CN113683309B - Microcrystalline glass and preparation method and application thereof - Google Patents
Microcrystalline glass and preparation method and application thereof Download PDFInfo
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- CN113683309B CN113683309B CN202110983971.2A CN202110983971A CN113683309B CN 113683309 B CN113683309 B CN 113683309B CN 202110983971 A CN202110983971 A CN 202110983971A CN 113683309 B CN113683309 B CN 113683309B
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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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
- C03C10/0018—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 containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—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 containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
Abstract
The invention provides microcrystalline glass, which comprises a glass substrate and a composite microcrystalline glass layer coated on the surface of the glass substrate; wherein the composite microcrystalline glass layer comprises beta-spodumene in a hexagonal crystal form, beta-spodumene in a tetragonal crystal form and other glass. The surface of the microcrystalline glass has very high Vickers hardness and compressive stress, so that the surface hardness and the drop resistance of the glass are obviously improved, and the microcrystalline glass is easy to process and low in cost.
Description
Technical Field
The invention relates to the field of glass, in particular to microcrystalline glass and a preparation method and application thereof.
Background
With the rapid development of the smart technology industry and the popularization of digital products in recent years, smart phones, tablet computers and the like equipped with touch screens have become indispensable parts in life, and the protective material of the cover plate at the outermost layer of the touch screen becomes a high-strength armor for protecting the touch screen. The cover plate of the traditional touch screen is mainly made of high-alumina glass, is mainly applied to the outmost layer of the touch screen and has the functions of impact resistance, scratch resistance, oil stain resistance, fingerprint resistance, light transmittance enhancement and the like. Currently, high-alumina glass is widely applied to various electronic consumer products with touch control function and display function.
In the traditional technology, high-aluminosilicate glass and lithium-aluminosilicate glass are developed by means of increasing the content of alumina, adding lithium oxide and the like, and the performances of impact resistance, scratch resistance, falling resistance, sweat corrosion resistance and the like of the glass are improved by one-time or multiple-time chemical strengthening. But due to the inherent brittleness and lower crack propagation resistance of the glass material, the drop resistance of the glass material on rough ground is limited to a great extent, particularly the multiple drop resistance, and is usually lower than 1.4 meters; and the Vickers hardness of the alloy is usually 550Kgf/mm 2 ～680Kgf/mm 2 While it is difficult to exceed 700Kgf/mm 2 I.e., less scratch resistance.
Also, a high strength glass-ceramic having a lithium feldspar and lithium silicate structure, which is an integrally crystallized glass-ceramic having high mechanical strength and fracture resistance, is prepared by conventional techniques. However, it contains more than 10 wt% of Li 2 O component due to Li 2 The O reserve is limited, and the cost is high throughout the year, so that the cost of the glass ceramics is very high and is more than 10 times higher than that of the similar lithium-aluminum-silicon glass; and because of the integral crystallization, the glass is similar to ceramics in the post-processing process of the glass, and the processing difficulty and the cost are far higher than those of the glass substrate.
Disclosure of Invention
Based on the structure, the invention provides the microcrystalline glass, wherein a composite microcrystalline glass layer containing a beta-spodumene crystal phase is formed on the surface of a glass substrate, and the surface of the microcrystalline glass has very high Vickers hardness and compressive stress, so that the surface hardness and the anti-falling performance of the glass are obviously improved, and the microcrystalline glass is easy to process and low in cost.
The invention is realized by the following technical scheme.
The microcrystalline glass comprises a glass substrate and a composite microcrystalline glass layer coated on the surface of the glass substrate;
wherein the composite microcrystalline glass layer comprises hexagonal beta-spodumene, tetragonal beta-spodumene and other glass.
In one embodiment, the composite glass-ceramic layer comprises, by mass, 19.2% to 88.5% of the hexagonal form of β -spodumene, 3% to 75.8% of the tetragonal form of β -spodumene, and 5% to 14.8% of the other glass.
In one embodiment, the other glass comprises SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O and other oxides; the other oxide is selected from K 2 O、MgO、ZrO 2 、B 2 O 3 、P 2 O 5 And ZnO; and/or
The glass substrate comprises SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O and other oxides; the other oxide is selected from K 2 O、MgO、ZrO 2 、B 2 O 3 、P 2 O 5 And ZnO.
