CN105731790B - A kind of alkali-free alumina silicate glass composition, alkali-free alumina silicate glass and its preparation method and application - Google Patents
A kind of alkali-free alumina silicate glass composition, alkali-free alumina silicate glass and its preparation method and application Download PDFInfo
- Publication number
- CN105731790B CN105731790B CN201610161879.7A CN201610161879A CN105731790B CN 105731790 B CN105731790 B CN 105731790B CN 201610161879 A CN201610161879 A CN 201610161879A CN 105731790 B CN105731790 B CN 105731790B
- Authority
- CN
- China
- Prior art keywords
- composition
- glass
- alkali
- alumina silicate
- silicate glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000005368 silicate glass Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 109
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 23
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 230000004927 fusion Effects 0.000 claims abstract description 11
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 12
- 230000003628 erosive effect Effects 0.000 claims description 12
- 239000008395 clarifying agent Substances 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 239000003518 caustics Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 238000003754 machining Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- -1 mechanical strength Substances 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000002419 bulk glass Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000004293 potassium hydrogen sulphite Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/35—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being liquid crystals
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
The present invention relates to field of glass production technology, a kind of alkali-free alumina silicate glass composition, alkali-free alumina silicate glass and its preparation method and application are disclosed.On the basis of the weight of alkali-free alumina silicate glass composition, in terms of oxide, the composition contains the SiO of 63-72wt%2, 15-20wt% Al2O3, 4-10wt% MgO, 2-6wt% CaO, 0.01-2.5wt% SrO, 2-8wt% BaO, 0.1-1.5wt% In2O3With the SnO of 0.1-0.3wt%2.Glass of the invention strain point with higher, lower fusion temperature, the lower coefficient of expansion, higher chemical stability, higher Young's modulus, higher transmitance, lower density and lower liquidus temperature, TFT-LCD, OLED glass substrate especially suitable for low temperature polycrystalline silicon LTPS technology.
Description
Technical field
The present invention relates to field of glass production technology, and in particular, to a kind of alkali-free alumina silicate glass composition, nothing
Alkali alumina silicate glass and its preparation method and application.
Background technique
Low temperature polycrystalline silicon (Low Temperature Poly-silicon, abbreviation LTPS) is membrane transistor liquid of new generation
The manufacturing process of crystal display (TFT-LCD) is it with high-resolution, anti-with the maximum difference of traditional amorphous silicon displays
The advantages that answering speed fast, high brightness, high aperture, in addition since the silicon crystalline arrangement of LTPS-TFT LCD is compared with a-Si orderliness,
So that high 100 times or more relatively of electron mobility, peripheral drive circuit can be made on the glass substrate simultaneously, reach system
The target of integration saves space and drives the cost of IC.As the fast development of flat panel display and portable electronic produce
Product such as laptop, tablet computer, smart phone and intelligent wearable device are rapidly popularized, and liquid crystal display is played the part of wherein
Role it is more and more important, with lightening, high-res, high image quality LCD products more market received.
Low temperature polycrystalline silicon TFT needs repeatedly to handle at relatively high temperatures in the fabrication process, and substrate must be in multiple high temp
It cannot deform in treatment process, just to base plate glass performance, more stringent requirements are proposed for this, and preferred strain point is higher than 650
DEG C, more preferably above 670 DEG C, 700 DEG C, 720 DEG C, 740 DEG C, so that substrate is received in panel processing procedure with heat small as far as possible
Contracting, therefore the higher the better for the strain point temperature of substrate.The thermal expansion coefficient of glass substrate needs the thermal expansion coefficient with silicon simultaneously
It is close, reduction stress and destruction as far as possible, therefore the preferred thermal linear expansion coefficient of base plate glass is 28 × 10-7/℃-39×
10-7/ DEG C between.For the ease of production, production cost is reduced, the glass as display base plate there should be lower fusing
Temperature and liquidus temperature.But most of silicate glass high temperature viscosities and low temperature viscosity can keep similar speedup, with
LTPS technology is higher and higher to thermal stability requirement (high strain point), and high temperature viscosity constant amplitude often occurs, is even significantly increased.
