CN111807705A

CN111807705A - Glass ceramics, glass ceramics product and manufacturing method thereof

Info

Publication number: CN111807705A
Application number: CN202010603759.4A
Authority: CN
Inventors: 原保平; 于天来; 蒋焘; 刘振禹; 聂小兵
Original assignee: CDGM Glass Co Ltd
Current assignee: CDGM Glass Co Ltd
Priority date: 2020-06-29
Filing date: 2020-06-29
Publication date: 2020-10-23
Anticipated expiration: 2040-06-29
Also published as: CN114907014B; CN114907014A; CN111807705B

Abstract

The invention provides microcrystalline glass, which comprises the following components in percentage by weight: SiO 2₂：46～68％；Al₂O₃：11～30％；Na₂O：5～18％；ZnO：3～13％；TiO₂: 1 to 9% of (TiO)₂+ZnO)/Al₂O₃0.2 to 1.5. Through reasonable component design, the microcrystalline glass obtained by the invention has excellent mechanical properties and is suitable for electronic equipment or display equipment.

Description

Glass ceramics, glass ceramics product and manufacturing method thereof

Technical Field

The present invention relates to a glass ceramic, a glass ceramic product and a method for producing the same, and more particularly to a glass ceramic having excellent mechanical properties and suitable for use in electronic devices or display devices, a glass ceramic product and a method for producing the same.

Background

In recent years, with the rise and development of consumer electronics, glass is widely used in such electronic devices as a transparent and good-performance material. Devices such as LED and LCD displays and computer monitors may have "touch" functionality which necessitates the glass used therein to be in contact with various objects such as a user's finger and/or a stylus device, and as such, the glass needs to be sufficiently strong and chemically stable to withstand normal contact without damage. In addition, such glass is also applicable to portable electronic products, such as mobile phones (cell phones), tablet computers, personal media terminals, and the like, wherein the glass is required to withstand not only conventional "touch" contact from the application for a long time, but also accidental bending, scratching, and impact that may occur during use, which puts higher demands on the relative performance of the glass.

A glass ceramics is a material in which crystals are precipitated inside the glass by heat treatment of the glass. The crystallized glass can have physical properties that cannot be obtained in glass due to the crystals dispersed therein. For example, mechanical strength such as flexural strength and fracture toughness, etching characteristics to acidic or alkaline chemical solutions, thermal properties such as thermal expansion coefficient, and the like, and increase and decrease in glass transition temperature are exemplified. The microcrystalline glass has higher mechanical properties, and because the microcrystalline is formed in the glass, the bending resistance, the wear resistance and the like of the microcrystalline glass have obvious advantages compared with the common glass. Based on the above advantages, the microcrystalline glass or the microcrystalline glass product processed by the microcrystalline glass is applied to display equipment or electronic equipment with high requirements on drop resistance, pressure resistance and scratch resistance. Therefore, the development of a microcrystalline glass and a microcrystalline glass product which have excellent mechanical properties and are suitable for display equipment or electronic equipment with high requirements on drop resistance, pressure resistance and scratch resistance becomes an objective pursued by technologists.

Disclosure of Invention

The invention aims to provide microcrystalline glass with excellent mechanical properties and a microcrystalline glass product.

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

(1) the microcrystalline glass comprises the following components in percentage by weight: SiO 2₂：46～68％；Al₂O₃：11～30％；Na₂O：5～18％；ZnO：3～13％；TiO₂: 1 to 9% of (TiO)₂+ZnO)/Al₂O₃0.2 to 1.5.

(2) The glass-ceramic according to (1), which comprises the following components in percentage by weight: li₂O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or P₂O₅: 0-6%; and/or ZrO₂: 0-6%; and/or a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(3) Microcrystalline glass comprising SiO as a component₂、Al₂O₃、Na₂O, ZnO and TiO₂The components of which are expressed in weight percent, wherein (TiO)₂+ZnO)/Al₂O₃0.2 to 1.5, wherein the glass ceramic contains a spinel crystal phase, wherein the spinel crystal phase has a higher weight percentage than other crystal phases present in the glass ceramic.

(4) Microcrystalline glass having a composition comprising SiO₂、Al₂O₃And ZnO, the microcrystalline glass contains a spinel crystal phase.

(5) The glass-ceramic according to any one of (3) or (4), which comprises, in terms of weight percent: SiO 2₂: 46-68%; and/or Al₂O₃: 11-30%; and/or Na₂O: 5-18%; and/or ZnO: 3-13%; and/or TiO₂: 1-9%; and/or Li₂O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or P₂O₅: 0-6%; and/or ZrO₂: 0-6%; and/or a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(6) The crystallized glass according to any one of (1) to (5), which comprises the following components in percentage by weight: (TiO)₂+ZnO)/Al₂O₃0.3 to 0.9, preferably (TiO)₂+ZnO)/Al₂O₃0.4 to 0.7.

(7) The crystallized glass according to any one of (1) to (6), which comprises the following components in percentage by weight: al (Al)₂O₃/SiO₂0.2 to 0.62, preferably Al₂O₃/SiO₂0.25 to 0.55, more preferably Al₂O₃/SiO₂0.3 to 0.5.

(8) The crystallized glass according to any one of (1) to (7), which comprises the following components in percentage by weight: SiO 2₂/(Na₂O + ZnO) of 2.0 to 8.0, preferably SiO₂/(Na₂O + ZnO) of 2.5 to 6.0, more preferably SiO₂/(Na₂O + ZnO) of 2.5 to 5.5.

(9) The crystallized glass according to any one of (1) to (8), which comprises the following components in percentage by weight: li₂O/ZnO is 1.0 or less, and Li is preferable₂O/ZnO is 0.8 or less, and Li is more preferable₂The O/ZnO ratio is 0.7 or less.

(10) The crystallized glass according to any one of (1) to (9), which comprises the following components in percentage by weight: al (Al)₂O₃/(MgO + ZnO) is 2.5 or more, and Al is preferable₂O₃/(MgO + ZnO) is 2.5 to 10.0, more preferably Al₂O₃/(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable₂O₃The ratio of (MgO + ZnO) is 2.7 to 4.0.

(11) The crystallized glass according to any one of (1) to (10), which comprises the following components in percentage by weight: the ratio MgO/ZnO is 0.5 or less, preferably 0.4 or less, and more preferably 0.3 or less.

(12) The microcrystalline glass according to any one of (1) to (11)The glass comprises the following components in percentage by weight: (MgO + ZnO + Na)₂O)/TiO₂1.0 to 10.0, preferably (MgO + ZnO + Na)₂O)/TiO₂1.5 to 8.0, more preferably (MgO + ZnO + Na)₂O)/TiO₂Is 2.0 to 4.0.

(13) The crystallized glass according to any one of (1) to (12), which comprises the following components in percentage by weight: na (Na)₂O/(TiO₂+Li₂O) is 0.5 to 9.0, preferably Na₂O/(TiO₂+Li₂O) is 0.8 to 7.0, more preferably Na₂O/(TiO₂+Li₂O) is 1.0 to 5.0.

(14) The crystallized glass according to any one of (1) to (13), which comprises the following components in percentage by weight: (P)₂O₅+ZrO₂) The content of/ZnO is 1.1 or less, preferably (P)₂O₅+ZrO₂) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable₂O₅+ZrO₂) the/ZnO is 0.1 to 0.7.

(15) The crystallized glass according to any one of (1) to (14), which comprises the following components in percentage by weight: SiO 2₂: 50-66%; and/or Al₂O₃: 15-28%; and/or Na₂O: 6-15%; and/or ZnO: 4-12%; and/or TiO₂: 2-8%; and/or Li₂O: 0 to 5 percent; and/or MgO: 0 to 3 percent; and/or K₂O: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or Ln₂O₃: 0 to 4 percent; and/or B₂O₃: 0 to 3 percent; and/or P₂O₅: 0 to 4 percent; and/or ZrO₂: 0 to 5 percent; and/or a clarifying agent: 0 to 1 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(16) The crystallized glass according to any one of (1) to (15), which comprises the following components in percentage by weight: SiO 2₂: 50-64%; and/or Al₂O₃: 16-25%; and/or Na₂O: 6.5-12%; and/or ZnO: 5-10%; and/or TiO₂: 2.5-6.5%; and/or Li₂O: 0 to 3 percent; and/or MgO: 0 to 1.5 percent; and/or K₂O: 0.5-2.5%; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or CaO: 0 to 1 percent; and/or Ln₂O₃: 0 to 3 percent; and/or B₂O₃: 0 to 1 percent; and/or P₂O₅: 0.2-3%; and/or ZrO₂: 0 to 3 percent; and/or a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(17) The crystallized glass according to any one of (1) to (16), which comprises the following components in percentage by weight: AgO: 0-2%, preferably AgO: 0 to 1 percent; and/or CuO: 0 to 2%, preferably CuO: 0 to 1 percent; and/or Cu₂O: 0 to 2%, preferably Cu₂O：0～1％。

(18) The crystallized glass of any one of (1) to (17), which does not contain B in the component₂O₃(ii) a And/or does not contain CaO; and/or no BaO; and/or does not contain SrO; and/or does not contain F; and/or does not contain Ta₂O₅(ii) a And/or do not contain La₂O₃(ii) a And/or does not contain Gd₂O₃。

(19) The crystallized glass according to any one of (1) to (18), wherein the crystallized glass contains a spinel crystal phase; and/or a lithium phosphate crystalline phase; and/or quartz and quartz solid solution crystalline phases; and/or a zirconium silicate crystalline phase; and/or a lithium silicate crystalline phase.

(20) The glass-ceramic according to any one of (1) to (19), wherein the total amount of crystal phases in the glass-ceramic accounts for 5 to 60 wt%, preferably 10 to 50 wt%, and more preferably 15 to 40 wt% of the glass-ceramic.

(21) The crystallized glass according to any one of (1) to (20), wherein the crystallized glass contains a spinel crystal phase having a weight percentage higher than that of other crystal phases, preferably 10 to 50% by weight of the spinel crystal phase with respect to the crystallized glass, and more preferably 15 to 40% by weight of the spinel crystal phase with respect to the crystallized glass.

(22) The crystallized glass according to any one of (1) to (21), which does not contain quartz or a quartz solid solution crystal phase; and/or does not contain a lithium silicate crystalline phase.

(23) The crystallized glass according to any one of (1) to (22), wherein the crystallized glass having a thickness of 0.55mm has a haze of 0.3% or less, preferably 0.15% or less, more preferably 0.1% or less; and/or 0.55mm thick microcrystalline glass, the average transmittance at a wavelength of 400-800 nm is more than 85%, preferably more than 86%, more preferably more than 88%; and/or 0.55mm thick glass ceramics, and has a 550nm wavelength transmittance of 85% or more, preferably 87% or more, and more preferably 90% or more.

(24) The crystallized glass according to any one of (1) to (23), wherein the crystallized glass has a crystallinity of 20% or more, preferably 30% or more, and more preferably 40% or more; and/or a crystal grain size of 70nm or less, preferably 50nm or less, more preferably 40nm or less, and further preferably 30nm or less; and/or a ball drop test height of 500mm or more, preferably 700mm or more, more preferably 900mm or more.

(25) The crystallized glass according to any one of (1) to (24), wherein the crystallized glass further contains a coloring agent, and the crystallized glass can be made to have different colors.

(26) The glass ceramic according to (25), wherein the glass ceramic has a colorant containing, in terms of weight percent: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni₂O₃: 0 to 4%, preferably Ni₂O₃: 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co₂O₃: 0 to 2%, preferably Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0 to 7%, preferably Fe₂O₃: 0.2-5%; and/or MnO₂: 0 to 4%, preferably MnO₂: 0.1-3%; and/or Er₂O₃: 0 to 8%, preferably Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0 to 8%, preferably Nd₂O₃: 0.4-6%; and/or Cu₂O: 0 to 4%, preferably Cu₂O: 0.5-3%; and/or Pr₂O₅: 0 to 8%, preferably Pr₂O₅: 0.4-6%; and/or CeO₂: 0 to 4%, preferably CeO₂：0.5～3％。

(27) A crystallized glass product comprising the crystallized glass according to any one of (1) to (26).