In one embodiment, the thickness of the composite microcrystalline glass layer is 2-90 μm.
The invention also provides a preparation method of the microcrystalline glass, which comprises the following steps:
preparing a glass prefabricated part, and performing primary crystallization and secondary crystallization on the glass prefabricated part to prepare the composite microcrystalline glass layer;
wherein the temperature of the first crystallization is 630-700 ℃, and the time of the first crystallization is 2-10 h;
and after the first crystallization is finished, heating, and carrying out second crystallization, wherein the temperature of the second crystallization is 780-830 ℃, and the time of the second crystallization is 0.5-4 h.
In one embodiment, the raw materials of the glass prefabricated member are mixed, melted for 7-9 h at 1500-1650 ℃, then cooled to 1300-1500 ℃, kept warm for 1.5-2.5 h, molded, prepared into a glass block, annealed and cooled after the glass block is hardened;
wherein the raw material of the glass preform comprises SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O and other oxides; the other oxide is selected from K 2 O、MgO、ZrO 2 、B 2 O 3 、P 2 O 5 And ZnO.
In one embodiment, the raw material of the glass preform comprises 50 to 68 mass percent of SiO 2 、18％～29.5％Al 2 O 3 、2％～6.5％Li 2 O、3％～10％Na 2 O and 0.1-15% of other oxides.
In one embodiment, the temperature of the first crystallization is 660-700 ℃, and the time of the first crystallization is 2-10 h.
In one embodiment, the temperature of the second crystallization is 810-830 ℃, and the time of the second crystallization is 1-4 h.
In one embodiment, the temperature rise rate is 2-10 deg.C/min.
The invention also provides application of the microcrystalline glass in protective glass, special glass and architectural glass of electronic devices.
Compared with the prior art, the microcrystalline glass has the following beneficial effects:
the microcrystalline glass comprises a glass substrate and a composite microcrystalline glass layer which is formed on the surface of the glass substrate and contains a beta-spodumene crystal phase and other glass, wherein the beta-spodumene comprises a hexagonal crystal form and a tetragonal crystal form. The composite microcrystalline glass layer can form a uniform and compact compressive stress layer on the surface of glass, so that the composite microcrystalline glass layer has very high Vickers hardness and compressive stress, and the surface hardness and the drop resistance of the whole glass are obviously improved.
In addition, the microcrystalline glass provided by the invention keeps the advantage that the glass substrate is easy to process, and is low in cost and easy to industrialize.
Drawings
FIG. 1 is an XRD pattern of a sample provided by the present invention; wherein: the XRD spectrum of the microcrystalline glass preform composite microcrystalline glass layer provided in example 6 is represented by 1, the XRD spectrum of the microcrystalline glass preform composite microcrystalline glass layer provided in example 12 is represented by 2, the XRD spectrum of the microcrystalline glass preform composite microcrystalline glass layer provided in example 1 is represented by 3, the XRD spectrum of the hexagonal beta-spodumene sample is represented by 4, and the XRD spectrum of the tetragonal beta-spodumene sample is represented by 5;
FIG. 2 is a sectional scanning electron microscope image of a sample provided in example 2 of the present invention.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying examples. The preferred embodiments of the present invention are given in the examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides microcrystalline glass, which comprises a glass substrate and a composite microcrystalline glass layer coated on the surface of the glass substrate;
wherein the composite microcrystalline glass layer comprises hexagonal beta-spodumene, tetragonal beta-spodumene and other glass.
In a specific example, the composite microcrystalline glass layer comprises 19.2-88.5% of beta-spodumene in a hexagonal crystal form, 3-75.8% of beta-spodumene in a tetragonal crystal form and 5-14.8% of other glass in percentage by mass.
In the glass-ceramic, the component species of the other glass are consistent with the composition of the glass matrix.
In one particular example, the other glass comprises SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O and other oxides; the other oxide is selected from K 2 O、MgO、ZrO 2 、B 2 O 3 、P 2 O 5 And ZnO.
In one particular example, the glass substrate comprises SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O and other oxides; the other oxide is selected from K 2 O、MgO、ZrO 2 、B 2 O 3 、P 2 O 5 And ZnO.
