CN115572048B - Method for improving solar light transmittance of ultra-white float glass - Google Patents
Method for improving solar light transmittance of ultra-white float glass Download PDFInfo
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- CN115572048B CN115572048B CN202211407277.7A CN202211407277A CN115572048B CN 115572048 B CN115572048 B CN 115572048B CN 202211407277 A CN202211407277 A CN 202211407277A CN 115572048 B CN115572048 B CN 115572048B
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- 238000002834 transmittance Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000005329 float glass Substances 0.000 title claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 171
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000001816 cooling Methods 0.000 claims abstract description 35
- 238000005498 polishing Methods 0.000 claims abstract description 17
- 239000006060 molten glass Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 18
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000005485 electric heating Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 33
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 16
- 238000009792 diffusion process Methods 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007667 floating Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003487 electrochemical reaction Methods 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 description 56
- 239000010410 layer Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 239000000156 glass melt Substances 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000006124 Pilkington process Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 235000001418 Echinochloa stagnina Nutrition 0.000 description 1
- 240000001327 Echinochloa stagnina Species 0.000 description 1
- 235000001797 Lavandula macra Nutrition 0.000 description 1
- 235000001803 Lavandula setifera Nutrition 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
- C03B18/18—Controlling or regulating the temperature of the float bath; Composition or purification of the float bath
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
- C03B18/20—Composition of the atmosphere above the float bath; Treating or purifying the atmosphere above the float bath
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
Abstract
The invention discloses a method for improving solar transmittance of ultra-white float glass, which comprises the steps of flowing molten glass into a tin bath from a runner, forming the molten glass on the surface of the molten tin floating in the tin bath to form a glass belt, wherein the viscosity of the glass belt in a polishing flattening area is 10 2.7 ‑10 3.2 During Pa.S, controlling the cooling rate C of the thin layer of the contact surface of the lower surface of the glass ribbon and the molten tin in the tin bath Molten tin on lower surface of glass ribbon And cooling rate C of the thin layer of the surface of the glass ribbon in contact with the shielding gas Glass ribbon upper surface-shielding gas C Molten tin on lower surface of glass ribbon And C Glass ribbon upper surface-shielding gas Is a ratio of (2). Under the condition of not changing the original glass components and the iron oxide content in the raw materials, the invention reduces the generation of more Fe due to electrochemical reaction caused by the enrichment of iron element to the lower surface and the diffusion of tin element into the glass in the forming process of the glass ribbon by controlling the cooling speed of the upper surface and the lower surface of the glass ribbon in the tin bath 2+ Thereby improving the sunlight transmittance of the glass, and has simple method and obvious effect.
Description
Technical Field
The invention belongs to the technical field of glass manufacturing, and particularly relates to a method for improving solar transmittance of ultra-white float glass.
Background
The float process of producing super white glass is mainly used in solar power generation, high-grade building, automobile glass and other industries, and the most important performance index is transmittance, especially in solar power generation industry, such as photo-thermal and photovoltaic power generation, to improve solar transmittanceHigher requirements are imposed. Since the content of impurity elements in the ultra-white glass is small, the transmittance is affected by the content of iron oxide contained therein, wherein iron is contained in the glass as Fe in the glass 2+ And Fe (Fe) 3+ In two valence states, fe 2+ Two strong absorption bands in the range 950-1100nm and 2050-2200 nm; fe (Fe) 3+ There are three absorption bands in the 380nm, 420nm and 435nm ultraviolet regions. Therefore, when the content of iron oxide in the ultra-white glass is constant, the valence state of iron (Fe 2+ Content) is the most dominant factor affecting solar light transmittance.
