CN114276001A - Float glass preparation method with low bubble content and float glass - Google Patents
Float glass preparation method with low bubble content and float glass Download PDFInfo
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- CN114276001A CN114276001A CN202111101513.8A CN202111101513A CN114276001A CN 114276001 A CN114276001 A CN 114276001A CN 202111101513 A CN202111101513 A CN 202111101513A CN 114276001 A CN114276001 A CN 114276001A
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- glass
- iron oxide
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- titanium dioxide
- float glass
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- 239000005329 float glass Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 112
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000011521 glass Substances 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 41
- 239000000156 glass melt Substances 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 239000008395 clarifying agent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 20
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000006060 molten glass Substances 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 56
- 239000007822 coupling agent Substances 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000004408 titanium dioxide Substances 0.000 claims description 27
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 14
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 14
- 238000009832 plasma treatment Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 125000004423 acyloxy group Chemical group 0.000 claims description 12
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 12
- 239000006004 Quartz sand Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 4
- 239000006025 fining agent Substances 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 238000005352 clarification Methods 0.000 abstract description 18
- 230000007547 defect Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract description 6
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 abstract description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical group [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Glass Compositions (AREA)
Abstract
The invention relates to the technical field of float glass, and discloses a method for preparing float glass with low bubble content and the float glass. The preparation method comprises the following steps: uniformly mixing glass raw materials and a clarifying agent, and heating and melting to obtain a glass melt; the clarifying agent comprises the following components: sodium sulfate, carbon powder, and iron oxide @ titanium dioxide particles; clarifying the glass melt at the temperature of 1400 ℃ and 1550 ℃, heating to the temperature of 1860 ℃ and 1880 ℃, stirring for 20-30min, cooling to the temperature of 1400 ℃ and 1550 ℃, and continuing stirring for 1.5-2.5h to obtain glass liquid; and carrying out float forming and annealing on the molten glass to obtain the float glass with low bubble content. According to the invention, the iron oxide @ titanium dioxide particles are added into the clarifying agent, so that the clarifying effect of sodium sulfate and carbon powder can be fully exerted, and the phenomenon that sulfur oxide remains in glass and forms bubbles after clarification is finished can be reduced, so that the bubble defect of float glass is reduced.
Description
Technical Field
The invention relates to the technical field of float glass, in particular to a method for preparing float glass with low bubble content and the float glass.
Background
Float forming is one of the common methods for producing flat glass at present. In the production process, after the batch materials of the melting furnace are melted into glass liquid, the glass liquid flows onto the liquid level of molten metallic tin through a runner connected with the melting furnace and a tin bath, under the action of the gravity, the surface tension and the drawing force of the glass liquid, the glass liquid is spread to form a glass strip, polishing and thinning are completed in the tin bath, when the glass strip at the tail end of the tin bath is cooled to about 600 ℃, the glass strip to be hardened is led out from the tin bath, enters an annealing furnace through a transitional roller table, and is annealed and cooled to form flat glass, which is sometimes called float glass.
The melting of float glass is a process in which a complex physicochemical reaction of multi-component mineral raw materials occurs at high temperature and is converted into a uniform amorphous substance. During this process, 10-20% of the gases contained in the glass batch materials are released, and the physicochemical reactions of the various components in the raw materials also release large amounts of gases, which are estimated to be thousands of times the volume of the glass melt. After the raw materials are decomposed and the glass melt is formed, part of gas can remain in the glass body in the form of visible bubbles, so that the bubble defects of the glass occur, and the properties of the glass product, such as beauty, transparency, mechanical strength and the like, are influenced. Blister defects are the most commonly encountered and most problematic glass defects in the float glass melting process.