In a specific example, the composite microcrystalline glass layer has a thickness of 2 μm to 90 μm. It is understood that in the present invention, the thickness of the composite microcrystalline glass layer includes, but is not limited to, 2 μm, 3 μm, 4 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm.
The invention also provides a preparation method of the microcrystalline glass, which comprises the following steps:
preparing a glass prefabricated part, and performing primary crystallization and secondary crystallization on the glass prefabricated part to prepare a composite microcrystalline glass layer;
wherein the temperature of the first crystallization is 630-700 ℃, and the time of the first crystallization is 2-10 h;
and after the first crystallization is finished, heating, and carrying out second crystallization, wherein the temperature of the second crystallization is 780-830 ℃, and the time of the second crystallization is 0.5-4 h.
After the glass prefabricated member is subjected to a specific twice crystallization process, a layer, namely a composite microcrystalline glass layer, is uniformly separated out on the surface layer, an intermediate glass layer is remained, and the composite microcrystalline glass layer and the glass layer form microcrystalline glass together.
In one particular example, the preparation of the glass preform comprises the steps of: mixing the raw materials of the glass prefabricated member, melting for 7-9 h at 1500-1650 ℃, then cooling to 1300-1500 ℃, preserving heat for 1.5-2.5 h, forming, preparing a glass block, annealing after the glass block is hardened, and cooling;
wherein the raw material of the glass preform comprises SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O and other oxides; the other oxide is selected from K 2 O、MgO、ZrO 2 、B 2 O 3 、P 2 O 5 And ZnO.
It is to be understood that in the present invention, only SiO is contained 2 、Al 2 O 3 、Li 2 O、Na 2 O and other oxide species may be used as starting materials, including but not limited to: quartz sand, aluminium hydroxide, lithium carbonate/spodumene, sodium carbonate, sodium nitrate.
In a specific example, the raw material of the glass preform includes 50% to 68% SiO in mass percentage 2 、18％～29.5％Al 2 O 3 、2％～6.5％Li 2 O、3％～10％Na 2 O and 0.1-15% of other oxides.
Preferably, the temperature of the first crystallization is 660 to 700 ℃.
Preferably, the time for the first crystallization is 2h to 10 h.
Preferably, the temperature of the second crystallization is 810 ℃ to 830 ℃.
Preferably, the time of the second crystallization is 1h to 4 h.
In a specific example, the rate of temperature rise is 2 ℃/min to 10 ℃/min. As can be appreciated, in the present invention, the rate of temperature rise includes, but is not limited to, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min, 10 deg.C/min.
The invention also provides application of the microcrystalline glass in protective glass, special glass and architectural glass of electronic devices. It is understood that electronic devices include, but are not limited to, smart display devices, mobile devices, and the like.
It is understood that in the present invention, the above-mentioned glass ceramics can be obtained in the conventional flat glass manufacturing process, and the manufacturing process is not limited to the float forming process, the overflow down-draw process, the up-draw process, the flat-draw process, the rolling process, etc.
The following describes the microcrystalline glass and the method for producing the same in further detail with reference to specific examples. The starting materials used in the following examples are all commercially available products unless otherwise specified.
Example 1
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
58% SiO 2 22% of Al 2 O 3 0.5% of K 2 O, 1.5% of MgO and 10% of Na 2 O, 4% Li 2 O, 2% ZrO 2 1% of B 2 O 3 1% of ZnO;
after fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：645℃，4h；
TT2：800℃，1h；
the heating rate was 10 ℃/min.
Example 2
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: preparation of glass preform
Mixing the following raw materials in percentage by mass:
58% SiO 2 20% of Al 2 O 3 4% of K 2 O, 4% MgO, 4.5% Na 2 O, 5% of Li 2 O, 4.5% ZrO 2 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass prefabricated member according to the following crystallization process, wherein TT1 refers to the time and temperature of the first-step crystallization process, and TT2 refers to the time and temperature of the second-step crystallization process:
TT1：630℃，6h；
TT2：810℃，1h；
the heating rate was 5 ℃/min.
