WO2024088033A1 - Glass ceramic, glass ceramic product, and manufacturing method therefor - Google Patents

Glass ceramic, glass ceramic product, and manufacturing method therefor 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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French (fr)
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/en

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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

A glass ceramic product, comprising the following components in percentages by weight: SiO2: 40-60%; Al2O3: 20-40%; Li2O: 2-15%; Na2O: 3-20%; and P2O5+ZrO2: 1-15%. By means of the reasonable component design, the glass ceramic product has good mechanical properties, and meets the application thereof in fields such as display devices or electronic devices.

Description

微晶玻璃、微晶玻璃制品及其制造方法Glass-ceramics, glass-ceramics products and methods for producing the same 技术领域Technical Field
本发明涉及一种微晶玻璃，尤其是涉及一种具有优异的机械性能的微晶玻璃、微晶玻璃制品及其制造方法。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.
背景技术Background technique
近年来，随着消费电子产品的不断兴起和发展，玻璃作为一种透明且性能良好的材料，大量应用于此类电子器件中。例如LED和LCD显示器以及电脑监测器等设备，便携式电子产品(如移动电话、平板电脑和个人媒体终端等)，应用于其中的玻璃不仅需要能长时间承受来自应用中的常规“触摸”接触，还需要能承受在使用过程中可能发生的偶然弯折、划伤和冲击，这就对玻璃的相关性能提出了更高的要求。In recent years, with the continuous rise and development of consumer electronic products, glass, as a transparent and high-performance material, has been widely used in such electronic devices. For example, devices such as LED and LCD displays and computer monitors, portable electronic products (such as mobile phones, tablets and personal media terminals, etc.), the glass used in them not only needs to withstand the regular "touch" contact from the application for a long time, but also needs to withstand the accidental bending, scratches and impacts that may occur during use, which puts higher requirements on the relevant performance of the glass.
微晶玻璃是一种通过对玻璃进行热处理而在玻璃内部析出结晶的材料，具有比常规的玻璃更优异的机械性能，在玻璃中形成微晶，其抗弯、耐磨以及抗摔等性能相对于常规玻璃都有明显的优势。另一方面，微晶玻璃还可以通过化学强化，进一步提高机械性能。基于以上优点，目前有将微晶玻璃或其处理后得到的微晶玻璃制品应用于抗摔、抗压、耐划等要求较高的显示设备或电子设备中，尤其在便携式电子设备(如手机、手表、PAD等)的前后盖应用中。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. On the other hand, 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.).
因此，开发一款具有优异机械性能，且适用于显示设备或电子设备的微晶玻璃及微晶玻璃制品，成为了科技人员所追求的目标。Therefore, developing a glass-ceramic and glass-ceramic product with excellent mechanical properties and suitable for display devices or electronic devices has become the goal pursued by scientific and technological personnel.
发明内容Summary of the invention
本发明所要解决的技术问题是提供一种具有优异的机械性能的微晶玻璃和微晶玻璃制品。The technical problem to be solved by the present invention is to provide a microcrystalline glass and microcrystalline glass products with excellent mechanical properties.
本发明解决技术问题所采用的技术方案是：The technical solution adopted by the present invention to solve the technical problem is:
(1)微晶玻璃制品，其组分按重量百分比表示，含有：SiO2：40～60％；Al2O3：20～40％；Li2O：2～15％；Na2O：3～20％；P2O5+ZrO2：1～15％。 (1) 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%.
(2)根据(1)所述的微晶玻璃制品，其组分按重量百分比表示，还含有：K2O：0～8％；和/或ZnO：0～6％；和/或B2O3：0～6％；和/或RO：0～8％；和/或TiO2：0～5％；和/或Ln2O3：0～5％；和/或澄清剂：0～2％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。(2) The glass-ceramic product according to (1), further comprising, expressed in weight percentage, 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 .
(3)微晶玻璃制品，其组分按重量百分比表示，由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％；澄清剂：0～2％组成，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。(3) 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 .
(4)微晶玻璃制品，其组分中含有SiO2、Al2O3、Li2O和Na2O，所述微晶玻璃制品含有霞石晶相，所述微晶玻璃制品的表面应力为150MPa以上。(4) 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.
(5)微晶玻璃制品，其主要晶相含有霞石晶相，所述微晶玻璃制品的维氏硬度为750kgf/mm2以上。(5) 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.
(6)微晶玻璃制品，其组分按重量百分比表示，含有SiO2：40～60％；Al2O3：20～40％；Li2O：2～15％；Na2O：3～20％，所述微晶玻璃制品含有霞石晶相。(6) 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.
(7)微晶玻璃制品，其组分中含有SiO2、Al2O3、Li2O和Na2O，1mm以下厚度的微晶玻璃制品的四点弯曲强度为700MPa以上。(7) 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.
(8)微晶玻璃制品，其组分中含有SiO2、Al2O3、Li2O和Na2O，1mm以下厚度的微晶玻璃制品的雾度为0.15％以下。(8) 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.
(9)微晶玻璃制品，含有霞石晶相，1mm以下厚度的微晶玻璃制品550nm波长的光透过率为88％以上。(9) 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.
(10)微晶玻璃制品，含有霞石晶相，所述微晶玻璃制品的离子交换层深度为50μm以上。(10) 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 μm.
(11)根据(4)～(10)任一所述的微晶玻璃制品，其组分按重量百分比表示，含有：SiO2：40～60％；和/或Al2O3：20～40％；和/或Li2O：2～ 15％；和/或Na2O：3～20％；和/或P2O5+ZrO2：1～15％。(11) The glass-ceramic product according to any one of (4) to (10), wherein the composition, expressed in weight percentage, comprises: SiO 2 : 40 to 60%; and/or Al 2 O 3 : 20 to 40%; and/or Li 2 O: 2 to 30%. 15%; and/or Na 2 O: 3-20%; and/or P 2 O 5 + ZrO 2 : 1-15%.
(12)根据(4)～(11)任一所述的微晶玻璃制品，其组分按重量百分比表示，还含有：K2O：0～8％；和/或ZnO：0～6％；和/或B2O3：0～6％；和/或RO：0～8％；和/或TiO2：0～5％；和/或Ln2O3：0～5％；和/或澄清剂：0～2％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。(12) The glass-ceramic product according to any one of (4) to (11), further comprising, expressed in weight percentage, 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 .
(13)根据(1)～(12)任一所述的微晶玻璃制品，其组分按重量百分比表示，其中：(Al2O3+Na2O)/P2O5为3.0～30.0，优选(Al2O3+Na2O)/P2O5为4.0～20.0，更优选(Al2O3+Na2O)/P2O5为5.0～15.0，进一步优选(Al2O3+Na2O)/P2O5为6.0～10.0。(13) The glass-ceramic product according to any one of (1) to (12), wherein the components are expressed in weight percentage, wherein: (Al 2 O 3 +Na 2 O)/P 2 O 5 is 3.0 to 30.0, preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 4.0 to 20.0, more preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 5.0 to 15.0, and further preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 6.0 to 10.0.
(14)根据(1)～(13)任一所述的微晶玻璃制品，其组分按重量百分比表示，其中：SiO2/Al2O3为1.2～2.8，优选SiO2/Al2O3为1.3～2.5，更优选SiO2/Al2O3为1.5～2.2，进一步优选SiO2/Al2O3为1.6～2.0。(14) The glass-ceramic product according to any one of (1) to (13), wherein the components are expressed in weight percentage, wherein: SiO2 / Al2O3 is 1.2 to 2.8, preferably SiO2 / Al2O3 is 1.3 to 2.5, more preferably SiO2 / Al2O3 is 1.5 to 2.2, and further preferably SiO2 / Al2O3 is 1.6 to 2.0.
(15)根据(1)～(14)任一所述的微晶玻璃制品，其组分按重量百分比表示，其中：SiO2/(Na2O+B2O3)为2.0～15.0，优选SiO2/(Na2O+B2O3)为3.0～10.0，更优选SiO2/(Na2O+B2O3)为4.0～8.0，进一步优选SiO2/(Na2O+B2O3)为5.0～7.0。(15) The glass-ceramic product according to any one of (1) to ( 14 ), wherein the components are expressed in weight percentage, wherein: SiO2 /( Na2O + B2O3 ) is 2.0 to 15.0 , preferably SiO2 /( Na2O + B2O3 ) is 3.0 to 10.0, more preferably SiO2/(Na2O+B2O3 ) is 4.0 to 8.0, and further preferably SiO2 /( Na2O + B2O3 ) is 5.0 to 7.0 .
(16)根据(1)～(15)任一所述的微晶玻璃制品，其组分按重量百分比表示，其中：(Na2O+Li2O)/SiO2为0.1～0.8，优选(Na2O+Li2O)/SiO2为0.15～0.7，更优选(Na2O+Li2O)/SiO2为0.2～0.6，进一步优选(Na2O+Li2O)/SiO2为0.25～0.5。(16) The glass-ceramic product according to any one of (1) to (15), 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.
(17)根据(1)～(16)任一所述的微晶玻璃制品，其组分按重量百分比表示，其中：(ZrO2+ZnO)/Na2O为2.0以下，优选(ZrO2+ZnO)/Na2O为1.5以下，更优选(ZrO2+ZnO)/Na2O为0.01～1.0，进一步优选(ZrO2+ZnO)/Na2O为0.1～0.5。(17) The glass-ceramic product according to any one of (1) to (16), wherein the components are expressed in weight percentage, wherein: ( ZrO2 +ZnO)/ Na2O is less than 2.0, preferably ( ZrO2 +ZnO)/ Na2O is less than 1.5, more preferably ( ZrO2 +ZnO)/ Na2O is 0.01 to 1.0, and further preferably ( ZrO2 +ZnO)/ Na2O is 0.1 to 0.5.
(18)根据(1)～(17)任一所述的微晶玻璃制品，其组分按重量百分比表示，其中：(P2O5+Na2O)/Li2O为0.5～8.0，优选(P2O5+Na2O)/Li2O 为0.8～5.0，更优选(P2O5+Na2O)/Li2O为1.0～3.0，进一步优选(P2O5+Na2O)/Li2O为1.5～2.5。(18) The glass-ceramic product according to any one of (1) to (17), wherein the components are expressed in weight percentage, wherein: (P 2 O 5 +Na 2 O)/Li 2 O is 0.5 to 8.0, preferably (P 2 O 5 +Na 2 O)/Li 2 O The (P 2 O 5 +Na 2 O)/Li 2 O ratio is preferably 0.8 to 5.0 , more preferably 1.0 to 3.0, and still more preferably 1.5 to 2.5.
(19)根据(1)～(18)任一所述的微晶玻璃制品，其组分按重量百分比表示，其中：K2O/ZrO2为0.1以上，优选K2O/ZrO2为0.2～10.0，更优选K2O/ZrO2为0.3～5.0，进一步优选K2O/ZrO2为0.4～1.5。(19) The glass-ceramic product according to any one of (1) to (18), wherein the components are expressed in weight percentage, wherein: K2O / ZrO2 is greater than 0.1, preferably K2O / ZrO2 is 0.2 to 10.0, more preferably K2O / ZrO2 is 0.3 to 5.0, and further preferably K2O / ZrO2 is 0.4 to 1.5.
(20)根据(1)～(19)任一所述的微晶玻璃制品，其组分按重量百分比表示，其中：(ZnO+RO+B2O3+TiO2)/P2O5为1.5以下，优选(ZnO+RO+B2O3+TiO2)/P2O5为1.0以下，更优选(ZnO+RO+B2O3+TiO2)/P2O5为0.5以下，进一步优选(ZnO+RO+B2O3+TiO2)/P2O5为0.2以下，所述RO为MgO、CaO、SrO、BaO中的一种或多种。(20) The glass-ceramic product according to any one of (1) to ( 19 ), wherein the components are expressed in weight percentage, wherein: (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 1.5 , preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 1.0, more preferably (ZnO+ RO + B2O3 + TiO2 ) / P2O5 is less than 0.5 , and further preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 0.2 , and the RO is one or more of MgO, CaO, SrO, and BaO.
(21)根据(1)～(20)任一所述的微晶玻璃制品，其组分按重量百分比表示，其中：SiO2：43～55％，优选SiO2：46～53％；和/或Al2O3：23～36％，优选Al2O3：25.5～32％；和/或Li2O：3～13％，优选Li2O：5.5～11％；和/或Na2O：5～15％，优选Na2O：6.5～12％；和/或P2O5+ZrO2：2～12％，优选P2O5+ZrO2：4～10％；和/或K2O：0～5％，优选K2O：0.1～3％；和/或ZnO：0～3％，优选ZnO：0～1％；和/或B2O3：0～3％，优选B2O3：0～1％；和/或RO：0～5％，优选RO：0～2％；和/或TiO2：0～3％，优选TiO2：0～1％；和/或Ln2O3：0～3％，优选Ln2O3：0～1％；和/或澄清剂：0～1％，优选澄清剂：0～0.5％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。(21) The glass-ceramic product according to any one of (1) to (20), wherein the components are expressed in weight percentage, wherein: SiO 2 : 43-55%, preferably SiO 2 : 46-53%; and/or Al 2 O 3 : 23-36%, preferably Al 2 O 3 : 25.5-32%; and/or Li 2 O : 3-13%, preferably Li 2 O : 5.5-11%; and/or Na 2 O : 5-15%, preferably Na 2 O : 6.5-12%; and/or P 2 O 5 + ZrO 2 : 2-12%, preferably P 2 O 5 + ZrO 2 : 4-10%; and/or K 2 O : 0-5%, preferably K 2 O : 0.1-3%; and/or ZnO : 0-3%, preferably ZnO : 0-1%; and/or B 2 O 3 : 0-3%, preferably B 2 O 3 2 O 3 : 0-1%; and/or RO: 0-5%, preferably RO: 0-2%; and/or TiO 2 : 0-3%, preferably TiO 2 : 0-1%; and/or Ln 2 O 3 : 0-3%, preferably Ln 2 O 3 : 0-1%; and/or clarifier: 0-1%, preferably clarifier: 0-0.5%, wherein RO is one or more of MgO, CaO, SrO and BaO, and Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 and Y 2 O 3 .
(22)根据(1)～(21)任一所述的微晶玻璃制品，其组分按重量百分比表示，其中：ZrO2：0～6％，优选ZrO2：0～5％，更优选ZrO2：0.1～3％；和/或P2O5：0～10％，优选P2O5：1～8％，更优选P2O5：2～6％。(22) The glass-ceramic product according to any one of (1) to (21), wherein the components, expressed in weight percentage, are: ZrO 2 : 0-6%, preferably ZrO 2 : 0-5%, more preferably ZrO 2 : 0.1-3%; and/or P 2 O 5 : 0-10%, preferably P 2 O 5 : 1-8%, more preferably P 2 O 5 : 2-6%.
(23)根据(1)、(2)、(4)～(12)任一所述的微晶玻璃制品，其组分按重量百分比表示，还含有：Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～5％，优选Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～2％，更优选Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～1％。 (23) The glass-ceramic product according to any one of (1), ( 2 ), (4) to ( 12 ), further comprising, 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% .
(24)根据(1)～(23)任一所述的微晶玻璃制品，其组分中不含有SrO；和/或不含有BaO；和/或不含有MgO；和/或不含有CaO；和/或不含有ZnO；和/或不含有PbO；和/或不含有As2O3；和/或不含有TiO2；和/或不含有B2O3；和/或不含有Y2O3；和/或不含有La2O3；和/或不含有Gd2O3。(24) The glass-ceramic product according to any one of (1) to (23), 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 .
(25)根据(1)～(24)任一所述的微晶玻璃制品，所述微晶玻璃制品含有霞石晶相；和/或硅酸锂晶相；和/或磷酸锂晶相；和/或透锂长石晶相；和/或石英晶相。(25) According to any one of the microcrystalline glass products described in (1) to (24), 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.
(26)根据(1)～(25)任一所述的微晶玻璃制品，所述微晶玻璃制品的主要晶相为霞石晶相，或微晶玻璃制品只含有霞石晶相。(26) According to any one of (1) to (25), 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.
(27)根据(1)～(26)任一所述的微晶玻璃制品，所述微晶玻璃制品中，霞石晶相占微晶玻璃制品的重量百分比为10～80％，优选霞石晶相占微晶玻璃制品的重量百分比为20～70％，更优选霞石晶相占微晶玻璃制品的重量百分比为30～60％。(27) According to any one of the microcrystalline glass products described in (1) to (26), in the microcrystalline glass product, 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%.
(28)根据(1)～(27)任一所述的微晶玻璃制品，所述微晶玻璃制品的离子交换层深度为50μm以上，优选为60μm以上，更优选为80μm以上，进一步优选为100μm以上；和/或维氏硬度为750kgf/mm2以上，优选为780kgf/mm2以上，更优选为800kgf/mm2以上，进一步优选为810kgf/mm2以上；和/或晶粒尺寸为80nm以下，优选为60nm以下，更优选为50nm以下，进一步优选为40nm以下；和/或表面应力为150MPa以上，优选为170MPa以上，更优选为190MPa以上。(28) According to any one of the microcrystalline glass products described in (1) to (27), the ion exchange layer depth of the microcrystalline glass product is greater than 50 μm, preferably greater than 60 μm, more preferably greater than 80 μm, and further preferably greater than 100 μm; 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.
(29)根据(1)～(28)任一所述的微晶玻璃制品，1mm以下厚度的微晶玻璃制品，其四点弯曲强度为700MPa以上，优选为750MPa以上，更优选为800MPa以上；和/或落球试验高度为1100mm以上，优选为1300mm以上，更优选为1500mm以上；和/或雾度为0.15％以下，优选为0.12％以下，更优选为0.10％以下；和/或550nm波长的光透过率为88％以上，优选为89％以上，更优选为90％以上，进一步优选为91％以上；和/或400～800nm的平均光∣B∣值为1.5以下，优选为1.0以下，更优选为0.8以下。 (29) 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 |B| value of 400 to 800 nm is 1.5 or less, preferably 1.0 or less, and more preferably 0.8 or less.