Therefore, in the production of float glass, it is usually necessary to add a fining agent, to refine the glass after it has been melted, and then to flow it into a tin bath for shaping. Sodium sulfate (mirabilite) is one of the commonly used glass clarifiers, and its decomposition temperature is 1200 ℃, and it is often used in combination with carbon powder to lower the decomposition temperature and reduce the generation of sulfur-containing (elemental sulfur) bubbles (for example, patent application No. CN 202011391642.0). Gases generated after the sodium sulfate and the carbon powder are decomposed at high temperature are mainly sulfur dioxide and carbon dioxide, wherein the solubility of the sulfur dioxide in the glass melt is very low, and after the clarification is finished, the sulfur dioxide remained in the glass liquid is easy to form micro-bubbles, so that the clarification effect is poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing float glass with low bubble content and the float glass. The preparation method adopts the clarifying agent added with the iron oxide @ titanium dioxide particles, can fully play the clarifying effect of the clarifying agent, and reduces the bubble defect in the float glass.
The specific technical scheme of the invention is as follows:
a method for preparing float glass with low bubble content comprises the following steps:
(1) uniformly mixing glass raw materials and a clarifying agent, and heating and melting to obtain a glass melt; the clarifying agent comprises the following components: sodium sulfate, carbon powder, and iron oxide @ titanium dioxide particles;
(2) clarifying the glass melt at the temperature of 1400 ℃ and 1550 ℃ for 2.5-3.5h, heating to the temperature of 1860 ℃ and 1880 ℃, stirring for 20-30min, cooling to the temperature of 1400 ℃ and 1550 ℃, and continuing stirring for 1.5-2.5h to obtain glass liquid;
(3) and carrying out float forming on the molten glass, and then annealing to obtain the float glass with low bubble content.
The clarifying agent is added with iron oxide @ titanium dioxide particles, and the titanium dioxide is adopted to coat the iron oxide, so that the clarifying agent has the following effects: in the clarification stage, under the obstruction of titanium dioxide, ferric oxide does not play a role, at the moment, sodium sulfate and carbon powder play a role in clarification, sulfur dioxide and carbon dioxide are mainly generated, and compared with sulfur trioxide, the solubility of the sulfur dioxide in the glass melt is poor, so that the effect of a clarifier is favorably fully played, other gases are driven to escape from the glass melt in a large amount, and the residue of sulfur oxide in the glass after the clarification is finished is reduced. After the clarification is finished, the titanium dioxide is melted by heating treatment (1860-1880 ℃) to release the coated ferric oxide, and the ferric oxide can play the following two roles: on the one hand, the catalyst can catalyze the oxidation of sulfur dioxide into sulfur trioxide, and the sulfur trioxide has higher solubility in a glass melt; on the other hand, the solubility of sulfur trioxide in glass can be improved. By the above two actions, the iron oxide can prevent part of the sulfur oxides from being dissolved in the glass melt and remaining in the glass in the form of microbubbles after the completion of the refining.
Preferably, in the step (1), the glass raw material comprises the following components in parts by weight: 100 parts of quartz sand, 10-20 parts of aluminum oxide, 8-13 parts of magnesium oxide, 15-25 parts of sodium carbonate, 0-3 parts of calcium carbonate and 0-5 parts of potassium carbonate.
Preferably, in the step (1), the mass ratio of the glass raw material to the fining agent is 1: 0.05-0.07.
Preferably, in the step (1), the mass ratio of the sodium sulfate to the carbon powder to the iron oxide @ titanium dioxide particles in the clarifier is 1:0.7-0.9: 0.10-0.15.
Preferably, in step (1), the iron oxide @ titanium dioxide particles are prepared as follows:
(1.1) iron oxide activation: carrying out plasma treatment on the ferric oxide to obtain surface activated ferric oxide;
(1.2) titanium dioxide coating: adding the surface-activated iron oxide into the titanate coupling agent solution, fully dispersing, and stirring for reacting for 3-5 h; the solvent is then removed, aerobic calcination is performed, and milling is performed to obtain iron oxide @ titanium dioxide particles.
In the preparation process, the titanate coupling agent is grafted to the hydroxyl on the surface of the iron oxide, and then is converted into titanium dioxide through aerobic calcination, so that the titanium dioxide-coated iron oxide core-shell structure particles are formed. Because the titanate coupling agent is combined with the ferric oxide through a covalent bond, the combination fastness of the titanium dioxide shell layer and the ferric oxide core layer and the uniformity of the titanium dioxide shell layer can be improved, and the titanium dioxide shell layer can play a good role in blocking in a clarification stage. In the step (1.1), the hydroxyl content of the surface of the iron oxide can be improved by carrying out plasma treatment on the iron oxide, so that the compactness of a titanium dioxide shell layer is improved, and the iron oxide can better play a role in blocking in a clarification stage.
