Glass ceramic, glass ceramic product and manufacturing method thereof

Abstract

The invention provides a glass ceramic and a glass ceramic product with excellent scratch resistance. The microcrystalline glass product comprises the following components in percentage by weight: 43-50% of SiO2; al2O3: 27.5% to 35%; 8.5% to 12% of ZnO; 0.1 to 5 percent of Li2O; 2 to 6 percent of TiO2; and 0-5% of MgO, wherein the ratio of (ZnO + MgO + SiO2) / Al2O3 is 1.5-2.15. Through reasonable component design, the obtained microcrystalline glass product has excellent scratch resistance.

Description

Technical Field

[0001] The present invention relates to a glass-ceramics, and particularly to a glass-ceramics and glass-ceramics products having excellent scratch resistance. Background Art

[0002] Glass-ceramics is a material in which crystals precipitate inside the glass by heat-treating the glass, and has more excellent mechanical properties than conventional glass. Its bending resistance, wear resistance, and drop resistance are significantly superior to those of conventional glass. With the continuous rise and development of consumer electronics products, etc., the application of glass-ceramics is increasing, such as devices like LED and LCD displays and computer monitors, and portable electronic products (such as mobile phones, tablet computers, and personal media terminals), etc. Although glass-ceramics is becoming more and more drop-resistant, compared with high-aluminum glass, the glass-ceramics in the prior art has poor scratch resistance and is difficult to meet the requirements for use as a cover plate material. Therefore, developing a glass-ceramics with excellent scratch resistance has become the goal pursued by technical personnel. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide a glass-ceramics and glass-ceramics products having excellent scratch resistance.

[0004] The technical solution adopted by the present invention to solve the technical problem is:

[0005] (1) A glass-ceramics product, the components of which are expressed in weight percentages and contain: SiO2: 43-50%; Al2O3: 27.5-35%; ZnO: 8.5-12%; Li2O: 0.1-5%; TiO2: 2-6%; MgO: 0-5%, wherein (ZnO + MgO + SiO2) / Al2O3 is 1.5-2.15.

[0006] (2) The glass-ceramics product according to (1), the components of which are expressed in weight percentages and further contain: Na2O: 0-7%; and / or ZrO2: 0-5%; and / or K2O: 0-3%; and / or B2O3: 0-4%; and / or CaO + BaO + SrO: 0-5%; and / or Ln2O3: 0-8%; and / or clarifying agent: 0-2%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

[0007] (3) A glass-ceramics product, the components of which contain SiO2, Al2O3, ZnO, Li2O, and TiO2, the components of which are expressed in weight percentages and contain 0-5% of MgO, wherein (ZnO + MgO + SiO2) / Al2O3 is 1.5-2.15, and the scratch width of the glass-ceramics product is less than 30 μm.

[0008] (4) The glass-ceramic article according to (3), in terms of weight percentage, contains: SiO2: 43 to 50%; and / or Al2O3: 27.5 to 35%; and / or ZnO: 8.5 to 12%; and / or Li2O: 0.1 to 5%; and / or TiO2: 2 to 6%; and / or Na2O: 0 to 7%; and / or ZrO2: 0 to 5%; and / or K2O: 0 to 3%; and / or B2O3: 0 to 4%; and / or CaO + BaO + SrO: 0 to 5%; and / or Ln2O3: 0 to 8%; and / or clarifying agent: 0 to 2%, wherein the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

[0009] (5) A glass-ceramic article, the components of which contain SiO2, Al2O3, ZnO, Li2O, and TiO2, and the glass-ceramic article contains a spinel crystal phase.

[0010] (6) A glass-ceramic article contains a spinel crystal phase, and the grain size of the glass-ceramic article is below 70 nm.

[0011] (7) A glass-ceramic article contains a spinel crystal phase, and the Young's modulus of the glass-ceramic article is 80 to 105 GPa.

[0012] (8) A glass-ceramic article contains a spinel crystal phase. For a glass-ceramic article with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 to 800 nm is 85% or more.

[0013] (9) A glass-ceramic article, the components of which contain SiO2, Al2O3, and ZnO, and the surface stress of the glass-ceramic article is 40 MPa or more.

[0014] (10) The glass-ceramic article according to any one of (5) to (9), in terms of weight percentage, contains: SiO2: 43 to 50%; Al2O3: 27.5 to 35%; ZnO: 8.5 to 12%; Li2O: 0.1 to 5%; TiO2: 2 to 6%.

[0015] (11) The glass-ceramic article according to any one of (5) to (10), in terms of weight percentage, further contains: MgO: 0 to 5%; and / or Na2O: 0 to 7%; and / or ZrO2: 0 to 5%; and / or K2O: 0 to 3%; and / or B2O3: 0 to 4%; and / or CaO + BaO + SrO: 0 to 5%; and / or Ln2O3: 0 to 8%; and / or clarifying agent: 0 to 2%, wherein the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

[0016] (12) Glass-ceramic product, the components of which are expressed by weight percentage and contain: SiO2: 43-50%; Al2O3: 27.5-35%; ZnO: 8.5-12%; Li2O: 0.1-5%; TiO2: 2-6%.

[0017] (13) The glass-ceramic product according to (12), the components of which are expressed by weight percentage, further contain: MgO: 0-5%; and / or Na2O: 0-7%; and / or ZrO2: 0-5%; and / or K2O: 0-3%; and / or B2O3: 0-4%; and / or CaO+BaO+SrO: 0-5%; and / or Ln2O3: 0-8%; and / or clarifying agent: 0-2%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0018] (14) Glass-ceramic product, the components of which are expressed by weight percentage, consists of SiO2: 43-50%; Al2O3: 27.5-35%; ZnO: 8.5-12%; Li2O: 0.1-5%; TiO2: 2-6%; MgO: 0-5%; Na2O: 0-7%; ZrO2: 0-5%; K2O: 0-3%; B2O3: 0-4%; CaO+BaO+SrO: 0-5%; Ln2O3: 0-8%; clarifying agent: 0-2%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0019] (15) The glass-ceramic product according to any one of (1)-(14), the components of which are expressed by weight percentage, satisfy one or more of the following 6 cases:

[0020] 1) (ZnO+MgO+SiO2) / Al2O3 is 1.5-2.15, preferably (ZnO+MgO+SiO2) / Al2O3 is 1.6-2.15, more preferably (ZnO+MgO+SiO2) / Al2O3 is 1.8-2.1;

[0021] 2) Al2O3 / Li2O is 11.0-60.0, preferably Al2O3 / Li2O is 12.0-40.0, more preferably Al2O3 / Li2O is 13.0-20.0;

[0022] 3) (ZnO+MgO) / (Li2O+Na2O) is 1.5-5.0, preferably (ZnO+MgO) / (Li2O+Na2O) is 1.7-4.5, more preferably (ZnO+MgO) / (Li2O+Na2O) is 1.8-4.0;

[0023] 4) (TiO2 + ZrO2) / (Li2O + Na2O) is 0.5 to 5.0, preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 3.0, more preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 1.5;

[0024] 5) SiO2 / Al2O3 is 1.3 to 1.8, preferably SiO2 / Al2O3 is 1.4 to 1.7, more preferably SiO2 / Al2O3 is 1.45 to 1.67;

[0025] 6) (Al2O3 + Ln2O3) / Li2O is 14.5 to 100.0, preferably (Al2O3 + Ln2O3) / Li2O is 15.0 to 60.0, more preferably (Al2O3 + Ln2O3) / Li2O is 16.0 to 40.0, where Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0026] (16) The glass-ceramic article according to any one of (1) to (14), in terms of weight percentage, contains: SiO2: 44 to 49%, preferably SiO2: 44 to 48%; and / or Al2O3: 28 to 34%, preferably Al2O3: 28 to 33%; and / or Li2O: 1 to 5%, preferably Li2O: 1 to 4%; and / or ZnO: 9 to 12%, preferably ZnO: 9 to 11%; and / or TiO2: 2 to 5%, preferably TiO2: 2 to 4%; and / or K2O: 0 to 2%, preferably K2O: 0 to 1%; and / or Ln2O3: 0.1 to 6%, preferably Ln2O3: 0.1 to 3%; and / or ZrO2: 0.5 to 4%, preferably ZrO2: 1 to 3%; and / or Na2O: 1 to 6%, preferably Na2O: 2 to 5%; and / or MgO: 1 to 4%, preferably MgO: 1 to 3%; and / or B2O3: 0 to 2%, preferably B2O3: 0 to 1%; and / or CaO + BaO + SrO: 0 to 4%, preferably CaO + BaO + SrO: 0 to 2%; and / or clarifying agent: 0 to 1%, preferably clarifying agent: 0 to 0.5%, where Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0027] (17) The glass-ceramic article according to any one of (1) to (14), in terms of weight percentage, its components contain: Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 5%, preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 2%, more preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 1%, further preferably does not contain Nb2O5, and / or does not contain WO3, and / or does not contain Bi2O3, and / or does not contain Ta2O5, and / or does not contain TeO2.

[0028] (18) The glass-ceramic article according to any one of (1) to (14), the glass-ceramic article does not contain P2O5, and / or does not contain B2O3, and / or does not contain SnO2, and / or does not contain SnO.

[0029] (19) The glass-ceramic article according to any one of (1) to (14), the glass-ceramic article contains a spinel crystal phase, preferably the spinel crystal phase has a higher weight percentage than other crystal phases, more preferably the weight percentage of the spinel crystal phase in the glass-ceramic article is 20 to 50%, further preferably the weight percentage of the spinel crystal phase in the glass-ceramic article is 30 to 50%, and even more preferably the weight percentage of the spinel crystal phase in the glass-ceramic article is 30 to 45%.

[0030] (20) The glass-ceramic article according to (19), the spinel crystal phase is ZnAl2O4.

[0031] (21) The glass-ceramic article according to any one of (1) to (14), the glass-ceramic article does not contain a spodumene crystal phase, and / or does not contain a zirconia crystal phase, and / or does not contain a quartz crystal phase, and / or does not contain a quartz solid solution crystal phase, and / or does not contain a Zn2SiO4 crystal phase.

[0032] (22) The glass-ceramic product according to any one of (1) to (14), wherein the grain size of the glass-ceramic product is 70 nm or less, preferably 60 nm or less, more preferably less than 50 nm, and further preferably 48 nm or less; and / or the surface stress is 40 MPa or more, preferably 80 - 200 MPa, more preferably 100 - 200 MPa; and / or the height of the ball-drop test is 800 mm or more, preferably 1000 mm or more, more preferably 1200 mm or more; and / or the drop resistance is 800 mm or more, preferably 1000 mm or more, more preferably 1200 mm or more; and / or the extrusion resistance strength is 200 N or more, preferably 250 N or more, more preferably 300 N or more; and / or the Young's modulus E is 80 - 105 GPa, preferably 85 - 105 GPa, more preferably 90 - 105 GPa; and / or the scratch width is less than 30 μm, preferably 25 μm or less, more preferably 20 μm or less; and / or the Vickers hardness is 600 kgf / mm 2 or more, preferably 650 - 800 kgf / mm 2 , more preferably 680 - 800 kgf / mm 2 ; and / or for a glass-ceramic product with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 - 800 nm is 85% or more, preferably 87% or more, more preferably 88% or more.

