CN117447074A - Alkali-free high-elastic modulus borosilicate glass composition, and preparation method and application thereof - Google Patents
Alkali-free high-elastic modulus borosilicate glass composition, and preparation method and application thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 239000005388 borosilicate glass Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title description 6
- 239000011521 glass Substances 0.000 claims abstract description 135
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 23
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 9
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 13
- 239000004973 liquid crystal related substance Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000005482 strain hardening Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 9
- 238000006124 Pilkington process Methods 0.000 abstract description 4
- 229910052787 antimony Inorganic materials 0.000 abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 abstract description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052788 barium Inorganic materials 0.000 abstract description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 239000008395 clarifying agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
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- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133302—Rigid substrates, e.g. inorganic substrates
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
- G02F1/133331—Cover glasses
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention relates to an alkali-free high elastic modulus borosilicate glass composition consisting of a composition having the following ranges in mol%: siO (SiO) 2 59～69；B 2 O 3 5～11.5；Al 2 O 3 8～15.5；CaO 2.5～8.5；MgO 3.5～7.5；SrO 4～8.5；Y 2 O 3 0.1～0.6；Bi 2 O 3 0.05～0.15；ZrO 2 0.5～1.5；SnO 2 0.16 to 0.40. The invention is suitable for large-scale industrial production of high-generation electronic glass, including float method, overflow method and other technological production modes; the alkali-free high-elastic modulus borosilicate glass composition formula belongs to an environment-friendly system, and the glass composition does not contain any heavy metals such as barium, arsenic, antimony and the like, so that the glass substrate is lighter and environment-friendly; the alkali-free borosilicate glass composition with high elastic modulus has the elastic modulus higher than 82GPa and strainThe point temperature is above 690 ℃, and the density is less than 2.55g/cm 3 The thermal expansion coefficient at 20-300 ℃ is (35-39). Times.10 ‑7 The melting temperature is 1615-1640 ℃ and meets the performance requirement of high-generation substrate glass.
Description
Technical Field
The invention belongs to the technical field of high-generation electronic display glass, and particularly relates to an alkali-free borosilicate glass composition with high elastic modulus, and a preparation method and application thereof.
Background
With the development of information display technology, display panels are gradually developed in the direction of energy saving, environmental protection, weight saving, size increasing and thinning. In the high-generation large-size glass substrate, the size of the G8.5 generation glass substrate is 2500 x 2200mm, the size of the G10.5 generation glass substrate is 3370 x 2940mm, the size of the G11 generation glass substrate is 3320 x 3000mm, and the thickness of the plate width is less than 0.5mm.
For glass substrate manufacturers, higher requirements are put on substrate glass properties, and the selected substrate glass composition is required for producing glass substrate raw sheets with larger sizes, so that not only can the quality of liquid crystal substrates and various property requirements put on the preparation process be met, but also the glass substrate raw sheets with larger sizes are suitable for production. The sagging of large-sized glass sheets, which is subjected to multiple steps such as annealing, cutting, processing, inspection, cleaning, etc., after the glass sheet is formed, affects the ability to load, unload, and separate glass sheets in a box that carries the glass between processing points, and similar problems exist for panel manufacturers, so that high-generation electronic display glass substrates should have as low a density and as high an elastic modulus as possible.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides an alkali-free borosilicate glass composition with high elastic modulus, a preparation method and application thereof, which can solve the technical problems of low elastic modulus and sagging and easy deformation of the prior high-generation large-size electronic glass substrate, and the specific technical scheme is as follows:
the invention provides an alkali-free high elastic modulus borosilicate glass composition, which consists of the following components in mol percent:
SiO 2 59～69；B 2 O 3 5～11.5；Al 2 O 3 8～15.5；CaO 2.5～8.5；MgO 3.5～7.5；SrO 4～8.5；Y 2 O 3 0.1～0.6；Bi 2 O 3 0.05～0.15；ZrO 2 0.5～1.5；SnO 2 0.16～0.40。
as a preferred embodiment of the present invention, the glass composition consists of a composition having the following range in mole%:
SiO 2 62～67；B 2 O 3 6～9.5；Al 2 O 3 9～14.5；CaO 3.5～7.5；MgO 4.5～7；SrO 5～8；Y 2 O 3 0.15～0.45；Bi 2 O 3 0.05～0.1；ZrO 2 0.6～1.2；SnO 2 0.2～0.36。
as a preferred embodiment of the present invention, the glass composition comprises the following components in percentage by weight: b (B) 2 O 3 /(SiO 2 +Al 2 O 3 )≤0.16。
As a preferred embodiment of the present invention, the glass composition comprises the following components in percentage by weight: al (Al) 2 O 3 /(SiO 2 +Al 2 O 3 )≥0.10。
As a preferred embodiment of the present invention, the glass composition comprises the following components in percentage by weight: caO/(CaO+MgO+SrO) is more than or equal to 0.18 and less than or equal to 0.55.