(28) The crystallized glass article according to (27), wherein the crystallized glass article having a thickness of 0.55mm has a haze of 0.3% or less, preferably 0.15% or less, more preferably 0.1% or less; and/or a microcrystalline glass product having a thickness of 0.55mm, wherein the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 86% or more, and more preferably 88% or more; and/or a microcrystalline glass product having a thickness of 0.55mm, and has a transmittance at a wavelength of 550nm of 85% or more, preferably 87% or more, and more preferably 90% or more.

(29) The crystallized glass product according to any one of (27) and (28), wherein a crystallinity of the crystallized glass product is 20% or more, preferably 30% or more, and more preferably 40% or more; and/or the crystal grain size is 70nm or less, preferably 50nm or less, more preferably 40nm or less, and further preferably 30nm or less.

(30) The crystallized glass product according to any one of (27) to (29), wherein the crystallized glass product has a surface stress of 800MPa or more, preferably 1000MPa or more, and more preferably 1100MPa or more; and/or the depth of the ion exchange layer is 25 μm or more, preferably 28 μm or more, and more preferably 30 μm or more.

(31) The crystallized glass product according to any one of (27) to (30), wherein a falling ball test height of the crystallized glass product is 900mm or more, preferably 1000mm or more, and more preferably 1100nm or more; and/or a fracture toughness of 1MPa m^1/2Above, preferably 1.2MPa · m^1/2More preferably 1.3MPa · m or more^1/2The above; and/or a Vickers hardness of 600kgf/mm²Above, preferably 650kgf/mm²Above, more preferably 680kgf/mm²The above; and/or a four-point bending strength of 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more.

The invention also provides a glass cover plate:

(32) a glass cover plate made of the glass-ceramic according to any one of (1) to (26), and/or the glass-ceramic product according to any one of (27) to (31).

The invention also provides a glass component:

(33) a glass component produced from the glass ceramics according to any one of (1) to (26), and/or the glass ceramics product according to any one of (27) to (31).

The present invention also provides a display device:

(34) a display device comprising the glass-ceramic according to any one of (1) to (26), and/or comprising the glass-ceramic product according to any one of (27) to (31), and/or comprising the glass cover plate according to (32), and/or comprising the glass component according to (33).

The invention also provides an electronic device:

(35) an electronic device comprising the glass ceramic of any one of (1) to (26), and/or comprising the glass ceramic product of any one of (27) to (31), and/or comprising the glass cover plate of (32), and/or comprising the glass component of (33).

The invention also provides a manufacturing method of the microcrystalline glass product, which comprises the following steps:

(36) a method of making a crystallized glass article, the method comprising the steps of:

forming a matrix glass, the components of the matrix glass, expressed in weight percent, comprising: SiO 2₂：46～68％；Al₂O₃：11～30％；Na₂O：5～18％；ZnO：3～13％；TiO₂: 1 to 9% of (TiO)₂+ZnO)/Al₂O₃0.2 to 1.5.

And forming microcrystalline glass by crystallizing the matrix glass, and forming a microcrystalline glass product by chemically strengthening the microcrystalline glass.

(37) The method for producing a crystallized glass product according to (36), wherein the base glass further contains, in terms of the components by weight: li₂O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or P₂O₅: 0-6%; and/or ZrO₂: 0-6%; and/or a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(38) The method for producing a crystallized glass product according to any one of (36) and (37), wherein the matrix glass contains, in terms of the components by weight: SiO 2₂: 50-66%, preferably SiO₂: 50-64%; and/or Al₂O₃: 15-28%, preferably Al₂O₃: 16-25%; and/or Na₂O: 6-15%, preferably Na₂O: 6.5-12%; and/or ZnO: 4-12%, preferably ZnO: 5-10%; and/or TiO₂: 2-8%, preferably TiO₂: 2.5-6.5%; and/or Li₂O: 0 to 5%, preferably Li₂O: 0 to 3 percent; and/or MgO: 0-3%, preferably MgO: 0 to 1.5 percent; and/or K₂O: 0 to 3%, preferably K₂O: 0.5-2.5%; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or Ln₂O₃: 0 to 4%, preferably Ln₂O₃: 0 to 3 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or P₂O₅: 0 to 4%, preferably P₂O₅: 0.2-3%; and/or ZrO₂: 0 to 5%, preferably ZrO₂: 0 to 3 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(39) The method for producing a crystallized glass product according to any one of (36) to (38), wherein the matrix glass comprises, in terms of weight percent: (TiO)₂+ZnO)/Al₂O₃0.3 to 0.9, preferably (TiO)₂+ZnO)/Al₂O₃0.4 to 0.7; and/or Al₂O₃/SiO₂0.2 to 0.62, preferably Al₂O₃/SiO₂0.25 to 0.55, more preferably Al₂O₃/SiO₂0.3 to 0.5; and/or SiO₂/(Na₂O + ZnO) of 2.0 to 8.0, preferably SiO₂/(Na₂O + ZnO) of 2.5 to 6.0, more preferably SiO₂/(Na₂O + ZnO) is 2.5 to 5.5; and/or Li₂O/ZnO is 1.0 or less, and Li is preferable₂O/ZnO is 0.8 or less, and Li is more preferable₂O/ZnO is less than 0.7; and/or Al₂O₃/(MgO + ZnO) is 2.5 or more, and Al is preferable₂O₃/(MgO + ZnO) is 2.5 to 10.0, more preferably Al₂O₃/(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable₂O₃/(MgO + ZnO) is 2.7 to 4.0; and/or MgO/ZnO is 0.5 or less, preferably MgO/ZnO is 0.4 or less, more preferably MgO/ZnO is 0.3 or less; and/or (MgO + ZnO + Na)₂O)/TiO₂1.0 to 10.0, preferably (MgO + ZnO + Na)₂O)/TiO₂1.5 to 8.0, more preferably (MgO + ZnO + Na)₂O)/TiO₂2.0 to 4.0; and/or Na₂O/(TiO₂+Li₂O) is 0.5 to 9.0, preferably Na₂O/(TiO₂+Li₂O) is 0.8 to 7.0, more preferably Na₂O/(TiO₂+Li₂O) is 1.0 to 5.0; and/or (P)₂O₅+ZrO₂) The content of/ZnO is 1.1 or less, preferably (P)₂O₅+ZrO₂) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable₂O₅+ZrO₂) the/ZnO is 0.1 to 0.7.

(40) The method for producing a crystallized glass product according to any one of (36) to (39), wherein the matrix glass comprises, in terms of weight percent: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni₂O₃: 0 to 4%, preferably Ni₂O₃: 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co₂O₃: 0 to 2%, preferably Co₂O₃: 0.05-1.8%; and/orFe₂O₃: 0 to 7%, preferably Fe₂O₃: 0.2-5%; and/or MnO₂: 0 to 4%, preferably MnO₂: 0.1-3%; and/or Er₂O₃: 0 to 8%, preferably Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0 to 8%, preferably Nd₂O₃: 0.4-6%; and/or Cu₂O: 0 to 4%, preferably Cu₂O: 0.5-3%; and/or Pr₂O₅: 0 to 8%, preferably Pr₂O₅: 0.4-6%; and/or CeO₂: 0 to 4%, preferably CeO₂：0.5～3％。

(41) The method for producing a crystallized glass product according to any one of (36) to (40), wherein the melting temperature of the formed matrix glass is 1250 to 1650 ℃, and preferably 1380 to 1600 ℃; and/or the melting time is 5-24 hours, preferably 8-12 hours.

(42) The method for producing a crystallized glass product according to any one of (36) to (41), wherein the crystallization process includes the steps of: the temperature is raised to a specified crystallization treatment temperature, and after the temperature reaches the crystallization treatment temperature, the temperature is kept for a certain time, and then the temperature is lowered. The crystallization temperature is 600-750 ℃, preferably 650-700 ℃, and the retention time at the crystallization temperature is 0-8 hours, preferably 1-6 hours.

(43) The method for producing a crystallized glass product according to any one of (36) to (42), wherein the crystallization process includes the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.

(44) The method for manufacturing a crystallized glass article according to (43), said crystallization process comprising the steps of: the temperature of the No. 1 is 550-630 ℃, and the temperature of the No. 2 is 650-750 ℃; the holding time at the temperature of 1 st is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

(45) The method for producing a crystallized glass product according to any one of (36) to (44), wherein the chemical strengthening process comprises: immersing the microcrystalline glass in a salt bath of molten Na salt at the temperature of 430-470 ℃ for 6-20 hours, preferably at the temperature of 435-460 ℃ for 8-13 hours; and/or immersing the microcrystalline glass in a salt bath for melting K salt at the temperature of 400-450 ℃ for 1-8 hours, wherein the preferable time range is 2-4 hours; and/or immersing the metal alloy in a salt bath mixed with K salt and Na salt at the temperature of 350-450 ℃ for 0.5-8 hours to perform ion exchange, wherein the preferable time range is 1-4 hours.

(46) The method for producing a crystallized glass product according to any one of (36) to (45), wherein the total amount of crystal phases in the crystallized glass product is in a range of 5 to 60% by weight, preferably 10 to 50% by weight, and more preferably 15 to 40% by weight of the crystallized glass product.

(47) The method for producing a crystallized glass product according to any one of (36) to (46), wherein the crystallized glass product contains a spinel crystal phase having a higher weight percentage than other crystal phases, preferably 10 to 50 weight% of the spinel crystal phase in the crystallized glass product, and more preferably 15 to 40 weight% of the spinel crystal phase in the crystallized glass product.

(48) According to the method for producing a crystallized glass product of any one of (36) to (47), the crystallized glass product having a thickness of 0.55mm has a haze of 0.3% or less, preferably 0.15% or less, and more preferably 0.1% or less; and/or a microcrystalline glass product having a thickness of 0.55mm, wherein the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 86% or more, and more preferably 88% or more; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 85% or more, preferably 87% or more, more preferably 90% or more; and/or the degree of crystallinity of the glass-ceramic article is 20% or more, preferably 30% or more, more preferably 40% or more; and/or the crystallite size of the glass-ceramic product is 70nm or less, preferably 50nm or less, more preferably 40nm or less, and further preferably 30nm or less; and/or the surface stress of the glass-ceramic product is 800MPa or more, preferably 1000MPa or more, more preferably 1100MPa or more; and/or the ion exchange layer depth of the glass-ceramic product is 25 μm or more, preferably 28 μm or more, more preferably 30 μm or more; and/or glass ceramicsThe height of the product in the falling ball test is more than 900mm, preferably more than 1000mm, and more preferably more than 1100 nm; and/or the fracture toughness of the glass-ceramic product is 1 MPa.m^1/2Above, preferably 1.2MPa · m^1/2More preferably 1.3MPa · m or more^1/2The above; and/or the Vickers hardness of the glass-ceramic article is 600kgf/mm²Above, preferably 650kgf/mm²Above, more preferably 680kgf/mm²The above; and/or the four-point bending strength of the glass-ceramic product is 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more.

The invention also provides a manufacturing method of the microcrystalline glass, which comprises the following steps:

(49) a method for producing a crystallized glass, comprising the steps of:

And forming microcrystalline glass by the matrix glass through a crystallization process.

