CN114772945A - Coated fireproof glass with sunlight control and low radiation functions and preparation method thereof - Google Patents
Coated fireproof glass with sunlight control and low radiation functions and preparation method thereof Download PDFInfo
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- CN114772945A CN114772945A CN202210430491.8A CN202210430491A CN114772945A CN 114772945 A CN114772945 A CN 114772945A CN 202210430491 A CN202210430491 A CN 202210430491A CN 114772945 A CN114772945 A CN 114772945A
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- 239000011521 glass Substances 0.000 title claims abstract description 94
- 230000005855 radiation Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 22
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 229910000077 silane Inorganic materials 0.000 claims description 15
- 230000009970 fire resistant effect Effects 0.000 claims description 13
- 239000005388 borosilicate glass Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000002834 transmittance Methods 0.000 claims description 9
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002310 reflectometry Methods 0.000 claims description 4
- 230000002265 prevention Effects 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 78
- 238000012360 testing method Methods 0.000 abstract description 9
- 239000011247 coating layer Substances 0.000 abstract description 6
- 238000005496 tempering Methods 0.000 abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- QZRLETONGKUVFA-UHFFFAOYSA-N [K].[Cs] Chemical compound [K].[Cs] QZRLETONGKUVFA-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3482—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising silicon, hydrogenated silicon or a silicide
-
- 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
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
-
- 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
-
- 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
- C03C2218/152—Deposition methods from the vapour phase by cvd
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention relates to the technical field of glass manufacturing, in particular to coated fireproof glass with sunlight control and low radiation functions and a preparation method thereof; the coating layer comprises a silicon dioxide layer, an amorphous silicon layer and a fluorine-doped tin dioxide layer which are sequentially arranged; after the fireproof coated glass provided by the invention is applied to glass manufacturing, the stress of the manufactured glass after tempering reaches more than 90Mpa, the stress deviation of the plate surface is less than 5Mpa, the fireproof coated glass has the functions of sunlight control and low radiation, and can be fireproof, and the fireproof coated glass reaches 90 minutes after a fireproof test.
Description
Technical Field
The invention relates to the technical field of glass manufacturing, in particular to coated fireproof glass with functions of sunlight control and low radiation and a preparation method thereof.
Background
The fireproof glass mainly plays a role in controlling the spread of fire or isolating smoke during fire prevention, and is a measure type fireproof material, and the fireproof effect of the fireproof glass is evaluated by the fireproof performance. It is a special glass which is processed and treated by a special process and can keep the integrity and heat insulation performance in a specified fire resistance test. The original sheet glass of the fireproof glass can be float plane glass, toughened glass, composite fireproof glass and can also be made of single fireproof glass.
CN211222353U discloses a low-emissivity fire-proof glass structure, which is a fire-proof glass with a multi-layer film system structure, and the main functional layer is silver, and the coated glass with this structure cannot be used in a single layer, but can only be made into hollow glass, etc., and silver can be corroded when contacting with the outside.
The main functional layer disclosed in the preparation method of the CN100455530C high-strength monolithic low-emissivity coated fireproof glass is indium oxide doped with tin, the preparation method is liquid phase spraying, and the cesium potassium fireproof glass with the fireproof function is used. The uniformity of the film layer can not be guaranteed by liquid phase spraying, and the cost of ITO is high, so that the ITO coating is not easy to popularize; the cesium potassium fireproof glass is a product which is larger in market at present, but has lower fire resistance rating, and is initially replaced by a product with better fire resistance rating.
