CN114907014A - Glass ceramics, glass ceramics product and manufacturing method thereof - Google Patents

Abstract

The invention provides microcrystalline glass, which comprises the following components in percentage by weight: SiO 2 ₂ ：46～68％；Al ₂ O ₃ ：11～30％；Na ₂ O：5～18％；ZnO：3～13％；TiO ₂ : 1 to 9% of (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.2 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

The present application is a divisional application of an invention patent application entitled "glass ceramics, glass ceramics products and methods for producing the same" having application No. 202010603759.4 and having application date of 29/06/2020.

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 that necessitates glass applied thereto 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 robust to withstand routine 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 2 ₂ ：46～68％；Al ₂ O ₃ ：11～30％；Na ₂ O：5～18％；ZnO：3～13％；TiO ₂ : 1 to 9% of (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.2 to 1.5.

(2) The glass-ceramic according to (1), which comprises the following components in percentage by weight: li ₂ O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K ₂ O: 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 Ln ₂ O ₃ : 0 to 5 percent; and/or B ₂ O ₃ : 0 to 5 percent; and/or P ₂ O ₅ : 0-6%; and/or ZrO ₂ : 0-6%; and/or a clarifying agent: 0-2% of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One or more of (a).

(3) The microcrystalline glass contains SiO in the component ₂ 、Al ₂ O ₃ 、Na ₂ O, ZnO and TiO ₂ The components of which are expressed in weight percent, wherein (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.2 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 SiO ₂ 、Al ₂ O ₃ And ZnO, the microcrystalline glass contains a spinel crystal phase.

(5) The microcrystalline glass according to any one of (3) and (4)The glass comprises the following components in percentage by weight: SiO 2 ₂ : 46-68%; and/or Al ₂ O ₃ : 11-30%; and/or Na ₂ O: 5-18%; and/or ZnO: 3-13%; and/or TiO ₂ : 1-9%; and/or Li ₂ O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K ₂ O: 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 Ln ₂ O ₃ : 0 to 5 percent; and/or B ₂ O ₃ : 0 to 5 percent; and/or P ₂ O ₅ : 0-6%; and/or ZrO ₂ : 0-6%; and/or a clarifying agent: 0-2% of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One 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)/Al ₂ O ₃ 0.3 to 0.9, preferably (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.4 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) ₂ O ₃ /SiO ₂ 0.2 to 0.62, preferably Al ₂ O ₃ /SiO ₂ 0.25 to 0.55, more preferably Al ₂ O ₃ /SiO ₂ 0.3 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 2 ₂ /(Na ₂ O + ZnO) of 2.0 to 8.0, preferably SiO ₂ /(Na ₂ O + ZnO) of 2.5 to 6.0, more preferably SiO ₂ /(Na ₂ O + 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: li ₂ O/ZnO is 1.0 or less, and Li is preferable ₂ O/ZnO is 0.8 or less, and Li is more preferable ₂ The 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 ₂ O ₃ /(MgO + ZnO) is 2.5 or more, and Al is preferable ₂ O ₃ /(MgO + ZnO) is 2.5 to 10.0, more preferably Al ₂ O ₃ /(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable ₂ O ₃ The 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 crystallized glass according to any one of (1) to (11), which comprises the following components in percentage by weight: (MgO + ZnO + Na) ₂ O)/TiO ₂ 1.0 to 10.0, preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 1.5 to 8.0, more preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ Is 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) ₂ O/(TiO ₂ +Li ₂ O) is 0.5 to 9.0, preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 0.8 to 7.0, more preferably Na ₂ O/(TiO ₂ +Li ₂ O) 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) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 1.1 or less, preferably (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 0.1 to 1.0, more preferably (P) ₂ O ₅ +ZrO ₂ ) 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 2 ₂ : 50-66%; and/or Al ₂ O ₃ : 15-28%; and/or Na ₂ O: 6-15%; and/or ZnO: 4-12%; and/or TiO ₂ : 2-8%; and/or Li ₂ O: 0 to 5 percent; and/or MgO: 0 to 3 percent; and/or K ₂ O: 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 Ln ₂ O ₃ : 0 to 4 percent; and/or B ₂ O ₃ : 0 to 3 percent; and/or P ₂ O ₅ ：0-4%; and/or ZrO ₂ : 0 to 5 percent; and/or a clarifying agent: 0 to 1 percent of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One 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 2 ₂ : 50-64%; and/or Al ₂ O ₃ : 16-25%; and/or Na ₂ O: 6.5-12%; and/or ZnO: 5-10%; and/or TiO ₂ : 2.5-6.5%; and/or Li ₂ O: 0 to 3 percent; and/or MgO: 0 to 1.5 percent; and/or K ₂ O: 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 Ln ₂ O ₃ : 0 to 3 percent; and/or B ₂ O ₃ : 0 to 1 percent; and/or P ₂ O ₅ : 0.2-3%; and/or ZrO ₂ : 0 to 3 percent; and/or a clarifying agent: 0 to 0.5 percent of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One 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 Cu ₂ O: 0 to 2%, preferably Cu ₂ O：0～1％。

(18) The crystallized glass of any one of (1) to (17), which does not contain B in the component ₂ O ₃ (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 Ta ₂ O ₅ (ii) a And/or do not contain La ₂ O ₃ (ii) a And/or does not contain Gd ₂ O ₃ 。