[0033] (23) Glass-ceramic, the components of which are expressed by weight percentage and contain: SiO2: 43 - 50%; Al2O3: 27.5 - 35%; ZnO: 8.5 - 12%; Li2O: 0.1 - 5%; TiO2: 2 - 6%; MgO: 0 - 5%, where (ZnO + MgO + SiO2) / Al2O3 is 1.5 - 2.15.

[0034] (24) The glass-ceramic according to (23), the components of which are expressed by weight percentage and further contain: Na2O: 0 - 7%; and / or ZrO2: 0 - 5%; and / or K2O: 0 - 3%; and / or B2O3: 0 - 4%; and / or CaO + BaO + SrO: 0 - 5%; and / or Ln2O3: 0 - 8%; and / or clarifying agent: 0 - 2%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0035] (25) Glass-ceramic, the components of which contain SiO2, Al2O3, ZnO, Li2O and TiO2, the components of which are expressed by weight percentage and contain 0 - 5% of MgO, where (ZnO + MgO + SiO2) / Al2O3 is 1.5 - 2.15, and the glass-ceramic contains a spinel crystal phase.

[0036] (26) The glass-ceramics according to (25), in terms of weight percentage of components, contains: SiO2: 43 - 50%; and / or Al2O3: 27.5 - 35%; and / or ZnO: 8.5 - 12%; and / or Li2O: 0.1 - 5%; and / or TiO2: 2 - 6%; and / or Na2O: 0 - 7%; and / or ZrO2: 0 - 5%; and / or K2O: 0 - 3%; and / or B2O3: 0 - 4%; and / or CaO + BaO + SrO: 0 - 5%; and / or Ln2O3: 0 - 8%; and / or clarifying agent: 0 - 2%, where the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0037] (27) Glass-ceramics, whose components contain SiO2, Al2O3, ZnO, Li2O and TiO2, and the glass-ceramics contain a spinel crystal phase.

[0038] (28) Glass-ceramics, containing a spinel crystal phase, and the grain size of the glass-ceramics is below 70 nm.

[0039] (29) Glass-ceramics, containing a spinel crystal phase, and the Young's modulus of the glass-ceramics is 80 - 105 GPa.

[0040] (30) Glass-ceramics, whose components contain SiO2, Al2O3, ZnO, and for the glass-ceramics with a thickness below 2.0 mm, the average light transmittance at a wavelength of 400 - 800 nm is above 85%.

[0041] (31) Glass-ceramics, whose components contain SiO2, Al2O3, ZnO, and the Vickers hardness of the glass-ceramics is 500 kgf / mm 2 or more.

[0042] (32) The glass-ceramics according to any one of (27) - (31), in terms of weight percentage of components, contains: SiO2: 43 - 50%; Al2O3: 27.5 - 35%; ZnO: 8.5 - 12%; Li2O: 0.1 - 5%; TiO2: 2 - 6%.

[0043] (33) The glass-ceramics according to any one of (27) - (32), in terms of weight percentage of components, further contains: MgO: 0 - 5%; and / or Na2O: 0 - 7%; and / or ZrO2: 0 - 5%; and / or K2O: 0 - 3%; and / or B2O3: 0 - 4%; and / or CaO + BaO + SrO: 0 - 5%; and / or Ln2O3: 0 - 8%; and / or clarifying agent: 0 - 2%, where the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0044] (34) Glass-ceramics, the components of which are expressed in weight percentages, contain: SiO2: 43-50%; Al2O3: 27.5-35%; ZnO: 8.5-12%; Li2O: 0.1-5%; TiO2: 2-6%.

[0045] (35) The glass-ceramics according to (34), the components of which are expressed in weight percentages, further contain: MgO: 0-5%; and / or Na2O: 0-7%; and / or ZrO2: 0-5%; and / or K2O: 0-3%; and / or B2O3: 0-4%; and / or CaO+BaO+SrO: 0-5%; and / or Ln2O3: 0-8%; and / or clarifying agent: 0-2%, where the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0046] (36) Glass-ceramics, the components of which are expressed in weight percentages, consist of SiO2: 43-50%; Al2O3: 27.5-35%; ZnO: 8.5-12%; Li2O: 0.1-5%; TiO2: 2-6%; MgO: 0-5%; Na2O: 0-7%; ZrO2: 0-5%; K2O: 0-3%; B2O3: 0-4%; CaO+BaO+SrO: 0-5%; Ln2O3: 0-8%; clarifying agent: 0-2%, where the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0047] (37) The glass-ceramics according to any one of (23)-(36), the components of which are expressed in weight percentages, satisfy one or more of the following 6 cases:

[0048] 1) (ZnO + MgO + SiO2) / Al2O3 is 1.5-2.15, preferably (ZnO + MgO + SiO2) / Al2O3 is 1.6-2.15, more preferably (ZnO + MgO + SiO2) / Al2O3 is 1.8-2.1;

[0049] 2) Al2O3 / Li2O is 11.0-60.0, preferably Al2O3 / Li2O is 12.0-40.0, more preferably Al2O3 / Li2O is 13.0-20.0;

[0050] 3) (ZnO + MgO) / (Li2O + Na2O) is 1.5-5.0, preferably (ZnO + MgO) / (Li2O + Na2O) is 1.7-4.5, more preferably (ZnO + MgO) / (Li2O + Na2O) is 1.8-4.0;

[0051] 4) The value of (TiO2 + ZrO2) / (Li2O + Na2O) is from 0.5 to 5.0, preferably (TiO2 + ZrO2) / (Li2O + Na2O) is from 0.7 to 3.0, more preferably (TiO2 + ZrO2) / (Li2O + Na2O) is from 0.7 to 1.5;

[0052] 5) The value of SiO2 / Al2O3 is from 1.3 to 1.8, preferably SiO2 / Al2O3 is from 1.4 to 1.7, more preferably SiO2 / Al2O3 is from 1.45 to 1.67;

[0053] 6) The value of (Al2O3 + Ln2O3) / Li2O is from 14.5 to 100.0, preferably (Al2O3 + Ln2O3) / Li2O is from 15.0 to 60.0, more preferably (Al2O3 + Ln2O3) / Li2O is from 16.0 to 40.0, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0054] (38) The glass-ceramics according to any one of (23) to (36), in terms of weight percentage, contain: SiO2: 44 to 49%, preferably SiO2: 44 to 48%; and / or Al2O3: 28 to 34%, preferably Al2O3: 28 to 33%; and / or Li2O: 1 to 5%, preferably Li2O: 1 to 4%; and / or ZnO: 9 to 12%, preferably ZnO: 9 to 11%; and / or TiO2: 2 to 5%, preferably TiO2: 2 to 4%; and / or K2O: 0 to 2%, preferably K2O: 0 to 1%; and / or Ln2O3: 0.1 to 6%, preferably Ln2O3: 0.1 to 3%; and / or ZrO2: 0.5 to 4%, preferably ZrO2: 1 to 3%; and / or Na2O: 1 to 6%, preferably Na2O: 2 to 5%; and / or MgO: 1 to 4%, preferably MgO: 1 to 3%; and / or B2O3: 0 to 2%, preferably B2O3: 0 to 1%; and / or CaO + BaO + SrO: 0 to 4%, preferably CaO + BaO + SrO: 0 to 2%; and / or fining agent: 0 to 1%, preferably fining agent: 0 to 0.5%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0055] (39) The glass-ceramics according to any one of (23) to (36), in terms of weight percentage, contains: Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 5%, preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 2%, more preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 1%, further preferably does not contain Nb2O5, and / or does not contain WO3, and / or does not contain Bi2O3, and / or does not contain Ta2O5, and / or does not contain TeO2.

[0056] (40) The glass-ceramics according to any one of (23) to (36), does not contain P2O5, and / or does not contain B2O3, and / or does not contain SnO2, and / or does not contain SnO.

[0057] (41) The glass-ceramics according to any one of (23) to (36), contains a spinel crystal phase, preferably the spinel crystal phase has a higher weight percentage than other crystal phases, more preferably the weight percentage of the spinel crystal phase in the glass-ceramics is 20 to 50%, further preferably the weight percentage of the spinel crystal phase in the glass-ceramics is 30 to 50%, still further preferably the weight percentage of the spinel crystal phase in the glass-ceramics is 30 to 45%.

[0058] (42) The glass-ceramics according to any one of (23) to (36), the spinel crystal phase is ZnAl2O4.

[0059] (43) The glass-ceramics according to any one of (23) to (36), does not contain a spodumene crystal phase, and / or does not contain a zirconia crystal phase, and / or does not contain a quartz crystal phase, and / or does not contain a quartz solid solution crystal phase, and / or does not contain a Zn2SiO4 crystal phase.

[0060] (44) The glass-ceramics according to any one of (23) to (36), the grain size of the glass-ceramics is 70 nm or less, preferably 60 nm or less, more preferably less than 50 nm, further preferably 48 nm or less; and / or the Vickers hardness is 500 kgf / mm 2 or more, preferably 600 to 750 kgf / mm 2 , more preferably 650 to 750 kgf / mm 2 ; and / or the Young's modulus is 80 to 105 GPa, preferably 85 to 105 GPa, more preferably 90 to 105 GPa; and / or for the glass-ceramics with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 to 800 nm is 85% or more, preferably 87% or more, more preferably 88% or more.

[0061] (45) Substrate glass, the components of which are expressed in weight percentages and contain: SiO2: 43-50%; Al2O3: 27.5-35%; ZnO: 8.5-12%; Li2O: 0.1-5%; TiO2: 2-6%.