Example 3
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
56% SiO 2 26% of Al 2 O 3 1% of K 2 O, 1.5% of MgO and 2% of Na 2 O, 7% of Li 2 O, 1% ZrO 2 1% of B 2 O 3 0.5% of P 2 O 5 4% of ZnO;
after fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：680℃，4h；
TT2：810℃，1h；
the temperature rise rate was 2 ℃/min.
Example 4
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
61% SiO 2 23% of Al 2 O 3 1.3% of K 2 O, 1.5% of MgO and 4.2% of Na 2 O, 3.5% of Li 2 O, 1% ZrO 2 3% of B 2 O 3 0.5% of P 2 O 5 1% of ZnO;
after fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：650℃，10h；
TT2：800℃，2h；
the heating rate was 10 ℃/min.
Example 5
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: preparation of glass preform
Mixing the following raw materials in percentage by mass:
68% SiO 2 18% of Al 2 O 3 1% of K 2 O, 1.5% of MgO and 4% of Na 2 O, 4.5% of Li 2 O, 1% ZrO 2 1.5% of B 2 O 3 0.5% of P 2 O 5 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：660℃，4h；
TT2：810℃，1h；
the heating rate was 5 ℃/min.
Example 6
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
59% SiO 2 25% of Al 2 O 3 1% of K 2 O, 1.5% of MgO and 3% of Na 2 O, 2% of Li 2 O, 0.5% ZrO 2 3% of B 2 O 3 5% of P 2 O 5 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：675℃，4h；
TT2：795℃，1h；
the temperature rise rate was 10 ℃/min.
Example 7
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: preparation of glass preform
Mixing the following raw materials in percentage by mass:
58% SiO 2 22% of Al 2 O 3 1% of K 2 O, 1% MgO, 3% Na 2 O, 6% Li 2 O, 2% ZrO 2 3% of B 2 O 3 2% of P 2 O 5 2% of ZnO;
after fully and uniformly mixing, melting for 8h at the temperature of 1500-plus-1650 ℃ by a platinum crucible, stirring by a platinum stirring paddle, after the stirring paddle is drawn out, cooling to the temperature of 1300-plus-1500 ℃, preserving heat for 2h for homogenization, casting the mixture on an iron mould to form a glass block with the size of about 80 to 160mm, preheating the glass block to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of microcrystalline glass
Crystallizing the glass prefabricated member according to the following crystallization process, wherein TT1 refers to the time and temperature of the first-step crystallization process, and TT2 refers to the time and temperature of the second-step crystallization process:
TT1：690℃，4h；
TT2：820℃，1h；
the heating rate was 2 ℃/min.
Example 8
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
50% SiO 2 29.5% of Al 2 O 3 1.4% of K 2 O, 0.5% of MgO and 7% of Na 2 O, 4% of Li 2 O, 1% ZrO 2 5% of B 2 O 3 1.6% of P 2 O 5 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：680℃，6h；
TT2：810℃，1h；
the heating rate was 5 ℃/min.
Example 9
The embodiment provides microcrystalline glass and a preparation method thereof, which specifically comprise the following steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
57% SiO 2 23% of Al 2 O 3 1.5% of K 2 O, 3.5% of MgO and 4.5% of Na 2 O, 4% Li 2 O, 4% ZrO 2 0.5% of B 2 O 3 1% of P 2 O 5 1% of ZnO;
after fully and uniformly mixing, melting for 8h at the temperature of 1500-plus-1650 ℃ by a platinum crucible, stirring by a platinum stirring paddle, after the stirring paddle is drawn out, cooling to the temperature of 1300-plus-1500 ℃, preserving heat for 2h for homogenization, casting the mixture on an iron mould to form a glass block with the size of about 80 to 160mm, preheating the glass block to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：660℃，4h；
TT2：810℃，0.5h；
the temperature rise rate was 5 ℃/min.
Example 10
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
56% SiO 2 26% of Al 2 O 3 1.4% of K 2 O, 3.5% of MgO and 5% of Na 2 O, 4.5% of Li 2 O, 3.6% ZrO 2 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass prefabricated member according to the following crystallization process, wherein TT1 refers to the time and temperature of the first-step crystallization process, and TT2 refers to the time and temperature of the second-step crystallization process:
TT1：650℃，6h；
TT2：790℃，2h；
the temperature rise rate was 2 ℃/min.