CN108249779A relates to a coating film layer that can realize electrical heating, the coating film layer is including setting up in outermost resistance adjustment layer, resistance adjustment layer includes fluorine-doped tin dioxide layer and set up in the second silica dioxide layer of fluorine-doped tin dioxide layer outside. According to the electrically heated coating layer provided by the invention, the resistance base number of the coating layer is increased by arranging the second silicon dioxide layer, and the resistance of the coating layer is adjusted to a proper range by arranging the fluorine-doped tin dioxide layer with adjustable fluorine content; the electrical heating coating layer provided by the invention can adjust the square resistance value to be more than 70 omega by adjusting the fluorine content of fluorine-doped tin dioxide, can reach more than 50 omega after glass tempering, and can meet the effect of controlling frost condensation through electrical heating. Meanwhile, the Haze (degree of Haze) of the obtained coated glass can be reduced to be below 0.5 percent due to the existence of the second silicon dioxide layer. However, the solar control has low radiation and fire-resistant functions.
Therefore, in view of the above disadvantages, it is desirable to provide a novel low-emissivity refractory glass.
Disclosure of Invention
The invention aims to solve the technical problems that the existing glass has low fire-resistant grade, generally does not have a sunlight control effect and has high radiance, and provides a film layer with the functions of sunlight control and low radiance, coated fireproof glass and a preparation method thereof, and sunlight-controlled low-radiance fireproof glass with low transmittance.
In order to solve the above technical problems, in a first aspect, the present invention provides a film with solar control and low radiation functions, where the film with solar control and low radiation functions includes a silicon dioxide layer, an amorphous silicon layer, and a fluorine-doped tin dioxide layer, which are sequentially disposed.
The film layer with the functions of sunlight control and low radiation is provided with a silicon dioxide layer, an amorphous silicon layer and a fluorine-doped tin dioxide layer. The silicon dioxide layer is used as a dielectric layer and can prevent sodium ions in the glass substrate from diffusing into the film layer, and meanwhile, the silicon dioxide layer can increase the bonding capacity of the amorphous silicon layer and the glass substrate. The amorphous silicon layer is an absorption layer, can effectively reduce the transmittance of visible light and solar energy, and has a sunlight control function. The fluorine-doped tin dioxide layer can reduce radiation and has an excellent infrared ray reflecting function.
Preferably, the thickness of the silicon dioxide layer is 10 to 30nm, and may be, for example, 10nm, 12nm, 15nm, 17nm, 20nm, 23nm, 25nm, 28nm, or 30 nm.
Preferably, the thickness of the silicon dioxide layer is 15-25 nm.
In the invention, the thickness of the silicon dioxide layer can influence the diffusion of sodium ions in the glass substrate to the film layer, and the other two films form a film system structure with required color.
Preferably, the amorphous silicon layer has a thickness of 30 to 60nm, such as 30nm, 35nm, 40nm, 42nm, 44nm, 45nm, 50nm, 55nm, or 60 nm.
Preferably, the amorphous silicon layer has a thickness of 40 to 50 nm.
In the present invention, the thickness variation of the amorphous silicon layer mainly determines the transmittance and reflectance of the coated glass, and forms a film system structure with a desired color with the other two films.
Preferably, the thickness of the fluorine-doped tin dioxide layer is 270-450 nm; for example, it may be 300nm, 310nm, 320nm, 330nm, 340nm, 350nm, 360nm, 370nm, 380nm, 390nm, or 400 nm.
Preferably, the thickness of the fluorine-doped tin dioxide layer is 330-380 nm.
Preferably, the proportion of fluorine in the fluorine-doped tin dioxide layer is 0.5% to 5%, preferably 1% to 3%. In the present invention, the proportion of fluorine in the fluorine-doped tin dioxide layer is calculated with respect to the total molar amount of fluorine relative to tin dioxide and fluorine.
In the invention, the thickness change of the fluorine-doped tin dioxide layer mainly determines the square resistance and the radiance of the glass, and a film system structure with required color is formed on the other two layers of films.
In a second aspect, the present invention provides a coated fire-resistant glass comprising the film layer with solar control and low-emissivity function of the first aspect and a borosilicate glass substrate, wherein the borosilicate glass substrate is connected with the silica layer in the film layer with solar control and low-emissivity function.
Preferably, the coated fire-proof glass has a reflectivity of 18% to 35%, for example, 18%, 23%, 25%, 30%, 31%, 32%, 33%, 34%, 35%, etc., preferably 30% to 33%.
