CN111943514A

CN111943514A - Glass-ceramic and glass-ceramic article

Info

Publication number: CN111943514A
Application number: CN202010604237.6A
Authority: CN
Inventors: 原保平; 于天来; 蒋焘; 粟勇
Original assignee: CDGM Glass Co Ltd
Current assignee: Huawei Technologies Co Ltd; CDGM Glass Co Ltd
Priority date: 2020-06-29
Filing date: 2020-06-29
Publication date: 2020-11-17
Anticipated expiration: 2040-06-29
Also published as: CN111943514B

Abstract

The invention provides a glass ceramic, which comprises the following components in percentage by mole: SiO 2₂：48～65％；Al₂O₃：10～20％；Li₂O：12～29％；ZnO：0.1～8％；P₂O₅：0.1～6.5％；ZrO₂: 0.1 to 8% of Al₂O₃/SiO₂0.18 to 0.38. Through reasonable component design, the glass ceramic obtained by the invention is suitable for chemical strengthening; meanwhile, the glass ceramic and the glass ceramic product obtained by the invention have excellent mechanical properties and meet the use requirements of display equipment or electronic equipment.

Description

Glass-ceramic and glass-ceramic article

Technical Field

The invention relates to a glass ceramic, in particular to a glass ceramic capable of being chemically strengthened.

Background

In recent years, with the rise and development of consumer electronics, glass is widely used in such electronic devices as a transparent and good-performance material. Devices such as LED and LCD displays and computer monitors may have "touch" functionality which necessitates the glass used therein to be in contact with various objects such as a user's finger and/or a stylus device, and as such, the glass needs to be sufficiently strong and chemically stable to withstand normal contact without damage. In addition, such glass is also applicable to portable electronic products, such as mobile phones, tablet computers, personal media terminals, etc., where the glass needs 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 properties of the glass.

The glass ceramic has physical properties that cannot be obtained by ordinary glass due to the crystals dispersed therein, and has significant advantages in bending resistance, abrasion resistance, and the like, compared to ordinary glass. Based on the above advantages, glass ceramics are currently applied to display devices or electronic devices with high requirements on drop resistance, pressure resistance, scratch resistance and the like. The research in the prior art finds that the glass ceramic treated by the chemical strengthening process can obtain more excellent mechanical properties, but the glass ceramic on the market at present is not easy to be chemically strengthened, or the properties of the glass ceramic after chemical strengthening are difficult to meet the requirements of being applied to display equipment or electronic equipment. Therefore, development of a glass ceramic suitable for chemical strengthening and having excellent mechanical properties has been demanded in the development of the times.

Disclosure of Invention

The invention aims to provide a glass ceramic which has excellent mechanical properties and is suitable for chemical strengthening.

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

(1) glass-ceramic, the composition of which, expressed in mole percent, contains: SiO 2₂：48～65％；Al₂O₃：10～20％；Li₂O：12～29％；ZnO：0.1～8％；P₂O₅：0.1～6.5％；ZrO₂: 0.1 to 8% of Al₂O₃/SiO₂0.18 to 0.38.

(2) The glass-ceramic according to (1), whose composition, expressed in mole percent, further comprises: na (Na)₂O: 0 to 4 percent; and/or MgO: 0 to 7 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or TiO₂: 0 to 4 percent; and/or a clarifying agent: 0 to 1 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(3) The glass ceramic contains quartz and quartz solid solution crystal phase, and the components of the glass ceramic contain SiO₂、Al₂O₃、Li₂O, ZnO and ZrO₂The composition of the material comprises, in mole percent, 0-7% of MgO, wherein: al (Al)₂O₃/SiO₂0.18 to 0.38 (ZrO)₂+MgO+ZnO)/Al₂O₃0.15 to 1.5.

(4) The glass-ceramic according to (3), whose composition, expressed in mole percent, contains: SiO 2₂: 48-65%; and/or Al₂O₃: 10-20%; and/or Na₂O: 0 to 4 percent; and/or ZnO: 0.1-8%; and/or TiO₂: 0 to 4 percent; and/or Li₂O: 12-29%; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or P₂O₅: 0.1-6.5%; and/or ZrO₂: 0.1-8%; and/or a clarifying agent: 0 to 1 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(5) Glass-ceramics, the composition of which, expressed in mole percent, is represented by SiO₂：48～65％；Al₂O₃：10～20％；Li₂O：12～29％；ZnO：0.1～8％；P₂O₅：0.1～6.5％；ZrO₂：0.1～8％；Na₂O：0～4％；MgO：0～7％；K₂O：0～5％；SrO：0～3％；BaO：0～3％；CaO：0～3％；Ln₂O₃：0～5％；B₂O₃：0～5％；TiO₂: 0 to 4 percent; clarificationPreparation: 0 to 1 percent of the composition, the Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(6) The glass-ceramic according to any one of (1) to (5), whose composition is expressed in mol%, wherein: al (Al)₂O₃/SiO₂0.18 to 0.38; and/or ZnO/Li₂O is 0.03 to 0.55; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.03 to 0.22; and/or P₂O₅/Al₂O₃0.08 to 0.4; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.15 to 1.5; and/or (Li)₂O+ZrO₂)/SiO₂0.2 to 0.7; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.25 to 0.8.

(7) The glass-ceramic according to any one of (1) to (6), whose composition is expressed in mol%, wherein: SiO 2₂: 50-62%; and/or Al₂O₃: 11.5-18%; and/or Na₂O: 0 to 3 percent; and/or ZnO: 1-6%; and/or TiO₂: 0-2%; and/or Li₂O: 14-24%; and/or MgO: 1.5-6%; and/or K₂O: 0 to 3.5 percent; and/or SrO: 0-2%; and/or BaO: 0-2%; and/or CaO: 0-2%; and/or Ln₂O₃: 0-2%; and/or B₂O₃: 0 to 3 percent; and/or P₂O₅: 1-4.5%; and/or ZrO₂: 0.5-7.5%; and/or a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(8) The glass-ceramic according to any one of (1) to (7), whose composition is expressed in mol%, wherein: al (Al)₂O₃/SiO₂0.2 to 0.35; and/or ZnO/Li₂O is 0.05 to 0.4; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.05 to 0.18; and/or P₂O₅/Al₂O₃0.08 to 0.3; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.3 to 1.0; and/or (Li)₂O+ZrO₂)/SiO₂0.25 to 0.55; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.3 to 0.65.

(9) The glass-ceramic according to any one of (1) to (8), whose composition is expressed in mol%, wherein: SiO 2₂: 52-58%; and/or Al₂O₃: 13-16%; and/or Na₂O: 0-2%; and/or ZnO: 1-6%; and/or TiO₂: 0 to 1.5 percent; and/or Li₂O: 16-21%; and/or MgO: 1.5-4.5%; and/or K₂O: 0 to 2.5 percent; and/or SrO: 0 to 1.5 percent; and/or BaO: 0 to 1 percent; and/or CaO: 0 to 1 percent; and/or Ln₂O₃: 0 to 1 percent; and/or B₂O₃: 0 to 1 percent; and/or P₂O₅: 1.5-4%; and/or ZrO₂: 1-6%; and/or a clarifying agent: 0 to 0.25 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(10) The glass-ceramic according to any one of (1) to (9), whose composition is expressed in mol%, wherein: al (Al)₂O₃/SiO₂0.23 to 0.3; and/or ZnO/Li₂O is 0.08 to 0.25; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.06 to 0.15; and/or P₂O₅/Al₂O₃0.1 to 0.25; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.4 to 0.75; and/or (Li)₂O+ZrO₂)/SiO₂0.3 to 0.5; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.35 to 0.55.

(11) The glass-ceramic according to any one of (1) to (10), whose composition is expressed in mol%, wherein: k₂O: 0-2%; and/or ZnO: 1.5-4.5%; and/or P₂O₅: 1.8-3.5%; and/or ZrO₂：1～5％。

(12) According to(1) The glass-ceramic according to any one of (1) to (11), wherein B is not contained in the composition₂O₃(ii) a And/or does not contain CaO; and/or no BaO; and/or does not contain SrO; and/or does not contain TiO₂(ii) a And/or do not contain La₂O₃(ii) a And/or does not contain Gd₂O₃。

(13) The glass-ceramic according to any one of (1) to (12), wherein the glass-ceramic contains quartz and a quartz solid solution; and/or eucryptite; and/or lithium zinc phosphate; and/or petalite; and/or a lithium silicate crystalline phase.

(14) The glass ceramic according to any one of (1) to (13), wherein the total amount of crystal phases in the glass ceramic is 10 to 80 wt%, preferably 15 to 75 wt%, and more preferably 20 to 70 wt% of the glass ceramic.

(15) The glass ceramic according to any one of (1) to (14), wherein the glass ceramic contains a crystal phase of quartz or a quartz solid solution, and the crystal phase of quartz or a quartz solid solution has a weight percentage higher than that of other crystal phases, preferably the crystal phase of quartz or a quartz solid solution accounts for 20 to 70% by weight of the glass ceramic, more preferably the crystal phase of quartz or a quartz solid solution accounts for 25 to 65% by weight of the glass ceramic, and even more preferably the crystal phase of quartz or a quartz solid solution accounts for 30 to 60% by weight of the glass ceramic.

(16) The glass-ceramic according to any one of (1) to (15), wherein petalite is not contained in the glass-ceramic; and/or does not contain a lithium silicate crystalline phase.

(17) The glass ceramic according to any one of (1) to (16), wherein the glass ceramic having a thickness of 0.6mm has a haze of 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and still more preferably 0.1% or less; and/or 0.6mm thick glass ceramic, the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 87% or more, more preferably 89% or more; and/or a glass ceramic having a thickness of 0.6mm, and has a transmittance at a wavelength of 550nm of 85% or more, preferably 90% or more, and more preferably 91% or more.

(18) The glass-ceramic according to any one of (1) to (17), wherein the glass-ceramic has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more; and/or a crystal grain size of 50nm or less, preferably 40nm or less, more preferably 30nm or less; and/or a ball drop test height of 1000mm or more, preferably 1100mm or more, more preferably 1200mm or more.

(19) The glass-ceramic according to any one of (1) to (18), wherein the glass-ceramic has a thermal expansion coefficient of 70X 10^-7/K～120×10^-7Preferably 75X 10,/K^-7/K～110×10^-7More preferably 80X 10,/K^-7/K～100×10^-7K; and/or the refractive index is 1.51 to 1.57, preferably 1.52 to 1.56, and more preferably 1.53 to 1.55.