(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 Ni ₂ O ₃ : 0 to 4%, preferably Ni ₂ O ₃ : 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co ₂ O ₃ : 0 to 2%, preferably Co ₂ O ₃ : 0.05-1.8%; and/or Fe ₂ O ₃ : 0 to 7%, preferably Fe ₂ O ₃ : 0.2-5%; and/or MnO ₂ : 0 to 4%, preferably MnO ₂ : 0.1-3%; and/or Er ₂ O ₃ : 0 to 8%, preferably Er ₂ O ₃ : 0.4-6%; and/or Nd ₂ O ₃ : 0 to 8%, preferably Nd ₂ O ₃ : 0.4-6%; and/or Cu ₂ O: 0 to 4%, preferably Cu ₂ O: 0.5-3%; and/or Pr ₂ O ₅ : 0 to 8%, preferably Pr ₂ O ₅ : 0.4-6%; and/or CeO ₂ : 0 to 4%, preferably CeO ₂ ：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 of any one of (27) to (30), wherein the crystallized glass product has a falling ball test height of 900mm or more, preferably 1000mm or more, and more preferablyIs over 1100 nm; and/or a fracture toughness of 1MPa m ^1/2 Above, preferably 1.2MPa · m ^1/2 More preferably 1.3MPa · m or more ^1/2 The above; and/or a Vickers hardness of 600kgf/mm ² Above, preferably 650kgf/mm ² More preferably 680kgf/mm ² The 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 crystallized glass according to any one of (1) to (26), and/or made of the crystallized glass 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 crystallized glass according to any one of (1) to (26), and/or comprising the crystallized glass 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 2 ₂ ：46～68％；Al ₂ O ₃ ：11～30％；Na ₂ O：5～18％；ZnO：3～13％；TiO ₂ : 1 to 9% of (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.2 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: li ₂ O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K ₂ O: 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 Ln ₂ O ₃ : 0 to 5 percent; and/or B ₂ O ₃ : 0 to 5 percent; and/or P ₂ O ₅ : 0-6%; and/or ZrO ₂ : 0-6%; and/or a clarifying agent: 0-2% of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One 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 2 ₂ : 50-66%, preferably SiO ₂ : 50-64%; and/or Al ₂ O ₃ : 15-28%, preferably Al ₂ O ₃ : 16-25%; and/or Na ₂ O: 6-15%, preferably Na ₂ O: 6.5-12%; and/or ZnO: 4-12%, preferably ZnO: 5-10%; and/or TiO ₂ : 2-8%, preferably TiO ₂ : 2.5-6.5%; and/or Li ₂ O: 0 to 5%, preferably Li ₂ O: 0 to 3 percent; and/or MgO: 0-3%, preferably MgO: 0 to 1.5 percent; and/or K ₂ O: 0 to 3%, preferably K ₂ O: 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 Ln ₂ O ₃ : 0 to 4%, preferably Ln ₂ O ₃ : 0 to 3 percent; and/or B ₂ O ₃ : 0 to 3%, preferably B ₂ O ₃ : 0 to 1 percent; and/or P ₂ O ₅ : 0 to 4%, preferably P ₂ O ₅ : 0.2-3%; and/or ZrO ₂ : 0 to 5%, preferably ZrO ₂ : 0 to 3 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One 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)/Al ₂ O ₃ 0.3 to 0.9, preferably (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.4 to 0.7; and/or Al ₂ O ₃ /SiO ₂ 0.2 to 0.62, preferably Al ₂ O ₃ /SiO ₂ 0.25 to 0.55, more preferably Al ₂ O ₃ /SiO ₂ 0.3 to 0.5; and/or SiO ₂ /(Na ₂ O + ZnO) of 2.0 to 8.0, preferably SiO ₂ /(Na ₂ O + ZnO) of 2.5 to 6.0, more preferably SiO ₂ /(Na ₂ O + ZnO) is 2.5 to 5.5; and/or Li ₂ O/ZnO is 1.0 or less, and Li is preferable ₂ O/ZnO is 0.8 or less, and Li is more preferable ₂ O/ZnO is 0.7 or less; and/or Al ₂ O ₃ /(MgO + ZnO) is 2.5 or more, and Al is preferable ₂ O ₃ /(MgO + ZnO) is 2.5 to 10.0, more preferably Al ₂ O ₃ /(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable ₂ O ₃ /(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) ₂ O)/TiO ₂ 1.0 to 10.0, preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 1.5 to 8.0, more preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 2.0 to 4.0; and/or Na ₂ O/(TiO ₂ +Li ₂ O) is 0.5 to 9.0, preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 0.8 to 7.0, more preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 1.0 to 5.0; and/or (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 1.1 or less, preferably (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable ₂ O ₅ +ZrO ₂ ) 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 Ni ₂ O ₃ : 0 to 4%, preferably Ni ₂ O ₃ : 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co ₂ O ₃ : 0 to 2%, preferably Co ₂ O ₃ : 0.05-1.8%; and/or Fe ₂ O ₃ : 0 to 7%, preferably Fe ₂ O ₃ : 0.2-5%; and/or MnO ₂ : 0 to 4%, preferably MnO ₂ : 0.1-3%; and/or Er ₂ O ₃ : 0 to 8%, preferably Er ₂ O ₃ : 0.4-6%; and/or Nd ₂ O ₃ : 0 to 8%, preferably Nd ₂ O ₃ : 0.4-6%; and/or Cu ₂ O: 0 to 4%, preferably Cu ₂ O: 0.5-3%; and/or Pr ₂ O ₅ : 0 to 8%, preferably Pr ₂ O ₅ : 0.4-6%; and/or CeO ₂ : 0 to 4%, preferably CeO ₂ ：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 producing 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 substrate in a salt bath of a mixture of K salt and Na salt at a temperature of about 350 ℃ to 450 ℃ for 0.5 to 8 hours to perform ion exchange, preferably for 1 to 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, 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 a transmittance at a wavelength of 550nm of 85%Above, 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 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 nm; and/or the fracture toughness of the glass-ceramic product is 1 MPa.m ^1/2 Above, preferably 1.2 MPa.m ^1/2 More preferably 1.3MPa · m or more ^1/2 The above; and/or the Vickers hardness of the glass-ceramic article is 600kgf/mm ² Above, preferably 650kgf/mm ² Above, more preferably 680kgf/mm ² The 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:

forming a matrix glass, the components of the matrix glass, expressed in weight percent, comprising: SiO 2 ₂ ：46～68％；Al ₂ O ₃ ：11～30％；Na ₂ O：5～18％；ZnO：3～13％；TiO ₂ : 1 to 9% of (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.2 to 1.5.

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: li ₂ O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K ₂ O: 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 Ln ₂ O ₃ : 0 to 5 percent; and/or B ₂ O ₃ : 0 to 5 percent; and/or P ₂ O ₅ : 0-6%; and/or ZrO ₂ : 0-6%; and/or a clarifying agent: 0-2% of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One 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 2 ₂ : 50 to 66%, preferably SiO ₂ : 50-64 percent; and/or Al ₂ O ₃ : 15-28%, preferably Al ₂ O ₃ : 16-25%; and/or Na ₂ O: 6 to 15%, preferably Na ₂ O: 6.5-12%; and/or ZnO: 4-12%, preferably ZnO: 5-10%; and/or TiO ₂ : 2-8%, preferably TiO ₂ : 2.5-6.5%; and/or Li ₂ O: 0 to 5%, preferably Li ₂ O: 0 to 3 percent; and/or MgO: 0-3%, preferably MgO: 0 to 1.5 percent; and/or K ₂ O: 0 to 3%, preferably K ₂ O: 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 Ln ₂ O ₃ : 0 to 4%, preferably Ln ₂ O ₃ : 0 to 3 percent; and/or B ₂ O ₃ : 0 to 3%, preferably B ₂ O ₃ : 0 to 1 percent; and/or P ₂ O ₅ : 0 to 4%, preferably P ₂ O ₅ : 0.2-3%; and/or ZrO ₂ : 0 to 5%, preferably ZrO ₂ : 0 to 3 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One 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)/Al ₂ O ₃ 0.3 to 0.9, preferably (Ti)O ₂ +ZnO)/Al ₂ O ₃ 0.4 to 0.7; and/or Al ₂ O ₃ /SiO ₂ 0.2 to 0.62, preferably Al ₂ O ₃ /SiO ₂ 0.25 to 0.55, more preferably Al ₂ O ₃ /SiO ₂ 0.3 to 0.5; and/or SiO ₂ /(Na ₂ O + ZnO) of 2.0 to 8.0, preferably SiO ₂ /(Na ₂ O + ZnO) of 2.5 to 6.0, more preferably SiO ₂ /(Na ₂ O + ZnO) is 2.5 to 5.5; and/or Li ₂ O/ZnO is 1.0 or less, and Li is preferable ₂ O/ZnO is 0.8 or less, and Li is more preferable ₂ O/ZnO is less than 0.7; and/or Al ₂ O ₃ /(MgO + ZnO) is 2.5 or more, and Al is preferable ₂ O ₃ /(MgO + ZnO) is 2.5 to 10.0, more preferably Al ₂ O ₃ /(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable ₂ O ₃ /(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) ₂ O)/TiO ₂ 1.0 to 10.0, preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 1.5 to 8.0, more preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 2.0 to 4.0; and/or Na ₂ O/(TiO ₂ +Li ₂ O) is 0.5 to 9.0, preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 0.8 to 7.0, more preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 1.0 to 5.0; and/or (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 1.1 or less, preferably (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable ₂ O ₅ +ZrO ₂ ) 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, the following components: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni ₂ O ₃ : 0 to 4%, preferably Ni ₂ O ₃ : 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co ₂ O ₃ : 0 to 2%, preferably Co ₂ O ₃ : 0.05-1.8%; and/or Fe ₂ O ₃ : 0 to 7%, preferably Fe ₂ O ₃ : 0.2-5%; and/or MnO ₂ : 0 to 4%, preferably MnO ₂ : 0.1-3%; and/or Er ₂ O ₃ : 0 to 8%, preferably Er ₂ O ₃ : 0.4-6%; and/or Nd ₂ O ₃ : 0 to 8%, preferably Nd ₂ O ₃ : 0.4-6%; and/or Cu ₂ O: 0 to 4%, preferably Cu ₂ O: 0.5-3%; and/or Pr ₂ O ₅ : 0 to 8%, preferably Pr ₂ O ₅ : 0.4-6%; and/or CeO ₂ : 0 to 4%, preferably CeO ₂ ：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 glass ceramics according to (56), 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.

