CN117700111A - Tempered glass, microcrystalline glass and preparation method and application thereof - Google Patents

Tempered glass, microcrystalline glass and preparation method and application thereof Download PDF

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Publication number
CN117700111A
CN117700111A CN202211116089.9A CN202211116089A CN117700111A CN 117700111 A CN117700111 A CN 117700111A CN 202211116089 A CN202211116089 A CN 202211116089A CN 117700111 A CN117700111 A CN 117700111A
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China
Prior art keywords
glass
ceramic
mass content
treatment
microcrystalline
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CN202211116089.9A
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Chinese (zh)
Inventor
平文亮
蒋江
刘红刚
王明忠
肖子凡
王琰
康庆伟
赵北玉
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CSG Holding Co Ltd
Xianning CSG Photoelectric Glass Co Ltd
Qingyuan CSG New Energy Saving Materials Co Ltd
Original Assignee
CSG Holding Co Ltd
Xianning CSG Photoelectric Glass Co Ltd
Qingyuan CSG New Energy Saving Materials Co Ltd
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Application filed by CSG Holding Co Ltd, Xianning CSG Photoelectric Glass Co Ltd, Qingyuan CSG New Energy Saving Materials Co Ltd filed Critical CSG Holding Co Ltd
Priority to CN202211116089.9A priority Critical patent/CN117700111A/en
Priority to PCT/CN2022/124239 priority patent/WO2024055374A1/en
Publication of CN117700111A publication Critical patent/CN117700111A/en
Pending legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to reinforced glass, microcrystalline glass and a preparation method and application thereof. The microcrystalline glass comprises the following components in percentage by mass: siO (SiO) 2 54～66％、Al 2 O 3 17～28％、MgO 0.5～4％、Na 2 O 2～8％、Li 2 O 2～6.5％、P 2 O 5 0.5 to 2 percent of TiO 2 1 to 5 percent; wherein the crystalline phase of the glass-ceramic comprises beta-spodumene. The microcrystalline glass comprises SiO with specific content 2 、Al 2 O 3 、MgO、Li 2 O、Na 2 O、P 2 O 5 TiO (titanium dioxide) 2 The crystalline phase of the glass-ceramic comprises beta-spodumene. After chemical strengthening, the microcrystalline glass has higher compressive stress and better crack extension resistance; thus having better impact resistanceThe impact performance is not easy to break to generate fine glass fragments after being impacted, and the use safety is higher.

Description

Tempered glass, microcrystalline glass and preparation method and application thereof
Technical Field
The invention relates to the technical field of glass products, in particular to reinforced glass and microcrystalline glass as well as a preparation method and application thereof.
Background
Microcrystalline glass, also known as glass ceramic, generally refers to a base glass of a specific composition, which washes out a large number of crystals under a heat treatment process to form a crystalline phase and a multiphase complex of glass phases, which combines the excellent properties of glass and ceramic. The microcrystalline glass has the advantages of high mechanical strength and excellent insulating property, and is especially suitable for being used as protective glass of electronic consumer products.
However, in order to further obtain higher mechanical strength, the conventional technology also generally performs a chemical strengthening treatment on the glass ceramics. The glass ceramics subjected to chemical strengthening treatment has higher compressive stress, but has poorer fracture toughness, so that the glass ceramics has poorer anti-falling performance, is easy to crack to generate a large number of fine fragments, and has poorer use safety.
Disclosure of Invention
Based on the above, it is necessary to provide a tempered glass and a glass ceramic which have both higher compressive stress and better crack propagation resistance, and a preparation method and application thereof.
The invention provides microcrystalline glass, which comprises the following components in percentage by mass:
wherein the crystalline phase of the glass ceramic comprises beta-spodumene.
In any embodiment, the devitrification degree of the microcrystalline glass is more than or equal to 55%.
In any embodiment, the mass content of the beta-spodumene in the microcrystalline glass is 23% -90%.
In any embodiment, the crystalline phase of the glass-ceramic further comprises eucryptite.
In any embodiment, the glass ceramic comprises less than or equal to 32% of eucryptite by mass.
In any embodiment, the glass ceramic satisfies at least one of the conditions (1) to (11):
(1) The SiO is 2 The mass content of (2) is 54% -63%;
(2) The Al is 2 O 3 The mass content of (2) is 18% -27%;
(3) The K is 2 The mass content of O is 0-1.5%;
(4) The mass content of MgO is 0.5-3.5%;
(5) The Na is 2 The mass content of O is 3.5-6%;
(6) The Li is 2 The mass content of O is 3-6.5%;
(7) The ZrO 2 The mass content of (2) is 1% -4%;
(8) The B is 2 O 3 The mass content of (2) is 0-3%;
(9) The P is 2 O 5 The mass content of (2) is 0.5% -1%;
(10) The mass content of the ZnO is 0-1%;
(11) The TiO 2 The mass content of (2) is 1-4%.