(50) The method for producing a glass ceramic according to (49), wherein the matrix glass further contains, in terms of the components by weight: li₂O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or P₂O₅: 0-6%; and/or ZrO₂: 0-6%; and/or a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(51) The method for producing a glass-ceramic according to any one of (49) and (50), wherein the matrix glass comprises, in terms of the components by weight: SiO 2₂: 50-66%, preferably SiO₂: 50-64%; and/or Al₂O₃: 15-28%, preferably Al₂O₃: 16-25%; and/or Na₂O: 6-15%, preferably Na₂O: 6.5-12%; and/or ZnO: 4-12%, preferably ZnO: 5-10%; and/or TiO₂: 2-8%, preferably TiO₂: 2.5-6.5%; and/or Li₂O: 0 to 5%, preferably Li₂O: 0 to 3 percent; and/or MgO: 0-3%, preferably MgO: 0 to 1.5 percent; and/or K₂O: 0 to 3%, preferably K₂O: 0.5-2.5%; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or Ln₂O₃: 0 to 4%, preferably Ln₂O₃: 0 to 3 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or P₂O₅: 0 to 4%, preferably P₂O₅: 0.2-3%; and/or ZrO₂: 0 to 5%, preferably ZrO₂: 0 to 3 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(52) The method for producing a glass-ceramic according to any one of (49) to (51), wherein the matrix glass comprises, in terms of weight percent: (TiO)₂+ZnO)/Al₂O₃0.3 to 0.9, preferably (TiO)₂+ZnO)/Al₂O₃0.4 to 0.7; and/or Al₂O₃/SiO₂0.2 to 0.62, preferably Al₂O₃/SiO₂0.25 to 0.55, more preferably Al₂O₃/SiO₂0.3 to 0.5; and/or SiO₂/(Na₂O + ZnO) of 2.0 to 8.0, preferably SiO₂/(Na₂O + ZnO) of 2.5 to 6.0, more preferably SiO₂/(Na₂O + ZnO) is 2.5 to 5.5; and/or Li₂O/ZnO is 1.0 or less, and Li is preferable₂O/ZnO is 0.8 or less, and Li is more preferable₂O/ZnO is less than 0.7; and/or Al₂O₃/(MgO + ZnO) is 2.5 or more, and Al is preferable₂O₃/(MgO + ZnO) is 2.5 to 10.0, more preferably Al₂O₃/(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable₂O₃/(MgO + ZnO) is 2.7 to 4.0; and/or MgO/ZnO is 0.5 or less, preferably MgO/ZnO is 0.4 or less, more preferably MgO/ZnO is 0.3 or less; and/or (MgO + ZnO + Na)₂O)/TiO₂1.0 to 10.0, preferably (MgO + ZnO + Na)₂O)/TiO₂1.5 to 8.0, more preferably (MgO + ZnO + Na)₂O)/TiO₂2.0 to 4.0; and/or Na₂O/(TiO₂+Li₂O) is 0.5 to 9.0, preferably Na₂O/(TiO₂+Li₂O) is 0.8 to 7.0, more preferably Na₂O/(TiO₂+Li₂O) is 1.0 to 5.0; and/or (P)₂O₅+ZrO₂) The content of/ZnO is 1.1 or less, preferably (P)₂O₅+ZrO₂) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable₂O₅+ZrO₂) the/ZnO is 0.1 to 0.7.

(53) The method for producing a glass-ceramic according to any one of (49) to (52), wherein the matrix glass comprises, in terms of weight percent: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni₂O₃: 0 to 4%, preferably Ni₂O₃: 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co₂O₃: 0 to 2%, preferably Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0 to 7%, preferably Fe₂O₃: 0.2-5%; and/or MnO₂: 0 to 4%, preferably MnO₂: 0.1-3%; and/or Er₂O₃: 0 to 8%, preferably Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0 to 8%, preferably Nd₂O₃: 0.4-6%; and/or Cu₂O: 0 to 4%, preferably Cu₂O: 0.5-3%; and/or Pr₂O₅: 0 to 8%, preferably Pr₂O₅: 0.4-6%; and/or CeO₂: 0 to 4%, preferably CeO₂：0.5～3％。

(54) The process for producing a glass-ceramic according to any one of (49) to (53), wherein the melting temperature of the resulting matrix glass is 1250 to 1650 ℃, preferably 1380 to 1600 ℃; and/or the melting time is 5-24 hours, preferably 8-12 hours.

(55) The method for producing crystallized glass according to any one of (49) to (54), wherein the crystallization process includes the steps of: the temperature is raised to a specified crystallization treatment temperature, and after the temperature reaches the crystallization treatment temperature, the temperature is kept for a certain time, and then the temperature is lowered. The crystallization temperature is 600-750 ℃, preferably 650-700 ℃, and the retention time at the crystallization temperature is 0-8 hours, preferably 1-6 hours.

(56) The method for producing crystallized glass according to any one of (49) to (55), wherein the crystallization process includes the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.

(57) The method for producing a crystallized glass according to (56), wherein the crystallization process includes the steps of: the temperature of the No. 1 is 550-630 ℃, and the temperature of the No. 2 is 650-750 ℃; the holding time at the temperature of 1 st is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

(58) The method for producing a crystallized glass according to any one of (49) to (57), wherein the crystallized glass has a total amount of crystal phases in a range of 5 to 60% by weight, preferably 10 to 50% by weight, and more preferably 15 to 40% by weight, based on the crystallized glass.

(59) The method for producing a glass ceramic according to any one of (49) to (58), wherein the glass ceramic contains a spinel crystal phase, and the spinel crystal phase has a higher weight percentage than other crystal phases, and preferably the spinel crystal phase accounts for 10 to 50% by weight of the glass ceramic, and more preferably the spinel crystal phase accounts for 15 to 40% by weight of the glass ceramic.

(60) According to the process for producing a crystallized glass of any one of (49) to (59), the crystallized glass having a thickness of 0.55mm has a haze of 0.3% or less, preferably 0.15% or less, more preferably 0.1% or less; and/or 0.55mm thick microcrystalline glass, the average transmittance at a wavelength of 400-800 nm is more than 85%, preferably more than 86%, more preferably more than 88%; and/or 0.55mm thick glass ceramics, having a 550nm wavelength transmittance of 85% or more, preferably 87% or more, more preferably 90% or more; and/or the degree of crystallinity of the glass ceramics is 20% or more, preferably 30% or more, more preferably 40% or more; and/or the crystallite size of the glass ceramics is 70nm or less, preferably 50nm or less, more preferably 40nm or less, and further preferably 30nm or less; and/or the crystallized glass has a falling ball test height of 500mm or more, preferably 700mm or more, and more preferably 900mm or more.

The invention has the beneficial effects that: through reasonable component design, the microcrystalline glass and the microcrystalline glass product obtained by the invention have excellent mechanical properties and are suitable for electronic equipment or display equipment.

Detailed Description

The crystallized glass and the crystallized glass article of the present invention are materials having a crystal phase and a glass phase, which are different from amorphous solids. The crystalline phases of the glass-ceramic and glass-ceramic articles can be identified by the angle of the peak appearing in the X-ray diffraction pattern of the X-ray diffraction analysis and/or measured by TEMEDX.

The inventors of the present invention have made extensive experiments and studies, and have found that a glass ceramic and/or a glass ceramic product of the present invention can be obtained at a low cost by specifying the content and content ratio of specific components constituting the glass ceramic and the glass ceramic product to specific values and precipitating specific crystal phases.

The ranges of the respective components (components) of the matrix glass, the glass ceramics and the glass ceramics product of the present invention will be described below. In the present specification, the contents of the respective components are all expressed in weight percent (wt%) with respect to the total amount of the substance of the matrix glass, or the glass ceramics product converted into the composition of the oxide, if not specifically stated. Here, the "composition in terms of oxide" means that when an oxide, a complex salt, a hydroxide, or the like used as a raw material of a composition component of a matrix glass, a glass-ceramic, or a glass-ceramic product of the present invention is decomposed at melting and converted into an oxide, the total amount of the oxide is 100%. In the present specification, the term "glass" refers to a matrix glass before crystallization, the term "glass matrix" refers to a crystallized glass after crystallization, and the term "glass-ceramic product" refers to a chemically strengthened glass-ceramic.

Unless otherwise indicated in a specific context, numerical ranges set forth herein include upper and lower values, and "above" and "below" include end-point values, as well as all integers and fractions within the range, and are not limited to the specific values recited in the defined range. The term "about" as used herein means that the formulations, parameters, and other quantities and characteristics are not, and need not be, exact, and can be approximate and/or larger or smaller, if desired, reflecting tolerances, conversion factors, measurement error and the like. The term "and/or" as used herein is inclusive, e.g., "a; and/or B "means A alone, B alone, or both A and B.

In the crystallized glass and the crystallized glass product of the present invention, the crystal phase contains a spinel crystal phase; and/or a lithium phosphate crystalline phase; and/or quartz and quartz solid solution crystalline phases; and/or a zirconium silicate crystalline phase; and/or lithium silicate crystals, and the like.

In some embodiments of the present invention, the crystalline phase comprises one or more of a spinel crystalline phase, a lithium phosphate crystalline phase, a quartz and quartz solid solution crystalline phase, a zirconium silicate crystalline phase, and a lithium silicate crystalline phase.

In some embodiments of the invention, the crystalline phase in the glass-ceramic or glass-ceramic article comprises predominantly a spinel crystalline phase having a higher weight percentage than other crystalline phases, preferably 10 to 50 weight percent of the spinel crystalline phase in the glass-ceramic or glass-ceramic article, more preferably 15 to 40 weight percent of the spinel crystalline phase in the glass-ceramic or glass-ceramic article. In some embodiments, the spinel crystalline phase comprises about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50% by weight of the glass-ceramic or glass-ceramic article.

In some embodiments of the present invention, the microcrystalline glass or microcrystalline glass article preferably does not contain quartz and quartz solid solution crystalline phases; and/or does not contain a lithium silicate crystalline phase to achieve the excellent mechanical and optical properties of the present invention, as well as lower haze and smaller grain size, among others.

In some embodiments of the present invention, it is preferable that the total amount of the crystalline phase in the glass-ceramic or glass-ceramic article is in the range of 5 to 60% by weight of the glass-ceramic or glass-ceramic article; in some embodiments, it is more preferable that the total amount of crystalline phases in the glass-ceramic or glass-ceramic article is in the range of 10 to 50% by weight of the glass-ceramic or glass-ceramic article; in some embodiments, it is further preferred that the total amount of crystalline phases in the glass-ceramic or glass-ceramic article is in the range of 15 to 40% by weight of the glass-ceramic or glass-ceramic article to achieve the superior mechanical and optical properties of the present invention. In some embodiments, the total amount of crystalline phase is about 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60% by weight of the glass ceramic or glass ceramic article.

SiO₂The glass is a necessary component for forming a glass network structure in the invention, can improve the chemical strengthening performance of the microcrystalline glass, improve the surface stress of the microcrystalline glass product, and is beneficial to improving the falling ball test height of the microcrystalline glass product, if SiO is used₂The content of (b) is less than 46%, the above effect is not significant. Thus, SiO₂The lower limit of the content is 46%, and the preferable lower limit is 50%. If SiO₂The content is more than 68 percent, and the glassThe difficulty of glass melting is increased, which is not beneficial to the forming of glass. Thus, SiO₂The upper limit of the content is 68%, preferably 66%, more preferably 64%. In some embodiments, about 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68% SiO may be included₂。

Al₂O₃Is an essential component for forming the glass network structure, and in some embodiments is a component for forming the crystalline phase; is beneficial to the chemical strengthening of the microcrystalline glass and improves the ion exchange capacity of the microcrystalline glass and the surface stress of the microcrystalline glass product, but if the content of the microcrystalline glass is less than 11 percent, the effect is not obvious. Thus, Al₂O₃The lower limit of the content is 11%, preferably 15%, more preferably 16%. On the other hand, if Al₂O₃The content of (b) exceeds 30%, the difficulty of melting the glass increases. Thus Al₂O₃The upper limit of the content is 30%, preferably 28%, more preferably 25%. In some embodiments, about 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% Al may be included₂O₃。

In some embodiments of the invention, the Al is added by reacting Al with a metal₂O₃/SiO₂Within the range of 0.2-0.62, the structure of the matrix glass can be more compact, the strength of the matrix glass is improved, and the ion exchange layer depth, the surface stress and the Vickers hardness of the microcrystalline glass product are improved. Therefore, Al is preferable₂O₃/SiO₂0.2 to 0.62, more preferably Al₂O₃/SiO₂0.25 to 0.55, and more preferably Al₂O₃/SiO₂0.3 to 0.5. In some embodiments, Al₂O₃/SiO₂May be 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.62.

