阅读说明：本技术 一种钠玻璃、化学强化玻璃及化学强化玻璃的制备方法 (Sodium glass, chemically strengthened glass and preparation method of chemically strengthened glass ) 是由 胡伟 谈宝权 张延起 覃文城 黄昊 陈芳华 黄文泽 于 2019-11-01 设计创作，主要内容包括：本发明公开了一种钠玻璃、化学强化玻璃及化学强化玻璃的制备方法。所述钠玻璃包含下述摩尔百分比的元素：所述钠玻璃包含下述摩尔百分比的元素：3％～11.5％的Na、17％～24％的Si、5.6％～10.5％的Al、0.25％～5％的Mg、58％～62％的O。优选的,所述钠玻璃包含下述摩尔百分比的元素：3.79％～11.03％的Na、17.62％～23.67％的Si、5.68％～10.5％的Al、0％～3.79％的Li、0.29％～4.90％的Mg、58.52％～61.52％的O、总和0.01％～0.25％的Cl与S；其中,Na含量与Li含量的比值为1～11.5。所述钠玻璃特别适用于高速移动交通工具挡风玻璃的钠玻璃,其具有低脆度、高强度、高安全性、低膨胀系数、高耐磨、高透过率、等厚平板、大尺寸、厚度范围较大、介电常数较低的优点。以所述钠玻璃为原料可通过一步离子交换制得强度高且安全性高的强化玻璃。(The invention discloses sodium glass, chemically strengthened glass and a preparation method of the chemically strengthened glass. The sodium glass comprises the following elements in mole percent: the sodium glass comprises the following elements in mole percent: 3 to 11.5 percent of Na, 17 to 24 percent of Si, 5.6 to 10.5 percent of Al, 0.25 to 5 percent of Mg and 58 to 62 percent of O. Preferably, the soda glass contains the following elements in mole percent: 3.79 to 11.03 percent of Na, 17.62 to 23.67 percent of Si, 5.68 to 10.5 percent of Al, 0 to 3.79 percent of Li, 0.29 to 4.90 percent of Mg, 58.52 to 61.52 percent of O and Cl and S with the total of 0.01 to 0.25 percent; wherein the ratio of the Na content to the Li content is 1-11.5. The sodium glass is particularly suitable for the sodium glass of a windshield of a high-speed moving vehicle, and has the advantages of low brittleness, high strength, high safety, low expansion coefficient, high wear resistance, high transmittance, uniform-thickness flat plates, large size, large thickness range and low dielectric constant. The sodium glass is taken as a raw material, and the strengthened glass with high strength and high safety can be prepared through one-step ion exchange.)

1. Sodium glass, characterized in that it comprises the following elements in mol percent: 3 to 11.5 percent of Na, 17 to 24 percent of Si, 5.6 to 10.5 percent of Al, 0.25 to 5 percent of Mg, 58 to 62 percent of O and more than 1 percent of other elements.

2. The soda glass according to claim 1, characterized in that it comprises the following elements in mol%: 3.79 to 11.03 percent of Na, 17.62 to 23.67 percent of Si, 5.68 to 10.5 percent of Al, 0.01 to 3.79 percent of Li, 0.29 to 4.90 percent of Mg, 58.52 to 61.52 percent of O and Cl and S with the total of 0.01 to 0.25 percent; wherein the content of S is 0.01-0.22%, and the ratio of Na content to Li content is 1-11.5.

3. The soda glass according to claim 2, characterised in that it comprises, in mole percentages, the following oxides: 6 to 18 percent of Na₂O, SiO 60% or more₂9% or more of Al₂O₃1 to 6% of Li₂O, MgO of more than or equal to 1 percent and SO of 0.01 to 0.2 percent₃。

4. The soda glass according to claim 2, wherein the soda glass has an elastic modulus of 65 to 88.2GPa and a Vickers hardness of 490 to 592kgf/mm²And the brittleness is 57.5-72.3.

5. The soda glass according to claim 2, wherein the soda glass has a dielectric constant of 5.5 to 7.75 at a frequency of 1MHZ to 3.5GHZ and an expansion coefficient of 57 x 10 at a temperature of 20 to 400 ℃^-7/℃～101×10^-7/° c; the temperature corresponding to the viscosity of the sodium glass is lg3(visc./(Poise)), 1250-1493 ℃, the liquidus temperature is 1060-1300 ℃, the softening point temperature is 710-880 ℃, and the transition point Tg temperature is 515-620 ℃.

6. The soda glass according to claim 2, further comprising, in mole percent, the following oxides: 0.5% -2% of ZrO₂(ii) a Wherein Li₂O content of 2% or more, SiO₂The content of (A) is 62 to 75 percent, and Al₂O₃9 to 17 percent of Na₂Content of O and Li₂The sum of the contents of O is 9 to 20 percent, and MgOThe content of (A) is 2-12%.

7. The soda glass according to claim 6, wherein a blending index θ of O and Si in the soda glass is 0.35 to 1.10.

8. The soda glass of claim 6, wherein the soda glass has a total alkali metal oxide content greater than Al₂O₃Content of (A), Na₂Content of O and Li₂The ratio of the content of O is 1-9.

9. The soda glass according to claim 6, further comprising, in mole percent, the following oxides: 1% -4% of B₂O₃(ii) a Wherein the total content of alkali metal oxide and Al₂O₃Difference of contents of (A) and (B)₂O₃The absolute value of the ratio of the contents of (a) is 1 or more.

10. The soda glass according to claim 6, wherein the soda glass has an elastic modulus of 65 to 77GPa and a dielectric constant of 5.59 to 7.58 at a frequency of 1MHZ to 3.5 GHZ; when the viscosity of the sodium glass is lg3(visc./(Poise)), the corresponding temperature is 1274-1493 ℃, the liquid line temperature is 1086-1300 ℃, and the softening point temperature is 726-876 ℃; the soda glass comprises an amorphous part and a plurality of shaped parts; the size of each shaping part is 5-100 nm; the average size of all of the shaped portions is less than 50 nm; the average size of all the shaped portions is less than 30 nm; the average size of all the shaping parts is 10-30 nm; the shaped part comprises nepheline and ZrO₂One or more of cordierite, spinel, a solid solution of beta-quartz, petalite and lithium silicate.

11. The soda glass of claim 6, wherein Al in the soda glass₂O₃Is 9 to 15.5 percent, and the sodium glass also comprises sodium silicateComprises the following oxides: 0.5-2% of rare earth oxide and 0.5-4% of K₂O, 0 to 7% of P₂O₅(ii) a Wherein the rare earth oxide at least comprises CeO₂And CeO₂The content of (A) is more than or equal to 0.5 percent; k₂O、Na₂O and Li₂The sum of the contents of O is 1 to 20 percent.

12. The soda glass as claimed in claim 11, wherein the soda glass has an elastic modulus of 65.6 to 75.4Gpa and a vickers hardness of 510 to 592kgf/mm²The brittleness is 60-69.2, and the expansion coefficient of the sodium glass at the temperature of 20-400 ℃ is 60 multiplied by 10^-7/℃～100.3×10^-7/° c; when the viscosity of the sodium glass is lg3(visc./(Poise)), the corresponding temperature is 1299-1493 ℃, the liquidus temperature is 1112-1300 ℃, the softening point temperature is 745-876 ℃, and the transition point Tg temperature is 515-579 ℃.

13. The soda glass according to claim 11, wherein in said soda glass, Na is present in a mole percentage₂9-15.5% of O, Li₂The content of O is 2-5%.

14. The soda glass according to claim 13, wherein the soda glass has an elastic modulus of 67.2 to 75.4Gpa, a brittleness of 60 to 68.5, a dielectric constant of 5.87 to 7.52 at a frequency of 1MHZ to 3.5GHZ, and an expansion coefficient of 71 x 10 at a temperature of 20 to 400 ℃^-7/℃～100.3×10^-7/° c; the temperature corresponding to the viscosity of the sodium glass is lg3(visc./(Poise)), 1330-1450 ℃, the liquidus temperature is 1130-1255 ℃, and the softening point temperature is 745-850 ℃.

15. The soda glass according to claim 2, wherein the thickness of the soda glass is 0.4 to 10mm, and the size of the soda glass increases by 0.05 to 0.1% after ion exchange treatment.

16. A chemically strengthened glass, which is formed by ion exchange of the soda glass according to claims 1 to 15 in a salt bath, wherein a compressive stress layer formed on a surface of the chemically strengthened glass by the ion exchange has a thickness of one tenth or less of a thickness of the glass, and a surface compressive stress of 600MPa or more; the compressive stress layer has a compressive stress curve, the compressive stress curve is a rounded curve extending from the surface of the chemically strengthened glass to a maximum depth of the compressive stress layer and having a gradually decreasing slope; the chemically strengthened glass has a tensile stress linear density of 20000 to 75000Mpa/mm, a thickness of 0.4 to 10mm, a Vickers hardness of more than 520HV, an average visible light transmittance of 90 to 92%, and a temperature of 1300 ℃ or less at a viscosity of lg4 (visc./(Poise)).

17. The chemically strengthened glass according to claim 16, wherein the surface compressive stress is 650 to 1100 MPa; the tensile stress linear density of the chemically strengthened glass is 28000-58000 Mpa/mm; an ion exchange layer depth formed on the surface of the chemically strengthened glass by ion exchange is at least 20um greater than the compressive stress layer depth; the chemically strengthened glass has an expansion coefficient of 50 multiplied by 10 under the temperature condition of-100 to 100 DEG C^-7/℃～100×10^-7/° c; in the static pressure destructive test, the area of the largest broken piece formed by breaking the chemically strengthened glass having the dimensions of length × width × thickness of 50mm × 50mm × 0.7mm is 5% to 45% of the total area of the chemically strengthened glass subjected to the test.

18. A method for preparing chemically strengthened glass, which is characterized in that the method comprises the steps of placing the sodium glass of claims 1-15 in a mixed salt bath for ion exchange to prepare the chemically strengthened glass of claims 17-18; the mixed salt bath contains at least three metal ions which are respectively K⁺、Na⁺、Li⁺Wherein, K is⁺The molar amount of (A) is more than 68% of the total molar amount of the metal ions, and Na⁺The content of Li in the mixed salt bath is not less than 500ppm⁺In the mixed salt bathThe content is 20 to 1000 ppm.

19. The preparation method according to claim 18, wherein the preparation method is single-time ion exchange, the ion exchange time is 3-12 hours, and the ion exchange temperature is 390-500 ℃; in the mixed salt bath, Na⁺The molar amount of (a) is less than 30% of the total molar amount of alkali metal ions; the mixed salt bath contains nitrate ions NO₃ ^-，NO₃ ^-The molar amount of (a) is more than 95% of the total molar amount of the anions; the mixed salt bath contains hydroxide ions OH^-，OH^-The molar weight of the (B) accounts for 1.1 to 2.5 percent of the total molar weight of anions; li in the mixed salt bath⁺The content of (A) is 20-600 ppm; the mixed salt bath also comprises other anions: CO 2₃ ^2-Or/and PO₄ ^3-。

Technical Field

The invention belongs to the technical field of glass and glass manufacturing, and particularly relates to sodium glass, chemically strengthened glass and a preparation method of the chemically strengthened glass.

Background

Ion-exchange strengthened glass is used more and more widely because of its high strength. For example, windshields of high-speed moving vehicles (especially civil aircraft, military aircraft and high-speed trains), protective cover plates of handheld electronic terminals and electric automobiles adopt strengthened glass, so that the thickness can be reduced, energy is saved, and the working mileage of batteries is prolonged.

The material of the windshield commonly used for aviation, automobiles and high-speed trains at present is generally high-alumina-silica glass, and the high-alumina-silica glass has high melting clarification difficulty, high glass liquid viscosity, difficult bubble discharge and difficult control of the production process due to high aluminum content. Meanwhile, the high-alumina-silica glass has the problems of low overall impact strength, poor safety and auto-explosion risk, and a series of safety accidents caused by the breakage of windshields of civil aircrafts frequently occur in the near term. In order to further improve the impact strength of the glass, most manufacturers form lithium aluminosilicate glass by introducing a large amount of Li as a main alkali metal component into the glass, so that the depth DOL of the compressive stress of the obtained strengthened glass is usually more than 100um, and more internal tensile stress can be accommodated, but the internal tensile stress is increased, and the stability and the safety of the glass are reduced; among all elements which can be ion exchanged, lithium ions are the smallest, so that the surface compressive stress and the surface hardness generated after ion exchange are too low, irreversible micro scratches and cracks are easy to generate, safety problems are induced, and the problems of instantaneous strength release and complete breakage of glass are solved; li is a rare element and also is the most important component of a lithium battery, the cost of Li is always increased and high with the application of a large amount of new energy and batteries, and in the lithium aluminosilicate glass, the cost of only a lithium raw material accounts for more than 40% of the cost of the glass, so that the production cost of the lithium aluminosilicate glass is high, and meanwhile, because lithium has a very high crystallization tendency, the production process of the lithium aluminosilicate glass is difficult to control due to the high lithium content, and the lithium aluminosilicate glass is not the best choice.

The invention designs sodium glass with a special formula, which has the advantages of low brittleness, high strength, high safety, low expansion coefficient, high wear resistance, high transmittance and low dielectric constant, and the sodium glass is subjected to a one-step ion exchange chemical strengthening process to obtain strengthened glass with gradually reduced and gradually changed single compressive stress, so that the strengthened glass obtained in the way not only has higher destructive strength, but also has excellent safety, and the self-explosion risk is far less than that of the strengthened glass in the prior art, and can be widely applied to windshields of various aviation, high-speed trains and automobile products, protective glass of electronic products and the like. In addition, because lithium has a very good viscosity reducing effect, and simultaneously, the elastic modulus of the glass can be properly improved, and a small amount of lithium is added into the sodium glass, the production process is simple and easy to control, the production cost is low, and the network structure matching is more reasonable.

Disclosure of Invention

The technical problem to be solved by the invention is to provide sodium glass which is particularly suitable for windshields of high-speed moving vehicles and has the advantages of low brittleness, high strength, high safety, low expansion coefficient, high wear resistance, high transmittance, uniform-thickness flat plates, large size, large thickness range and low dielectric constant.

Another technical problem to be solved by the present invention is to provide a chemically strengthened glass, which is obtained by chemically strengthening the soda glass.

The invention also aims to provide a preparation method of chemically strengthened glass, wherein the preparation method refers to a process for preparing the strengthened glass from the soda glass.

