CN104276756A - Alkali-free glass - Google Patents
Alkali-free glass Download PDFInfo
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- CN104276756A CN104276756A CN201310528672.5A CN201310528672A CN104276756A CN 104276756 A CN104276756 A CN 104276756A CN 201310528672 A CN201310528672 A CN 201310528672A CN 104276756 A CN104276756 A CN 104276756A
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- 239000011521 glass Substances 0.000 title claims abstract description 117
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 239000000758 substrate Substances 0.000 abstract description 31
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 11
- 238000002844 melting Methods 0.000 abstract description 10
- 230000008018 melting Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000005401 electroluminescence Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 16
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 239000005357 flat glass Substances 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000004031 devitrification Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000007665 sagging Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical group 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- -1 content is too much Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000006132 parent glass Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004017 vitrification 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
- C03C3/089—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
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- 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
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/08—Doped silica-based glasses containing boron or halide
- C03C2201/10—Doped silica-based glasses containing boron or halide containing boron
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses alkali-free glass. The glass comprises the following chemical components by mole percent: 68.5-72% of SiO2, 12.6-15% of Al2O3, 1-3.7% of B2O3, 0.1-5.5% of MgO, 4-7% of CaO, 0.05-4% of ZnO, 1-3.5% of SrO and 0.05-0.1% of SnO. The alkali-free glass has the advantages of high chemical stability, high strain point, high Young modulus, low coefficient of expansion, low melting temperature, low liquidus temperature, and the like. The high temperature viscosity can be obviously reduced via ZnO and MgO in the formula composition, so that the alkali-free glass has lower melting temperature. The material can be widely suitable for manufacturing the glass substrates of flat panel displays, photovoltaic devices or other photoelectric devices and is especially suitable for manufacturing the glass substrates, and the like of TFT-LCD (thin film transistor-liquid crystal display) using the LTPS (low temperature poly-silicon) technology, and OEL (organic electroluminescence).
Description
Technical field
The invention belongs to field of glass production technology, relate to a kind of formula of glass substrate being widely used in making plane display, illumination, photovoltaic device or other photoelectric devices, specifically a kind of alkaline earth aluminates glass of alkali-free metal.
Background technology
Along with the fast development of photovoltaic industry, the demand of various display device is constantly increased, the active matrix liquid crystal display LTPS TFT-LCD device of such as active matrix liquid crystal display AMLCD, Organic Light Emitting Diode OLED and application of cold temperature polycrystalline silicon technology, these display devices all produce thin film transistor TFT technology based on use thin film semiconductor material.The silica-based TFT of main flow can be divided into non-crystalline silicon (a-Si) TFT, polysilicon (p-Si) TFT and silicon single crystal (SCS) TFT, wherein non-crystalline silicon (a-Si) TFT is the technology that present main flow TFT-LCD applies, non-crystalline silicon (a-Si) TFT technology, the treatment temp in procedure for producing can complete at 300-450 DEG C of temperature.LTPS polysilicon (p-Si) TFT needs repeatedly to process at relatively high temperatures in processing procedure process, substrate can not must deform in multiple high temp treating processes, this just proposes higher requirement to base plate glass performance, preferred strain point higher than 650 DEG C, more preferably higher than 670 DEG C, 700 DEG C.The coefficient of expansion of glass substrate needs the expansion coefficient similar with silicon simultaneously, and reduce stress and destruction as far as possible, therefore the preferred thermal linear expansion coefficient of base plate glass is between 28-39 × 10-7/ DEG C.For the ease of producing, reduce production cost, the glass as display base plate should have lower temperature of fusion and liquidus temperature.
For the glass substrate of plane display, need to form nesa coating, insulating film, semi-conductor (polysilicon, amorphous silicon etc.) film and metallic membrane by technology such as sputtering, chemical vapor deposition (CVD)s at underlying substrate glass surface, then various circuit and figure is formed by photoetch (Photo-etching) technology, if glass contains alkalimetal oxide (Na
2o, K
2o, Li
2o), in heat treatment process, alkalimetal ion diffuses into deposited semiconductor material, and infringement semiconductor film characteristic, therefore, alkali-free metal oxide answered by glass, it is preferred that both with SiO
2, Al
2o
3, B
2o
3, alkaline earth metal oxide RO(RO=Mg, Ca, Sr) etc. be the alkaline earth aluminates glass of principal constituent.
The strain point of most of silicate glass increases along with the increase of glass-former content and the minimizing of modifier content.But high temperature melting and clarification difficulty can be caused simultaneously, cause refractory corrosion to aggravate, increase energy consumption and production cost.Therefore, improved by component, also will ensure that high temperature viscosity there will not be large lifting while low temperature viscosity is increased, even reduce the best breach being only and improving strain point.
In the course of processing of glass substrate, base plate glass is horizontal positioned, and glass is under Gravitative Loads, and what have to a certain degree is sagging, and sagging degree is directly proportional to the density of glass, be inversely proportional to the Young's modulus of glass.Along with Substrate manufacture is towards the development in large size, slimming direction, in manufacture, the sagging of sheet glass must draw attention.Therefore should design composition, make base plate glass have alap density and Young's modulus high as far as possible.
Universal along with smart mobile phone and panel computer, opens the epoch of intelligent mobile.Mobile phone is in the past confined to communication function, but the performance comprising the smart machine of smart mobile phone and panel computer is at present close with notebook, make to allow people rely on the accessibility of radio communication all the time not in the commercial affairs and the recreation that perform and enjoy higher level.Under such trend, require also to improve constantly to display performance, especially also promote the image quality of intelligent movable equipment, visual performance requriements out of doors, simultaneously in order to alleviate the use burden of portable equipment, weight, lower thickness become inevitable megatrend.Under this trend guides, display panel is to future development that is lightening, ultra high-definition display, and panel making technology manages temperature development to higher height; Monolithic glass is through art breading simultaneously, and it is even thinner that thickness reaches 0.25mm, 0.2mm, 0.1mm.The current mainly chemical reduction of the mode making glass thinning, specifically, use hydrofluoric acid or buffered hydrofluoric acid solution to corrode glass substrate, its thinning principle is as follows:
Main chemical reactions: 4HF+SiO
2=SiF
4+ 2H
2o
Secondary chemical reaction: RO+2H
+=R
2++ H
2o(R represents alkaline-earth metal etc.)
Surface quality after chemical reduction technique and thinning glass substrate and parent glass form certain relation, and existing TFT-LCD base plate glass frequently occurs the bad deficient point such as " pit ", " sags and crests " in chemical reduction process, adds production cost.The glass with high chemical stability has better surface quality after thinning, therefore the TFT-LCD base plate glass of high chemical stability is researched and developed, can reduce the production costs such as second polishing, improving product quality and good article rate, producing for large industrialized has larger benefit.
Along with the development of lightening trend, in G5 generation, G6 generation, G7 generation, G8 generation etc., more advanced lines glass substrate was produced, the glass substrate of horizontal positioned due to deadweight produce sagging, be warped into important subject.For the glass substrate producer, the multiple links such as annealed after glass board material is shaping, cutting, processing, inspection, cleaning, impact is transported in the casing of glass the ability loading, take out and separate by the sagging of sized rectangular glass substrate between processing stand.Counter plate manufacturers, similar problem exists equally.Larger sag or warpage can cause fragmentation rate to improve and CF making technology is reported to the police, and have a strong impact on product yield.If when supporting substrate both sides, two ends, the maximum sag of chain (S) of glass substrate can be expressed as follows:
K is constant, and ρ is density, and E is Young's modulus, and l is for supporting interval, and t is thickness of glass substrate.Wherein, (ρ/E) is the inverse than modulus.Referring to the ratio of elasticity modulus of materials and density than modulus, be also called " than Young's modulus " or " specific rigidity ", is that structure design is to one of important requirement of material.Lighter than material weight under the higher explanation same stiffness of modulus, or under equal in quality, rigidity is larger.From above formula, when l, t mono-timing, ρ diminishes after E strengthens can reduce sag of chain, therefore should make the density that base plate glass tool is as far as possible low and high Young's modulus of trying one's best, namely have as far as possible large ratio modulus.Due to the sharply reduction of thickness, glass after thinning occurs that physical strength reduces, be more easily out of shape.Reduce density, increase than modulus and intensity, reduction glass fragility becomes the factor that glass production person needs emphasis to consider.
In order to obtain still non-alkali glass, utilizing fining gases, from glass melt, expelling the gas produced during glass reaction, in addition when homogenizing fusing, needing the fining gases again utilizing generation, increasing alveolar layer footpath, make it float, take out the small bubble of participation thus.
, the viscosity as the glass melt of glass substrate for plane display device is high, need with higher temperature melting.In the glass substrate of this kind, usually cause Vitrification at 1300-1500 degree, deaeration under the high temperature more than 1500 degree, to homogenize.Therefore, in finings, widely use the As that can produce fining gases in wide temperature range (1300-1700 degree scope)
2o
3.