Preferably, the coated fire-proof glass has a transmittance of 23% to 35%, for example, 23%, 25%, 26%, 31%, 35%, etc., preferably 23% to 26%.
Preferably, the square resistance of the coated fireproof glass is 11-26 Ω, for example, 16 Ω, 17 Ω, 18 Ω or 19 Ω, preferably 16-19 Ω.
Preferably, the emissivity of the coated fireproof glass is 0.11-0.25, for example, 0.14, 0.15, 0.16, 0.17 or 0.18, and preferably 0.14-0.18.
The film surface of the coated fireproof glass provided by the invention is bright purple red, the chromaticity coordinate is 54.63, 11.98 and 4.27.
In a third aspect, the invention provides a method for preparing the coated fireproof glass, which comprises the following steps:
(1) introducing a first mixed gas containing silane into a reactor, and reacting on the surface of a borosilicate glass substrate to prepare a silicon dioxide layer;
(2) introducing a second mixed gas containing silane into a reactor, and reacting on the surface of the silicon dioxide layer obtained in the step (1) to prepare an amorphous silicon layer;
(3) and (3) introducing a third mixed gas containing trichloro monobutyl tin steam into the reactor, and reacting on the surface of the amorphous silicon layer obtained in the step (2) to obtain the coated fireproof glass.
In the present invention, the surface temperature of the borosilicate glass substrate is generally controlled to be 640 to 660 ℃. The borosilicate glass substrate of the present invention is not particularly limited, and generally has an expansion coefficient of 3.3 x 10-7/K～4*10-7Substrates in the/K range are sufficient.
In the invention, all reactors are specially designed and manufactured, so that the vapor of the coating material can be uniformly distributed on the surface of the glass, the material reacts on the surface of the hot glass to form a film layer, and the tail gas is discharged out of the reactor through a specially designed channel. The glass surface temperature corresponding to the preparation of the silicon dioxide layer is 650-660 ℃, and the used reactor is provided with 1 feeding channel and two exhaust channels. The glass surface temperature corresponding to the amorphous silicon layer is 645-655 ℃, and the reactor used has 1 feed channel and 1 exhaust channel. The glass surface temperature corresponding to the preparation of the fluorine-doped tin dioxide layer is 640-650 ℃, the used reactor is provided with a plurality of feeding channels and a plurality of exhaust channels, and 1 reactor or a plurality of reactors can be selected according to the thickness of the film layer.
In the invention, each layer is prepared by adopting a chemical vapor deposition method, the preparation process is gradual, and the preparation efficiency is high.
Preferably, the first mixed gas in the step (1) is composed of silane, oxygen, ethylene and nitrogen.
In the present invention, the silane used refers to monosilane. The unit of the gas amount of the invention is L/m2The meaning of the unit is: the volume of the amount of gas used per square meter of glass is several liters.
Preferably, the total gas amount of the first mixed gas is 1.32-2.73L/m2It may be, for example, 1.32L/m2、1.43L/m2、1.52L/m2、1.68L/m2、1.79L/m2、1.85L/m2、1.9L/m2、1.95L/m2、2L/m2、2.1L/m2、2.11L/m2、2.45L/m2、2.67L/m2、2.73L/m2Etc., preferably 1.9 to 2.1L/m2；
Preferably, the amount of the silane gas in the first mixed gas is 0.01-0.07L/m2For example, it may be 0.01L/m2、0.02L/m2、0.03L/m2、0.04L/m2、0.05L/m2、0.05L/m2、0.06L/m2Or 0.07L/m2Etc., preferably 0.03 to 0.05L/m2。
Preferably, the amount of the oxygen in the first mixed gas is 0.04-0.30L/m2For example, it may be 0.04L/m2、0.06L/m2、0.09L/m2、0.12L/m2、0.14L/m2、0.15L/m2、0.16L/m2、0.17L/m2、0.18L/m2、0.25L/m2Or 0.30L/m2Etc., preferably 0.12 to 0.2L/m2。
Preferably, the amount of the ethylene gas in the first mixed gas0.06-0.45L/m2For example, it may be 0.06L/m2、0.17L/m2、0.23L/m2、0.24L/m2、0.25L/m2、0.26L/m2、0.27L/m2、0.28L/m2、0.35L/m2、0.42L/m2Or 0.45L/m2Etc., preferably 0.18 to 0.3L/m2。
Preferably, the amount of the nitrogen gas in the first mixed gas is 1.21 to 1.91L/m2It may be, for example, 1.21L/m2、1.34L/m2、1.48L/m2、1.50L/m2、1.52L/m2、1.55L/m2、1.58L/m2、1.60L/m2、1.78L/m2、1.84L/m2、1.86L/m2Or 1.91L/m2Etc., preferably 1.4 to 1.7L/m2。
Preferably, the second mixed gas in the step (2) is composed of silane, ethylene and nitrogen.
