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US-12623956-B2 - Glass-ceramic and substrate thereof

US12623956B2US 12623956 B2US12623956 B2US 12623956B2US-12623956-B2

Abstract

A glass ceramic substrate contains a glass ceramic having a compressive stress layer on a surface thereof and a crystalline phase containing LiAlSi 4 O 10 , quartz, and quartz solid solution. The glass ceramic has 60 to 80% of SiO 2 , 4 to 20% of Al 2 O 3 , more than 0 but less than or equal to 15% of Li 2 O, more than 0 but less than or equal to 12% of Na 2 O, 0 to 5% of K 2 O; more than 0 but less than or equal to 5% of ZrO 2 , 0 to 5% of P 2 O 5 , and 0 to 10% of TiO 2 . The quartz and the quartz solid solution crystalline phase account for 15 to 30% of the glass ceramic by wt %, the LiAlSi 4 O 10 crystalline phase accounts for not greater than 15% of the glass ceramic by wt %, and a ratio of ZrO 2 /Li 2 O is more than 0 but less than or equal to 0.35.

Inventors

  • Tianlai YU
  • Baoping YUAN
  • Xiaobing NIE

Assignees

  • CDGM GLASS CO., LTD

Dates

Publication Date
20260512
Application Date
20230428
Priority Date
20171201

Claims (20)

