CN106398332B - Super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant and preparation method thereof - Google Patents
Super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant and preparation method thereof Download PDFInfo
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- CN106398332B CN106398332B CN201610805133.5A CN201610805133A CN106398332B CN 106398332 B CN106398332 B CN 106398332B CN 201610805133 A CN201610805133 A CN 201610805133A CN 106398332 B CN106398332 B CN 106398332B
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- film
- pad pasting
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
- B60J1/20—Accessories, e.g. wind deflectors, blinds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The present invention discloses a kind of super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant and preparation method thereof, including the organic basement membrane of transparent flexible, nano-particle layer and the transparent nano rough textured film set gradually；The present invention settles mixed method by Cluster deposition and vacuum cold spray or airless injection mist, prepares wear-resisting, transparent nano rough textured film comprising the organic basement membrane of transparent flexible, micron particles protrusion.Pad pasting of the present invention ensure that the good transparency first；Secondly, the cooperation based on nanometer rough textured film and micron particles protrusion realizes good super-hydrophobic automatic cleaning effect；Again, it is firmly combined between micron particles and nanometer rough textured film or between base, there is wear-resistant property；Finally, it selects corrosion resistant nonmetallic materials to prepare and is used as pad pasting film material, realize excellent corrosion resistance.In short, realizing super-hydrophobic coat under the premise of meeting coating translucency, while there is wear-resisting, corrosion resistant performance, significantly improves automobile adhesive film performance.
Description
Technical field
The present invention relates to coating technology field, more particularly to a kind of wear resistant corrosion resistant can be used for glass for vehicle window it is super-hydrophobic
Automatically cleaning pad pasting and preparation method thereof.
Background technology
Automobile glass for vehicle window in the rainy day travels is easy to be influenced by rainwater, to influence driver in the process of moving
Correct judgement is made to road conditions, thus causes traffic accident and even causes casualties.Front truck glass pane can pass through rain brush
It solves the problems, such as, but survey glass pane and most of vehicle rear window to be solved by means of hydrophobic type glass or glass-film.However, by
Often lifted in side window glass and bear serious surface abrasion at its sealing joint strip, there is no so far excellent abrasive resistance glass or
Glass-film is available.
Invention content
The purpose of the present invention is to provide a kind of super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant and its preparations
Method, to solve the above technical problems.Pad pasting of the present invention includes the organic basement membrane of transparent flexible, transparent nano rough textured film, micron
Grain protrusion.The pad pasting further increased on the basis of traditional glass for vehicle window pad pasting super-hydrophobic, automatically cleaning, it is wear-resistant and corrosion
Characteristic.
To achieve the goals above, the present invention adopts the following technical scheme that：
The super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant, including set gradually the organic basement membrane of transparent flexible,
Micron particles layer and transparent nano rough textured film.
Further, the organic basement membrane of the transparent flexible is the adhering film to glass of high-molecular organic material.
Further, the organic basement membrane of the transparent flexible, be high-molecular organic material adhesive film material on the basis of it is compound
It is heat-insulated, every ultraviolet light, the pad pasting of unidirectional one or more of hidden characteristic.
Further, the transparent nano rough textured film, surface undulation is averagely no more than 200nm, thickness is no more than 5 μm；
The material of transparent nano rough textured film is one or more of silica, yttrium oxide, titanium oxide or zinc oxide.
Further, micron particles layer is the micron particles that surface of the average height no more than 15 μm is distributed；Micron particles
Granular materials is silica, zirconium oxide, yttrium oxide, titanium oxide, zinc oxide, silicon nitride, silicon carbide, titanium nitride or titanium carbide in layer
One or more of.
Further, the light transmittance of the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of the wear resistant corrosion resistant is not less than 85%,
Hydrophobic contact angle is not less than 165 °.
Further, one layer of bottom nanometer rough textured film is equipped between transparent nano rough textured film and the organic basement membrane of transparent flexible；
It is 0.5~3 μm no more than 200nm, thickness that bottom nanometer rough film surface, which rises and falls averagely,；The material of bottom nanometer rough textured film is oxygen
One or more of SiClx, yttrium oxide, titanium oxide or zinc oxide.