Preferably, in the step (1.2), in the titanate coupling agent solution, the titanate coupling agent is isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, and the solvent is a mixed solvent of ethanol and water; the pH of the titanate coupling agent solution is 3-4.
Isopropyl tri (dioctyl pyrophosphato acyloxy) titanate is adopted as a titanate coupling agent, wherein pyrophosphate groups can be hydrolyzed to generate phosphate groups with negative electricity; when the pH value is within the range of 3-4, the surface of the iron oxide is positively charged, and can be combined with phosphate groups with negative charges through electrostatic attraction, so that the grafting amount of the titanate coupling agent on the surface of the iron oxide is improved, and the compactness of a titanium dioxide shell layer is improved.
Preferably, in step (1.1), the power of the plasma treatment is 200-.
Preferably, in the step (1.2), the concentration of the titanate coupling agent solution is 0.007 to 0.010 mol/L; the mass-volume ratio of the surface activated iron oxide to the titanate coupling agent solution is 1g:20-30 mL.
Preferably, in step (1.2), the temperature of the aerobic calcination is 600-650 ℃ and the time is 6-8 h.
A float glass obtained by the preparation method.
Compared with the prior art, the invention has the following advantages:
(1) the iron oxide @ titanium dioxide particles are added into the clarifying agent, so that the clarifying effect of sodium sulfate and carbon powder can be fully exerted, and the phenomenon that sulfur oxides remain in glass and form bubbles after clarification is reduced, so that the bubble defect of float glass is reduced; (2) in the preparation process of the iron oxide @ titanium dioxide particles, the iron oxide is subjected to plasma treatment, and titanium dioxide is formed in an aerobic calcination mode by adopting a titanate coupling agent, so that the compactness and uniformity of a titanium dioxide shell layer can be improved, the bonding fastness between the titanium dioxide shell layer and an iron oxide core layer is improved, and the titanium dioxide shell layer can better play a role in blocking in a clarification stage.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A method for preparing float glass with low bubble content comprises the following steps:
(1) preparation of iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: carrying out plasma treatment on the ferric oxide with the power of 200-300W, the air flow rate of 250-350mL/min and the time of 2-4min to obtain the surface activated ferric oxide;
(1.2) titanium dioxide coating: adding surface-activated iron oxide into a titanate coupling agent solution of 10-13g/L, wherein the mass-volume ratio of the surface-activated iron oxide to the titanate coupling agent solution is 1g:20-30mL, fully dispersing, and stirring for reacting for 3-5 h; then removing the solvent, carrying out aerobic calcination for 6-8h at the temperature of 600-650 ℃, and grinding to obtain iron oxide @ titanium dioxide particles;
optionally, in the titanate coupling agent solution, the titanate coupling agent is isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, and the solvent is a mixed solvent of ethanol and water with the pH value of 3-4;
(2) uniformly mixing glass raw materials and a clarifying agent, and heating and melting to obtain a glass melt; the glass raw material comprises the following components in parts by weight: 100 parts of quartz sand, 10-20 parts of aluminum oxide, 8-13 parts of magnesium oxide, 15-25 parts of sodium carbonate, 0-3 parts of calcium carbonate and 0-5 parts of potassium carbonate; the clarifying agent comprises sodium sulfate, carbon powder and iron oxide @ titanium dioxide particles in a mass ratio of 1:0.7-0.9: 0.10-0.15; the mass ratio of the glass raw material to the clarifying agent is 1: 0.05-0.07;
(3) clarifying the glass melt at the temperature of 1400 ℃ and 1550 ℃ for 2.5-3.5h, heating to the temperature of 1860 ℃ and 1880 ℃, stirring for 20-30min, cooling to the temperature of 1400 ℃ and 1550 ℃, and continuing stirring for 1.5-2.5h to obtain glass liquid;
(4) and carrying out float forming on the molten glass, and then annealing to obtain the float glass with low bubble content.