In a second aspect, the present invention also provides a method for preparing the glass ceramics according to the first aspect, which comprises the following steps:
preparing raw materials according to the components of the microcrystalline glass;
melting the raw materials into clear glass liquid;
shaping the clarified glass liquid to prepare precursor glass;
and (3) sequentially carrying out nucleation treatment and crystallization treatment on the precursor glass to prepare the microcrystalline glass.
In any embodiment, the temperature of the nucleating process is 630 ℃ to 700 ℃; the nucleating treatment time is 2-10 hours;
the crystallization treatment temperature is 780-830 ℃; the crystallization treatment time is 0.5-4 h.
In a third aspect, the present invention also provides a tempered glass obtained by subjecting the glass ceramic of the first aspect to a chemical strengthening treatment.
In any embodiment, the surface stress value of the reinforced glass is more than or equal to 645MPa, and the depth of deep stress Dol-Na is more than or equal to 138 mu m.
In any embodiment, the tempered glass satisfies at least one of the conditions (i) to (iii):
the surface Vickers hardness of the reinforced glass is more than or equal to 730Hv;
(ii) the ring pressure intensity of the reinforced glass is more than or equal to 650N;
(iii) the 180-mesh sand paper of the reinforced glass has a falling height of more than or equal to 1.5m.
In a fourth aspect, the present invention also provides a method for preparing a tempered glass, comprising the steps of:
carrying out first strengthening treatment on microcrystalline glass in first molten salt; the first molten salt comprises 40-60% of sodium nitrate and 40-60% of potassium nitrate by mass percent;
carrying out second strengthening treatment on the microcrystalline glass subjected to the first strengthening treatment in second molten salt; the second molten salt comprises 0-4% of sodium nitrate and 96-100% of potassium nitrate by mass percent.
In any embodiment, the temperature of the first strengthening treatment is 440 ℃ to 500 ℃; the time of the first strengthening treatment is 4-16 hours;
the temperature of the second strengthening treatment is 380-420 ℃; the time of the second strengthening treatment is 1-4 h.
In a fifth aspect, the present invention also provides an application of the tempered glass of the third aspect in preparing an electronic product.
In a sixth aspect, the present invention provides an electronic product, including a main body and a cover glass embedded in the main body, where the cover glass is the tempered glass of the third aspect.
The components of the glass ceramics comprise SiO with specific content 2 、Al 2 O 3 、MgO、Li 2 O、Na 2 O、P 2 O 5 TiO (titanium dioxide) 2 And the like, the crystalline phase of the glass-ceramic includes beta-spodumene. Through reasonable component proportion, the microcrystalline glass has higher compressive stress and better crack expansibility resistance after chemical strengthening, and has higher surface Vickers hardness and higher ring compressive strength; therefore, the glass has better impact resistance, is not easy to break to generate fine glass fragments after being impacted, and has higher use safety.
Drawings
FIG. 1 is a flow chart of a method for producing glass ceramics according to an embodiment of the present invention;
FIG. 2 is a flowchart of a method for producing tempered glass according to an embodiment of the present invention;
FIG. 3 is an X-ray diffraction (XRD) pattern of glass ceramic of example 19 of the present invention;
FIG. 4 is an external view of the tempered glass of example 1 according to the present invention after falling ball test;
FIG. 5 is an external view of the tempered glass of comparative example 1 according to the present invention after falling ball test.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. 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. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention provides microcrystalline glass, which comprises the following components in percentage by mass:
wherein the crystalline phase of the glass-ceramic comprises beta-spodumene.
The components of the glass ceramics comprise SiO with specific content 2 、Al 2 O 3 、MgO、Li 2 O、Na 2 O、P 2 O 5 TiO (titanium dioxide) 2 And the like, the crystalline phase of the glass-ceramic includes beta-spodumene. Chemical composition of beta-spodumene LiAl (SiO 3 ) 2 Belongs to tetragonal system, has thermal cracking property, and can improve the mechanical strength and thermal shock resistance of microcrystalline glass. Through reasonable component proportion, the microcrystalline glass has higher compressive stress and better crack expansibility resistance after chemical strengthening, and has higher surface Vickers hardness and higher ring compressive strength; thus having better impact resistance and not easy to break to generate fine glass fragments after being impactedThe use safety is higher.
In addition, compared with the microcrystalline glass of the traditional lithium disilicate system, the microcrystalline glass has the advantages that Li 2 The content of O is low, and the production cost of the glass ceramics can be greatly reduced.
