RARE EARTH-DOPED REINFORCED GLASS-CERAMIC, AND PREPARATION METHOD AND USE THEREFOR

Abstract

Provided in the present invention is a rare earth-doped reinforced glass-ceramic, and a preparation method and a use therefor. Raw materials rare earth-doped reinforced glass-ceramic comprise at least one of the following rare earth oxides: Ta.sub.2O.sub.5, La.sub.2O.sub.3, Y.sub.2O.sub.3, Tm.sub.2O.sub.3, or Nb.sub.2O.sub.5. In the present invention, a glass article doped with at least one rare earth oxide from among Ta.sub.2O.sub.5, La.sub.2O.sub.3, Y.sub.2O.sub.3, Tm.sub.2O.sub.3, or Nb.sub.2O.sub.5 is subjected to thermal treatment and ion exchange to produce the rare-earth doped reinforced glass-ceramic. In the rare earth-doped reinforced glass-ceramic, due to the high field strength and high accumulation effects of the rear earth element, the crystal size of the glass-ceramic is caused to low, and the crystal ratio thereof to be high, thus being able to effectively improve the mechanical performance and visible light transmittance of the glass-ceramic, and effectively controlling uniform devitrification of the glass. The invention is suitable for use in cover panels of electronic devices.

Claims

1. A reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises at least one rare earth oxides selected from the group consisting of Ta.sub.2O.sub.5, La.sub.2O.sub.3, Y.sub.2O.sub.3, Tm.sub.2O.sub.3 and Nb.sub.2O.sub.5.

2. The reinforced glass ceramic doped with rare earth according to claim 1, wherein the reinforced glass ceramic is prepared from the following components in mole percentage: from 65% to 75% of SiO.sub.2, from 3% to 12% of Al.sub.2O.sub.3, from 0.5% to 5% of P.sub.2O.sub.5, from 0% to 3% of B.sub.2O.sub.3, from 0% to 5% of MgO, from 0% to 3% of ZnO, from 0.5% to 5% of ZrO.sub.2, from 0% to 1.5% of TiO.sub.2, from 0.5% to 6% of Na.sub.2O, from 10% to 25% of Li.sub.2O, from 0% to 0.3% of CeO.sub.2, and from 0% to 0.5% of SnO.sub.2; and at least one of the following rare earth oxides: from 0% to 6% of Ta.sub.2O.sub.5, from 0% to 6% of La.sub.2O.sub.3, from 0% to 6% of Y.sub.2O.sub.3, from 0% to 6% of Tm.sub.2O.sub.3, and from 0% to 6% of Nb.sub.2O.sub.5.

3. The reinforced glass ceramic doped with rare earth according to claim 2, wherein the rare earth oxide has a mole percent of 6% or less.

4. The reinforced glass ceramic doped with rare earth according to claim 1, wherein a crystal phase of the reinforced glass ceramic is at least one of lithium disilicate, ZrO.sub.2 crystal, β-quartz solid solution, and petalite; and crystals in the crystal phase have a size ranging from 10-80 nm.

5. The reinforced glass ceramic doped with rare earth according to claim 4, wherein the crystals in the crystal phase have a size ranging from 20-60 nm.

6. The reinforced glass ceramic doped with rare earth according to claim 1, wherein the reinforced glass ceramic has a molar volume of 24.5 cm.sup.3/mol or less, and wherein the molar volume of the reinforced glass ceramic is calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

7. The reinforced glass ceramic doped with rare earth according to claim 1, wherein the reinforced glass ceramic has a tensile strength linear density ranging from 20000-70000 MPa/mm, a depth of compressive stress layer of 70 μm or more, and a surface compressive stress of 500 MPa or more.

8. The reinforced glass ceramic doped with rare earth according to claim 7, wherein the reinforced glass ceramic has the tensile strength linear density ranging from 30000-50000 MPa/mm, the depth of compressive stress layer of 90 μm or more, and the surface compressive stress of 800 MPa or more.

9. The reinforced glass ceramic doped with rare earth according to claim 1, wherein the reinforced glass ceramic has a Young's modulus of more than 80 GPa, and an average visible light transmittance of 89% or more.

10. A method for preparing the reinforced glass ceramic doped with rare earth according to claim 1, comprising: S1. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material; S2. heat-treating the glass article obtained in step S1 to obtain a glass ceramic; and S3. performing an ion exchange on the glass ceramic obtained in step S2 to prepare the reinforced glass ceramic.

11. The method for preparing the reinforced glass ceramic doped with rare earth according to claim 10, wherein the step S2 comprises: S21. performing a first heat treatment on the glass article obtained in step S1; and S22. performing a second heat treatment on the product obtained in step S21 to prepare the glass ceramic.

12. The method for preparing the reinforced glass ceramic doped with rare earth according to claim 11, wherein the first heat treatment is performed at a temperature of 500-650° C. for a time of 0.5-5 hours.