(20) The glass-ceramic according to any one of (1) to (19), wherein the glass-ceramic further contains a colorant, whereby the glass-ceramic can be rendered into different colors.

(21) The glass-ceramic according to (20), wherein the coloring agent comprises, in mol%: NiO: 0-2%; and/or Ni₂O₃: 0-2%; and/or a CoO: 0 to 1 percent; and/or Co₂O₃: 0 to 1 percent; and/or Fe₂O₃: 0 to 4 percent; and/or MnO₂: 0-2%; and/or Er₂O₃: 0 to 4 percent; and/or Nd₂O₃: 0 to 4 percent; and/or Cu₂O: 0-2%; and/or Pr₂O₅: 0 to 4 percent; and/or CeO₂：0～2％。

(22) The glass-ceramic according to any one of (1) to (4), wherein the glass-ceramic further contains an antimicrobial component of 2% or less, preferably 1% or less, in terms of mole percent, and the antimicrobial component is Ag, AgO, Cu, CuO, Cu₂One or more of O.

(23) A glass-ceramic article comprising the glass-ceramic according to any one of (1) to (22).

(24) A glass-ceramic article having a composition, expressed in mole percent, comprising: SiO 2₂：48～65％；Al₂O₃：10～20％；Li₂O：12～29％；ZnO：0.1～8％；P₂O₅：0.1～6.5％；ZrO₂: 0.1 to 8% of Al₂O₃/SiO₂0.18 to 0.38.

(25) The glass-ceramic article of (24), having a composition, expressed in mole percent, further comprising: na (Na)₂O: 0 to 4 percent; and/or MgO: 0 to 7 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or TiO₂: 0 to 4 percent; and/or a clarifying agent: 0 to 1 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(26) A glass-ceramic article having a composition, expressed in mole percent, comprising: SiO 2₂：48～65％；Al₂O₃：10～20％；Li₂O：12～29％；ZnO：0.1～8％；P₂O₅：0.1～6.5％；ZrO₂：0.1～8％；Na₂O：0～4％；MgO：0～7％；K₂O：0～5％；SrO：0～3％；BaO：0～3％；CaO：0～3％；Ln₂O₃：0～5％；B₂O₃：0～5％；TiO₂: 0 to 4 percent; a clarifying agent: 0 to 1 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(27) The glass-ceramic article according to any one of (24) to (26), having a composition, expressed in terms of mole percent, wherein: al (Al)₂O₃/SiO₂0.18 to 0.38; and/or ZnO/Li₂O is 0.03 to 0.55; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.03 to 0.22; and/or P₂O₅/Al₂O₃0.08 to 0.4; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.15 to 1.5; and/or (Li)₂O+ZrO₂)/SiO₂0.2 to 0.7; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.25 to 0.8.

(28) The glass-ceramic article according to any one of (24) to (27), having a composition, expressed in terms of mole percent, wherein: SiO 2₂: 50-62%; and/or Al₂O₃: 11.5-18%; and/or Na₂O: 0 to 3 percent; and/or ZnO: 1-6%; and/or TiO₂: 0-2%; and/or Li₂O: 14-24%; and/or MgO: 1.5-6%; and/or K₂O: 0 to 3.5 percent; and/or SrO: 0-2%; and/or BaO: 0-2%; and/or CaO: 0-2%; and/or Ln₂O₃: 0-2%; and/or B₂O₃: 0 to 3 percent; and/or P₂O₅: 1-4.5%; and/or ZrO₂: 0.5-7.5%; and/or a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(29) The glass-ceramic article according to any one of (24) to (28), having a composition, expressed in terms of mole percent, wherein: al (Al)₂O₃/SiO₂0.2 to 0.35; and/or ZnO/Li₂O is 0.05 to 0.4; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.05 to 0.18; and/or P₂O₅/Al₂O₃0.08 to 0.3; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.3 to 1.0; and/or (Li)₂O+ZrO₂)/SiO₂0.25 to 0.55; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.3 to 0.65.

(30) The glass-ceramic article according to any one of (24) to (29), having a composition, expressed in terms of mole percent, wherein: SiO 2₂: 52-58%; and/or Al₂O₃: 13-16%; and/or Na₂O: 0-2%; and/or ZnO: 1-6%; and/or TiO₂: 0 to 1.5 percent; and/or Li₂O: 16-21%; and/or MgO: 1.5-4.5%; and/or K₂O: 0 to 2.5 percent; and/or SrO: 0 to 1.5 percent; and/or BaO: 0 to 1 percent; and/or CaO: 0 to 1 percent; and/or Ln₂O₃: 0 to 1 percent; and/or B₂O₃: 0 to 1 percent; and/or P₂O₅: 1.5-4%; and/or ZrO₂: 1-6%; and/or a clarifying agent: 0 to 0.25 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(31) The glass-ceramic article according to any one of (24) to (30), having a composition, expressed in terms of mole percent, wherein: al (Al)₂O₃/SiO₂0.23 to 0.3; and/or ZnO/Li₂O is 0.08 to 0.25; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.06 to 0.15; and/or P₂O₅/Al₂O₃0.1 to 0.25; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.4 to 0.75; and/or (Li)₂O+ZrO₂)/SiO₂0.3 to 0.5; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.35 to 0.55.

(32) The glass-ceramic article according to any one of (24) to (31), having a composition, expressed in terms of mole percent, wherein: k₂O: 0-2%; and/or ZnO: 1.5-4.5%; and/or P₂O₅: 1.8-3.5%; and/or ZrO₂：1～5％。

(33) The glass-ceramic article according to any one of (24) to (32), wherein the composition does not contain B₂O₃(ii) a And/or does not contain CaO; and/or no BaO; and/or does not contain SrO; and/or does not contain TiO₂(ii) a And/or do not contain La₂O₃(ii) a And/or does not contain Gd₂O₃。

(34) The glass-ceramic article according to any one of (24) to (33), wherein the glass-ceramic article contains quartz and a quartz solid solution; and/or eucryptite; and/or lithium zinc phosphate; and/or petalite; and/or a lithium silicate crystalline phase.

(35) The glass-ceramic article according to any one of (24) to (34), wherein a total amount of crystal phases in the glass-ceramic article is 10 to 80 wt%, preferably 15 to 75 wt%, and more preferably 20 to 70 wt% of the glass-ceramic article.

(36) The glass-ceramic article according to any one of (24) to (35), wherein the glass-ceramic article contains a crystal phase of quartz or a quartz solid solution, and the crystal phase of quartz or a quartz solid solution has a higher weight percentage than other crystal phases, preferably the crystal phase of quartz or a quartz solid solution accounts for 20 to 70 weight percent of the glass-ceramic article, more preferably the crystal phase of quartz or a quartz solid solution accounts for 25 to 65 weight percent of the glass-ceramic article, and even more preferably the crystal phase of quartz or a quartz solid solution accounts for 30 to 60 weight percent of the glass-ceramic article.

(37) The glass-ceramic article of any one of (24) to (36), wherein petalite is not present in the glass-ceramic article; and/or does not contain a lithium silicate crystalline phase.

(38) The glass-ceramic article according to any one of (23) to (37), wherein the haze of the glass-ceramic article having a thickness of 0.6mm is 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and still more preferably 0.1% or less; and/or a glass ceramic article having a thickness of 0.6mm, and having an average transmittance at a wavelength of 400 to 800nm of 85% or more, preferably 87% or more, more preferably 89% or more; and/or a glass-ceramic article having a thickness of 0.6mm, and has a transmittance at a wavelength of 550nm of 85% or more, preferably 90% or more, more preferably 91% or more.

(39) The glass-ceramic article according to any one of (23) to (38), wherein a crystallinity of the glass-ceramic article is 20% or more, preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more; and/or the crystal grain size is 50nm or less, preferably 40nm or less, more preferably 30nm or less.

(40) The glass ceramic article according to any one of (23) to (39), wherein the glass ceramic article has a surface stress of 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more; and/or the depth of the ion exchange layer is 5 μm or more, preferably 10 μm or more, and more preferably 20 μm or more.

(41) The glass-ceramic article according to any one of (23) to (40), wherein the glass-ceramic article has a ball drop test height of 1200mm or more, preferably 1300mm or more, and more preferably 1400mm or more; and/or a fracture toughness of 1MPa m^1/2Above, preferably 1.1MPa · m^1/2More preferably 1.2MPa · m or more^1/2The above; and/or a Vickers hardness of 650kgf/mm²Above, preferably 680kgf/mm²Above, more preferably 700kgf/mm²The above; and/or a four-point bending strength of 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more.

(42) The glass-ceramic article according to any one of (24) to (41), comprising: NiO: 0-2%; and/or Ni₂O₃: 0-2%; and/or a CoO: 0 to 1 percent; and/or Co₂O₃: 0 to 1 percent; and/or Fe₂O₃: 0 to 4 percent; and/or MnO₂: 0-2%; and/or Er₂O₃: 0 to 4 percent; and/or Nd₂O₃: 0 to 4 percent; and/or Cu₂O: 0-2%; and/or Pr₂O₅: 0 to 4 percent; and/or CeO₂：0～2％。

(43) The glass-ceramic article of any one of (24) - (42), further comprising, in mole percent, less than 2% antimicrobial component, preferably less than 1% antimicrobial component, the antimicrobial component being Ag, AgO, Cu, CuO, Cu₂One or more of O.

(44) A matrix glass, the composition of which, expressed in mole percent, comprises: SiO 2₂：48～65％；Al₂O₃：10～20％；Li₂O：12～29％；ZnO：0.1～8％；P₂O₅：0.1～6.5％；ZrO₂: 0.1 to 8% of Al₂O₃/SiO₂0.18 to 0.38.

(45) The matrix glass according to (44), whose composition is expressed in mol%, further comprising: na (Na)₂O: 0 to 4 percent; and/or MgO: 0 to 7 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or TiO₂: 0 to 4 percent; and/or a clarifying agent: 0 to 1 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(46) The matrix glass according to any one of (44) or (45), whose composition is expressed in mol%, wherein: al (Al)₂O₃/SiO₂0.18 to 0.38; and/or ZnO/Li₂O is 0.03 to 0.55; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.03 to 0.22; and/or P₂O₅/Al₂O₃0.08 to 0.4; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.15 to 1.5; and/or (Li)₂O+ZrO₂)/SiO₂0.2 to 0.7; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.25 to 0.8.