In some embodiments, the devitrification degree of the glass-ceramic is greater than or equal to 55%. The devitrification degree of the glass ceramics is within the range, and the glass ceramics has better mechanical properties. Optionally, the devitrification degree of the glass ceramics is more than or equal to 55 percent, more than or equal to 60 percent, more than or equal to 65 percent, more than or equal to 70 percent, more than or equal to 75 percent, more than or equal to 80 percent, more than or equal to 85 percent or more than or equal to 90 percent. In some embodiments, the devitrification degree of the glass-ceramic is 55% to 93%, 72.3% to 88.5%, or 80% to 90%.
The beta-spodumene crystal phase has the properties of low expansion, high mechanical strength and the like, and can improve the mechanical strength and heat resistance of microcrystalline glass. In some of these embodiments, the beta-spodumene content of the glass-ceramic is 23% to 90% by mass. Optionally, the mass content of the beta-spodumene in the glass-ceramic is in a range of any of the following values: 23%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%. Further, the mass content of the beta-spodumene in the glass ceramic is 23% -81%, 43.2% -88.5% or 52% -90%.
In some of these embodiments, the crystalline phase of the glass-ceramic further includes eucryptite. Chemical composition of eucryptite LiAlSiO 4 Has lower expansion coefficient, higher strength, hardness and wear resistance, and can improve the mechanical strength of the glass ceramics. In some embodiments, the mass content of eucryptite in the glass-ceramic is less than or equal to 32%. Optionally, the mass content of eucryptite in the glass-ceramic is in a range of any of the following values: 0.5%, 10%, 15%, 20%, 25%, 30% or 32%. Further, the mass content of the eucryptite in the microcrystalline glass is 0-30%, 0-30.7% or 7% -32%.
In some embodiments, the glass phase content of the glass ceramic is less than or equal to 45 percent by mass. Optionally, the glass phase in the glass ceramic has a mass content in the range of any of the following values: 7%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45%. Further, the mass content of the glass phase in the glass ceramics is 7% -45%, 11.5% -27.7% or 10% -20%.
In some embodiments, the average transmittance of the glass ceramics at 400 nm-780 nm is more than or equal to 49.8%. Optionally, the average transmittance of the glass ceramics at 400 nm-780 nm is in the range of any of the following values: 49.8%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 91.8%.
SiO 2 Is an oxide related to glass forming and can be used for stabilizing glass and microcrystalline glass network structures. In an embodiment of the invention, siO in the glass ceramics 2 The mass content of (2) is 54-66%. Optionally, siO in glass ceramics 2 The mass content of (2) is in the range of any of the following numerical compositions: 54%, 55%, 56%, 58%, 60%, 62%, 63%, 65% or 66%. Further, siO in glass ceramics 2 The mass content of (2) is 54-63% or 56-65%.
Al 2 O 3 The network may also be stabilized and also provide improved mechanical properties and chemical durability. In an embodiment of the invention, al in the glass-ceramic 2 O 3 The mass content of (3) is 17-28%. Optionally, al in the glass-ceramic 2 O 3 The mass content of (2) is in the range of any of the following numerical compositions: 17%, 18%, 20%, 22%, 24%, 25%, 26%, 27% or 28%. Further, al in glass ceramics 2 O 3 The mass content of (2) is 18-27%.
Li 2 O is one of the constituents forming the beta-spodumene crystalline phase and also acts as a co-solvent and as a component enhancing ion exchange capacity. In an embodiment of the present invention, li in the glass-ceramic 2 The mass content of O is 2-6.5%. Optionally Li in glass ceramics 2 The mass content of O is in the range of any of the following values: 2%, 3%, 4%, 5%, 6% or 6.5%. Further, li in glass ceramics 2 The mass content of O is 2% -6%, 3% -6.5% or 2% -5%.
Na 2 Action of O with Li 2 O is similar, but excessive Na is used as a cosolvent and a component for enhancing ion exchange capacity in glass ceramics 2 The O can reach excessive glass phase participated by the glass ceramics, and the mechanical strength of the glass product is affected. In an embodiment of the invention, na in the glass ceramics 2 The mass content of O is 2-8%. Optionally, na in the glass ceramics 2 The mass content of O is in the range of any of the following values: 2%, 3%, 4%, 5%, 6%, 7% or 8%. Further, na in glass ceramics 2 The mass content of O is 3.5-6% or 4-6%.
K 2 Action of O Na 2 O approaches, which also results in excessive glassy phase retention, and K 2 Too much O is unfavorable for the chemical strengthening performance of the glass ceramics, and can reduce the power of Na-K ion exchange. In an embodiment of the invention, K is in glass ceramics 2 The mass content of O is 0-2%. Optionally, K in glass ceramics 2 The mass content of O is in the range of any of the following values: 0. 0.5%, 1%, 1.5% or 2%. Further, K in glass ceramics 2 The mass content of O is 0-1.5%.