A float glass obtained by the above preparation method.
Example 1
A method for preparing float glass with low bubble content comprises the following steps:
(1) preparation of iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: carrying out plasma treatment on the ferric oxide with the power of 200W, the air flow rate of 250mL/min and the time of 4min to obtain surface activated ferric oxide;
(1.2) titanium dioxide coating: dissolving isopropyl tri (dioctyl pyrophosphato acyloxy) titanate in a mixed solvent of ethanol and water (the volume ratio of ethanol to water is 10:1), adjusting the pH to 3, and obtaining a titanate coupling agent solution with the concentration of 0.007 mol/L; adding surface-activated iron oxide into a titanate coupling agent solution, wherein the mass-volume ratio of the surface-activated iron oxide to the titanate coupling agent solution is 1g:30mL, and stirring and reacting for 5 hours after ultrasonic dispersion is uniform; then, removing the solvent by rotary evaporation, carrying out aerobic calcination for 8h under the conditions that the volume concentration of oxygen is 72% and the temperature is 600 ℃, and grinding to obtain iron oxide @ titanium dioxide particles;
(2) uniformly mixing glass raw materials (100 parts of quartz sand, 10 parts of aluminum oxide, 8 parts of magnesium oxide, 25 parts of sodium carbonate and 3 parts of calcium carbonate) and a clarifying agent (5.7 parts of sodium sulfate, 4 parts of carbon powder and 0.57 part of iron oxide @ titanium dioxide particles) in parts by weight, and heating and melting for 0.5h at 1550 ℃ to obtain a glass melt;
(3) clarifying the glass melt at 1550 ℃ for 3.5h, heating to 1880 ℃, stirring for 20min, cooling to 1550 ℃, and continuing stirring for 1.5h to obtain glass liquid;
(4) and cooling the molten glass to 1200 ℃, flowing into a tin bath for float forming, and then annealing to obtain the float glass with low bubble content.
A float glass obtained by the above preparation method.
Example 2
A method for preparing float glass with low bubble content comprises the following steps:
(1) preparation of iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: carrying out plasma treatment on the ferric oxide, wherein the power is 250W, the air flow rate is 300mL/min, and the time is 3min, so as to obtain surface activated ferric oxide;
(1.2) titanium dioxide coating: dissolving isopropyl tri (dioctyl pyrophosphato acyloxy) titanate in a mixed solvent of ethanol and water (the volume ratio of ethanol to water is 10:1), adjusting the pH to 3.5, and obtaining a titanate coupling agent solution with the concentration of 0.008 mol/L; adding surface-activated iron oxide into a titanate coupling agent solution, wherein the mass-volume ratio of the surface-activated iron oxide to the titanate coupling agent solution is 1g:25mL, and stirring for reaction for 4 hours after uniform ultrasonic dispersion; then, removing the solvent by rotary evaporation, carrying out aerobic calcination for 7h under the conditions that the volume concentration of oxygen is 75% and the temperature is 630 ℃, and grinding to obtain iron oxide @ titanium dioxide particles;
(2) uniformly mixing glass raw materials (100 parts by weight of quartz sand, 15 parts by weight of aluminum oxide, 10 parts by weight of magnesium oxide, 20 parts by weight of sodium carbonate, 1.5 parts by weight of calcium carbonate and 2.5 parts by weight of potassium carbonate) and a clarifying agent (4.7 parts by weight of sodium sulfate, 3.7 parts by weight of carbon powder and 0.5 part by weight of iron oxide @ titanium dioxide particles), and heating and melting the mixture at 1450 ℃ for 1 hour to obtain a glass melt;
(3) clarifying the glass melt at 1500 ℃ for 3h, heating to 1870 ℃, stirring for 25min, cooling to 1500 ℃, and continuing stirring for 2h to obtain glass liquid;
(4) and cooling the molten glass to 1200 ℃, flowing into a tin bath for float forming, and then annealing to obtain the float glass with low bubble content.
A float glass obtained by the above preparation method.
