Search

CN-122003388-A - Glass ceramics, glass ceramics product and method for producing the same

CN122003388ACN 122003388 ACN122003388 ACN 122003388ACN-122003388-A

Abstract

The invention provides a microcrystalline glass product which comprises the following components in percentage by weight, wherein R 2 O is one or two of Na 2 O、K 2 O in ：SiO 2 ：65～78％;R 2 O：2～12％;Li 2 O：5～15％;Al 2 O 3 ：3～12％;ZrO 2 ：1.5～10％;CeO 2 ：0.01～0.6％;Ag 2 O：0.01～0.8％,. Through reasonable component design, the substrate glass can be treated through crystallization technology to obtain microcrystalline glass with blackened parts and transparent parts. The glass ceramics obtained by the invention are suitable for chemical strengthening, and the glass ceramics and glass ceramics products made of the glass ceramics have excellent mechanical properties.

Inventors

  • HU BIN
  • YUAN BAOPING
  • YU TIANLAI
  • JIANG DAO
  • WU WENXU

Assignees

  • 成都光明光电股份有限公司

Dates

Publication Date
20260508
Application Date
20240607
Priority Date
20240422

Claims (20)

  1. The microcrystalline glass product is characterized by comprising one or two of ：SiO 2 ：65～78％;R 2 O：2～12％;Li 2 O：5～15％;Al 2 O 3 ：3～12％;ZrO 2 ：1.5～10％;CeO 2 ：0.01～0.6％;Ag 2 O：0.01～0.8％, R 2 O and Na 2 O、K 2 O in percentage by weight.
  2. The glass ceramic product according to claim 1, further comprising, in weight percent, 0-1% of Sb 2 O 3 and/or 0-0.5% of SnO 2 and/or 0-5% of MO and/or 0-5% of Ln 2 O 3 and/or 0-1% of Fe 2 O 3 , wherein MO is one or more of MgO, caO, srO, baO, znO and Ln 2 O 3 is one or more of La 2 O 3 、Gd 2 O 3 、Y 2 O 3 .
  3. The microcrystalline glass product is characterized by comprising SiO 2 ：65～78％;R 2 O：2～12％;Li 2 O：5～15％;Al 2 O 3 ：3～12％;ZrO 2 ：1.5～10％;CeO 2 ：0.01～0.6％;Ag 2 O：0.01～0.8％;Sb 2 O 3 ：0～1％;SnO 2 ：0～0.5％;MO：0～5％;Ln 2 O 3 ：0～5％;Fe 2 O 3 ：0～1％ parts by weight, wherein R 2 O is one or two of Na 2 O、K 2 O, MO is one or more of MgO, caO, srO, baO, znO, and Ln 2 O 3 is one or more of La 2 O 3 、Gd 2 O 3 、Y 2 O 3 .
  4. A glass-ceramic product according to any one of claims 1 to 3, wherein the components, expressed in weight percent, satisfy one or more of the following 14 conditions: 1) SiO 2 /Li 2 O is 5.5-10.0, preferably SiO 2 /Li 2 O is 6.0-9.0, more preferably SiO 2 /Li 2 O is 7.0-8.5; 2) (Sb 2 O 3 +SnO 2 )/Ag 2 O is 0.1 to 5.0, preferably (Sb 2 O 3 +SnO 2 )/Ag 2 O is 0.5 to 3.5, more preferably (Sb 2 O 3 +SnO 2 )/Ag 2 O is 1.0 to 2.6); 3) (K 2 O+Na 2 O)/ZrO 2 is 0.5 to 7.1, preferably (K 2 O+Na 2 O)/ZrO 2 is 0.7 to 4.5, more preferably (K 2 O+Na 2 O)/ZrO 2 is 0.8 to 2.5; 4) Ag 2 O/CeO 2 is 1.0-10.0, preferably Ag 2 O/CeO 2 is 1.5-6.5, and more preferably Ag 2 O/CeO 2 is 2.0-4.5; 5) Li 2 O/ZrO 2 is 1.0 to 7.5, preferably Li 2 O/ZrO 2 is 1.2 to 5.0, more preferably Li 2 O/ZrO 2 is 1.4 to 4.3, and even more preferably Li 2 O/ZrO 2 is 1.6 to 3.0; 6) (SiO 2 +Li 2 O)/ZrO 2 is 8.0 to 55.0, preferably (SiO 2 +Li 2 O)/ZrO 2 is 10.0 to 37.0, more preferably (SiO 2 +Li 2 O)/ZrO 2 is 12.0 to 25.0, still more preferably (SiO 2 +Li 2 O)/ZrO 2 is 13.0 to 20.0; 7) ZrO 2 /(Ag 2 O+CeO 2 ) of 2.3 to 50.0, preferably ZrO 2 /(Ag 2 O+CeO 2 ) of 6.5 to 35.0, more preferably ZrO 2 /(Ag 2 O+CeO 2 ) of 8.5 to 20.0, still more preferably ZrO 2 /(Ag 2 O+CeO 2 ) of 11.0 to 18.0; 8) (Ag 2 O+SnO 2 +Sb 2 O 3 )/CeO 2 is 1.0 to 30.0, preferably (Ag 2 O+SnO 2 +Sb 2 O 3 )/CeO 2 is 3.0 to 20.0, more preferably (Ag 2 O+SnO 2 +Sb 2 O 3 )/CeO 2 is 5.0 to 12.5, still more preferably (Ag 2 O+SnO 2 +Sb 2 O 3 )/CeO 2 is 7.5 to 10.0; 9) (Sb 2 O 3 +SnO 2 +CeO 2 )/Ag 2 O is 0.1 to 10.0, preferably (Sb 2 O 3 +SnO 2 +CeO 2 )/Ag 2 O is 0.4 to 5.0, more preferably (Sb 2 O 3 +SnO 2 +CeO 2 )/Ag 2 O is 0.7 to 3.7, still more preferably (Sb 2 O 3 +SnO 2 +CeO 2 )/Ag 2 O is 1.5 to 3.2); 10 SnO 2 /(CeO 2 +SnO 2 ) of 0 to 0.9, preferably SnO 2 /(CeO 2 +SnO 2 ) of 0 to 0.6, more preferably SnO 2 /(CeO 2 +SnO 2 ) of 0 to 0.5; 11 R 2 O+Li 2 O+Al 2 O 3 to 30%, preferably R 2 O+Li 2 O+Al 2 O 3 to 17.5 to 29.5%, more preferably R 2 O+Li 2 O+Al 2 O 3 to 18.5 to 26%, still more preferably R 2 O+Li 2 O+Al 2 O 3 to 20 to 25%; 12 (SiO 2 +Al 2 O 3 )/(Li 2 O+Na 2 O+K 2 O) is 3.0 to 7.5, preferably (SiO 2 +Al 2 O 3 )/(Li 2 O+Na 2 O+K 2 O) is 3.7 to 6.5, more preferably (SiO 2 +Al 2 O 3 )/(Li 2 O+Na 2 O+K 2 O) is 4.3 to 6.0, still more preferably (SiO 2 +Al 2 O 3 )/(Li 2 O+Na 2 O+K 2 O) is 4.8 to 5.8; 13 MO/ZrO 2 is 2.5 or less, preferably MO/ZrO 2 is 1.5 or less, more preferably MO/ZrO 2 is 0.5 or less; 14 0.05-1.2% of Sb 2 O 3 +SnO 2 , preferably 0.1-1% of Sb 2 O 3 +SnO 2 , more preferably 0.2-0.7% of Sb 2 O 3 +SnO 2 , wherein R 2 O is one or two of Na 2 O、K 2 O and MO is one or more of MgO, caO, srO, baO, znO.
  5. A glass ceramic product according to any one of claims 1 to 3, wherein the components are expressed in weight percent, wherein 68 to 77% of SiO 2 , preferably 69.5 to 75.5% of SiO 2 ; and/or R 2 O3-10%, preferably 4-8%, and/or Li 2 O7-13%, preferably Li 2 O8.5-12%, and/or Al 2 O 3 4-10%, preferably Al 2 O 3 5-9%, and/or ZrO 2 2-8%, preferably ZrO 2 3-6.5%, and/or CeO 2 0.07-0.4%, preferably CeO 2 0.08-0.3%, and/or Ag 2 O0.1-0.6%, preferably Ag 2 O0.2-0.5%, and/or Sb 2 O 3 0.01-0.7%, preferably Sb 2 O 3 0.07-0.5%, and/or SnO 2 0-0.3%, preferably SnO 2 :0.2%, and/or MO 0-3%, preferably MO 0-1%, more preferably no MO, and/or one of Ln 2 O 3 -3%, preferably Na 2 O0.2-0.5%, and/or Fe 2 O 3 - 2 O 3 % of 3-0.3%, and/or one of 3-3%, preferably Fe 2 O 3 -3%, and/or 3-3% of Fe 2 O 3 , CaO, srO, baO, znO, ln 2 O 3 is one or more of La 2 O 3 、Gd 2 O 3 、Y 2 O 3 .
  6. A glass-ceramic product according to any one of claims 1 to 3, wherein the glass-ceramic product comprises one or more blackened portions and one or more transparent portions, or the glass-ceramic product is entirely blackened.
