CN114276001B - 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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- CN114276001B CN114276001B CN202111101513.8A CN202111101513A CN114276001B CN 114276001 B CN114276001 B CN 114276001B CN 202111101513 A CN202111101513 A CN 202111101513A CN 114276001 B CN114276001 B CN 114276001B
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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 24
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 114
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 95
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000011521 glass Substances 0.000 claims abstract description 54
- 239000002245 particle Substances 0.000 claims abstract description 41
- 239000000156 glass melt Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 239000008395 clarifying agent Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 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
- 239000007788 liquid Substances 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
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 57
- 239000007822 coupling agent Substances 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000004408 titanium dioxide Substances 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 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
- 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
- 238000006243 chemical reaction Methods 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
- 239000002904 solvent Substances 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
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 3
- 239000006025 fining agent Substances 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims 1
- 238000005352 clarification Methods 0.000 abstract description 19
- 230000007547 defect Effects 0.000 abstract description 9
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052815 sulfur oxide Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 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 10
- 239000012046 mixed solvent Substances 0.000 description 9
- 239000006060 molten glass Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 230000001105 regulatory effect Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 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
- 230000004888 barrier function 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
- 230000002349 favourable effect Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical group [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000007858 starting material Substances 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
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- 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 float glass preparation method with low bubble content and float glass. The preparation method comprises the following steps: uniformly mixing a glass raw material 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 1400-1550 ℃, heating to 1860-1880 ℃, stirring for 20-30min, cooling to 1400-1550 ℃, and continuously stirring for 1.5-2.5h to obtain glass liquid; and (3) carrying out float forming and annealing on the glass liquid to obtain the float glass with low bubble content. According to the invention, the ferric 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 meanwhile, the phenomenon that sulfur oxides remain in glass and form 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 preparation method of float glass with low bubble content and float glass.
Background
Float forming is one of the current methods of making sheet glass. In the production process, after the melting furnace batch is melted into glass liquid, the glass liquid flows onto the molten metal tin liquid surface through a launder connected with a melting furnace and a tin bath, the glass liquid can be spread out to form glass belts under the action of self gravity, surface tension and drawing force, polishing and thinning are completed in the tin bath, when the glass belts at the tail end of the tin bath are cooled to about 600 ℃, the glass belts to be hardened are led out of the tin bath, then enter an annealing kiln through a transition roller table, and are annealed and cooled to form flat glass, which is sometimes called float glass.
Melting of float glass is a process in which multi-component mineral raw materials undergo complex physicochemical reactions at high temperatures to convert into homogeneous amorphous materials. During this process, 10-20% of the gas contained in the glass batch will be released, and at the same time, the physicochemical reactions of the various components in the raw materials will also release a large amount of gas, estimated to be about 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 bubble defects appear in the glass, and the properties of the glass product such as attractive appearance, transparency, mechanical strength and the like are affected. Bubble defects are the most commonly encountered and difficult glass defects during float glass melting.
Therefore, in the production of float glass, it is often necessary to add a fining agent, to perform fining after the glass is melted, and then to flow into a tin bath for forming. Sodium sulfate (mirabilite) is one of the commonly used glass clarifiers, and has a decomposition temperature of 1200 ℃ and is often used in combination with carbon powder to reduce the decomposition temperature and reduce the generation of sulfur-containing (elemental sulfur) bubbles (e.g., patent application number CN 202011391642.0). The generated gas after the sodium sulfate and the carbon powder are decomposed at high temperature is mainly sulfur dioxide and carbon dioxide, wherein the solubility of the sulfur dioxide in the glass melt is very low, and after clarification is finished, the sulfur dioxide remained in the glass melt 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 float glass preparation method with low bubble content and float glass. The preparation method adopts the clarifier added with the ferric oxide and titanium dioxide particles, can fully play the clarification function of the clarifier, 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, comprising the following steps:
(1) Uniformly mixing a glass raw material 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 glass melt at 1400-1550 ℃ for 2.5-3.5h, heating to 1860-1880 ℃, stirring for 20-30min, cooling to 1400-1550 ℃, and continuously stirring for 1.5-2.5h to obtain glass liquid;
(3) And (3) carrying out float forming on the glass liquid, and then annealing to obtain the float glass with low bubble content.