The technical scheme adopted by the invention for solving the problems is to provide sodium glass, wherein the sodium glass comprises the following elements in mole percentage: the sodium glass comprises the following elements in mole percent: 3 to 11.5 percent of Na, 17 to 24 percent of Si, 5.6 to 10.5 percent of Al, 0.25 to 5 percent of Mg and 58 to 62 percent of O.

As a preferable aspect of the soda glass provided by the invention, the soda glass contains the following elements in mol percent: 3.79 to 11.03 percent of Na, 17.62 to 23.67 percent of Si, 5.68 to 10.5 percent of Al, 0.01 to 3.79 percent of Li, 0.29 to 4.90 percent of Mg, 58.52 to 61.52 percent of O and Cl and S with the total of 0.01 to 0.25 percent; wherein the content of S is 0.01-0.22%, the ratio of Na content to Li content is 1-11.5, and the ratio of Na content to Li content is 1-11.5.

As a preference of the soda glass provided by the invention, the soda glass comprises the following oxides in mole percentage: 6 to 18 percent of Na₂O, SiO 60% or more₂9% or more of Al₂O₃1 to 6% of Li₂O, MgO of more than or equal to 1 percent and SO of 0.01 to 0.2 percent₃。

The sodium glass provided by the invention preferably has an elastic modulus of 65-88.2 Gpa and a Vickers hardness of 490-592 kgf/mm²And the brittleness is 57.5-72.3. Wherein the content of the first and second substances,the common product solves the problem of high strength, which is divided into impact resistance, falling resistance, probe resistance and roller resistance, and the patent aims to solve the problems of improving safety and increasing comprehensive strength by reducing the brittleness of the productThe Vickers hardness is introduced to reflect the plastic deformation capability of the glass, and although the plastic deformation capability of the glass is lower, the Vickers hardness and the elastic modulus of the glass are controlled within a reasonable range, so that the brittleness of the glass can be effectively reduced.

The preferable sodium glass provided by the invention has a dielectric constant of 5.5-7.75 under the condition that the frequency is 1 MHZ-3.5 GHZ.

The sodium glass provided by the invention preferably has an expansion coefficient of 57 x 10 at the temperature of 20-400 DEG C^-7/℃～101×10^-7/℃。

The preferable sodium glass provided by the invention has the density of 2.38-2.52g/cm under the temperature condition of 20 DEG C³。

Preferably, the temperature corresponding to the viscosity of the soda glass lg3(visc./(Poise)) is 1250-1493 ℃; the liquid line temperature is 1060-1300 ℃; the softening point temperature is 710-880 ℃; the Tg temperature of the transition point is 515-620 ℃.

As a preference of the soda glass provided by the invention, the soda glass further comprises the following oxides in mole percentage: 0.5% -2% of ZrO₂(ii) a Wherein Li₂O content of 2% or more, SiO₂The content of (A) is 62 to 75 percent, and Al₂O₃9 to 17 percent of Na₂Content of O and Li₂The sum of the contents of O is 9 to 20 percent, and the content of MgO is 2 to 12 percent.

The soda glass provided by the invention preferably contains more alkali metal oxide than Al₂O₃Content of (A), Na₂Content of O and Li₂The ratio of the content of O is 1-9.

Preferably, the blending index theta of O and Si in the soda glass is 0.35-1.10. Wherein the blending indexWherein X is the ratio of the content of O to the content of Si in the sodium glass. Further, the adjustmentThe blending index theta is 0.61-1.10, and further the blending index theta is 0.71-1.10.

As a preference of the soda glass provided by the invention, the soda glass further comprises the following oxides in mole percentage: 1% -4% of B₂O₃(ii) a Wherein the total content of alkali metal oxide and Al₂O₃Difference of contents of (A) and (B)₂O₃The absolute value of the ratio of the contents of (a) is 1 or more.

The sodium glass provided by the invention preferably has an elastic modulus of 65-77 Gpa, a dielectric constant of 5.59-7.58 under the condition that the frequency is 1 MHZ-3.5 GHZ, and a density at 20 ℃ of 2.387-2.495 g/cm³。

The preferable soda glass provided by the invention has the corresponding temperature of 1274-1493 ℃, the liquid line temperature of 1086-1300 ℃ and the softening point temperature of 726-876 ℃ when the viscosity of the soda glass is lg3 (visc./(Poise)).

As a preference of the soda glass provided by the invention, the soda glass includes an amorphous portion and a plurality of shaped portions; the size of each shaping part is 5-100 nm; the average size of all of the shaped portions is less than 50 nm; the average size of all of the shaped portions is less than 30 nm.

Preferably, the average size of all the shaped parts is 10 to 30 nm.

As a preference of the sodium glass provided by the invention, the shaped part comprises nepheline and ZrO₂One or more of cordierite, spinel, a solid solution of beta-quartz, petalite and lithium silicate.

As the preference of the soda glass provided by the invention, Al in the soda glass₂O₃Is 9 to 15.5 percent, and the sodium glass also comprises the following oxides in percentage by mol: 0.5-2% of rare earth oxide and 0.5-4% of K₂O, 0 to 7% of P₂O₅(ii) a Wherein the rare earth oxide at least comprises CeO₂And CeO₂The content of (A) is more than or equal to 0.5 percent; k₂O、Na₂O and Li₂Of the content of OAnd 1 to 20 percent of the total amount.

The soda glass provided by the invention preferably has an elastic modulus of 65.6-75.4 Gpa and a Vickers hardness of 510-592 kgf/mm²The expansion coefficient of the sodium glass at the temperature of 20-400 ℃ is 60 multiplied by 10^-7/℃～100.3×10^-7The density at 20 ℃ is 2.39-2.491 g/cm³。

Preferably, the soda glass provided by the invention has a temperature of 1299-1493 ℃, a liquidus temperature of 1112-1300 ℃, a softening point temperature of 745-876 ℃ and a transition point Tg temperature of 515-579 ℃ when the viscosity of the soda glass is lg3 (visc./(Poise)).

The sodium glass provided by the invention preferably has an elastic modulus of 67-75.4 Gpa and a density at 20 ℃ of 2.417-2.48 g/cm³。

Preferably, the sodium glass provided by the invention has brittleness of 60-69.2.

The soda glass provided by the invention is preferably Na₂9-15.5% of O, Li₂The content of O is 2-5%.

The sodium glass provided by the invention preferably has an elastic modulus of 67.2-75.4 Gpa, a brittleness of 60-68.5, a dielectric constant of 5.87-7.52 under the condition of a frequency of 1 MHZ-3.5 GHz, and an expansion coefficient of 71 x 10 under the temperature condition of 20-400 DEG C^-7/℃～100.3×10^-7The density at 20 ℃ is 2.42-2.48 g/cm³(ii) a The temperature is 1330-1450 ℃ when the viscosity of the sodium glass is lg3(visc./(Poise)), the liquidus temperature is 1130-1255 ℃, and the softening point temperature is 745-850 DEG C

In the soda glass, Na is preferably added to the soda glass in a molar percentage₂The content of O is 11-15.5%, and Li₂The content of O is 2-5%.

The preferable sodium glass provided by the invention has the thickness of 0.4-10 mm.

The preferable sodium glass provided by the invention has the thickness of 0.4-8 mm.