But, As
2o
3toxicity very strong, when the process of the manufacturing process of glass or cullet, likely contaminate environment and bring healthy problem, its use is restricted.
Once trial antimony clarification carrys out substitute for arsenic clarification.But there is the problem causing environment and healthy aspect in antimony itself.Although Sb
2o
3toxicity unlike As
2o
3such height, but Sb
2o
3remain poisonous.And compared with arsenic, the temperature that antimony produces fining gases is lower, and the validity removing this kind of glass blister is lower.
Summary of the invention
The object of the present invention is to provide a kind of design of components of environmentally friendly, the more perfect flat-panel screens glass substrate of performance, even if provide a kind of finings not use As
2o
3and/or Sb
2o
3, there is not the formula of the glass substrate becoming surface imperfection yet, devise non-alkali glass, utilize the obtained glass substrate of this formula to meet environmental requirement, not containing As
2o
3, Sb
2o
3and compound, this glass is not containing heavy metal barium and compound thereof simultaneously, there is higher chemical stability, there is higher strain point, there is higher Young's modulus, there is higher transmitance, there is lower temperature of fusion, there is lower liquidus temperature, there is lower density, meet flat pannel display industry development trend.Be suitable for merging the multiple molding mode such as glass tube down-drawing, float glass process to manufacture.
The technical solution used in the present invention is: a kind of non-alkali glass, and in described glass, the molar content of each chemical composition is:
SiO
2 68.5-72%，
Al
2O
3 12.6-15%，
B
2O
3 1-3.7%，
MgO 0.1-5.5%，
CaO 4-7%，
ZnO 0.05-4%，
SrO 1-3.5%，
SnO 0.05-0.1%。
The invention has the beneficial effects as follows: 1), the present invention has environment friendly, not containing any hazardous and noxious substances, finings uses tin protoxide SnO, SnO holds facile material, and known nothing is harmful to character, when being used alone it as glass fining agent, there is the temperature range of higher generation fining gases, be applicable to the elimination of this kind of glass blister; 2), by control SiO
2+ Al
2o
3>83%, SrO/R ' O<0.25, (MgO+ZnO)/R ' O>0.35,0.8<R ' O/Al
2o
3<1.2, can make glass have the good characteristics such as higher chemical stability, strain point, Young's modulus and lower temperature of fusion, liquidus temperature simultaneously; 3) glass substrate, produced by means of glass ingredient formula provided by the invention can reach following technical indicator after testing: 10%HF acid solution (22 DEG C/20min) erosion amount <4.8mg/cm2; Be 28 ~ 34 × 10 at the thermal expansivity of 50 ~ 350 degree
-7/ DEG C; Strain point is more than 700 DEG C; Density is less than 2.5g/cm
3, liquidus temperature is lower than 1150 DEG C, and in per kilogram glass substrate, the bubbles number of bubble diameter in > 0.1mm is invisible; 4) the higher SiO, owing to containing in instant component
2with Al
2o
3resultant, ensure that resistance to chemical corrosion is excellent, and a certain proportion of MgO+ZnO that simultaneously arranges in pairs or groups effectively can reduce temperature of fusion, and bring larger space to product line Yield lmproved, the production cost such as fuel, electric power is minimized simultaneously.
Embodiment
A kind of non-alkali glass, in described glass, the molar content of each chemical composition is:
SiO
2 68.5-72%，
Al
2O
3 12.6-15%，
B
2O
3 1-3.7%，
MgO 0.1-5.5%，
CaO 4-7%，
ZnO 0.05-4%，
SrO 1-3.5%，
SnO 0.05-0.1%。
Preferably, SiO
2with Al
2o
3molar content sum be greater than 83%.
Preferably, SrO/(MgO+CaO+ZnO+SrO) <0.25.
Preferably, (MgO+ZnO)/(MgO+CaO+ZnO+SrO) >0.35.
Preferably, 0.8<(MgO+CaO+ZnO+SrO)/Al
2o
3<1.2.
Preferably, Al
2o
3molar content be 13-14.5%.
Preferably, the molar content of ZnO is 0.5-3%.
Preferably, B
2o
3molar content be 1.5-3.5%.
Preferably, SiO
2molar content be 69-71%.
Preferably, the molar content of SrO is 1.5-3.0%.
When implementing, after first the raw material uniform stirring including the corresponding oxide molar percent composition of above-mentioned each glass substrate being mixed, again by mixing raw material melt-processed, stir with platinum rod and discharge bubble and make glass metal homogenizing, then its temperature is reduced to shaping required glass substrate forming temperature range, pass through annealing theory, produce the thickness of the glass substrate that flat-panel screens needs, again simple cold work is carried out to shaping glass substrate, finally test is carried out to the Basic Physical Properties of glass substrate and become qualified product.