Li₂O in the present invention promotes melting of the glass raw materialIn particular, high Al in the glass composition of the invention₂O₃In the case of content; while Li₂O can promote crystal formation, is a component mainly substituted with sodium and potassium ions in the chemical strengthening process, can increase the surface stress after chemical strengthening, and can improve the ball drop test height of the microcrystalline glass product, and if Li is excessively contained₂O, crystal growth is not easily controlled at the time of crystallization, resulting in an increase in haze of the crystallized glass and the crystallized glass article. Thus, Li in the present invention₂The content of O is 0 to 6%, preferably 0 to 5%, more preferably 0 to 3%. In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% Li may be included₂O。

In the invention, more than 5% of Na is contained₂O is favorable for improving the chemical strengthening performance of the microcrystalline glass, improving the surface stress and the ion exchange layer depth of a microcrystalline glass product, reducing the solid low-temperature viscosity of the glass, effectively promoting the crystal precipitation during the heat treatment of the glass, and preferably contains more than 6 percent of Na₂O, more preferably 6.5% or more of Na₂And O. If Na₂When the content of O exceeds 18%, the hardness of the glass and the crystallized glass is lowered, and aggregation of glass crystal grains is promoted in the crystallization process of the glass, so that the haze of the crystallized glass and the crystallized glass product is increased, and the transmittance is lowered. Thus, Na₂The upper limit of the O content is 18%, preferably 15%, more preferably 12%. In some embodiments, about 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18% Na may be included₂O。

K₂O is an optional component which contributes to the improvement of low-temperature melting property and formability of the glass, but if K is contained excessively₂O, the chemical stability and the hardness of the glass are easily lowered. Thus, K₂The content of O is 0 to 5%, preferably 0 to 3%, more preferably 0.5 to 2.5%. In some embodiments, it may comprise about 0%, 0.5%, 1%,1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% K₂O。

ZnO can improve the melting performance of glass, improve the crystallization temperature of the glass, improve the crystallinity of the microcrystalline glass and the microcrystalline glass product, and is beneficial to improving the falling ball test height of the microcrystalline glass and the microcrystalline glass product; in some embodiments of the present invention, ZnO is a component forming a crystalline phase, and the above effects are obtained in the present invention by containing ZnO at 3% or more, preferably 4% or more, and more preferably 5% or more. However, if the glass contains an excessive amount of ZnO, the chemical strengthening performance of the glass and the glass ceramic is not good, and the ion exchange layer depth of the glass ceramic product is likely to be reduced, thereby reducing the strength of the glass ceramic product. Therefore, the upper limit of the ZnO content is 13%, preferably 12%, and more preferably 10%. In some embodiments, about 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13% ZnO may be included.

In some embodiments of the invention, the SiO is provided by₂/(Na₂O + ZnO) is within the range of 2.0-8.0, so that the crystal grains of the matrix glass can be refined in the crystallization process, the microcrystalline glass and the microcrystalline glass product can obtain finer crystal grains, the strength of the microcrystalline glass and the microcrystalline glass product can be improved, and the falling ball test height of the microcrystalline glass and the microcrystalline glass product can be improved. Therefore, SiO is preferable₂/(Na₂O + ZnO) of 2.0 to 8.0, more preferably SiO₂/(Na₂O + ZnO) of 2.5 to 6.0, and further preferably SiO₂/(Na₂O + ZnO) of 2.5 to 5.5. In some embodiments, the SiO₂/(Na₂O + ZnO) may have a value of 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0.

In some embodiments of the invention, the lithium ion battery is prepared by reacting Li₂The O/ZnO is below 1.0, which is beneficial to improving the fracture toughness and four-point bending strength of the microcrystalline glass and the microcrystalline glass product. Therefore, Li is preferable₂O/ZnO is 1.0 or less, and Li is more preferable₂O/ZnO is 0.8 or less, and Li is more preferable₂The O/ZnO ratio is 0.7 or less. In some embodiments, Li₂The O/ZnO can be 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0.

MgO can improve the melting performance of glass, refine crystal grains and reduce the haze of the microcrystalline glass and the microcrystalline glass product; however, if MgO is contained excessively, the crystallization temperature range becomes narrow, which is disadvantageous in the production of glass ceramics. Therefore, the MgO content is 0 to 5.5%, preferably 0 to 3%, more preferably 0 to 1.5%. In some embodiments, MgO may be included at about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%.

In some embodiments of the invention, the Al is added by reacting Al with a metal₂O₃If the ratio of MgO + ZnO is more than 2.5, the crystallinity and the Vickers hardness of the microcrystalline glass and the microcrystalline glass product can be improved, the surface stress of the microcrystalline glass product can be improved, and the falling ball test height of the microcrystalline glass and the microcrystalline glass product can be improved. Therefore, Al is preferred in the present invention₂O₃/(MgO + ZnO) is 2.5 or more, and Al is more preferable₂O₃/(MgO + ZnO) is 2.5 to 10.0, and Al is more preferable₂O₃/(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable₂O₃The ratio of (MgO + ZnO) is 2.7 to 4.0. In some embodiments of the invention, Al₂O₃The value of/(MgO + ZnO) may be 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0.

In some embodiments of the present invention, if the MgO/ZnO ratio exceeds 0.5, the crystallite size of the crystallized glass or crystallized glass article becomes large, and the haze and strength of the crystallized glass or crystallized glass article tend to decrease. Therefore, the MgO/ZnO ratio is preferably 0.5 or less, more preferably 0.4 or less, and still more preferably 0.3 or less. In some embodiments, the MgO/ZnO value may be 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5.

TiO₂The nucleating agent of the microcrystalline glass is used for nucleating in the crystallization process of the glass, promoting the formation of crystals in the glass and improving the falling ball test height of the microcrystalline glass and microcrystalline glass products, and the nucleating agent contains more than 1 percent of TiO₂In order to obtain the above-described effects, it is preferably 2% or more, and more preferably 2.5% or more. If TiO₂The content of (A) exceeds 9%, the transmittance of the glass, the glass-ceramic and the glass-ceramic product is reduced, and the preparation of the product with high transparency is not facilitated, therefore, TiO₂The upper limit of the content is 9%, preferably 8%, more preferably 6.5%. In some embodiments, about 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9% of TiO may be included₂。

In some embodiments of the invention, if (MgO + ZnO + Na)₂O)/TiO₂Below 1.0, the glass becomes poor in melting property and the melting temperature rises, on the other hand, the crystallizability of the crystallized glass and the crystallized glass article decreases; if (MgO + ZnO + Na)₂O)/TiO₂When the amount exceeds 10.0, the crystallization process of the glass becomes difficult to control, and other crystal phases which are not desired to be contained in the glass-ceramic tend to appear, so that it is preferable to use (MgO + ZnO + Na) in the present invention₂O)/TiO₂In the range of 1.0 to 10.0. Further, by using (MgO + ZnO + Na)₂O)/TiO₂In the range of 1.5 to 8.0, the haze of the microcrystalline glass and the microcrystalline glass product can be effectively reduced, and the transmittance of the microcrystalline glass and the microcrystalline glass product can be improved, so that (MgO + ZnO + Na) is more preferable₂O)/TiO₂1.5 to 8.0, and more preferably (MgO + ZnO + Na)₂O)/TiO₂Is 2.0 to 4.0. In some embodiments, (MgO + ZnO + Na)₂O)/TiO₂The value of (b) may be 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0.

In some embodiments of the invention, if Na₂O and TiO₂And Li₂Ratio Na between total contents of O₂O/(TiO₂+Li₂O) less than 0.5, microcrystalline glass andthe transmittance of the microcrystalline glass product is reduced if Na₂O/(TiO₂+Li₂O) exceeds 9.0, the crystallinity of the crystallized glass and the crystallized glass article decreases, and the haze becomes large. Therefore, Na is preferred₂O/(TiO₂+Li₂O) is 0.5 to 9.0, more preferably Na₂O/(TiO₂+Li₂O) is 0.8 to 7.0, and Na is more preferable₂O/(TiO₂+Li₂O) is 1.0 to 5.0. In some embodiments, Na₂O/(TiO₂+Li₂O) may have a value of 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0.

In some embodiments of the invention, the composition is prepared by reacting (TiO)₂+ZnO)/Al₂O₃Within the range of 0.2-1.5, the chemical strengthening performance of the microcrystalline glass can be improved, the ion exchange layer depth of the microcrystalline glass product is increased, the fracture toughness and the four-point bending strength of the microcrystalline glass product are improved, and preference is given To (TiO)₂+ZnO)/Al₂O₃0.3 to 0.9, more preferably (TiO)₂+ZnO)/Al₂O₃0.4 to 0.7. In some embodiments, (TiO)₂+ZnO)/Al₂O₃May be 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2.

P₂O₅Contributes to the improvement of the low-temperature melting property of the glass, P₂O₅And ZrO₂And TiO₂And the combined action can increase the nucleation amount of the microcrystalline glass and the microcrystalline glass product and refine grains. But if it contains P excessively₂O₅The tendency of phase separation of the glass is easily increased, and the chemical stability of the glass is reduced. Thus, P in the present invention₂O₅The content is in the range of 0 to 6%, preferably 0 to 4%, more preferably 0.2 to 3%. In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% P may be included₂O₅。

ZrO₂Reducible glassTendency to devitrify during molding, ZrO₂And P₂O₅And TiO₂The combined action can improve the nucleation amount of the microcrystalline glass and the microcrystalline glass product and reduce the haze of the microcrystalline glass and the microcrystalline glass product; on the other hand, if ZrO is contained excessively₂The difficulty of glass melting increases. Thus, ZrO in the invention₂The content is in the range of 0 to 6%, preferably 0 to 5%, more preferably 0 to 3%. In some embodiments, ZrO may be included at about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%₂。

In some embodiments of the invention, if (P)₂O₅+ZrO₂) with/ZnO exceeding 1.1, the falling ball test height of the crystallized glass and crystallized glass product is reduced, and (P) is preferable for obtaining a higher falling ball test height₂O₅+ZrO₂) The content of/ZnO is 1.1 or less. Further, if (P)₂O₅+ZrO₂) A value of/ZnO less than 0.1 is more preferable because haze of the crystallized glass or crystallized glass product becomes large and the increase in transmittance is not favorable (P)₂O₅+ZrO₂) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable₂O₅+ZrO₂) the/ZnO is 0.1 to 0.7. In some embodiments, (P)₂O₅+ZrO₂) the/ZnO may be 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1.

SrO is an optional component for improving the low-temperature melting property of the glass and suppressing devitrification at the time of glass forming, and when the content is too large, the devitrification tendency of the glass increases. Therefore, in the present invention, the SrO content is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably no SrO is contained. In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% SrO may be included.

BaO is an optional component which contributes to the improvement of glass forming properties of the glass, and when the content is too large, glass forming is not facilitated. Therefore, the content of BaO in the present invention is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably contains no BaO. In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% BaO may be included.

CaO can increase the hardness of the glass, and when the content is too high, the glass is creamed during the forming process, which is not favorable for obtaining qualified glass products. Therefore, in the present invention, the content of CaO is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably no CaO is contained. In some embodiments, CaO may be included at about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.

B₂O₃Helps to optimize the melting property of the matrix glass, and when the content thereof is too high, the chemical stability of the matrix glass is lowered, so that B₂O₃The content of (B) is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably no B is contained₂O₃. In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% B may be included₂O₃。

Ln₂O₃(Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of) is an optional component for improving the hardness and chemical stability of the glass ceramics, inhibiting the glass from forming and crystallizing, reducing the chemical strengthening performance of the glass and the glass ceramics when the content is excessive, and reducing the strength of the glass and the glass ceramics products. Ln in the invention₂O₃The content is in the range of 0 to 5%, preferably 0 to 4%, more preferably 0 to 3%. In the present invention, in order to obtain excellent properties, it is preferable that La is not contained₂O₃And/or does not contain Gd₂O₃. In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% Ln may be included₂O₃。

In some embodiments, the glass, glass-ceramic or glass-ceramic article may further comprise 0-2% fining agent to enhance the glass, glass-ceramic or glass-ceramic compositionDefoaming capability of glass or glass-ceramic articles. The fining agent includes, but is not limited to, Sb₂O₃、SnO₂、SnO、CeO₂One or more of, F, Cl and Br, preferably Sb₂O₃、SnO₂SnO as a fining agent. The upper limit of the content of the above-mentioned clarifying agent, when it is present alone or in combination, is preferably 1%, more preferably 0.5%. In some embodiments, one or more of the above fining agents are present in an amount of about 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%.

