阅读说明：本技术 一种高弹性模量碱铝硅酸盐玻璃及其制备方法 (High-elastic-modulus alkali aluminosilicate glass and preparation method thereof ) 是由 孙雪峰 韩正伟 何智钢 蔡礼貌 巩瑞龙 于 2021-09-15 设计创作，主要内容包括：本发明提供了一种高弹性模量碱铝硅酸盐玻璃及其制备方法。本发明提供的高弹性模量碱铝硅酸盐玻璃,包括组分A和组分B；所述组分A中,按氧化物的质量比百分比计,包括以下组分：SiO-(2),60％～72％；Al-(2)O-(3),3％～13％；CaO,4％～14％；MgO,5％～10％；Na-(2)O,12％～15％；组分B,质量为组分A质量的0％～2.5％,且不为端点0％；所述组分B为La-(2)O-(3)。上述玻璃能够有效提高弹性模量、剪切模量,并且经化学强化后,具有较好的强化性能。(The invention provides alkali aluminosilicate glass with high elastic modulus and a preparation method thereof. The high-elasticity modulus alkali aluminosilicate glass provided by the invention comprises a component A and a component B; the component A comprises the following components in percentage by mass of oxides: SiO 2 2 ，60％～72％；Al 2 O 3 ，3％～13％；CaO，4％～14％；MgO，5％～10％；Na 2 12 to 15 percent of O; the component B accounts for 0-2.5% of the component A by mass and is not 0% of the endpoint; the component B is La 2 O 3 . The glass can effectively improve the elastic modulus and the shear modulus, and has better strengthening performance after being chemically strengthened.)

1. An alkali aluminosilicate glass with high elastic modulus is characterized by comprising a component A and a component B;

the component A comprises the following components in percentage by mass of oxides:

the component B is La₂O₃。

2. The alkali aluminosilicate glass with high elastic modulus according to claim 1, wherein the mass ratio of each component is as follows:

3. the alkali aluminosilicate glass with high elastic modulus according to claim 1, wherein the mass ratio of each component is as follows:

4. the alkali aluminosilicate glass with high elastic modulus according to claim 1, wherein the mass ratio of each component is as follows:

5. the alkali aluminosilicate glass with high elastic modulus according to claim 1, wherein the mass ratio of each component is as follows:

6. the alkali aluminosilicate glass with high elastic modulus according to claim 1, wherein the mass ratio of each component is as follows:

7. a method for producing the high elastic modulus alkali aluminosilicate glass according to any one of claims 1 to 6, comprising the steps of:

a) mixing quartz sand, alumina, dolomite, magnesium oxide, soda ash and LaCl₃·7H₂Mixing O to obtain a mixture;

b) heating and melting the mixture to obtain molten glass;

c) and pouring the molten glass into a mold for molding, and annealing to obtain the glass.

8. The preparation method according to claim 7, wherein the heating and melting temperature is 1550-1650 ℃ and the time is 4-6 h;

the annealing temperature is 550-650 ℃, and the annealing time is 2-3 h.

9. The method of claim 7, wherein the step c) comprises:

c1) pouring the molten glass into a mold for molding, and annealing to obtain a glass sheet;

c2) putting the glass sheet on KNO₃And strengthening in molten salt to obtain the strengthened glass.

10. The method as claimed in claim 7, wherein the temperature for strengthening in step c2) is 380-430 ℃.

Technical Field

The invention relates to the field of glass materials, in particular to alkali aluminosilicate glass with high elastic modulus and a preparation method thereof.

Background

In the float ultra-thin electronic glass industry, a glass sheet can be applied to an electronic product after the procedures of polishing, strengthening and the like. In the process of glass deep processing, the glass is inevitably deformed by external force, and if the deformation is too large, the normal use of the glass is affected. There are many factors affecting the deformation of glass, and the elastic modulus of glass itself is an important factor. The glass with high elastic modulus has strong capability of resisting external force without deformation, and the deformation is small in the deep processing process. The soda-lime glass and aluminosilicate glass currently commercially available (e.g., corning's "gorilla" glass) have a relatively low modulus of elasticity of 65-75 GPa.

In addition, other prior art glasses also have a poor modulus of elasticity. For example, patent application 201180011289.1, relates to a high modulus of elasticity lithium aluminosilicate glass and a method for its preparation₂O、CeO₂、B₂O₃Etc., but the elastic modulus thereof is at most 82 GPa. The invention patent application CN201610127466.7 relates to a glass containing SrO and Y₂O₃Etc. with elastic modulus lower than 85 GPa.