(47) The matrix glass according to any one of (44) to (46), which has the composition, expressed in mol%, wherein: SiO 2₂: 50-62%; and/or Al₂O₃: 11.5-18%; and/or Na₂O: 0 to 3 percent; and/or ZnO: 1-6%; and/or TiO₂: 0-2%; and/or Li₂O: 14-24%; and/or MgO: 1.5-6%; and/or K₂O: 0 to 3.5 percent; and/or SrO: 0-2%; and/or BaO: 0-2%; and/or CaO: 0-2%; and/or Ln₂O₃: 0-2%; and/or B₂O₃: 0 to 3 percent; and/or P₂O₅: 1-4.5%; and/or ZrO₂: 0.5-7.5%; and/or a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(48) The matrix glass according to any one of (44) to (47), which has the composition, expressed in mol%, wherein: al (Al)₂O₃/SiO₂0.2 to 0.35; and/or ZnO/Li₂O is 0.05 to 0.4; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.05 to 0.18; and/or P₂O₅/Al₂O₃0.08 to 0.3; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.3 to 1.0; and/or (Li)₂O+ZrO₂)/SiO₂0.25 to 0.55; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.3 to 0.65.

(49) The matrix glass according to any one of (44) to (48), which has the composition, expressed in mol%, wherein: SiO 2₂: 52-58%; and/or Al₂O₃: 13-16%; and/or Na₂O: 0-2%; and/or ZnO: 1-6%; and/or TiO₂: 0 to 1.5 percent; and/or Li₂O: 16-21%; and/or MgO: 1.5-4.5%; and/or K₂O: 0 to 2.5 percent; and/or SrO: 0 to 1.5 percent; and/or BaO: 0 to 1 percent; and/or CaO: 0 to 1 percent; and/or Ln₂O₃: 0 to 1 percent; and/or B₂O₃: 0 to 1 percent; and/or P₂O₅: 1.5-4%; and/or ZrO₂: 1-6%; and/or a clarifying agent: 0 to 0.25 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(50) The matrix glass according to any one of (44) to (49), which has the composition, expressed in mol%, wherein: al (Al)₂O₃/SiO₂0.23 to 0.3; and/or ZnO/Li₂O is 0.08 to 0.25; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.06 to 0.15; and/or P₂O₅/Al₂O₃0.1 to 0.25; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.4 to 0.75; and/or (Li)₂O+ZrO₂)/SiO₂0.3 to 0.5; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.35 to 0.55.

(51) The matrix glass according to any one of (44) to (50), which has the composition, expressed in mol%, wherein: k₂O: 0-2%; and/or ZnO: 1.5-4.5%; and/or P₂O₅: 1.8-3.5%; and/or ZrO₂：1～5％。

(52) The matrix glass according to any one of (44) to (51), comprising: NiO: 0-2%;and/or Ni₂O₃: 0-2%; and/or a CoO: 0 to 1 percent; and/or Co₂O₃: 0 to 1 percent; and/or Fe₂O₃: 0 to 4 percent; and/or MnO₂: 0-2%; and/or Er₂O₃: 0 to 4 percent; and/or Nd₂O₃: 0 to 4 percent; and/or Cu₂O: 0-2%; and/or Pr₂O₅: 0 to 4 percent; and/or CeO₂：0～2％。

(53) The base glass according to any one of (44) to (52), which further contains an antimicrobial component of 2% or less, preferably 1% or less, in terms of mol%, the antimicrobial component being Ag, AgO, Cu, CuO, Cu₂One or more of O.

(54) The matrix glass according to any one of (44) to (53), wherein the component does not contain B₂O₃(ii) a And/or does not contain CaO; and/or no BaO; and/or does not contain SrO; and/or does not contain TiO₂(ii) a And/or do not contain La₂O₃(ii) a And/or does not contain Gd₂O₃。

(55) The base glass according to any one of (44) to (54), wherein the base glass has a thermal expansion coefficient of 50X 10^-7/K～80×10^-7Preferably 55X 10,/K^-7/K～75×10^-7More preferably 60X 10,/K^-7/K～70×10^-7K; and/or the refractive index is 1.50 to 1.55, preferably 1.51 to 1.54, and more preferably 1.52 to 1.54.

(56) A glass cover plate made of the glass ceramic according to any one of (1) to (22); and/or using the glass-ceramic article of any one of (23) to (43); and/or a base glass according to any one of (44) to (55).

(57) A glass component made of the glass ceramic according to any one of (1) to (22); and/or using the glass-ceramic article of any one of (23) to (43); and/or a base glass according to any one of (44) to (55).

(58) A display device comprising the glass-ceramic according to any one of (1) to (22); and/or a glass-ceramic article comprising any one of (23) to (43); and/or a glass composition comprising the matrix glass according to any one of (44) to (55); and/or a glass cover plate comprising (56); and/or the glass component (57) is contained.

(59) An electronic device comprising the glass ceramic according to any one of (1) to (22); and/or a glass-ceramic article comprising any one of (23) to (43); and/or a glass composition comprising the matrix glass according to any one of (44) to (55); and/or a glass cover plate comprising (56); and/or the glass component (57) is contained.

The invention has the beneficial effects that: through reasonable component design, the glass ceramic obtained by the invention is suitable for chemical strengthening; meanwhile, the glass ceramic and the glass ceramic product obtained by the invention have excellent mechanical properties and meet the use requirements of display equipment or electronic equipment.

Detailed Description

The glass-ceramic and glass-ceramic articles of the present invention are materials having a crystalline phase and a glass phase, as distinguished from amorphous solids. The crystalline phases of the glass-ceramic and glass-ceramic articles can be identified by the angle of the peaks 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 obtained the glass-ceramic or glass-ceramic article of the present invention at a low cost by specifying the content and content ratio of specific components constituting the glass-ceramic or glass-ceramic article to specific values and precipitating specific crystal phases.

In the glass-ceramic and glass-ceramic articles of the present invention, the crystalline phase contains quartz and quartz solid solutions; and/or eucryptite; and/or lithium zinc phosphate; and/or petalite; and/or lithium silicate, and the like.

In some embodiments of the present invention, the crystal phase in the glass-ceramic or glass-ceramic article mainly comprises quartz and a quartz solid solution, the quartz and the quartz solid solution have a higher weight percentage than other crystal phases, preferably the quartz and the quartz solid solution account for 20 to 70 weight percent of the glass-ceramic or glass-ceramic article, more preferably the quartz and the quartz solid solution crystal phase accounts for 25 to 65 weight percent of the glass-ceramic or glass-ceramic article, and even more preferably the quartz and the quartz solid solution crystal phase accounts for 30 to 60 weight percent of the glass-ceramic or glass-ceramic article. In some embodiments, the quartz and quartz solid solution crystalline phases comprise 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%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70% by weight of the glass-ceramic or glass-ceramic article.

In some embodiments of the invention, to achieve the excellent properties desired in the present invention, the glass-ceramic or glass-ceramic article preferably does not contain petalite; and/or does not contain a lithium silicate crystalline phase.

In some embodiments of the present invention, it is preferred that the total amount of crystalline phases in the glass-ceramic or glass-ceramic article is in the range of 10 to 80% by weight of the glass-ceramic or glass-ceramic article; in some embodiments, it is more preferred that the total amount of crystalline phases in the glass-ceramic or glass-ceramic article is in the range of 15 to 75 weight percent 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 20 to 70 weight percent of the glass-ceramic or glass-ceramic article. In some embodiments, the total amount of crystalline phases is 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%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80% by weight of the glass-ceramic or glass-ceramic article.

The ranges of the respective components (components) of the matrix glass, glass ceramic and glass ceramic article of the present invention will be described below. In the present specification, the contents of the respective components are all expressed in terms of mole percent (mol%) relative to the total amount of the matrix glass, or glass ceramic article substance converted into the composition of oxides, if not specifically stated otherwise. Here, the term "composition in terms of oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the composition components of the matrix glass, glass ceramic, or glass ceramic article of the present invention are decomposed in the melt and converted into oxides, the total molar amount of the oxides is 100%. In the present specification, the term "glass" refers to a matrix glass before crystallization, the term "glass ceramic" refers to a glass ceramic after crystallization, and the product obtained by chemically strengthening the glass ceramic is a glass ceramic product.

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 "and/or" as used herein is inclusive, e.g., "a; and/or B "means A alone, B alone, or both A and B.

SiO₂Is an essential component constituting the glass, glass-ceramic and glass-ceramic article of the present invention, and is one of the main components forming a crystal phase after heat treatment of the glass, if SiO₂When the content of (A) is 48% or less, devitrification resistance and strength of the matrix glass are deteriorated, and therefore SiO is contained₂The lower limit of the content is 48%, preferably 50%, more preferably 52%. If SiO₂The content is more than 65 percent, the glass smelting difficulty is increased, and the glass is not beneficial to forming, so that the SiO is₂The upper limit of the content is 65%, preferably 62%. Further, by using SiO₂The content is below 58 percent, which is beneficial to obtaining quartz and quartz solid solution crystal phase and expected quartz and quartz solid solution crystal phase content, and simultaneously can reduce the haze of glass ceramics and glass ceramic products and improve the glass ceramicsTransmittance of porcelain and glass-ceramic articles. SiO is therefore further preferred₂The upper limit of the content is 58%.

Al₂O₃Is one of components which can form a crystal phase of the glass ceramic, can form a network structure of the glass, is favorable for chemical strengthening of the glass ceramic, increases the ion exchange layer depth of the glass ceramic product, but if the content thereof is less than 10%, the above effect is not good, and preferably Al₂O₃The lower limit of the content is 11.5%. Further, if Al is contained in an amount of 13% or more₂O₃The method is beneficial to the molding of glass, the reduction of the crystallization temperature of the glass and the crystallization process of the glass. Therefore, Al is more preferable₂O₃The lower limit of the content of (B) is 13%. On the other hand, if Al₂O₃When the content of (b) exceeds 20%, the difficulty of melting the glass increases, and the number of defects in the glass increases, which tends to lower the strength of the matrix glass. Thus, Al₂O₃The upper limit of the content is 20%, preferably 18%, more preferably 16%.

