CN113402165B

CN113402165B - Glass composition, chemically strengthened glass, and method for producing same

Info

Publication number: CN113402165B
Application number: CN202110857815.1A
Authority: CN
Inventors: 马赫; 袁帅; 曹生硕; 王友明; 梁荻; 陈雪梅
Original assignee: CDGM Glass Co Ltd
Current assignee: CDGM Glass Co Ltd
Priority date: 2021-07-28
Filing date: 2021-07-28
Publication date: 2022-07-29
Anticipated expiration: 2041-07-28
Also published as: CN113402165A

Abstract

The invention discloses a glass composition, which comprises the following components in percentage by mole: si ⁴⁺ ：30～50％；Al ³⁺ ：20～35％；La ³⁺ +Y ³⁺ : greater than 0 but less than or equal to 4%; b is ³⁺ ：7～20％；Na ⁺ ：5～15％；Li ⁺ : 1 to 10 percent. Through reasonable component design, the glass composition obtained by the invention has proper high-temperature viscosity and excellent production performance; the glass composition is suitable for chemical strengthening, and the chemically strengthened glass obtained after chemical strengthening has excellent mechanical properties and is suitable for devices and equipment with high scratch resistance and high wear resistance requirements.

Description

Glass composition, chemically strengthened glass, and method for producing same

Technical Field

The present invention relates to a glass composition, and more particularly, to a glass composition suitable for chemical strengthening, a chemically strengthened glass made therefrom, and a method for manufacturing the same.

Background

Chemical strengthening is a physical process in which ions with two different ionic radii are mutually replaced by utilizing diffusion and migration of ions on the surface of glass to form compressive stress on the surface of the glass. Description of chemical strengthening ProcessExamples of the type are Na in sodium-containing silicate glasses ⁺ In coating bath K ⁺ And (4) substitution. Chemically strengthened glass is glass whose strength is greatly improved by chemical strengthening. The main mechanism for improving the glass strength in the chemical strengthening process is that the volume difference of exchanged ions in the process forms compressive stress on the surface of the glass, and the unstable expansion of micro cracks and subsurface cracks on the surface of the glass is prevented.

Chemically strengthened glass is commonly used in electronic device panels, backsheets, windows, doors and windows. However, the electronic device panel glass and the window glass inevitably come into contact with dust having a higher hardness to form scratches, and the destabilization and extension of the scratches due to impact or collision cause a decrease in the impact strength of the glass, increasing the possibility of failure. The mechanical properties such as microhardness and elastic modulus of the glass are improved, the degree of scratch damage is favorably reduced, and the possibility of failure of the glass due to impact after long-term use is reduced. However, the mechanical properties of chemically strengthened glass are incompatible with the ease with which it can be produced. If the mechanical properties of the chemically strengthened glass are improved, the viscosity of the molten glass is increased in the melting process, which is not favorable for eliminating the internal defects of bubbles, stones and the like in the molten glass.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a glass composition which has proper high-temperature viscosity and excellent production performance, and is suitable for chemical strengthening.

The invention also provides chemically strengthened glass which has excellent mechanical properties.

The technical scheme adopted by the invention for solving the technical problem is as follows:

(1) A glass composition having components, expressed in mole percent, with cations comprising: si ⁴⁺ ：30～50％；Al ³⁺ ：20～35％；La ³⁺ +Y ³⁺ : greater than 0 but less than or equal to 4%; b ³⁺ ：7～20％；Na ⁺ ：5～15％；Li ⁺ ：1～10％。

(2) The glass composition according to (1), whose components are expressed in mole percent, the cations further comprising: k ⁺ : 0 to 5 percent; and/or Ag ⁺ : 0-2%; and/or Rb ⁺ : 0-2%; and/or Zn ²⁺ : 0 to 5 percent; and/or Mg ²⁺ : 0 to 10 percent; and/or Ca ² ⁺ : 0 to 10 percent; and/or Sr ²⁺ : 0 to 5 percent; and/or Ba ²⁺ : 0 to 5 percent; and/or Zr ⁴⁺ : 0-2%; and/or P ⁵⁺ : 0 to 4 percent; and/or Sb ³⁺ : 0 to 0.5 percent; and/or Sn ⁴⁺ : 0 to 1 percent; and/or Ce ⁴⁺ ：0～0.5％。

(3) A glass composition having the composition, expressed in mole percent, as cations: si ⁴⁺ ：30～50％；Al ³⁺ ：20～35％；La ³⁺ +Y ³⁺ : greater than 0 but less than or equal to 4%; b is ³⁺ ：7～20％；Na ⁺ ：5～15％；Li ⁺ ：1～10％；K ⁺ ：0～5％；Ag ⁺ ：0～2％；Rb ⁺ ：0～2％；Zn ²⁺ ：0～5％；Mg ²⁺ ：0～10％；Ca ²⁺ ：0～10％；Sr ²⁺ ：0～5％；Ba ²⁺ ：0～5％；Zr ⁴⁺ ：0～2％；P ⁵⁺ ：0～4％；Sb ³⁺ ：0～0.5％；Sn ⁴⁺ ：0～1％；Ce ⁴⁺ ：0～0.5％。

(4) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: la ³⁺ /(La ³⁺ +Y ³⁺ ) 0.2 to 0.8, preferably La ³⁺ /(La ³⁺ +Y ³⁺ ) 0.3 to 0.7, more preferably La ³⁺ /(La ³⁺ +Y ³⁺ ) 0.4 to 0.6.

(5) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: al (Al) ³⁺ +B ³⁺ 29 to 50%, preferably Al ³⁺ +B ³⁺ 32 to 48%, more preferably Al ³⁺ +B ³⁺ 35 to 45 percent.

(6) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: la ³⁺ /B ³⁺ Is 0.25 or less, preferably La ³⁺ /B ³⁺ Is 0.2 or less, more preferably La ³⁺ /B ³⁺ Is 0.15 or less.

(7) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: al (aluminum) ³⁺ /(2×La ³⁺ +Y ³⁺ +B ³⁺ +P ⁵⁺ ) 1 to 2.5, preferably Al ³⁺ /(2×La ³⁺ +Y ³⁺ +B ³⁺ +P ⁵⁺ ) 1.2 to 2.2, more preferably Al ³⁺ /(2×La ³⁺ +Y ³⁺ +B ³⁺ +P ⁵⁺ ) 1.4 to 2.

(8) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: li ⁺ /(Li ⁺ +Na ⁺ ) In the range of 0.1 to 0.5, preferably Li ⁺ /(Li ⁺ +Na ⁺ ) 0.15 to 0.4, more preferably Li ⁺ /(Li ⁺ +Na ⁺ ) 0.2 to 0.3.

(9) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ 10 to 23%, preferably Li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ 13.5 to 22%, and Li is more preferable ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ 16 to 21.5 percent.

(10) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: al (Al) ³⁺ /(Li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ ) Is 1.1 or more, preferably Al ³⁺ /(Li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ ) Is 1.15 or more, more preferably Al ³⁺ /(Li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ ) 1.2 to 2.5.

(11) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: si ⁴⁺ : 33 to 47%, preferably Si ⁴⁺ : 36-44%; and/or Al ³⁺ : 22.5 to 32.5%, preferably Al ³⁺ : 25-30%; and/or La ³⁺ +Y ³ ⁺ : 0.1 to 3%, preferably La ³⁺ +Y ³⁺ : 0.2-2%; and/or B ³⁺ : 8.5-17%, preferably B ³⁺ : 10-15 percent; and/or Na ⁺ : 6 to 14%, preferably Na ⁺ : 7-13%; and/or Li ⁺ : 1.5 to 9%, preferably Li ⁺ : 2-8%; and/or K ⁺ : 0 to 3%, preferably K ⁺ : 0-2%; and/or Ag ⁺ : 0 to 1%, preferably Ag ⁺ : 0 to 0.2%, and more preferably not containing Ag ⁺ (ii) a And/or Rb ⁺ : 0 to 1%, preferably Rb ⁺ : 0 to 0.2%, and more preferably does not contain Rb ⁺ (ii) a And/or Zn ²⁺ : 0 to 3%, preferably Zn ²⁺ : 0.5-2%; and/or Mg ²⁺ : 1 to 9%, preferably Mg ²⁺ : 2-8%; and/or Ca ²⁺ : 0 to 4%, preferably Ca ²⁺ : 0-2%; and/or Sr ²⁺ : 0 to 1%, preferably Sr ²⁺ : 0 to 0.5%, and more preferably does not contain Sr ²⁺ (ii) a And/or Ba ²⁺ : 0 to 1%, preferably Ba ²⁺ : 0 to 0.5%, and more preferably no Ba ²⁺ (ii) a And/or Zr ⁴⁺ : 0 to 1%, preferably Zr ⁴⁺ : 0 to 0.5%, and more preferably does not contain Zr ⁴⁺ (ii) a And/or P ⁵⁺ : 0 to 2.25%, preferably P ⁵⁺ : 0 to 1.75 percent; and/or Sb ³⁺ : 0 to 0.2%, preferably Sb ³⁺ : 0 to 0.1 percent; and/or Sn ⁴⁺ : 0.05 to 0.4%, preferably Sn ⁴⁺ : 0.1-0.3%; and/or Ce ⁴⁺ : 0 to 0.2%, preferably Ce ⁴⁺ ：0～0.1％。

