CN113683314A - Low-emissivity film, coated glass and preparation method thereof - Google Patents
Low-emissivity film, coated glass and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 23
- 239000010959 steel Substances 0.000 claims abstract description 23
- 239000010410 layer Substances 0.000 claims description 289
- 239000000758 substrate Substances 0.000 claims description 64
- 229910007667 ZnOx Inorganic materials 0.000 claims description 23
- 239000011229 interlayer Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 239000007888 film coating Substances 0.000 claims description 11
- 238000009501 film coating Methods 0.000 claims description 11
- 229910004205 SiNX Inorganic materials 0.000 claims description 10
- 239000011241 protective layer Substances 0.000 claims description 9
- 238000005496 tempering Methods 0.000 claims description 8
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims description 7
- 229910001120 nichrome Inorganic materials 0.000 claims description 7
- 229910007717 ZnSnO Inorganic materials 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- AKJVMGQSGCSQBU-UHFFFAOYSA-N zinc azanidylidenezinc Chemical compound [Zn++].[N-]=[Zn].[N-]=[Zn] AKJVMGQSGCSQBU-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 13
- 239000004332 silver Substances 0.000 abstract description 13
- 230000005540 biological transmission Effects 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000007935 neutral effect Effects 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- 238000005452 bending Methods 0.000 description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 229910000599 Cr alloy Inorganic materials 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 229910001297 Zn alloy Inorganic materials 0.000 description 4
- 229910002065 alloy metal Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
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- 230000003595 spectral effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
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- 239000006062 low-transmittance glass Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
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- 210000004243 sweat Anatomy 0.000 description 1
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- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
- B32B17/1022—Metallic coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/02—Re-forming glass sheets
- C03B23/023—Re-forming glass sheets by bending
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/04—Tempering or quenching glass products using gas
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
-
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
- C03C17/366—Low-emissivity or solar control coatings
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a low-emissivity film, coated glass and a preparation method thereof, wherein a ZrO layer, a Cr layer or a CrNx layer and the like are introduced at the position of a specific film layer through the structural design of the low-emissivity film, so that the low-emissivity film has the advantages of neutral transmission color, high temperature resistance, shading property, good wear resistance, good oxidation resistance and the like, is simultaneously suitable for preparing flat steel and bent steel coated glass, and can be used for preparing steel three-silver coated glass.
Description
Technical Field
The embodiment of the invention relates to the technical field of films or building materials, in particular to a low-emissivity film, coated glass and a preparation method thereof.
Background
Because the bent steel glass is provided with a radian, the film coating is difficult to be carried out by the existing equipment, so that the method of coating the film first and then tempering is adopted when the bent steel coated glass is produced.
The existing film material is mainly applied to flat steel film coating, the adaptive process is firstly toughening and then film coating, and the film material is applied to the firstly film coating and then toughening process, so that the film material is easily oxidized in the toughening process, and the color tone and the energy conservation are influenced.
The three-silver glass is coated glass with a multi-layer composite film structure, and the coating film contains three independent silver layers, so that the energy-saving property is good. With the popularization of the three-silver glass in the market, the three-silver glass becomes the mainstream of high-end building materials and has considerable market acceptance. Because the protective film of the three-silver glass has a multilayer structure, the production of the bent steel three-silver glass has great challenge, the problem of heavy color tone is easy to occur after the coating film is subjected to a toughening process, and when the coating film is seen from the indoor to the outdoor, the outdoor color is greatly changed, so that the neutral and natural effects cannot be achieved. Or, in order to pursue the color of the glass, the application requirements are difficult to meet at the expense of the performance of the product such as energy conservation and the like.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
The embodiment of the invention provides a low-emissivity film, which has the advantages of neutral transmission color, high temperature resistance, shading property, wear resistance and good oxidation resistance, and is particularly suitable for preparing bent steel coated glass.