In some embodiments of the invention, the Al is added by reacting Al with a metal₂O₃/SiO₂Within the range of 0.18-0.38, the structure of the matrix glass can be more compact, the strength of the matrix glass is improved, the ball drop test height of the glass ceramic is increased, the depth and the surface stress of an ion exchange layer of the glass ceramic product are improved, and the Vickers hardness of the glass ceramic product is improved. Therefore, Al is preferable₂O₃/SiO₂0.18 to 0.38, more preferably Al₂O₃/SiO₂0.2 to 0.35, and more preferably Al₂O₃/SiO₂0.23 to 0.3.

Li₂O can promote the melting of the glass, reduce the melting temperature of the glass, promote the formation of crystals in the crystallization process, is a component mainly substituted by sodium ions, potassium ions and the like in the chemical strengthening process, can increase the surface stress of the glass ceramic product after chemical strengthening and improve the ball drop test height of the glass ceramic product, but if the content of O is less than 12 percent, the effect is not good. Thus, Li₂The lower limit of the O content is 12%, preferably 14%, more preferably16 percent. If Li is contained excessively₂O, when the glass is crystallized, the crystal tends to be large, and the haze of the glass ceramic or the glass ceramic article tends to increase, resulting in a decrease in the light transmittance. Thus, Li₂The upper limit of the O content is 29%, preferably 24%, more preferably 21%.

Na₂O can reduce the crystallization temperature of the glass, facilitate the crystallization process of the glass, facilitate the improvement of the chemical strengthening properties of the glass ceramic, and in some embodiments, facilitate the improvement of the hot bending process of the glass ceramic and glass ceramic articles; however, in the present invention, if Na is contained excessively₂O, which tends to cause more broken bonds in the glass and decrease the strength of the matrix glass, adversely affects the strength of the glass-ceramic and glass-ceramic articles. Therefore, Na is preferred in the present invention₂The content of O is 0 to 4%, more preferably 0 to 3%, and still more preferably 0 to 2%.

K₂O is beneficial to expanding the ranges of glass forming temperature and crystallization temperature, is beneficial to chemical strengthening and can improve the depth of an ion exchange layer of the glass ceramic product; but if it contains K excessively₂O, the decrease in chemical stability and the decrease in hardness of the glass are likely to occur. Thus, K₂The upper limit of the content of O is preferably 5%, more preferably 3.5%, still more preferably 2.5%, and still more preferably 2%.

The ZnO can improve the melting performance of the glass, can enter the glass to participate in forming a crystal phase, improves the content of the crystal phase of the glass, and increases the falling ball test height of the glass ceramic and the glass ceramic product, and the ZnO can be contained by more than 0.1 percent to obtain the effect, preferably more than 0.5 percent, more preferably more than 1 percent, and further preferably more than 1.5 percent. On the other hand, if ZnO is contained excessively, the thermal expansion coefficient of the glass ceramic or glass ceramic article after crystallization or chemical strengthening becomes large, which is disadvantageous for the subsequent further processing. Therefore, the upper limit of the ZnO content is 8%, preferably 7.5%, more preferably 6%, and still more preferably 4.5%.

In some embodiments of the invention, if ZnO/Li₂O is less than0.03, the content of the crystal phase of the glass ceramic and the glass ceramic article decreased, and the four-point bending strength became poor; if ZnO/Li₂With O exceeding 0.55, the hardness and fracture toughness of the glass-ceramic and glass-ceramic articles decrease. Therefore, ZnO/Li is preferred in the present invention₂O is 0.03 to 0.55, and ZnO/Li is more preferable₂O is 0.05 to 0.4, and ZnO/Li is more preferable₂O is 0.08 to 0.25.

MgO can enter the glass to participate in forming a crystal phase, so that the crystal phase content of the glass is improved, and the falling ball test height of the glass ceramic and the glass ceramic product is increased; however, if the MgO content is too high, the devitrification resistance of the glass is lowered, the crystallization temperature range of the glass is narrowed, the crystallization process is not easily controlled, and it is difficult to obtain desired glass ceramics and glass ceramic articles. Therefore, the MgO content in the present invention is 0 to 7%, preferably 1.5 to 6%, and more preferably 1.5 to 4.5%.

P₂O₅The method is beneficial to improving the low-temperature melting property of the glass, can form crystal nuclei in the glass, can enter the network structure of the glass, and reduces the haze of the glass ceramic and the glass ceramic product. In the invention, more than 0.1 percent of P is contained₂O₅In order to obtain the above effects, it is preferable to contain 1% or more of P₂O₅More preferably 1.5% or more of P₂O₅More preferably, it contains 1.8% or more of P₂O₅. But if it contains P excessively₂O₅It is easy to increase the phase separation of the matrix glass and to decrease the chemical stability of the matrix glass, glass ceramic and glass ceramic article. Thus, P₂O₅The upper limit of the content is 6.5%, preferably 4.5%, more preferably 4%, and still more preferably 3.5%.

In some embodiments of the invention, if (P)₂O₅+ZnO)/(SiO₂+ MgO) is less than 0.03, the crystallinity of the glass-ceramic and glass-ceramic article decreases, the grain size becomes larger; if (P)₂O₅+ZnO)/(SiO₂+ MgO) exceeds 0.22, the devitrification resistance of the matrix glass decreases, and at the same time the strength of the glass-ceramic and glass-ceramic articles decreases, and the falling ball test height decreases. Therefore, (P) is preferable₂O₅+ZnO)/(SiO₂+ MgO) of 0.03 to 0.22, more preferably (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.05 to 0.18, more preferably (P)₂O₅+ZnO)/(SiO₂And + MgO) is 0.06 to 0.15.

In some embodiments of the invention, P is prepared by reacting P with a compound of formula (I)₂O₅/Al₂O₃The value of (A) is within the range of 0.08-0.4, the forming performance of the matrix glass can be optimized, the processing performance of the glass ceramic and the glass ceramic product can be optimized, the haze of the glass ceramic and the glass ceramic product can be reduced, the transmittance of the glass ceramic and the glass ceramic product can be improved, and P is preferably selected₂O₅/Al₂O₃A value of (A) is 0.08 to 0.3, more preferably P₂O₅/Al₂O₃The value of (b) is 0.1 to 0.25.

ZrO₂Can reduce the formation crystallization of matrix glass, and P₂O₅Can cooperate with each other, broaden the crystallization temperature range of the glass, improve the nucleation amount of the glass ceramic and reduce the haze of the glass ceramic and the glass ceramic product. In the present invention, by containing ZrO in an amount of 0.1% or more₂In order to obtain the above effects, it is preferable to contain ZrO in an amount of 0.5% or more₂More preferably, at least 1% of ZrO₂. On the other hand, if ZrO is contained excessively₂Therefore, the glass is difficult to melt, and inclusions are likely to occur in the glass, thereby lowering the strength and transmittance of the glass. Thus, ZrO₂The upper limit of the content is 8%, preferably 7.5%, more preferably 6%, and still more preferably 5%.

In some embodiments of the invention, the (ZrO) is prepared by reacting₂+MgO+ZnO)/Al₂O₃The value of (A) is 0.15 or more, the crystal grains of the glass ceramic can be refined, the types of crystal phases in the glass ceramic can be increased, and the crystallinity and the strength of the glass ceramic can be improved. If, however, (ZrO)₂+MgO+ZnO)/Al₂O₃The value of (A) exceeds 1.5, the thermal expansion coefficients of the matrix glass and the glass ceramic are increased, and the difficulty of subsequent processing is increased; on the other hand, the chemical strengthening property of the glass ceramic is reduced, the depth of the ion exchange layer is reduced, and the surface stress is reduced. Therefore, (ZrO)₂+MgO+ZnO)/Al₂O₃The value of (b) is 0.15 to 1.5, more preferably (ZrO)₂+MgO+ZnO)/Al₂O₃The value of (b) is 0.3 to 1.0, and (ZrO) is more preferable₂+MgO+ZnO)/Al₂O₃The value of (A) is 0.4 to 0.75.

In some embodiments of the invention, (if) Li₂O+ZrO₂)/SiO₂Below 0.2, the falling ball test heights of the glass-ceramic and glass-ceramic articles deteriorate if (Li)₂O+ZrO₂)/SiO₂Above 0.7, the grain size and haze of the glass-ceramic and glass-ceramic articles increase, and the transmittance decreases. Therefore, (Li) is preferable₂O+ZrO₂)/SiO₂0.2 to 0.7, more preferably (Li)₂O+ZrO₂)/SiO₂0.25 to 0.55, and more preferably (Li)₂O+ZrO₂)/SiO₂0.3 to 0.5.

In some embodiments of the invention, the composition is prepared by reacting (Li)₂O+ZrO₂+ZnO)/SiO₂The value of (C) is in the range of 0.25 to 0.8, and the fracture toughness and four-point bending strength of the glass ceramic and the glass ceramic article can be improved, preferably (Li)₂O+ZrO₂+ZnO)/SiO₂The value of (B) is 0.3 to 0.65, more preferably (Li)₂O+ZrO₂+ZnO)/SiO₂The value of (A) is 0.35 to 0.55.

TiO₂Is an optional component which is helpful for reducing the melting temperature of the matrix glass and improving the chemical stability. If TiO₂Too high a content of (A) reduces the transmittance of the glass, glass-ceramic and glass-ceramic articles, which is disadvantageous for the preparation of highly transparent products, and therefore, TiO₂The content is in the range of 0 to 4%, preferably 0 to 2%, more preferably 0 to 1.5%, and further preferably not containing TiO₂。

SrO is an optional component for improving the low-temperature melting property of the glass and suppressing devitrification when the matrix glass is formed, and when the content is too large, it is not favorable for forming the matrix glass. Therefore, in the present invention, the SrO content is in the range of 0 to 3%, preferably 0 to 2%, more preferably 0 to 1.5%, and further preferably no SrO is contained.

BaO is an optional component which is helpful for improving the glass forming performance of the glass, and when the content is excessive, the chemical strengthening performance of the glass ceramic is not good, and the strength of the glass ceramic product is easily reduced. Therefore, the content of BaO in the present invention is in the range of 0 to 3%, preferably 0 to 2%, more preferably 0 to 1%, and further preferably contains no BaO.

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 3%, preferably 0 to 2%, more preferably 0 to 1%, and further preferably no CaO is contained.

