CN104211300A - Formula of glass substrate with high modular ratio - Google Patents
Formula of glass substrate with high modular ratio Download PDFInfo
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- CN104211300A CN104211300A CN201310378656.2A CN201310378656A CN104211300A CN 104211300 A CN104211300 A CN 104211300A CN 201310378656 A CN201310378656 A CN 201310378656A CN 104211300 A CN104211300 A CN 104211300A
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- glass substrate
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Abstract
The invention discloses a formula of a glass substrate with a high modular ratio. The formula is characterized by comprising the following components in mole percentage: 66% to 74% of SiO2, 11% to 16% of Al2O3, 2% to 9.5% of B2O3, 1% to 6.5% of MgO, 3% to 7% of CaO, 0.5% to 4% of SrO, 0.01 to 1.5% of Y2O3, and 0.01% to 0.15% of SnO. The glass substrate, which is made according to the provided formula, has the following technical parameters: a thermal expansion coefficient of 28-36*10<-7>/DEG C at a temperature of 50 to 350 DEG C; a strain point greater than 720 DEG C; a density less than 2.48 g/cm3, a liquidus temperature less than 1150 DEG C, a modular ratio greater than 33 GPa/(g/cm3), an elasticity modulus greater than 82 GPa, and a melting temperature (a corresponding temperature corresponding to a viscosity of 200 poises) less than 1650 DEG C.
Description
Technical field
The invention belongs to glass manufacturing area, relate to a kind of high specific modulus and intensity, reduction glass fragility be widely used in make flat panel display device and planar lighting device, be particularly suitable for the formula of low-temperature polysilicon film transistor liquid-crystal display (LTPS TFT-LCD) base plate glass, organic electro-luminescent display (OEL) base plate glass and organic electric-excitation luminescent illuminating device base plate glass.
Background technology
Along with the fast development of photovoltaic industry, the demand of various display device is constantly increased, 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.At present, TFT 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.
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.
For the glass substrate of plane display, need by sputtering, the technology such as chemical vapor deposition (CVD) form nesa coating at underlying substrate glass surface, insulating film, semi-conductor (polysilicon, amorphous silicon etc.) film and metallic membrane, then various circuit and figure is formed by photoetch (Photo-etching) technology, if glass contains alkalimetal oxide (Na2O, K2O, Li2O), in heat treatment process, alkalimetal ion diffuses into deposited semiconductor material, infringement semiconductor film characteristic, therefore, alkali-free metal oxide answered by glass, it is preferred that both with SiO2, Al2O3, B2O3, alkaline earth metal oxide RO(RO=Mg, Ca, etc. Sr) be the alkaline earth aluminoborosilicate glass of principal constituent.
Plane display is towards two large future developments: be on the one hand maximize, lightening; 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 color film 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.
On the other hand, 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 the image quality of intelligent movable equipment, visual performance requriements out of doors are also promoted.Under this trend guides, display panel is to future development that is lightening, ultra high-definition display, and panel making technology thinks higher height reason temperature development; Monolithic glass is through art breading simultaneously, and it is even thinner that thickness reaches 0.25mm, 0.2mm.Due to the sharply reduction of thickness, glass after thinning occurs that physical strength reduces, be more easily out of shape.Increase than modulus and intensity, reduction glass fragility becomes the factor that glass production person needs emphasis to consider.
Summary of the invention
The object of the present invention is to provide a kind of have high elastic coefficient, high strain-point, high resistance to chemicals corrodibility, low density, low-expansion coefficient, low liquidus temperature, alkali-free metal, not containing the aluminium borosilicate glass of high specific modulus of any hazardous and noxious substances, devise the formula of the glass substrate of high specific modulus, apply formula of the present invention and can produce former of the glass substrate meeting above-mentioned property indices.