Example 3
A method for preparing float glass with low bubble content comprises the following steps:
(1) preparation of iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: carrying out plasma treatment on the ferric oxide with the power of 300W, the air flow rate of 350mL/min and the time of 2min to obtain surface activated ferric oxide;
(1.2) titanium dioxide coating: dissolving isopropyl tri (dioctyl pyrophosphato acyloxy) titanate in a mixed solvent of ethanol and water (the volume ratio of ethanol to water is 10:1), adjusting the pH value to 4, and obtaining a titanate coupling agent solution with the concentration of 0.010 mol/L; adding surface-activated iron oxide into a titanate coupling agent solution, wherein the mass-volume ratio of the surface-activated iron oxide to the titanate coupling agent solution is 1g:20mL, and stirring for reaction for 3h after uniform ultrasonic dispersion; then, removing the solvent by rotary evaporation, carrying out aerobic calcination for 6h under the conditions that the volume concentration of oxygen is 80% and the temperature is 650 ℃, and grinding to obtain iron oxide @ titanium dioxide particles;
(2) uniformly mixing glass raw materials (100 parts of quartz sand, 20 parts of aluminum oxide, 13 parts of magnesium oxide, 15 parts of sodium carbonate and 5 parts of potassium carbonate) and a clarifying agent (3.7 parts of sodium sulfate, 3.3 parts of carbon powder and 0.5 part of iron oxide @ titanium dioxide particles) in parts by weight, and heating and melting the mixture at 1400 ℃ for 1.5 hours to obtain a glass melt;
(3) clarifying the glass melt at 1400 ℃ for 2.5h, heating to 1860 ℃, stirring for 30min, cooling to 1400 ℃, and continuing stirring for 2.5h to obtain glass liquid;
(4) and cooling the molten glass to 1200 ℃, flowing into a tin bath for float forming, and then annealing to obtain the float glass with low bubble content.
A float glass obtained by the above preparation method.
Example 4
A method for preparing float glass with low bubble content comprises the following steps:
(1) preparation of iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: carrying out plasma treatment on the ferric oxide, wherein the power is 250W, the air flow rate is 300mL/min, and the time is 3min, so as to obtain surface activated ferric oxide;
(1.2) titanium dioxide coating: dissolving isopropyl triisostearate in a mixed solvent of ethanol and water (the volume ratio of ethanol to water is 10:1), and adjusting the pH to 3.5 to obtain a titanate coupling agent solution with the concentration of 0.008 mol/L; adding surface-activated iron oxide into a titanate coupling agent solution, wherein the mass-volume ratio of the surface-activated iron oxide to the titanate coupling agent solution is 1g:25mL, and stirring for reaction for 4 hours after uniform ultrasonic dispersion; then, removing the solvent by rotary evaporation, carrying out aerobic calcination for 7h under the conditions that the volume concentration of oxygen is 75% and the temperature is 630 ℃, and grinding to obtain iron oxide @ titanium dioxide particles;
(2) uniformly mixing glass raw materials (100 parts by weight of quartz sand, 15 parts by weight of aluminum oxide, 10 parts by weight of magnesium oxide, 20 parts by weight of sodium carbonate, 1.5 parts by weight of calcium carbonate and 2.5 parts by weight of potassium carbonate) and a clarifying agent (4.7 parts by weight of sodium sulfate, 3.7 parts by weight of carbon powder and 0.5 part by weight of iron oxide @ titanium dioxide particles), and heating and melting the mixture at 1450 ℃ for 1 hour to obtain a glass melt;
(3) clarifying the glass melt at 1500 ℃ for 3h, heating to 1870 ℃, stirring for 25min, cooling to 1500 ℃, and continuing stirring for 2h to obtain glass liquid;
(4) and cooling the molten glass to 1200 ℃, flowing into a tin bath for float forming, and then annealing to obtain the float glass with low bubble content.
A float glass obtained by the above preparation method.
