CN112811814A - High strain point alkali-free aluminoborosilicate glass easy to clarify - Google Patents

High strain point alkali-free aluminoborosilicate glass easy to clarify Download PDF

Info

Publication number
CN112811814A
CN112811814A CN202110160850.8A CN202110160850A CN112811814A CN 112811814 A CN112811814 A CN 112811814A CN 202110160850 A CN202110160850 A CN 202110160850A CN 112811814 A CN112811814 A CN 112811814A
Authority
CN
China
Prior art keywords
glass
alkali
clarify
point
strain
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.)
Withdrawn
Application number
CN202110160850.8A
Other languages
Chinese (zh)
Inventor
彭寿
张冲
赵凤阳
王萍萍
王巍巍
高强
韩娜
石丽芬
杨勇
柯震坤
李金威
李常青
周刚
曹欣
单传丽
倪嘉
崔介东
仲召进
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CNBM Bengbu Design and Research Institute for Glass Industry Co Ltd
Original Assignee
CNBM Bengbu Design and Research Institute for Glass Industry Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by CNBM Bengbu Design and Research Institute for Glass Industry Co Ltd filed Critical CNBM Bengbu Design and Research Institute for Glass Industry Co Ltd
Priority to CN202110160850.8A priority Critical patent/CN112811814A/en
Publication of CN112811814A publication Critical patent/CN112811814A/en
Withdrawn legal-status Critical Current

Links

Images

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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • 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
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to an easily-clarified high-strain-point alkali-free aluminoborosilicate glass which is characterized by being prepared from the following raw materials in percentage by weight: SiO 22 57%～65%、B2O3 7%～8.5%、Al2O3 4%～21%、CaO 1%～6.5%、MgO 1%～5.5%、SrO 1%～10.5%、CeO2 0.1%～0.8%、SrCl2 0.5 to 1.5 percent. The invention has the advantages that: by adjusting the proportion of the components, the alkali-free aluminosilicate glass provided by the invention is easy to clarify at 1620 ℃, bubbles with the diameter larger than 0.1mm are invisible, and the alkali-free aluminosilicate glass does not contain elements harmful to the environment, and is suitable for industrial large-scale production; a strain point of 682 to 692 ℃, a coefficient of thermal expansion of (32 to 33.5) × 10‑7between/DEG C, the heat point of constructing a circuit on the substrate glass at the later stage can be completely satisfiedAnd (6) processing requirements.