Example 11
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
56% SiO 2 25% of Al 2 O 3 1.5% of K 2 O, 1% of MgO and 7% of Na 2 O, 5% of Li 2 O, 2% ZrO 2 1% of B 2 O 3 1.5% of P 2 O 5 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：645℃，4h；
TT2：810℃，1h；
the temperature rise rate was 5 ℃/min.
Example 12
The embodiment provides microcrystalline glass and a preparation method thereof, which specifically comprise the following steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
55% SiO 2 25% of Al 2 O 3 1% of K 2 O, 2% of MgO and 4% of Na 2 O, 6.5% of Li 2 O, 1% ZrO 2 3% of B 2 O 3 0.5% of P 2 O 5 2% of ZnO;
after fully and uniformly mixing, melting for 8h at the temperature of 1500-plus-1650 ℃ by a platinum crucible, stirring by a platinum stirring paddle, after the stirring paddle is drawn out, cooling to the temperature of 1300-plus-1500 ℃, preserving heat for 2h for homogenization, casting the mixture on an iron mould to form a glass block with the size of about 80 to 160mm, preheating the glass block to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：690℃，4h；
TT2：820℃，1h；
the heating rate was 10 ℃/min.
Example 13
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
60.5% SiO 2 24% of Al 2 O 3 1% of K 2 O, 1.5% of MgO and 4% of Na 2 O, 4.5% of Li 2 O, 1% ZrO 2 3% of B 2 O 3 0.5% of P 2 O 5 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of microcrystalline glass
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：700℃，2h；
TT2：820℃，1h；
the temperature rise rate was 5 ℃/min.
Example 14
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
63% SiO 2 22% of Al 2 O 3 1% of K 2 O, 1% MgO, 4.5% Na 2 O, 5% of Li 2 O, 1% ZrO 2 2% of B 2 O 3 0.5% of P 2 O 5 ；
After fully and uniformly mixing, melting for 8h at the temperature of 1500-plus-1650 ℃ by a platinum crucible, stirring by a platinum stirring paddle, after the stirring paddle is drawn out, cooling to the temperature of 1300-plus-1500 ℃, preserving heat for 2h for homogenization, casting the mixture on an iron mould to form a glass block with the size of about 80 to 160mm, preheating the glass block to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：650℃，4h；
TT2：810℃，1.5h；
the heating rate was 10 ℃/min.
Example 15
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
55% SiO 2 25% of Al 2 O 3 9% of Na 2 O, 3% of Li 2 O, 3% of B 2 O 3 4% of P 2 O 5 1% of ZnO;
after fully and uniformly mixing, melting for 8h at the temperature of 1500-plus-1650 ℃ by a platinum crucible, stirring by a platinum stirring paddle, after the stirring paddle is drawn out, cooling to the temperature of 1300-plus-1500 ℃, preserving heat for 2h for homogenization, casting the mixture on an iron mould to form a glass block with the size of about 80 to 160mm, preheating the glass block to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：650℃，10h；
TT2：820℃，2h；
the heating rate was 2 ℃/min.
Example 16
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: preparation of glass preform
Mixing the following raw materials in percentage by mass:
53% SiO 2 28% of Al 2 O 3 1.5% of MgO and 7% of Na 2 O, 3% of Li 2 O, 3.5% ZrO 2 1% of B 2 O 3 3% of P 2 O 5 ；
After fully and uniformly mixing, melting for 8h at the temperature of 1500-plus-1650 ℃ by a platinum crucible, stirring by a platinum stirring paddle, after the stirring paddle is drawn out, cooling to the temperature of 1300-plus-1500 ℃, preserving heat for 2h for homogenization, casting the mixture on an iron mould to form a glass block with the size of about 80 to 160mm, preheating the glass block to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：660℃，6h；
TT2：810℃，4h；
the heating rate was 10 ℃/min.
Example 17
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: preparation of glass preform
Mixing the following raw materials in percentage by mass:
57% SiO 2 25% of Al 2 O 3 1.5% of K 2 O, 3.5% of MgO and 4.5% of Na 2 O, 4% Li 2 O, 3% ZrO 2 0.5% of B 2 O 3 1% of ZnO;
after fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：630℃，8h；
TT2：810℃，1h；
the heating rate was 10 ℃/min.
