CN102515524A - Boroaluminosilicate glass substrate and preparation method thereof - Google Patents
Boroaluminosilicate glass substrate and preparation method thereof Download PDFInfo
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- CN102515524A CN102515524A CN2011104502200A CN201110450220A CN102515524A CN 102515524 A CN102515524 A CN 102515524A CN 2011104502200 A CN2011104502200 A CN 2011104502200A CN 201110450220 A CN201110450220 A CN 201110450220A CN 102515524 A CN102515524 A CN 102515524A
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- oxide
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- boroalumino silicate
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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
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Abstract
The invention discloses a boroaluminosilicate glass substrate and a preparation method thereof. The boroaluminosilicate glass substrate comprises the following components, by mass, 57-65% of silicon oxide, 13.8-18.5% of aluminum oxide, 8-15% of boron oxide, 0-5% of magnesium oxide, 5-10.5% of calcium oxide, 0-6.5% of strontium oxide, 0-5% of barium oxide, 0-1.5% of zinc oxide, 0-1.0% of tin oxide, 0-0.5% of cerium oxide, and less than 0.2% of impurities. The boroaluminosilicate glass substrate of the present invention is a glass substrate with characteristics of low expansion coefficient, low density, high strain point temperature, high chemical stability, low refractive index and high transmissivity.
Description
Technical field
The invention belongs to indicating meter and use the glass technology field, relate to a kind of Boroalumino silicate glasses substrate and preparation method thereof.
Background technology
Along with society constantly develops, the level of informatization is increasingly high, the application of flat-panel screens also more and more widely, various display equipments are popularized fast in the fields such as civilian, military affairs.Lightening, portable, low voltage, low power consuming, do not produce static, advantage such as radiationless, good for health shows liquid crystal flat-panel and is accepted by market.Under such trend, flat-panel monitor manufacturer constantly increases the demand of glass substrate, and is simultaneously also increasingly high for the lightening requirement of glass substrate.
Because constantly popularizing and application of FPD, producing in batches and reducing production costs becomes the competitive strategy of each manufacturer.Reduce production costs, will start with from each link of producing on the one hand, also must increase the size of glass substrate simultaneously, make the glass substrate of under identical time and ME, producing to cut out the more panel of polylith, improve production capacity with this.
According to the production characteristics of glass fusion and moulding process, consider simultaneously to require at present to reduce production costs, improve the demand of product quality, when making base plate glass, consider that following several respects require:
The requirement of 1, producing according to liquid crystal panel, base plate glass must possess the lower coefficient of expansion.Because in the panel production process, rapid heating and refrigerative that base plate glass will stand repeatedly impact, and substrate possibly cracked in heat treatment process.The lower coefficient of expansion can reduce because the thermal stresses that temperature head causes reduces the generation of crackle.In addition, the lower coefficient of expansion can mate with polysilicon and amorphous silicon material.
2, base plate glass will have sufficiently high strain point temperature.(strain point temperature of base plate glass is greater than 650 ℃).In base plate glass was produced, sheet glass will be through 500 ℃～600 ℃ pyroprocessing, and base plate glass possibly produce defective or buckling deformation, can prevent substrate deformation greater than 650 ℃ strain point temperatures.
3, base plate glass has lower density (less than 2.45g/cm
3) and the high Young's modulus of trying one's best.Along with the increase of liquid crystal glass base size, hope to reduce the density and the thickness of glass substrate, be convenient to carrying and moving of flat-panel screens like this.In addition, in the glass substrate production process, glass sheet size is big more, because the sagging amount of conducting oneself with dignity is big more; Saggingly be directly proportional, be inversely proportional to Young's modulus, therefore with the density of glass substrate; In base plate glass is produced, reduce the density of sheet glass as far as possible, improve the Young's modulus of sheet glass simultaneously.
4, except that above-mentioned some requirement, base plate glass also must have very high chemicalstability.In the production process of liquid crystal panel, form nesa coating, insulating film, semiconductor film and metallic membrane on the base plate glass surface through technology such as sputter, chemical gaseous phase depositions, form various circuit and figure through optical lithography then.In film deposition and photoetch stage, base plate glass will stand various thermal treatments and chemical treatment.In heat treatment process, alkalimetal ion diffuses into deposited semiconductor material easily, and the infringement membrane property becomes to analyze in glass, and base plate glass must have high chemicalstability, has the stronger reagent of anti-strong acid performance.