(30)根据(7)～(9)、(29)任一所述的微晶玻璃制品，所述微晶玻璃制品的厚度为0.2～1mm，优选为0.3～0.9mm，更优选为0.5～0.8mm，进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。(30) According to any one of (7) to (9) and (29), 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.
(31)根据(1)、(2)、(4)～(12)任一所述的微晶玻璃制品，其组分按重量百分比表示，还含有：NiO：0～4％；和/或Ni2O3：0～4％；和/或CoO：0～2％；和/或Co2O3：0～2％；和/或Fe2O3：0～7％；和/或MnO2：0～4％；和/或Er2O3：0～8％；和/或Nd2O3：0～8％；和/或Cu2O：0～4％；和/或Pr2O3：0～8％；和/或CeO2：0～4％。(31) The glass-ceramic product according to any one of (1), (2), (4) to (12), further comprising, expressed in weight percentage, the following: 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 3 : 0-8%; and/or CeO 2 : 0-4%.
(32)微晶玻璃，其组分按重量百分比表示，含有：SiO2：40～60％；Al2O3：20～40％；Li2O：2～15％；Na2O：3～20％；P2O5+ZrO2：1～15％。(32) 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%.
(33)根据(32)所述的微晶玻璃，其组分按重量百分比表示，还含有：K2O：0～8％；和/或ZnO：0～6％；和/或B2O3：0～6％；和/或RO：0～8％；和/或TiO2：0～5％；和/或Ln2O3：0～5％；和/或澄清剂：0～2％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。(33) 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 .
(34)微晶玻璃，其组分按重量百分比表示，由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％；澄清剂：0～2％组成，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。(34) 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 .
(35)微晶玻璃，其组分中含有SiO2、Al2O3、Li2O和Na2O，所述微晶玻璃含有霞石晶相，所述微晶玻璃的维氏硬度为650kgf/mm2以上。(35) 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.
(36)微晶玻璃，其主要晶相含有霞石晶相，所述微晶玻璃的维氏硬度为650kgf/mm2以上。(36) Glass-ceramics, wherein the main crystal phase contains a nepheline crystal phase, and the Vickers hardness of the glass-ceramics is greater than 650 kgf/ mm2 .
(37)微晶玻璃，其组分按重量百分比表示，含有SiO2：40～60％；Al2O3：20～40％；Li2O：2～15％；Na2O：3～20％，所述微晶玻璃含有霞石晶相。(37) 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.
(38)微晶玻璃，其组分中含有SiO2、Al2O3、Li2O和Na2O，1mm以下 厚度的微晶玻璃的本体落球高度为1000mm以上。(38) Glass-ceramics, containing SiO 2 , Al 2 O 3 , Li 2 O and Na 2 O, with a diameter of less than 1 mm The drop height of the main body of the microcrystalline glass with a thickness of 1000mm or more.
(39)微晶玻璃，其组分中含有SiO2、Al2O3、Li2O和Na2O，1mm以下厚度的微晶玻璃的雾度为0.15％以下。(39) 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.
(40)微晶玻璃，含有霞石晶相，1mm以下厚度的微晶玻璃550nm波长的光透过率为88％以上。(40) Microcrystalline glass containing nepheline crystal phase, wherein the light transmittance at a wavelength of 550 nm of microcrystalline glass with a thickness of less than 1 mm is greater than 88%.
(41)微晶玻璃，其组分中含有SiO2、Al2O3、Li2O和Na2O，所述微晶玻璃中，霞石晶相占微晶玻璃的重量百分比为10～80％。(41) 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%.
(42)根据(35)～(41)任一所述的微晶玻璃，其组分按重量百分比表示，含有：SiO2：40～60％；和/或Al2O3：20～40％；和/或Li2O：2～15％；和/或Na2O：3～20％；和/或P2O5+ZrO2：1～15％。(42) The glass-ceramics according to any one of (35) to (41), wherein the components, expressed in weight percentage, include: SiO2 : 40-60%; and/or Al2O3 : 20-40%; and/or Li2O : 2-15%; and/or Na2O : 3-20%; and/ or P2O5 + ZrO2 : 1-15%.
(43)根据(35)～(42)任一所述的微晶玻璃，其组分按重量百分比表示，还含有：K2O：0～8％；和/或ZnO：0～6％；和/或B2O3：0～6％；和/或RO：0～8％；和/或TiO2：0～5％；和/或Ln2O3：0～5％；和/或澄清剂：0～2％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。(43) The glass-ceramics according to any one of (35) to (42), further comprising, expressed in weight percentage, 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 .
(44)根据(32)～(43)任一所述的微晶玻璃，其组分按重量百分比表示，其中：(Al2O3+Na2O)/P2O5为3.0～30.0，优选(Al2O3+Na2O)/P2O5为4.0～20.0，更优选(Al2O3+Na2O)/P2O5为5.0～15.0，进一步优选(Al2O3+Na2O)/P2O5为6.0～10.0。(44) The glass-ceramics according to any one of (32) to (43), wherein the components are expressed in weight percentage, wherein: (Al 2 O 3 +Na 2 O)/P 2 O 5 is 3.0 to 30.0, preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 4.0 to 20.0, more preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 5.0 to 15.0, and further preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 6.0 to 10.0.
(45)根据(32)～(44)任一所述的微晶玻璃，其组分按重量百分比表示，其中：SiO2/Al2O3为1.2～2.8，优选SiO2/Al2O3为1.3～2.5，更优选SiO2/Al2O3为1.5～2.2，进一步优选SiO2/Al2O3为1.6～2.0。(45) The glass-ceramics according to any one of (32) to (44), wherein the components are expressed in weight percentage, wherein: SiO 2 /Al 2 O 3 is 1.2 to 2.8, preferably SiO 2 /Al 2 O 3 is 1.3 to 2.5, more preferably SiO 2 /Al 2 O 3 is 1.5 to 2.2, and further preferably SiO 2 /Al 2 O 3 is 1.6 to 2.0.
(46)根据(32)～(45)任一所述的微晶玻璃，其组分按重量百分比表示，其中：SiO2/(Na2O+B2O3)为2.0～15.0，优选SiO2/(Na2O+B2O3)为3.0～10.0，更优选SiO2/(Na2O+B2O3)为4.0～8.0，进一步优选SiO2/(Na2O+B2O3)为5.0～7.0。(46) The glass-ceramics according to any one of (32) to (45), wherein the components are expressed in weight percentage, wherein: SiO 2 /(Na 2 O + B 2 O 3 ) is 2.0 to 15.0, preferably SiO 2 /(Na 2 O + B 2 O 3 ) is 3.0 to 10.0, more preferably SiO 2 /(Na 2 O + B 2 O 3 ) is 4.0 to 8.0, and further preferably SiO 2 /(Na 2 O + B 2 O 3 ) is 5.0 to 7.0.
(47)根据(32)～(46)任一所述的微晶玻璃，其组分按重量百分 比表示，其中：(Na2O+Li2O)/SiO2为0.1～0.8，优选(Na2O+Li2O)/SiO2为0.15～0.7，更优选(Na2O+Li2O)/SiO2为0.2～0.6，进一步优选(Na2O+Li2O)/SiO2为0.25～0.5。(47) The glass-ceramics according to any one of (32) to (46), wherein the components are as follows: 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)根据(32)～(47)任一所述的微晶玻璃，其组分按重量百分比表示，其中：(ZrO2+ZnO)/Na2O为2.0以下，优选(ZrO2+ZnO)/Na2O为1.5以下，更优选(ZrO2+ZnO)/Na2O为0.01～1.0，进一步优选(ZrO2+ZnO)/Na2O为0.1～0.5。(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.
(49)根据(32)～(48)任一所述的微晶玻璃，其组分按重量百分比表示，其中：(P2O5+Na2O)/Li2O为0.5～8.0，优选(P2O5+Na2O)/Li2O为0.8～5.0，更优选(P2O5+Na2O)/Li2O为1.0～3.0，进一步优选(P2O5+Na2O)/Li2O为1.5～2.5。(49) The glass-ceramics according to any one of (32) to (48), wherein the components are expressed in weight percentage, wherein: (P 2 O 5 +Na 2 O)/Li 2 O is 0.5 to 8.0, preferably (P 2 O 5 +Na 2 O)/Li 2 O is 0.8 to 5.0, more preferably (P 2 O 5 +Na 2 O)/Li 2 O is 1.0 to 3.0, and further preferably (P 2 O 5 +Na 2 O)/Li 2 O is 1.5 to 2.5.
(50)根据(32)～(49)任一所述的微晶玻璃，其组分按重量百分比表示，其中：K2O/ZrO2为0.1以上，优选K2O/ZrO2为0.2～10.0，更优选K2O/ZrO2为0.3～5.0，进一步优选K2O/ZrO2为0.4～1.5。(50) The glass-ceramics according to any one of (32) to (49), wherein the components are expressed in weight percentage, wherein: K2O / ZrO2 is greater than 0.1, preferably K2O / ZrO2 is 0.2 to 10.0, more preferably K2O / ZrO2 is 0.3 to 5.0, and further preferably K2O / ZrO2 is 0.4 to 1.5.
(51)根据(32)～(50)任一所述的微晶玻璃，其组分按重量百分比表示，其中：(ZnO+RO+B2O3+TiO2)/P2O5为1.5以下，优选(ZnO+RO+B2O3+TiO2)/P2O5为1.0以下，更优选(ZnO+RO+B2O3+TiO2)/P2O5为0.5以下，进一步优选(ZnO+RO+B2O3+TiO2)/P2O5为0.2以下，所述RO为MgO、CaO、SrO、BaO中的一种或多种。(51) The glass-ceramics according to any one of (32) to ( 50 ), wherein the components are expressed in weight percentage, wherein: (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 1.5 , preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 1.0 , more preferably (ZnO+RO+ B2O3 + TiO2 ) / P2O5 is less than 0.5 , and further preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 0.2 , and the RO is one or more of MgO, CaO, SrO, and BaO.
(52)根据(32)～(51)任一所述的微晶玻璃，其组分按重量百分比表示，其中：SiO2：43～55％，优选SiO2：46～53％；和/或Al2O3：23～36％，优选Al2O3：25.5～32％；和/或Li2O：3～13％，优选Li2O：5.5～11％；和/或Na2O：5～15％，优选Na2O：6.5～12％；和/或P2O5+ZrO2：2～12％，优选P2O5+ZrO2：4～10％；和/或K2O：0～5％，优选K2O：0.1～3％；和/或ZnO：0～3％，优选ZnO：0～1％；和/或B2O3：0～3％，优选B2O3：0～1％；和/或RO：0～5％，优选RO：0～2％；和/或TiO2：0～3％，优选TiO2：0～1％；和/或Ln2O3：0～3％，优选Ln2O3：0～1％；和/或澄清剂：0～1％，优选澄清剂：0～0.5％， 所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。(52) The glass-ceramics according to any one of (32) to (51), wherein the components are expressed in weight percentage, wherein: SiO 2 : 43-55%, preferably SiO 2 : 46-53%; and/or Al 2 O 3 : 23-36%, preferably Al 2 O 3 : 25.5-32%; and/or Li 2 O : 3-13%, preferably Li 2 O : 5.5-11%; and/or Na 2 O : 5-15%, preferably Na 2 O : 6.5-12%; and/or P 2 O 5 + ZrO 2 : 2-12%, preferably P 2 O 5 + ZrO 2 : 4-10%; and/or K 2 O : 0-5%, preferably K 2 O: 0.1-3%; and/or ZnO: 0-3%, preferably ZnO: 0-1%; and/or B 2 O 3 : 0-3%, preferably B 2 O 3 2 O 3 : 0-1%; and/or RO: 0-5%, preferably RO: 0-2%; and/or TiO 2 : 0-3%, preferably TiO 2 : 0-1%; and/or Ln 2 O 3 : 0-3%, preferably Ln 2 O 3 : 0-1%; and/or clarifier: 0-1%, preferably clarifier: 0-0.5%, The RO is one or more of MgO, CaO, SrO, and BaO, and the Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , and Y 2 O 3 .
(53)根据(32)～(52)任一所述的微晶玻璃，其组分按重量百分比表示，其中：ZrO2：0～6％，优选ZrO2：0～5％，更优选ZrO2：0.1～3％；和/或P2O5：0～10％，优选P2O5：1～8％，更优选P2O5：2～6％。(53) The glass-ceramics according to any one of (32) to (52), wherein the components are expressed in weight percentage, wherein: ZrO 2 : 0-6%, preferably ZrO 2 : 0-5%, more preferably ZrO 2 : 0.1-3%; and/or P 2 O 5 : 0-10%, preferably P 2 O 5 : 1-8%, more preferably P 2 O 5 : 2-6%.
(54)根据(32)、(33)、(35)～(43)任一所述的微晶玻璃，其组分按重量百分比表示，还含有：Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～5％，优选Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～2％，更优选Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～1％。(54) 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% .
(55)根据(32)～(54)任一所述的微晶玻璃，其组分中不含有SrO；和/或不含有BaO；和/或不含有MgO；和/或不含有CaO；和/或不含有ZnO；和/或不含有PbO；和/或不含有As2O3；和/或不含有TiO2；和/或不含有B2O3；和/或不含有Y2O3；和/或不含有La2O3；和/或不含有Gd2O3。(55) The glass-ceramics according to any one of (32) to (54), 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 .
(56)根据(32)～(55)任一所述的微晶玻璃，所述微晶玻璃含有霞石晶相；和/或硅酸锂晶相；和/或磷酸锂晶相；和/或透锂长石晶相；和/或石英晶相。(56) According to any one of the microcrystalline glass described in (32) to (55), 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.
(57)根据(32)～(56)任一所述的微晶玻璃，所述微晶玻璃的主要晶相为霞石晶相，或微晶玻璃只含有霞石晶相。(57) According to any one of the microcrystalline glass described in (32) to (56), the main crystal phase of the microcrystalline glass is the nepheline crystal phase, or the microcrystalline glass only contains the nepheline crystal phase.
(58)根据(32)～(57)任一所述的微晶玻璃，所述微晶玻璃中，霞石晶相占微晶玻璃的重量百分比为10～80％，优选霞石晶相占微晶玻璃的重量百分比为20～70％，更优选霞石晶相占微晶玻璃的重量百分比为30～60％。(58) According to any one of the microcrystalline glass described in (32) to (57), in the microcrystalline glass, 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%.
(59)根据(32)～(58)任一所述的微晶玻璃，所述微晶玻璃的晶粒尺寸为80nm以下，优选为60nm以下，更优选为50nm以下，进一步优选为40nm以下；和/或维氏硬度为650kgf/mm2以上，优选为680kgf/mm2以上，更优选为700kgf/mm2以上。(59) The 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 .
(60)根据(32)～(59)任一所述的微晶玻璃，1mm以下厚度的微 晶玻璃，其本体落球高度为1000mm以上，优选为1200mm以上，更优选为1400mm以上；和/或雾度为0.15％以下，优选为0.12％以下，更优选为0.10％以下；和/或550nm波长的光透过率为88％以上，优选为89％以上，更优选为90％以上，进一步优选为91％以上；和/或400～800nm的平均光∣B∣值为1.5以下，优选为1.0以下，更优选为0.8以下。(60) The glass-ceramics according to any one of (32) to (59), wherein the glass-ceramics has a thickness of 1 mm or less. 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 |B| value at 400-800nm is less than 1.5, preferably less than 1.0, more preferably less than 0.8.
(61)根据(38)～(40)、(60)任一所述的微晶玻璃，所述微晶玻璃的厚度为0.2～1mm，优选为0.3～0.9mm，更优选为0.5～0.8mm，进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。(61) According to any one of (38) to (40) and (60), 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.
(62)根据(32)、(33)、(35)～(43)任一所述的微晶玻璃，其组分按重量百分比表示，还含有：NiO：0～4％；和/或Ni2O3：0～4％；和/或CoO：0～2％；和/或Co2O3：0～2％；和/或Fe2O3：0～7％；和/或MnO2：0～4％；和/或Er2O3：0～8％；和/或Nd2O3：0～8％；和/或Cu2O：0～4％；和/或Pr2O3：0～8％；和/或CeO2：0～4％。(62) The glass-ceramics according to any one of (32), (33), (35) to (43), wherein its components, expressed in weight percentage, further contain: NiO: 0 to 4%; and/or Ni 2 O 3 : 0 to 4%; and/or CoO: 0 to 2%; and/or Co 2 O 3 : 0 to 2%; and/or Fe 2 O 3 : 0 to 7%; and/or MnO 2 : 0 to 4%; and/or Er 2 O 3 : 0 to 8%; and/or Nd 2 O 3 : 0 to 8%; and/or Cu 2 O: 0 to 4%; and/or Pr 2 O 3 : 0 to 8%; and/or CeO 2 : 0 to 4%.
(63)基质玻璃，其组分按重量百分比表示，含有：SiO2：40～60％；Al2O3：20～40％；Li2O：2～15％；Na2O：3～20％；P2O5+ZrO2：1～15％。(63) 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%.
(64)根据(63)所述的基质玻璃，其组分按重量百分比表示，还含有：K2O：0～8％；和/或ZnO：0～6％；和/或B2O3：0～6％；和/或RO：0～8％；和/或TiO2：0～5％；和/或Ln2O3：0～5％；和/或澄清剂：0～2％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。(64) The matrix glass according to (63), wherein its components, expressed in weight percentage, further contain: 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 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 .
(65)基质玻璃，其组分按重量百分比表示，由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％；澄清剂：0～2％组成，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。(65) 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 .
(66)根据(63)～(65)任一所述的基质玻璃，其组分按重量百分比表示，其中：(Al2O3+Na2O)/P2O5为3.0～30.0，优选(Al2O3+Na2O)/P2O5 为4.0～20.0，更优选(Al2O3+Na2O)/P2O5为5.0～15.0，进一步优选(Al2O3+Na2O)/P2O5为6.0～10.0。(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.
(67)根据(63)～(66)任一所述的基质玻璃，其组分按重量百分比表示，其中：SiO2/Al2O3为1.2～2.8，优选SiO2/Al2O3为1.3～2.5，更优选SiO2/Al2O3为1.5～2.2，进一步优选SiO2/Al2O3为1.6～2.0。(67) The matrix glass according to any one of (63) to (66) , wherein the components are expressed in weight percentage, wherein: SiO2 / Al2O3 is 1.2 to 2.8, preferably SiO2 / Al2O3 is 1.3 to 2.5, more preferably SiO2 / Al2O3 is 1.5 to 2.2, and further preferably SiO2 / Al2O3 is 1.6 to 2.0 .
(68)根据(63)～(67)任一所述的基质玻璃，其组分按重量百分比表示，其中：SiO2/(Na2O+B2O3)为2.0～15.0，优选SiO2/(Na2O+B2O3)为3.0～10.0，更优选SiO2/(Na2O+B2O3)为4.0～8.0，进一步优选SiO2/(Na2O+B2O3)为5.0～7.0。(68) The matrix glass according to any one of (63) to ( 67 ), wherein the components are expressed in weight percentage, wherein: SiO2 /( Na2O + B2O3 ) is 2.0 to 15.0, preferably SiO2 /( Na2O + B2O3 ) is 3.0 to 10.0 , more preferably SiO2 /( Na2O +B2O3 ) is 4.0 to 8.0, and further preferably SiO2 /( Na2O + B2O3 ) is 5.0 to 7.0 .
(69)根据(63)～(68)任一所述的基质玻璃，其组分按重量百分比表示，其中：(Na2O+Li2O)/SiO2为0.1～0.8，优选(Na2O+Li2O)/SiO2为0.15～0.7，更优选(Na2O+Li2O)/SiO2为0.2～0.6，进一步优选(Na2O+Li2O)/SiO2为0.25～0.5。(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)根据(63)～(69)任一所述的基质玻璃，其组分按重量百分比表示，其中：(ZrO2+ZnO)/Na2O为2.0以下，优选(ZrO2+ZnO)/Na2O为1.5以下，更优选(ZrO2+ZnO)/Na2O为0.01～1.0，进一步优选(ZrO2+ZnO)/Na2O为0.1～0.5。(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.
(71)根据(63)～(70)任一所述的基质玻璃，其组分按重量百分比表示，其中：(P2O5+Na2O)/Li2O为0.5～8.0，优选(P2O5+Na2O)/Li2O为0.8～5.0，更优选(P2O5+Na2O)/Li2O为1.0～3.0，进一步优选(P2O5+Na2O)/Li2O为1.5～2.5。(71) The matrix glass according to any one of (63) to (70), wherein the components are expressed in weight percentage, wherein: (P 2 O 5 +Na 2 O)/Li 2 O is 0.5 to 8.0, preferably (P 2 O 5 +Na 2 O)/Li 2 O is 0.8 to 5.0, more preferably (P 2 O 5 +Na 2 O)/Li 2 O is 1.0 to 3.0, and further preferably (P 2 O 5 +Na 2 O)/Li 2 O is 1.5 to 2.5.
(72)根据(63)～(71)任一所述的基质玻璃，其组分按重量百分比表示，其中：K2O/ZrO2为0.1以上，优选K2O/ZrO2为0.2～10.0，更优选K2O/ZrO2为0.3～5.0，进一步优选K2O/ZrO2为0.4～1.5。(72) The matrix glass according to any one of (63) to (71), wherein the components are expressed in weight percentage, wherein: K2O / ZrO2 is greater than 0.1, preferably K2O / ZrO2 is 0.2 to 10.0, more preferably K2O / ZrO2 is 0.3 to 5.0, and further preferably K2O / ZrO2 is 0.4 to 1.5.
(73)根据(63)～(72)任一所述的基质玻璃，其组分按重量百分比表示，其中：(ZnO+RO+B2O3+TiO2)/P2O5为1.5以下，优选(ZnO+RO+B2O3+TiO2)/P2O5为1.0以下，更优选(ZnO+RO+B2O3+TiO2)/P2O5为0.5以下，进一步优 选(ZnO+RO+B2O3+TiO2)/P2O5为0.2以下，所述RO为MgO、CaO、SrO、BaO中的一种或多种。(73) The matrix glass according to any one of (63) to ( 72 ), wherein the components are expressed in weight percentage, wherein: (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 1.5 , preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 1.0, more preferably (ZnO+ RO + B2O3 + TiO2 )/ P2O5 is less than 0.5 , and further preferably (ZnO+RO+B 2 O 3 +TiO 2 )/P 2 O 5 is selected to be less than 0.2, and the RO is one or more of MgO, CaO, SrO, and BaO.
(74)根据(63)～(73)任一所述的基质玻璃，其组分按重量百分比表示，其中：SiO2：43～55％，优选SiO2：46～53％；和/或Al2O3：23～36％，优选Al2O3：25.5～32％；和/或Li2O：3～13％，优选Li2O：5.5～11％；和/或Na2O：5～15％，优选Na2O：6.5～12％；和/或P2O5+ZrO2：2～12％，优选P2O5+ZrO2：4～10％；和/或K2O：0～5％，优选K2O：0.1～3％；和/或ZnO：0～3％，优选ZnO：0～1％；和/或B2O3：0～3％，优选B2O3：0～1％；和/或RO：0～5％，优选RO：0～2％；和/或TiO2：0～3％，优选TiO2：0～1％；和/或Ln2O3：0～3％，优选Ln2O3：0～1％；和/或澄清剂：0～1％，优选澄清剂：0～0.5％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。(74) The matrix glass according to any one of (63) to (73), wherein the components are expressed in weight percentage, wherein: SiO2 : 43-55%, preferably SiO2 : 46-53%; and/or Al2O3 : 23-36 %, preferably Al2O3 : 25.5-32%; and/or Li2O : 3-13%, preferably Li2O : 5.5-11%; and/or Na2O : 5-15% , preferably Na2O : 6.5-12%; and/or P2O5 + ZrO2 : 2-12%, preferably P2O5 +ZrO2: 4-10 %; and/or K2O : 0-5 %, preferably K2O : 0.1-3%; and/or ZnO: 0-3%, preferably ZnO: 0-1%; and/or B2O3 : 0-3%, preferably B2 O 3 : 0-1%; and/or RO: 0-5%, preferably RO: 0-2%; and/or TiO 2 : 0-3%, preferably TiO 2 : 0-1%; and/or Ln 2 O 3 : 0-3%, preferably Ln 2 O 3 : 0-1%; and/or clarifier: 0-1%, preferably clarifier: 0-0.5%, wherein RO is one or more of MgO, CaO, SrO and BaO, and Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 and Y 2 O 3 .
(75)根据(63)～(74)任一所述的基质玻璃，其组分按重量百分比表示，其中：ZrO2：0～6％，优选ZrO2：0～5％，更优选ZrO2：0.1～3％；和/或P2O5：0～10％，优选P2O5：1～8％，更优选P2O5：2～6％。(75) The matrix glass according to any one of (63) to (74), wherein the components are expressed in weight percentage, wherein: ZrO 2 : 0-6%, preferably ZrO 2 : 0-5%, more preferably ZrO 2 : 0.1-3%; and/or P 2 O 5 : 0-10%, preferably P 2 O 5 : 1-8%, more preferably P 2 O 5 : 2-6%.
(76)根据(63)或(64)所述的基质玻璃，其组分按重量百分比表示，还含有：Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～5％，优选Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～2％，更优选Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～1％。(76) The matrix glass according to (63) or (64), wherein the components , expressed in weight percentage, further contain: Yb2O3 + Nb2O5 + WO3 + Bi2O3 +Ta2O5+TeO2+ GeO2 : 0-5 % , preferably Yb2O3 + Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2+GeO2: 0-2%, more preferably Yb2O3+Nb2O5+WO3 + Bi2O3 + Ta2O5 + TeO2 + GeO2 : 0-1 % .
(77)根据(63)～(65)任一所述的基质玻璃，其组分中不含有SrO；和/或不含有BaO；和/或不含有MgO；和/或不含有CaO；和/或不含有ZnO；和/或不含有PbO；和/或不含有As2O3；和/或不含有TiO2；和/或不含有B2O3；和/或不含有Y2O3；和/或不含有La2O3；和/或不含有Gd2O3。(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 .
(78)根据(63)或(64)所述的基质玻璃，其组分按重量百分比表示，还含有：NiO：0～4％；和/或Ni2O3：0～4％；和/或CoO：0～2％；和/或Co2O3：0～2％；和/或Fe2O3：0～7％；和/或MnO2：0～4％；和/或Er2O3：0～8％；和/或Nd2O3：0～8％；和/或Cu2O：0～4％；和/或Pr2O3：0～8％；和/或 CeO2：0～4％。(78) The matrix glass according to (63) or (64), wherein the components, expressed in weight percentage, further comprise: 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 3 : 0-8%; and/or CeO 2 : 0-4%.
(79)微晶玻璃成形体，含有(32)～(62)任一所述的微晶玻璃。(79) A microcrystalline glass molded body comprising the microcrystalline glass described in any one of (32) to (62).
(80)玻璃盖板，含有(1)～(31)任一所述的微晶玻璃制品，和/或(32)～(62)任一所述的微晶玻璃，和/或(63)～(78)任一所述的基质玻璃，和/或(79)所述的微晶玻璃成形体。(80) 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).
(81)玻璃元器件，含有(1)～(31)任一所述的微晶玻璃制品，和/或(32)～(62)任一所述的微晶玻璃，和/或(63)～(78)任一所述的基质玻璃，和/或(79)所述的微晶玻璃成形体。(81) 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).
(82)显示设备，含有(1)～(31)任一所述的微晶玻璃制品，和/或(32)～(62)任一所述的微晶玻璃，和/或(63)～(78)任一所述的基质玻璃，和/或(79)所述的微晶玻璃成形体，和/或(80)所述的玻璃盖板，和/或(81)所述的玻璃元器件。(82) 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).
(83)电子设备，含有(1)～(31)任一所述的微晶玻璃制品，和/或(32)～(62)任一所述的微晶玻璃，和/或(63)～(78)任一所述的基质玻璃，和/或(79)所述的微晶玻璃成形体，和/或(80)所述的玻璃盖板，和/或(81)所述的玻璃元器件。(83) 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).
(84)根据(1)～(31)任一所述微晶玻璃制品的制造方法，所述方法包括以下步骤：形成基质玻璃，将基质玻璃通过晶化工艺形成微晶玻璃，再将所述微晶玻璃通过化学强化工艺形成微晶玻璃制品。(84) According to any one of the methods for manufacturing microcrystalline glass products described in (1) to (31), 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.
(85)根据(84)所述的微晶玻璃制品的制造方法，所述晶化工艺包括以下步骤：升温至规定的晶化处理温度，在达到晶化处理温度之后，将其温度保持一定的时间，然后再进行降温，该晶化处理温度为580～750℃，优选为600～700℃，在晶化处理温度下的保持时间为0～8小时，优选为1～6小时。(85) According to the method for manufacturing microcrystalline glass products described in (84), 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.
(86)根据(84)所述的微晶玻璃制品的制造方法，所述晶化工艺包括以下步骤：在第1温度下进行成核工艺的处理，然后在比成核工艺温度高的第2温度下进行晶体生长工艺的处理。 (86) According to the method for manufacturing a microcrystalline glass product described in (84), 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.
(87)根据(86)所述的微晶玻璃制品的制造方法，所述晶化工艺包括以下步骤：第1温度为500～620℃，第2温度为620～750℃；在第1温度下的保持时间为0～24小时，优选为2～15小时；在第2温度下的保持时间为0～10小时，优选为0.5～6小时。(87) According to the method for manufacturing microcrystalline glass products described in (86), 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.
(88)根据(84)～(87)任一所述的微晶玻璃制品的制造方法，所述化学强化工艺包括：微晶玻璃浸没于350～470℃的温度的熔融Na盐的盐浴中1～36小时，优选温度范围为380～460℃，优选时间范围为2～10小时；和/或微晶玻璃浸没于360～450℃的温度下熔融K盐的盐浴中1～36小时，优选时间范围为1～10小时；和/或微晶玻璃浸没于360～450℃的温度下熔融K盐和Na盐的混合盐浴中1～36小时，优选时间范围为2～24小时。(88) According to the method for manufacturing microcrystalline glass products described in any one of (84) to (87), 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.
(89)根据(32)～(62)任一所述的微晶玻璃的制造方法，所述方法包括以下步骤：形成基质玻璃，然后将基质玻璃通过晶化工艺形成微晶玻璃。(89) A method for manufacturing glass-ceramics according to any one of (32) to (62), comprising the steps of forming a matrix glass and then subjecting the matrix glass to a crystallization process to form glass-ceramics.
(90)根据(89)所述的微晶玻璃的制造方法，所述晶化工艺包括以下步骤：升温至规定的晶化处理温度，在达到晶化处理温度之后，将其温度保持一定的时间，然后再进行降温，该晶化处理温度为580～750℃，优选为600～700℃，在晶化处理温度下的保持时间为0～8小时，优选为1～6小时。(90) According to the method for manufacturing microcrystalline glass described in (89), 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.
(91)根据(89)所述的微晶玻璃的制造方法，所述晶化工艺包括以下步骤：在第1温度下进行成核工艺的处理，然后在比成核工艺温度高的第2温度下进行晶体生长工艺的处理。(91) According to the method for manufacturing microcrystalline glass described in (89), 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.
(92)根据(91)所述的微晶玻璃的制造方法，所述晶化工艺包括以下步骤：第1温度为500～620℃，第2温度为620～750℃；在第1温度下的保持时间为0～24小时，优选为2～15小时；在第2温度下的保持时间为0～10小时，优选为0.5～6小时。(92) According to the method for manufacturing microcrystalline glass described in (91), 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.
(93)根据(79)所述的微晶玻璃成形体的制造方法，所述方法包括 将微晶玻璃研磨或抛光制成微晶玻璃成形体，或在一定温度下将基质玻璃或微晶玻璃通过热弯工艺或压型工艺制成微晶玻璃成形体。(93) A method for manufacturing a glass-ceramic molded body according to (79), the method comprising: The glass-ceramics is ground or polished to form a glass-ceramics molded body, or the matrix glass or glass-ceramics is subjected to a heat bending process or a pressing process at a certain temperature to form a glass-ceramics molded body.
(94)根据(79)所述的微晶玻璃成形体的制造方法，所述方法包括以下步骤：将基质玻璃进行一次晶化热处理过程，包括升温、保温核化、升温、保温晶化、降温至室温，形成预晶化玻璃；将预晶化玻璃进行热加工成型得到微晶玻璃成形体。(94) According to the method for manufacturing a microcrystalline glass molded body described in (79), 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.
(95)根据(79)所述的微晶玻璃成形体的制造方法，所述方法包括以下步骤：(95) The method for producing a glass-ceramic formed body according to (79), the method comprising the following steps:
1)升温预热：将基质玻璃或预晶化玻璃或微晶玻璃放置于模具内，模具在热弯机中依次通过各个升温站点，并在各站点停留一定时间保温，预热区温度为400～800℃，压力为0.01～0.05MPa，时间为40～200s；1) 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;
2)加压成型：模具在经过预热后转运到成型站点，热弯机对模具施加一定压力，压力范围为0.1～0.8Mpa，成型站点温度范围为650～850℃，成型时间范围40～200s；2) Pressurized molding: After preheating, the mold is transferred to the molding station. The hot bending machine applies a certain pressure to the mold. The pressure range is 0.1-0.8Mpa. The temperature range of the molding station is 650-850℃, and the molding time range is 40-200s.
3)保压降温：将模具转运至降温站点逐站降温，降温温度范围750～500℃，压力为0.01～0.05Mpa，时间为40～200s。3) Maintaining pressure and cooling: 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, and the time is 40-200s.
本发明的有益效果是：通过合理的组分设计，本发明获得的微晶玻璃或微晶玻璃制品具有优异的机械性能，满足显示设备或电子设备等领域的应用。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.
具体实施方式Detailed ways
本发明的微晶玻璃和微晶玻璃制品是具有晶相(有时候也称为晶体)和玻璃相的材料，其有别于非晶质固体。微晶玻璃和微晶玻璃制品的晶相可以通过X射线衍射分析的X射线衍射图案中出现的峰值角度进行辨别和/或通过TEMEDX测得。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.
本发明的发明人经过反复试验和研究，对于构成微晶玻璃和微晶玻璃制品的特定成分，通过将其含量以及含量比例规定为特定值并使其析出特定的晶相，得到了本发明的微晶玻璃或微晶玻璃制品。 After repeated experiments and studies, 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.
下面，对本发明基质玻璃、微晶玻璃及微晶玻璃制品的各组分(成分)的范围进行说明。在本说明书中，如果没有特殊说明，各组分的含量全部采用相对于换算成氧化物的组成的基质玻璃、或微晶玻璃、或微晶玻璃制品物质总量的重量百分比(wt％)表示。在这里，所述“换算成氧化物的组成”是指，作为本发明的基质玻璃、微晶玻璃或微晶玻璃制品组成成分的原料而使用的氧化物、复合盐及氢氧化物等熔融时分解并转变为氧化物的情况下，将该氧化物的物质总重量作为100％。此外，在本说明书中仅称为玻璃时为结晶化(即晶化工艺处理)前的基质玻璃，基质玻璃结晶化(即晶化工艺处理)后称为微晶玻璃，微晶玻璃制品是指微晶玻璃经化学强化后得到的产品。Next, the scope of each component (ingredient) of the matrix glass, microcrystalline glass and microcrystalline glass products of the present invention is described. In this specification, unless otherwise specified, 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. Here, 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%. In addition, in this specification, when it is only referred to as glass, it is the matrix glass before crystallization (i.e., crystallization process treatment), the matrix glass after crystallization (i.e., crystallization process treatment) is called microcrystalline glass, and microcrystalline glass products refer to products obtained after chemical strengthening of microcrystalline glass.
除非在具体情况下另外指出，本文所列出的数值范围包括上限和下限值，“以上”和“以下”包括端点值，以及在该范围内的所有整数和分数，而不限于所限定范围时所列的具体值。本文所使用的术语“约”指配方、参数和其他数量以及特征不是、且无需是精确的，如有需要，可以近似和/或更大或更低，这反映公差、换算因子和测量误差等。本文所称“和/或”是包含性的，例如“A；和/或B”，是指只有A，或者只有B，或者同时有A和B。Unless otherwise indicated in specific cases, the numerical ranges listed herein include upper and lower limits, and "above" and "below" include the endpoints, as well as all integers and fractions within the range, without limitation to the specific values listed when defining the range. The term "about" as used herein means that the formula, parameters and other quantities and features are not and need not be exact, and may be approximate and/or larger or lower if necessary, reflecting tolerances, conversion factors and measurement errors, etc. "And/or" as used herein is inclusive, for example, "A; and/or B" means only A, or only B, or both A and B.
在一些实施方式中，本发明微晶玻璃或微晶玻璃制品的晶相含有霞石晶相(包含锂霞石和/或钠霞石)，具体而言，含有锂霞石、或含有钠霞石、或同时含有锂霞石和钠霞石。本发明微晶玻璃还可以存在除霞石晶相以外的其他晶相，如硅酸锂晶相(一硅酸锂和二硅酸锂中的一种或两种)；和/或磷酸锂晶相；和/或透锂长石晶相；和/或石英晶相。In some embodiments, 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.
在本发明的一些实施方式中，微晶玻璃或微晶玻璃制品中的晶相只含有霞石晶相(锂霞石和钠霞石中的一种或两种)。In some embodiments of the present invention, the crystal phase in the glass-ceramic or glass-ceramic products contains only nepheline crystal phase (one or both of eucryptite and sodium nepheline).
在一些实施方式中，微晶玻璃或微晶玻璃制品中含有霞石晶相和其他晶相的情况下，微晶玻璃或微晶玻璃制品的主要晶相为霞石晶相，即霞石晶相具有比其他晶相更高的重量百分比。 In some embodiments, when the microcrystalline glass or microcrystalline glass products contain nepheline crystal phase and other crystal phases, 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.