Preferably, the soda glass provided by the invention further comprises 0.01-0.25% of S in mol percentage.

The sodium glass provided by the invention is preferably sodium glass, wherein the mole percentage content of S in the sodium glass is 0.01-0.22%,

the sodium glass provided by the invention is preferably sodium glass, wherein the mole percentage content of S in the sodium glass is 0.01-0.15%.

Preferably, the size of the soda glass is increased by 0.05-0.1% after the soda glass is subjected to ion exchange treatment.

In order to solve the technical problem, the invention also provides chemically strengthened glass, which is formed by placing the sodium glass in a salt bath for ion exchange, wherein the thickness of a compressive stress layer formed on the surface of the chemically strengthened glass through ion exchange is less than or equal to one tenth of the thickness of the glass, and the surface compressive stress is more than or equal to 600 MPa; the compressive stress layer has a compressive stress curve, the compressive stress curve is a rounded curve extending from the surface of the chemically strengthened glass to a maximum depth of the compressive stress layer and having a gradually decreasing slope; the chemically strengthened glass has a tensile stress linear density of 20000 to 75000Mpa/mm, a thickness of 0.4 to 10mm, a Vickers hardness of more than 520HV, an average visible light transmittance of 90 to 92%, and a temperature of 1300 ℃ or less at a viscosity of lg4 (visc./(Poise)).

Preferably, the surface compressive stress of the chemically strengthened glass provided by the invention is 650 to 1100 MPa.

As the optimization of the chemically strengthened glass provided by the invention, the surface compressive stress is 700-900 MPa.

Preferably, the chemically strengthened glass provided by the invention has a tensile stress linear density of 28000-58000 MPa/mm.

Preferably, the chemically strengthened glass provided by the invention has a tensile stress linear density of 28000-50000 MPa/mm.

Preferably, in the chemically strengthened glass of the present invention, the depth of the ion exchange layer formed on the surface of the chemically strengthened glass by ion exchange is at least 20 μm greater than the depth of the compressive stress layer.

The chemical strengthening glass provided by the invention preferably has an expansion coefficient of 50 multiplied by 10 under the temperature condition of-100 to 100 DEG C^-7/℃～100×10^-7/℃。

Preferably, in the chemically strengthened glass provided by the present invention, in a static pressure destructive test, an area of a largest fragment formed by breaking the chemically strengthened glass having a length × width × thickness dimension of 50mm × 50mm × 0.7mm is 5% to 45% of a total area of the chemically strengthened glass subjected to the test.

In addition, the invention also provides a preparation method of the chemically strengthened glass, which is to place the sodium glass in the mixed salt bath for ion exchange to prepare the chemically strengthened glass; the mixed salt bath contains at least three metal ions which are respectively K⁺、Na⁺、Li⁺Wherein, K is⁺The molar amount of (A) is more than 68% of the total molar amount of the metal ions, and Na⁺The content of Li in the mixed salt bath is not less than 500ppm⁺The content of the salt in the mixed salt bath is 20-1000 ppm.

As a preferable aspect of the production method provided by the present invention, in the mixed salt bath, K⁺Molar amount of (A)>Na⁺Molar amount of (A)>Li⁺The molar amount of (c).

As a preferable aspect of the production method provided by the present invention, in the mixed salt bath, Na⁺The molar amount of (b) is 30% or less of the total molar amount of alkali metal ions.

As a preferable aspect of the production method provided by the present invention, in the mixed salt bath, Na⁺The molar amount of (a) is less than 25% of the total molar amount of alkali metal ions.

Preferably, in the preparation method provided by the present invention, the mixed salt bath further contains non-ionic alumina, and the non-ionic alumina accounts for 2% or less of the mass of the mixed salt bath.

As a preference of the preparation method provided by the present invention, the preparation method is a single ion exchange.

As the optimization of the preparation method provided by the invention, the ion exchange time is 3-12 hours, and the ion exchange temperature is 390-500 ℃.

Preferably, the mixed salt bath contains nitrate ion NO₃ ^-，NO₃ ^-The molar amount of (a) is 95% or more of the total molar amount of the anions.

Preferably, the mixed salt bath contains hydroxide ions OH^-，OH^-The molar amount of (a) is 2.5% or less of the total molar amount of anions.

As a preference of the preparation method provided by the present invention, the mixed salt bath further comprises other anions: CO 2₃ ^2-Or/and PO₄ ^3-。

Preferably, in the preparation method provided by the invention, Li in the mixed salt bath⁺The content of (B) is 20-600 ppm.

Preferably, the mixed salt bath contains hydroxide ions OH^-，OH^-The molar amount of (a) is 1.1% or more of the total molar amount of anions.

Drawings

FIG. 1 is a schematic diagram illustrating the comparison of DOI and DOL in a chemically strengthened glass according to the present invention;

FIG. 2 example 75 provides a DOI profile and a DOL profile within a chemically strengthened glass.

Detailed Description

Before describing the soda glass, the preparation method and the chemically strengthened glass, it is necessary to explain some terms and some methods for measuring physicochemical properties.

Method for measuring compressive stress value (CS): the measurements were carried out using an optical waveguide Surface Stress Meter (Orihara Surface Stress Meter, FSM6000 LE).

The detection method of the depth of layer (DOL) of the compressive stress comprises the following steps: the measurements were carried out using an optical waveguide Surface Stress Meter (Orihara Surface Stress Meter, FSM6000 LE).

The detection method of the tensile stress value (CT) comprises the following steps: after the compressive Stress distribution data of the Surface and the interior of the glass are obtained by measuring with an optical waveguide Surface Stress Meter (FSM 6000LE), the compressive Stress, the maximum tensile Stress, the average tensile Stress and the tensile Stress distribution are obtained by fitting with Orihara Pmc software.

DOI indicates the depth of penetration of alkali metal ions into the glass due to the ion exchange process and can be determined by Electron Probe Microanalysis (EPMA) or glow discharge-optical emission spectroscopy (GD-OES). The DOI of the chemically strengthened glass provided by the present invention is generally much greater than DOL.

Tensile stress linear density: the strengthened glass is formed by ion exchange in salt bath, a stress layer is formed in the glass during the ion exchange process, the tensile Stress layer is provided with an upper boundary which is at a certain interval with the upper Surface of the tempered glass and a lower boundary which is at a certain interval with the lower Surface of the tempered glass, a curve which is drawn by taking the tensile Stress at a certain point on a line segment which is perpendicular to the upper boundary and the lower boundary in the tensile Stress layer and has upper and lower end points respectively on the upper boundary and the lower boundary as a Y axis and the distance between the corresponding point and the upper boundary as an X axis is taken as a tensile Stress curve, and the ratio of the fixed integral of the tensile Stress curve and the thickness of the tempered glass is taken as the tensile Stress linear density, namely the ratio of the sum of the tensile stresses of the tempered glass measured by an Orihara Surface Stress Meter, FSM6000LE Stress Meter to the thickness of the glass.

Static pressure destructive test method:

1) the sample size was: length × width × thickness is 50mm × 50mm × 0.7 mm;

2) the operation method comprises the following steps: the description of the obtuse stress release test method is provided in the fifth stage 2019 of automobile technology and materials published by Waila, Suwencheng, Neibao and the like in ISSN1003-8817 under the unified publication No. CN 22-1187/U.