The method for improving the sunlight transmittance of the ultra-white glass is commonly used at present, the content of ferric oxide in the ultra-white glass is continuously reduced, so that raw materials with lower iron content are needed to be adopted, the production cost is increased, meanwhile, the reduction of the content of ferric oxide in the glass can cause good heat permeability of molten glass, the temperature gradient in the vertical direction is small, and the clarification difficulty of the glass is increased. The Chinese patent with publication number 103011595A proposes a glass component for improving the photovoltaic transmittance of glass, and the proposed glass component for improving the photovoltaic transmittance of glass comprises the following components in percentage by mass: 58-62% of quartz sand, 17-21% of sodium carbonate, 11-14% of dolomite, 6-8% of limestone and 0.5-0.7% of mirabilite; the glass component also comprises an additive; the additive is as follows: sodium nitrate, cerium oxide and manganese dioxide; the adding amount of the sodium nitrate is 0.3-2.0%; the addition amount of the cerium oxide is 0.2% -0.8%; the addition amount of the manganese dioxide is 0.02% -0.30%. The patent adds sodium nitrate, cerium oxide and manganese dioxide into glass to increase the oxidability of the glass and lead Fe to be added into the glass 2+ To Fe 3+ Conversion, reduction of Fe 2+ And the solar light is absorbed, so that the band transmittance of the photovoltaic solar energy is improved. However, the addition of the oxidizing agents sodium nitrate, cerium oxide and manganese dioxide in the glass increases the production cost firstly, and secondly, the introduction of Sr and Mn in the glass can cause strong ultraviolet absorption, reduce the ultraviolet transmittance and influence the improvement of the sunlight (300-2500 nm) transmittance. Therefore, how to improve the solar transmittance of the ultra-white glass under the condition of not changing the components of the ultra-white glass is an urgent problem to be solved at present。
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for improving the solar transmittance of ultra-white float glass. The method is suitable for the production process requirements of float glass, and improves the transmittance of the glass to sunlight under the condition of not changing the component formula of the glass and the content of ferric oxide in the raw materials of the glass.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for improving solar transmittance of ultra-white float glass comprises flowing molten, clarified and homogenized molten glass into a tin bath from a runner, forming molten glass on the surface of the molten tin floating in the tin bath to form a glass ribbon, wherein the viscosity of the glass ribbon in a polishing flattening area is 10 2.7 -10 3.2 Controlling the cooling rate C of the thin layer of the contact surface between the lower surface of the glass ribbon and the molten tin in the molten tin bath during Pa.S Molten tin on lower surface of glass ribbon And cooling rate C of the thin layer of the surface of the glass ribbon in contact with the shielding gas Glass ribbon upper surface-shielding gas And the C Molten tin on lower surface of glass ribbon And C Glass ribbon upper surface-shielding gas Is a ratio of (2).
Further, the cooling speed C of the thin layer of the contact surface between the lower surface of the glass ribbon and the molten tin Molten tin on lower surface of glass ribbon Controlling at 95-147 deg.C/min.
Further, the cooling speed C of the thin layer of the contact surface between the lower surface of the glass ribbon and the molten tin Molten tin on lower surface of glass ribbon Controlling the temperature at 115 ℃/min-130 ℃/min.
Further, the cooling rate C of the thin layer of the contact surface between the upper surface of the glass ribbon and the protective gas Glass ribbon upper surface-shielding gas Controlling at 84-132 deg.C/min.
Further, the cooling rate C of the thin layer of the contact surface between the upper surface of the glass ribbon and the protective gas Glass ribbon upper surface-shielding gas Controlling at 100-120 deg.C/min.
Further, the C Molten tin on lower surface of glass ribbon And C Glass ribbon upper surface-shielding gas The ratio of (2) is 1.0-1.5.
Further, the cooling speed of the thin layer of the contact surface between the lower surface of the glass ribbon and the molten tin is controlled by using a molten tin cooler, adjusting the air quantity of a fan at the bottom of the molten tin bath, or controlling the temperature of the glass ribbon entering the molten tin bath.
Further, the cooling speed of the contact surface between the upper surface of the glass ribbon and the shielding gas is controlled by inserting or taking out the water drum in the space of the tin bath, switching on or switching off the electric heating of the tin bath, adjusting the flow and the temperature of the shielding gas, or controlling the temperature of the glass ribbon entering the tin bath.
Further, the temperature difference of the molten tin in the polishing area satisfies the following relationship:
wherein, delta T is the temperature difference of tin liquid in the polishing area; epsilon is a coefficient, and the value of epsilon is between 0.1 and 1.3; h is the glass thickness.
Compared with the prior art, the invention has the positive and beneficial effects that:
(1) The invention controls the cooling speed of the glass ribbon in the tin bath, the contact surface thin layer of the lower surface of the glass ribbon and the tin liquid and the contact surface thin layer of the upper surface of the glass ribbon and the shielding gas, and adjusts the ratio of the cooling speed of the thin layers on the upper surface and the lower surface of the glass ribbon, thereby realizing the flattening and polishing of the glass and simultaneously controlling the diffusion direction of elements in the glass melt under the condition of not changing the original glass component formula and the content of ferric oxide in the raw materials, and reducing the generation of more Fe due to the electrochemical reaction caused by the enrichment of iron elements to the lower surface and the diffusion of tin elements into the glass in the tin bath forming process of the glass ribbon 2+ The content of the glass is improved, so that the solar light transmittance of the glass is improved, and the method is simple and practical and has excellent effect.
