WO2024088033A1 - Vitrocéramique, produit en vitrocéramique et leur procédé de fabrication - Google Patents

Vitrocéramique, produit en vitrocéramique et leur procédé de fabrication Download PDF

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Publication number
WO2024088033A1
WO2024088033A1 PCT/CN2023/123354 CN2023123354W WO2024088033A1 WO 2024088033 A1 WO2024088033 A1 WO 2024088033A1 CN 2023123354 W CN2023123354 W CN 2023123354W WO 2024088033 A1 WO2024088033 A1 WO 2024088033A1
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Prior art keywords
glass
microcrystalline glass
less
weight percentage
microcrystalline
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PCT/CN2023/123354
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English (en)
Chinese (zh)
Inventor
王静
李玫
韩建军
蒋焘
陈雪梅
李继忠
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成都光明光电股份有限公司
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Publication of WO2024088033A1 publication Critical patent/WO2024088033A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition

Definitions

  • the present invention relates to a glass-ceramic, and in particular to a glass-ceramic with excellent mechanical properties, a glass-ceramic product and a manufacturing method thereof.
  • Glass-ceramics is a material that is formed by heat-treating the glass to precipitate crystals inside the glass. It has better mechanical properties than conventional glass.
  • the microcrystals formed in the glass have obvious advantages over conventional glass in terms of bending resistance, wear resistance, and drop resistance.
  • the mechanical properties of glass-ceramics can be further improved through chemical strengthening. Based on the above advantages, glass-ceramics or glass-ceramics products obtained after treatment are currently used in display devices or electronic devices with high requirements for drop resistance, pressure resistance, and scratch resistance, especially in the front and back covers of portable electronic devices (such as mobile phones, watches, PADs, etc.).
  • the technical problem to be solved by the present invention is to provide a microcrystalline glass and microcrystalline glass products with excellent mechanical properties.
  • a microcrystalline glass product wherein the components are expressed in weight percentage as follows: SiO 2 : 40-60%; Al 2 O 3 : 20-40%; Li 2 O: 2-15%; Na 2 O: 3-20%; P 2 O 5 +ZrO 2 : 1-15%.
  • Microcrystalline glass products whose components, expressed in weight percentage, are composed of SiO2 : 40-60%; Al2O3 : 20-40% ; Li2O : 2-15%; Na2O: 3-20%; P2O5 + ZrO2 : 1-15%; K2O : 0-8%; ZnO: 0-6%; B2O3 : 0-6%; RO: 0-8%; TiO2 : 0-5%; Ln2O3 : 0-5%; and clarifier: 0-2 %, wherein RO is one or more of MgO, CaO, SrO, and BaO, and Ln2O3 is one or more of La2O3 , Gd2O3 , and Y2O3 .
  • RO is one or more of MgO, CaO, SrO, and BaO
  • Ln2O3 is one or more of La2O3 , Gd2O3 , and Y2O3 .
  • a glass-ceramic product wherein the components thereof include SiO 2 , Al 2 O 3 , Li 2 O and Na 2 O, the glass-ceramic product contains a nepheline crystal phase, and the surface stress of the glass-ceramic product is greater than 150 MPa.
  • a microcrystalline glass product wherein the main crystal phase contains a nepheline crystal phase, and the Vickers hardness of the microcrystalline glass product is 750 kgf/ mm2 or more.
  • a microcrystalline glass product wherein the components thereof, expressed in weight percentage, include SiO 2 : 40-60%; Al 2 O 3 : 20-40%; Li 2 O: 2-15%; and Na 2 O: 3-20%, and the microcrystalline glass product contains a nepheline crystal phase.
  • a glass-ceramic product wherein the components thereof include SiO 2 , Al 2 O 3 , Li 2 O and Na 2 O, wherein the glass-ceramic product has a four-point bending strength of 700 MPa or more with a thickness of less than 1 mm.
  • a glass-ceramic product wherein the components thereof include SiO 2 , Al 2 O 3 , Li 2 O and Na 2 O, wherein the haze of the glass-ceramic product having a thickness of 1 mm or less is 0.15% or less.
  • Microcrystalline glass products containing nepheline crystal phase wherein the microcrystalline glass products having a thickness of less than 1 mm have a light transmittance of more than 88% at a wavelength of 550 nm.
  • a microcrystalline glass product comprising a nepheline crystal phase, wherein the depth of the ion exchange layer of the microcrystalline glass product is greater than 50 ⁇ m.
  • the microcrystalline glass product contains a nepheline crystal phase; and/or a lithium silicate crystal phase; and/or a lithium phosphate crystal phase; and/or a petalite crystal phase; and/or a quartz crystal phase.
  • the main crystal phase of the microcrystalline glass product is the nepheline crystal phase, or the microcrystalline glass product only contains the nepheline crystal phase.
  • the weight percentage of the nepheline crystal phase in the microcrystalline glass product is 10 to 80%, preferably the weight percentage of the nepheline crystal phase in the microcrystalline glass product is 20 to 70%, and more preferably the weight percentage of the nepheline crystal phase in the microcrystalline glass product is 30 to 60%.
  • the ion exchange layer depth of the microcrystalline glass product is greater than 50 ⁇ m, preferably greater than 60 ⁇ m, more preferably greater than 80 ⁇ m, and further preferably greater than 100 ⁇ m; and/or the Vickers hardness is greater than 750 kgf/ mm2 , preferably greater than 780 kgf/ mm2 , more preferably greater than 800 kgf/ mm2 , and further preferably greater than 810 kgf/ mm2 ; and/or the grain size is less than 80 nm, preferably less than 60 nm, more preferably less than 50 nm, and further preferably less than 40 nm; and/or the surface stress is greater than 150 MPa, preferably greater than 170 MPa, and more preferably greater than 190 MPa.
  • the microcrystalline glass product according to any one of (1) to (28), for a microcrystalline glass product with a thickness of less than 1 mm, has a four-point bending strength of 700 MPa or more, preferably 750 MPa or more, and more preferably 800 MPa or more; and/or a drop ball test height of 1100 mm or more, preferably 1300 mm or more, and more preferably 1500 mm or more; and/or a haze of 0.15% or less, preferably 0.12% or less, and more preferably 0.10% or less; and/or a light transmittance of 550 nm wavelength of 88% or more, preferably 89% or more, more preferably 90% or more, and further preferably 91% or more; and/or an average optical
  • the thickness of the microcrystalline glass product is 0.2 to 1 mm, preferably 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm or 0.75 mm.
  • Glass-ceramics whose components, expressed in percentage by weight, contain: SiO 2 : 40-60%; Al 2 O 3 : 20-40%; Li 2 O: 2-15%; Na 2 O: 3-20%; P 2 O 5 +ZrO 2 : 1-15%.
  • the glass-ceramics according to (32), further comprises, expressed in weight percentage, the following: K2O : 0-8%; and/or ZnO: 0-6%; and/or B2O3 : 0-6%; and/or RO : 0-8%; and/or TiO2 : 0-5%; and/or Ln2O3 : 0-5%; and/or a clarifier : 0-2 % , wherein RO is one or more of MgO, CaO, SrO, and BaO, and Ln2O3 is one or more of La2O3 , Gd2O3 , and Y2O3 .
  • Glass-ceramics whose components, expressed in weight percentage, are composed of SiO2 : 40-60% ; Al2O3 : 20-40 % ; Li2O : 2-15%; Na2O: 3-20%; P2O5 +ZrO2: 1-15%; K2O : 0-8%; ZnO: 0-6%; B2O3 : 0-6% ; RO: 0-8%; TiO2: 0-5%; Ln2O3 : 0-5%; and a clarifier: 0-2 %, wherein RO is one or more of MgO, CaO, SrO, and BaO, and Ln2O3 is one or more of La2O3 , Gd2O3 , and Y2O3 .
  • RO is one or more of MgO, CaO, SrO, and BaO
  • Ln2O3 is one or more of La2O3 , Gd2O3 , and Y2O3 .
  • Glass-ceramics comprising SiO 2 , Al 2 O 3 , Li 2 O and Na 2 O, the glass-ceramics containing a nepheline crystal phase, and having a Vickers hardness of 650 kgf/mm 2 or more.
