Microcrystalline glass, microcrystalline glass product, and manufacturing method therefor

Patent metadata

Field	Value
Publication number	US-11807569-B2
Application number	US-202217706964-A
Country	US
Kind code	B2
Filing date	Mar 29, 2022
Priority date	Oct 26, 2018
Publication date	Nov 7, 2023
Grant date	Nov 7, 2023

Abstract

The present invention discloses a microcrystalline glass, a microcrystalline glass product, and a manufacturing method therefor. The main crystal phase of the microcrystalline glass comprises lithium silicate and a quartz crystal phase. The haze of the microcrystalline glass of the thickness of 0.55 mm is below 0.6%. The microcrystalline glass comprises the following components in percentage by weight: SiO 2 : 65-85%; Al 2 O 3 : 1-15%; Li 2 O: 5-15%; ZrO 2 : 0.1-10%; P 2 O 5 : 0.1-10%; K 2 O: 0-10%; MgO: 0-10%; ZnO: 0-10%. A four-point bending strength of the microcrystalline glass product is more than 600 Mpa.

First claim

The invention claimed is:

1. A microcrystalline glass product, wherein a four-point bending strength of the microcrystalline glass product is above 600 MPa, and the microcrystalline glass product comprises, in percentage by weight, 65-85% of SiO 2 , 5.83-11.29% of Al 2 O 3 , 5-15% of Li 2 O, 0.1-6.52% of ZrO 2 , 0.79-2.5% of P 2 O 5 , 0<K 2 O≤6.42%, 0-10% of MgO, 0-10% of ZnO, 0-5% of Na 2 O, and 0-1% of BaO,
wherein (SiO 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 is 40-90, (Al 2 O 3 +Li 2 O)/P 2 O 5 is 8.5-20, Li 2 O/(K 2 O+ZrO 2 ) is 2.3-4.0, and (SiO 2 +Li 2 O)/Al 2 O 3 is 9.1-12.

2. The microcrystalline glass product according to claim 1 , further comprising, in percentage by weight, 0-5% of SrO, and/or 0-5% of TiO 2 , and/or 0-5% Y 2 O 3 , and/or 0-3% of B 2 O 3 , and/or 0-2% of a clarifiant.

3. The microcrystalline glass product according to claim 1 , wherein the content of each component satisfies one or more of the following 5 conditions: 1) (Al 2 O 3 +Li 2 O)/P 2 O 5 is 8.5-14; 2) (SiO 2 +Li 2 O)/P 2 O 5 is 40-80; 3) (SiO 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 is 45-85; 4) (K 2 O+MgO)/ZrO 2 is 0.6-1.2; 5) Li 2 O/(K 2 O+ZrO 2 ) is 2.5-3.5.

4. The microcrystalline glass product according to claim 1 , comprising, in percentage by weight, 70-80% of SiO 2 , and/or 5.83-10% of Al 2 O 3 , and/or 7-15% of Li 2 O, and/or 0.5-6% of ZrO 2 , 0<K 2 O≤5, and/or 0-5% of MgO, and/or 0-5% of ZnO, and/or 0-1% of SrO; and/or 0-1% of TiO 2 , and/or 0-1% of Y 2 O 3 , and/or 0-3% of Na 2 O, and/or 0.1-2% of B 2 O 3 , and/or 0-1% of the clarifiant.

5. The microcrystalline glass product according to claim 1 , wherein the content of each component satisfies one or more of the following 6 conditions: 1) (SiO 2 +Li 2 O)/Al 2 O 3 is 10-12; 2) (Al 2 O 3 +Li 2 O)/P 2 O 5 is 8.5-14; 3) (SiO 2 +Li 2 O)/P 2 O 5 is 40-70; 4) (SiO 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 is 46-80; 5) (K 2 O+MgO)/ZrO 2 is 0.7-1.1; 6) Li 2 O/(K 2 O+ZrO 2 ) is 2.8-3.3.