Example 5
A method for preparing float glass with low bubble content comprises the following steps:
(1) preparation of iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: carrying out plasma treatment on the ferric oxide, wherein the power is 250W, the air flow rate is 300mL/min, and the time is 3min, so as to obtain surface activated ferric oxide;
(1.2) titanium dioxide coating: dissolving isopropyl tri (dioctyl pyrophosphato acyloxy) titanate in a mixed solvent of ethanol and water (the volume ratio of ethanol to water is 10:1) to obtain a titanate coupling agent solution with the concentration of 0.008 mol/L; adding surface-activated iron oxide into a titanate coupling agent solution, wherein the mass-volume ratio of the surface-activated iron oxide to the titanate coupling agent solution is 1g:25mL, and stirring for reaction for 4 hours after uniform ultrasonic dispersion; then, removing the solvent by rotary evaporation, carrying out aerobic calcination for 7h under the conditions that the volume concentration of oxygen is 75% and the temperature is 630 ℃, and grinding to obtain iron oxide @ titanium dioxide particles;
(2) uniformly mixing glass raw materials (100 parts by weight of quartz sand, 15 parts by weight of aluminum oxide, 10 parts by weight of magnesium oxide, 20 parts by weight of sodium carbonate, 1.5 parts by weight of calcium carbonate and 2.5 parts by weight of potassium carbonate) and a clarifying agent (4.7 parts by weight of sodium sulfate, 3.7 parts by weight of carbon powder and 0.5 part by weight of iron oxide @ titanium dioxide particles), and heating and melting the mixture at 1450 ℃ for 1 hour to obtain a glass melt;
(3) clarifying the glass melt at 1500 ℃ for 3h, heating to 1870 ℃, stirring for 25min, cooling to 1500 ℃, and continuing stirring for 2h to obtain glass liquid;
(4) and cooling the molten glass to 1200 ℃, flowing into a tin bath for float forming, and then annealing to obtain the float glass with low bubble content.
A float glass obtained by the above preparation method.
Comparative example 1
A method of making float glass comprising the steps of:
(1) uniformly mixing glass raw materials (100 parts of quartz sand, 15 parts of aluminum oxide, 10 parts of magnesium oxide, 20 parts of sodium carbonate, 1.5 parts of calcium carbonate and 2.5 parts of potassium carbonate) and a clarifying agent (4.7 parts of sodium sulfate and 3.7 parts of carbon powder) in parts by weight, and heating and melting for 1h at 1450 ℃ to obtain a glass melt;
(2) clarifying the glass melt at 1500 ℃ for 3h, heating to 1870 ℃, stirring for 25min, cooling to 1500 ℃, and continuing stirring for 2h to obtain glass liquid;
(3) and cooling the molten glass to 1200 ℃, flowing into a tin bath for float forming, and then annealing to obtain the float glass.
A float glass obtained by the above preparation method.
Comparative example 2
A method of making float glass comprising the steps of:
(1) preparation of iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: carrying out plasma treatment on the ferric oxide, wherein the power is 250W, the air flow rate is 300mL/min, and the time is 3min, so as to obtain surface activated ferric oxide;
(1.2) titanium dioxide coating: dissolving isopropyl tri (dioctyl pyrophosphato acyloxy) titanate in a mixed solvent of ethanol and water (the volume ratio of ethanol to water is 10:1), adjusting the pH to 3.5, and obtaining a titanate coupling agent solution with the concentration of 0.008 mol/L; adding surface-activated iron oxide into a titanate coupling agent solution, wherein the mass-volume ratio of the surface-activated iron oxide to the titanate coupling agent solution is 1g:25mL, and stirring for reaction for 4 hours after uniform ultrasonic dispersion; then, removing the solvent by rotary evaporation, carrying out aerobic calcination for 7h under the conditions that the volume concentration of oxygen is 75% and the temperature is 630 ℃, and grinding to obtain iron oxide @ titanium dioxide particles;
(2) uniformly mixing glass raw materials (100 parts by weight of quartz sand, 15 parts by weight of aluminum oxide, 10 parts by weight of magnesium oxide, 20 parts by weight of sodium carbonate, 1.5 parts by weight of calcium carbonate and 2.5 parts by weight of potassium carbonate) and a clarifying agent (4.7 parts by weight of sodium sulfate, 3.7 parts by weight of carbon powder and 0.5 part by weight of iron oxide @ titanium dioxide particles), and heating and melting the mixture at 1450 ℃ for 1 hour to obtain a glass melt;
(3) clarifying the glass melt at 1500 ℃ for 3h to obtain glass liquid;
(4) and cooling the molten glass to 1200 ℃, flowing into a tin bath for float forming, and then annealing to obtain the float glass.
