CN104326664A - Aluminosilicate glass containing germanium oxide and gallium oxide - Google Patents
Aluminosilicate glass containing germanium oxide and gallium oxide Download PDFInfo
- Publication number
- CN104326664A CN104326664A CN201310747648.0A CN201310747648A CN104326664A CN 104326664 A CN104326664 A CN 104326664A CN 201310747648 A CN201310747648 A CN 201310747648A CN 104326664 A CN104326664 A CN 104326664A
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- Prior art keywords
- glass
- oxide
- mass percentage
- gallium oxide
- containing germanium
- Prior art date
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Links
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 title claims abstract description 21
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 19
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000005354 aluminosilicate glass Substances 0.000 title abstract 2
- 239000011521 glass Substances 0.000 claims abstract description 76
- 239000000126 substance Substances 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005368 silicate glass Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 10
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 5
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 abstract description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910005534 GaO2 Inorganic materials 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 239000005358 alkali aluminosilicate glass Substances 0.000 abstract 1
- 239000008395 clarifying agent Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000003280 down draw process Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 description 13
- 238000004031 devitrification Methods 0.000 description 6
- 239000005357 flat glass Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003426 chemical strengthening reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
The invention discloses aluminosilicate glass containing germanium oxide and gallium oxide. The glass comprises, by mass, 50-70% of SiO2, 10-25% of Al2O3, 10-20% of Na2O, 0-3% of K2O, 0-5% of B2O3, 1-5% of GeO2, 0.1-3% of GaO2, and a clarifying agent that is at least one selected from SnO2, SO3, F and CeO2, wherein the content of the four components is limited to 0-0.2% of SnO2, 0-0.2% of SO3, 0-0.5% of F and 0-0.5% of CeO2. Glass substrate is produced by an overflow down-drawing method after a certain amount of germanium oxide and gallium oxide is added in high-alkali aluminosilicate glass. Reinforced glass substrate treated by chemical reinforcement has high mechanical strength; and the glass substrate is difficult to bend, has good chemical resistance, low density, proper expansion coefficient and high Young's modulus, and can be used as a glass material for protecting screen surfaces of display products.
Description
Technical field
The invention belongs to field of glass production technology, relate to a kind of screen surface protection glass formula that can be used as display product, specifically a kind of be applicable to chemical enhanced, containing the alumina silicate glass of germanium oxide and gallium oxide.
Background technology
Along with modern times display and the development of touch screen technology science and technology, advanced flat pannel display intelligent artifact emerges in an endless stream, as: mobile phone, LCD TV, liquid-crystal display, Cash Machine, billboard media machine etc., a lot of function and transaction are all come by finger or pen touch display screen, and this just proposes more requirement to touch-screen cover-plate glass: (1) has high physical strength; (2) high Young's modulus; (3) low density; (4) can be cheap and supply in large quantities; (5) bubble excellent quality.
Summary of the invention
The present invention is in order to comply with market the demand to touch-screen cover-plate glass; provide a kind of be applicable to chemical enhanced, containing the alumina silicate glass of germanium oxide and gallium oxide; this glass can be produced into glass substrate by overflow downdraw; then after chemical intensification treatment; obtain the glass substrate that physical strength is good, using the demand of the satisfied screen surface protection glass material as display product.
The technical solution used in the present invention is: a kind of alumina silicate glass containing germanium oxide and gallium oxide, and key is: in described glass, the mass percentage of each chemical composition is:
SiO
250~70%，
Al
2O
310~25%，
Na
2O 10~20%，
K
2O 0~3%，
B
2O
30~5%，
GeO
21~5%，
GaO
20.1~3%，
SnO is selected from at least one
2, SO
3, F and CeO
2finings, above-mentioned four kinds of its content of composition are defined as:
SnO
20-0.2%，
SO
3 0-0.2%，
F 0-0.5%，
CeO
20-0.5%。
Preferably, GeO
2mass percentage be 2 ~ 4%.
Preferably, GaO
2mass percentage be 0.5 ~ 2.5%.
Preferably, B
2o
3mass percentage be 1 ~ 3%.
Preferably, K
2the mass percentage of O is 1 ~ 2.8%.
Preferably, Na
2the mass percentage of O is 13 ~ 16%.
Preferably, Al
2o
3mass percentage be 12-15%.
Preferably, SnO
2mass percentage be 0.05 ~ 0.15%.
Preferably, SO
3mass percentage be 0.05 ~ 0.15%.
