CN111620547B - Alkali-free boroaluminosilicate glass raw material granules and preparation method thereof - Google Patents
Alkali-free boroaluminosilicate glass raw material granules and preparation method thereof Download PDFInfo
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- CN111620547B CN111620547B CN202010576970.1A CN202010576970A CN111620547B CN 111620547 B CN111620547 B CN 111620547B CN 202010576970 A CN202010576970 A CN 202010576970A CN 111620547 B CN111620547 B CN 111620547B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B1/00—Preparing the batches
- C03B1/02—Compacting the glass batches, e.g. pelletising
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/225—Refining
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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- 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
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Abstract
The invention discloses an alkali-free boroaluminosilicate glass raw material granulation body and a preparation method thereof, which are characterized in that: (1) the weight percentages are as follows: 50-65% SiO 2 、10‑20% Al 2 O 3 、3‑10% CaCO 3 、1‑6% MgO、1‑12% B 2 O 3 、6‑13% SrCO 3 And 0-0.2% SnO + SnO 2 +CeO 2、 1-10% of silica sol binder, mixing the raw materials, fully and uniformly mixing, feeding into an extrusion molding machine, controlling the pressure of the extrusion molding machine at 30-150MPa, and extruding to form spherical or flaky granules with the diameter of 0.5-3 mm; (2) calcining the formed granules at the temperature of 750-920 ℃ for 1-1.5h to obtain the alkali-free boroaluminosilicate glass raw material granules. The invention has the advantages that: the prepared granules have high mechanical strength and small particle size, and the minimum particle size can reach 0.5 mm; the neutral silica sol binder is used, and has no corrosion effect on mixing equipment and extrusion forming equipment; the glass prepared by the granulating body has excellent clarifying effect, and the thermodynamic property, the mechanical property and the optical property of the glass are improved in different ranges.
Description
Technical Field
The invention belongs to the technical field of glass production, and relates to an alkali-free boroaluminosilicate glass raw material granulation body and a preparation method thereof.
Background
The TFT liquid crystal display mode has a pixel response speed 600 times faster than that of the old LCD screen. The advanced silicon electrode is added to greatly increase the pixel response speed of the liquid crystal screen and reduce the delay phenomenon of the picture. Meanwhile, higher technical requirements are put on the glass substrate. At present, mainstream substrate glass products in the market belong to alkali-free boron aluminum silicate glass systems.
The alkali-free boroaluminosilicate glass can generate a large amount of gas in a melting stage, and because the glass does not contain alkali metal and the content of aluminum in raw materials exceeds 12%, the alkali-free boroaluminosilicate glass has the process characteristics that the melting temperature is high, the viscosity is high, the clarification is very difficult, and the existence of bubbles influences the optical uniformity, the transmittance, the mechanical strength and other properties of the glass, and belongs to serious defects for plate glass. Therefore, the glass production process needs to add proper clarifying agents to eliminate bubbles in the glass production process.
At present, alkali-free boroaluminosilicate glass clarifying agents on the market are mainly tin oxide, stannous oxide, sulfide, halide and the like, but the addition amount of the tin oxide, the stannous oxide, the sulfide, the halide and the like is large, the clarifying efficiency is not high, and the good clarifying effect cannot be achieved. And the sulfide and the halide can cause certain harm to human bodies and environment.
It is known in the market that a disc type granulator and the like are used for granulating raw materials by adding water into the raw materials, but the produced granules have the defects of high humidity, weak compressive strength and the like due to overlarge water content, and the problems of poor composition uniformity, raw material waste and the like of glass generated by the granulation processes for solving the problem that glass raw material powder scatters are solved, and the problems that the granules are suitable for transportation and the clarification effect of sintered and formed glass is improved are not solved.
Chinese patent publication No. CN103547541A describes that in alkali-free glass, a boron source and an alkaline earth metal source react to form a hydrate, thereby obtaining a granulated body having excellent strength; that is, in the granulation process, boron oxide or boric acid is used as at least a part of the boron source, and an alkaline earth metal carbonate is used as at least a part of the alkaline earth metal source.
