Microcrystalline glass, microcrystalline glass articles and applications thereof

Abstract

This application relates to glass-ceramics, glass-ceramic products, and their applications. The aforementioned glass-ceramics and glass-ceramic products, expressed as a percentage by weight, contain the following components: SiO2: 46%–60%; Al2O3: 20%–26%; MgO: 6.5%–14%; ZnO: 0.1%–8%; Li2O: greater than or equal to 0.1% but less than 5%; TiO2: greater than 0% but less than 5%; CaO: 0–4.5%, wherein the ratio of (SiO2+Al2O3) / (MgO+ZnO+CaO) is 4.0–8.0, and the ratio of Li2O / TiO2 is 0.3–2.5. Through reasonable component design, the glass-ceramics and glass-ceramic products obtained in this application possess high Young's modulus and ultraviolet light transmittance, making them suitable for fabricating large-size glass wafers and meeting the application needs of semiconductor manufacturing and other fields.

Description

Technical Field

[0001] This application relates to the field of glass-ceramic technology, and in particular to glass-ceramic, glass-ceramic products and their applications. Background Technology

[0002] With the development of the times, glass materials have been widely used in various fields, such as construction, imaging, medicine, and electronics. Due to its excellent mechanical stability, chemical stability, light transmittance, and the ability to achieve ultra-large sizes at a relatively low cost, glass is a material with great development potential for semiconductor chip packaging carriers. Glass materials used as carriers are often fabricated into large-sized glass sheets. The higher the Young's modulus of the glass material, the less prone it is to deformation during application. In particular, a higher Young's modulus means less likelihood of warping and breakage under stress during the packaging process, thus improving yield. When glass materials are used in semiconductor packaging, ultraviolet laser lift-off technology is commonly employed. Compared to traditional lift-off techniques, ultraviolet laser lift-off technology offers advantages such as high yield and low cost. However, it requires the carrier glass to have high transmittance in the ultraviolet light band. The higher the light transmittance of the glass in the ultraviolet light band, the higher the debonding efficiency during packaging, and the lower the risk of wafer warpage. Summary of the Invention

[0003] For the reasons mentioned above, the technical problem to be solved by this application is to provide a glass-ceramic and glass-ceramic articles with high Young's modulus and ultraviolet light transmittance, and to provide their applications.

[0004] The technical solution adopted by this application to solve the technical problem is:

[0005] (1) Microcrystalline glass, whose composition is expressed as a percentage by weight, contains: SiO2: 46% to 60%; Al2O3: 20% to 26%; MgO: 6.5% to 14%; ZnO: 0.1% to 8%; Li2O: greater than or equal to 0.1% but less than 5%; TiO2: greater than 0% but less than 5%; CaO: 0 to 4.5%, of which (SiO2+Al2O3) / (MgO+ZnO+CaO) is 4.0 to 8.0, and Li2O / TiO2 is 0.3 to 2.5.

[0006] (2) The microcrystalline glass according to (1) further contains, by weight percentage: Na2O: less than 4%; and / or K2O: less than 5%; and / or ZrO2: less than 5%; and / or Sb2O3: 0 to 3%.

[0007] (3) The microcrystalline glass according to (1) or (2) has components expressed as weight percentages that satisfy one or more of the following conditions:

[0008] 1) The content of Al2O3+ZnO+Na2O is 20.5%~32%, preferably 23%~31%, more preferably 24%~29.5%, and even more preferably 25.5%~28.5%;

[0009] 2) The ratio of (SiO2+Al2O3) / (MgO+ZnO+CaO) is 4.5 to 7.5, preferably 5.0 to 6.5;

[0010] 3) The Li2O / TiO2 ratio is 0.6–2.0, preferably 0.8–1.5;

[0011] 4) The ratio of (MgO+ZnO+Al2O3) / ZnO is 5.0 to 50.0, preferably 6.0 to 20.0, and more preferably 7.0 to 10.0;

[0012] 5) The ratio of (MgO+ZnO+Li2O) / Al2O3 is 0.3 to 1.0, preferably 0.4 to 0.8, and more preferably 0.5 to 0.7;

[0013] 6) The ratio of (MgO+ZnO) / Li2O is 4.0 to 13.0, preferably 4.5 to 11.5, and more preferably 5.0 to 9.5;

[0014] 7) The Al2O3 / (Na2O+K2O) ratio is 9.0 to 82.0, preferably 10.0 to 50.0, more preferably 15.0 to 30.0, and even more preferably 20.0 to 25.0;

[0015] 8) The ratio of (K2O+CaO) / TiO2 is 0.1 to 3.5, preferably 0.5 to 2.0, and more preferably 0.8 to 1.2;

[0016] 9) The ratio of (MgO+Al2O3+SiO2) / (TiO2+ZrO2) is 15.0 to 28.0, preferably 17.0 to 26.0, and more preferably 19.0 to 24.0.

[0017] (4) The microcrystalline glass according to (1) or (2) has the following components expressed as weight percentages: SiO2: 49%–58%, preferably SiO2: 51%–55%; and / or Al2O3: 21%–25%, preferably Al2O3: 21.5%–24.5%; and / or MgO: 7%–12%, preferably MgO: 8%–11%; and / or ZnO: 1%–6%, preferably ZnO: 2%–5%; and / or Li2O: 0.5%–4.5%, preferably Li2O: 1%–3%; And / or TiO2: 0.5%–4.5%, preferably TiO2: 1%–3%; and / or Na2O: 0.1%–3%, preferably Na2O: 0.5%–2%; and / or K2O: 0.1%–4%, preferably K2O: 0.5%–2%; and / or ZrO2: 0.1%–4.5%, preferably ZrO2: 1%–3%; and / or CaO: 0.1%–4%, preferably CaO: 0.5%–2%; and / or Sb2O3: 0.1%–2%, preferably Sb2O3: 0.2%–1%.

[0018] (5) The microcrystalline glass according to (1) or (2) is free from P2O5; and / or B2O3; and / or La2O3; and / or Gd2O3; and / or Y2O3; and / or Yb2O3; and / or Fe2O3; and / or Eu2O3.

[0019] (6) The glass-ceramic according to (1) or (2), wherein the crystalline phase of the glass-ceramic contains MgAl2Si3O 10 Crystal phase, MgAl2Si4O 12 Crystal phase, Mg2Al4Si5O 18 One or more of the crystalline phases.

[0020] (7) The microcrystalline glass according to (1) or (2), wherein the microcrystalline glass contains MgAl2Si3O 10 Crystal phase, and MgAl2Si3O 10 The crystalline phase has a higher weight percentage than other crystalline phases, and preferably the microcrystalline glass contains only MgAl2Si3O. 10 Crystal phase.

[0021] (8) The microcrystalline glass according to (1) or (2) wherein the crystalline phase content in the microcrystalline glass is 20% to 60%, preferably 30% to 60%, and more preferably 40% to 60%.

[0022] (9) The microcrystalline glass according to (1) or (2), wherein the drop ball test height of the microcrystalline glass is 400 mm to 1200 mm, the sample size of the drop ball test is 50 mm × 50 mm × 1 mm, and a 132 g steel ball is used, preferably 500 mm to 1200 mm, more preferably 600 mm to 1200 mm; and / or the Vickers hardness is 600 kgf / mm². 2 ~800kgf / mm 2 The preferred value is 650 kgf / mm 2 ~800kgf / mm 2 More preferably 700 kgf / mm 2 ~800kgf / mm 2 ; and / or a Young's modulus of 90 GPa to 120 GPa, preferably 95 GPa to 120 GPa, more preferably 100 GPa to 120 GPa; and / or a coefficient of thermal expansion of 20 to 300 °C of 20 × 10⁻⁶. -7 / ℃~50×10 -7 / ℃, preferably 30×10 -7 / ℃~47×10 -7 / ℃, more preferably 35×10 -7 / ℃~44×10 -7 / ℃; and / or microcrystalline glass with a thickness of less than 2.0 mm, having a light transmittance of 40% or more at 355 nm, preferably 50% or more, and more preferably 70% or more.

[0023] (10) The microcrystalline glass according to (9) has a thickness of 0.2 mm to 2.0 mm, preferably 0.3 mm to 1.5 mm, more preferably 0.5 mm to 1.0 mm, and even more preferably 0.5 mm, 0.8 mm or 1.0 mm.

[0024] (11) A microcrystalline glass product made of any of the microcrystalline glass described in (1) to (10).

[0025] (12) Microcrystalline glass products, whose components are expressed as weight percentages, contain: SiO2: 46% to 60%; Al2O3: 20% to 26%; MgO: 6.5% to 14%; ZnO: 0.1% to 8%; Li2O: greater than or equal to 0.1% but less than 5%; TiO2: greater than 0% but less than 5%; CaO: 0 to 4.5%, of which (SiO2+Al2O3) / (MgO+ZnO+CaO) is 4.0 to 8.0, and Li2O / TiO2 is 0.3 to 2.5.

[0026] (13) The microcrystalline glass product according to (12) further contains, by weight percentage: Na2O: less than 4%; and / or K2O: less than 5%; and / or ZrO2: less than 5%; and / or Sb2O3: 0 to 3%.