The preparation method of the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant, includes the following steps：
(1) attachment film surface pre-processes：Remove the spot of the organic membrane surface attachment of transparent flexible or absorption；
(2) micro- in organic one layer of the membrane surface preparation of transparent flexible by the way of vacuum cold spray or airless injection sedimentation
Rice grain；
(3) it is 10 in pressure-5~104In the chamber of Pa by way of Cluster deposition, in the organic basement membrane table of transparent flexible
Face deposition prepares layer of transparent nanometer rough textured film, and cluster refers to the atom aggregates that atom number is no less than 3 not more than 200.
Further, using plasma method for activating surface is gone back in step (1) makes organic membrane surface molecule generate dangling bond.
Further, it is first 10 in pressure before preparing micron particles in step (2)-5~104Pass through cluster in the chamber of Pa
The mode of deposition prepares one layer of bottom nanometer rough textured film in the organic membrane surface deposition of step (1) pretreated transparent flexible；
Micron particles are deposited on bottom nanometer rough textured film；Transparent nano rough textured film is deposited on micron particles and bottom nanometer rough textured film
On.
Further, the airless injection sedimentation is to fall micron particles injection dispersion after natural subsidence in chamber
In bottom nanometer rough film surface；Alternatively, be in chamber by electrification micron particles injection dispersion after gravity natural subsidence
It falls in bottom nanometer rough film surface；Alternatively, be in chamber by electrification micron particles injection dispersion through its settle path
Collision is in bottom nanometer rough film surface after accelerating under the electric field action of upper setting.
Compared with the existing technology, the invention has the advantages that：
The present invention discloses a kind of super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant and preparation method thereof, passes through group
Cluster deposits and vacuum cold spray or airless injection mist settle mixed method, prepares comprising the organic basement membrane of transparent flexible, transparent
Wear-resisting, the corrosion-resistant super-hydrophobic automatic cleaning coating of nanometer rough textured film, micron particles protrusion.Pad pasting according to the present invention, first
It ensure that the good transparency；Secondly, the cooperation based on nanometer rough textured film and micron particles protrusion realizes good super-hydrophobic
Automatic cleaning action；Again, it is firmly combined between micron particles and nanometer rough textured film or between base, there is wear-resistant property；Most
Afterwards, it selects corrosion resistant nonmetallic materials to prepare and is used as pad pasting film material, realize excellent corrosion resistance.In short,
It realizes that hydrophobic contact angle is not less than 165 ° of super-hydrophobic coat under the premise of meeting coating light transmittance not less than 85%, has simultaneously
Wear-resisting, corrosion resistant performance, significantly improves automobile adhesive film performance.
Description of the drawings
Fig. 1 is that three step preparation methods deposit schematic diagram；
Fig. 2 is three step preparation method structural schematic diagrams；
Fig. 3 is that four steps preparation method deposits schematic diagram；
Fig. 4 is four steps preparation method structural schematic diagram.
Specific implementation mode
It is the specific embodiment that inventor provides below, it should be noted that these embodiments are the present invention preferably examples
Son is used for it will be understood by those skilled in the art that the present invention, but the invention is not limited in these embodiments.
Embodiment 1：
A kind of preparation method of the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant, comprises the steps of：
To 1 surface preparation of the organic basement membrane of transparent flexible, the spot of the attachment of removal surface or absorption, further use etc. from
Daughter method for activating surface makes organic 1 surface molecular of basement membrane of transparent flexible generate dangling bond, so that subsequent film combines.Then, it adopts
The Zirconium oxide powder for being 1~3 μm with grain size, one layer of the preparation on the organic basement membrane 1 of transparent flexible by way of vacuum cold spray
Micron particles layer 2.Then, use grain silica in pressure for 10-5~104In the chamber of Pa by way of Cluster deposition,
Attachment film surface deposition prepares one layer of surface layer nanometer rough textured film 3, which refers to the atom that atom number is no less than 3 not more than 200
Aggregation forms firm connection when Cluster deposition by means of its huge surface energy and depositing base.Surface layer nanometer rough textured film 3 be
Surface undulation is averagely no more than 200nm, thickness is 0.2~0.5 μm.Entire coating deposition process as shown in Figure 1, finally obtain as
Film structure shown in Fig. 2 has hydrophobic contact angle under the premise of prepared pad pasting realizes the light transmittance ensured not less than 85%
Ultra-hydrophobicity not less than 165 °, while there is wear-resisting, corrosion resistant performance.