Chinese patent publication No. CN105555727A describes that in alkali-free and boron-free glass, CaO.2Al is essentially contained in the glass raw material 2 O 3 Namely, a composition of at least one of calcium oxide and calcium hydroxide and alumina in CaO 2Al 2 O 3 The water is added to the granules to form a gel-like hydrate, and the gel-like hydrate acts as a binder for the granules.
The binder described in the above patents has an acidic or alkaline corrosive effect on the granulation equipment, reducing the service life of the granulation equipment, and the binder described in the above patents contains a large amount of water so that the binding effect is limited, and the strength of the granules is insufficient, so that the production efficiency of the granules is low and the breakage rate during transportation is high; further, the above patent does not describe that the high-temperature calcination process is performed using the prepared granules, and further, the granules capable of producing glass products having excellent refining effects are obtained.
Disclosure of Invention
The invention aims to solve the problems that the strength of a granulating body produced by the prior art is not enough and equipment is corroded in the preparation process, and provides an alkali-free boroaluminosilicate glass raw material granulating body and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an alkali-free boroaluminosilicate glass raw material granulation body is characterized by being prepared from the following raw materials in percentage by weight: 50-65% SiO 2 、10-20% Al 2 O 3 、3-10% CaCO 3 、1-6% MgO、1-12% B 2 O 3 、6-13% SrCO 3 And 0-0.2% SnO + SnO 2 +CeO 2、 1-10% of silica sol binder.
Further, the alkali-free boroaluminosilicate glass raw material granules are characterized by being prepared from the following raw materials in percentage by weight: 52-60% SiO 2 、12-18% Al 2 O 3 、3-9% CaCO 3 、1-5% MgO、2-10% B 2 O 3 、6-12% SrCO 3 And 0.05-0.2% SnO + SnO 2 +CeO 2、 5-8% of silica sol binder.
Further, the alkali-free boroaluminosilicate glass raw material granules are characterized by being prepared from the following raw materials in percentage by weight: 53-59% SiO 2 、13-17% Al 2 O 3 、5-9% CaCO 3 、2-5% MgO、5-10% B 2 O 3 、8-12% SrCO 3 And 0.05-0.2% SnO + SnO 2 +CeO 2、 6-8% of silica sol binder.
Further, the particle diameter D50 of the glass raw material is 10 to 75 μm.
Further, the particle diameter D50 of the glass raw material is 25 to 55 μm.
A preparation method of alkali-free boroaluminosilicate glass raw material granules is characterized by comprising the following steps:
(1) mixing the raw materials according to the weight percentage, fully and uniformly mixing the raw materials, then sending the mixture into an extrusion molding machine, controlling the pressure of the extrusion molding machine to be 30-150MPa, and extruding the mixture to form spherical or flaky granules with the diameter of 0.5-3 mm;
(2) calcining the formed granules at the temperature of 750-920 ℃ for 1-1.5h to obtain the alkali-free boroaluminosilicate glass raw material granules.
A method for preparing glass by using alkali-free boroaluminosilicate glass raw material granules is characterized by comprising the following steps: placing the alkali-free boroaluminosilicate glass raw material granules in a high-temperature furnace body, heating to 1600-1650 ℃ for melting, preserving the heat of the molten material at 1650 ℃ for 3h for fully melting and clarifying, finally annealing in an annealing furnace at 600 ℃, and cooling for molding.
The glass raw material and the silica sol binder are fully and uniformly mixed to prepare the granules, so that the uniformity of the glass raw material is improved, the thermodynamic property, the mechanical property and the optical property of a glass product are further improved, the granules are calcined at high temperature, carbonate in the granules is decomposed into oxides, and gases such as carbon dioxide, water vapor and the like in the raw material are released, so that the release amount of the carbon dioxide in the subsequent working section (high-temperature melting process) of the glass raw material granules is greatly reduced, and the clarification effect of the glass product is remarkably improved.