13. The method for preparing the reinforced glass ceramic doped with rare earth according to claim 12, wherein the second heat treatment is performed at a temperature of 600-750° C. for a time of 0.5-5 hours.

14. The method for preparing the reinforced glass ceramic doped with rare earth according to claim 10, wherein the ion exchange is a kind of single chemical strengthening or multiple chemical strengthening in a salt bath, wherein the salt bath comprises at least one of potassium salt, sodium salt, and lithium salt, and wherein the potassium salt is KNO.sub.3, the sodium salt is NaNO.sub.3 or NaNO.sub.2, and the lithium salt is LiNO.sub.3.

15. The method for preparing the reinforced glass ceramic doped with rare earth according to claim 14, wherein in the salt bath for the single chemical strengthening, the mass fraction of the sodium salt ranges from 0.5% to 30%, the mass fraction of the lithium salt ranges from 0% to 5%, and the mass fraction of the potassium salt ranges from 65% to 100%.

16. The method for preparing the reinforced glass ceramic doped with rare earth according to claim 15, wherein the multiple chemical strengthening is a double chemical strengthening, and the salt bath for the double chemical strengthening comprises a first salt bath and a second salt bath.

17. The method for preparing the reinforced glass ceramic doped with rare earth according to claim 16, wherein the sodium salt in the first salt bath has a mass fraction ranges from 30% to 100%, and the potassium salt has a mass fraction ranges from 0% to 70%.

18. The method for preparing the reinforced glass ceramic doped with rare earth according to claim 17, wherein the sodium salt in the second salt bath has the mass fraction ranges from 0% to 15%, the lithium salt has a mass fraction ranges from 0% to 5%, and the potassium salt has a mass fraction ranges from 80% to 100%.

19. The method for preparing the reinforced glass ceramic doped with rare earth according to claim 18, wherein the single chemical strengthening or the multiple chemical strengthening is performed at a temperature of 400-520° C. for a total time of 2-20 hours.

20. Use of the reinforced glass ceramic doped with rare earth according to claim 1 in a cover plate of an electronic product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0034] In order to describe the technical content, structural features, objects and effects achieved of the present invention in detail, the following detailed descriptions are provided in conjunction with the embodiments.

[0035] One aspect of the present invention provides a reinforced glass ceramic doped with rare earth, and the raw material of the reinforced glass ceramic comprises at least one of the following rare earth oxides: Ta.sub.2O.sub.5, La.sub.2O.sub.3, Y.sub.2O.sub.3, Tm.sub.2O.sub.3, Nb.sub.2O.sub.5.

[0036] Another aspect of the present invention provides a method for preparing the reinforced glass ceramic doped with rare earth provided by the present invention, comprising the following steps:

[0037] S1. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0038] S2. heat-treating the glass article obtained in step S1 to obtain a glass ceramic; and

[0039] S3. performing an ion exchange on the glass ceramic obtained in step S2 to prepare the reinforced glass ceramic.

[0040] Another aspect of the present invention provides use of the reinforced glass ceramic doped with rare earth provided by the present invention in a cover plate of an electronic product.

[0041] As can be seen from the above description, the reinforced glass ceramic doped with rare earth and the preparation method and use thereof provided by the present invention have the following beneficial effects.

[0042] The present invention provides a reinforced glass ceramic doped with rare earth, which is produced with a glass article doped with at least one rare earth oxides chosen among Ta.sub.2O.sub.5, La.sub.2O.sub.3, Y.sub.2O.sub.3, Tm.sub.2O.sub.3, and Nb.sub.2O.sub.5, through heat-treating and ion-exchanging. Such reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which can effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. In addition, the reinforced glass ceramic doped with rare earth can be applied to the cover plate of electronic products, further improving the overall performance of the cover plate of electronic products.

EXAMPLE 1

[0043] In a specific embodiment, the present invention provided a reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises rare earth oxide La.sub.2O.sub.3, the reinforced glass ceramic comprises the crystal phase of petalite, and crystals in a crystal phase of the reinforced glass ceramic have a size range of 10-20 nm.

[0044] In this example, the reinforced glass ceramic doped with rare earth was prepared from the following components in mole percentage: 65 mol % of SiO.sub.2, 12 mol % of Al.sub.2O.sub.3, 0.5 mol % of P.sub.2O.sub.5, 1 mol % of ZrO.sub.2, 0.5 mol % of Na.sub.2O, 19.7 mol % of Li.sub.2O, 0.3 mol % of CeO.sub.2, 0.1 mol % of SnO.sub.2, and 0.9 mol % of La.sub.2O.sub.3.

[0045] To be illustrative, the rare earth oxide has a mole percent of 0.9 mol %.

[0046] The reinforced glass ceramic has a molar volume of 24.1 cm.sup.3/mol, wherein the molar volume of the reinforced glass ceramic was calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

[0047] To be illustrative, the reinforced glass ceramic has a tensile strength linear density of 70000 MPa/mm, a depth of compressive stress layer of 140 μm, and a surface compressive stress of 650 MPa.