(12) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: la ³⁺ : 0 to 2.5%, preferably La ³⁺ : 0.1 to 2%, more preferably La ³⁺ : 0.15 to 1.5%, and/or Y ³⁺ : 0 to 2.5%, preferably Y ³⁺ : 0.1 to 2%, more preferably Y ³⁺ ：0.15～1.5％。

(13) The glass composition according to any one of (1) to (3), wherein Zn is contained in the glass composition ²⁺ 、Mg ² ⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ Preferably, the glass composition contains Zn at the same time ²⁺ 、Mg ²⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ More preferably, the glass composition contains Zn simultaneously ²⁺ 、Mg ²⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ Of the above two components, and further preferably, the glass composition contains Zn at the same time ²⁺ And Mg ²⁺ 。

(14) The glass composition according to any one of (1) to (3), wherein the glass composition has the following composition in terms of mole percent, and the anion contains: o is ^2- : 98-100%, preferably O ^2- : 99 to 100%, more preferably O ^2- : 99.5 to 100%, and preferably O ^2- ：99.9～100％。

(15) The glass composition according to any one of (1) to (3), wherein μ of the glass composition ₁₄₀₀ 120 dPas or less, preferably 100 dPas or less, more preferably 88 to 96 dPas; and/or water resistance D _w Is 2 or more, preferably 1; and/or a Young's modulus E of 7800X 10 ⁷ Pa or more, preferably 8200X 10 ⁷ Pa or more, more preferably 8300X 10 ⁷ Pa is above; and/or a micro Vickers hardness of 630X 10 ⁷ Pa or more, preferably 640X 10 ⁷ Pa or more, more preferably 645X 10 ⁷ ～665×10 ⁷ Pa。

(16) A chemically strengthened glass comprising the glass composition according to any one of (1) to (15).

(17) The chemically strengthened glass according to (16), wherein the chemically strengthened glass has a Vickers microhardness of 680X 10 ⁷ Pa or more, preferably 685X 10 ⁷ Pa or more, more preferably 690X 10 ⁷ ～705×10 ⁷ Pa; and/or the surface stress value CS is greater than 800 MPa; and/or the ratio DOL/d of the depth of the stress layer to the thickness of the chemically strengthened glass is 0.05 or more, preferably 0.07 or more, and more preferably 0.09 or more.

(18) A glass preform made of the glass composition as defined in any one of (1) to (15), or made of the chemically strengthened glass as defined in any one of (16) to (17).

(19) A glass member made of the glass composition as defined in any one of (1) to (15), the chemically strengthened glass as defined in any one of (16) to (17), or the glass preform as defined in (18).

(20) An apparatus comprising the glass composition according to any one of (1) to (15), and/or comprising the chemically strengthened glass according to any one of (16) to (17), and/or comprising the glass device according to (19).

(21) A method for producing chemically strengthened glass, the method comprising the steps of: forming the glass composition according to any one of (1) to (15), forming a chemically strengthened glass from the glass composition by a chemical strengthening process, or forming a chemically strengthened glass from the glass composition by a chemical strengthening process after producing a glass molded body from the glass composition by various processes.

(22) The method for producing a chemically strengthened glass as described in (21), wherein the glass is produced into a glass shaped body by a grinding or polishing process or a hot bending or press molding process at a certain temperature.

(23) The method for producing a chemically strengthened glass according to (21), wherein the chemical strengthening process is a process of immersing the glass composition or the glass shaped body in a single salt bath, or a process of immersing the glass composition or the glass shaped body in a plurality of salt baths having the same or different compositions.

(24) The method for manufacturing chemically strengthened glass according to (21), wherein the chemical strengthening process is a 1-step ion exchange method, in the ion exchange method, the molten salt of the salt bath is composed of two or more compounds according to a certain proportion, at least one of the compounds contains K salt or Na salt, preferably K salt, the temperature of the salt bath is 300-530 ℃, preferably 360-490 ℃, more preferably 410-460 ℃, and the time of the salt bath is 4-64 h, preferably 8-32 h, more preferably 10-24 h.

(25) The method for manufacturing chemically strengthened glass according to (21), wherein the chemical strengthening process is a 2-step ion exchange method, in the ion exchange method, the molten salt of the first-step salt bath is composed of two or more compounds according to a certain proportion, wherein the molten salt at least contains one or two of K salt and Na salt, preferably contains K salt and Na salt at the same time, the temperature of the first-step salt bath is 400-510 ℃, preferably 420-500 ℃, and the time of the first-step salt bath is 4-32 hours, preferably 8-24 hours; the molten salt of the second-step salt bath is composed of one or more than one compounds according to a certain proportion, wherein at least one of the compounds contains K salt or Na salt, preferably K salt, the temperature range of the second-step salt bath is 400-510 ℃, preferably 420-500 ℃, and more preferably the same as the temperature of the first-step salt bath; the time range of the salt bath in the second step is 0.5-16 h, preferably 0.5-8 h, and more preferably 0.5-4 h.

The invention has the beneficial effects that: through reasonable component design, the glass composition obtained by the invention has proper high-temperature viscosity and excellent production performance; the glass composition is suitable for chemical strengthening, and the chemically strengthened glass obtained after chemical strengthening has excellent mechanical properties and is suitable for devices and equipment with high scratch resistance and high wear resistance requirements.

Drawings

FIG. 1 is a graph of viscosity versus temperature for example 1 of the present invention.

FIG. 2 is a graph of viscosity versus temperature for inventive example 8.

FIG. 3 is a graph of viscosity versus temperature for example 21 of the present invention.

FIG. 4 is a graph of viscosity versus temperature for inventive example 24.

FIG. 5 is a microscopic Vickers hardness test chart of example 5 of the present invention.

FIG. 6 is a microscopic Vickers hardness test chart of example 13 of the present invention.

FIG. 7 is a microscopic Vickers hardness test chart of example 14 of the present invention.

FIG. 8 is a microscopic Vickers hardness test chart of example 20 of the present invention.

Fig. 9 is a stress-distance graph of example 28 of the present invention.

Detailed Description

The glass composition of the present invention and the chemically strengthened glass of the present invention are described in detail below, but the present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this. In the present invention, "glass composition" is defined as glass that has not been chemically strengthened (sometimes simply referred to as glass), and the glass formed by subjecting the glass composition to a chemical strengthening process is "chemically strengthened glass".

[ glass composition ]

In the present invention, the contents of the respective constituent components (components) of the glass composition and the chemically strengthened glass are, unless otherwise specified, expressed as a percentage (mol%) of the cation to the total mole of all the cation components and as a percentage (mol%) of the anion to the total mole of all the anion components.

Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means only A, or only B, or both A and B.

It should be noted that the ion valences of the components described in the present invention are representative values used for convenience, and are not different from other ion valences. The ion valence of each component present in the glass may be different from the representative value. For example, P is usually present in the glass in a state where the ion valence is 5, and hence "P" is used in the present specification ⁵⁺ "as a representative, but there is a possibility that the ion valence is in other states, and this is also within the scope of the present invention.

< regarding cationic component >

Si ⁴⁺ Is a component of a network former of glass, and has the effects of maintaining the stability of glass and the forming viscosity suitable for melting glass, and improving the chemical stability of glass. But if Si ⁴⁺ Too high a content of (b) may result in glass being refractory. Thus, Si ⁴⁺ The content of (B) is in the range of 30 to 50%, preferably 33 to 47%, more preferably 36 to 44%.