Example 18
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
58.5% SiO 2 25% of Al 2 O 3 1.5% of K 2 O, 3.5% of MgO and 4.5% of Na 2 O, 4% Li 2 O, 2.5% ZrO 2 0.5% of B 2 O 3 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of microcrystalline glass
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：645℃，10h；
TT2：780℃，4h；
the heating rate was 5 ℃/min.
Example 19
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
61% SiO 2 24% of Al 2 O 3 1% of K 2 O, 1% MgO, 4% Na 2 O, 5% of Li 2 O, 2% ZrO 2 2% of B 2 O 3 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass prefabricated member according to the following crystallization process, wherein TT1 refers to the time and temperature of the first-step crystallization process, and TT2 refers to the time and temperature of the second-step crystallization process:
TT1：645℃，4h；
TT2：810℃，1h；
the heating rate was 2 ℃/min.
Example 20
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
62% SiO 2 24% of Al 2 O 3 0.5% of K 2 O, 0.5% MgO, 4.5% Na 2 O, 5% of Li 2 O, 1% ZrO 2 2% of B 2 O 3 0.5% of P 2 O 5 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：690℃，4h；
TT2：820℃，0.5h；
the heating rate was 10 ℃/min.
Example 21
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
62% SiO 2 23% of Al 2 O 3 0.5% of K 2 O, 0.5% MgO, 5% Na 2 O, 5% of Li 2 O, 2% ZrO 2 1.5% of B 2 O 3 0.5% of P 2 O 5 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：645℃，4h；
TT2：810℃，1h；
the heating rate was 2 ℃/min.
Example 22
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
62% SiO 2 23% of Al 2 O 3 1% of K 2 O, 0.5% of MgO and 5% of Na 2 O, 5% of Li 2 O, 1.5% ZrO 2 1.5% of B 2 O 3 0.5% of P 2 O 5 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：645℃，4h；
TT2：810℃，1h；
the heating rate was 5 ℃/min.
Example 23
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
56% SiO 2 23% of Al 2 O 3 4% of K 2 O, 7% of Na 2 O, 3% of Li 2 O, 2% ZrO 2 3% of P 2 O 5 2% of ZnO;
after fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：650℃，10h；
TT2：810℃，1.5h；
the temperature rise rate was 10 ℃/min.
Example 24
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
55% SiO 2 25% of Al 2 O 3 3% of K 2 O, 7% of Na 2 O, 4% Li 2 O, 2% of B 2 O 3 4% of P 2 O 5 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of microcrystalline glass
Crystallizing the glass prefabricated member according to the following crystallization process, wherein TT1 refers to the time and temperature of the first-step crystallization process, and TT2 refers to the time and temperature of the second-step crystallization process:
TT1：660℃，10h；
TT2：830℃，1h；
the heating rate was 5 ℃/min.
Example 25
The embodiment provides microcrystalline glass and a preparation method thereof, and the microcrystalline glass comprises the following specific steps:
the method comprises the following steps: production of glass preform
Mixing the following raw materials in percentage by mass:
56% SiO 2 25% of Al 2 O 3 3% of MgO and 7% of Na 2 O, 3% of Li 2 O, 3.5% ZrO 2 1% of B 2 O 3 1.5% of P 2 O 5 ；
After fully and uniformly mixing, melting for 8h at 1650 ℃ with a platinum crucible, stirring with a platinum stirring paddle, after the stirring paddle is drawn out, cooling to 1300-1500 ℃, preserving heat for 2h, homogenizing, casting onto an iron mold to form a glass block with the size of about 80 x 160mm, preheating to 450 ℃ before casting, immediately transferring the glass block to an annealing furnace for annealing after hardening, preserving heat for 2h, then cooling for 6 h to 140 ℃, naturally cooling, and taking out for later use.
Step two: preparation of glass ceramics
Crystallizing the glass preform according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:
TT1：700℃，2h；
TT2：820℃，1h；
the heating rate was 10 ℃/min.