在一些实施方式中，霞石晶相占微晶玻璃或微晶玻璃制品的重量百分比为10～80％，优选霞石晶相占微晶玻璃或微晶玻璃制品的重量百分比为20～70％，更优选霞石晶相占微晶玻璃或微晶玻璃制品的重量百分比为30～60％。在一些实施方式中，霞石晶相占微晶玻璃或微晶玻璃制品的重量百分比约为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％。In some embodiments, 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%. In some embodiments, 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%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, 101%, 10 1%, 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%.
SiO2是本发明的基质玻璃、微晶玻璃和微晶玻璃制品的基础组分，可用于稳定玻璃和微晶玻璃的网络结构，其是结晶化后形成霞石晶相的组分之一，如果SiO2的含量在40％以下，在微晶玻璃中形成晶体会变少并且晶体容易变粗，影响微晶玻璃和微晶玻璃制品的雾度，以及微晶玻璃制品的落球试验高度等性能。因此，SiO2含量的下限为40％，优选下限为43％，更优选下限为46％。如果SiO2的含量超过60％，玻璃熔化温度较高，澄清困难，并且不容易成型，影响玻璃的一致性，且影响玻璃和微晶玻璃的热弯，并且对微晶玻璃制品的表面应力和离子交换层深度不利。因此，SiO2含量的上限为60％，优选上限为55％，更优选上限为53％。在一些实施方式中，可包含约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％的SiO2。 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%. If the content of SiO2 exceeds 60%, the glass melting temperature is high, clarification is difficult, and it is not easy to form, which affects the consistency of the glass, and affects the hot bending of glass and glass-ceramics, and is unfavorable to the surface stress and ion exchange layer depth of the glass-ceramics products. Therefore, the upper limit of the SiO2 content is 60%, preferably 55%, and more preferably 53%. In some embodiments, 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是形成玻璃网状结构的组分，其是有助于稳定玻璃成型、提高化学稳定性的重要成分，还可改善玻璃的机械性能，增加微晶玻璃制品离子交换层深度和表面应力。但Al2O3含量过高，玻璃的熔融性与耐失透性降低，并且晶化时晶体容易增大，降低微晶玻璃和微晶玻璃制品的强度。因此， 本发明中Al2O3的含量为20～40％，优选为23～36％，更优选为25.5～32％。在一些实施方式中，可包含约20％、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％、32.5％、33％、33.5％、34％、34.5％、35％、35.5％、36％、36.5％、37％、37.5％、38％、38.5％、39％、39.5％、40％的Al2O3。 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%. In some embodiments, about 20%, 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%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%, 36.5%, 37%, 37.5%, 38%, 38.5%, 39%, 39.5%, 40% Al2O3 may be included .
在一些实施方式中，将SiO2的含量与Al2O3的含量之间的比值SiO2/Al2O3控制在1.2～2.8范围内，可提高微晶玻璃和微晶玻璃制品的四点弯曲强度，提高微晶玻璃和微晶玻璃制品的光透过率。因此，优选SiO2/Al2O3为1.2～2.8，更优选SiO2/Al2O3为1.3～2.5。进一步的，控制SiO2/Al2O3在1.5～2.2范围内，还可进一步降低微晶玻璃和微晶玻璃制品的∣B∣值，提高微晶玻璃制品的表面应力。因此，进一步优选SiO2/Al2O3为1.5～2.2，更进一步优选SiO2/Al2O3为1.6～2.0。在一些实施方式中，SiO2/Al2O3的值可为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。In some embodiments, 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. Further, by controlling SiO 2 /Al 2 O 3 within the range of 1.5 to 2.2, the |B| value of glass-ceramics and glass-ceramics products can be further reduced, and the surface stress of glass-ceramics products can be increased. Therefore, 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. In some embodiments, 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可促进玻璃的熔化，降低玻璃的熔炼温度，可通过晶化后形成锂霞石晶相，也是化学强化过程中主要与钠、钾离子进行置换的组分，可增大微晶玻璃制品的表面应力，有助于提升微晶玻璃制品的落球试验高度，并且可增加微晶玻璃和微晶玻璃制品的介电常数。另一方面，如果过多地含有Li2O，则很容易使玻璃的化学稳定性降低，且会使微晶玻璃和微晶玻璃制品的光透射率劣化。因此，本发明中Li2O的含量为2～15％，优选为3～13％，更优选为5.5～11％。在一些实施方式中，可包含约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％的Li2O。 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%. In some embodiments, 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.
Na2O可通过晶化后参与析晶形成钠霞石晶相，也可以参与化学强化，并且可以提高玻璃的熔融性。另一方面，如果Na2O的含量过高，则容易导 致晶化过程中析出晶粒增大或析出的晶相种类发生变化。因此，本发明中Na2O的含量为3～20％，优选为5～15％，更优选为6.5～12％。在一些实施方式中，可包含约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％的Na2O。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. On the other hand, if 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%. In some embodiments, 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.
在一些实施方式中，将Na2O和Li2O的合计含量Na2O+Li2O与SiO2的含量之间的比值(Na2O+Li2O)/SiO2控制在0.1～0.8范围内，有利于微晶玻璃和微晶玻璃制品得到期望的晶相含量，同时细化晶粒，提高微晶玻璃和微晶玻璃制品的硬度。因此，优选(Na2O+Li2O)/SiO2为0.1～0.8，更优选(Na2O+Li2O)/SiO2为0.15～0.7。进一步的，控制(Na2O+Li2O)/SiO2在0.2～0.6范围内，还可进一步提高微晶玻璃和微晶玻璃制品的光透过率，并优化雾度。因此，进一步优选(Na2O+Li2O)/SiO2为0.2～0.6，更进一步优选(Na2O+Li2O)/SiO2为0.25～0.5。在一些实施方式中，(Na2O+Li2O)/SiO2的值可为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。In some embodiments, 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. Furthermore, 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是有助于提高玻璃的低温熔融性与成形性的可选组分，但如果过多地含有K2O，则很容易产生玻璃化学稳定性的降低。因此，K2O的含量为0～8％，优选为0～5％，更优选为0.1～3％。在一些实施方式中，可包含约0％、大于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％的K2O。 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能够在玻璃中形成晶核，促进晶体均匀生长，并且有助于提高玻璃的低温熔化性；但如果过多地含有P2O5，则很容易使玻璃产生耐失透性降低及玻璃分相，且微晶玻璃和微晶玻璃制品的机械性能有劣化的趋势。因此，本发明中P2O5的含量为0～10％，优选为1～8％，更优选为2～6％。在一些实施方式中，可包含约0％、大于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％的P2O5。 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%. In some embodiments, 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 .
在一些实施方式中，将Al2O3和Na2O的合计含量Al2O3+Na2O与P2O5的含量之间的比值(Al2O3+Na2O)/P2O5控制在3.0～30.0范围内，有利于微晶玻璃和微晶玻璃制品获得期望的晶相含量，并提高微晶玻璃和微晶玻璃制品的维氏硬度，提高落球试验高度。因此，优选(Al2O3+Na2O)/P2O5为3.0～30.0，更优选(Al2O3+Na2O)/P2O5为4.0～20.0。进一步的，控制(Al2O3+Na2O)/P2O5在5.0～15.0范围内，还可进一步优化微晶玻璃和微晶玻璃制品的四点弯曲强度，提高微晶玻璃制品的离子交换层深度。因此，进一步优选(Al2O3+Na2O)/P2O5为5.0～15.0，更进一步优选(Al2O3+Na2O)/P2O5为6.0～10.0。在一些实施方式中，(Al2O3+Na2O)/P2O5的值可为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。In some embodiments, 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. Furthermore, by controlling (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. In some embodiments, 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.
在一些实施方式中，将P2O5和Na2O的合计含量P2O5+Na2O与Li2O的含量之间的比值(P2O5+Na2O)/Li2O控制在0.5～8.0范围内，有利于提高微晶玻璃和微晶玻璃制品的落球试验高度，提高微晶玻璃制品的离子交换层深度。因此，优选(P2O5+Na2O)/Li2O为0.5～8.0，更优选(P2O5+Na2O)/Li2O为0.8～5.0。进一步的，控制(P2O5+Na2O)/Li2O在1.0～3.0范围内，还可进一步优化微晶玻璃和微晶玻璃制品的硬度和∣B∣值。因此，进一步优选(P2O5+Na2O)/Li2O为1.0～3.0，更进一步优选(P2O5+Na2O)/Li2O为1.5～2.5。在一些实施方式中，(P2O5+Na2O)/Li2O的值可为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。In some embodiments, 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. Furthermore, controlling (P2O5 + Na2O)/Li2O within the range of 1.0 to 3.0 can further optimize the hardness and | B | value of the microcrystalline glass and microcrystalline glass products. Therefore, (P 2 O 5 +Na 2 O)/Li 2 O is more preferably 1.0 to 3.0, and (P 2 O 5 +Na 2 O)/Li 2 O is still more preferably 1.5 to 2.5. In some embodiments, 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具有结晶析出形成晶核的作用，同时有助于提高玻璃的化学稳定 性，研究发现，ZrO2还可通过在熔制过程中显著降低玻璃失透以及降低液相线温度，来提高玻璃的稳定性；但如果过多地含有ZrO2，则玻璃的耐失透性容易降低，同时玻璃晶化过程控制难度增加，因此，ZrO2的含量为0～6％，优选为0～5％，更优选为0.1～3％。在一些实施方式中，可包含约0％、大于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％的ZrO2。 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%. 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% ZrO 2 may be included.
在一些实施方式中，将K2O的含量与ZrO2的含量之间的比值K2O/ZrO2控制在0.1以上，有利于细化晶粒，降低微晶玻璃和微晶玻璃制品的雾度和晶粒尺寸。因此，优选K2O/ZrO2为0.1以上，更优选K2O/ZrO2为0.2～10.0。进一步的，控制K2O/ZrO2在0.3～5.0范围内，还可进一步优化微晶玻璃和微晶玻璃制品的光透过率，防止微晶玻璃制品的离子交换层深度变差。因此，进一步优选K2O/ZrO2为0.3～5.0，更进一步优选K2O/ZrO2为0.4～1.5。在一些实施方式中，K2O/ZrO2的值可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、4.8、4.9、5.0、5.5、6.0、6.5、7.0、7.5、8.0、8.5、9.0、9.5、10.0。In some embodiments, 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. Therefore, it is further preferred that 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. In some embodiments, 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, 4.8, 4.9, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0.
在一些实施方式中，将P2O5和ZrO2的合计含量P2O5+ZrO2控制在1～15％范围内，有利于细化晶粒，降低微晶玻璃和微晶玻璃制品的晶粒尺寸，同时降低微晶玻璃和微晶玻璃制品的∣B∣值，提高微晶玻璃和微晶玻璃制品的光透过率。因此，优选P2O5+ZrO2为1～15％，更优选P2O5+ZrO2为2～12％，进一步优选P2O5+ZrO2为4～10％。在一些实施方式中，P2O5+ZrO2可为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％。 In some embodiments, 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 |B| value of microcrystalline glass and microcrystalline glass products, and improving the light transmittance of microcrystalline glass and microcrystalline glass products. Therefore, preferably, P2O5 + ZrO2 is 1 to 15%, more preferably , P2O5 + ZrO2 is 2 to 12%, and further preferably , P2O5 + ZrO2 is 4 to 10%. In some embodiments, 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%.
ZnO可提高玻璃的熔化性能，改善玻璃的化学稳定性，晶化时细化晶粒，将ZnO含量的上限控制在6％以下，还可以抑制耐失透性降低。因此，ZnO含量为0～6％，优选为0～3％，更优选为0～1％。在一些实施方式中，可包含约0％、大于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％的ZnO。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.
在一些实施方式中，将ZrO2和ZnO的合计含量ZrO2+ZnO与Na2O的含量之间的比值(ZrO2+ZnO)/Na2O控制在2.0以下，有利于降低微晶玻璃和微晶玻璃制品的雾度和晶粒尺寸，提高微晶玻璃和微晶玻璃制品的落球试验高度。因此，优选(ZrO2+ZnO)/Na2O为2.0以下，更优选(ZrO2+ZnO)/Na2O为1.5以下，进一步优选(ZrO2+ZnO)/Na2O为0.01～1.0，更进一步优选(ZrO2+ZnO)/Na2O为0.1～0.5。在一些实施方式中，(ZrO2+ZnO)/Na2O的值可为0、大于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。In some embodiments, 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. Therefore, it is preferred that ( 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. In some embodiments, 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可以改善玻璃的网络结构，调整微晶玻璃的化学强化性能，若其含量过多，则不利于玻璃成型，在成型时容易析晶，且化学稳定性降低。因此B2O3的含量为0～6％，优选为0～3％，更优选为0～1％。在一些实施方式中，可包含约0％、大于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％的B2O3。 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 .
在一些实施方式中，将SiO2的含量与Na2O和B2O3的合计含量Na2O+B2O3之间的比值SiO2/(Na2O+B2O3)控制在2.0～15.0范围内，有利于提高微晶玻璃制品的离子交换层深度，提高微晶玻璃和微晶玻璃制品的四点弯曲强度。因此，优选SiO2/(Na2O+B2O3)为2.0～15.0，更优选SiO2/(Na2O+B2O3)为3.0～10.0。进一步的，控制SiO2/(Na2O+B2O3)在4.0～8.0范围内，还可进一步优化微晶玻璃制品的表面应力，提高微晶玻璃和微晶玻璃制品的落球试验高度。因此，进一步优选SiO2/(Na2O+B2O3)为4.0～8.0，更进一步优选SiO2/ (Na2O+B2O3)为5.0～7.0。在一些实施方式中，SiO2/(Na2O+B2O3)的值可为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。In some embodiments, 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. Furthermore, 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. In some embodiments, 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 .
碱土金属氧化物RO(RO为MgO、CaO、SrO、BaO中的一种或多种)有助于提高玻璃的耐失透性，增强玻璃的强度；但其含量高时，玻璃的晶化性能降低，不利于微晶玻璃得到期望的晶相种类及晶粒尺寸。因此，RO的含量为0～8％，优选为0～5％，更优选为0～2％。在一些实施方式中，可包含约0％、大于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％的RO。Alkaline earth metal oxides RO (RO is one or more of MgO, CaO, SrO, BaO) help to improve the devitrification resistance of glass and enhance the strength of glass; but when its content is high, the crystallization performance of glass is reduced, which is not conducive to obtaining the desired crystal phase type and grain size of microcrystalline glass. Therefore, the content of RO is 0-8%, preferably 0-5%, and more preferably 0-2%. 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% RO may be included.
TiO2是一种有助于降低玻璃的熔化温度、提高化学稳定性的可选组分，本发明中含有5％以下的TiO2，可以使玻璃的晶化过程变得容易控制，优选TiO2的含量为3％以下，更优选为1％以下。在一些实施方式中，进一步优选不含有TiO2。在一些实施方式中，可包含约0％、大于0％、0.01％、0.05％、0.1％、0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％的TiO2。 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. Preferably, 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.
在一些实施方式中，将ZnO、RO、B2O3、TiO2的合计含量ZnO+RO+B2O3+TiO2与P2O5的含量之间的比值(ZnO+RO+B2O3+TiO2)/P2O5控制在1.5以下，有利于降低微晶玻璃和微晶玻璃制品的雾度，提高光透过率，提高微晶玻璃制品的表面应力。因此，优选(ZnO+RO+B2O3+TiO2)/P2O5为1.5以下，更优选(ZnO+RO+B2O3+TiO2)/P2O5为1.0以下，进一步优选(ZnO+RO+B2O3+TiO2)/P2O5为0.5以下，更进一步优选(ZnO+RO+B2O3+TiO2)/P2O5为0.2以下。在一些实施方式中，(ZnO+RO+B2O3+TiO2)/P2O5的值可为0、大于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。In some embodiments, 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. Therefore, (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 . In some embodiments, 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.
Ln2O3(Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种)可降低玻璃的熔炼难度，含量过多时会导致玻璃晶化时形成晶体困难，微晶玻璃和微晶玻璃制 品的落球试验高度下降。因此，Ln2O3含量的上限为5％，优选上限为3％，更优选上限为1％。在一些实施方式中，可包含约0％、大于0％、0.01％、0.05％、0.1％、0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％的Ln2O3。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.
在一些实施方式中,基质玻璃、微晶玻璃或微晶玻璃制品还可含有0～2％的澄清剂，以提高基质玻璃、微晶玻璃或微晶玻璃制品的除泡能力，这种澄清剂包括但不限于Sb2O3、SnO2、SnO、F(氟)、Cl(氯)和Br(溴)中的一种或多种，优选Sb2O3、SnO2作为澄清剂，更优选Sb2O3作为澄清剂。上述澄清剂单独或组合存在时，其含量的上限优选为1％，更优选上限为0.5％。在一些实施方式中，上述澄清剂中的一种或多种的含量约为0％、大于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％。In some embodiments, 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. When the above clarifiers exist alone or in combination, the upper limit of their content is preferably 1%, and more preferably 0.5%. In some embodiments, 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%.
在不影响本发明基质玻璃、微晶玻璃或微晶玻璃制品的性能的情况下，可以适当含有上述未提及的其他组分，如Yb2O3、Nb2O5、WO3、Bi2O3、Ta2O5、TeO2、GeO2等，但为维持本发明基质玻璃、微晶玻璃或微晶玻璃制品的优异性能，优选Yb2O3、Nb2O5、WO3、Bi2O3、Ta2O5、TeO2、GeO2的各自含量或合计含量为5％以下，更优选为2％以下，进一步优选为1％以下，更进一步优选不含有。Without affecting the performance of the matrix glass, glass-ceramics or glass-ceramics products of the present invention, 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. However, in order to maintain the excellent performance of the matrix glass, glass-ceramics or glass-ceramics products of the present invention, 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和As2O3是有毒物质，即使少量的含有也不符合环保的要求，因此本发明在一些实施方式中优选不含有PbO和As2O3。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.