Al ³⁺ Is a network former component of glass. Al (Al) ³⁺ Can liftThe chemical stability of the glass is high, and the loose glass grid is formed, so that the strength of the glass is easily improved through a chemical strengthening process. At the same time, the glass contains Al in an appropriate amount ³⁺ And also has the function of reducing the possibility of the glass breaking under the conditions of scratching, pressing in of hard objects and the like. However, Al ³⁺ Excessive content can cause the internal defects of bubbles, stripes, stones and the like in the glass to be difficult to eliminate. Therefore, Al in the present invention ³⁺ The content of (b) is in the range of 20 to 35%, preferably 22.5 to 32.5%, more preferably 25 to 30%.

La ³⁺ Is a network modifying component of glass in which [ LaO ] is added ₆ ]Form exists of La ³⁺ Has the effects of inhibiting the formation of boron-oxygen tetrahedron and increasing the content of boron-oxygen trihedron, which is beneficial to Na ⁺ 、Li ⁺ And the migration efficiency in chemical strengthening. La ³⁺ And the high-temperature viscosity of the glass can be reduced, and the melting of the glass and the elimination of the internal defects are facilitated. The inventor finds that La is subjected to a great deal of experimental study ³⁺ The Young modulus and the micro Vickers hardness of the glass can be obviously improved, and the glass chemical strengthening performance and the surface compressive stress and the stress layer depth of the chemically strengthened glass are improved. However, La ³⁺ The softening temperature of the glass can be obviously improved, and the secondary hot processing technologies such as glass profiling and the like are not facilitated; on the other hand, La ³⁺ In case of excess, La ³⁺ Network exosomes tend to form in the glass and tend to agglomerate in the glass, resulting in microscopic inhomogeneities in the glass. The inventors of the present invention have found through a large number of experiments that La ³⁺ When the content is too high, the glass is liable to be crystallized during the secondary heat treatment, and the glass is liable to be microcracked during the chemical strengthening. On the other hand, La ³⁺ The cost of raw materials is high, and the control of the glass cost is not facilitated when a large amount of raw materials are contained. Therefore, La in the present invention ³⁺ The content of (b) is in the range of 0 to 2.5%, preferably 0.1 to 2%, more preferably 0.15 to 1.5%.

Y ³⁺ Has the effect of increasing Na ⁺ 、Li ⁺ The effect of the migration efficiency of the plasma during the chemical strengthening process. The inventor finds that Y is proved by a large amount of experimental researches ³⁺ When the content is proper, the light of the glass can be improvedTransmittance and hardness. However, Y ³⁺ Too high content can result in too high glass softening temperature and easily cause crystallization in the secondary heat treatment process of the glass. Thus, Y ³⁺ The content of (b) is in the range of 0 to 2.5%, preferably 0.1 to 2%, more preferably 0.15 to 1.5%.

La in the invention ³⁺ And Y ³⁺ Is favorable for eliminating Al ³⁺ The internal defect caused by over-high content is beneficial to improving the Al content ³⁺ Content in the glass. On the other hand, to avoid La ³⁺ And Y ³⁺ The excessive content of La results in the reduction of glass performance, and the inventors found through a large number of experimental studies that La is added ³⁺ And Y ³⁺ The total content La of ³⁺ +Y ³⁺ Is limited to more than 0 but not more than 4%, preferably 0.1 to 3%, more preferably 0.2 to 2%.

In the glass, La ³⁺ And Y ³⁺ Has the effect of mixed rare earth elements, and in silicate glass, the coexistence of the silicate glass and the glass in the glass is beneficial to improving the mechanical property and the chemical stability of the glass, so that the glass preferably contains La simultaneously ³⁺ And Y ³⁺ . Further, the inventors have found through extensive experimental studies that La can be controlled ³⁺ /(La ³⁺ +Y ³⁺ ) In the range of 0.2 to 0.8, preferably La ³⁺ /(La ³⁺ +Y ³⁺ ) 0.3 to 0.7, more preferably La ³⁺ /(La ³⁺ +Y ³⁺ ) When the content is 0.4-0.6, the effect of improving the mechanical property and the chemical stability of the glass is optimal.

B ³⁺ Is a network former component of glass. B ³⁺ The melting process of the glass batch can be improved, and the high-temperature viscosity of the molten glass can be obviously reduced; but B ³⁺ Too high a content of (b) may degrade the chemical strengthening property of the glass. Thus, B ³⁺ The content of (b) is in the range of 7 to 20%, preferably 8.5 to 17%, more preferably 10 to 15%.

Al ³⁺ 、B ³⁺ All have coordination forms that are relatively easily changed in glass. Under the conditions that the glass is scratched and pressed by hard objects, the pressure of the contact position can reach the magnitude of GPa. In Al ³⁺ And B ³⁺ Total content of Al ³⁺ +B ³⁺ Higher case is Al ³⁺ 、B ³⁺ The glass can be plastically deformed in a coordination mode under pressure, relaxation stress is generated to a certain extent, and the severity of scratches of the glass under scraping is reduced. However, Al ³⁺ +B ³⁺ Too high of a material may result in Si in the glass ⁴⁺ The content decreases, which in turn leads to a decrease in the strength of the glass substrate. Thus, Al ³⁺ +B ³⁺ The content of (b) is 29 to 50%, preferably 32 to 48%, more preferably 35 to 45%.

The inventor finds that La is contained in the glass through a large amount of experiments ³⁺ In the case of (B) ³⁺ The content is increased, so that the water resistance of the glass is improved. Therefore, in order to impart excellent water resistance to the glass, it is preferable to control La ³⁺ /B ³⁺ Is 0.25 or less, more preferably La ³ ⁺ /B ³⁺ Is 0.2 or less, and La is more preferable ³⁺ /B ³⁺ Is 0.15 or less.

The inventor finds out through a great deal of experimental research that Al is controlled ³⁺ /(2×La ³⁺ +Y ³⁺ +B ³⁺ +P ⁵⁺ ) Within the range of 1-2.5, the high-temperature viscosity of the glass can be further optimized, the internal quality of the glass is improved, and the bubble degree and the streak degree grade of the glass are improved. Therefore, Al is preferable ³⁺ /(2×La ³⁺ +Y ³⁺ +B ³⁺ +P ⁵⁺ ) 1 to 2.5, more preferably Al ³⁺ /(2×La ³⁺ +Y ³⁺ +B ³⁺ +P ⁵⁺ ) 1.2 to 2.2, and further preferably Al ³⁺ /(2×La ³⁺ +Y ³⁺ +B ³⁺ +P ⁵⁺ ) 1.4 to 2.

Na ⁺ Is a glass network external component, and Na is used in the chemical strengthening process ⁺ Participate in ion exchange and play a role in providing a surface compressive stress layer. At the same time, Na ⁺ It also has the effects of improving the meltability of glass and reducing the softening temperature of glass. However, Na ⁺ Too high a content may decrease the chemical stability of the glass and may be disadvantageous for the enhancement of the strength of the glass. Thus, Na ⁺ The content of (b) is 5 to 15%, preferably 6 to 14%, more preferably 7 to 13%.

Li ⁺ Outside the glass networkBulk component, in the chemical strengthening process, Li ⁺ Participate in ion exchange and play a role in providing a surface compressive stress layer. Meanwhile, Li ⁺ Has strong fluxing action and is beneficial to improving the content of components in the glass which are beneficial to the strength of the glass. However, Li ⁺ The content of (A) is too high, the glass is easy to crystallize, and the subsequent thermal processing is not facilitated. Thus, Li ⁺ The content of (b) is 1 to 10%, preferably 1.5 to 9%, more preferably 2 to 8%.

Na ⁺ And Li ⁺ All play a role in generating ion exchange and providing a surface pressure stress layer in the chemical strengthening process. Li ⁺ Has an ionic radius of less than Na ⁺ In the chemical strengthening process, Li in the glass ⁺ Has a much faster diffusion rate than Na ⁺ The diffusion rate of (c). Therefore, while containing Li ⁺ And Na ⁺ In the glass of (2), Li ⁺ Is the main source of deep lamination stress in the glass. Control of Li ⁺ With Li ⁺ And Na ⁺ Total content of (2) Li ⁺ +Na ⁺ Ratio of (A) to (B) Li ⁺ /(Li ⁺ +Na ⁺ ) The method plays a key role in optimizing the stress distribution of the chemically strengthened glass. Li is preferably limited in the invention ⁺ /(Li ⁺ +Na ⁺ ) The range of (A) is 0.1 to 0.5, more preferably 0.15 to 0.4, still more preferably 0.2 to 0.3, and the glass has an excellent chemical strengthening effect.