[0027] (14) The microcrystalline glass article according to (12) or (13) has components expressed as a percentage by weight that satisfy one or more of the following conditions:

[0028] 1) The content of Al2O3+ZnO+Na2O is 20.5%~32%, preferably 23%~31%, more preferably 24%~29.5%, and even more preferably 25.5%~28.5%;

[0029] 2) The ratio of (SiO2+Al2O3) / (MgO+ZnO+CaO) is 4.5 to 7.5, preferably 5.0 to 6.5;

[0030] 3) The Li2O / TiO2 ratio is 0.6–2.0, preferably 0.8–1.5;

[0031] 4) The ratio of (MgO+ZnO+Al2O3) / ZnO is 5.0 to 50.0, preferably 6.0 to 20.0, and more preferably 7.0 to 10.0;

[0032] 5) The ratio of (MgO+ZnO+Li2O) / Al2O3 is 0.3 to 1.0, preferably 0.4 to 0.8, and more preferably 0.5 to 0.7;

[0033] 6) The ratio of (MgO+ZnO) / Li2O is 4.0 to 13.0, preferably 4.5 to 11.5, and more preferably 5.0 to 9.5;

[0034] 7) The Al2O3 / (Na2O+K2O) ratio is 9.0 to 82.0, preferably 10.0 to 50.0, more preferably 15.0 to 30.0, and even more preferably 20.0 to 25.0;

[0035] 8) The ratio of (K2O+CaO) / TiO2 is 0.1 to 3.5, preferably 0.5 to 2.0, and more preferably 0.8 to 1.2;

[0036] 9) The ratio of (MgO+Al2O3+SiO2) / (TiO2+ZrO2) is 15.0 to 28.0, preferably 17.0 to 26.0, and more preferably 19.0 to 24.0.

[0037] (15) The microcrystalline glass article according to (12) or (13) comprises, by weight percentage: SiO2: 49%–58%, preferably SiO2: 51%–55%; and / or Al2O3: 21%–25%, preferably Al2O3: 21.5%–24.5%; and / or MgO: 7%–12%, preferably MgO: 8%–11%; and / or ZnO: 1%–6%, preferably ZnO: 2%–5%; and / or Li2O: 0.5%–4.5%, preferably Li2O: 1%– 3%; and / or TiO2: 0.5%–4.5%, preferably TiO2: 1%–3%; and / or Na2O: 0.1%–3%, preferably Na2O: 0.5%–2%; and / or K2O: 0.1%–4%, preferably K2O: 0.5%–2%; and / or ZrO2: 0.1%–4.5%, preferably ZrO2: 1%–3%; and / or CaO: 0.1%–4%, preferably CaO: 0.5%–2%; and / or Sb2O3: 0.1%–2%, preferably Sb2O3: 0.2%–1%.

[0038] (16) The microcrystalline glass article according to (12) or (13) is free from P2O5; and / or B2O3; and / or La2O3; and / or Gd2O3; and / or Y2O3; and / or Yb2O3; and / or Fe2O3; and / or Eu2O3.

[0039] (17) The glass-ceramic article according to (12) or (13), wherein the crystalline phase of the glass-ceramic article contains MgAl2Si3O 10 Crystal phase, MgAl2Si4O 12 Crystal phase, Mg2Al4Si5O 18 One or more of the crystalline phases.

[0040] (18) The microcrystalline glass article according to (12) or (13), wherein the microcrystalline glass article contains MgAl2Si3O 10 Crystal phase, and MgAl2Si3O 10 The crystalline phase has a higher weight percentage than other crystalline phases, and preferably the microcrystalline glass product contains only MgAl2Si3O. 10 Crystal phase.

[0041] (19) The microcrystalline glass product according to (12) or (13) has a crystalline phase content of 20% to 60%, preferably 30% to 60%, and more preferably 40% to 60%.

[0042] (20) The microcrystalline glass product according to (12) or (13), wherein the drop ball test height of the microcrystalline glass product is 600 mm to 1700 mm, the sample size of the drop ball test is 50 mm × 50 mm × 1 mm, a 132 g steel ball is used, preferably 900 mm to 1700 mm, more preferably 1100 mm to 1700 mm; and / or the Vickers hardness is 700 kgf / mm². 2 ~900kgf / mm 2 The preferred value is 750 kgf / mm 2 ~900kgf / mm 2 More preferably 800 kgf / mm 2 ~900kgf / mm 2 ; and / or a Young's modulus of 90 GPa to 120 GPa, preferably 95 GPa to 120 GPa, more preferably 100 GPa to 120 GPa; and / or a coefficient of thermal expansion of 20 to 300 °C of 20 × 10⁻⁶. -7 / ℃~50×10 -7 / ℃, preferably 30×10 -7 / ℃~47×10 -7 / ℃, more preferably 35×10 -7 / ℃~44×10 -7 / ℃; and / or microcrystalline glass articles with a thickness of less than 2.0 mm, wherein the light transmittance at 355 nm is 40% or more, preferably 50% or more, and more preferably 70% or more.

[0043] (21) The microcrystalline glass product according to (20) has a thickness of 0.2 mm to 2.0 mm, preferably 0.3 mm to 1.5 mm, more preferably 0.5 mm to 1.0 mm, and even more preferably 0.5 mm, 0.8 mm or 1.0 mm.

[0044] (22) A glass wafer made of any of the microcrystalline glass described in (1) to (10), or made of any of the microcrystalline glass products described in (11) to (21).

[0045] (23) A glass cover containing any of the microcrystalline glass described in (1) to (10), and / or a microcrystalline glass article containing any of the microcrystalline glass described in (11) to (21).

[0046] (24) Glass components containing any of the microcrystalline glass described in (1) to (10), and / or articles containing any of the microcrystalline glass described in (11) to (21).

[0047] (25) An electronic device comprising any of the microcrystalline glass described in (1) to (10), and / or comprising any of the microcrystalline glass articles described in (11) to (21), and / or comprising the glass cover plate described in (23), and / or comprising the glass components described in (24).

[0048] (26) A display device comprising any of the microcrystalline glass described in (1) to (10), and / or comprising any of the microcrystalline glass articles described in (11) to (21), and / or comprising the glass cover plate described in (23), and / or comprising the glass components described in (24).

[0049] The beneficial effects of this application are: through reasonable component design, the microcrystalline glass and microcrystalline glass products obtained by this application have high Young's modulus and ultraviolet light transmittance, which are suitable for manufacturing large-size glass wafers, etc., to meet the application needs of semiconductor manufacturing and other fields. Detailed Implementation

[0050] Microcrystalline glass is a material produced by heat-treating a substrate glass to induce crystallization within the glass. It possesses superior mechanical properties compared to conventional glass, effectively mitigating microcrack propagation and cracking issues in ordinary glass. Furthermore, microcrystalline glass can be chemically strengthened to form microcrystalline glass products, further enhancing its mechanical properties.

[0051] The microcrystalline glass and microcrystalline glass articles of this application are materials having a crystalline phase (sometimes also called crystal) and a glassy phase, which are different from amorphous solids. The crystalline phase of the microcrystalline glass and microcrystalline glass articles can be identified by the peak angle appearing in the X-ray diffraction pattern of X-ray diffraction analysis and / or measured by TEMEDX.

[0052] Through repeated experiments and research, the inventors of this application have obtained the microcrystalline glass or microcrystalline glass products of this application by specifying the content and proportion of specific components constituting microcrystalline glass and microcrystalline glass products to specific values ​​and causing them to precipitate specific crystalline phases.

[0053] The following describes the scope of each component (ingredient) of the matrix glass, glass-ceramic, and glass-ceramic articles of this application. Unless otherwise specified, the content, total content, and overall content of each component in this specification are all expressed as a weight percentage (wt%) relative to the total amount of material in the matrix glass, glass-ceramic, or glass-ceramic article converted to oxides. Here, "composition converted to oxides" refers to the total amount of oxides used in the glass raw materials that are components of the matrix glass, glass-ceramic, or glass-ceramic articles of this application, when these oxides, complex salts, and hydroxides decompose and transform into oxides upon melting, and the total amount of such oxides is taken as 100%. Furthermore, in this specification, when referred to simply as "glass," it refers to the matrix glass before crystallization (i.e., crystallization process treatment); after crystallization (i.e., crystallization process treatment), it is referred to as glass-ceramic; and glass-ceramic articles refer to products obtained by chemically strengthening glass-ceramic.

[0054] Unless otherwise specified in the specific context, the numerical ranges listed herein include upper and lower limits. "Above" and "below" include endpoint values ​​and all integers and fractions within the range, not limited to the specific values ​​listed when the range is defined. The term "and / or" as used herein is inclusive; for example, "A and / or B" means either only A, or only B, or both A and B.