Preferably, the total gas amount of the second mixed gas is 2.25-3.20L/m2For example, it may be 2.25L/m2、2.34L/m2、2.51L/m2、2.60L/m2、2.64L/m2、2.7L/m2、2.73L/m2、2.75L/m2、2.79L/m2、2.85L/m2、2.95L/m2、3.12L/m2Or 3.20L/m2Etc., preferably 2.5 to 2.8L/m2。
Preferably, the amount of the silane gas in the second mixed gas is 0.10-0.30L/m2For example, it may be 0.10L/m2、0.12L/m2、0.15L/m2、0.16L/m2、0.17L/m2、0.18L/m2、0.19L/m2、0.20L/m2、0.25L/m2Or 0.30L/m2Etc., preferably 0.16 to 0.21L/m2。
Preferably, the amount of the ethylene gas in the second mixed gas is 0.15-0.45L/m2For example, it may be 0.15L/m2、0.21L/m2、0.25L/m2、0.26L/m2、0.27L/m2、0.28L/m2、0.29L/m2、0.30L/m2、0.31L/m2、0.35L/m2、0.40L/m2Or 0.45L/m2Etc., preferably 0.25 to 0.32L/m2。
Preferably, the amount of the nitrogen gas in the second mixed gas is 2.00-2.45L/m2For example, it may be 2.00L/m2、2.12L/m2、2.20L/m2、2.21L/m2、2.22L/m2、2.23L/m2、2.24L/m2、2.25L/m2、2.26L/m2、2.27L/m2、2.28L/m2、2.33L/m2、2.38L/m2Or 2.45L/m2And so on.
Preferably, the third mixed gas in the step (3) consists of trichloro monobutyl tin vapor, trifluoroacetic acid vapor, nitrogen, oxygen and water vapor.
Preferably, the total gas amount of the third mixed gas is 23.05-26.15L/m2It may be, for example, 23.05L/m2、23.25L/m2、23.42L/m2、23.83L/m2、24.54L/m2、25.13L/m2、25.46L/m2、25.89L/m2Or 26.15L/m2And so on.
Preferably, in the third mixed gas, the gas amount of the trichloro monobutyl tin vapor is 0.8-1.3L/m2For example, it may be 0.8L/m2、0.9L/m2、1.0L/m2、1.1L/m2、1.2L/m2Or 1.3L/m2Etc., preferably 0.9 to 1.2L/m2。
Preferably, in the third mixed gas, the amount of the trifluoroacetic acid vapor is 0.35-0.55L/m2For example, it may be 0.35L/m2、0.38L/m2、0.42L/m2、0.43L/m2、0.44L/m2、0.45L/m2、0.46L/m2、0.51L/m2Or 0.55L/m2Etc., preferably 0.4 to 0.5L/m2。
Preferably, the amount of nitrogen in the third mixed gas is 13.2-13.8L/m2It may be, for example, 13.2L/m2、13.3L/m2、13.4L/m2、13.5L/m2、13.6L/m2、13.7L/m2Or 13.8L/m2And so on.