Under the premise of existing refractory technology and cell furnace production technology, the every bit increase of high temperature viscosity is all to glass production
The significant challenge of technology.Such as, in existing amorphous silicon glass substrate production technique, fusion temperature is often beyond 1550 DEG C, even
1600 DEG C, more even 1650 DEG C, with the promotion of glass melting temperature, glass metal and its volatile matter are to refractory material and platinum device
Erosion rate increases in geometric multiple, brings two catastrophic consequences: first is that defect is increased sharply, yield is had a greatly reduced quality；Second is that producing
The line service life substantially shortens, and is serious disaster from investment and environmental angle.It claims with LTPS technology to glass substrate
It increases, how improving low temperature viscosity, (viscosity is greater than 107Region more than pool, i.e. temperature are lower than softening point region below)
Effectively reducing high temperature viscosity simultaneously becomes the major tasks of LTPS glass technology research and development.
Summary of the invention
The purpose of the invention is to overcome drawbacks described above in the prior art, a kind of alkali-free alumina silicate glass use is provided
Composition, alkali-free alumina silicate glass and its preparation method and application.
To achieve the goals above, in a first aspect, the present invention provides a kind of alkali-free alumina silicate glass composition, with
On the basis of the weight of the composition, in terms of oxide, the composition contains the SiO of 63-72wt%2, 15-20wt% Al2O3、
The In of BaO, 0.1-1.5wt% of SrO, 2-8wt% of CaO, 0.01-2.5wt% of MgO, 2-6wt% of 4-10wt%2O3With
The SnO of 0.1-0.3wt%2。
Under preferable case, by weight percentage, MgO/RO > 0.4, wherein RO=MgO+CaO+SrO+BaO.
Under preferable case, by weight percentage, SiO2+Al2O3> 83wt%.
Under preferable case, on the basis of the weight of the composition, In2O3Content be 0.5-1.2wt%.
Under preferable case, on the basis of the weight of the composition, the content of MgO is 5-8wt%.
Under preferable case, on the basis of the weight of the composition, the content of BaO is 3.5-7.5wt%.
Under preferable case, on the basis of the weight of the composition, Al2O3Content be 16-18.5wt%.
Under preferable case, on the basis of the weight of the composition, SnO2Content be 0.15-0.25wt%.
Under preferable case, on the basis of the weight of the composition, the content of CaO is 3-5.5wt%.
Under preferable case, the composition also contains clarifying agent, and the clarifying agent is more preferably sulfate, nitric acid
At least one of salt, chloride and fluoride；On the basis of the weight of the composition, the content of clarifying agent is not more than 1wt%.
Second aspect, the present invention provides a kind of method for preparing alkali-free alumina silicate glass, this method includes sending out this
The bright alkali-free alumina silicate glass successively carries out melt process, forming processes, annealing and machining with composition
Processing.
The third aspect, the present invention provides the alkali-free alumina silicate glass that the above method is prepared.
Under preferable case, the strain point of the alkali-free alumina silicate glass is not less than 740 DEG C, and fusion temperature is lower than 1620
DEG C, liquidus temperature is lower than 1150 DEG C, and the thermal expansion coefficient within the scope of 50-350 DEG C is 30 × 10-7/℃-38×10-7/ DEG C, it is close
Degree is not more than 2.47g/cm3, the erosion amount of the HF solution acid corrosion 20min of 5wt% is not more than 3mg/cm at 24 ± 0.5 DEG C2, 90
The erosion amount of the NaOH solution caustic corrosion 20h of 5wt% is not more than 0.5mg/cm at ± 5 DEG C2, it is seen that light transmission rate is higher than 91%,
Young's modulus is higher than 80GPa.
Fourth aspect, the present invention provides alkali-free alumina silicate glass composition of the present invention or alkali-free manosil ASs
Salt glass is preparing the application in display device and/or photoelectric device, preferably preparation TFT-LCD glass substrate and/or
Application in OLED glass substrate.
Alkali-free alumina silicate glass composition of the invention is a kind of material side of environmental type glass, can use and overflow
It flows down daraf(reciprocal of farad) and is produced into glass substrate.It is the glass being prepared strain point with higher, lower fusion temperature, lower swollen
Swollen coefficient, higher chemical stability and mechanical performance, higher Young's modulus, higher transmitance, lower density and compared with
Low liquidus temperature (the In in formula composition2O3, MgO have reduce high temperature viscosity of glass and do not reduce low temperature viscosity, improve
The effect of chemical durability of glass), meet the development trend of flat panel display, especially suitable for low temperature polycrystalline silicon LTPS technology
TFT-LCD, OLED glass substrate.