B₂O₃Helps to optimize the melting property of the matrix glass, and when the content thereof is too high, the chemical stability of the matrix glass is lowered, so that B₂O₃The content of (B) is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably no B is contained₂O₃。

Ln₂O₃(Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of) are optional components for improving the hardness and chemical stability of the glass ceramic and inhibiting the glass from forming and crystallizing, and when the content is excessive, the glass is easy to become opaque after crystallization. Ln in the invention₂O₃The content is in the range of 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%. In the present invention, in order to obtain excellent properties, it is preferable that La is not contained₂O₃And/or does not contain Gd₂O₃。

In some embodiments, the glass, glass-ceramic or glass-ceramic article may further comprise 0-1% of a fining agent to enhance the defoaming capability of the glass, glass-ceramic or glass-ceramic article. Such fining agents include, but are not limited to, Sb₂O₃、SnO₂、SnO、CeO₂One or more of, F, Cl and Br, preferably Sb₂O₃、SnO₂SnO as a fining agent. The upper limit of the content of the above-mentioned clarifying agent is preferably 0.5%, more preferably 0.25%, when it is present alone or in combination.

PbO and As₂O₃Is a toxic substanceEven a small amount of the compound does not meet the environmental protection requirement, so that the compound of the present invention preferably does not contain PbO and As in some embodiments₂O₃。

In some embodiments of the present invention, a base glass, glass-ceramic, or glass-ceramic article can be made to exhibit different colors by including a colorant in the base glass, glass-ceramic, or glass-ceramic article, the colorant comprising: NiO: 0-2%; and/or Ni₂O₃: 0-2%; and/or a CoO: 0 to 1 percent; and/or Co₂O₃: 0 to 1 percent; and/or Fe₂O₃: 0 to 4 percent; and/or MnO₂: 0-2%; and/or Er₂O₃: 0 to 4 percent; and/or Nd₂O₃: 0 to 4 percent; and/or Cu₂O: 0-2%; and/or Pr₂O₅: 0 to 4 percent; and/or CeO₂: 0 to 2 percent. The content of the colorant in mole percent and the function thereof are detailed as follows:

the brown or green matrix glass, glass ceramic or glass ceramic product prepared by the invention uses NiO and Ni₂O₃Or Pr₂O₅Is a colorant. NiO and Ni₂O₃For the colouring agent, for the preparation of a brown or green matrix glass, glass-ceramic or glass-ceramic article, the two components can be used individually or in mixtures, each in a quantity of generally less than 2%, preferably less than 1.5%, and if the quantity exceeds 1%, the colouring agent is not very soluble in the matrix glass, glass-ceramic or glass-ceramic article, each in a quantity of less than 0.1%, for example less than 0.1%, the matrix glass, glass-ceramic or glass-ceramic article being not visibly coloured. NiO and Ni, if used in admixture₂O₃The total amount is generally 2% or less, and the lower limit of the total amount is 0.1% or more. Using Pr₂O₅As a colorant for green matrix glass, glass ceramic or glass ceramic articles, it is used alone, generally in an amount of 4% or less, preferably 3% or less, with the lower limit of the amount being 0.2% or more, e.g., less than 0.4%, and the matrix glass, glass ceramic or glass ceramic article being inconspicuous in color.

Blue prepared by the inventionMatrix glass, glass-ceramic or glass-ceramic articles, using CoO or Co₂O₃The two colorant components can be used alone or in combination as a colorant, and are each present in an amount of generally 1% or less, preferably 0.8% or less, and if the amount exceeds 1%, the colorant is not well soluble in the matrix glass, glass-ceramic or glass-ceramic article, and the lower limit of the amount is 0.05% or more, e.g., less than 0.05%, respectively, and the matrix glass, glass-ceramic or glass-ceramic article is not conspicuous in color. CoO and Co, if used in admixture₂O₃The total amount is not more than 2%, and the lower limit of the total amount is not less than 0.05%.

The yellow matrix glass, glass-ceramic or glass-ceramic article prepared by the invention uses Cu₂O or CeO₂The two colorant components are used alone or in combination as a colorant, and have a lower limit of 0.2% or more, e.g., less than 0.2%, a non-noticeable color of the matrix glass, glass-ceramic or glass-ceramic, and Cu alone₂O is 2% or less, preferably 1.5% or less, and if the content exceeds 2%, the matrix glass is easily crystallized. Using CeO alone₂The content is usually 2% or less, preferably 1.5% or less, and for example, the content exceeds 2%, and the gloss of the matrix glass, glass ceramic or glass ceramic article is not good. At the same time, a small amount of CeO₂Added to glass with a defoaming effect, CeO₂Can also be used as a clarifying agent in glass. When two kinds of colorants are used in combination, the total amount is generally 2% or less, and the lower limit of the total amount is 0.2% or more.

The black or smoky grey matrix glass, glass-ceramic or glass-ceramic articles prepared according to the invention are based on Fe alone₂O₃Is a colorant; or using Fe₂O₃And CoO; or using Fe₂O₃And Co₂O₃Two colorants used in combination; or using Fe₂O₃Three colorants mixed together, CoO and NiO; or using Fe₂O₃、Co₂O₃And NiO. Preparation of black and smoky grey matrix glass, glass ceramicColoring agent for porcelain or glass-ceramic products mainly uses Fe₂O₃The coloring is contained in an amount of 4% or less, preferably 3% or less, and the lower limit of the content is 0.2% or more. CoO and Co₂O₃Absorbing in visible light, and increasing the coloration of the substrate glass, glass-ceramic or glass-ceramic article, typically with Fe₂O₃The content of each component is 0.4% or less, and the lower limit is 0.05% or more. In some embodiments, about 0.05%, 0.1%, 0.2%, 0.3%, 0.4% of CoO and/or Co may be included₂O₃. NiO absorbs visible light and can increase the degree of coloration of the base glass, glass ceramic or glass ceramic product, and is generally used in a mixture in which the content is 0.5% or less and the lower limit of the total amount is 0.05% or more.

The purple matrix glass, glass ceramic or glass ceramic article prepared by the invention uses MnO₂As a colorant, it is used in an amount of generally 2% or less, preferably 1.5% or less, and in an amount of 0.1% or more, for example, less than 0.1%, and the color of the matrix glass, glass ceramic or glass ceramic article is not conspicuous.

The pink matrix glass, glass ceramic or glass ceramic product prepared by the invention uses Er₂O₃The content of the colorant used is generally 4% or less, preferably 3% or less. Because of rare earth element Er₂O₃The coloring efficiency is low, and when the content exceeds 4%, the color of the matrix glass, glass ceramic or glass ceramic article cannot be further deepened, but the cost is increased, and the lower limit of the content is more than 0.2%, for example, less than 0.2%, and the color of the matrix glass, glass ceramic or glass ceramic article is not conspicuous.

The mauve substrate glass, glass ceramic or glass ceramic product prepared by the invention uses Nd₂O₃The content of the colorant used is generally 4% or less, preferably 3% or less. Due to rare earth element Nd₂O₃The coloring efficiency is low, the use of more than 4% of the base glass, glass-ceramic or glass-ceramic composition does not further darken the color of the base glass, glass-ceramic or glass-ceramic composition, but rather increases the cost, the lower limit of the content being more than 0.2%, for example less than 0.2%, of the baseThe glass, glass-ceramic or glass-ceramic article is not visibly colored.

The red matrix glass, glass ceramic or glass ceramic product prepared by the invention uses Er₂O₃、Nd₂O₃And MnO₂The 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, glass ceramic or glass ceramic product₂O₃And Nd₂O₃Coloring rare earth, relatively weak coloring ability, Er₂O₃The usage amount is within 3 percent, Nd₂O₃The usage amount is less than 2 percent, MnO₂The coloring is strong, the using amount is within 1 percent, and the lower limit of the total using amount of the mixed coloring agent is more than 0.5 percent.

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

In some embodiments of the present invention, the crystalline phase in the glass-ceramic and glass-ceramic articles comprises quartz and quartz solid solutions; and/or eucryptite; and/or lithium zinc phosphate, providing high strength to the glass-ceramic and glass-ceramic articles of the present invention, the glass-ceramic and glass-ceramic articles having high fracture toughness; the ball drop test height and four-point bending strength of the glass ceramic and glass ceramic article become large. The glass-ceramics of the present invention may also be ion exchanged to obtain additional mechanical strength. The glass ceramic and the glass ceramic product can obtain proper grain size through reasonable component design, and have high strength. The glass ceramics and glass ceramic products of the invention have good crystallinity, so that the glass ceramics and glass ceramic products of the invention 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 haze of the glass ceramic or glass ceramic product of the invention can affect the transmittance of the glass ceramic or glass ceramic product, namely, the light transmittance is affected, and the smaller the grain, the higher the transmittance; the smaller the haze, the higher the transmittance. In some embodiments, the haze of the glass-ceramic article or glass-ceramic having a thickness of 0.6mm is 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and even more preferably 0.1% or less. In some embodiments, the glass-ceramic article or glass-ceramic has a grain size of 50nm or less, preferably 40nm or less, and more preferably 30nm or less. On the other hand, it has been found through studies that the smaller the difference in refractive index between the crystal phase and the glass phase in the glass ceramic, the higher the transparency of the glass ceramic or glass ceramic article.

In some embodiments, the glass-ceramic or glass-ceramic article of the present invention exhibits high transparency in the visible range (i.e., the glass-ceramic or glass-ceramic article is transparent). The glass ceramic or glass ceramic article exhibits a high transmittance in the visible light range, and in some embodiments, the glass ceramic or glass ceramic article having a thickness of 0.6mm has an average light transmittance of from 400 to 800nm of 85% or more, preferably 87% or more, and more preferably 89% or more. In some preferred embodiments, the glass-ceramic article or glass-ceramic having a thickness of 0.6mm has a light transmittance of 85% or more, preferably 90% or more, and more preferably 91% or more at 550 nm.

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

The matrix glass, glass-ceramic and glass-ceramic articles of the present invention may be produced and manufactured by the following method:

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 the 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 heat treatment temperature, the temperature is maintained for a certain period of time, and then the temperature is lowered. The temperature of the crystallization treatment is preferably 580 to 950 ℃, and the holding time at the crystallization treatment temperature is preferably 600 to 850 ℃, and more preferably 0 to 8 hours, and even 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 580 to 650 ℃, and the 2 nd temperature is preferably 650 to 850 ℃. 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 glass or glass-ceramic described herein may 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 glass ceramic 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 substrate glass or glass ceramic molded body 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 glasses, glass-ceramics and glass-ceramic articles described herein can be of any thickness that is reasonably useful.

