CN115572048A - 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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- CN115572048A CN115572048A CN202211407277.7A CN202211407277A CN115572048A CN 115572048 A CN115572048 A CN 115572048A CN 202211407277 A CN202211407277 A CN 202211407277A CN 115572048 A CN115572048 A CN 115572048A
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- glass
- tin
- protective gas
- glass ribbon
- ultra
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- 238000002834 transmittance Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000005329 float glass Substances 0.000 title claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 176
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000001816 cooling Methods 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000005498 polishing Methods 0.000 claims abstract description 16
- 230000001681 protective effect Effects 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 30
- 238000009792 diffusion process Methods 0.000 abstract description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003487 electrochemical reaction Methods 0.000 abstract description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 description 45
- 239000010410 layer Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 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
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000006124 Pilkington process Methods 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-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
- 230000008859 change Effects 0.000 description 3
- 239000000156 glass melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting 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
- 238000005204 segregation Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- GSJBKPNSLRKRNR-UHFFFAOYSA-N $l^{2}-stannanylidenetin Chemical compound [Sn].[Sn] GSJBKPNSLRKRNR-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 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
- 239000006060 molten glass Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 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
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000012535 impurity Substances 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
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 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
- 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
- 230000005855 radiation Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000010583 slow cooling Methods 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
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
Images
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 light transmittance of ultra-white float glass, which comprises the steps of enabling glass liquid to flow into a tin bath from a flow channel, enabling the glass liquid to float on the surface of the tin liquid in the tin bath for forming to form a glass belt, and enabling the viscosity of the glass belt in a polishing and flattening area to be 10 2.7 ‑10 3.2 When Pa.S, the cooling speed C of the thin layer of the contact surface between the lower surface of the glass belt and the molten tin in the tin bath is controlled Tin liquor on lower surface of glass strip And the cooling rate C of the thin layer of the upper surface of the glass ribbon in contact with the protective gas Glass ribbon upper surface-protective gas And C and tin liquor on lower surface of glass strip And C Glass ribbon upper surface-protective gas The ratio of (a) to (b). The invention controls the cooling speed of the upper surface and the lower surface of the glass belt in the tin bath under the condition of not changing the original glass components and the content of ferric oxide in the raw materials,reduce the generation of more Fe generated by electrochemical reaction caused by the concentration of iron element to the lower surface and the diffusion of tin element to the glass in the tin bath forming process of the glass strip 2+ Thereby improving the solar light transmittance of the glass, and the method is simple and has obvious effect.
Description
Technical Field
The invention belongs to the technical field of glass manufacturing, and particularly relates to a method for improving solar light transmittance of ultra-white float glass.
Background
The float-process produced ultra-white glass is mainly used in the industries of solar power generation, high-grade buildings, automobile glass and the like, the most important performance index is the transmittance, and particularly, when the float-process produced ultra-white glass is used in the solar power generation industry such as photo-thermal and photovoltaic power generation, higher requirements are provided for the solar transmittance. Since the content of impurity elements in the ultra-white glass is small, the influence of the ultra-white glass on the transmittance is determined by the content of iron oxide contained in the ultra-white glass, wherein iron is contained in the ultra-white glass and Fe is contained in the ultra-white glass 2+ And Fe 3+ In two valence states, fe 2+ Two strong absorption bands in the range of 950-1100nm and 2050-2200 nm; fe 3+ Three absorption bands are in the ultraviolet regions of 380nm, 420nm and 435 nm. Therefore, when the content of iron oxide in the ultra-white glass is constant, the valence state of iron (Fe) in the glass 2+ Content) is the most dominant factor affecting solar light transmittance.