The invention adds ferric oxide@titanium dioxide particles into the clarifying agent, adopts titanium dioxide to coat the ferric oxide, and has the following functions: in the clarification stage, under the barrier of titanium dioxide, ferric oxide does not play a role, at the moment, sodium sulfate and carbon powder play a clarification role, mainly generate sulfur dioxide and carbon dioxide, and compared with sulfur trioxide, the sulfur dioxide has poorer solubility in glass melt, is favorable for fully playing the role of a clarifier, drives other gases to largely escape from the glass melt, and reduces the residue of sulfur oxides in the glass after clarification. After clarification, titanium dioxide is melted by heating (1860-1880 ℃), wherein the encapsulated iron oxide is released, and the iron oxide can play the following two roles: on the one hand, sulfur dioxide can be catalyzed to oxidize into sulfur trioxide, and the sulfur trioxide has higher solubility in glass melt; on the other hand, the solubility of sulfur trioxide in glass can be improved. By both of these actions, the iron oxide prevents a part of the sulfur oxides from being dissolved in the glass melt after the completion of fining and remaining in the glass in the form of microbubbles.
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 clarifying agent is 1:0.05-0.07.
Preferably, in the step (1), the mass ratio of sodium sulfate to carbon powder to iron oxide@titanium dioxide particles in the clarifying agent is 1:0.7-0.9:0.10-0.15.
Preferably, in the step (1), the preparation method of the iron oxide@titanium dioxide particles comprises the following steps:
(1.1) iron oxide activation: performing plasma treatment on the ferric oxide to obtain surface-activated ferric oxide;
(1.2) titanium dioxide coating: adding the surface activated ferric oxide into the titanate coupling agent solution, fully dispersing, and stirring for reaction for 3-5h; and then removing the solvent, performing aerobic calcination and grinding to obtain the iron oxide@titanium dioxide particles.
In the preparation process, the titanate coupling agent is grafted to hydroxyl on the surface of the ferric oxide, and then is converted into titanium dioxide through aerobic calcination, so that the titanium dioxide coated ferric oxide core-shell structure particles are formed. The titanate coupling agent and the ferric oxide are combined through covalent bonds, so that the combination fastness of the titanium dioxide shell layer and the iron oxide core layer and the uniformity of the titanium dioxide shell layer can be improved, and the titanium dioxide shell layer can play a better blocking role in a clarification stage. In the step (1.1), the hydroxyl content of the surface of the ferric oxide can be improved by carrying out plasma treatment on the ferric oxide, so that the compactness of the titanium dioxide shell layer is improved, and the ferric 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 pyrophosphoryloxy) titanate, and a solvent ethanol and water mixed solvent; the pH value of the titanate coupling agent solution is 3-4.
Isopropyl tri (dioctyl pyrophosphoryl oxy) titanate is adopted as a titanate coupling agent, wherein pyrophosphate groups can be hydrolyzed to generate negatively charged phosphate groups; when the pH is in the range of 3-4, the surface of the ferric oxide has positive charges, and can be combined with negatively charged phosphate groups through electrostatic attraction, so that the grafting amount of the titanate coupling agent on the surface of the ferric oxide can be improved, and the compactness of a titanium dioxide shell layer can be improved.
Preferably, in the step (1.1), the power of the plasma treatment is 200-300W, the air flow rate is 250-350mL/min, and the time is 2-4min.
Preferably, in the step (1.2), the concentration of the titanate coupling agent solution is 0.007 to 0.010mol/L; the mass volume ratio of the surface activated ferric oxide to the titanate coupling agent solution is 1g:20-30mL.
Preferably, in the step (1.2), the temperature of the aerobic calcination is 600-650 ℃ and the time is 6-8h.
A float glass obtained by the 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 meanwhile, the phenomenon that sulfur oxides remain in glass and form bubbles after clarification is finished can be 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, titanium dioxide is formed by adopting a mode of aerobic calcination of a titanate coupling agent, the compactness and uniformity of a titanium dioxide shell layer can be improved, and the bonding fastness between the titanium dioxide shell layer and an iron oxide core layer is improved, so that the titanium dioxide shell layer can better play a blocking role in a clarification stage.
Detailed Description
The invention is further described below with reference to examples.