In the present invention, SiO
2molar content be 68.5 ~ 72%.SiO
2be glass-former, if content is too low, be unfavorable for the corrosive enhancing of endurance, the coefficient of expansion can be made too high, the easy devitrification of glass; Improve SiO
2content contributes to glass lightweight, and thermal expansivity reduces, and strain point increases, and chemical resistant properties increases, but high temperature viscosity raises, and be unfavorable for like this melting, general kiln is difficult to meet, so SiO
2content be 68.5 ~ 72%, SiO
2preferred molar content be 69-71%.
Al
2o
3molar content be 12.6 ~ 15%, in order to improve the intensity of glass structure, if content is lower than 12.6%, the easy devitrification of glass, is also easily subject to the erosion of extraneous aqueous vapor and chemical reagent.The A1 of high-content
2o
3contribute to strain point of glass, the increasing of bending strength, but easily there is crystallization in too high glass, glass can be made to be difficult to melt, therefore A1 simultaneously
2o
3content be 12.6 ~ 15%, A1
2o
3preferred molar content be 13-14.5%.
B
2o
3content be 1 ~ 3.7mol%, B
2o
3effect more special, it can generate glass separately, is also a kind of well fusing assistant, B under high temperature melting condition
2o
3be difficult to form [BO
4], can high temperature viscosity be reduced, during low temperature B have capture free oxygen formed [BO
4] trend, make structure be tending towards tight, improve the low temperature viscosity of glass, prevent the generation of crystallization.But too much B
2o
3strain point of glass can be made significantly to reduce, therefore B
2o
3content be 1 ~ 3.7%, B
2o
3preferred molar content be 1.5-3.5%.
MgO has and significantly promotes glass Young's modulus and than modulus, reduces high temperature viscosity, makes glass be easy to the feature melted.When alkaline-earth metal resultant is less in alkali-free silicate glass, introduce the network-modifying ion Mg that strength of electric field is larger
2+, easily produce local accumulation effect in the structure, nearest neighbour distance increased.Introduce more Al in this case
2o
3, B
2o
3deng oxide compound, with [AlO
4], [BO
4] state is when existing, because these polyhedrons are with negative electricity, attract subnetwork outer cationic, the degree of gathering of glass, crystallization ability are declined; When alkaline-earth metal resultant is more, network fracture is more serious, introduces MgO, the silicon-oxy tetrahedron of fracture can be made to reconnect and devitrification of glass ability is declined.Therefore to note and Al when adding MgO
2o
3, B
2o
3mixing ratio.Relative to other alkaline earth metal oxides, the existence of MgO can bring the lower coefficient of expansion and density, higher chemically-resistant, strain point and Young's modulus.If MgO is greater than 5.5mol%, glass endurance can be deteriorated, simultaneously the easy devitrification of glass.It is unfavorable that too low content of MgO contrast modulus improves.Therefore its content is 0.1-5.5mol%.
The molar content of CaO is 4 ~ 7%, and calcium oxide is in order to promote melting and the adjustment glass ware forming of glass.If calcium oxide content is less than 4%, cannot reduce the viscosity of glass, content is too much, and glass easily can occur crystallization, and thermal expansivity also can amplitude variation be greatly, unfavorable to successive process greatly.So the content of CaO is 4 ~ 7%.
The molar content of SrO is 1 ~ 3.5%, and strontium oxide is as fusing assistant and prevent glass from occurring crystallization, if content is too much, glass density can be too high, causes the mole overweight of product.So the content of SrO is defined as 1 ~ 3.5%.
The molar content of ZnO is 0.05-4%, and bivalent metal oxide is different to characteristics influence according to its status in the periodic table of elements, can be divided into two classes: a class is the alkaline earth metal oxide being positioned at main group, its ion R
2+there are 8 exoelectron structures; Equations of The Second Kind is positioned at periodictable subgroup (as ZnO, CdO etc.), its ion R
2+have 18 outer electronic structures, both structural states are different from affecting glass property in glass.ZnO can reduce glass high temperature viscosity (as 1500 degree), is conducive to eliminating bubble; Below softening temperature, there is the chemical resistant properties promoting intensity, hardness, increase glass simultaneously, reduce the effect of thermal expansion coefficient of glass.In non-alkali glass system, add appropriate ZnO and contribute to suppressing crystallization, can recrystallization temperature be reduced.In theory, ZnO is in non-alkali glass, after introducing glass as network outer body, general with [ZnO under high temperature
4] form exist, comparatively [ZnO
6] glass structure is more loose, compare under being in the identical condition of high temperature with the glass not containing ZnO, the glass viscosity containing ZnO is less, atomic motion speed is larger, cannot form nucleus, need to reduce temperature further, just be conducive to the formation of nucleus, thus, reduce the crystallization ceiling temperature of glass.ZnO content too much can make the strain point of glass significantly reduce.So the content of ZnO is defined as 0.05-4 % by mole, more preferably, the molar content of ZnO is 0.5-3%.
In the present invention, the tin protoxide SnO of 0.05 ~ 0.1% can also be added with in glass composition, finings when melting as glass or defrother, to improve the melting mole of glass.If content is too much, glass substrate devitrification can be caused, so its addition is no more than 0.1mol%.
Provide the specific embodiment that in formula, each component measures with Mole percent below, see table 1,2:
Table 1
Table 2
As can be seen from table 1, table 2, the present invention fills a prescription obtained that non-alkali glass meets environmental requirement, has the advantages such as high chemical stability, high strain-point, high Young's modulus, low-expansion coefficient, low melting temperature, low liquidus temperature.
Claims (10)
1. a non-alkali glass, is characterized in that: in described glass, the molar content of each chemical composition is:
SiO
2 68.5-72%，
Al
2O
3 12.6-15%，
B
2O
3 1-3.7%，
MgO 0.1-5.5%，
CaO 4-7%，
ZnO 0.05-4%，
SrO 1-3.5%，
SnO 0.05-0.1%。
2. a kind of non-alkali glass according to claim 1, is characterized in that: SiO
2with Al
2o
3molar content sum be greater than 83%.
3. a kind of non-alkali glass according to claim 1, is characterized in that: SrO/(MgO+CaO+ZnO+SrO) <0.25.
4. a kind of non-alkali glass according to claim 1, is characterized in that: (MgO+ZnO)/(MgO+CaO+ZnO+SrO) >0.35.
5. a kind of non-alkali glass according to claim 1, is characterized in that: 0.8<(MgO+CaO+ZnO+SrO)/Al
2o
3<1.2.
6. a kind of non-alkali glass according to claim 1, is characterized in that: Al
2o
3molar content be 13-14.5%.
7. a kind of non-alkali glass according to claim 1, is characterized in that: the molar content of ZnO is 0.5-3%.
8. a kind of non-alkali glass according to claim 1, is characterized in that: B
2o
3molar content be 1.5-3.5%.
9. a kind of non-alkali glass according to claim 1, is characterized in that: SiO
2molar content be 69-71%.
10. a kind of non-alkali glass according to claim 1, is characterized in that: the molar content of SrO is 1.5-3.0%.
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| US20190161388A1 (en) * | 2016-08-05 | 2019-05-30 | AGC Inc. | Alkali-free glass substrate, laminated substrate, and glass substrate production method |
| CN110746111A (en) * | 2019-09-29 | 2020-02-04 | 彩虹显示器件股份有限公司 | Glass substrate and application thereof as glass substrate |
| CN110818251A (en) * | 2019-11-19 | 2020-02-21 | 蚌埠中光电科技有限公司 | Glass composition and preparation method of glass |
| CN114174234A (en) * | 2019-06-26 | 2022-03-11 | 康宁公司 | Alkali-free glass insensitive to thermal history |
| CN117105526A (en) * | 2023-08-28 | 2023-11-24 | 北京工业大学 | High-stability long-service-life substrate glass for liquid crystal display |
| CN117209139A (en) * | 2023-09-19 | 2023-12-12 | 北京工业大学 | Preparation method of alkali-free low-boron high-aluminum substrate glass batch |
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| CN110746111A (en) * | 2019-09-29 | 2020-02-04 | 彩虹显示器件股份有限公司 | Glass substrate and application thereof as glass substrate |
| CN110818251A (en) * | 2019-11-19 | 2020-02-21 | 蚌埠中光电科技有限公司 | Glass composition and preparation method of glass |
| CN117105526A (en) * | 2023-08-28 | 2023-11-24 | 北京工业大学 | High-stability long-service-life substrate glass for liquid crystal display |
| CN117105526B (en) * | 2023-08-28 | 2024-03-19 | 北京工业大学 | High-stability long-service-life substrate glass for liquid crystal display |
| CN117209139A (en) * | 2023-09-19 | 2023-12-12 | 北京工业大学 | Preparation method of alkali-free low-boron high-aluminum substrate glass batch |
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