(2) The invention cools the thin layer of the contact surface between the lower surface of the glass ribbon and the molten tin
C Molten tin on lower surface of glass ribbon Controlled at 95-147 deg.C/min, preferably 115-130 deg.C/min, under a glass ribbonThe cooling speed of the thin layer at the contact surface of the surface and the tin liquid influences the polishing of the glass ribbon and the diffusion segregation of valence changing ions. When C Molten tin on lower surface of glass ribbon When the cooling speed is less than 95 ℃/min, the lower the viscosity of the thin layer of the contact surface between the lower surface of the glass belt and the tin liquid is, the more favorable the tin ions in the tin bath are diffused and the iron element in the glass is diffused and segregated to the contact surface between the glass belt and the tin liquid due to the gravity factor, so that the oxidation-reduction reaction is promoted to generate more Fe 2+ The absorption of the glass infrared band is caused, so that the transmittance of glass sunlight is reduced; when C Molten tin on lower surface of glass ribbon When the speed of cooling is more than 147 ℃ per minute, the viscosity of the contact surface of the glass belt and the molten tin is rapidly increased, the polishing time is insufficient, the lower surface of the glass is corrugated, and the product quality is affected.
(3) The invention ensures the cooling speed C of the thin layer of the contact surface between the upper surface of the glass ribbon and the protective gas Glass ribbon upper surface-shielding gas The cooling speed of the thin layer of the contact surface between the upper surface of the glass ribbon and the protective gas is controlled to be 84-132 ℃ per minute, preferably 100-120 ℃ per minute, so that the stripping polishing and forming conditions are affected. When C Glass ribbon upper surface-shielding gas When the speed is less than 84 ℃/min, the viscosity is too low due to too low cooling speed, so that the surface tension of the glass in the subsequent forming stage is high, and the glass is difficult to form; when C Glass ribbon upper surface-shielding gas When the speed is higher than 132 ℃ per minute, the viscosity is increased rapidly due to the excessively high cooling speed, and the polishing time of the glass is short, so that the surface unevenness of the glass affects the quality.
(4) At the same time, by ensuring C in the invention Molten tin on lower surface of glass ribbon And C Glass ribbon upper surface-shielding gas The ratio between the two is 1.0-1.5, namely C Molten tin on lower surface of glass ribbon And C Glass ribbon upper surface-shielding gas To be matched with each other, if C Glass ribbon upper surface-shielding gas Too fast to be C Molten tin on lower surface of glass ribbon The viscosity of the upper surface of the glass is high, and elements with higher density in the melt, such as iron, are more beneficial to diffusing and segregation to the lower surface, so that oxidation-reduction reaction is promoted to generate more Fe 2+ Causing absorption of the infrared band of the glass and thereby reducing the glassTransmittance of sunlight; if C Glass ribbon upper surface-shielding gas Too slow to C Molten tin on lower surface of glass ribbon The cooling speed of the contact surface of the glass belt and the shielding gas is slower than that of the contact surface of the glass belt and the molten tin, and the upper surface viscosity of the glass is low, so that the glass is not beneficial to glass molding.
Drawings
FIG. 1 is a schematic view of the structure of a glass ribbon of the present invention floating on the surface of a molten tin bath;
FIG. 2 is a schematic view of the layered structure of a glass ribbon of the present invention;
FIG. 3 is a graph showing absorption curves of glasses of example 6 and comparative example 3 of the present invention at different wavelengths;
wherein, the names represented by the reference numerals in the figures are as follows:
1. a shielding gas; 2. a glass ribbon; 3. tin liquid; 4. a glass upper surface and a protective gas thin layer; 5. a center layer; 6. the lower surface of the glass is contacted with the tin liquid for a thin layer.
Detailed Description
The present invention will be described in further detail with reference to the drawings, principles and embodiments for better understanding of the technical aspects of the present invention by those skilled in the art.
As shown in FIG. 1, the upper surface of the glass ribbon is contacted with a shielding gas and the lower surface is contacted with a molten tin bath in a molten tin bath. The contact medium is different, so that the heat transfer modes of the upper surface and the lower surface are different. The heat transfer mode of the upper surface is mainly radiation and convection, the heat transfer mode of the lower surface is conduction and convection, the temperature reduction is limited to the extremely thin surface layer of the glass as shown in fig. 2 due to poor heat conductivity of the glass, the condition that the surface temperature is low and the internal temperature is high occurs in the cooling process, and the viscosity of the extremely thin surface layer of the upper surface and the lower surface of the glass is lower than that of the intermediate layer.