  • Glass-ceramics whose components, expressed in weight percentage, contain SiO 2 : 40-60%; Al 2 O 3 : 20-40%; Li 2 O: 2-15%; Na 2 O: 3-20%, and the glass-ceramics contains a nepheline crystal phase.
  • Glass-ceramics comprising SiO 2 , Al 2 O 3 , Li 2 O and Na 2 O, wherein the haze of the glass-ceramics having a thickness of 1 mm or less is 0.15% or less.
  • Glass-ceramics comprising SiO 2 , Al 2 O 3 , Li 2 O and Na 2 O, wherein the weight percentage of the nepheline crystal phase in the glass-ceramics is 10 to 80%.
  • the ratio is represented by (Na 2 O + Li 2 O) / SiO 2 , wherein: (Na 2 O + Li 2 O) / SiO 2 is 0.1 to 0.8, preferably (Na 2 O + Li 2 O) / SiO 2 is 0.15 to 0.7, more preferably (Na 2 O + Li 2 O) / SiO 2 is 0.2 to 0.6, and further preferably (Na 2 O + Li 2 O) / SiO 2 is 0.25 to 0.5.
  • (48) The glass-ceramics according to any one of (32) to (47), wherein the components are expressed in weight percentage, wherein: (ZrO 2 +ZnO)/Na 2 O is less than 2.0, preferably (ZrO 2 +ZnO)/Na 2 O is less than 1.5, more preferably (ZrO 2 +ZnO)/Na 2 O is 0.01 to 1.0, and further preferably (ZrO 2 +ZnO)/Na 2 O is 0.1 to 0.5.
  • the glass-ceramics according to any one of (32), ( 33 ), (35) to ( 43 ), further comprises, expressed in weight percentage, the following : Yb2O3 + Nb2O5 + WO3 + Bi2O3 + Ta2O5 +TeO2+ GeO2 : 0 to 5%, preferably Yb2O3 + Nb2O5 + WO3 +Bi2O3+ Ta2O5 + TeO2 + GeO2 : 0 to 2 %, more preferably Yb2O3 + Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2 + GeO2 : 0 to 1% .
  • the microcrystalline glass contains a nepheline crystal phase; and/or a lithium silicate crystal phase; and/or a lithium phosphate crystal phase; and/or a petalite crystal phase; and/or a quartz crystal phase.
  • the main crystal phase of the microcrystalline glass is the nepheline crystal phase, or the microcrystalline glass only contains the nepheline crystal phase.
  • the weight percentage of the nepheline crystal phase in the microcrystalline glass is 10 to 80%, preferably the weight percentage of the nepheline crystal phase in the microcrystalline glass is 20 to 70%, and more preferably the weight percentage of the nepheline crystal phase in the microcrystalline glass is 30 to 60%.
  • microcrystalline glass according to any one of (32) to (58), wherein the grain size of the microcrystalline glass is less than 80 nm, preferably less than 60 nm, more preferably less than 50 nm, and further preferably less than 40 nm; and/or the Vickers hardness is greater than 650 kgf/ mm2 , preferably greater than 680 kgf/ mm2 , and more preferably greater than 700 kgf/ mm2 .
  • Crystal glass whose main body ball drop height is more than 1000mm, preferably more than 1200mm, more preferably more than 1400mm; and/or the haze is less than 0.15%, preferably less than 0.12%, more preferably less than 0.10%; and/or the light transmittance at a wavelength of 550nm is more than 88%, preferably more than 89%, more preferably more than 90%, further preferably more than 91%; and/or the average light
  • the thickness of the microcrystalline glass is 0.2 to 1 mm, preferably 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, and further preferably 0.55 mm or 0.6 mm or 0.68 mm or 0.7 mm or 0.75 mm.
  • Matrix glass whose components, expressed in weight percentage, contain: SiO2 : 40-60%; Al2O3 : 20-40% ; Li2O : 2-15%; Na2O: 3-20 %; P2O5 + ZrO2 : 1-15%.
  • Matrix glass whose components, expressed in weight percentage, are composed of SiO2 : 40-60% ; Al2O3 : 20-40% ; Li2O : 2-15%; Na2O : 3-20%; P2O5 +ZrO2: 1-15%; K2O : 0-8%; ZnO: 0-6%; B2O3 : 0-6% ; RO: 0-8%; TiO2 : 0-5%; Ln2O3 : 0-5%; and clarifier: 0-2 %, wherein RO is one or more of MgO, CaO, SrO, and BaO, and Ln2O3 is one or more of La2O3 , Gd2O3 , and Y2O3 .
  • RO is one or more of MgO, CaO, SrO, and BaO
  • Ln2O3 is one or more of La2O3 , Gd2O3 , and Y2O3 .
  • (66) The matrix glass according to any one of ( 63 ) to (65), wherein the composition is expressed in weight percentage , wherein: ( Al2O3 + Na2O )/ P2O5 is 3.0 to 30.0, preferably ( Al2O3 + Na2O )/ P2O5
  • the (Al 2 O 3 + Na 2 O)/P 2 O 5 is preferably 4.0 to 20.0, more preferably 5.0 to 15.0 , and still more preferably 6.0 to 10.0.
  • (69) The matrix glass according to any one of (63) to (68), wherein the components are expressed in weight percentage, wherein: (Na 2 O + Li 2 O) / SiO 2 is 0.1 to 0.8, preferably (Na 2 O + Li 2 O) / SiO 2 is 0.15 to 0.7, more preferably (Na 2 O + Li 2 O) / SiO 2 is 0.2 to 0.6, and further preferably (Na 2 O + Li 2 O) / SiO 2 is 0.25 to 0.5.
  • (70) The matrix glass according to any one of (63) to (69), wherein the components are expressed in weight percentage, wherein: (ZrO 2 + ZnO)/Na 2 O is less than 2.0, preferably (ZrO 2 + ZnO)/Na 2 O is less than 1.5, more preferably (ZrO 2 + ZnO)/Na 2 O is 0.01 to 1.0, and further preferably (ZrO 2 + ZnO)/Na 2 O is 0.1 to 0.5.
  • (77) The matrix glass according to any one of (63) to (65), wherein its components do not contain SrO; and/or do not contain BaO; and/or do not contain MgO; and/or do not contain CaO; and/or do not contain ZnO; and/or do not contain PbO; and/or do not contain As 2 O 3 ; and/or do not contain TiO 2 ; and/or do not contain B 2 O 3 ; and/or do not contain Y 2 O 3 ; and/or do not contain La 2 O 3 ; and/or do not contain Gd 2 O 3 .
  • a microcrystalline glass molded body comprising the microcrystalline glass described in any one of (32) to (62).
  • a glass cover plate comprising the microcrystalline glass product described in any one of (1) to (31), and/or the microcrystalline glass described in any one of (32) to (62), and/or the matrix glass described in any one of (63) to (78), and/or the microcrystalline glass formed body described in (79).
  • a glass component comprising a microcrystalline glass product as described in any one of (1) to (31), and/or a microcrystalline glass as described in any one of (32) to (62), and/or a matrix glass as described in any one of (63) to (78), and/or a microcrystalline glass formed body as described in (79).
  • a display device comprising a microcrystalline glass product as described in any one of (1) to (31), and/or a microcrystalline glass as described in any one of (32) to (62), and/or a matrix glass as described in any one of (63) to (78), and/or a microcrystalline glass formed body as described in (79), and/or a glass cover as described in (80), and/or a glass component as described in (81).
  • An electronic device comprising a glass-ceramic product as described in any one of (1) to (31), and/or a glass-ceramic product as described in any one of (32) to (62), and/or a matrix glass as described in any one of (63) to (78), and/or a glass-ceramic formed body as described in (79), and/or a glass cover as described in (80), and/or a glass component as described in (81).
  • the method comprises the following steps: forming a matrix glass, subjecting the matrix glass to a crystallization process to form a microcrystalline glass, and then subjecting the microcrystalline glass to a chemical strengthening process to form a microcrystalline glass product.
  • the crystallization process includes the following steps: heating to a specified crystallization treatment temperature, maintaining the temperature for a certain period of time after reaching the crystallization treatment temperature, and then cooling down, the crystallization treatment temperature is 580-750°C, preferably 600-700°C, and the holding time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.
  • the crystallization process includes the following steps: performing a nucleation process at a first temperature, and then performing a crystal growth process at a second temperature higher than the nucleation process temperature.
