en) | Nano-structured product | |
| JP2011504207A (en) | Breathable membrane and method for making the membrane | |
| WO2008078346A1 (en) | Hybrid coating that is water-repellent and humidity-proof for reinforced composite polymer materials deposited through pecvd | |
| CN105688687B (en) | The preparation process of double-hydropholic film | |
| CN107740262A (en) | A kind of hydrophobic fabric and preparation method thereof | |
| US20200316881A1 (en) | Polymeric material having micro-nano composite structure, device including the same, and method of manufacturing the polymeric material | |
| Wei et al. | Functionalization of textile materials by plasma enhanced modification | |
| Hu et al. | Highly durable and robust superhydrophobic/superoleophilic cotton fabric with well-designed roughness for oil/water separation | |
| Li et al. | Modification of unsaturated polyester resins (UP) and reinforced UP resins via plasma treatment | |
| Steiner et al. | Nanostructuring of polymer surfaces by magnetron plasma treatment | |
| Sugihara et al. | Promoting the adhesion of high‐performance polymer fibers using functional plasma polymer coatings | |
| CN113430812B (en) | Preparation method of super-wetting coating | |
| CN109232957A (en) | A kind of PEDOT-PET/ graphene quantum dot composite construction conductive film and preparation method thereof | |
| CN110450441A (en) | A kind of modifying super hydrophobicity PVC heat shrink films and its preparation process | |
| Hegemann | Stain repellent finishing on fabrics | |
| CN109666175A (en) | Condensate and its manufacturing method through surface structuration | |
| CN113308872A (en) | Functional textile material, preparation method thereof and application thereof in environmental water replenishing or evaporation prevention | |
| CN109273627B (en) | Sealing method of shell for electrochemical energy storage device with high water oxygen molecule barrier property |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |