CN108911501A - A kind of high rigidity Aluminiu, boron silicate glass without alkali and the preparation method and application thereof suitable for floating process production - Google Patents
A kind of high rigidity Aluminiu, boron silicate glass without alkali and the preparation method and application thereof suitable for floating process production Download PDFInfo
- Publication number
- CN108911501A CN108911501A CN201810897758.8A CN201810897758A CN108911501A CN 108911501 A CN108911501 A CN 108911501A CN 201810897758 A CN201810897758 A CN 201810897758A CN 108911501 A CN108911501 A CN 108911501A
- Authority
- CN
- China
- Prior art keywords
- glass
- alkali
- high rigidity
- floating process
- aluminiu
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000005368 silicate glass Substances 0.000 title claims abstract description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003513 alkali Substances 0.000 title claims abstract description 23
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 23
- 238000007667 floating Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 78
- 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 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002585 base Substances 0.000 claims abstract description 21
- 239000005357 flat glass Substances 0.000 claims abstract description 21
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 20
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 14
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 238000000137 annealing Methods 0.000 claims abstract description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 229910001018 Cast iron Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000005407 aluminoborosilicate glass Substances 0.000 claims 3
- FGUJWQZQKHUJMW-UHFFFAOYSA-N [AlH3].[B] Chemical compound [AlH3].[B] FGUJWQZQKHUJMW-UHFFFAOYSA-N 0.000 claims 1
- 235000019589 hardness Nutrition 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 23
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000003280 down draw process Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011900 installation process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019587 texture Nutrition 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1218—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition or structure of the substrate
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The present invention discloses a kind of high rigidity Aluminiu, boron silicate glass without alkali and preparation method suitable for floating process production.The glass is indicated with mass percent, based on oxide content, has consisting of：SiO2：55.0~65.0%, Al2O3：11.0~29.0%, B2O3：2.0~9.0%, MgO：2.4~5.0%, SrO：4.6~10.0%, CaO：2.5~5.5%.The present invention provides Vickers hardnesses to be higher than 670kgf/mm2, strain point be more than 680 DEG C, glass melting temperature 1620~1660 DEG C, annealing temperature 700 DEG C, can be used floating process production, high elastic modulus, chemical stability it is good, it is widely portable to flat panel displaying element or the base plate glass of other photoelectric devices, is particularly suitable for TFT-LCD base plate glass.
Description
Technical field
The invention belongs to field of glass production technology, and in particular to one kind can be widely applied to display industry thin film transistor (TFT)
Liquid crystal display (TFT-LCD) high rigidity Aluminiu, boron silicate glass without alkali and the preparation method and application thereof.
Background technique
TFT-LCD have stable operating voltage, energy saving, lightweight high image quality, full color, fine definition, high-resolution,
A variety of good characteristics such as radiationless and pollution-free, have been widely used.Key foundation material of the base plate glass as TFT-LCD
Material mainly has both sides to act on：One is the thickness for making liquid crystal molecule keep certain；The other is carrying driving is had to
Transparent electrode and switching element.Currently, Aluminiu, boron silicate glass without alkali is widely used to TFT- due to its excellent performance
LCD substrate material, the quality of base plate glass influence TFT-LCD performance huge.
Alkali-free aluminoborosilicate base plate glass as TFT-LCD baseplate material must the following conditions：
(1) there is high rigidity, it is ensured that base plate glass is not scratched and destroys by other in end processing sequences.
(2) strict control alkali metal (Na2O、K2O etc.) introducing, in heat treatment process, if containing alkali metal from
Son will lead to alkali metal film forming and spread in semiconductor substance, cause membrane property to deteriorate, but lack alkali metal oxide (R2O it) helps
It is molten, lead to that glass melting is difficult, clarification is difficult, homo-effect is poor, so in general control glass alkali content in 1000~2000ppm,.
(3) has good chemical stability, this is because needing in TFT-LCD device fabrication process in base plate glass
It is upper to carry out the operation such as multiple film, etching and chemical attack.
(4) strain point is higher than 650 DEG C, to guarantee the stability of the high temperature process of glass in panel manufacturing process.
(5) there is suitable thermal expansion coefficient, in 25~300 DEG C of thermal expansion coefficients between 3.0~3.8 × 10-6/ DEG C,
Suitable matching degree can be kept with peripheral parts, since device in the fabrication process can be by multiple, quick liter repeatedly
Cooling avoids deformation caused by glass bending and peripheral devices in following process glass heat treatment process from deviation occur.
(6) density will be lower than 2.55g/cm3, large scale display panel is prepared to lighting, slimming development.
(7) there is high elasticity modulus, generally higher than 65Gpa preferably reaches 70Gpa or more, avoids working as in industrial production
It is middle to prepare large-sized base plate glass and depending condition occur and make glass breaking.
(8) alkali-free aluminium borosilicic acid base plate glass will also guarantee molten in glass other than the condition for meeting above (1)~(7)
The defects of process processed reaches preferable clarification, homo-effect, and bubble, crackle is not present in the base plate glass after guaranteeing forming.
Based on the requirement of the above property, TFT-LCD base plate glass is generally made of Aluminiu, boron silicate glass without alkali, ingredient
For SiO2、Al2O3、B2O3, RO (MgO, SrO and CaO) composition, introduce raw material be generally quartz sand, aluminium oxide, boric acid, lightweight oxygen
Change magnesium, strontium carbonate and calcium carbonate raw material.To guarantee glass smelting effect, it is ensured that when enough mixings, melted, clarification and homogenizing
Between.
The addition of alkaline-earth metal intermediate oxide and suitable proportion reduce glass melting temperature and high temperature viscosity, shorten glass
The material of glass is conducive to glass Quick-forming, can be improved the hardness of glass again to a certain extent, and alkaline earth oxide makees glass
The network outer body of glass structure is present in glass spaces position, so that the connection of key is stronger in glass network structure, more
Step up close, improves the compaction rate of glass structure.
The EAGLE XG slim Glass LCD sheet glass dimension that U.S. CORNING limited liability company completely newly releases
Family name's hardness is 640kgf/mm2, the minimum weightlessness ratio 1.83mg/cm in mass fraction 5%NaOH solution2；Patent CN1328531 A
A kind of glass for flat-panel monitor is disclosed, the strain temperature highest of glass only has 660 DEG C, and the fusion temperature of glass reaches
To 1700 DEG C；Disclosed in patent CN101400614 A glass combination with high thermal stability and chemical stability and
Preparation method is added to BaO, Sb in composition2O3、As2O3Equal heavy metallic oxides and noxious material, also added ZrO2、
SnO2With rare earth oxide La2O3Component, the composition glass are prepared suitable for press over system；It is disclosed in patent CN101801872 A
A kind of glass combination and production and preparation method thereof of suitable glass tube down-drawing, contains BaO, TiO in composition2、MnO、ZnO、Nb2O5、
MoO3、Ta2O5And the substances such as rare earth oxide, and be illustrated for down draw process performance；In 102531386 A of patent CN
A kind of alkali-free glass compositions with high thermal stability and chemical stability are disclosed, are selected in the preparation process of glass
SnO2、Fe2O3、CeO2、Sb2O3、As2O3Or mixtures thereof be used as clarifying agent；A kind of liquid is disclosed in patent CN101544467A
Brilliant substrate glass material and preparation method thereof, but contain ZnO in composition, and be added to BaO, Ba (NO3)2It is disagreeableness to environment
Component.
An important performance indexes of the hardness as base plate glass, due to Thin Film Transistor-LCD (TFT-LCD)
Base plate glass will pass through multiple cold treatment and heat treatment in post-production and installation process, to avoid base plate glass subsequent
It is not scratched in processing and treatment process and is destroyed by other, high rigidity is applied to pass in TFT-LCD to base plate glass
It is important.Currently, the glass Vickers hardness for TFT-LCD substrate is generally in 630kgf/mm2Left and right.
Summary of the invention
The present invention provides a kind of high rigidity alkali-free aluminium borosilicate suitable for floating process production to solve above-mentioned technical problem
Silicate glass and the preparation method and application thereof.
The present invention is achieved through the following technical solutions：
A kind of high rigidity Aluminiu, boron silicate glass without alkali suitable for floating process production, is indicated with mass percent, is pressed
Oxide content meter has consisting of：
In above scheme, the SiO2And Al2O3The sum of mass percentage be not more than 83%.
In above scheme, by mass, 0.24≤(MgO+SrO+CaO)/SiO2≤0.32。
In above scheme, by mass, 0.59≤(MgO+SrO+CaO)/Al2O3≤1.19。
In above scheme, by mass, 0.08≤B2O3/Al2O3≤0.41。
In above scheme, by mass, 0.26≤Al2O3/SiO2≤0.45。
In above scheme, the liquidus temperature of glass raw material is at 1050~1170 DEG C, and operating temperature range is 920~1250
DEG C, strain point is higher than 680 DEG C.
In above scheme, Vickers hardness is higher than 670kgf/mm2, elasticity modulus is in 80.0~90.0GPa, in volume fraction
It is weightless than being 5.19~6.70mg/cm in 10%HF solution2, weightless than being 1.12 in mass fraction 5%NaOH solution
~1.74mg/cm2, and the linear expansion coefficient at 25~300 DEG C is less than or equal to 38 × 10-7/℃。
The method of the high rigidity Aluminiu, boron silicate glass without alkali, using floating process, processing step is：Match above-mentioned
After mixing than weighed oxide, it melts, in 1620~1660 DEG C of 2~3h of heat preservation, then falls the glass metal melted
Enter rapid shaping in the stainless steel cast iron vessel for be preheated to 200~300 DEG C, controls in 650-720 DEG C of annealing 2~3h, Zhi Housui
Aluminiu, boron silicate glass without alkali sample is made in furnace natural cooling.
The high rigidity Aluminiu, boron silicate glass without alkali for being suitable for floating process production is aobvious in tft liquid crystal
Show the application in the base plate glass of device (TFT-LCD) panel.
The present invention this Aluminiu, boron silicate glass without alkali in order to obtain, first is that passing through control SiO2And Al2O3Amount, addition
Variety classes alkaline earth oxide reduces high temperature viscosity of glass and glass melting temperature, shortens frit, accelerates forming of glass.Two
It is by adjusting mol ratio (the preferably MgO of alkaline earth oxide (MgO, CaO, SrO) type:CaO:The molar ratio of SrO=
4:3:And SiO 3)2、Al2O3、B2O3Mass content optimize the hardness of glass.Third is that strict control processing parameter, including
The process parameter optimizings glass properties such as glass melting temperature, melting time, annealing temperature and sufficient annealing time.
The invention has the advantages that：The alkaline earth oxide of suitable proportion is added in glass composition of the invention
Selection with excellent floating process parameter can effectively reduce high temperature viscosity of glass and glass melting temperature, shortening strip, raising glass are hard
Degree.The present invention provides Vickers hardnesses to be higher than 670kgf/mm2, strain point be more than 680 DEG C, glass melting temperature 1620~1660 DEG C,
Annealing temperature 700 DEG C, can be used floating process production, high elastic modulus, chemical stability it is good, be widely portable to plate
The base plate glass of display element or other photoelectric devices is particularly suitable for TFT-LCD base plate glass.
Specific embodiment
The present invention is furtherd elucidate below with reference to embodiment, but the contents of the present invention are not limited solely to following reality
Example is applied, embodiment is not construed as limitation of the invention.