A float glass obtained by the above preparation method.
Comparative example 3
A method of making float glass comprising the steps of:
(1) preparation of iron oxide @ titanium dioxide particles: dissolving isopropyl tri (dioctyl pyrophosphato acyloxy) titanate in a mixed solvent of ethanol and water (the volume ratio of ethanol to water is 10:1), adjusting the pH to 3.5, and obtaining a titanate coupling agent solution with the concentration of 0.008 mol/L; adding iron oxide into a titanate coupling agent solution, wherein the mass volume ratio of the iron oxide to the titanate coupling agent solution is 1g:25mL, and stirring and reacting for 4 hours after ultrasonic dispersion is uniform; then, removing the solvent by rotary evaporation, carrying out aerobic calcination for 7h under the conditions that the volume concentration of oxygen is 75% and the temperature is 630 ℃, and grinding to obtain iron oxide @ titanium dioxide particles;
(2) uniformly mixing glass raw materials (100 parts by weight of quartz sand, 15 parts by weight of aluminum oxide, 10 parts by weight of magnesium oxide, 20 parts by weight of sodium carbonate, 1.5 parts by weight of calcium carbonate and 2.5 parts by weight of potassium carbonate) and a clarifying agent (4.7 parts by weight of sodium sulfate, 3.7 parts by weight of carbon powder and 0.5 part by weight of iron oxide @ titanium dioxide particles), and heating and melting the mixture at 1450 ℃ for 1 hour to obtain a glass melt;
(3) clarifying the glass melt at 1500 ℃ for 3h, heating to 1870 ℃, stirring for 25min, cooling to 1500 ℃, and continuing stirring for 2h to obtain glass liquid;
(4) and cooling the molten glass to 1200 ℃, flowing into a tin bath for float forming, and then annealing to obtain the float glass.
A float glass obtained by the above preparation method.
Test example
Reference standard GB/T7962.8-2010 colorless optical glass test method part 8: degree of bubbling degree, measured for float glass obtained in examples 1 to 5 and comparative examples 1 to 3 per 100cm3The total cross-sectional area S of the bubbles contained in the air bubble, and the degree of the bubbles is judged according to the cross-sectional area S, and the result is shown in Table 1.
TABLE 1
| S(mm2/100cm3) | Degree of bubble | |
| Example 1 | 0.03 | A00 |
| Example 2 | 0.01 | A00 |
| Example 3 | 0.03 | A00 |
| Example 4 | 0.07 | A0 |
| Example 5 | 0.06 | A0 |
| Comparative example 1 | 0.28 | B |
| Comparative example 2 | 0.27 | B |
| Comparative example 3 | 0.18 | A |
Data analysis and conclusions:
(1) the clarifier of comparative example 1 has no iron oxide @ titanium dioxide particles added, comparative example 2 has no temperature raising treatment after clarification, and other raw materials and preparation processes are the same as those of example 2. As can be seen from table 1, the blister defects in the float glass of example 2 are significantly smaller compared to comparative examples 1 and 2. The reason is that: in the clarification stage, under the obstruction of titanium dioxide, ferric oxide does not play a role, at the moment, sodium sulfate and carbon powder play a role in clarification, sulfur dioxide and carbon dioxide are mainly generated, the role of a clarifier is fully played, other gases are driven to escape from a glass melt in a large amount, and the residue of sulfur oxide in the glass after clarification is reduced; after clarification is finished, titanium dioxide is melted through heating treatment, the wrapped iron oxide is released, the iron oxide can catalyze sulfur dioxide to be oxidized into sulfur trioxide, the solubility of the sulfur trioxide in glass is improved, and therefore the phenomenon that sulfur oxide remains in the glass and forms bubbles after clarification is reduced.