In order to obtain the excellent properties of the glass, glass-ceramic or glass-ceramic product of the present invention, such as mechanical properties, optical properties, productivity and chemical strengthening properties, it is preferable in some embodiments of the present invention that B is not included₂O₃(ii) a And/or does not contain CaO; and/or does not contain F; and/or does not contain Ta₂O₅。

PbO and As₂O₃Are toxic substances and do not meet the environmental requirements even when contained in small amounts, and thus the present invention preferably does not contain PbO and As in some embodiments₂O₃。

In some embodiments of the present invention, a substrate glass, a glass-ceramic, or a glass-ceramic article having a color can be produced by including a colorant in the substrate glass, the glass-ceramic, or the glass-ceramic article, the colorant including: NiO: 0 to 4 percent; and/or Ni₂O₃: 0 to 4 percent; and/or a CoO: 0-2%; and/or Co₂O₃: 0-2%; and/or Fe₂O₃: 0 to 7 percent; and/or MnO₂: 0 to 4 percent; and/or Er₂O₃: 0-8%; and/or Nd₂O₃: 0-8%; and/or Cu₂O: 0 to 4 percent; and/or Pr₂O₅: 0-8%; and/or CeO₂: 0 to 4 percent. The content of the colorant in percentage by weight and the function thereof are detailed as follows:

the brown or green substrate glass prepared by the invention is microCrystal glass or glass-ceramic product made of NiO and Ni₂O₃Or Pr₂O₅Is a colorant. NiO and Ni₂O₃For the colouring agent, for the preparation of a brown or green matrix glass, glass ceramic or glass ceramic product, the two components can be used individually or in admixture, each in a content of generally less than 4%, preferably less than 3%, and if the content exceeds 4%, the colouring agent is not very soluble in the matrix glass, glass ceramic or glass ceramic product, each in a content below 0.1%, such as below 0.1%, and the matrix glass, glass ceramic or glass ceramic product is not visibly coloured. In some embodiments, about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4% NiO or Ni may be included₂O₃. NiO and Ni, if used in admixture₂O₃The total amount is generally 4% or less, and the lower limit of the total amount is 0.1% or more. In some embodiments, about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4% of NiO and Ni may be included₂O₃. Using Pr₂O₅The colorant for green matrix glass, glass ceramics or glass ceramics is used alone, and is generally contained in an amount of 8% or less, preferably 6% or less, and the lower limit of the content is 0.4% or more, for example, less than 0.4%, and the matrix glass, glass ceramics or glass ceramics product is not conspicuous in color. In some embodiments, about 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4% may be included4.2%, 4.4%, 4.6%, 4.8%, 5%, 5.2%, 5.4%, 5.6%, 5.8%, 6%, 6.2%, 6.4%, 6.6%, 6.8%, 7%, 7.2%, 7.4%, 7.6%, 7.8%, 8% Pr₂O₅。

The blue matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses CoO or Co₂O₃The two colorant components may be used alone or in combination as a colorant, and their respective contents are generally 2% or less, preferably 1.8% or less, and if the content exceeds 2%, the colorant is not well soluble in the matrix glass, the crystallized glass or the crystallized glass product, and its respective lower limit is 0.05% or more, e.g., less than 0.05%, and the matrix glass, the crystallized glass or the crystallized glass product is not conspicuous in color. In some embodiments, about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2% of CoO or Co may be included₂O₃. CoO and Co, if used in admixture₂O₃The total amount is not more than 2%, and the lower limit of the total amount is not less than 0.05%. In some embodiments, about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2% of CoO and Co may be included₂O₃。

The yellow matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses Cu₂O or CeO₂The two colorant components are used alone or in combination as colorant, and have a lower limit of 0.5% or more, such as less than 0.5%, no apparent color of the matrix glass, microcrystalline glass or microcrystalline glass product, and Cu alone₂O is 4% or less, preferably 3% or less, and if the content exceeds 4%, the matrix glass is easily crystallized. In some embodiments, about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, may be included,2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4% Cu₂And O. Using CeO alone₂The content is generally 4% or less, preferably 3% or less, and if the content exceeds 4%, the substrate glass, the crystallized glass or the crystallized glass product is poor in gloss. In some embodiments, CeO of about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4% may be included₂. At the same time, a small amount of CeO₂Added to glass with a defoaming effect, CeO₂Can also be used as a clarifying agent in glass. When two kinds of colorants are used in combination, the total amount is generally 4% or less, and the lower limit of the total amount is 0.5% or more. In some embodiments, CeO of about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4% may be included₂And Cu₂O。

The black or smoke gray matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention independently uses Fe₂O₃Is a colorant; or using Fe₂O₃And CoO; or using Fe₂O₃And Co₂O₃Two colorants used in combination; or using Fe₂O₃Three colorants mixed together, CoO and NiO; or using Fe₂O₃、Co₂O₃And NiO. Colorants for the production of black and smoky grey matrix glass, glass ceramics or glass ceramic articles using predominantly Fe₂O₃Coloring, in an amount of 7% or less, preferably 5% or less, which is preferredThe lower limit of the amount is above 0.2%, and in some embodiments, about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.5%, 5.5%, 6%, 6.5%, 7% Fe may be included₂O₃. CoO and Co₂O₃Can absorb visible light to increase the coloring degree of matrix glass, microcrystalline glass or microcrystalline glass products, and is generally combined with Fe₂O₃The content of each component is 0.6% or less, and the lower limit is 0.2% or more. In some embodiments, about 0.2%, 0.3%, 0.4%, 0.5%, 0.6% CoO and/or Co may be included₂O₃. NiO absorbs visible light and can increase the degree of coloration of the base glass, glass ceramic or glass ceramic product, and is generally used in a mixture in which the content is 1% or less and the lower limit of the total amount is 0.2% or more. In some embodiments, NiO may be included at about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%.

The purple matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses MnO₂As a coloring agent, it is used in an amount of generally 4% or less, preferably 3% or less, and the lower limit thereof is 0.1% or more, for example, less than 0.1%, and the color of the matrix glass, the glass ceramics or the glass ceramics article is not conspicuous. In some embodiments, about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4% MnO may be included₂。

Er is used in the pink substrate glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention₂O₃Is a colorantThe content is generally 8% or less, preferably 6% or less. Because of rare earth element Er₂O₃The coloring efficiency is low, when the content exceeds 8%, the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product cannot be further deepened, and the cost is increased, and the lower limit of the content is more than 0.4%, such as less than 0.4%, and the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product is not obvious. In some embodiments, about 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, 5%, 5.2%, 5.4%, 5.6%, 5.8%, 6%, 6.2%, 6.4%, 6.6%, 6.8%, 7%, 7.2%, 7.4%, 7.6%, 7.8%, 8% Er may be included₂O₃。

The mauve substrate glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses Nd₂O₃The content of the colorant used is generally 8% or less, preferably 6% or less. Due to rare earth element Nd₂O₃The coloring efficiency is low, the use content is more than 8 percent, the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product cannot be further deepened, the cost is increased, the lower limit of the content is more than 0.4 percent, such as less than 0.4 percent, and the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product is not obvious. In some embodiments, about 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, 5%, 5.2%, 5.4%, 5.6%, 5.8%, 6%, 6.2%, 6.4%, 6.6%, 6.8%, 7%, 7.2%, 7.4%, 7.6%, 7.8%, 8% Nd may be included₂O₃。

Er is used for the red matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention₂O₃、Nd₂O₃And MnO₂The mixed colorant, Er ion in the glass has absorption at 400-500nm, Mn ion has absorption mainly at 500nm, and Nd ion has strong absorption mainly at 580nmThe red matrix glass, the microcrystalline glass or the microcrystalline glass product can be prepared by mixing the three substances, and because of Er₂O₃And Nd₂O₃Coloring rare earth, relatively weak coloring ability, Er₂O₃The usage amount is less than 6 percent, Nd₂O₃The usage amount is less than 4 percent, MnO₂The coloring is strong, the usage amount is within 2 percent, and the lower limit of the total amount of the mixed coloring agent is more than 0.9 percent.

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

In some embodiments of the present invention, the crystalline phase in the microcrystalline glass and the microcrystalline glass article contains a spinel crystalline phase, which provides high strength to the microcrystalline glass and the microcrystalline glass article of the present invention, and the microcrystalline glass article have high fracture toughness; the height of the falling ball test and the four-point bending strength of the microcrystalline glass and the microcrystalline glass product become large. The glass-ceramic of the invention can also be ion exchanged to obtain additional mechanical strength. The invention can make the microcrystalline glass and the microcrystalline glass product obtain proper grain size through reasonable component design, and make the microcrystalline glass and the microcrystalline glass product have high strength. The microcrystalline glass and the microcrystalline glass product have good crystallinity, so that the microcrystalline glass and the microcrystalline glass product have excellent mechanical properties. The crystallinity is the complete degree of crystallization, the arrangement of mass points in the complete crystal is regular, the diffraction line is strong, sharp and symmetrical, and the half-height width of a diffraction peak is close to the width measured by an instrument; the crystals with poor crystallinity have defects such as dislocation and the like, so that diffraction line peaks are wide and diffuse. The poorer the crystallinity, the weaker the diffraction power, the wider the diffraction peak until it disappears in the background.

The grain size and the haze of the microcrystalline glass or the microcrystalline glass product can influence the transmittance of the microcrystalline glass or the microcrystalline glass product, namely the light transmittance is influenced, and the smaller the grain is, the higher the transmittance is; the smaller the haze, the higher the transmittance. In some embodiments, the 0.55mm thick devitrified glass article or glass-ceramic has a haze of 0.3% or less, preferably 0.15% or less, and more preferably 0.1% or less. In some embodiments, the crystallite glass article or crystallite glass has a grain size of 50nm or less, preferably 40nm or less, more preferably 30nm or less.

In some embodiments, the microcrystalline glass or microcrystalline glass article of the present invention exhibits high transparency in the visible range (i.e., the microcrystalline glass or microcrystalline glass article is transparent). The microcrystalline glass or the microcrystalline glass product has high transmittance in a visible light range, and in some embodiments, the microcrystalline glass product or the microcrystalline glass with a thickness of 0.55mm has an average light transmittance of 400 to 800nm of 85% or more, preferably 86% or more, and more preferably 88% or more. In some preferred embodiments, the microcrystalline glass article or microcrystalline glass having a thickness of 0.55mm has a light transmittance of 85% or more, preferably 87% or more, and more preferably 90% or more at 550 nm.

In some embodiments, an antimicrobial component may be added to the matrix glass, microcrystalline glass, or microcrystalline glass article. The crystallized glass or crystallized glass article described herein may be used in applications such as kitchens or countertops where exposure to harmful bacteria is likely. Antimicrobial components that may be added to the matrix glass, glass-ceramic, or glass-ceramic article include, but are not limited to, Ag, AgO, Cu, CuO, Cu₂O, and the like. In some embodiments, the antimicrobial components described above are present at 2% or less, preferably 1% or less, alone or in combination.

The matrix glass, the glass-ceramic and the glass-ceramic product of the invention can be produced and manufactured by the following methods:

and (3) generation of matrix glass: the raw materials are uniformly mixed according to the component proportion, the uniform mixture is put into a crucible made of platinum or quartz, the melting is carried out for 5-24 hours in an electric furnace or a gas furnace within the temperature range of 1250-1650 ℃ according to the melting difficulty of glass composition, the preferred temperature is 1380-1600 ℃, the preferred time is 8-12 hours, the mixture is stirred to be uniform, then the mixture is cooled to the proper temperature and cast into a mould, and the mixture is slowly cooled to obtain the glass.

The matrix glass of the present invention can be shaped by a well-known method.

The matrix glass of the invention is crystallized by a crystallization process after molding or after molding processing, and crystals are uniformly precipitated in the glass. The crystallization may be performed in 1 stage or 2 stages, and preferably 2 stages. The treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature. The crystallization process performed at the 1 st temperature is referred to as a 1 st crystallization process, and the crystallization process performed at the 2 nd temperature is referred to as a 2 nd crystallization process.

In order to obtain desired physical properties of the glass-ceramic, the preferred crystallization process is:

the above-mentioned crystallization treatment is performed in 1 stage, and the nucleus formation process and the crystal growth process can be continuously performed. That is, the temperature is raised to a predetermined crystallization temperature, and after reaching the crystallization temperature, the temperature is maintained for a predetermined time, and then the temperature is lowered. The crystallization temperature is preferably 600 to 750 ℃, more preferably 650 to 700 ℃, and the holding time at the crystallization temperature is preferably 0 to 8 hours, more preferably 1 to 6 hours, in order to precipitate a desired crystal phase.

When the crystallization is performed in 2 stages, the 1 st temperature is preferably 550 to 630 ℃ and the 2 nd temperature is preferably 650 to 750 ℃. The holding time at the temperature of 1 st is preferably 0 to 24 hours, more preferably 2 to 15 hours. The holding time at the 2 nd temperature is preferably 0 to 10 hours, more preferably 0.5 to 6 hours.

The above-mentioned holding time of 0 hour means that the temperature is lowered or raised less than 1 minute after the temperature is reached.

In some embodiments, the matrix or glass-ceramic described herein can be fabricated into shaped bodies, including but not limited to sheets, by various processes, including but not limited to slot draw, float, roll, and other sheet forming processes known in the art. Alternatively, the matrix glass or glass-ceramic may be formed by a float process or a roll process as is well known in the art.

