CN106277811B - A kind of film plating process of glass substrate and glass surface - Google Patents
A kind of film plating process of glass substrate and glass surface Download PDFInfo
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- CN106277811B CN106277811B CN201610662629.1A CN201610662629A CN106277811B CN 106277811 B CN106277811 B CN 106277811B CN 201610662629 A CN201610662629 A CN 201610662629A CN 106277811 B CN106277811 B CN 106277811B
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- glass
- film
- microballoon
- reverse micelle
- micron order
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2453—Coating containing SnO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2456—Coating containing TiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
Abstract
The present invention provides a kind of glass substrates, are surface-treated to obtain through reverse micelle microballoon microemulsion by glass；The reverse micelle microballoon microemulsion includes the chemical corrosion liquid of nonpolar solvent and surfactant package；The glass substrate is cheated with micron order hole.The present invention provides a kind of film plating process of glass surface, are surface-treated using reverse micelle microballoon microemulsion to glass, obtain the glass substrate that there is micron order hole to cheat；The plated film on the glass baseplate surface, the glass material after obtaining plated film.Present invention application reverse micelle microballoon etching glass surface forms the structure in micron order hole hole；Gained glass substrate is that glass is cheated in micron order hole, porous structure is presented, surface area is big.The present invention carries out plated film in micron order hole hole glass surface, and film can be embedded into glass orifice, the wavy three-dimensional membrane structure in available section.The binding force between film and substrate and between film layer is improved using the film plating process of glass substrate provided by the invention.
Description
Technical field
The present invention relates to coating technique field more particularly to the film plating process of a kind of glass substrate and glass surface.
Background technique
Glass material has good optics, electricity, mechanically and chemically stability, therefore glass substrate is in optics device
It is had a wide range of applications in terms of part, microwave device, building aspect and automobile etc..In glass surface plating metal, alloy or metal
Oxidation film can assign glass new function, usually be widely used in the fields such as building, photovoltaic, electronics.
Existing coating film on glass technology mainly includes magnetron sputtering method, sol-gel technique, chemical vapour deposition technique, true
Empty evaporation coating techniques etc., wherein adhesiveness between film and glass has been largely fixed film in practical applications
Reliability and stability.The Chinese patent literature of 103613289 A of Publication No. CN discloses a kind of chemical on the glass substrate
Copper coating plates coppersmith using traditional chemical again after drying this method comprises: coating one layer of organic film on the glass substrate
Process copper layer；Wherein organic film preparation method the following steps are included: (1) by organic film material with 0.1%~
20% percent by volume is dissolved in volatile organic solvent；(2) by the organic solvent with spin coating, spraying, immersion or painting
Brush method is coated on glass substrate；(3) the glass substrate drying of the to be coated organic solvent is dried；(4) by glass
Substrate carries out imidization or hot setting using the characteristic of organic film material.
The above method mainly by coating one layer of organic film in glass baseplate surface, then using traditional copper coating into
Row plated film, this can improve the binding force between film and glass substrate to a certain extent.But due to glass body and membrane material
Heterogeneity and interface mainly combined by physical action, chemical action, therefore, it is also desirable to there is more feasible methods
The binding force of film and glass is further enhanced, so as to improve the stability and reliability of film function.
Summary of the invention
In view of this, the application provides the film plating process of a kind of glass substrate and glass surface, use is provided by the invention
Glass substrate carries out plated film, can improve the binding force between film and matrix and film layer.
The present invention provides a kind of glass substrate, is surface-treated to obtain through reverse micelle microballoon microemulsion by glass；It is described anti-
Micella microballoon microemulsion includes the chemical corrosion liquid of nonpolar solvent and surfactant package；
The glass substrate is cheated with micron order hole.
Preferably, the nonpolar solvent in linear paraffin, substituted straight chain alkane, branched paraffin and aromatic hydrocarbon one
Kind is several.
Preferably, the surfactant is selected from sodium alkyl benzene sulfonate, sodium alkyl sulfonate, sodium alkyl sulfate, fatty alcohol
Polyethenoxy ether sodium sulfate, sodium alkyl sulfonate etc., dodecyl trimethyl ammonium bromide, cetyl trimethylammonium bromide, 16
Alkyl front three ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, cetyl trimethyl ammonium heteropoly acids, dodecyl beet
Alkali, N- amido propyl dimethyl carboxymethyl ammonium glycine betaine, polyol-based non-ionic surfactant, polyoxyethylene-type nonionic table
One or more of face activating agent and PULLRONIC F68 type nonionic surfactant.
Preferably, the chemical corrosion liquid is selected from acids corrosive liquid or bases corrosive liquid.
Preferably, the reverse micelle microballoon microemulsion further includes alcohol.
The present invention provides a kind of film plating process of glass surface, comprising the following steps:
A) glass is surface-treated using reverse micelle microballoon microemulsion, obtains the glass base that there is micron order hole to cheat
Plate；The reverse micelle microballoon microemulsion includes the chemical corrosion liquid of nonpolar solvent and surfactant package；
B) the plated film on the glass baseplate surface, the glass material after obtaining plated film.
Preferably, the step A) in, the nonpolar solvent from linear paraffin, substituted straight chain alkane, branched paraffin and
One or more of aromatic hydrocarbon；The chemical corrosion liquid is selected from acids corrosive liquid or bases corrosive liquid.