6. The microcrystalline glass product according to claim 1 , comprising, in percentage by weight, 70-76% of SiO 2 , and/or 5.83-9.8% of Al 2 O 3 , and/or 8-12.5% of Li 2 O, and/or 1-5% of ZrO 2 , and/or 1-2% of P 2 O 5 , 0<K 2 O≤3, and/or 0.3-2% of MgO, and/or 0-3% of ZnO, and/or 0-1% of Na 2 O, and/or 0-1% of Sb 2 O 3 , and/or 0-1% of SnO 2 , and/or 0-1% of SnO.

7. The microcrystalline glass product according to claim 1 , wherein the content of each component satisfies one or more of the following 4 conditions: 1)(Al 2 O 3 +Li 2 O)/P 2 O 5 is 8.5-14; 2) (SiO 2 +Li 2 O)/P 2 O 5 is 42-60; 3)(SiO 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 is 48-80; 4) (K 2 O+MgO)/ZrO 2 is 0.8-1.0.

8. The microcrystalline glass product according to claim 1 , comprising, in percentage by weight, 8% to less than 10% of Li 2 O, and/or not comprising SrO, and/or not comprising BaO, and/or not comprising TiO 2 , and/or not comprising Y 2 O 3 , and/or not comprising GeO 2 , and/or not comprising CaO, and/or not comprising Cs 2 O, and/or not comprising PbO, and/or not comprising B 2 O 3 , and/or not comprising As 2 O 3 , and/or not comprising La 2 O 3 , and/or not comprising Tb 2 O 3 .

9. The microcrystalline glass product according to claim 1 , wherein the content of each component satisfies one or more of the following 3 conditions: 1) (SiO 2 +Li 2 O)/P 2 O 5 is 45-60; 2) (Al 2 O 3 +Li 2 O)/P 2 O 5 is 8.89-14; 3) (SiO 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 is 48-68.93.

10. The microcrystalline glass product according to claim 1 , wherein a main crystalline phase thereof comprises lithium silicate and quartz, or a crystallinity of the main crystalline phase is above 75%.

11. The microcrystalline glass product according to claim 1 , wherein a surface stress is above 300 MPa, and/or a depth of an ion exchange layer is above 80 μm, and/or a falling ball test height is above 1,200 mm, and/or a fracture toughness is above 1.5 MPa·m 1/2 , and/or a four-point bending strength is above 700 MPa, and/or the haze for a thickness of below 0.4%, and/or a grain size is below 50 nm, and/or a thermal refractive index coefficient is below −1.1×10 −6 /° C., and/or an average light transmittance for a thickness of 1 mm at a wavelength of 400-800 nm is above 88%, and/or a light transmittance for a thickness of 0.55 mm at a wavelength of 550 nm is above 91%.

12. The microcrystalline glass product according to claim 1 , further comprising a colorant, wherein the colorant comprises, in percentage by weight of the microcrystalline glass product, 0-4% of NiO, and/or 0-4% of Ni 2 O 3 , and/or 0-2% of CoO, and/or 0-2% of Co 2 O 3 , and/or 0-7% of Fe 2 O 3 , and/or 0-4% of MnO 2 , and/or 0-8% of Er 2 O 3 , and/or 0-8% of Nd 2 O 3 , and/or 0-4% of Cu 2 O, and/or 0-8% of Pr 2 O 3 , and/or 0-4% of CeO 2 .

13. A microcrystalline glass, wherein a haze of the microcrystalline glass of a thickness of 0.55 mm is below 0.6%, and the microcrystalline glass comprises, in percentage by weight, 65-85% of SiO 2 , 5.83-11.29% of Al 2 O 3 , 5-15% of Li 2 O, 0.1-6.52% of ZrO 2 , 0.79-2.5% of P 2 O 5 , 0<K 2 O≤6.42%, 0-10% of MgO, 0-10% of ZnO, and 0-1% of BaO, wherein (SiO 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 is 40-90, (Al 2 O 3 +Li 2 O)/P 2 O 5 is 8.5-20, Li 2 O/(K 2 O+ZrO 2 ) is 2.3-4.0, and (SiO 2 +Li 2 O)/Al 2 O 3 is 9.1-12.

