阅读说明：本技术 一种易澄清的高应变点无碱铝硼硅酸盐玻璃 (High strain point alkali-free aluminoborosilicate glass easy to clarify ) 是由 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 于 2021-02-05 设计创作，主要内容包括：本发明涉及一种易澄清的高应变点无碱铝硼硅酸盐玻璃,其特征在于由以下重量百分比的原料制成：SiO-(2 )57%～65%、B-2O-(3 )7%～8.5%、Al-2O-(3 )4%～21%、CaO 1%～6.5%、MgO 1%～5.5%、SrO 1%～10.5%、CeO-(2 )0.1%～0.8%、SrCl-(2 )0.5%～1.5%。本发明的优点：本发明提供的无碱铝硅酸盐玻璃通过调整这组分的占比,使得玻璃在1620℃高温状态下易于澄清,直径大于0.1mm的气泡不可见,不含对环境有害的元素,适合工业大规模生产；应变点在682～692℃、热膨胀系数在(32～33.5)×10～(-7)/℃之间,可以完全满足后期在基板玻璃上构建电路的热处理要求。(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 2 2 57%～65%、B 2 O 3 7%～8.5%、Al 2 O 3 4%～21%、CaO 1%～6.5%、MgO 1%～5.5%、SrO 1%～10.5%、CeO 2 0.1%～0.8%、SrCl 2 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 ‑7 between/DEG C, the heat point of constructing a circuit on the substrate glass at the later stage can be completely satisfiedAnd (6) processing requirements.)

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 ℃.

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.