[0062] (46) The substrate glass according to (34), the components of which are expressed in weight percentages, further contains: MgO: 0-5%; and / or Na2O: 0-7%; and / or ZrO2: 0-5%; and / or K2O: 0-3%; and / or B2O3: 0-4%; and / or CaO+BaO+SrO: 0-5%; and / or Ln2O3: 0-8%; and / or fining agent: 0-2%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0063] (47) Substrate glass, the components of which are expressed in weight percentages, consists of SiO2: 43-50%; Al2O3: 27.5-35%; ZnO: 8.5-12%; Li2O: 0.1-5%; TiO2: 2-6%; MgO: 0-5%; Na2O: 0-7%; ZrO2: 0-5%; K2O: 0-3%; B2O3: 0-4%; CaO+BaO+SrO: 0-5%; Ln2O3: 0-8%; fining agent: 0-2%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0064] (48) The substrate glass according to any one of (45)-(47), the components of which are expressed in weight percentages, satisfies one or more of the following 6 cases:

[0065] 1) (ZnO+MgO+SiO2) / Al2O3 is 1.5-2.15, preferably (ZnO+MgO+SiO2) / Al2O3 is 1.6-2.15, more preferably (ZnO+MgO+SiO2) / Al2O3 is 1.8-2.1;

[0066] 2) Al2O3 / Li2O is 11.0-60.0, preferably Al2O3 / Li2O is 12.0-40.0, more preferably Al2O3 / Li2O is 13.0-20.0;

[0067] 3) (ZnO+MgO) / (Li2O+Na2O) is 1.5-5.0, preferably (ZnO+MgO) / (Li2O+Na2O) is 1.7-4.5, more preferably (ZnO+MgO) / (Li2O+Na2O) is 1.8-4.0;

[0068] 4) The value of (TiO2 + ZrO2) / (Li2O + Na2O) is from 0.5 to 5.0, preferably (TiO2 + ZrO2) / (Li2O + Na2O) is from 0.7 to 3.0, more preferably (TiO2 + ZrO2) / (Li2O + Na2O) is from 0.7 to 1.5;

[0069] 5) The value of SiO2 / Al2O3 is from 1.3 to 1.8, preferably SiO2 / Al2O3 is from 1.4 to 1.7, more preferably SiO2 / Al2O3 is from 1.45 to 1.67;

[0070] 6) The value of (Al2O3 + Ln2O3) / Li2O is from 14.5 to 100.0, preferably (Al2O3 + Ln2O3) / Li2O is from 15.0 to 60.0, more preferably (Al2O3 + Ln2O3) / Li2O is from 16.0 to 40.0, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0071] (49) For the base glass according to any one of (45) - (47), its components are expressed by weight percentage and contain: SiO2: 44 - 49%, preferably SiO2: 44 - 48%; and / or Al2O3: 28 - 34%, preferably Al2O3: 28 - 33%; and / or Li2O: 1 - 5%, preferably Li2O: 1 - 4%; and / or ZnO: 9 - 12%, preferably ZnO: 9 - 11%; and / or TiO2: 2 - 5%, preferably TiO2: 2 - 4%; and / or K2O: 0 - 2%, preferably K2O: 0 - 1%; and / or Ln2O3: 0.1 - 6%, preferably Ln2O3: 0.1 - 3%; and / or ZrO2: 0.5 - 4%, preferably ZrO2: 1 - 3%; and / or Na2O: 1 - 6%, preferably Na2O: 2 - 5%; and / or MgO: 1 - 4%, preferably MgO: 1 - 3%; and / or B2O3: 0 - 2%, preferably B2O3: 0 - 1%; and / or CaO + BaO + SrO: 0 - 4%, preferably CaO + BaO + SrO: 0 - 2%; and / or clarifying agent: 0 - 1%, preferably clarifying agent: 0 - 0.5%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0072] (50) The base glass according to any one of (45) to (47), in terms of weight percentage of its components, contains: Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 5%, preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 2%, more preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 1%, and further preferably does not contain Nb2O5, and / or does not contain WO3, and / or does not contain Bi2O3, and / or does not contain Ta2O5, and / or does not contain TeO2.

[0073] (51) The base glass according to any one of (45) to (47), does not contain P2O5, and / or does not contain B2O3, and / or does not contain SnO2, and / or does not contain SnO in the base glass.

[0074] (52) The glass cover plate contains the glass-ceramic article according to any one of (1) to (22), and / or the glass-ceramic according to any one of (23) to (44).

[0075] (53) The glass component contains the glass-ceramic article according to any one of (1) to (22), and / or the glass-ceramic according to any one of (23) to (44).

[0076] (54) The electronic device contains the glass-ceramic article according to any one of (1) to (22), and / or the glass-ceramic according to any one of (23) to (44), and / or the glass cover plate according to (52), and / or the glass component according to (53).

[0077] (55) The display device contains the glass-ceramic article according to any one of (1) to (22), and / or the glass-ceramic according to any one of (23) to (44), and / or the glass cover plate according to (52), and / or the glass component according to (53).

[0078] (56) The manufacturing method of the glass-ceramic article according to any one of (1) to (22), the method includes the following steps: forming a base glass, forming a glass-ceramic from the base glass through a crystallization process, and then forming a glass-ceramic article from the glass-ceramic through a chemical strengthening process.

[0079] (57) The manufacturing method of the glass-ceramic article according to (56), the forming of the base glass includes the following steps: mixing the raw materials evenly according to the component ratio, then putting them into a crucible, melting in an electric furnace or a gas furnace within a temperature range of 1500 to 1700 °C for 5 to 24 hours, preferably the melting temperature is 1500 to 1600 °C, and then obtaining the base glass after clarification, homogenization, forming, and annealing. The clarification temperature is 1550 to 1650 °C, and the annealing temperature is 550 to 650 °C.

[0080] (58) The manufacturing method of the glass-ceramics product according to (56), wherein the crystallization process comprises the following steps: heating to a specified crystallization temperature, maintaining the temperature for a certain period of time after reaching the crystallization temperature, and then cooling down. The crystallization temperature is 600 to 800 °C, preferably 650 to 750 °C, and the holding time at the crystallization temperature is 1 to 10 hours, preferably 3 to 6 hours.

[0081] (59) The manufacturing method of the glass-ceramics product according to (56), wherein the crystallization process comprises the following steps: performing a nucleation process treatment at a first temperature, and then performing a crystal growth process treatment at a second temperature.

[0082] (60) The manufacturing method of the glass-ceramics product according to (59), wherein the crystallization process comprises: the first temperature is 600 to 700 °C, the second temperature is greater than 750 °C but less than or equal to 900 °C, the holding time at the first temperature is 1 to 6 hours, and the holding time at the second temperature is 2 to 5 hours.

[0083] (61) The manufacturing method of the glass-ceramics product according to (56), wherein the chemical strengthening process comprises: immersing the glass-ceramics in a molten Na salt bath at 350 to 470 °C for 1 to 36 hours, preferably in the temperature range of 400 to 460 °C, preferably in the time range of 2 to 15 hours; and / or immersing the glass-ceramics in a mixed salt bath of molten K salt and Na salt at 360 to 460 °C for 1 to 36 hours, preferably in the time range of 2 to 24 hours.

[0084] (62) The manufacturing method of the glass-ceramics according to any one of (23) to (44), wherein the method comprises the following steps: forming a base glass, and then forming the glass-ceramics from the base glass through a crystallization process.

[0085] (63) The manufacturing method of the glass-ceramics according to (62), wherein forming the base glass comprises the following steps: mixing the raw materials evenly according to the component ratio, then placing them in a crucible, melting in an electric furnace or a gas furnace within the temperature range of 1500 to 1700 °C for 5 to 24 hours, preferably the melting temperature is 1500 to 1600 °C, and then obtaining the base glass through clarification, homogenization, shaping, and annealing. The clarification temperature is 1550 to 1650 °C, and the annealing temperature is 550 to 650 °C.

[0086] (64) The manufacturing method of the glass-ceramics according to (62), wherein the crystallization process comprises the following steps: heating to a specified crystallization temperature, maintaining the temperature for a certain period of time after reaching the crystallization temperature, and then cooling down. The crystallization temperature is 600 - 800 °C, preferably 650 - 750 °C, and the holding time at the crystallization temperature is 1 - 10 hours, preferably 3 - 6 hours.

[0087] (65) The manufacturing method of the glass-ceramics according to (62), wherein the crystallization process comprises the following steps: performing a nucleation process treatment at a first temperature, and then performing a crystal growth process treatment at a second temperature.

[0088] (66) The manufacturing method of the glass-ceramics according to (65), wherein the crystallization process comprises: the first temperature is 600 - 700 °C, the second temperature is greater than 750 °C but less than or equal to 900 °C, the holding time at the first temperature is 1 - 6 hours, and the holding time at the second temperature is 2 - 5 hours.

[0089] The beneficial effects of the present invention are: through reasonable component design, the glass-ceramics and glass-ceramic products obtained by the present invention have excellent scratch resistance. Description of the Drawings

[0090] Figure 1 It is the XRD pattern of the glass-ceramic product of Example 1 of the present invention.

[0091] Figure 2 It is a schematic diagram of scratch comparison between the glass-ceramic product of Example 1 of the present application and high-aluminum glass. Detailed Embodiments

[0092] The glass-ceramics and glass-ceramic products of the present invention are materials with crystalline phases (sometimes also referred to as crystals) and glass phases, which are different from amorphous solids. The crystalline phases of the glass-ceramics and glass-ceramic products can be identified by the peak angles appearing in the X-ray diffraction pattern of X-ray diffraction analysis.

[0093] The inventors of the present invention have conducted repeated experiments and research. For the specific components constituting the glass-ceramics and glass-ceramic products, by specifying their contents and content ratios as specific values and precipitating specific crystalline phases, the glass-ceramics and glass-ceramic products of the present invention are obtained.

[0094] Next, the ranges of the components (constituents) of the base glass, glass-ceramics, and glass-ceramic articles of the present invention will be described. In this specification, unless otherwise specified, the contents, total contents, and overall contents of the components are all expressed as weight percentages (wt%) relative to the total amount of the base glass, or glass-ceramics, or glass-ceramic article substance in terms of the composition converted to oxides. Here, the "composition converted to oxides" means that when oxides, double salts, hydroxides, etc., used as raw materials for the components of the base glass, glass-ceramics, or glass-ceramic article of the present invention decompose and turn into oxides during melting, the total amount of the oxides is taken as 100%. In addition, in this specification, when only referred to as glass, it refers to the base glass before crystallization (i.e., crystallization process treatment), and after the base glass is crystallized (i.e., crystallization process treatment), it is called glass-ceramics. A glass-ceramic article refers to a product obtained by chemically strengthening the glass-ceramics.

[0095] Unless otherwise indicated in specific cases, the numerical ranges listed herein include the upper and lower limit values, "above" and "below" include the endpoint values, and all integers and fractions within the range, and are not limited to the specific values listed when defining the range. As used herein, "and / or" is inclusive, for example, "A; and / or B" means only A, or only B, or both A and B at the same time.

[0096] In some embodiments of the present invention, the crystal phase in the glass-ceramics or glass-ceramic article contains a spinel crystal phase. Preferably, the spinel crystal phase includes a zinc-aluminum spinel crystal phase (ZnAl2O4). In some embodiments, it is preferably free of the Zn2SiO4 crystal phase to prevent the scratch resistance and the height of the ball-drop test of the glass-ceramics and glass-ceramic articles of the present invention from deteriorating.