(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 microcrystalline glass or the microcrystalline glass article is in a range of 5 to 60% by weight of the microcrystalline glass or the microcrystalline glass 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.

SiO ₂ The 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 used ₂ The content of (b) is less than 46%, the above effect is not significant. Thus, SiO ₂ The lower limit of the content is 46%, and the preferable lower limit is 50%. If SiO ₂ The content is more than 68 percent, the glass smelting difficulty is increased, and the glass molding is not facilitated. Thus, SiO ₂ The 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 included ₂ 。

Al ₂ O ₃ Is 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, Al ₂ O ₃ The lower limit of the content is 11%, preferably 15%, more preferably 16%. On the other hand, if Al ₂ O ₃ The content of (b) exceeds 30%, the difficulty of melting the glass increases. Thus Al ₂ O ₃ The 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 included ₂ O ₃ 。

In some embodiments of the invention, the Al is added by reacting Al with a metal ₂ O ₃ /SiO ₂ Within 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 microcrystalline glass is favorably improvedIon exchange layer depth, surface stress, and vickers hardness of the glass article. Therefore, Al is preferable ₂ O ₃ /SiO ₂ 0.2 to 0.62, more preferably Al ₂ O ₃ /SiO ₂ 0.25 to 0.55, more preferably Al ₂ O ₃ /SiO ₂ 0.3 to 0.5. In some embodiments, Al ₂ O ₃ /SiO ₂ May be 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.62.

Li ₂ O in the present invention promotes melting of the glass raw material, particularly, high Al in the glass composition of the present invention ₂ O ₃ In the case of content; while Li ₂ O 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 contained ₂ O, 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 invention ₂ The 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 included ₂ O。

In the invention, more than 5% of Na is contained ₂ O 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 Na ₂ O, more preferably 6.5% or more of Na ₂ And O. If Na ₂ When 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, Na ₂ The 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% may be included11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18% Na ₂ O。

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

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 by ₂ /(Na ₂ O + 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 preferable ₂ /(Na ₂ O + ZnO) of 2.0 to 8.0, more preferably SiO ₂ /(Na ₂ O + ZnO) of 2.5 to 6.0, more preferablySiO ₂ /

(Na ₂ O + ZnO) of 2.5 to 5.5. In some embodiments, the SiO ₂ /(Na ₂ O + 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 Li ₂ The 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 preferable ₂ O/ZnO is 1.0 or less, and Li is more preferable ₂ O/ZnO is 0.8 or less, and Li is more preferable ₂ The O/ZnO ratio is 0.7 or less. In some embodiments, Li ₂ The 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 metal ₂ O ₃ And if the content 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 invention ₂ O ₃ /(MgO + ZnO) is 2.5 or more, and Al is more preferable ₂ O ₃ /(MgO + ZnO) is 2.5 to 10.0, and Al is more preferable ₂ O ₃ /(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable ₂ O ₃ /

(MgO + ZnO) is 2.7 to 4.0. In some embodiments of the invention, Al ₂ O ₃ The value of/((MgO + ZnO)) can 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.

TiO ₂ The 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 TiO ₂ In order to obtain the above-described effects, it is preferably 2% or more, and more preferably 2.5% or more. If TiO ₂ The 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, TiO ₂ The 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 included ₂ 。

In some embodiments of the present invention, if (MgO + ZnO + Na) ₂ O)/TiO ₂ Below 1.0, the glass becomes poor in melting property and the melting temperature increases, on the other hand, the crystallinities of the crystallized glass and the crystallized glass article decrease; if (MgO + ZnO + Na) ₂ O)/TiO ₂ When 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 invention ₂ O)/TiO ₂ In the range of 1.0 to 10.0. Further, by using (MgO + ZnO + Na) ₂ O)/TiO ₂ Within the range of 1.5-8.0, the haze of the microcrystalline glass and the microcrystalline glass products can be effectively reduced, and the microcrystalline glass products are improvedThe transmittance of the product is more preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 1.5 to 8.0, and more preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ Is 2.0 to 4.0. In some embodiments, (MgO + ZnO + Na) ₂ O)/TiO ₂ The 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 Na ₂ O and TiO ₂ And Li ₂ Ratio Na between total contents of O ₂ O/(TiO ₂ +Li ₂ O) less than 0.5, the transmittance of the glass-ceramic and the glass-ceramic product decreases, and Na) is contained ₂ O/(TiO ₂ +Li ₂ O) exceeds 9.0, the crystallinity of the crystallized glass and the crystallized glass article decreases, and the haze becomes large. Therefore, Na is preferred ₂ O/(TiO ₂ +Li ₂ O) is 0.5 to 9.0, more preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 0.8 to 7.0, and Na is more preferable ₂ O/(TiO ₂ +Li ₂ O) is 1.0 to 5.0. In some embodiments, Na ₂ O/(TiO ₂ +Li ₂ O) 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)/Al ₂ O ₃ Within 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)/Al ₂ O ₃ 0.3 to 0.9, more preferably (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.4 to 0.7. In some embodiments, (TiO) ₂ +ZnO)/Al ₂ O ₃ The value of (b) can 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.

P ₂ O ₅ Contributes to the improvement of the low-temperature melting property of the glass, P ₂ O ₅ And ZrO ₂ And TiO ₂ And 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 excessively ₂ O ₅ The tendency of phase separation of the glass is easily increased, and the chemical stability of the glass is reduced. Thus, P in the present invention ₂ O ₅ The 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 included ₂ O ₅ 。

ZrO ₂ Can reduce the crystallization tendency and ZrO during glass forming ₂ And P ₂ O ₅ And TiO 2 ₂ The 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 excessively ₂ The difficulty of glass melting increases. Thus, ZrO in the invention ₂ The 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) ₂ O ₅ +ZrO ₂ ) 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 height ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 1.1 or less. Further, if (P) ₂ O ₅ +ZrO ₂ ) 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) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable ₂ O ₅ +ZrO ₂ ) the/ZnO is 0.1 to 0.7. In some embodiments, (P) ₂ O ₅ +ZrO ₂ ) 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 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%.