Preferably, the mass percentage of F is 0.05 ~ 0.35%.
Preferably, CeO
2mass percentage be 0.05 ~ 0.35%.
The invention has the beneficial effects as follows: the present invention is compared with previous patent, by in high-alkali alumina silicate glass, add a certain amount of germanium oxide and gallium oxide, the physical strength of glass can not only be improved, reduce the high temperature viscosity of glass, can also ion-exchange in favourable promotion chemical intensification treatment, improve glass reinforced effect.
Containing the glass substrate that the high-alkali alumina silicate glass of germanium oxide and gallium oxide is produced by overflow downdraw; hardened glass substrate after chemical intensification treatment has high physical strength and glass substrate is difficult to flexure, good chemical resistant properties, low density, the suitable coefficient of expansion, high Young's modulus, can be used as the screen surface protection glass material of display product.
The present invention is utilized to fill a prescription obtained glass at the KNO of 420-460 DEG C
3carry out the chemical intensification treatment of more than 5 hours in melting salt, the stress formed on surface is all at more than 600Mpa, and the thickness of compressive stress layer is more than 50 μm; And the Young's modulus of glass is greater than 70Gpa, density is less than 2.50 g/cm
3, can be made the glass substrate of 0.5 ~ 2mm by overflow downdraw, after chemical enhanced, glass substrate can be suitable as touch-screen cover-plate glass.
Embodiment
Be described the composition that can contain in glass formula of the present invention below, the containing ratio of each composition represents with weight percent.
SiO
2be the main component forming glass skeleton, there is the physical strength improving strain point of glass, chemical stability and glass, reduce thermal expansivity and the density of glass.When content is below 50%, chemical durability of glass is bad, but when content is more than 70%, the high temperature viscosity of glass increases, and makes glass smelting temperature too high, fusing difficulty.In order to obtain high Young's modulus, be suitable for the glass of rapid chemical strengthening, SiO
2limited proportion is 50-70%.
GeO
2be glass-former, the Young's modulus of glass can be improved, increase Na+, K+ ion-exchange speed and answer varying depth, improve strength of glass, but the cost of raw material itself is high, in addition, a large amount of containing devitrification resistance deterioration, be defined as 1 ~ 5% with its content, its preferable range is 2 ~ 4%.
GaO
2can reduce liquidus temperature, improve glass meltability, improve glass chemistry performance, but the cost of raw material itself be high, in addition, a large amount of containing devitrification resistance deterioration, be therefore defined as 0.1-3%, preferable range is 0.5 ~ 2.5%.
Al
2o
3intermediate oxide, improve glass hard (HRC65Yi Shang) and physical strength, raising glass chemical stability and the ion-exchange of glass surface can be accelerated.When content is below 10%, ion-exchange effect is bad, and the chemical stability of glass is bad, works as Al
2o
3content is more than 25%, and glass viscosity increases, devitrification resistance degradation.Therefore, Al
2o
3content be 10-25%, more preferably content is 12-15%.
B
2o
3being the meltbility for improving glass, reducing the viscosity of glass and being conducive to the composition of glass clarifying.When content is more than 5%, the phase-splitting tendency of glass can be made to increase and the increase of boron volatile quantity, be difficult to realize homogenizing of glass, be unfavorable for the stability improving glass, the ion-exchange speed of glass can be reduced simultaneously.Its content is defined as 0-5%, preferred 1-3%.
Na
2o is ion-exchange composition, can also reduce glass melting temperature simultaneously, improve the tendency towards devitrification of glass, improves meltbility and the plasticity of glass, improves the devitrification resistance of glass.Na
2the containing ratio of O less than 10% time, ion-exchange performance is poor, and strengthening effect is weak.Work as Na
2when the containing ratio of O is more than 20%, then the thermal expansivity of glass is excessive, and chemical stability and resistance to sudden heating reduce.Therefore, by Na
2o content is defined as 10-20%, preferred 13-16%.
K
2o can reduce glass high temperature viscosity, the meltbility of glass and plasticity are improved, and with improved by mutual diffusion during Na+ ion-exchange chemical enhanced in ion-exchange speed obtain required stress and deepen the degree of depth of compressive stress layer, glass devitrification resistance can also be improved.Work as K
2when the content of O is more than 3%, can ion-exchange speed be hindered, affect strengthening effect.Therefore, by K
2o content lower limit is more than 0%, can not only improve etch-rate, can also shorten the time of ion exchange treatment, be defined as 0-3%, preferred 1-2.8%.