Preferably, the step A) in, the time of the surface treatment is 0.5h~10h, the temperature of the surface treatment
It is 10 DEG C~120 DEG C.
Preferably, the step B) in, the mode of the plated film is magnetron sputtering method or chemical vapour deposition technique.
Preferably, the step A) before further include: glass is washed using cleaning solution, the glass after being washed
Glass；The cleaning solution includes aqueous solution or anhydrous solvent；
The step A) are as follows: the glass after washing is surface-treated using reverse micelle microballoon microemulsion, it is cleaned, it obtains
To the glass substrate cheated with micron order hole.
Compared with prior art, present invention application reverse micelle microballoon etching glass surface forms the structure in micron order hole hole；
Gained glass substrate is that glass is cheated in micron order hole, porous structure is presented, surface area is big, stable structure, wear-resisting.Also, this hair
Bright to carry out plated film in micron order hole hole glass surface, film can be embedded into glass orifice, and available section is wavy
Three-dimensional membrane structure.Therefore, it is not only increased between film and substrate using the film plating process of glass substrate provided by the invention
Binding force, and the binding force between film layer is improved, so as to improve the stability and reliability of film function, it is conducive to application.
Detailed description of the invention
Fig. 1 is the surface SEM figure that glass is cheated in the micron order hole that embodiment 1 is prepared；
Fig. 2 is the section SEM figure that glass is cheated in the micron order hole that embodiment 1 is prepared；
Fig. 3 is the surface atom force microscope 3D figure that glass is cheated in the micron order hole that embodiment 1 is prepared；
Fig. 4 is the surface laser microscope 3D figure that glass is cheated in the micron order hole that embodiment 1 is prepared；
Fig. 5 is that embodiment 1 is schemed in the surface SEM that upper plated film is cheated in glass micron order hole；
Fig. 6 is that embodiment 1 is schemed in the section SEM that upper plated film is cheated in glass micron order hole；
Fig. 7 is the scratch test figure of AZO film on sheet glass surface；
Fig. 8 is the scratch test figure of AZO film on cellular glass surface of the present invention.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of glass substrates, are surface-treated to obtain through reverse micelle microballoon microemulsion by glass；It is described
Reverse micelle microballoon microemulsion includes the chemical corrosion liquid of nonpolar solvent and surfactant package；
The glass substrate is cheated with micron order hole.
Glass substrate provided by the invention is that glass is cheated in micron order hole, porous structure is presented, surface area is big, and structure is steady
It is fixed, it is wear-resisting, it is conducive to plated film.
There is glass baseplate surface provided in an embodiment of the present invention hole to cheat pattern, wherein and deep hole can be 100nm~600nm,
It is near coal-mine it is wide be 1 μm~3 μm, that is, have micron order hole hole.The glass substrate is by glass by reverse micelle microballoon microemulsion
Surface treatment obtains, wherein the glass is substrate or substrate material commonly used in the art, and the present invention is not particularly limited.?
In the embodiment of the present invention, glass-cutting can be subjected to subsequent processing at required size.Present invention preferably employs the glass after washing
It is surface-treated；Glass after the washing can be used cleaning solution and wash to obtain.
In an embodiment of the present invention, the cleaning solution includes aqueous solution or anhydrous solvent, can be the impurity of glass surface
It cleans up, but its surface texture is not made to generate variation.Wherein, the aqueous solution such as water, acid solution, aqueous slkali or detergent
Aqueous solution etc.；The anhydrous solvent such as ethyl alcohol, acetone or emulsion etc..The cleaning solution is preferably distilled water, dilute hydrochloric acid, dilute sulphur
Two or more in acid, ammonium hydroxide, dehydrated alcohol, distilled water and acetone.Herein, when cleaning solution is two or more
When substance, i.e., glass is respectively washed using both or two or more substances.The cleaning solution is more preferably dilute hydrochloric acid, dilute sulphur
Acid, ammonium hydroxide, dehydrated alcohol, distilled water and acetone；Wherein, the mass concentration of dilute hydrochloric acid and dilute sulfuric acid can be 5%~20%, such as
7%.When in an embodiment of the present invention, using cleaning solution cleaning glass, dilute hydrochloric acid, dilute sulfuric acid, ammonium hydroxide, dehydrated alcohol, distillation
The volume ratio of water and acetone is preferably (1~2): (1~2): (1~2): (10~20): (10~20): (10~20), more preferably
For (1~1.8): (1~1.8): (1~1.8): (12~18): (12~18): (12~18).Herein, the volume ratio indicates phase
Volume ratio relationship between mutually, to sequence and type is used, there is no limit.
The present invention can in order successively wash cleaning solution to glass；In some embodiments of the invention, described
Cleaning solution is followed successively by dilute hydrochloric acid, acetone, distilled water.In some embodiments of the invention, the cleaning solution is followed successively by acetone, second
Alcohol, distilled water.In other embodiments of the invention, the cleaning solution is followed successively by dilute hydrochloric acid, distilled water.Of the invention another
In some embodiments, the cleaning solution is followed successively by ammonium hydroxide, acetone, distilled water.It is described clear in other embodiments of the invention
Washing lotion is followed successively by dilute sulfuric acid, dehydrated alcohol, distilled water.In these embodiments, the ratio of substance used is all satisfied above-mentioned volume
Than.