  • the crystallization process includes the following steps: the first temperature is 500-620°C, and the second temperature is 620-750°C; the holding time at the first temperature is 0-24 hours, preferably 2-15 hours; the holding time at the second temperature is 0-10 hours, preferably 0.5-6 hours.
  • the chemical strengthening process includes: the microcrystalline glass is immersed in a salt bath of molten Na salt at a temperature of 350 to 470°C for 1 to 36 hours, preferably in the temperature range of 380 to 460°C, and the preferred time range is 2 to 10 hours; and/or the microcrystalline glass is immersed in a salt bath of molten K salt at a temperature of 360 to 450°C for 1 to 36 hours, preferably in the time range of 1 to 10 hours; and/or the microcrystalline glass is immersed in a mixed salt bath of molten K salt and Na salt at a temperature of 360 to 450°C for 1 to 36 hours, preferably in the time range of 2 to 24 hours.
  • the crystallization process includes the following steps: heating to a specified crystallization treatment temperature, maintaining the temperature for a certain period of time after reaching the crystallization treatment temperature, and then cooling down, the crystallization treatment temperature is 580 to 750°C, preferably 600 to 700°C, and the holding time at the crystallization treatment temperature is 0 to 8 hours, preferably 1 to 6 hours.
  • the crystallization process includes the following steps: performing a nucleation process at a first temperature, and then performing a crystal growth process at a second temperature higher than the nucleation process temperature.
  • the crystallization process includes the following steps: the first temperature is 500-620°C, and the second temperature is 620-750°C; the holding time at the first temperature is 0-24 hours, preferably 2-15 hours; the holding time at the second temperature is 0-10 hours, preferably 0.5-6 hours.
  • the method includes the following steps: subjecting the matrix glass to a crystallization heat treatment process, including heating, heat preservation and nucleation, heating, heat preservation and crystallization, and cooling to room temperature to form a pre-crystallized glass; and heat-processing the pre-crystallized glass to obtain a microcrystalline glass molded body.
  • Heating and preheating Place the matrix glass or pre-crystallized glass or microcrystalline glass in the mold.
  • the mold passes through each heating station in the hot bending machine in turn and stays at each station for a certain period of time to keep warm.
  • the temperature in the preheating zone is 400-800°C, the pressure is 0.01-0.05MPa, and the time is 40-200s;
  • the mold is transferred to the cooling station for cooling step by step.
  • the cooling temperature range is 750-500°C
  • the pressure is 0.01-0.05Mpa
  • the time is 40-200s.
  • the beneficial effect of the present invention is that through reasonable component design, the microcrystalline glass or microcrystalline glass products obtained by the present invention have excellent mechanical properties and meet the application requirements in the fields of display devices or electronic devices.
  • the glass-ceramics and glass-ceramics products of the present invention are materials having a crystalline phase (sometimes also referred to as crystal) and a glass phase, which are different from amorphous solids.
  • the crystalline phase of the glass-ceramics and glass-ceramics products can be identified by the peak angles appearing in the X-ray diffraction pattern of X-ray diffraction analysis and/or measured by TEMEDX.
  • the inventors of the present invention obtained the microcrystalline glass or microcrystalline glass products of the present invention by regulating the content and content ratio of specific components constituting microcrystalline glass and microcrystalline glass products to specific values and precipitating specific crystalline phases.
  • each component (ingredient) of the matrix glass, microcrystalline glass and microcrystalline glass products of the present invention is described.
  • the content of each component is expressed as a weight percentage (wt%) relative to the total amount of matrix glass, microcrystalline glass or microcrystalline glass product material converted into an oxide composition.
  • the "composition converted into oxides” means that when oxides, composite salts and hydroxides used as raw materials for the matrix glass, microcrystalline glass or microcrystalline glass product components of the present invention decompose and transform into oxides when melted, the total weight of the oxide material is taken as 100%.
  • the matrix glass before crystallization i.e., crystallization process treatment
  • the matrix glass after crystallization i.e., crystallization process treatment
  • microcrystalline glass products refer to products obtained after chemical strengthening of microcrystalline glass.
  • the crystal phase of the glass-ceramic or glass-ceramic product of the present invention contains a nepheline crystal phase (including eucryptite and/or sodium nepheline), specifically, contains eucryptite, or contains sodium nepheline, or contains both eucryptite and sodium nepheline.
  • the glass-ceramic of the present invention may also contain other crystal phases besides the nepheline crystal phase, such as a lithium silicate crystal phase (one or both of lithium monosilicate and lithium disilicate); and/or a lithium phosphate crystal phase; and/or a petalite crystal phase; and/or a quartz crystal phase.
  • the crystal phase in the glass-ceramic or glass-ceramic products contains only nepheline crystal phase (one or both of eucryptite and sodium nepheline).
  • the main crystal phase of the microcrystalline glass or microcrystalline glass products is the nepheline crystal phase, that is, the nepheline crystal phase has a higher weight percentage than other crystal phases.
  • the weight percentage of the nepheline crystal phase in the glass-ceramic or glass-ceramic product is 10-80%, preferably the weight percentage of the nepheline crystal phase in the glass-ceramic or glass-ceramic product is 20-70%, and more preferably the weight percentage of the nepheline crystal phase in the glass-ceramic or glass-ceramic product is 30-60%.
  • the weight percentage of the nepheline crystal phase in the glass-ceramic or glass-ceramic product is about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%
  • SiO2 is the basic component of the matrix glass, glass-ceramics and glass-ceramics products of the present invention, which can be used to stabilize the network structure of glass and glass-ceramics. It is one of the components that form the nepheline crystal phase after crystallization. If the content of SiO2 is below 40%, the crystals formed in the glass-ceramics will become less and the crystals are easy to become coarse, affecting the haze of the glass-ceramics and glass-ceramics products, as well as the performance of the drop ball test height of the glass-ceramics products. Therefore, the lower limit of the SiO2 content is 40%, preferably 43%, and more preferably 46%.
  • the upper limit of the SiO2 content is 60%, preferably 55%, and more preferably 53%.
  • the SiO2 may comprise about 40%, 40.5%, 41%, 41.5%, 42%, 42.5%, 43%, 43.5%, 44%, 44.5%, 45%, 45.5%, 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%.
  • Al2O3 is a component that forms the glass network structure . It is an important component that helps stabilize glass molding and improve chemical stability. It can also improve the mechanical properties of glass and increase the depth of the ion exchange layer and surface stress of microcrystalline glass products. However, if the Al2O3 content is too high, the glass's melting and devitrification resistance will decrease, and the crystals will easily increase during crystallization, reducing the strength of microcrystalline glass and microcrystalline glass products. Therefore, In the present invention, the content of Al 2 O 3 is 20 to 40%, preferably 23 to 36%, and more preferably 25.5 to 32%.
  • the ratio of SiO 2 to Al 2 O 3 , SiO 2 /Al 2 O 3, is controlled within the range of 1.2 to 2.8, which can improve the four-point bending strength of glass-ceramics and glass-ceramics products, and improve the light transmittance of glass-ceramics and glass-ceramics products. Therefore, SiO 2 /Al 2 O 3 is preferably 1.2 to 2.8, and SiO 2 /Al 2 O 3 is more preferably 1.3 to 2.5.
  • SiO 2 /Al 2 O 3 is further preferably 1.5 to 2.2, and SiO 2 /Al 2 O 3 is further preferably 1.6 to 2.0.
  • the value of SiO2 / Al2O3 may be 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, 2.55, 2.6, 2.65, 2.7, 2.75 , 2.8.
  • Li2O can promote the melting of glass, reduce the melting temperature of glass, form eucryptite crystal phase after crystallization, and is also the main component replaced with sodium and potassium ions in the chemical strengthening process. It can increase the surface stress of microcrystalline glass products, help to improve the drop ball test height of microcrystalline glass products, and increase the dielectric constant of microcrystalline glass and microcrystalline glass products. On the other hand, if too much Li2O is contained, it is easy to reduce the chemical stability of glass, and deteriorate the light transmittance of microcrystalline glass and microcrystalline glass products. Therefore, the content of Li2O in the present invention is 2-15%, preferably 3-13%, and more preferably 5.5-11%.
  • about 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15% Li2O may be included.