  7. The glass-ceramic article according to claim 6, wherein the glass-ceramic article comprises a lithium silicate crystal phase, preferably a lithium metasilicate crystal phase, more preferably, the weight percentage of the lithium metasilicate crystal phase in the blackened portion of the glass-ceramic article is 5 to 50%, further preferably, the weight percentage of the lithium metasilicate crystal phase in the blackened portion of the glass-ceramic article is 5 to 40%, still further preferably, the weight percentage of the lithium metasilicate crystal phase in the blackened portion of the glass-ceramic article is 10 to 30%.
  8. The glass-ceramic product according to claim 6, wherein the glass-ceramic product has an average transmittance T 400-800nm in the range of 400 to 800nm of at least 85.0%, preferably at least 88.0%, more preferably at least 90.0%, still more preferably at least 91.0%, still more preferably at least 91.5 to 95.0% and/or has an average transmittance T 400-800nm in the range of 400 to 800nm of at least 5.0%, preferably at most 3.0%, more preferably at most 1.5%, still more preferably at most 1.2%, still more preferably at most 0.5%, and/or has a transmittance T 870nm in the range of 870nm of at most 15.0%, preferably at most 0.1 to 12.5%, preferably at most 0.1 to 12%, more preferably at most 0.10%, still more preferably at most 0.1.10%, still more preferably at most 0.35%, still at most 0.0.0% to 3%, preferably at most 0.35%, and/or more preferably at most 0.0.35%, at most 0.0 to 3.5%, more preferably at most 0.0.35%.
  9. The glass-ceramic article according to claim 8, wherein the glass-ceramic article has a thickness of 0.5 to 1.5mm, preferably 0.8 to 1.2mm, more preferably 0.5mm, 0.7mm, 0.8mm, 0.9mm, 1.0mm, 1.1mm, 1.2mm.
  10. A glass-ceramic product according to any one of claims 1 to 3, wherein the glass-ceramic product has a falling ball test height II of 800mm or more, preferably 900mm or more, more preferably 1000mm or more, and even more preferably 1100mm or more.
  11. The microcrystalline glass is characterized by comprising one or two of R 2 O and Na 2 O、K 2 O, wherein the R 2 O is ：SiO 2 ：65～78％;R 2 O：2～12％;Li 2 O：5～15％;Al 2 O 3 ：3～12％;ZrO 2 ：1.5～10％;CeO 2 ：0.01～0.6％;Ag 2 O：0.01～0.8％,, and the Na 2 O、K 2 O is contained in the microcrystalline glass.
  12. The glass ceramic according to claim 11, further comprising, in weight percent, 0-1% of Sb 2 O 3 , and/or 0-0.5% of SnO 2 , and/or 0-5% of MO, and/or 0-5% of Ln 2 O 3 , and/or 0-1% of Fe 2 O 3 , wherein MO is one or more of MgO, caO, srO, baO, znO, and Ln 2 O 3 is one or more of La 2 O 3 、Gd 2 O 3 、Y 2 O 3 .
  13. The microcrystalline glass is characterized by comprising SiO 2 ：65～78％;R 2 O：2～12％;Li 2 O：5～15％;Al 2 O 3 ：3～12％;ZrO 2 ：1.5～10％;CeO 2 ：0.01～0.6％;Ag 2 O：0.01～0.8％;Sb 2 O 3 ：0～1％;SnO 2 ：0～0.5％;MO：0～5％;Ln 2 O 3 ：0～5％;Fe 2 O 3 ：0～1％ parts by weight, wherein R 2 O is one or two of Na 2 O、K 2 O, MO is one or more of MgO, caO, srO, baO, znO, and Ln 2 O 3 is one or more of La 2 O 3 、Gd 2 O 3 、Y 2 O 3 .