本发明的一些实施方式中，通过含有着色剂，可以制备出具有颜色的基质玻璃、微晶玻璃或微晶玻璃制品，可使基质玻璃、微晶玻璃或微晶玻璃制品呈现不同的颜色，优选着色剂含有：NiO：0～4％；和/或Ni2O3：0～4％；和/或CoO：0～2％；和/或Co2O3：0～2％；和/或Fe2O3：0～7％；和/或MnO2：0～4％；和/或Er2O3：0～8％；和/或Nd2O3：0～8％；和/或Cu2O：0～4％；和/或Pr2O5：0～8％；和/或CeO2：0～4％。其着色剂重量百分比含量及其作用详述如下：In some embodiments of the present invention, by containing a colorant, a matrix glass, a microcrystalline glass or a microcrystalline glass product with color can be prepared, and the matrix glass, the microcrystalline glass or the microcrystalline glass product can present different colors. Preferably, 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:
本发明制备的褐色或绿色基质玻璃、微晶玻璃或微晶玻璃制品，使用 NiO、Ni2O3或Pr2O5为着色剂。NiO和Ni2O3为着色剂，用于制备褐色或绿色基质玻璃、微晶玻璃或微晶玻璃制品，两种组分可以单独使用或者混合使用，其分别含量一般为4％以下，优选为3％以下，如果含量超过4％，着色剂不能很好溶于基质玻璃、微晶玻璃或微晶玻璃制品中，其分别的含量下限在0.1％以上，如低于0.1％，基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显。在一些实施方式中，可包含约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 brown or green matrix glass, glass-ceramic or glass-ceramic product prepared by the present invention is used 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. In some embodiments, 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%,
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％的NiO或Ni2O3。如混合使用时，NiO和Ni2O3合计量一般为4％以下，合计量下限在0.1％以上。在一些实施方式中，可包含约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％的NiO和Ni2O3。使用Pr2O5作为绿色基质玻璃、微晶玻璃或微晶玻璃制品着色剂，单独使用，一般含量为8％以下，优选含量为6％以下，其含量下限在0.4％以上，如低于0.4％，基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显。在一些实施方式中，可包含约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％的Pr2O5。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% NiO or Ni 2 O 3. When used in combination, 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%. In some embodiments, 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% 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 lower limit of the content is above 0.4%. If it is below 0.4%, the color of the matrix glass, microcrystalline glass or microcrystalline glass products is not obvious. In some embodiments, 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 % Pr2O5 may be included.
本发明制备的蓝色基质玻璃、微晶玻璃或微晶玻璃制品，使用CoO或Co2O3为着色剂，两种着色剂组分可以单独使用或者混合使用，其分别的含量都一般为2％以下，优选为1.8％以下，如果含量超过了2％，着色剂不能很好溶于基质玻璃、微晶玻璃或微晶玻璃制品中，其分别的含量下限在0.05％以上，如低于0.05％，基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显。 在一些实施方式中，可包含约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％的CoO或Co2O3。如混合使用时，CoO和Co2O3合计量不超过2％，合计量下限在0.05％以上。在一些实施方式中，可包含约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％的CoO和Co2O3。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. In some embodiments, 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. When used in combination, 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%. In some embodiments, 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.
本发明制备的黄色基质玻璃、微晶玻璃或微晶玻璃制品，使用Cu2O或CeO2为着色剂，两种着色剂组分单独使用或者混合使用，其分别的含量下限在0.5％以上，如低于0.5％，基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显，单独使用Cu2O为4％以下，优选为3％以下，如果含量超过4％，容易使基质玻璃析晶。在一些实施方式中，可包含约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％的Cu2O。单独使用CeO2含量一般为4％以下，优选为3％以下，如含量超过4％，基质玻璃、微晶玻璃或微晶玻璃制品光泽不好。在一些实施方式中，可包含约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％的CeO2。如果两种着色剂混合使用时，其合计量一般为4％以下，合计量下限在0.5％以上。在一些实施方式中，可包含约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％的CeO2和Cu2O。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. In some embodiments, 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. In some embodiments, 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%. In some embodiments, 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% CeO2 and Cu2O may be included.
本发明制备的黑色或烟灰色基质玻璃、微晶玻璃或微晶玻璃制品，单独使用Fe2O3为着色剂；或者使用Fe2O3和CoO两种混合使用的着色剂；或 者使用Fe2O3和Co2O3两种混合使用的着色剂；或者使用Fe2O3、CoO和NiO三种混合使用的着色剂；或者使用Fe2O3、Co2O3和NiO三种混合使用的着色剂。制备黑色和烟灰色基质玻璃、微晶玻璃或微晶玻璃制品的着色剂主要使用Fe2O3着色，含量为7％以下，优选为5％以下，其含量下限在0.2％以上，在一些实施方式中，可包含约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％的Fe2O3。CoO和Co2O3在可见光有吸收，可以加深基质玻璃、微晶玻璃或微晶玻璃制品的着色程度，一般与Fe2O3混合使用时各自的含量为0.6％以下，下限在0.2％以上。在一些实施方式中，可包含约0.2％、0.3％、0.4％、0.5％、0.6％的CoO和/或Co2O3。NiO在可见光有吸收，可以加深基质玻璃、微晶玻璃或微晶玻璃制品的着色程度，一般混合使用时其含量为1％以下，合计量下限在0.2％以上。在一些实施方式中，可包含约0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1.0％的NiO。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%. In some embodiments, 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. Generally, when mixed with Fe 2 O 3, their respective contents are less than 0.6%, and the lower limit is more than 0.2%. In some embodiments, CoO and/or Co 2 O 3 can be included in an amount of about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%. NiO absorbs visible light and can deepen the coloring of the matrix glass, glass-ceramics or glass-ceramics products. Generally, when mixed, its content is less than 1%, and the lower limit of the total amount is more than 0.2%. In some embodiments, 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%.
本发明制备的紫色基质玻璃、微晶玻璃或微晶玻璃制品，使用MnO2为着色剂，使用含量一般为4％以下，优选在3％以下，其含量下限在0.1％以上，如低于0.1％，基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显。在一些实施方式中，可包含约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％的MnO2。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. In some embodiments, 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.
本发明制备的粉色基质玻璃、微晶玻璃或微晶玻璃制品，使用Er2O3为着色剂，使用含量一般为8％以下，优选在6％以下。由于稀土元素Er2O3着色效率低，当使用含量超过8％，也不能使基质玻璃、微晶玻璃或微晶玻璃制品的颜色进一步的加深，反而增加成本，其含量下限在0.4％以上，如低于 0.4％，基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显。在一些实施方式中，可包含约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％的Er2O3。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. In some embodiments, 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 %.
本发明制备的紫红色基质玻璃、微晶玻璃或微晶玻璃制品，使用Nd2O3为着色剂，使用含量一般为8％以下，优选在6％以下。由于稀土元素Nd2O3着色效率低，使用含量超过了8％，也不能使基质玻璃、微晶玻璃或微晶玻璃制品的颜色进一步的加深，反而增加成本，其含量下限在0.4％以上，如低于0.4％，基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显。在一些实施方式中，可包含约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％的Nd2O3。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. In some embodiments, 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.
本发明制备的红色基质玻璃、微晶玻璃或微晶玻璃制品，使用Er2O3、Nd2O3和MnO2混合着色剂，玻璃中Er离子在400-500nm有吸收，Mn离子主要在500nm处有吸收，Nd离子主要在580nm处有强的吸收，三种物质的混合，可以制备红色基质玻璃、微晶玻璃或微晶玻璃制品，由于Er2O3和Nd2O3为稀土着色，着色能力比较弱，Er2O3使用量在6％以内，Nd2O3使用量在4％以内，MnO2着色强，使用量在2％范围内，其使用混合着色剂合计量的下限在0.9％以上。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, and 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%, and 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%.
本文所记载的“不含有”“0％”是指没有故意将该化合物、分子或元素等作为原料添加到本发明基质玻璃、微晶玻璃或微晶玻璃制品中；但作为生产基质玻璃、微晶玻璃或微晶玻璃制品的原材料和/或设备，会存在某些不是故意添加的杂质或组分，会在最终的基质玻璃、微晶玻璃或微晶玻璃制品中少量或痕量含有，此种情形也在本发明专利的保护范围内。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.
本发明的一些实施方式中，微晶玻璃和微晶玻璃制品中晶相含有霞石 晶相，为本发明微晶玻璃和微晶玻璃制品提供高的强度，微晶玻璃和微晶玻璃制品的落球试验高度和四点弯曲强度变大。在一些实施方式中，微晶玻璃或微晶玻璃制品含有锂霞石晶相，在一些实施方式中，微晶玻璃或微晶玻璃制品含有钠霞石晶相，在一些实施方式中，微晶玻璃或微晶玻璃制品同时含有锂霞石和钠霞石晶相。本发明微晶玻璃化学强化性能优异，还可通过化学强化工艺处理成为微晶玻璃制品，以获得优异的机械强度。通过合理的组分设计，可使本发明微晶玻璃和微晶玻璃制品获得合适的晶粒大小，使本发明微晶玻璃和微晶玻璃制品具有高的强度。本发明中微晶玻璃和微晶玻璃制品具有合适含量的晶相，使本发明微晶玻璃和微晶玻璃制品具有优异的机械性能。In some embodiments of the present 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. In some embodiments, 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. Through reasonable component design, 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.
本发明微晶玻璃或微晶玻璃制品中晶粒尺寸和晶相种类会影响微晶玻璃或微晶玻璃制品的雾度和光透过率。在一些实施方式中，1mm以下厚度的微晶玻璃制品或微晶玻璃的雾度为0.15％以下，优选为0.12％以下，更优选为0.10％以下。在一些实施方式中，微晶玻璃制品或微晶玻璃的晶粒尺寸为80nm以下，优选为60nm以下，更优选为50nm以下。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. In some embodiments, 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%. In some embodiments, 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.
在一些实施方式中，本发明微晶玻璃或微晶玻璃制品中晶相含量和折射率影响微晶玻璃或微晶玻璃制品的∣B∣值，在可见光范围观察微晶玻璃或微晶玻璃制品出现偏蓝或者偏黄，影响产品的光学性能，在LAB(物质颜色的色度值)中用∣B∣值进行标示。本发明微晶玻璃或微晶玻璃制品在可见光范围中呈现低∣B∣值，在一些实施方式中，1mm以下厚度的微晶玻璃制品或微晶玻璃400～800nm的平均光∣B∣值为1.5以下，优选为1.0以下，更优选为0.8以下。In some embodiments, the crystalline content and refractive index of the glass-ceramics or glass-ceramics products of the present invention affect the |B| value of 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 |B| value in LAB (chromaticity value of the color of the substance). The glass-ceramics or glass-ceramics products of the present invention exhibit low |B| values in the visible light range. In some embodiments, the average optical |B| 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.
在一些实施方式中，本发明微晶玻璃或微晶玻璃制品在可见光范围中呈现高的透明度(即微晶玻璃或微晶玻璃制品是透明的)。微晶玻璃或微晶玻璃制品在可见光范围中呈现高的透过率，在一些优选的实施方式中，1mm以下厚度的微晶玻璃制品或微晶玻璃550nm的光透过率优选为88％以上，更优选为89％以上，进一步优选为90％以上。 In some embodiments, 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. In some preferred embodiments, 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.
在一些实施方式中，可将抗微生物成分添加到基质玻璃、微晶玻璃或微晶玻璃制品中。本文所述的微晶玻璃或微晶玻璃制品可用于例如厨房或餐饮工作台面的应用，其中很可能暴露于有害细菌。基质玻璃、微晶玻璃或微晶玻璃制品含有的抗微生物组分包括但不限Ag,AgO,Cu,CuO,Cu2O等。在一些实施方式中,上述抗微生物组分的单独或组合含量为2％以下，优选为1％以下。In some embodiments, 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%.
本发明的基质玻璃、微晶玻璃和微晶玻璃制品可以通过如下方法进行生产和制造：The matrix glass, glass-ceramics and glass-ceramics products of the present invention can be produced and manufactured by the following methods:
生成基质玻璃：按照组分比例将原料混合均匀，将均匀的混合物放入铂制或石英制的坩埚中，根据玻璃组成的熔化难易度，在电炉或燃气炉中在1250～1650℃的温度范围内进行5～24小时。熔化，搅拌使其均匀后，降至适当的温度并浇铸到模具中，缓慢冷却而成。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℃ 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.
本发明的基质玻璃可以通过众所周知的方法进行成型。The matrix glass of the present invention can be formed by a well-known method.
本发明的基质玻璃，在成型后或成型加工后通过晶化工艺进行晶化处理，在玻璃内部均匀地析出结晶。该晶化处理可以通过1个阶段进行，也可以通过2个阶段进行，优选采用2个阶段进行晶化处理。在第1温度下进行成核工艺的处理，然后在比成核工艺温度高的第2温度下进行晶体生长工艺的处理。将在第1温度下进行的晶化处理称为第1晶化处理，将在第2温度下进行的晶化处理称为第2晶化处理。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, and the crystallization treatment carried out at the second temperature is called the second crystallization treatment.
为了使微晶玻璃得到所期望的物理性质，优选的晶化工艺为：In order to obtain the desired physical properties of glass-ceramics, the preferred crystallization process is:
上述通过1个阶段进行晶化处理，可以连续地进行核形成工艺与结晶生长工艺。即，升温至规定的晶化处理温度，在达到晶化处理温度之后，将其温度保持一定的时间，然后再进行降温。该晶化处理温度优选为580～750℃，为了能够析出所期望的晶相，更优选为600～700℃，在晶化处理温度下的保持时间优选为0～8小时，更优选为1～6小时。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.
上述通过2个阶段进行晶化处理时，第1温度优选为500～620℃，第2温度优选为620～750℃。在第1温度下的保持时间优选为0～24小时，更优 选为2～15小时。在第2温度下的保持时间优选为0～10小时，更优选为0.5～6小时。When the crystallization treatment is performed in two stages, the first temperature is preferably 500 to 620° C., and 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.
上述保持时间0小时，是指在达到该温度后不到1分钟又开始降温或升温。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.
在一些实施方式中，可通过各种工艺将本文所述的基质玻璃或微晶玻璃制造成成形体，所述成形体包括但不限于片材，所述工艺包括但不限于狭缝拉制、浮法、辊压和本领域公知的其他形成片材的工艺。或者，可通过浮法或辊压法来形成基质玻璃或微晶玻璃。本发明所述成形体还包括透镜、棱镜等。In some embodiments, 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. Alternatively, 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.
本发明的基质玻璃或微晶玻璃，可以采用研磨或抛光加工等方法制造片材的玻璃成形体或微晶玻璃成形体，但制造玻璃成形体或微晶玻璃成形体的方法，并不限定于这些方法。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.
本发明的基质玻璃或微晶玻璃，可以在一定温度下采用热弯工艺或压型工艺等方法制备形成各种形状的玻璃成形体或微晶玻璃成形体，但并不限定于这些方法。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.
在一些实施方式中，可以采用热弯工艺制成玻璃成形体或微晶玻璃成形体。所述热弯工艺是将2D或2.5D玻璃或微晶玻璃置放于模具中，在热弯机中依次进行包括升温预热、加压成型、保压降温等步骤制得3D曲面的玻璃成形体或微晶玻璃成形体的过程。In some embodiments, 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.
在一些实施方式中，微晶玻璃成形体具有2.5D或3D构造，即微晶玻璃成形体具有非平面构造。本文所述的“非平面构造”是指在一种2.5D或3D形状中，微晶玻璃成形体的至少一部分向外延伸或者沿着与由2D基质玻璃的原始、布局配置所限定的平面的夹角进行延伸。由基质玻璃形成的2.5D或3D微晶玻璃成形体可具有一个或多个凸起或弯曲部分。In some embodiments, the glass-ceramic forming body has a 2.5D or 3D configuration, i.e., the glass-ceramic forming body has a non-planar configuration. As used herein, "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.
在一些实施方式中，结合微晶玻璃中晶相的生长和晶相的转变等特性，微晶玻璃成形体的制造方法为热弯工艺方法。具体而言，所述方法包括预晶化和热加工成型。本发明所述的预晶化是将基质玻璃通过控制晶化工艺 形成预晶化玻璃，所述预晶化玻璃的结晶度未达到目标微晶玻璃成型体的性能指标所需要的结晶度。预晶化玻璃再通过热加工成型工艺形成微晶玻璃成形体。In some embodiments, in combination with the growth and transformation of the crystal phase in the microcrystalline glass, the method for manufacturing the microcrystalline glass formed body is a hot bending process. Specifically, 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.
在一些实施方式中，微晶玻璃成形体的制造方法包括以下步骤：In some embodiments, a method for manufacturing a glass-ceramic formed body comprises the following steps:
1)将基质玻璃进行一次晶化热处理过程，包括升温、保温核化、升温、保温晶化、降温至室温，形成预晶化玻璃；1) subjecting the matrix glass to a crystallization heat treatment process, including heating, heat preservation nucleation, heating, heat preservation crystallization, and cooling to room temperature to form pre-crystallized glass;
2)将预晶化玻璃进行热加工成型得到微晶玻璃成形体。2) The pre-crystallized glass is heat-processed and formed into a microcrystalline glass formed body.
本发明所述的晶化热处理过程包括将基质玻璃在一定温度Th和时间th下进行核化，再在一定温度Tc和时间tc下进行晶化，所获得的预晶化玻璃的结晶度未达到目标微晶玻璃成形体的性能指标所需要的结晶度。应用XRD测试数据，通过Rietveld全谱拟合精修法计算出预晶化玻璃的结晶度中主晶相总含量为Ic1。本发明的预晶化从工艺过程上来说是一个完整过程，包含核化工艺一步，晶化工艺一段、两段或三段及以上等等，是一个完整的从升温、保温，再次升温、保温……，然后再按工艺降至室温的过程。区别于部分文献或专利中提及的一次晶化、二次晶化……，本发明实际上只是一个完整晶化工艺中的第一段晶化，第二段晶化……，其中间是连续的，并没有出现降至室温后再次升温晶化的过程。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. Using XRD test data, 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. Different from the primary crystallization, secondary crystallization... mentioned in some documents or patents, 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.