  • Na 2 O can participate in crystallization to form sodium nepheline crystal phase after crystallization, and can also participate in chemical strengthening and improve the melting property of glass.
  • the content of Na 2 O is too high, it is easy to cause During the crystallization process, the precipitated grains increase or the type of precipitated crystal phase changes. Therefore, the content of Na2O in the present invention is 3-20%, preferably 5-15%, and more preferably 6.5-12%.
  • about 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20% Na2O may be included.
  • the ratio of the total content of Na 2 O and Li 2 O (Na 2 O+Li 2 O) to the content of SiO 2 ((Na 2 O+Li 2 O)/SiO 2) ) is controlled within the range of 0.1 to 0.8, which is beneficial for obtaining the desired crystalline content of the glass-ceramics and glass-ceramics products, while refining the grains and improving the hardness of the glass-ceramics and glass-ceramics products. Therefore, preferably (Na 2 O+Li 2 O)/SiO 2 is 0.1 to 0.8, and more preferably (Na 2 O+Li 2 O)/SiO 2 is 0.15 to 0.7.
  • controlling (Na 2 O+Li 2 O)/SiO 2 within the range of 0.2 to 0.6 can further improve the light transmittance of the glass-ceramics and glass-ceramics products, and optimize the haze. Therefore, it is further preferred that (Na 2 O + Li 2 O) / SiO 2 is 0.2 to 0.6, and it is further preferred that (Na 2 O + Li 2 O) / SiO 2 is 0.25 to 0.5. In some embodiments, the value of (Na 2 O + Li 2 O) / SiO 2 may 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.
  • K2O is an optional component that helps improve the low temperature melting property and formability of the glass. However, if K2O is contained in excess, the chemical stability of the glass is easily reduced. Therefore, the content of K2O is 0-8%, preferably 0-5%, and more preferably 0.1-3%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% K2O may be contained.
  • P2O5 can form crystal nuclei in glass, promote uniform crystal growth, and help improve the low-temperature melting property of glass; however , if P2O5 is contained too much, it is easy to reduce the resistance to devitrification and glass phase separation, and the mechanical properties of microcrystalline glass and microcrystalline glass products tend to deteriorate. Therefore, the content of P2O5 in the present invention is 0-10%, preferably 1-8%, and more preferably 2-6%.
  • it may contain about 0 %, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% P 2 O 5 .
  • the ratio of the total content of Al 2 O 3 and Na 2 O (Al 2 O 3 +Na 2 O) to the content of P 2 O 5 (Al 2 O 3 +Na 2 O)/P 2 O 5 ) is controlled within the range of 3.0 to 30.0, which is beneficial for the microcrystalline glass and microcrystalline glass products to obtain the desired crystalline phase content, and to improve the Vickers hardness of the microcrystalline glass and microcrystalline glass products, and to improve the height of the drop ball test. Therefore, it is preferred that (Al 2 O 3 +Na 2 O)/P 2 O 5 is 3.0 to 30.0, and it is more preferred that (Al 2 O 3 +Na 2 O)/P 2 O 5 is 4.0 to 20.0.
  • (Al 2 O 3 +Na 2 O)/P 2 O 5 within the range of 5.0 to 15.0, the four-point bending strength of the microcrystalline glass and the microcrystalline glass products can be further optimized, and the ion exchange layer depth of the microcrystalline glass products can be improved. Therefore, it is further preferred that (Al 2 O 3 +Na 2 O)/P 2 O 5 is 5.0 to 15.0, and it is further preferred that (Al 2 O 3 +Na 2 O)/P 2 O 5 is 6.0 to 10.0.
  • the value of (Al 2 O 3 +Na 2 O)/P 2 O 5 may be 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 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, 24.5, 25.0, 25.5, 26.0, 26.5, 27.0, 27.5, 28.0, 28.5, 29.0, 29.5, 30.0.
  • the ratio of the total content of P2O5 and Na2O (P2O5 + Na2O ) to the content of Li2O (( P2O5 + Na2O )/ Li2O ) is controlled within the range of 0.5 to 8.0, which is beneficial to increasing the drop ball test height of the microcrystalline glass and microcrystalline glass products and increasing the ion exchange layer depth of the microcrystalline glass products. Therefore, preferably ( P2O5 + Na2O )/ Li2O is 0.5 to 8.0, and more preferably ( P2O5 + Na2O )/ Li2O is 0.8 to 5.0.
  • controlling (P2O5 + Na2O)/Li2O within the range of 1.0 to 3.0 can further optimize the hardness and
  • the value of ( P2O5 + Na2O )/ Li2O may be 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, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0.
  • ZrO2 has the function of crystallization and precipitation to form crystal nuclei, and also helps to improve the chemical stability of glass. Studies have shown that ZrO 2 can also significantly reduce the devitrification of glass and lower the liquidus temperature during the melting process to improve the stability of the glass; however, if too much ZrO 2 is contained, the devitrification resistance of the glass is easily reduced, and the difficulty of controlling the glass crystallization process increases. Therefore, the content of ZrO 2 is 0-6%, preferably 0-5%, and more preferably 0.1-3%.
  • 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% ZrO 2 may be included.
  • controlling the ratio of K 2 O content to ZrO 2 content, K 2 O/ZrO 2 , to be above 0.1 is beneficial to grain refinement and reducing the haze and grain size of microcrystalline glass and microcrystalline glass products. Therefore, it is preferred that K 2 O/ZrO 2 is above 0.1, and it is more preferred that K 2 O/ZrO 2 is 0.2 to 10.0. Furthermore, controlling K 2 O/ZrO 2 to be within the range of 0.3 to 5.0 can further optimize the light transmittance of microcrystalline glass and microcrystalline glass products and prevent the depth of the ion exchange layer of microcrystalline glass products from deteriorating.
  • K 2 O/ZrO 2 is 0.3 to 5.0, and it is further preferred that K 2 O/ZrO 2 is 0.4 to 1.5.
  • K 2 O/ZrO The value of 2 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, 1.75, 1.8, 1.85, 1.9, 1.95, 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,
  • the total content of P2O5 and ZrO2 , P2O5 + ZrO2, is controlled within the range of 1 to 15%, which is beneficial to grain refinement, reducing the grain size of microcrystalline glass and microcrystalline glass products, while reducing the
  • P2O5 + ZrO2 may be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7 %, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%.
  • the ZnO can improve the melting performance of glass, improve the chemical stability of glass, refine grains during crystallization, control the upper limit of ZnO content below 6%, and inhibit the reduction of devitrification resistance. Therefore, the ZnO content is 0-6%, preferably 0-3%, and more preferably 0-1%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% ZnO may be included.
  • the ratio of the total content of ZrO2 and ZnO ZrO2 + ZnO to the content of Na2O ( ZrO2 + ZnO) / Na2O is controlled to be below 2.0, which is beneficial to reducing the haze and grain size of the microcrystalline glass and microcrystalline glass products, and increasing the drop ball test height of the microcrystalline glass and microcrystalline glass products.
  • ( ZrO2 + ZnO) / Na2O is 2.0 or less, more preferably ( ZrO2 + ZnO) / Na2O is 1.5 or less, further preferably ( ZrO2 + ZnO) / Na2O is 0.01 to 1.0, and further preferably ( ZrO2 + ZnO) / Na2O is 0.1 to 0.5.
  • the value of ( ZrO2 + ZnO)/ Na2O may be 0, greater than 0, 0.01, 0.05, 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, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0.
  • B2O3 can improve the network structure of glass and adjust the chemical strengthening performance of microcrystalline glass. If its content is too much, it is not conducive to glass molding, and it is easy to crystallize during molding, and the chemical stability is reduced. Therefore, the content of B2O3 is 0-6%, preferably 0-3%, and more preferably 0-1%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% B2O3 can be included .
  • the ratio of SiO 2 to the total content of Na 2 O and B 2 O 3 (Na 2 O+B 2 O 3 ) (SiO 2 /(Na 2 O+B 2 O 3 )) is controlled within the range of 2.0 to 15.0, which is beneficial to increasing the depth of the ion exchange layer of the microcrystalline glass product and improving the four-point bending strength of the microcrystalline glass and the microcrystalline glass product. Therefore, preferably SiO 2 /(Na 2 O+B 2 O 3 ) is 2.0 to 15.0, and more preferably SiO 2 /(Na 2 O+B 2 O 3 ) is 3.0 to 10.0.