General examples
A method for preparing float glass with low bubble content, comprising the following steps:
(1) Preparing iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: performing 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 surface activated ferric oxide;
(1.2) titanium dioxide coating: adding surface activated ferric oxide into 10-13g/L titanate coupling agent solution, wherein the mass volume ratio of the surface activated ferric oxide to the titanate coupling agent solution is 1g:20-30mL, and stirring for reaction for 3-5h after full dispersion; then removing the solvent, performing aerobic calcination for 6-8 hours at 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 pyrophosphoryloxy) titanate, and the solvent is a mixed solvent of ethanol and water with the pH of 3-4;
(2) Uniformly mixing a glass raw material and a clarifying agent, and heating and melting to obtain a glass melt; the glass raw materials comprise 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 ferric 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 glass melt at 1400-1550 ℃ for 2.5-3.5h, heating to 1860-1880 ℃, stirring for 20-30min, cooling to 1400-1550 ℃, and continuously stirring for 1.5-2.5h to obtain glass liquid;
(4) And (3) carrying out float forming on the glass liquid, and then annealing to obtain the float glass with low bubble content.
Float glass obtained by the preparation method.
Example 1
A method for preparing float glass with low bubble content, comprising the following steps:
(1) Preparing iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: performing plasma treatment on the ferric oxide, wherein the power is 200W, the air flow rate is 250mL/min, and the time is 4min, so as to obtain surface-activated ferric oxide;
(1.2) titanium dioxide coating: dissolving isopropyl tri (dioctyl pyrophosphoryloxy) titanate in a mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 10:1), and regulating the pH value to 3 to obtain a titanate coupling agent solution with the concentration of 0.007 mol/L; adding surface activated ferric oxide into a titanate coupling agent solution, wherein the mass volume ratio of the surface activated ferric oxide to the titanate coupling agent solution is 1g to 30mL, and stirring for reaction for 5h after ultrasonic dispersion is uniform; then removing the solvent by rotary evaporation, performing aerobic calcination for 8 hours under the conditions that the volume concentration of oxygen is 72 percent 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 ferric oxide@titanium dioxide particles) by weight, and heating and melting at 1550 ℃ for 0.5h to obtain a glass melt;
(3) Clarifying the glass melt at 1550 ℃ for 3.5 hours, heating to 1880 ℃, stirring for 20 minutes, cooling to 1550 ℃, and continuously stirring for 1.5 hours 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.
Float glass obtained by the preparation method.
Example 2
A method for preparing float glass with low bubble content, comprising the following steps:
(1) Preparing iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: performing 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 pyrophosphoryloxy) titanate in a mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 10:1), and regulating the pH value to 3.5 to obtain a titanate coupling agent solution with the concentration of 0.008 mol/L; adding surface activated ferric oxide into a titanate coupling agent solution, wherein the mass volume ratio of the surface activated ferric oxide to the titanate coupling agent solution is 1g to 25mL, and stirring for reaction for 4h after ultrasonic dispersion is uniform; then removing the solvent by rotary evaporation, performing aerobic calcination for 7 hours under the conditions that the oxygen volume concentration is 75 percent and the temperature is 630 ℃, and grinding to obtain iron oxide@titanium dioxide particles;
(2) Uniformly mixing glass raw materials (100 parts of quartz sand, 15 parts of alumina, 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, 3.7 parts of carbon powder and 0.5 part of ferric oxide@titanium dioxide particles) by weight, and heating and melting for 1 hour at 1450 ℃ to obtain a glass melt;
(3) Clarifying the glass melt at 1500 ℃ for 3 hours, heating to 1870 ℃, stirring for 25 minutes, cooling to 1500 ℃, and continuously stirring for 2 hours 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.
Float glass obtained by the preparation method.
Example 3
A method for preparing float glass with low bubble content, comprising the following steps:
(1) Preparing iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: performing plasma treatment on the ferric oxide, wherein the power is 300W, the air flow rate is 350mL/min, and the time is 2min, so as to obtain surface-activated ferric oxide;
(1.2) titanium dioxide coating: dissolving isopropyl tri (dioctyl pyrophosphoryloxy) titanate in a mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 10:1), and regulating the pH value to 4 to obtain a titanate coupling agent solution with the concentration of 0.010mol/L; adding surface activated ferric oxide into a titanate coupling agent solution, wherein the mass volume ratio of the surface activated ferric oxide to the titanate coupling agent solution is 1g to 20mL, and stirring for reaction for 3h after ultrasonic dispersion is uniform; then removing the solvent by rotary evaporation, performing aerobic calcination for 6 hours under the conditions that the oxygen volume concentration is 80 percent 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 ferric oxide@titanium dioxide particles) by weight, and heating and melting for 1.5 hours at 1400 ℃ to obtain a glass melt;
(3) Clarifying the glass melt at 1400 ℃ for 2.5 hours, heating to 1860 ℃, stirring for 30 minutes, cooling to 1400 ℃, and continuously stirring for 2.5 hours 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.