For improving the melting quality of glass, eliminate the air inclusions of glass, in addition to the aforementioned ingredients, be also selected from the finings of SnO2, SO3, F and CeO2 in composition of the present invention containing at least one, its content is defined as: SnO
20-0.2, SO
30-0.2, F 0-0.5, CeO
20-0.5.
During concrete enforcement: weigh the conventional raw materials such as each oxide compound, carbonate and nitrate by each embodiment listed in table 1, table 2, add after abundant mixing in platinum crucible, melt at 1580-1620 DEG C of temperature, clarify 10 hours, melten glass liquid is poured in the stainless steel cast iron grinding tool after preheating, be configured as the plate glass goods of regulation, then by glass in the lehr 600-650 DEG C annealing 1 hour, cool to 450-550 DEG C with the cooling rate of 1-5 DEG C/min subsequently, then powered-down furnace cooling is to room temperature.
Glass the present invention obtained carries out grinding and polishing, is processed into the glass specimen of the specification of 50 × 50 × 1mm, at the KNO of temperature 430 DEG C
3in fused salt, 5 hours chemical enhanced time, carry out ion exchange treatment, make the K ion in the Na ion of glass surface and above-mentioned treatment solution carry out ion-exchange, obtain chemically toughened glass.Glass block is processed into various required sample and is used for performance test, in table 1, table 2, list the glass properties of each embodiment and comparative example oxide compound composition (wt%) and correspondence in detail.
Wherein glass density ρ adopts Archimedes method to measure; The thermal expansivity of 20-400 DEG C adopts dilatometer to measure, and represents with average coefficient of expansion; The annealing point of glass and strain point adopt Orton ANS-800 test; The softening temperature of glass adopts Orton SP-1100A to measure; The high temperature viscosity of glass adopts Orton RSV-1600 to measure, and calculates working point T by Fulcher (also referred to as VFT formula)
w, T
m; Refractive index n
demploying Abbe refractometer is measured; Visible light transmittance rate adopts spectrophotometer measurement; Surface stress instrument FSM-6000LE measures bearing stress and the compressive stress layer thickness of chemical enhanced rear glass.
Table 1
Table 2
As can be seen from table 1, table 2, can be proved again by each embodiment: the glass substrate produced by means of glass ingredient principle provided by the invention can reach following technical indicator after testing: the chemical intensification treatment carrying out 5 hours in the melting salt of 430 DEG C, the stress formed on surface is all at more than 600Mpa, and the thickness of compressive stress layer is more than 50 μm; The Young's modulus of glass is greater than 70Gpa, and density is less than 2.50 g/cm
3, can be made the glass substrate of 0.5 ~ 2mm by overflow downdraw, after chemical enhanced, glass substrate can be suitable as touch-screen cover-plate glass.
Claims (10)
1. contain an alumina silicate glass for germanium oxide and gallium oxide, it is characterized in that: in described glass, the mass percentage of each chemical composition is:
SiO
250~70%，
Al
2O
310~25%，
Na
2O 10~20%，
K
2O 0~3%，
B
2O
30~5%，
GeO
21~5%，
GaO
20.1~3%，
SnO is selected from at least one
2, SO
3, F and CeO
2finings, above-mentioned four kinds of its content of composition are defined as:
SnO
2 0-0.2%，
SO
3 0-0.2%，
F 0-0.5%，
CeO
20-0.5%。
2. a kind of alumina silicate glass containing germanium oxide and gallium oxide according to claim 1, is characterized in that: GeO
2mass percentage be 2 ~ 4%.
3. a kind of alumina silicate glass containing germanium oxide and gallium oxide according to claim 1, is characterized in that: GaO
2mass percentage be 0.5 ~ 2.5%.
4. a kind of alumina silicate glass containing germanium oxide and gallium oxide according to claim 1, is characterized in that: B
2o
3mass percentage be 1 ~ 3%.
5. a kind of alumina silicate glass containing germanium oxide and gallium oxide according to claim 1, is characterized in that: K
2the mass percentage of O is 1 ~ 2.8%.
6. a kind of alumina silicate glass containing germanium oxide and gallium oxide according to claim 1, is characterized in that: Na
2the mass percentage of O is 13 ~ 16%.