5, each item performance of base plate glass must satisfy the needs that liquid crystal panel is produced.But for the production of base plate glass self, it is very crucial how to produce the few product of quality height, defective.The glass that strain point is high, the coefficient of expansion is low, temperature of fusion must be very high, and the glass viscosity is necessarily very big, and so aborning, the defect Control difficulty is inevitable very big, and simultaneous temperature is high, must increase the erosion of refractory materials.Influence the life-span of kiln.Therefore, in process of production, must weigh the relation of specification of quality and production efficiency.At present; Glass substrate manufacturer is when selecting starting material; The give overall consideration to content of basic metal, earth alkali metal and other various impurity that various starting material introduce of capital; Should guarantee that various foreign matter contents are incorporated into performance and the quality that does not influence glass in the glass, also will consider the cost and the production efficiency of whole production.About the problem of alkali metal content, some patents of the U.S. had proposed the limited field of alkali metal content.
Finings is the subsidiary material that need interpolation in the glass production.Consider the environmental protection factor, during base plate glass is produced, progressively eliminated and used As
2O
3And Sb
2O
3As finings, the finings that replaces has SnO
2, CeO
2Deng.In actual production, because the add-on of cerium oxide can have influence on the refraction of glass, and add-on is excessive, also can make the glass colour jaundice, the amount that therefore adds has certain restriction.
Summary of the invention
The problem that the present invention solves is to provide a kind of Boroalumino silicate glasses substrate and preparation method thereof, and this glass substrate chemicalstability is high, and is functional, the especially improvement through finings, oxygen-free arsenic and weisspiessglanz in the glass substrate.
The present invention realizes through following technical scheme:
A kind of Boroalumino silicate glasses substrate by massfraction, comprises following component:
57%～65% silicon oxide, 13.8%～18.5% aluminum oxide, 8%～15% boron oxide, 0～5% Natural manganese dioxide, 5%～10.5% quicklime, 0～6.5% strontium oxide, 0～5% barium oxide; 0～1.5% zinc oxide, 0～1.0% White tin oxide and 0～0.5% cerium oxide, foreign matter content is less than 0.2%.
Further, described Boroalumino silicate glasses substrate by massfraction, comprises following component:
58%～63% silicon oxide, 15%～16.5% aluminum oxide, 8.8%～11% boron oxide, 1～3% Natural manganese dioxide, 5.85%～7% quicklime, 1～5% strontium oxide, 1～5% barium oxide, 0.2～1.5% zinc oxide, 0.2～0.6% White tin oxide and 0.20～0.5% cerium oxide.
Further, described Boroalumino silicate glasses substrate by massfraction, comprises following component:
59.5%～61.5% silicon oxide, 15.5%～16.5% aluminum oxide, 9.62%～9.95% boron oxide, 0.5～1.55% Natural manganese dioxide, 5.85%～6.95% quicklime, 2.55～4.25% strontium oxide, 2.45～3% barium oxide, 0.35～1.15% zinc oxide, 0.10～0.25% White tin oxide and 0.20～0.40% cerium oxide.
Described Boroalumino silicate glasses substrate also wrap the zirconium white of massfraction 0～0.08%, and massfraction is less than 0.01% titanium oxide.
Described Boroalumino silicate glasses substrate in massfraction, comprises 0.02～0.03% zirconium white and 0.002%～0.01% titanium oxide.
Described Boroalumino silicate glasses substrate, the content sum of silicon oxide and aluminum oxide surpasses 75%, and the ratio of aluminum oxide and boron oxide is between 1.2～2.2, and Natural manganese dioxide and calcium oxide content sum are between 5%～10%.
Described Boroalumino silicate glasses substrate, strontium oxide and barium oxide content sum are between 0～8%, and White tin oxide and cerium oxide content sum are between 0～1.2%.
Described Boroalumino silicate glasses substrate, the summation of White tin oxide and cerium oxide are between 0.2～1.0%, and the ratio of White tin oxide and cerium oxide is between 0.5～5.0.
Fe in the described impurity
2O
3＜0.05%, SO
3＜0.03%, Cl＜0.03%; The massfraction of alkali metal oxide content is lower than 0.1%.
A kind of preparation method of Boroalumino silicate glasses substrate may further comprise the steps:
1) takes by weighing the silicon oxide of each feed composition 57%～65%, 13.8%～18.5% aluminum oxide, 8%～15% boron oxide, 0～5% Natural manganese dioxide, 5%～10.5% quicklime, 0～6.5% strontium oxide, 0～5% barium oxide according to following mass ratio; 0～1.5% zinc oxide, 0～1.0% White tin oxide and 0～0.5% cerium oxide, each feed composition sum 100%;
2) with behind each feed composition thorough mixing, under 1550 ℃～1650 ℃ temperature, be fused into glass metal, be shaped to glass substrate through overflow downdraw again.