The technical solution used in the present invention is: a kind of formula of glass substrate of high specific modulus, and key is: in above-mentioned glass substrate, the molar percentage of each moiety is respectively:
SiO
2 66%~74%，
Al
2O
3 11%~16%，
B
2O
3 2%~9.5%，
MgO 1~6.5%，
CaO 3~7%，
SrO 0.5~4%，
Y
2O
3 0.01%~1.5%，
SnO 0.01~0.15%。
In the present invention, one of most critical is Y
2o
3young's modulus and the strain point of glass can be significantly improved, the temperature of fusion of glass can be reduced simultaneously.In the present invention, Y
2o
3content be 0.01 ~ 1.5mol%.Y
2o
3when content is more than 1.5mol%, unfavorable to devitrification of glass stability, and too increase glass cost, Y simultaneously
2o
3there is larger proportion, add and density too much can be caused to increase, thus the lifting of restriction ratio modulus.Therefore its scope is 0.01 ~ 5mol%, preferably 0.1 ~ 1.5mol%; Two are strontium oxides as fusing assistant and prevent glass from occurring crystallization, if content is too much, glass density can be too high, causes the quality of product overweight, is unfavorable for improving, so the content of SrO is defined as 0.4 ~ 4mol% than modulus; Three is that 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
+, 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 6.5mol%, 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 1 ~ 6.5mol%.
The invention has the beneficial effects as follows: the glass substrate produced by means of glass ingredient formula provided by the invention can reach following technical indicator after testing:
Be 28 ~ 36 × 10 at the thermal expansivity of 50 ~ 350 degree
-7/ DEG C; Strain point is more than 720 DEG C, and density is less than 2. 48g/cm
3, liquidus temperature is lower than 1150 degree.
With the Basic Physical Properties of top glass substrate can be stable reach:
Than modulus higher than 33GPa/ (g/cm
3), Young's modulus is higher than 82GPa, and density is lower than 2.48 g/cm
3, thermal expansivity is lower than 36 × 10
-7/ DEG C (50 ~ 350 DEG C), strain point temperature is higher than 720 DEG C, and temperature of fusion (temperature corresponding when viscosity is 200 pool) is lower than 1650 DEG C, and liquidus temperature is lower than 1150 DEG C, and liquidus viscosity is greater than 100,000 pool.
Embodiment
A formula for the glass substrate of high specific modulus, importantly: in above-mentioned glass substrate, the molar percentage of each moiety is respectively:
SiO
2 66%~74%，
Al
2O
3 11%~16%，
B
2O
3 2%~9.5%，
MgO 1~6.5%，
CaO 3~7%，
SrO 0.5~4%，
Y
2O
3 0.01%~1.5%，
SnO 0.01~0.15%。
SiO in this recipe ingredient
2content be 66 ~ 74mol%.SiO
2be glass-former, if content is lower than 66%, 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, and increases than modulus, but high temperature viscosity raises, and be unfavorable for like this melting, general kiln is difficult to meet, so SiO
2content be 66 ~ 74mol%.
Al
2o
3content be 11 ~ 16mol%, in order to improve the intensity of glass structure, if content is lower than 11%, 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, bending strength, increasing than modulus, but easily there is crystallization in too high glass, glass can be made to be difficult to melt, therefore A1 simultaneously
2o
3content be 11 ~ 16mol%.
B
2o
3content be 2 ~ 9.5mol%, 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 2 ~ 9.5mol%.
The content of CaO is 3 ~ 7mol%, and calcium oxide is in order to promote melting and the adjustment glass ware forming of glass.If calcium oxide content is less than 3mol%, 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 3 ~ 7mol%.
The content of SrO is 0.5 ~ 4mol%, 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 quality of product overweight, is unfavorable for improving than modulus.So the content of SrO is defined as 0.5 ~ 4mol%.
Finings when SnO melts as glass or defrother, to improve the melting quality of glass.If content is too much, glass substrate devitrification can be caused, so its addition is no more than 0.15mol%.
Described Y
2o
3molar percentage be 0.1 ~ 1.0mol%.