In a first aspect, an embodiment of the present invention provides a low-emissivity film, including:
the solar cell comprises a first dielectric layer, a first Ag layer protection layer, a first dielectric protection layer, a second dielectric layer, a first shading layer, a second Ag layer protection layer, a second dielectric protection layer, a third dielectric layer, a second shading layer, a third Ag layer protection layer, a third dielectric protection layer, a fourth dielectric layer and a ZrO layer which are sequentially stacked; the first sunshade layer and the second sunshade layer are Cr layers or CrN layers independentlyxAnd (3) a layer.
Wherein the dielectric layer serves as a connection, which relieves the internal stress of the entire film structure.
The Ag layer protective layer protects the Ag layer from oxidation during the coating process, and the dielectric protective layer can further prolong the oxidation resistance time.
CrNxA layer formed by introducing nitrogen gas during the Cr-plating. A Cr layer or CrN layer is arranged between the second dielectric layer and the second Ag layer and between the third dielectric layer and the third Ag layerxThe layer can reduce the green and yellow transmission of the film layer, adjust the visible light transmittance and improve the shading performance. In addition, a Cr layer or CrNxThe layer has better heat absorption effect, is easier to be heated when the product is toughened, can save the heating time and reduce the production energy consumption.
For shading coefficient, Cr < CrNxHowever, Cr hardness is relatively high, and the stress uniformity of the film layer is not as good as CrNx。CrNxThe stress is more uniform, the upper part and the lower part of the middle part of the film layer are supported, and the stress of the whole film layer can be better balanced.
The first sunshade layer and the second sunshade layer are both CrNxThe layer is used for preparing bent steel three-silver sandwich glass, the tested color tone a is 0, b is-1 to-3, the product is neutral transmission color, and the shading coefficient is 0.26.
The ZrO layer can improve high temperature resistance, wear resistance and oxidation resistance and improve hot workability.
According to some embodiments of the invention, the ZrO layer may be 3 to 15 nm.
According to some embodiments of the invention, the first dielectric is a dielectric materialThe first dielectric layer, the second dielectric layer, the third dielectric layer and the fourth dielectric layer are independently a silicon nitride layer or an oxide layer, a zinc nitride layer or an oxide layer, ZnSnOxOne or more of the layer, the titanium oxide layer and the aluminum oxide layer.
The first dielectric layer may be a first SiN layer sequentially stackedxLayer, first ZnOxLayer, wherein the first ZnOxA layer arranged on the first SiNxBetween the layer and the first Ag layer.
The first SiNxThe layer may be 20 to 30 nm.
The first ZnOxThe layer may be 7 to 12 nm.
The second dielectric layer may be a first ZnSnO sequentially stacked on the first dielectric protective layerxLayer, second ZnOxAnd (3) a layer.
The first ZnSnOxThe layer may be 40 to 60 nm.
The second ZnOxThe layer may be 7 to 12 nm.
The third dielectric layer may be a second ZnSnO sequentially stacked on the second dielectric protective layerxLayer, third ZnOxAnd (3) a layer.
The second ZnSnOxThe layer may be 50 to 70 nm.
The third ZnOxThe layer may be 7 to 12 nm.
The fourth dielectric layer may be second SiNxThe layer may have a thickness of 20 to 40 nm.
According to some embodiments of the present invention, the first Ag layer protection layer, the second Ag layer protection layer, and the third Ag layer protection layer may be a metal, an oxide of a metal, or a nitride of a metal, or a combination thereof, wherein the metal may be a single metal or an alloy metal, such as Ni, Cr, Zn, Al, Ni alloy, Cr alloy, Zn alloy, or Al alloy, and the first Ag layer protection layer, the second Ag layer protection layer, and the third Ag layer protection layer may be Ni layer or NiCr layer, which may better adjust visible light transmittance.
The first Ag layer protection layer may be 0.5 to 3 nm.
The second Ag layer protection layer may be 0.5 to 3 nm.
The third Ag layer protection layer may be 0.5-5 nm.