Embodiment 2：
A kind of preparation method of the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant, comprises the steps of：
To 1 surface preparation of the organic basement membrane of transparent flexible, the spot of the attachment of removal surface or absorption, in favor of subsequent film knot
It closes.Use grain size for 2~5 μm of yttrium oxide powder, by way of airless injection sedimentation, by the micron of electrification in chamber
Grain injection dispersion is fallen after gravity natural subsidence in the organic basement membrane of transparent flexible, at the time of particle contacts transparent flexible organic basement membrane
Electric discharge, which occurs, with surface makes micron particles be firmly bonded to surface, forms micron particles layer 2.Use titanium oxide in pressure for 10-5
~104In the chamber of Pa by way of Cluster deposition, one layer of surface layer nanometer rough textured film 3, the group are prepared in attachment film surface deposition
Cluster refers to the atom aggregates that atom number is no less than 3 not more than 200, when Cluster deposition by means of its huge surface energy with it is heavy
Product matrix forms firm connection.Surface layer nanometer rough textured film 3 is that surface undulation is averagely no more than 150nm, thickness is 0.3~1 μm
The film of rough surface.Film structure as shown in Figure 2 is finally obtained, it is saturating not less than 85% that prepared pad pasting realizes guarantee
Under the premise of light rate, has the ultra-hydrophobicity that hydrophobic contact angle is not less than 160 °, while there is wear-resisting, corrosion resistant performance.
Embodiment 3：
A kind of preparation method of the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant, comprises the steps of：
To 1 surface preparation of the organic basement membrane of transparent flexible, the spot of the attachment of removal surface or absorption, further use etc. from
Daughter method for activating surface makes organic membrane surface molecule generate dangling bond, so that follow-up nanometer rough textured film combines.Using yttrium oxide
It is 10 in pressure-5~104In the chamber of Pa by way of Cluster deposition, prepared in organic 1 surface of the basement membrane deposition of transparent flexible
One layer of bottom nanometer rough textured film 4 forms firm connection when Cluster deposition by means of its huge surface energy and depositing base.Bottom
Nanometer rough textured film 4 is the film that surface undulation is averagely no more than 100nm, the rough surface that thickness is 0.5~3 μm.Then, it uses
The silicon carbide powder that grain size is 1~3 μm, prepares one layer of micron particles layer 2 by way of vacuum cold spray.Then, using oxygen
Change yttrium is continued deposition by way of Cluster deposition and forms surface layer nanometer rough textured film 3 again, meanwhile, it is deposited on micron particles and bottom
Material near nanometer rough textured film 4 interface is by the interface enhancing between micron particles and bottom nanometer rough textured film 4.Surface layer nanometer is thick
Rough film 3 is the film that surface undulation is averagely no more than 200nm, the rough surface that thickness is 0.2~1.5 μm.Entire coating deposition
For process as shown in figure 3, finally obtaining film structure as shown in Figure 4, it is saturating not less than 85% that prepared pad pasting realizes guarantee
Under the premise of light rate, has the ultra-hydrophobicity that hydrophobic contact angle is not less than 165 °, while there is wear-resisting, corrosion resistant performance.
Embodiment 4：
A kind of preparation method of the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant, comprises the steps of：
To 1 surface preparation of the organic basement membrane of transparent flexible, the spot of the attachment of removal surface or absorption, in favor of follow-up nanometer
Rough textured film combines.Use silica in pressure for 10-5~104In the chamber of Pa by way of Cluster deposition, in attachment film surface
Deposition prepares one layer of bottom nanometer rough textured film 4, is formed securely by means of its huge surface energy and depositing base when Cluster deposition
In conjunction with.Bottom nanometer rough textured film 4 is the film that surface undulation is averagely no more than 200nm, the rough surface that thickness is 0.5~3 μm.