本发明所述热加工成型，是指在一定温度、时间、压力等条件下，对所述预晶化玻璃经过热加工工艺成型处理，所述热加工成型包括一次以上的热加工工艺，所述热加工工艺包括但不限于在一定温度、时间、压力等条件下对预晶化玻璃进行压制成型、弯曲成型或拉制成型。在热加工成型过程中，有时形状复杂的成型体无法通过一次热加工完成，可能需要进行两次以上的多次热加工才能实现。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. In 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.
在一些实施方式中，微晶玻璃成形体的制造方法为热弯工艺方法。具体而言，在一些实施方式中，微晶玻璃成形体的制造方法包括以下步骤：In some embodiments, 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:
1)升温预热：将基质玻璃或预晶化玻璃或微晶玻璃放置于模具内，模具在热弯机中依次通过各个升温站点，并在各站点停留一定时间保温。预 热区温度为400～800℃，压力为0.01～0.05MPa，时间为40～200s。在一些实施方式中，对于5个预热站点的热弯机来说，一般初始升温稳定设定在500℃左右，后续站点逐渐升高温度，相邻两站点间的温度梯度由低温向高温逐渐缩小，最后一个预热站与压型第一站点温度温差在20℃范围内即可。1) 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, and the time is 40-200s. In some embodiments, for a heat bending machine with 5 preheating stations, the initial temperature rise is generally set to be stable at about 500°C, and the subsequent stations gradually increase the temperature, and the temperature gradient between two adjacent stations gradually decreases from low temperature to high temperature, and the temperature difference between the last preheating station and the first press station is within 20°C.
2)加压成型：模具在经过预热后转运到成型站点，热弯机对模具施加一定压力，压力范围为0.1～0.8Mpa，压力大小根据玻璃厚度、弧度等因素确定，成型站点温度范围为650～850℃，成型时间范围40～200s。2) Pressurized molding: After preheating, the mold is transferred to the molding station. 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℃, and the molding time range is 40-200s.
3)保压降温：将模具转运至降温站点逐站降温。控制降温温度范围750～500℃，压力为0.01～0.05Mpa，时间为40～200s。3) Maintaining pressure and cooling: The mold is transferred to the cooling station and cooled down step by step. The cooling temperature range is controlled at 750-500℃, the pressure is 0.01-0.05Mpa, and the time is 40-200s.
微晶玻璃成形体采用热弯工艺成型除了需要控制如普通高铝玻璃的外观质量，同时还需要控制热弯过程中的晶体生长发育对微晶玻璃性能的影响，如用于显示设备或电子设备外壳的3D曲面微晶玻璃，需要密切关注热弯后的光透过率、雾度、∣B∣值以及其均匀性等。In addition to controlling the appearance quality of ordinary high-aluminum glass, 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. For example, 3D curved microcrystalline glass used for display devices or electronic equipment casings requires close attention to light transmittance, haze, |B| value and uniformity after hot bending.
热弯前后晶相变化量决定微晶玻璃成形体尺寸均匀性、量产可能性和成本控制等，本发明基质玻璃和微晶玻璃具有优异的热加工性能，在经过热弯成型后，晶相含量的变化量在20％以下，优选在15％以下，进一步优选10％以下，可保证热弯后得到的微晶玻璃成形体的雾度和∣B∣值等的均匀性。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 |B| value of the microcrystalline glass formed body obtained after hot bending.
本发明所述的基质玻璃、微晶玻璃和微晶玻璃制品可具有合理有用的任何厚度。The matrix glass, glass-ceramic, and glass-ceramic articles described herein can have any reasonably useful thickness.
本发明的微晶玻璃除了通过析出晶体提高机械特性之外，还可以通过形成压缩应力层获得更优异的机械性能，从而制成微晶玻璃制品。In addition to improving the mechanical properties by precipitating crystals, 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.
在一些实施方式中，可将基质玻璃或微晶玻璃加工成片材，和/或造型(如打孔、热弯等)，定形后抛光和/或扫光，再通过化学强化工艺进行化学强化，形成微晶玻璃制品。在一些实施方式中，可将微晶玻璃成形体通过化学强化工艺进行化学强化，形成微晶玻璃制品。In some embodiments, 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. In some embodiments, the glass-ceramics formed body can be chemically strengthened through a chemical strengthening process to form a glass-ceramics product.
本发明所述的化学强化，即是离子交换法。在离子交换过程中，基质 玻璃或微晶玻璃或微晶玻璃成形体中的较小的金属离子被靠近基质玻璃或微晶玻璃或微晶玻璃成形体的具有相同价态的较大金属离子置换或“交换”。用较大的离子置换较小的离子，在基质玻璃或微晶玻璃或微晶玻璃成形体的表面形成压缩应力，内部形成张应力。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.
在一些实施方式中,金属离子是单价碱金属离子(例如Na+、K+、Rb+、Cs+等),离子交换通过将基质玻璃或微晶玻璃或微晶玻璃成形体浸没在包含较大的金属离子的至少一种熔融盐的盐浴中来进行，该较大的金属离子用于置换基质玻璃或微晶玻璃或微晶玻璃成形体中的较小的金属离子。或者，其他单价金属离子例如Ag+、Tl+、Cu+等也可用于交换单价离子。用来化学强化基质玻璃或微晶玻璃或微晶玻璃成形体的一种或更多种离子交换过程可包括但不限于：将其浸没在单一盐浴中，或者将其浸没在具有相同或不同组成的多个盐浴中，在浸没之间有洗涤和/或退火步骤。In some embodiments, 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. Alternatively, 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.
在一些实施方式中,基质玻璃或微晶玻璃或微晶玻璃成形体可通过在浸没于约350～470℃的温度的熔融Na盐(如NaNO3)的盐浴中约1～36小时来进行离子交换，优选温度范围为380～460℃，优选时间范围为2～10小时。在这种实施方式中,Na离子置换基质玻璃或微晶玻璃或微晶玻璃成形体中的部分Li离子，从而形成表面压缩层且呈现高机械性能。在一些实施方式中，基质玻璃或微晶玻璃或微晶玻璃成形体可通过在浸没于约360～450℃的温度下熔融K盐(如KNO3)的盐浴中1～36小时来进行离子交换，优选时间范围为1～10小时。在一些实施方式中，基质玻璃或微晶玻璃或微晶玻璃成形体可通过在浸没于约360～450℃的温度下熔融K盐和Na盐的混合盐浴中1～36小时来进行离子交换，优选时间范围为2～24小时。In some embodiments, 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. In this embodiment, 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. In some embodiments, 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. In some embodiments, 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.
本发明微晶玻璃或微晶玻璃制品各项性能指标采用以下方法测试：The various performance indicators of the glass-ceramics or glass-ceramics products of the present invention are tested by the following methods:
[雾度][Haze]
采用分光测色仪美能达CM-3600A，以1mm以下的样品制备，以GB2410-80为标准进行测试。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.
[晶粒尺寸] [Grain size]
利用SEM扫描电镜进行测定，微晶玻璃通过在HF酸中进行表面处理，再对微晶玻璃表面进行喷金，在SEM扫描电镜下进行表面扫描，确定其晶粒的大小。Using a SEM scanning electron microscope, 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.
[光透过率][Light transmittance]
本文所述的光透过率均为外部透过率，有时候简称透过率。The light transmittances described in this article are all external transmittances, sometimes referred to as transmittance.
将样品加工成1mm以下并进行相对面平行抛光，利用分光测色仪美能达CM-3600A测定550nm的光透过率。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.
[表面应力]和[离子交换层深度][Surface stress] and [Ion exchange layer depth]
利用玻璃表面应力仪SLP-2000进行表面应力测定。The surface stress was measured using a glass surface stress meter SLP-2000.
利用玻璃表面应力仪SLP-2000进行离子交换层深度测定。The depth of the ion exchange layer was measured using a glass surface stress meter SLP-2000.
作为测定条件以样品的折射率为1.56、光学弹性常数为24.5[(nm/cm)/Mpa]进行计算。The calculation was performed under the measurement conditions that the refractive index of the sample was 1.56 and the photoelastic constant was 24.5 [(nm/cm)/Mpa].
[落球试验高度][Drop ball test height]
将长宽为150mm×73mm，厚度为1mm以下的微晶玻璃制品样品放置在玻璃承载夹具上，使132g的钢球从规定高度落下，样品不发生断裂而能够承受的冲击的最大落球试验高度。具体地说，试验从落球试验高度400mm开始实施，在不发生断裂的情况下，通过400mm、500mm、600mm、700mm及以上依次改变高度，每次间隔100mm。对于具有“落球试验高度”的实施例，以微晶玻璃制品为试验对象。在实施例中记录为1600mm的试验数据，表示该样品承受了1500mm冲击仍未破碎，升高到1600mm测试时发生了破碎，因此落球试验高度为1600mm。本发明中落球试验高度有时候简称落球高度。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. Specifically, 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. For the embodiments with a "drop ball test height", 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.
[本体落球高度][Body drop height]
将长宽为150mm×73mm，厚度为1mm以下的微晶玻璃样品放置在玻璃承载夹具上，使32g的钢球从规定高度落下，样品不发生断裂而能够承受的冲击的最大落球试验高度即为本体落球高度。具体地说，试验从落球试验高度400mm开始实施，在不发生断裂的情况下，通过400mm、500mm、600mm、 700mm及以上依次改变高度，每次间隔100mm。对于具有“本体落球高度”的实施例，以微晶玻璃为试验对象，即为微晶玻璃的落球试验高度。在实施例中记录为1300mm的试验数据，表示该样品承受了1200mm冲击仍未破碎，升高到1300mm测试时发生了破碎，因此本体落球高度为1300mm。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. Specifically, 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. For the embodiments with "body drop ball height", 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.
[四点弯曲强度][Four-point bending strength]
采用微机控制电子万能试验机CMT6502，样品规格为1mm以下厚度，以ASTM C 158-2002为标准进行测试。本发明中有时候将四点弯曲强度简称为弯曲强度。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. In the present invention, the four-point bending strength is sometimes referred to as the bending strength.
[维氏硬度][Vickers hardness]
用相对面夹角为136°的金刚石四角锥压头在试验面上压入金字塔形状的凹陷时的负荷除以通过凹陷的长度计算出的表面积(mm2)的值表示。使试验负荷为200g、保持时间为20秒进行。本发明中有时候将维氏硬度简称为硬度。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. In the present invention, Vickers hardness is sometimes referred to as simply hardness.
[∣B∣值][|B|value]
使用美能达CM-700d进行B值检测。样品规格为1mm以下厚度，用配套校正长筒和短筒分别进行仪器零位校准和白板校准，校准后用长筒再进行对空测试，判定仪器稳定校准可靠性(B≤0.05)，仪器校正合格后将产品放置在零位长筒上进行测试。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.
∣B∣值是B值的绝对值。The |B| value is the absolute value of the B value.
本发明微晶玻璃制品具有以下性能：The microcrystalline glass product of the present invention has the following properties:
1)在一些实施方式中，1mm以下厚度的微晶玻璃制品的四点弯曲强度为700MPa以上，优选为750MPa以上，更优选为800MPa以上。该厚度优选为0.2～1mm，更优选为0.3～0.9mm，进一步优选为0.5～0.8mm，更进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。1) In some embodiments, 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.
2)在一些实施方式中，微晶玻璃制品的离子交换层深度为50μm以上，优选为60μm以上，更优选为80μm以上，进一步优选为100μm以上。2) In some embodiments, the depth of the ion exchange layer of the microcrystalline glass product is 50 μm or more, preferably 60 μm or more, more preferably 80 μm or more, and further preferably 100 μm or more.
3)在一些实施方式中，1mm以下厚度的微晶玻璃制品的落球试验高度 为1100mm以上，优选为1300mm以上，更优选为1500mm以上。该厚度优选为0.2～1mm，更优选为0.3～0.9mm，进一步优选为0.5～0.8mm，更进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。3) In some embodiments, 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.
4)在一些实施方式中，微晶玻璃制品的维氏硬度(Hv)为750kgf/mm2以上，优选为780kgf/mm2以上，更优选为800kgf/mm2以上，进一步优选为810kgf/mm2以上。4) In some embodiments, 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.
5)在一些实施方式中，微晶玻璃制品的晶粒尺寸为80nm以下，优选为60nm以下，更优选为50nm以下，进一步优选为40nm以下。5) In some embodiments, 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.
6)在一些实施方式中，微晶玻璃制品的表面应力为150MPa以上，优选为170MPa以上，更优选为190MPa以上。6) In some embodiments, 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.
7)在一些实施方式中，1mm以下厚度的微晶玻璃制品的雾度为0.15％以下，优选为0.12％以下，更优选为0.10％以下。该厚度优选为0.2～1mm，更优选为0.3～0.9mm，进一步优选为0.5～0.8mm，更进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。7) In some embodiments, 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.
8)在一些实施方式中，1mm以下厚度的微晶玻璃制品，550nm波长的光透过率为88％以上，优选为89％以上，更优选为90％以上，进一步优选为91％以上。该厚度优选为0.2～1mm，更优选为0.3～0.9mm，进一步优选为0.5～0.8mm，更进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。8) In some embodiments, 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.
9)在一些实施方式中，1mm以下厚度的微晶玻璃制品，400～800nm的平均光∣B∣值为1.5以下，优选为1.0以下，更优选为0.8以下。该厚度优选为0.2～1mm，更优选为0.3～0.9mm，进一步优选为0.5～0.8mm，更进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。9) In some embodiments, for a glass-ceramic product having a thickness of less than 1 mm, the average optical |B| 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.
本发明微晶玻璃具有以下性能：The microcrystalline glass of the present invention has the following properties:
1)在一些实施方式中，微晶玻璃的晶粒尺寸为80nm以下，优选为60nm以下，更优选为50nm以下，进一步优选为40nm以下。1) In some embodiments, 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.
2)在一些实施方式中，1mm以下厚度的微晶玻璃的雾度为0.15％以下，优选为0.12％以下，更优选为0.10％以下。该厚度优选为0.2～1mm，更优选 为0.3～0.9mm，进一步优选为0.5～0.8mm，更进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。2) In some embodiments, 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.
3)在一些实施方式中，1mm以下厚度的微晶玻璃，550nm波长的光透过率为88％以上，优选为89％以上，更优选为90％以上，进一步优选为91％以上。该厚度优选为0.2～1mm，更优选为0.3～0.9mm，进一步优选为0.5～0.8mm，更进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。3) In some embodiments, 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.
4)在一些实施方式中，1mm以下厚度的微晶玻璃的本体落球高度为1000mm以上，优选为1200mm以上，更优选为1400mm以上。该厚度优选为0.2～1mm，更优选为0.3～0.9mm，进一步优选为0.5～0.8mm，更进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。4) In some embodiments, 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.
5)在一些实施方式中，1mm以下厚度的微晶玻璃，400～800nm的平均光∣B∣值为1.5以下，优选为1.0以下，更优选为0.8以下。该厚度优选为0.2～1mm，更优选为0.3～0.9mm，进一步优选为0.5～0.8mm，更进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。5) In some embodiments, for a glass-ceramic having a thickness of less than 1 mm, the average optical |B| 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.
6)在一些实施方式中，微晶玻璃的维氏硬度(Hv)为650kgf/mm2以上，优选为680kgf/mm2以上，更优选为700kgf/mm2以上。6) In some embodiments, 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.
本发明的微晶玻璃、微晶玻璃制品、基质玻璃、玻璃成形体、微晶玻璃成形体由于具有上述优异的性能，可广泛制作成玻璃盖板或玻璃元器件；同时，本发明微晶玻璃、微晶玻璃制品、基质玻璃、玻璃成形体、微晶玻璃成形体可应用于电子设备或显示设备中，如手机、手表、电脑、触摸显示屏等,用于制造移动电话、智能电话、平板电脑、笔记本电脑、PDA、电视机、个人电脑、MTA机器或工业显示器的防护玻璃，或用于制造触摸屏、防护窗、汽车车窗、火车车窗、航空机械窗、触摸屏防护玻璃，或用于制造硬盘基材或太阳能电池基材，或用于制造白色家电，如用于制造冰箱部件或厨具。The 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.
实施例Example
为了进一步清楚地阐释和说明本发明的技术方案，提供以下的非限制 性实施例。本发明实施例经过诸多努力以确保数值的精确性，但是必须考虑到存在一些误差和偏差。微晶玻璃或微晶玻璃制品的组成基于氧化物以重量％给出，且已标准化成100％。In order to further clearly explain and illustrate the technical solution of the present invention, the following non-limiting The present invention has been described in detail in detail with reference to the accompanying drawings. Every effort has been made to ensure the accuracy of the numerical values, but some errors and deviations must be taken into account. The composition of the glass-ceramic or glass-ceramic article is given in % by weight based on the oxides and is normalized to 100%.
<微晶玻璃实施例><Glass-ceramic Example>
本实施例采用上述微晶玻璃的制造方法得到具有表1～表3所示的组成的微晶玻璃。另外，通过本发明所述的测试方法测定各微晶玻璃的特性，并将测定结果表示在表1～表3中，以下实施例中本体落球高度、雾度、光透过率、∣B∣值等所采用测试样品的厚度为0.7mm。This embodiment adopts the above-mentioned method for manufacturing microcrystalline glass to obtain microcrystalline glass having the composition shown in Tables 1 to 3. In addition, 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. The thickness of the test sample used for the body drop ball height, haze, light transmittance, |B| value, etc. in the following embodiments is 0.7 mm.
表1.