Float glass obtained by the preparation method.
Example 4
A method for preparing float glass with low bubble content, comprising the following steps:
(1) Preparing iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: performing 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 titanate in a mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 10:1), and regulating the pH value to 3.5 to obtain a titanate coupling agent solution with the concentration of 0.008 mol/L; adding surface activated ferric oxide into a titanate coupling agent solution, wherein the mass volume ratio of the surface activated ferric oxide to the titanate coupling agent solution is 1g to 25mL, and stirring for reaction for 4h after ultrasonic dispersion is uniform; then removing the solvent by rotary evaporation, performing aerobic calcination for 7 hours under the conditions that the oxygen volume concentration is 75 percent and the temperature is 630 ℃, and grinding to obtain iron oxide@titanium dioxide particles;
(2) Uniformly mixing glass raw materials (100 parts of quartz sand, 15 parts of alumina, 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, 3.7 parts of carbon powder and 0.5 part of ferric oxide@titanium dioxide particles) by weight, and heating and melting for 1 hour at 1450 ℃ to obtain a glass melt;
(3) Clarifying the glass melt at 1500 ℃ for 3 hours, heating to 1870 ℃, stirring for 25 minutes, cooling to 1500 ℃, and continuously stirring for 2 hours 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.
Float glass obtained by the preparation method.
Example 5
A method for preparing float glass with low bubble content, comprising the following steps:
(1) Preparing iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: performing 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 pyrophosphoryloxy) titanate in a mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 10:1) to obtain a titanate coupling agent solution with the concentration of 0.008 mol/L; adding surface activated ferric oxide into a titanate coupling agent solution, wherein the mass volume ratio of the surface activated ferric oxide to the titanate coupling agent solution is 1g to 25mL, and stirring for reaction for 4h after ultrasonic dispersion is uniform; then removing the solvent by rotary evaporation, performing aerobic calcination for 7 hours under the conditions that the oxygen volume concentration is 75 percent and the temperature is 630 ℃, and grinding to obtain iron oxide@titanium dioxide particles;
(2) Uniformly mixing glass raw materials (100 parts of quartz sand, 15 parts of alumina, 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, 3.7 parts of carbon powder and 0.5 part of ferric oxide@titanium dioxide particles) by weight, and heating and melting for 1 hour at 1450 ℃ to obtain a glass melt;
(3) Clarifying the glass melt at 1500 ℃ for 3 hours, heating to 1870 ℃, stirring for 25 minutes, cooling to 1500 ℃, and continuously stirring for 2 hours 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.
Float glass obtained by the 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) by weight, and heating and melting at 1450 ℃ for 1h to obtain a glass melt;
(2) Clarifying the glass melt at 1500 ℃ for 3 hours, heating to 1870 ℃, stirring for 25 minutes, cooling to 1500 ℃, and continuously stirring for 2 hours 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.
Float glass obtained by the preparation method.
Comparative example 2
A method of making float glass comprising the steps of:
(1) Preparing iron oxide @ titanium dioxide particles:
(1.1) iron oxide activation: performing 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 pyrophosphoryloxy) titanate in a mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 10:1), and regulating the pH value to 3.5 to obtain a titanate coupling agent solution with the concentration of 0.008 mol/L; adding surface activated ferric oxide into a titanate coupling agent solution, wherein the mass volume ratio of the surface activated ferric oxide to the titanate coupling agent solution is 1g to 25mL, and stirring for reaction for 4h after ultrasonic dispersion is uniform; then removing the solvent by rotary evaporation, performing aerobic calcination for 7 hours under the conditions that the oxygen volume concentration is 75 percent and the temperature is 630 ℃, and grinding to obtain iron oxide@titanium dioxide particles;
(2) Uniformly mixing glass raw materials (100 parts of quartz sand, 15 parts of alumina, 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, 3.7 parts of carbon powder and 0.5 part of ferric oxide@titanium dioxide particles) by weight, and heating and melting for 1 hour at 1450 ℃ to obtain a glass melt;
(3) Clarifying the glass melt at 1500 ℃ for 3 hours 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.
Float glass obtained by the preparation method.