Then, use grain size for 1~3 μm of alpha-silicon nitride powders, by way of airless injection sedimentation, by the micron of electrification in chamber
Particle injection dispersion is collided after accelerating under settling the electric field action being arranged on path at it on 4 surface of bottom nanometer rough textured film,
Electric discharge, which occurs, with surface at the time of particle contact bottom layer nanometer 4 surface of rough textured film makes micron particles be firmly bonded to surface, is formed
One layer of micron particles layer 2.Then, using silica again by Cluster deposition by the way of continue deposition formed surface layer nanometer rough textured film
3, meanwhile, it is deposited on micron particles and the material near 4 interface of bottom nanometer rough textured film is coarse by micron particles and bottom nanometer
Interface enhancing between film 4.Surface layer layer nanometer rough textured film 3 is that surface undulation is averagely no more than 200nm, thickness is 0.5~3 μm
The film of rough surface.Film structure as shown in Figure 4 is finally obtained, it is saturating not less than 85% that prepared pad pasting realizes guarantee
Under the premise of light rate, has the ultra-hydrophobicity that hydrophobic contact angle is not less than 165 °, while there is wear-resisting, corrosion resistant performance.
Embodiment 5：
A kind of preparation method of the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant, comprises the steps of：
To 1 surface preparation of the organic basement membrane of transparent flexible, the spot of the attachment of removal surface or absorption, further use etc. from
Daughter method for activating surface makes organic membrane surface molecule generate dangling bond, so that follow-up nanometer rough textured film combines.Using titanium oxide
It is 10 in pressure-5~104In the chamber of Pa by way of Cluster deposition, prepared in organic 1 surface of the basement membrane deposition of transparent flexible
One layer of bottom nanometer rough textured film 4 forms firm connection when Cluster deposition by means of its huge surface energy and depositing base.Bottom
4 surface undulation of nanometer rough textured film is averagely no more than the film of 200nm, the rough surface that thickness is 0.5~3 μm.Then, using grain
The yttrium oxide powder that diameter is 1~3 μm, by way of airless injection sedimentation, by the injection point of the micron particles of electrification in chamber
Dissipate fallen after gravity natural subsidence at the time of 4 surface of bottom nanometer rough textured film, particle contact bottom layer nanometer 4 surface of rough textured film with
Electric discharge, which occurs, for surface makes micron particles be firmly bonded to surface, forms one layer of micron particles layer 2.Then, led to again using titanium nitride
Cross Cluster deposition mode continue deposition formed surface layer nanometer rough textured film 3, meanwhile, be deposited on micron particles and bottom nanometer be coarse
Material near 4 interface of film is by the interface enhancing between micron particles and bottom nanometer rough textured film 4.Surface layer nanometer rough textured film 3 be
Surface undulation is averagely no more than the film of 200nm, the rough surface that thickness is 0.3~1 μm.Finally obtain patch as shown in Figure 4
Membrane structure under the premise of prepared pad pasting realizes the light transmittance ensured not less than 85%, has hydrophobic contact angle and is not less than 165 °
Ultra-hydrophobicity, while there is wear-resisting, corrosion resistant performance.
Claims (9)
1. the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant, which is characterized in that including the transparent flexible set gradually
Organic basement membrane, micron particles layer and transparent nano rough textured film；It is equipped between transparent nano rough textured film and the organic basement membrane of transparent flexible
One layer of bottom nanometer rough textured film；It is 0.5~3 μm no more than 200nm, thickness that bottom nanometer rough film surface, which rises and falls averagely,；Bottom
The material of nanometer rough textured film is one or more of silica, yttrium oxide, titanium oxide or zinc oxide.
2. the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant according to claim 1, which is characterized in that described
The organic basement membrane of transparent flexible be high-molecular organic material adhering film to glass.
3. the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant according to claim 1, which is characterized in that described
The organic basement membrane of transparent flexible, be compounded on the basis of the adhesive film material for being high-molecular organic material it is heat-insulated, every ultraviolet light, unidirectional hidden
One or more of cover the pad pasting of characteristic.