A preferred embodiment of the invention, in alkali-free alumina silicate glass composition, with weight percent
Meter, MgO/RO > 0.4 (RO=MgO+CaO+SrO+BaO), SiO2+Al2O3When > 83wt%, in terms of oxide, glass composition
In the SiO containing certain content2、Al2O3、MgO、CaO、SrO、BaO、In2O3And SnO2, it is prepared into using this glass with composition
The glass arrived, what physical characteristic can be stable reaches: strain point is not less than 740 DEG C, and fusion temperature is lower than 1620 DEG C, liquidus curve
Temperature is lower than 1150 DEG C, and the thermal expansion coefficient within the scope of 50-350 DEG C is 30 × 10-7/℃-38×10-7/ DEG C, density is not more than
2.47g/cm3, it is that 20min is corroded at 24 ± 0.5 DEG C in 5wt%HF solution in concentration, erosion amount is not more than 3.0mg/cm2；?
Concentration is that 20h is corroded at 90 ± 5 DEG C in 5wt%NaOH solution, and erosion amount is not more than 0.5mg/cm2；By 5wt%HF solution,
Glass surface after 5wt%NaOH solution corrodes is equal without the bad deficient point such as " pit ", " sags and crests ", it is seen that light transmission rate is higher than
91%, Young's modulus is higher than 80GPa.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In the present invention, be free of in glass composition or glass it will be understood by those skilled in the art that " alkali-free " refers to
Alkali metal (six alkali metal elements of group ia i.e. in the periodic table of elements).
In a first aspect, the present invention provides a kind of alkali-free alumina silicate glass compositions, it is with the weight of the composition
Benchmark, in terms of oxide, the composition contains the SiO of 63-72wt%2, 15-20wt% Al2O3, 4-10wt% MgO, 2-
The In of BaO, 0.1-1.5wt% of SrO, 2-8wt% of CaO, 0.01-2.5wt% of 6wt%2O3With 0.1-0.3wt%'s
SnO2。
The present inventor is under study for action it has furthermore been found that by weight percentage, when MgO/RO > 0.4, wherein RO
=MgO+CaO+SrO+BaO can further increase the comprehensive performance for the glass being prepared, improve strain point, reduce liquid phase
Line temperature simultaneously improves chemical stability.Therefore, it is strained to further increase the comprehensive performance for the glass being prepared, improve
Point reduces liquidus temperature and improves chemical stability, under preferable case, by weight percentage, MgO/RO > 0.4, wherein
RO=MgO+CaO+SrO+BaO.
The present inventor is under study for action it has furthermore been found that by weight percentage, SiO2+Al2O3When > 83wt%, energy
The comprehensive performance for the glass being prepared enough is further increased, strain point is improved, reduces liquidus temperature and improve chemical stabilization
Property.Therefore, in order to further increase the comprehensive performance for the glass being prepared, improve strain point, reduce and liquidus temperature and mention
High chemical stability, under preferable case, by weight percentage, SiO2+Al2O3> 83wt%.
In glass composition of the invention, SiO2It is glass former, content is too low, easily leads to strain point reduction, heat
The coefficient of expansion increases, acid resistance, alkali resistance decline；Improve SiO2Content can reduce the thermal expansion coefficient of glass, improve glass
The performances such as thermal stability, chemical stability, but fusion temperature increases, and general kiln is difficult to meet, and may cause analysis
It is brilliant.Therefore, comprehensively consider, on the basis of the weight of the composition, in terms of oxide, SiO2Content be 63-72wt%.
In glass composition of the invention, Al2O3Belong to intermediate oxide, to improve the intensity of glass structure, if
Content is lower than 15wt%, and glass is easy devitrification, is also easy the erosion by extraneous aqueous vapor and chemical reagent.The Al of high-content2O3Have
Help the raising of strain point of glass, mechanical strength, chemical stability, but excessively high glass is easy to appear crystallization, while can make
Glass is obtained to be difficult to dissolve.Therefore, comprehensively consider, on the basis of the weight of the composition, in terms of oxide, Al2O3Content be
15-20wt%, preferably 16-18.5wt%.
In glass composition of the invention, MgO is network modifying oxide, can be improved chemical durability of glass and drop
Low high temperature viscosity.But if content of MgO is greater than 10wt%, glass endurance can be deteriorated, while glass is easy devitrification.Therefore, comprehensive
It closes and considers, on the basis of the weight of the composition, in terms of oxide, the content of MgO is 4-10wt%, preferably 5-8wt%.