[0048] In addition, the reinforced glass ceramic has a Young's modulus of 89.2 GPa, and an average visible light transmittance of 91.5%.

[0049] This example also provided a method for preparing the reinforced glass ceramic doped with rare earth, comprising:

[0050] a. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0051] b. performing a first heat treatment on the glass article obtained in step a at 600° C. for 0.5 hour;

[0052] c. performing a second heat treatment on the product obtained in step b at 660° C. for 1 hour to obtain a glass ceramic;

[0053] d. performing an ion-exchanging on the glass ceramic obtained in step c in a salt bath containing 10% NaNO.sub.3 and 90% KNO.sub.3 at 420° C. for 4 hours, to prepare the reinforced glass ceramic.

[0054] The reinforced glass ceramic doped with rare earth was prepared by heat-treating and ion-exchanging the glass article doped with rare earth oxide La.sub.2O.sub.3. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. It can be used for cover plates of electronic devices.

EXAMPLE 2

[0055] In a specific embodiment, the present invention provided a reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises rare earth oxide Ta.sub.2O.sub.5, the reinforced glass ceramic comprises the crystal phase of lithium disilicate and β-quartz solid solution, and the crystals in a crystal phase of the reinforced glass ceramic have a size range of 35-45 nm.

[0056] In this example, the reinforced glass ceramic doped with rare earth was prepared from the following components in mole percentage: 75 mol % of SiO.sub.2, 3 mol % of Al.sub.2O.sub.3, 1 mol % of P.sub.2O.sub.5, 1 mol % of B.sub.2O.sub.3, 0.8 mol % of MgO, 0.5 mol % of ZnO, 1.5 mol % of ZrO.sub.2, 1 mol % of Na.sub.2O, 10 mol % of Li.sub.2O, 0.3 mol % of CeO.sub.2, 0.15 mol % of SnO.sub.2, and 6 mol % of Ta.sub.2O.sub.5.

[0057] To be illustrative, the rare earth oxide has a mole percent of 6 mol %. The reinforced glass ceramic has a molar volume of 22.1 cm.sup.3/mol, wherein the molar volume of the reinforced glass ceramic was calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

[0058] To be illustrative, the reinforced glass ceramic has a tensile strength linear density of 40000 MPa/mm, a depth of compressive stress layer of 90 μm, and a surface compressive stress of 710 MPa.

[0059] In addition, the reinforced glass ceramic has a Young's modulus of 84.5 GPa, and an average visible light transmittance of 90.4%.

[0060] This example also provided a method for preparing the reinforced glass ceramic doped with rare earth, comprising:

[0061] a. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0062] b. performing a first heat treatment on the glass article obtained in step a at 560° C. for 2.5 hours;

[0063] c. performing a second heat treatment on the product obtained in step b at 610° C. for 2 hours to obtain a glass ceramic;

[0064] d. performing a first ion exchanging on the glass ceramic prepared in step c in a first salt bath containing 100% of NaNO.sub.3 at 450° C. for 3 hours;

[0065] e. performing a second ion exchanging on the product obtained in step d in a second salt bath containing 15% of NaNO.sub.3 and 90% of KNO.sub.3 at 450° C. for 2 hours to prepare the reinforced glass ceramic.

[0066] The reinforced glass ceramic doped with rare earth was prepared by heat-treating and ion-exchanging the glass article doped with rare earth oxide Ta.sub.2O.sub.5. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. It can be used for cover plates of electronic devices.

EXAMPLE 3

[0067] In a specific embodiment, the present invention provided a reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises rare earth oxide Tm.sub.2O.sub.3, the reinforced glass ceramic comprises the crystal phase of ZrO.sub.2 and petalite, and crystals in a crystal phase of the reinforced glass ceramic have a size range of 30-40 nm.

[0068] In this example, the reinforced glass ceramic doped with rare earth was prepared from the following components in mole percentage: 69 mol % of SiO.sub.2, 5 mol % of Al.sub.2O.sub.3, 5 mol % of P.sub.2O.sub.5, 1 mol % of MgO, 5 mol % of ZrO.sub.2, 2 mol % of Na.sub.2O, 11 mol % of Li.sub.2O, and 2 mol % of Tm.sub.2O.sub.3.

[0069] To be illustrative, the rare earth oxide has a mole percent of 2 mol %.

[0070] The reinforced glass ceramic has a molar volume of 23.8 cm.sup.3/mol, wherein the molar volume of the reinforced glass ceramic was calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

[0071] To be illustrative, the reinforced glass ceramic has a tensile strength linear density of 60000 MPa/mm, a depth of compressive stress layer of 120 μm, and a surface compressive stress of 880 MPa.

[0072] In addition, the reinforced glass ceramic has a Young's modulus of 83.1 GPa, and an average visible light transmittance of 90.6%.