The glass ceramic of the present invention can be produced into a glass ceramic article 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 processed into sheets, and/or shaped (e.g., punched, hot bent, etc.), shaped, polished and/or swept, and 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. Replacing the smaller ions with larger ions creates a compressive stress in the matrix glass or glass-ceramic, forming 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 that are used to displace 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 immersing a molten Na salt (e.g., NaNO) 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 glass ceramic, 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 some embodiments, the matrix glass or glass-ceramic may be mixed by melting a K salt and a Na salt (e.g., KNO) by immersion at a temperature of about 350 ℃ to 450 ℃₃And NaNO₃) The salt bath is subjected to ion exchange for 0.5 to 8 hours, and the preferable time range is 1 to 4 hours.

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

The matrix glass and/or glass ceramic product of the invention has various performance indexes tested by the following methods:

[ coefficient of thermal expansion ]

Coefficient of thermal expansion (alpha)_20℃-120℃) The test was carried out according to the test method GB/T7962.16-2010.

[ refractive index ]

The refractive index (nd) was measured according to GB/T7962.1-2010 method.

[ haze ]

A haze tester EEL57D was used, prepared from 0.6mm 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 glass ceramic in HF (hydrofluoric acid), carrying out gold spraying on the surface of the glass ceramic, and carrying out surface scanning under the SEM, so as to determine the size of crystal grains of the glass ceramic.

[ light transmittance ]

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

The sample is processed into a thickness of 0.6mm, 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 0.6mm 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.

[ falling ball test height of glass ceramics ]

The height test method for the ball drop test of the glass ceramic 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 "ball drop test height a", glass ceramics were used as test objects. The test data recorded as 800mm in the examples shows that the glass ceramic did not break and received impact even when the steel ball was dropped from a height of 800 mm.

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

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

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

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

[ falling ball test height of glass-ceramic article ]

The falling ball test height test method of the glass ceramic article is as follows:

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, 950, 1000 and more without breaking. For the examples having the "ball drop test height B", glass-ceramic articles were used as test objects. The test data recorded as 1000mm in the examples shows that the steel ball was dropped from the height of 1000mm without breaking and receiving impact. The drop test height is sometimes referred to herein as the drop height.

[ 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 depression²) The values of (b) indicate (a). The test load was set to 100(N) and the holding time was set to 15 (sec). In the present invention, Vickers hardness is sometimes referred to simply as hardness.

The matrix glass of the present invention has the following properties:

1) in some embodiments, the matrix glass has a coefficient of thermal expansion (α)_20℃-120℃) Has a lower limit of 50X 10^-7A preferred lower limit of 55X 10^-7A more preferable lower limit is 60X 10^-7A maximum of 80X 10,/K^-7Preferably, the upper limit is 75X 10^-7More preferably, the upper limit is 70X 10^-7/K。

2) In some embodiments, the matrix glass has a refractive index (nd) with a lower limit of 1.50, preferably a lower limit of 1.51, more preferably a lower limit of 1.52, and an upper limit of 1.55, preferably an upper limit of 1.54.

The glass ceramic of the invention has the following properties:

1) in some embodiments, the glass-ceramic has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

2) In some embodiments, the glass-ceramic has a grain size of 50nm or less, preferably 40nm or less, preferably 30nm or less.

3) In some embodiments, the 0.6mm thick glass-ceramic has a haze of 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and even more preferably 0.1% or less.

4) In some embodiments, the glass-ceramic having a thickness of 0.6mm has an average transmittance of 85% or more, preferably 87% or more, and more preferably 89% or more at a wavelength of 400 to 800 nm.

5) In some embodiments, the glass-ceramic having a thickness of 0.6mm has a transmittance at a wavelength of 550nm of 85% or more, preferably 90% or more, and more preferably 91% or more.

6) In some embodiments, the glass-ceramic has a ball drop test height of 1000mm or more, preferably 1100mm or more, and more preferably 1200mm or more.

7) In some embodiments, the glass-ceramic has a coefficient of thermal expansion (α)_20℃-120℃) Has a lower limit of 70X 10^-7A preferred lower limit of 75X 10^-7A more preferable lower limit is 80X 10^-7K, upper limit of 120X 10^-7Preferably, the upper limit is 110X 10^-7More preferably, the upper limit is 100X 10^-7/K。

8) In some embodiments, the glass-ceramic has a refractive index (nd) with a lower limit of 1.51, preferably a lower limit of 1.52, more preferably a lower limit of 1.53, and an upper limit of 1.57, preferably an upper limit of 1.56, more preferably an upper limit of 1.55.

The glass-ceramic article of the present invention has the following properties:

1) in some embodiments, the glass-ceramic article has a surface stress of 600MPa or greater, preferably 650MPa or greater, and more preferably 700MPa or greater.

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

3) In some embodiments, the glass-ceramic article has an ion exchange layer depth of 5 μm or more, preferably 10 μm or more, and more preferably 20 μm or more.

4) In some embodiments, the glass-ceramic article has a ball drop test height of 1200mm or more, preferably 1300mm or more, and more preferably 1400mm or more.

5) In some embodiments, the glass-ceramic article has a fracture toughness of 1 MPa-m^1/2Above, preferably 1.1MPa · m^1/2More preferably 1.2MPa · m or more^1/2The above.

6) In some embodimentsVickers hardness (H) of glass-ceramic article_v) Is 650kgf/mm²Above, preferably 680kgf/mm²Above, more preferably 700kgf/mm²The above.

7) In some embodiments, the glass-ceramic article has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

8) In some embodiments, the glass-ceramic article has a grain size of 50nm or less, preferably 40nm or less, and more preferably 30nm or less.

9) In some embodiments, the 0.6mm thick glass-ceramic article has a haze of 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and even more preferably 0.1% or less.

10) In some embodiments, the glass-ceramic article having a thickness of 0.6mm has an average transmittance of 85% or more, preferably 87% or more, and more preferably 89% or more at a wavelength of 400 to 800 nm.

11) In some embodiments, the glass-ceramic article having a thickness of 0.6mm has a 550nm transmittance of 85% or more, preferably 90% or more, and more preferably 91% or more.

The glass ceramic, the glass ceramic product and the matrix glass have the excellent performances, so that the glass ceramic, the glass ceramic product and the matrix glass can be widely made into glass cover plates or glass components; meanwhile, the glass ceramic, glass ceramic product and matrix glass of the present invention are applied to electronic devices or display devices, such as mobile phones, watches, computers, touch display screens, etc., for manufacturing protective glass for mobile phones, smart phones, tablet computers, notebook computers, PDAs, televisions, unmanned aerial vehicles, personal computers, MTA machines or industrial displays, or for manufacturing touch screens, protective windows, automobile windows, train windows, aircraft mechanical windows, touch screen protective glass, or for manufacturing hard disk substrates or solar cell substrates, or for manufacturing white home appliances, such as for manufacturing 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 mole% based on the oxide and has been normalized to 100%.

The examples of the matrix glass shown in tables 1 to 3 below were manufactured and tested according to the manufacturing method and performance test method of the matrix glass described above.

Table 1.

Table 2.

Table 3.

The examples of glass-ceramics shown in tables 4-6 below were manufactured and tested according to the methods for manufacturing glass-ceramics and the methods for testing the properties described above.

Table 4.

Table 5.

Table 6.

The examples of the glass-ceramic articles shown in tables 7 to 9 below were obtained by chemically strengthening the glass-ceramics shown in tables 4 to 6 described above according to the chemical strengthening method described above, and were tested according to the performance test method described above.

Table 7.

Table 8.

Table 9.

Claims

1. Glass-ceramic, characterized in that its composition, expressed in mole percentages, contains: SiO 2₂：48～65％；Al₂O₃：10～20％；Li₂O：12～29％；ZnO：0.1～8％；P₂O₅：0.1～6.5％；ZrO₂: 0.1 to 8% of Al₂O₃/SiO₂0.18 to 0.38.

2. The glass-ceramic according to claim 1, characterized in that its composition, expressed in mole percentages, further comprises: na (Na)₂O: 0 to 4 percent; and/or MgO: 0 to 7 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or TiO₂: 0 to 4 percent; and/or a clarifying agent: 0 to 1 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

3. The glass ceramic is characterized by containing quartz and quartz solid solution crystal phase, and SiO in the components₂、Al₂O₃、Li₂O, ZnO and ZrO₂The composition of the material comprises, in mole percent, 0-7% of MgO, wherein: al (Al)₂O₃/SiO₂0.18 to 0.38 (ZrO)₂+MgO+ZnO)/Al₂O₃0.15 to 1.5.

4. The glass-ceramic according to claim 3, characterized in that its composition, expressed in mole percentages, contains: SiO 2₂: 48-65%; and/or Al₂O₃: 10-20%; and/or Na₂O: 0 to 4 percent; and/or ZnO: 0.1-8%; and/or TiO₂: 0 to 4 percent; and/or Li₂O: 12-29%; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or P₂O₅: 0.1-6.5%; and/or ZrO₂: 0.1-8%; and/or a clarifying agent: 0 to 1 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

5. Glass-ceramic, characterized in that its composition, expressed in mole percentage, is represented by SiO₂：48～65％；Al₂O₃：10～20％；Li₂O：12～29％；ZnO：0.1～8％；P₂O₅：0.1～6.5％；ZrO₂：0.1～8％；Na₂O：0～4％；MgO：0～7％；K₂O：0～5％；SrO：0～3％；BaO：0～3％；CaO：0～3％；Ln₂O₃：0～5％；B₂O₃：0～5％；TiO₂: 0 to 4 percent; a clarifying agent: 0 to 1 percent of the composition, the Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

6. The glass-ceramic according to any one of claims 1 to 5, having a composition expressed in mole percent, wherein: al (Al)₂O₃/SiO₂0.18 to 0.38; and/orZnO/Li₂O is 0.03 to 0.55; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.03 to 0.22; and/or P₂O₅/Al₂O₃0.08 to 0.4; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.15 to 1.5; and/or (Li)₂O+ZrO₂)/SiO₂0.2 to 0.7; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.25 to 0.8.