According to some embodiments of the present invention, the first dielectric protection layer, the second dielectric protection layer, and the third dielectric protection layer may be a metal, an oxide of a metal, a nitride of a metal, or a combination thereof, wherein the metal may be a single metal or an alloy metal, such as Ni, Cr, Zn, Al, a Ni alloy, a Cr alloy, a Zn alloy, or an Al alloy, and the first dielectric protection layer, the second dielectric protection layer, and the third dielectric protection layer may be aluminum-doped zinc oxide (AZO) and may have a thickness of 5 to 10 nm.
According to some embodiments of the invention, the first and second sunshade layers are both CrNxAnd (3) a layer.
The first sunshade layer may be 0.5 to 3 nm.
The second sunshade layer can be 0.5-3 nm.
According to some embodiments of the invention, the first Ag layer may be 4-15 nm.
The second Ag layer may be 8-20 nm.
The third Ag layer may be 10-20 nm.
In a second aspect, an embodiment of the present invention further provides a coated glass, including a first glass substrate and the low-emissivity film, where the low-emissivity film is attached to the first glass substrate, and the first dielectric layer of the low-emissivity film is attached to a surface of the first glass substrate.
The coated glass can be in a single layer structure, a sandwich structure or a hollow structure, and can be in a planar or non-planar structure (such as a cambered surface structure).
According to some embodiments of the present invention, the coated glass is a triple silver interlayer glass, that is, the coated glass further includes a second glass substrate and an interlayer, and the second glass substrate is attached to the other surface of the first glass substrate opposite to the low-emissivity film through the interlayer.
The first glass substrate and the second glass substrate may have the same thickness or different thicknesses. The thickness of the first glass substrate and the second glass substrate may be 5mm, 6mm, 8mm, 10mm, 12mm, or the like.
According to some embodiments of the invention, the first glass substrate and the second glass substrate are both bent steel glass, the shading coefficient can be less than or equal to 0.26, and the transmission hues a and b can be as follows: -5 ≦ a ≦ 5, -5 ≦ b ≦ 5.
According to some embodiments of the invention, the interlayer may be EVA (ethylene vinyl acetate), PVB (polyvinyl butyral), SGP (Sentry Glas Plus), etc., and may be 0.38mm, 0.76mm, 1.14mm, 1.52mm, etc., in thickness.
In a third aspect, an embodiment of the present invention further provides a method for preparing coated glass, including: and coating a film on the surface of a first glass substrate to form the low-radiation film on the surface of the first glass substrate, wherein the first dielectric layer of the low-radiation film is attached to the surface of the first glass substrate.
According to some embodiments of the invention, the method of preparing further comprises: and tempering the first glass substrate after film coating.
The tempering may be a bending treatment. Based on the excellent characteristics of neutral transmission color, good sun-shading property, good heat resistance and the like of the low-radiation film, the method can be suitable for the processes of film coating before tempering, and can be used for preparing the bent steel coated glass.
According to some embodiments of the invention, the method of preparing further comprises: and arranging an interlayer between the second glass substrate and the first glass substrate after film coating, attaching the interlayer to the other side surface of the first glass substrate opposite to the low-emissivity film, laminating, and performing pressure molding.
According to some embodiments of the present aspect, the second glass substrate is tempered glass. In the case where the first glass substrate is bent glass reinforced plastic, the second glass substrate is bent glass reinforced plastic.
According to some embodiments of the present aspect, before providing an interlayer between the second glass substrate and the first glass substrate after the coating, the method further comprises: and cleaning the second glass substrate and the first glass substrate after film coating.
According to some embodiments of the invention, the press forming is performed by using vacuum bag press and autoclave press.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the example serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a schematic structural view of a coated glass according to an embodiment of the present invention.