Compared with prior art, the present invention has following beneficial technical effects:
Boroalumino silicate glasses substrate provided by the invention, its density is less than 2.45g/cm
3, in 0 ℃～300 ℃ scopes, thermal linear expansion coefficient is 33～38 * 10 in the time of 30～380 ℃
-7/ ℃.Softening point temperature is higher than 958 ℃, and the annealing point temperature is higher than 700 ℃, and strain point temperature is not less than 650 ℃, can be up to more than 670 ℃, and the glass transmitance is greater than 92%; Be a kind of low-expansion coefficient, low density, high strain-point temperature have higher chemicalstability, and the lower specific refractory power and the liquid crystal glass base of higher transmittance meet the use and the requirement of flat-panel monitor.
Boroalumino silicate glasses substrate provided by the invention; Be lower than 0.1% in order to reach alkali metal oxide content; And the requirement of oxygen-free arsenic and weisspiessglanz; On forming, selected for use multiple alkaline earth metal oxide to adjust the physics and the chemical property of glass, formed use and the requirement of satisfying flat-panel monitor fully to reach glass; And glass has added cerium oxide and White tin oxide in forming jointly as finings, has reached good clarifying effect.
Embodiment
Below in conjunction with concrete embodiment the present invention is done further detailed description, said is to explanation of the present invention rather than qualification.
For low-expansion coefficient is provided; Low density, high strain-point temperature, higher chemicalstability, the lower specific refractory power and the glass substrate of higher transmittance; And require alkali metal oxide content to be lower than 0.1%; Oxygen-free arsenic and weisspiessglanz, thereby on forming, selected for use multiple alkaline earth metal oxide to adjust the physics and the chemical property of glass, form use and the requirement of satisfying flat-panel monitor fully to reach glass; And glass has added cerium oxide and White tin oxide in forming jointly as finings.
The Boroalumino silicate glasses substrate that is provided by massfraction, comprises following component:
57%～65% silicon oxide, 13.8%～18.5% aluminum oxide, 8%～15% boron oxide, 0～5% Natural manganese dioxide, 5%～10.5% quicklime, 0～6.5% strontium oxide, 0～5% barium oxide; 0～1.5% zinc oxide, 0～1.0% White tin oxide and 0～0.5% cerium oxide, foreign matter content is less than 0.2%.
Concrete, glass is formed SiO
2Content be 57%～65%, SiO
2Be the formation skeleton of glass, it can reduce the thermal expansivity of glass, improves the thermostability of glass, chemicalstability, softening temperature, thermotolerance, hardness, physical strength, viscosity etc., but SiO
2Content increases, and needs higher temperature of fusion, and the fusion defective is increased.SiO
2Granularity and size composition also very big to the influence of glass production, particle is too big, fusing difficulty, and possibly produce glass defect such as calculus striped, particle is too little, foreign matter content is high, flies upward easily.
AL
2O
3Belong to intermediate oxide AL
2O
3Can reduce the crystallization tendency of glass, improve thermostability, chemicalstability, the physical strength of glass, improve the strain point temperature of glass, if but too high levels, the then easy crystallization of glass.AL during glass is formed
2O
3Content be 13.8%～18.5%.
B
2O
3Also be the glass-former oxide compound, its effect in glass is more special, when high temperature, can reduce the viscosity of glass, when low temperature, then can improve the viscosity of glass.B
2O
3Can reduce the thermal expansivity of glass, improve the thermostability of glass, chemicalstability is improved the gloss of glass, in glass production, also plays a part solubility promoter, quickens the clarification of glass, reduces the crystallizing power of glass.But during too high levels, the coefficient of expansion of glass is increased, the strain point of glass reduces.Therefore, B during glass is formed
2O
3Content be limited in 8%～15% scope.
CaO is a network modifying oxide, in glass, can improve the chemicalstability and the physical strength of glass, but during too high levels, can reduce the chemical resistant properties of glass, and the tendency towards devitrification of glass is increased.The content of CaO is chosen within 5%～10.5% the scope.