[0097] In some embodiments, the spinel crystal phase has a higher weight percentage than other crystal phases in the glass-ceramics or glass-ceramic article, preferably the zinc-aluminum spinel crystal phase (ZnAl2O4). In some embodiments, the weight percentage of the spinel crystal phase in the glass-ceramics or glass-ceramic article is 20-50%, preferably the weight percentage of the spinel crystal phase in the glass-ceramics or glass-ceramic article is 30-50%, more preferably the weight percentage of the spinel crystal phase in the glass-ceramics or glass-ceramic article is 30-45%. In some embodiments, the weight percentage of the spinel crystal phase in the glass-ceramics or glass-ceramic article is 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%.

[0098] In some embodiments, the glass-ceramics or glass-ceramic articles of the present invention preferably do not contain spodumene crystal phase and / or zirconia crystal phase. The glass-ceramics or glass-ceramic articles of the present invention can obtain relatively high light transmittance, excellent extrusion resistance and scratch resistance, and can be used to manufacture cover glass for electronic devices or display devices with relatively high transparency requirements.

[0099] In some embodiments, the glass-ceramics or glass-ceramic articles of the present invention preferably do not contain quartz crystal phase and / or quartz solid solution crystal phase to prevent the deterioration of the light transmittance of the glass-ceramics or glass-ceramic articles of the present invention.

[0100] SiO2 is a network-forming component of the glass-ceramics and glass-ceramic articles of the present invention, which can improve the chemical stability of the matrix glass, glass-ceramics and glass-ceramic articles. If the content of SiO2 is too low, it is difficult to form glass, and the chemical stability of the glass-ceramics and glass-ceramic articles deteriorates. If the content of SiO2 is too high, the viscosity of the glass increases, and it is difficult to precipitate crystals during the manufacturing process of the glass-ceramics and glass-ceramic articles, and the crystal phase content of the glass-ceramics and glass-ceramic articles decreases. Therefore, the content of SiO2 in the present invention is 43-50%, preferably 44-49%, more preferably 44-48%. In some embodiments, SiO2 may include 43%, 43.5%, 44%, 44.5%, 45%, 45.5%, 46%, 46.5%, 47%, 47.5%, 48%, 48.5%, 49%, 49.5%, 50%.

[0101] Al2O3 can improve the scratch resistance of glass-ceramics and glass-ceramic articles. The inventors found through a large number of experimental studies that when the content of Al2O3 exceeds a certain threshold, the high-coordination aluminum ions are connected to three oxygens through covalent bonds. Compared with the two-coordination bridging oxygens, this bond type has stronger ionicity, weaker bond energy and greater flexibility. During energy loading and unloading, these bonds undergo an easier bond breaking-closing process, which locally dissipates mechanical energy, and there is not enough energy to break the O-Si or O-Al bonds. Therefore, the scratch resistance of glass-ceramics and glass-ceramic articles can be improved. In addition, Al2O3 is also a necessary component for forming the crystal phase of the present invention, which can improve the mechanical properties of glass-ceramics and glass-ceramic articles. However, if the content of Al2O3 is too high, glass melting is difficult and the melting temperature is high. Therefore, the content of Al2O3 in the present invention is 27.5-35%, preferably 28-34%, more preferably 28-33%. In some embodiments, Al2O3 may include 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%.

[0102] The inventor found through a large number of experimental studies that, in some embodiments, by controlling the ratio SiO2 / Al2O3 between the content of SiO2 and the content of Al2O3 within the range of 1.3 to 1.8, the drop resistance of the glass-ceramics and glass-ceramic products can be improved. Therefore, in the present invention, SiO2 / Al2O3 is preferably 1.3 to 1.8, more preferably SiO2 / Al2O3 is 1.4 to 1.7, and further preferably SiO2 / Al2O3 is 1.45 to 1.67. In some embodiments, the value of SiO2 / Al2O3 is 1.3, 1.31, 1.33, 1.35, 1.37, 1.4, 1.41, 1.43, 1.45, 1.47, 1.5, 1.51, 1.53, 1.55, 1.57, 1.6, 1.61, 1.63, 1.65, 1.67, 1.7, 1.71, 1.73, 1.75, 1.77, 1.8.

[0103] ZnO can improve the properties such as Young's modulus, Vickers hardness, and extrusion resistance of glass-ceramics and glass-ceramic products. If the content of ZnO is too low, the viscosity of the glass is relatively large, which is not conducive to the forming of the glass; if the content of ZnO is higher than 12%, the glass structure is loose, and a large amount of Al2O3 enters the crystal, resulting in poor scratch resistance of the glass-ceramics and glass-ceramic products, the scratch width of the glass-ceramic products is more than 30 μm, and at the same time, crystals are likely to precipitate on the surface during the forming of the glass, and white dots are generated inside. Therefore, in the present invention, the content of ZnO is 8.5 to 12%, preferably 9 to 12%, and more preferably 9 to 11%. In some embodiments, ZnO with contents of 8.5%, 8.7%, 9%, 9.3%, 9.5%, 9.7%, 10%, 10.3%, 10.5%, 10.7%, 11%, 11.3%, 11.5%, 11.7%, 12% can be included.

[0104] MgO helps to reduce the viscosity of the glass. During crystallization, it can refine the crystal grains and improve the transmittance of the glass-ceramics and glass-ceramic products. If the content of MgO is too high, serious surface crystallization will occur during the crystallization of the glass, and the transmittance of the glass-ceramics and glass-ceramic products will decrease instead. Therefore, in the present invention, the content of MgO is 0-5%, preferably 1-4%, and more preferably 1-3%. In some embodiments, it may contain 0%, greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5% of MgO.

[0105] The inventors found through a large number of experimental studies that in some embodiments, by controlling the ratio (ZnO + MgO + SiO2) / Al2O3 between the total content of ZnO, MgO, and SiO2 (ZnO + MgO + SiO2) and the content of Al2O3 within the range of 1.5-2.15, it is beneficial to improve the scratch resistance of the glass-ceramics and glass-ceramic products. Therefore, it is preferred that (ZnO + MgO + SiO2) / Al2O3 is 1.5-2.15, more preferably (ZnO + MgO + SiO2) / Al2O3 is 1.6-2.15, and further preferably (ZnO + MgO + SiO2) / Al2O3 is 1.8-2.1. In some embodiments, the value of (ZnO + MgO + SiO2) / Al2O3 is 1.5, 1.53, 1.55, 1.57, 1.6, 1.63, 1.65, 1.67, 1.7, 1.73, 1.75, 1.77, 1.8, 1.83, 1.85, 1.87, 1.9, 1.93, 1.95, 1.97, 2.0, 2.01, 2.02, 2.03, 2.04, 2.05, 2.06, 2.07, 2.08, 2.09, 2.1, 2.11, 2.12, 2.13, 2.14, 2.15.

[0106] Li2O can reduce the viscosity of the glass and the melting temperature of the glass. At the same time, it also participates in chemical strengthening, increases the surface stress of the glass-ceramic products, and increases the height of the ball-drop test of the glass-ceramic products. If the content of Li2O is too high, it is easy to generate a quartz solid solution crystal phase, reducing the transmittance of the glass-ceramic and the glass-ceramic products. Therefore, in the present invention, the content of Li2O is 0.1-5%, preferably 1-5%, and more preferably 1-4%. In some embodiments, it may contain 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of Li2O.

[0107] In some embodiments, controlling the ratio Al2O3 / Li2O between the content of Al2O3 and the content of Li2O within the range of 11.0-60.0 is beneficial to increasing the height of the ball-drop test of the glass-ceramic and the glass-ceramic products and increasing the anti-extrusion strength. Therefore, preferably, Al2O3 / Li2O is 11.0-60.0, more preferably Al2O3 / Li2O is 12.0-40.0, and further preferably Al2O3 / Li2O is 13.0-20.0. In some embodiments, the value of Al2O3 / Li2O is 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, 16.0, 16.5, 17.0, 17.5, 18.0, 18.5, 19.0, 19.5, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 25.0, 26.0, 27.0, 28.0, 29.0, 30.0, 31.0, 32.0, 33.0, 34.0, 35.0, 36.0, 37.0, 38.0, 39.0, 40.0, 41.0, 42.0, 43.0, 44.0, 45.0, 46.0, 47.0, 48.0, 49.0, 50.0, 51.0, 52.0, 53.0, 54.0, 55.0, 56.0, 57.0, 58.0, 59.0, 60.0.

[0108] The function of Na2O is to promote glass melting and improve the chemical strengthening performance of glass. However, if there is too much Na2O, it is easy to cause more broken bonds in the glass, resulting in a decrease in the strength of the matrix glass, which is instead unfavorable to the strength of the glass-ceramics and glass-ceramic products. Therefore, in the present invention, the content of Na2O is 0-7%, preferably 1-6%, and more preferably 2-5%. In some embodiments, it may contain 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, 6.5%, 7% of Na2O.

[0109] In some embodiments, by controlling the ratio (ZnO + MgO) / (Li2O + Na2O) between the total content of ZnO and MgO, ZnO + MgO, and the total content of Li2O and Na2O, Li2O + Na2O, within the range of 1.5-5.0, it is beneficial to improve the extrusion resistance strength and the ball-drop test height of the glass-ceramics and glass-ceramic products of the present invention. Therefore, it is preferred that (ZnO + MgO) / (Li2O + Na2O) is 1.5-5.0, more preferably (ZnO + MgO) / (Li2O + Na2O) is 1.7-4.5, and further preferably (ZnO + MgO) / (Li2O + Na2O) is 1.8-4.0. In some embodiments, the value of (ZnO + MgO) / (Li2O + Na2O) is 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0.

[0110] TiO2 and ZrO2 are nucleating agents for the glass-ceramics and glass-ceramic products of the present invention. The simultaneous use of these two nucleating agents can maximize the number of crystal nuclei in the glass-ceramics and glass-ceramic products. With more crystal nuclei, the crystal phase growth is stable and the size is uniform. If the content of TiO2 is too high, it will cause serious coloring (brownish-yellow) of the glass-ceramics and glass-ceramic products, reducing the transmittance in the visible light region. If the content of ZrO2 is too high, the melting difficulty of the glass increases. Therefore, in the present invention, the content of TiO2 is 2-6%, preferably 2-5%, more preferably 2-4%. The content of ZrO2 is 0-5%, preferably 0.5-4%, more preferably 1-3%. In some embodiments, TiO2 with contents of 2%, 2.1%, 2.3%, 2.5%, 2.7%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, 4.7%, 5%, 5.3%, 5.5%, 5.7%, 6% can be included. In some embodiments, ZrO2 with contents of 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5% can be included.