In the figure: low-emissivity film 100, first dielectric layer 110, and first SiNxLayer 111, first ZnOxLayer 112, first Ag layer 120, first Ag layer protective layer 130, first dielectric protective layer 140, second dielectric layer 150, first ZnSnOxLayer 151, second ZnOxLayer 152, first solar shading layer 160, second Ag layer 170, second Ag layer protection layer 180, second dielectric protection layer 190, third dielectric layer 210, second ZnSnOxLayer 211, third ZnOxLayer 212, second solar shading layer 220, third Ag layer 230, third Ag layer protection layer 240, third dielectric protection layer 250, fourth dielectric layer 260, ZrO layer 270; a first glass substrate 200.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The terms:
medium-low transmittance, which generally means that the transmittance of solar energy is less than 60%, and the percentage of ultraviolet light, visible light and infrared light transmitting through the glass is the transmittance in the solar spectrum range;
bending steel, namely non-planar tempering;
flat steel means flat tempering.
Fig. 1 is a schematic structural diagram of a coated glass according to an embodiment, and the coated glass includes a first glass substrate 200 and a low-emissivity film 100.
The low-emissivity film 100 includes a first dielectric layer 110, a first Ag layer 120, a first Ag layer protection layer 130, a first dielectric protection layer 140, a second dielectric layer 150, a first shading layer 160, a second Ag layer 170, a second Ag layer protection layer 180, a second dielectric protection layer 190, a third dielectric layer 210, a second shading layer 220, a third Ag layer 230, a third Ag layer protection layer 240, a third dielectric protection layer 250, a fourth dielectric layer 260, and a ZrO layer 270, which are sequentially stacked on a surface of a first glass substrate 200.
Wherein the first sunshade layer 160 and the second sunshade layer 220 are Cr layer or CrN layer independentlyxLayer of CrNxThe layer is formed by introducing nitrogen gas during Cr plating. Cr layer or CrNxThe layer can improve the color tone, improve the conditions of greenish and yellowish transmission color, adjust the visible light transmittance and improve the shading property. In addition, the heat absorption effect is good, and the glass is easy to heat, so that when the glass is used for preparing the bent steel coated glass, the heating time of the coated glass in the toughening process can be saved, and the production energy consumption is reduced.
It should be noted that, in terms of sun-shading properties, Cr is smaller than CrNxHowever, Cr has a relatively high hardness, which may cause non-uniformity of stress in the film. And CrNxThe layer stress is more uniform, plays a role in starting and stopping in the film, and can better balance the internal stress of the film.
As an example, the first sunshade layer 160 may be 0.5 to 3 nm. The second sunshade layer 220 may be 0.5 to 3 nm.
The dielectric layer serves as a connection and can relieve internal stress of the whole film structure. The material of the dielectric layer can be selected from silicon nitride or oxide, zinc nitride or oxide, ZnSnOxTitanium oxide, aluminum oxide, and the like. One of them can be selected, and multiple of them can be selected for multilayer compounding.
As an example, the first dielectric layer 110 is a first SiNx layer 111 and a first ZnOx layer 112 sequentially stacked on the surface of the first glass substrate 200. The thickness of the first SiNx layer 111 may be 20-30 nm, and the thickness of the first ZnOx layer 112 may be 7-12 nm.
As an example, the second dielectric layer 150 is a first ZnSnOx layer 151 and a second ZnOx layer 152 sequentially stacked on the first dielectric protection layer 140. The first ZnSnOx layer 151 may be 40 to 60 nm. The second ZnOx layer 152 may be 7 to 12 nm.
As an example, the third dielectric layer 210 is a second ZnSnOx layer 211 and a third ZnOx layer 212 which are sequentially stacked and disposed on the second dielectric protection layer 190. The second ZnSnOx layer 211 may be 50 to 70 nm. The third ZnOx layer 212 may be 7 to 12 nm.
The fourth dielectric layer 260 also functions as a link layer 270, and by introducing the ZrO layer 270 as an outer layer, high temperature resistance, wear resistance, and oxidation resistance can be improved, and hot workability can be improved.
By way of example, the fourth dielectric layer 260 is second SiNxThe layer may have a thickness of 20 to 40 nm.
As an example, the ZrO layer 270 may be 3 to 15 nm.