[0073] This example also provided a method for preparing the reinforced glass ceramic doped with rare earth, comprising:

[0074] a. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0075] b. performing a first heat treatment on the glass article obtained in step a at 580° C. for 4 hours;

[0076] c. performing a second heat treatment on the product obtained in step b at 680° C. for 1.5 hours to obtain a glass ceramic;

[0077] d. performing a first ion exchanging on the glass ceramic prepared in step c in a first salt bath containing 98% of NaNO.sub.3 and 2% of KNO.sub.3 at 500° C. for 4 hours;

[0078] e. performing a second ion exchanging on the product obtained in step d in a second salt bath containing 5% of NaNO.sub.3, 0.2% of LiNO.sub.3 and 94.8% of KNO.sub.3 at 500° C. for 4 hours to prepare the reinforced glass ceramic.

[0079] The reinforced glass ceramic doped with rare earth was prepared by heat-treating and ion-exchanging the glass article doped with rare earth oxide Tm.sub.2O.sub.3. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. It can be used for cover plates of electronic devices.

EXAMPLE 4

[0080] In a specific embodiment, the present invention provided a reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises rare earth oxide Nb.sub.2O.sub.5, the reinforced glass ceramic comprises the crystal phase of lithium disilicate, and crystals in a crystal phase of the reinforced glass ceramic have the size of 70-80 nm.

[0081] In this example, the reinforced glass ceramic doped with rare earth was prepared from the following components in mole percentage: 66 mol % of SiO.sub.2, 4 mol % of Al.sub.2O.sub.3, 1.5 mol % of P.sub.2O.sub.5, 1.7 mol % of ZrO.sub.2, 0.5 mol % of Na.sub.2O, 25 mol % of Li.sub.2O, 0.1 mol % of CeO.sub.2, 0.2 mol % of SnO.sub.2, and 1 mol % of Nb.sub.2O.sub.5.

[0082] To be illustrative, the rare earth oxide has a mole percent of 1 mol %.

[0083] The reinforced glass ceramic has a molar volume of 24 cm.sup.3/mol, wherein the molar volume of the reinforced glass ceramic was calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

[0084] To be illustrative, the reinforced glass ceramic has a tensile strength linear density of 20000 MPa/mm, a depth of compressive stress layer of 110 μm, and a surface compressive stress of 800 MPa.

[0085] In addition, the reinforced glass ceramic has a Young's modulus of 87.6 GPa, and an average visible light transmittance of 89%.

[0086] This example also provided a method for preparing the reinforced glass ceramic doped with rare earth, comprising:

[0087] a. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0088] b. performing a first heat treatment on the glass article obtained in step a at 500° C. for 5 hours;

[0089] c. performing a second heat treatment on the product obtained in step b at 600° C. for 5 hours to obtain a glass ceramic;

[0090] d. performing a first ion exchanging on the glass ceramic prepared in step c in a first salt bath containing 90% of NaNO.sub.3 and 10% of KNO.sub.3 at 400° C. for 5 hours;

[0091] e. performing a second ion exchanging on the product obtained in step d in a second salt bath containing 1.5% of NaNO.sub.3, 98% of KNO.sub.3 and 0.5% of LiNO.sub.3 at 400° C. for 15 hours to prepare the reinforced glass ceramic.

[0092] The reinforced glass ceramic doped with rare earth was prepared by heat-treating and ion-exchanging the glass article doped with rare earth oxide Nb.sub.2O.sub.5. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. It can be used for cover plates of electronic devices.

EXAMPLE 5

[0093] In a specific embodiment, the present invention provided a reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises rare earth oxide Y.sub.2O.sub.3, the reinforced glass ceramic comprises the crystal phase of β-quartz solid solution, and crystals in a crystal phase of the reinforced glass ceramic have a size range of 60-70 nm.

[0094] In this example, the reinforced glass ceramic doped with rare earth was prepared from the following components in mole percentage: 70 mol % of SiO.sub.2, 7 mol % of Al.sub.2O.sub.3, 2 mol % of B.sub.2O.sub.3, 3 mol % of ZnO, 2 mol % of ZrO.sub.2, 0.5 mol % of Na.sub.2O, 12 mol % of Li.sub.2O, 0.5 mol % of SnO.sub.2, and 3 mol % of Y.sub.2O.sub.3.

[0095] To be illustrative, the rare earth oxide has a mole percent of 3 mol %.

[0096] The reinforced glass ceramic has a molar volume of 22.5 cm.sup.3/mol, wherein the molar volume of the reinforced glass ceramic was calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

[0097] To be illustrative, the reinforced glass ceramic has a tensile strength linear density of 40000 MPa/mm, a depth of compressive stress layer of 130 μm, and a surface compressive stress of 500 MPa.

[0098] In addition, the reinforced glass ceramic has a Young's modulus of 82.9 GPa, and an average visible light transmittance of 89.9%.