Comparative example 3
A method of making float glass comprising the steps of:
(1) Preparing iron oxide @ titanium dioxide particles: dissolving isopropyl tri (dioctyl pyrophosphoryloxy) titanate in a mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 10:1), and regulating the pH value to 3.5 to obtain a titanate coupling agent solution with the concentration of 0.008 mol/L; adding ferric oxide into a titanate coupling agent solution, wherein the mass volume ratio of the ferric oxide to the titanate coupling agent solution is 1g to 25mL, and stirring for reaction for 4h after ultrasonic dispersion is uniform; then removing the solvent by rotary evaporation, performing aerobic calcination for 7 hours under the conditions that the oxygen volume concentration is 75 percent and the temperature is 630 ℃, and grinding to obtain iron oxide@titanium dioxide particles;
(2) Uniformly mixing glass raw materials (100 parts of quartz sand, 15 parts of alumina, 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, 3.7 parts of carbon powder and 0.5 part of ferric oxide@titanium dioxide particles) by weight, and heating and melting for 1 hour at 1450 ℃ to obtain a glass melt;
(3) Clarifying the glass melt at 1500 ℃ for 3 hours, heating to 1870 ℃, stirring for 25 minutes, cooling to 1500 ℃, and continuously stirring for 2 hours 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.
Float glass obtained by the preparation method.
Test case
Reference standard GB/T7962.8-2010 colorless optical glass test method part 8: bubble degree (bubble degree) the float glasses obtained in examples 1 to 5 and comparative examples 1 to 3 were examined per 100cm 3 The total cross-sectional area S of the bubbles contained in the air bubbles is determined according to the total cross-sectional area S, and the results are shown in Table 1.
TABLE 1
| S(mm 2 /100cm 3 ) | Bubble degree level | |
| Example 1 | 0.03 | A 00 |
| Example 2 | 0.01 | A 00 |
| Example 3 | 0.03 | A 00 |
| Example 4 | 0.07 | A 0 |
| Example 5 | 0.06 | A 0 |
| Comparative example 1 | 0.28 | B |
| Comparative example 2 | 0.27 | B |
| Comparative example 3 | 0.18 | A |
Data analysis and conclusion:
(1) The clarifying agent of comparative example 1 was not added with iron oxide @ titanium dioxide particles, and the clarifying agent of comparative example 2 was not subjected to temperature raising treatment after clarification, and other raw materials and preparation processes were the same as in example 2. As can be seen from table 1, the bubble 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 barrier of titanium dioxide, ferric oxide does not play a role, at the moment, sodium sulfate and carbon powder play a clarification role, mainly generate sulfur dioxide and carbon dioxide, are favorable for fully playing the role of a clarifier, drive other gases to escape from the glass melt in a large quantity, and reduce the residue of sulfur oxide in the glass after clarification; after the clarification is finished, titanium dioxide is melted by heating, wherein the encapsulated iron oxide is released, and the iron oxide can catalyze the oxidation of sulfur dioxide into sulfur trioxide and improve the solubility of the sulfur trioxide in the glass, so that sulfur oxides remained in the glass and form bubbles after the clarification is finished.
(2) Comparative example 3 in the preparation of iron oxide @ titanium dioxide particles, iron oxide was not plasma treated and the other materials and preparation process were the same as in example 2. As can be seen from table 1, the bubble defects in the float glass of example 2 are significantly smaller than those of comparative example 3. The reason is that: the hydroxyl content of the surface of the ferric oxide can be improved by carrying out plasma treatment on the ferric oxide, so that the compactness of the titanium dioxide shell layer is improved, and the ferric oxide can better play a role in blocking in a clarification stage.
(3) Example 4 isopropyl tri (dioctyl pyrophosphoyloxy) titanate was replaced with isopropyl triisostearate, example 5 the pH of the titanate coupling agent solution was not adjusted to 3.5, and the other starting materials and preparation process were the same as in example 2. As can be seen from table 1, the bubble defects in the float glass of example 2 are relatively small compared to examples 4 and 5. The reason is that: isopropyl tri (dioctyl pyrophosphoryl oxy) titanate is adopted as a titanate coupling agent, wherein pyrophosphate groups can be hydrolyzed to generate negatively charged phosphate groups; when the pH is in the range of 3-4, the surface of the ferric oxide has positive charges, and can be combined with negatively charged phosphate groups through electrostatic attraction, so that the grafting amount of the titanate coupling agent on the surface of the ferric oxide can be improved, and the compactness of a titanium dioxide shell layer can be improved.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (9)
1. A method for preparing float glass with low bubble content, which is characterized by comprising the following steps:
(1) Uniformly mixing a glass raw material 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; the preparation method of the iron oxide@titanium dioxide particles comprises the following steps:
(1.1) iron oxide activation: performing plasma treatment on the ferric oxide to obtain surface-activated ferric oxide;
(1.2) titanium dioxide coating: adding the surface activated ferric oxide into the titanate coupling agent solution, fully dispersing, and stirring for reaction for 3-5h; then removing the solvent, performing aerobic calcination, and grinding to obtain iron oxide@titanium dioxide particles;
(2) Clarifying glass melt at 1400-1550 ℃ for 2.5-3.5h, heating to 1860-1880 ℃, stirring for 20-30min, cooling to 1400-1550 ℃, and continuously stirring for 1.5-2.5h to obtain glass liquid;
(3) And (3) carrying out float forming on the glass liquid, and then annealing to obtain the float glass with low bubble content.