Description

High strain point alkali-free aluminoborosilicate glass easy to clarify
Technical Field
The invention relates to the technical field of special glass, in particular to alkali-free aluminoborosilicate glass with high strain point and easy clarification.
Background
With the development of science and technology, the display technology is gradually developed towards more energy-saving, environmental protection and light weight, and the flat panel display technology has replaced the traditional CRT display technology to become the mainstream display technology at present. The key material (glass substrate) in flat panel display technology is alkali-free aluminoborosilicate glass.
The glass substrate for flat panel display needs to build a driving display circuit on the glass substrate in the later period, needs to be repeatedly subjected to heat treatment, and the highest heating temperature needs to reach more than 650 ℃, so that the substrate glass cannot have any viscous flow in the glass in the temperature range, and certain rigidity is kept. Therefore, a higher demand is placed on the performance of the glass substrate, i.e., the strain point of the glass substrate is greater than 670 ℃. If the strain point of the glass substrate is low, the glass can deform in the heat treatment process, and thermal stress can be brought when the temperature is reduced, so that the internal structure of the glass is changed. In addition, the thermal expansion coefficient of the glass substrate needs to be close to that of the silicon substrate, so as to minimize the stress failure caused by the heat treatment procedure, which requires that the thermal expansion coefficient of the glass is (28-38) × 10-7Between/° c.
Although the existing glass substrate meets the heat treatment requirement of circuit construction in performance technology, the alkali-free aluminoborosilicate glass has the defects of high viscosity, high melting temperature, difficult clarification, easy generation of bubbles and difficult forming preparation in the melting process. And the bubbles are the main defects in the production process of the glass substrate, and the alkali-free aluminoborosilicate glass for flat panel display meets the heat treatment requirement and also meets the requirement that the diameter of the bubbles in the glass is less than 0.1 mm.
Disclosure of Invention
The invention aims to solve the problems of high viscosity, high melting temperature, difficult clarification, easy generation of bubbles and the like in the melting process of the conventional high-strain-point glass (alkali-free aluminoborosilicate glass) for flat panel display, and provides the easily clarified high-strain-point alkali-free aluminoborosilicate glass.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an easily-clarified high-strain-point alkali-free aluminoborosilicate glass is characterized by being prepared from the following raw materials in percentage by weight:
SiO2 57%～65%、B2O3 7%～8.5%、Al2O3 4%～21%、CaO 1%～6.5%、MgO 1%～5.5%、SrO 1%～10.5%、CeO2 0.1%～0.8%、SrCl2 0.5%～1.5%。
further, the high-strain-point alkali-free aluminoborosilicate glass easy to clarify is characterized by being prepared from the following raw materials in percentage by weight: SiO 22 57%～58.5%、B2O3 8%～8.5%、Al2O3 16%～21%、CaO 5.5%～6.5%、MgO 1%～2.5%、SrO 6%～7%、CeO2 0.1%～0.25%、SrCl2 0.5%～0.8%。
Further, the high-strain-point alkali-free aluminoborosilicate glass easy to clarify is characterized by being prepared from the following raw materials in percentage by weight: SiO 22 59%～60.5%、B2O3 7%～7.8%、Al2O3 10%～15%、CaO 2%～3.5%、MgO 4%～4.5%、SrO 7.5%～9%、CeO2 0.3%～0.45%、SrCl2 0.8%～1%。
Further, the high-strain-point alkali-free aluminoborosilicate glass easy to clarify is characterized by being prepared from the following raw materials in percentage by weight: SiO 22 62%～63.5%、B2O3 7%～8%、Al2O3 4%～9%、CaO 1%～1.5%、MgO 3%～3.5%、SrO 8%～10.5%、CeO2 0.5%～0.8%、SrCl2 1.1%～1.4%。
Further, the strain point of the high strain point alkali-free aluminoborosilicate glass which is easy to clarify is more than 680 ℃.
Furthermore, the strain point of the easily-clarified high-strain-point alkali-free aluminoborosilicate glass is 682-692 ℃.
In the present invention, the glass former oxide is SiO2 And B2O3The intermediate oxide of the glass is Al2O3The external oxides of the glass network are CaO, MgO and SrO, and the auxiliary additive of the glass is CeO2、SrCl2。
SiO2 And B2O3For forming oxides of the glass, SiO2With silicon-oxygen tetrahedron [ SiO ]4]The structural units form an irregular network structure to become a framework of the glass. If S is in the glassiO2The content is higher, and the strain point and the high-temperature viscosity of the glass are correspondingly increased; while if SiO2The glass structure is not easy to form when the content is low, the properties such as strain point, melting temperature and the like are reduced, B2O3Can reduce the thermal expansion coefficient, reduce the viscosity of glass at a high temperature stage, and simultaneously play a role of fluxing and accelerating the melting and clarification of glass liquid, so the SiO of the invention2And B2O3The total mass percentage of the glass accounts for 64-73.5% of the total mass of the glass.
Al2O3The oxide is a network intermediate oxide, can reduce the crystallization tendency of the glass and increase the viscosity of the glass. But Al2O3When the content of (A) is excessive, the melting temperature of the glass can be increased, the viscosity of the glass is increased, and clarification and homogenization of glass liquid are not facilitated; taken together, the Al of the invention2O3The appropriate range of the glass substrate is 4% -21%, and in the range, the glass substrate can be ensured to have a higher strain point and be easy to clarify at high temperature.
CaO, MgO and SrO are glass extranet oxides, and the extranet oxides mainly have the function of fine-tuning and improving some properties of the glass. CaO promotes fining and homogenization of the molten glass at high temperatures by reducing the viscosity of the molten glass; MgO can replace part of CaO, so that the hardening speed of the glass is reduced, the forming performance of the glass is improved, and SrO can increase the chemical stability and the devitrification resistance of the glass and influence the melting process of the glass.