[0099] This example also provided a method for preparing the reinforced glass ceramic doped with rare earth, comprising:

[0100] a. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0101] b. performing a first heat treatment on the glass article obtained in step a at 650° C. for 1 hour;

[0102] c. performing a second heat treatment the product obtained in step b at 750° C. for 3 hours to obtain a glass ceramic;

[0103] d. performing an ion-exchanging on the glass ceramic obtained in step c in a salt bath containing 30% of NaNO.sub.3 and 70% of KNO.sub.3 at 470° C. for 6 hours to prepare the reinforced glass ceramic.

[0104] The reinforced glass ceramic doped with rare earth was prepared by heat-treating and ion-exchanging the glass article doped with rare earth oxide Y.sub.2O.sub.3. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. It can be used for cover plates of electronic devices.

EXAMPLE 6

[0105] In a specific embodiment, the present invention provided a reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises rare earth oxides Ta.sub.2O5 and Tm.sub.2O.sub.3, the reinforced glass ceramic comprises the crystal phases of β-quartz solid solution and lithium disilicate, and crystals in a crystal phase of the reinforced glass ceramic have a size range of 40-50 nm.

[0106] In this example, the reinforced glass ceramic doped with rare earth was prepared from the following components in mole percentage: 71 mol % of SiO.sub.2, 4.5 mol % of Al.sub.2O.sub.3, 3 mol % of B.sub.2O.sub.3, 5 mol % of MgO, 0.5 mol % of ZrO.sub.2, 1.5 mol % of TiO.sub.2, 1.5 mol % of Na.sub.2O, 10.85 mol % of Li.sub.2O, 0.15 mol % of SnO.sub.2, 1 mol % of Ta.sub.2O.sub.5, and 1 mol % of Tm.sub.2O.sub.3.

[0107] To be illustrative, the rare earth oxide has a mole percent of 2 mol %.

[0108] The reinforced glass ceramic has a molar volume of 23.6 cm.sup.3/mol, wherein the molar volume of the reinforced glass ceramic was calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

[0109] To be illustrative, the reinforced glass ceramic has a tensile strength linear density of 30000 MPa/mm, a depth of compressive stress layer of 115 μm, and a surface compressive stress of 810 MPa.

[0110] In addition, the reinforced glass ceramic has a Young's modulus of 85 GPa, and an average visible light transmittance of 90.7%.

[0111] This example also provided a method for preparing the reinforced glass ceramic doped with rare earth, comprising:

[0112] a. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0113] b. performing a first heat treatment on the glass article obtained in step a at 620° C. for 2 hours;

[0114] c. performing a second heat treatment on the product obtained in step b at 710° C. for 2.5 hours to obtain a glass ceramic;

[0115] d. performing a first ion exchanging on the glass ceramic prepared in step c in a first salt bath containing 30% of NaNO.sub.3 and 70% of KNO.sub.3 at 480° C. for 3 hours;

[0116] e. performing a second ion exchanging on the product obtained in step d in a second salt bath containing 8% of NaNO.sub.3 and 92% of KNO.sub.3 at 480° C. for 1 hour to prepare the reinforced glass ceramic.

[0117] The reinforced glass ceramic doped with rare earth was prepared by heat-treating and ion-exchanging the glass article doped with rare earth oxides Ta.sub.2O.sub.5 and Tm.sub.2O.sub.3. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. It can be used for cover plates of electronic devices.

EXAMPLE 7

[0118] In a specific embodiment, the present invention provided a reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises rare earth oxide Y.sub.2O.sub.3, the reinforced glass ceramic comprises the crystal phases of ZrO.sub.2 and β-quartz solid solution, and crystals in a crystal phase of the reinforced glass ceramic have a size range of 50-60 nm.

[0119] In this example, the reinforced glass ceramic doped with rare earth was prepared from the following components in mole percentage: 73 mol % of SiO.sub.2, 3.5 mol % of Al.sub.2O.sub.3, 2 mol % of P.sub.2O.sub.5, 1 mol % of ZnO, 3 mol % of ZrO.sub.2, 0.5 mol % of TiO.sub.2, 6 mol % of Na.sub.2O, 10.4 mol % of Li.sub.2O, 0.1 mol % of SnO.sub.2, and 0.5 mol % of Y.sub.2O.sub.3.

[0120] To be illustrative, the rare earth oxide has a mole percent of 0.5 mol %.

[0121] The reinforced glass ceramic has a molar volume of 24.5 cm.sup.3/mol, wherein the molar volume of the reinforced glass ceramic was calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

[0122] To be illustrative, the reinforced glass ceramic has a tensile strength linear density of 25000 MPa/mm, a depth of compressive stress layer of 70 μm, and a surface compressive stress of 950 MPa.

[0123] In addition, the reinforced glass ceramic has a Young's modulus of 81 GPa, and an average visible light transmittance of 90.1%.