The Vickers hardness, modulus of elasticity, compressive strength, dielectric constant, coefficient of expansion, density, viscosity, liquidus temperature, softening point temperature, transition point Tg temperature, visible light average transmittance, viscosity referred to herein are determined using methods common in the art.

The crystalline form of the shaped portion within the soda glass can be obtained by XRD analysis.

The sodium glass provided by the invention comprises the following elements in mole percentage: 3 to 11.5 percent of Na, 17 to 24 percent of Si, 5.6 to 10.5 percent of Al, 0.25 to 5 percent of Mg and 58 to 62 percent of O. Preferably, the soda glass contains the following elements in mole percent: 3.79 to 11.03 percent of Na, 17.62 to 23.67 percent of Si, 5.68 to 10.5 percent of Al, 0.01 to 3.79 percent of Li, 0.29 to 4.90 percent of Mg and 58.52 to 61.52 percent of O; wherein the ratio of the Na content to the Li content is 1-11.5. The content of Si is controlled by controlling the content of O in the sodium glass raw components and a certain functional relation, so that the glass network structure taking Si as a core is controlled, and the glass has a better complete network structure. The sodium glass has certain characteristics of low content of Li and small content of Li, and mainly aims to reduce the high-temperature viscosity of the glass, facilitate melting, optimize the glass structure, improve the elasticity of the glass and construct a good network structure. In a word, the components of the sodium glass designed by the invention can comprehensively improve the network quality of the sodium glass, further realize higher intrinsic strength of the glass and improve the shock resistance and the compressive stress storage capacity of the sodium glass. In addition, the thickness range of the sodium glass easy to form is 0.4-10.0mm, preferably 0.4-8mm, transparent, equal-thickness and large-size glass can be obtained through the float normal line production, the thickness can be applied to the front windshield, and the thickness can be applied to the side window.

In some embodiments, the soda glass comprises the following oxides: 6 to 18 percent of Na₂O, SiO 60% or more₂9% or more of Al₂O₃1 to 6% of Li₂O, and MgO with the content of more than or equal to 1 percent. The sodium glass has a certain contentAmount of Al₂O₃The wear resistance of the sodium glass is obviously improved; controlling Al₂O₃The content of more than or equal to 9 percent is beneficial to improving the network structure size and the network integrity of the glass, and can improve the storage capacity of the compressive stress formed by ion exchange. Incorporation of MgO and relatively small amounts of Li in glass₂The O, Mg and Li ions have higher field strength, have an aggregation effect at low temperature, can greatly tamp the glass network and increase the elasticity of the glass under the condition that the glass network is relatively complete, so the anti-falling capability of the glass is increased, the two elements have a melting promoting effect at high temperature, the melting difficulty of the glass is reduced, the Li has higher crystallization inclination, and the glass is sodium glass mainly exchanging K-Na ions, so the introduction amount of the Li needs to be controlled.

In the above embodiment, the sodium glass has an elastic modulus of 65 to 88.2GPa and a Vickers hardness of 490 to 592kgf/mm²And the brittleness is 57.5-72.3. Wherein the content of the first and second substances,the brittleness formula is defined in the special example, Vickers hardness is introduced in the formula to reflect the plastic deformation capability of the glass, and the Vickers hardness and the elastic modulus of the glass are controlled within a reasonable range although the plastic deformation capability of the glass is lower, so that the brittleness of the glass can be effectively reduced.

The dielectric constant of the soda glass in the above embodiment is 5.5 to 7.75 under the condition that the frequency is 1MHZ to 3.5 GHZ. The sodium glass has low dielectric constant and small electrostatic adsorption, so that the sodium glass does not influence microwave communication in high-speed motion.

The sodium glass of the embodiment has an expansion coefficient of 57 multiplied by 10 under the temperature condition of 20-400 DEG C^-7/℃～101×10^-7V. C. Low expansion coefficient, no generation in large temperature rangeGreater deformation, stress and strain, thus significantly improving the safety and confidence of the glass. Therefore, when the application scene of the product is extremely cold and hot, the safety of the product is ensured by the small expansion size.

The density of the sodium glass in the embodiment is 2.38-2.52g/cm under the temperature condition of 20 DEG C³. The invention controls the density range of the sodium glass to be 2.38-2.52g/cm³The glass has smaller density and substantially larger atom packing density, thereby having relatively larger plastic deformation capacity, reducing the brittleness of the glass and increasing the toughness of the glass.

In the above embodiment, when the viscosity of the soda glass is lg3(visc./(Poise)), the corresponding temperature is 1250-1493 ℃; the liquid line temperature is 1060-1300 ℃; the softening point temperature is 710-880 ℃; the Tg temperature of the transition point is 515-620 ℃. In the composition of soda glass, MgO and Li are controlled₂The content of O is small, so that the viscosity of the glass at high temperature is directly influenced, and the soda-alumina-silica glass has good viscosity and temperature gradient change characteristics and has a great effect on large-size forming; the sodium glass has a lower softening point which is lower than that of common high-alumina sodium glass by more than 50 ℃, and is more suitable for hot-forming required by various complex shapes.

In the embodiment, the size of the sodium glass is increased by 0.05-0.1% after the sodium glass is subjected to ion exchange treatment. That is, the dimensional change of the soda glass before and after the chemical strengthening treatment is not large, and the control is easy.

In some embodiments, the soda glass further comprises, in mole percent, the following oxides: 0.5% -2% of ZrO₂(ii) a Wherein Li₂O content of 2% or more, SiO₂The content of (A) is 62 to 75 percent, and Al₂O₃9 to 17 percent of Na₂Content of O and Li₂The sum of the contents of O is 9 to 20 percent, and the content of MgO is 2 to 12 percent; and the total content of alkali metal oxides is greater than Al₂O₃Content of (A), Na₂Content of O and Li₂The ratio of the content of O is 1-9.

Soda glass projectile as described in the above examplesA natural modulus of 65 to 77Gpa, a dielectric constant of 5.59 to 7.58 at a frequency of 1MHZ to 3.5GHZ, and a density of 2.387 to 2.495g/cm at 20 DEG C³. By adding appropriate amount of ZrO₂While to Li₂Content of O, SiO₂Content of (C), Al₂O₃Further control of the content of (A) and Na₂Content of O and Li₂The control of the ratio of the contents of O enables the density of the soda glass to reach a smaller value with the elastic modulus and the dielectric constant of the soda glass kept at good levels.

The soda glass in the above embodiment has a viscosity of lg3(visc./(Poise)), a corresponding temperature of 1274 to 1493 ℃, a liquidus temperature of 1086 to 1300 ℃, and a softening point temperature of 726 to 876 ℃.

In some embodiments, the blending index theta of O and Si in the sodium glass is 0.35-1.10; more preferably, the blending index theta is 0.61-1.10; more preferably, the blending index θ is 0.71 to 1.10. Wherein the blending indexWherein X is the ratio of the content of O to the content of Si in the sodium glass.

In some embodiments, the soda glass further comprises, in mole percent, the following oxides: 1% -4% of B₂O₃(ii) a Wherein the total content of alkali metal oxide and Al₂O₃Difference of contents of (A) and (B)₂O₃The absolute value of the ratio of the contents of (a) is 1 or more.