MgO is favorable for reducing the high-temperature viscosity of the base glass, modifying the glass structure body and improving the strength and chemical stability of the base glass. In the embodiment of the invention, the mass content of MgO in the glass ceramics is 0.5-4%. Optionally, the mass content of MgO in the glass ceramics is in the range of any of the following values: 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5% or 4%. Further, the mass content of MgO in the glass ceramics is 0.5% -3.5%.
ZnO has the function similar to MgO, is beneficial to reducing the high-temperature viscosity of the base glass, modifying the glass structure body and improving the strength and chemical stability of the base glass. In the embodiment of the invention, the mass content of ZnO in the glass ceramics is 0-3%. Optionally, the mass content of ZnO in the glass ceramics is in the range of any of the following values: 0. 0.5%, 1%, 1.5%, 2%, 2.5% or 3%. Further, the mass content of ZnO in the glass ceramics is 0 to 1 percent.
ZrO 2 As a common useThe nucleating agent is added. ZrO (ZrO) 2 Li can be increased by significantly reducing glass devitrification and lowering liquidus temperature during formation 2 O-Al 2 O 3 -SiO 2 Stability of the glass system. In an embodiment of the present invention, zrO in glass ceramics 2 The mass content of (2) is 0-4%. Optionally, zrO in glass-ceramic 2 The mass content of (2) is in the range of any of the following numerical compositions: 0. 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5% or 4%. Further, zrO in glass ceramics 2 The mass content of (2) is 1-4%.
TiO 2 With ZrO 2 Similarly, fine nuclei can be formed in the glass, but too much causes yellowing of the base glass. In an embodiment of the invention, tiO in the glass ceramics 2 The mass content of (2) is 1-5%. Optionally, tiO in glass ceramics 2 The mass content of (2) is in the range of any of the following numerical compositions: 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%. Further, tiO in glass ceramics 2 The mass content of (2) is 1-4%.
P 2 O 5 Can be used as a nucleating agent to promote glass nucleation. In an embodiment of the invention, P in the glass-ceramic 2 O 5 The mass content of (2) is 0.5-2%. Optionally, P in glass-ceramic 2 O 5 The mass content of (2) is in the range of any of the following numerical compositions: 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8% or 2%. Further, P in glass ceramics 2 O 5 The mass content of (2) is 0.5-1%.
B 2 O 3 Helping to provide a base glass with a low melting temperature. In addition, B is added to the base glass 2 O 3 Promote the phase separation, nucleation and crystallization of the base glass and shorten the crystallization time of the base glass. In an embodiment of the invention, B in the glass-ceramic 2 O 3 The mass content of (2) is 0-5%. Optionally, B in glass ceramics 2 O 3 The mass content of (2) is in the range of any of the following numerical compositions: 0. 0.5%, 1%, 1.5%, 2%, 2.5%, 3%3.5%, 4%, 4.5% or 5%. Further, B in the glass ceramics 2 O 3 The mass content of (2) is 0-3%.
In some embodiments, the glass ceramic comprises the following components in percentage by mass: siO (SiO) 2 54％～66％、Al 2 O 3 17％～28％、K 2 O 0～2％、MgO 0.5％～4％、Na 2 O 2％～8％、Li 2 O 2％～6.5％、ZrO 2 0～0.5％、B 2 O 3 0～5％、P 2 O 5 0.5 to 2 percent, 0 to 3 percent of ZnO and TiO 2 1% -5%; wherein, the microcrystalline glass comprises the following components in percentage by mass: 43.2 to 88.5 percent of beta-spodumene crystalline phase, 0 to 30.7 percent of eucryptite crystalline phase and 11.5 to 27.7 percent of glass phase.
In some embodiments, the glass ceramic comprises the following components in percentage by mass: siO (SiO) 2 54％～63％、Al 2 O 3 18％～27％、K 2 O 0～1.5％、MgO 0.5％～3.5％、Na 2 O 4％～6％、Li 2 O 3％～6.5％、ZrO 2 1％～1.5％、B 2 O 3 0～3％、P 2 O 5 0.5 to 2 percent of ZnO, 0 to 1 percent of TiO 2 3% -4%; wherein, the microcrystalline glass comprises the following components in percentage by mass: 23 to 81 percent of beta-spodumene crystalline phase, 7 to 32 percent of eucryptite crystalline phase and 7 to 45 percent of glass phase.