Present invention application reverse micelle microballoon microemulsion etching glass surface forms the structure in micron order hole hole and improves table
Area.The reverse micelle microballoon microemulsion is also referred to as reverse micelle microballoon liquid, reverse micelle microballoon lotion etc. comprising nonpolar solvent.
The nonpolar solvent preferably is selected from one or more of linear paraffin, substituted straight chain alkane, branched paraffin and aromatic hydrocarbon, such as just
The linear paraffins such as hexane, normal heptane, normal octane, n -nonane, n-decane, isopentane, neopentane, -5 ethyl octane of 3- methyl, 2,
Branched paraffins, the aromatic hydrocarbon such as benzene or alkylbenzene and the carbon tetrachloride, two such as 3- dimethylbutane, 5- propyl -4- isopropyl nonane
The substituted straight chains alkane such as chlorination carbon.The nonpolar solvent is more preferably from one or more of linear paraffin and branched paraffin；
In some embodiments of the invention, the nonpolar solvent is n-hexane and 3- methyl -5- ethyl octane.Of the invention one
In a little embodiments, the nonpolar solvent is pentane.In other embodiments of the invention, the nonpolar solvent is positive
Heptane and isopentane.In other embodiments of the invention, the nonpolar solvent is n-decane and 5- propyl -4- isopropyl
Nonane.In other embodiments of the invention, the positive polarity solvent is isopentane and 3- methyl -5- ethyl octane.Work as institute
State nonpolar solvent be two kinds of substances when, the volume ratio of the two can be 1:1.
In the present invention, the reverse micelle microballoon microemulsion includes the chemical corrosion liquid of surfactant package.Wherein, institute
Stating surfactant includes cationic surfactant, anionic surfactant, amphoteric surfactant, non-ionic surface work
Property agent etc., preferably cationic surfactant or anionic surfactant.The surfactant is more preferably from alkylbenzene
The anionic surfaces such as sodium sulfonate, sodium alkyl sulfonate, sodium alkyl sulfate, sodium sulfate of polyethenoxy ether of fatty alcohol, sodium alkyl sulfonate
Activating agent, dodecyl trimethyl ammonium bromide, cetyl trimethylammonium bromide, cetyl front three ammonium chloride, dodecyl
The cationic surfactants such as dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium heteropoly acids, empgen BB, N-
The amphoteric surfactantes such as amido propyl dimethyl carboxymethyl ammonium glycine betaine, polyol type, polyoxyethylene-type and polyoxyethylene-are poly-
The nonionic surfactants such as oxypropylene type；Selected surfactant is preferably one such or several.
In the present invention, the surfactant wraps up aqueous chemical corrosion liquid.The chemical corrosion liquid preferably is selected from acid
Class corrosive liquid or bases corrosive liquid, such as HCl, H2SO4、HNO3、HF、HPO3、H2CO3、CH3The acids corrosive liquid such as COOH solution,
NaOH、KOH、NaHCO3、Na2HPO4、NH4The bases corrosive liquid such as OH solution, selected chemical corrosion liquid are one such or several
Kind.The chemical corrosion liquid is more preferably from HCl, H2SO4、HNO3、HF、H2CO3、CH3COOH、NaOH、KOH、NaHCO3、Na2HPO4
And NH4Two or more solution in OH；Wherein, H2SO4Mass concentration can be able to be for the mass concentration of 98%, HF
The mass concentration of 40%, HCl can be 37%, and the concentration of bases corrosive liquid is preferably 0.1M~1M.In some implementations of the invention
In example, the chemical corrosion liquid includes H2SO4And HF.In some embodiments of the invention, the chemical corrosion liquid includes
H2SO4, HF and HCl.In other embodiments of the invention, the chemical corrosion liquid includes KOH and NaHCO3.In the present invention
Other embodiments in, the chemical corrosion liquid includes.NaOH and Na2HPO4.In other embodiments of the invention, institute
Stating chemical corrosion liquid is HF.
Wherein, HCl, H2SO4、HNO3、HF、H2CO3、CH3COOH、NaOH、KOH、NaHCO3、Na2HPO4、NH4Mole of OH
Than preferably (2~5): (0.2~5): (0.2~5): (2~20): (2~5): (0.2~5): (0.2~5): (2~20): (2
~5): (0.2~5): (0.2~5): (2~20), more preferably (2~5): (0.3~5): (0.3~5): (2~18): (2~
5): (0.3~5): (0.3~5): (2~18): (2~5): (0.3~5): (0.3~5): (2~18).Herein, the molar ratio
The proportionate relationship for indicating the amount of mutual substance, to type, there is no limit.When above-mentioned aqueous chemical corrosion liquid chooses two
When kind or three kinds of solution, it is all satisfied above-mentioned molar ratio.
In the present invention, it is also preferable to include alcohol for the reverse micelle microballoon microemulsion, more preferably include the alcohol of C2~C12.Institute
State alcohol include but is not limited to normal propyl alcohol, glycerine, n-butanol, 1,4- butanediol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol,
Isopropanol, isoamyl alcohol, preferably glycerine, n-butanol, 1,4-butanediol or isoamyl alcohol.