7. The glass-ceramic according to any one of claims 1 to 5, having a composition expressed in mole percent, wherein: SiO 2₂: 50-62%; and/or Al₂O₃: 11.5-18%; and/or Na₂O: 0 to 3 percent; and/or ZnO: 1-6%; and/or TiO₂: 0-2%; and/or Li₂O: 14-24%; and/or MgO: 1.5-6%; and/or K₂O: 0 to 3.5 percent; and/or SrO: 0-2%; and/or BaO: 0-2%; and/or CaO: 0-2%; and/or Ln₂O₃: 0-2%; and/or B₂O₃: 0 to 3 percent; and/or P₂O₅: 1-4.5%; and/or ZrO₂: 0.5-7.5%; and/or a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

8. The glass-ceramic according to any one of claims 1 to 5, having a composition expressed in mole percent, wherein: al (Al)₂O₃/SiO₂0.2 to 0.35; and/or ZnO/Li₂O is 0.05 to 0.4; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.05 to 0.18; and/or P₂O₅/Al₂O₃0.08 to 0.3; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.3 to 1.0; and/or (Li)₂O+ZrO₂)/SiO₂0.25 to 0.55; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.3 to 0.65.

9. The glass-ceramic according to any one of claims 1 to 5, having a composition expressed in mole percent, wherein: SiO 2₂: 52-58%; and/or Al₂O₃: 13-16%; and/or Na₂O: 0-2%; and/or ZnO: 1-6%; and/or TiO₂: 0 to 1.5 percent; and/or Li₂O: 16-21%; and/or MgO: 1.5-4.5%; and/or K₂O: 0 to 2.5 percent; and/or SrO: 0 to 1.5 percent; and/or BaO: 0 to 1 percent; and/or CaO: 0 to 1 percent; and/or Ln₂O₃: 0 to 1 percent; and/or B₂O₃: 0 to 1 percent; and/or P₂O₅: 1.5-4%; and/or ZrO₂: 1-6%; and/or a clarifying agent: 0 to 0.25 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

10. The glass-ceramic according to any one of claims 1 to 5, having a composition expressed in mole percent, wherein: al (Al)₂O₃/SiO₂0.23 to 0.3; and/or ZnO/Li₂O is 0.08 to 0.25; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.06 to 0.15; and/or P₂O₅/Al₂O₃0.1 to 0.25; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.4 to 0.75; and/or (Li)₂O+ZrO₂)/SiO₂0.3 to 0.5; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.35 to 0.55.

11. The glass-ceramic according to any one of claims 1 to 5, having a composition expressed in mole percent, wherein: k₂O: 0-2%; and/or ZnO: 1.5-4.5%; and/or P₂O₅: 1.8-3.5%; and/or ZrO₂：1～5％。

12. The glass-ceramic according to any of claims 1 to 5, wherein the component does not contain B₂O₃(ii) a And/or does not contain CaO; and/or no BaO; and/or does not contain SrO; and/or does not contain TiO₂(ii) a And/or do not contain La₂O₃(ii) a And/or does not contain Gd₂O₃。

13. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic contains quartz and a quartz solid solution; and/or eucryptite; and/or lithium zinc phosphate; and/or petalite; and/or a lithium silicate crystalline phase.

14. The glass-ceramic according to any one of claims 1 to 5, wherein the total amount of crystalline phases in the glass-ceramic is in the range of 10 to 80% by weight, preferably 15 to 75% by weight, more preferably 20 to 70% by weight of the glass-ceramic.

15. The glass-ceramic according to any of claims 1 to 5, wherein the glass-ceramic comprises quartz and quartz solid solution crystalline phases, and the quartz and quartz solid solution crystalline phases have a higher weight percentage than other crystalline phases, preferably the quartz and quartz solid solution crystalline phases constitute 20 to 70 weight percent of the glass-ceramic, more preferably the quartz and quartz solid solution crystalline phases constitute 25 to 65 weight percent of the glass-ceramic, and even more preferably the quartz and quartz solid solution crystalline phases constitute 30 to 60 weight percent of the glass-ceramic.

16. The glass-ceramic according to any one of claims 1 to 5, wherein petalite is not contained in the glass-ceramic; and/or does not contain a lithium silicate crystalline phase.

17. The glass-ceramic according to any one of claims 1 to 5, wherein the haze of the glass-ceramic having a thickness of 0.6mm is 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and still more preferably 0.1% or less; and/or 0.6mm thick glass ceramic, the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 87% or more, more preferably 89% or more; and/or a glass ceramic having a thickness of 0.6mm, and has a transmittance at a wavelength of 550nm of 85% or more, preferably 90% or more, and more preferably 91% or more.

18. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and further preferably 50% or more; and/or a crystal grain size of 50nm or less, preferably 40nm or less, more preferably 30nm or less; and/or a ball drop test height of 1000mm or more, preferably 1100mm or more, more preferably 1200mm or more.

19. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic has a coefficient of thermal expansion of 70 x 10^-7/K～120×10^-7Preferably 75X 10,/K^-7/K～110×10^-7More preferably 80X 10,/K^-7/K～100×10^-7K; and/or the refractive index is 1.51 to 1.57, preferably 1.52 to 1.56, and more preferably 1.53 to 1.55.

20. The glass-ceramic according to any one of claims 1 to 4, wherein the glass-ceramic further comprises a colorant to impart a different color to the glass-ceramic.

21. The glass-ceramic according to claim 20, characterized in that its colouring agent comprises, expressed in mole percentages: NiO: 0-2%; and/or Ni₂O₃: 0-2%; and/or a CoO: 0 to 1 percent; and/or Co₂O₃: 0 to 1 percent; and/or Fe₂O₃: 0 to 4 percent; and/or MnO₂: 0-2%; and/or Er₂O₃: 0 to 4 percent; and/or Nd₂O₃: 0 to 4 percent; and/or Cu₂O: 0-2%; and/or Pr₂O₅: 0 to 4 percent; and/or CeO₂：0～2％。

22. Glass-ceramic according to any one of claims 1 to 4, characterized in that it further contains, expressed in molar percentage, less than 2% of an antimicrobial component, preferably less than 1% of an antimicrobial component, the antimicrobial component being Ag, AgO, Cu, CuO, Cu₂One or more of O.

23. A glass-ceramic article made of the glass-ceramic of any one of claims 1 to 22.

24. Glass-ceramic article, characterized in that its composition, expressed in mole percentages, comprises: SiO 2₂：48～65％；Al₂O₃：10～20％；Li₂O：12～29％；ZnO：0.1～8％；P₂O₅：0.1～6.5％；ZrO₂: 0.1 to 8% of Al₂O₃/SiO₂0.18 to 0.38.

25. The glass-ceramic article of claim 24, further comprising, in mole percent: na (Na)₂O: 0 to 4 percent; and/or MgO: 0 to 7 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or TiO₂: 0 to 4 percent; and/or a clarifying agent: 0 to 1 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

26. Glass-ceramic article, characterized in that its composition is expressed in mole percentagesComprising: SiO 2₂：48～65％；Al₂O₃：10～20％；Li₂O：12～29％；ZnO：0.1～8％；P₂O₅：0.1～6.5％；ZrO₂：0.1～8％；Na₂O：0～4％；MgO：0～7％；K₂O：0～5％；SrO：0～3％；BaO：0～3％；CaO：0～3％；Ln₂O₃：0～5％；B₂O₃：0～5％；TiO₂: 0 to 4 percent; a clarifying agent: 0 to 1 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

27. The glass-ceramic article of any one of claims 24-26, wherein the composition is expressed in mole percent, and wherein: al (Al)₂O₃/SiO₂0.18 to 0.38; and/or ZnO/Li₂O is 0.03 to 0.55; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.03 to 0.22; and/or P₂O₅/Al₂O₃0.08 to 0.4; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.15 to 1.5; and/or (Li)₂O+ZrO₂)/SiO₂0.2 to 0.7; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.25 to 0.8.

28. The glass-ceramic article of any one of claims 24-26, wherein the composition is expressed in mole percent, and wherein: SiO 2₂: 50-62%; and/or Al₂O₃: 11.5-18%; and/or Na₂O: 0 to 3 percent; and/or ZnO: 1-6%; and/or TiO₂: 0-2%; and/or Li₂O: 14-24%; and/or MgO: 1.5-6%; and/or K₂O: 0 to 3.5 percent; and/or SrO: 0-2%; and/or BaO: 0-2%; and/or CaO: 0-2%; and/or Ln₂O₃: 0-2%; and/or B₂O₃: 0 to 3 percent; and/or P₂O₅: 1-4.5%; and/or ZrO₂: 0.5-7.5%; and/or a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

29. The glass-ceramic article of any one of claims 24-26, wherein the composition is expressed in mole percent, and wherein: al (Al)₂O₃/SiO₂0.2 to 0.35; and/or ZnO/Li₂O is 0.05 to 0.4; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.05 to 0.18; and/or P₂O₅/Al₂O₃0.08 to 0.3; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.3 to 1.0; and/or (Li)₂O+ZrO₂)/SiO₂0.25 to 0.55; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.3 to 0.65.

30. The glass-ceramic article of any one of claims 24-26, wherein the composition is expressed in mole percent, and wherein: SiO 2₂: 52-58%; and/or Al₂O₃: 13-16%; and/or Na₂O: 0-2%; and/or ZnO: 1-6%; and/or TiO₂: 0 to 1.5 percent; and/or Li₂O: 16-21%; and/or MgO: 1.5-4.5%; and/or K₂O: 0 to 2.5 percent; and/or SrO: 0 to 1.5 percent; and/or BaO: 0 to 1 percent; and/or CaO: 0 to 1 percent; and/or Ln₂O₃: 0 to 1 percent; and/or B₂O₃: 0 to 1 percent; and/or P₂O₅: 1.5-4%; and/or ZrO₂: 1-6%; and/or a clarifying agent: 0 to 0.25 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

31. According to the rightThe glass-ceramic article of any one of claims 24 to 26, wherein the composition is expressed in mole percent, wherein: al (Al)₂O₃/SiO₂0.23 to 0.3; and/or ZnO/Li₂O is 0.08 to 0.25; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.06 to 0.15; and/or P₂O₅/Al₂O₃0.1 to 0.25; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.4 to 0.75; and/or (Li)₂O+ZrO₂)/SiO₂0.3 to 0.5; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.35 to 0.55.