In glass composition of the invention, CaO is network modifying oxide, can reduce the viscosity of glass at high temperature,
Promote the fusing and clarification of glass, but when content is higher, the crystallization of glass can be made to be inclined to and increased, thermal expansion coefficient also can big amplitude variation
Greatly.Therefore, comprehensively consider, on the basis of the weight of the composition, in terms of oxide, CaO content 2-6wt%, preferably 3-
5.5wt%.
In glass composition of the invention, SrO can be improved the chemical stability of glass and accelerate glass melting, but contain
Clarification can be made secondary bubble occur when measuring excessively high, also result in glass density increase.Therefore, comprehensively consider, with the composition
On the basis of weight, in terms of oxide, SrO content is 0.01-2.5wt%.
In glass composition of the invention, BaO for reducing glass viscosity and promote the melting of glass and prevent glass
There is crystallization in glass, if content is excessive, will lead to glass density increase.Therefore, comprehensively consider, using the weight of the composition as base
Standard, in terms of oxide, BaO content is 2-8wt%, preferably 3.5-7.5wt%.Wherein, in the composition, with the composition
On the basis of weight, the incorporation way of BaO is BaCO3、BaSO4With Ba (NO3)2At least one of, and in terms of BaO, BaSO4With/
Or Ba (NO3)2Content be 0.1-2.5wt%.BaSO4Silicate reaction process can be effectively facilitated and reduce high temperature surface tension,
On tank furnace material mountain back segment cause alveolar layer seethe with partial pressure change, effectively facilitate fusing and clarifying process.
In glass composition of the invention, In2O3For network modifying oxide, there is the viscosity for reducing glass, improve glass
The effect of glass strain point, endurance and dielectric properties, and glass surface tension can be substantially reduced.But too high levels have increase glass
The effect of the density and refractive index of glass, In2O3It is unfavorable that content stablizes devitrification of glass when being more than 1.5%, and influences the saturating of glass
Cross rate.Therefore, comprehensively consider, on the basis of the weight of the composition, in terms of oxide, In2O3Content be 0.1-1.5wt%,
Preferably 0.5-1.2wt%.
In glass composition of the invention, on the basis of the weight of the composition, in terms of oxide, SnO2Content be
0.1-0.3wt%, preferably 0.15-0.25wt%.
It will be understood by those skilled in the art that in alkali-free alumina silicate glass composition of the invention, composition
Contain SiO2、Al2O3、MgO、CaO、SrO、BaO、In2O3And SnO2Refer to that the composition contains compound containing Si, chemical combination containing Al
Object, compound containing Mg, compound containing Ca, compound containing Sr, compound containing Ba, compound containing In and compound containing Sn, before such as containing
Carbonate, nitrate, sulfate, the oxide etc. of each element are stated, and the content of the aforementioned each component referred to is with each element
Oxide meter, the carbonate of specific each element, nitrate, sulfate, oxide to be selected as those skilled in the art institute ripe
Know, details are not described herein.
In glass composition of the invention, according to the difference of glass preparation technique, composition can also be containing as glass
Clarifying agent when glass melts, the clarifying agent is preferably at least one of sulfate, nitrate, chloride and fluoride；With
On the basis of the weight of the composition, the content of clarifying agent is not more than 1wt%.The specific choice of clarifying agent is not limited particularly
It is fixed, can be various selections commonly used in the art, such as sulfate can be barium sulfate, nitrate can for strontium nitrate and/or
Barium nitrate, chloride can be barium chloride and/or strontium chloride, and fluoride can be calcirm-fluoride.
In glass composition of the invention, when preparing alkali-free alumina silicate glass using it, why glass is enabled to
Glass has aforementioned excellent comprehensive performance, the mutual cooperation being mainly attributed in composition between each component, especially SiO2、
Al2O3、MgO、CaO、SrO、BaO、In2O3And SnO2Between mating reaction, each group of more particularly aforementioned certain content point it
Between mutual cooperation.
Second aspect, the present invention provides a kind of alkali-free alumina silicate glass, described on the basis of the weight of the glass
Glass contains the SiO of 63-72wt%2, 15-20wt% Al2O3, 4-10wt% MgO, 2-6wt% CaO, 0.01-
The In of BaO, 0.1-1.5wt% of SrO, 2-8wt% of 2.5wt%2O3With the SnO of 0.1-0.3wt%2。
Preferably, in alkali-free alumina silicate glass, by weight percentage, MgO/RO > 0.4, wherein RO=MgO+CaO+
SrO+BaO。
Preferably, in alkali-free alumina silicate glass, by weight percentage, SiO2+Al2O3> 83wt%.