MgO also is a network modifying oxide, can reduce the high temperature viscosity of glass, increases low temperature viscosity, improves the chemicalstability and the physical strength of glass, can also reduce crystallization tendency and crystallization velocity, and the content of MgO is chosen within 0～1.5% the scope.
BaO is as the divalence network modifying oxide, and it can increase specific refractory power, density, gloss and the chemicalstability of glass, and is more serious to the erosion of refractory materials.Based on base plate glass environmental protection and lightening development trend, the add-on of BaO must be controlled, and the content of BaO is chosen within 0～5% the scope.
Compare with BaO, SrO also can absorb X ray well, has the density of not making simultaneously and increases; Do not make linear expansivity raise; And can not make the strain point too much characteristic that descends, and also make the raising of fusion property, do not have too much detrimentally affect for acid resistance with to the weather resistance of alkaline etchant resist stripping liquid yet; Therefore, selected 0～6.5% SrO for use.
ZnO can reduce the high temperature viscosity of glass, reduces the thermal expansivity of glass, improves chemicalstability and the thermostability and the specific refractory power of glass, but during too high levels, possibly reduce the strain point of glass, and ZnO content is controlled at 0～1.5%.
Consider the environmental protection factor, the present invention has eliminated As when selecting finings for use
2O
3And Sb
2O
3As finings, and selected 0～1.0%SnO for use
2As finings, also increased by 0～0.5% cerium oxide especially and improved clarifying effect.Under the glass smelting temperature, CeO
2Can decompose and emit oxygen.
4CeO
2→2Ce
2O+3O
2↑
Described base plate glass can be according to following method manufacturing: the compound for preparing is joined in the calciner, under 1550 ℃～1650 ℃ temperature, be fused into glass metal, be shaped to glass plate-like through overflow downdraw again, promptly can obtain glass substrate.
Further, finings is taked the mode of Preblend in introducing the preparing glass charge compound.At first tindioxide and cerium oxide and silica powder are mixed, and then join in the feed bin of batching, with other various raw material weigh batchings.
Provide concrete embodiment proportioning below, and the detected result of performance index such as density of each embodiment sample, the coefficient of expansion, softening point temperature, strain point temperature, specific refractory power, transmitance, shown in the table specific as follows:
Claims (10)
1. a Boroalumino silicate glasses substrate is characterized in that, by massfraction, comprises following component:
57%～65% silicon oxide, 13.8%～18.5% aluminum oxide, 8%～15% boron oxide, 0～5% Natural manganese dioxide, 5%～10.5% quicklime, 0～6.5% strontium oxide, 0～5% barium oxide; 0～1.5% zinc oxide, 0～1.0% White tin oxide and 0～0.5% cerium oxide, foreign matter content is less than 0.2%.
2. Boroalumino silicate glasses substrate as claimed in claim 1 is characterized in that, by massfraction, comprises following component:
58%～63% silicon oxide, 15%～16.5% aluminum oxide, 8.8%～11% boron oxide, 1～3% Natural manganese dioxide, 5.85%～7% quicklime, 1～5% strontium oxide, 1～5% barium oxide, 0.2～1.5% zinc oxide, 0.2～0.6% White tin oxide and 0.20～0.5% cerium oxide.
3. Boroalumino silicate glasses substrate as claimed in claim 1 is characterized in that, by massfraction, comprises following component:
59.5%～61.5% silicon oxide, 15.5%～16.5% aluminum oxide, 9.62%～9.95% boron oxide, 0.5～1.55% Natural manganese dioxide, 5.85%～6.95% quicklime, 2.55～4.25% strontium oxide, 2.45～3% barium oxide, 0.35～1.15% zinc oxide, 0.10～0.25% White tin oxide and 0.20～0.40% cerium oxide.
4. Boroalumino silicate glasses substrate as claimed in claim 1 is characterized in that, also wraps the zirconium white of massfraction 0～0.08%, and massfraction is less than 0.01% titanium oxide.
5. Boroalumino silicate glasses substrate as claimed in claim 1 is characterized in that, described Boroalumino silicate glasses substrate in massfraction, comprises 0.02～0.03% zirconium white and 0.002%～0.01% titanium oxide.
6. like any one described Boroalumino silicate glasses substrate in the claim 1～5; It is characterized in that; The content sum of silicon oxide and aluminum oxide surpasses 75%, and the ratio of aluminum oxide and boron oxide is between 1.2～2.2, and Natural manganese dioxide and calcium oxide content sum are between 5%～10%.