In some embodiments, the glass ceramic comprises the following components in percentage by mass: siO (SiO) 2 56％～65％、Al 2 O 3 20％～25％、K 2 O 0～1.5％、MgO 0.5％～3.5％、Na 2 O 3.5％～6％、Li 2 O 2％～5％、ZrO 2 2％～4％、B 2 O 3 0～2％、P 2 O 5 0.5 to 1 percent of ZnO, 0 to 1 percent of TiO 2 1 to 3.5 percent; wherein, the microcrystalline glass comprises the following components in percentage by mass: 52-90% of beta-spodumene crystalline phase, 0-30% of eucryptite crystalline phase and 10-20% of glass phase.
Referring to fig. 1, another embodiment of the present invention further provides a method for preparing glass ceramics, which includes steps S110 to S140 for preparing glass ceramics according to the first aspect, wherein:
step S110: the raw materials are prepared according to the components of the microcrystalline glass.
Step S120: melting the raw materials into clear glass liquid.
In some of these embodiments, in step S120, the melting temperature is 1500 ℃ to 1650 ℃. The melting time is 4-10 h.
Step S130: the clear glass liquid is molded to prepare precursor glass.
In some embodiments, in step S130, the forming process is selected from one of a float forming process, an overflow down-draw process, an up-draw process, a flat draw process, and a calendaring process.
Step S140: and (3) sequentially carrying out nucleation treatment and crystallization treatment on the precursor glass to prepare the microcrystalline glass.
In some of these embodiments, in step S140, the temperature of the nucleation process is 630 ℃ to 700 ℃; the nucleating treatment time is 2-10 h.
In some of these embodiments, in step S140, the crystallization process is performed at a temperature of 780 ℃ to 830 ℃; the crystallization treatment time is 0.5-4 h.
In another embodiment of the present invention, a tempered glass is provided, which is obtained by subjecting the glass ceramic of the first aspect to a chemical strengthening treatment.
The protection glass of the intelligent electronic equipment falls and breaks, so that failure is caused, the breaking degree of the glass in the industry needs to be controlled, and a plurality of glasses can obtain higher mechanical strength through chemical strengthening, but the internal stress is too large, the protection glass is in a crushing state after breaking, the average size of fragments is less than 2mm, excessive broken cracks prevent the continuous use of intelligent equipment such as mobile phones and the like, and the broken cracks shield pictures; on the other hand, broken glass which is too thin is easy to fall off, and risks of entering the eyes of consumers or risks of being swallowed by children and the like are caused.
The inventor found that the reinforced glass is obtained by chemically reinforcing the crystal glass with the specific composition ratio. The reinforced glass has higher surface stress and better crack extension resistance, and the reinforced glass has better anti-drop performance and scratch resistance on a rough surface. The average size of fragments after the tempered glass is broken is large, the fragments are not easy to fall off, and the use safety is good.
In some of these embodiments, the strengthened glass has a surface stress value of greater than or equal to 645MPa and a deep stress depth Dol-Na of greater than or equal to 138 μm. In some embodiments, the surface stress value of the strengthened glass is 645MPa to 1045MPa, 745MPa to 904MPa, 867MPa to 984MPa, or 979MPa to 1045MPa. The depth of deep stress Dol-Na is 138 μm to 159 μm, 138 μm to 154 μm, 139 μm to 159 μm or 143 μm to 157 μm.
In some of these embodiments, the strengthened glass has a surface Vickers hardness of 730Hv or greater. In some embodiments, the strengthened glass has a surface vickers hardness of 730Hv to 822Hv, 734Hv to 766Hv, 734Hv to 779Hv, or 773Hv to 822Hv.
In some of these embodiments, the strengthened glass has a ring crush strength of 650N or greater. In some embodiments, the strengthened glass has a ring crush strength of 650N to 903N, 668N to 893N, 662N to 903N, or 653N to 892N.
In some of these embodiments, the 180 mesh sandpaper of the tempered glass falls to a height of 1.5m or more. In some embodiments, the 180 mesh sandpaper of the tempered glass falls to a height of 1.7m to 1.9m, 1.7m to 2.0m, or 1.8m to 2.0m.
Referring to fig. 2, another embodiment of the present invention further provides a method for preparing tempered glass, which includes the following steps S210 and S220 to prepare the tempered glass of the third aspect:
step S210: carrying out first strengthening treatment on microcrystalline glass in first molten salt; the first molten salt comprises 40-60% of sodium nitrate and 40-60% of potassium nitrate by mass percent.
In some of these embodiments, in step S210, the temperature of the first strengthening treatment is 440 ℃ to 500 ℃; the time of the first strengthening treatment is 4-16 h.
Step S220: carrying out second strengthening treatment on the microcrystalline glass subjected to the first strengthening treatment in second molten salt; the second molten salt comprises 0-4% of sodium nitrate and 96-100% of potassium nitrate by mass percent.
In some of these embodiments, the temperature of the second strengthening treatment in step S220 is 380 ℃ to 420 ℃; the second strengthening treatment time is 1-4 h.