K ⁺ Is a glass network external component, a small amount of K ⁺ The meltability of the glass can be improved. In the present invention, K ⁺ The content of (b) is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 2%.

Ag ⁺ Is a glass network external component, and the glass contains a small amount of Ag ⁺ Does not significantly affect the strength and appearance of the glass, Ag ⁺ The glass may also be rendered antimicrobial. But Ag ⁺ Is relatively costly and tends to color the glass under poorly controlled melting conditions. Thus, Ag in the present invention ⁺ The content of (B) is in the range of 0 to 2%, preferably 0 to 1%, more preferably 0 to 0.2%, further preferably not containing Ag ⁺ 。

Rb ⁺ Is a glass network outer body component.Rb ⁺ Having a relative K ⁺ The larger ionic radius is more prone to reduce the connection degree of the glass network, and is not beneficial to improving the mechanical property of the glass. Meanwhile, Rb ⁺ The raw material cost of the catalyst is obviously higher than that of Na ⁺ And K ⁺ . Thus, Rb in the glasses of the invention ⁺ The content of (B) is in the range of 0 to 2%, preferably 0 to 1%, more preferably 0 to 0.2%, and further preferably no Rb ⁺ 。

Monovalent element component Li in glass ⁺ 、Na ⁺ 、K ⁺ 、Ag ⁺ 、Rb ⁺ All have the effect of reducing the integrity of the glass network if the total content of Li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ Too high is not favorable for improving the strength and chemical stability of the glass. However, if Li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ If the amount is too low, the glass is not easily melted. Therefore, Li is preferable ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ The range of (A) is 10 to 23%, more preferably 13.5 to 22%, and still more preferably 16 to 21.5%.

B ³⁺ The coordination is important to the performance of the glass of the invention. B is ³⁺ Having [ BO ] in glass ₃ ]、[BO ₄ ]Two coordination states. [ BO ] ₄ ]Coordination structure comparison [ BO ₃ ]But in which the B — O bond is too short, the ion transfer efficiency during chemical strengthening is severely reduced. [ BO ] ₃ ]The structure is in a plane triangle shape, and the glass has the function of compacting a glass network within the composition range of the glass, and simultaneously does not obviously influence the ion migration efficiency in the chemical strengthening process, so the glass is expected to be B ³⁺ Mainly comprises [ BO ₃ ]The form exists. The inventors have found through extensive experimental studies that it is preferable to limit Al in order to obtain the above-mentioned effects ³⁺ /(Li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ ) Has a value of 1.1 or more, more preferably Al ³⁺ /(Li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ ) The value of (A) is 1.15 or more, and Al is more preferable ³⁺ /(Li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ ) Is/are as followsThe value is 1.2 to 2.5.

Zn ²⁺ Is a network intermediate component of the glass, Zn relative to other alkaline earth metal components ²⁺ The tendency to enter the glass network is greatest. At the same time, Zn ²⁺ It also has the effect of imparting gloss to the appearance of the glass. Zn ²⁺ At lower contents, the glass has the effect of reducing the melting temperature and the tendency to devitrify, and does not have a significant effect on the ion diffusion coefficient of the glass. But if Zn ²⁺ Too high a content easily causes devitrification of the glass and lowers the chemical strengthening property of the glass. Thus, Zn ²⁺ The content of (b) is in the range of 0 to 5%, preferably 0 to 3%, and more preferably 0.5 to 2%.

Mg ²⁺ Is a network intermediate component of glass. Mg (magnesium) ²⁺ Has the strengthening effect on the glass network, and simultaneously has the effects of improving the melting property of the glass and reducing the softening temperature of the glass. However, Mg ²⁺ Too much of (b) may degrade the chemical strengthening properties of the glass. Thus, Mg ²⁺ The content of the glass is 0 to 10%, preferably 1 to 9%, and more preferably 2 to 8%.

Ca ²⁺ Is a network intermediate component of glass. Ca ²⁺ Has the functions of strengthening glass network, improving glass melting property and reducing glass softening temperature. Ca ²⁺ The effect of improving the Young's modulus of glass is better than that of Mg ²⁺ However, contains Ca ²⁺ The glass releases Ca in the salt bath for chemical strengthening ²⁺ And a trace amount of Ca ²⁺ The salt bath for chemical strengthening will be deactivated. Thus Ca ²⁺ The content of (b) is in the range of 0 to 10%, preferably 0 to 4%, more preferably 0 to 2%.

Sr ²⁺ And Ba ²⁺ Is a network intermediate component of glass. Sr ²⁺ And Ba ²⁺ Has larger ionic radius, and has the effect of reducing the melting temperature of the glass when the content is lower. However, Sr ²⁺ And Ba ²⁺ Has the adverse effects of promoting phase separation of the glass and reducing the chemical stability of the glass. Therefore, Sr in the present invention ²⁺ The content of (b) is in the range of 0 to 5%, preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably Sr is not contained ²⁺ (ii) a Ba in the invention ²⁺ The content of (B) is in the range of 0 to 5%, preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably not containing Ba ²⁺ 。

In some embodiments of the invention, it is preferred that the glass also contain Zn ²⁺ 、Mg ²⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ Two or more components in the glass are beneficial to constructing mixed alkaline earth metal effect in the glass, can improve the strength of the glass and improve the meltability of the glass, and more preferably, the glass simultaneously contains Zn ²⁺ 、Mg ²⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ Two or three or four components of (1), further preferably the glass contains Zn together ²⁺ 、Mg ²⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ More preferably, the glass contains Zn together with the two components of (1) ²⁺ And Mg ²⁺ 。

Zr ⁴⁺ Has the functions of improving the chemical stability of the glass and increasing the ion diffusion coefficient of the glass, Zr ⁴⁺ The drop resistance of the glass can also be improved. However, Al is contained in the glass of the present invention ³⁺ In the case of a high content, Zr ⁴⁺ The solubility in the glass is reduced, and the glass is prone to generate defects such as stones. Thus, Zr ⁴⁺ The content of (B) is in the range of 0 to 2%, preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably no Zr is contained ⁴⁺ 。

P ⁵⁺ Is a network former component of glass. In the high aluminosilicate glass system of the present invention, a small amount of P is contained ⁵⁺ Has the effects of improving the meltability of the glass and reducing the crystallization of the glass. P ⁵⁺ And the glass network can be modified, so that the effect of chemically strengthening the glass is improved. At the same time, a small amount of P ⁵⁺ The hardness and the corrosion resistance of the glass cannot be obviously influenced; suitably containing P ⁵⁺ And the glass has the beneficial effect of improving the light transmittance of the glass. However, P ⁵⁺ Volatile in continuous production, volatile falls into molten glass to cause ingredient nonuniformity, and contains P ⁵⁺ The glass is easy to generate phase separation at the lower temperature of the electric melting and all-platinum continuous melting production line, and is not beneficial to the production of the glass. Accordingly, the present invention P ⁵⁺ The content of (b) is 0 to 4%, preferably 0 to 2.25%, more preferably 0 to 1.75%.

Sb ³⁺ Can change the valence state of elements in molten glass along with temperature, and has the function of easily eliminating bubbles in the glass. Sb ³⁺ The content of (b) is in the range of 0 to 0.5%, preferably 0 to 0.2%, more preferably 0 to 0.1%.

Sn ⁴⁺ Can change the valence state of elements in molten glass along with temperature, and has the function of easily eliminating bubbles in the glass. Relative Sb ³⁺ ，Sn ⁴⁺ The effective action temperature of (b) is higher, and is more suitable for use in the present invention. However, the mode of refining the glass of the present invention is not limited to the use of Sn ⁴⁺ . Thus, Sn ⁴⁺ The content of (b) is in the range of 0 to 1%, preferably 0.05 to 0.4%, more preferably 0.1 to 0.3%.