A kind of preparation method of high rigidity Aluminiu, boron silicate glass without alkali provided by the present invention, steps are as follows：
1) selection of raw material：According to SiO255.0~65.0%, Al2O311.0~29.0%, B2O32.0~9.0%,
MgO 2.4~5.0%, SrO 4.6~10.0%, 2.5~5.5% ingredient of CaO, by percentage to the quality, the sum of each oxide
Meet 100%, wherein SiO2、Al2O3、B2O3, MgO, CaO, SrO be respectively by quartz sand, aluminium oxide, boric acid, light magnesium oxide, carbon
Sour calcium, strontium carbonate introduce；
2) mass fraction of batch is calculated according to above-mentioned each oxide mass score and weigh about 200g batch, mix
After uniformly, it is added in platinum-rhodium alloy crucible and melts, in 1620~1660 DEG C of 2~3h of heat preservation, then fall the glass metal melted
Enter rapid shaping in the stainless steel cast iron die for be preheated to 200~300 DEG C, controls in 700 DEG C of 2~3h of annealing, certainly with furnace later
It is so cooling, to eliminate stress present in glass, a kind of high rigidity Aluminiu, boron silicate glass without alkali sample is made.
The compositing range of each ingredient is illustrated below.
In glass system, SiO2It is that glass network generates oxide body, is the basic skeleton structure of glass.Glass of the present invention
SiO in glass component2Content suitably increases SiO between 55~65% (mass percents, not specified then identical below)2
The hardness of glass can be made to increase, promote strain point, improve chemical stability, reduce thermal expansion coefficient.But its content is super
Crossing 65% or more causes melting temperature to increase, and increases tendency towards devitrification；If content is lower than 55%, the strain point of glass is lower,
And the coefficient of expansion increases, therefore preferred SiO2The component of content 57.0~60.0%, more preferable 57.4% or more 60.0% or less.
Al2O3It can inhibit the split-phase of glass, reduce thermal expansion coefficient, improve strain point, improve elasticity modulus.Al2O3Contain
Amount is in 11~29%, suitably increase Al2O3The durability of glass can be improved, reduce thermal expansion coefficient.If Al2O3Content is lower than
11%, then it can not show by adding Al2O3Obtained from effect, content is more than 29% glass infusibility to be caused to melt or devitrification, because
This preferably 15.0~28.5% component, more preferable content is 15.0% or more below 25.5%.
B2O32.0~9.0%, the strain point of glass is can be improved in it for content control, reduces linear expansion coefficient and high temperature is viscous
Degree, is a kind of good fluxing agent.Due to B under the high temperature conditions2O3With [BO3] form exist be difficult to form [BO4], to drop
Low high temperature viscosity, [BO when low temperature3] capture free oxygen to [BO4] conversion, so that the compaction rate of glass increases, promotion glass is hard
Degree.Its fluxing effect is deteriorated when boron oxide content is lower than 2.0%, and clarifying effect is deteriorated when also can be glass smelting, but content is high
In the reduction of 9% or more strain point, elasticity modulus is greatly lowered, and in addition boron volatilization increase leads to component design and reality when high temperature
There is certain deviation, reduces component deviation by supplementing suitable boron oxide, thus preferred B2O3The group of content 2.0~6.5%
Point.
The high temperature viscosity and glass melting temperature of glass can be effectively reduced in alkaline earth oxide RO (MgO, CaO and SrO), contracting
The material of short glass, is conducive to Quick-forming, belongs to network outer body.MgO have do not reduce reduce in the case where strain point it is high
Warm viscosity makes glass be easy to melt, also can reduce tendency towards devitrification, since its radius is small, Mg2+It is all octahedra under normal circumstances
Form is present in glass structure, can be filled in network interstitial site, be conducive to close structure.Introduction volume is more than 5% meeting
Lead to short texture, hardness reduces, and preferably content of MgO is 2.4~5.0%, more preferable 3.0% or more 5% or less.CaO is helped
In reduce glass fusing point and liquidus temperature, but content be more than 5% will lead to strain point reduce and the coefficient of expansion increase, therefore
Control CaO content is advisable 2.5~5.5%, and more preferable 3.0% or more 5.5% or less.Mg2+And Ca2+The radius of ion is smaller,
Charge is higher, polarizability is stronger, thus influences on the elasticity modulus of base plate glass very big.SrO too high levels are not in comparison
Conducive to elasticity modulus is increased, its relative molecular mass score of Sr member procatarxis is larger, has a great impact to density, the content of SrO
Control is 4.6~10.0%, more preferable 9% or less 4.6% or more.