Described B
2o
3molar percentage be 4 ~ 8.5mol%.
The molar percentage of described MgO is 1.5 ~ 6mol%.
Described MgO and Al
2o
3molar percentage sum between 14% ~ 22%.
Al
2o
3/ (MgO+CaO+SrO+Y
2o
3) value be greater than 0.8.
SrO/ (MgO+CaO+SrO+Y
2o
3) value be less than 0.3.
SiO
2with Al
2o
3molar percentage sum be greater than 81%.
The present invention is when implementing, see table 1, 2, according to table 1, each Example formulations ratio in 2 gets raw material, according to the composition Homogeneous phase mixing in addition of correspondence, again by the temperature of 1600 ~ 1640 DEG C, high-temperature digestion 14 ~ 20 hours in platinum crucible, in fusion processes, stir by platinum stirring rod, to promote the homogeneity of each composition in glass, 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 the Basic Physical Properties of glass substrate is tested.Thermal expansivity, strain point, liquidus temperature, high temperature viscosity, Young's modulus, density can be obtained respectively, than the characteristic data such as modulus, optical transmittance, be presented at respectively in table 1, table 2.
The technical measurement that glass property listed by embodiment in table 1,2 is commonly used according to glass art.Thermal linear expansion coefficient adopts horizontal expander instrument to measure, and the thermal linear expansion coefficient (CTE) within the scope of 50-350 degree represents with × 10-7/ DEG C; Strain point adopts the test of curved beam viscometer, and unit is with DEG C to represent; Density adopts Archimedes method to measure, and unit is g/cm3; High temperature viscosity adopts drum type brake to rotate high temperature viscosimeter and measures, and utilizes VFT formulae discovery temperature of fusion, and unit is DEG C (temperature when temperature of fusion refers to that glass melt viscosity reaches 200 pool); Liquidus temperature adopts normal gradients stove to measure, and unit is DEG C; Young's modulus adopts resonant method test; Transmitance adopts ultraviolet-visible spectrophotometer test, and unit is %.
Provide the specific embodiment (table 1, table 2) that in formula, each component measures with molar percentage below:
Table 1
Table 2
Can be proved again by each embodiment: the glass substrate produced by means of glass ingredient principle provided by the invention can reach following technical indicator after testing: be 28 ~ 36 × 10 at the thermal expansivity of 50 ~ 350 degree
-7/ DEG C; Strain point is more than 720 DEG C, and density is less than 2.48g/cm
3, liquidus temperature lower than 1150 degree, than modulus higher than 33GPa/ (g/cm
3), Young's modulus is higher than 82GPa, and temperature of fusion (temperature corresponding when viscosity is 200 pool) is lower than 1650 DEG C.
Claims (8)
1. a formula for the glass substrate of high specific modulus, is characterized in that: in above-mentioned glass substrate, the molar percentage of each moiety is respectively:
SiO
2 66%~74%，
Al
2O
3 11%~16%，
B
2O
3 2%~9.5%，
MgO 1~6.5%，
CaO 3~7%，
SrO 0.5~4%，
Y
2O
3 0.01%~1.5%，
SnO 0.01~0.15%。
2. the formula of the glass substrate of a kind of high specific modulus according to claim 1, is characterized in that: described Y
2o
3molar percentage be 0.1 ~ 1.0mol%.
3. the formula of the glass substrate of a kind of high specific modulus according to claim 1, is characterized in that: described B
2o
3molar percentage be 4 ~ 8.5mol%.
4. the formula of the glass substrate of a kind of high specific modulus according to claim 1, is characterized in that: the molar percentage of described MgO is 1.5 ~ 6mol%.
5. the formula of the glass substrate of a kind of high specific modulus according to claim 1, is characterized in that: described MgO and Al
2o
3molar percentage sum between 14% ~ 22%.
