CN114772945B - 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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- CN114772945B CN114772945B CN202210430491.8A CN202210430491A CN114772945B CN 114772945 B CN114772945 B CN 114772945B CN 202210430491 A CN202210430491 A CN 202210430491A CN 114772945 B CN114772945 B CN 114772945B
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- 239000011521 glass Substances 0.000 title claims abstract description 107
- 230000005855 radiation Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 24
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 19
- 238000005496 tempering Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 84
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 230000009970 fire resistant effect Effects 0.000 claims description 19
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 18
- 229910000077 silane Inorganic materials 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- 239000005388 borosilicate glass Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000002834 transmittance Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 claims description 5
- 238000002310 reflectometry Methods 0.000 claims description 5
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000002265 prevention Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 80
- 239000011247 coating layer Substances 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 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
- 239000003086 colorant Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 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
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 239000011159 matrix material Substances 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
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
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 manufacture, the stress of the manufactured glass reaches more than 90Mpa after tempering, the stress deviation of the plate surface is less than 5Mpa, the fireproof coated glass has the functions of solar control and low radiation, can prevent fire, and the coated fireproof glass is subjected to fire resistance test for 90 minutes.
Description
Technical Field
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.
Background
The fireproof glass has the main function of controlling the spread of fire or isolating smoke during fireproof, and is one fireproof material with fireproof effect evaluated in fireproof performance. The glass is special glass which is processed and treated by special technology and can keep the integrity and heat insulation in a specified fire resistance test. The original glass of the fireproof glass can be float plane glass, toughened glass, and the composite fireproof glass can also be manufactured by single fireproof glass.
CN211222353U discloses a low-emissivity fire-proof glass structure, which is fire-proof glass with a multi-layer film structure, and the main functional layer is silver, so that the coated glass with the structure cannot be used in a single layer, and can only be made into hollow glass, etc., and silver can be corroded when being contacted with the outside.
The main functional layer disclosed in the preparation method of the CN100455530C high-strength monolithic low-emissivity coated fireproof glass is tin-doped indium oxide, the preparation method is liquid-phase spraying, and the fireproof glass is cesium-potassium fireproof glass with fireproof function. The uniformity of the film layer cannot be guaranteed by liquid phase spraying, and the manufacturing cost of ITO is high, so that the ITO is not easy to popularize; cesium-potassium fireproof glass is a product which occupies a larger market but has lower fire resistance grade, and is initially replaced by a product with better fire resistance grade.
CN108249779a relates to a coating layer capable of realizing electric heating, the coating layer includes a resistance adjusting layer disposed on the outermost layer, and the resistance adjusting layer includes a fluorine-doped tin dioxide layer and a second silicon dioxide layer disposed on the outer side of the fluorine-doped tin dioxide layer. According to the electric heating coating layer, the resistance base number of the coating layer is improved 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 square resistance value of the electrically heated coating layer provided by the invention can be regulated to be more than 70 omega by regulating the fluorine content of fluorine-doped tin dioxide, and after glass tempering, the electrically heated coating layer can reach more than 50 omega, and can meet the effect of controlling frost and condensation by electric heating. Meanwhile, the Haze (Haze) of the obtained coated glass can be reduced to below 0.5% due to the existence of the second silicon dioxide layer. However, its solar control low emissivity and fire resistant functions are generally.
Accordingly, in view of the above shortcomings, there is a need to provide a new type of low emissivity refractory glass.
Disclosure of Invention
The invention aims to solve the technical problems that the existing glass is low in fire resistance level, generally has no solar control effect and high in emissivity, and aims to overcome the defects in the prior art, the invention provides a film layer with solar control and low-emissivity functions, coated fireproof glass, a preparation method of the film layer, and the low-emissivity solar control and low-emissivity fireproof glass.
In order to solve the technical problems, in a first aspect, the invention provides a film layer with a solar control and low radiation function, wherein the film layer with the solar control and low radiation function comprises a silicon dioxide layer, an amorphous silicon layer and a fluorine-doped tin dioxide layer which are sequentially arranged.
The film layer with the sunlight control and low radiation functions is provided by the invention, and has a three-layer structure of 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, so that sodium ions in the glass substrate can be prevented from diffusing into the film layer, and meanwhile, the silicon dioxide layer can increase the bonding capability 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 excellent infrared ray reflection function.