14. The microcrystalline glass according to claim 13 , further comprising, in percentage by weight, 0-5% of SrO, and/or 0-5% of TiO 2 , and/or 0-5% Y 2 O 3 , and/or 0-3% of B 2 O 3 , and/or 0-2% of a clarifiant.

15. The microcrystalline glass according to claim 13 , wherein the content of each component satisfies one or more of the following 5 conditions: 1) (Al 2 O 3 +Li 2 O)/P 2 O 5 is 8.5-14; 2) (SiO 2 +Li 2 O)/P 2 O 5 is 40-80; 3) (SiO 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 is 45-85; 4) (K 2 O+MgO)/ZrO 2 is 0.6-1.2; 5) Li 2 O/(K 2 O+ZrO 2 ) is 2.5-3.5.

16. The microcrystalline glass according to claim 13 , comprising, in percentage by weight, 70-80% of SiO 2 , and/or 5.83-10% of Al 2 O 3 , and/or 7-15% of Li 2 O, and/or 0.5-6% of ZrO 2 , 0<K 2 O≤5, and/or 0-5% of MgO, and/or 0-5% of ZnO, and/or 0-1% of SrO, and/or 0-1% of TiO 2 , and/or 0-1% of Y 2 O 3 , and/or 0-3% of Na 2 O, and/or 0.1-2% of B 2 O 3 , and/or 0-1% of the clarifiant.

17. The microcrystalline glass according to claim 13 , wherein the content of each component satisfies one or more of the following 6 conditions: 1) (SiO 2 +Li 2 O)/Al 2 O 3 is 10-12; 2) (Al 2 O 3 +Li 2 O)/P 2 O 5 is 8.5-14; 3) (SiO 2 +Li 2 O)/P 2 O 5 is 40-70; 4) (SiO 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 is 46-80; 5) (K 2 O+MgO)/ZrO 2 is 0.7-1.1; 6) Li 2 O/(K 2 O+ZrO 2 ) is 2.8-3.3.

18. The microcrystalline glass according to claim 13 , comprising, in percentage by weight, 70-76% of SiO 2 , and/or 5.83-9.8% of Al 2 O 3 , and/or 8-12.5% of Li 2 O, and/or 1-5% of ZrO 2 , and/or 1-2% of P 2 O 5 , 0<K 2 O≤3, and/or 0.3-2% of MgO, and/or 0-3% of ZnO, and/or 0-1% of Na 2 O, and/or 0-1% of Sb 2 O 3 , and/or 0-1% of SnO 2 , and/or 0-1% of SnO.

19. The microcrystalline glass according to claim 13 , wherein the content of each component satisfies one or more of the following 4 conditions: 1) (Al 2 O 3 +Li 2 O)/P 2 O 5 is 8.5-14; 2) (SiO 2 +Li 2 O)/P 2 O 5 is 42-60; 3) (SiO 2 +Al 2 O 3 +Li 2 O+ZrO 2 )/P 2 O 5 is 48-80; 4) (K 2 O+MgO)/ZrO 2 is 0.8-1.0.

20. The microcrystalline glass according to claim 13 , comprising, in percentage by weight, 9% to less than 10% of Li 2 O, and/or not comprising SrO; and/or not comprising BaO; and/or not comprising TiO 2 ; and/or not comprising Y 2 O 3 ; and/or not comprising GeO 2 ; and/or not comprising C

Assignees

• Cdgm Glass Co Ltd

Inventors

• Yu Tianlai
• Yuan Baoping
• Liu Zhenyu

Classifications

• C03C10/0027 Primary

  containing SiO2, Al2O3, Li2O as main constituents · CPC title

• C03C10/0009 Primary

  containing silica as main constituent · CPC title

• C03C10/0054

  containing PbO, SnO2, B2O3 · CPC title

• C03C3/097 Primary

  containing phosphorus, niobium or tantalum · CPC title

• C03C10/00 Primary

  Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition · CPC title