  14. The glass ceramic according to any one of claims 11 to 13, wherein the components thereof, expressed in weight percent, satisfy one or more of the following 14 conditions: 1) SiO 2 /Li 2 O is 5.5-10.0, preferably SiO 2 /Li 2 O is 6.0-9.0, more preferably SiO 2 /Li 2 O is 7.0-8.5; 2) (Sb 2 O 3 +SnO 2 )/Ag 2 O is 0.1 to 5.0, preferably (Sb 2 O 3 +SnO 2 )/Ag 2 O is 0.5 to 3.5, more preferably (Sb 2 O 3 +SnO 2 )/Ag 2 O is 1.0 to 2.6); 3) (K 2 O+Na 2 O)/ZrO 2 is 0.5 to 7.1, preferably (K 2 O+Na 2 O)/ZrO 2 is 0.7 to 4.5, more preferably (K 2 O+Na 2 O)/ZrO 2 is 0.8 to 2.5; 4) Ag 2 O/CeO 2 is 1.0-10.0, preferably Ag 2 O/CeO 2 is 1.5-6.5, and more preferably Ag 2 O/CeO 2 is 2.0-4.5; 5) Li 2 O/ZrO 2 is 1.0 to 7.5, preferably Li 2 O/ZrO 2 is 1.2 to 5.0, more preferably Li 2 O/ZrO 2 is 1.4 to 4.3, and even more preferably Li 2 O/ZrO 2 is 1.6 to 3.0; 6) (SiO 2 +Li 2 O)/ZrO 2 is 8.0 to 55.0, preferably (SiO 2 +Li 2 O)/ZrO 2 is 10.0 to 37.0, more preferably (SiO 2 +Li 2 O)/ZrO 2 is 12.0 to 25.0, still more preferably (SiO 2 +Li 2 O)/ZrO 2 is 13.0 to 20.0; 7) ZrO 2 /(Ag 2 O+CeO 2 ) of 2.3 to 50.0, preferably ZrO 2 /(Ag 2 O+CeO 2 ) of 6.5 to 35.0, more preferably ZrO 2 /(Ag 2 O+CeO 2 ) of 8.5 to 20.0, still more preferably ZrO 2 /(Ag 2 O+CeO 2 ) of 11.0 to 18.0; 8) (Ag 2 O+SnO 2 +Sb 2 O 3 )/CeO 2 is 1.0 to 30.0, preferably (Ag 2 O+SnO 2 +Sb 2 O 3 )/CeO 2 is 3.0 to 20.0, more preferably (Ag 2 O+SnO 2 +Sb 2 O 3 )/CeO 2 is 5.0 to 12.5, still more preferably (Ag 2 O+SnO 2 +Sb 2 O 3 )/CeO 2 is 7.5 to 10.0; 9) (Sb 2 O 3 +SnO 2 +CeO 2 )/Ag 2 O is 0.1 to 10.0, preferably (Sb 2 O 3 +SnO 2 +CeO 2 )/Ag 2 O is 0.4 to 5.0, more preferably (Sb 2 O 3 +SnO 2 +CeO 2 )/Ag 2 O is 0.7 to 3.7, still more preferably (Sb 2 O 3 +SnO 2 +CeO 2 )/Ag 2 O is 1.5 to 3.2); 10 SnO 2 /(CeO 2 +SnO 2 ) of 0 to 0.9, preferably SnO 2 /(CeO 2 +SnO 2 ) of 0 to 0.6, more preferably SnO 2 /(CeO 2 +SnO 2 ) of 0 to 0.5; 11 R 2 O+Li 2 O+Al 2 O 3 to 30%, preferably R 2 O+Li 2 O+Al 2 O 3 to 17.5 to 29.5%, more preferably R 2 O+Li 2 O+Al 2 O 3 to 18.5 to 26%, still more preferably R 2 O+Li 2 O+Al 2 O 3 to 20 to 25%; 12 (SiO 2 +Al 2 O 3 )/(Li 2 O+Na 2 O+K 2 O) is 3.0 to 7.5, preferably (SiO 2 +Al 2 O 3 )/(Li 2 O+Na 2 O+K 2 O) is 3.7 to 6.5, more preferably (SiO 2 +Al 2 O 3 )/(Li 2 O+Na 2 O+K 2 O) is 4.3 to 6.0, still more preferably (SiO 2 +Al 2 O 3 )/(Li 2 O+Na 2 O+K 2 O) is 4.8 to 5.8; 13 MO/ZrO 2 is 2.5 or less, preferably MO/ZrO 2 is 1.5 or less, more preferably MO/ZrO 2 is 0.5 or less; 14 0.05-1.2% of Sb 2 O 3 +SnO 2 , preferably 0.1-1% of Sb 2 O 3 +SnO 2 , more preferably 0.2-0.7% of Sb 2 O 3 +SnO 2 , wherein R 2 O is one or two of Na 2 O、K 2 O and MO is one or more of MgO, caO, srO, baO, znO.