With the higher and higher requirements of the market on the deformation of electronic glass, the glass is required to have better deformation resistance and higher elastic modulus.

Disclosure of Invention

In view of the above, the present invention aims to provide an alkali aluminosilicate glass with high elastic modulus and a preparation method thereof. The high-elasticity-modulus alkali aluminosilicate glass provided by the invention can improve the elasticity modulus and has better over-deformation resistance; and after the strengthening processing, the surface compressive stress and the pressure layer depth are good.

The invention provides high-elasticity modulus alkali aluminosilicate glass which comprises a component A and a component B;

the component A comprises the following components in percentage by mass of oxides:

the mass of the component B is 0-2.5% of that of the component A, and the mass is not 0% of the endpoint;

the component B is La₂O₃。

Preferably, the mass ratio of each component is as follows:

the mass of the component B is 1.5-2.5% of that of the component A.

Preferably, the mass ratio of each component is as follows:

the mass of the component B is 1.5 percent of that of the component A.

Preferably, the mass ratio of each component is as follows:

the mass of the component B is 2.5 percent of that of the component A.

Preferably, the mass ratio of each component is as follows:

the mass of the component B is 1.5 percent of that of the component A.

Preferably, the mass ratio of each component is as follows:

the mass of the component B is 2.5 percent of that of the component A.

The invention also provides a preparation method of the alkali aluminosilicate glass with high elastic modulus in the technical scheme, which comprises the following steps:

a) mixing quartz sand, alumina, dolomite, magnesium oxide, soda ash and LaCl₃·7H₂Mixing O to obtain a mixture;

b) heating and melting the mixture to obtain molten glass;

c) and pouring the molten glass into a mold for molding, and annealing to obtain the glass.

8. The preparation method according to claim 7, wherein the heating and melting temperature is 1550-1650 ℃ and the time is 4-6 h;

the annealing temperature is 550-650 ℃, and the annealing time is 2-3 h.

Preferably, the step c) comprises:

c1) pouring the molten glass into a mold for molding, and annealing to obtain a glass sheet;

c2) putting the glass sheet on KNO₃And strengthening in molten salt to obtain the strengthened glass.

Preferably, in the step c2), the strengthening temperature is 380-430 ℃.

The high-elasticity modulus alkali aluminosilicate glass provided by the invention comprises a component A and a component B, wherein the component A is composed of a component SiO₂、Al₂O₃、CaO、MgO、Na₂O is formed by combining a certain proportion and a specific component B, namely La is introduced₂O₃The glass can effectively improve the elastic modulus and the shear modulus, and has better strengthening performance after being chemically strengthened. The elastic modulus of the glass is related to chemical bond force among particles, the chemical bond force among the particles is related to complex factors such as atomic radius, valence number, attraction between ions and oxygen ions, and the like, particularly, the glass contains a plurality of oxide components, the interaction and influence among different components are complex,according to the invention, the components are matched according to a certain proportion, so that the elastic modulus and the shear modulus of the glass can be better improved, and the glass shows better strengthening performance after being chemically strengthened.

The experimental result shows that the elastic modulus of the glass provided by the invention reaches more than 90MPa, and the shear modulus reaches more than 37MPa, so that the glass provided by the invention has better deformation resistance; after chemical strengthening, the surface compressive stress CS of the glass reaches more than 748MPa, the depth DoL of a stress layer reaches more than 14 mu m, and the glass shows excellent chemical strengthening performance.

Detailed Description

The invention provides high-elasticity modulus alkali aluminosilicate glass which comprises a component A and a component B;

the component A comprises the following components in percentage by mass of oxides:

the mass of the component B is 0-2.5% of that of the component A, and the mass is not 0% of the endpoint;

the component B is La₂O₃。

The high-elasticity modulus alkali aluminosilicate glass provided by the invention comprises a component A and a component B, wherein the component A is composed of a component SiO₂、Al₂O₃、CaO、MgO、Na₂O is formed by combining a certain proportion and a specific component B, namely La is introduced₂O₃The glass can effectively improve the elastic modulus and the shear modulus, and has better strengthening performance after being chemically strengthened. The elastic modulus of the glass is related to the chemical bond force among the particles, the chemical bond force among the particles is related to complex factors such as atomic radius, valence electron number, ion and oxygen ion attraction, and particularly, the glass contains a plurality of oxide components, and the interaction and influence among different components are complexAnd (4) performance.

In the invention, preferably, the mass ratio of each component is as follows:

the mass of the component B is 1.5-2.5% of that of the component A.