The method for improving the solar light transmittance of the ultra-white glass commonly used at present is to continuously reduce the content of iron oxide in the ultra-white glass, 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 the iron oxide in the glass can cause that the heat permeability of molten glass is good, the temperature gradient in the vertical direction is small, and the clarification difficulty of the glass is increased. The Chinese patent with the publication number of 103011595A provides a glass component for improving the photovoltaic transmittance of glass, and the glass component for improving the photovoltaic transmittance of glass comprises the following components in percentage by mass: 58 to 62 percent of quartz sand, 17 to 21 percent of soda ash, 11 to 14 percent of dolomite, 6 to 8 percent of limestone and 0.5 to 0.7 percent of mirabilite; the above-mentionedThe glass component also comprises an additive; the additive is as follows: sodium nitrate, cerium oxide and manganese dioxide; the addition amount of the sodium nitrate is 0.3 to 2.0 percent; the addition amount of the cerium oxide is 0.2 to 0.8 percent; 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 oxidizability of the glass and enable Fe 2+ To Fe 3+ Conversion, reduction of Fe 2+ The absorption of sunlight improves the wave band transmittance of photovoltaic solar energy. However, the addition of the oxidants sodium nitrate, cerium oxide and manganese dioxide in the patent firstly increases the production cost, and secondly, the introduction of Sr and Mn into the glass causes strong ultraviolet absorption, reduces the ultraviolet transmittance and influences the improvement of the sunlight (300-2500 nm) transmittance. Therefore, how to improve the solar light transmittance of the ultra-white glass under the condition of not changing the components of the ultra-white glass is a problem which needs to be solved urgently 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 light 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 formula of glass components and the content of ferric oxide in raw materials thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for improving solar light transmittance of ultra-white float glass comprises the steps of enabling molten, clarified and homogenized glass liquid to flow into a tin bath from a flow channel, enabling the glass liquid to float on the surface of the tin liquid in the tin bath to be formed to form a glass belt, and enabling the viscosity of the glass belt in a polishing and flattening area to be 10 2.7 -10 3.2 When Pa.S, controlling the cooling speed C of the thin layer of the contact surface between the lower surface of the glass belt and the molten tin in the tin bath Tin liquor on lower surface of glass strip And the cooling rate C of the thin layer of the upper surface of the glass ribbon in contact with the protective gas Glass ribbon upper surface-protective gas And said C Tin liquor on lower surface of glass strip And C Glass ribbon upper surface-protective gas Is measured in the measurement.
Further, the method can be used for preparing a novel materialThe cooling rate C of the thin layer of the contact surface of the lower surface of the glass strip and the molten tin Tin liquor on lower surface of glass strip Controlling the temperature at 95-147 deg.c/min.
Further, the cooling speed C of the thin layer of the contact surface of the lower surface of the glass strip and the molten tin Tin liquor on lower surface of glass strip Controlling the temperature at 115-130 deg.c/min.
Further, the cooling rate C of the thin layer of the upper surface of the glass ribbon in contact with the protective gas Glass ribbon upper surface-protective gas Controlling the temperature at 84-132 deg.c/min.
Further, the cooling rate C of the thin layer of the upper surface of the glass ribbon in contact with the protective gas Glass ribbon upper surface-protective gas The temperature is controlled to be between 100 and 120 ℃/min.
Further, said C Tin liquor on lower surface of glass strip And C Glass ribbon upper surface-protective gas The ratio of (A) to (B) is 1.0-1.5.
Further, the cooling speed of the thin layer of the contact surface of the lower surface of the glass ribbon and molten tin is controlled by using a molten tin cooler, adjusting the air quantity of a blower at the bottom of the molten tin bath or controlling the temperature of the glass ribbon entering the molten tin bath.
Furthermore, the cooling speed of the contact surface of the upper surface of the glass ribbon and the protective gas is controlled by inserting or taking out a water bag in the tin bath space, turning on or off the electric heating of the tin bath, adjusting the flow and the temperature of the protective gas, or controlling the temperature of the glass ribbon entering the tin bath.