  • controlling SiO 2 /(Na 2 O+B 2 O 3 ) within the range of 4.0 to 8.0 can further optimize the surface stress of the microcrystalline glass product and increase the drop ball test height of the microcrystalline glass and the microcrystalline glass product. Therefore, it is more preferred that SiO 2 /(Na 2 O+B 2 O 3 ) is 4.0 to 8.0, and it is still more preferred that SiO 2 /(Na 2 O+B 2 O 3 ) is 4.0 to 8.0.
  • ( Na2O + B2O3 ) is 5.0 to 7.0.
  • the value of SiO2 /( Na2O + B2O3 ) may be 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5 , 15.0 .
  • RO Alkaline earth metal oxides
  • RO Alkaline earth metal oxides
  • the content of RO is 0-8%, preferably 0-5%, and more preferably 0-2%.
  • about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% RO may be included.
  • TiO2 is an optional component that helps to lower the melting temperature of glass and improve chemical stability.
  • the present invention contains less than 5% TiO2 , which can make the crystallization process of glass easy to control.
  • the content of TiO2 is less than 3%, and more preferably less than 1%. In some embodiments, it is further preferred that TiO2 is not contained. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% TiO2 may be contained.
  • the ratio of the total content of ZnO, RO, B2O3 , and TiO2 (ZnO+ RO + B2O3 + TiO2) to the content of P2O5 (ZnO+RO+ B2O3 + TiO2 )/ P2O5 ) is controlled below 1.5 , which is beneficial to reducing the haze of microcrystalline glass and microcrystalline glass products, improving light transmittance, and increasing the surface stress of microcrystalline glass products.
  • (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is preferably 1.5 or less, more preferably (ZnO+RO+ B2O3 + TiO2 ) / P2O5 is 1.0 or less, further preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is 0.5 or less , and further preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is 0.2 or less .
  • the value of (ZnO+RO+ B2O3 + TiO2 )/ P2O5 may be 0, greater than 0, 0.01, 0.05, 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.
  • Ln 2 O 3 (Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , and Y 2 O 3 ) can reduce the difficulty of melting glass. Excessive content will lead to difficulty in forming crystals during glass crystallization. The height of the ball drop test of the product decreases. Therefore, the upper limit of the Ln 2 O 3 content is 5%, preferably 3%, and more preferably 1%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% Ln 2 O 3 may be included.
  • the matrix glass, glass-ceramic or glass-ceramic product may further contain 0-2% of a clarifier to improve the defoaming ability of the matrix glass, glass-ceramic or glass-ceramic product, and the clarifier includes but is not limited to one or more of Sb 2 O 3 , SnO 2 , SnO, F (fluorine), Cl (chlorine) and Br (bromine), preferably Sb 2 O 3 and SnO 2 are used as clarifiers, and more preferably Sb 2 O 3 is used as clarifiers.
  • the upper limit of their content is preferably 1%, and more preferably 0.5%.
  • the amount of one or more of the above clarifiers is 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%, or 2%.
  • glass-ceramics or glass-ceramics products of the present invention may be appropriately contained.
  • other components not mentioned above such as Yb 2 O 3 , Nb 2 O 5 , WO 3 , Bi 2 O 3 , Ta 2 O 5 , TeO 2 , GeO 2 , etc., may be appropriately contained.
  • the individual content or total content of Yb 2 O 3 , Nb 2 O 5 , WO 3 , Bi 2 O 3 , Ta 2 O 5 , TeO 2 , and GeO 2 is preferably less than 5%, more preferably less than 2%, further preferably less than 1%, and further preferably not contained.
  • PbO and As 2 O 3 are toxic substances. Even if they are contained in a small amount, they do not meet the requirements of environmental protection. Therefore, in some embodiments of the present invention, it is preferred that PbO and As 2 O 3 are not contained.
  • the colorant contains: NiO: 0-4%; and/or Ni 2 O 3 : 0-4%; and/or CoO: 0-2%; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0-7%; and/or MnO 2 : 0-4%; and/or Er 2 O 3 : 0-8%; and/or Nd 2 O 3 : 0-8%; and/or Cu 2 O: 0-4%; and/or Pr 2 O 5 : 0-8%; and/or CeO 2 : 0-4%.
  • the weight percentage content of the colorant and its function are described in detail as follows:
  • NiO, Ni 2 O 3 or Pr 2 O 5 are colorants.
  • NiO and Ni 2 O 3 are colorants used to prepare brown or green matrix glass, glass-ceramics or glass-ceramics products.
  • the two components can be used alone or in combination. Their respective contents are generally less than 4%, preferably less than 3%. If the content exceeds 4%, the colorant cannot be well dissolved in the matrix glass, glass-ceramics or glass-ceramics products. The lower limits of their respective contents are above 0.1%. If the content is less than 0.1%, the color of the matrix glass, glass-ceramics or glass-ceramics products is not obvious.
  • the composition may contain about 0.1%, 0.2%, 0.3%, 0.4%, 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%,
  • the total amount of NiO and Ni 2 O 3 is generally less than 4%, and the lower limit of the total amount is more than 0.1%.
  • NiO and Ni2O3 may be included .
  • Pr2O5 is used as a colorant for green matrix glass, microcrystalline glass or microcrystalline glass products. It is used alone, and the content is generally below 8%, preferably below 6%.
  • the blue matrix glass, microcrystalline glass or microcrystalline glass product prepared by the present invention uses CoO or Co2O3 as a colorant.
  • the two colorant components can be used alone or in combination. Their respective contents are generally below 2%, preferably below 1.8%. If the content exceeds 2%, the colorant cannot be well dissolved in the matrix glass, microcrystalline glass or microcrystalline glass product. The lower limit of their respective contents is above 0.05%. If it is lower than 0.05%, the color of the matrix glass, microcrystalline glass or microcrystalline glass product is not obvious.
  • about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 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% of CoO or Co 2 O 3 may be included.
  • the total amount of CoO and Co 2 O 3 does not exceed 2%, and the lower limit of the total amount is above 0.05%.
  • about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 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% CoO and Co2O3 may be included.
  • the yellow matrix glass, glass-ceramics or glass-ceramics products prepared by the present invention use Cu2O or CeO2 as a colorant.
  • the two colorant components are used alone or in combination, and the lower limit of their respective contents is above 0.5%. If it is lower than 0.5%, the color of the matrix glass, glass-ceramics or glass-ceramics products is not obvious.
  • the content of Cu2O used alone is below 4%, preferably below 3%. If the content exceeds 4%, the matrix glass is easily crystallized.
  • about 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% Cu 2 O may be included.
  • the content of CeO 2 used alone is generally below 4%, preferably below 3%. If the content exceeds 4%, the gloss of the matrix glass, microcrystalline glass or microcrystalline glass products is not good.
  • CeO 2 may be included in an amount of about 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 %. If two colorants are mixed, the total amount is generally less than 4%, and the lower limit of the total amount is more than 0.5%.
  • the black or smoke-grey matrix glass, glass-ceramic or glass-ceramic product prepared by the present invention uses Fe 2 O 3 alone as a colorant; or uses a mixture of Fe 2 O 3 and CoO as a colorant; or Or use Fe 2 O 3 and Co 2 O 3 as a colorant; or use Fe 2 O 3 , CoO and NiO as a colorant; or use Fe 2 O 3 , Co 2 O 3 and NiO as a colorant.
  • the colorant used to prepare black and smoke gray matrix glass, microcrystalline glass or microcrystalline glass products mainly uses Fe 2 O 3 for coloring, and the content is less than 7%, preferably less than 5%, and the lower limit of its content is more than 0.2%.
  • it may contain about 0.2%, 0.3%, 0.4%, 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%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0% Fe 2 O 3. CoO and Co 2 O 3 have absorption in visible light and can deepen the coloring degree of matrix glass, microcrystalline glass or microcrystalline glass products.
  • NiO absorbs visible light and can deepen the coloring of the matrix glass, glass-ceramics or glass-ceramics products.
  • its content is less than 1%, and the lower limit of the total amount is more than 0.2%.
  • NiO can be included in an amount of about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%.