SrCl2、CeO2The glass additive is added into glass raw materials as a glass auxiliary additive and mainly has the function of promoting the clarification of molten glass. SrCl2Can be gasified and volatilized at high temperature, can effectively promote the clarification of the molten glass, and the SrCl in the invention takes the economic cost into consideration2The preferable content is 0.5% to 1.5%. CeO (CeO)2Is a strong oxidant which can release oxygen at high temperature and release O2Diffusing into the bubbles of the surrounding molten glass, absorbing and combining other bubbles in the molten glass, increasing and floating the bubbles, and finally discharging the bubbles to achieve the purpose of clarification, wherein the reaction temperature is within the range ofAbove 1400 ℃ is a more ideal high-temperature clarifying agent, but the glass is yellow due to excessive addition, and the CeO of the invention2The appropriate content of (B) is 0.1% -0.8%.
The invention has the advantages that:
by adjusting the proportion of the components, the alkali-free aluminosilicate glass provided by the invention is easy to clarify at 1620 ℃, bubbles with the diameter larger than 0.1mm are invisible, and the alkali-free aluminosilicate glass does not contain elements harmful to the environment, and is suitable for industrial large-scale production; a strain point of 682 to 692 ℃, a coefficient of thermal expansion of (32 to 33.5) × 10-7between/DEG C, the heat treatment requirement of constructing a circuit on the substrate glass at the later stage can be completely met.
Drawings
FIG. 1 is a view showing a state where a glass of example 1 is melted at 1620 ℃ for 30 min;
FIG. 2 is a diagram showing the state in which the glass of example 1 is melted at 1620 ℃ for 60 min;
FIG. 3 is a view showing the state where the glass of example 1 is melted at 1620 ℃ for 90 min;
FIG. 4 is a view showing the state where the glass of example 1 is melted at 1620 ℃ for 120 min;
FIG. 5 is a view showing a state where the glass of example 2 is melted at 1620 ℃ for 30 min;
FIG. 6 is a diagram showing the state where the glass of example 2 is melted at 1620 ℃ for 60 min;
FIG. 7 is a view showing the state where the glass of example 2 is melted at 1620 ℃ for 90 min;
FIG. 8 is a view showing the state where the glass of example 2 is melted at 1620 ℃ for 120 min;
FIG. 9 is a view showing a state where glass of example 3 is melted at 1620 ℃ for 30 min;
FIG. 10 is a view showing a state where the glass of example 3 is melted at 1620 ℃ for 60 min;
FIG. 11 is a view showing the state where the glass of example 3 is melted at 1620 ℃ for 90 min;
FIG. 12 is a view showing the state in which the glass of example 3 is melted at 1620 ℃ for 120 min;
FIG. 13 is a view showing a state where the glass of example 4 is melted at 1620 ℃ for 30 min;
FIG. 14 is a view showing a state where the glass of example 4 is melted at 1620 ℃ for 60 min;
FIG. 15 is a view showing the state where the glass of example 4 is melted at 1620 ℃ for 90 min;
FIG. 16 is a view showing the state where the glass of example 4 is melted at 1620 ℃ for 120 min;
FIG. 17 is a view showing a state in which a glass of example 5 is melted at 1620 ℃ for 30 min;
FIG. 18 is a view showing a state where the glass of example 5 is melted at 1620 ℃ for 60 min;
FIG. 19 is a view showing the state where the glass of example 5 is melted at 1620 ℃ for 90 min;
FIG. 20 is a view showing the state in which the glass of example 5 was melted at 1620 ℃ for 120 min.
Detailed Description
The following detailed description of the present invention is provided to illustrate and explain the present invention and not to limit the present invention.
An easily-clarified high-strain-point alkali-free aluminoborosilicate glass comprises the following specific implementation steps:
in the embodiments 1-5, a high-temperature melting furnace is adopted, the raw materials are weighed according to the following weight percentage in the table 1, and are uniformly mixed through a mixing system to obtain a glass batch; melting the glass batch, raising the temperature to 1450 ℃ at the speed of 5 ℃/min, then raising the temperature to 1620 ℃ at the speed of 3 ℃/min, and preserving the temperature for 120 min; after the heat preservation time is finished, pouring the melted glass liquid into a mould for forming, and annealing in an annealing furnace at the cooling speed of 3 ℃/min; the annealing temperature is 650 ℃; the glass samples were cut, polished and tested for properties.
Wherein the strain point of the glass is measured by a wire drawing method, and the reference standard is the method specified by ASTM C336; the thermal expansion coefficient is measured by using a vertical thermal expansion instrument according to an average linear thermal expansion coefficient of 30-380 ℃, and the reference standard is a method specified in ISO 7991.
TABLE 1 examples base glass composition (300 g batch)
Examples SiO2 B2O3 Al2O3 CaO MgO SrO CeO2 SrCl2
Example one 57.5 8.5 17.2 5.7 5.3 4.2 0.3 1.3
Example two 58.5 8.3 16.5 2.8 5.1 6.9 0.6 1.3
EXAMPLE III 59.5 7.5 13.5 5.2 5 7.8 0.5 1
Example four 61.8 7.8 11.5 4.5 3.8 8.5 0.7 1.4
EXAMPLE five 64.5 7.5 8.5 5.4 2.5 10.2 0.6 0.8
The glass samples in examples 1-5 were tested and observed at high temperature, the high-temperature melting furnace was used to observe the melting state of the glass at high temperature, and visually observe the presence or absence of bubbles in the molten glass, the test results are shown in Table 2, and the high-temperature melting observation graphs of the samples are shown in FIGS. 1-4.
Table 2 strain point and coefficient of thermal expansion of the glasses of the examples
Examples Example one Example two EXAMPLE III Example four EXAMPLE five
Strain point (. degree. C.) 689.3 690.2 687.5 684.2 682.6
Coefficient of thermal expansion (10)-7/℃） 33.5 32.8 32.9 32.6 32.3
The number of bubbles with diameter larger than 0.1mm 0 0 0 0 0
According to the test result, the strain point of the prepared glass is more than 680 ℃, and the glass is easy to clarify at 1620 ℃ and has no obvious large bubbles.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; those skilled in the art can make numerous possible variations and modifications to the present teachings, or modify equivalent embodiments to equivalent variations, without departing from the scope of the present teachings, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (6)