[0124] This example also provided a method for preparing the reinforced glass ceramic doped with rare earth, comprising:

[0125] a. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0126] b. performing a first heat treatment on the glass article obtained in step a at 610° C. for 3 hours;

[0127] c. performing a second heat treatment on the product obtained in step b at 730° C. for 4 hours to obtain a glass ceramic;

[0128] d. performing an ion exchanging on the glass ceramic obtained in step c in a salt bath containing 0.5% of NaNO.sub.3 and 99.5% of KNO.sub.3 at 520° C. for 2 hours to prepare the reinforced glass ceramic.

[0129] The reinforced glass ceramic doped with rare earth was prepared by heat-treating and ion-exchanging the glass article doped with rare earth oxide Y.sub.2O.sub.3. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. It can be used for cover plates of electronic devices.

EXAMPLE 8

[0130] In a specific embodiment, the present invention provided a reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises rare earth oxides La.sub.2O.sub.3 and Nb.sub.2O.sub.5, the reinforced glass ceramic comprises the crystal phases of lithium disilicate and petalite, and crystals in a crystal phase of the reinforced glass ceramic have a size range of 15-25 nm.

[0131] In this example, the reinforced glass ceramic doped with rare earth was prepared from the following components in mole percentage: 67 mol % of SiO.sub.2, 7 mol % of Al.sub.2O.sub.3, 0.5 mol % of P.sub.2O.sub.5, 0.8 mol % of ZrO.sub.2, 0.5 mol % of Na.sub.2O, 22 mol % of Li.sub.2O, 0.2 mol % of CeO.sub.2, 1.5 mol % of La.sub.2O.sub.3, and 0.5 mol % of Nb.sub.2O.sub.5.

[0132] To be illustrative, the rare earth oxide has a mole percent of 2 mol %.

[0133] The reinforced glass ceramic has a molar volume of 23.5 cm.sup.3/mol, wherein the molar volume of the reinforced glass ceramic was calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

[0134] To be illustrative, the reinforced glass ceramic has a tensile strength linear density of 50000 MPa/mm, a depth of compressive stress layer of 100 μm, and a surface compressive stress of 790 MPa.

[0135] In addition, the reinforced glass ceramic has a Young's modulus of 86.5 GPa, and an average visible light transmittance of 91%.

[0136] This example also provided a method for preparing the reinforced glass ceramic doped with rare earth, comprising:

[0137] a. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0138] b. performing a first heat treatment on the glass article obtained in step a at 540° C. for 2 hours;

[0139] c. performing a second heat treatment on the product obtained in step b at 640° C. for 0.5 hour to obtain a glass ceramic;

[0140] d. performing a first ion exchanging on the glass ceramic prepared in step c in a first salt bath containing 60% of NaNO.sub.3 and 40% of KNO.sub.3 at 460° C. for 4 hours;

[0141] e. performing a second ion exchanging on the product obtained in step d in a second salt bath containing 100% of KNO.sub.3 at 460° C. for 2 hours to prepare the reinforced glass ceramic.

[0142] The reinforced glass ceramic doped with rare earth was prepared by heat-treating and ion-exchanging the glass article doped with rare earth oxides La.sub.2O.sub.3 and Nb.sub.2O.sub.5. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. It can be used for cover plates of electronic devices.

EXAMPLE 9

[0143] In a specific embodiment, the present invention provided a reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises rare earth oxide La.sub.2O.sub.3, the reinforced glass ceramic comprises the crystal phases of lithium disilicate, petalite and β-quartz solid solution, and crystals in a crystal phase of the reinforced glass ceramic have a size range of 30-45 nm.

[0144] In this example, the reinforced glass ceramic doped with rare earth was prepared from the following components in mole percentage: 75 mol % of SiO.sub.2, 3 mol % of Al.sub.2O.sub.3, 1 mol % of P.sub.2O.sub.5, 1 mol % of B.sub.2O.sub.3, 0.8 mol % of MgO, 0.5 mol % of ZnO, 1.5 mol % of ZrO.sub.2, 1 mol % of Na.sub.2O, 10 mol % of Li.sub.2O, 0.5 mol % of CeO.sub.2, 0.15 mol % of SnO.sub.2, and 6 mol % of La.sub.2O.sub.3.

[0145] To be illustrative, the rare earth oxide has a mole percent of 6 mol %.

[0146] The reinforced glass ceramic has a molar volume of 22.3 cm.sup.3/mol, wherein the molar volume of the reinforced glass ceramic was calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

[0147] To be illustrative, the reinforced glass ceramic has a tensile strength linear density of 42000 MPa/mm, a depth of compressive stress layer of 89 μm, and a surface compressive stress of 730 MPa.

[0148] In addition, the reinforced glass ceramic has a Young's modulus of 89.3 GPa, and an average visible light transmittance of 91.2%.