In the float formed polishing leveling zone, the glass can be considered as a viscoelastic fluid in which diffusion of various elements in the glass is always in progress, the amount of diffusion being affected by the diffusion coefficient, which can be expressed by the Stokes-Einstein diffusion relationship equation:
wherein D is diffusion coefficient, K β The Boltzmann constant, T is temperature, eta is viscosity, and r is radius. It can be seen that the higher the viscosity of the glass liquid, the smaller the diffusion coefficient, and the more difficult the diffusion; the higher the temperature, the greater the diffusion coefficient, and the easier the diffusion.
Assuming that the diffusion of the elements in the glass takes place as oxides in the melt, the denser elements in the glass melt will diffuse downward due to the influence of gravity, such as the density of iron oxide in the glass component (FeO density of 5.7g/cm 3 ，Fe 2 O 3 Has a density of 5.24g/cm 3 ) Much greater than the density of the glass melt (the density of the glass melt is about 2.3 g/cm) 3 ) Therefore, the iron element is inevitably diffused and offset to the lower surface under the condition of proper viscosity. At the same time, sn exists in the tin bath due to oxidation and other reasons 2+ 、Sn 4+ The ions are diffused into the glass ribbon due to concentration differences by the contact of the molten tin with the lower surface of the glass ribbon.
Since two kinds of valence oxides of Sn and Fe exist on the lower surface of the glass ribbon, the Fe element is located at a higher position of the Sn element according to the oxidation-reduction pair order obtained by Dules (Tress), so that the lower valence oxides of tin can be oxidized as shown in the following formula.
Fe 3+ +Sn 2+ ＝Fe 2+ +Sn 4+
When the tin surface is enriched with iron element, fe 3+ The content of Sn in the alloy is also increased, and the alloy is easy to be matched with Sn on the surface 2+ Reaction takes place to lead Fe in the glass 2+ The content is increased, so that the absorbance of the glass to the infrared spectrum is increased, and the solar light transmittance of the glass is reduced.
The temperature difference of the tin liquid in the polishing area satisfies the following relationship:
wherein, delta T is the temperature difference of tin liquid in the polishing area; epsilon is a coefficient, and the value of epsilon is between 0.1 and 1.3; h is the glass thickness.
The glass components in examples 1-12 and comparative examples 1-6 in the present invention are identical, and specifically comprise the following components in weight percent: 72.6% of silicon dioxide, 8.4% of calcium oxide, 3.5% of magnesium oxide, 1.02% of aluminum oxide and R 2 O13.98% (R is either or both of Na and K), the other 0.5%, and the iron oxide content was selected to be 80ppm.
The thicknesses of the glass in the examples and the comparative examples in the present invention are three, namely 2mm, 3mm and 4mm.
The methods for producing glass according to the examples and comparative examples of the present invention are as follows: the production is carried out by adopting a float process, the batch is mixed uniformly and then is sent into a melting furnace, molten glass is molded in a tin bath after being melted, clarified and homogenized, and the cooling speed C of a thin layer of the contact surface of the lower surface of the glass belt and the tin liquid is set Molten tin on lower surface of glass ribbon And cooling rate C of the thin layer of the surface of the glass ribbon in contact with the shielding gas Glass ribbon upper surface-shielding gas And C Molten tin on lower surface of glass ribbon And C Glass ribbon upper surface-shielding gas And (3) cooling and forming, and then annealing, cutting and packaging. The cooling rates of the upper and lower surfaces of the glass ribbon, the temperature difference between the glass ribbon and the polishing zone, and specific parameters of the thickness of the glass in each example were different from those in the comparative example, and are specifically shown in table 1.
The temperature of the molten tin in the polishing area is tested by adopting a thermocouple.
The absorbance and the solar light transmittance of the ultra-white glass are tested by using a Lambda1050 plus ultraviolet-visible-near infrared spectrophotometer, the wavelength range is set to 300-2500nm, and the wavelength interval is 5 nm.