1. An easily-clarified high-strain-point alkali-free aluminoborosilicate glass is characterized by being prepared from the following raw materials in percentage by weight: SiO 22 57%～65%、B2O3 7%～8.5%、Al2O3 4%～21%、CaO 1%～6.5%、MgO 1%～5.5%、SrO 1%～10.5%、CeO2 0.1%～0.8%、SrCl2 0.5%～1.5%。
2. The alkali-free aluminoborosilicate glass with a high strain point, which is easy to clarify as claimed in claim 1, wherein said glass is prepared from the following raw materials in percentage by weight: SiO 22 57%～58.5%、B2O3 8%～8.5%、Al2O3 16%～21%、CaO 5.5%～6.5%、MgO 1%～2.5%、SrO 6%～7%、CeO2 0.1%～0.25%、SrCl2 0.5%～0.8%。
3. A disposable diaper as set forth in claim 1The clarified high-strain-point alkali-free aluminoborosilicate glass is characterized by being prepared from the following raw materials in percentage by weight: SiO 22 59%～60.5%、B2O3 7%～7.8%、Al2O3 10%～15%、CaO 2%～3.5%、MgO 4%～4.5%、SrO 7.5%～9%、CeO2 0.3%～0.45%、SrCl2 0.8%～1%。
4. The alkali-free aluminoborosilicate glass with a high strain point, which is easy to clarify as claimed in claim 1, wherein said glass is prepared from the following raw materials in percentage by weight: SiO 22 62%～63.5%、B2O3 7%～8%、Al2O3 4%～9%、CaO 1%～1.5%、MgO 3%～3.5%、SrO 8%～10.5%、CeO2 0.5%～0.8%、SrCl2 1.1%～1.4%。
5. An alkali-free aluminoborosilicate glass with a high strain point which is easy to clarify as defined in any one of claims 1 to 4, wherein: the strain point of the high-strain-point alkali-free aluminoborosilicate glass which is easy to clarify is more than 680 ℃.
6. An alkali-free aluminoborosilicate glass with a high strain point which is easy to clarify as defined in any one of claims 1 to 4, wherein: the strain point of the high-strain-point alkali-free aluminoborosilicate glass easy to clarify is 682-692 ℃.
CN202110160850.8A 2021-02-05 2021-02-05 High strain point alkali-free aluminoborosilicate glass easy to clarify Withdrawn CN112811814A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110160850.8A CN112811814A (en) 2021-02-05 2021-02-05 High strain point alkali-free aluminoborosilicate glass easy to clarify