In the present invention, the sum of the contents of the components in the component a is preferably 100%, that is, the component a is composed of the above components. In some embodiments of the invention, SiO in component A₂The content of (A) is 65% or 69%; in some embodiments of the invention, Al in component A₂O₃The content of (A) is 5% or 10%; in other embodiments of the present invention, the CaO content of component a is 4% or 6%; in other embodiments of the present invention, the MgO content of component A is 5% or 6%. In other embodiments of the present invention, Na in component A₂The O content was 15%. In other embodiments of the present invention, component B, i.e., La₂O₃The mass ratio of (a) to the component A is 1.5% or 2.5%; the invention introduces specific La₂O₃The components can be well combined and matched with the component A, so that the elastic modulus of the glass is improved.

In one embodiment of the invention, the mass ratio of each component is as follows:

the mass of the component B is 1.5 percent of that of the component A.

In another embodiment of the invention, the mass ratio of each component is as follows:

the mass of the component B is 2.5 percent of that of the component A.

In another embodiment of the invention, the mass ratio of each component is as follows:

the mass of the component B is 1.5 percent of that of the component A.

In another embodiment of the invention, the mass ratio of each component is as follows:

the mass of the component B is 2.5 percent of that of the component A.

The invention also provides a preparation method of the alkali aluminosilicate glass with high elastic modulus, which comprises the following steps:

a) mixing quartz sand, alumina, dolomite, magnesium oxide, soda ash and LaCl₃·7H₂Mixing O to obtain a mixture;

b) heating and melting the mixture to obtain molten glass;

c) and pouring the molten glass into a mold for molding, and annealing to obtain the glass.

With respect to step a):

the quartz sand, the alumina, the dolomite, the magnesia, the soda ash and the LaCl₃·7H₂O corresponds to SiO in the glass₂、Al₂O₃、CaO、MgO、Na₂O、La₂O₃The components, i.e. the respective oxide components, are introduced by means of the raw materials in the above-described forms. The dosage of the raw materials is based on the composition proportion of corresponding oxides in the target glass, namely, the raw materials are inversely calculated according to the component composition of the target glassAnd (4) feeding materials according to the material dosage ratio. The mixing mode is not particularly limited, and all the materials can be uniformly mixed.

With respect to step b):

in the invention, the temperature of the heating and melting is 1550-1650 ℃, and in some embodiments of the invention, 1550 ℃. The heat preservation time for heating and melting is 4-6 h, and in some embodiments of the invention is 5 h. Heating and melting to obtain molten glass.

With respect to step c):

in the present invention, the annealing temperature is 550 to 650 ℃, and in some embodiments of the present invention is 580 ℃. The annealing time is 2-3 h, and in some embodiments of the invention is 3 h. And annealing and naturally cooling to obtain the glass.

In the present invention, after the glass is obtained by annealing, chemical strengthening is preferably further performed. Namely, the step c) specifically comprises the following steps: c1) pouring the molten glass into a mold for molding, and annealing to obtain a glass sheet; c2) putting the glass sheet on KNO₃And strengthening in molten salt to obtain the strengthened glass. Wherein the temperature of the chemical strengthening is preferably 380-430 ℃; the time for the chemical strengthening is preferably 4 hours.

According to the formula of the alkali aluminosilicate glass with high elastic modulus, the molten glass has high elastic modulus, so that the deformation resistance is improved; and after chemical strengthening, the composite material has better strengthening performance. Specifically, the elastic modulus of the glass reaches over 90 GPa; after the glass is chemically strengthened at 380-430 ℃, the glass has higher surface Compressive Stress (CS) and deeper stress layer depth (DoL), the surface Compressive Stress (CS) can reach 500-950 MPa, and the stress layer depth (DoL) can reach 10-30 mu m.

The experimental result shows that the elastic modulus of the glass provided by the invention reaches more than 90MPa, and the shear modulus reaches more than 37MPa, so that the glass provided by the invention has better deformation resistance; after chemical strengthening, the surface compressive stress CS of the glass reaches more than 748MPa, the depth DoL of a stress layer reaches more than 14 mu m, and the glass shows excellent chemical strengthening performance.

For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. In the following examples, the mass ratio of component B means the mass ratio of component B to the whole component A.

Example 1

1. The glass comprises the following components:

and (2) component A:

2. preparation of glass

S1, mixing quartz sand, alumina, dolomite, magnesia, soda ash and LaCl₃·7H₂Mixing O to obtain a mixture;

wherein, the feeding proportion of the raw materials is based on the proportion of each oxide in the glass product.