In another embodiment of the present invention, there is also provided an application of the tempered glass of the third aspect in preparing an electronic product.
In another embodiment of the present invention, an electronic product is provided, which includes a main body and a cover glass embedded in the main body, wherein the cover glass is the tempered glass of the third aspect.
The tempered glass, the glass ceramic and the preparation method thereof according to the present invention are further described below by way of specific examples.
The preparation method comprises the steps of mixing the components (mass percentages) designed in the examples 1-24 and the comparative examples 1-8 according to the compositions shown in the tables 1-4, melting the components for 8 hours at 1500-1650 ℃ by using a platinum crucible, stirring the components by using a platinum stirring paddle, cooling the components to 1300-1500 ℃ after the stirring paddle is pulled out, preserving heat for 2 hours for homogenization, casting the components on an iron mold to form glass blocks with the size of 80mm or 160mm, preheating the components to 450 ℃ before casting the mold, immediately transferring the glass blocks into an annealing furnace for annealing, preserving heat for 2 hours, cooling the components for 140 ℃ after 6 hours, naturally cooling the components, and taking the components out for later use.
Glass samples of examples 1 to 24 and comparative examples 1 to 8 were cut into glass sheets of 70 x 140 x 0.7mm by a STX-1203 wire-electrode cutting machine of Shenyang Ke-ji, thinned and polished by a Shenzhen Heidel HD-640-5L double-sided lapping polisher, and then subjected to CNC edging, and surface Vickers hardness was measured by using a FALCON400 durometer of Netherlands.
The samples of examples 1 to 24 and comparative examples 1 to 8 were processed according to the nucleation and crystallization processes shown in tables 1 to 4, and the crystallized samples were cut and polished to obtain sections for use. The above samples were cut into 20X 20mm, and their crystalline phase types were tested by Bruker X-ray diffractometer Bruker D8 advance, and their different crystalline phase ratios and amorphous phase ratios were calculated by TOPAS software simulation, and recorded in tables 1 to 4.
Treating the crystallized sample by a secondary strengthening process, wherein the first chemical strengthening is carried out by soaking the crystallized sample in a mixed solution of 40-60 wt% of sodium nitrate and 60-40 wt% of potassium nitrate at 440-500 ℃ for 4-16 h; the second chemical strengthening is carried out by soaking in a mixed solution of 96-100 wt% of potassium nitrate and 4-0 wt% of sodium nitrate at 380-420 ℃ for 1-4 h; the Na-K surface compressive stress CS (Mpa) and the Li-Na exchange stress depth Dol_0 (μm) were tested by SLP2000 and FSM-6000LE surface stress meters, the surface Vickers hardness was tested using a FALCON400 durometer from Netherlands, the transmittance in the wavelength range of 400nm to 780nm was tested using a Lambda950 UV-visible spectrophotometer from Perkinelmer, U.S. Perkinelmer, the ring compressive strength (upper ring phi=16 mm, lower ring phi=32 mm) was tested by a PT-307A universal tester from Przert, the 180 mesh sandpaper drop height was tested by a GP-2112-T directional drop tester from Shenzhen high, and the glass crush crack morphology was observed and recorded in tables 1 to 4. The degree of fracture is different, dividing the glass fracture into two layers of crushing and breaking, wherein the average size of crushed fragments is less than 5mm or the intact glass area is less than 1/3, which is not acceptable; if the glass is broken, the average breaking size is larger than 5mm, and the presence of more than 1/3 of the glass area is satisfactory.
TABLE 1
The glass components of examples 1 to 8, in mass percent, comprise: siO (SiO) 2 54％～66％、Al 2 O 3 17％～28％、K 2 O 0～2％、MgO 0.5％～4％、Na 2 O 2％～8％、Li 2 O 2％～6.5％、ZrO 2 0～0.5％、B 2 O 3 0～5％、P 2 O 5 0.5 to 2 percent, 0 to 3 percent of ZnO and TiO 2 1％～5％。The surface Vickers hardness of the precursor glass is 578 Hv-628 Hv. After nucleation and crystallization treatment, the microcrystalline glass comprises the following phase components in percentage by mass: 43.2 to 88.5 percent of beta-spodumene crystalline phase, 0 to 30.7 percent of eucryptite crystalline phase and 11.5 to 27.7 percent of glass phase; the glass ceramics has transparent or semitransparent appearance, and the average transmittance of 400-780 nm is 62.9-91.2%. After two-step chemical strengthening treatment, the surface stress value (K-Na compressive stress CS) of the glass is 745-904 MPa, and the depth of deep stress (Li-Na exchange stress depth Dol-Na) is 138.4-153.6 μm. The surface Vickers hardness of the reinforced microcrystalline glass is more than or equal to 284 Hv, the surface ball falling height of 180 meshes is more than or equal to 1.7m, the ring pressure is more than or equal to 668MPa, and the broken appearance is broken.