  1. 1 . A glass ceramic substrate, comprising: a glass ceramic having a compressive stress layer on a surface thereof, wherein the glass ceramic comprises 60 to 80% of SiO 2 ; 4 to 20% of Al 2 O 3 ; more than 0 but less than or equal to 15% of Li 2 O; more than 0 but less than or equal to 12% of Na 2 O; 0 to 5% of K 2 O; more than 0 but less than or equal to 5% of ZrO 2 ; 0 to 5% of P 2 O 5 ; and 0 to 10% of TiO 2 ; and a crystalline phase containing LiAlSi 4 O 10 , quartz, and quartz solid solution, wherein the quartz and the quartz solid solution crystalline phase account for 15 to 30% of the glass ceramic by wt %, the LiAlSi 4 O 10 crystalline phase accounts for not greater than 15% of the glass ceramic by wt %, and wherein a ratio of ZrO 2 /Li 2 O is more than 0 but less than or equal to 0.35.
  2. 2 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic further comprising more than 0 but less than or equal to 5% of B 2 O 3 ; and/or more than 0 but less than or equal to 2% of MgO; and/or more than 0 but less than or equal to 2% of ZnO; and/or more than 0 but less than or equal to 5% of CaO; and/or more than 0 but less than or equal to 5% of BaO; and/or more than 0 but less than or equal to 3% of FeO; and/or more than 0 but less than or equal to 2% of SnO 2 ; and/or more than 0 but less than or equal to 5% of SrO; and/or more than 0 but less than or equal to 10% of La 2 O 3 ; and/or more than 0 but less than or equal to 10% of Y 2 O 3 ; and/or to 10% of Nb 2 O 5 ; and/or more than 0 but less than or equal to 10% of Ta 2 O 5 ; and/or more than 0 but less than or equal to 5% of WO 3 .
  3. 3 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic consisting of 60 to 80% of SiO 2 , 4 to 20% of Al 2 O 3 ; more than 0 but less than or equal to 15% of Li 2 O; more than 0 but less than or equal to 12% of Na 2 O; more than 0 but less than or equal to 5% of ZrO 2 ; and one or more selected from the group consisting of more than 0 but less than or equal to 5% of P 2 O 5 , more than 0 but less than or equal to 10% of TiO 2 , more than 0 but less than or equal to 5% of B 2 O 3 , more than 0 but less than or equal to 5% of K 2 O, more than 0 but less than or equal to 2% of MgO, more than 0 but less than or equal to 2% of ZnO, more than 0 but less than or equal to 5% of CaO, more than 0 but less than or equal to 5% of BaO, more than 0 but less than or equal to 3% of FeO, more than 0 but less than or equal to 2% of SnO 2 , more than 0 but less than or equal to 5% of SrO, more than 0 but less than or equal to 10% of La 2 O 3 , more than 0 but less than or equal to 10% of Y 2 O 3 , more than 0 but less than or equal to 10% of Nb 2 O 5 , more than 0 but less than or equal to 10% of Ta 2 O 5 , more than 0 but less than or equal to 5% of WO 3 , more than 0 but less than or equal to 5% of a clarificant.
  4. 4 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic SiO 2 accounts for 65 to 78%; and/or Al 2 O 3 accounts for 5 to 18%; and/or more than 0 but less than or equal to 12% of Li 2 O; and/or Na 2 O accounts for 0.5 to 10%; and/or ZrO 2 accounts for 0.4 to 3%; and/or P 2 O 5 accounts for 0.4 to 3%; and/or B 2 O 3 accounts for 0 to 4%; and/or K 2 O accounts for 0.5 to 4%; and/or MgO accounts for more than 0 but less than or equal to 2%; and/or ZnO accounts for more than 0 but less than or equal to 2%; and/or CaO accounts for 0 to 4%; and/or BaO accounts for 0 to 4%; and/or FeO accounts for 0 to 1%; and/or SnO 2 accounts for 0.01 to 1%; and/or SrO accounts for 0 to 3%; and/or La 2 O 3 accounts for 0 to 9%; and/or Y 2 O 3 accounts for 0 to 9%; and/or Nb 2 O 5 accounts for 0 to 8%; and/or Ta 2 O 5 accounts for 0 to 8%; and/or WO 3 accounts for 0 to 2%; and/or the clarificant contains As 2 O 3 , Sb 2 O 3 , and CeO 2 and at least one selected from F, Cl, NOx, and SOx with a content of 0 to 5%.
  5. 5 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic SiO 2 /Li 2 O ratio is 4 to 10; and/or ZrO 2 /Li 2 O ratio is greater than 0 but less than or equal to 0.3; and/or Al 2 O 3 /(Na 2 O+Li 2 O) ratio is 0.5 to 2; and/or Li 2 O/Na 2 O ratio is 0.8 to 8.
  6. 6 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic SiO 2 accounts for 68 to 75%; and/or Al 2 O 3 accounts for 6 to 15%; and/or Li 2 O accounts for 6 to 10%; and/or Na 2 O accounts for 2 to 8%; and/or ZrO 2 accounts for 0.8 to 2%; and/or P 2 O 5 accounts for 0.8 to 2%; and/or TiO 2 accounts for 1 to 4%; and/or B 2 O 3 accounts for greater than 0% but less than 2%; and/or K 2 O accounts for 0.8 to 3%; and/or CaO accounts for 0 to 3%; and/or BaO accounts for 0 to 3%; and/or SnO 2 accounts for 0.05 to 0.4%; and/or SrO accounts for 0 to 1%; and/or La 2 O 3 accounts for greater than 0 but less than or equal to 8%; and/or Y 2 O 3 accounts for greater than 0 but less than or equal to 8%; and/or Nb 2 O 5 accounts for 0 to 5%; and/or Ta 2 O 5 accounts for 0 to 5%; and/or WO 3 accounts for 0 to 1%; and/or the clarificant accounts for 0 to 2%.