Preferably, the amount of the oxygen in the third mixed gas is 6.5-7L/m2It may be, for example, 6.5L/m2、6.6L/m2、6.7L/m2、6.8L/m2、6.9L/m2Or 7L/m2And the like.
Preferably, in the third mixed gas, the amount of the water vapor is 2.2 to 3.5L/m2It may be, for example, 2.2L/m2、2.3L/m2、2.4L/m2、2.5L/m2、2.6L/m2、2.7L/m2、2.8L/m2、2.9L/m2、3L/m2、3.2L/m2、3.4L/m2Or 3.5L/m2Etc., preferably 2.7 to 3.1L/m2。
In a fourth aspect, the invention provides a solar control, low-emissivity, fire-resistant glass, which comprises the coated fire-resistant glass of the second aspect.
Preferably, the glass stress of the fireproof glass with the functions of solar control and low radiation is 90-200 MPa;
preferably, the plate surface stress deviation of the fireproof glass with the solar control and low-radiation functions is not higher than 5 MPa.
The fireproof glass with the functions of solar control and low radiation is obtained by tempering coated fireproof glass, and the deviation of the tested glass stress and the plate surface stress is also a result obtained by testing after tempering.
The fireproof coating layer provided by the invention has low cost and the expansion coefficient is 3.3 x 10-7/K～4*10-7The dielectric layer, the sun-shading layer and the functional layer are prepared on the borosilicate glass substrate of the/K by utilizing an on-line chemical vapor deposition method, the high-grade fireproof glass with the function of controlling low radiation by sunlight is prepared after the glass is tempered by a proper process, and the fire resistance test can reach more than 90 minutes.
The implementation of the invention has the following beneficial effects:
the glass provided by the invention organically combines the sunlight control function, the low radiation function and the fireproof function together, and provides the fireproof glass with a certain transmittance and the infrared ray reflection function, the film layer is combined with the glass substrate through chemical bonds through high-temperature reaction, the fireproof glass has excellent chemical stability and high temperature resistance, and the fireproof performance can reach more than 90 minutes through a fireproof test, and the fireproof glass has the performances of low transmittance and low reflectivity.
Detailed Description
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the following examples of the present invention, the borosilicate glass substrate used was borosilicate glass.
Example 1
The coated fireproof glass is prepared by the following steps
(1) Will be from 0.04L/m20.16L/m of silane (b)20.25L/m of oxygen (g)21.55L/m of ethylene (C)2The first mixed gas of (2) is introduced into a reactor, and reacted on the surface of the borosilicate glass substrate to prepare a silica layer.
(2) Will be from 0.18L/m20.28L/m of silane (b)22.24L/m of ethylene2Introducing a second mixed gas composed of nitrogen into the reactor, and reacting on the surface of the silicon dioxide layer obtained in the step (1) to prepare an amorphous silicon layer;
(3) will be from 1L/m20.44L/m of monobutyl tin trichloride vapor2Trifluoroacetic acid vapor of (2), 13.5L/m26.8L/m of nitrogen gas22.8L/m of oxygen2And (3) introducing a third mixed gas consisting of water vapor into the reactor, and reacting on the surface of the amorphous silicon layer obtained in the step (2) to obtain the coated fireproof glass.
Examples 2-9 are substantially the same as example 1 except for the differences in film thickness and gas amount, and the specific compositions are shown in table 1 below.
Comparative examples 1-4 are essentially the same procedure as example 1 except that a certain film layer is absent and the specific composition is shown in table 1 below.
In Table 1, tin represents trichloromonobutyltin vapor, fluoroepifluorotrifluoroacetic acid vapor, and water represents water vapor. In Table 1, the thickness is in nm and the gas amount is in L/m2。
TABLE 1
The performance of the coated fire-resistant glass prepared in examples 1-9 and comparative examples 1-4 was tested according to the method specified in GB/T18915-2013 "coated glass", and the reflectivity, transmittance, sheet resistance, emissivity, chromaticity coordinates (L, a × b), and film surface color of the glass were tested, and the specific test results are shown in table 2 below.