  15. The glass ceramic according to any one of claims 11 to 13, wherein the glass ceramic comprises, by weight, 68 to 77% of SiO 2 , preferably 69.5 to 75.5% of SiO 2 ; and/or R 2 O3-10%, preferably 4-8%, and/or Li 2 O7-13%, preferably Li 2 O8.5-12%, and/or Al 2 O 3 4-10%, preferably Al 2 O 3 5-9%, and/or ZrO 2 2-8%, preferably ZrO 2 3-6.5%, and/or CeO 2 0.07-0.4%, preferably CeO 2 0.08-0.3%, and/or Ag 2 O0.1-0.6%, preferably Ag 2 O0.2-0.5%, and/or Sb 2 O 3 0.01-0.7%, preferably Sb 2 O 3 0.07-0.5%, and/or SnO 2 0-0.3%, preferably SnO 2 :0.2%, and/or MO 0-3%, preferably MO 0-1%, more preferably no MO, and/or one of Ln 2 O 3 -3%, preferably Na 2 O0.2-0.5%, and/or Fe 2 O 3 - 2 O 3 % of 3-0.3%, and/or one of 3-3%, preferably Fe 2 O 3 -3%, and/or 3-3% of Fe 2 O 3 , CaO, srO, baO, znO, ln 2 O 3 is one or more of La 2 O 3 、Gd 2 O 3 、Y 2 O 3 .
  16. The glass-ceramic according to any one of claims 11 to 13, wherein the glass-ceramic comprises one or more blackened portions and one or more transparent portions, or the glass-ceramic is entirely blackened.
  17. The glass-ceramic according to claim 16, wherein the glass-ceramic contains a lithium silicate crystal phase, preferably a lithium metasilicate crystal phase, more preferably, the weight percentage of the lithium metasilicate crystal phase in the blackened portion of the glass-ceramic is 5 to 50%, further preferably, the weight percentage of the lithium metasilicate crystal phase in the blackened portion of the glass-ceramic is 5 to 40%, still further preferably, the weight percentage of the lithium metasilicate crystal phase in the blackened portion of the glass-ceramic is 10 to 30%.
  18. The glass-ceramic according to claim 16, wherein the glass-ceramic has an average transmittance T 400-800nm of 85.0% or more, preferably 88.0% or more, more preferably 90.0% or more, still more preferably 91.0% or more, and further preferably 91.5 to 95.0% in a band of 400 to 800nm, and/or has an average transmittance T 400-800nm of 5.0% or less, preferably 3.0% or less, more preferably 1.5% or less, still more preferably 1.2% or less, still more preferably 0.5% or less, and/or has a transmittance T 870nm of 15.0% or less, preferably 0.1 to 12.5%, still more preferably 0.1 to 10%, still more preferably 0.0.0.0 to 35%, and further preferably 0.10% or more preferably 0.35% or less in a band of 400 to 800nm, and/or has a transmittance T 400-800nm of 0.0% or less, preferably 3.0% or 3.5% or less, more preferably 1.2 to 1.5% or more, still more preferably 0.5% or 0.0% or 0.35% or 3.35% or 3 to 3.0% in a blackened portion of the glass-ceramic in a band of 0 to 800 nm.
  19. The glass-ceramic according to claim 18, wherein the thickness of the glass-ceramic is 0.5-1.5 mm, preferably 0.8-1.2 mm, more preferably 0.5mm, 0.7mm, 0.8mm, 0.9mm, 1.0mm, 1.1mm, 1.2mm.
  20. The matrix glass is characterized by comprising one or two of the components of ：SiO 2 ：65～78％;R 2 O：2～12％;Li 2 O：5～15％;Al 2 O 3 ：3～12％;ZrO 2 ：1.5～10％;CeO 2 ：0.01～0.6％;Ag 2 O：0.01～0.8％, R 2 O and Na 2 O、K 2 O in percentage by weight.