Preferably, the thickness of the silica layer is 10 to 30nm, and may be, for example, 10nm, 12nm, 15nm, 17nm, 20nm, 23nm, 25nm, 28nm, 30nm, or the like.
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 matrix into the film layer, and the film system structure with the required color is formed by the other two films.
Preferably, the amorphous silicon layer has a thickness of 30 to 60nm, for example, 30nm, 35nm, 40nm, 42nm, 44nm, 45nm, 50nm, 55nm, 60nm, or the like.
Preferably, the thickness of the amorphous silicon layer is 40-50 nm.
In the invention, the thickness variation of the amorphous silicon layer mainly determines the transmittance and the reflectivity of the coated glass, and forms a film system structure with other two films with required colors.
Preferably, the thickness of the fluorine-doped tin dioxide layer is 270-450 nm; for example, 300nm, 310nm, 320nm, 330nm, 340nm, 350nm, 360nm, 370nm, 380nm, 390nm or 400nm, etc.
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% -5%, preferably 1% -3%. In the invention, the proportion of fluorine in the fluorine-doped tin dioxide layer is calculated relative to the total molar quantity of fluorine in the tin dioxide and fluorine.
In the invention, the thickness change of the fluorine doped tin dioxide layer mainly determines the sheet resistance and the emissivity of the glass, and the other two layers of films form a film system structure with required colors.
In a second aspect, the invention provides coated fire-resistant glass, which comprises the film layer with the solar control and low-radiation function and a borosilicate glass substrate, wherein the borosilicate glass substrate is connected with a silicon dioxide layer in the film layer with the solar control and low-radiation function.
Preferably, the reflectivity of the coated fireproof glass is 18% -35%, for example, 18%, 23%, 25%, 30%, 31%, 32%, 33%, 34% or 35%, and preferably 30% -33%.
Preferably, the transmittance of the coated fireproof glass is 23% to 35%, for example, 23%, 25%, 26%, 31% or 35%, and preferably 23% to 26%.
Preferably, the square resistance of the coated fireproof glass is 11-26 omega, for example, 16 omega, 17 omega, 18 omega or 19 omega, and the like, and preferably 16-19 omega.
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 color of the film surface of the coated fireproof glass provided by the invention is bright mauve, the chromaticity coordinate is L=54.63, a=11.98 and b=4.27.
In a third aspect, the present invention provides a method for preparing coated fire-resistant glass according to the second aspect, the method comprising the steps of:
(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 the surface of the silicon dioxide layer obtained in the step (1) to prepare an amorphous silicon layer;
(3) And (3) introducing the third mixed gas containing the trichloromonobutyl tin steam into a 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 640 to 660 ℃. The borosilicate glass substrate of the present invention is not particularly limited, and has an expansion coefficient of 3.3×10 -7 /K～4*10 -7 Substrates in the range of/K are sufficient.
In the invention, all reactors are specially designed and manufactured, so that the vapor of a coating material can be uniformly distributed on the surface of glass, the material reacts on the surface of hot glass to form a film layer, and tail gas is discharged from the reactors through a specially designed channel. The glass surface temperature corresponding to the silicon dioxide layer is 650-660 ℃, and the reactor used 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 temperature of the surface of the glass corresponding to 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 gradually changed, and the preparation efficiency is high.
Preferably, the first mixed gas in step (1) consists of silane, oxygen, ethylene and nitrogen.
In the present invention, the silane used refers to monosilane. The unit of the gas quantity of the invention is L/m 2 The meaning of the unit refers to: the volume of gas used per square meter of glass is how much liters.