[0111] In some embodiments, by controlling the ratio (TiO2 + ZrO2) / (Li2O + Na2O) of the total content of TiO2 and ZrO2 (TiO2 + ZrO2) to the total content of Li2O and Na2O (Li2O + Na2O) within the range of 0.5 to 5.0, it is beneficial to improve the light transmittance of the glass-ceramics and glass-ceramic products. Therefore, it is preferred that (TiO2 + ZrO2) / (Li2O + Na2O) is 0.5 to 5.0, more preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 3.0, and further preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 1.5. In some embodiments, the value of (TiO2 + ZrO2) / (Li2O + Na2O) is 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0.

[0112] K2O helps to reduce the melting temperature of the glass, is beneficial to chemical strengthening, and can increase the depth of the ion exchange layer of the glass-ceramics and glass-ceramic products. However, if the content of K2O is too high, it is easy to cause a decrease in the chemical stability of the glass and a decline in mechanical strength. Therefore, in the present invention, the content of K2O is 0 to 3%, preferably 0 to 2%, and more preferably 0 to 1%. In some embodiments, it may contain 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% of K2O.

[0113] Ln2O3 (Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3) can improve the structural compactness of glass-ceramics and glass-ceramic products, and improve the scratch resistance of glass-ceramics and glass-ceramic products. When the content is too high, it will cause difficulties in forming crystals during the crystallization of glass-ceramics and glass-ceramic products, resulting in a decrease in the crystal phase content of glass-ceramics and glass-ceramic products, and a decrease in the height of the ball-drop test of glass-ceramics and glass-ceramic products. Therefore, in the present invention, the content of Ln2O3 is 0 to 8%, preferably 0.1 to 6%, and more preferably 0.1 to 3%. In some embodiments, it may include 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8% of Ln2O3.

[0114] In some embodiments, controlling the ratio (Al2O3 + Ln2O3) / Li2O between the total content of Al2O3 and Ln2O3 (Ln2O3 + TiO2) and the content of Li2O within the range of 14.5 to 100.0 is beneficial to improving the scratch resistance of the glass-ceramics and glass-ceramic products. Therefore, it is preferred that (Al2O3 + Ln2O3) / Li2O is 14.5 to 100.0, more preferably (Al2O3 + Ln2O3) / Li2O is 15.0 to 60.0, and still more preferably (Al2O3 + Ln2O3) / Li2O is 16.0 to 40.0. In some embodiments, the value of (Al2O3 + Ln2O3) / Li2O is 14.5, 15.0, 16.0, 17.0, 18.0, 19.0, 20.0, 21.0, 22.0, 23.0, 24.0, 25.0, 26.0, 27.0, 28.0, 29.0, 30.0, 31.0, 32.0, 33.0, 34.0, 35.0, 36.0, 37.0, 38.0, 39.0, 40.0, 41.0, 42.0, 43.0, 44.0, 45.0, 46.0, 47.0, 48.0, 49.0, 50.0, 51.0, 52.0, 53.0, 54.0, 55.0, 56.0, 57.0, 58.0, 59.0, 60.0, 61.0, 62.0, 63.0, 64.0, 65.0, 66.0, 67.0, 68.0, 69.0, 70.0, 71.0, 72.0, 73.0, 74.0, 75.0, 76.0, 77.0, 78.0, 79.0, 80.0, 81.0, 82.0, 83.0, 84.0, 85.0, 86.0, 87.0, 88.0, 89.0, 90.0, 91.0, 92.0, 93.0, 94.0, 95.0, 96.0, 97.0, 98.0, 99.0, 100.0.

[0115] B2O3 is used as a flux, which helps with the melting of the glass. However, if the content of B2O3 is too high, the chemical stability of the glass-ceramics and glass-ceramic products will deteriorate. Additionally, boron volatilization easily forms streaks, resulting in non-uniformity inside the glass-ceramics and glass-ceramic products. Therefore, the content of B2O3 is 0 to 4%, preferably 0 to 2%, and more preferably 0 to 1%. In some embodiments, it is further preferred that B2O3 is not contained. In some embodiments, it may contain about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4% of B2O3.

[0116] CaO, BaO, and SrO do not participate in the formation of the crystal phase and are retained in the residual glass phase of the glass-ceramics and glass-ceramic products, which is beneficial for reducing the melting temperature and processing temperature. However, too high a content will damage the nucleation and crystallization during the process of the matrix glass transforming into glass-ceramics, having an adverse effect on the chemical stability of the glass-ceramics and glass-ceramic products. Therefore, the total content of CaO, BaO, and SrO, CaO + BaO + SrO, is 0 to 5%, preferably 0 to 4%, and more preferably 0 to 2%. In some embodiments, CaO + BaO + SrO is 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%.

[0117] In some embodiments, the base glass, glass-ceramics or glass-ceramic article may further contain 0 to 2% of a fining agent to improve the defoaming ability of the base glass, glass-ceramics or glass-ceramic article. Such fining agents include, but are not limited to, one or more of Sb2O3, SnO2, SnO, CeO2, F (fluorine) compounds, Cl (chlorine) compounds and Br (bromine) compounds, and Sb2O3 is preferably used as the fining agent. In some embodiments, it is preferred not to contain SnO2 and / or not to contain SnO, which is beneficial to the precipitation of spinel crystal phases in the glass-ceramics and glass-ceramic articles of the present invention, especially the formation of ZnAl2O4 crystal phases, ensuring the desired crystal phase types are obtained, preventing the formation of spodumene crystal phases and zirconia crystal phases, and being beneficial to improving the properties such as the extrusion resistance and scratch resistance of the glass-ceramics and glass-ceramic articles. When the above-mentioned fining agents are present alone or in combination, the upper limit of their content is preferably 2%, more preferably the upper limit is 1%, and further preferably the upper limit is 0.5%. In some embodiments, the content of one or more of the fining agents is 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%.

[0118] Without affecting the performance of the base glass, glass-ceramics or glass-ceramic article of the present invention, other components not mentioned above, such as Nb2O5, WO3, Bi2O3, Ta2O5, TeO2, etc., can be appropriately contained. However, to maintain the excellent performance of the base glass, glass-ceramics or glass-ceramic article of the present invention, the respective content or the total content of Nb2O5, WO3, Bi2O3, Ta2O5, TeO2 is preferably 5% or less, more preferably 2% or less, further preferably 1% or less, and even more preferably not contained.

[0119] In some embodiments, the base glass, glass-ceramics, and glass-ceramic article of the present invention preferably do not contain P2O5. The glass-ceramics or glass-ceramic article of the present invention can obtain better scratch resistance and can be used to manufacture cover glasses for electronic devices or display devices with higher requirements for scratch resistance.

[0120] PbO and As2O3 are toxic substances, and even a small amount of them does not meet the environmental protection requirements. Therefore, in some embodiments of the present invention, it is preferred not to contain PbO and / or As2O3.

[0121] "Not containing" and "0%" as described in this document mean that the compound, molecule, element, etc. are not deliberately added as raw materials to the base glass, glass-ceramics or glass-ceramics products of the present invention; however, as raw materials and / or equipment for producing base glass, glass-ceramics or glass-ceramics products, there will be certain impurities or components that are not deliberately added and will be contained in small amounts or traces in the final base glass, glass-ceramics or glass-ceramics products. Such a situation is also within the scope of protection of this invention patent.

[0122] The grain size and crystal phase type in the glass-ceramics or glass-ceramics products of the present invention will affect the light transmittance of the glass-ceramics or glass-ceramics products. The smaller the grain size, the higher the light transmittance. In some embodiments, the glass-ceramics or glass-ceramics products of the present invention exhibit high transparency in the visible light range. The glass-ceramics or glass-ceramics products exhibit high transmittance in the visible light range. In some embodiments, the average light transmittance of the glass-ceramics products with a thickness of less than 2.0 mm or the glass-ceramics in the range of 400-800 nm is preferably 85% or more, more preferably 87% or more, and further preferably 88% or more.

[0123] The base glass, glass-ceramics and glass-ceramics products of the present invention can be produced and manufactured by the following methods:

[0124] Generating base glass: Mix the raw materials (oxides, hydroxides, double salts, boric acid, etc.) evenly according to the component ratio, put the evenly mixed raw materials into a crucible (such as a platinum or quartz crucible), and melt them in an electric furnace or gas furnace at a temperature range of 1500-1700 °C for 5-24 hours according to the melting difficulty of the glass composition. The preferred melting temperature is 1500-1600 °C; then obtain the base glass after clarification, homogenization, forming and annealing. The preferred clarification temperature is 1550-1650 °C, and the preferred annealing temperature is 550-650 °C.

[0125] The base glass of the present invention can be formed by well-known methods.

[0126] The base glass of the present invention is subjected to a crystallization treatment through a crystallization process after forming or forming and processing, and crystals are precipitated uniformly inside the glass to form glass-ceramics. This crystallization treatment can be carried out in one stage or in two stages. It is preferably carried out in two stages. The two-stage crystallization treatment is to carry out a nucleation process treatment at the first temperature, and then carry out a crystal growth process treatment at the second temperature. The crystallization treatment carried out at the first temperature is called the first crystallization treatment, and the crystallization treatment carried out at the second temperature is called the second crystallization treatment.

[0127] In order to enable the glass-ceramics to obtain the desired physical and chemical properties, the preferred crystallization process is:

[0128] The above crystallization treatment is carried out in one stage, and the nucleation process and the crystal growth process can be carried out continuously. That is, the temperature is raised to a specified crystallization treatment temperature, and after reaching the crystallization treatment temperature, the temperature is maintained for a certain period of time, and then the temperature is lowered. The crystallization treatment temperature is preferably 600-800 °C, and more preferably 650-750 °C in order to precipitate the desired crystal phase. The holding time at the crystallization treatment temperature is preferably 1-10 hours, and more preferably 3-6 hours.

[0129] When the above crystallization treatment is carried out in two stages, the first temperature is preferably 600-700 °C, the second temperature is preferably greater than 750 °C but less than or equal to 900 °C, the holding time at the first temperature is preferably 1-6 hours, and the holding time at the second temperature is preferably 2-5 hours.

[0130] In some embodiments, the vitreous matrix or glass-ceramics described herein can be formed into a shaped body by various processes, and the shaped body includes but is not limited to sheets, and the processes include but are not limited to slot drawing, float process, roll pressing and other processes for forming sheets known in the art. Alternatively, the vitreous matrix or glass-ceramics can be formed by the float process or roll pressing method known in the art. The shaped bodies of the present invention also include lenses, prisms, etc.

[0131] The vitreous matrix or glass-ceramics of the present invention can be used to manufacture glass shaped bodies or glass-ceramic shaped bodies of sheets by methods such as grinding or polishing, but the methods for manufacturing glass shaped bodies or glass-ceramic shaped bodies are not limited to these methods.