32. The glass-ceramic article of any one of claims 24-26, wherein the composition is expressed in mole percent, and wherein: k₂O: 0-2%; and/or ZnO: 1.5-4.5%; and/or P₂O₅: 1.8-3.5%; and/or ZrO₂：1～5％。

33. The glass-ceramic article of any one of claims 24-26, wherein the composition does not contain B₂O₃(ii) a And/or does not contain CaO; and/or no BaO; and/or does not contain SrO; and/or does not contain TiO₂(ii) a And/or do not contain La₂O₃(ii) a And/or does not contain Gd₂O₃。

34. The glass-ceramic article of any one of claims 24-26, wherein the glass-ceramic article comprises quartz and a solid solution of quartz; and/or eucryptite; and/or lithium zinc phosphate; and/or petalite; and/or a lithium silicate crystalline phase.

35. The glass-ceramic article of any one of claims 24-26, wherein the total amount of crystalline phases in the glass-ceramic article is in a range from 10 wt% to 80 wt%, preferably from 15 wt% to 75 wt%, and more preferably from 20 wt% to 70 wt%.

36. The glass-ceramic article of any one of claims 24-26, wherein the glass-ceramic article comprises quartz and quartz solid solution crystalline phases, and wherein the quartz and quartz solid solution crystalline phases comprise a greater weight percentage than other crystalline phases, preferably the quartz and quartz solid solution crystalline phases comprise 20-70 wt% of the glass-ceramic article, more preferably the quartz and quartz solid solution crystalline phases comprise 25-65 wt% of the glass-ceramic article, and even more preferably the quartz and quartz solid solution crystalline phases comprise 30-60 wt% of the glass-ceramic article.

37. The glass-ceramic article of any one of claims 24-26, wherein the glass-ceramic article does not comprise petalite; and/or does not contain a lithium silicate crystalline phase.

38. The glass-ceramic article of any one of claims 23-26, wherein the glass-ceramic article having a thickness of 0.6mm has a haze of 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and even more preferably 0.1% or less; and/or a glass ceramic article having a thickness of 0.6mm, and having an average transmittance at a wavelength of 400 to 800nm of 85% or more, preferably 87% or more, more preferably 89% or more; and/or a glass-ceramic article having a thickness of 0.6mm, and has a transmittance at a wavelength of 550nm of 85% or more, preferably 90% or more, more preferably 91% or more.

39. The glass-ceramic article of any one of claims 23-26, wherein the glass-ceramic article has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more; and/or the crystal grain size is 50nm or less, preferably 40nm or less, more preferably 30nm or less.

40. The glass-ceramic article of any one of claims 23-26, wherein the glass-ceramic article has a surface stress of 600MPa or greater, preferably 650MPa or greater, and more preferably 700MPa or greater; and/or the depth of the ion exchange layer is 5 μm or more, preferably 10 μm or more, and more preferably 20 μm or more.

41. The glass-ceramic article of any one of claims 23-26, wherein the glass-ceramic article has a ball drop test height of 1200mm or greater, preferably 1300mm or greater, and more preferably 1400mm or greater; and/or a fracture toughness of 1MPa m^1/2Above, preferably 1.1MPa · m^1/2More preferably 1.2MPa · m or more^1/2The above; and/or a Vickers hardness of 650kgf/mm²Above, preferably 680kgf/mm²Above, more preferably 700kgf/mm²The above; and/or a four-point bending strength of 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more.

42. The glass-ceramic article of any one of claims 24-26, comprising: NiO: 0-2%; and/or Ni₂O₃: 0-2%; and/or a CoO: 0 to 1 percent; and/or Co₂O₃: 0 to 1 percent; and/or Fe₂O₃: 0 to 4 percent; and/or MnO₂: 0-2%; and/or Er₂O₃: 0 to 4 percent; and/or Nd₂O₃: 0 to 4 percent; and/or Cu₂O: 0-2%; and/or Pr₂O₅: 0 to 4 percent; and/or CeO₂：0～2％。

43. The glass-ceramic article of any one of claims 24-26, further comprising, in mole percent, less than 2% of an antimicrobial component, preferably less than 1% of an antimicrobial component, the antimicrobial component being Ag, AgO, Cu, CuO, Cu₂One or more of O.

44. Matrix glass, characterized in that its composition, expressed in mole percentages,comprises the following components: SiO 2₂：48～65％；Al₂O₃：10～20％；Li₂O：12～29％；ZnO：0.1～8％；P₂O₅：0.1～6.5％；ZrO₂: 0.1 to 8% of Al₂O₃/SiO₂0.18 to 0.38.

45. The matrix glass according to claim 44, further comprising, in mole percent: na (Na)₂O: 0 to 4 percent; and/or MgO: 0 to 7 percent; and/or K₂O: 0 to 5 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or Ln₂O₃: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or TiO₂: 0 to 4 percent; and/or a clarifying agent: 0 to 1 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

46. The matrix glass according to any one of claims 44 or 45, having a composition expressed in mole percent, wherein: al (Al)₂O₃/SiO₂0.18 to 0.38; and/or ZnO/Li₂O is 0.03 to 0.55; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.03 to 0.22; and/or P₂O₅/Al₂O₃0.08 to 0.4; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.15 to 1.5; and/or (Li)₂O+ZrO₂)/SiO₂0.2 to 0.7; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.25 to 0.8.

47. The matrix glass according to any one of claims 44 or 45, having a composition expressed in mole percent, wherein: SiO 2₂: 50-62%; and/or Al₂O₃: 11.5-18%; and/or Na₂O: 0 to 3 percent; and/or ZnO: 1-6%; and/or TiO₂: 0-2%; and/or Li₂O: 14-24%; and/or MgO: 1.5-6%; and/or K₂O: 0 to 3.5 percent; and/or SrO: 0-2%; and/or BaO: 0-2%; and/or CaO: 0-2%; and/or Ln₂O₃: 0-2%; and/or B₂O₃: 0 to 3 percent; and/or P₂O₅: 1-4.5%; and/or ZrO₂: 0.5-7.5%; and/or a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

48. The matrix glass according to any one of claims 44 or 45, having a composition expressed in mole percent, wherein: al (Al)₂O₃/SiO₂0.2 to 0.35; and/or ZnO/Li₂O is 0.05 to 0.4; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.05 to 0.18; and/or P₂O₅/Al₂O₃0.08 to 0.3; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.3 to 1.0; and/or (Li)₂O+ZrO₂)/SiO₂0.25 to 0.55; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.3 to 0.65.

49. The matrix glass according to any one of claims 44 or 45, having a composition expressed in mole percent, wherein: SiO 2₂: 52-58%; and/or Al₂O₃: 13-16%; and/or Na₂O: 0-2%; and/or ZnO: 1-6%; and/or TiO₂: 0 to 1.5 percent; and/or Li₂O: 16-21%; and/or MgO: 1.5-4.5%; and/or K₂O: 0 to 2.5 percent; and/or SrO: 0 to 1.5 percent; and/or BaO: 0 to 1 percent; and/or CaO: 0 to 1 percent; and/or Ln₂O₃: 0 to 1 percent; and/or B₂O₃: 0 to 1 percent; and/or P₂O₅: 1.5-4%; and/or ZrO₂: 1-6%; and/or clarificationCleaning agent: 0 to 0.25 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

50. The matrix glass according to any one of claims 44 or 45, having a composition expressed in mole percent, wherein: al (Al)₂O₃/SiO₂0.23 to 0.3; and/or ZnO/Li₂O is 0.08 to 0.25; and/or (P)₂O₅+ZnO)/(SiO₂+ MgO) of 0.06 to 0.15; and/or P₂O₅/Al₂O₃0.1 to 0.25; and/or (ZrO)₂+MgO+ZnO)/Al₂O₃0.4 to 0.75; and/or (Li)₂O+ZrO₂)/SiO₂0.3 to 0.5; and/or (Li)₂O+ZrO₂+ZnO)/SiO₂0.35 to 0.55.

51. The matrix glass according to any one of claims 44 or 45, having a composition expressed in mole percent, wherein: k₂O: 0-2%; and/or ZnO: 1.5-4.5%; and/or P₂O₅: 1.8-3.5%; and/or ZrO₂：1～5％。

52. The matrix glass according to any one of claims 44 or 45, comprising: NiO: 0-2%; and/or Ni₂O₃: 0-2%; and/or a CoO: 0 to 1 percent; and/or Co₂O₃: 0 to 1 percent; and/or Fe₂O₃: 0 to 4 percent; and/or MnO₂: 0-2%; and/or Er₂O₃: 0 to 4 percent; and/or Nd₂O₃: 0 to 4 percent; and/or Cu₂O: 0-2%; and/or Pr₂O₅: 0 to 4 percent; and/or CeO₂：0～2％。

53. The matrix glass according to any one of claims 44 or 45, whereinThe matrix glass then contains, in mol%, less than 2%, preferably less than 1%, of an antimicrobial component, the antimicrobial component being Ag, AgO, Cu, CuO, Cu₂One or more of O.

54. The matrix glass according to claim 44 or 45, wherein the component does not contain B₂O₃(ii) a And/or does not contain CaO; and/or no BaO; and/or does not contain SrO; and/or does not contain TiO₂(ii) a And/or do not contain La₂O₃(ii) a And/or does not contain Gd₂O₃。

55. The matrix glass of claim 44 or 45, wherein the matrix glass has a coefficient of thermal expansion of 50 x 10^-7/K～80×10^-7Preferably 55X 10,/K^-7/K～75×10^-7More preferably 60X 10,/K^-7/K～70×10^-7K; and/or the refractive index is 1.50 to 1.55, preferably 1.51 to 1.54, and more preferably 1.52 to 1.54.

56. The glass cover plate is characterized by being made of the glass ceramic according to any one of claims 1 to 22; and/or made using the glass-ceramic article of any one of claims 23 to 43; and/or is made of the matrix glass of any one of claims 44 to 55.

57. A glass component, characterized by being made of the glass ceramic according to any one of claims 1 to 22; and/or made using the glass-ceramic article of any one of claims 23 to 43; and/or is made of the matrix glass of any one of claims 44 to 55.

58. A display device comprising the glass-ceramic according to any one of claims 1 to 22; and/or a glass-ceramic article comprising any one of claims 23 to 43; and/or comprising a matrix glass according to any one of claims 44 to 55; and/or comprising the glass cover plate of claim 56; and/or comprising a glass component as claimed in claim 57.

59. An electronic device comprising the glass-ceramic according to any one of claims 1 to 22; and/or a glass-ceramic article comprising any one of claims 23 to 43; and/or comprising a matrix glass according to any one of claims 44 to 55; and/or comprising the glass cover plate of claim 56; and/or comprising a glass component as claimed in claim 57.