6. the formula of the glass substrate of a kind of high specific modulus according to claim 1, is characterized in that: Al
2o
3/ (MgO+CaO+SrO+Y
2o
3) value be greater than 0.8.
7. the formula of the glass substrate of a kind of high specific modulus according to claim 1, is characterized in that: SrO/ (MgO+CaO+SrO+Y
2o
3) value be less than 0.3.
8. the formula of the glass substrate of a kind of high specific modulus according to claim 1, is characterized in that: SiO
2with Al
2o
3molar percentage sum be greater than 81%.
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|---|---|---|---|
| CN201310378656.2A CN104211300A (en) | 2013-08-27 | 2013-08-27 | Formula of glass substrate with high modular ratio |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310378656.2A CN104211300A (en) | 2013-08-27 | 2013-08-27 | Formula of glass substrate with high modular ratio |
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| CN104211300A true CN104211300A (en) | 2014-12-17 |
Family
ID=52093266
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017091981A1 (en) * | 2015-12-01 | 2017-06-08 | Kornerstone Materials Technology Company, Ltd. | Low-boron, barium-free, alkaline earth aluminosilicate glass and its applications |
| JP2019032918A (en) * | 2017-08-08 | 2019-02-28 | 日本電気硝子株式会社 | Glass substrate for magnetic recording medium |
| CN114349336A (en) * | 2022-01-13 | 2022-04-15 | 浙江大学 | Low-expansion borosilicate transparent colored glaze and preparation method and application thereof |
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| CN102690058A (en) * | 2012-04-01 | 2012-09-26 | 东旭集团有限公司 | Silicate glass substrate used for flat panel display |
| US20130037105A1 (en) * | 2011-08-12 | 2013-02-14 | Bruce Gardiner Aitken | Fusion formable alkali-free intermediate thermal expansion coefficient glass |
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| JP2001348247A (en) * | 2000-05-31 | 2001-12-18 | Asahi Glass Co Ltd | Alkaline-free glass |
| CN103261110A (en) * | 2010-11-30 | 2013-08-21 | 康宁股份有限公司 | Glass articles/materials for use as touchscreen substrates |
| US20130037105A1 (en) * | 2011-08-12 | 2013-02-14 | Bruce Gardiner Aitken | Fusion formable alkali-free intermediate thermal expansion coefficient glass |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017091981A1 (en) * | 2015-12-01 | 2017-06-08 | Kornerstone Materials Technology Company, Ltd. | Low-boron, barium-free, alkaline earth aluminosilicate glass and its applications |
| CN108349785A (en) * | 2015-12-01 | 2018-07-31 | 科立视材料科技有限公司 | Low boron barium-free alkaline earth aluminates glass and its application |
| JP2018535918A (en) * | 2015-12-01 | 2018-12-06 | コーナーストーン・マテリアルズ・テクノロジー・カンパニー・リミテッドＫｏｒｎｅｒｓｔｏｎｅ Ｍａｔｅｒｉａｌｓ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏｍｐａｎｙ， Ｌｔｄ． | Low boron and barium free alkaline earth aluminosilicate glass and its applications |
| CN108349785B (en) * | 2015-12-01 | 2021-03-26 | 科立视材料科技有限公司 | Low-boron barium-free alkaline earth aluminosilicate glass and application thereof |
| JP2019032918A (en) * | 2017-08-08 | 2019-02-28 | 日本電気硝子株式会社 | Glass substrate for magnetic recording medium |
| JP7276645B2 (en) | 2017-08-08 | 2023-05-18 | 日本電気硝子株式会社 | Glass substrate for magnetic recording media |
| CN114349336A (en) * | 2022-01-13 | 2022-04-15 | 浙江大学 | Low-expansion borosilicate transparent colored glaze and preparation method and application thereof |
| CN114349336B (en) * | 2022-01-13 | 2022-09-27 | 浙江大学 | Low-expansion borosilicate transparent colored glaze and preparation method and application thereof |
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Application publication date: 20141217 |
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