[0149] This example also provided a method for preparing the reinforced glass ceramic doped with rare earth, comprising:

[0150] a. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0151] b. performing a first heat treatment on the glass article obtained in step a at 530° C. for 2 hours;

[0152] c. performing a second heat treatment on the product obtained in step b at 620° C. for 1.5 hours to obtain a glass ceramic;

[0153] d. performing an ion exchanging on the glass ceramic obtained in step c in a salt bath containing 30% of NaNO.sub.3, 65% of KNO.sub.3 and 5% of LiNO.sub.3 at 400° C. for 20 hours to prepare the reinforced glass ceramic.

[0154] The reinforced glass ceramic doped with rare earth was prepared by heat-treating and ion-exchanging the glass article doped with rare earth oxide La.sub.2O.sub.3. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. It can be used for cover plates of electronic devices.

EXAMPLE 10

[0155] In a specific embodiment, the present invention provided a reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises rare earth oxide Y.sub.2O.sub.3, the reinforced glass ceramic comprises the crystal phases of lithium disilicate, petalite and β-quartz solid solution, and crystals in a crystal phase of the reinforced glass ceramic have a size range of 35-40 nm.

[0156] In this example, the reinforced glass ceramic doped with rare earth was prepared from the following components in mole percentage: 75 mol % of SiO.sub.2, 3 mol % of Al.sub.2O.sub.3, 1 mol % of P.sub.2O.sub.5, 1 mol % of B.sub.2O.sub.3, 0.8 mol % of MgO, 0.5 mol % of ZnO, 1.5 mol % of ZrO.sub.2, 1 mol % of Na.sub.2O, 10 mol % of Li.sub.2O, 0.5 mol % of CeO.sub.2, 0.15 mol % of SnO.sub.2, and 6 mol % of Y.sub.2O.sub.3.

[0157] To be illustrative, the rare earth oxide has a mole percent of 6 mol %.

[0158] The reinforced glass ceramic has a molar volume of 22.2 cm.sup.3/mol, wherein the molar volume of the reinforced glass ceramic was calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

[0159] To be illustrative, the reinforced glass ceramic has a tensile strength linear density of 43000 MPa/mm, a depth of compressive stress layer of 90 μm, and a surface compressive stress of 740 MPa.

[0160] In addition, the reinforced glass ceramic had a Young's modulus of 89.5 GPa, and an average visible light transmittance of 90.3%.

[0161] This example also provided a method for preparing the reinforced glass ceramic doped with rare earth, comprising:

[0162] a. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0163] b. performing a first heat treatment on the glass article obtained in step a at 550° C. for 2.5 hours;

[0164] c. performing a second heat treatment on the product obtained in step b at 610° C. for 1 hour to obtain a glass ceramic;

[0165] d. performing an ion exchanging on the glass ceramic obtained in step c in a salt bath containing 32% of NaNO.sub.2, 65% of KNO.sub.3 and 3% of LiNO.sub.3 at 480° C. for 8 hours to prepare the reinforced glass ceramic.

[0166] The reinforced glass ceramic doped with rare earth was prepared by heat-treating and ion-exchanging the glass article doped with rare earth oxide Y.sub.2O.sub.3. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. It can be used for cover plates of electronic devices.

EXAMPLE 11

[0167] In a specific embodiment, the present invention provided a reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises rare earth oxide Tm.sub.2O.sub.3, the reinforced glass ceramic comprises the crystal phases of lithium disilicate and petalite, and crystals in a crystal phase of the reinforced glass ceramic have a size range of 35-50 nm.

[0168] In this example, the reinforced glass ceramic doped with rare earth was prepared from the following components in mole percentage: 75 mol % of SiO.sub.2, 3 mol % of Al.sub.2O.sub.3, 1 mol % of P.sub.2O.sub.5, 1 mol % of B.sub.2O.sub.3, 0.8 mol % of MgO, 0.5 mol % of ZnO, 1.5 mol % of ZrO.sub.2, 1 mol % of Na.sub.2O, 10 mol % of Li.sub.2O, 0.5 mol % of CeO.sub.2, 0.15 mol % of SnO.sub.2, and 6 mol % of Tm.sub.2O.sub.3.

[0169] To be illustrative, the rare earth oxide has a mole percent of 6 mol %.

[0170] The reinforced glass ceramic has a molar volume of 22.4 cm.sup.3/mol, wherein the molar volume of the reinforced glass ceramic was calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

[0171] To be illustrative, the reinforced glass ceramic has a tensile strength linear density of 45000 MPa/mm, a depth of compressive stress layer of 95 μm, and a surface compressive stress of 760 MPa.

[0172] In addition, the reinforced glass ceramic has a Young's modulus of 89.8 GPa, and an average visible light transmittance of 91%.