TABLE 2
According to the data in table 2, when the silicon dioxide layer is less than 15nm, the diffusion of sodium ions into the film layer cannot be well prevented, and the sheet resistance is increased; when the thickness of the silicon dioxide layer is too large, the haze of the film layer is not easy to control due to the appearance of the film layer. When the amorphous silicon layer is too thick, the film layer is easy to break and crack during the secondary hot working. The fluorine-doped tin dioxide layer is too thick, so that the stress deviation of the glass plate surface is larger due to the strong infrared ray reflecting capacity of the fluorine-doped tin dioxide layer.
As can be seen from the data in comparative examples 1-4, when the silica layer is absent from the coated fire-resistant glass: diffusion of sodium ions into the film layer cannot be prevented and the sheet resistance increases.
When the coated fire-proof glass lacks the amorphous silicon layer: the transmittance is greatly increased and the function of sunlight control is not provided.
When the coated fire-resistant glass lacks the fluorine-doped tin dioxide layer: the low-radiation function is not provided, and the radiation rate reaches 0.83.
The coated fireproof glass provided by the embodiments 1-9 and the comparative examples 1-4 is toughened, and the specific toughening process comprises the following steps: the temperature is 780-820 ℃, the heating time is 50-60s/mm, and the hot glass is suddenly cooled by air, cooled and tempered. And tempering to obtain the fireproof glass with the functions of sunlight control and low radiation.
Performing glass stress test on the sunlight-controlled low-radiation fireproof glass (after tempering) according to the provisions of GB/T18144 glass stress test method, and further obtaining the plate surface stress deviation; according to GB 15763.1-2009 first part of safety glass for buildings: fire resistance tests were carried out according to the methods specified for fire-resistant glass. The results of the tests are shown in table 3 below.
TABLE 3
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A film layer with solar control and low radiation functions is characterized in that: the film layer with the sunlight control and low radiation functions comprises a silicon dioxide layer, an amorphous silicon layer and a fluorine-doped tin dioxide layer which are sequentially arranged.
2. The solar control, low-emissivity film of claim 1, wherein: the thickness of the silicon dioxide layer is 10-30 nm;
preferably, the thickness of the silicon dioxide layer is 15-25 nm.
3. The solar control, low-emissivity functional film of claim 1 or 2, wherein: the thickness of the amorphous silicon layer is 30-60 nm;
preferably, the amorphous silicon layer has a thickness of 40 to 50 nm.
4. The solar control, low-emissivity functional film of any one of claims 1-3, wherein: the thickness of the fluorine-doped tin dioxide layer is 270-450 nm;
preferably, the thickness of the fluorine-doped tin dioxide layer is 330-380 nm;
preferably, the proportion of fluorine in the fluorine-doped tin dioxide layer is between 0.5% and 5%, preferably between 1% and 3%.
5. The coated fireproof glass is characterized in that: the coated fire-resistant glass comprises the film layer with the solar control and low-radiation functions and a borosilicate glass substrate, wherein the borosilicate glass substrate is connected with the silicon dioxide layer in the film layer with the solar control and low-radiation functions;
preferably, the reflectivity of the coated fireproof glass is 18-35%, preferably 30-33%;
preferably, the transmittance of the coated fireproof glass is 23-35%, preferably 23-26%;
preferably, the square resistance of the coated fireproof glass is 11-26 omega, and preferably 16-19 omega;
preferably, the emissivity of the coated fireproof glass is 0.11-0.25, and preferably 0.14-0.18.
6. The method for preparing the coated fire-resistant glass according to claim 5, wherein the method comprises the following steps: the preparation method comprises the following steps:
(1) introducing a first mixed gas containing silane into a reactor, and reacting on the surface of a borosilicate glass substrate to prepare a silicon dioxide layer;
(2) introducing a second mixed gas containing silane into a reactor, and reacting on the surface of the silicon dioxide layer obtained in the step (1) to prepare an amorphous silicon layer;
(3) and (3) introducing a third mixed gas containing trichloro monobutyl tin steam into the reactor, and reacting on the surface of the amorphous silicon layer obtained in the step (2) to obtain the coated fireproof glass.