  7. 7 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic SiO 2 /Li 2 O ratio is 4.5 to 9.5; and/or ZrO 2 /Li 2 O ratio is greater than 0 but less than 0.35; and/or Al 2 O 3 /(Na 2 O+Li 2 O) ratio is 0.7 to 1.8; and/or Li 2 O/Na 2 O ratio is 1.5 to 7.5.
  8. 8 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic Na 2 O accounts for 4 to 8%, and/or Al 2 O 3 accounts for 7 to 15%; and/or ZrO 2 accounts for 1 to 2%; and/or P 2 O 5 accounts for 1 to 2%; and/or K 2 O accounts for 1 to 3%; and/or CaO accounts for 0 to 1%; and/or BaO accounts for 0 to 1%; and/or SnO 2 accounts for 0.05 to 0.2%; and/or the clarificant accounts for 0 to 1%; and/or SiO 2 /Li 2 O ratio is 5 to 9; and/or ZrO 2 /Li 2 O ratio is greater than 0 but less than or equal to 0.30; and/or Al 2 O 3 /(Na 2 O+Li 2 O) ratio is 1 to 1.5; and/or Li 2 O/Na 2 O ratio is 2 to 7.
  9. 9 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic TiO 2 accounts for 0.5 to 5%, and/or ZrO 2 +P 2 O 5 +TiO 2 account for 0.5 to 10%.
  10. 10 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic TiO 2 accounts for 1.5 to 4%, and/or ZrO 2 +P 2 O 5 +TiO 2 account for 2 to 6%.
  11. 11 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic NiO and/or Ni 2 O 3 with total amount thereof not greater than 6%, and a lower limit of the total amount thereof greater than 0.1%; or containing Pr 2 O 5 with content not greater than 8%, and a lower limit of the content thereof greater than 0.4%; or containing CoO and/or Co 2 O 3 with total amount thereof not greater than 2%, and a lower limit of the total amount thereof greater than 0.05%; or contains Cu 2 O and/or CeO 2 with total amount thereof not greater than 4%, and a lower limit of the total amount thereof greater than 0.5%; or containing Fe 2 O 3 with content not greater than 8%, or containing Fe 2 O 3 and CoO with CoO not greater than 0.3%; or containing Fe 2 O 3 and Co 2 O 3 with Co 2 O 3 not greater than 0.3%; or containing Fe 2 O 3 , CoO and NiO; or containing Fe 2 O 3 , Co 2 O 3 and NiO; or containing Fe 2 O 3 , CoO and Co 2 O 3 with a lower limit of the total amount of CoO and Co 2 O 3 greater than 0.2%; or containing Fe 2 O 3 , CoO, NiO and Co 2 O 3 ; or containing MnO 2 with content not greater than 4%, and lower limit of the content greater than 0.1%; or containing Er 2 O 3 with content not greater than 8%, and a lower limit of the content thereof greater than 0.4%; or containing Nd 2 O 3 with content not greater than 8%, and a lower limit of the content thereof greater than 0.4%; or containing Er 2 O 3 , Nd 2 O 3 and MnO 2 with Er 2 O 3 content within 6%, Nd 2 O 3 content within 4%, and MnO 2 content within 2%, and a lower limit of the total amount thereof greater than 0.9%; or containing Cr 2 O 3 with content not greater than 4%, and a lower limit of the content thereof greater than 0.2%; or containing V 2 O 5 with content not greater than 4%, and a lower limit of the content thereof greater than 0.2%.
  12. 12 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic a Li 2 Si 2 O 5 crystalline phase accounts for 20 to 40% of the glass ceramic by wt %.
  13. 13 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic the Li 2 Si 2 O 5 crystalline phase and the quartz and the quartz solid solution crystalline phase are main crystalline phases, the total content thereof is lower than 50% of the glass ceramic by wt %.
  14. 14 . The glass ceramic substrate according to claim 1 , having a Vickers hardness (Hv) is above 600 kgf/mm 2 .
  15. 15 . The glass ceramic substrate according to claim 1 , wherein the glass ceramic substrate does not break when a 32 g steel ball falls down from a height of 500 mm.
  16. 16 . The glass ceramic substrate according to claim 1 , having a three-point bending strength is more than 450 Mpa.
  17. 17 . The glass ceramic substrate according to claim 11 , having a compressive stress value of more than 300 Mpa.
  18. 18 . The glass ceramic substrate according to claim 11 , wherein the compressive stress layer has a thickness above 1 μm.
  19. 19 . A portable electronic device, containing the glass ceramic substrate according to claim 1 .
  20. 20 . A method for preparing the glass ceramic substrate according to claim 1 , comprising: shaping the glass ceramic; chemically tempering the shaped glass ceramic in a molten salt bath to form the compressive stress layer on a surface thereof.