Description

Glass ceramics, glass ceramics product and method for producing the same Technical Field The invention relates to microcrystalline glass, in particular to microcrystalline glass suitable for chemical strengthening. Background In recent years, with the continuous rising and development of consumer electronics, glass is used in a large amount as a transparent material with good performance in electronic devices. Since electronic devices have many precise electronic components inside, it is necessary to provide a cover plate or a case to protect the electronic components inside. Along with the diversification of market demands, the use scene of the protective cover glass is more and more complex, and the protective cover glass plays a role of not only protecting internal electronic devices, but also has other functions in some cases. For example, in the vital sign monitoring of a smart watch, a glass material needs to be partially transparent, but needs to be shielded from light elsewhere to avoid the interference of stray light, so that the glass material needs to have two parts, namely black and transparent, which presents new challenges to the glass manufacturing process technology. In the prior art, the cover plate material can be manufactured by adopting two different transparent and black materials through an embedded design mode, but because the two materials have different strength and large expansion coefficient difference, through holes are required to be processed, microcracks exist on the inner wall of glass, the strength of the cover plate material is reduced, the processing of smaller holes or abnormal patterns is difficult, and the manufacturing cost is high. The light-sensitive microcrystalline glass is microcrystalline glass with a large number of specific crystals generated in an irradiation area after the substrate glass is subjected to structural change in a glass body under the irradiation of ultraviolet light to generate crystal nuclei and is subjected to heat treatment at a certain temperature. The exposed part has high crystallinity, the color of the glass becomes dark, the light transmittance is reduced, the glass is not crystallized and still remains transparent in the unexposed part, so that the black and transparent parts simultaneously exist in the glass material through mask exposure. On the other hand, the glass materials used to make protective cover sheets are also required to have excellent mechanical properties so that they can withstand prolonged periods of conventional "touch" contact from use, as well as occasional bending, scoring and impact damage that may occur. In order to increase the resistance to damage caused by accidental external forces, the strength of the glass material may be increased by means of chemical strengthening. However, the photosensitive glass ceramics in the prior art cannot be chemically strengthened, or the chemical strengthening effect is poor due to the 'non-uniformity' (the difference between the structure of the crystallized part and the structure of the non-crystallized part) of the photosensitive glass ceramics, so that the use of high-performance electronic equipment and the like is difficult to meet. Disclosure of Invention For the above reasons, the technical problem to be solved by the present invention is to provide a matrix glass which can be used for manufacturing glass ceramics having a blackened portion and a transparent portion. The invention also provides glass ceramics suitable for chemical strengthening, and the glass ceramics and glass ceramics products made of the glass ceramics have excellent mechanical properties. The invention solves the technical problems by adopting the following solution: (1) The microcrystalline glass product comprises one or two of the components of ：SiO2：65～78％;R2O：2～12％;Li2O：5～15％;Al2O3：3～12％;ZrO2：1.5～10％;CeO2：0.01～0.6％;Ag2O：0.01～0.8％, R 2 O and Na 2O、K2 O in percentage by weight. (2) The glass ceramic product according to (1), which comprises, by weight, 0-1% of Sb 2O3, 0-0.5% of SnO 2, 0-5% of MO, 0-5% of Ln 2O3, and/or 0-1% of Fe 2O3, wherein MO is one or more of MgO, caO, srO, baO, znO, and Ln 2O3 is one or more of La 2O3、Gd2O3、Y2O3. (3) The microcrystalline glass product comprises SiO2：65～78％;R2O：2～12％;Li2O：5～15％;Al2O3：3～12％;ZrO2：1.5～10％;CeO2：0.01～0.6％;Ag2O：0.01～0.8％;Sb2O3：0～1％;SnO2：0～0.5％;MO：0～5％;Ln2O3：0～5％;Fe2O3：0～1％ of which the components are expressed in percentage by weight, wherein R 2 O is one or two of Na 2O、K2 O, MO is one or more of MgO, caO, srO, baO, znO, and Ln 2O3 is one or more of La 2O3、Gd2O3、Y2O3. (4) The glass ceramic product comprises SiO 2、R2O、Li2O、Al2O3、ZrO2、CeO2 and Ag 2 O, wherein R 2 O is one or two of Na 2O、K2 O, and the falling ball test height II of the glass ceramic product is more than 800 mm. (5) The microcrystalline glass product comprises one or more blackened parts and one or more transparent parts, wherein the microcrystalline glass product contains a lithium