In the present invention, the reverse micelle microballoon microemulsion may be simply referred to as lotion, microemulsion, reaction solution.In the present invention one
In a little embodiments, the reaction solution preferably includes n-hexane, normal heptane, normal octane, n -nonane, n-decane, isopentane, new penta
Alkane, 3- methyl -5- ethyl octane, 2,3- dimethylbutane, 5- propyl -4- isopropyl nonane, benzene or alkylbenzene, carbon tetrachloride,
The combination of one or more of carbon dichloride nonpolar solvent and alcohol, more preferably n-hexane, normal heptane, normal octane, positive nonyl
Alkane, n-decane, isopentane, neopentane, -5 ethyl octane of 3- methyl, 2,3- dimethylbutane, 5- propyl -4- isopropyl nonane,
The combination of one of benzene or alkylbenzene, carbon tetrachloride, carbon dichloride and alcohol.At this point, the n-hexane, normal heptane, normal octane,
N -nonane, n-decane, isopentane, neopentane, -5 ethyl octane of 3- methyl, 2,3- dimethylbutane, 5- propyl -4- isopropyl nonyl
The molar ratio of one of alkane, benzene or alkylbenzene, carbon tetrachloride, carbon dichloride and alcohol is preferably (1~3): (0.1~1).
The present invention is not particularly limited the source of the reverse micelle microballoon microemulsion, preferably in accordance with the following methods with obtained
To: nonpolar solvent and alcohol are mixed in water, surfactant is added, obtains oily phase；The oil is added in chemical corrosion liquid
Phase, mixing, obtains reverse micelle microballoon microemulsion.Wherein, the temperature of two steps mixing is both preferably room temperature, more preferably 20 DEG C~50
℃.The time of two steps mixing is both preferably 2h~20h, more preferably 5~20h.The present invention is to the reverse micelle microballoon microemulsion
Dosage be also not particularly limited, can submerge or cover glass surface.
The present invention also provides a kind of film plating process of glass surface, comprising the following steps:
A) glass is surface-treated using reverse micelle microballoon microemulsion, obtains the glass base that there is micron order hole to cheat
Plate；The reverse micelle microballoon microemulsion includes the chemical corrosion liquid of nonpolar solvent and surfactant package；
B) the plated film on the glass baseplate surface, the glass material after obtaining plated film.
Glass surface film plating process provided by the invention is a kind of three-dimensional coating technique, can improve film and glass substrate,
And the binding force between film layer.
The embodiment of the present invention can carry out subsequent processing by glass-cutting at required size.The glass is commonly used in the art
Substrate or substrate material, the present invention is not particularly limited.The present invention it is also preferable to include: glass is washed using cleaning solution
It washs, the glass after being washed.
Glass is put into cleaning solution before surface treatment and is washed or cleaned, glass surface by the embodiment of the present invention
Impurity clean up, and the structure of glass surface does not generate variation, is conducive to subsequent processing.The cleaning solution preferably includes water
Solution or anhydrous solvent, content is consistent with previously described corresponding contents, and this is no longer going to repeat them.In implementation of the invention
In example, the mode of the washing is preferably cleaned by ultrasonic；1min~120min, preferably 10min~100min can be cleaned by ultrasonic.
After obtaining cleaning solution treated glass, the embodiment of the present invention by it in reverse micelle microballoon microemulsion, certain
Temperature range is surface-treated, and after handling a period of time, obtains micron order hole hole glass, that is, with micron order hole hole
Glass substrate.
In the present invention, the reverse micelle microballoon microemulsion includes the chemistry corruption of nonpolar solvent and surfactant package
Lose liquid.The present invention is surface-treated glass using reverse micelle microballoon microemulsion, during processing, the lotion and glass table
Face is reacted, and makes micron order hole hole structure in glass surface.The reaction is hydro-thermal reaction, can etching glass surface.By institute
Reaction treatment is stated, the glass that surface has micron order hole hole, glass substrate as described above can be obtained.
Wherein, the content of the reverse micelle microballoon microemulsion is as it was noted above, this is no longer going to repeat them.Preferably,
When the clarification of reverse micelle microballoon microemulsion, then glass is put into and is wherein surface-treated.The time of the surface treatment is preferred
For 0.5h~10h, more preferably 1h~10h, most preferably 1h~9h.The temperature of the surface treatment is preferably 10 DEG C~120
DEG C, more preferably 20 DEG C~120 DEG C, most preferably 30 DEG C~100 DEG C.
After glass after obtaining reaction treatment, the present invention is obtained it is also preferable to include cleaning with micron order hole
The glass substrate in hole.
In the present invention, after the hydro-thermal reaction it is also preferable to include by glass be put into cleaning solution clean 5min~
100min, more preferably cleaning 10min~90min, most preferably cleaning 15min~60min.The cleaning solution preferably is selected from dilute salt
One or more of acid, dilute sulfuric acid, dehydrated alcohol, distilled water and acetone, more preferably dilute hydrochloric acid, dilute sulfuric acid, dehydrated alcohol,
Two or more in distilled water and acetone.Herein, when cleaning solution be two or more substance when, i.e., using this two
Kind or two or more substances are respectively washed glass.The cleaning solution is most preferably dilute hydrochloric acid, dilute sulfuric acid, dehydrated alcohol, distilled water
And acetone；The embodiment of the present invention using cleaning solution cleaning glass when, dilute hydrochloric acid, dilute sulfuric acid, ammonium hydroxide, dehydrated alcohol, distilled water and
The volume ratio of acetone is preferably (1~2): (1~2): (1~2): (10~20): (10~20): (10~20), more preferably (1
~1.8): (1~1.8): (1~1.8): (12~18): (12~18): (12~18).Herein, the volume ratio indicate mutually it
Between volume ratio relationship, to use sequence and type there is no limit.