As a preferred embodiment of the present invention, the glass composition comprises the following components in percentage by weight: zrO of 0.45.ltoreq. 2 /(ZrO 2 +Y 2 O 3 )≤0.9。
As a preferred embodiment of the present invention, the glass composition has a thermal expansion coefficient of (35-39). Times.10 at 20-300 DEG C -7 The temperature of the strain point is higher than 690 ℃, the elastic modulus is higher than 82GPa, and the density is lower than 2.55g/cm 3 。
The invention also provides a preparation method of the alkali-free high-elasticity-modulus borosilicate glass composition, which comprises the following steps:
step S1: mixing and stirring the raw materials corresponding to the oxide mole percentage components uniformly;
step S2: melting and processing the uniformly mixed raw materials, stirring the raw materials by using a platinum rod to discharge bubbles, and homogenizing glass liquid;
step S3: the temperature of the homogenized glass liquid is reduced to a temperature range required by the molding of the glass substrate, and the thickness of the glass substrate required by the liquid crystal display is manufactured through annealing treatment;
step S4: cold working the formed glass substrate;
step S5: and testing the basic physical characteristics of the liquid crystal glass substrate after the cold processing treatment, and judging whether the liquid crystal glass substrate is qualified or not.
In step S2, the melting temperature at the time of melt processing of the uniformly mixed raw materials is 1615 to 1640 ℃.
The invention also provides application of the alkali-free high-elastic modulus borosilicate glass composition in large-size liquid crystal display glass.
The beneficial effects of the invention are as follows:
1. the alkali-free high-elastic modulus borosilicate glass composition is suitable for large-scale industrial production of high-generation electronic glass, including process production modes such as a float method and an overflow method;
2. the alkali-free high-elastic modulus borosilicate glass composition formula belongs to an environment-friendly system, and the glass composition does not contain any heavy metals such as barium, arsenic, antimony and the like, so that the glass substrate is lighter and environment-friendly;
3. the alkali-free borosilicate glass composition with high elastic modulus has the elastic modulus higher than 82GPa, the strain point temperature higher than 690 ℃ and the density less than 2.55g/cm 3 The thermal expansion coefficient at 20-300 ℃ is (35-39). Times.10 -7 At a temperature of 1615-1 DEG C640 ℃ and meets the performance requirements of high-generation substrate glass.
Drawings
FIG. 1 shows a flow chart of a method of making an alkali-free high modulus borosilicate glass composition of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to solve the technical problems in the background art, the following alkali-free borosilicate glass composition with high elastic modulus is provided:
in the present invention, the term mol% is understood as the percentage mass content in mol.
An alkali-free high modulus borosilicate glass composition consisting of a composition having the following range in mole percent (mol%):
SiO 2 59～69；B 2 O 3 5～11.5；Al 2 O 3 8～15.5；CaO 2.5～8.5；MgO 3.5～7.5；SrO 4～8.5；Y 2 O 3 0.1～0.6；Bi 2 O 3 0.05～0.15；ZrO 2 0.5～1.5；SnO 2 0.16～0.40。
preferably, the glass composition consists of a composition having the following range in mole percent (mol%):
SiO 2 62～67；B 2 O 3 6～9.5；Al 2 O 3 9～14.5；CaO 3.5～7.5；MgO 4.5～7；SrO 5～8；Y 2 O 3 0.15～0.45；Bi 2 O 3 0.05～0.1；ZrO 2 0.6～1.2；SnO 2 0.2～0.36。
preferably, the glass composition has the following proportions: b (B) 2 O 3 /(SiO 2 +Al 2 O 3 )≤0.16。
Preferably, the glass composition has the following proportions: al (Al) 2 O 3 /(SiO 2 +Al 2 O 3 )≥0.10。
Preferably, the glass composition has the following proportions: caO/(CaO+MgO+SrO) is more than or equal to 0.18 and less than or equal to 0.55.