Table 1.

表2.

Table 2.

表3.

table 3.

<微晶玻璃制品实施例><Glass-ceramic product example>
本实施例采用上述微晶玻璃制品的制造方法得到具有表4～表6所示组成的微晶玻璃制品。另外，通过本发明所述的测试方法测定各微晶玻璃制品的特性，并将测定结果表示在表4～表6中，以下实施例中四点弯曲强度、落球试验高度、雾度、光透过率、∣B∣值等所采用测试样品的厚度为0.7mm。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. In addition, 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. The thickness of the test sample used for the four-point bending strength, drop ball test height, haze, light transmittance, |B| value, etc. in the following embodiments is 0.7 mm.
表4.

Table 4.

表5.

table 5.

表6.

Table 6.

Claims (66)

  1. 微晶玻璃制品，其特征在于，其组分按重量百分比表示，含有：SiO2：40～60％；Al2O3：20～40％；Li2O：2～15％；Na2O：3～20％；P2O5+ZrO2：1～15％。The microcrystalline glass product is characterized in that the components thereof, 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%; P 2 O 5 +ZrO 2 : 1-15%.
  2. 根据权利要求1所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，还含有：K2O：0～8％；和/或ZnO：0～6％；和/或B2O3：0～6％；和/或RO：0～8％；和/或TiO2：0～5％；和/或Ln2O3：0～5％；和/或澄清剂：0～2％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。The microcrystalline glass product according to claim 1 is characterized in that, expressed in terms of weight percentage, it further contains: 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 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 .
  3. 微晶玻璃制品，其特征在于，其组分按重量百分比表示，由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％；澄清剂：0～2％组成，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。The microcrystalline glass product is characterized in that its 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 .
  4. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，其中：(Al2O3+Na2O)/P2O5为3.0～30.0，优选(Al2O3+Na2O)/P2O5为4.0～20.0，更优选(Al2O3+Na2O)/P2O5为5.0～15.0，进一步优选(Al2O3+Na2O)/P2O5为6.0～10.0。The microcrystalline glass product according to any one of claims 1 to 3, characterized in that its components are expressed in weight percentage, wherein: (Al 2 O 3 +Na 2 O)/P 2 O 5 is 3.0 to 30.0, preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 4.0 to 20.0, more preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 5.0 to 15.0, and further preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 6.0 to 10.0.
  5. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，其中：SiO2/Al2O3为1.2～2.8，优选SiO2/Al2O3为1.3～2.5，更优选SiO2/Al2O3为1.5～2.2，进一步优选SiO2/Al2O3为1.6～2.0。The glass-ceramic product according to any one of claims 1 to 3 is characterized in that its components are expressed in weight percentage, wherein: SiO2 / Al2O3 is 1.2-2.8, preferably SiO2/Al2O3 is 1.3-2.5, more preferably SiO2/Al2O3 is 1.5-2.2 , and further preferably SiO2 / Al2O3 is 1.6-2.0 .
  6. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，其中：SiO2/(Na2O+B2O3)为2.0～15.0，优选SiO2/(Na2O+B2O3)为3.0～10.0，更优选SiO2/(Na2O+B2O3)为4.0～8.0，进一步优选SiO2/(Na2O+B2O3)为5.0～7.0。The glass-ceramic product according to any one of claims 1 to 3, characterized in that its components are expressed in weight percentage, wherein: SiO2 /( Na2O + B2O3 ) is 2.0-15.0, preferably SiO2 /( Na2O + B2O3 ) is 3.0-10.0 , more preferably SiO2 / ( Na2O + B2O3 ) is 4.0-8.0 , and further preferably SiO2 /( Na2O + B2O3 ) is 5.0-7.0 .
  7. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，其中：(Na2O+Li2O)/SiO2为0.1～0.8，优选(Na2O+Li2O)/SiO2为0.15～0.7，更优选(Na2O+Li2O)/SiO2为0.2～0.6，进一步优选(Na2O+Li2O)/SiO2为0.25～0.5。The glass-ceramic product according to any one of claims 1 to 3 is characterized in that its 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.
  8. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，其中：(ZrO2+ZnO)/Na2O为2.0以下，优选(ZrO2+ZnO)/Na2O 为1.5以下，更优选(ZrO2+ZnO)/Na2O为0.01～1.0，进一步优选(ZrO2+ZnO)/Na2O为0.1～0.5。The microcrystalline glass product according to any one of claims 1 to 3, characterized in that 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 It is 1.5 or less, 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.
  9. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，其中：(P2O5+Na2O)/Li2O为0.5～8.0，优选(P2O5+Na2O)/Li2O为0.8～5.0，更优选(P2O5+Na2O)/Li2O为1.0～3.0，进一步优选(P2O5+Na2O)/Li2O为1.5～2.5。The glass-ceramic product according to any one of claims 1 to 3, characterized in that its components are expressed in weight percentage, wherein: (P 2 O 5 +Na 2 O)/Li 2 O is 0.5 to 8.0, preferably (P 2 O 5 +Na 2 O)/Li 2 O is 0.8 to 5.0, more preferably (P 2 O 5 +Na 2 O)/Li 2 O is 1.0 to 3.0, and further preferably (P 2 O 5 +Na 2 O)/Li 2 O is 1.5 to 2.5.
  10. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，其中：K2O/ZrO2为0.1以上，优选K2O/ZrO2为0.2～10.0，更优选K2O/ZrO2为0.3～5.0，进一步优选K2O/ZrO2为0.4～1.5。The microcrystalline glass product according to any one of claims 1 to 3 is characterized in that its components are expressed in weight percentage, wherein: K2O / ZrO2 is greater than 0.1, preferably K2O / ZrO2 is 0.2-10.0, more preferably K2O / ZrO2 is 0.3-5.0, and further preferably K2O / ZrO2 is 0.4-1.5.
  11. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，其中：(ZnO+RO+B2O3+TiO2)/P2O5为1.5以下，优选(ZnO+RO+B2O3+TiO2)/P2O5为1.0以下，更优选(ZnO+RO+B2O3+TiO2)/P2O5为0.5以下，进一步优选(ZnO+RO+B2O3+TiO2)/P2O5为0.2以下，所述RO为MgO、CaO、SrO、BaO中的一种或多种。The microcrystalline glass product according to any one of claims 1 to 3, characterized in that its components are expressed in weight percentage, wherein: (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 1.5 , preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 1.0 , more preferably (ZnO+RO+ B2O3 + TiO2 ) / P2O5 is less than 0.5 , and further preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 0.2 , and the RO is one or more of MgO, CaO, SrO, and BaO.
  12. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，其中：SiO2：43～55％，优选SiO2：46～53％；和/或Al2O3：23～36％，优选Al2O3：25.5～32％；和/或Li2O：3～13％，优选Li2O：5.5～11％；和/或Na2O：5～15％，优选Na2O：6.5～12％；和/或P2O5+ZrO2：2～12％，优选P2O5+ZrO2：4～10％；和/或K2O：0～5％，优选K2O：0.1～3％；和/或ZnO：0～3％，优选ZnO：0～1％；和/或B2O3：0～3％，优选B2O3：0～1％；和/或RO：0～5％，优选RO：0～2％；和/或TiO2：0～3％，优选TiO2：0～1％；和/或Ln2O3：0～3％，优选Ln2O3：0～1％；和/或澄清剂：0～1％，优选澄清剂：0～0.5％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。The microcrystalline glass product according to any one of claims 1 to 3, characterized in that its components are expressed in weight percentage, wherein: SiO 2 : 43-55%, preferably SiO 2 : 46-53%; and/or Al 2 O 3 : 23-36%, preferably Al 2 O 3 : 25.5-32%; and/or Li 2 O: 3-13%, preferably Li 2 O: 5.5-11%; and/or Na 2 O: 5-15%, preferably Na 2 O: 6.5-12%; and/or P 2 O 5 + ZrO 2 : 2-12%, preferably P 2 O 5 + ZrO 2 : 4-10%; and/or K 2 O: 0-5%, preferably K 2 O: 0.1-3%; and/or ZnO: 0-3%, preferably ZnO: 0-1%; and/or B 2 O 3 : 0-3%, preferably B 2 O 3 : 0-1%; and/or RO: 0-5%, preferably RO: 0-2%; and/or TiO 2 : 0-3%, preferably TiO 2 : 0-1%; and/or Ln 2 O 3 : 0-3%, preferably Ln 2 O 3 : 0-1%; and/or clarifier: 0-1%, preferably clarifier: 0-0.5%, wherein RO is one or more of MgO, CaO, SrO, and BaO, and Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , and Y 2 O 3 .
  13. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，其中：ZrO2：0～6％，优选ZrO2：0～5％，更优选ZrO2：0.1～3％；和/或P2O5：0～10％，优选P2O5：1～8％，更优选P2O5：2～6％。The glass-ceramic product according to any one of claims 1 to 3, characterized in that its components are expressed in weight percentage, wherein: ZrO2 : 0-6%, preferably ZrO2 : 0-5%, more preferably ZrO2 : 0.1-3%; and/or P2O5 : 0-10%, preferably P2O5 : 1-8%, more preferably P2O5 : 2-6 %.
  14. 根据权利要求1或2所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，还含有：Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～5％，优选Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～2％，更优选 Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～1％。The microcrystalline glass product according to claim 1 or 2, characterized in that , the components thereof, expressed in weight percentage, further contain : Yb2O3 + Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2+GeO2 : 0-5%, preferably Yb2O3 +Nb2O5 + WO3 + Bi2O3+Ta2O5 + TeO2 + GeO2 : 0-2 %, more preferably Yb2O3 + Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2 +GeO2: 0-1 %.
  15. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，所述微晶玻璃制品含有霞石晶相；和/或硅酸锂晶相；和/或磷酸锂晶相；和/或透锂长石晶相；和/或石英晶相。The microcrystalline glass product according to any one of claims 1 to 3 is characterized in that 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.
  16. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，所述微晶玻璃制品的主要晶相为霞石晶相，或微晶玻璃制品只含有霞石晶相。The microcrystalline glass product according to any one of claims 1 to 3 is characterized in that 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.
  17. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，所述微晶玻璃制品中，霞石晶相占微晶玻璃制品的重量百分比为10～80％，优选霞石晶相占微晶玻璃制品的重量百分比为20～70％，更优选霞石晶相占微晶玻璃制品的重量百分比为30～60％。The microcrystalline glass product according to any one of claims 1 to 3 is characterized in that, in the microcrystalline glass product, 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%.
  18. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，所述微晶玻璃制品的离子交换层深度为50μm以上，优选为60μm以上，更优选为80μm以上，进一步优选为100μm以上；和/或维氏硬度为750kgf/mm2以上，优选为780kgf/mm2以上，更优选为800kgf/mm2以上，进一步优选为810kgf/mm2以上；和/或晶粒尺寸为80nm以下，优选为60nm以下，更优选为50nm以下，进一步优选为40nm以下；和/或表面应力为150MPa以上，优选为170MPa以上，更优选为190MPa以上。The microcrystalline glass product according to any one of claims 1 to 3 is characterized in that the ion exchange layer depth of the microcrystalline glass product is 50 μm or more, preferably 60 μm or more, more preferably 80 μm or more, and further preferably 100 μm or more; and/or the Vickers hardness 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; and/or the grain size is 80 nm or less, preferably 60 nm or less, more preferably 50 nm or less, and further preferably 40 nm or less; and/or the surface stress is 150 MPa or more, preferably 170 MPa or more, and more preferably 190 MPa or more.
  19. 根据权利要求1～3任一所述的微晶玻璃制品，其特征在于，1mm以下厚度的微晶玻璃制品，其四点弯曲强度为700MPa以上，优选为750MPa以上，更优选为800MPa以上；和/或落球试验高度为1100mm以上，优选为1300mm以上，更优选为1500mm以上；和/或雾度为0.15％以下，优选为0.12％以下，更优选为0.10％以下；和/或550nm波长的光透过率为88％以上，优选为89％以上，更优选为90％以上，进一步优选为91％以上；和/或400～800nm的平均光∣B∣值为1.5以下，优选为1.0以下，更优选为0.8以下。The microcrystalline glass product according to any one of claims 1 to 3 is characterized in that the 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 the drop ball test height is more than 1100 mm, preferably more than 1300 mm, and more preferably more than 1500 mm; and/or the haze is less than 0.15%, preferably less than 0.12%, and more preferably less than 0.10%; and/or the light transmittance at a wavelength of 550 nm is more than 88%, preferably more than 89%, more preferably more than 90%, and further preferably more than 91%; and/or the average optical |B| value at 400 to 800 nm is less than 1.5, preferably less than 1.0, and more preferably less than 0.8.
  20. 根据权利要求19所述的微晶玻璃制品，其特征在于，所述微晶玻璃制品的厚度为0.2～1mm，优选为0.3～0.9mm，更优选为0.5～0.8mm，进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。The microcrystalline glass product according to claim 19 is characterized in that 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 or 0.6 mm or 0.68 mm or 0.7 mm or 0.75 mm.
  21. 根据权利要求1或2所述的微晶玻璃制品，其特征在于，其组分按重量百分比表示，还含有：NiO：0～4％；和/或Ni2O3：0～4％；和/或CoO：0～2％； 和/或Co2O3：0～2％；和/或Fe2O3：0～7％；和/或MnO2：0～4％；和/或Er2O3：0～8％；和/或Nd2O3：0～8％；和/或Cu2O：0～4％；和/或Pr2O3：0～8％；和/或CeO2：0～4％。The microcrystalline glass product according to claim 1 or 2, characterized in that, expressed in terms of weight percentage, it further contains: NiO: 0-4%; and/or Ni 2 O 3 : 0-4%; and/or CoO: 0-2%; and/or Co2O3 : 0-2 %; and/or Fe2O3 : 0-7%; and/or MnO2 : 0-4% ; and/or Er2O3 : 0-8%; and/or Nd2O3 : 0-8%; and/or Cu2O : 0-4%; and/or Pr2O3 : 0-8 %; and/or CeO2 : 0-4 %.
  22. 微晶玻璃，其特征在于，其组分按重量百分比表示，含有：SiO2：40～60％；Al2O3：20～40％；Li2O：2～15％；Na2O：3～20％；P2O5+ZrO2：1～15％。The microcrystalline glass is characterized in that its 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%; P 2 O 5 +ZrO 2 : 1-15%.
  23. 根据权利要求22所述的微晶玻璃，其特征在于，其组分按重量百分比表示，还含有：K2O：0～8％；和/或ZnO：0～6％；和/或B2O3：0～6％；和/或RO：0～8％；和/或TiO2：0～5％；和/或Ln2O3：0～5％；和/或澄清剂：0～2％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。The microcrystalline glass according to claim 22 is characterized in that its components, expressed in weight percentage, further contain: 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 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 .
  24. 微晶玻璃，其特征在于，其组分按重量百分比表示，由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％；澄清剂：0～2％组成，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。The microcrystalline glass is characterized in that its 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 .
  25. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，其组分按重量百分比表示，其中：(Al2O3+Na2O)/P2O5为3.0～30.0，优选(Al2O3+Na2O)/P2O5为4.0～20.0，更优选(Al2O3+Na2O)/P2O5为5.0～15.0，进一步优选(Al2O3+Na2O)/P2O5为6.0～10.0。The glass-ceramics according to any one of claims 22 to 24 is characterized in that its components are expressed in weight percentage, wherein: (Al 2 O 3 +Na 2 O)/P 2 O 5 is 3.0 to 30.0, preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 4.0 to 20.0, more preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 5.0 to 15.0, and further preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 6.0 to 10.0.
  26. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，其组分按重量百分比表示，其中：SiO2/Al2O3为1.2～2.8，优选SiO2/Al2O3为1.3～2.5，更优选SiO2/Al2O3为1.5～2.2，进一步优选SiO2/Al2O3为1.6～2.0。The glass-ceramics according to any one of claims 22 to 24 is characterized in that its components are expressed in weight percentage, wherein: SiO 2 /Al 2 O 3 is 1.2 to 2.8, preferably SiO 2 /Al 2 O 3 is 1.3 to 2.5, more preferably SiO 2 /Al 2 O 3 is 1.5 to 2.2, and further preferably SiO 2 /Al 2 O 3 is 1.6 to 2.0.
  27. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，其组分按重量百分比表示，其中：SiO2/(Na2O+B2O3)为2.0～15.0，优选SiO2/(Na2O+B2O3)为3.0～10.0，更优选SiO2/(Na2O+B2O3)为4.0～8.0，进一步优选SiO2/(Na2O+B2O3)为5.0～7.0。The glass-ceramics according to any one of claims 22 to 24 is characterized in that its components are expressed in weight percentage, wherein: SiO 2 /(Na 2 O + B 2 O 3 ) is 2.0 to 15.0, preferably SiO 2 /(Na 2 O + B 2 O 3 ) is 3.0 to 10.0, more preferably SiO 2 /(Na 2 O + B 2 O 3 ) is 4.0 to 8.0, and further preferably SiO 2 /(Na 2 O + B 2 O 3 ) is 5.0 to 7.0.
  28. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，其组分按重量百分比表示，其中：(Na2O+Li2O)/SiO2为0.1～0.8，优选(Na2O+Li2O)/SiO2为0.15～0.7，更优选(Na2O+Li2O)/SiO2为0.2～0.6，进一步优选(Na2O+Li2O) /SiO2为0.25～0.5。The glass-ceramics according to any one of claims 22 to 24, characterized in that 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 0.25～0.5.
  29. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，其组分按重量百分比表示，其中：(ZrO2+ZnO)/Na2O为2.0以下，优选(ZrO2+ZnO)/Na2O为1.5以下，更优选(ZrO2+ZnO)/Na2O为0.01～1.0，进一步优选(ZrO2+ZnO)/Na2O为0.1～0.5。The glass-ceramics according to any one of claims 22 to 24 is characterized in that its 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.
  30. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，其组分按重量百分比表示，其中：(P2O5+Na2O)/Li2O为0.5～8.0，优选(P2O5+Na2O)/Li2O为0.8～5.0，更优选(P2O5+Na2O)/Li2O为1.0～3.0，进一步优选(P2O5+Na2O)/Li2O为1.5～2.5。The glass-ceramics according to any one of claims 22 to 24 is characterized in that its components are expressed in weight percentage, wherein: (P 2 O 5 +Na 2 O)/Li 2 O is 0.5 to 8.0, preferably (P 2 O 5 +Na 2 O)/Li 2 O is 0.8 to 5.0, more preferably (P 2 O 5 +Na 2 O)/Li 2 O is 1.0 to 3.0, and further preferably (P 2 O 5 +Na 2 O)/Li 2 O is 1.5 to 2.5.
  31. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，其组分按重量百分比表示，其中：K2O/ZrO2为0.1以上，优选K2O/ZrO2为0.2～10.0，更优选K2O/ZrO2为0.3～5.0，进一步优选K2O/ZrO2为0.4～1.5。The glass-ceramics according to any one of claims 22 to 24 is characterized in that its components are expressed in weight percentage, wherein: K2O / ZrO2 is greater than 0.1, preferably K2O / ZrO2 is 0.2-10.0, more preferably K2O / ZrO2 is 0.3-5.0, and further preferably K2O / ZrO2 is 0.4-1.5.
  32. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，其组分按重量百分比表示，其中：(ZnO+RO+B2O3+TiO2)/P2O5为1.5以下，优选(ZnO+RO+B2O3+TiO2)/P2O5为1.0以下，更优选(ZnO+RO+B2O3+TiO2)/P2O5为0.5以下，进一步优选(ZnO+RO+B2O3+TiO2)/P2O5为0.2以下，所述RO为MgO、CaO、SrO、BaO中的一种或多种。The glass-ceramics according to any one of claims 22 to 24 is characterized in that its components are expressed in weight percentage, wherein: (ZnO+RO+ B2O3 + TiO2 ) /P2O5 is less than 1.5, preferably (ZnO+RO+B2O3 + TiO2 ) / P2O5 is less than 1.0 , more preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 0.5 , and further preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is less than 0.2, and the RO is one or more of MgO, CaO, SrO, and BaO.
  33. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，其组分按重量百分比表示，其中：SiO2：43～55％，优选SiO2：46～53％；和/或Al2O3：23～36％，优选Al2O3：25.5～32％；和/或Li2O：3～13％，优选Li2O：5.5～11％；和/或Na2O：5～15％，优选Na2O：6.5～12％；和/或P2O5+ZrO2：2～12％，优选P2O5+ZrO2：4～10％；和/或K2O：0～5％，优选K2O：0.1～3％；和/或ZnO：0～3％，优选ZnO：0～1％；和/或B2O3：0～3％，优选B2O3：0～1％；和/或RO：0～5％，优选RO：0～2％；和/或TiO2：0～3％，优选TiO2：0～1％；和/或Ln2O3：0～3％，优选Ln2O3：0～1％；和/或澄清剂：0～1％，优选澄清剂：0～0.5％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。The glass-ceramics according to any one of claims 22 to 24, characterized in that the components thereof are expressed in weight percentage, wherein: SiO 2 : 43-55%, preferably SiO 2 : 46-53%; and/or Al 2 O 3 : 23-36%, preferably Al 2 O 3 : 25.5-32%; and/or Li 2 O: 3-13%, preferably Li 2 O: 5.5-11%; and/or Na 2 O: 5-15%, preferably Na 2 O: 6.5-12%; and/or P 2 O 5 +ZrO 2 : 2-12%, preferably P 2 O 5 +ZrO 2 : 4-10%; and/or K 2 O: 0-5%, preferably K 2 O: 0.1-3%; and/or ZnO: 0-3%, preferably ZnO: 0-1%; and/or B 2 O 3 : 0-3%, preferably B 2 O 3 : 0-1%; and/or RO: 0-5%, preferably RO: 0-2%; and/or TiO 2 : 0-3%, preferably TiO 2 : 0-1%; and/or Ln 2 O 3 : 0-3%, preferably Ln 2 O 3 : 0-1%; and/or clarifier: 0-1%, preferably clarifier: 0-0.5%, wherein RO is one or more of MgO, CaO, SrO, and BaO, and Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , and Y 2 O 3 .
  34. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，其组分按重量百分比表示，其中：ZrO2：0～6％，优选ZrO2：0～5％，更优选ZrO2：0.1～3％；和/或P2O5：0～10％，优选P2O5：1～8％，更优选P2O5：2～6％。 The glass-ceramics according to any one of claims 22 to 24 is characterized in that its components are expressed in weight percentage, wherein: ZrO 2 : 0-6%, preferably ZrO 2 : 0-5%, more preferably ZrO 2 : 0.1-3%; and/or P 2 O 5 : 0-10%, preferably P 2 O 5 : 1-8%, more preferably P 2 O 5 : 2-6%.