7. a kind of alumina silicate glass containing germanium oxide and gallium oxide according to claim 1, is characterized in that: Al
2o
3mass percentage be 12-15%.
8. a kind of alumina silicate glass containing germanium oxide and gallium oxide according to claim 1, is characterized in that: SnO
2mass percentage be 0.05 ~ 0.15%.
9. a kind of alumina silicate glass containing germanium oxide and gallium oxide according to claim 1, is characterized in that: SO
3mass percentage be 0.05 ~ 0.15%.
10. a kind of alumina silicate glass containing germanium oxide and gallium oxide according to claim 1, is characterized in that: the mass percentage of F is 0.05 ~ 0.35%, CeO
2mass percentage be 0.05 ~ 0.35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310747648.0A CN104326664B (en) | 2013-12-31 | 2013-12-31 | A kind of alumina silicate glass containing germanium oxide and gallium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310747648.0A CN104326664B (en) | 2013-12-31 | 2013-12-31 | A kind of alumina silicate glass containing germanium oxide and gallium oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104326664A true CN104326664A (en) | 2015-02-04 |
| CN104326664B CN104326664B (en) | 2017-12-15 |
Family
ID=52401492
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105236737A (en) * | 2015-09-10 | 2016-01-13 | 姜宏 | High-performance super-high-aluminum float glass component |
| CN105502928A (en) * | 2015-12-30 | 2016-04-20 | 东旭科技集团有限公司 | Composition for aluminosilicate glass and application thereof |
| CN105621881A (en) * | 2015-12-30 | 2016-06-01 | 东旭科技集团有限公司 | Composition for alumina silicate glass and alumina silicate glass as well as application of composition and alumina silicate glass |
| CN105819684A (en) * | 2016-04-01 | 2016-08-03 | 东旭科技集团有限公司 | Composition for glass, alumina borosilicate glass, preparation method of alumina borosilicate glass and applications of composition for glass and alumina borosilicate glass |
| CN106365441A (en) * | 2016-08-27 | 2017-02-01 | 赵碧华 | Lead-free glass material for windows and preparation method thereof |
| EP3611140A4 (en) * | 2017-05-23 | 2020-04-29 | Huawei Technologies Co., Ltd. | Aluminosilicate glass, chemically strengthened glass, and applications thereof |
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| CN101454252A (en) * | 2006-05-25 | 2009-06-10 | 日本电气硝子株式会社 | Tempered glass and process for producing the same |
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| CN102417301A (en) * | 2011-08-22 | 2012-04-18 | 河南国控宇飞电子玻璃有限公司 | Glass composition and glass made of the composition, preparation method and purpose |
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| CN101679105A (en) * | 2007-06-07 | 2010-03-24 | 日本电气硝子株式会社 | Hardened glass substrate, and method for production thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105236737A (en) * | 2015-09-10 | 2016-01-13 | 姜宏 | High-performance super-high-aluminum float glass component |
| CN105502928A (en) * | 2015-12-30 | 2016-04-20 | 东旭科技集团有限公司 | Composition for aluminosilicate glass and application thereof |
| CN105621881A (en) * | 2015-12-30 | 2016-06-01 | 东旭科技集团有限公司 | Composition for alumina silicate glass and alumina silicate glass as well as application of composition and alumina silicate glass |
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| CN105502928B (en) * | 2015-12-30 | 2018-12-11 | 东旭科技集团有限公司 | A kind of alumina silicate glass composition and application thereof |
| CN105819684A (en) * | 2016-04-01 | 2016-08-03 | 东旭科技集团有限公司 | Composition for glass, alumina borosilicate glass, preparation method of alumina borosilicate glass and applications of composition for glass and alumina borosilicate glass |
| CN105819684B (en) * | 2016-04-01 | 2018-06-29 | 东旭科技集团有限公司 | A kind of glass composition, aluminium borosilicate glass and its preparation method and application |
| CN106365441A (en) * | 2016-08-27 | 2017-02-01 | 赵碧华 | Lead-free glass material for windows and preparation method thereof |
| EP3611140A4 (en) * | 2017-05-23 | 2020-04-29 | Huawei Technologies Co., Ltd. | Aluminosilicate glass, chemically strengthened glass, and applications thereof |
| JP2020520886A (en) * | 2017-05-23 | 2020-07-16 | 華為技術有限公司Ｈｕａｗｅｉ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｃｏ．，Ｌｔｄ． | Aluminosilicate glass, chemically strengthened glass and applications |
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