  • the purple matrix glass, glass-ceramics or glass-ceramics products prepared by the present invention use MnO2 as a colorant, and the content is generally below 4%, preferably below 3%, and the lower limit of the content is above 0.1%. If it is lower than 0.1%, the color of the matrix glass, glass-ceramics or glass-ceramics products is not obvious.
  • about 0.1%, 0.2%, 0.3%, 0.4%, 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% MnO2 may be included.
  • the pink matrix glass, microcrystalline glass or microcrystalline glass product prepared by the present invention uses Er 2 O 3 as a colorant, and the content of Er 2 O 3 is generally below 8%, preferably below 6%. Due to the low coloring efficiency of the rare earth element Er 2 O 3 , when the content exceeds 8%, it cannot further deepen the color of the matrix glass, microcrystalline glass or microcrystalline glass product, but increases the cost. The lower limit of its content is above 0.4%. If it is below 0.6%, the coloring efficiency of Er 2 O 3 is not high. 0.4%, the color of the matrix glass, glass-ceramic or glass-ceramic article is not obvious.
  • Er 2 O 3 may be included in an amount of about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2 %, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0 %.
  • the purple-red matrix glass, glass-ceramics or glass-ceramics products prepared by the present invention use Nd2O3 as a colorant, and the content of Nd2O3 is generally below 8%, preferably below 6%. Since the rare earth element Nd2O3 has low coloring efficiency, even if the content exceeds 8%, the color of the matrix glass, glass-ceramics or glass-ceramics products cannot be further deepened, but the cost is increased. The lower limit of the content is above 0.4%. If it is less than 0.4%, the color of the matrix glass, glass-ceramics or glass-ceramics products is not obvious.
  • about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Nd2O3 may be included.
  • the red matrix glass, microcrystalline glass or microcrystalline glass products prepared by the present invention use Er2O3 , Nd2O3 and MnO2 mixed colorants.
  • Er ions in the glass have absorption at 400-500nm
  • Mn ions mainly absorb at 500nm
  • Nd ions mainly have strong absorption at 580nm.
  • the mixture of the three substances can prepare red matrix glass, microcrystalline glass or microcrystalline glass products. Since Er2O3 and Nd2O3 are rare earth colorants, their coloring ability is relatively weak.
  • the usage amount of Er2O3 is within 6%
  • the usage amount of Nd2O3 is within 4%
  • MnO2 has strong coloring and the usage amount is within 2%.
  • the lower limit of the total amount of the mixed colorants used is above 0.9%.
  • the "does not contain” and "0%” recorded in this article mean that the compound, molecule or element is not intentionally added as a raw material to the matrix glass, microcrystalline glass or microcrystalline glass product of the present invention; however, as raw materials and/or equipment for producing matrix glass, microcrystalline glass or microcrystalline glass products, there will be certain impurities or components that are not intentionally added, which will be contained in small amounts or trace amounts in the final matrix glass, microcrystalline glass or microcrystalline glass product, and this situation is also within the scope of protection of the patent of this invention.
  • the crystal phase of the glass-ceramic and the glass-ceramic product contains nepheline
  • the crystalline phase provides high strength for the glass-ceramics and glass-ceramics products of the present invention, and the drop ball test height and four-point bending strength of the glass-ceramics and glass-ceramics products are increased.
  • the glass-ceramics or glass-ceramics products contain a eucryptite crystalline phase, in some embodiments, the glass-ceramics or glass-ceramics products contain a sodium cryptite crystalline phase, and in some embodiments, the glass-ceramics or glass-ceramics products contain both eucryptite and sodium cryptite crystalline phases.
  • the glass-ceramics of the present invention have excellent chemical strengthening properties and can also be processed into glass-ceramics products through a chemical strengthening process to obtain excellent mechanical strength.
  • the glass-ceramics and glass-ceramics products of the present invention can obtain a suitable grain size, so that the glass-ceramics and glass-ceramics products of the present invention have high strength.
  • the glass-ceramics and glass-ceramics products in the present invention have a suitable content of crystalline phase, so that the glass-ceramics and glass-ceramics products of the present invention have excellent mechanical properties.
  • the grain size and crystalline phase type in the glass-ceramics or glass-ceramics products of the present invention will affect the haze and light transmittance of the glass-ceramics or glass-ceramics products.
  • the haze of the glass-ceramics products or glass-ceramics with a thickness of less than 1 mm is less than 0.15%, preferably less than 0.12%, and more preferably less than 0.10%.
  • the grain size of the glass-ceramics products or glass-ceramics is less than 80 nm, preferably less than 60 nm, and more preferably less than 50 nm.
  • the crystalline content and refractive index of the glass-ceramics or glass-ceramics products of the present invention affect the
  • the glass-ceramics or glass-ceramics products When the glass-ceramics or glass-ceramics products are observed in the visible light range, they appear bluish or yellowish, affecting the optical properties of the product, which is indicated by the
  • value in LAB chromaticity value of the color of the substance.
  • value in LAB chromaticity value of the color of the substance.
  • the glass-ceramics or glass-ceramics products of the present invention exhibit low
  • value of the glass-ceramics products or glass-ceramics with a thickness of less than 1 mm at 400 to 800 nm is less than 1.5, preferably less than 1.0, and more preferably less than 0.8.
  • the glass-ceramics or glass-ceramics products of the present invention exhibit high transparency in the visible light range (i.e., the glass-ceramics or glass-ceramics products are transparent).
  • the glass-ceramics or glass-ceramics products exhibit high transmittance in the visible light range.
  • the light transmittance of the glass-ceramics products or glass-ceramics with a thickness of less than 1 mm at 550 nm is preferably 88% or more, more preferably 89% or more, and even more preferably 90% or more.
  • an antimicrobial component can be added to the matrix glass, glass-ceramic, or glass-ceramic product.
  • the glass-ceramic or glass-ceramic product described herein can be used in applications such as kitchen or dining countertops, where exposure to harmful bacteria is likely.
  • the antimicrobial components contained in the matrix glass, glass-ceramic, or glass-ceramic product include but are not limited to Ag, AgO, Cu, CuO, Cu 2 O, etc. In some embodiments, the content of the above antimicrobial components alone or in combination is less than 2%, preferably less than 1%.
  • the matrix glass, glass-ceramics and glass-ceramics products of the present invention can be produced and manufactured by the following methods:
  • Forming matrix glass Mix the raw materials evenly according to the component ratio, put the uniform mixture into a platinum or quartz crucible, and melt it in an electric furnace or gas furnace at a temperature range of 1250-1650°C for 5-24 hours according to the melting difficulty of the glass composition. After melting and stirring to make it uniform, it is cooled to an appropriate temperature and cast into a mold and slowly cooled.
  • the matrix glass of the present invention can be formed by a well-known method.
  • the matrix glass of the present invention is subjected to crystallization treatment by a crystallization process after forming or after forming processing, and crystallization is uniformly separated out inside the glass.
  • the crystallization treatment can be carried out by one stage, or by two stages, and preferably by two stages.
  • the treatment of the nucleation process is carried out at the first temperature, and then the treatment of the crystal growth process is carried out at the second temperature higher than the nucleation process temperature.
  • the crystallization treatment carried out at the first temperature is called the first crystallization treatment
  • the crystallization treatment carried out at the second temperature is called the second crystallization treatment.
  • the preferred crystallization process is:
  • the above-mentioned 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 580 to 750°C, and in order to precipitate the desired crystalline phase, it is more preferably 600 to 700°C.
  • the holding time at the crystallization treatment temperature is preferably 0 to 8 hours, and more preferably 1 to 6 hours.
  • the first temperature is preferably 500 to 620° C.
  • the second temperature is preferably 620 to 750° C.
  • the holding time at the first temperature is preferably 0 to 24 hours, more preferably
  • the holding time at the second temperature is preferably 0 to 10 hours, more preferably 0.5 to 6 hours.
  • the above-mentioned holding time of 0 hours means that the temperature starts to drop or rise again within less than 1 minute after reaching the temperature.
  • the matrix glass or glass-ceramics described herein can be manufactured into a formed body by various processes, including but not limited to sheets, and the processes include but are not limited to slit drawing, float process, rolling and other processes for forming sheets known in the art.
  • the matrix glass or glass-ceramics can be formed by float process or rolling process.
  • the formed body of the present invention also includes lenses, prisms, etc.