Preferably, in alkali-free alumina silicate glass, on the basis of the weight of the glass, In2O3Content be 0.5-
1.2wt%.
Preferably, in alkali-free alumina silicate glass, on the basis of the weight of the glass, the content of MgO is 5-8wt%.
Preferably, in alkali-free alumina silicate glass, on the basis of the weight of the glass, the content of BaO is 3.5-
7.5wt%.
Preferably, in alkali-free alumina silicate glass, on the basis of the weight of the glass, Al2O3Content be 16-
18.5wt%.
Preferably, in alkali-free alumina silicate glass, on the basis of the weight of the glass, SnO2Content be 0.15-
0.25wt%.
Preferably, in alkali-free alumina silicate glass, on the basis of the weight of the glass, the content of CaO is 3-
5.5wt%.
The third aspect, the present invention provides a kind of method for preparing alkali-free alumina silicate glass, this method includes sending out this
The bright alkali-free alumina silicate glass successively carries out melt process, forming processes, annealing and machining with composition
Processing.
In method of the invention, aforementioned corresponding contents are referred to for the specific restriction of glass composition and are described, herein
It repeats no more.
In the case of process of the present invention it is preferred, the condition of melt process includes: temperature lower than 1650 DEG C, and the time is greater than
1h.Those skilled in the art can specific melting temperature and melting time, (such as temperature be 1550- determines according to actual conditions
1650 DEG C, time 8-12h), this is well known to those skilled in the art, and details are not described herein.
In the case of process of the present invention it is preferred, the condition of annealing includes: that temperature is 650-800 DEG C, and the time is greater than
0.1h.Those skilled in the art can specific annealing temperature and annealing time determines according to actual conditions, this is this field skill
Known to art personnel, details are not described herein.
In method of the invention, for machining processes, there is no particular limitation, can be common various in this field
Machining mode, such as can be cut for the product for obtaining annealing, grind, polish.
Fourth aspect, the present invention provides the alkali-free alumina silicate glass that the above method is prepared.
It will be understood by those skilled in the art that being with the weight of glass in alkali-free alumina silicate glass of the invention
Benchmark, the SiO containing 63-72wt%2, 15-20wt% Al2O3, 4-10wt% MgO, 2-6wt% CaO, 0.01-
The In of BaO, 0.1-1.5wt% of SrO, 2-8wt% of 2.5wt%2O3With the SnO of 0.1-0.3wt%2。
The preferred scope of the content of specific each oxide refers to aforementioned corresponding contents description, and details are not described herein.
Under preferable case, alkali-free alumina silicate glass of the invention, strain point is not less than 740 DEG C, and fusion temperature is lower than
1620 DEG C, liquidus temperature is lower than 1150 DEG C, and the thermal expansion coefficient within the scope of 50-350 DEG C is 30 × 10-7/℃-38×10-7/
DEG C, density is not more than 2.47g/cm3, the erosion amount of the HF solution acid corrosion 20min of 5 weight % is not more than at 24 ± 0.5 DEG C
3mg/cm2, the erosion amount of the NaOH solution caustic corrosion 20h of 5 weight % is not more than 0.5mg/cm at 90 ± 5 DEG C2, it is seen that light penetrates
Rate is higher than 91%, and Young's modulus is higher than 80GPa.
5th aspect, the present invention provides alkali-free alumina silicate glass composition of the present invention or alkali-free manosil ASs
Salt glass is preparing the application in display device and/or photoelectric device, preferably preparation TFT-LCD glass substrate and/or
Application in OLED glass substrate.
Embodiment
The present invention will be described in detail by way of examples below.It is unless otherwise instructed, used in following embodiment
Each material can be commercially available, and unless otherwise instructed, method used is the conventional method of this field.
In following embodiment and comparative example, glass density, unit g/cm are measured according to Archimedes method3。
Referring to the thermal expansion coefficient of glass that ASTM E-228 uses horizontal expander instrument to measure 50-350 DEG C, unit 10-7/
℃。
Glass Young's modulus, unit GPa are measured using material mechanical test machine referring to ASTM C-623.