[0132] The vitreous matrix or glass-ceramics of the present invention can be prepared into glass shaped bodies or glass-ceramic shaped bodies of various shapes by methods such as hot bending process or pressing process at a certain temperature, but are not limited to these methods.

[0133] In some embodiments, a glass shaped body or a glass-ceramic shaped body can be formed by a hot bending process. The hot bending process is a process of placing 2D or 2.5D glass or glass-ceramics in a mold and sequentially performing steps including heating and preheating, pressure forming, and pressure maintaining and cooling in a hot bending machine to obtain a 3D curved glass shaped body or glass-ceramic shaped body.

[0134] In some embodiments, the glass-ceramic shaped body has a 2.5D or 3D structure, that is, the glass-ceramic shaped body has a non-planar structure. The "non-planar structure" described herein means that in a 2.5D or 3D shape, at least a part of the glass-ceramic shaped body extends outward or extends along an angle with the plane defined by the original layout configuration of the 2D vitreous matrix. The 2.5D or 3D glass-ceramic shaped body formed from the vitreous matrix can have one or more convex or curved parts.

[0135] The substrate glass, glass-ceramics, and glass-ceramic articles according to the present invention can have any thickness that is reasonably useful.

[0136] In addition to improving mechanical properties by precipitating crystals, the glass-ceramics of the present invention can also obtain more excellent mechanical properties by forming a compressive stress layer, thereby making glass-ceramic articles.

[0137] In some embodiments, the substrate glass or glass-ceramics can be processed into sheets and / or shaped (such as punching, hot bending, etc.), polished and / or buffed after shaping, and then chemically strengthened through a chemical strengthening process.

[0138] The chemical strengthening according to the present invention includes the ion exchange method. During the ion exchange process, smaller metal ions in the substrate glass or glass-ceramics are replaced or "exchanged" by larger metal ions of the same valence state that are close to the substrate glass or glass-ceramics. Replacing smaller ions with larger ions builds compressive stress in the substrate glass or glass-ceramics, forming a compressive stress layer.

[0139] In some embodiments, the metal ions are monovalent alkali metal ions (such as Na + , K + , Rb + , Cs + , etc.). The ion exchange is carried out by immersing the substrate glass or glass-ceramics in a salt bath containing at least one molten salt of a larger metal ion, and the larger metal ion is used to replace the smaller metal ions in the substrate glass. One or more ion exchange processes for chemically strengthening the substrate glass or glass-ceramics can include, but are not limited to: immersing it in a single salt bath, or immersing it in multiple salt baths with the same or different compositions, with washing and / or annealing steps between immersions.

[0140] In some embodiments, the substrate glass or glass-ceramics can be ion-exchanged by immersing them in a salt bath of molten Na salt (such as NaNO3) at a temperature of about 350 - 470 °C for about 1 - 36 hours, preferably in the temperature range of 400 - 460 °C, and preferably in the time range of 2 - 15 hours. In this embodiment, Na ions replace some Li ions in the substrate glass or glass-ceramics, thereby forming a surface compressive layer and exhibiting high mechanical properties. In some embodiments, the substrate glass or glass-ceramics can be ion-exchanged by immersing them in a mixed salt bath of molten K salt and Na salt at a temperature of about 360 - 460 °C for 1 - 36 hours, preferably in the time range of 2 - 24 hours.

[0141] The glass-ceramics involved in the present invention have efficient low-temperature ion-exchange performance. In some embodiments, the surface stress of the glass-ceramics products can reach over 40 Mpa at a relatively low ion-exchange temperature and within a relatively short exchange time. After ion exchange, the hardness of the glass-ceramics products is significantly improved. The main reason is that ion exchange forms a relatively high compressive stress on the surface of the glass-ceramics products through the "jamming effect", which increases the anti-deformation performance and hardness of the glass-ceramics products. In some embodiments, after chemical strengthening of the glass-ceramics of the present invention, the Vickers hardness of the obtained glass-ceramics products can reach 600 kgf / mm 2 or above.

[0142] The glass-ceramics products of the present invention have excellent scratch resistance. In some embodiments, after chemical strengthening of the glass-ceramics of the present invention, the scratch width of the obtained glass-ceramics products is less than 30 μm.

[0143] The performance indexes of the glass-ceramics and / or glass-ceramics products of the present invention are tested by the following methods:

[0144] [Grain size]

[0145] It is measured by using a SEM scanning electron microscope. The sample is surface-treated in HF acid, then sputtered with gold on the sample surface, and surface-scanned under the SEM scanning electron microscope to determine the grain size.

[0146] [Light transmittance]

[0147] The light transmittance described herein is all external transmittance, sometimes simply referred to as transmittance.

[0148] The sample is processed into a thickness of less than 2 mm and polished with parallel opposite surfaces, and the average light transmittance at 400 - 800 nm is measured by using a Hitachi U-41000 spectrophotometer.

[0149] [Surface stress (CS)]

[0150] The surface stress is measured by using a glass surface stress meter SLP-2000.

[0151] As the measurement conditions, the refractive index of the sample is 1.57 and the photoelastic constant is 28 [(nm / cm) / Mpa] for calculation.

[0152] [Scratch resistance]

[0153] The scratch resistance of the present invention is characterized by the scratch width. A Knoop micro-indentation hardness tester is used, and the indenter is a conical Knoop indenter. A sample of 145 mm × 67 mm × 0.7 mm is placed on the stage to fix the sample to be tested. A fixed load of 8 (N) is applied to the indenter, and a track of a preset distance is scribed on the surface of the sample to be tested at a preset speed by the indenter. The scratch width is observed under a microscope. The scratch resistance of the sample is judged according to the scratch width. The wider the scratch, the worse the scratch resistance of the sample.

[0154] [Drop resistance]

[0155] The drop resistance test is carried out using a directional drop tester WH-2101. By loading glass products of the same specification (each weighing 20 g, 2 pieces are loaded) on the 2D sample, and 80-mesh sandpaper is laid on the base, and the sample of 145 mm × 67 mm × 0.7 mm is directly dropped on the sandpaper from a specified height. The height at which the sample can withstand the impact without breaking is the drop resistance. Specifically, the test starts from a height of 600 mm, and the height is sequentially changed through 700 mm, 800 mm, 900 mm, 1000 mm and above without breaking. For the examples with "drop resistance", the microcrystalline glass products are used as the test objects. The test data recorded as 1000 mm in the examples indicates that even the microcrystalline glass products with a load can withstand the impact without breaking when dropped from a height of 1000 mm. The maximum test height of the drop tester WH-2101 is 2000 mm.

[0156] [Falling ball test height]

[0157] The sample of 145 mm × 67 mm × 0.7 mm is placed on a glass holding fixture, and a 132 g steel ball is dropped from a specified height. The landing point is the center point of the sample. The maximum falling ball test height at which the sample can withstand the impact without breaking. Specifically, the falling ball test height starts from 400 mm and drops once at each height. If the sample does not break, it is sequentially raised by 100 mm and the test continues until the sample breaks. For the examples with "falling ball test height", the microcrystalline glass products are used as the test objects. The test data recorded as 1700 mm in the examples indicates that even when the steel ball is dropped from a height of 1700 mm, the microcrystalline glass products can withstand the impact without breaking. In the present invention, the falling ball test height is sometimes abbreviated as the falling ball height.

[0158] [Vickers hardness]

[0159] The load (N) when a diamond square pyramid indenter with a relative face angle of 136° is pressed into a pyramid-shaped depression on the test surface is divided by the surface area (mm 2) The value is represented by conducting the test with a test load of 100 (N) and a holding time of 15 (seconds). In the present invention, Vickers hardness is sometimes simply referred to as hardness.

[0160] [Crushing strength]

[0161] Using a microcomputer-controlled electronic universal testing machine CMT6502, place a sample of 145 mm × 67 mm × 0.7 mm on a glass carrier fixture. The extrusion rod is designed with a mushroom head, with a diameter of ￠10 mm and a downward pressing speed of 5 mm / min until the sample is damaged. It needs to be calibrated with a jig before testing, and the test point is at the center position. Click the test button until the sample is crushed by extrusion, and record the pressure (N) when the sample is broken. For the embodiments with "crushing strength", the microcrystalline glass products are used as the test objects. The test data recorded as 500 N in the embodiments indicates that the maximum extrusion force that the microcrystalline glass product can withstand before breaking is 500 N.

[0162] [Young's modulus]

[0163] Young's modulus (E) is measured by ultrasonic testing of the longitudinal wave velocity and transverse wave velocity, and then calculated according to the following formula.

[0164]

[0165] G = V S 2 ρ

[0166] In the formula: E is Young's modulus, Pa;

[0167] G is the shear modulus, Pa;

[0168] V T is the transverse wave velocity, m / s;

[0169] V S is the longitudinal wave velocity, m / s;

[0170] ρ is the glass density, g / cm 3 .

[0171] The microcrystalline glass products of the present invention have the following properties:

[0172] 1) In some embodiments, the grain size of the microcrystalline glass product is 70 nm or less, preferably 60 nm or less, more preferably less than 50 nm, and further preferably 48 nm or less.

[0173] 2) In some embodiments, the surface stress (CS) of the microcrystalline glass product is 40 MPa or more, preferably 80 - 200 MPa, and more preferably 100 - 200 MPa.

[0174] 3) In some embodiments, the dropping ball test height of the glass-ceramic article is above 800 mm, preferably above 1000 mm, more preferably above 1200 mm.

[0175] 4) In some embodiments, the drop resistance of the glass-ceramic article is above 800 mm, preferably above 1000 mm, more preferably above 1200 mm.

[0176] 5) In some embodiments, the extrusion resistance strength of the glass-ceramic article is above 200 N, preferably above 250 N, more preferably above 300 N.

[0177] 6) In some embodiments, the Young's modulus (E) of the glass-ceramic article is 80 - 105 GPa, preferably 85 - 105 GPa, more preferably 90 - 105 GPa.

[0178] 7) In some embodiments, the scratch width of the glass-ceramic article is less than 30 μm, preferably 25 μm or less, more preferably 20 μm or less.

[0179] 8) In some embodiments, the Vickers hardness (H v ) of the glass-ceramic article is above 600 kgf / mm 2 , preferably 650 - 800 kgf / mm 2 , more preferably 680 - 800 kgf / mm 2 .

[0180] 9) In some embodiments, for a glass-ceramic article with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 - 800 nm is above 85%, preferably above 87%, more preferably above 88%. The thickness is preferably 0.2 - 2.0 mm, more preferably 0.3 - 1.0 mm, and further preferably 0.5 - 1.0 mm.