Ce ⁴⁺ Can be used as a clarifier, but contains Ce ⁴⁺ The ultraviolet absorption limit of the glass can be shifted to the right, which can cause the color of the glass to be yellow and the appearance to be undesirable. Thus, Ce ⁴⁺ The content of (b) is in the range of 0 to 0.5%, preferably 0 to 0.2%, more preferably 0 to 0.1%, and further preferably, Ce is not contained ⁴⁺ 。

Ti ⁴⁺ Is a glass network intermediate element. Ti ⁴⁺ Having a higher field strength, but Ti ⁴⁺ Has the function of a nucleating agent in the glass and is not beneficial to the preparation of the glass by a melting method. Therefore, the present invention preferably does not contain Ti ⁴⁺ 。

For environmental friendliness, the glasses according to the invention are preferably free of Pb ²⁺ And As ³⁺ 。

< regarding the anionic Components >

The glass composition of the present invention is an oxide glass, and the anionic component mainly contains O ^2- ，O ^2- The content is 98-100%, preferably 99-100%, more preferably 99.5-100%, and further preferably 99.9-100%. A certain amount of SO is contained in the glass due to the melting requirement of the glass, impurities in raw materials, residual clarifying agent and the like ₄ ^2- 、Cl ^- 、S ^2- Plasma anions not forming part of the inventionInfluence of (1), except for O ^2- Other anions than (e.g. SO) ₄ ^2- 、Cl ^- 、S ^2- Etc.) is 2% or less, preferably 1% or less, more preferably 0.5% or less, and still more preferably 0.1% or less.

"0%" or "0%" is not included in the present invention, and means that the compound, molecule, ion, element or the like is not intentionally added to the glass of the present invention as a raw material; however, it is also within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for producing the glass, and may be present in small or trace amounts in the final glass.

< method for producing glass composition >

The method for producing the glass composition of the present invention comprises: common raw materials for glass (such as oxides, hydroxides, carbonates, sulfates, nitrates, phosphates, metaphosphates, etc.) are weighed and mixed correspondingly according to the composition of the glass composition, and the mixed raw materials are placed in a melting apparatus, heated, and melted. The melting of the raw materials of the glass composition of the present invention can be accomplished in a refractory chamber or a platinum chamber. Under the condition that the raw material melting process is finished in the refractory material cavity, the molten glass is conveyed into the platinum material cavity through a platinum pipeline for clarification and homogenization. The melting temperature of the glass composition is 1350-1600 ℃, and preferably 1450-1550 ℃. After the above raw materials are completely melted and vitrified, the temperature of the molten glass is raised and the glass is refined. The clarification temperature of the glass composition is 1500-1650 ℃, and is preferably 1540-1610 ℃. The settling time is 2-24 h, preferably 4-12 h. Homogenizing the clarified molten glass by stirring with a stirrer, or continuously supplying the homogenized molten glass to a glass outflow pipeline for outflow, and rapidly cooling and solidifying the molten glass in a glass mold to obtain a glass composition; or pouring the mixture into a mold with a specific shape from a melting container, and carrying out processes of quenching, solidification and annealing to obtain the glass composition. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.

[ chemically strengthened glass and Process for producing the same ]

Forming chemically strengthened glass by a chemical strengthening process on the glass composition; or the glass composition is made into a glass forming body through various processes, and then the chemically strengthened glass is formed through a chemical strengthening process.

The glass shaped body is obtained by cold working and/or hot working a glass composition. For example, the glass composition of the present invention can be used to produce a glass shaped article by a method such as grinding or polishing, but the production of a glass shaped article is not limited to these methods. The glass composition of the present invention can be produced into glass shaped articles having various shapes by a method such as hot bending or press molding at a certain temperature, but the production of the glass shaped articles is not limited to these methods. The glass shaped body includes, but is not limited to, a sheet, a block, a non-planar shape, and the like. The term "non-planar shape" refers to a shape having a surface comprising one or more curved surfaces of any shape. The glass shaped bodies of the present invention can have any reasonably useful size range, such as thickness or diameter.

In some embodiments, the glass compositions described herein can be manufactured into glass shaped bodies, including but not limited to sheets, by various processes, including but not limited to slot draw, float, roll, and other processes of forming sheets. Alternatively, the glass composition may be formed by a float process or a roll process, and a glass shaped body may be formed.

In some embodiments, the glass composition may be processed into sheets, and/or shaped (e.g., punched, hot bent, etc.), shaped, polished and/or swept, and chemically strengthened by a chemical strengthening process.

In some embodiments, the chemical strengthening process of the present invention comprises an ion exchange process.

The ion exchange method according to the present invention is a method in which when a glass composition or a glass molded article is immersed in a molten salt having a predetermined composition, monovalent metal cations (for example, Li) in the glass composition or the glass molded article ⁺ 、Na ⁺ 、K ⁺ 、Ag ⁺ 、Rb ⁺ ) To near the glassOther monovalent metal cations of compositions or glass-forming bodies (e.g. Na) ⁺ 、K ⁺ 、Ag ⁺ 、Rb ⁺ 、Cs ⁺ ) The substitution is carried out.

In some embodiments, the ion exchange process of the present invention is to immerse the glass composition or glass shaped body in a single salt bath, or to immerse the glass composition or glass shaped body in multiple salt baths of the same or different composition. In the case of ion exchange using multiple salt baths of different compositions, there may be a washing and/or heat treatment step between each ion exchange step.

The preferred ion exchange method of the present invention is a 1-step ion exchange method or a 2-step ion exchange method.

In some embodiments, the molten salt of the salt bath in the 1-step ion exchange process of the present invention may be composed of two or more compounds in a ratio wherein at least one of the compounds contains a K salt (e.g., KNO) ₃ ) Or Na salt (such as NaNO) ₃ ) Preferably containing K salts (e.g. KNO) ₃ ) The temperature range of the salt bath is 300-530 ℃, the preferable temperature range is 360-490 ℃, the more preferable temperature range is 410-460 ℃, and the time range of the salt bath is 4-64 h, the preferable time range is 8-32 h, and the more preferable time range is 10-24 h. In the process range of the invention, practitioners in the art can select appropriate process parameters according to actual needs.

In some embodiments, the molten salt of the first salt bath in the 2-step ion exchange process of the present invention may be composed of two or more compounds in a ratio that includes at least a K salt (e.g., KNO) ₃ ) And Na salts (e.g., NaNO) ₃ ) Preferably containing both K salts (e.g. KNO) ₃ ) And Na salts (e.g., NaNO) ₃ ) The temperature range of the first-step salt bath is 400-510 ℃, the preferable range is 420-500 ℃, and the time range of the first-step salt bath is 4-32 hours, and the preferable range is 8-24 hours. The molten salt of the second salt bath may be composed of one or more compounds in a certain proportion, wherein at least one of them contains K salt (such as KNO) ₃ ) Or Na salt (e.g. NaNO) ₃ ) Preferably containing a K salt (e.g. KNO) ₃ ). The temperature range of the salt bath in the second step is 400-510 ℃, preferablySelecting the temperature to be 420-500 ℃, and more preferably selecting the temperature to be the same as the temperature of the first-step salt bath; the time range of the second-step salt bath is 0.5-16 h, preferably 0.5-8 h, and more preferably 0.5-4 h. In the process range of the invention, practitioners in the art can select appropriate process parameters according to actual needs.

In some embodiments, the chemical strengthening process described herein may be used in conjunction with a thermal strengthening process in which the glass composition or glass shaped body is heated and then rapidly cooled. The glass composition of the present invention can also be used to obtain a tempered glass having a certain value in use by a conventional common heat tempering method.

The properties of the glass composition and the chemically strengthened glass of the present invention will be described below.

< glass viscosity (. mu.)

The viscosity (. mu.) of the glass composition was measured in the range of 900 to 1550 ℃ using ASTM C965-96. In the present document, "mu" is defined ₁₄₀₀ "viscosity of the glass composition at a temperature of 1400. + -. 1 ℃ in dPas. In some embodiments, for ease of illustration, μ is used ₁₄₀₀ The high temperature viscosity of the glass composition is characterized.

The glass has higher aluminum content and overhigh viscosity, and is difficult to eliminate intrinsic defects; if the viscosity is too low, the Vickers hardness of the obtained glass is low. Thus, in some embodiments, μ of a glass composition of the invention ₁₄₀₀ The value is 120 dPas or less, preferably 100 dPas or less, and more preferably 88 to 96 dPas.

To improve the surface quality of the chemically strengthened glass, the glass composition should have as good a water resistance as possible. The water resistance (D) of the glass is determined according to the test method of GB/T17129 _w )。

In some embodiments, the water resistance (D) of the glass compositions of the present invention _w ) Is 2 or more, preferably 1.