TABLE 2
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The glass components of examples 9 to 16, in mass percent, comprise: siO (SiO) 2 54％～63％、Al 2 O 3 18％～27％、K 2 O 0～1.5％、MgO 0.5％～3.5％、Na 2 O 4％～6％、Li 2 O 3％～6.5％、ZrO 2 1％～1.5％、B 2 O 3 0～3％、P 2 O 5 0.5 to 2 percent, 0 to 1 percent of ZnO and TiO 2 3 to 4 percent. The surface Vickers hardness of the precursor glass is 584-630 Hv. After nucleation and crystallization treatment, the microcrystalline glass comprises the following phase components in percentage by mass: 23-81% of beta-spodumene crystalline phase, 7-32% of eucryptite crystalline phase and 7-45% of glass phase; the glass ceramics has transparent or semitransparent appearance and average thickness of 400-780 nmThe transmittance is 49.8 to 91.4 percent. After two-step chemical strengthening treatment, the surface stress value (K-Na compressive stress CS) of the glass is 867-984 MPa, and the depth of deep stress (Li-Na exchange stress depth Dol-Na) is 139.5-158.4 μm. The surface Vickers hardness of the reinforced microcrystalline glass is more than or equal to 739Hv, the surface ball falling height of 180 meshes is more than or equal to 1.7m, the ring pressure is more than or equal to 662MPa, and the broken appearance is broken.
TABLE 3 Table 3
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The glass components of examples 17 to 24, in mass percent, comprise: siO (SiO) 2 56％～65％、Al 2 O 3 20％～25％、K 2 O 0～1.5％、MgO 0.5％～3.5％、Na 2 O 3.5％～6％、Li 2 O 2％～5％、ZrO 2 2％～4％、B 2 O 3 0～2％、P 2 O 5 0.5 to 1 percent of ZnO, 0 to 1 percent of TiO 2 1 to 3.5 percent. The surface Vickers hardness of the precursor glass is 576 Hv-635 Hv. After nucleation and crystallization treatment, the microcrystalline glass comprises the following phase components in percentage by mass: 52-90% of beta-spodumene crystalline phase, 0-30% of eucryptite crystalline phase and 10-20% of glass phase; the glass ceramics has transparent or semitransparent appearance, and the average transmittance of 400-780 nm is 69.5-91.8%. After two-step chemical strengthening treatment, the surface stress value (K-Na compressive stress CS) of the glass is 979MPa to 1045MPa, and the depth of deep stress (Li-Na exchange stress depth Dol-Na) is 148.4 μm to 156.4 μm. The surface Vickers hardness of the reinforced microcrystalline glass is more than or equal to 773Hv, the surface ball falling height of 180 meshes is more than or equal to 1.8m, the ring pressure is more than or equal to 653MPa, and the broken appearance is broken.
Referring to FIG. 3, which is an XRD pattern for the glass-ceramic of example 19, it can be seen that the glass-ceramic of example 19 has characteristic peaks of beta-spodumene and eucryptite.
TABLE 4 Table 4
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The glass compositions or crystalline phases of the glass-ceramics of comparative examples 1 to 8 are different from those of examples 1 to 24. The surface Vickers hardness of the precursor glass is 576 Hv-635 Hv. The glass ceramics has transparent or semitransparent appearance, and the average transmittance of 400-780 nm is 69.5-91.8%. After two-step chemical strengthening treatment, the surface stress value (K-Na compressive stress CS) of the glass is 673 MPa-1141 MPa, and the depth of deep stress (Li-Na exchange stress depth Dol-Na) is 121 μm-137 μm. The surface Vickers hardness of the reinforced microcrystalline glass is 692 Hv-732 Hv, the surface ball falling height of 180 meshes is 1.4 m-1.9 m, and the ring pressure is 490 MPa-623 MPa. The mechanical properties of the tempered glass were inferior to those of examples 1 to 24, and the tempered glass of comparative examples 1 to 3 and 7 was crushed after breakage, resulting in a small size of chips.
Referring to fig. 4 and 5, fig. 4 is an external view of the tempered glass of example 1 after breakage, and fig. 5 is an external view of the tempered glass of comparative example 1 after breakage; it can be seen that the tempered glass of example 1 has a larger size and a smaller range of fragments after breakage; the tempered glass of comparative example 1, however, had smaller size of fragments generated after breakage, and the fragments spread throughout the whole glass, affecting continued use of the glass product.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that, based on the technical solutions provided by the present invention, those skilled in the art obtain technical solutions through logical analysis, reasoning or limited experiments, all of which are within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.