B ₂ O ₃ Helps to optimize the melting properties of the matrix glass, and when the content thereof is too high, the chemical stability of the matrix glass is lowered, and thus B ₂ O ₃ The content of (B) is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably no B is contained ₂ O ₃ . In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% B may be included ₂ O ₃ 。

Ln ₂ O ₃ (Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One or more of) is an optional component for improving the hardness and chemical stability of the glass ceramics, inhibiting glass forming and crystallization, reducing the chemical strengthening performance of the glass and the glass ceramics when the content is excessive, and reducing the chemical strengthening performance of the glass and the glass ceramicsStrength of the article. Ln in the invention ₂ O ₃ The 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 contained ₂ O ₃ And/or does not contain Gd ₂ O ₃ . In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% Ln may be included ₂ O ₃ 。

In some embodiments, the glass, microcrystalline glass or microcrystalline glass product can further comprise 0-2% of a fining agent to improve the defoaming capability of the glass, microcrystalline glass or microcrystalline glass product. The fining agent includes, but is not limited to, Sb ₂ O ₃ 、SnO ₂ 、SnO、CeO ₂ One or more of, F, Cl and Br, preferably Sb ₂ O ₃ 、SnO ₂ SnO 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 included ₂ O ₃ (ii) a And/or does not contain CaO; and/or does not contain F; and/or does not contain Ta ₂ O ₅ 。

PbO and As ₂ O ₃ Are 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 embodiments ₂ O ₃ 。

In some embodiments of the present invention, the substrate glass, microcrystalline glass, or microcrystalline glass article may be made to exhibit different colors by including a colorant in the substrate glass, microcrystalline glass, or microcrystalline glass article having a color, the colorant comprisingComprises the following steps: NiO: 0 to 4 percent; and/or Ni ₂ O ₃ : 0 to 4 percent; and/or a CoO: 0-2%; and/or Co ₂ O ₃ : 0-2%; and/or Fe ₂ O ₃ : 0 to 7 percent; and/or MnO ₂ : 0 to 4 percent; and/or Er ₂ O ₃ : 0-8%; and/or Nd ₂ O ₃ : 0-8%; and/or Cu ₂ O: 0 to 4 percent; and/or Pr ₂ O ₅ : 0-8%; and/or CeO ₂ : 0 to 4 percent. The content of the colorant in percentage by weight and the function thereof are detailed as follows:

NiO and Ni are used for preparing the brown or green matrix glass, the microcrystalline glass or the microcrystalline glass product ₂ O ₃ Or Pr ₂ O ₅ Is a colorant. NiO and Ni ₂ O ₃ For 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 included ₂ O ₃ . NiO and Ni, if used in admixture ₂ O ₃ The 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%, or,3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4% NiO and Ni ₂ O ₃ . Using Pr ₂ O ₅ The 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%, 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% Pr may be included ₂ O ₅ 。

The blue matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses CoO or Co ₂ O ₃ The 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 included ₂ O ₃ . CoO and Co, if used in admixture ₂ O ₃ The 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 included ₂ O ₃ 。

The yellow matrix glass, the microcrystalline glass or the glass ceramic prepared by the inventionMicrocrystalline glass product using Cu ₂ O or CeO ₂ The 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 alone ₂ O 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%, 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% Cu may be included ₂ And O. Using CeO alone ₂ The content is generally 4% or less, preferably 3% or less, and if the content exceeds 4%, the substrate glass, glass ceramics or glass ceramics product has poor 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 included ₂ . At the same time, a small amount of CeO ₂ Added to glass with a defoaming effect, CeO ₂ Can also be used as a clarifying agent in glass. When two 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 included ₂ And Cu ₂ O。

The black or smoky grey matrix glass, glass ceramics or glass ceramics prepared by the invention use F alonee ₂ O ₃ Is a colorant; or using Fe ₂ O ₃ And CoO; or using Fe ₂ O ₃ And Co ₂ O ₃ Two colorants used in combination; or using Fe ₂ O ₃ Three colorants mixed together, CoO and NiO; or using Fe ₂ O ₃ 、Co ₂ O ₃ And NiO. Colorants for the production of black and smoky grey matrix glass, glass ceramics or glass ceramic articles using predominantly Fe ₂ O ₃ Coloration, at a level of 7% or less, preferably 5% or less, with a lower limit of 0.2% or more, and in some embodiments, may comprise 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%, 3.8%, 3.9%, 4%, 4.5%, 5.5%, 6%, 6.5%, 7% Fe ₂ O ₃ . CoO and Co ₂ O ₃ Can absorb visible light to increase the coloring degree of matrix glass, microcrystalline glass or microcrystalline glass products, and is generally combined with Fe ₂ O ₃ The 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 included ₂ O ₃ . 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 MnO ₂ The colorant is used in an amount of generally 4% or less, preferably 3% or less, with the lower limit of the amount being 0.1% or more, e.g., less than 0.1%, and a matrix glass, a glass-ceramic or a glass-ceramicThe glass product has no obvious color. 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 included ₂ 。

Er is used in the pink substrate glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention ₂ O ₃ The content of the colorant used is generally 8% or less, preferably 6% or less. Because of rare earth element Er ₂ O ₃ The 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 included ₂ O ₃ 。

The mauve substrate glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses Nd ₂ O ₃ The content of the colorant used is generally 8% or less, preferably 6% or less. Due to the rare earth element Nd ₂ O ₃ The 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% may be included%, 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 ₂ O ₃ 。

Er is used for the red matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention ₂ O ₃ 、Nd ₂ O ₃ And MnO ₂ The mixed colorant, Er ion in the glass has absorption at 400-500nm, Mn ion has absorption mainly at 500nm, Nd ion has strong absorption mainly at 580nm, and the mixture of the three substances can prepare red matrix glass, microcrystalline glass or microcrystalline glass product ₂ O ₃ And Nd ₂ O ₃ Coloring rare earth, relatively weak coloring ability, Er ₂ O ₃ The usage amount is less than 6 percent, Nd ₂ O ₃ The usage amount is less than 4 percent, MnO ₂ The 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 product or microcrystalline glass having a thickness of 0.55mm has a light transmittance of 85% or more at 550nm, preferably 87% or more, and more preferably 90% or more.

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. Can be added into matrixAntimicrobial components of the glass, glass-ceramic or glass-ceramic article include, but are not limited to, Ag, AgO, Cu, CuO, Cu ₂ O, 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. In the ion exchange process, 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 closer 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 metal ions in the matrix glass. 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., KNO ₃ And NaNO ₃ ) 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 transmittance described herein is the external transmittance, sometimes referred to simply as the transmittance.