The Ag layer has high reflectivity to infrared rays and good heat insulation performance. As an example, the first Ag layer 120 may be 4-15 nm, the second Ag layer 170 may be 8-20 nm, and the third Ag layer 230 may be 10-20 nm.
The first Ag layer protecting layer 130, the second Ag layer protecting layer 180, and the third Ag layer protecting layer 240 protect the Ag layer, and may be a metal, an oxide of a metal, or a nitride of a metal, or a combination thereof. The metal may be a single metal or an alloy metal, such as Ni, Cr, Zn, Al, Ni alloy, Cr alloy, Zn alloy, or Al alloy, and the first Ag layer protection layer 130, the second Ag layer protection layer 180, and the third Ag layer protection layer 240 may be the same or different. As an example, the first Ag layer protection layer 130, the second Ag layer protection layer 180, and the third Ag layer protection layer 240 may be Ni layers or NiCr layers, which are beneficial to adjusting visible light transmittance, so as to obtain the medium-low transmittance glass. The Ni layer or NiCr layer can be matched with the first sunshade layer 160 and the second sunshade layer 220, and the shading property can be further improved.
As an example, the first Ag layer protecting layer 130 may be 0.5 to 3 nm. The second Ag layer protection layer 180 may be 0.5 to 3 nm. The third Ag layer protection layer 240 may be 0.5-5 nm.
The dielectric protective layer is used in cooperation with the Ag layer protective layer to improve the protection of the Ag layer, and may be selected from a metal, an oxide of a metal, a nitride of a metal, or a combination thereof, wherein the metal may be a single metal or an alloy metal, such as Ni, Cr, Zn, Al, a Ni alloy, a Cr alloy, a Zn alloy, or an Al alloy. By way of example, the first dielectric protection layer 140, the second dielectric protection layer 190, and the third dielectric protection layer 250 are all aluminum-doped zinc oxide (AZO), and the thickness may be 5 to 10 nm.
The coated glass of the embodiment can be used for preparing three-silver interlayer glass, and one surface of the coated glass, which is far away from the low-emissivity film 100, is attached to a second glass substrate through an interlayer.
The thicknesses of the first glass substrate 200 and the second glass substrate may be the same or different. The thickness of the first glass substrate 200, the second glass substrate may be 5mm, 6mm, 8mm, 10mm, 12mm, etc.
The interlayer may be EVA, PVB, SGP, etc., and the thickness may be 0.38mm, 0.76mm, 1.14mm, 1.52mm, etc.
The following description will be given with reference to specific examples.
Examples
A triple silver interlayer glass comprising: a second glass substrate (6mm), PVB (1.52mm), a first glass substrate 200(6mm) and a low-emissivity film 100 which are laminated in sequence, wherein the low-emissivity film 100 comprises SiN laminated on the surface of the other side, opposite to the PVB, of the first glass substrate in sequencex(20~30nm)、ZnOx(7~12nm)、Ag(4~15nm)、NiCr(0.5~3nm)、AZO(5~10nm)、ZnSnOx(40~60nm)、ZnOx(7~12nm)、CrNx(0.5~3nm)、Ag(8~20nm)、NiCr(0.5~3nm)、AZO(5~10nm)、ZnSnOx(50~70nm)、ZnOx(7~12nm)、CrNx(0.5~3nm)、NiCr(0.5~5nm)、Ag(10~20nm)、AZO(5~10nm)、SiNx(20~40nm)、ZrO(3~15nm)。
The preparation method of the three-silver interlayer glass comprises the following steps:
(1) film coating: according to the structure of the low-emissivity film 100, the first glass substrate 200 is sequentially coated with corresponding film materials, so that the low-emissivity film 100 is formed on one surface of the first glass substrate, and the coated first glass substrate is obtained.
(2) Bending steel: and performing steel bending treatment on the second glass substrate and the first glass substrate after being coated with the film, wherein the steel bending treatment comprises the following specific steps: and heating the second glass substrate and the first glass substrate subjected to film coating until the second glass substrate and the first glass substrate are softened, then performing arc-changing forming, and finally performing air cooling.