[0055] In some embodiments, the crystalline phase in the glass-ceramic or glass-ceramic articles of this application contains MgAl2Si3O. 10 Crystal phase, MgAl2Si4O 12 Crystal phase, Mg2Al4Si5O 18 One or more of the following crystalline phases: crystalline phase, etc. Preferably, in some embodiments, MgAl2Si3O in the glass-ceramic or glass-ceramic article... 10 The crystalline phase has a higher weight percentage than other crystalline phases. More preferably, in some embodiments, the crystalline phase of the glass-ceramic or glass-ceramic article contains only MgAl2Si3O. 10 Crystal phase. Through the presence of MgAl2Si3O 10 Crystalline phases can effectively adjust the coefficient of thermal expansion of glass-ceramics and glass-ceramic products, thereby improving their thermal stability and Young's modulus. In this document, the weight percentage of the crystalline phase in the glass-ceramic (or glass-ceramic product) is referred to as the crystalline phase content. In some embodiments, the crystalline phase content in the glass-ceramic is 20%–60%, preferably 30%–60%, and more preferably 40%–60%. In some embodiments, the MgAl2Si3O in the glass-ceramic... 10The crystalline phase content is 20%–60%, preferably 30%–60%, and more preferably 40%–60%. In some embodiments, the crystalline phase content in the microcrystalline glass article is 20%–60%, preferably 30%–60%, and more preferably 40%–60%. In some embodiments, the MgAl2Si3O in the microcrystalline glass article... 10 The crystalline phase content is 20%–60%, preferably 30%–60%, and more preferably 40%–60%. In some embodiments, the crystalline phase content in the glass-ceramic or glass-ceramic product can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0056] SiO2 is one of the main components that forms glass and participates in the formation of the crystalline phase. Its silicon-oxygen tetrahedral structure forms a continuous network framework for the glass, improving the mechanical strength and chemical stability of the matrix glass, glass-ceramic, and glass-ceramic products, while reducing the coefficient of thermal expansion. If the SiO2 content is below 46%, the mechanical strength and chemical stability of the matrix glass, glass-ceramic, and glass-ceramic products are poor. If the SiO2 content exceeds 60%, the glass viscosity is too high at high temperatures, making it difficult to process materials during glass manufacturing and easily leading to defects such as bubbles and inclusions. Therefore, the SiO2 content is 46%–60%, preferably 49%–58%, and more preferably 51%–55%. In some embodiments, the SiO2 content can be 46%, 46.5%, 47%, 47.5%, 48%, 48.5%, 49%, 49.5%, 50%, 50.5%, 51%, 51.5%, 52%, 52.5%, 53%, 53.5%, 54%, 54.5%, 55%, 55.5%, 56%, 56.5%, 57%, 57.5%, 58%, 58.5%, 59%, 59.5%, 60%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0057] Al2O3, as an intermediate component in the network, can enter the silicon-oxygen network to form an aluminum-silicon tetrahedral structure, effectively strengthening the network framework of the glass. As a major component participating in the formation of the crystalline phase, Al2O3 can significantly improve the mechanical strength, hardness, and damage resistance of glass-ceramics and glass-ceramic products, while greatly improving chemical stability and reducing the tendency for crystallization during the manufacturing process of the matrix glass. When the Al2O3 content is too high, the viscosity of the glass increases, the melting temperature is high, and defects such as stone formation are easily generated. Therefore, the Al2O3 content is 20% to 26%, preferably 21% to 25%, and more preferably 21.5% to 24.5%. In some embodiments, the Al2O3 content can be 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0058] MgO can reduce the high-temperature viscosity of glass, improve melting and refining properties, and enhance molding and processability. In glass-ceramics and glass-ceramic products, MgO can form a crystalline phase together with Al2O3, improving the chemical stability and mechanical strength of the glass-ceramics and glass-ceramic products, and reducing the coefficient of thermal expansion. However, if the MgO content is too high, the coefficient of thermal expansion of the glass will increase, and the ultraviolet light transmittance will decrease. Therefore, the MgO content is 6.5% to 14%, preferably 7% to 12%, and more preferably 8% to 11%. In some embodiments, the MgO content can be 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0059] ZnO can reduce the high-temperature viscosity of glass, improve its melting and forming properties, and enhance the chemical stability, mechanical strength, and light transmittance of matrix glass, glass-ceramics, and glass-ceramic products. It can also suppress the tendency for crystallization during the manufacturing process of matrix glass. However, if the ZnO content is too high, it will increase the coefficient of thermal expansion of the matrix glass, glass-ceramics, and glass-ceramic products. Therefore, the ZnO content is 0.1%–8%, preferably 1%–6%, and more preferably 2%–5%. In some embodiments, the ZnO content can be 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%, 2.3%, 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%, 6.3%, 6.5%, 6.7%, 7%, 7.3%, 7.5%, 7.7%, 8%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0060] In some embodiments, controlling the total content of MgO, ZnO, and Al2O3, such that the ratio of MgO+ZnO+Al2O3 to ZnO (MgO+ZnO+Al2O3) / ZnO is within the range of 5.0 to 50.0, is beneficial for improving the Vickers hardness of glass-ceramics and glass-ceramic products. Therefore, in this application, it is preferred that (MgO+ZnO+Al2O3) / ZnO be 5.0 to 50.0, more preferably 6.0 to 20.0, and even more preferably 7.0 to 10.0. In some implementations, (MgO+ZnO+Al2O3) / ZnO can be 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9 1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.3, 11.5, 11.7, 12.0, 12.3, 12.5, 12.7, 13.0, 13.3, 13.5, 13.7, 14.0, 14.3, 14.5, 14.7, 15.0, 15.3, 15.5, 15.7, 16.0, 16.3, 1 6.5, 16.7, 17.0, 17.3, 17.5, 17.7, 18.0, 18.3, 18.5, 18.7, 19.0, 19.3, 19.5, 19.7, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 24.5, 25.0, 25.5, 26.0, 26.5, 27.0, 27.5, 28.0, 28.5, 29.0, 29.5, 30.0, 30.5, 31.0, 31.5, 32.0, 32 0.5, 33.0, 33.5, 34.0, 34.5, 35.0, 35.5, 36.0, 36.5, 37.0, 37.5, 38.0, 38.5, 39.0, 39.5, 40.0, 40.5, 41.0, 41.5, 42.0, 42.5, 43.0, 43.5, 44.0, 44.5, 45.0, 45.5, 46.0, 46.5, 47.0, 47.5, 48.0, 48.5, 49.0, 49.5, 50.0, etc., as well as all ranges and subranges between the above values.It should be understood that, in the implementation plan, any of the above scopes can be combined with any other scopes.

[0061] CaO can reduce the high-temperature viscosity of glass, improve melting, clarifying and forming properties, strengthen the network structure of glass, and enhance the chemical stability and mechanical strength of matrix glass, glass-ceramic, and glass-ceramic products. However, if the CaO content is too high, it will increase the coefficient of thermal expansion of matrix glass, glass-ceramic, and glass-ceramic products, and reduce light transmittance. Therefore, the CaO content is 0–4.5%, preferably 0.1%–4%, and more preferably 0.5%–2%. In some embodiments, the CaO content can be 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%, 2.3%, 2.5%, 2.7%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0062] In some embodiments, controlling the ratio (SiO2+Al2O3) / (MgO+ZnO+CaO) between the total content of SiO2 and Al2O3 (SiO2+Al2O3) and the total content of MgO, ZnO, and CaO (MgO+ZnO+CaO) in the range of 4.0 to 8.0 is beneficial to improving the Young's modulus of glass-ceramics and glass-ceramic products. Therefore, it is preferable that (SiO2+Al2O3) / (MgO+ZnO+CaO) is 4.0 to 8.0, more preferably (SiO2+Al2O3) / (MgO+ZnO+CaO) is 4.5 to 7.5, and even more preferably (SiO2+Al2O3) / (MgO+ZnO+CaO) is 5.0 to 6.5. In some embodiments, (SiO2+Al2O3) / (MgO+ZnO+CaO) can be 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0063] Li₂O can significantly reduce the high-temperature viscosity of glass, improve melting and forming properties, and also enhance the mechanical strength of glass-ceramics and glass-ceramic products to a certain extent, reduce the coefficient of thermal expansion, decrease the crystallization tendency of the matrix glass, and improve the light transmittance of glass-ceramics and glass-ceramic products. However, excessive Li₂O content can lead to a decrease in the chemical stability of glass-ceramics and glass-ceramic products. Therefore, the Li₂O content is greater than or equal to 0.1% but less than 5%, preferably 0.5% to 4.5%, and more preferably 1% to 3%. In some embodiments, the Li₂O content can be 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%, 2.3%, 2.5%, 2.7%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, 4.7%, 4.9%, less than 5%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0064] In some embodiments, controlling the total content of MgO, ZnO, and Li2O, and the ratio of MgO+ZnO+Li2O to Al2O3 (MgO+ZnO+Li2O) / Al2O3 within the range of 0.3 to 1.0, is beneficial for reducing the coefficient of thermal expansion of glass-ceramics and glass-ceramic products. Therefore, in this application, it is preferred that (MgO+ZnO+Li2O) / Al2O3 be 0.3 to 1.0, more preferably 0.4 to 0.8, and even more preferably 0.5 to 0.7. In some embodiments, (MgO+ZnO+Li2O) / Al2O3 can be 0.3, 0.33, 0.35, 0.37, 0.4, 0.43, 0.45, 0.47, 0.5, 0.53, 0.55, 0.57, 0.6, 0.63, 0.65, 0.67, 0.7, 0.73, 0.75, 0.77, 0.8, 0.83, 0.85, 0.87, 0.9, 0.93, 0.95, 0.97, 1.0, etc., as well as all ranges and subranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0065] In some embodiments, controlling the ratio of the total content of MgO and ZnO (MgO+ZnO) to the content of Li2O (MgO+ZnO) / Li2O within the range of 4.0 to 13.0 is beneficial for improving the drop ball test height of the microcrystalline glass and microcrystalline glass articles of this application. Therefore, in this application, (MgO+ZnO) / Li2O is preferably 4.0 to 13.0, more preferably 4.5 to 11.5, and even more preferably 5.0 to 9.5. In some embodiments, (MgO+ZnO) / Li2O can be 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.3, 11.5, 11.7, 12.0, 12.3, 12.5, 12.7, 13.0, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0066] Na₂O can reduce the high-temperature viscosity of glass, greatly improve melting, clarifying, and forming properties, and enhance the chemical stability and mechanical strength of glass-ceramics and glass-ceramic products. However, excessive Na₂O content will increase the coefficient of thermal expansion of glass-ceramics and glass-ceramic products. Therefore, the Na₂O content is less than 4%, preferably 0.1% to 3%, and more preferably 0.5% to 2%. In some embodiments, the Na₂O content can be 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%, 2.3%, 2.5%, 2.7%, 3%, 3.3%, 3.5%, 3.7%, 3.9%, less than 4%, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation plan, any of the above scopes can be combined with any other scopes.