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 ] 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 indicates that the crystallized glass product was not broken and received an impact even when the steel ball was dropped from a 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 test is carried out 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 depression ² ) 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 article 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 ^1/2 Above, preferably 1.2MPa · m ^1/2 More preferably 1.3MPa · m or more ^1/2 The above.

6) In some embodiments, the microcrystalline glass article has a Vickers hardness (H) _v ) Is 600kgf/mm ² Above, preferably 650kgf/mm ² Above, more preferably 680kgf/mm ² The 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 microcrystalline glass products shown in tables 4 to 6 below were obtained by chemically strengthening the microcrystalline glass described in tables 1 to 3 according to the chemical strengthening method described above, and were tested according to the performance test method described above.

Table 4.

Table 5.

Table 6.

Claims (80)

1. The microcrystalline glass is characterized by comprising the following components in percentage by weight: SiO 2 ₂ ：46～67％；Al ₂ O ₃ ：11～30％；Na ₂ O：5～18％；ZnO：3～13％；TiO ₂ : 1 to 9% of (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.2 to 1.5.

2. The glass-ceramic according to claim 1, characterized in that it further comprises, in weight percent: li ₂ O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K ₂ O: 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 Ln ₂ O ₃ : 0 to 5 percent; and/or B ₂ O ₃ : 0 to 5 percent; and/or P ₂ O ₅ : 0-6%; and/or ZrO ₂ : 0-6%; and/or a clarifying agent: 0 to 2 percent of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One or more of (a).

3. The microcrystalline glass is characterized in that the components contain SiO ₂ 、Al ₂ O ₃ 、Na ₂ O, ZnO and TiO ₂ The components of which are expressed in weight percent, wherein (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.2 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. Microcrystalline glass having a composition comprising SiO ₂ 、Al ₂ O ₃ And ZnO, the microcrystalline glass contains a spinel crystal phase.

5. Glass-ceramic according to claim 3 or 4, characterized in that its composition is expressed in percentages by weightThe method comprises the following steps: SiO 2 ₂ : 46-67%; and/or Al ₂ O ₃ : 11-30%; and/or Na ₂ O: 5-18%; and/or ZnO: 3-13%; and/or TiO ₂ : 1-9%; and/or Li ₂ O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K ₂ O: 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 Ln ₂ O ₃ : 0 to 5 percent; and/or B ₂ O ₃ : 0 to 5 percent; and/or P ₂ O ₅ : 0-6%; and/or ZrO ₂ : 0-6%; and/or a clarifying agent: 0-2% of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One or more of (a).

6. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition, expressed in weight percentages, is such that: (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.2 to 1.5, preferably (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.3 to 0.9, more preferably (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.4 to 0.7.

7. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition, expressed in weight percentages, is such that: al (Al) ₂ O ₃ /SiO ₂ 0.2 to 0.62, preferably Al ₂ O ₃ /SiO ₂ 0.25 to 0.55, more preferably Al ₂ O ₃ /SiO ₂ 0.3 to 0.5.

8. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition, expressed in weight percentages, is such that: SiO 2 ₂ /(Na ₂ O + ZnO) of 2.0 to 8.0, preferably SiO ₂ /(Na ₂ O + ZnO) of 2.5 to 6.0, more preferably SiO ₂ /(Na ₂ O + ZnO) of 2.5 to 5.5.

9. According to any of claims 1 to 4The microcrystalline glass is characterized by comprising the following components in percentage by weight: li ₂ O/ZnO is 1.0 or less, and Li is preferable ₂ O/ZnO is 0.8 or less, and Li is more preferable ₂ The O/ZnO ratio is 0.7 or less.

10. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition, expressed in weight percentages, is such that: al (Al) ₂ O ₃ /(MgO + ZnO) is 2.5 or more, and Al is preferable ₂ O ₃ /(MgO + ZnO) is 2.5 to 10.0, more preferably Al ₂ O ₃ /(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable ₂ O ₃ The ratio of (MgO + ZnO) is 2.7 to 4.0.

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

12. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition, expressed in weight percentages, is such that: (MgO + ZnO + Na) ₂ O)/TiO ₂ 1.0 to 10.0, preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 1.5 to 8.0, more preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ Is 2.0 to 4.0.

13. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition, expressed in weight percentages, is such that: na (Na) ₂ O/(TiO ₂ +Li ₂ O) is 0.5 to 9.0, preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 0.8 to 7.0, more preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 1.0 to 5.0.

14. A glass-ceramic according to any one of claims 1 to 4, characterized in that its composition, expressed in weight percentages, is such that: (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 1.1 or less, preferably (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable ₂ O ₅ +ZrO ₂ ) the/ZnO is 0.1 to 0.7.

15. A glass-ceramic according to any one of claims 1 to 4, characterized in that the composition thereof, expressed in weight percentage, comprises: SiO 2 ₂ : 50 to 66%, preferably SiO ₂ : 50-64%; and/or Al ₂ O ₃ : 15-28%, preferably Al ₂ O ₃ : 16-25%; and/or Na ₂ O: 6-15%, preferably Na ₂ O: 6.5-12%; and/or ZnO: 4-12%, preferably ZnO: 5-10%; and/or TiO ₂ : 2-8%, preferably TiO ₂ : 2.5-6.5%; and/or Li ₂ O: 0 to 5%, preferably Li ₂ O: 0 to 3 percent; and/or MgO: 0-3%, preferably MgO: 0 to 1.5 percent; and/or K ₂ O: 0 to 3%, preferably K ₂ O: 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 Ln ₂ O ₃ : 0 to 4%, preferably Ln ₂ O ₃ : 0 to 3 percent; and/or B ₂ O ₃ : 0 to 3%, preferably B ₂ O ₃ : 0 to 1 percent; and/or P ₂ O ₅ : 0 to 4%, preferably P ₂ O ₅ : 0.2-3%; and/or ZrO ₂ : 0 to 5%, preferably ZrO ₂ : 0 to 3 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One or more of (a).

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

17. The microcrystalline glass according to any one of claims 1 to 4, characterised in that the component does not contain B ₂ O ₃ (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 Ta ₂ O ₅ (ii) a And/or do not contain La ₂ O ₃ (ii) a And/or does not contain Gd ₂ O ₃ 。

18. The 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 glass-ceramic according to any one of claims 1 to 4, wherein the total amount of the crystalline phases in the glass-ceramic 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 glass-ceramic.

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, more preferably 0.1% or less; and/or microcrystalline glass with a thickness of 0.55mm, wherein the average transmittance at a wavelength of 400-800 nm is more than 85%, preferably more than 86%, and 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 glass-ceramic according to any one of claims 1 to 4, wherein the glass-ceramic 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 the ball drop test height is 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.