Preferably, the glass composition has the following proportions: zrO of 0.45.ltoreq. 2 /(ZrO 2 +Y 2 O 3 )≤0.9。
Preferably, the glass composition has a coefficient of thermal expansion of (35-39). Times.10 at 20-300 DEG C -7 The temperature of the strain point is higher than 690 ℃, the elastic modulus is higher than 82GPa, and the density is lower than 2.55g/cm 3 。
By adopting the technical scheme, the alkali-free high-elastic modulus borosilicate glass composition is suitable for large-scale industrial production of high-generation electronic glass, including the process production modes of a float method, an overflow method and the like;
the alkali-free high-elastic modulus borosilicate glass composition formula belongs to an environment-friendly system, and the glass composition does not contain any heavy metals such as barium, arsenic, antimony and the like, so that the glass substrate is lighter and environment-friendly;
the alkali-free high-elastic modulus borosilicate glass composition has an elastic modulus higher than 82GPa, a strain point temperature higher than 690 ℃ and a density less than 2.55g/cm 3 The linear expansion coefficient at 20-300 ℃ is (35-39). Times.10 -7 The melting temperature is 1615-1640 ℃ and meets the performance requirement of high-generation substrate glass.
In the present invention, siO 2 59 to 69 mol% of a glass-forming oxide, siO 2 With silicon oxygen tetrahedra [ SiO ] 4 ]The structural units of the glass form an irregular network structure, and become a framework of the glass. If SiO in glass 2 The content is more than 69 mol percent, the viscosity of the glass can be correspondingly increased, and the melting is difficult; and if SiO 2 When the content is less than 59 mol%, the thermal expansion, elastic modulus and strain point of the glass are correspondingly reduced, and the performance index requirements in the invention cannot be satisfied.
B 2 O 3 Also a glass network forming body, can independently form glass, and can reduce thermal expansionThe expansion coefficient reduces the viscosity of the glass at a high temperature stage, and simultaneously plays a role in fluxing, and accelerates the melting and clarification of the glass liquid. B in the invention 2 O 3 5 to 11.5 mol% of B in the glass 2 O 3 When the content is more than 11.5 mol%, the strain point of the glass is lowered, and the phase separation tendency of the glass is increased, B 2 O 3 The content is less than 5 mol percent, the glass viscosity cannot be effectively reduced in a high-temperature stage, and the fluxing effect cannot be achieved.
Al 2 O 3 As network intermediate oxide for increasing strain point and elastic modulus of glass, al 2 O 3 When the content of the (B) is too high, the melting temperature of the glass can be increased, the viscosity of the glass is increased, and the clarification and homogenization of glass liquid are not facilitated; al (Al) 2 O 3 When the content of (C) is too low, devitrification and molding of the glass are difficult, and comprehensively considering the Al of the invention 2 O 3 The suitable range of (2) is 8 to 15.5 mol%.
In the invention, B 2 O 3 With boron-oxygen triangle [ BO ] 3 ]And boron oxygen tetrahedra [ BO ] 4 ]Too much B is present as structural units 2 O 3 Resulting in a glass network structure [ BO 3 ]The triangular body structure units are increased, so that the strain point and melting temperature of the glass are reduced; adding cationic Al with the same coordination number 3+ Substituted Si 4+ After that, since the Al-O bond is stronger than the Si-O bond, at the same time [ AlO 4 ]The tetrahedral structure exists in the network, plays a role in repairing the network, ensures that the network of the glass is more complete, and ensures that the elastic modulus of the glass is increased and the thermal expansion coefficient is reduced. Thus, siO 2 、B 2 O 3 、Al 2 O 3 The three components interact together to determine the network structure of the glass, and directly influence the strain point, the elastic modulus and the melting temperature of the glass. When Al is 2 O 3 /(SiO 2 +Al 2 O 3 )≥0.10，B 2 O 3 /(SiO 2 +Al 2 O 3 ) The elastic modulus of the glass is higher than 82GPa, the strain point temperature is higher than 690 ℃, and the melting temperature is lower than 1640 ℃ and is less than or equal to 0.16.
CaO promotes the clarification and homogenization of the glass liquid by reducing the viscosity of the glass liquid at high temperature, plays a role of fluxing, the content of CaO is more than 8.5 mol percent, the thermal expansion of the glass is obviously increased, and the devitrification tendency of the glass is increased; the CaO content is less than 2.5 mol%, which does not act as a fluxing agent and increases the viscosity of the glass, thereby making glass melting difficult, and in the invention, the CaO content is between 2.5 mol% and 8.5 mol%.
MgO can replace part of CaO, so that the hardening speed of the glass is slowed down, and the forming performance of the glass is improved; srO can increase the chemical stability and resistance to devitrification of the glass while affecting the glass melting process. Thus, the MgO of the present invention is suitably in the range of 3.5 to 7.5 mol%; a suitable range for SrO is 4 mol% to 8.5 mol%.