In some embodiments, the soda glass includes an amorphous portion and a plurality of shaped portions; the size of each shaping part is 5-100 nm; the average size of all of the shaped portions is less than 50 nm; the average size of all of the shaped portions is less than 30 nm. Preferably, the average size of all the fixed parts is 10-30 nm. Preferably, the shaped portion comprises nepheline and ZrO₂One or more of cordierite, spinel, a solid solution of beta-quartz, petalite and lithium silicate.

At one endIn some embodiments, the soda glass includes Al₂O₃Is 9 to 15.5 percent, and the sodium glass also comprises the following oxides in percentage by mol: 0.5-2% of rare earth oxide and 0.5-4% of K₂O, 0 to 7% of P₂O₅(ii) a Wherein the rare earth oxide at least comprises CeO₂And CeO₂The content of (A) is more than or equal to 0.5 percent; k₂O、Na₂O and Li₂The sum of the contents of O is 1 to 20 percent.

The soda glass of the above embodiment, wherein the soda glass has an elastic modulus of 65.6 to 75.4GPa and a Vickers hardness of 510 to 592kgf/mm²The expansion coefficient of the sodium glass at the temperature of 20-400 ℃ is 60 multiplied by 10^-7/℃～100.3×10^-7The density at 20 ℃ is 2.39-2.491 g/cm³. By adding appropriate amount of rare earth oxide and reacting with K₂O、Na₂O and Li₂The sum of the contents of O is controlled so that the density of the soda glass can be reduced while maintaining the elastic modulus, Vickers hardness, and expansion coefficient of the soda glass at a satisfactory level.

The soda glass described in the above examples has a viscosity of lg3(visc./(Poise)), a temperature corresponding to 1299 to 1493 ℃, a liquidus temperature of 1112 to 1300 ℃, a softening point temperature of 745 to 876 ℃, and a transition point Tg temperature of 515 to 579 ℃.

The brittleness of the soda glass in the above embodiment is 60 to 69.2. By adding appropriate amount of rare earth oxide and reacting with K₂O、Na₂O and Li₂The sum of the contents of O is controlled, so that the brittleness of the sodium glass is stabilized at a reliable level.

In some embodiments, the soda glass is Na₂9-15.5% of O, Li₂The content of O is 2-5%. Preferably, in the soda glass, Na₂The content of O is 11-15.5%.

The sodium glass described in the above embodiment has an elastic modulus of 67.2 to 75.4GPa, a brittleness of 60 to 68.5, a dielectric constant of 5.87 to 7.52 at a frequency of 1MHZ to 3.5GHZ, and a dielectric constant of 20 to 400The expansion coefficient under the temperature condition of DEG C is 71 multiplied by 10^-7/℃～100.3×10^-7The density at 20 ℃ is 2.42-2.48 g/cm³(ii) a The temperature corresponding to the viscosity of the sodium glass is lg3(visc./(Poise)), 1330-1450 ℃, the liquidus temperature is 1130-1255 ℃, and the softening point temperature is 745-850 ℃.

In some embodiments, the soda glass further comprises 0.01 to 0.25% S by mole percentage. Preferably, the mole percentage content of S in the sodium glass is 0.01-0.22%, and more preferably, the mole percentage content of S in the sodium glass is 0.01-0.15%.

The preparation method of the chemically strengthened glass provided by the invention is a process for preparing the chemically strengthened glass provided by the invention after the sodium glass provided by the invention is placed in a mixed salt bath for ion exchange.

The mixed salt bath contains at least three metal ions which are respectively K⁺、Na⁺、Li⁺Wherein, K is⁺The molar amount of (A) is more than 68% of the total molar amount of the metal ions, and Na⁺The content of Li in the mixed salt bath is not less than 500ppm⁺The content of the salt in the mixed salt bath is 20-1000 ppm. Using said mixed salt bath to pass K⁺-Na⁺The ion replacement is the main chemical reaction to form CS less than 50 microns on the surface of the soda glass, so that the impact strength of the glass can be improved, and the safety of the glass can be ensured. During ion exchange, K is introduced⁺、Na⁺、Li⁺Ternary ion whose main ion exchange reaction is foreign K⁺With Na in glass⁺Carrying out a displacement reaction; alkali metal ion K in salt bath⁺、Na⁺、Li⁺Can be exchanged with each other, and Na is introduced into the salt bath⁺And Li⁺To balance K⁺-Na⁺Ion exchange reaction, control of K⁺The speed and the degree of the sodium glass entering the sodium glass control the size and the total amount of CS formed on the surface of the sodium glass, so that overhigh internal stress CT is avoided, and the safety of the glass is reduced. Preferably, K⁺Molar amount of (A)>Na⁺Molar amount of (A)>Li⁺Is prepared from (A) and (B)The molar amount is as follows. Wherein due to Li⁺The activity of the ion is greatest, therefore Li⁺The mol content of the ions is set to be the lowest among the alkali metal ions; introduction of Li into salt bath⁺Another important reason for the lower ion content is the control of Na in the salt bath⁺Ion-displacing Li in glass⁺Additional CS is formed, resulting in excessive internal stress CT, reducing the safety of the glass. Further preferably, Na⁺Is less than 30%, even less than 25%, of the total molar amount of alkali metal ions. More preferably, Li in the mixed salt bath⁺The content of (B) is 20-600 ppm.

The ion exchange time is 3-12 hours, and the temperature of the mixed salt bath in the ion exchange process is kept at 390-500 ℃.

In some embodiments, the mixed salt bath comprises nitrate ion NO₃ ^-，NO₃ ^-The molar amount of (a) is more than 95% of the total molar amount of the anions; the mixed salt bath contains hydroxide ions OH^-，OH^-The molar amount of (a) is less than 2.5% of the total molar amount of anions; the mixed salt bath also comprises other anions: CO 2₃ ^2-Or/and PO₄ ^3-. The anion effect in the mixed salt bath cannot be ignored and is an important characteristic of the invention, different anions have different complexing abilities to cations, and the generated compound characteristics are also different.

In some embodiments, the manufacturing process is a single ion exchange, that is, the soda glass is only chemically strengthened once during the manufacturing process. Because the salt bath is a mixed salt bath, two ion exchanges of potassium-sodium ion exchange and sodium-lithium ion exchange are included in the single ion exchange process.

The chemically strengthened glass provided by the invention is obtained by chemically strengthening sodium glass provided by the invention as raw material glass according to the preparation method provided by the invention. The detection analysis of the chemically strengthened glass by using the conventional detection means in the field can find that: the thickness of the compressive stress layer formed on the surface of the chemically strengthened glass through ion exchange is less than or equal to 50 mu m, and the surface compressive stress is more than or equal to 600 MPa; the compressive stress layer has a compressive stress curve, the compressive stress curve is a rounded curve extending from the surface of the chemically strengthened glass to a maximum depth of the compressive stress layer and having a gradually decreasing slope; the chemically strengthened glass has the tensile stress linear density of 20000-75000 Mpa/mm, the thickness of 0.4-10 mm, the Vickers hardness of more than 520HV, the average visible light transmittance of 90-92% and the temperature of 1300 ℃ or less when the viscosity is lg4 (visc./(Poise)). The chemical strengthened glass has higher surface compressive stress CS and lower tensile stress CT, which shows that the chemical strengthened glass with higher CS and lower CT can be effectively formed by effectively controlling the degree of ion exchange reaction through the quaternary ion exchange salt bath. The chemically strengthened glass retains the elasticity endowed by the unique component design of the corresponding sodium glass, and simultaneously obtains higher impact resistance and safety through ion exchange.