The present invention can in order successively clean cleaning solution to glass；In some embodiments of the invention, described
Cleaning solution is preferably distilled water.For convenient for distinguishing, can will be used before surface treatment cleaning solution be known as the first cleaning solution, at surface
Cleaning solution used is known as the second cleaning solution after reason.In the present invention, the mode of above-mentioned cleaning is preferably cleaned by ultrasonic.It is above-mentioned super
Sound cleaning after preferably air-dry, the present invention to the air-dried mode without limit, using known to those skilled in the art
Air-dried mode, can be to be dried with nitrogen or hot blast drying etc..
Glass of the invention is after above-mentioned processing, and more regular " cratered " shape pattern is presented in surface, having a size of micro-
Meter level.The present invention carries out plated film, the glass material after obtaining plated film on the surface of such glass substrate, and surface, which has, cuts
Face three-dimensional membrane structure wave-shaped.
In an embodiment of the present invention, the mode of the plated film can be magnetron sputtering method or chemical vapour deposition technique (CVD).
The present invention is not particularly limited magnetron sputtering method plated film, can plate a tunic or multilayer film；Al-Doped ZnO film can be plated
(AZO film), indium tin oxide films (ito thin film), titanium deoxid film, DLC film (DLC film), SiCO siloxicon film
One of or it is a variety of.The present invention is also not particularly limited chemical vapour deposition technique plating made membrane, it is preferred to use atmospheric pressure cvd method
Plated film；SnO can be coated with2: F (FTO) film, SnO2:F/SnO2: Sb (SUN-E) film etc..
In conclusion the present invention not only increases the bonded area between film and substrate and film layer, while film is embedded in
To in glass orifice, all improve the binding force between film and substrate and film layer, so as to improve film function stability and can
By property, it is conducive to application.
For a further understanding of the application, below with reference to embodiment to glass substrate provided by the present application and glass surface
Film plating process is specifically described.
In following embodiment, related solution concentration is mass concentration.Glass used is purchased from the prosperous public affairs of Hainan Air China three
Department is common float glass process soda-lime-silica glass, with a thickness of 3mm, ingredient referring to table 1, table 1 be glass used in the embodiment of the present invention at
Point.
The ingredient of glass used in 1 embodiment of the present invention of table
Embodiment 1
By glass-cutting at required size.
Glass is put into cleaning solution and is cleaned by ultrasonic 10min: in 1:10:10 ratio measure dilute hydrochloric acid (7%), acetone,
Distilled water, i.e. measurement 10mL dilute hydrochloric acid, 100mL acetone, 100mL distilled water in order successively carry out cleaning solution to glass clear
It washes.
By cleaning solution, treated that glass is put into reverse micelle microballoon liquid, carries out reaction treatment.The tool of reverse micelle microballoon liquid
Body preparation method includes: the ratio in 10:10:1, measures n-hexane (30mL), 3- methyl -5- ethyl octane (30mL) and the third three
Surfactant dodecyltrimethylammonium is added in the teflon seal container for filling distilled water in alcohol (3mL)
3g measures 1mL H2SO4(98%) and 1mL HF (40%) is in the above-mentioned teflon seal container for filling oily phase, will be upper
Reagent mixing is stated, after mixing evenly, is configured to reverse micelle microballoon liquid.Stirring, after the clarification of reverse micelle microballoon liquid, by above-mentioned washing
Glass substrate afterwards is put into the lotion, is surface-treated 5h under conditions of temperature is 60 DEG C.
Glass after reaction treatment is put into distilled water and is cleaned by ultrasonic 10min, surface is obtained and is cheated with micron order hole
Glass, i.e., micron order hole cheat glass.
Morphology observation, analysis are carried out to gained micron order hole hole glass, Fig. 1 is the micron order hole that embodiment 1 is prepared
The surface SEM figure of glass is cheated, Fig. 2 is the section SEM figure that glass is cheated in the micron order hole that embodiment 1 is prepared, and Fig. 3 is embodiment
The atomic force microscope 3D figure of the 1 micron order hole hole glass being prepared, Fig. 4 are the micron order hole hole that embodiment 1 is prepared
The surface laser microscope 3D of glass schemes.From Fig. 1 and Fig. 2 it is clear that the glass surface after surface treatment is cheated with hole
Pattern, hole depth are 100nm~600nm, and near coal-mine width is 1 μm~3 μm.Also, Fig. 3 test scope is 25*25 microns, sweep speed
For 1Hz；Fig. 4 laser microscope test scope is 95*70 microns.From the further visible surface of Fig. 3 and Fig. 4 treated glass table
It is cheated with micron order hole in face.
Embodiment 2
By glass-cutting at required size.
Glass is put into cleaning solution and is cleaned by ultrasonic 10min: measuring acetone, ethyl alcohol, distilled water in the ratio of 3:3:2, i.e.,
60mL acetone, 60mL ethyl alcohol are measured, 40mL distilled water in order successively cleans cleaning solution to glass.