The substrate glass or the glass ceramics of the present invention can be produced into a sheet glass molded body by a method such as grinding or polishing, but the method for producing the glass molded body is not limited to these methods.

The matrix glass or glass-ceramic shaped article of the present invention can be produced into various shapes at a certain temperature by a method such as hot bending or press molding, and is not limited to these methods.

The matrix glass, microcrystalline glass, and microcrystalline glass articles of the present invention may have any thickness that is reasonably useful.

The crystallized glass of the present invention can be produced into a crystallized glass product by forming a compressive stress layer to obtain higher strength in addition to improving mechanical properties by precipitation crystallization.

In some embodiments, the substrate glass or glass ceramic may be formed into a sheet, and/or shaped (e.g., punched, hot bent, etc.), shaped, polished and/or scanned, and then chemically strengthened by a chemical strengthening process.

The chemical strengthening method is an ion exchange method. During the ion exchange process, the smaller metal ions in the matrix glass or glass-ceramic are replaced or "exchanged" by larger metal ions having the same valence state that are adjacent to the matrix glass or glass-ceramic. And replacing the smaller ions with the larger ions to build a compressive stress in the matrix glass or the microcrystalline glass to form a compressive stress layer.

In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., Na)⁺、K⁺、Rb⁺、Cs⁺Etc.), ion exchange is performed by immersing the matrix glass or glass-ceramic in a salt bath of at least one molten salt containing larger metal ions for replacing the smaller metals in the matrix glassIons. Alternatively, other monovalent metal ions such as Ag⁺、Tl⁺、Cu⁺Etc. may also be used to exchange monovalent ions. One or more ion exchange processes used to chemically strengthen the matrix glass or glass-ceramic may include, but are not limited to: it is immersed in a single salt bath or in a plurality of salt baths of the same or different composition with washing and/or annealing steps between the immersions.

In some embodiments, the matrix glass or glass-ceramic may be formed by melting a Na salt (e.g., NaNO) by immersion at a temperature of about 430 ℃ to 470 ℃₃) The salt bath is subjected to ion exchange for about 6 to 20 hours, preferably at a temperature of between 435 and 460 ℃ for 8 to 13 hours. In this embodiment, Na ions replace part of Li ions in the matrix glass or the glass ceramics, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the matrix glass or glass-ceramic may be formed by melting a K salt (e.g., KNO) by immersion at a temperature of about 400 ℃ to 450 ℃₃) The salt bath is subjected to ion exchange for 1 to 8 hours, and the preferable time range is 2 to 4 hours. In this embodiment, K ions replace a part of Li ions and/or Na ions in the matrix glass or the glass ceramics, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the matrix glass or glass-ceramic may be mixed by immersing the molten K and Na salts at a temperature of about 350 ℃ to 450 ℃ (e.g., KNO₃And NaNO₃) The salt bath is subjected to ion exchange for 0.5 to 8 hours, and the preferable time range is 1 to 4 hours.

In some embodiments, there are also an ion implantation method of implanting ions into a surface layer of a base glass or a glass ceramics, and a thermal tempering method of heating a base glass or a glass ceramics and then rapidly cooling it.

The performance indexes of the microcrystalline glass and/or the microcrystalline glass product are tested by adopting the following method:

[ haze ]

A haze tester EEL57D was used, prepared from 0.55mm thick glass samples and tested according to GB 2410-80.

[ grain size ]

And (3) determining by using an SEM (scanning electron microscope), carrying out surface treatment on the microcrystalline glass in HF (hydrofluoric acid), carrying out gold spraying on the surface of the microcrystalline glass, and carrying out surface scanning under the SEM, so as to determine the size of the crystal grains.

[ light transmittance ]

The light transmittances described herein are external transmittances, sometimes simply referred to as transmittances.

The sample is processed into a thickness of 0.55mm, the opposite surfaces are polished in parallel, and the average light transmittance of 400-800 nm is measured by a Hitachi U-41000 spectrophotometer.

The sample was processed to a thickness of 0.55mm and the opposed faces were polished in parallel, and the light transmittance at 550nm was measured by means of a Hitachi U-41000 spectrophotometer.

[ degree of crystallinity ]

The XRD diffraction peaks were compared with the database spectra, and the degree of crystallinity was obtained by calculating the proportion of the diffraction intensity of the crystalline phase in the intensity of the entire spectrum, and was internally calibrated by using pure quartz crystals.

[ surface stress ] and [ depth of ion exchange layer ]

And (4) carrying out surface stress measurement by using a glass surface stress meter FSM-6000 LEUV.

Ion exchange layer depth was measured using a glass surface stress meter SLP-2000.

The refractive index of the sample was 1.54 and the optical elastic constant was 25.3[ (nm/cm)/MPa, which were used as the measurement conditions.

[ falling ball test height of crystallized glass article ]

The height test method for the falling ball test of the microcrystalline glass product comprises the following steps:

A150X 57X 0.55mm sample was placed on a glass carrier jig, and 132g of a steel ball was dropped from a predetermined height to a maximum ball drop test height at which the sample could withstand an impact without breaking. Specifically, the test was conducted from a ball drop test height of 800mm, and the height was changed in the order of 850mm, 900mm, 950mm, 1000mm and more without breaking. For the examples having the "falling ball test height B", a crystallized glass article was used as a test object. The test data recorded as 1000mm in the examples shows that the crystallized glass product was not broken and received an impact even when the steel ball was dropped from the height of 1000 mm. The drop test height is sometimes referred to herein as the drop height.

[ falling ball test height of crystallized glass ]

The height test method for the ball drop test of the microcrystalline glass comprises the following steps:

A150X 57X 0.55mm sample was placed on a glass carrier jig, and 32g of a steel ball was dropped from a predetermined height to a maximum ball drop test height at which the sample could withstand an impact without breaking. Specifically, the test was conducted from a ball drop test height of 400mm, and the height was changed in the order of 450mm, 500mm, 550mm, 600mm, 650mm, 700mm and more without breaking. For the examples having the "falling ball test height a", glass ceramics was used as the test object. The test data recorded as 800mm in the examples shows that the glass ceramics were not broken and received an impact even when the steel ball was dropped from a height of 800 mm.

[ fracture toughness ]

The method for directly measuring the size of the indentation propagation crack is used, the specification of a sample is 2mm multiplied by 4mm multiplied by 20mm, after the sample is chamfered, ground and polished, a Vickers hardness indenter is used for applying 49N force on the sample and maintaining the force for 30s, after the indentation is made, the fracture strength is measured by a three-point bending method.

[ four-point bending Strength ]

The glass is tested by adopting a microcomputer control electronic universal tester CMT6502, the glass specification is 150 multiplied by 57 multiplied by 0.55mm, and the ASTM C158-2002 is taken as a standard.

[ Vickers hardness ]

The load (N) when a pyramid-shaped depression was pressed into a test surface by a diamond quadrangular pyramid indenter having an included angle of 136 degrees with respect to the surface was divided by the surface area (mm) calculated from the length of the depression²) The values of (b) indicate (a). The test load was set to 100(N) and the holding time was set to 15 (sec). In the present invention, Vickers hardness is sometimes referred to simply as hardness.

The microcrystalline glass has the following properties:

1) in some embodiments, the microcrystalline glass has a crystallinity of 20% or more, preferably 30% or more, and more preferably 40% or more.

2) In some embodiments, the crystallite glass has a crystal grain size of 70nm or less, preferably 50nm or less, more preferably 40nm or less, and even more preferably 30nm or less.

3) In some embodiments, the 0.55mm thick glass ceramic has a haze of 0.3% or less, preferably 0.15% or less, and more preferably 0.1% or less.

4) In some embodiments, the microcrystalline glass having a thickness of 0.55mm has an average transmittance of 85% or more, preferably 86% or more, and more preferably 88% or more at a wavelength of 400 to 800 nm.

5) In some embodiments, the 0.55mm thick glass ceramics have a 550nm wavelength transmittance of 85% or more, preferably 87% or more, and more preferably 90% or more.

6) In some embodiments, the glass ceramic has a falling ball test height of 500mm or more, preferably 700mm or more, and more preferably 900mm or more.

The microcrystalline glass product has the following properties:

1) in some embodiments, the surface stress of the microcrystalline glass article is 800MPa or greater, preferably 1000MPa or greater, and more preferably 1100MPa or greater.

2) In some embodiments, the microcrystalline glass article has a four-point flexural strength of 600MPa or greater, preferably 650MPa or greater, and more preferably 700MPa or greater.

3) In some embodiments, the ion exchange layer depth of the crystallized glass product is 25 μm or more, preferably 28 μm or more, and more preferably 30 μm or more.

4) In some embodiments, the crystallized glass article has a falling ball test height of 900mm or more, preferably 1000mm or more, and more preferably 1100mm or more.

5) In some embodiments, the microcrystalline glass article has a fracture toughness of 1 MPa-m^1/2Above, preferably 1.2MPa · m^1/2More preferably 1.3MPa · m or more^1/2The above.

6) In some embodiments, the microcrystalline glass article has a Vickers hardness (H)_v) Is 600kgf/mm²Above, preferably 650kgf/mm²Above, more preferably 680kgf/mm²The above.

7) In some embodiments, the microcrystalline glass article has a crystallinity of 20% or more, preferably 30% or more, and more preferably 40% or more.

8) In some embodiments, the crystallite glass product has a grain size of 70nm or less, preferably 50nm or less, more preferably 40nm or less, and even more preferably 30nm or less.

9) In some embodiments, the 0.55mm thick microcrystalline glass article has a haze of 0.3% or less, preferably 0.15% or less, and more preferably 0.1% or less.

10) In some embodiments, the microcrystalline glass product having a thickness of 0.55mm has an average transmittance of 85% or more, preferably 86% or more, and more preferably 88% or more at a wavelength of 400 to 800 nm.

11) In some embodiments, the 0.55mm thick glass-ceramic product has a 550nm wavelength transmittance of 85% or more, preferably 87% or more, and more preferably 90% or more.

The microcrystalline glass and the microcrystalline glass product have the excellent performance, so that the microcrystalline glass and the microcrystalline glass product can be widely made into glass cover plates or glass components; meanwhile, the microcrystalline glass product and the matrix glass of the invention are applied to electronic equipment or display equipment, such as mobile phones, watches, computers, touch display screens and the like, are used for manufacturing protective glass of mobile phones, smart phones, tablet computers, notebook computers, PDAs, televisions, unmanned planes, personal computers, MTA machines or industrial displays, or are used for manufacturing touch screens, protective windows, automobile windows, train windows, aviation machinery windows and touch screen protective glass, or are used for manufacturing hard disk substrates or solar cell substrates, or are used for manufacturing white household appliances, such as refrigerator parts or kitchen ware.

Examples

In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided. Many efforts have been made to ensure accuracy with respect to numbers in the embodiments of the invention, but some errors and deviations should be accounted for. The composition is itself given in weight% on oxide basis and has been standardized to 100%.

Examples of the glass ceramics shown in tables 1 to 3 below were manufactured and tested according to the above-described methods for manufacturing glass ceramics and the methods for testing the properties thereof.

Table 1.

Table 2.

Table 3.

The examples of the crystallized glass products shown in tables 4 to 6 below were obtained by chemically strengthening the crystallized glasses shown in tables 1 to 3 according to the above-described chemical strengthening method, and were tested according to the above performance test method.

Table 4.

Table 5.

Table 6.

Claims

1. The microcrystalline glass is characterized by comprising the following components in percentage by weight: SiO 2₂：46～68％；Al₂O₃：11～30％；Na₂O：5～18％；ZnO：3～13％；TiO₂: 1 to 9% of (TiO)₂+ZnO)/Al₂O₃0.2 to 1.5.

2. The glass-ceramic according to claim 1, characterized in that it further comprises, in weight percent: li₂O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or P₂O₅: 0-6%; and/or ZrO₂: 0-6%; and/or a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

3. The microcrystalline glass is characterized in that the components contain SiO₂、Al₂O₃、Na₂O, ZnO and TiO₂The components of which are expressed in weight percent, wherein (TiO)₂+ZnO)/Al₂O₃0.2 to 1.5, wherein the glass ceramic comprises a spinel crystal phase, wherein the spinel crystal phase has a higher weight percentage than other crystal phases present in the glass ceramic.