Preferably, the total gas amount of the first mixed gas is 1.32-2.73L/m 2 For example, it may be 1.32L/m 2 、1.43L/m 2 、1.52L/m 2 、1.68L/m 2 、1.79L/m 2 、1.85L/m 2 、1.9L/m 2 、1.95L/m 2 、2L/m 2 、2.1L/m 2 、2.11L/m 2 、2.45L/m 2 、2.67L/m 2 、2.73L/m 2 And the like, preferably 1.9 to 2.1L/m 2 ；
Preferably, in the first mixed gas, the gas amount of the silane is 0.01-0.07L/m 2 For example, it may be 0.01L/m 2 、0.02L/m 2 、0.03L/m 2 、0.04L/m 2 、0.05L/m 2 、0.05L/m 2 、0.06L/m 2 Or 0.07L/m 2 And the like, preferably 0.03 to 0.05L/m 2 。
Preferably, in the first mixed gas, the gas amount of the oxygen is 0.04-0.30L/m 2 For example, it may be 0.04L/m 2 、0.06L/m 2 、0.09L/m 2 、0.12L/m 2 、0.14L/m 2 、0.15L/m 2 、0.16L/m 2 、0.17L/m 2 、0.18L/m 2 、0.25L/m 2 Or 0.30L/m 2 Etc., preferably 0.12 to 0.2L/m 2 。
Preferably, in the first mixed gas, the gas amount of the ethylene is 0.06-0.45L/m 2 For example, it may be 0.06L/m 2 、0.17L/m 2 、0.23L/m 2 、0.24L/m 2 、0.25L/m 2 、0.26L/m 2 、0.27L/m 2 、0.28L/m 2 、0.35L/m 2 、0.42L/m 2 Or 0.45L/m 2 And the like, preferably 0.18 to 0.3L/m 2 。
Preferably, in the first mixed gas, the gas amount of the nitrogen is 1.21-1.91L/m 2 For example, it may be 1.21L/m 2 、1.34L/m 2 、1.48L/m 2 、1.50L/m 2 、1.52L/m 2 、1.55L/m 2 、1.58L/m 2 、1.60L/m 2 、1.78L/m 2 、1.84L/m 2 、1.86L/m 2 Or 1.91L/m 2 Etc., preferably 1.4 to 1.7L/m 2 。
Preferably, the second mixed gas in step (2) consists of silane, ethylene and nitrogen.
Preferably, the total gas amount of the second mixed gasIs 2.25 to 3.20L/m 2 For example, it may be 2.25L/m 2 、2.34L/m 2 、2.51L/m 2 、2.60L/m 2 、2.64L/m 2 、2.7L/m 2 、2.73L/m 2 、2.75L/m 2 、2.79L/m 2 、2.85L/m 2 、2.95L/m 2 、3.12L/m 2 Or 3.20L/m 2 And the like, preferably 2.5 to 2.8L/m 2 。
Preferably, in the second mixed gas, the gas amount of the silane is 0.10-0.30L/m 2 For example, it may be 0.10L/m 2 、0.12L/m 2 、0.15L/m 2 、0.16L/m 2 、0.17L/m 2 、0.18L/m 2 、0.19L/m 2 、0.20L/m 2 、0.25L/m 2 Or 0.30L/m 2 Etc., preferably 0.16 to 0.21L/m 2 。
Preferably, in the second mixed gas, the gas amount of the ethylene is 0.15-0.45L/m 2 For example, it may be 0.15L/m 2 、0.21L/m 2 、0.25L/m 2 、0.26L/m 2 、0.27L/m 2 、0.28L/m 2 、0.29L/m 2 、0.30L/m 2 、0.31L/m 2 、0.35L/m 2 、0.40L/m 2 Or 0.45L/m 2 And the like, preferably 0.25 to 0.32L/m 2 。
Preferably, in the second mixed gas, the gas amount of the nitrogen is 2.00-2.45L/m 2 For example, it may be 2.00L/m 2 、2.12L/m 2 、2.20L/m 2 、2.21L/m 2 、2.22L/m 2 、2.23L/m 2 、2.24L/m 2 、2.25L/m 2 、2.26L/m 2 、2.27L/m 2 、2.28L/m 2 、2.33L/m 2 、2.38L/m 2 Or 2.45L/m 2 Etc.
Preferably, the third mixed gas in step (3) is composed of tributyltin trichloride vapor, trifluoroacetic acid vapor, nitrogen, oxygen and water vapor.
Preferably, the total gas amount of the third mixed gas is 23.05-26.15L/m 2 For example, it may be 23.05L/m 2 、23.25L/m 2 、23.42L/m 2 、23.83L/m 2 、24.54L/m 2 、25.13L/m 2 、25.46L/m 2 、25.89L/m 2 Or 26.15L/m 2 Etc.