[0173] This example also provided a method for preparing the reinforced glass ceramic doped with rare earth, comprising:

[0174] a. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0175] b. performing a first heat treatment on the glass article obtained in step a at 520° C. for 4 hours;

[0176] c. performing a second heat treatment on the product obtained in step b at 600° C. for 0.5 hour to obtain a glass ceramic;

[0177] d. performing an ion exchanging on the glass ceramic obtained in step c in a salt bath containing 100% of KNO.sub.3 at 470° C. for 8.5 hours to prepare the reinforced glass ceramic.

[0178] The reinforced glass ceramic doped with rare earth was prepared by heat-treating and ion-exchanging the glass article doped with rare earth oxide Tm.sub.2O.sub.3. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. It can be used for cover plates of electronic devices.

EXAMPLE 12

[0179] In a specific embodiment, the present invention provided a reinforced glass ceramic doped with rare earth, wherein the raw material of the reinforced glass ceramic comprises rare earth oxide Nb.sub.2O.sub.5, the reinforced glass ceramic comprises the crystal phases of lithium disilicate, petalite, ZrO.sub.2 and β-quartz solid solution, and crystals in a crystal phase of the reinforced glass ceramic have a size range of 65-75 nm.

[0180] In this example, the reinforced glass ceramic doped with rare earth was prepared from the following components in mole percentage: 75 mol % of SiO.sub.2, 3 mol % of Al.sub.2O.sub.3, 1 mol % of P.sub.2O.sub.5, 1 mol % of B.sub.2O.sub.3, 0.8 mol % of MgO, 0.5 mol % of ZnO, 1.5 mol % of ZrO.sub.2, 1 mol % of Na.sub.2O, 10 mol % of Li.sub.2O, 0.5 mol % of CeO.sub.2, 0.15 mol % of SnO.sub.2, and 6 mol % of Nb.sub.2O.sub.5.

[0181] To be illustrative, the rare earth oxide has a mole percent of 6 mol %.

[0182] The reinforced glass ceramic has a molar volume of 23 cm.sup.3/mol, wherein the molar volume of the reinforced glass ceramic was calculated according to the equation: V.sub.m=Σx.sub.iM.sub.i/ρ, where V.sub.m is the molar volume of the reinforced glass ceramic; x.sub.i and M.sub.i are the molar fraction and molar mass of each oxide constituting the reinforced glass ceramic, respectively; and ρ is the density of the glass article of the reinforced glass ceramic.

[0183] To be illustrative, the reinforced glass ceramic has a tensile strength linear density of 48000 MPa/mm, a depth of compressive stress layer of 110 μm, and a surface compressive stress of 820 MPa.

[0184] In addition, the reinforced glass ceramic has a Young's modulus of 88.7 GPa, and an average visible light transmittance of 90.7%.

[0185] This example also provided a method for preparing the reinforced glass ceramic doped with rare earth, comprising:

[0186] a. preparing a glass article as a glass ceramic precursor according to the mole percent of each raw material;

[0187] b. performing a first heat treatment on the glass article obtained in step a at 570° C. for 1.5 hours;

[0188] c. performing a second heat treatment on the product obtained in step b at 610° C. for 3 hours to obtain a glass ceramic;

[0189] d. performing a first ion exchanging on the glass ceramic prepared in step c in a first salt bath containing 45% of NaNO.sub.2 and 55% of KNO.sub.3 at 520° C. for 1 hour;

[0190] e. performing a second ion exchanging on the product obtained in step d in a second salt bath containing 15% of NaNO.sub.2, 80% of KNO.sub.3 and 5% of LiNO.sub.3 at 400° C. for 1 hour to prepare the reinforced glass ceramic.

[0191] Glass article doped with rare earth oxide Nb.sub.2O.sub.5 were heat-treated and ion-exchanged to obtain reinforced glass ceramic doped with rare earths. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. It can be used for cover plates of electronic devices.

[0192] To sum up, the reinforced glass ceramic doped with rare earth and the preparation method and use thereof provided by the present invention have the following beneficial effects.

[0193] The reinforced glass ceramic doped with rare earth was prepared by heat-treating and ion-exchanging the glass article doped with at least one of rare earth oxides chosen among Ta.sub.2O.sub.5, La.sub.2O.sub.3, Y.sub.2O.sub.3, Tm.sub.2O.sub.3, and Nb.sub.2O.sub.5. This reinforced glass ceramic doped with rare earth has small crystal size and a high crystal ratio due to the high field strength and high accumulation effect of the rear earth elements, which could effectively improve the mechanical properties and visible light transmittance of glass ceramic, as well as effectively control the homogeneous crystallization of glass. In addition, the reinforced glass ceramic doped with rare earth can be applied to the cover plate of electronic products, further improving the overall performance of the cover plate of electronic products.

[0194] The above are merely examples of the present invention, which are not intended to limit the scope of the present invention. Any equivalent structures or equivalent processes made by utilizing the contents of the description of the present invention, or any direct or indirect utilization in other related technical fields, are also included in the protection scope of the present invention.