2. The method of claim 1, wherein in step (1), the glass raw materials comprise 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 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. A method according to claim 1 or 3, wherein in step (1), the mass ratio of sodium sulfate, carbon powder and iron oxide @ titanium dioxide particles in the clarifier is 1:0.7-0.9:0.10-0.15.
5. The method according to claim 1, wherein in the step (1.2), the titanate coupling agent is isopropyl tri (dioctyl pyrophosphoryl oxy) titanate, a solvent mixture of ethanol and water; the pH value of the titanate coupling agent solution is 3-4.
6. The method of claim 1, wherein in step (1.1), the plasma treatment is performed at a power of 200 to 300W, an air flow rate of 250 to 350mL/min, and a time of 2 to 4min.
7. The method of claim 1 or 5, wherein in step (1.2), the concentration of the titanate coupling agent solution is 0.007 to 0.010mol/L; the mass volume ratio of the surface activated ferric oxide to the titanate coupling agent solution is 1g:20-30mL.
8. The method according to claim 1 or 5, wherein in the step (1.2), the aerobic calcination is performed at 600 to 650 ℃ for 6 to 8 hours.
9. Float glass obtainable by the process according to any one of claims 1 to 8.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH101329A (en) * | 1996-06-14 | 1998-01-06 | Nippon Sheet Glass Co Ltd | Glass composition for chemical strengthening and chemically strengthed glass article |
| CN103384648A (en) * | 2011-02-21 | 2013-11-06 | Lg化学株式会社 | Method for forming glass surface lubricating layer and method for manufacturing glass using same |
| WO2015056594A1 (en) * | 2013-10-18 | 2015-04-23 | コニカミノルタ株式会社 | Infrared shielding film and laminated glass |
| CN105837039A (en) * | 2016-05-19 | 2016-08-10 | 台玻安徽玻璃有限公司 | Manufacturing method of high strength float glass |
| CN112125528A (en) * | 2020-10-06 | 2020-12-25 | 青岛蓝创科信新能源科技有限公司 | High modulus glass fiber with excellent alkali resistance and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4302896A1 (en) * | 1993-02-02 | 1994-08-04 | Degussa | Iron oxide-containing titanium dioxide powder |
| US7584632B2 (en) * | 2005-07-28 | 2009-09-08 | Corning Incorporated | Method of increasing the effectiveness of a fining agent in a glass melt |
| DE202009018722U1 (en) * | 2008-02-26 | 2012-11-21 | Corning Inc. | Refining agent for silicate glasses |
| US11697608B2 (en) * | 2019-10-01 | 2023-07-11 | Owens-Brockway Glass Container Inc. | Selective chemical fining of small bubbles in glass |
-
2021
- 2021-09-18 CN CN202111101513.8A patent/CN114276001B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH101329A (en) * | 1996-06-14 | 1998-01-06 | Nippon Sheet Glass Co Ltd | Glass composition for chemical strengthening and chemically strengthed glass article |
| CN103384648A (en) * | 2011-02-21 | 2013-11-06 | Lg化学株式会社 | Method for forming glass surface lubricating layer and method for manufacturing glass using same |
| WO2015056594A1 (en) * | 2013-10-18 | 2015-04-23 | コニカミノルタ株式会社 | Infrared shielding film and laminated glass |
| CN105837039A (en) * | 2016-05-19 | 2016-08-10 | 台玻安徽玻璃有限公司 | Manufacturing method of high strength float glass |
| CN112125528A (en) * | 2020-10-06 | 2020-12-25 | 青岛蓝创科信新能源科技有限公司 | High modulus glass fiber with excellent alkali resistance and preparation method thereof |
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