  35. 根据权利要求22或23所述的微晶玻璃，其特征在于，其组分按重量百分比表示，还含有：Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～5％，优选Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～2％，更优选Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～1％。The glass-ceramics according to claim 22 or 23 is characterized in that its components, expressed in weight percentage , further contain : Yb2O3 + Nb2O5 + WO3 + Bi2O3 +Ta2O5 + TeO2+GeO2 : 0-5 % , preferably Yb2O3+Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2 +GeO2 : 0-2 % , more preferably Yb2O3 + Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2 + GeO2 : 0-1 % .
  36. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，所述微晶玻璃含有霞石晶相；和/或硅酸锂晶相；和/或磷酸锂晶相；和/或透锂长石晶相；和/或石英晶相。The microcrystalline glass according to any one of claims 22 to 24 is characterized in that 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.
  37. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，所述微晶玻璃的主要晶相为霞石晶相，或微晶玻璃只含有霞石晶相。The microcrystalline glass according to any one of claims 22 to 24 is characterized in that the main crystal phase of the microcrystalline glass is the nepheline crystal phase, or the microcrystalline glass only contains the nepheline crystal phase.
  38. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，所述微晶玻璃中，霞石晶相占微晶玻璃的重量百分比为10～80％，优选霞石晶相占微晶玻璃的重量百分比为20～70％，更优选霞石晶相占微晶玻璃的重量百分比为30～60％。The glass-ceramics according to any one of claims 22 to 24 is characterized in that, in the glass-ceramics, the weight percentage of the nepheline crystal phase in the glass-ceramics is 10 to 80%, preferably the weight percentage of the nepheline crystal phase in the glass-ceramics is 20 to 70%, and more preferably the weight percentage of the nepheline crystal phase in the glass-ceramics is 30 to 60%.
  39. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，所述微晶玻璃的晶粒尺寸为80nm以下，优选为60nm以下，更优选为50nm以下，进一步优选为40nm以下；和/或维氏硬度为650kgf/mm2以上，优选为680kgf/mm2以上，更优选为700kgf/mm2以上。The microcrystalline glass according to any one of claims 22 to 24 is characterized in that 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/mm 2 , preferably greater than 680 kgf/mm 2 , and more preferably greater than 700 kgf/mm 2 .
  40. 根据权利要求22～24任一所述的微晶玻璃，其特征在于，1mm以下厚度的微晶玻璃，其本体落球高度为1000mm以上，优选为1200mm以上，更优选为1400mm以上；和/或雾度为0.15％以下，优选为0.12％以下，更优选为0.10％以下；和/或550nm波长的光透过率为88％以上，优选为89％以上，更优选为90％以上，进一步优选为91％以上；和/或400～800nm的平均光∣B∣值为1.5以下，优选为1.0以下，更优选为0.8以下。The microcrystalline glass according to any one of claims 22 to 24 is characterized in that the microcrystalline glass with a thickness of less than 1 mm has a body ball drop height of more than 1000 mm, preferably more than 1200 mm, and more preferably more than 1400 mm; and/or the haze is less than 0.15%, preferably less than 0.12%, and more preferably less than 0.10%; and/or the light transmittance at a wavelength of 550 nm is more than 88%, preferably more than 89%, more preferably more than 90%, and further preferably more than 91%; and/or the average light |B| value at 400 to 800 nm is less than 1.5, preferably less than 1.0, and more preferably less than 0.8.
  41. 根据权利要求40所述的微晶玻璃，其特征在于，所述微晶玻璃的厚度为0.2～1mm，优选为0.3～0.9mm，更优选为0.5～0.8mm，进一步优选为0.55mm或0.6mm或0.68mm或0.7mm或0.75mm。The microcrystalline glass according to claim 40 is characterized in that 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.
  42. 根据权利要求22或23所述的微晶玻璃，其特征在于，其组分按重量百分比表示，还含有：NiO：0～4％；和/或Ni2O3：0～4％；和/或CoO：0～2％；和/或Co2O3：0～2％；和/或Fe2O3：0～7％；和/或MnO2：0～4％；和/或Er2O3：0～8％；和/或Nd2O3：0～8％；和/或Cu2O：0～4％；和/或Pr2O3：0～8％；和/或CeO2：0～ 4％。The microcrystalline glass according to claim 22 or 23 is characterized in that, expressed in terms of weight percentage, it further 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 3 : 0-8%; and/or CeO 2 : 0-10 ... 4%.
  43. 基质玻璃，其特征在于，其组分按重量百分比表示，含有：SiO2：40～60％；Al2O3：20～40％；Li2O：2～15％；Na2O：3～20％；P2O5+ZrO2：1～15％。The matrix glass is characterized in that its 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%; P 2 O 5 +ZrO 2 : 1-15%.
  44. 根据权利要求43所述的基质玻璃，其特征在于，其组分按重量百分比表示，还含有：K2O：0～8％；和/或ZnO：0～6％；和/或B2O3：0～6％；和/或RO：0～8％；和/或TiO2：0～5％；和/或Ln2O3：0～5％；和/或澄清剂：0～2％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。The matrix glass according to claim 43 is characterized in that its components, expressed in weight percentage, further contain: 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 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 .
  45. 根据权利要求43或44所述的基质玻璃，其特征在于，其组分按重量百分比表示，其中：(Al2O3+Na2O)/P2O5为3.0～30.0，优选(Al2O3+Na2O)/P2O5为4.0～20.0，更优选(Al2O3+Na2O)/P2O5为5.0～15.0，进一步优选(Al2O3+Na2O)/P2O5为6.0～10.0；和/或SiO2/Al2O3为1.2～2.8，优选SiO2/Al2O3为1.3～2.5，更优选SiO2/Al2O3为1.5～2.2，进一步优选SiO2/Al2O3为1.6～2.0；和/或SiO2/(Na2O+B2O3)为2.0～15.0，优选SiO2/(Na2O+B2O3)为3.0～10.0，更优选SiO2/(Na2O+B2O3)为4.0～8.0，进一步优选SiO2/(Na2O+B2O3)为5.0～7.0；和/或(Na2O+Li2O)/SiO2为0.1～0.8，优选(Na2O+Li2O)/SiO2为0.15～0.7，更优选(Na2O+Li2O)/SiO2为0.2～0.6，进一步优选(Na2O+Li2O)/SiO2为0.25～0.5；和/或(ZrO2+ZnO)/Na2O为2.0以下，优选(ZrO2+ZnO)/Na2O为1.5以下，更优选(ZrO2+ZnO)/Na2O为0.01～1.0，进一步优选(ZrO2+ZnO)/Na2O为0.1～0.5；和/或(P2O5+Na2O)/Li2O为0.5～8.0，优选(P2O5+Na2O)/Li2O为0.8～5.0，更优选(P2O5+Na2O)/Li2O为1.0～3.0，进一步优选(P2O5+Na2O)/Li2O为1.5～2.5；和/或K2O/ZrO2为0.1以上，优选K2O/ZrO2为0.2～10.0，更优选K2O/ZrO2为0.3～5.0，进一步优选K2O/ZrO2为0.4～1.5；和/或(ZnO+RO+B2O3+TiO2)/P2O5为1.5以下，优选(ZnO+RO+B2O3+TiO2)/P2O5为1.0以下，更优选(ZnO+RO+B2O3+TiO2)/P2O5为0.5以下，进一步优选(ZnO+RO+B2O3+TiO2)/P2O5为0.2以下，所述RO为MgO、CaO、SrO、BaO中的一种或多种。The matrix glass according to claim 43 or 44, characterized in that its components are expressed in weight percentage, wherein: (Al 2 O 3 +Na 2 O)/P 2 O 5 is 3.0-30.0, preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 4.0-20.0, more preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 5.0-15.0, and further preferably (Al 2 O 3 +Na 2 O)/P 2 O 5 is 6.0-10.0; and/or SiO 2 /Al 2 O 3 is 1.2-2.8, preferably SiO 2 /Al 2 O 3 is 1.3-2.5, more preferably SiO 2 /Al 2 O 3 is 1.5-2.2, and further preferably SiO 2 /Al 2 O 3 is 1.6-2.0; and/or SiO 2 /(Na 2 O+B 2 O 3 ) is 2.0 to 15.0, preferably SiO 2 /(Na 2 O + B 2 O 3 ) is 3.0 to 10.0, more preferably SiO 2 /(Na 2 O + B 2 O 3 ) is 4.0 to 8.0, and further preferably SiO 2 /(Na 2 O + B 2 O 3 ) is 5.0 to 7.0; and/or (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; and/or (ZrO 2 + ZnO) / Na 2 O is 2.0 or less, preferably (ZrO 2 + ZnO) / Na 2 O is 2.0 or less, and further preferably (ZrO 2 + ZnO) / Na 2 O is 2.0 or less. (ZrO 2 + ZnO) / Na 2 O is 1.5 or less, 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; and/or (P 2 O 5 + Na 2 O) / Li 2 O is 0.5 to 8.0, preferably (P 2 O 5 + Na 2 O) / Li 2 O is 0.8 to 5.0, more preferably (P 2 O 5 + Na 2 O) / Li 2 O is 1.0 to 3.0, and further preferably (P 2 O 5 + Na 2 O) / Li 2 O is 1.5 to 2.5; and/or K 2 O / ZrO 2 is 0.1 or more, preferably K 2 O / ZrO 2 is 0.2 to 10.0, more preferably K 2 O / ZrO 2 is 0.3 to 5.0, and further preferably K 2 O / ZrO 2 is 1.5 to 2.5. 2 is 0.4-1.5; and/or (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is 1.5 or less, preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is 1.0 or less, more preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is 0.5 or less , further preferably (ZnO+RO+ B2O3 + TiO2 )/ P2O5 is 0.2 or less , and the RO is one or more of MgO, CaO , SrO, and BaO.
  46. 根据权利要求43或44所述的基质玻璃，其特征在于，其组分按重量百分比表示，其中：SiO2：43～55％，优选SiO2：46～53％；和/或Al2O3：23～36％，优选Al2O3：25.5～32％；和/或Li2O：3～13％，优选Li2O：5.5～11％；和/或Na2O： 5～15％，优选Na2O：6.5～12％；和/或P2O5+ZrO2：2～12％，优选P2O5+ZrO2：4～10％；和/或K2O：0～5％，优选K2O：0.1～3％；和/或ZnO：0～3％，优选ZnO：0～1％；和/或B2O3：0～3％，优选B2O3：0～1％；和/或RO：0～5％，优选RO：0～2％；和/或TiO2：0～3％，优选TiO2：0～1％；和/或Ln2O3：0～3％，优选Ln2O3：0～1％；和/或澄清剂：0～1％，优选澄清剂：0～0.5％，所述RO为MgO、CaO、SrO、BaO中的一种或多种，Ln2O3为La2O3、Gd2O3、Y2O3中的一种或多种。The matrix glass according to claim 43 or 44, characterized in that its components are expressed in weight percentage, wherein: SiO 2 : 43-55%, preferably SiO 2 : 46-53%; and/or Al 2 O 3 : 23-36%, preferably Al 2 O 3 : 25.5-32%; and/or Li 2 O: 3-13%, preferably Li 2 O: 5.5-11%; and/or Na 2 O: 5-15%, preferably Na 2 O: 6.5-12%; and/or P 2 O 5 + ZrO 2 : 2-12%, preferably P 2 O 5 + ZrO 2 : 4-10%; and/or K 2 O: 0-5%, preferably K 2 O: 0.1-3%; and/or ZnO: 0-3%, preferably ZnO: 0-1%; and/or B 2 O 3 : 0-3%, preferably B 2 O 3 : 0-1%; and/or RO: 0-5%, preferably RO: 0-2%; and/or TiO 2 : 0-3%, preferably TiO 2 : 0-1%; and/or Ln 2 O 3 : 0-3%, preferably Ln 2 O 3 : 0-1%; and/or clarifier: 0-1%, preferably clarifier: 0-0.5%, wherein RO is one or more of MgO, CaO, SrO, and BaO, and Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , and Y 2 O 3 .
  47. 根据权利要求43或44所述的基质玻璃，其特征在于，其组分按重量百分比表示，其中：ZrO2：0～6％，优选ZrO2：0～5％，更优选ZrO2：0.1～3％；和/或P2O5：0～10％，优选P2O5：1～8％，更优选P2O5：2～6％。The matrix glass according to claim 43 or 44, characterized in that its components are expressed in weight percentage, wherein: ZrO2 : 0-6 % , preferably ZrO2 : 0-5%, more preferably ZrO2 : 0.1-3%; and/or P2O5 : 0-10%, preferably P2O5 : 1-8%, more preferably P2O5 : 2-6 %.
  48. 根据权利要求43或44所述的基质玻璃，其特征在于，其组分按重量百分比表示，还含有：Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～5％，优选Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～2％，更优选Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2：0～1％。The matrix glass according to claim 43 or 44, characterized in that its components , expressed in weight percentage, further contain : Yb2O3 + Nb2O5 + WO3 + Bi2O3 +Ta2O5 +TeO2+GeO2: 0-5%, preferably Yb2O3+Nb2O5+WO3 + Bi2O3 + Ta2O5 + TeO2 + GeO2 : 0-2 % , more preferably Yb2O3 + Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2 + GeO2 : 0-1 %.
  49. 根据权利要求43或44所述的基质玻璃，其特征在于，其组分按重量百分比表示，还含有：NiO：0～4％；和/或Ni2O3：0～4％；和/或CoO：0～2％；和/或Co2O3：0～2％；和/或Fe2O3：0～7％；和/或MnO2：0～4％；和/或Er2O3：0～8％；和/或Nd2O3：0～8％；和/或Cu2O：0～4％；和/或Pr2O3：0～8％；和/或CeO2：0～4％。The matrix glass according to claim 43 or 44 is characterized in that its components, expressed in weight percentage, further contain: 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 3 : 0-8%; and/or CeO 2 : 0-4%.
  50. 微晶玻璃成形体，其特征在于，含有权利要求22～42任一所述的微晶玻璃。A glass-ceramic molded body, characterized in that it contains the glass-ceramic according to any one of claims 22 to 42.
  51. 玻璃盖板，其特征在于，含有权利要求1～21任一所述的微晶玻璃制品，和/或权利要求22～42任一所述的微晶玻璃，和/或权利要求43～49任一所述的基质玻璃，和/或权利要求50所述的微晶玻璃成形体。A glass cover plate, characterized in that it contains the microcrystalline glass product described in any one of claims 1 to 21, and/or the microcrystalline glass described in any one of claims 22 to 42, and/or the matrix glass described in any one of claims 43 to 49, and/or the microcrystalline glass formed body described in claim 50.
  52. 玻璃元器件，其特征在于，含有权利要求1～21任一所述的微晶玻璃制品，和/或权利要求22～42任一所述的微晶玻璃，和/或权利要求43～49任一所述的基质玻璃，和/或权利要求50所述的微晶玻璃成形体。A glass component, characterized in that it contains the microcrystalline glass product described in any one of claims 1 to 21, and/or the microcrystalline glass described in any one of claims 22 to 42, and/or the matrix glass described in any one of claims 43 to 49, and/or the microcrystalline glass formed body described in claim 50.
  53. 显示设备，其特征在于，含有权利要求1～21任一所述的微晶玻璃制品，和/或权利要求22～42任一所述的微晶玻璃，和/或权利要求43～49任一所述的基质玻璃，和/或权利要求50所述的微晶玻璃成形体，和/或权利要求51所 述的玻璃盖板，和/或权利要求52所述的玻璃元器件。A display device, characterized in that it contains the microcrystalline glass product according to any one of claims 1 to 21, and/or the microcrystalline glass according to any one of claims 22 to 42, and/or the matrix glass according to any one of claims 43 to 49, and/or the microcrystalline glass formed body according to claim 50, and/or the matrix glass according to claim 51. The glass cover plate described in claim 51, and/or the glass component described in claim 52.
  54. 电子设备，其特征在于，含有权利要求1～21任一所述的微晶玻璃制品，和/或权利要求22～42任一所述的微晶玻璃，和/或权利要求43～49任一所述的基质玻璃，和/或权利要求50所述的微晶玻璃成形体，和/或权利要求51所述的玻璃盖板，和/或权利要求52所述的玻璃元器件。An electronic device, characterized in that it contains the microcrystalline glass product described in any one of claims 1 to 21, and/or the microcrystalline glass described in any one of claims 22 to 42, and/or the matrix glass described in any one of claims 43 to 49, and/or the microcrystalline glass formed body described in claim 50, and/or the glass cover plate described in claim 51, and/or the glass component described in claim 52.
  55. 权利要求1～21任一所述微晶玻璃制品的制造方法，其特征在于，所述方法包括以下步骤：形成基质玻璃，将基质玻璃通过晶化工艺形成微晶玻璃，再将所述微晶玻璃通过化学强化工艺形成微晶玻璃制品。The method for manufacturing a glass-ceramic product according to any one of claims 1 to 21 is characterized in that the method comprises the following steps: forming a matrix glass, forming a glass-ceramic by a crystallization process of the matrix glass, and then forming a glass-ceramic product by a chemical strengthening process of the glass-ceramic.
  56. 根据权利要求55所述的微晶玻璃制品的制造方法，其特征在于，所述晶化工艺包括以下步骤：升温至规定的晶化处理温度，在达到晶化处理温度之后，将其温度保持一定的时间，然后再进行降温，该晶化处理温度为580～750℃，优选为600～700℃，在晶化处理温度下的保持时间为0～8小时，优选为1～6小时。According to the manufacturing method of microcrystalline glass products described in claim 55, it is characterized in that the crystallization process includes the following steps: heating to a specified crystallization treatment temperature, after reaching the crystallization treatment temperature, maintaining the temperature for a certain period of time, 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.
  57. 根据权利要求55所述的微晶玻璃制品的制造方法，其特征在于，所述晶化工艺包括以下步骤：在第1温度下进行成核工艺的处理，然后在比成核工艺温度高的第2温度下进行晶体生长工艺的处理。The method for manufacturing a microcrystalline glass product according to claim 55 is characterized in that 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.
  58. 根据权利要求57所述的微晶玻璃制品的制造方法，其特征在于，所述晶化工艺包括以下步骤：第1温度为500～620℃，第2温度为620～750℃；在第1温度下的保持时间为0～24小时，优选为2～15小时；在第2温度下的保持时间为0～10小时，优选为0.5～6小时。The method for manufacturing microcrystalline glass products according to claim 57 is characterized in that the crystallization process includes the following steps: the first temperature is 500-620°C, 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.
  59. 根据权利要求55～58任一所述的微晶玻璃制品的制造方法，其特征在于，所述化学强化工艺包括：微晶玻璃浸没于350～470℃的温度的熔融Na盐的盐浴中1～36小时，优选温度范围为380～460℃，优选时间范围为2～10小时；和/或微晶玻璃浸没于360℃～450℃的温度下熔融K盐的盐浴中1～36小时，优选时间范围为1～10小时；和/或微晶玻璃浸没于360～450℃的温度下熔融K盐和Na盐的混合盐浴中1～36小时，优选时间范围为2～24小时。The method for manufacturing a microcrystalline glass product according to any one of claims 55 to 58 is characterized in that the chemical strengthening process comprises: 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 preferably in the time range of 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.
  60. 权利要求22～42任一所述的微晶玻璃的制造方法，其特征在于，所述方法包括以下步骤：形成基质玻璃，然后将基质玻璃通过晶化工艺形成微晶玻璃。 The method for manufacturing microcrystalline glass according to any one of claims 22 to 42 is characterized in that the method comprises the following steps: forming a matrix glass, and then forming microcrystalline glass through a crystallization process of the matrix glass.
  61. 根据权利要求60所述的微晶玻璃的制造方法，其特征在于，所述晶化工艺包括以下步骤：升温至规定的晶化处理温度，在达到晶化处理温度之后，将其温度保持一定的时间，然后再进行降温，该晶化处理温度为580～750℃，优选为600～700℃，在晶化处理温度下的保持时间为0～8小时，优选为1～6小时。According to the manufacturing method of microcrystalline glass as described in claim 60, it is characterized in that the crystallization process includes the following steps: heating to a specified crystallization treatment temperature, after reaching the crystallization treatment temperature, maintaining the temperature for a certain period of time, 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.
  62. 根据权利要求60所述的微晶玻璃的制造方法，其特征在于，所述晶化工艺包括以下步骤：在第1温度下进行成核工艺的处理，然后在比成核工艺温度高的第2温度下进行晶体生长工艺的处理。The method for manufacturing microcrystalline glass according to claim 60 is characterized in that 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.
  63. 根据权利要求62所述的微晶玻璃的制造方法，其特征在于，所述晶化工艺包括以下步骤：第1温度为500～620℃，第2温度为620～750℃；在第1温度下的保持时间为0～24小时，优选为2～15小时；在第2温度下的保持时间为0～10小时，优选为0.5～6小时。The method for manufacturing microcrystalline glass according to claim 62 is characterized in that the crystallization process includes the following steps: the first temperature is 500-620°C, 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.
  64. 权利要求50所述的微晶玻璃成形体的制造方法，其特征在于，所述方法包括将微晶玻璃研磨或抛光制成微晶玻璃成形体，或在一定温度下将基质玻璃或微晶玻璃通过热弯工艺或压型工艺制成微晶玻璃成形体。The method for manufacturing a microcrystalline glass formed body as described in claim 50 is characterized in that the method includes grinding or polishing the microcrystalline glass to form a microcrystalline glass formed body, or subjecting the matrix glass or microcrystalline glass to a heat bending process or a pressing process at a certain temperature to form a microcrystalline glass formed body.
  65. 权利要求50所述的微晶玻璃成形体的制造方法，其特征在于，所述方法包括以下步骤：将基质玻璃进行一次晶化热处理过程，包括升温、保温核化、升温、保温晶化、降温至室温，形成预晶化玻璃；将预晶化玻璃进行热加工成型得到微晶玻璃成形体。The method for manufacturing a microcrystalline glass formed body as described in claim 50 is characterized in that the method includes the following steps: subjecting the matrix glass to a crystallization heat treatment process, including heating, heat preservation for nucleation, heating, heat preservation for crystallization, and cooling to room temperature to form pre-crystallized glass; and subjecting the pre-crystallized glass to heat processing and molding to obtain a microcrystalline glass formed body.
  66. 权利要求50所述的微晶玻璃成形体的制造方法，其特征在于，所述方法包括以下步骤：The method for manufacturing a glass-ceramic formed body according to claim 50, characterized in that the method comprises the following steps:
    1)升温预热：将基质玻璃或预晶化玻璃或微晶玻璃放置于模具内，模具在热弯机中依次通过各个升温站点，并在各站点停留一定时间保温，预热区温度为400～800℃，压力为0.01～0.05MPa，时间为40～200s；1) 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;
    2)加压成型：模具在经过预热后转运到成型站点，热弯机对模具施加一定压力，压力范围为0.1～0.8Mpa，成型站点温度范围为650～850℃，成型时间范围40～200s；2) Pressurized molding: After preheating, the mold is transferred to the molding station. The hot bending machine applies a certain pressure to the mold. The pressure range is 0.1-0.8Mpa. The temperature range of the molding station is 650-850℃, and the molding time range is 40-200s.
    3)保压降温：将模具转运至降温站点逐站降温，降温温度范围750～500℃，压力为0.01～0.05Mpa，时间为40～200s。 3) Maintaining pressure and cooling: 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, and the time is 40-200s.
PCT/CN2023/123354 2022-10-25 2023-10-08 Glass ceramic, glass ceramic product, and manufacturing method therefor WO2024088033A1 (en)

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