Strain point of glass (10 is measured using bent beam high-temperature viscosimeter referring to ASTM C-33614.5Dpas strain point
Tst), unit is DEG C.
The fusion temperature (10 of cartridge type rotation high-temperature viscosimeter measurement glass is used referring to ASTM C-9652Dpas fusing
Temperature Tm), unit is DEG C.
Glass liquidus temperature is measured using temperature gradient furnace method referring to ASTM C-829, unit is DEG C.
Use (90 ± 5 DEG C/20h) measurement glass of 5wt%HF solution (24 ± 0.5 DEG C/20min) and 5wt%NaOH solution
Chemical corrosion resistance, unit mg/cm2。
Visible light transmittance rate is measured using UV-2550 ultraviolet-visible spectrophotometer, unit %.
Embodiment 1-8
Forming weighing each component according to glass shown in table 1, (wherein, the introducing form of BaO is BaCO3, the content of BaO is
BaCO3Content in terms of BaO), it mixes, mixture is poured into platinum crucible, then heating 10 is small in 1620 DEG C of high temperature furnaces
When, and stirred using platinum stick bubble is discharged.The glass metal melted is poured into stainless steel cast iron grinding tool, is configured to advise
Fixed both bulk glasses product, then in the lehr by glassware, 760 DEG C are annealed 2 hours, close power supply furnace cooling to 25
℃.Glassware is cut, ground, is polished, is then cleaned up and is dried with deionized water, glass finished-product is made.Point
The other various performances to each glass finished-product are measured, and the results are shown in Table 1.
Table 1
Embodiment 9-16
According to the method for embodiment 6, the difference is that, the performance of mixture ingredient (corresponding glass composition) and obtained product
Measurement result is shown in Table 2.
Table 2
Comparative example 1-2
According to the method for embodiment 6, the difference is that, the performance of mixture ingredient (corresponding glass composition) and obtained product
Measurement result is shown in Table 3.
Table 3
Data in table 1-2 and table 3 are compared it is found that the glass that the present invention is prepared has significantly higher strain
Point, lower fusion temperature, lower liquidus temperature and obvious preferable chemical stability.
Embodiment 15 in embodiment 6 in table 1 and table 2 is compared it is found that MgO/RO > 0.4, wherein RO=MgO+CaO+SrO
When+BaO, the comprehensive performance for the glass material being prepared can be further increased, and improves strain point, reduce liquidus temperature
With raising chemical stability.
Embodiment 16 in embodiment 6 in table 1 and table 2 is compared it is found that by weight percentage, SiO2+Al2O3> 83wt%
When, the comprehensive performance for the glass material being prepared can be further increased, and improve strain point, reduce liquidus temperature and mention
High chemical stability.
Method of the invention utilizes the SiO containing certain content2、Al2O3、MgO、CaO、SrO、BaO、In2O3And SnO2's
The glass that glass is prepared with composition, especially in glass composition, by weight percentage, MgO/RO > 0.4 (RO=
MgO+CaO+SrO+BaO)、SiO2+Al2O3When > 83wt%, strain point is not less than 740 DEG C, and fusion temperature is lower than 1620 DEG C, liquid phase
Line temperature is lower than 1150 DEG C, and the thermal expansion coefficient within the scope of 50-350 DEG C is 30 × 10-7/℃-38×10-7/ DEG C, density is little
In 2.47g/cm3, the erosion amount of the HF solution acid corrosion 20min of 5 weight % is not more than 3mg/cm at 24 ± 0.5 DEG C2, 90 ± 5 DEG C
The erosion amount of the NaOH solution caustic corrosion 20h of lower 5 weight % is not more than 0.5mg/cm2, it is seen that light transmission rate is higher than 91%, Young
Modulus is higher than 80GPa.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (15)
1. a kind of alkali-free alumina silicate glass composition, which is characterized in that on the basis of the weight of the composition, with oxide
Meter, the composition contain the SiO of 63-72wt%2, 15-20wt% Al2O3, 4-10wt% MgO, 2-6wt% CaO,
The In of BaO, 0.1-1.5wt% of SrO, 2-8wt% of 0.01-2.5wt%2O3With the SnO of 0.1-0.3wt%2；
By weight percentage, MgO/RO > 0.4, wherein RO=MgO+CaO+SrO+BaO；
By weight percentage, SiO2+Al2O3> 83wt%.