Description

TECHNICAL FIELD The present invention relates to a glass ceramic and a substrate using the glass ceramic as a matrix. In particular, the present invention relates to a glass ceramic and substrate applicable to protective components such as portable electronic devices or optical devices and having high thermal conductivity and high strength. BACKGROUND Back covers are required for portable electronic devices such as smart phones, tablet PCs and other optical devices to protect internal electronic devices. Protective materials for the back covers, especially for electronic devices requiring wireless signals should have relatively high thermal conductivity, individualized colors and relatively high strength, can be used in harsh environments, and have good processing performance. In the past, metals were usually used as the protective materials for the back covers, but metal back covers would seriously affect reception of signals and could only be designed as sectional type. With development of 5G signals, the metal back covers are no longer feasible. Ceramic materials have good texture and relatively high thermal conductivity without impact on signals, but have poor processability and higher cost compared with glass. At present, simple glass has low thermal conductivity and insufficient strength, which restrains its use as a back cover material for electronic devices. Glass ceramic, also known as microcrystalline glass, separates out crystals in glass by heat treatment. Through internal dispersed crystals, glass ceramic can have physical properties unavailable in glass. Examples include mechanical strength such as Young's modulus and fracture toughness, etching properties for acidic or alkaline chemicals, thermal properties such as thermal expansion coefficient, increase and disappearance of glass transition temperature. Glass ceramic has higher mechanical properties and can improve thermal conductivity of glass due to formation of microcrystals in the glass. However, the glass ceramic in the past is not applicable to the protective materials due to poor thermal conductivity and strength. In addition, the conventional glass ceramic is rather unfit to be used as the protective material due to low productivity as a result of high viscosity or high devitrification resistance of raw glass. Japanese Patent Document (made public under special permission) No. 2014-114200 discloses a glass ceramic substrate for information recording media. After chemical tempering, the glass ceramic substrate is unable to obtain a sufficient compressive stress and cannot form a deeper stress layer. SUMMARY A technical problem to be solved by the present invention is to provide a glass ceramic and substrate with relatively high thermal conductivity and strength. The technical solution of the invention for solving the technical problem is as follows: a glass ceramic, contains the following components by wt %: 60 to 80% of SiO2; 4 to 20% of Al2O3; 0 to 15% of Li2O; more than 0 but less than or equal to 12% of Na2O; 0 to 5% of K2O; more than 0 but less than or equal to 5% of ZrO2; 0 to 5% of P2O5; and 0 to 10% of TiO2, wherein a crystalline phase contains at least one selected from R2SiO3, R2Si2O5, R2TiO3, R4Ti5O12, R3PO3, RAlSi2O6, RAlSiO4O10, R2Al2Si2O8, R4Al4Si5O18, quartz and quartz solid solution, and R is at least one selected from Li, Na and K. Further, the glass ceramic also contains 0 to 5% of B2O3; and/or 0 to 2% of MgO; and/or 0 to 2% of ZnO; and/or 0 to 5% of CaO; and/or 0 to 5% of BaO; and/or 0 to 3% of FeO; and/or 0 to 2% of SnO2; and/or 0 to 5% of SrO; and/or 0 to 10% of La2O3; and/or 0 to 10% of Y2O3; and/or 0 to 10% of Nb2O5; and/or 0 to 10% of Ta2O5; and/or 0 to 5% of WO3. A glass ceramic, is composed of the following components by wt %: 60 to 80% of SiO2; 4 to 20% of Al2O3; 0 to 15% of Li2O; more than 0 but less than or equal to 12% of Na2O; more than 0 but less than or equal to 5% of ZrO2; 0 to 5% of P2O5; 0 to 10% of TiO2; 0 to 5% of B2O3; 0 to 5% of K2O; 0 to 2% of MgO; 0 to 2% of ZnO; 0 to 5% of CaO; 0 to 5% of BaO; 0 to 3% of FeO; 0 to 2% of SnO2; 0 to 5% of SrO; 0 to 10% of La2O3; 0 to 10% of Y2O3; 0 to 10% of Nb2O5; 0 to 10% of Ta2O5; 0 to 5% of WO3; and 0 to 5% of a clarificant, wherein a crystalline phase contains at least one selected from R2SiO3, R2Si2O5, R2TiO3, R4Ti5O12, R3PO3, RAlSi2O6, RAlSiO4O10, R2Al2Si2O8, R4Al4Si5O18, quartz and quartz solid solution, and R is at least one selected from Li, Na and K. Further, SiO2 accounts for 65 to 78%; and/or Al2O3 accounts for 5 to 18%; and/or 0 to 12% of Li2O; and/or Na2O accounts for 0.5 to 10%; and/or ZrO2 accounts for 0.4 to 3%; and/or P2O5 accounts for 0.4 to 3%; and/or B2O3 accounts for 0 to 4%; and/or K2O accounts for 0.5 to 4%; and/or MgO accounts for more than 0 but less than or equal to 2%; and/or ZnO accounts for more than 0 but less than or equal to 2%; and/or CaO accounts for 0 to 4%; and/or BaO accounts for 0 to 4%; and/or FeO accounts for 0 to 1%; a