[0067] In some embodiments, by controlling the total content of Al2O3, ZnO, and Na2O (Al2O3+ZnO+Na2O) within the range of 20.5% to 32%, the drop ball test height of glass-ceramic and glass-ceramic products can be improved. Therefore, in this application, the preferred content of Al2O3+ZnO+Na2O is 20.5% to 32%, more preferably 23% to 31%, further preferably 24% to 29.5%, and even more preferably 25.5% to 28.5%. In some embodiments, Al2O3+ZnO+Na2O can be 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0068] K₂O has a good fluxing effect, which can reduce the high-temperature viscosity of glass and improve its melting and forming processing performance. K₂O can form a mixed alkali effect with Na₂O and Li₂O, making it easier to achieve stable control of the thermal expansion coefficient of glass-ceramics and glass-ceramic products than with single alkali metals. However, K₂O can damage the glass network framework and is not conducive to the chemical strengthening of glass-ceramics into glass-ceramic products. Therefore, the K₂O content is less than 5%, preferably 0.1% to 4%, and more preferably 0.5% to 2%. In some embodiments, the K2O content can be 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%, 2.3%, 2.5%, 2.7%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, 4.7%, 4.9%, less than 5%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0069] In some embodiments, by controlling the content of Al2O3 and the total content of Na2O and K2O, Al2O3 / (Na2O+K2O) to be in the range of 9.0 to 82.0, the Young's modulus of glass-ceramics and glass-ceramic products can be improved. Therefore, in this application, Al2O3 / (Na2O+K2O) is preferably 9.0 to 82.0, more preferably 10.0 to 50.0, even more preferably 15.0 to 30.0, and even more preferably 20.0 to 25.0.In some implementations, Al2O3 / (Na2O+K2O) can be 5.0, 5.3, 5.5, 5.7, 6.0, 6.3, 6.5, 6.7, 7.0, 7.3, 7.5, 7.7, 8.0, 8.3, 8.5, 8.7, 9.0, 9.3, 9.5, 9.7, 10.0, 10.3, 10.5, 10.7, 11.0, 11.3, 11.5, 11.7, 12.0, 12.3, 12.5, 12.7, 13.0, 13.3, 13.5, 13.7, 14.0, 14.3, 14.5, 14.7, 15.0, 15.3, 15.5, 15.7, 16.0, 16.3, 16.5, 16.7, 17.0, 17.3, 17.5, 17.7, 18.0, 18.3, 18.5, 18.7, 19.0, 19.3, 19.5, 19.7, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 24.5, 25.0, 25.5, 26.0, 26.5, 27.0, 27.5, 28.0, 28. 5, 29.0, 29.5, 30.0, 30.5, 31.0, 31.5, 32.0, 32.5, 33.0, 33.5, 34.0, 34.5, 35.0, 35.5, 36.0, 36.5, 37.0, 37.5, 38.0, 38.5, 39.0, 39.5, 40.0, 40.5, 41.0, 41.5, 42.0, 42.5, 43.0, 43.5, 44.0, 44.5, 45.0, 45.5, 46.0, 46.5, 47.0, 47.5, 48.0, 4 8.5, 49.0, 49.5, 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, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0070] TiO2, as a network intermediate and nucleating agent, can participate in the formation of glass networks, improve structural density and chemical stability, and effectively reduce the crystallization activation energy during crystallization heat treatment, inducing uniform microcrystallization of the glass and refining the grains. However, excessive TiO2 content can cause runaway crystallization of the glass and affect the light transmittance of the glass in the ultraviolet band (e.g., at 355 nm). Therefore, the TiO2 content is greater than 0% but less than 5%, preferably 0.5% to 4.5%, and more preferably 1% to 3%. In some embodiments, the TiO2 content can be 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%, 2.3%, 2.5%, 2.7%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, 4.7%, 4.9%, less than 5%, and all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0071] In some embodiments, controlling the ratio of Li2O to TiO2 content (Li2O / TiO2) within the range of 0.3 to 2.5 is beneficial to improving the light transmittance of glass-ceramics and glass-ceramic products in the ultraviolet band (e.g., at 355 nm). Therefore, in this application, a Li2O / TiO2 ratio of 0.3 to 2.5 is preferred, a Li2O / TiO2 ratio of 0.6 to 2.0 is more preferred, and a Li2O / TiO2 ratio of 0.8 to 1.5 is even more preferred. In some implementations, Li₂O / TiO₂ can be 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45, 2.5, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in implementations, any of the above ranges can be combined with any other range.

[0072] In some embodiments, controlling the ratio of the total content of K2O and CaO (K2O+CaO) to the content of TiO2 (K2O+CaO) / TiO2 within the range of 0.1 to 3.5 is beneficial for reducing the coefficient of thermal expansion of glass-ceramic and glass-ceramic products. Therefore, in this application, it is preferred that (K2O+CaO) / TiO2 be 0.1 to 3.5, more preferably 0.5 to 2.0, and even more preferably 0.8 to 1.2. In some implementations, the ratio of (K₂O+CaO) / TiO₂ can be 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, or 1.7. 5, 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45, 2.5, 2.55, 2.6, 2.65, 2.7, 2.75, 2.8, 2.85, 2.9, 2.95, 3.0, 3.05, 3.1, 3.15, 3.2, 3.25, 3.3, 3.35, 3.4, 3.45, 3.5, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0073] ZrO2 can strengthen the glass network structure, improve the thermal stability of glass, increase the hardness, flexural strength, and chemical stability of glass-ceramics and glass-ceramic products, and reduce the coefficient of thermal expansion. ZrO2 can work synergistically with TiO2, acting as a highly efficient nucleating agent during the microcrystallization process, guiding the uniform precipitation of crystalline phases, refining grains, and regulating the crystalline phase composition and microstructure. However, ZrO2 has low solubility in glass, and excessive content can lead to the formation of stones, making glass melting difficult. Therefore, the ZrO2 content is less than 5%, preferably 0.1% to 4.5%, and more preferably 1% to 3%. In some embodiments, the ZrO2 content can be 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%, 2.3%, 2.5%, 2.7%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, 4.7%, 4.9%, less than 5%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0074] In some embodiments, by controlling the ratio (MgO+Al2O3+SiO2) / (TiO2+ZrO2) between the total content of MgO, Al2O3, and SiO2 (MgO+Al2O3+SiO2) and the total content of TiO2 and ZrO2 (TiO2+ZrO2), it is beneficial to improve the crystalline phase content of the glass-ceramic and glass-ceramic products of this application. Therefore, in this application, it is preferred that (MgO+Al2O3+SiO2) / (TiO2+ZrO2) be 15.0-28.0, more preferably (MgO+Al2O3+SiO2) / (TiO2+ZrO2) be 17.0-26.0, and even more preferably (MgO+Al2O3+SiO2) / (TiO2+ZrO2) be 19.0-24.0. In some embodiments, (MgO+Al2O3+SiO2) / (TiO2+ZrO2) can be 15.0, 15.3, 15.5, 15.7, 16.0, 16.3, 16.5, 16.7, 17.0, 17.3, 17.5, 17.7, 18.0, 18.3, 18.5, 18.7, 19.0, 19.3, 19.5, 19.7, 20.0, 20.3, 20.5, 20.7, 21 0, 21.3, 21.5, 21.7, 22.0, 22.3, 22.5, 22.7, 23.0, 23.3, 23.5, 23.7, 24.0, 24.3, 24.5, 24.7, 25.0, 25.3, 25.5, 25.7, 26.0, 26.3, 26.5, 26.7, 27.0, 27.3, 27.5, 27.7, 28.0, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0075] Sb₂O₃, as a clarifying and oxidizing agent, can adjust the viscosity of the glass melt and stabilize the glass structure. Even a small amount can significantly improve the glass melting effect, but excessive content can affect the valence state of Ti ions in the glass, resulting in uneven glass color. Therefore, the content of Sb₂O₃ is 0-3%, preferably 0.1%-2%, and more preferably 0.2%-1%. In some embodiments, the content of Sb₂O₃ can be 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%, 2.3%, 2.5%, 2.7%, 3%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0076] In order to enable the microcrystalline glass and microcrystalline glass articles of this application to obtain the excellent performance desired in this application, it is preferred that the microcrystalline glass and microcrystalline glass articles do not contain P2O5, and / or do not contain B2O3, and / or do not contain La2O3, and / or do not contain Gd2O3, and / or do not contain Y2O3, and / or do not contain Yb2O3, and / or do not contain Fe2O3, and / or do not contain Eu2O3.

[0077] PbO and As2O3 are toxic substances, and even small amounts do not meet environmental protection requirements. Therefore, in some embodiments of this application, it is preferred that PbO and As2O3 are not present.

[0078] The terms "not containing", "0", and "0%" used herein refer to the fact that the compound, molecule, or element was not intentionally added as a raw material to the matrix glass, glass-ceramic, or glass-ceramic product of this application. However, as raw materials and / or equipment used in the production of matrix glass, glass-ceramic, or glass-ceramic products, there may be certain impurities or components that are not intentionally added, which may be present in small or trace amounts (less than 0.01%) in the final matrix glass, glass-ceramic, or glass-ceramic product. Such cases are also within the scope of protection of this patent application.

[0079] In this application, the matrix glass and the microcrystalline glass have the same composition and content.

[0080] The substrate glass, glass-ceramic, and glass-ceramic articles of this application can be produced and manufactured by the following methods:

[0081] Forming the matrix glass: Glass raw materials (oxides, hydroxides, complex salts, etc.) are mixed uniformly according to their composition. The uniform mixture is placed in a furnace (e.g., a platinum or quartz crucible). Depending on the melting ease of the glass composition, melting is carried out in an electric or gas furnace at a temperature range of 1450℃ to 1650℃ for 5 to 24 hours, preferably at a melting temperature of 1500℃ to 1600℃. The matrix glass is then obtained after clarification, homogenization, shaping, and annealing. The clarification temperature is preferably 1550℃ to 1630℃, and the annealing temperature is preferably 550℃ to 650℃. In some embodiments, the melting temperature can be 1450°C, 1460°C, 1470°C, 1480°C, 1490°C, 1500°C, 1510°C, 1520°C, 1530°C, 1540°C, 1550°C, 1560°C, 1570°C, 1580°C, 1590°C, 1600°C, 1610°C, 1620°C, 1630°C, 1640°C, 1650°C, etc., as well as all ranges and subranges between the above values. In some implementations, the melting time can be 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours, 15 hours, 15.5 hours, 16 hours, 16.5 hours, 17 hours, 17.5 hours, 18 hours, 18.5 hours, 19 hours, 19.5 hours, 20 hours, 20.5 hours, 21 hours, 21.5 hours, 22 hours, 22.5 hours, 23 hours, 23.5 hours, 24 hours, etc., as well as all ranges and subranges between the above values. In some embodiments, the clarifying temperature can be 1550°C, 1560°C, 1570°C, 1580°C, 1590°C, 1600°C, 1610°C, 1620°C, 1630°C, etc., and all ranges and sub-ranges between these values. In some embodiments, the annealing temperature can be 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, etc., and all ranges and sub-ranges between these values.

[0082] The matrix glass of this application can be formed by well-known methods.

[0083] The matrix glass of this application undergoes a crystallization process after molding or processing, resulting in the uniform precipitation of crystals within the glass to form microcrystalline glass. This crystallization process can be performed in one stage or two stages, preferably in two stages. The two-stage crystallization process involves a nucleation process at a first temperature, followed by a crystal growth process at a second temperature. The crystallization process performed at the first temperature is referred to as the first crystallization process, and the crystallization process performed at the second temperature is referred to as the second crystallization process.

[0084] To achieve the desired physicochemical properties in glass-ceramics, the preferred crystallization process is as follows:

[0085] The crystallization process described above, performed in a single stage, allows for continuous nucleation and crystal growth. Specifically, the temperature is raised to a predetermined crystallization temperature, maintained for a certain period, and then cooled. The preferred crystallization temperature is 600°C to 850°C, and more preferably 650°C to 800°C to precipitate the desired crystalline phase. The holding time at the crystallization temperature is preferably 5 to 30 hours, and more preferably 10 to 20 hours. In some embodiments, the crystallization temperature can be 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, 690°C, 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C, 780°C, 790°C, 800°C, 810°C, 820°C, 830°C, 840°C, 850°C, etc., as well as all ranges and subranges between the above values. The holding time at the crystallization treatment temperature can be 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours, 15 hours, 15.5 hours, 16 hours, 16.5 hours, 17 hours, 17.5 hours, and 18 hours. Hours, 18.5 hours, 19 hours, 19.5 hours, 20 hours, 20.5 hours, 21 hours, 21.5 hours, 22 hours, 22.5 hours, 23 hours, 23.5 hours, 24 hours, 24.5 hours, 25 hours, 25.5 hours, 26 hours, 26.5 hours, 27 hours, 27.5 hours, 28 hours, 28.5 hours, 29 hours, 29.5 hours, 30 hours, etc., as well as all ranges and subranges between the above values.

[0086] When performing the crystallization treatment in two stages as described above, the first temperature is preferably 600℃ to 750℃, the second temperature is preferably greater than 750℃ but less than or equal to 900℃, the holding time at the first temperature is preferably 1 hour to 10 hours, and the holding time at the second temperature is preferably 5 hours to 20 hours. In some embodiments, the first temperature can be 600℃, 610℃, 620℃, 630℃, 640℃, 650℃, 660℃, 670℃, 680℃, 690℃, 700℃, 710℃, 720℃, 730℃, 740℃, 750℃, etc., as well as all ranges and sub-ranges between the above values. In some embodiments, the second temperature can be greater than 750°C, 751°C, 755°C, 760°C, 770°C, 780°C, 790°C, 800°C, 810°C, 820°C, 830°C, 840°C, 850°C, 860°C, 870°C, 880°C, 890°C, 900°C, etc., as well as all ranges and sub-ranges between the above values. In some embodiments, the holding time at the first temperature can be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, etc., as well as all ranges and sub-ranges between the above values. In some implementations, the holding time at the second temperature can be 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours, 15 hours, 15.5 hours, 16 hours, 16.5 hours, 17 hours, 17.5 hours, 18 hours, 18.5 hours, 19 hours, 19.5 hours, 20 hours, etc., as well as all ranges and subranges between the above values.

[0087] In some embodiments, the matrix glass or glass-ceramic described herein can be manufactured into shaped articles using various processes, including but not limited to sheets, and the processes include but not limited to slot drawing, float glass, roll forming, and other sheet forming processes known in the art. Alternatively, the matrix glass or glass-ceramic can be formed using float glass or roll forming methods known in the art.

[0088] The substrate glass or microcrystalline glass of this application can be manufactured into sheet glass or microcrystalline glass by methods such as grinding or polishing, but the method of manufacturing the glass or microcrystalline glass is not limited to these methods.

[0089] The matrix glass, microcrystalline glass, and microcrystalline glass articles described in this application may have any reasonably useful thickness.

[0090] In addition to improving mechanical properties through precipitation crystallization, the microcrystalline glass of this application can also obtain superior mechanical properties by forming a compressive stress layer, thereby making microcrystalline glass products.

[0091] In some embodiments, the substrate glass or microcrystalline glass can be processed into sheets and / or shaped, polished and / or swept after shaping, and then chemically strengthened through a chemical strengthening process.

[0092] The chemical strengthening described in this application is the ion exchange method. During ion exchange, smaller metal ions in the matrix glass or glass-ceramic are replaced or "exchanged" by larger metal ions with the same valence state located near the matrix glass or glass-ceramic. Replacing smaller ions with larger ions creates compressive stress in the matrix glass or glass-ceramic, forming a compressive stress layer.

[0093] In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., Na+). + K + 、Rb + Cs + Ion exchange is carried out by immersing a matrix glass or glass-ceramic in a salt bath containing at least one molten salt containing larger metal ions, which replace smaller metal ions in the matrix glass. One or more ion exchange processes used to chemically strengthen a matrix glass or glass-ceramic may include, but are not limited to, immersion in a single salt bath, or immersion in multiple salt baths having the same or different compositions, with washing and / or annealing steps between immersions.

[0094] In some embodiments, the matrix glass or glass-ceramic can be subjected to ion exchange in a salt bath of molten Na salt (such as NaNO3) or K salt (such as KNO3) at a temperature of about 400°C to 520°C for about 1 hour to 36 hours, preferably in the temperature range of 420°C to 480°C, and preferably in the time range of 2 hours to 15 hours. In this embodiment, Na ions in the salt bath replace some of the Li ions in the matrix glass or glass-ceramic, or K ions in the salt bath replace some of the Li ions and / or Na ions in the matrix glass or glass-ceramic, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the temperature of the molten Na salt bath can be 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, etc., as well as all ranges and subranges between the above values. In some embodiments, the ion exchange time can be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours, 15 hours, 15.5 hours, 16 hours, 16.5 hours, 17 hours, or 17. 5 hours, 18 hours, 18.5 hours, 19 hours, 19.5 hours, 20 hours, 20.5 hours, 21 hours, 21.5 hours, 22 hours, 22.5 hours, 23 hours, 23.5 hours, 24 hours, 24.5 hours, 25 hours, 25.5 hours, 26 hours, 26.5 hours, 27 hours, 27.5 hours, 28 hours, 28.5 hours, 29 hours, 29.5 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, 36 hours, etc., as well as all ranges and subranges between the above values.

[0095] In some embodiments, the matrix glass or glass-ceramic can be ion-exchanged by immersion in a mixed salt bath of molten K and Na salts at a temperature of about 380°C to 480°C for 1 hour to 36 hours, preferably within a time range of 2 hours to 24 hours. In some embodiments, the temperature of the mixed salt bath of molten K and Na salts can be 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, etc., as well as all ranges and subranges between these values. In some embodiments, the ion exchange time can be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours, 15 hours, 15.5 hours, 16 hours, 16.5 hours, 17 hours, or 17. 5 hours, 18 hours, 18.5 hours, 19 hours, 19.5 hours, 20 hours, 20.5 hours, 21 hours, 21.5 hours, 22 hours, 22.5 hours, 23 hours, 23.5 hours, 24 hours, 24.5 hours, 25 hours, 25.5 hours, 26 hours, 26.5 hours, 27 hours, 27.5 hours, 28 hours, 28.5 hours, 29 hours, 29.5 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, 36 hours, etc., as well as all ranges and subranges between the above values.