4. A glass-ceramic according to claim 3, characterized in that its composition, expressed in weight percentage, contains: SiO 2₂: 46-68%; and/or Al₂O₃: 11-30%; and/or Na₂O: 5-18%; and/or ZnO: 3-13%; and/or TiO₂: 1-9%; and/or Li₂O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or P₂O₅: 0-6%; and/or ZrO₂: 0-6%; and/or a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

5. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition is expressed in weight percentage, wherein: (TiO)₂+ZnO)/Al₂O₃0.3 to 0.9, preferably (TiO)₂+ZnO)/Al₂O₃0.4 to 0.7.

6. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition is in weight percentIs shown, in which: al (Al)₂O₃/SiO₂0.2 to 0.62, preferably Al₂O₃/SiO₂0.25 to 0.55, more preferably Al₂O₃/SiO₂0.3 to 0.5.

7. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition is expressed in weight percentage, wherein: SiO 2₂/(Na₂O + ZnO) of 2.0 to 8.0, preferably SiO₂/(Na₂O + ZnO) of 2.5 to 6.0, more preferably SiO₂/(Na₂O + ZnO) of 2.5 to 5.5.

8. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition is expressed in weight percentage, wherein: li₂O/ZnO is 1.0 or less, and Li is preferable₂O/ZnO is 0.8 or less, and Li is more preferable₂The O/ZnO ratio is 0.7 or less.

9. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition is expressed in weight percentage, wherein: al (Al)₂O₃/(MgO + ZnO) is 2.5 or more, and Al is preferable₂O₃/(MgO + ZnO) is 2.5 to 10.0, more preferably Al₂O₃/(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable₂O₃The ratio of (MgO + ZnO) is 2.7 to 4.0.

10. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition is expressed in weight percentage, wherein: the ratio MgO/ZnO is 0.5 or less, preferably 0.4 or less, and more preferably 0.3 or less.

11. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition is expressed in weight percentage, wherein: (MgO + ZnO + Na)₂O)/TiO₂1.0 to 10.0, preferably (MgO + ZnO + Na)₂O)/TiO₂1.5 to 8.0, more preferably (MgO + ZnO + Na)₂O)/TiO₂Is 2.0 to 4.0.

12. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition is expressed in weight percentage, wherein: na (Na)₂O/(TiO₂+Li₂O) is 0.5 to 9.0, preferably Na₂O/(TiO₂+Li₂O) is 0.8 to 7.0, more preferably Na₂O/(TiO₂+Li₂O) is 1.0 to 5.0.

13. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition is expressed in weight percentage, wherein: (P)₂O₅+ZrO₂) The content of/ZnO is 1.1 or less, preferably (P)₂O₅+ZrO₂) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable₂O₅+ZrO₂) the/ZnO is 0.1 to 0.7.

14. A glass-ceramic according to any one of claims 1 to 4, characterized in that the composition thereof, expressed in weight percentage, comprises: SiO 2₂: 50-66%; and/or Al₂O₃: 15-28%; and/or Na₂O: 6-15%; and/or ZnO: 4-12%; and/or TiO₂: 2-8%; and/or Li₂O: 0 to 5 percent; and/or MgO: 0 to 3 percent; and/or K₂O: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or Ln₂O₃: 0 to 4 percent; and/or B₂O₃: 0 to 3 percent; and/or P₂O₅: 0 to 4 percent; and/or ZrO₂: 0 to 5 percent; and/or a clarifying agent: 0 to 1 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

15. A glass-ceramic according to any one of claims 1 to 4, characterized in that the composition thereof, expressed in weight percentage, comprises: siO₂: 50-64%; and/or Al₂O₃: 16-25%; and/or Na₂O: 6.5-12%; and/or ZnO: 5-10%; and/or TiO₂: 2.5-6.5%; and/or Li₂O: 0 to 3 percent; and/or MgO: 0 to 1.5 percent; and/or K₂O: 0.5-2.5%; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or CaO: 0 to 1 percent; and/or Ln₂O₃: 0 to 3 percent; and/or B₂O₃: 0 to 1 percent; and/or P₂O₅: 0.2-3%; and/or ZrO₂: 0 to 3 percent; and/or a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

16. A glass-ceramic according to any one of claims 1 to 4, characterized in that the composition thereof, expressed in weight percentage, comprises: AgO: 0-2%, preferably AgO: 0 to 1 percent; and/or CuO: 0 to 2%, preferably CuO: 0 to 1 percent; and/or Cu₂O: 0 to 2%, preferably Cu₂O：0～1％。

17. The microcrystalline glass according to any one of claims 1 to 4, characterised in that it does not contain B in its composition₂O₃(ii) a And/or does not contain CaO; and/or no BaO; and/or does not contain SrO; and/or does not contain F; and/or does not contain Ta₂O₅(ii) a And/or do not contain La₂O₃(ii) a And/or does not contain Gd₂O₃。

18. A glass-ceramic according to any one of claims 1 to 4, wherein the glass-ceramic contains a spinel crystal phase; and/or a lithium phosphate crystalline phase; and/or quartz and quartz solid solution crystalline phases; and/or a zirconium silicate crystalline phase; and/or a lithium silicate crystalline phase.

19. A microcrystalline glass according to any of claims 1-4, characterised in that the total amount of crystalline phases in the microcrystalline glass is in the range of 5-60% by weight, preferably 10-50% by weight, more preferably 15-40% by weight of the microcrystalline glass.

20. A glass-ceramic according to any one of claims 1 to 4, characterized in that the glass-ceramic comprises a spinel crystal phase having a higher weight percentage than other crystal phases, preferably 10 to 50% by weight of the glass-ceramic, more preferably 15 to 40% by weight of the glass-ceramic.

21. The microcrystalline glass according to any one of claims 1 to 4, wherein the microcrystalline glass does not contain quartz and quartz solid solution crystal phases; and/or does not contain a lithium silicate crystalline phase.

22. The crystallized glass according to any one of claims 1 to 4, wherein the crystallized glass having a thickness of 0.55mm has a haze of 0.3% or less, preferably 0.15% or less, and more preferably 0.1% or less; and/or 0.55mm thick microcrystalline glass, the average transmittance at a wavelength of 400-800 nm is more than 85%, preferably more than 86%, more preferably more than 88%; and/or 0.55mm thick glass ceramics, and has a 550nm wavelength transmittance of 85% or more, preferably 87% or more, and more preferably 90% or more.

23. The crystallized glass according to any one of claims 1 to 4, wherein the crystallized glass has a crystallinity of 20% or more, preferably 30% or more, and more preferably 40% or more; and/or a crystal grain size of 70nm or less, preferably 50nm or less, more preferably 40nm or less, and further preferably 30nm or less; and/or a ball drop test height of 500mm or more, preferably 700mm or more, more preferably 900mm or more.

24. A glass-ceramic according to any one of claims 1 to 4, wherein the glass-ceramic further contains a colorant for making the glass-ceramic show different colors.

25. A glass-ceramic according to claim 24, characterized in that its colouring agents, expressed in weight percentage, contain: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni₂O₃: 0 to 4%, preferably Ni₂O₃: 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co₂O₃: 0 to 2%, preferably Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0 to 7%, preferably Fe₂O₃: 0.2-5%; and/or MnO₂: 0 to 4%, preferably MnO₂: 0.1-3%; and/or Er₂O₃: 0 to 8%, preferably Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0 to 8%, preferably Nd₂O₃: 0.4-6%; and/or Cu₂O: 0 to 4%, preferably Cu₂O: 0.5-3%; and/or Pr₂O₅: 0 to 8%, preferably Pr₂O₅: 0.4-6%; and/or CeO₂: 0 to 4%, preferably CeO₂：0.5～3％。

26. A crystallized glass product, which is characterized by being produced from the crystallized glass according to any one of claims 1 to 25.

27. A crystallized glass article according to claim 26, wherein the haze of the crystallized glass article with a thickness of 0.55mm is 0.3% or less, preferably 0.15% or less, more preferably 0.1% or less; and/or a microcrystalline glass product having a thickness of 0.55mm, wherein the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 86% or more, and more preferably 88% or more; and/or a microcrystalline glass product having a thickness of 0.55mm, and has a transmittance at a wavelength of 550nm of 85% or more, preferably 87% or more, and more preferably 90% or more.

28. The crystallized glass product according to claim 26, wherein the crystallized glass product has a crystallinity of 20% or more, preferably 30% or more, and more preferably 40% or more; and/or the crystal grain size is 70nm or less, preferably 50nm or less, more preferably 40nm or less, and further preferably 30nm or less.

29. The crystallized glass product according to claim 26, wherein the crystallized glass product has a surface stress of 800MPa or more, preferably 1000MPa or more, and more preferably 1100MPa or more; and/or the depth of the ion exchange layer is 25 μm or more, preferably 28 μm or more, and more preferably 30 μm or more.

30. The crystallized glass product according to claim 26, wherein the crystallized glass product has a falling ball test height of 900mm or more, preferably 1000mm or more, and more preferably 1100mm or more; and/or a fracture toughness of 1MPa m^1/2Above, preferably 1.2MPa · m^1/2More preferably 1.3MPa · m or more^1/2The above; and/or a Vickers hardness of 600kgf/mm²Above, preferably 650kgf/mm²Above, more preferably 680kgf/mm²The above; and/or a four-point bending strength of 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more.

31. Glass cover plate, characterized in that it is made of a glass ceramic as claimed in any one of claims 1 to 25 and/or a glass ceramic product as claimed in any one of claims 26 to 30.

32. A glass component, characterized in that it is made of the glass-ceramic according to any one of claims 1 to 25 and/or made of the glass-ceramic product according to any one of claims 26 to 30.

33. Display device, characterized in that it comprises a glass-ceramic according to any of claims 1 to 25, and/or comprises a glass-ceramic product according to any of claims 26 to 30, and/or comprises a glass cover plate according to claim 31, and/or comprises a glass component according to claim 32.

34. An electronic device comprising the glass ceramic according to any one of claims 1 to 25, and/or comprising the glass ceramic product according to any one of claims 26 to 30, and/or comprising the glass cover plate according to claim 31, and/or comprising the glass component according to claim 32.

35. A method for producing a crystallized glass product, characterized by comprising the steps of:

36. The method for producing a crystallized glass product according to claim 35, wherein the matrix glass further contains, in terms of the components by weight: li₂O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or P₂O₅: 0-6%; and/or ZrO₂: 0-6%; and/or a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

37. According to claimA method for producing a glass-ceramic article according to any of claims 35 or 36, wherein the matrix glass comprises, in terms of weight percent: SiO 2₂: 50-66%, preferably SiO₂: 50-64%; and/or Al₂O₃: 15-28%, preferably Al₂O₃: 16-25%; and/or Na₂O: 6-15%, preferably Na₂O: 6.5-12%; and/or ZnO: 4-12%, preferably ZnO: 5-10%; and/or TiO₂: 2-8%, preferably TiO₂: 2.5-6.5%; and/or Li₂O: 0 to 5%, preferably Li₂O: 0 to 3 percent; and/or MgO: 0-3%, preferably MgO: 0 to 1.5 percent; and/or K₂O: 0 to 3%, preferably K₂O: 0.5-2.5%; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or Ln₂O₃: 0 to 4%, preferably Ln₂O₃: 0 to 3 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or P₂O₅: 0 to 4%, preferably P₂O₅: 0.2-3%; and/or ZrO₂: 0 to 5%, preferably ZrO₂: 0 to 3 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

38. A method of manufacturing a glass-ceramic article according to any of claims 35 or 36, characterized in that the matrix glass has a composition expressed in weight percentage, wherein: (TiO)₂+ZnO)/Al₂O₃0.3 to 0.9, preferably (TiO)₂+ZnO)/Al₂O₃0.4 to 0.7; and/or Al₂O₃/SiO₂0.2 to 0.62, preferably Al₂O₃/SiO₂0.25 to 0.55, more preferably Al₂O₃/SiO₂0.3 to 0.5; and/or SiO₂/(Na₂O + ZnO) of 2.0 to 8.0, preferably SiO₂/(Na₂O + ZnO) of 2.5 to 6.0, more preferably SiO₂/(Na₂O + ZnO) is 2.5 to 5.5; and/or Li₂O/ZnO is 1.0 or less, and Li is preferable₂O/ZnO is 0.8 or less, and Li is more preferable₂O/ZnO is less than 0.7; and/or Al₂O₃/(MgO + ZnO) is 2.5 or more, and Al is preferable₂O₃/(MgO + ZnO) is 2.5 to 10.0, more preferably Al₂O₃/(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable₂O₃/(MgO + ZnO) is 2.7 to 4.0; and/or MgO/ZnO is 0.5 or less, preferably MgO/ZnO is 0.4 or less, more preferably MgO/ZnO is 0.3 or less; and/or (MgO + ZnO + Na)₂O)/TiO₂1.0 to 10.0, preferably (MgO + ZnO + Na)₂O)/TiO₂1.5 to 8.0, more preferably (MgO + ZnO + Na)₂O)/TiO₂2.0 to 4.0; and/or Na₂O/(TiO₂+Li₂O) is 0.5 to 9.0, preferably Na₂O/(TiO₂+Li₂O) is 0.8 to 7.0, more preferably Na₂O/(TiO₂+Li₂O) is 1.0 to 5.0; and/or (P)₂O₅+ZrO₂) The content of/ZnO is 1.1 or less, preferably (P)₂O₅+ZrO₂) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable₂O₅+ZrO₂) the/ZnO is 0.1 to 0.7.