Effect test
The glass preform obtained in the first step of examples 1 to 25 was cut into a 70 × 140 × 0.7mm glass sheet by a line cutter STX-1203 of shenyan crystal, polished by a HD-640-5L double-side grinding polisher of shenzhen heider, CNC-edged, and tested for surface vickers hardness using a FALCON400 hardness tester from netherlands rank.
The microcrystalline glasses obtained in the second step of examples 1 to 25 were tested for Vickers hardness by a FALCON400 hardness tester of anethod, the United states PerkinElmer Lamba 950 ultraviolet-visible spectrophotometer, which tests the transmittance in the wavelength range of 400-.
The microcrystalline glass obtained in the second step of examples 1 to 25 was cut, the cross section was polished and ground, then etched for 20 seconds with 5 vol% HF solution, and the surface crystal phase structure and the crystal phase layer thickness were tested by the seemer fly FEI Apreo scanning electron microscope.
The glass ceramics obtained in the second step of the above examples 1 to 25 are cut into 20 × 20mm, the crystal phase type of the composite glass ceramics layer is tested by Bruker D8 advance of Bruker, and the proportions of different crystal phases and amorphous phases in the composite glass ceramics layer are calculated by simulation of TOPAS software.
The composition, crystallite process parameters and effect test results for examples 1-8 are shown in table 1.
TABLE 1
The composition, crystallite process parameters and effect test results for examples 9-16 are shown in table 2.
TABLE 2
The composition, crystallite processing parameters and effect test results for examples 17-25 are shown in table 3.
TABLE 3
Wherein, the XRD patterns of example 1, example 6 and example 12 are respectively shown in fig. 1, it can be seen that the less beta-spodumene (tetragonal form) in the crystal phase layer, especially less than 10.4%, the transmittance of the 0.7mm sample is higher than 90%, and the sample is transparent; beta-spodumene (tetragonal form) is increasing, especially above 40%, and the 0.7mm sample has a transmittance of less than 72% and an opaque white appearance.
Fig. 2 is a typical sectional scanning electron microscope image of a sample in example 12, which shows that after the above glass composition is subjected to a proper crystallization process, a crystal phase layer with a thickness of 2 μm to 90 μm can be uniformly precipitated on a surface layer, and the crystal phase layer and the intermediate glass layer are combined together to form a surface-crystallized glass-ceramic composition, and a uniform and dense compressive stress layer is formed on the surface of the glass through volume change caused by surface crystallization, so that the surface hardness and the sandpaper drop resistance of the glass can be significantly improved.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present patent shall be subject to the content of the appended claims, and the description and drawings can be used to explain the content of the claims.
Claims (11)
1. The microcrystalline glass is characterized by comprising a glass substrate and a composite microcrystalline glass layer coated on the surface of the glass substrate;
wherein, the composite microcrystalline glass layer comprises 19.2 to 88.5 percent of beta-spodumene in hexagonal crystal form, 3 to 75.8 percent of beta-spodumene in tetragonal crystal form and 5 to 14.8 percent of other glass in percentage by mass.
2. Glass-ceramic according to claim 1, characterized in that the other glass comprises SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O and other oxides; the other oxide is selected from K 2 O、MgO、ZrO 2 、B 2 O 3 、P 2 O 5 And ZnO.
3. The glass-ceramic according to claim 1, wherein the glass substrate comprises SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O and other oxides; the other oxide is selected from K 2 O、MgO、ZrO 2 、B 2 O 3 、P 2 O 5 And ZnO.
4. The microcrystalline glass according to claim 1, wherein the composite microcrystalline glass layer has a thickness of 2 μm to 90 μm.
5. A method for preparing a glass-ceramic according to any one of claims 1 to 4, comprising the steps of:
preparing a glass prefabricated part, and performing primary crystallization and secondary crystallization on the glass prefabricated part to prepare the composite microcrystalline glass layer;
wherein the temperature of the first crystallization is 630-700 ℃, and the time of the first crystallization is 2-10 h;
and after the first crystallization is finished, heating, and performing second crystallization, wherein the temperature of the second crystallization is 780-830 ℃, and the time of the second crystallization is 0.5-4 h.