2. composition according to claim 1, which is characterized in that on the basis of the weight of the composition, In2O3Content
For 0.5-1.2wt%.
3. composition according to claim 1 or 2, which is characterized in that on the basis of the weight of the composition, MgO's contains
Amount is 5-8wt%.
4. composition according to claim 1 or 2, which is characterized in that on the basis of the weight of the composition, BaO's contains
Amount is 3.5-7.5wt%.
5. composition according to claim 1 or 2, which is characterized in that on the basis of the weight of the composition, Al2O3Contain
Amount is 16-18.5wt%.
6. composition according to claim 1 or 2, which is characterized in that on the basis of the weight of the composition, SnO2Contain
Amount is 0.15-0.25wt%.
7. composition according to claim 1 or 2, which is characterized in that on the basis of the weight of the composition, CaO's contains
Amount is 3-5.5wt%.
8. composition according to claim 1, which is characterized in that the composition also contains clarifying agent.
9. composition according to claim 8, which is characterized in that the clarifying agent be sulfate, nitrate, chloride and
At least one of fluoride.
10. composition according to claim 9, which is characterized in that on the basis of the weight of the composition, clarifying agent contains
Amount is not more than 1wt%.
11. a kind of method for preparing alkali-free alumina silicate glass, which is characterized in that this method includes that will appoint in claim 1-10
Alkali-free alumina silicate glass described in meaning one successively carries out melt process, forming processes, annealing and machinery with composition
Working process.
12. the alkali-free alumina silicate glass that method described in claim 11 is prepared.
13. alkali-free alumina silicate glass according to claim 12, which is characterized in that the alkali-free alumina silicate glass
Strain point is not less than 740 DEG C, and fusion temperature is lower than 1620 DEG C, and liquidus temperature is lower than 1150 DEG C, the heat within the scope of 50-350 DEG C
The coefficient of expansion is 30 × 10-7/℃-38×10-7/ DEG C, density is not more than 2.47g/cm3, the HF solution of 5wt% at 24 ± 0.5 DEG C
The erosion amount of acid corrosion 20min is not more than 3mg/cm2, the erosion amount of the NaOH solution caustic corrosion 20h of 5wt% is not at 90 ± 5 DEG C
Greater than 0.5mg/cm2, it is seen that light transmission rate is higher than 91%, and Young's modulus is higher than 80GPa.
14. alkali-free alumina silicate glass composition described in any one of claim 1-10 or claim 12 or 13 institutes
The alkali-free alumina silicate glass stated is preparing the application in display device and/or photoelectric device.
15. application according to claim 14, which is characterized in that in preparation TFT-LCD glass substrate and/or OLED glass
Application in substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610161879.7A CN105731790B (en) | 2016-03-18 | 2016-03-18 | A kind of alkali-free alumina silicate glass composition, alkali-free alumina silicate glass and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610161879.7A CN105731790B (en) | 2016-03-18 | 2016-03-18 | A kind of alkali-free alumina silicate glass composition, alkali-free alumina silicate glass and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105731790A CN105731790A (en) | 2016-07-06 |
| CN105731790B true CN105731790B (en) | 2018-12-25 |
Family
ID=56250960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610161879.7A Active CN105731790B (en) | 2016-03-18 | 2016-03-18 | A kind of alkali-free alumina silicate glass composition, alkali-free alumina silicate glass and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105731790B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109231816A (en) * | 2018-10-09 | 2019-01-18 | 成都中光电科技有限公司 | A kind of glass substrate and preparation method thereof can be used for LTPS |
| CN112441743A (en) * | 2020-11-26 | 2021-03-05 | 河南旭阳光电科技有限公司 | Alkali-free glass composition, alkali-free glass, preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631827A (en) * | 2005-02-06 | 2005-06-29 | 河南安彩高科股份有限公司 | Glass composition without alkali metal and its preparation method and application |
| CN101166697A (en) * | 2005-05-02 | 2008-04-23 | 旭硝子株式会社 | Alkali-free glass and method for production thereof |
| US20150037553A1 (en) * | 2012-02-29 | 2015-02-05 | Corning Incorporated | Low cte alkali-free boroaluminosilicate glass compositions and glass articles comprising the same |
| CN104736496A (en) * | 2013-03-25 | 2015-06-24 | 日本电气硝子株式会社 | Reinforced glass substrate and method for producing same |