25. A glass-ceramic according to claim 24, characterized in that its colouring agents, expressed in weight percentage, comprise: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni ₂ O ₃ : 0 to 4%, preferably Ni ₂ O ₃ : 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co ₂ O ₃ : 0 to 2%, preferably Co ₂ O ₃ : 0.05-1.8%; and/or Fe ₂ O ₃ : 0 to 7%, preferably Fe ₂ O ₃ : 0.2-5%; and/or MnO ₂ : 0 to 4%, preferably MnO ₂ : 0.1-3%; and/or Er ₂ O ₃ : 0 to 8%, preferably Er ₂ O ₃ : 0.4-6%; and/or Nd ₂ O ₃ : 0 to 8%, preferably Nd ₂ O ₃ : 0.4-6%; and/or Cu ₂ O: 0 to 4%, preferably Cu ₂ O: 0.5-3%; and/or Pr ₂ O ₅ : 0 to 8%, preferably Pr ₂ O ₅ : 0.4-6%; and/or CeO ₂ : 0 to 4%, preferably CeO ₂ ：0.5～3％。

26. A crystallized glass product comprising the crystallized glass according to any one of claims 1 to 25.

27. A microcrystalline glass product, characterized in that its composition, expressed in weight percent, contains: SiO 2 ₂ ：46～67％；Al ₂ O ₃ ：11～30％；Na ₂ O：5～18％；ZnO：3～13％；TiO ₂ ：1～9％。

28. A crystallized glass article according to claim 27, wherein the composition further comprises, in weight percent: li ₂ O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K ₂ O: 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 Ln ₂ O ₃ : 0 to 5 percent; and/or B ₂ O ₃ : 0 to 5 percent; and/or P ₂ O ₅ : 0-6%; and/or ZrO ₂ : 0-6%; and/or a clarifying agent: 0 to 2 percent of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One or more of (a).

29. A microcrystalline glass product according to any of claims 27 or 28, characterised in that its composition is expressed in weight% (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.2 to 1.5, preferably (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.3 to 0.9, more preferably (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.4 to 0.7; and/or Al ₂ O ₃ /SiO ₂ 0.2 to 0.62, preferably Al ₂ O ₃ /SiO ₂ 0.25 to 0.55, more preferably Al ₂ O ₃ /SiO ₂ 0.3 to 0.5; and/or SiO ₂ /(Na ₂ O + ZnO) of 2.0 to 8.0, preferably SiO ₂ /(Na ₂ O + ZnO) of 2.5 to 6.0, more preferably SiO ₂ /(Na ₂ O + ZnO) is 2.5 to 5.5; and/or Li ₂ O/ZnO is 1.0 or less, and Li is preferred ₂ O/ZnO is 0.8 or less, and Li is more preferable ₂ O/ZnO is 0.7 or less; and/or Al ₂ O ₃ and/(MgO + ZnO) is 2.5 or more, preferably Al ₂ O ₃ /(MgO + ZnO) is 2.5 to 10.0, more preferably Al ₂ O ₃ /(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable ₂ O ₃ /(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) ₂ O)/TiO ₂ 1.0 to 10.0, preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 1.5 to 8.0, more preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 2.0 to 4.0; and/or Na ₂ O/(TiO ₂ +Li ₂ O) is 0.5 to 9.0, preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 0.8 to 7.0, more preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 1.0 to 5.0; and/or (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 1.1 or less, preferably (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable ₂ O ₅ +ZrO ₂ ) the/ZnO is 0.1 to 0.7.

30. A crystallized glass product according to any of claims 27 or 28, characterized in that its composition, expressed in weight percentage, contains: SiO 2 ₂ : 50-66%, preferably SiO ₂ : 50-64%; and/or Al ₂ O ₃ : 15 to 28%, preferably Al ₂ O ₃ : 16-25%; and/or Na ₂ O: 6-15%, preferably Na ₂ O: 6.5-12%; and/or ZnO: 4-12%, preferably ZnO: 5-10%; and/or TiO ₂ : 2-8%, preferably TiO ₂ : 2.5-6.5%; and/or Li ₂ O: 0 to 5%, preferably Li ₂ O: 0 to 3 percent; and/or MgO: 0-3%, preferably MgO: 0 to 1.5 percent; and/or K ₂ O: 0 to 3%, preferably K ₂ O: 0.5-2.5%; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0 to 3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or Ln ₂ O ₃ : 0 to 4%, preferably Ln ₂ O ₃ : 0 to 3 percent; and/or B ₂ O ₃ : 0 to 3%, preferably B ₂ O ₃ : 0 to 1 percent; and/or P ₂ O ₅ ：0～4％，Preferably P ₂ O ₅ : 0.2-3%; and/or ZrO ₂ : 0 to 5%, preferably ZrO ₂ : 0 to 3 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One or more of (a).

31. A crystallized glass product according to any of claims 27 or 28, characterized in that its composition, expressed in weight percentage, contains: AgO: 0-2%, preferably AgO: 0 to 1 percent; and/or CuO: 0 to 2%, preferably CuO: 0 to 1 percent; and/or Cu ₂ O: 0 to 2%, preferably Cu ₂ O：0～1％。

32. A crystallized glass article according to any one of claims 27 or 28, wherein the composition does not contain B ₂ O ₃ (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 Ta ₂ O ₅ (ii) a And/or do not contain La ₂ O ₃ (ii) a And/or does not contain Gd ₂ O ₃ 。

33. A glass-ceramic article according to any of claims 27 or 28, characterized in that the glass-ceramic comprises a spinel crystalline 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.

34. A crystallized glass product according to any one of claims 27 or 28, wherein the total amount of crystalline 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.

35. A glass-ceramic article according to any of claims 27 or 28, characterized in that the glass-ceramic comprises a spinel crystalline phase having a higher weight percentage than other crystalline phases, preferably 10-50% by weight of the glass-ceramic, more preferably 15-40% by weight of the glass-ceramic.

36. The glass-ceramic article according to any one of claims 27 or 28, wherein the glass-ceramic does not contain quartz and quartz solid solution crystalline phases; and/or does not contain a lithium silicate crystalline phase.

37. A crystallized glass article according to any one of claims 26 to 28, 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 has a transmittance at a wavelength of 550nm of 85% or more, preferably 87% or more, and more preferably 90% or more.

38. A crystallized glass product according to any one of claims 26 to 28, 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.

39. A crystallized glass product according to any one of claims 26 to 28, 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.

40. A crystallized glass product according to any one of claims 26 to 28, wherein the crystallized glass product has a ball drop test height of 900mm or more, preferably 1000mm or more, and more preferably 1100mm or more; and/or a fracture toughness of 1MPam ^1/2 Above, preferably 1.2MPa · m ^1/2 More preferably 1.3MPa · m or more ^1/2 The above; and/or a Vickers hardness of 600kgf/mm ² Above, preferably 650kgf/mm ² Above, more preferably 680kgf/mm ² The above; and/or a four-point bending strength of 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more.

41. The glass cover plate is characterized by being made of the microcrystalline glass of any one of claims 1 to 25 and/or the microcrystalline glass product of any one of claims 26 to 40.

42. 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 40.

43. A display device comprising the crystallized glass according to any one of claims 1 to 25, and/or comprising the crystallized glass product according to any one of claims 26 to 40, and/or comprising the glass cover plate according to claim 41, and/or comprising the glass component according to claim 42.

44. 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 40, and/or comprising the glass cover plate according to claim 41, and/or comprising the glass component according to claim 42.

45. A method for producing a glass ceramic according to any one of claims 1 to 25, characterized by comprising: forming matrix glass, and forming microcrystalline glass on the matrix glass through a crystallization process.