Preferably, in the third mixed gas, the gas amount of the trichloromonobutyl tin vapor is 0.8-1.3L/m 2 For example, it may be 0.8L/m 2 、0.9L/m 2 、1.0L/m 2 、1.1L/m 2 、1.2L/m 2 Or 1.3L/m 2 Etc., preferably 0.9 to 1.2L/m 2 。
Preferably, in the third mixed gas, the gas amount of the trifluoroacetic acid vapor is 0.35-0.55L/m 2 For example, it may be 0.35L/m 2 、0.38L/m 2 、0.42L/m 2 、0.43L/m 2 、0.44L/m 2 、0.45L/m 2 、0.46L/m 2 、0.51L/m 2 Or 0.55L/m 2 Etc., preferably 0.4 to 0.5L/m 2 。
Preferably, in the third mixed gas, the gas amount of the nitrogen is 13.2-13.8L/m 2 For example, 13.2L/m 2 、13.3L/m 2 、13.4L/m 2 、13.5L/m 2 、13.6L/m 2 、13.7L/m 2 Or 13.8L/m 2 Etc.
Preferably, in the third mixed gas, the gas amount of the oxygen is 6.5 to 7L/m 2 For example, it may be 6.5L/m 2 、6.6L/m 2 、6.7L/m 2 、6.8L/m 2 、6.9L/m 2 Or 7L/m 2 Etc.
Preferably, in the third mixed gas, the gas amount of the water vapor is 2.2-3.5L/m 2 For example, it may be 2.2L/m 2 、2.3L/m 2 、2.4L/m 2 、2.5L/m 2 、2.6L/m 2 、2.7L/m 2 、2.8L/m 2 、2.9L/m 2 、3L/m 2 、3.2L/m 2 、3.4L/m 2 Or 3.5L/m 2 And the like, preferably 2.7 to 3.1L/m 2 。
In a fourth aspect, the present invention provides a fire-resistant glass with solar control, low-emissivity function, comprising the coated fire-resistant glass of the second aspect.
Preferably, the glass stress of the fireproof glass with the solar control and low radiation functions is 90-200 MPa;
preferably, the plate stress deviation of the fireproof glass with the solar control and low radiation functions is not higher than 5MPa.
The fireproof glass with the sunlight control and low radiation functions is obtained by tempering the coated fireproof glass, and the deviation of the stress of the glass and the stress of the plate surface is also the result obtained by the test after tempering.
The fireproof coating layer provided by the invention has low cost and has an expansion coefficient of 3.3 x 10 -7 /K～4*10 -7 The medium layer, the sunshade layer and the functional layer are prepared on the borosilicate glass substrate by an online chemical vapor deposition method, and the glass is toughened by a proper process to prepare the high-grade fireproof glass with the function of solar control and low radiation, 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, provides the fireproof glass with a certain transmittance and the infrared ray reflection function, and has excellent chemical stability and high temperature resistance through the combination of the film layer and the glass substrate through chemical bonds by high temperature reaction, and the fireproof performance can reach more than 90 minutes through a fireproof test, and has the performances of low transmittance and low reflectivity.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the following examples of the present invention, the borosilicate glass substrate used was high borosilicate glass.
Example 1
In the embodiment, the coated fireproof glass is prepared through the following steps of
(1) Will be composed of 0.04L/m 2 Silane of 0.16L/m 2 Oxygen of 0.25L/m 2 1.55L/m 2 The first mixed gas composed of nitrogen is led into a reactor to react on the surface of the borosilicate glass substrate to prepare the silicon dioxide layer.
(2) Will be composed of 0.18L/m 2 Silane of 0.28L/m 2 2.24L/m ethylene 2 Introducing a second mixed gas consisting of nitrogen into a reactor, and reacting the surface of the silicon dioxide layer obtained in the step (1) to prepare an amorphous silicon layer;
(3) Will be composed of 1L/m 2 0.44L/m of tributyltin trichloride vapor 2 Is 13.5L/m 2 6.8L/m nitrogen 2 2.8L/m 2 And (3) introducing a third mixed gas composed 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 were essentially identical to example 1 except for the thickness of the film and the amount of gas, and the specific composition is shown in Table 1 below.
Comparative examples 1-4 were essentially identical to the procedure of example 1, except that a film layer was absent, and the specific composition is shown in Table 1 below.