By cleaning solution, treated that glass is put into reverse micelle microballoon liquid, carries out reaction treatment.The tool of reverse micelle microballoon liquid
Body preparation method includes: the ratio in 10:1, measures pentane (60mL) and n-butanol (6mL) in the polytetrafluoro for filling distilled water
In ethylene sealing container, surfactant sodium alkyl benzene sulfonate and dodecyl trimethyl ammonium bromide 3g is added, measures 1mL
H2SO4(98%), 0.5mL HF (40%) and 0.5mLHCl (37%) is in the above-mentioned teflon seal container for filling oily phase
In, after mixing, it is configured to reverse micelle microballoon liquid.Stirring, after the clarification of reverse micelle microballoon liquid, by the glass after above-mentioned washing
Substrate is put into the lotion, and 1h is surface-treated under the conditions of at a temperature of 90 °C.
Glass after reaction treatment is put into distilled water and is cleaned by ultrasonic 10min, surface is obtained and is cheated with micron order hole
Glass.
Embodiment 3
By glass-cutting at required size.
Glass is put into cleaning solution and is cleaned by ultrasonic 10min: measuring dilute hydrochloric acid (7%), distilled water in the ratio of 1:15, i.e.,
10mL dilute hydrochloric acid is measured, 150mL distilled water in order successively cleans cleaning solution to glass.
By cleaning solution, treated that glass is put into reverse micelle microballoon liquid, carries out reaction treatment.The tool of reverse micelle microballoon liquid
Body preparation method includes: the ratio in 10:10:1, and measurement normal heptane (30mL), isopentane (30mL) and glycerine (3mL) are in Sheng
Have in the teflon seal container of distilled water, surfactant dodecyltrimethylammonium 3g is added, measures 1mL
KOH solution, 1mL NaHCO3Solution is in the above-mentioned teflon seal container for filling oily phase, KOH and NaHCO3Concentration difference
For 0.7M, 0.3M.After mixing, it is configured to reverse micelle microballoon liquid.Stirring is washed after the clarification of reverse micelle microballoon liquid by above-mentioned
Glass substrate after washing is put into the lotion, is surface-treated 3h under conditions of temperature is 70 DEG C.
Glass after reaction treatment is put into distilled water and is cleaned by ultrasonic 30min, surface is obtained and is cheated with micron order hole
Glass.
Embodiment 4
By glass-cutting at required size.
Glass is put into cleaning solution and is cleaned by ultrasonic 10min: measuring ammonium hydroxide, acetone, distilled water in the ratio of 1:15:15,
10mL ammonium hydroxide, 150mL acetone are measured, 150mL distilled water in order successively cleans cleaning solution to glass.
By cleaning solution, treated that glass is put into reverse micelle microballoon liquid, carries out reaction treatment.The tool of reverse micelle microballoon liquid
Body preparation method includes: the ratio in 10:10:1, measures n-decane (30mL), 5- propyl -4- isopropyl nonane (30mL) and 1,
Surfactant sodium alkyl benzene sulfonate 3g is added in the teflon seal container for filling distilled water in 4- butanediol (3mL),
Measure 1mL NaOH solution and 1mLNa2HPO4Solution is in the above-mentioned teflon seal container for filling oily phase, NaOH solution
And Na2HPO4The concentration of solution is respectively that 0.8M, 0.2M are configured to reverse micelle microballoon liquid after mixing.Stirring, to reverse micelle
After the clarification of microballoon liquid, the glass substrate after above-mentioned washing is put into the lotion, is surface-treated under conditions of temperature is 40 DEG C
6h。
Glass after reaction treatment is put into distilled water and is cleaned by ultrasonic 20min, surface is obtained and is cheated with micron order hole
Glass.
Embodiment 5
By glass-cutting at required size.
Glass is put into cleaning solution and is cleaned by ultrasonic 10min: measuring dilute sulfuric acid (7%), anhydrous second in the ratio of 1:10:10
Alcohol, distilled water, i.e. measurement 10mL dilute sulfuric acid (7%), 100mL dehydrated alcohol, 100mL distilled water, in order successively by cleaning solution
Glass substrate is cleaned.
By cleaning solution, treated that glass is put into reverse micelle microballoon liquid, carries out reaction treatment.The tool of reverse micelle microballoon liquid
Body preparation method includes: the ratio in 15:15:2, measures isopentane (30mL), -5 ethyl octane (30mL) of 3- methyl and isoamyl
Surfactant dodecyltrimethylammonium is added in the teflon seal container for filling distilled water in alcohol (4mL)
1.5g and cetyl front three ammonium chloride 1.5g measures 2ml HF (40%) and holds in the above-mentioned teflon seal for filling oily phase
In device, after mixing, it is configured to reverse micelle microballoon liquid.Stirring, after the clarification of reverse micelle microballoon liquid, by the glass after above-mentioned washing
Glass substrate is put into the lotion, is surface-treated 9h at normal temperature.
Glass after reaction treatment is put into distilled water and is cleaned by ultrasonic 30min, surface is obtained and is cheated with micron order hole
Glass.