6. The method for producing microcrystalline glass according to claim 5, wherein the production of the glass preform comprises the steps of: mixing the raw materials of the glass prefabricated part, melting for 7-9 h at 1500-1650 ℃, then cooling to 1300-1500 ℃, preserving heat for 1.5-2.5 h, forming, preparing a glass block, annealing after the glass block is hardened, and cooling;
wherein the raw material of the glass preform comprises SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O toAnd other oxides; the other oxide is selected from K 2 O、MgO、ZrO 2 、B 2 O 3 、P 2 O 5 And ZnO.
7. The method for producing microcrystalline glass according to claim 6, wherein the raw material of the glass preform comprises 50 to 68 mass% of SiO 2 、18％～29.5％Al 2 O 3 、2％～6.5％Li 2 O、3％～10％Na 2 O and 0.1-15% of other oxides.
8. The method for preparing glass-ceramic according to any one of claims 5 to 7, wherein the temperature of the first crystallization is 660 ℃ to 700 ℃, and the time of the first crystallization is 2h to 10 h.
9. The method for preparing glass ceramics according to any one of claims 5 to 7, wherein the temperature of the second crystallization is 810 ℃ to 830 ℃, and the time of the second crystallization is 1h to 4 h.
10. The method for preparing microcrystalline glass according to any one of claims 5 to 7, wherein the temperature rise rate is 2 ℃/min to 10 ℃/min.
11. Use of the glass-ceramic according to any one of claims 1 to 4 in protective glass, specialty glass and architectural glass for electronic devices.
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| DE2263234C3 (en) * | 1972-12-23 | 1975-07-10 | Jenaer Glaswerk Schott & Gen., 6500 Mainz | Process for the production of high-strength glass objects which are resistant to temperature changes by surface crystallization using ion exchange within the glass |
| US4814297A (en) * | 1987-04-01 | 1989-03-21 | Corning Glass Works | Strengthened glass article and method |
| CN1054957A (en) * | 1990-03-17 | 1991-10-02 | 中国科学院光电技术研究所 | Ultra-low-expansion glass ceramic |
| JP3829338B2 (en) * | 1994-11-25 | 2006-10-04 | 旭硝子株式会社 | Surface crystallized high-strength glass, its production method and its use |
| JP2004075441A (en) * | 2002-08-14 | 2004-03-11 | Huzhou Daikyo Hari Seihin Yugenkoshi | Lithium oxide-alumina-silica-based crystalline glass and crystallized glass, and method of manufacturing the crystalline glass and the crystallized glass |
| JP2008030978A (en) * | 2006-07-26 | 2008-02-14 | Nippon Electric Glass Co Ltd | Setter for heat treatment of glass substrate |
| JP5365975B2 (en) * | 2007-06-12 | 2013-12-11 | 日本電気硝子株式会社 | Crystallized glass article and method for producing the same |
| JP2010202460A (en) * | 2009-03-04 | 2010-09-16 | Nippon Electric Glass Co Ltd | Method for manufacturing crystallized glass, and crystallized glass |
| CN102849952B (en) * | 2012-09-28 | 2014-06-04 | 济南大学 | Method for promoting surface crystallization of glass |
| CN105859143A (en) * | 2016-03-31 | 2016-08-17 | 武汉理工大学 | Microcrystalline glass of high breaking strength and preparation method thereof |
| CN108821595A (en) * | 2018-06-22 | 2018-11-16 | 武汉理工大学 | A kind of high rigidity zero thermal expansion transparent glass-ceramics and preparation method thereof |
| CN108821570B (en) * | 2018-07-10 | 2021-06-08 | 山东康友光电科技股份有限公司 | Formula and method for preparing surface-strengthened transparent plate glass |
| CN111018356B (en) * | 2019-12-30 | 2022-05-10 | 重庆鑫景特种玻璃有限公司 | Microcrystalline glass with high crystal content and preparation method thereof |
-
2021
- 2021-08-25 CN CN202110983971.2A patent/CN113683309B/en active Active
- 2021-09-08 WO PCT/CN2021/117112 patent/WO2023024164A1/en unknown
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| CN113683309A (en) | 2021-11-23 |
| WO2023024164A1 (en) | 2023-03-02 |
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