[0181] The glass-ceramic of the present invention has the following properties:

[0182] 1) In some embodiments, the grain size of the glass-ceramic is 70 nm or less, preferably 60 nm or less, more preferably less than 50 nm, and further preferably 48 nm or less.

[0183] 2) In some embodiments, for a glass-ceramic with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 - 800 nm is above 85%, preferably above 87%, more preferably above 88%. The thickness is preferably 0.2 - 2.0 mm, more preferably 0.3 - 1.0 mm, and further preferably 0.5 - 1.0 mm.

[0184] 3) In some embodiments, the Vickers hardness (Hv ) is 500 kgf / mm 2 or more, preferably 600 - 750 kgf / mm 2 , more preferably 650 - 750 kgf / mm 2 .

[0185] 4) In some embodiments, the Young's modulus (E) of the glass-ceramics is 80 - 105 GPa, preferably 85 - 105 GPa, more preferably 90 - 105 GPa.

[0186] Due to the above excellent properties, the glass-ceramics, glass-ceramic products, and parent glasses of the present invention can be widely fabricated into glass covers or glass components; meanwhile, the glass-ceramics, glass-ceramic products, and parent glasses of the present invention can be applied to electronic devices or display devices, such as mobile phones, watches, computers, touch display screens, etc., for manufacturing protective glasses for mobile phones, smart phones, tablet computers, laptop computers, PDAs, televisions, personal computers, MTA machines or industrial displays, or for manufacturing touch screens, protective windows, automobile windows, train windows, aviation machinery windows, touch screen protective glasses, or for manufacturing hard disk substrates or solar cell substrates, or for manufacturing white household appliances, such as for manufacturing refrigerator components or kitchen utensils.

[0187] Examples

[0188] To further clearly illustrate and explain the technical solutions of the present invention, the following non-limiting examples are provided. In the examples of the present invention, numerous efforts have been made to ensure the accuracy of the numerical values, but some errors and deviations must be taken into account. The compositions themselves are given in weight percentages based on oxides and have been normalized to 100%.

[0189] <Examples of Glass-Ceramics>

[0190] In this example, the glass-ceramics having the compositions shown in Tables 1 - 3 were obtained by using the above method for manufacturing glass-ceramics. In addition, the properties of each glass-ceramic were measured by the testing method described in the present invention, and the measurement results are shown in Tables 1 - 3. In the following examples, the thickness of the test sample for the average light transmittance at wavelengths of 400 - 800 nm is 1 mm.

[0191] Table 1.

[0192]

[0193]

[0194] Table 2.

[0195]

[0196]

[0197] Table 3.

[0198]

[0199]

[0200] <Examples of glass-ceramics products>

[0201] In this example, the glass-ceramics products with the compositions shown in Tables 4 to 6 were obtained by using the manufacturing method of the above glass-ceramics products. In addition, the properties of each glass-ceramics product were measured by the test method described in the present invention, and the measurement results are shown in Tables 4 to 6. In the following examples, the thickness of the test sample for the average light transmittance at wavelengths of 400 to 800 nm was 1.0 mm.

[0202] Table 4.

[0203]

[0204]

[0205] Table 5.

[0206]

[0207]

[0208] Table 6.

[0209]

[0210]

[0211] The glass-ceramics products prepared in the examples of the present invention were tested:

[0212] The crystal phase was tested by using an X-ray diffractometer (XRD). Figure 1 This is the XRD pattern of the glass-ceramics product of Example 1 of this application. It can be seen from the XRD pattern that the crystal phase is zinc spinel (ZnAl2O4).

[0213] The scratch resistance of the glass-ceramics product was tested by using a Knoop micro-indentation hardness tester. Figure 2 This is a schematic diagram of the scratch comparison between the glass-ceramics product of Example 1 of this application and high-aluminum glass. Among them, the scratch width of the glass-ceramics product of Example 1 is 9 μm, and the scratch width of the high-aluminum glass is much larger than 9 μm, and the chipping is serious. From Figure 2 it can be seen that the glass-ceramics product of the present invention has a smaller scratch width and excellent scratch resistance.

Claims

1. Glass-ceramic product, characterized in that, Its components are expressed by weight percentage and contain: SiO2: 43 - 50%; Al2O3: 27.5 - 35%; ZnO: 8.5 - 12%; Li2O: 0.1 - 5%; TiO2: 2 - 6%; MgO: 0 - 5%, where (ZnO + MgO + SiO2) / Al2O3 is 1.5 - 2.

15.

2. The glass-ceramic article according to claim 1, characterized in that, Its components are expressed by weight percentage and also contain: Na2O: 0 - 7%; and / or ZrO2: 0 - 5%; and / or K2O: 0 - 3%; and / or B2O3: 0 - 4%; and / or CaO + BaO + SrO: 0 - 5%; and / or Ln2O3: 0 - 8%; and / or clarifying agent: 0 - 2%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

3. Glass-ceramic products, characterized in that, Its components contain SiO2, Al2O3, ZnO, Li2O and TiO2. Its components are expressed by weight percentage and contain 0 - 5% of MgO, where (ZnO + MgO + SiO2) / Al2O3 is 1.5 - 2.15, and the scratch width of the glass-ceramics product is less than 30 μm.

4. The glass-ceramic article according to claim 3, wherein, Its components are expressed by weight percentage and contain: SiO2: 43 - 50%; and / or Al2O3: 27.5 - 35%; and / or ZnO: 8.5 - 12%; and / or Li2O: 0.1 - 5%; and / or TiO2: 2 - 6%; and / or Na2O: 0 - 7%; and / or ZrO2: 0 - 5%; and / or K2O: 0 - 3%; and / or B2O3: 0 - 4%; and / or CaO + BaO + SrO: 0 - 5%; and / or Ln2O3: 0 - 8%; and / or clarifying agent: 0 - 2%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

5. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, Its components are expressed by weight percentage and satisfy one or more of the following 6 cases: 1) (ZnO + MgO + SiO2) / Al2O3 is 1.6 - 2.15, preferably (ZnO + MgO + SiO2) / Al2O3 is 1.8 - 2.1; 2) Al2O3 / Li2O is 11.0 - 60.0, preferably Al2O3 / Li2O is 12.0 - 40.0, more preferably Al2O3 / Li2O is 13.0 - 20.0; 3) (ZnO + MgO) / (Li2O + Na2O) is 1.5 - 5.0, preferably (ZnO + MgO) / (Li2O + Na2O) is 1.7 - 4.5, more preferably (ZnO + MgO) / (Li2O + Na2O) is 1.8 - 4.0; 4) (TiO2 + ZrO2) / (Li2O + Na2O) is 0.5 - 5.0, preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 - 3.0, more preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 - 1.5; 5) The SiO2 / Al2O3 is 1.3 to 1.8, preferably the SiO2 / Al2O3 is 1.4 to 1.7, more preferably the SiO2 / Al2O3 is 1.45 to 1.67; 6) (Al2O3 + Ln2O3) / Li2O is 14.5 to 100.0, preferably (Al2O3 + Ln2O3) / Li2O is 15.0 to 60.0, more preferably (Al2O3 + Ln2O3) / Li2O is 16.0 to 40.0, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

6. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, Its components are expressed by weight percentage and contain: SiO2: 44 to 49%, preferably SiO2: 44 to 48%; and / or Al2O3: 28 to 34%, preferably Al2O3: 28 to 33%; and / or Li2O: 1 to 5%, preferably Li2O: 1 to 4%; and / or ZnO: 9 to 12%, preferably ZnO: 9 to 11%; and / or TiO2: 2 to 5%, preferably TiO2: 2 to 4%; and / or K2O: 0 to 2%, preferably K2O: 0 to 1%; and / or Ln2O3: 0.1 to 6%, preferably Ln2O3: 0.1 to 3%; and / or ZrO2: 0.5 to 4%, preferably ZrO2: 1 to 3%; and / or Na2O: 1 to 6%, preferably Na2O: 2 to 5%; and / or MgO: 1 to 4%, preferably MgO: 1 to 3%; and / or B2O3: 0 to 2%, preferably B2O3: 0 to 1%; and / or CaO + BaO + SrO: 0 to 4%, preferably CaO + BaO + SrO: 0 to 2%; and / or clarifying agent: 0 to 1%, preferably clarifying agent: 0 to 0.5%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

7. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, Its components are expressed by weight percentage and contain: Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 5%, preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 2%, more preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 1%, further preferably does not contain Nb2O5, and / or does not contain WO3, and / or does not contain Bi2O3, and / or does not contain Ta2O5, and / or does not contain TeO2.

8. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, The glass-ceramic product does not contain P2O5, and / or does not contain B2O3, and / or does not contain SnO2, and / or does not contain SnO.

9. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, The glass-ceramic product contains a spinel crystal phase, preferably the spinel crystal phase has a higher weight percentage than other crystal phases, more preferably the spinel crystal phase accounts for 20 to 50% of the weight of the glass-ceramic product, further preferably the spinel crystal phase accounts for 30 to 50% of the weight of the glass-ceramic product, and even more preferably the spinel crystal phase accounts for 30 to 45% of the weight of the glass-ceramic product.

10. The glass-ceramic article according to claim 9, wherein The spinel crystal phase is ZnAl2O4.

11. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, The glass-ceramic product does not contain spodumene crystal phase, and / or does not contain zirconia crystal phase, and / or does not contain quartz crystal phase, and / or does not contain quartz solid solution crystal phase, and / or does not contain Zn2SiO4 crystal phase.

12. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, The grain size of the glass-ceramics product is below 70 nm, preferably below 60 nm, more preferably less than 50 nm, and further preferably below 48 nm; and / or the surface stress is 40 MPa or more, preferably 80 - 200 MPa, more preferably 100 - 200 MPa; and / or the height of the ball-drop test is 800 mm or more, preferably 1000 mm or more, more preferably 1200 mm or more; and / or the drop resistance is 800 mm or more, preferably 1000 mm or more, more preferably 1200 mm or more; and / or the extrusion resistance strength is 200 N or more, preferably 250 N or more, more preferably 300 N or more; and / or the Young's modulus E is 80 - 105 GPa, preferably 85 - 105 GPa, more preferably 90 - 105 GPa; and / or the scratch width is less than 30 μm, preferably 25 μm or less, more preferably 20 μm or less; and / or the Vickers hardness is 600 kgf / mm 2 or more, preferably 650 - 800 kgf / mm 2 , more preferably 680 - 800 kgf / mm 2 ; and / or for the glass-ceramics product with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 - 800 nm is 85% or more, preferably 87% or more, more preferably 88% or more.