Further, the temperature difference of the tin liquid in the polishing area satisfies the following relation:
wherein, the delta T is the temperature difference of tin liquor 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 following positive beneficial effects:
(1) The invention controls the glass ribbon to be in the tin bathThe cooling speed of the thin layer of the contact surface between the lower surface of the glass belt and the tin liquid and the thin layer of the contact surface between the upper surface of the glass belt and the protective gas, and the method for adjusting the ratio of the cooling speed of the thin layers of the upper surface and the lower surface of the glass belt realize flattening and polishing of glass, control the diffusion direction of elements in glass melt and reduce the generation of more Fe due to the electrochemical reaction of the enrichment of iron elements to the lower surface and the diffusion of tin elements to the glass in the tin bath forming process of the glass belt under the condition of not changing the original glass component formula and the content of iron oxide in the raw materials of the glass belt 2+ Thereby improving the solar light transmittance of the glass, 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 strip and the molten tin
C Tin liquor on lower surface of glass strip The cooling speed of the thin layer of the contact surface of the lower surface of the glass belt and the tin liquid influences the polishing of the glass belt and the diffusion segregation of valence-variable ions by controlling the temperature to be between 95 ℃/min and 147 ℃/min, preferably between 115 ℃/min and 130 ℃/min. When C is present Tin liquor on lower surface of glass strip When the temperature is lower than 95 ℃/min, the lower the thin layer viscosity of the contact surface between the lower surface of the glass strip and molten tin is due to the slow cooling speed, the more favorable the diffusion of tin ions in a tin bath and the diffusion segregation of iron elements in glass to the contact surface between the glass strip and the molten tin due to gravity factors are, the more Fe generated by redox reaction is promoted 2+ The absorption of the infrared band of the glass is caused, so that the transmittance of the glass to sunlight is reduced; when C is present Tin liquor on lower surface of glass strip When the temperature is higher than 147 ℃/min, the viscosity of the contact surface of the glass belt and the tin liquid is rapidly increased due to the excessively high cooling speed, and the polishing time is insufficient, so that the lower surface of the glass is corrugated, and the product quality is influenced.
(3) The invention cools the upper surface of the glass ribbon at a cooling rate C Glass ribbon upper surface-protective gas The cooling speed of the thin layer of the contact surface of the upper surface of the glass ribbon and the protective gas influences the stripping, polishing and forming conditions by controlling the cooling speed to be between 84 ℃/min and 132 ℃/min, preferably between 100 ℃/min and 120 ℃/min. When C is Glass ribbon upper surface-protective gas When the temperature is less than 84 ℃/min, the glass surface in the subsequent forming stage can be caused due to too low cooling speed and too low viscosityThe surface tension is large, and the glass is difficult to form; when C is present Glass ribbon upper surface-protective gas When the temperature is higher than 132 ℃/min, the viscosity is rapidly increased due to the excessively high cooling speed, and the quality is affected due to the fact that the glass surface is not flat due to the short polishing time.
(4) Meanwhile, the invention ensures C Tin liquor on lower surface of glass strip And C Glass ribbon upper surface-protective gas The ratio between the two is 1.0-1.5, namely C Tin liquor on lower surface of glass strip And C Glass ribbon upper surface-protective gas The two are matched if C Glass ribbon upper surface-protective gas Too fast than C Tin liquor on lower surface of glass strip The upper surface of the glass has high viscosity, and elements with higher density in the melt, such as iron, are more favorable for diffusing to the lower surface to generate segregation, so that the oxidation-reduction reaction is promoted to generate more Fe 2+ The absorption of infrared band of the glass is caused, thereby reducing the transmittance of the glass to sunlight; if C is Glass ribbon upper surface-protective gas Too slow than C Tin liquor on lower surface of glass strip The cooling speed of the contact surface of the glass belt and the protective gas is too slower than that of the contact surface of the glass belt and the tin liquid, and the viscosity of the upper surface of the glass is low, so that the glass is not beneficial to glass forming.
Drawings
FIG. 1 is a schematic view of a configuration in which a glass ribbon according to the present invention floats on the surface of molten tin;
FIG. 2 is a schematic view of the layered structure of the glass ribbon of the present invention;
FIG. 3 is a graph of the absorbance at different wavelengths for glasses according to example 6 and comparative example 3 of the present invention;
wherein, the names represented by the reference numbers in the figure are respectively as follows:
1. a shielding gas; 2. a glass ribbon; 3. tin liquid; 4. the upper surface of the glass is covered with a thin layer of protective gas; 5. a center layer; 6. the lower surface of the glass is in contact with the tin liquid.