[0096] The microcrystalline glass involved in this application possesses highly efficient low-temperature ion exchange performance. In some embodiments, at relatively low ion exchange temperatures and short exchange times, the surface stress of the microcrystalline glass product can reach over 40 MPa. After ion exchange, the hardness of the microcrystalline glass product is significantly improved, mainly because ion exchange forms a high compressive stress on the surface of the microcrystalline glass product through a "squeezing effect," thereby increasing the deformation resistance and hardness of the microcrystalline glass product. In some embodiments, after chemical strengthening, the microcrystalline glass of this application yields a Vickers hardness of up to 700 kgf / mm². 2 above.

[0097] The performance indicators of the microcrystalline glass and / or microcrystalline glass products in this application were tested using the following methods:

[0098] [Light transmittance]

[0099] The light transmittance mentioned in this article refers to external transmittance, sometimes simply referred to as transmittance.

[0100] The sample was processed to a thickness of less than 2.0 mm and the opposite surfaces were polished in parallel. The light transmittance at 355 nm was measured using a Hitachi U-41000 spectrophotometer.

[0101] [Drop test height]

[0102] A 50mm × 50mm × 1mm sample is placed on a glass bearing fixture, and a 132g steel ball is dropped from a specified height, with the impact point being the center of the sample. This is the maximum drop ball test height from which the sample can withstand the impact without breaking. Specifically, the drop ball test height starts at 400mm, with each height being dropped once. If the sample does not break, the height is increased by 100mm each time until the sample breaks. For the embodiment with "drop ball test height A," microcrystalline glass is used as the test object. For the embodiment with "drop ball test height B," microcrystalline glass products are used as the test object. In the embodiment, test data recorded as 1000mm indicates that the test sample withstood the impact without breaking when the steel ball was dropped from a height of 1000mm, but the sample broke at 1100mm. In this application, the drop ball test height is sometimes simply referred to as the drop ball height.

[0103] Vickers hardness

[0104] The load (N) when a diamond pyramid indenter with a 136° angle between its two faces is used to press a pyramid-shaped indentation into the test surface of the sample is calculated by dividing the surface area (mm) calculated by the length of the indentation. 2 The value is represented by ). The test is conducted with a load of 100 (N) and a holding time of 15 (seconds). In this application, Vickers hardness is sometimes simply referred to as hardness.

[0105] Young's modulus

[0106] Young's modulus (E) is obtained by ultrasonic testing of its longitudinal and transverse wave velocities, and then calculated using the following formula.

[0107]

[0108]

[0109] In the formula: E is Young's modulus, Pa;

[0110] G is the shear modulus, Pa;

[0111] V T The transverse wave velocity is in m / s;

[0112] V S The longitudinal wave velocity is given in m / s.

[0113] ρ is the density of glass, in g / cm³ 3.

[0114] Coefficient of thermal expansion

[0115] The coefficient of thermal expansion (α) was determined using a DIL 402 SE dual-bar dual-furnace dilatometer. The glass elongation ΔL at 20–300℃ was tested according to the national standard GB / T7962.16-2010, and then calculated using the following formula.

[0116]

[0117] In the formula: ΔL is the change in length caused by the temperature change;

[0118] L0 is the original length at the initial temperature of the sample;

[0119] ΔT represents the change in sample temperature.

[0120] The microcrystalline glass of this application has the following properties:

[0121] 1) In some embodiments, the light transmittance at 355nm for a microcrystalline glass with a thickness of 2.0mm or less is 40% or more, preferably 50% or more, and more preferably 70% or more. The thickness is preferably 0.2mm to 2.0mm, more preferably 0.3mm to 1.5mm, further preferably 0.5mm to 1.0mm, and even more preferably 0.5mm, 0.8mm, or 1.0mm. In some embodiments, the light transmittance at 355nm for a microcrystalline glass with a thickness of 2.0mm or less can be 40%, 43%, 45%, 47%, 50%, 53%, 55%, 57%, 60%, 63%, 65%, 67%, 70%, 73%, 75%, 77%, 80%, 83%, 85%, 87%, 90%, 93%, etc., and all ranges and sub-ranges between the above values.

[0122] 2) In some embodiments, the drop ball test height of the microcrystalline glass is 400mm to 1200mm, preferably 500mm to 1200mm, and more preferably 600mm to 1200mm. In some embodiments, the drop ball test height of the microcrystalline glass can be 400mm, 500mm, 600mm, 700mm, 800mm, 900mm, 1000mm, 1100mm, 1200mm, etc., as well as all ranges and sub-ranges between the above values.

[0123] 3) In some embodiments, the Vickers hardness (Hv) of the glass-ceramic is 600 kgf / mm. 2 ~800kgf / mm 2 The preferred value is 650 kgf / mm 2 ~800kgf / mm 2More preferably 700 kgf / mm 2 ~800kgf / mm 2 In some embodiments, the Vickers hardness of the glass-ceramic can be 600 kgf / mm². 2 610kgf / mm 2 620kgf / mm 2 630kgf / mm 2 640kgf / mm 2 650kgf / mm 2 660kgf / mm 2 670kgf / mm 2 680kgf / mm 2 690kgf / mm 2 700kgf / mm 2 710kgf / mm 2 720kgf / mm 2 730kgf / mm 2 740kgf / mm 2 750kgf / mm 2 760kgf / mm 2 770kgf / mm 2 780kgf / mm 2 790kgf / mm 2 800kgf / mm 2 And so on, as well as all ranges and subranges between the above values.

[0124] 4) In some embodiments, the Young's modulus (E) of the glass-ceramic is 90 GPa to 120 GPa, preferably 95 GPa to 120 GPa, and more preferably 100 GPa to 120 GPa. In some embodiments, the Young's modulus of the glass-ceramic can be 90 GPa, 91 GPa, 92 GPa, 93 GPa, 94 GPa, 95 GPa, 96 GPa, 97 GPa, 98 GPa, 99 GPa, 100 GPa, 101 GPa, 102 GPa, 103 GPa, 104 GPa, 105 GPa, 106 GPa, 107 GPa, 108 GPa, 109 GPa, 110 GPa, 111 GPa, 112 GPa, 113 GPa, 114 GPa, 115 GPa, 116 GPa, 117 GPa, 118 GPa, 119 GPa, 120 GPa, etc., as well as all ranges and subranges between the above values.

[0125] 5) In some embodiments, the coefficient of thermal expansion (α) of the microcrystalline glass at 20–300°C is 20 × 10⁻⁶. -7 / ℃~50×10 -7 / ℃, preferably 30×10 -7 / ℃~47×10 -7 / ℃, more preferably 35×10 -7 / ℃~44×10 -7 / ℃. In some embodiments, the coefficient of thermal expansion of the microcrystalline glass at 20–300℃ can be 20 × 10⁻⁶. -7 / ℃, 21×10 -7 / ℃, 22×10 -7 / ℃, 23×10 -7 / ℃, 24×10 -7 / ℃, 25×10 -7 / ℃, 26×10 -7 / ℃, 27×10 -7 / ℃, 28×10 -7 / ℃, 29×10 -7 / ℃, 30×10 -7 / ℃, 31×10 -7 / ℃, 32×10 -7 / ℃, 33×10 -7 / ℃, 34×10 -7 / ℃, 35×10 -7 / ℃, 36×10 -7 / ℃, 37×10 -7 / ℃, 38×10 -7 / ℃, 39×10 -7 / ℃, 40×10 -7 / ℃, 41×10 -7 / ℃, 42×10 -7 / ℃, 43×10 -7 / ℃, 44×10 -7 / ℃, 45×10 -7 / ℃, 46×10 -7 / ℃, 47×10 -7 / ℃, 48×10 -7 / ℃, 49×10 -7 / ℃, 50×10 -7 / ℃, etc., and all ranges and subranges between the above values.

[0126] The microcrystalline glass articles of this application have the following properties:

[0127] 1) In some embodiments, the light transmittance at 355nm for microcrystalline glass articles with a thickness of 2.0mm or less is 40% or more, preferably 50% or more, and more preferably 70% or more. The thickness is preferably 0.2mm to 2.0mm, more preferably 0.3mm to 1.5mm, further preferably 0.5mm to 1.0mm, and even more preferably 0.5mm, 0.8mm, or 1.0mm. In some embodiments, the light transmittance at 355nm for microcrystalline glass articles with a thickness of 2.0mm or less can be 40%, 43%, 45%, 47%, 50%, 53%, 55%, 57%, 60%, 63%, 65%, 67%, 70%, 73%, 75%, 77%, 80%, 83%, 85%, 87%, 90%, 93%, etc., as well as all ranges and sub-ranges between the above values.

[0128] 2) In some embodiments, the drop ball test height of the microcrystalline glass article is 600mm to 1700mm, preferably 900mm to 1700mm, and more preferably 1100mm to 1700mm. In some embodiments, the drop ball test height of the microcrystalline glass article can be 600mm, 700mm, 800mm, 900mm, 1000mm, 1100mm, 1200mm, 1300mm, 1400mm, 1500mm, 1600mm, 1700mm, etc., as well as all ranges and sub-ranges between the above values.

[0129] 3) In some embodiments, the Vickers hardness (Hv) of the microcrystalline glass article is 700 kgf / mm. 2 ~900kgf / mm 2 The preferred value is 750 kgf / mm 2 ~900kgf / mm 2 More preferably 800 kgf / mm 2 ~900kgf / mm 2 In some embodiments, the Vickers hardness of the microcrystalline glass article can be 700 kgf / mm². 2 710kgf / mm 2 720kgf / mm 2 730kgf / mm 2 740kgf / mm 2 750kgf / mm 2 760kgf / mm 2 770kgf / mm 2 780kgf / mm 2 790kgf / mm 2 800kgf / mm 2 810kgf / mm2 820kgf / mm 2 830kgf / mm 2 840kgf / mm 2 850kgf / mm 2 860kgf / mm 2 870kgf / mm 2 880kgf / mm 2 890kgf / mm 2 900kgf / mm 2 And so on, as well as all ranges and subranges between the above values.