Tin in table 1 represents tributyltin trichloride vapor, fluorine represents trifluoroacetic acid vapor, and water represents water vapor. The thickness is in nm and the gas amount is in L/m in Table 1 2 。
TABLE 1
The coated fire-resistant glasses prepared in examples 1-9 and comparative examples 1-4 were tested for their performance according to the method specified in GB/T18915-2013 coated glass, and the reflectance, transmittance, sheet resistance, emissivity, chromaticity coordinates (L, a, b) and film surface color of the glasses were tested, and specific test results are shown in Table 2 below.
TABLE 2
As can be seen from the data in table 2, the silicon dioxide layer does not prevent sodium ions from diffusing into the film well when the silicon dioxide layer is smaller than 15nm, and the sheet resistance increases; 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 defects of film breakage, film cracking and the like of the film layer are easily caused during 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 capability.
As can be seen from the data in comparative examples 1-4, when the coated fire-resistant glass lacks a silica layer: the diffusion of sodium ions into the film layer cannot be prevented, and the sheet resistance increases.
When the amorphous silicon layer is absent from the coated fire-resistant glass: the transmittance is greatly increased, and the solar control function is not provided.
When the coated fireproof glass lacks a fluorine-doped tin dioxide layer: the low-emissivity function is not provided, and the emissivity reaches 0.83.
The coated fireproof glass provided in examples 1-9 and comparative examples 1-4 is tempered by the specific tempering process: the temperature is 780-820 ℃, the heating time is 50-60s/mm, and the hot glass is cooled and tempered by sudden air cooling. After tempering, the fireproof glass with the sunlight control and low radiation functions is obtained.
Performing glass stress test on the fireproof glass (toughened) with solar control and low radiation according to the specification of GB/T18144 glass stress test method, so as to obtain plate surface stress deviation; according to GB 15763.1-2009 first part of a safety glass for construction: fire resistance tests were carried out by the methods prescribed for fire-resistant glass. The results of the test are shown in table 3 below.
TABLE 3 Table 3
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (44)
1. A film layer with solar control and low radiation functions, which is characterized in that: the film layer with the solar control and low radiation functions comprises a silicon dioxide layer, an amorphous silicon layer and a fluorine-doped tin dioxide layer which are sequentially continuous;
the thickness of the silicon dioxide layer is 15-25 nm; the thickness of the amorphous silicon layer is 40-50 nm; the thickness of the fluorine-doped tin dioxide layer is 330-380 nm; the proportion of fluorine in the fluorine-doped tin dioxide layer is 0.5% -5%, and the proportion of fluorine in the fluorine-doped tin dioxide layer is calculated by the total molar quantity of fluorine relative to tin dioxide and fluorine.
2. The solar control, low emissivity film of claim 1, wherein: the proportion of fluorine in the fluorine-doped tin dioxide layer is 1% -3%.
3. The utility model provides a coating film fire prevention glass which characterized in that: the coated fireproof glass comprises the film layer with the solar control and low radiation function and a borosilicate glass substrate, wherein the borosilicate glass substrate is connected with a silicon dioxide layer in the film layer with the solar control and low radiation function.
4. A coated fire resistant glass according to claim 3, wherein: the reflectivity of the coated fireproof glass is 18% -35%.
5. The coated fire resistant glass according to claim 4, wherein: the reflectivity of the coated fireproof glass is 30% -33%.
6. A coated fire resistant glass according to claim 3, wherein: the transmittance of the coated fireproof glass is 23% -35%.
7. The coated fire resistant glass according to claim 6, wherein: the transmittance of the coated fireproof glass is 23% -26%.
8. A coated fire resistant glass according to claim 3, wherein: the square resistance of the coated fireproof glass is 11-26 omega.
9. The coated fire resistant glass according to claim 8, wherein: the square resistance of the coated fireproof glass is 16-19 omega.
10. A coated fire resistant glass according to claim 3, wherein: the emissivity of the coated fireproof glass is 0.11-0.25.
11. The coated fire resistant glass according to claim 10, wherein: the emissivity of the coated fireproof glass is 0.14-0.18.
12. A method for preparing coated fire-resistant glass according to claim 3, wherein: 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 the surface of the silicon dioxide layer obtained in the step (1) to prepare an amorphous silicon layer;
(3) And (3) introducing the third mixed gas containing the trichloromonobutyl tin steam into a reactor, and reacting on the surface of the amorphous silicon layer obtained in the step (2) to obtain the coated fireproof glass.