The heating device comprises: a heating furnace and a convection fan.
For the first glass substrate after being coated, because the low-emissivity film 100 can reflect infrared rays, in order to ensure that the temperatures of the upper surface and the lower surface of the coated glass are consistent, the upper surface heating mode is heat conduction and convection heating combined, and the lower surface heating mode is heat conduction.
The heating pattern of the upper and lower surfaces is uniform for the second glass substrate.
The forming equipment consists of a forming mechanism (examples comprise a forming air grid and a hinge), an air blowing system (examples comprise an air compressor, an air supply pipeline and an air nozzle), a transmission (examples comprise a transmission roller) and a lifting system (examples comprise an upper air grid lifting cylinder and a lower air grid lifting cylinder). The forming apparatus is well known in the art and will not be described in detail.
The air grid is changed into arc under the action of the hinge when the glass is conveyed to the forming section, and the glass swings back and forth in the forming section and is formed according to the radian of the air grid under the action of self weight. And simultaneously blowing air to the surface of the glass to enable the glass to generate stress, and finally finishing glass bending steel.
(3) Arranging an interlayer:
before the interlayer is carried out, the glass after the steel bending is cleaned, the coated surface faces upwards when the coated first glass substrate is cleaned, the thickness of the glass is adjusted to be consistent with the thickness of the glass by a cleaning machine, the cleaning water is pure water, and the electrical conductivity is less than or equal to 10 mu/s.
And arranging an interlayer PVB between the cleaned second glass and the coated first glass substrate, adhering the other side surface of the first glass substrate 200, which is opposite to the low-radiation film 100, to the PVB, laminating, and pressing for molding.
Because glass has the radian, the pressure forming adopts vacuum bag pressure, autoclave shaping to ally oneself with usefulness, includes:
(301) wrapping silk cloth: after the sheet is combined, a high-temperature adhesive tape is used for fixing, and meanwhile, silk cloth and felt are used for sequentially wrapping the edge of the glass, so that the phenomenon that the vacuum bag is stuck with the glass to leave marks when the kettle is burnt is prevented.
(302) And (3) edge sealing of a vacuum bag: bagging, vacuumizing, sealing edges by using an edge sealing machine, and checking the sealing condition of the vacuum bag after edge sealing, particularly the corner position, so as to ensure no air leakage.
(303) Cold pumping: vacuumizing until the vacuum degree reaches-0.08 Mpa, and keeping for more than 10 minutes to ensure no air leakage.
(304) Pre-pumping: loading into a kettle, wherein the vacuum degree in the kettle is-0.08 Mpa, and the pre-pumping time is more than or equal to 15 minutes;
(305) and (3) burning the kettle: keeping the temperature at 135 deg.C and pressure at 1.2Mpa for more than 90min, and maintaining the vacuum degree at not less than-0.06 Mpa during heating and pressure increasing and pressure maintaining processes.
Comparative example 1
The commercially available flat steel medium-low transmittance three-silver interlayer glass matched with the color and phase modulation of the product of the embodiment is prepared by the process of tempering and coating.
Comparative example 2
The difference compared to the examples is that no ZrO layer is present.
Test example
Color tone: the test is carried out by using a desk type spectral colorimeter (YS6060), wherein test windows are respectively pasted on the inner surface and the outer surface of the glass, and a test button is pressed for direct reading.
Transmittance, reflectance, shading coefficient: and detecting by using a Lambda 950 spectrophotometer. The detection method comprises the following steps: and (3) turning on detection software, enabling the glass detection surface to face a light source, starting detection, obtaining spectral data, and calculating by using W5 software.
Photothermal ratio (selection coefficient): transmittance/shading coefficient.
Heat transfer coefficient: T/CECS 627-2019.