[0130] 4) In some embodiments, the Young's modulus (E) of the microcrystalline glass article is 90 GPa to 120 GPa, preferably 95 GPa to 120 GPa, and more preferably 100 GPa to 120 GPa. In some embodiments, the Young's modulus of the microcrystalline glass article can be 90 GPa, 91 GPa, 92 GPa, 93 GPa, 94 GPa, 95 GPa, 96 GPa, 97 GPa, 98 GPa, 99 GPa, 100 GPa, 101 GPa, 102 GPa, 103 GPa, 104 GPa, 105 GPa, 106 GPa, 107 GPa, 108 GPa, 109 GPa, 110 GPa, 111 GPa, 112 GPa, 113 GPa, 114 GPa, 115 GPa, 116 GPa, 117 GPa, 118 GPa, 119 GPa, 120 GPa, etc., as well as all ranges and subranges between the above values.

[0131] 5) In some embodiments, the coefficient of thermal expansion (α) of the microcrystalline glass article at 20–300°C is 20 × 10⁻⁶. -7 / ℃~50×10 -7 / ℃, preferably 30×10 -7 / ℃~47×10 -7 / ℃, more preferably 35×10 -7 / ℃~44×10 -7 / ℃. In some embodiments, the coefficient of thermal expansion of the microcrystalline glass article at 20–300℃ can be 20 × 10⁻⁶. -7 / ℃, 21×10 -7 / ℃, 22×10 -7 / ℃, 23×10 -7 / ℃, 24×10 -7 / ℃, 25×10 -7 / ℃, 26×10 -7 / ℃, 27×10 -7 / ℃, 28×10 -7 / ℃, 29×10 -7 / ℃, 30×10 -7 / ℃, 31×10 -7 / ℃, 32×10 -7 / ℃, 33×10 -7 / ℃, 34×10 -7 / ℃, 35×10 -7 / ℃, 36×10 -7 / ℃, 37×10 -7 / ℃, 38×10 -7 / ℃, 39×10 -7 / ℃, 40×10 -7 / ℃, 41×10 -7 / ℃, 42×10 -7 / ℃, 43×10 -7 / ℃, 44×10 -7 / ℃, 45×10 -7 / ℃, 46×10 -7 / ℃, 47×10 -7 / ℃, 48×10 -7 / ℃, 49×10 -7 / ℃, 50×10 -7 / ℃, etc., and all ranges and subranges between the above values.

[0132] The microcrystalline glass and microcrystalline glass products of this application, due to their superior properties, can be manufactured into glass wafers for use in the semiconductor manufacturing field. The microcrystalline glass, microcrystalline glass products, and glass wafers of this application can be applied in semiconductor manufacturing and other fields.

[0133] Due to the aforementioned superior properties, the microcrystalline glass and microcrystalline glass products of this application can be widely used to manufacture glass covers or glass components. These glass components can include, but are not limited to: optical elements such as lenses, prisms, mirrors, filters, and optical windows; electronic and semiconductor devices such as glass substrates, TGV interlayers, photomask substrates, encapsulation glass, and conductive glass; and special glass products such as fiber optic components, microfluidic chips, and metering gratings. Furthermore, the microcrystalline glass and microcrystalline glass products of this application can be applied to electronic devices or display devices, such as mobile phones, watches, computers, and touch screens. They can be used to manufacture protective glass for mobile phones, smartphones, tablets, laptops, PDAs, televisions, personal computers, MTA machines, or industrial displays; or to manufacture touch screens, protective windows, car windows, train windows, aircraft mechanical windows, and touch screen protective glass; or to manufacture hard drive substrates or solar cell substrates; or to manufacture white goods, such as refrigerator parts or kitchenware.

[0134] Example

[0135] To further clarify and illustrate the technical solution of this application, the following non-limiting embodiments are provided. While the embodiments of this application have made considerable efforts to ensure the accuracy of numerical values ​​(e.g., quantity, temperature, etc.), some errors and deviations must be taken into account. The composition itself is based on oxides and is given in weight % and has been normalized to 100%.

[0136] <Examples of Microcrystalline Glass>

[0137] This embodiment uses the above-described method for manufacturing microcrystalline glass to obtain microcrystalline glass with the compositions shown in Tables 1 to 5. Furthermore, the characteristics of each microcrystalline glass were measured using the testing method described in this application, and the measurement results are shown in Tables 6 to 10. In the following embodiments, the thickness of the test sample for light transmittance at 355 mm was 1.0 mm.

[0138] Table 1.

[0139]

[0140] Table 2.

[0141]

[0142] Table 3.

[0143]

[0144] Table 4.

[0145]

[0146] Table 5.

[0147]

[0148] Table 6.

[0149]

[0150] Table 7.

[0151]

[0152] Table 8.

[0153]

[0154] Table 9.

[0155]

[0156] Table 10.

[0157]

[0158] <Examples of Microcrystalline Glass Products>

[0159] This embodiment uses the above-described manufacturing method for microcrystalline glass products to obtain microcrystalline glass products with the compositions shown in Tables 11 to 15. Furthermore, the characteristics of each microcrystalline glass product were measured using the testing method described in this application, and the measurement results are shown in Tables 16 to 20. In the following embodiments, the thickness of the test sample for light transmittance at 355 mm was 1.0 mm.

[0160] Table 11.

[0161]

[0162] Table 12.

[0163]

[0164] Table 13.

[0165]

[0166] Table 14.

[0167]

[0168] Table 15.

[0169]

[0170] Table 16.

[0171]

[0172] Table 17.

[0173]

[0174] Table 18.

[0175]

[0176] Table 19.

[0177]

[0178] Table 20.

[0179] .

Claims

1. A microcrystalline glass, characterized in that, Its composition, expressed as a weight percentage, contains: SiO2: 46%–60%; Al2O3: 20%–26%; MgO: 6.5%–14%; ZnO: 0.1%–8%; Li2O: greater than or equal to 0.1% but less than 5%; TiO2: greater than 0% but less than 5%; CaO: 0–4.5%, of which (SiO2+Al2O3) / (MgO+ZnO+CaO) is 4.0–8.0, and Li2O / TiO2 is 0.3–2.

5.

2. The microcrystalline glass according to claim 1, characterized in that, Its components, expressed as a percentage by weight, also include: Na2O: less than 4%; and / or K2O: less than 5%; and / or ZrO2: less than 5%; and / or Sb2O3: 0–3%.

3. The microcrystalline glass according to claim 1 or 2, characterized in that, Its components, expressed as a weight percentage, satisfy one or more of the following conditions: 1) The content of Al2O3+ZnO+Na2O is 20.5%~32%, preferably 23%~31%, more preferably 24%~29.5%, and even more preferably 25.5%~28.5%; 2) The ratio of (SiO2+Al2O3) / (MgO+ZnO+CaO) is 4.5 to 7.5, preferably 5.0 to 6.5; 3) The Li2O / TiO2 ratio is 0.6–2.0, preferably 0.8–1.5; 4) The ratio of (MgO+ZnO+Al2O3) / ZnO is 5.0 to 50.0, preferably 6.0 to 20.0, and more preferably 7.0 to 10.0; 5) The ratio of (MgO+ZnO+Li2O) / Al2O3 is 0.3 to 1.0, preferably 0.4 to 0.8, and more preferably 0.5 to 0.7; 6) The ratio of (MgO+ZnO) / Li2O is 4.0 to 13.0, preferably 4.5 to 11.5, and more preferably 5.0 to 9.5; 7) The Al2O3 / (Na2O+K2O) ratio is 9.0 to 82.0, preferably 10.0 to 50.0, more preferably 15.0 to 30.0, and even more preferably 20.0 to 25.0; 8) The ratio of (K2O+CaO) / TiO2 is 0.1 to 3.5, preferably 0.5 to 2.0, and more preferably 0.8 to 1.2; 9) The ratio of (MgO+Al2O3+SiO2) / (TiO2+ZrO2) is 15.0 to 28.0, preferably 17.0 to 26.0, and more preferably 19.0 to 24.

0.

4. The microcrystalline glass according to claim 1 or 2, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 49%–58%, preferably SiO2: 51%–55%; and / or Al2O3: 21%–25%, preferably Al2O3: 21.5%–24.5%; and / or MgO: 7%–12%, preferably MgO: 8%–11%; and / or ZnO: 1%–6%, preferably ZnO: 2%–5%; and / or Li2O: 0.5%–4.5%, preferably Li2O: 1%–3%; and / or TiO2:

0. 5%–4.5%, preferably TiO2: 1%–3%; and / or Na2O: 0.1%–3%, preferably Na2O: 0.5%–2%; and / or K2O: 0.1%–4%, preferably K2O: 0.5%–2%; and / or ZrO2: 0.1%–4.5%, preferably ZrO2: 1%–3%; and / or CaO: 0.1%–4%, preferably CaO: 0.5%–2%; and / or Sb2O3: 0.1%–2%, preferably Sb2O3: 0.2%–1%.