7. like any one described Boroalumino silicate glasses substrate in the claim 1～5; It is characterized in that; Described Boroalumino silicate glasses substrate, strontium oxide and barium oxide content sum are between 0～8%, and White tin oxide and cerium oxide content sum are between 0～1.2%.
8. Boroalumino silicate glasses substrate as claimed in claim 7 is characterized in that, described Boroalumino silicate glasses substrate, and the summation of White tin oxide and cerium oxide is between 0.2～1.0%, and the ratio of White tin oxide and cerium oxide is between 0.5～5.0.
9. Boroalumino silicate glasses substrate as claimed in claim 1 is characterized in that, Fe in the described impurity
2O
3＜0.05%, SO
3＜0.03%, Cl＜0.03%; The massfraction of alkali metal oxide content is lower than 0.1%.
10. the preparation method of a Boroalumino silicate glasses substrate is characterized in that, may further comprise the steps:
1) takes by weighing the silicon oxide of each feed composition 57%～65%, 13.8%～18.5% aluminum oxide, 8%～15% boron oxide, 0～5% Natural manganese dioxide, 5%～10.5% quicklime, 0～6.5% strontium oxide, 0～5% barium oxide according to following mass ratio; 0～1.5% zinc oxide, 0～1.0% White tin oxide and 0～0.5% cerium oxide, each feed composition sum 100%;
2) with behind each feed composition thorough mixing, under 1550 ℃～1650 ℃ temperature, be fused into glass metal, be shaped to glass substrate through overflow downdraw again.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104502200A CN102515524A (en) | 2011-12-19 | 2011-12-19 | Boroaluminosilicate glass substrate and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104502200A CN102515524A (en) | 2011-12-19 | 2011-12-19 | Boroaluminosilicate glass substrate and preparation method thereof |
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|---|---|
| CN102515524A true CN102515524A (en) | 2012-06-27 |
Family
ID=46286668
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613273A (en) * | 2013-10-24 | 2014-03-05 | 芜湖东旭光电科技有限公司 | Alkali-free liquid crystal substrate glass |
| CN108196387A (en) * | 2018-01-02 | 2018-06-22 | 重庆京东方光电科技有限公司 | Underlay substrate and its manufacturing device, preparation method and display device |
| CN109052928A (en) * | 2018-09-04 | 2018-12-21 | 中国南玻集团股份有限公司 | Glass fining agent, Boroalumino silicate glasses and preparation method thereof, glass substrate and display |
| US10219328B2 (en) | 2013-07-16 | 2019-02-26 | Eurokera | Alkali-free aluminosilicate glasses, suitable as substrate for induction heating cooktops applications |
| CN113087502A (en) * | 2021-03-29 | 2021-07-09 | 电子科技大学 | High-strength high-modulus magnesium-aluminum silicon substrate material and preparation method thereof |
| CN115925439A (en) * | 2022-12-06 | 2023-04-07 | 凯龙蓝烽新材料科技有限公司 | Silicon carbide particle trap and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10219328B2 (en) | 2013-07-16 | 2019-02-26 | Eurokera | Alkali-free aluminosilicate glasses, suitable as substrate for induction heating cooktops applications |
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| CN108196387A (en) * | 2018-01-02 | 2018-06-22 | 重庆京东方光电科技有限公司 | Underlay substrate and its manufacturing device, preparation method and display device |
| CN109052928A (en) * | 2018-09-04 | 2018-12-21 | 中国南玻集团股份有限公司 | Glass fining agent, Boroalumino silicate glasses and preparation method thereof, glass substrate and display |
| CN109052928B (en) * | 2018-09-04 | 2021-11-05 | 中国南玻集团股份有限公司 | Glass clarifying agent, boroaluminosilicate glass, preparation method of boroaluminosilicate glass, glass substrate and display |
| CN113087502A (en) * | 2021-03-29 | 2021-07-09 | 电子科技大学 | High-strength high-modulus magnesium-aluminum silicon substrate material and preparation method thereof |
| CN113087502B (en) * | 2021-03-29 | 2022-01-25 | 电子科技大学 | High-strength high-modulus magnesium-aluminum silicon substrate material and preparation method thereof |
| CN115925439A (en) * | 2022-12-06 | 2023-04-07 | 凯龙蓝烽新材料科技有限公司 | Silicon carbide particle trap and preparation method thereof |
| CN115925439B (en) * | 2022-12-06 | 2024-01-23 | 凯龙蓝烽新材料科技有限公司 | Silicon carbide particle catcher and preparation method thereof |
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Application publication date: 20120627 |