  • the matrix glass or glass-ceramics of the present invention can be used to manufacture a glass molded body or a glass-ceramics molded body in the form of a sheet by grinding or polishing, but the method for manufacturing a glass molded body or a glass-ceramics molded body is not limited to these methods.
  • the matrix glass or glass-ceramics of the present invention can be prepared into glass molded bodies or glass-ceramics molded bodies of various shapes by heat bending or pressing at a certain temperature, but is not limited to these methods.
  • a glass forming body or a glass-ceramic forming body can be formed by a heat bending process.
  • the heat bending process is a process in which 2D or 2.5D glass or glass-ceramic is placed in a mold and a 3D curved glass forming body or glass-ceramic forming body is formed by sequentially performing steps including heating preheating, pressurizing, and cooling under pressure in a heat bending machine.
  • the glass-ceramic forming body has a 2.5D or 3D configuration, i.e., the glass-ceramic forming body has a non-planar configuration.
  • non-planar configuration means that in a 2.5D or 3D shape, at least a portion of the glass-ceramic forming body extends outward or along an angle with a plane defined by the original, laid-out configuration of the 2D matrix glass.
  • a 2.5D or 3D glass-ceramic forming body formed from a matrix glass may have one or more protrusions or curved portions.
  • the method for manufacturing the microcrystalline glass formed body is a hot bending process.
  • the method includes pre-crystallization and hot working forming.
  • the pre-crystallization of the present invention is to control the crystallization process of the matrix glass.
  • Pre-crystallized glass is formed, wherein the crystallinity of the pre-crystallized glass does not reach the crystallinity required by the performance index of the target micro-ceramic glass formed body.
  • the pre-crystallized glass is then formed into a micro-ceramic glass formed body through a thermal processing molding process.
  • a method for manufacturing a glass-ceramic formed body comprises the following steps:
  • the pre-crystallized glass is heat-processed and formed into a microcrystalline glass formed body.
  • the crystallization heat treatment process described in the present invention includes nucleating the matrix glass at a certain temperature Th and time th , and then crystallizing at a certain temperature Tc and time tc .
  • the crystallinity of the obtained pre-crystallized glass does not reach the crystallinity required by the performance index of the target microcrystalline glass forming body.
  • the total content of the main crystal phase in the crystallinity of the pre-crystallized glass is calculated by the Rietveld full spectrum fitting refinement method as Ic1 .
  • the pre-crystallization of the present invention is a complete process from the process, including a nucleation process, a crystallization process of one, two or three stages and above, etc., which is a complete process from heating, heat preservation, heating again, heat preservation..., and then cooling to room temperature according to the process.
  • the present invention is actually only the first stage crystallization, the second stage crystallization... in a complete crystallization process, which is continuous in the middle, and there is no process of heating again after cooling to room temperature.
  • the hot working forming of the present invention refers to the hot working process forming the pre-crystallized glass under certain conditions of temperature, time, pressure, etc., and the hot working forming includes more than one hot working process, and the hot working process includes but is not limited to pressing, bending or drawing the pre-crystallized glass under certain conditions of temperature, time, pressure, etc.
  • the hot working forming process sometimes a molded body with a complex shape cannot be completed by one hot working, and may need to be completed by multiple hot workings of more than two times.
  • the method for manufacturing the glass-ceramic formed body is a hot bending process. Specifically, in some embodiments, the method for manufacturing the glass-ceramic formed body includes the following steps:
  • Preheating Place the matrix glass or pre-crystallized glass or glass-ceramics in the mold, and the mold passes through each heating station in the hot bending machine in turn, and stays at each station for a certain period of time to keep warm.
  • the temperature of the hot zone is 400-800°C
  • the pressure is 0.01-0.05MPa
  • the time is 40-200s.
  • the initial temperature rise is generally set to be stable at about 500°C
  • the subsequent stations gradually increase the temperature
  • the temperature gradient between two adjacent stations gradually decreases from low temperature to high temperature
  • the temperature difference between the last preheating station and the first press station is within 20°C.
  • the hot bending machine applies a certain pressure to the mold.
  • the pressure range is 0.1-0.8Mpa.
  • the pressure is determined according to factors such as glass thickness and curvature.
  • the molding station temperature range is 650-850°C, and the molding time range is 40-200s.
  • the mold is transferred to the cooling station and cooled down step by step.
  • the cooling temperature range is controlled at 750-500°C, the pressure is 0.01-0.05Mpa, and the time is 40-200s.
  • the hot bending process of microcrystalline glass forming bodies also requires controlling the impact of crystal growth and development during the hot bending process on the performance of the microcrystalline glass.
  • 3D curved microcrystalline glass used for display devices or electronic equipment casings requires close attention to light transmittance, haze,
  • the change in the crystalline phase before and after hot bending determines the uniformity of the size of the microcrystalline glass formed body, the possibility of mass production and cost control.
  • the matrix glass and microcrystalline glass of the present invention have excellent thermal processing properties. After hot bending, the change in the crystalline phase content is less than 20%, preferably less than 15%, and further preferably less than 10%, which can ensure the uniformity of the haze and
  • the matrix glass, glass-ceramic, and glass-ceramic articles described herein can have any reasonably useful thickness.
  • the microcrystalline glass of the present invention can also obtain more excellent mechanical properties by forming a compressive stress layer, thereby making microcrystalline glass products.
  • the matrix glass or glass-ceramics can be processed into sheets, and/or shaped (such as punching, hot bending, etc.), polished and/or brushed after shaping, and then chemically strengthened through a chemical strengthening process to form a glass-ceramics product.
  • the glass-ceramics formed body can be chemically strengthened through a chemical strengthening process to form a glass-ceramics product.
  • the chemical strengthening described in the present invention is an ion exchange method. Smaller metal ions in the glass or glass-ceramic or glass-ceramic forming body are replaced or "exchanged" by larger metal ions of the same valence state that are adjacent to the host glass or glass-ceramic or glass-ceramic forming body. The replacement of smaller ions with larger ions creates compressive stresses on the surface of the host glass or glass-ceramic or glass-ceramic forming body and tensile stresses within the interior.
  • the metal ions are monovalent alkali metal ions (e.g., Na + , K + , Rb + , Cs + , etc.), and the ion exchange is performed by immersing the matrix glass or glass-ceramic or glass-ceramic forming body in a salt bath of at least one molten salt containing larger metal ions, which are used to replace smaller metal ions in the matrix glass or glass-ceramic or glass-ceramic forming body.
  • a salt bath of at least one molten salt containing larger metal ions which are used to replace smaller metal ions in the matrix glass or glass-ceramic or glass-ceramic forming body.
  • other monovalent metal ions such as Ag + , Tl + , Cu + , etc. can also be used to exchange monovalent ions.
  • One or more ion exchange processes used to chemically strengthen the matrix glass or glass-ceramic or glass-ceramic forming body may include, but are not limited to: immersing it in a single salt bath, or immersing it in multiple salt baths of the same or different compositions, with washing and/or annealing steps between immersions.
  • the matrix glass or glass-ceramic or glass-ceramic body can be ion-exchanged by immersing in a salt bath of molten Na salt (such as NaNO 3 ) at a temperature of about 350-470°C for about 1 to 36 hours, preferably in the temperature range of 380-460°C, and preferably in the time range of 2 to 10 hours.
  • Na ions replace part of the Li ions in the matrix glass or glass-ceramic or glass-ceramic body, thereby forming a surface compression layer and exhibiting high mechanical properties.
  • the matrix glass or glass-ceramic or glass-ceramic body can be ion-exchanged by immersing in a salt bath of molten K salt (such as KNO 3 ) at a temperature of about 360-450°C for 1 to 36 hours, preferably in the time range of 1 to 10 hours.
  • molten K salt such as KNO 3
  • the matrix glass or glass-ceramic or glass-ceramic body can be ion-exchanged by immersing in a mixed salt bath of molten K salt and Na salt at a temperature of about 360-450°C for 1 to 36 hours, preferably in the time range of 2 to 24 hours.
  • the spectrophotometer Minolta CM-3600A was used to prepare samples with a diameter of less than 1 mm and the test was carried out according to the GB2410-80 standard.
  • the microcrystalline glass is surface treated in HF acid, gold is sprayed on the surface of the microcrystalline glass, and the surface is scanned under the SEM scanning electron microscope to determine the size of its grains.