Detailed Description
For a better understanding of the patented technology by those skilled in the art, the invention is described in further detail with reference to the drawings, the principles and examples.
As shown in fig. 1, the glass ribbon is in contact with a protective gas on the top surface and a molten tin on the bottom surface in a tin bath. Because of the different contact media, 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 figure 2 due to poor heat conductivity of the glass, the condition of low surface temperature and high internal temperature 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 middle layer.
In the polished leveling zone of the float process, the glass can be considered as viscoelastic fluid, wherein the diffusion of various elements in the glass is always carried out, the diffusion amount is influenced by a diffusion coefficient, and the diffusion coefficient can be expressed by a Stokes-Einstein diffusion relation equation as follows:
wherein D is the diffusion coefficient, K β Is the boltzmann constant, T is the temperature, η is the viscosity, and r is the radius. It can be seen that the higher the viscosity of the glass liquid, the lower the diffusion coefficient, the more difficult the diffusion; the higher the temperature, the higher the diffusion coefficient, and the easier the diffusion.
Assuming that the diffusion of the elements in the glass in the melt takes place in the form of oxides, the denser elements in the glass melt will move downward by diffusion under the influence of gravity, such as the density of iron oxide in the glass components (FeO having a density of 5.7 g/cm) 3 ，Fe 2 O 3 Has a density of 5.24g/cm 3 ) Much greater than the density of the glass melt (which has a density of about 2.3 g/cm) 3 ) Therefore, the iron element inevitably undergoes diffusion migration toward the lower surface under the condition of appropriate viscosity. Meanwhile, sn exists in the tin liquid in the tin bath due to oxidation and the like 2+ 、Sn 4+ The ions are diffused into the lower surface of the glass ribbon due to concentration difference when the tin melt is in contact with the lower surface of the glass ribbon.
Since two kinds of valence-variable oxides of Sn and Fe exist on the lower surface of the glass ribbon, it is known that Fe is located at a higher position of Sn according to the order of oxidation-reduction pairs obtained by doles (Tress), and thus it is possible to oxidize a lower-valence oxide of Sn 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 (B) is increased, and Sn on the surface is easily mixed with 2+ Reaction is carried out to lead Fe in the glass 2+ The content is increased, which causes the spectral absorbance of the glass to the infrared region to be increased, thereby reducing the solar light transmittance of the glass.
The temperature difference of the tin liquid in the polishing area satisfies the following relation:
wherein, the delta T is the temperature difference of tin liquor 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 to 12 of the present invention are the same as those in comparative examples 1 to 6, and specifically include the following components in percentage by weight: 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 one or both of Na and K), the other 0.5%, and the iron oxide content was selected to be 80ppm.
The thicknesses of the glasses in the examples and comparative examples of the present invention are three, respectively, 2mm, 3mm, and 4mm.
The method for producing glass in the embodiment and the comparative example of the invention comprises the following steps: the production is carried out by float process, the batch materials are mixed evenly and then sent into melting furnace, the molten glass is formed in tin bath after melting, clarifying and homogenizing, and the cooling speed C of the thin layer of the contact surface of the lower surface of the glass belt and the molten tin is set according to Tin liquor on lower surface of glass strip And the cooling rate C of the thin layer of the upper surface of the glass ribbon in contact with the protective gas Glass ribbon upper surface-protective gas And C Tin liquor on lower surface of glass strip And C Glass ribbon upper surface-protective gas Cooling and forming, annealing, cutting and packaging. Each example and comparisonThe specific parameters of the cooling speed of the upper and lower surfaces of the glass ribbon, the temperature difference between the glass ribbon and the tin liquor in the polishing area and the thickness of the glass in the examples are different and are shown in Table 1.
The temperature of the tin liquor 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 adopting a Lambda1050 ultraviolet-visible-near infrared spectrophotometer, and the test is carried out by setting the wavelength range of 300-2500nm and the wavelength interval of 5 nm.