| CN105121374A (en) * | 2013-07-11 | 2015-12-02 | 日本电气硝子株式会社 | Glass |
-
2016
- 2016-03-18 CN CN201610161879.7A patent/CN105731790B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631827A (en) * | 2005-02-06 | 2005-06-29 | 河南安彩高科股份有限公司 | Glass composition without alkali metal and its preparation method and application |
| CN101166697A (en) * | 2005-05-02 | 2008-04-23 | 旭硝子株式会社 | Alkali-free glass and method for production thereof |
| US20150037553A1 (en) * | 2012-02-29 | 2015-02-05 | Corning Incorporated | Low cte alkali-free boroaluminosilicate glass compositions and glass articles comprising the same |
| CN104736496A (en) * | 2013-03-25 | 2015-06-24 | 日本电气硝子株式会社 | Reinforced glass substrate and method for producing same |
| CN105121374A (en) * | 2013-07-11 | 2015-12-02 | 日本电气硝子株式会社 | Glass |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105731790A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6289578B2 (en) | Alkali-free glass composition having high heat and chemical stability | |
| TWI677479B (en) | Glass substrate for display | |
| JP6539250B2 (en) | Glass substrate for flat panel display and method of manufacturing the same | |
| TWI673246B (en) | Glass substrate for flat panel display and manufacturing method thereof | |
| TWI567040B (en) | Glass compositions having high thermal and chemical stability | |
| TWI613174B (en) | Alkali-free glass and alkali-free glass plate using the same | |
| KR101409534B1 (en) | Glass substrate for flat panel display and manufacturing method thereof | |
| KR102282396B1 (en) | Composition for glass, alkaline earth aluminum silicate glass, manufacturing method and application thereof | |
| JPWO2009028570A1 (en) | Glass plate, method for producing the same, and method for producing TFT panel | |
| CN105859128A (en) | Composition for glass, low-surface-tension alkali-free glass as well as preparation method and application thereof | |
| WO2015030013A1 (en) | Non-alkali glass | |
| JP2005330176A (en) | No-alkali glass and liquid crystal display panel | |
| CN105731790B (en) | A kind of alkali-free alumina silicate glass composition, alkali-free alumina silicate glass and its preparation method and application | |
| WO2014208521A1 (en) | Alkali-free glass | |
| KR102229428B1 (en) | Alkali-free glass | |
| CN102399061A (en) | Alkali-free glass and liquid crystal display panel | |
| WO2014208524A1 (en) | Alkali-free glass | |
| WO2015166890A1 (en) | Non-alkali glass | |
| CN117550799A (en) | Composition for glass, alkali-free aluminosilicate glass, and preparation method and application thereof | |
| CN114716143A (en) | Alkali-free boroaluminosilicate glass for liquid crystal glass substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20160706 Assignee: Sichuan Gaosheng pharmaceutical packaging material technology Co.,Ltd. Assignor: TUNGHSU GROUP Co.,Ltd. Contract record no.: X2021990000507 Denomination of invention: The invention relates to a composition for alkali free aluminosilicate glass, an alkali free aluminosilicate glass and a preparation method and application thereof Granted publication date: 20181225 License type: Common License Record date: 20210818 |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20160706 Assignee: Zhejiang Lihui Intelligent Equipment Co.,Ltd. Assignor: WUHU DONGXU OPTOELECTRONIC EQUIPMENT TECHNOLOGY Co.,Ltd. Contract record no.: X2022980008187 Denomination of invention: The invention relates to a composition for alkali free aluminosilicate glass, alkali free aluminosilicate glass and a preparation method and application thereof Granted publication date: 20181225 License type: Common License Record date: 20220627 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20160706 Assignee: Qingdao fusion Photoelectric Technology Co.,Ltd. Assignor: TUNGHSU GROUP Co.,Ltd. Contract record no.: X2022110000014 Denomination of invention: Composition for alkali-free aluminosilicate glass, alkali-free aluminosilicate glass and preparation method and application thereof Granted publication date: 20181225 License type: Common License Record date: 20220812 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20160706 Assignee: Weifang Xingming Photoelectric Technology Co.,Ltd. Assignor: TUNGHSU GROUP Co.,Ltd. Contract record no.: X2023110000018 Denomination of invention: A composition for alkali-free aluminosilicate glass, alkali-free aluminosilicate glass and its preparation method and application Granted publication date: 20181225 License type: Common License Record date: 20230131 |
|
| EE01 | Entry into force of recordation of patent licensing contract |