Embodiment 6
Magnetron sputtering AZO film
In magnetron sputtering process, the setting of parameter is carried out.Select zinc oxide and quality of alumina ratio for the AZO of 98:2
Target, fixed target-substrate distance is 50mm, operating air pressure 0.5Pa, sputtering power 300W, argon gas flow 60sccm, sputtering
Time is 40min, chooses simple glass (sheet glass) and 1 gained micron order hole of embodiment and cheats that glass is each a piece of to be splashed simultaneously
It penetrates, the glass material after respectively obtaining plated film.Simple glass is purchased from Hainan Air China San Xin Corporation, is common float glass process sodium calcium silicon glass
Glass, with a thickness of 3mm, ingredient is referring to table 1.
Influence to magnetron sputtering in two kinds of glass surface plating single layer AZO films is studied, in the embodiment of the present invention 6,
The scanning electron microscope (SEM) photograph of AZO film is as shown in Figure 5 and Figure 6 on cellular glass surface, and Fig. 5 is embodiment 1 on the hole of glass micron order hole
The surface SEM of plated film schemes, and Fig. 6 is that embodiment 1 is schemed in the section SEM that upper plated film is cheated in glass micron order hole.Pass through nanometer mechanics system
Instrument of uniting according to known method tests scratch, and in the embodiment of the present invention 6, the scratch test of AZO film is surveyed on two kinds of glass surfaces
As shown in Figure 7 and Figure 8, Fig. 7 is the scratch test figure of AZO film on sheet glass surface for examination, and Fig. 8 is cellular glass table of the present invention
The scratch test figure of AZO film on face, data are shown in Table 2, and table 2 is AZO film on cellular glass of the present invention and sheet glass surface
Scratch test comparing result.As shown in Table 2, with surface be plane glass substrate compared with, it is thin on cellular glass surface
It is more than ten times larger that binding force between film and substrate and between film layer compares increasing.
The scratch test comparing result of AZO film on the cellular glass of the present invention of table 2 and sheet glass surface
| Critical value | |
| Sheet glass | 4.85mN |
| Cheat glass (cellular glass) in micron order hole | 50.04mN |
Embodiment 7
Magnetron sputtering ito thin film
In magnetron sputtering process, the setting of parameter is carried out.Selection ITO is sputtering target material, gas needed for opening, fixed target
Cardinal distance is 50mm, operating air pressure 1.0Pa, sputtering power 200W, argon gas flow 50sccm, and sputtering time is
20min, choose simple glass and micron order hole cheat glass it is each it is a piece of sputtered simultaneously, the glass material after respectively obtaining plated film
Material.
Influence to magnetron sputtering in two kinds of glass surface plating single layer ito thin films is studied: by embodiment 7 two
Ito thin film on kind of glass surface carries out scratch test test, with compared with surface is the glass substrate of plane, in cellular glass
Binding force on surface between film and substrate and between film layer compares 15 times of increase or more.
Embodiment 8
Magnetron sputtering titanium deoxid film
In magnetron sputtering process, the setting of parameter is carried out.Selection titanium dioxide is target, and gas needed for opening is fixed
Target-substrate distance is 50mm, operating air pressure 0.5Pa, sputtering power 200W, argon gas flow 60sccm, and sputtering time is
40min, choose simple glass and micron order hole cheat glass it is each it is a piece of sputtered simultaneously, the glass material after respectively obtaining plated film
Material.
Influence to magnetron sputtering in two kinds of glass surface plating single layer titanium deoxid films is studied, by embodiment
Titanium deoxid film in 8 on two kinds of glass surfaces carries out scratch test test, with compared with surface is the glass substrate of plane,
Binding force on cellular glass surface between film and substrate and between film layer, which compares, increases ten three times or more.
Embodiment 9
Magnetron sputtering two thin walls: SiCO and DLC film
In magnetron sputtering process, the setting of parameter is carried out.SiCO target and DLC target are selected, gas needed for opening, fixed target
Cardinal distance is 50mm, operating air pressure 0.5Pa, DLC target as sputter power is 200W, and SiCO target as sputter power is 150W, argon gas
Gas flow is 80sccm, and temperature is set as 200 DEG C, and sputtering time is respectively 20min, chooses simple glass and glass is cheated in micron order hole
Glass it is each it is a piece of progress and meanwhile sputter, the glass material after respectively obtaining plated film.
Influence to magnetron sputtering in two kinds of glass surface platings bilayer SiCO and DLC film is studied: by implementation
The double-deck SiCO and DLC film in example 9 on two kinds of glass surfaces carry out scratch test test, data and the glass on surface being plane
Glass substrate is compared, the binding force on cellular glass surface between film and substrate and between film layer compare increase nine times with
On.
Embodiment 10
Atmospheric pressure cvd method is coated with SnO2: F (FTO) film
In atmospheric pressure cvd coating process, major parameter is provided that selection monobutyl-tin-trichloride and trifluoroacetic acid and water is
Raw material, carrier gas used in this experiment are mainly dry air (can be directly as carrier gas and oxidant), carrier gas flux 20L/min,
Plating diaphragm nozzle distance substrate is 6mm, and substrate temperature is set as 400 DEG C~600 DEG C, and pedestal rate travel is 6mm/s, when plated film
Between be 105s, spray to glass baseplate surface from the outlet of plating diaphragm with carrier gas after the gasification of the evaporator that 150 DEG C of each group lease making, own
Operating environment carries out under normal pressure, chooses simple glass and each a piece of carry out thin-film-coating of glass is cheated in micron order hole, respectively
Glass material after to plated film.