In the invention, caO, mgO, srO belongs to alkaline earth metal oxide, wherein the alkaline earth metal oxide is an external glass network body and does not participate in the network structure of glass, and CaO, mgO, srO interaction provides free oxygen for the network formation body, so that the performance of the glass is further affected. Therefore, the CaO/(CaO+MgO+SrO) is limited to be less than or equal to 0.18 and less than or equal to 0.55, so that the density and viscosity of the glass are reduced, and the melting temperature is 1615-1640 ℃.
Bi 2 O 3 The viscosity of the glass can be obviously reduced, the melting temperature of the glass is reduced, but the addition amount is too large, the glass is easy to color, and the Bi in the invention 2 O 3 The suitable range of (2) is 0.05 mol% to 0.15 mol%.
Y 2 O 3 Can obviously improve the elastic modulus and the strain point of the glass and reduce the melting temperature of the glass, and in the invention, Y 2 O 3 The content of (C) is suitably in the range of 0.1 mol% to 0.6 mol%, Y 2 O 3 When the content exceeds 0.6 mol%, the glass is liable to devitrify, and the production cost of the glass is increased.
Oxide ZrO 2 And Y is equal to 2 O 3 As such, the elastic modulus of the glass can be significantly increased while the melting temperature of the glass is reduced, and excessive amounts increase the density of the glass. In the present invention, zrO 2 The content of (C) is 0.5 mol% to 1.5 mol%When the content exceeds 1.5 mol%, the glass density and manufacturing cost are greatly increased. Thus, zrO is not less than 0.45% by limiting the amount of ZrO in the present invention 2 /(ZrO 2 +Y 2 O 3 ) Not more than 0.90, the density and manufacturing cost of the glass can not be increased while the elastic modulus of the glass is increased and the melting temperature is reduced.
SnO 2 The glass material is added as a clarifying agent, oxygen can be discharged at high temperature, the released oxygen is diffused into bubbles of surrounding glass liquid, other bubbles in the combined glass liquid are absorbed, the diameters of the bubbles are increased and float upwards, and finally the bubbles are discharged to achieve the purpose of clarifying, so that the glass material is used for eliminating the bubbles of the glass liquid, the reaction temperature is above 1400 ℃, the glass material is a relatively ideal high-temperature clarifying agent, and the excessive addition is unfavorable for eliminating the bubbles, the SnO of the invention 2 The suitable content of (2) is 0.16 mol% to 0.40 mol%.
The glass oxide of the invention contains SiO with specific content 2 、B 2 O 3 、Al 2 O 3 、CaO、MgO、SrO、Y 2 O 3 、Bi 2 O 3 、ZrO 2 、SnO 2 Limit B 2 O 3 /(SiO 2 +Al 2 O 3 )≤0.16、Al 2 O 3 /(SiO 2 +Al 2 O 3 )≥0.10、0.18≤CaO/(CaO+MgO+SrO)≤0.55、0.45≤ZrO 2 /(ZrO 2 +Y 2 O 3 ) Less than or equal to 0.9; can solve the problems that the elastic modulus is higher than 82GPa, the strain point temperature is higher than 690 ℃, and the density is less than 2.55g/cm 3 At the same time, satisfies the thermal expansion coefficient of (35-39) x 10 at 20-300 DEG C -7 The melting temperature is 1615-1640 ℃.
The present invention also provides, in combination with the illustration of fig. 1, a method for preparing an alkali-free high elastic modulus borosilicate glass composition as described above, comprising the steps of:
step S1: mixing and stirring the raw materials corresponding to the oxide mole percentage components uniformly;
step S2: melting and processing the uniformly mixed raw materials, stirring the raw materials by using a platinum rod to discharge bubbles, and homogenizing glass liquid;
step S3: the temperature of the homogenized glass liquid is reduced to a temperature range required by the molding of the glass substrate, and the thickness of the glass substrate required by the liquid crystal display is manufactured through annealing treatment;
step S4: cold working the formed glass substrate;
step S5: and testing the basic physical characteristics of the liquid crystal glass substrate after the cold processing treatment, and judging whether the liquid crystal glass substrate is qualified or not.
Preferably, in step S2, the melting temperature at the time of melt processing of the uniformly mixed raw materials is 1615 to 1640 ℃.
The invention also provides application of the alkali-free borosilicate glass composition with high elastic modulus in large-size liquid crystal display glass.
The performance test of the present invention is compared as follows:
in the following examples and comparative examples, the elastic modulus was measured by the resonance method;
wherein, the strain point of the glass is measured by a wire drawing method, and the reference standard is measured by a method specified by ASTM C336;
density testing was measured by the Archimedes method in g/cm 3 ；
The thermal expansion coefficient is the average linear thermal expansion coefficient measured at 30-300 ℃ and measured by a vertical thermal expansion instrument, and the reference standard is the method specified in ISO 7991.