For a better understanding of the invention, the content that the present invention is further explained combined with specific embodiments below, but the present invention
The following examples are not limited solely to, a kind of high rigidity Aluminiu, boron silicate glass without alkali suitable for floating process production is excellent
Glass is selected to form：SiO257.0~60.0%, Al2O315.0~28.5%, B2O32.0~6.5%, MgO 3.0~5.0%,
SrO 6.5~9.0%, CaO 3.0~5.0%, and the sum of each oxide meets 100%.The oxide mass of specific each example
See Table 1 for details for percentage.
Table 1
Wherein, in table 1 each example performance test value, the density of glass measured using Archimedes's drainage；Springform
Amount measures elasticity modulus using MTS ceramics experimental system line-of-sight course；Vickers hardness is tested using full-automatic microhardness instrument；Glass
The water-bath at 20 DEG C of volume fraction 10%HF solution corrodes 20min and in mass fraction 5% respectively for chemical resistance test, i.e. glass
6h is corroded in water-bath at 95 DEG C of NaOH solution；Impedance analyzer Measuring Dielectric Constant；The average linear expansion coefficient of glass, strain point and
Softening point is expanded to measure using horizontal expander instrument；Fusion temperature, operating point are obtained using high-temperature viscosimeter measuring and calculation；Liquidus curve
Temperature is tested using thermal gradient furnace.
By 1 example of table it is found that Aluminiu, boron silicate glass without alkali provided by the invention Vickers hardness with higher, reaches
670kgf/mm2More than, elasticity modulus is higher than 80GPa, and strain point temperature is at 680 DEG C or more, in volume fraction 10%HF solution
Weightlessness is than being 5.19~6.70mg/cm2, weightless than being 1.12~1.74mg/cm in mass fraction 5%NaOH solution2, and
Linear expansion coefficient at 25~300 DEG C is less than or equal to 38 × 10-7/ DEG C, meet Thin Film Transistor-LCD (TFT-LCD) base
The performance requirement of glass sheet, glass melting temperature is at 1620~1660 DEG C, and liquidus temperature is at 1050~1170 DEG C, operating temperature model
920~1250 DEG C are trapped among, annealing temperature is suitable for floating process and produces at 700 DEG C.
Above embodiments are only exemplary embodiment of the present invention, are not used in the limitation present invention, protection scope of the present invention
It is defined by the claims.Those skilled in the art can within the spirit and scope of the present invention make respectively the present invention
Kind modification or equivalent replacement, this modification or equivalent replacement also should be regarded as being within the scope of the present invention.
Claims (10)
1. a kind of high rigidity Aluminiu, boron silicate glass without alkali suitable for floating process production, which is characterized in that use quality percentage
Than indicating, based on oxide content, there is consisting of：
2. the high rigidity Aluminiu, boron silicate glass without alkali according to claim 1 suitable for floating process production, feature
It is, SiO2And Al2O3The sum of mass percentage be not more than 83%.