Influence to aumospheric pressure cvd in two kinds of glass surface plating single layer SnO2:F films is studied: by right
SnO in embodiment 10 on two kinds of glass surfaces2: F film carries out scratch test test, with the glass substrate on surface being plane
It compares, the binding force on cellular glass surface between film and substrate and between film layer, which compares, increases twelvefold or more.
Embodiment 11
Atmospheric pressure cvd method is coated with SnO2:F/SnO2: Sb (SUN-E) film
In atmospheric pressure cvd coating process, major parameter is provided that selection monobutyl-tin-trichloride and trifluoroacetic acid and water is
Teleblem, monobutyl-tin-trichloride and antimony trichloride and water are counterdie.Carrier gas used in this experiment is mainly that dry air (can directly be made
For carrier gas and oxidant), counterdie and teleblem carrier gas flux are 25L/min, and plating diaphragm nozzle distance substrate is 6mm, substrate temperature
300 DEG C~500 DEG C are set as, pedestal rate travel is 5mm/s, and distance is 100mm between two plated film nozzles, and plated film time is
225s, counterdie and teleblem respectively enter corresponding pipeline, and evaporation tube temperature is 150 DEG C, and all operating environments are under normal pressure
It carries out, chooses simple glass and each a piece of carry out thin-film-coating of glass, the glass material after respectively obtaining plated film are cheated in micron order hole.
Bilayer SnO is plated in two kinds of glass surfaces to aumospheric pressure cvd2:F/SnO2: the influence of Sb film is ground
Study carefully: by the double-deck SnO in embodiment 11 on two kinds of glass surfaces2:F/SnO2: Sb film carry out scratch test test, with
Surface is that the glass substrate of plane is compared, the binding force on cellular glass surface between film and substrate and between film layer
Compare eight times or more of increase 10.
As seen from the above embodiment, present invention application reverse micelle microballoon etching glass surface forms the knot in micron order hole hole
Structure；Gained glass substrate is that glass is cheated in micron order hole, porous structure is presented, surface area is big, stable structure, wear-resisting.Also, this
Invention carries out plated film in micron order hole hole glass surface, and film can be embedded into glass orifice, and available section is wavy
Three-dimensional membrane structure.Therefore, it is not only increased between film and substrate using the film plating process of glass substrate provided by the invention
Binding force, and improve the binding force between film layer, so as to improve the stability and reliability of film function, be conducive to application.
The above is only a preferred embodiment of the present invention, it is noted that for making the professional technique of the art
Personnel are that by various modifications to these embodiments without departing from the technical principles of the invention, and these
Modification also should be regarded as the range that the present invention should protect.
Claims (8)
1. a kind of glass substrate, which is characterized in that be surface-treated to obtain through reverse micelle microballoon microemulsion by glass；The reverse micelle
Microballoon microemulsion is formed by the chemical corrosion liquid that alcohol, nonpolar solvent and surfactant wrap up；
The glass substrate is cheated with micron order hole；
The nonpolar solvent is selected from one or more of linear paraffin, substituted straight chain alkane, branched paraffin and aromatic hydrocarbon.
2. glass substrate according to claim 1, which is characterized in that the surfactant be selected from sodium alkyl benzene sulfonate,
Sodium alkyl sulfonate, sodium alkyl sulfate, sodium sulfate of polyethenoxy ether of fatty alcohol, sodium alkyl sulfonate etc., trimethyl bromine
Change ammonium, cetyl trimethylammonium bromide, cetyl front three ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, hexadecane
Base trimethyl ammonium heteropoly acids, empgen BB, N- amido propyl dimethyl carboxymethyl ammonium glycine betaine, polyol type it is non-from
Sub- surfactant, polyoxyethylene non-ionic surfactant and PULLRONIC F68 type nonionic surfactant
One or more of.
3. glass substrate according to claim 1, which is characterized in that the chemical corrosion liquid is selected from acids corrosive liquid or alkali
Class corrosive liquid.
4. a kind of film plating process of glass surface, comprising the following steps:
A) glass is surface-treated using reverse micelle microballoon microemulsion, obtains the glass substrate that there is micron order hole to cheat；Institute
Reverse micelle microballoon microemulsion is stated to be formed by the chemical corrosion liquid that alcohol, nonpolar solvent and surfactant wrap up；The nonpolarity
Solvent is selected from one or more of linear paraffin, substituted straight chain alkane, branched paraffin and aromatic hydrocarbon；
B) the plated film on the glass baseplate surface, the glass material after obtaining plated film.
5. film plating process according to claim 4, which is characterized in that the step A) in, the chemical corrosion liquid is selected from
Acids corrosive liquid or bases corrosive liquid.
6. film plating process according to claim 4, which is characterized in that the step A) in, the time of the surface treatment
For 0.5h~10h, the temperature of the surface treatment is 10 DEG C~120 DEG C.
7. film plating process according to claim 4, which is characterized in that the step B) in, the mode of the plated film is magnetic
Control sputtering method or chemical vapour deposition technique.
8. the film plating process according to any one of claim 4~7, which is characterized in that the step A) before further include:
Glass is washed using cleaning solution, the glass after being washed；The cleaning solution includes aqueous solution or anhydrous solvent；
The step A) are as follows: the glass after washing is surface-treated using reverse micelle microballoon microemulsion, it is cleaned, had
The glass substrate for thering is micron order hole to cheat.
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