  • the light transmittances described in this article are all external transmittances, sometimes referred to as transmittance.
  • the samples were processed to a thickness of less than 1 mm and the opposite surfaces were polished in parallel.
  • the light transmittance at 550 nm was measured using a Minolta CM-3600A spectrophotometer.
  • the surface stress was measured using a glass surface stress meter SLP-2000.
  • the depth of the ion exchange layer was measured using a glass surface stress meter SLP-2000.
  • a sample of a microcrystalline glass product with a length and width of 150mm ⁇ 73mm and a thickness of less than 1mm is placed on a glass supporting fixture, and a 132g steel ball is dropped from a specified height.
  • the maximum drop ball test height that the sample can withstand without breaking is the impact.
  • the test is implemented from a drop ball test height of 400mm. Without breaking, the height is changed in sequence through 400mm, 500mm, 600mm, 700mm and above, with an interval of 100mm each time.
  • microcrystalline glass products are used as test objects.
  • the test data recorded as 1600mm in the embodiment indicates that the sample has withstood an impact of 1500mm and has not broken. When it was raised to 1600mm for testing, it broke. Therefore, the drop ball test height is 1600mm.
  • the drop ball test height in the present invention is sometimes referred to as the drop ball height.
  • a glass-ceramic sample with a length and width of 150mm ⁇ 73mm and a thickness of less than 1mm is placed on a glass support fixture, and a 32g steel ball is dropped from a specified height.
  • the maximum drop ball test height that the sample can withstand without breaking is the body drop ball height.
  • the test starts from a drop ball test height of 400mm, and the test is carried out at 400mm, 500mm, 600mm, and 700mm without breaking. The height is changed from 700mm and above, with an interval of 100mm each time.
  • the microcrystalline glass is used as the test object, that is, the drop ball test height of the microcrystalline glass.
  • the test data recorded as 1300mm in the embodiment means that the sample has withstood an impact of 1200mm and has not broken. When it was raised to 1300mm for testing, it broke. Therefore, the body drop ball height is 1300mm.
  • a microcomputer-controlled electronic universal testing machine CMT6502 was used, and the sample specification was less than 1 mm thick, and the test was performed according to ASTM C 158-2002.
  • the four-point bending strength is sometimes referred to as the bending strength.
  • the value is expressed as the load when a diamond quadrangular pyramid indenter with an angle of 136° between opposing faces presses a pyramid-shaped depression into the test surface divided by the surface area (mm 2 ) calculated from the length of the depression.
  • the test load is 200 g and the holding time is 20 seconds.
  • Vickers hardness is sometimes referred to as simply hardness.
  • CM-700d Use Minolta CM-700d to test the B value.
  • the sample specification is less than 1mm thick.
  • Use the matching calibration long tube and short tube to perform instrument zero calibration and white plate calibration respectively. After calibration, use the long tube to perform air test again to determine the stability and calibration reliability of the instrument (B ⁇ 0.05). After the instrument is calibrated, place the product on the zero long tube for testing.
  • value is the absolute value of the B value.
  • microcrystalline glass product of the present invention has the following properties:
  • the four-point bending strength of the glass-ceramic product with a thickness of 1 mm or less is 700 MPa or more, preferably 750 MPa or more, and more preferably 800 MPa or more.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.
  • the depth of the ion exchange layer of the microcrystalline glass product is 50 ⁇ m or more, preferably 60 ⁇ m or more, more preferably 80 ⁇ m or more, and further preferably 100 ⁇ m or more.
  • the drop ball test height of a glass-ceramic article having a thickness of less than 1 mm is The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.
  • the Vickers hardness (H v ) of the microcrystalline glass product is 750 kgf/mm 2 or more, preferably 780 kgf/mm 2 or more, more preferably 800 kgf/mm 2 or more, and further preferably 810 kgf/mm 2 or more.
  • the grain size of the microcrystalline glass product is 80 nm or less, preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 40 nm or less.
  • the surface stress of the microcrystalline glass product is greater than 150 MPa, preferably greater than 170 MPa, and more preferably greater than 190 MPa.
  • the haze of the microcrystalline glass product with a thickness of 1 mm or less is 0.15% or less, preferably 0.12% or less, and more preferably 0.10% or less.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.
  • the light transmittance of the microcrystalline glass product with a thickness of 1 mm or less at a wavelength of 550 nm is 88% or more, preferably 89% or more, more preferably 90% or more, and further preferably 91% or more.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.
  • value at 400-800 nm is less than 1.5, preferably less than 1.0, and more preferably less than 0.8.
  • the thickness is preferably 0.2-1 mm, more preferably 0.3-0.9 mm, further preferably 0.5-0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.
  • microcrystalline glass of the present invention has the following properties:
  • the grain size of the glass-ceramics is 80 nm or less, preferably 60 nm or less, more preferably 50 nm or less, and further preferably 40 nm or less.
  • the haze of the microcrystalline glass with a thickness of less than 1 mm is less than 0.15%, preferably less than 0.12%, and more preferably less than 0.10%.
  • the thickness is preferably 0.2 to 1 mm, and more preferably It is 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.
  • the light transmittance of the microcrystalline glass with a thickness of 1 mm or less at a wavelength of 550 nm is 88% or more, preferably 89% or more, more preferably 90% or more, and further preferably 91% or more.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.
  • the body ball drop height of the microcrystalline glass with a thickness of 1 mm or less is 1000 mm or more, preferably 1200 mm or more, and more preferably 1400 mm or more.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.
  • value at 400-800 nm is less than 1.5, preferably less than 1.0, and more preferably less than 0.8.
  • the thickness is preferably 0.2-1 mm, more preferably 0.3-0.9 mm, further preferably 0.5-0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.
  • the Vickers hardness (H v ) of the glass-ceramics is 650 kgf/mm 2 or more, preferably 680 kgf/mm 2 or more, and more preferably 700 kgf/mm 2 or more.
  • microcrystalline glass, microcrystalline glass products, matrix glass, glass formed body, and microcrystalline glass formed body of the present invention can be widely made into glass cover plates or glass components due to the above-mentioned excellent properties; at the same time, the microcrystalline glass, microcrystalline glass products, matrix glass, glass formed body, and microcrystalline glass formed body of the present invention can be applied to electronic devices or display devices, such as mobile phones, watches, computers, touch screens, etc., for manufacturing protective glass for mobile phones, smart phones, tablet computers, laptops, PDAs, televisions, personal computers, MTA machines, or industrial displays, or for manufacturing touch screens, protective windows, car windows, train windows, aviation machinery windows, touch screen protective glass, or for manufacturing hard disk substrates or solar cell substrates, or for manufacturing white household appliances, such as for manufacturing refrigerator parts or kitchen utensils.
  • electronic devices or display devices such as mobile phones, watches, computers, touch screens, etc.
  • protective glass for mobile phones, smart phones, tablet computers, laptops, PDAs, televisions, personal computers, MTA machines, or industrial displays
  • This embodiment adopts the above-mentioned method for manufacturing microcrystalline glass to obtain microcrystalline glass having the composition shown in Tables 1 to 3.
  • the characteristics of each microcrystalline glass are measured by the test method described in the present invention, and the measurement results are shown in Tables 1 to 3.
  • value, etc. in the following embodiments is 0.7 mm.
  • This embodiment adopts the manufacturing method of the above-mentioned microcrystalline glass products to obtain microcrystalline glass products with the compositions shown in Tables 4 to 6.
  • the characteristics of each microcrystalline glass product are measured by the test method described in the present invention, and the measurement results are shown in Tables 4 to 6.
  • value, etc. in the following embodiments is 0.7 mm.

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Abstract

Un produit vitrocéramique, comprenant les composants suivants en pourcentages en poids : SiO2 : 40-60 % ; Al2O3 : 20-40 % ; Li2O : 2-15 % ; Na2O : 3-20 % ; et P2O5+ZrO2 : 1-15 %. Du fait d'une conception de composant appropriée, le produit en vitrocéramique présente de bonnes propriétés mécaniques, et permet son application dans des domaines tels que les dispositifs d'affichage ou les dispositifs électroniques.
PCT/CN2023/123354 2022-10-25 2023-10-08 Vitrocéramique, produit en vitrocéramique et leur procédé de fabrication WO2024088033A1 (fr)

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