Table 1 parameters and test results for glass production of different examples and comparative examples
As can be seen from the data in table 1, the examples in the cooling rate range set in the present invention achieved better solar transmittance than the comparative examples with the same thickness. However, when the cooling rate is too high, the lower surface waviness of the glasses of comparative examples 2, 4 and 6 is large and the flatness is poor, which affects the quality of the products. The solar transmittance performance was different in the case of the same glass material and the same thickness, and the transmittance change and the cause of the change can be more accurately described by the change of the absorbance of the glass at different wavelengths, and the absorbance of the glass with the thickness of 3mm in example 6 and comparative example 3 was tested, and the absorbance curves of the glass at different wavelengths are shown in fig. 3. As can be seen from FIG. 3, the absorbance of the glass of example 6 is significantly lower than that of the glass of comparative example 3 in the range of 840-2200nm, and the decrease in absorbance increases the transmittance of the glass in this wavelength region, indicating Fe in the glass having the greatest influence on absorption in this wavelength region 2+ The content is obviously reduced. It can be seen that the invention patent relates to C Glass upper surface-shielding gas And C Glass bottom surface-tin liquid The setting and adjustment of the glass can effectively improve the solar light transmittance of the glass under the condition of not changing the glass components and the technological parameters of the melting furnace.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. A method for improving solar transmittance of ultra-white float glass is characterized in that molten, clarified and homogenized glass liquid flows into a tin bath from a runner, the molten glass floats on the surface of the tin liquid in the tin bath to form a glass belt, and the viscosity of the glass belt in a polishing flattening area is 10 2.7 -10 3.2 Controlling the glass ribbon to be under the glass ribbon in a tin bath during Pa.SCooling rate C of thin layer of contact surface between surface and tin liquid Molten tin on lower surface of glass ribbon And cooling rate C of the thin layer of the surface of the glass ribbon in contact with the shielding gas Glass ribbon upper surface-shielding gas And the C Molten tin on lower surface of glass ribbon And C Glass ribbon upper surface-shielding gas Is a ratio of (2); cooling rate C of the thin layer of the contact surface between the lower surface of the glass ribbon and the molten tin Lower surface of glass ribbon - Tin liquid Controlling the temperature at 95-147 ℃/min; cooling rate C of the thin layer of the contact surface of the upper surface of the glass ribbon and the protective gas Glass ribbon upper surface-shielding gas Controlling at 84-132 deg.C/min.
2. The method for improving solar transmittance of ultra-white float glass according to claim 1, wherein the cooling rate C of the thin layer of the contact surface of the lower surface of the glass ribbon and the molten tin Molten tin on lower surface of glass ribbon Controlling the temperature at 115 ℃/min-130 ℃/min.
3. The method for improving solar transmittance of ultra-white float glass according to claim 1, wherein the cooling rate C of the surface thin layer of the upper surface of the glass ribbon contacted with the shielding gas Glass ribbon upper surface-shielding gas Controlling at 100-120 deg.C/min.
4. A method for increasing solar light transmittance of ultra-white float glass according to claim 1, wherein said C Molten tin on lower surface of glass ribbon And C Glass ribbon upper surface-shielding gas The ratio of (2) is 1.0-1.5.
5. The method for improving solar light transmittance of ultra-white float glass according to claim 1, wherein the cooling speed of the thin layer of the contact surface of the lower surface of the glass ribbon and the molten tin is controlled by adjusting the temperature difference between the glass ribbon and the molten tin by using a molten tin cooler, adjusting the air quantity of a fan at the bottom of the molten tin bath or controlling the temperature of the glass ribbon entering the molten tin.
6. The method for improving solar transmittance of ultra-white float glass according to claim 1, wherein the cooling rate of the contact surface between the upper surface of the glass ribbon and the shielding gas is controlled by inserting or removing a water drum in a space of a tin bath, turning on or off electric heating of the tin bath, adjusting the flow rate and temperature of the shielding gas, or controlling the temperature of the glass ribbon entering into tin liquid.
7. The method for improving solar light transmittance of ultra-white float glass according to claim 5, wherein the temperature difference of the molten tin in the polishing zone satisfies the following relationship:
wherein, delta T is the temperature difference of tin liquid in the polishing area; epsilon is a coefficient, and the value of epsilon is between 0.1 and 1.3; h is the glass thickness.
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| FR2951157A1 (en) * | 2009-10-12 | 2011-04-15 | Saint Gobain | FRITTE DE VERRE |
| US11261122B2 (en) * | 2013-04-15 | 2022-03-01 | Vitro Flat Glass Llc | Low iron, high redox ratio, and high iron, high redox ratio, soda-lime-silica glasses and methods of making same |
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| JP2014224011A (en) * | 2013-05-16 | 2014-12-04 | 旭硝子株式会社 | Glass plate, and manufacturing method of glass plate |
| WO2016182054A1 (en) * | 2015-05-13 | 2016-11-17 | 旭硝子株式会社 | Glass sheet |
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