< Young's modulus (E) >

Young's modulus (E) was measured according to the method specified in GB/T7962.6-2010.

In some embodiments, the inventive glass composition has a Young's modulus (E) of 7800X 10 ⁷ Pa or more, preferably 8200X 10 ⁷ Pa or more, more preferably 8300X 10 ⁷ Pa or above.

< micro Vickers hardness >

The micro vickers hardness was measured according to the following method: the glass composition or the chemically strengthened glass is subjected to a micro vickers hardness test. The test was carried out using a microhardness tester with a microscopic observation device. Using a rectangular parallelepiped sample having a plane of grinding and polishing, the area of the polishing plane of the sample should be larger than 1cm ² And should be much larger than the indenter tip size for the vickers hardness test. A standard vickers hardness indenter, i.e., a vickers hardness diamond indenter with an apex angle of 136 °, was used. And applying a test force of 200g on the indenter to enable the indenter to vertically contact with the polished plane of the sample, keeping for 20 seconds, removing the indenter, and converting the Vickers hardness according to the length of the diagonal line of the indentation. And (3) carrying out 7 times of micro Vickers hardness tests on a single sample, taking the average value as the result of the micro Vickers hardness tests on the sample, wherein the standard deviation is less than 5% of the result of the micro Vickers hardness tests.

The micro vickers hardness of the glass composition is related to the glass composition. The glass composition has high micro Vickers hardness, and is favorable for improving the micro Vickers hardness of the chemically strengthened glass and improving the scratch resistance and the wear resistance of the chemically strengthened glass.

In some embodiments, the glass compositions of the present invention have a micro vickers hardness of 630 x 10 ⁷ Pa or more, preferably 640X 10 ⁷ Pa or more, more preferably 645X 10 ⁷ ～665×10 ⁷ Pa。

The micro Vickers hardness of the chemically strengthened glass is related to the micro Vickers hardness and the chemical strengthening mode of the corresponding glass composition. The micro Vickers hardness of the chemically strengthened glass is improved, and the scratch resistance and the wear resistance of the chemically strengthened glass can be improved; however, when the micro vickers hardness of the corresponding glass composition is constant, the micro vickers hardness of the chemically strengthened glass is too high, and the ion exchange degree in the chemical strengthening process tends to increase, thereby increasing the risk of spontaneous explosion of the chemically strengthened glass.

In some embodiments, the chemically strengthened glass has a micro vickers hardness of 680 x 10 ⁷ Pa or more, preferably 685X 10 ⁷ Pa or more, more preferably 690X 10 ⁷ ～705×10 ⁷ Pa。

< surface stress value (CS) >

The surface stress value (CS) of the chemically strengthened glass of the invention was measured using an SLP-2000 photoelastic stress tester.

The surface stress value (CS) can be tested by using a sample with the thickness of 0.1-5 mm, and preferably 0.5-3 mm. In the examples of the present invention, the thickness of the sample used for the surface stress value test was 2 mm.

In some embodiments, the chemically strengthened glass of the present invention has a surface stress value (CS) of greater than 800 MPa.

< depth of stress layer (DOL) >

The stress layer Depth (DOL) of the chemically strengthened glass of the present invention was measured using an SLP-2000 photoelastic stress tester.

The stress layer depth refers to the vertical distance from the glass surface of the position where the compressive stress of the chemically strengthened glass is 0. The depth of the stress layer is expressed in DOL and has a unit of μm. The stress layer depth of the chemically strengthened glass of the invention was measured using an SLP-2000 photoelastic stress tester.

The depth of stress layer (DOL) can be measured using a sample having a thickness (d) of 0.1 to 5mm, preferably 0.5 to 3 mm. In the examples of the present invention, the thickness of the sample used for the depth of stress layer test was 2 mm.

In some embodiments, the chemically strengthened glass of the present invention has a depth of stress layer (DOL) greater than 180 μm.

In some embodiments, the chemically strengthened glass of the present invention has a ratio (DOL/d) of the depth of stress layer (DOL) to the thickness (d) of the chemically strengthened glass of 0.05 or more, preferably 0.07 or more, and more preferably 0.09 or more.

[ glass preform and glass Member ]

The glass preform can be produced from the glass composition produced by means of, for example, grinding or press molding such as hot press molding or precision press molding. That is, the glass composition may be subjected to mechanical processing such as grinding and polishing to produce a glass preform, or the glass composition may be subjected to preform for press molding, followed by reheat press molding and polishing to produce a glass preform, or the glass composition may be subjected to precision press molding to produce a preform obtained by polishing. It should be noted that the means for producing the glass preform is not limited to the above means.

The glass compositions, glass preforms of the present invention can be used to make glass components including, but not limited to, glass cover plates, prisms, lenses, and the like. As described above, the glass composition or the chemically strengthened glass of the present invention is useful for cover glass for applications such as mobile phones, wearable devices, display screens, and solar panels, and particularly, it is preferable that a glass molded body is formed from the glass composition of the present invention, and then the chemically strengthened glass is produced by the chemical strengthening process of the present invention to produce a glass element such as a cover glass (e.g., a panel or a back plate of a mobile phone, a smart watch, a computer, or the like). The glass composition of the present invention can be used to form a preform, and the preform can be used to manufacture a glass element such as a lens or a prism by reheat press forming, precision press forming or the like, and then be strengthened by a chemical strengthening process.

The glass preform and the glass member of the present invention can be formed of the above-described glass composition or chemically strengthened glass of the present invention. The glass preform of the present invention has excellent characteristics possessed by a glass composition or chemically strengthened glass; the glass element of the present invention has excellent characteristics possessed by a glass composition or chemically strengthened glass.

[ apparatus ]

The glass composition or the chemically strengthened glass and the glass element prepared from the glass composition or the chemically strengthened glass can be used for manufacturing parts such as panels and back plates of electronic equipment, portable communication equipment (such as mobile phones), intelligent wearing equipment, photographic equipment, camera equipment, display equipment, monitoring equipment and the like.

Examples

In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.

< glass composition examples >

The present invention provides glass compositions having compositions shown in tables 1 to 3, which were obtained by the above-described methods for producing glass compositions. The characteristics of each glass composition were measured by the test method described in the present invention, and the test results are shown in tables 1 to 3.

Table 1.

Table 2.

Table 3.

In Table 4, examples 25 to 32 were prepared by chemically strengthening the above glass composition by the chemical strengthening process of the present invention. The following examples were carried out by means of secondary ion exchange: the first step molten salt component is 20 wt% KNO ₃ + 80% by weight of NaNO ₃ The exchange temperature is 440 ℃, and the exchange time is 10 h; second step molten saltKNO with 98 wt% of component ₃ + 2% by weight of NaNO ₃ The exchange temperature was 420 ℃ and the exchange time was 1 h.

TABLE 4

Claims

1. Glass composition, characterized in that its components, expressed in molar percentages, have a cation comprising: si ⁴⁺ ：30～50％；Al ³⁺ ：20～35％；La ³⁺ +Y ³⁺ : greater than 0 but less than or equal to 4%; b is ³⁺ ：7～20％；Na ⁺ ：5～15％；Li ⁺ : 1 to 10% of La ³⁺ /(La ³⁺ +Y ³⁺ ) 0.2 to 0.8.

2. The glass composition according to claim 1, wherein the constituents thereof, expressed in mole percent, the cations further comprise: k ⁺ : 0 to 5 percent; and/or Ag ⁺ : 0-2%; and/or Rb ⁺ : 0-2%; and/or Zn ²⁺ : 0 to 5 percent; and/or Mg ²⁺ : 0 to 10 percent; and/or Ca ²⁺ : 0 to 10 percent; and/or Sr ²⁺ : 0 to 5 percent; and/or Ba ²⁺ : 0 to 5 percent; and/or Zr ⁴⁺ : 0-2%; and/or P ⁵⁺ : 0 to 4 percent; and/or Sb ³⁺ : 0 to 0.5 percent; and/or Sn ⁴⁺ : 0 to 1 percent; and/or Ce ⁴⁺ ：0～0.5％。

3. Glass composition, characterized in that its components, expressed in molar percentages, have the cation: si ⁴⁺ ：30～50％；Al ³⁺ ：20～35％；La ³⁺ +Y ³⁺ : greater than 0 but less than or equal to 4%; b is ³⁺ ：7～20％；Na ⁺ ：5～15％；Li ⁺ ：1～10％；K ⁺ ：0～5％；Ag ⁺ ：0～2％；Rb ⁺ ：0～2％；Zn ²⁺ ：0～5％；Mg ²⁺ ：0～10％；Ca ²⁺ ：0～10％；Sr ²⁺ ：0～5％；Ba ² ⁺ ：0～5％；Zr ⁴⁺ ：0～2％；P ⁵⁺ ：0～4％；Sb ³⁺ ：0～0.5％；Sn ⁴⁺ ：0～1％；Ce ⁴⁺ : 0 to 0.5% of La ³⁺ /(La ³⁺ +Y ³⁺ ) 0.2 to 0.8.

4. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: la ³⁺ /(La ³⁺ +Y ³⁺ ) 0.3 to 0.7.

5. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: la ³⁺ /(La ³⁺ +Y ³⁺ ) 0.4 to 0.6.

6. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: al (Al) ³⁺ +B ³⁺ Is 29 to 50%.

7. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: al (Al) ³⁺ +B ³⁺ Is 32 to 48 percent.

8. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: al (Al) ³⁺ +B ³⁺ 35 to 45 percent.

9. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: la ³⁺ /B ³⁺ Is 0.25 or less.

10. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: la ³⁺ /B ³⁺ Is 0.2 or less.

11. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: la ³⁺ /B ³⁺ Is 0.15 or less.

12. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: al (Al) ³⁺ /(2×La ³⁺ +Y ³⁺ +B ³⁺ +P ⁵⁺ ) 1 to 2.5.

13. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: al (Al) ³⁺ /(2×La ³⁺ +Y ³⁺ +B ³⁺ +P ⁵⁺ ) 1.2 to 2.2.

14. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: al (Al) ³⁺ /(2×La ³⁺ +Y ³⁺ +B ³⁺ +P ⁵⁺ ) 1.4 to 2.

15. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: li ⁺ /(Li ⁺ +Na ⁺ ) 0.1 to 0.5.

16. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: li ⁺ /(Li ⁺ +Na ⁺ ) 0.15 to 0.4.

17. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: li ⁺ /(Li ⁺ +Na ⁺ ) 0.2 to 0.3.

18. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ 10 to 23 percent.

19. Glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are such that: li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ 13.5 to 22 percent.

20. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ 16 to 21.5 percent.

21. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: al (Al) ³⁺ /(Li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ ) Is 1.1 or more.

22. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: al (Al) ³⁺ /(Li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ ) Is 1.15 or more.

23. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: al (Al) ³⁺ /(Li ⁺ +Na ⁺ +K ⁺ +Ag ⁺ +Rb ⁺ ) 1.2 to 2.5.

24. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: si ⁴⁺ : 33 to 47 percent; and/or Al ³⁺ : 22.5-32.5%; and/or La ³⁺ +Y ³⁺ : 0.1-3%; and/or B ³⁺ : 8.5-17%; and/or Na ⁺ : 6-14%; and/or Li ⁺ : 1.5-9%; and/or K ⁺ : 0 to 3 percent; and/or Ag ⁺ : 0 to 1 percent; and/or Rb ⁺ : 0 to 1 percent; and/or Zn ²⁺ : 0 to 3 percent; and/or Mg ²⁺ : 1-9%; and/or Ca ²⁺ : 0 to 4 percent; and/or Sr ²⁺ : 0 to 1 percent; and/or Ba ²⁺ : 0 to 1 percent; and/or Zr ⁴⁺ : 0 to 1 percent; and/or P ⁵⁺ : 0 to 2.25 percent; and/or Sb ³⁺ : 0 to 0.2 percent; and/or Sn ⁴ ⁺ : 0.05-0.4%; and/or Ce ⁴⁺ ：0～0.2％。

25. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: si ⁴⁺ : 36-44%; and/or Al ³⁺ : 25-30%; and/or La ³⁺ +Y ³⁺ : 0.2-2%; and/or B ³⁺ : 10-15%; and/or Na ⁺ : 7-13%; and/or Li ⁺ : 2-8%; and/or K ⁺ : 0-2%; and/or Ag ⁺ : 0 to 0.2 percent; and/or Rb ⁺ : 0 to 0.2 percent; and/or Zn ²⁺ : 0.5-2%; and/or Mg ²⁺ : 2-8%; and/or Ca ²⁺ : 0-2%; and/or Sr ²⁺ : 0 to 0.5 percent; and/or Ba ²⁺ : 0 to 0.5 percent; and/or Zr ⁴⁺ : 0 to 0.5 percent; and/or P ⁵⁺ : 0 to 1.75 percent; and/or Sb ³⁺ : 0 to 0.1 percent; and/or Sn ⁴⁺ : 0.1-0.3%; and/or Ce ⁴⁺ ：0～0.1％。

26. The glass composition according to any one of claims 1 to 3, wherein Ag is not contained ⁺ (ii) a And/or does not contain Rb ⁺ (ii) a And/or does not contain Sr ²⁺ (ii) a And/or do not contain Ba ²⁺ (ii) a And/or does not contain Zr ⁴⁺ 。

27. A method according to any one of claims 1 to 3The glass composition is characterized in that the components are expressed in mole percent, wherein: la ³⁺ : 0 to 2.5%, and/or Y ³⁺ ：0～2.5％。

28. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: la ³⁺ : 0.1-2%, and/or Y ³⁺ ：0.1～2％。

29. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: la ³⁺ : 0.15 to 1.5%, and/or Y ³⁺ ：0.15～1.5％。

30. The glass composition according to any one of claims 1 to 3, wherein Zn is contained in the glass composition at the same time ²⁺ 、Mg ²⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ Two or more components of (1).

31. The glass composition according to any one of claims 1 to 3, wherein Zn is contained in the glass composition at the same time ²⁺ 、Mg ²⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ Two or three or four components.

32. The glass composition according to any one of claims 1 to 3, wherein Zn is contained in the glass composition at the same time ²⁺ 、Mg ²⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ Two components of (a).

33. The glass composition according to any one of claims 1 to 3, wherein Zn is contained in the glass composition at the same time ²⁺ And Mg ²⁺ 。

34. The glass composition according to any of claims 1 to 3, wherein the glass compositionIn that its composition, expressed in mole percentages, the anion contains: o is ^2- ：98～100％。

35. A glass composition according to any one of claims 1 to 3, characterized in that the composition comprises, in mole percent, anions comprising: o is ^2- ：99～100％。

36. A glass composition according to any one of claims 1 to 3, characterized in that the composition comprises, in mole percent, anions comprising: o is ^2- ：99.5～100％。

37. Glass composition according to any one of claims 1 to 3, characterized in that the composition thereof, expressed in terms of mole percentages, comprises, as anions: o is ^2- ：99.9～100％。

38. The glass composition according to any one of claims 1 to 3, wherein the glass composition has a μ ₁₄₀₀ Is 120 dPas or less; and/or water resistance D _w Is more than 2 types; and/or a Young's modulus E of 7800X 10 ⁷ Pa is above; and/or a micro Vickers hardness of 630X 10 ⁷ Pa or above.

39. The glass composition according to any one of claims 1 to 3, wherein μ of the glass composition ₁₄₀₀ Is 100 dPas or less; and/or water resistance D _w Is of type 1; and/or a Young's modulus E of 8200X 10 ⁷ Pa is above; and/or a micro Vickers hardness of 640X 10 ⁷ Pa or above.

40. The glass composition according to any one of claims 1 to 3, wherein μ of the glass composition ₁₄₀₀ 88 to 96 dPas; and/or a Young's modulus E of 8300X 10 ⁷ Pa is above; and/or a micro Vickers hardness of 645X 10 ⁷ ～665×10 ⁷ Pa。

41. A chemically strengthened glass comprising the glass composition according to any one of claims 1 to 40.

42. The chemically strengthened glass according to claim 41, wherein the chemically strengthened glass has a micro Vickers hardness of 680 x 10 ⁷ Pa or above; and/or the surface stress value CS is greater than 800 MPa; and/or the ratio DOL/d of the depth of the stress layer to the thickness of the chemically strengthened glass is 0.05 or more.

43. The chemically strengthened glass according to claim 41, wherein the chemically strengthened glass has a micro Vickers hardness of 685 x 10 ⁷ Pa or above; and/or the ratio DOL/d of the depth of the stress layer to the thickness of the chemically strengthened glass is 0.07 or more.