13. Glass-ceramics, characterized in that, In terms of weight percentage, its components contain: SiO2: 43 - 50%; Al2O3: 27.5 - 35%; ZnO: 8.5 - 12%; Li2O: 0.1 - 5%; TiO2: 2 - 6%; MgO: 0 - 5%, where (ZnO + MgO + SiO2) / Al2O3 is 1.5 - 2.

15.

14. The glass-ceramics according to claim 13, characterized in that, In terms of weight percentage, its components further contain: Na2O: 0 - 7%; and / or ZrO2: 0 - 5%; and / or K2O: 0 - 3%; and / or B2O3: 0 - 4%; and / or CaO + BaO + SrO: 0 - 5%; and / or Ln2O3: 0 - 8%; and / or clarifying agent: 0 - 2%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

15. Glass-ceramics, characterized in that, Its components contain SiO2, Al2O3, ZnO, Li2O and TiO2. In terms of weight percentage, it contains 0 - 5% of MgO, where (ZnO + MgO + SiO2) / Al2O3 is 1.5 - 2.15, and the glass-ceramic contains spinel crystal phase.

16. The glass-ceramics according to claim 15, characterized in that, In terms of weight percentage, its components contain: SiO2: 43 - 50%; and / or Al2O3: 27.5 - 35%; and / or ZnO: 8.5 - 12%; and / or Li2O: 0.1 - 5%; and / or TiO2: 2 - 6%; and / or Na2O: 0 - 7%; and / or ZrO2: 0 - 5%; and / or K2O: 0 - 3%; and / or B2O3: 0 - 4%; and / or CaO + BaO + SrO: 0 - 5%; and / or Ln2O3: 0 - 8%; and / or clarifying agent: 0 - 2%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

17. The glass-ceramics according to any one of claims 13 to 16, characterized in that, In terms of weight percentage, its components satisfy one or more of the following 6 cases: 1) (ZnO + MgO + SiO2) / Al2O3 is 1.6 - 2.15, preferably (ZnO + MgO + SiO2) / Al2O3 is 1.8 - 2.1; 2) Al2O3 / Li2O is 11.0 - 60.0, preferably Al2O3 / Li2O is 12.0 - 40.0, more preferably Al2O3 / Li2O is 13.0 - 20.0; 3) (ZnO + MgO) / (Li2O + Na2O) is 1.5 - 5.0, preferably (ZnO + MgO) / (Li2O + Na2O) is 1.7 - 4.5, more preferably (ZnO + MgO) / (Li2O + Na2O) is 1.8 - 4.0; 4) (TiO2 + ZrO2) / (Li2O + Na2O) is 0.5 to 5.0, preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 3.0, more preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 1.5; 5) SiO2 / Al2O3 is 1.3 to 1.8, preferably SiO2 / Al2O3 is 1.4 to 1.7, more preferably SiO2 / Al2O3 is 1.45 to 1.67; 6) (Al2O3 + Ln2O3) / Li2O is 14.5 to 100.0, preferably (Al2O3 + Ln2O3) / Li2O is 15.0 to 60.0, more preferably (Al2O3 + Ln2O3) / Li2O is 16.0 to 40.0, where Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

18. The glass-ceramics according to any one of claims 13 to 16, characterized in that, Its components are expressed by weight percentage and contain: SiO2: 44 to 49%, preferably SiO2: 44 to 48%; and / or Al2O3: 28 to 34%, preferably Al2O3: 28 to 33%; and / or Li2O: 1 to 5%, preferably Li2O: 1 to 4%; and / or ZnO: 9 to 12%, preferably ZnO: 9 to 11%; and / or TiO2: 2 to 5%, preferably TiO2: 2 to 4%; and / or K2O: 0 to 2%, preferably K2O: 0 to 1%; and / or Ln2O3: 0.1 to 6%, preferably Ln2O3: 0.1 to 3%; and / or ZrO2: 0.5 to 4%, preferably ZrO2: 1 to 3%; and / or Na2O: 1 to 6%, preferably Na2O: 2 to 5%; and / or MgO: 1 to 4%, preferably MgO: 1 to 3%; and / or B2O3: 0 to 2%, preferably B2O3: 0 to 1%; and / or CaO + BaO + SrO: 0 to 4%, preferably CaO + BaO + SrO: 0 to 2%; and / or clarifying agent: 0 to 1%, preferably clarifying agent: 0 to 0.5%, where Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

19. The glass-ceramics according to any one of claims 13 to 16, characterized in that, Its components are expressed by weight percentage and contain: Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 5%, preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 2%, more preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 1%, further preferably does not contain Nb2O5, and / or does not contain WO3, and / or does not contain Bi2O3, and / or does not contain Ta2O5, and / or does not contain TeO2.

20. The glass-ceramics according to any one of claims 13 to 16, characterized in that, The glass-ceramics does not contain P2O5, and / or does not contain B2O3, and / or does not contain SnO2, and / or does not contain SnO.

21. The glass-ceramics according to any one of claims 13 to 16, characterized in that, The glass-ceramics contain a spinel crystal phase. Preferably, the spinel crystal phase has a higher weight percentage than other crystal phases. More preferably, the weight percentage of the spinel crystal phase in the glass-ceramics is 20-50%. Further preferably, the weight percentage of the spinel crystal phase in the glass-ceramics is 30-50%. Even more preferably, the weight percentage of the spinel crystal phase in the glass-ceramics is 30-45%.

22. The glass-ceramics according to claim 21, wherein, The spinel crystal phase is ZnAl2O4.

23. The glass-ceramics according to any one of claims 13 to 16, characterized in that, The glass-ceramics do not contain a spodumene crystal phase, and / or do not contain a zirconia crystal phase, and / or do not contain a quartz crystal phase, and / or do not contain a quartz solid solution crystal phase, and / or do not contain a Zn2SiO4 crystal phase.

24. The glass-ceramics according to any one of claims 13 to 16, characterized in that, The grain size of the glass-ceramics is below 70 nm, preferably below 60 nm, more preferably less than 50 nm, and further preferably below 48 nm; and / or the Vickers hardness is 500 kgf / mm 2 or above, preferably 600 - 750 kgf / mm 2 , more preferably 650 - 750 kgf / mm 2 ; and / or the Young's modulus is 80 - 105 GPa, preferably 85 - 105 GPa, more preferably 90 - 105 GPa; and / or for the glass-ceramics with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 - 800 nm is 85% or above, preferably 87% or above, more preferably 88% or above.

25. Glass cover plate, characterized in that, Containing the glass-ceramics article according to any one of claims 1-12, and / or the glass-ceramics according to any one of claims 13-24.

26. Glass component, characterized in that, Containing the glass-ceramics article according to any one of claims 1-12, and / or the glass-ceramics according to any one of claims 13-24.

27. An electronic device, characterized in that, Containing the glass-ceramics article according to any one of claims 1-12, and / or the glass-ceramics according to any one of claims 13-24, and / or the glass cover plate according to claim 25, and / or the glass component according to claim 26.

28. Display device, characterized in that, Containing the glass-ceramics article according to any one of claims 1-12, and / or the glass-ceramics according to any one of claims 13-24, and / or the glass cover plate according to claim 25, and / or the glass component according to claim 26.

29. The manufacturing method of the glass-ceramics product according to any one of claims 1 to 12, characterized in that, The method comprises the following steps: forming a base glass, forming glass-ceramics from the base glass through a crystallization process, and then forming a glass-ceramics article from the glass-ceramics through a chemical strengthening process.

30. The manufacturing method of the glass-ceramic article according to claim 29, characterized in that, The forming of the base glass comprises the following steps: Mixing the raw materials evenly according to the component ratio, then putting them into a crucible, melting in an electric furnace or a gas furnace within a temperature range of 1500-1700°C for 5-24 hours. Preferably, the melting temperature is 1500-1600°C. Then, after clarification, homogenization, shaping, and annealing, the base glass is obtained. The clarification temperature is 1550-1650°C, and the annealing temperature is 550-650°C.

31. The manufacturing method of the glass-ceramics product according to claim 29, characterized in that, The crystallization process comprises the following steps: heating to a specified crystallization treatment temperature, after reaching the crystallization treatment temperature, maintaining its temperature for a certain time, and then cooling. The crystallization treatment temperature is 600-800°C, preferably 650-750°C, and the holding time at the crystallization treatment temperature is 1-10 hours, preferably 3-6 hours.

32. The manufacturing method of the glass-ceramic article according to claim 29, wherein, The crystallization process comprises the following steps: performing a nucleation process treatment at a first temperature, and then performing a crystal growth process treatment at a second temperature.

33. The manufacturing method of the glass-ceramic article according to claim 32, characterized in that, The crystallization process includes: the first temperature is 600-700°C, the second temperature is greater than 750°C but less than or equal to 900°C, the holding time at the first temperature is 1-6 hours, and the holding time at the second temperature is 2-5 hours.

34. The manufacturing method of the glass-ceramic article according to claim 29, characterized in that, The chemical strengthening process includes: immersing the glass-ceramics in a molten Na-salt bath at 350-470°C for 1-36 hours, preferably in the temperature range of 400-460°C and preferably in the time range of 2-15 hours; and / or immersing the glass-ceramics in a mixed salt bath of molten K-salt and Na-salt at 360-460°C for 1-36 hours, preferably in the time range of 2-24 hours.

35. The manufacturing method of the glass-ceramics according to any one of claims 13 to 24, characterized in that, The method includes the following steps: forming a base glass, and then forming the glass-ceramics from the base glass through a crystallization process.

36. The manufacturing method of the glass-ceramics according to claim 35, wherein, The forming of the base glass includes the following steps: Mix the raw materials evenly according to the component ratio, then put them into a crucible, and melt them in an electric furnace or a gas furnace within the temperature range of 1500-1700°C for 5-24 hours, preferably at a melting temperature of 1500-1600°C, and then obtain the base glass after clarification, homogenization, forming, and annealing. The clarification temperature is 1550-1650°C, and the annealing temperature is 550-650°C.

37. The manufacturing method of the glass-ceramics according to claim 35, characterized in that, The crystallization process includes the following steps: heating to the specified crystallization treatment temperature, after reaching the crystallization treatment temperature, maintaining its temperature for a certain period of time, and then cooling down. The crystallization treatment temperature is 600-800°C, preferably 650-750°C, and the holding time at the crystallization treatment temperature is 1-10 hours, preferably 3-6 hours.

38. The manufacturing method of the glass-ceramics according to claim 35, characterized in that, The crystallization process includes the following steps: performing a nucleation process treatment at a first temperature, and then performing a crystal growth process treatment at a second temperature.

39. The manufacturing method of the glass-ceramics according to claim 38, characterized in that, The crystallization process includes: the first temperature is 600-700°C, the second temperature is greater than 750°C but less than or equal to 900°C, the holding time at the first temperature is 1-6 hours, and the holding time at the second temperature is 2-5 hours.

Images