In some embodiments, the chemically strengthened glass has a surface compressive stress of 650 to 1100MPa, preferably 700 to 900 MPa.

In some embodiments, the chemically strengthened glass has a tensile stress linear density of 28000 MPa/mm to 58000MPa/mm, preferably 28000 MPa/mm to 50000 MPa/mm. .

In some embodiments, the depth of the ion exchange layer formed by ion exchange at the surface of the chemically strengthened glass is at least 20um greater than the depth of the compressive stress layer. The maximum depth DOI of alkali metal ions entering the chemically strengthened glass through ion exchange can be detected through an electronic probe or SEM + EDS, and the maximum depth DOL of surface compressive stress, the maximum depth CS of surface compressive stress and the maximum depth CT of internal tensile stress can be detected through a waveguide optical surface stress meter, wherein the value of DOI is far larger than that of DOL (see figure 1).

In some embodiments, the chemically strengthened glass has an expansion coefficient of 50 x 10 at a temperature of-100 to 100 DEG C^-7/℃～100×10^-7V. C. The application scene of the chemically strengthened glass is a smaller expansion ruler in extreme cold and extreme heatThe size of the product is ensured.

In some embodiments, the area of the largest fragments formed by fracture of the chemically strengthened glass having a length by width by thickness dimension of 50mm by 0.7mm when tested in a hydrostatic destructive test is between 5% and 45% of the total area of the chemically strengthened glass being tested.

The chemically strengthened glass provided by the present invention can be used as cover glass for mobile electronic devices and touch enabled displays, and can also be used in displays (or as display articles) (e.g., billboards, points of sale systems, computers, navigation systems, etc.), building articles (walls, fixtures, panels, windows, etc.), transportation articles (e.g., in automotive applications, trains, airplanes, ships, etc.), appliances (e.g., washing machines, dryers, dishwashers, refrigerators, etc.), or any article that requires some resistance to breakage.

In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described in detail. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Examples 1 to 12

In examples 1-12, 12 different soda glasses were provided, and the soda glasses of examples 1-12 were all produced using float lines using commercial products as starting materials. The soda glass components in examples 1 to 12 are shown in tables 1 and 2.

TABLE 1

TABLE 2

Components

Example 7

Example 8

Example 9

Example 10

Example 11

Example 12

SiO2(mol％)

69.22％

72.30％

64.80％

60.20％

67.40％

66.16％

Al2O3(mol％)

12.03％

9.10％

9.50％

15.57％

12.80％

12.04％

P2O5(mol％)

0.30％

B2O3(mol％)

0.70％

0.70％

1.50％

0.38％

MgO(mol％)

1.52％

3.00％

7.80％

4.80％

2.10％

2.37％

Li2O(mol％)

4.50％

3.80％

5.60％

3.05％

2.50％

5.60％

Na2O(mol％)

11.00％

10.10％

12.00％

15.58％

11.20％

10.70％

K2O(mol％)

0.10％

1.40％

ZnO(mol％)

0.05％

0.03％

ZrO2(mol％)

0.50％

2.00％

1.15％

TiO2(mol％)

0.05％

SnO2(mol％)

0.83％

0.50％

0.24％

Tm2O3(mol％)

0.20％

CeO2(mol％)

0.03％

0.50％

0.50％

Total

100.00％

100.00％

100.00％

100.00％

100.00％

100.00％

β

2.444

2.658

2.143

5.108

4.480

1.911

In tables 1 and 2, β means Na₂Content of O and Li₂The ratio of the content of O.

The mole percent content of each element contained in the soda glass of examples 1 to 12 can be obtained by calculation and is shown in tables 3 and 4.

TABLE 3

Kind of element

Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Si(mol％)

18.38％

23.67％

17.62％

20.67％

20.10％

19.20％

Al(mol％)

9.38％

5.68％

10.50％

7.11％

6.91％

6.61％

P(mol％)

0.00％

0.00％

0.00％

0.00％

0.00％

0.00％

B(mol％)

0.00％

0.59％

2.33％

0.00％

0.00％

0.36％

Mg(mol％)

1.19％

0.95％

0.29％

3.87％

4.90％

2.98％

Li(mol％)

1.23％

3.79％

1.75％

0.65％

2.29％

2.59％

Na(mol％)

11.03％

3.79％

6.93％

7.42％

5.88％

9.28％

K(mol％)

0.00％

0.00％

0.80％

0.00％

0.00％

0.11％

Zn(mol％)

0.09％

0.00％

0.00％

0.00％

0.00％

0.00％

Zr(mol％)

0.00％

0.00％

0.00％

0.00％

0.00％

0.00％

Ti(mol％)

0.00％

0.00％

0.00％

0.00％

0.00％

0.00％

Sn(mol％)

0.16％

0.02％

0.05％

0.06％

0.07％

0.35％

Tm(mol％)

0.00％

0.00％

0.00％

0.00％

0.00％

0.00％

Ce(mol％)

0.00％

0.00％

0.04％

0.06％

0.06％

0.00％

O(mol％)

58.55％

61.52％

59.69％

60.16％

59.80％

58.52％

total

100.00％

100.00％

100.00％

100.00％

100.00％

100.00％

θ

51.11％

107.78％

36.12％

74.87％

68.92％

62.50％

TABLE 4

Kind of element

Example 7

Example 8

Example 9

Example 10

Example 11

Example 12

Si(mol％)

21.37％

22.84％

20.82％

18.38％

20.64％

20.53％

Al(mol％)

7.43％

5.75％

6.11％

9.51％

7.84％

7.47％

P(mol％)

0.00％

0.00％

0.00％

0.18％

0.00％

0.00％

B(mol％)

0.43％

0.44％

0.00％

0.00％

0.92％

0.24％

Mg(mol％)

0.47％

0.95％

2.51％

1.47％

0.64％

0.74％

Li(mol％)

2.78％

2.40％

3.60％

1.86％

1.53％

3.48％

Na(mol％)

6.79％

6.38％

7.71％

9.51％

6.86％

6.64％

K(mol％)

0.06％

0.00％

0.00％

0.00％

0.00％

0.87％

Zn(mol％)

0.02％

0.00％

0.01％

0.00％

0.00％

0.00％

Zr(mol％)

0.00％

0.16％

0.00％

0.00％

0.61％

0.36％

Ti(mol％)

0.02％

0.00％

0.00％

0.00％

0.00％

0.00％

Sn(mol％)

0.26％

0.16％

0.08％

0.00％

0.00％

0.00％

Tm(mol％)

0.00％

0.00％

0.00％

0.00％

0.00％

0.12％

Ce(mol％)

0.00％

0.00％

0.01％

0.15％

0.15％

0.00％

O(mol％)

60.38％

60.93％

59.15％

58.94％

60.80％

59.56％

total

100.00％

100.00％

100.00％

100.00％

100.00％

100.00％

θ

83.17％

99.84％

81.63％

49.48％

71.64％

75.74％

In the case of tables 3 and 4,wherein X is the ratio of the content of O to the content of Si.