44. The chemically strengthened glass according to claim 41, wherein the chemically strengthened glass has a micro Vickers hardness of 690 x 10 ⁷ ～705×10 ⁷ Pa; and/or the ratio DOL/d of the depth of the stress layer to the thickness of the chemically strengthened glass is 0.09 or more.

45. A glass preform made of the glass composition according to any one of claims 1 to 40 or the chemically strengthened glass according to any one of claims 41 to 44.

46. A glass component made of the glass composition according to any one of claims 1 to 40, or made of the chemically strengthened glass according to any one of claims 41 to 44, or made of the glass preform according to claim 45.

47. An apparatus comprising the glass composition according to any one of claims 1 to 40, and/or comprising the chemically strengthened glass according to any one of claims 41 to 44, and/or comprising the glass element according to claim 46.

48. A method for producing chemically strengthened glass, characterized by comprising the steps of: a glass composition according to any one of claims 1 to 40, which is formed into a chemically strengthened glass by a chemical strengthening process, or a glass composition is formed into a glass molded product and then formed into a chemically strengthened glass by a chemical strengthening process.

49. The method of claim 48, wherein the glass is formed into a glass shaped body by a grinding or polishing process, or by a hot bending or pressing process at a certain temperature.

50. The method of manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is immersing the glass composition or glass shaped body in a single salt bath or immersing the glass composition or glass shaped body in multiple salt baths of the same or different compositions.

51. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 1-step ion exchange method in which the molten salt of the salt bath is composed of two or more compounds in a certain proportion, at least one of the compounds contains K salt or Na salt, the temperature of the salt bath is 300-530 ℃, and the time of the salt bath is 4-64 hours.

52. The method for producing a chemically strengthened glass as claimed in claim 48, wherein the chemical strengthening process is a 1-step ion exchange method in which a molten salt in a salt bath is composed of two or more compounds at a given ratio, at least one of the compounds contains a K salt or a Na salt, the temperature of the salt bath is 300 to 530 ℃ and the time of the salt bath is 8 to 32 hours.

53. The method for producing a chemically strengthened glass as claimed in claim 48, wherein the chemical strengthening process is a 1-step ion exchange method in which a molten salt in a salt bath is composed of two or more compounds at a given ratio, at least one of the compounds contains a K salt or a Na salt, the temperature of the salt bath is 300 to 530 ℃ and the time of the salt bath is 10 to 24 hours.

54. The method for producing a chemically strengthened glass as claimed in claim 48, wherein the chemical strengthening process is a 1-step ion exchange method in which a molten salt in a salt bath is composed of two or more compounds at a given ratio, at least one of the compounds contains a K salt or a Na salt, the temperature of the salt bath is 360 to 490 ℃ and the time of the salt bath is 4 to 64 hours.

55. The method for producing a chemically strengthened glass as claimed in claim 48, wherein the chemical strengthening process is a 1-step ion exchange method in which a molten salt in a salt bath is composed of two or more compounds at a given ratio, at least one of the compounds contains a K salt or a Na salt, the temperature of the salt bath is 360 to 490 ℃ and the time of the salt bath is 8 to 32 hours.

56. The method for producing a chemically strengthened glass as claimed in claim 48, wherein the chemical strengthening process is a 1-step ion exchange method in which a molten salt in a salt bath is composed of two or more compounds at a given ratio, at least one of the compounds contains a K salt or a Na salt, the temperature of the salt bath is 360 to 490 ℃ and the time of the salt bath is 10 to 24 hours.

57. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 1-step ion exchange method in which the molten salt of the salt bath is composed of two or more compounds in a certain proportion, at least one of the compounds contains K salt or Na salt, the temperature of the salt bath is 410-460 ℃, and the time of the salt bath is 4-64 hours.

58. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 1-step ion exchange method, in the ion exchange method, the molten salt of the salt bath is composed of two or more compounds according to a certain proportion, at least one of the compounds contains K salt or Na salt, the temperature of the salt bath is 410-460 ℃, and the time of the salt bath is 8-32 hours.

59. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 1-step ion exchange method, in the ion exchange method, the molten salt of the salt bath is composed of two or more compounds according to a certain proportion, at least one of the compounds contains K salt or Na salt, the temperature of the salt bath is 410-460 ℃, and the time of the salt bath is 10-24 hours.

60. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 1-step ion exchange method, in the ion exchange method, the molten salt of the salt bath is composed of two or more compounds according to a certain proportion, at least one of the compounds contains K salt, the temperature of the salt bath is 300-530 ℃, and the time of the salt bath is 4-64 h.

61. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 1-step ion exchange method, in the ion exchange method, the molten salt of the salt bath is composed of two or more compounds according to a certain proportion, at least one of the compounds contains K salt, the temperature of the salt bath is 360-490 ℃, and the time of the salt bath is 8-32 hours.

62. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 1-step ion exchange method, in the ion exchange method, the molten salt of the salt bath is composed of two or more compounds according to a certain proportion, at least one of the compounds contains K salt, the temperature of the salt bath is 410-460 ℃, and the time of the salt bath is 10-24 hours.

63. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 2-step ion exchange method in which the molten salt of the first-step salt bath is composed of two or more compounds in a certain proportion, wherein the molten salt at least contains one or two of K salt and Na salt, the temperature of the first-step salt bath is 400 to 510 ℃, and the time of the first-step salt bath is 4 to 32 hours; the molten salt of the second-step salt bath is composed of one or more than one compound according to a certain proportion, wherein at least one compound contains K salt or Na salt, and the temperature range of the second-step salt bath is 400-510 ℃; the time range of the salt bath in the second step is 0.5-16 h.

64. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 2-step ion exchange method in which the molten salt of the first-step salt bath is composed of two or more compounds in a certain proportion, wherein the molten salt at least contains one or two of K salt and Na salt, the temperature of the first-step salt bath is 420 to 500 ℃, and the time of the first-step salt bath is 8 to 24 hours; the molten salt of the second-step salt bath is composed of one or more than one compounds according to a certain proportion, wherein at least one of the compounds contains K salt or Na salt, and the temperature range of the second-step salt bath is 420-500 ℃; the time range of the salt bath in the second step is 0.5-8 h.

65. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 2-step ion exchange method in which the molten salt of the first-step salt bath is composed of two or more compounds in a certain proportion, wherein the molten salt at least contains one or two of K salt and Na salt, the temperature of the first-step salt bath is 420 to 500 ℃, and the time of the first-step salt bath is 8 to 24 hours; the molten salt of the second-step salt bath is composed of one or more than one compound according to a certain proportion, wherein at least one compound contains K salt or Na salt, and the temperature range of the second-step salt bath is the same as that of the first-step salt bath; the time range of the salt bath in the second step is 0.5-4 h.

66. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 2-step ion exchange method, in the ion exchange method, the molten salt of the first-step salt bath is composed of two or more compounds according to a certain proportion, wherein the molten salt contains K salt and Na salt, the temperature of the first-step salt bath is 400-510 ℃, and the time of the first-step salt bath is 4-32 hours; the molten salt of the second-step salt bath is composed of one or more than one compounds according to a certain proportion, wherein at least one of the compounds contains K salt, and the temperature range of the second-step salt bath is 400-510 ℃; the time range of the salt bath in the second step is 0.5-16 h.

67. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 2-step ion exchange method, in the ion exchange method, the molten salt of the first-step salt bath is composed of two or more compounds according to a certain proportion, wherein the molten salt contains K salt and Na salt, the temperature of the first-step salt bath is 420-500 ℃, and the time of the first-step salt bath is 8-24 hours; the molten salt of the second-step salt bath is composed of one or more than one compounds according to a certain proportion, wherein at least one of the compounds contains K salt, and the temperature range of the second-step salt bath is 420-500 ℃; the time range of the salt bath in the second step is 0.5-8 h.

68. The method for manufacturing chemically strengthened glass according to claim 48, wherein the chemical strengthening process is a 2-step ion exchange method, in the ion exchange method, the molten salt of the first-step salt bath is composed of two or more compounds according to a certain proportion, wherein the molten salt contains K salt and Na salt, the temperature of the first-step salt bath is 420-500 ℃, and the time of the first-step salt bath is 8-24 hours; the molten salt of the second-step salt bath is composed of one or more than one compound according to a certain proportion, wherein at least one compound contains K salt, and the temperature range of the second-step salt bath is the same as that of the first-step salt bath; the time range of the second-step salt bath is 0.5-4 h.