46. The method for producing a glass-ceramic according to claim 45, wherein a melting temperature of a matrix glass to be formed is 1250 to 1650 ℃, preferably 1380 to 1600 ℃; and/or the melting time is 5-24 hours, preferably 8-12 hours.

47. The method for manufacturing glass ceramic according to claim 45, wherein the crystallization process includes the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 600-750 ℃, preferably 650-700 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

48. The method for manufacturing glass ceramic according to claim 45, 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.

49. The method for manufacturing glass-ceramic according to claim 48, 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.

50. A method for producing a crystallized glass product according to any one of claims 26 to 40, which comprises the steps of: forming matrix glass, forming microcrystalline glass by the crystallization process of the matrix glass, and forming a microcrystalline glass product by the chemical strengthening process of the microcrystalline glass.

51. The method for producing a glass-ceramic article according to claim 50, wherein the melting temperature for forming the matrix glass is 1250 to 1650 ℃, preferably 1380 to 1600 ℃; and/or the melting time is 5-24 hours, preferably 8-12 hours.

52. The method for manufacturing a glass-ceramic article according to claim 50, wherein the crystallization process comprises the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 600-750 ℃, preferably 650-700 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

53. The method of manufacturing a crystallized glass article according to claim 50, 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.

54. The method of manufacturing a crystallized glass article according to claim 53, 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.

55. The method for manufacturing a crystallized glass article according to claim 50, 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.

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

forming a matrix glass, the components of the matrix glass, expressed in weight percent, comprising: SiO 2 ₂ ：46～67％；Al ₂ O ₃ ：11～30％；Na ₂ O：5～18％；ZnO：3～13％；TiO ₂ : 1 to 9% of (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.2 to 1.5;

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

57. The method for producing a crystallized glass product according to claim 56, wherein the matrix glass further contains, in terms of the components by weight: li ₂ O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K ₂ O: 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 Ln ₂ O ₃ : 0 to 5 percent; and/or B ₂ O ₃ : 0 to 5 percent; and/or P ₂ O ₅ : 0-6%; and/or ZrO ₂ : 0-6%; and/or a clarifying agent: 0-2% of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One or more of (a).

58. A method for manufacturing a glass-ceramic article according to any of claims 56 or 57, wherein the matrix glass comprises, in weight percent: SiO 2 ₂ : 50-66%, preferably SiO ₂ : 50-64%; and/or Al ₂ O ₃ : 15-28%, preferably Al ₂ O ₃ : 16-25%; and/or Na ₂ O: 6-15%, preferably Na ₂ O: 6.5-12%; and/or ZnO: 4-12%, preferably ZnO: 5-10%; and/or TiO ₂ : 2-8%, preferably TiO ₂ : 2.5-6.5%; and/or Li ₂ O: 0 to 5%, preferably Li ₂ O: 0 to 3 percent; and/or MgO: 0-3%, preferably MgO: 0 to 1.5 percent; and/orK ₂ O: 0 to 3%, preferably K ₂ O: 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 Ln ₂ O ₃ : 0 to 4%, preferably Ln ₂ O ₃ : 0 to 3 percent; and/or B ₂ O ₃ : 0 to 3%, preferably B ₂ O ₃ : 0 to 1 percent; and/or P ₂ O ₅ : 0 to 4%, preferably P ₂ O ₅ : 0.2-3%; and/or ZrO ₂ : 0 to 5%, preferably ZrO ₂ : 0 to 3 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One or more of (a).

59. A method for manufacturing a glass-ceramic article according to any of claims 56 or 57, wherein the matrix glass has a composition expressed in weight percentage, wherein: (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.3 to 0.9, preferably (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.4 to 0.7; and/or Al ₂ O ₃ /SiO ₂ 0.2 to 0.62, preferably Al ₂ O ₃ /SiO ₂ 0.25 to 0.55, more preferably Al ₂ O ₃ /SiO ₂ 0.3 to 0.5; and/or SiO ₂ /(Na ₂ O + ZnO) of 2.0 to 8.0, preferably SiO ₂ /(Na ₂ O + ZnO) of 2.5 to 6.0, more preferably SiO ₂ /(Na ₂ O + ZnO) is 2.5-5.5; and/or Li ₂ O/ZnO is 1.0 or less, and Li is preferred ₂ O/ZnO is 0.8 or less, and Li is more preferable ₂ O/ZnO is less than 0.7; and/or Al ₂ O ₃ /(MgO + ZnO) is 2.5 or more, and Al is preferable ₂ O ₃ /(MgO + ZnO) is 2.5 to 10.0, more preferably Al ₂ O ₃ /(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable ₂ O ₃ /(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) ₂ O)/TiO ₂ 1.0 to 10.0, preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 1.5 to 8.0, more preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 2.0 to 4.0; and/or Na ₂ O/(TiO ₂ +Li ₂ O) is 0.5 to 9.0, preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 0.8 to 7.0, more preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 1.0 to 5.0; and/or (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 1.1 or less, preferably (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 0.1 to 1.0, more preferably (P) ₂ O ₅ +ZrO ₂ ) the/ZnO is 0.1 to 0.7.

60. A method for manufacturing a glass-ceramic article according to any of claims 56 or 57, wherein the matrix glass comprises, in weight percent: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni ₂ O ₃ : 0 to 4%, preferably Ni ₂ O ₃ : 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co ₂ O ₃ : 0 to 2%, preferably Co ₂ O ₃ : 0.05-1.8%; and/or Fe ₂ O ₃ : 0 to 7%, preferably Fe ₂ O ₃ : 0.2-5%; and/or MnO ₂ : 0 to 4%, preferably MnO ₂ : 0.1-3%; and/or Er ₂ O ₃ : 0 to 8%, preferably Er ₂ O ₃ : 0.4-6%; and/or Nd ₂ O ₃ : 0 to 8%, preferably Nd ₂ O ₃ : 0.4-6%; and/or Cu ₂ O: 0 to 4%, preferably Cu ₂ O: 0.5-3%; and/or Pr ₂ O ₅ : 0 to 8%, preferably Pr ₂ O ₅ : 0.4-6%; and/or CeO ₂ : 0 to 4%, preferably CeO ₂ ：0.5～3％。

61. The method for producing a glass-ceramic article according to any one of claims 56 and 57, wherein a melting temperature for forming the matrix glass is 1250 to 1650 ℃, preferably 1380 to 1600 ℃; and/or the melting time is 5-24 hours, preferably 8-12 hours.

62. A method of manufacturing a glass-ceramic article according to any of claims 56 or 57, wherein the crystallization process comprises the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 600-750 ℃, preferably 650-700 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

63. A method of manufacturing a glass-ceramic article according to any of claims 56 or 57, 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.

64. The method of manufacturing a crystallized glass article according to claim 63, 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.

65. A method of manufacturing a glass-ceramic article according to any of claims 56 or 57, 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 substrate in a salt bath of a mixture of K salt and Na salt at a temperature of about 350 ℃ to 450 ℃ for 0.5 to 8 hours to perform ion exchange, preferably for 1 to 4 hours.

66. A method for manufacturing a glass-ceramic article according to any one of claims 56 or 57, wherein the total amount of crystal phases in the glass-ceramic article is 5-60 wt%, preferably 10-50 wt%, more preferably 15-40 wt% of the glass-ceramic article.