It can be seen that the contents of the O element and the Si element in the soda glasses of examples 1 to 12 have the following characteristics:

the ratio of the content of O to the content of Si is X, wherein X satisfies:individual also satisfies:individual also satisfies:

examples 13 to 28

In examples 13 to 28, 16 different soda glasses were provided, and all of the soda glasses of examples 13 to 28 were produced using commercially available products as raw materials by float method. The soda glass components in examples 13 to 28 are shown in tables 5 to 7.

TABLE 5

TABLE 6

TABLE 7

In tables 5 to 7, β means Na₂Content of O and Li₂The ratio of the content of O; na (Na)₂O+Li₂O represents Na₂Content of O and Li₂Sum of the contents of O; r₂O represents the total content of alkali metal oxides, i.e., Na₂O、Li₂O and K₂The total content of O; (R)₂O-Al₂O₃)/B₂O₃The ratio of the difference between the alkali metal oxide content and the alumina content to the boron oxide content is shown.

It can be seen that Na is contained in the soda glasses of examples 13 to 28₂O、Li₂The content of O has the following characteristics: na (Na)₂Content of O and Li₂The sum of the contents of O is 9 to 20 percent, and Na₂Content of O and Li₂The ratio of the content of O is 1-9.

Total alkali metal oxide content, Al, in the soda glasses of examples 13 to 28₂O₃Content of (A) and B₂O₃Has the following characteristics: the total content of alkali metal oxide is greater than Al₂O₃And the total content of alkali metal oxides and Al₂O₃Difference of contents of (A) and (B)₂O₃The absolute value of the ratio of the contents of (a) is 1 or more.

Examples 29 to 47

In examples 29 to 47, 19 different soda glasses were provided, and all of the soda glasses of examples 29 to 47 were produced using a float line using a commercially available product as a raw material. The soda glass components in examples 29 to 47 are shown in tables 8 to 10.

TABLE 8

TABLE 9

Watch 10

In tables 8 to 10, beta means Na₂Content of O and Li₂The ratio of the content of O; na (Na)₂O+Li₂O represents Na₂Content of O and Li₂Sum of the contents of O; r₂O represents the total content of alkali metal oxidesI.e. Na₂O、Li₂O and K₂The total content of O; (R)₂O-Al₂O₃)/B₂O₃Expressing the ratio of the difference between the content of alkali metal oxide and the content of alumina to the content of boron oxide; REO represents the total content of rare earth oxides, i.e., CeO₂And Tm₂O₃The total content of (a).

It can be seen that Na is contained in the soda glasses of examples 29 to 47₂O、Li₂The content of O has the following characteristics: na (Na)₂Content of O and Li₂The sum of the contents of O is 9 to 20 percent, and Na₂Content of O and Li₂The ratio of the content of O is 1-9.

Total alkali Metal oxide content, Al, in the soda glasses of examples 29 to 47₂O₃Content of (A) and B₂O₃Has the following characteristics: the total content of alkali metal oxide is greater than Al₂O₃1 to 20%, and the total content of alkali metal oxides and Al₂O₃Difference of contents of (A) and (B)₂O₃The absolute value of the ratio of the contents of (a) is 1 or more.

The content of the rare earth oxide in the soda glasses of examples 29 to 47 has the following characteristics: the rare earth oxide at least comprises CeO₂And CeO₂The content of (A) is more than or equal to 0.5 percent; the total content of the rare earth oxide is 0.5-2%.

The soda glasses of examples 1 to 47 were subjected to physicochemical property tests using the above-mentioned test methods, and the results are shown in tables 11 to 18.

TABLE 11

TABLE 12

Watch 13

TABLE 14

Watch 15

TABLE 16

TABLE 17

Watch 18

The sodium glasses of examples 1-47 were analyzed for viscosity temperature properties by calculation based on the Herbert formula, and the results are shown in Table 19 below.

Watch 19

Watch 20

TABLE 21

TABLE 22

TABLE 23

Watch 24

TABLE 25

Watch 26

Watch 27

Watch 28

Watch 29

Watch 30

The viscosity-temperature properties of the soda glasses of examples 1 to 47 were computationally analyzed based on the Fluegel formula, and the results are shown in Table 31 below.

Watch 31

Watch 32

Watch 33

Watch 34

Watch 35

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Table 41

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Examples 48 to 58

Examples 48 to 58 provide 11 mixed salt baths which can be used in the preparation process according to the invention. The components of the mixed salt bath provided in examples 48 to 58 and the amounts of solid alumina added are shown in tables 43 to 44.

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In the mixed salt bath provided in examples 48 to 58, the amount of solid alumina added was 0.8% by mass or more of the mixed salt bath.

By computational analysis, it can be concluded that the contents of the respective ions per mole of the mixed salt bath in the mixed salt baths provided in examples 48 to 58 are shown in tables 45 and 46.

TABLE 45

TABLE 46

In the mixed salt bath provided in examples 48 to 58, K⁺Molar amount of (A)>Na⁺Molar amount of (A)>Li⁺The molar amount of (c).

Further analysis revealed that the percentages of each type of cation in the total amount of cations and the percentages of each type of anion in the total amount of anions in the mixed salt baths provided in examples 48 to 58 are shown in tables 47 and 48.

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In the mixed salt bath provided in examples 48 to 58, K⁺Molar amount of (A)>Na⁺Molar amount of (A)>Li⁺Molar amount of (A), K⁺The molar amount of (A) is more than 68% of the total molar amount of the metal ions, and Na⁺Is less than 30% (even less than 25%) of the total molar amount of alkali metal ions. NO₃ ^-The molar amount of (A) is more than 95% of the total molar amount of anions, and OH^-The molar amount of (a) is 2.5% or less of the total molar amount of anions.

Further analysis can lead to the concentrations of each type of cation in the mixed salt baths provided in examples 48 to 58 being shown in tables 49 and 50.

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Examples 48 to 58 provide a mixed salt bath of Na⁺The content of Li in the mixed salt bath is not less than 500ppm⁺The content of Al in the mixed salt bath is 20-1000 ppm³⁺In the mixed salt bathThe amount is 2000ppm or less.

Examples 59 to 76

Examples 59-76 provide 18 chemically strengthened glasses according to the present invention. The raw materials for chemically strengthened glass provided in examples 59 to 76 and the parameters during the strengthening process are shown in tables 59 to 76.

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Table 52

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The chemical strengthening of examples 59-76 was examined using the above-mentioned examination method, and the results are shown in tables 57-59.

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In tables 57-59, Dol _ K represents the depth of penetration of potassium ions in the salt bath into the glass, i.e., Dol corresponding to chemically strengthened glass; dol _ Na represents the depth of sodium ions in the salt bath penetrating into the glass, namely the DOI of the corresponding chemically strengthened glass.

To further illustrate that the ion exchange depth of layer (DOI) in the chemically strengthened glass provided by the present invention is at least 20um greater than the depth of layer of compressive stress (DOL). We also plot the DOI and DOL profiles within the chemically strengthened glass provided in example 75, see fig. 2, where the dashed curve is the DOI profile within the chemically strengthened glass provided in example 75 and the solid curve is the DOL profile within the chemically strengthened glass provided in example 75.

While embodiments of the present invention have been described, the present invention is not limited to the above-described embodiments, which are intended to be illustrative rather than limiting, and many modifications may be made by those skilled in the art without departing from the spirit and the scope of the invention as defined by the appended claims.