5. The microcrystalline glass according to claim 1 or 2, characterized in that, The microcrystalline glass composition does not contain P2O5; and / or B2O3; and / or La2O3; and / or Gd2O3; and / or Y2O3; and / or Yb2O3; and / or Fe2O3; and / or Eu2O3.

6. The microcrystalline glass according to claim 1 or 2, characterized in that, The crystalline phase in the microcrystalline glass contains MgAl2Si3O 10 Crystal phase, MgAl2Si4O 12 Crystal phase, Mg2Al4Si5O 18 One or more of the crystalline phases.

7. The microcrystalline glass according to claim 1 or 2, characterized in that, The microcrystalline glass contains MgAl2Si3O 10 Crystal phase, and MgAl2Si3O 10 The crystalline phase has a higher weight percentage than other crystalline phases, and preferably the microcrystalline glass contains only MgAl2Si3O. 10 Crystal phase.

8. The microcrystalline glass according to claim 1 or 2, characterized in that, The crystalline phase content in the microcrystalline glass is 20% to 60%, preferably 30% to 60%, and more preferably 40% to 60%.

9. The microcrystalline glass according to claim 1 or 2, characterized in that, The drop ball test height of the microcrystalline glass is 400mm to 1200mm, the sample size for the drop ball test is 50mm × 50mm × 1mm, and a 132g steel ball is used. Preferably, the drop ball height is 500mm to 1200mm, more preferably 600mm to 1200mm; and / or the Vickers hardness is 600kgf / mm². 2 ~800kgf / mm 2 The preferred value is 650 kgf / mm 2 ~800kgf / mm 2 More preferably 700 kgf / mm 2 ~800kgf / mm 2 ; and / or a Young's modulus of 90 GPa to 120 GPa, preferably 95 GPa to 120 GPa, more preferably 100 GPa to 120 GPa; and / or a coefficient of thermal expansion of 20 to 300 °C of 20 × 10⁻⁶. -7 / ℃~50×10 -7 / ℃, preferably 30×10 -7 / ℃~47×10 -7 / ℃, more preferably 35×10 -7 / ℃~44×10 -7 / ℃; and / or microcrystalline glass with a thickness of less than 2.0 mm, having a light transmittance of 40% or more at 355 nm, preferably 50% or more, and more preferably 70% or more.

10. The microcrystalline glass according to claim 9, characterized in that, The thickness of the microcrystalline glass is 0.2mm to 2.0mm, preferably 0.3mm to 1.5mm, more preferably 0.5mm to 1.0mm, and even more preferably 0.5mm, 0.8mm, or 1.0mm.

11. A microcrystalline glass product, characterized in that, It is made of the microcrystalline glass described in any one of claims 1 to 10.

12. A microcrystalline glass product, characterized in that, Its composition, expressed as a weight percentage, contains: SiO2: 46%–60%; Al2O3: 20%–26%; MgO: 6.5%–14%; ZnO: 0.1%–8%; Li2O: greater than or equal to 0.1% but less than 5%; TiO2: greater than 0% but less than 5%; CaO: 0–4.5%, of which (SiO2+Al2O3) / (MgO+ZnO+CaO) is 4.0–8.0, and Li2O / TiO2 is 0.3–2.

5.

13. The microcrystalline glass article according to claim 12, characterized in that, Its components, expressed as a percentage by weight, also include: Na2O: less than 4%; and / or K2O: less than 5%; and / or ZrO2: less than 5%; and / or Sb2O3: 0–3%.

14. The microcrystalline glass article according to claim 12 or 13, characterized in that, Its components, expressed as a weight percentage, satisfy one or more of the following conditions: 1) The content of Al2O3+ZnO+Na2O is 20.5%~32%, preferably 23%~31%, more preferably 24%~29.5%, and even more preferably 25.5%~28.5%; 2) The ratio of (SiO2+Al2O3) / (MgO+ZnO+CaO) is 4.5 to 7.5, preferably 5.0 to 6.5; 3) The Li2O / TiO2 ratio is 0.6–2.0, preferably 0.8–1.5; 4) The ratio of (MgO+ZnO+Al2O3) / ZnO is 5.0 to 50.0, preferably 6.0 to 20.0, and more preferably 7.0 to 10.0; 5) The ratio of (MgO+ZnO+Li2O) / Al2O3 is 0.3 to 1.0, preferably 0.4 to 0.8, and more preferably 0.5 to 0.7; 6) The ratio of (MgO+ZnO) / Li2O is 4.0 to 13.0, preferably 4.5 to 11.5, and more preferably 5.0 to 9.5; 7) The Al2O3 / (Na2O+K2O) ratio is 9.0 to 82.0, preferably 10.0 to 50.0, more preferably 15.0 to 30.0, and even more preferably 20.0 to 25.0; 8) The ratio of (K2O+CaO) / TiO2 is 0.1 to 3.5, preferably 0.5 to 2.0, and more preferably 0.8 to 1.2; 9) The ratio of (MgO+Al2O3+SiO2) / (TiO2+ZrO2) is 15.0 to 28.0, preferably 17.0 to 26.0, and more preferably 19.0 to 24.

0.

15. The microcrystalline glass article according to claim 12 or 13, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 49%–58%, preferably SiO2: 51%–55%; and / or Al2O3: 21%–25%, preferably Al2O3: 21.5%–24.5%; and / or MgO: 7%–12%, preferably MgO: 8%–11%; and / or ZnO: 1%–6%, preferably ZnO: 2%–5%; and / or Li2O: 0.5%–4.5%, preferably Li2O: 1%–3%; and / or TiO2:

0. 5%–4.5%, preferably TiO2: 1%–3%; and / or Na2O: 0.1%–3%, preferably Na2O: 0.5%–2%; and / or K2O: 0.1%–4%, preferably K2O: 0.5%–2%; and / or ZrO2: 0.1%–4.5%, preferably ZrO2: 1%–3%; and / or CaO: 0.1%–4%, preferably CaO: 0.5%–2%; and / or Sb2O3: 0.1%–2%, preferably Sb2O3: 0.2%–1%.

16. The microcrystalline glass article according to claim 12 or 13, characterized in that, The microcrystalline glass product does not contain P2O5; and / or B2O3; and / or La2O3; and / or Gd2O3; and / or Y2O3; and / or Yb2O3; and / or Fe2O3; and / or Eu2O3.

17. The microcrystalline glass article according to claim 12 or 13, characterized in that, The crystalline phase in the microcrystalline glass product contains MgAl2Si3O 10 Crystal phase, MgAl2Si4O 12 Crystal phase, Mg2Al4Si5O 18 One or more of the crystalline phases.

18. The microcrystalline glass article according to claim 12 or 13, characterized in that, The microcrystalline glass product contains MgAl2Si3O 10 Crystal phase, and MgAl2Si3O 10 The crystalline phase has a higher weight percentage than other crystalline phases, and preferably the microcrystalline glass product contains only MgAl2Si3O. 10 Crystal phase.

19. The microcrystalline glass article according to claim 12 or 13, characterized in that, The crystalline phase content in the microcrystalline glass product is 20% to 60%, preferably 30% to 60%, and more preferably 40% to 60%.

20. The microcrystalline glass article according to any one of claims 11 to 13, characterized in that, The drop ball test height of the microcrystalline glass product is 600mm to 1700mm, the sample size for the drop ball test is 50mm × 50mm × 1mm, and a 132g steel ball is used, preferably 900mm to 1700mm, more preferably 1100mm to 1700mm; and / or the Vickers hardness is 700kgf / mm². 2 ~900kgf / mm 2 The preferred value is 750 kgf / mm 2 ~900kgf / mm 2 More preferably 800 kgf / mm 2 ~900kgf / mm 2 ; and / or a Young's modulus of 90 GPa to 120 GPa, preferably 95 GPa to 120 GPa, more preferably 100 GPa to 120 GPa; and / or a coefficient of thermal expansion of 20 to 300 °C of 20 × 10⁻⁶. -7 / ℃~50×10 -7 / ℃, preferably 30×10 -7 / ℃~47×10 -7 / ℃, more preferably 35×10 -7 / ℃~44×10 -7 / ℃; and / or microcrystalline glass articles with a thickness of less than 2.0 mm, wherein the light transmittance at 355 nm is 40% or more, preferably 50% or more, and more preferably 70% or more.

21. The microcrystalline glass article according to claim 20, characterized in that, The thickness of the microcrystalline glass product is 0.2mm to 2.0mm, preferably 0.3mm to 1.5mm, more preferably 0.5mm to 1.0mm, and even more preferably 0.5mm, 0.8mm, or 1.0mm.

22. A glass wafer, characterized in that, Made of the microcrystalline glass according to any one of claims 1 to 10, or made of the microcrystalline glass article according to any one of claims 11 to 21.

23. A glass cover plate, characterized in that, The product contains the microcrystalline glass according to any one of claims 1 to 10, and / or contains the microcrystalline glass article according to any one of claims 11 to 21.

24. A glass component, characterized in that, The product contains the microcrystalline glass according to any one of claims 1 to 10, and / or contains the microcrystalline glass article according to any one of claims 11 to 21.

25. An electronic device, characterized in that, The product contains the microcrystalline glass according to any one of claims 1 to 10, and / or contains the microcrystalline glass article according to any one of claims 11 to 21, and / or contains the glass cover plate according to claim 23, and / or contains the glass component according to claim 24.

26. A display device, characterized in that, The product contains the microcrystalline glass according to any one of claims 1 to 10, and / or contains the microcrystalline glass article according to any one of claims 11 to 21, and / or contains the glass cover plate according to claim 23, and / or contains the glass component according to claim 24.

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