7. The method of manufacturing according to claim 6, characterized in that: the first mixed gas in the step (1) consists of silane, oxygen, ethylene and nitrogen;
preferably, the total gas amount of the first mixed gas is 1.32-2.73L/m2Preferably 1.9 to 2.1L/m2；
Preferably, the gas amount of the silane is 0.01-0.07L/m2Preferably 0.03 to 0.05L/m2；
Preferably, the amount of the oxygen gas is 0.04-0.30L/m2Preferably 0.12 to 0.2L/m2；
Preferably, the gas amount of the ethylene is 0.06-0.45L/m2Preferably 0.18 to 0.3L/m2；
Preferably, the gas amount of the nitrogen is 1.21-1.91L/m2Preferably 1.4 to 1.7L/m2。
8. The production method according to claim 6 or 7, characterized in that: the second mixed gas in the step (2) consists of silane, ethylene and nitrogen;
preferably, the total gas amount of the second mixed gas is 2.25-3.20L/m2Preferably 2.5 to 2.8L/m2；
Preferably, the gas amount of the silane is 0.10-0.30L/m2Preferably 0.16 to 0.21L/m2；
Preferably, the gas amount of the ethylene is 0.15-0.45L/m2Preferably 0.25 to 0.32L/m2；
Preferably, the gas amount of the nitrogen is 2.00-2.45L/m2。
9. The production method according to any one of claims 6 to 8, characterized in that: the third mixed gas in the step (3) consists of trichloro monobutyl tin steam, trifluoroacetic acid steam, nitrogen, oxygen and water vapor;
preferably, the total gas amount of the third mixed gas is 23.05-26.15L/m2；
Preferably, the gas amount of the trichloro monobutyl tin vapor is 0.8-1.3L/m2Preferably 0.9 to 1.2L/m2；
Preferably, the gas amount of the trifluoroacetic acid steam is 0.35-0.55L/m2Preferably 0.4 to 0.5L/m2；
Preferably, the gas amount of the nitrogen is 13.2-13.8L/m2；
Preferably, the gas amount of the oxygen is 6.5-7L/m2；
Preferably, the amount of the steam is 2.2-3.5L/m2Preferably 2.7 to 3.1L/m2。
10. The utility model provides a fire prevention glass with sunshine control, low radiation function which characterized in that: the solar control, low-emissivity, fire-resistant glass comprises the coated fire-resistant glass of claim 5;
preferably, the stress of the fireproof glass with the sunlight control and low radiation functions is 90-200 MPa;
preferably, the surface stress deviation of the fireproof glass plate with the functions of solar control and low radiation is not higher than 5 MPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1263874A (en) * | 1998-08-21 | 2000-08-23 | 北美埃尔夫爱托化学股份有限公司 | Glass with coating and preventing sunlight |
| CN101602273A (en) * | 2009-07-22 | 2009-12-16 | 天津南玻节能玻璃有限公司 | A kind of diamond-like carbon film-coating glass and preparation method thereof |
| CN106431004A (en) * | 2016-09-06 | 2017-02-22 | 江苏秀强玻璃工艺股份有限公司 | Blue-light-cutoff and anti-reflexion dual-function coated glass and preparation method therefor |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263874A (en) * | 1998-08-21 | 2000-08-23 | 北美埃尔夫爱托化学股份有限公司 | Glass with coating and preventing sunlight |
| CN101602273A (en) * | 2009-07-22 | 2009-12-16 | 天津南玻节能玻璃有限公司 | A kind of diamond-like carbon film-coating glass and preparation method thereof |
| CN106431004A (en) * | 2016-09-06 | 2017-02-22 | 江苏秀强玻璃工艺股份有限公司 | Blue-light-cutoff and anti-reflexion dual-function coated glass and preparation method therefor |
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