(2) Comparative example 3 iron oxide was not plasma treated during the preparation of iron oxide @ titanium dioxide particles, and the other raw materials and preparation were the same as in example 2. As can be seen from table 1, the blister defects are significantly smaller in the float glass of example 2 compared to comparative example 3. The reason is that: the hydroxyl content of the surface of the iron oxide can be improved by carrying out plasma treatment on the iron oxide, so that the compactness of a titanium dioxide shell is improved, and the iron oxide can better play a role in blocking in a clarification stage.
(3) Example 4 isopropyl tris (dioctyl pyrophosphato acyloxy) titanate was replaced with isopropyl triisostearate, example 5 did not adjust the pH of the titanate coupling agent solution to 3.5, and the other raw materials and preparation procedures were the same as in example 2. As can be seen from table 1, the blister defects in the float glass of example 2 are relatively small compared to examples 4 and 5. The reason is that: isopropyl tri (dioctyl pyrophosphato acyloxy) titanate is adopted as a titanate coupling agent, wherein pyrophosphate groups can be hydrolyzed to generate phosphate groups with negative electricity; when the pH value is within the range of 3-4, the surface of the iron oxide is positively charged, and can be combined with phosphate groups with negative charges through electrostatic attraction, so that the grafting amount of the titanate coupling agent on the surface of the iron oxide is improved, and the compactness of a titanium dioxide shell layer is improved.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing float glass with low bubble content is characterized by comprising the following steps:
(1) uniformly mixing glass raw materials and a clarifying agent, and heating and melting to obtain a glass melt; the clarifying agent comprises the following components: sodium sulfate, carbon powder, and iron oxide @ titanium dioxide particles;
(2) clarifying the glass melt at the temperature of 1400 ℃ and 1550 ℃ for 2.5-3.5h, heating to the temperature of 1860 ℃ and 1880 ℃, stirring for 20-30min, cooling to the temperature of 1400 ℃ and 1550 ℃, and continuing stirring for 1.5-2.5h to obtain glass liquid;
(3) and carrying out float forming on the molten glass, and then annealing to obtain the float glass with low bubble content.
2. The method according to claim 1, wherein in the step (1), the glass raw material comprises the following components in parts by weight: 100 parts of quartz sand, 10-20 parts of aluminum oxide, 8-13 parts of magnesium oxide, 15-25 parts of sodium carbonate, 0-3 parts of calcium carbonate and 0-5 parts of potassium carbonate.
3. The production method according to claim 1, wherein in the step (1), the mass ratio of the glass raw material to the fining agent is 1:0.05 to 0.07.
4. The method according to claim 1 or 3, wherein in step (1), the mass ratio of the sodium sulfate, the carbon powder and the iron oxide @ titanium dioxide particles in the clarifier is 1:0.7-0.9: 0.10-0.15.
5. The method of claim 1, wherein in step (1), said iron oxide @ titanium dioxide particles are prepared as follows:
(1.1) iron oxide activation: carrying out plasma treatment on the ferric oxide to obtain surface activated ferric oxide;
(1.2) titanium dioxide coating: adding the surface-activated iron oxide into the titanate coupling agent solution, fully dispersing, and stirring for reacting for 3-5 h; the solvent is then removed, aerobic calcination is performed, and milling is performed to obtain iron oxide @ titanium dioxide particles.
6. The preparation method according to claim 5, wherein in the step (1.2), the titanate coupling agent solution is prepared by mixing isopropyl tris (dioctyl pyrophosphato acyloxy) titanate, ethanol solvent and water; the pH of the titanate coupling agent solution is 3-4.
7. The method as claimed in claim 5, wherein in step (1.1), the power of the plasma treatment is 200-300W, the air flow rate is 250-350mL/min, and the time is 2-4 min.
8. The process of claim 5 or 6, wherein in step (1.2), the titanate coupling agent solution is at a concentration of 0.007 to 0.010 mol/L; the mass-volume ratio of the surface activated iron oxide to the titanate coupling agent solution is 1g:20-30 mL.
9. The process according to claim 5 or 6, wherein in step (1.2), the temperature of the aerobic calcination is 600-650 ℃ and the time is 6-8 h.
10. A float glass obtained by the production method according to any one of claims 1 to 9.
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