The example products have a hue a of 0 and b of-1 to-3, and are seen to be neutral in transmission. The shading coefficient SC is 0.26, see Table 1. When the existing coating is applied to a process of coating first and then toughening, even if neutral tone can be realized, the sun-shading coefficient is generally over 0.3.
It can also be seen from table 1 that the product of the present embodiment can achieve a level similar to that of a product plated after first steel in terms of color and performance, and fills a technical gap that the existing similar coating is difficult to be applied to the process of plating after steel.
TABLE 1
To compare the influence of the ZrO layer on the plating performance, the oxidation resistance and wear resistance of the example product and the comparative example 2 product were tested.
Antioxidant experiment: the membrane surface was stained with sweat, the product of comparative example 2 without the addition of zirconia layer, the glass membrane surface was oxidized within 12 hours, and the oxidation resistance time of the membrane surface of the product of the example reached more than 48 hours.
Grinding experiment: the glass surface was ground by placing the glass on a grinder with the surface of the glass facing upward, pressing down a grinding wheel (500g) at a grinding speed of 200 revolutions. Comparison of Permeability before and after grinding, product T of comparative example 2Before grinding-TAfter grinding0.5, and example product TBefore grinding-TAfter grinding=0.1~0.2。
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the foregoing and various other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention.
Claims (10)
1. A low emissivity film, comprising:
the solar cell comprises a first dielectric layer, a first Ag layer protection layer, a first dielectric protection layer, a second dielectric layer, a first shading layer, a second Ag layer protection layer, a second dielectric protection layer, a third dielectric layer, a second shading layer, a third Ag layer protection layer, a third dielectric protection layer, a fourth dielectric layer and a ZrO layer which are sequentially stacked;
the first sunshade layer and the second sunshade layer are Cr layers or CrNx layers independently.
2. The low emissivity film of claim 1, wherein the first dielectric layer, the second dielectric layer, the third dielectric layer, and the fourth dielectric layer are independently a silicon nitride layer or an oxide layer, a zinc nitride layer or an oxide layer, ZnSnOxOne or more of the layer, the titanium oxide layer and the aluminum oxide layer.
3. The low emissivity film of claim 2, wherein the first dielectric layer comprises a first SiN layer disposed in a sequential stackxLayer, first ZnOxLayer, wherein the first ZnOxA layer arranged on the first SiNxBetween a layer and the first Ag layer; and optionally, the second dielectric layer comprises a first ZnSnO layer sequentially laminated and arranged on the first dielectric protective layerxLayer, second ZnOxA layer; and optionally, the third dielectric layer comprises a second ZnSnO sequentially stacked and arranged on the second dielectric protection layerxLayer, third ZnOxA layer; and optionally, the fourth dielectric layer is second SiNxAnd (3) a layer.
4. The low emissivity film of claim 1, wherein the first, second, and third Ag layer protecting layers are independently Ni or NiCr layers.
5. The low emissivity film of claim 1, wherein the first, second, and third dielectric caps are AZO.
6. The low emissivity film of claim 1, wherein the first solar shading layer has a thickness of 0.5 to 3 nm; and optionally, the thickness of the second sun-shading layer is 0.5-3 nm.
7. A coated glass, comprising:
a first glass substrate;
the low-emissivity film of any one of claims 1 to 6, attached to the first glass substrate, wherein the first dielectric layer of the low-emissivity film is attached to a surface of the first glass substrate.
8. The coated glass of claim 7, further comprising a second glass substrate and an interlayer, wherein the second glass substrate is attached to the other surface of the first glass substrate opposite to the low-emissivity film through the interlayer.
9. The coated glass of claim 8, wherein the first glass substrate and the second glass substrate are both bent steel glass.
10. A preparation method of coated glass is characterized by comprising the following steps:
coating a first glass substrate surface to form the low-radiation film according to any one of claims 1 to 6 on the first glass substrate surface, wherein the first dielectric layer of the low-radiation film is attached to the first glass substrate surface;
and optionally, tempering the first glass substrate after film coating.
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