The invention has the advantages that:
1. the alkali-free boroaluminosilicate glass raw material granules prepared by the method have high mechanical strength, and the problem of loosening and damage of the granules in the transportation process is effectively avoided; the prepared granules have small grain diameter which can reach 0.5mm at the minimum, and the uniformity of the molten glass body can be further improved.
2. The neutral silica sol binder is used, so that the material mixing equipment and the extrusion forming equipment are not corroded, the service life of the equipment is prevented from being shortened, and the production efficiency of the granules is high; the obtained granules are extruded and formed, and high-temperature calcination treatment is also needed, and silicon-oxygen bonds are formed by dehydration among hydroxyl groups of the silica sol-silica nanometer granules at high temperature, so that the nanometer granules, the granules and an adhered object are sintered into a whole, and the mechanical strength of the granules is further improved; in the high-temperature calcination process, carbonate in the granules can be decomposed into oxides to release gases such as carbon dioxide and water vapor in the raw materials, so that the carbon dioxide release amount of the glass raw material granules in the subsequent working section (high-temperature melting process) is greatly reduced, and the clarification effect of glass products is remarkably improved.
3. The alkali boroaluminosilicate glass raw material granulation body is used for preparing glass, the clarification effect is excellent, and the uniformity of the glass prepared by melting is improved, so that the thermodynamic property, the mechanical property and the optical property of the glass are improved in different ranges.
Drawings
FIG. 1 is a diagram of the molten state of a sample of example 1 clarified at 1600 ℃ for 3 h;
FIG. 2 is a graph of the melt state of a sample of example 2 clarified at 1600 ℃ for 3 h;
FIG. 3 is a graph of the melt state of a sample of example 3 clarified at 1600 ℃ for 3 h;
FIG. 4 is a graph of the melt state of a sample of example 4 clarified at 1600 ℃ for 3 h;
FIG. 5 is a graph of the melt state of a sample of example 5 clarified at 1600 ℃ for 3 h;
FIG. 6 is a graph of the melting state of the sample of example 6 at 1600 ℃ for 3h of clarification.
FIG. 7 is a drawing of a granulated body having a particle diameter of 0.5 mm.
Detailed Description
Example 1
A preparation method of alkali-free boroaluminosilicate glass comprises the following specific implementation steps:
(1) mixing the raw materials with the D50 value of 50 mu m according to the raw material proportion in the following table 1, fully and uniformly mixing, then sending into an extrusion molding machine, controlling the pressure of the extrusion molding machine at 120MPa, and extruding to form spherical granules with the diameter of 0.5 mm;
(2) calcining the formed granules at the temperature of 750-920 ℃ for 1-1.5h to obtain alkali-free boroaluminosilicate glass raw material granules;
(3) placing the alkali-free boroaluminosilicate glass raw material granules in a high-temperature furnace body, heating to 1600-1650 ℃ for melting, preserving the heat of the molten material at 1650 ℃ for 3h for fully melting and clarifying, finally annealing in an annealing furnace at 600 ℃, and cooling for molding.
The glass melting process was recorded graphically and completely during batch melting using a high temperature melt vision system from czech GLASS SERVICE.
TABLE 1 weight percent ratio of each raw material in examples 1-7
From example 1 and example 2, it can be seen that: the adding amount of the silica sol as a binder plays a key role in the production efficiency of the extruded and formed granules and the compressive strength of the granules, when the adding amount of the silica sol is 6wt.%, the production efficiency reaches 87%, and the compressive strength of the granules reaches 45MPa, so that the prepared granules cannot be damaged due to insufficient strength in the transportation process.
As can be seen from FIG. 1, comparative example 2, example 3 and example 4, a fining agent (SnO) 2 ) And after the calcination process, the clarification effect of the glass sample is very good; the glass fining effect of example 3, with no fining agent added, is still significantly better than that of example 4, with only fining agent added and no calcination process.
Comparing example 2, example 5 and example 6, it can be seen that the change of the calcination time and the calcination temperature also has a great influence on the fining effect of the glass sample, and the fining effect of example 2 is significantly better than that of example 5 and example 6.