TABLE 1 parameters and test results for the production of glass for the different examples and comparative examples
As can be seen from the data in table 1, the examples within the cooling rate range set by the present invention achieve better solar transmittance than the comparative examples with the same thickness. However, when the cooling rate is too high, the glasses of comparative examples 2, 4 and 6 have the problems of large waviness and poor flatness on the lower surface, which affects the product quality. The solar transmittance performance is different under the condition of the same glass raw material and the same thickness, the change of the transmittance and the reason of the change can be more accurately described through the change of the absorbance of the glass to different wavelengths, the absorbance of the glass with the thickness of 3mm in the example 6 and the comparative example 3 is tested, and the absorption curve of the glass under different wavelengths is shown in figure 3. As can be seen from FIG. 3, the absorbance of the glass of example 6 between 840 and 2200nm is significantly lower than that of the glass of comparative example 3, and a decrease in absorbance increases the transmittance of the glass in this wavelength region, indicating Fe in the glass that most affects absorption in this wavelength region 2+ The content is obviously reduced. It can be seen that the invention provides the following patent pair C Glass upper surface-protective gas And C Surface-tin liquid on glass The setting adjustment can effectively improve the solar light transmittance of the glass under the condition of not changing glass components and melting furnace process parameters.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The method for improving the solar light transmittance of ultra-white float glass is characterized in that molten, clarified and homogenized glass liquid flows into a tin bath from a flow channel, the glass liquid floats on the surface of the tin liquid in the tin bath to be molded to form a glass belt, and the viscosity of the glass belt in a polishing and leveling area is 10 2.7 -10 3.2 When Pa.S, controlling the cooling speed C of the thin layer of the contact surface of the lower surface of the glass belt and the molten tin in the tin bath Tin liquor on lower surface of glass strip And the cooling rate C of the thin layer of the upper surface of the glass ribbon in contact with the protective gas Glass ribbon upper surface-protective gas And said C Tin liquor on lower surface of glass strip And C Glass ribbon upper surface-protective gas The ratio of (a) to (b).
2. The method for improving the solar light transmittance of the ultra-white float glass according to claim 1, wherein the cooling speed C of the thin layer on the contact surface of the lower surface of the glass strip and the molten tin is C Tin liquor on lower surface of glass strip Controlling the temperature at 95-147 deg.c/min.
3. The method for improving the solar transmittance of ultra-white float glass according to claim 2, 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 is Tin liquor on lower surface of glass strip Controlling the temperature at 115-130 deg.c/min.
4. The method of claim 1, wherein the cooling of the thin layer of the protective gas contact surface on the upper surface of the glass ribbon is performed in a manner that enhances the solar light transmittance of the ultra-white float glassSpeed C Glass ribbon upper surface-protective gas Controlling the temperature at 84-132 deg.c/min.
5. The method of claim 4, wherein the cooling rate C of the thin layer of the protective gas contacting surface of the upper surface of the glass ribbon is a rate of cooling Glass ribbon upper surface-protective gas Controlling the temperature at 100-120 deg.c/min.
6. The method for improving solar light transmittance of ultra-white float glass according to claim 1, wherein C is Tin liquor on lower surface of glass strip And C Glass ribbon upper surface-protective gas The ratio of (A) to (B) is 1.0-1.5.
7. The method for improving the solar light transmittance of the ultra-white float glass according to claim 1, wherein the cooling rate 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 volume of a bottom fan of a molten tin bath, or controlling the temperature of the glass ribbon entering the molten tin.
8. The method of claim 1, wherein the cooling rate of the upper surface of the glass ribbon in contact with the shielding gas is controlled by inserting or removing a water pocket in the space of the tin bath, turning on or off electrical heating of the tin bath, adjusting the flow and temperature of the shielding gas, or controlling the temperature of the glass ribbon entering the molten tin.
9. The method for improving solar light transmittance of ultra-white float glass according to claim 7, wherein the temperature difference of the tin liquid in the polishing zone satisfies the following relationship:
wherein, the delta T is the temperature difference of tin liquor in the polishing area; epsilon is a coefficient, and the value of epsilon is between 0.1 and 1.3; and h is the glass thickness.
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