3. the high rigidity Aluminiu, boron silicate glass without alkali according to claim 1 suitable for floating process production, feature
It is, by mass, 0.24≤(MgO+SrO+CaO)/SiO2≤0.32。
4. the high rigidity Aluminiu, boron silicate glass without alkali according to claim 1 suitable for floating process production, feature
It is, by mass, 0.59≤(MgO+SrO+CaO)/Al2O3≤1.19。
5. the high rigidity Aluminiu, boron silicate glass without alkali according to claim 1 suitable for floating process production, feature
It is, by mass, 0.08≤B2O3/Al2O3≤0.41。
6. the high rigidity Aluminiu, boron silicate glass without alkali according to claim 1 suitable for floating process production, feature
It is, by mass, 0.26≤Al2O3/SiO2≤0.45。
7. described in any item high rigidity alkali-free aluminoborosilicate glass suitable for floating process production according to claim 1~6
Glass, which is characterized in that the liquidus temperature of glass raw material at 1050~1170 DEG C, answer at 920~1250 DEG C by operating temperature range
Height is higher than 680 DEG C.
8. described in any item high rigidity alkali-free aluminoborosilicate glass suitable for floating process production according to claim 1~6
Glass, which is characterized in that Vickers hardness is higher than 670kgf/mm2, elasticity modulus is in 80.0~90.0GPa, in volume fraction 10%HF
It is weightless than being 5.19~6.70mg/cm in solution2, in mass fraction 5%NaOH solution it is weightless than for 1.12~
1.74mg/cm2, and the linear expansion coefficient at 25~300 DEG C is less than or equal to 38 × 10-7/℃。
9. the method for preparing the described in any item high rigidity Aluminiu, boron silicate glass without alkali of claim 1~6, which is characterized in that
Using floating process, processing step is：Weighed oxide will be matched after mixing by any one of claim 1~6 is described,
Then the glass metal melted is poured into 1620~1660 DEG C of 2~3h of heat preservation and is preheated to 200~300 DEG C of stainless steel by melting
The alkali-free aluminium boron is made later with furnace natural cooling in 650-720 DEG C of 2~3h of annealing in rapid shaping in cast iron vessel, control
Silicate glass.
10. described in any item high rigidity alkali-free aluminoborosilicate glass suitable for floating process production according to claim 1~6
Application of the glass in the base plate glass of LCD panel of thin-film transistor.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810781184 | 2018-07-17 | ||
| CN2018107811848 | 2018-07-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108911501A true CN108911501A (en) | 2018-11-30 |
Family
ID=64394621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810897758.8A Pending CN108911501A (en) | 2018-07-17 | 2018-08-08 | A kind of high rigidity Aluminiu, boron silicate glass without alkali and the preparation method and application thereof suitable for floating process production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108911501A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183103A (en) * | 2019-05-06 | 2019-08-30 | 中建材蚌埠玻璃工业设计研究院有限公司 | Silicate glass containing boron and aluminium without alkali clarifying agent and its application method |
| CN111943506A (en) * | 2020-07-20 | 2020-11-17 | 广东金刚玻璃科技股份有限公司 | Formula of non-conductive touch control mirror display glass |
| CN113735450A (en) * | 2021-09-09 | 2021-12-03 | 温州市康尔微晶器皿有限公司 | Transparent high-hardness magnesium-aluminum-silicon microcrystalline glass and preparation method thereof |
| CN116102254A (en) * | 2022-12-23 | 2023-05-12 | 中建材玻璃新材料研究院集团有限公司 | OLED glass substrate composition and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285325A (en) * | 1999-08-21 | 2001-02-28 | 肖特玻璃制造厂 | Aluminiu, boron silicate glass without alkali and application thereof |
| CN1303829A (en) * | 2000-01-12 | 2001-07-18 | 肖特玻璃制造厂 | Silicate glass containing boron and aluminium without alkali and its use |