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110160850.8A CN112811814A (en) 2021-02-05 2021-02-05 High strain point alkali-free aluminoborosilicate glass easy to clarify

Publications (1)

Publication Number Publication Date
CN112811814A true CN112811814A (en) 2021-05-18

Family

ID=75861743

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110160850.8A Withdrawn CN112811814A (en) 2021-02-05 2021-02-05 High strain point alkali-free aluminoborosilicate glass easy to clarify

Country Status (1)

Country Link
CN (1) CN112811814A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114477762A (en) * 2021-12-24 2022-05-13 中建材蚌埠玻璃工业设计研究院有限公司 Boron-free aluminosilicate glass

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114477762A (en) * 2021-12-24 2022-05-13 中建材蚌埠玻璃工业设计研究院有限公司 Boron-free aluminosilicate glass
CN114477762B (en) * 2021-12-24 2024-03-15 中建材玻璃新材料研究院集团有限公司 Boron-free aluminosilicate glass

Similar Documents

Publication Publication Date Title
JP6758608B2 (en) Non-alkali glass substrate
JP5761025B2 (en) Glass plate for substrate, method for producing the same, and method for producing TFT panel
JPWO2009131053A1 (en) GLASS PLATE FOR DISPLAY PANEL, ITS MANUFACTURING METHOD, AND TFT PANEL MANUFACTURING METHOD
CN104445932B (en) Pink aluminosilicate glass
CN110028240B (en) Aluminosilicate glass and preparation method thereof
TW201323366A (en) Phosphate optical glass
JP7340088B2 (en) Alkali-free aluminoborosilicate glass raw material
JP5708484B2 (en) Glass plate for substrate
CN114394744A (en) Low borosilicate glass and preparation method thereof
CN114195392A (en) Glass composition, microcrystalline glass, and preparation method and application thereof
CN115947539A (en) Aluminosilicate glass for display substrate and preparation method thereof
CN112811814A (en) High strain point alkali-free aluminoborosilicate glass easy to clarify
CN112456795A (en) High-viscosity glass with lower surface tension
CN102775056A (en) Manufacturing method for fireproof glass cotton
CN110330226B (en) Alkali-free aluminoborosilicate glass and preparation method and application thereof
CN116102254A (en) OLED glass substrate composition and preparation method thereof
CN109111104B (en) Boron-aluminum silicate glass and preparation method thereof
CN110183103A (en) Silicate glass containing boron and aluminium without alkali clarifying agent and its application method
CN110818256B (en) Alkali-free high-alumina borosilicate glass and preparation method thereof
CN112499964A (en) Substrate glass for TFT-LCD screen and preparation method thereof
CN102584007B (en) A kind of formula of environment-friendly type TFT-LCD base plate glass
KR101748500B1 (en) Batch Composition for Preparing Long Glass Fiber
CN113979633B (en) Preparation method of sodium-calcium-silicon glass for high-hardness chemical tempering
CN113173704B (en) TFT-LCD substrate glass prepared by using environment-friendly clarifying agent
CN115925250B (en) High softening point medium borosilicate glass, reinforced glass, preparation method and application thereof

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
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20210518