39. A method for manufacturing a glass-ceramic article according to any of claims 35 or 36, wherein the matrix glass comprises, in weight percent: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni₂O₃: 0 to 4%, preferably Ni₂O₃: 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co₂O₃: 0 to 2%, preferably Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0 to 7%, preferably Fe₂O₃: 0.2-5%; and/or MnO₂: 0 to 4%, preferably MnO₂: 0.1-3%; and/or Er₂O₃: 0 to 8%, preferably Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0 to 8%, preferably Nd₂O₃: 0.4-6%; and/or Cu₂O: 0 to 4%, preferably Cu₂O: 0.5-3%; and/or Pr₂O₅: 0 to 8%, preferably Pr₂O₅: 0.4-6%; and/or CeO₂: 0 to 4%, preferably CeO₂：0.5～3％。

40. The method for producing a crystallized glass product according to any one of claims 35 and 36, wherein the melting temperature of the resulting matrix glass is 1250 to 1650 ℃, preferably 1380 to 1600 ℃; and/or the melting time is 5-24 hours, preferably 8-12 hours.

41. A method of manufacturing a crystallized glass article according to any one of claims 35 or 36, wherein the crystallization process comprises the steps of: the temperature is raised to a specified crystallization treatment temperature, and after the temperature reaches the crystallization treatment temperature, the temperature is kept for a certain time, and then the temperature is lowered. The crystallization temperature is 600-750 ℃, preferably 650-700 ℃, and the retention time at the crystallization temperature is 0-8 hours, preferably 1-6 hours.

42. A method of manufacturing a crystallized glass article according to any one of claims 35 or 36, wherein the crystallization process comprises the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.

43. The method of manufacturing a crystallized glass article according to claim 42, wherein the crystallization process includes the steps of: the temperature of the No. 1 is 550-630 ℃, and the temperature of the No. 2 is 650-750 ℃; the holding time at the temperature of 1 st is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

44. A method of manufacturing a crystallized glass article according to any one of claims 35 or 36, wherein the chemical strengthening process comprises: immersing the microcrystalline glass in a salt bath of molten Na salt at the temperature of 430-470 ℃ for 6-20 hours, preferably at the temperature of 435-460 ℃ for 8-13 hours; and/or immersing the microcrystalline glass in a salt bath for melting K salt at the temperature of 400-450 ℃ for 1-8 hours, wherein the preferable time range is 2-4 hours; and/or immersing the metal alloy in a salt bath mixed with K salt and Na salt at the temperature of 350-450 ℃ for 0.5-8 hours to perform ion exchange, wherein the preferable time range is 1-4 hours.

45. A method for manufacturing a glass-ceramic article according to any of claims 35 or 36, wherein the total amount of crystal phases in the glass-ceramic article is 5-60 wt%, preferably 10-50 wt%, and more preferably 15-40 wt% of the glass-ceramic article.

46. A method of manufacturing a glass-ceramic article according to any of claims 35 or 36, characterized in that the glass-ceramic article comprises a spinel crystalline phase having a higher weight percentage than other crystalline phases, preferably 10-50% by weight of the glass-ceramic article, more preferably 15-40% by weight of the glass-ceramic article.

47. The method for producing a crystallized glass article according to any one of claims 35 and 36, wherein the haze of the crystallized glass article having a thickness of 0.55mm is 0.3% or less, preferably 0.15% or less, more preferably 0.1% or less; and/or a microcrystalline glass product having a thickness of 0.55mm, wherein the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 86% or more, and more preferably 88% or more; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 85% or more, preferably 87% or more, more preferably 90% or more; and/or crystallization of glass-ceramic articlesThe degree is 20% or more, preferably 30% or more, more preferably 40% or more; and/or the crystallite size of the glass-ceramic product is 70nm or less, preferably 50nm or less, more preferably 40nm or less, and further preferably 30nm or less; and/or the surface stress of the glass-ceramic product is 800MPa or more, preferably 1000MPa or more, more preferably 1100MPa or more; and/or the ion exchange layer depth of the glass-ceramic product is 25 μm or more, preferably 28 μm or more, more preferably 30 μm or more; and/or the height of the microcrystalline glass product in a falling ball test is more than 900mm, preferably more than 1000mm, and more preferably more than 1100 mm; and/or the fracture toughness of the glass-ceramic product is 1 MPa.m^1/2Above, preferably 1.2MPa · m^1/2More preferably 1.3MPa · m or more^1/2The above; and/or the Vickers hardness of the glass-ceramic article is 600kgf/mm²Above, preferably 650kgf/mm²Above, more preferably 680kgf/mm²The above; and/or the four-point bending strength of the glass-ceramic product is 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more.

48. A method for producing a crystallized glass, characterized by comprising:

49. The method for producing a glass-ceramic according to claim 48, wherein the matrix glass further contains, in terms of the components by weight: li₂O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or P₂O₅: 0-6%; and/or ZrO₂: 0-6%; and/or a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

50. A process for producing a glass-ceramic according to any one of claims 48 and 49, wherein the matrix glass comprises, in terms of weight percent: SiO 2₂: 50-66%, preferably SiO₂: 50-64%; and/or Al₂O₃: 15-28%, preferably Al₂O₃: 16-25%; and/or Na₂O: 6-15%, preferably Na₂O: 6.5-12%; and/or ZnO: 4-12%, preferably ZnO: 5-10%; and/or TiO₂: 2-8%, preferably TiO₂: 2.5-6.5%; and/or Li₂O: 0 to 5%, preferably Li₂O: 0 to 3 percent; and/or MgO: 0-3%, preferably MgO: 0 to 1.5 percent; and/or K₂O: 0 to 3%, preferably K₂O: 0.5-2.5%; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or Ln₂O₃: 0 to 4%, preferably Ln₂O₃: 0 to 3 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or P₂O₅: 0 to 4%, preferably P₂O₅: 0.2-3%; and/or ZrO₂: 0 to 5%, preferably ZrO₂: 0 to 3 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

51. A method for producing a crystallized glass according to any one of claims 48 and 49, wherein the method comprisesThe matrix glass comprises the following components in percentage by weight: (TiO)₂+ZnO)/Al₂O₃0.3 to 0.9, preferably (TiO)₂+ZnO)/Al₂O₃0.4 to 0.7; and/or Al₂O₃/SiO₂0.2 to 0.62, preferably Al₂O₃/SiO₂0.25 to 0.55, more preferably Al₂O₃/SiO₂0.3 to 0.5; and/or SiO₂/(Na₂O + ZnO) of 2.0 to 8.0, preferably SiO₂/(Na₂O + ZnO) of 2.5 to 6.0, more preferably SiO₂/(Na₂O + ZnO) is 2.5 to 5.5; and/or Li₂O/ZnO is 1.0 or less, and Li is preferable₂O/ZnO is 0.8 or less, and Li is more preferable₂O/ZnO is less than 0.7; and/or Al₂O₃/(MgO + ZnO) is 2.5 or more, and Al is preferable₂O₃/(MgO + ZnO) is 2.5 to 10.0, more preferably Al₂O₃/(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable₂O₃/(MgO + ZnO) is 2.7 to 4.0; and/or MgO/ZnO is 0.5 or less, preferably MgO/ZnO is 0.4 or less, more preferably MgO/ZnO is 0.3 or less; and/or (MgO + ZnO + Na)₂O)/TiO₂1.0 to 10.0, preferably (MgO + ZnO + Na)₂O)/TiO₂1.5 to 8.0, more preferably (MgO + ZnO + Na)₂O)/TiO₂2.0 to 4.0; and/or Na₂O/(TiO₂+Li₂O) is 0.5 to 9.0, preferably Na₂O/(TiO₂+Li₂O) is 0.8 to 7.0, more preferably Na₂O/(TiO₂+Li₂O) is 1.0 to 5.0; and/or (P)₂O₅+ZrO₂) The content of/ZnO is 1.1 or less, preferably (P)₂O₅+ZrO₂) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable₂O₅+ZrO₂) the/ZnO is 0.1 to 0.7.

52. A process for producing a glass-ceramic according to any one of claims 48 and 49, wherein the matrix glass comprises, in terms of weight percent: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni₂O₃: 0 to 4%, preferably Ni₂O₃: 0.1-3%; and/orAnd (3) CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co₂O₃: 0 to 2%, preferably Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0 to 7%, preferably Fe₂O₃: 0.2-5%; and/or MnO₂: 0 to 4%, preferably MnO₂: 0.1-3%; and/or Er₂O₃: 0 to 8%, preferably Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0 to 8%, preferably Nd₂O₃: 0.4-6%; and/or Cu₂O: 0 to 4%, preferably Cu₂O: 0.5-3%; and/or Pr₂O₅: 0 to 8%, preferably Pr₂O₅: 0.4-6%; and/or CeO₂: 0 to 4%, preferably CeO₂：0.5～3％。

53. The method for producing a glass-ceramic according to any of claims 48 or 49, wherein the melting temperature of the resulting matrix glass is 1250 to 1650 ℃, preferably 1380 to 1600 ℃; and/or the melting time is 5-24 hours, preferably 8-12 hours.

54. A method for manufacturing crystallized glass according to any one of claims 48 and 49, wherein the crystallization process includes the steps of: the temperature is raised to a specified crystallization treatment temperature, and after the temperature reaches the crystallization treatment temperature, the temperature is kept for a certain time, and then the temperature is lowered. The crystallization temperature is 600-750 ℃, preferably 650-700 ℃, and the retention time at the crystallization temperature is 0-8 hours, preferably 1-6 hours.

55. A method for manufacturing crystallized glass according to any one of claims 48 and 49, wherein the crystallization process includes the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.

56. The method for manufacturing glass-ceramic according to claim 55, wherein the crystallization process comprises the steps of: the temperature of the No. 1 is 550-630 ℃, and the temperature of the No. 2 is 650-750 ℃; the holding time at the temperature of 1 st is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

57. A method for manufacturing a crystallized glass according to any one of claims 48 and 49, wherein the total amount of crystal phases in the crystallized glass is in the range of 5 to 60% by weight, preferably 10 to 50% by weight, and more preferably 15 to 40% by weight of the crystallized glass.

58. A method of producing a glass-ceramic according to any of claims 48 or 49, wherein the glass-ceramic contains a spinel crystal phase having a higher weight percentage than other crystal phases, preferably 10-50% by weight of the glass-ceramic, more preferably 15-40% by weight of the glass-ceramic.

59. The method for producing a crystallized glass according to any one of claims 48 and 49, wherein the haze of the crystallized glass having a thickness of 0.55mm is 0.3% or less, preferably 0.15% or less, more preferably 0.1% or less; and/or 0.55mm thick microcrystalline glass, the average transmittance at a wavelength of 400-800 nm is more than 85%, preferably more than 86%, more preferably more than 88%; and/or 0.55mm thick glass ceramics, having a 550nm wavelength transmittance of 85% or more, preferably 87% or more, more preferably 90% or more; and/or the degree of crystallinity of the glass ceramics is 20% or more, preferably 30% or more, more preferably 40% or more; and/or the crystallite size of the glass ceramics is 70nm or less, preferably 50nm or less, more preferably 40nm or less, and further preferably 30nm or less; and/or the crystallized glass has a falling ball test height of 500mm or more, preferably 700mm or more, and more preferably 900mm or more.