S2, heating and melting the mixture at 1550 ℃ for 5 hours to obtain molten glass.

And S4, pouring the molten glass into a mold for molding, annealing at 580 ℃ for 3h, and cooling to room temperature to obtain the glass.

3. Performance testing

The glass samples obtained were subjected to the following performance tests, respectively:

(1) after the obtained glass was cut, the elastic modulus was measured, and the test results are shown in Table 1.

(2) The obtained glass is subjected to chemical strengthening deep processing and then the strengthening performance is tested:

putting the cut glass into KNO₃Strengthening is carried out in molten salt, and the strengthening conditions are as follows: the temperature is 420 ℃ and the time is 4 h. Thereafter, the samples were tested for reinforcement properties, and the results are shown in Table 1.

(3) The resulting glasses were tested for melting temperature, working point, softening point and the results are shown in table 1.

Example 2

1. The glass comprises the following components:

and (2) component A:

2. preparation of glass

S1, mixing quartz sand, alumina, dolomite, magnesia, soda ash and LaCl₃·7H₂Mixing O to obtain a mixture;

wherein, the feeding proportion of the raw materials is based on the proportion of each oxide in the glass product.

S2, heating and melting the mixture at 1550 ℃ for 5 hours to obtain molten glass.

And S4, pouring the molten glass into a mold for molding, annealing at 580 ℃ for 3h, and cooling to room temperature to obtain the glass.

3. Performance testing

Each performance test was conducted according to the test method of example 1, and the test results are shown in Table 1.

Example 3

1. The glass comprises the following components:

and (2) component A:

2. preparation of glass

S1, mixing quartz sand, alumina, dolomite, magnesia, soda ash and LaCl₃·7H₂Mixing O to obtain a mixture;

wherein, the feeding proportion of the raw materials is based on the proportion of each oxide in the glass product.

S2, heating and melting the mixture at 1550 ℃ for 5 hours to obtain molten glass.

And S4, pouring the molten glass into a mold for molding, annealing at 580 ℃ for 3h, and cooling to room temperature to obtain the glass.

3. Performance testing

Each performance test was conducted according to the test method of example 1, and the test results are shown in Table 1.

Example 4

1. The glass comprises the following components:

and (2) component A:

2. preparation of glass

S1, mixing quartz sand, alumina, dolomite, magnesia, soda ash and LaCl₃·7H₂Mixing O to obtain a mixture;

wherein, the feeding proportion of the raw materials is based on the proportion of each oxide in the glass product.

S2, heating and melting the mixture at 1550 ℃ for 5 hours to obtain molten glass.

And S4, pouring the molten glass into a mold for molding, annealing at 580 ℃ for 3h, and cooling to room temperature to obtain the glass.

3. Performance testing

Each performance test was conducted according to the test method of example 1, and the test results are shown in Table 1.

Comparative example 1

1. The glass comprises the following components: the difference from example 3 is that component B (La) is not incorporated₂O₃). The method comprises the following specific steps:

2. preparing glass: the same as in example 3.

3. And (3) performance testing: the same as in example 3.

TABLE 1 glass compositions and Properties of examples 1-4 and comparative example 1

As can be seen from the test results in Table 1, compared with comparative example 1, the elastic modulus and the shear modulus of the glass provided by embodiments 1 to 4 of the invention are obviously improved, the elastic modulus reaches more than 90MPa, and the shear modulus reaches more than 37MPa, so that the deformation resistance of the glass provided by the invention is improved. Meanwhile, the chemical strengthening performance of the glass is obviously improved in the embodiments 1-4, after the glass is chemically strengthened, the surface compressive stress CS of the glass reaches more than 748MPa, and the depth DoL of a stress layer reaches more than 14 mu m.

Comparative example 2

1. The glass comprises the following components: the difference from example 1 is that component B (La) is not introduced₂O₃). The method comprises the following specific steps:

2. preparing glass: the same as in example 1.

3. And (3) performance testing: the glass was tested for elastic modulus and shear modulus with reference to example 1 and compared to the effect of example 1, with the results shown in table 2.

TABLE 2 modulus of elasticity and shear modulus of comparative example 2

	Modulus of elasticity/GPa	Shear modulus/GPa
			Example 1	94.5	38.9
Comparative example 2	71.8	29.6

As can be seen from the test results in Table 2, the elastic modulus and shear modulus of the glass obtained in example 1 are significantly improved as compared with those of comparative example 2.

The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.