Specific examples of the components of the alkali-free boroaluminosilicate glass in mole percent are given below (see tables 1 and 2 for details)
Table 1:
table 2:
as can be seen from the examples in tables 1 and 2, compared with the comparative example, the alkali-free high-elasticity modulus borosilicate glass composition for the high-generation electronic display glass provided by the invention has the elasticity modulus higher than 82GPa, the strain point temperature higher than 690 ℃ and the density lower than 2.55g/cm 3 The thermal expansion coefficient at 20-300 ℃ is (35-39). Times.10 -7 The melting temperature is 1615-1640 ℃, so that the performance requirement of the high-generation substrate glass is well met, and the glass is very suitable for float process production.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. An alkali-free high modulus borosilicate glass composition characterized in that the glass composition consists of a composition having the following range in mole percent:
SiO 2 59～69；B 2 O 3 5～11.5；Al 2 O 3 8～15.5；CaO 2.5～8.5；MgO 3.5～7.5；SrO 4～8.5；Y 2 O 3 0.1～0.6；Bi 2 O 3 0.05～0.15；ZrO 2 0.5～1.5；SnO 2 0.16～0.40。
2. the alkali-free high modulus borosilicate glass composition according to claim 1, wherein said glass composition comprises a composition having the following range in mole percent:
SiO 2 62～67；B 2 O 3 6～9.5；Al 2 O 3 9～14.5；CaO 3.5～7.5；MgO 4.5～7；SrO 5～8；Y 2 O 3 0.15～0.45；Bi 2 O 3 0.05～0.1；ZrO 2 0.6～1.2；SnO 2 0.2～0.36。
3. an alkali-free high modulus borosilicate glass composition according to claim 1 or 2, wherein said glass compositionThe ratio of (2) is as follows: b (B) 2 O 3 /(SiO 2 +Al 2 O 3 )≤0.16。
4. An alkali-free high modulus borosilicate glass composition according to claim 1 or 2, wherein said glass composition comprises the following proportions: al (Al) 2 O 3 /(SiO 2 +Al 2 O 3 )≥0.10。
5. An alkali-free high modulus borosilicate glass composition according to claim 1 or 2, wherein said glass composition comprises the following proportions: caO/(CaO+MgO+SrO) is more than or equal to 0.18 and less than or equal to 0.55.
6. An alkali-free high modulus borosilicate glass composition according to claim 1 or 2, wherein said glass composition comprises the following proportions: zrO of 0.45.ltoreq. 2 /(ZrO 2 +Y 2 O 3 )≤0.9。
7. An alkali-free high modulus borosilicate glass composition according to claim 1 or 2, wherein: the glass composition has a thermal expansion coefficient of (35-39) x 10 at 20-300 DEG C -7 The temperature of the strain point is higher than 690 ℃, the elastic modulus is higher than 82GPa, and the density is lower than 2.55g/cm 3 。
8. A method of making the alkali-free high modulus borosilicate glass composition according to claim 1 or 2, comprising the steps of:
step S1: mixing and stirring the raw materials corresponding to the oxide mole percentage components uniformly;
step S2: melting and processing the uniformly mixed raw materials, stirring the raw materials by using a platinum rod to discharge bubbles, and homogenizing glass liquid;
step S3: the temperature of the homogenized glass liquid is reduced to a temperature range required by the molding of the glass substrate, and the thickness of the glass substrate required by the liquid crystal display is manufactured through annealing treatment;
step S4: cold working the formed glass substrate;
step S5: and testing the basic physical characteristics of the liquid crystal glass substrate after the cold processing treatment, and judging whether the liquid crystal glass substrate is qualified or not.
9. The method of making an alkali-free high modulus borosilicate glass composition according to claim 8, wherein: in step S2, the melting temperature at the time of melting the uniformly mixed raw materials is 1615-1640 ℃.
10. Use of the alkali-free high elastic modulus borosilicate glass composition according to claim 1 or 2 in large size liquid crystal display glass.
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| CN113412243A (en) * | 2019-02-07 | 2021-09-17 | Ａｇｃ株式会社 | Alkali-free glass |
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| CN108911501A (en) * | 2018-07-17 | 2018-11-30 | 武汉理工大学 | A kind of high rigidity Aluminiu, boron silicate glass without alkali and the preparation method and application thereof suitable for floating process production |
| CN113412243A (en) * | 2019-02-07 | 2021-09-17 | Ａｇｃ株式会社 | Alkali-free glass |
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