13. The method of manufacturing according to claim 12, wherein: the first mixed gas in the step (1) consists of silane, oxygen, ethylene and nitrogen.
14. The method of manufacturing according to claim 13, wherein: the total gas amount of the first mixed gas is 1.32-2.73L/m 2 。
15. The method of manufacturing according to claim 14, wherein: the total gas amount of the first mixed gas is 1.9-2.1L/m 2 。
16. The method of manufacturing according to claim 13, wherein: the gas amount of the silane in the first mixed gas is 0.01-0.07L/m 2 。
17. The method of manufacturing according to claim 16, wherein: the gas amount of the silane in the first mixed gas is 0.03-0.05L/m 2 。
18. The method of manufacturing according to claim 13, wherein: the gas amount of the oxygen is 0.04-0.30L/m 2 。
19. The method of manufacturing according to claim 18, wherein: the gas amount of the oxygen is 0.12-0.2L/m 2 。
20. The method of manufacturing according to claim 13, wherein: the gas amount of the ethylene is 0.06-0.45L/m 2 。
21. The method of manufacturing according to claim 20, wherein: the gas amount of the ethylene is 0.18-0.3L/m 2 。
22. The method of manufacturing according to claim 13, wherein: the gas amount of the nitrogen is 1.21-1.91L/m 2 。
23. The method of manufacturing according to claim 22, wherein: the gas amount of the nitrogen is 1.4-1.7L/m 2 。
24. The method of manufacturing according to claim 12, wherein: the second mixed gas in the step (2) consists of silane, ethylene and nitrogen.
25. The method of manufacturing according to claim 24, wherein: the total gas amount of the second mixed gas is 2.25-3.20L/m 2 。
26. The method of manufacturing according to claim 25, wherein: the total gas amount of the second mixed gas is 2.5-2.8L/m 2 。
27. The method of manufacturing according to claim 24, wherein: the gas amount of the silane in the second mixed gas is 0.10-0.30L/m 2 。
28. The method of claim 27, wherein: the gas amount of the silane in the second mixed gas is 0.16-0.21L/m 2 。
29. The method of manufacturing according to claim 24, wherein: the gas amount of the ethylene is 0.15-0.45L/m 2 。
30. The method of manufacturing according to claim 29, wherein: the gas amount of the ethylene is 0.25-0.32L/m 2 。
31. The method of manufacturing according to claim 24, wherein: the gas amount of the nitrogen is 2.00-2.45L/m 2 。
32. The method of manufacturing according to claim 12, wherein: the third mixed gas in the step (3) consists of tributyltin trichloride vapor, trifluoroacetic acid vapor, nitrogen, oxygen and water vapor.
33. The method of manufacturing according to claim 32, wherein: the total gas amount of the third mixed gas is 23.05-26.15L/m 2 。
34. The method of manufacturing according to claim 32, wherein: the gas amount of the trichloromonobutyl tin vapor is 0.8-1.3L/m 2 。
35. The method of manufacturing according to claim 34, wherein: the gas amount of the trichloromonobutyl tin vapor is 0.9-1.2L/m 2 。
36. The method of manufacturing according to claim 32, wherein: the gas amount of the trifluoroacetic acid steam is 0.35-0.55L/m 2 。
37. The method of manufacturing according to claim 36, wherein: gas amount of the trifluoroacetic acid vaporIs 0.4 to 0.5L/m 2 。
38. The method of manufacturing according to claim 32, wherein: the gas amount of the nitrogen is 13.2-13.8L/m 2 。
39. The method of manufacturing according to claim 32, wherein: the gas amount of the oxygen is 6.5-7L/m 2 。
40. The method of manufacturing according to claim 32, wherein: the gas amount of the water vapor is 2.2-3.5L/m 2 。
41. The method of claim 40, wherein: the gas amount of the water vapor is 2.7-3.1L/m 2 。
42. A fire-resistant glazing with solar control, low emissivity features: the fireproof glass with the sunlight control and low radiation functions is obtained by tempering the coated fireproof glass according to claim 3.
43. The solar control, low emissivity coated glass of claim 42 wherein: the stress of the fireproof glass with the sunlight control and low radiation functions is 90-200 MPa.
44. The solar control, low emissivity coated glass of claim 42 wherein: the stress deviation of the fireproof glass plate surface with the sunlight control and low radiation functions is not higher than 5MPa.
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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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