The change in the refining effect of the alkali-free borosilicate glass by the pretreatment process proposed by the invention is evident by comparing example 2 with example 7, the number of blisters in the glass of example 2 being significantly less than the number of blisters in the glass of example 7.
By comparing example 4 with example 7, it can be seen that the single granulation also has a great effect of improving the fining performance of the glass.
By comparing the examples, we can conclude that the production efficiency of the granules is the highest when the addition amount of the silica sol is 6wt.%, and the compressive strength of the granules is also greatly improved after high-temperature calcination; adding a clarifying agent SnO 2 The high-temperature calcination temperature is 890 ℃ and the high-temperature calcination time is 1h, which have a decisive influence on the clarification effect of the molten and formed glass.
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this means. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (4)
1. A preparation method of alkali-free boroaluminosilicate glass raw material granules is characterized by comprising the following steps:
(1) weighing the following raw materials in percentage by weight: 50-65% SiO 2 、10-20% Al 2 O 3 、3-10% CaCO 3 、1-6% MgO、1-12% B 2 O 3 、6-13% SrCO 3 And 0-0.2% SnO + SnO 2 +CeO 2、 1-10% of neutral silica sol binder, wherein the particle size D50 of the glass raw material is 10-75 μm; mixing the raw materials, feeding into an extrusion molding machine after fully and uniformly mixing, controlling the pressure of the extrusion molding machine at 30-150MPa, and extruding to form spherical or flaky granules with the diameter of 0.5-3 mm;
(2) calcining the formed granules at the temperature of 750-920 ℃ for 1-1.5h to obtain alkali-free boroaluminosilicate glass raw material granules;
(3) placing the alkali-free boroaluminosilicate glass raw material granules in a high-temperature furnace body, heating to 1600-1650 ℃ for melting, preserving the heat of the molten material at 1650 ℃ for 3h for fully melting and clarifying, finally annealing in an annealing furnace at 600 ℃, and cooling for molding.
2. The method of claim 1, wherein the method comprises: the material is prepared from the following raw materials in percentage by weight: 52-60% SiO 2 、12-18% Al 2 O 3 、3-9% CaCO 3 、1-5% MgO、2-10% B 2 O 3 、6-12% SrCO 3 And 0.05-0.2% SnO + SnO 2 +CeO 2、 5-8% of neutral silica sol binder.
3. The method of claim 1, wherein the method comprises: the material is prepared from the following raw materials in percentage by weight: 53-59% SiO 2 、13-17% Al 2 O 3 、5-9% CaCO 3 、2-5% MgO、5-10% B 2 O 3 、8-12% SrCO 3 And 0.05-0.2% SnO + SnO 2 +CeO 2、 6-8% of neutral silica sol binder.
4. The method for producing alkali-free boroaluminosilicate glass raw material granules according to claim 1, 2 or 3, wherein: the particle size D50 of the glass raw material is 25-55 μm.
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| DE10034985C1 (en) * | 2000-07-19 | 2001-09-06 | Schott Glas | Production of an alkali-free aluminosilicate glass used as a substrate glass for displays comprises adding tin oxide as refining agent to the starting materials, melting the glass and hot molding the glass |
| JP4977965B2 (en) * | 2005-05-02 | 2012-07-18 | 旭硝子株式会社 | Alkali-free glass and method for producing the same |
| CN102584008B (en) * | 2011-12-20 | 2014-10-22 | 东旭集团有限公司 | Formula for light environment-friendly alkali-free boron-alumina silicate glass used in liquid crystal display (LCD) |
| CN108793728A (en) * | 2018-09-05 | 2018-11-13 | 中建材蚌埠玻璃工业设计研究院有限公司 | High-aluminum alkali-free borosilicate glass fining agent and defecation method |
| CN110183103B (en) * | 2019-05-06 | 2023-05-02 | 中建材玻璃新材料研究院集团有限公司 | Clarifying agent for alkali-free boroaluminosilicate glass and use method thereof |
| CN110818256B (en) * | 2019-12-31 | 2021-05-04 | 中建材蚌埠玻璃工业设计研究院有限公司 | Alkali-free high-alumina borosilicate glass and preparation method thereof |
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