Claims (15)

1. The microcrystalline glass is characterized by comprising the following components in percentage by mass:
wherein the crystalline phase of the glass ceramic comprises beta-spodumene.
2. The glass-ceramic according to claim 1, wherein the devitrification degree of the glass-ceramic is not less than 55%.
3. The glass-ceramic according to claim 1, wherein the mass content of the beta-spodumene in the glass-ceramic is 23% -90%.
4. The glass-ceramic of claim 1, wherein the crystalline phase of the glass-ceramic further comprises eucryptite.
5. The glass-ceramic according to claim 4, wherein the mass content of eucryptite in the glass-ceramic is not more than 32%.
6. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic satisfies at least one of the conditions (1) to (11):
(1) The SiO is 2 The mass content of (2) is 54% -63%;
(2) The Al is 2 O 3 The mass content of (2) is 18% -27%;
(3) The K is 2 The mass content of O is 0-1.5%;
(4) The mass content of MgO is 0.5-3.5%;
(5) The Na is 2 The mass content of O is 3.5-6%;
(6) The Li is 2 The mass content of O is 3-6.5%;
(7) The ZrO 2 The mass content of (2) is 1% -4%;
(8) The B is 2 O 3 The mass content of (2) is 0-3%;
(9) The P is 2 O 5 The mass content of (2) is 0.5% -1%;
(10) The mass content of the ZnO is 0-1%;
(11) The TiO 2 The mass content of (2) is 1-4%.
7. A method for producing a glass ceramic according to any one of claims 1 to 6, comprising the steps of:
preparing raw materials according to the components of the microcrystalline glass;
melting the raw materials into clear glass liquid;
shaping the clarified glass liquid to prepare precursor glass;
and (3) sequentially carrying out nucleation treatment and crystallization treatment on the precursor glass to prepare the microcrystalline glass.
8. The method for producing glass ceramics according to claim 7, wherein the temperature of the nucleation treatment is 630 ℃ to 700 ℃; the nucleating treatment time is 2-10 hours;
the crystallization treatment temperature is 780-830 ℃; the crystallization treatment time is 0.5-4 h.
9. A tempered glass obtained by subjecting the glass ceramic as defined in any one of claims 1 to 6 to a chemical tempering treatment.
10. The strengthened glass according to claim 9, wherein the strengthened glass has a surface stress value of at least 645MPa and a deep stress depth Dol-Na of at least 138 μm.
11. The tempered glass of claim 9, wherein the tempered glass satisfies at least one of the conditions (i) to (iii):
the surface Vickers hardness of the reinforced glass is more than or equal to 730Hv;
(ii) the ring pressure intensity of the reinforced glass is more than or equal to 650N;
(iii) the 180-mesh sand paper of the reinforced glass has a falling height of more than or equal to 1.5m.
12. A method for producing a tempered glass, comprising the steps of producing the tempered glass according to any one of claims 9 to 11:
carrying out first strengthening treatment on microcrystalline glass in first molten salt; the first molten salt comprises 40-60% of sodium nitrate and 40-60% of potassium nitrate by mass percent;
carrying out second strengthening treatment on the microcrystalline glass subjected to the first strengthening treatment in second molten salt; the second molten salt comprises 0-4% of sodium nitrate and 96-100% of potassium nitrate by mass percent.
13. The method for producing a tempered glass according to claim 12, wherein the temperature of the first tempering treatment is 440 ℃ to 500 ℃; the time of the first strengthening treatment is 4-16 hours;
the temperature of the second strengthening treatment is 380-420 ℃; the time of the second strengthening treatment is 1-4 h.
14. Use of the tempered glass of any one of claims 9 to 11 for manufacturing an electronic product.
15. An electronic product comprising a main body and a cover glass fitted to the main body, wherein the cover glass is the tempered glass according to any one of claims 9 to 11.
CN202211116089.9A 2022-09-14 2022-09-14 Tempered glass, microcrystalline glass and preparation method and application thereof Pending CN117700111A (en)

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* Cited by examiner, † Cited by third party
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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
US4212678A (en) * 1977-09-07 1980-07-15 Corning Glass Works Rapidly crystallized beta-spodumene glass-ceramic materials
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 Ultralow-expansion glass ceramics
JP3311308B2 (en) * 1998-03-03 2002-08-05 株式会社オハラ Glass ceramic substrate for perpendicular magnetic recording media
US6506699B1 (en) * 1998-10-23 2003-01-14 Kabushiki Kaisha Ohara Negative thermal expansion glass ceramic and method for producing the same
CN110615610B (en) * 2019-10-10 2020-09-04 清远南玻节能新材料有限公司 Lithium-zirconium aluminosilicate glass, tempered glass, preparation methods of lithium-zirconium aluminosilicate glass and tempered glass, and display device

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