| CN101591141A (en) * | 2008-05-30 | 2009-12-02 | 康宁股份有限公司 | Boroalumino silicate glasses |
| CN102399060A (en) * | 2010-09-14 | 2012-04-04 | 旭硝子株式会社 | Alkali-free glass and liquid crystal display panel |
-
2018
- 2018-08-08 CN CN201810897758.8A patent/CN108911501A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285325A (en) * | 1999-08-21 | 2001-02-28 | 肖特玻璃制造厂 | Aluminiu, boron silicate glass without alkali and application thereof |
| CN1303829A (en) * | 2000-01-12 | 2001-07-18 | 肖特玻璃制造厂 | Silicate glass containing boron and aluminium without alkali and its use |
| CN101591141A (en) * | 2008-05-30 | 2009-12-02 | 康宁股份有限公司 | Boroalumino silicate glasses |
| CN102399060A (en) * | 2010-09-14 | 2012-04-04 | 旭硝子株式会社 | Alkali-free glass and liquid crystal display panel |
Non-Patent Citations (1)
| Title |
|---|
| 王伟等: "《玻璃生产工艺技术》", 31 May 2013, 武汉：武汉理工大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183103A (en) * | 2019-05-06 | 2019-08-30 | 中建材蚌埠玻璃工业设计研究院有限公司 | Silicate glass containing boron and aluminium without alkali clarifying agent and its application method |
| CN110183103B (en) * | 2019-05-06 | 2023-05-02 | 中建材玻璃新材料研究院集团有限公司 | Clarifying agent for alkali-free boroaluminosilicate glass and use method thereof |
| CN111943506A (en) * | 2020-07-20 | 2020-11-17 | 广东金刚玻璃科技股份有限公司 | Formula of non-conductive touch control mirror display glass |
| CN113735450A (en) * | 2021-09-09 | 2021-12-03 | 温州市康尔微晶器皿有限公司 | Transparent high-hardness magnesium-aluminum-silicon microcrystalline glass and preparation method thereof |
| CN116102254A (en) * | 2022-12-23 | 2023-05-12 | 中建材玻璃新材料研究院集团有限公司 | OLED glass substrate composition and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI401219B (en) | Glass plate manufacturing method and glass plate manufacturing apparatus | |
| CN108911501A (en) | A kind of high rigidity Aluminiu, boron silicate glass without alkali and the preparation method and application thereof suitable for floating process production | |
| JP5537144B2 (en) | Glass composition and glass substrate for flat panel display using the same | |
| KR20220021022A (en) | Glass | |
| KR20050109929A (en) | Alkali-free glass | |
| JP2005306719A (en) | Glass for display substrate | |
| JP4898792B2 (en) | High-deformation point glass composition for substrates | |
| JP6663010B2 (en) | Low boron and barium free alkaline earth aluminosilicate glass and its application | |
| JP7448890B2 (en) | Alkali-free glass plate | |
| JP2001348247A (en) | Alkaline-free glass | |
| JP2022121511A (en) | glass | |
| JP4686858B2 (en) | Glass substrate for flat panel display | |
| JP2022105215A (en) | Glass | |
| CN102030475B (en) | Environmentally-friendly alkali-free aluminoborosilicate glass for TFT-LCD | |
| CN109809687A (en) | A kind of base plate glass for high resolution display | |
| CN110255894A (en) | High elastic modulus Aluminiu, boron silicate glass without alkali and preparation method thereof suitable for floating process production | |
| CN108503214A (en) | A kind of high strain-point Aluminiu, boron silicate glass without alkali and preparation method thereof | |
| JP2020172423A (en) | Alkali-free glass plate | |
| JP2004244257A (en) | Glass substrate for flat panel display device | |
| JP4756428B2 (en) | Glass substrate for flat panel display | |
| JP4958062B2 (en) | Glass substrate for flat panel display | |
| CN114716143B (en) | Alkali-free boroaluminosilicate glass for liquid crystal glass substrate | |
| US20210380469A1 (en) | Alkali-free glass plate | |
| CN108947237A (en) | A kind of alkali-free silicate glass of low-expansion coefficient high strain-point | |
| CN117105526B (en) | High-stability long-service-life substrate glass for liquid crystal display |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181130 |
|
| RJ01 | Rejection of invention patent application after publication |