4. the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant according to claim 1, which is characterized in that described
Transparent nano rough textured film, surface undulation averagely be no more than 200nm, thickness be no more than 5 μm；The material of transparent nano rough textured film is
One or more of silica, yttrium oxide, titanium oxide or zinc oxide.
5. the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant according to claim 1, which is characterized in that micro-
The micron particles that surface of the rice grain layer average height no more than 15 μm is distributed；In micron particles layer granular materials be silica,
One or more of zirconium oxide, yttrium oxide, titanium oxide, zinc oxide, silicon nitride, silicon carbide, titanium nitride or titanium carbide.
6. the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant according to claim 1, which is characterized in that described
The light transmittance of the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant is not less than 85%, and hydrophobic contact angle is not less than 165 °.
7. the preparation side of the super-hydrophobic automatic cleaning glass for vehicle window pad pasting of wear resistant corrosion resistant according to any one of claims 1 to 6
Method, which is characterized in that include the following steps：
(1) attachment film surface pre-processes：Remove the spot of the organic membrane surface attachment of transparent flexible or absorption；
(2) in the organic membrane surface of transparent flexible by the way of the sedimentation of vacuum cold spray, airless injection sedimentation or vacuum spraying
Prepare one layer of micron particles；
(3) it is 10 in pressure-5~104It is heavy in the organic membrane surface of transparent flexible in the chamber of Pa by way of Cluster deposition
Product prepares layer of transparent nanometer rough textured film, and cluster refers to the atom aggregates that atom number is no less than 3 not more than 200.
8. the preparation method described in claim 7, which is characterized in that step goes back using plasma method for activating surface in (1)
Organic membrane surface molecule is set to generate dangling bond.
9. the preparation method described in claim 7, which is characterized in that be first 10 in pressure before preparing micron particles in step (2)-5~104It is heavy in the organic membrane surface of step (1) pretreated transparent flexible in the chamber of Pa by way of Cluster deposition
Product prepares one layer of bottom nanometer rough textured film；Micron particles are deposited on bottom nanometer rough textured film；Transparent nano rough textured film is deposited on
On micron particles and bottom nanometer rough textured film；The airless injection sedimentation is that micron particles are sprayed dispersion through certainly in chamber
So fallen in bottom nanometer rough film surface after sedimentation；Alternatively, be in chamber by electrification micron particles injection dispersion through gravity
It is fallen after natural subsidence in bottom nanometer rough film surface；The vacuum spraying sedimentation, is the micron by electrification in chamber
Collision is in bottom nanometer rough film surface after grain injection dispersion accelerates under the electric field action through being arranged on its sedimentation path.
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| CN108912747A (en) * | 2017-04-18 | 2018-11-30 | 吴瑛 | For glass or the anion coating of rupture pressure disc and preparation method thereof |
| CN109957345B (en) | 2017-12-26 | 2020-09-25 | 清华大学 | Hydrophobic membrane |
| CN109958380B (en) | 2017-12-26 | 2021-04-02 | 清华大学 | Hydrophobic window and house and automobile using same |
| CN109959980B (en) | 2017-12-26 | 2020-09-08 | 清华大学 | Hydrophobic mirror and automobile using same |
| CN109955785A (en) | 2017-12-26 | 2019-07-02 | 清华大学 | Hydrophobic mirror and the automobile for using the hydrophobic mirror |
| CN109958379B (en) | 2017-12-26 | 2021-01-05 | 清华大学 | Hydrophobic window and house and automobile using same |
| CN108276922A (en) * | 2018-01-19 | 2018-07-13 | 全椒光太胶粘制品有限公司 | A kind of manufacturing method of automobile-used isolation film |
| CN113528040A (en) * | 2021-07-28 | 2021-10-22 | 宁波泰意德过滤技术有限公司 | Heat-insulating anti-ultraviolet glass film and preparation method thereof |
| CN117510946A (en) * | 2022-07-28 | 2024-02-06 | 华为技术有限公司 | Light-transmitting plate, structural member and light sensing device |
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| CN204977691U (en) * | 2015-09-22 | 2016-01-20 | 郑州艾比利特节能科技有限公司 | Thermal -insulated self -cleaning glass pad pasting keeps warm |
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