67. A method of manufacturing a glass-ceramic article according to any of claims 56 or 57, 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.

68. The method for producing a crystallized glass article according to any one of claims 56 and 57, 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 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-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 microcrystalline glass product is 800MPa or more, preferably 1000MPa or more, and 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 ^1/2 Above, preferably 1.2MPa · m ^1/2 More preferably 1.3MPa · m or more ^1/2 The above; and/or the Vickers hardness of the glass-ceramic article is 600kgf/mm ² Above, preferably 650kgf/mm ² Above, more preferably 680kgf/mm ² The 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.

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

forming a matrix glass, the matrix glass having a composition, expressed in weight percent, comprising: SiO 2 ₂ ：46～67％；Al ₂ O ₃ ：11～30％；Na ₂ O：5～18％；ZnO：3～13％；TiO ₂ : 1 to 9% of (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.2 to 1.5;

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

70. The method for producing a glass-ceramic according to claim 69, wherein the matrix glass further contains, in terms of the components by weight: li ₂ O: 0-6%; and/or MgO: 0 to 5.5 percent; and/or K ₂ O: 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 Ln ₂ O ₃ : 0 to 5 percent; and/or B ₂ O ₃ : 0 to 5 percent; and/or P ₂ O ₅ : 0-6%; and/or ZrO ₂ : 0-6%; and/or a clarifying agent: 0-2% of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One or more of (a).

71. A method for producing glass-ceramic according to any one of claims 69 or 70, wherein the matrix glass comprises, in terms of weight percent, the following: SiO 2 ₂ : 50-66%, preferably SiO ₂ : 50-64%; and/or Al ₂ O ₃ : 15-28%, preferably Al ₂ O ₃ : 16-25%; and/or Na ₂ O: 6-15%, preferably Na ₂ O: 6.5-12%; and/or ZnO: 4-12%, preferably ZnO: 5-10%; and/or TiO ₂ : 2-8%, preferably TiO ₂ : 2.5-6.5%; and/or Li ₂ O: 0 to 5%, preferably Li ₂ O: 0 to 3 percent; and/or MgO: 0-3%, preferably MgO: 0 to 1.5 percent; and/or K ₂ O: 0 to 3%, preferably K ₂ O: 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 Ln ₂ O ₃ : 0 to 4%, preferably Ln ₂ O ₃ : 0 to 3 percent; and/or B ₂ O ₃ : 0 to 3%, preferably B ₂ O ₃ : 0 to 1 percent; and/or P ₂ O ₅ : 0 to 4%, preferably P ₂ O ₅ : 0.2-3%; and/or ZrO ₂ : 0 to 5%, preferably ZrO ₂ : 0 to 3 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln ₂ O ₃ Is La ₂ O ₃ 、Gd ₂ O ₃ 、Y ₂ O ₃ 、Yb ₂ O ₃ One or more of (a).

72. A method for manufacturing glass-ceramic according to any one of claims 69 or 70, wherein the matrix glass has a composition expressed in weight percentage, wherein: (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.3 to 0.9, preferably (TiO) ₂ +ZnO)/Al ₂ O ₃ 0.4 to 0.7; and/or Al ₂ O ₃ /SiO ₂ 0.2 to 0.62, preferably Al ₂ O ₃ /SiO ₂ 0.25 to 0.55, more preferably Al ₂ O ₃ /SiO ₂ 0.3 to 0.5; and/or SiO ₂ /(Na ₂ O + ZnO) of 2.0 to 8.0, preferably SiO ₂ /(Na ₂ O + ZnO) of 2.5 to 6.0, more preferably SiO ₂ /(Na ₂ O + ZnO) is 2.5 to 5.5; and/or Li ₂ O/ZnO is 1.0 or less, and Li is preferable ₂ O/ZnO is 0.8 or less, and Li is more preferable ₂ O/ZnO is 0.7 or less; and/or Al ₂ O ₃ /(MgO + ZnO) is 2.5 or more, and Al is preferable ₂ O ₃ /(MgO + ZnO) is 2.5 to 10.0, more preferably Al ₂ O ₃ /(MgO + ZnO) is 2.6 to 6.0, and Al is more preferable ₂ O ₃ /(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) ₂ O)/TiO ₂ 1.0 to 10.0, preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 1.5 to 8.0, more preferably (MgO + ZnO + Na) ₂ O)/TiO ₂ 2.0 to 4.0; and/or Na ₂ O/(TiO ₂ +Li ₂ O) is 0.5 to 9.0, preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 0.8 to 7.0, more preferably Na ₂ O/(TiO ₂ +Li ₂ O) is 1.0 to 5.0; and/or (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 1.1 or less, preferably (P) ₂ O ₅ +ZrO ₂ ) The content of/ZnO is 0.1 to 1.0, and (P) is more preferable ₂ O ₅ +ZrO ₂ ) the/ZnO is 0.1 to 0.7.

73. A method for producing glass-ceramic according to any one of claims 69 or 70, wherein the matrix glass comprises, in terms of weight percent, the following: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni ₂ O ₃ : 0 to 4%, preferably Ni ₂ O ₃ : 0.1-3%; and/or a CoO: 0 to 2%, preferably CoO: 0.05-1.8%; and/or Co ₂ O ₃ : 0 to 2%, preferably Co ₂ O ₃ : 0.05-1.8%; and/or Fe ₂ O ₃ : 0 to 7%, preferably Fe ₂ O ₃ : 0.2-5%; and/or MnO ₂ : 0 to 4%, preferably MnO ₂ : 0.1-3%; and/or Er ₂ O ₃ : 0 to 8%, preferably Er ₂ O ₃ : 0.4-6%; and/or Nd ₂ O ₃ : 0 to 8%, preferably Nd ₂ O ₃ : 0.4-6%; and/or Cu ₂ O: 0 to 4%, preferably Cu ₂ O: 0.5-3%; and/or Pr ₂ O ₅ : 0 to 8%, preferably Pr ₂ O ₅ : 0.4-6%; and/or CeO ₂ : 0 to 4%, preferably CeO ₂ ：0.5～3％。

74. The method for producing a glass-ceramic according to any one of claims 69 to 70, wherein a melting temperature at which the matrix glass is formed is 1250 to 1650 ℃, preferably 1380 to 1600 ℃; and/or the melting time is 5-24 hours, preferably 8-12 hours.

75. A method for manufacturing crystallized glass according to any one of claims 69 to 70, wherein the crystallization process includes the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 600-750 ℃, preferably 650-700 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

76. A method for manufacturing crystallized glass according to any one of claims 69 to 70, 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.

77. The method for manufacturing glass-ceramic according to claim 76, 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.

78. A method for manufacturing glass ceramics according to any of claims 69 or 70, wherein the total amount of crystal phases in the glass ceramics accounts for 5-60% by weight of the glass ceramics, preferably 10-50% by weight of the glass ceramics, and more preferably 15-40% by weight of the glass ceramics.

79. A method of producing a glass ceramic according to any one of claims 69 to 70, wherein the glass ceramic contains 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.

80. The method for producing a crystallized glass according to any one of claims 69 to 70, 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.