CN115417601A - Method for preparing microcrystalline glass - Google Patents
Method for preparing microcrystalline glass Download PDFInfo
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- CN115417601A CN115417601A CN202210963474.0A CN202210963474A CN115417601A CN 115417601 A CN115417601 A CN 115417601A CN 202210963474 A CN202210963474 A CN 202210963474A CN 115417601 A CN115417601 A CN 115417601A
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- 239000011521 glass Substances 0.000 title claims abstract description 163
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000005728 strengthening Methods 0.000 claims abstract description 19
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- 230000008018 melting Effects 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 239000006104 solid solution Substances 0.000 claims abstract description 8
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- 238000005342 ion exchange Methods 0.000 claims description 19
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- 150000003839 salts Chemical class 0.000 claims description 10
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 8
- 239000002241 glass-ceramic Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 7
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 6
- 238000000265 homogenisation Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 15
- 239000006121 base glass Substances 0.000 description 30
- 238000002425 crystallisation Methods 0.000 description 20
- 230000008025 crystallization Effects 0.000 description 19
- 150000002500 ions Chemical class 0.000 description 19
- 239000013078 crystal Substances 0.000 description 12
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- 239000010410 layer Substances 0.000 description 10
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- 239000000126 substance Substances 0.000 description 6
- 229910010293 ceramic material Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000156 glass melt Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 229910010100 LiAlSi Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- 239000006018 Li-aluminosilicate Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
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- 210000001808 exosome Anatomy 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000006058 strengthened glass Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- 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
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
Abstract
The invention provides a method for preparing microcrystalline glass, which comprises the following steps: uniformly mixing glass raw materials, melting, homogenizing, molding, annealing and micro-crystallizing, wherein the glass raw materials enable the prepared microcrystalline glass to contain Li x Al x Si 1‑x O 2 A solid solution; the method also comprises the step of chemically strengthening the microcrystalline glass after the microcrystallization treatment. The microcrystalline glass prepared by the method has high visible light transmittance, high strength, high hardness and high impact resistance.
Description
Technical Field
The application relates to the technical field of glass, in particular to a method for preparing microcrystalline glass.
Background
After the aluminosilicate glass is subjected to ion strengthening treatment, a Layer of high surface Compressive Stress (CS) and an ion strengthening Layer (DOL) with a certain Depth are formed on the surface Layer of the glass, so that the surface hardness, the impact resistance, the scratch resistance and the damage resistance of the glass are rapidly improved, and the aluminosilicate glass is widely applied to cover plate protection materials of touch display products. With the coming of the 5G communication era and the gradual maturity of the wireless charging technology, the rear cover made of metal materials is forced to be eliminated, and glass and ceramic materials in non-metal materials become the first choice for mobile display terminal products. Although the high-alumina glass has good transmittance at present, the strength of the high-alumina glass is not high enough, so that the high-alumina glass is still limited to be used as an appearance protection material of mobile electronic equipment, and the ceramic material has the advantage of high strength, but the transmittance of the ceramic material is still too low, the processing difficulty of the ceramic material is higher, and the large-scale production is difficult, so the cost is higher, and the use of the ceramic material in the mobile electronic equipment is limited. The traditional glass has larger brittleness, and the surface of the traditional glass is easy to generate micro cracks, so that the actual mechanical strength of the traditional glass is 2 to 3 orders of magnitude lower than the theoretical mechanical strength, namely the glass has lower breaking strength, fracture toughness, surface hardness and other properties. In order to improve the scratch resistance and the drop resistance of the glass, the glass is generally strengthened to prepare strengthened glass. The introduction of compressive stress at the surface of the glass is a common method of strengthening glass. The ion exchange method is usually adopted for ultra-thin glass, and the compressive stress layer formed on the surface of the glass can improve the strength of the glass to a certain extent. However, for a large-screen mobile phone, the hardness and the impact strength of the screen glass are difficult to be obtained, and the scratch-proof performance becomes a short plate while the anti-crushing performance is improved. In addition, 5G mobile phones are expected to be put into commercial use in recent years, and the applications of the revolution of 5G communication and wireless charging place more severe requirements on the front cover material used for mobile terminals.
Therefore, it is highly desirable to provide a front cover material that can satisfy the requirements of a 5G mobile phone and has good scratch resistance, high transmittance and mechanical strength.
Disclosure of Invention
The purpose of the disclosure is to provide a method for preparing microcrystalline glass, and the prepared microcrystalline glass has high transmittance, good scratch resistance and mechanical strength.
In order to achieve the above object, in one aspect, the present disclosure provides a method for manufacturing a glass ceramic, wherein the method comprises the steps of:
uniformly mixing glass raw materials, melting, homogenizing, molding, annealing and micro-crystallizing, wherein the glass raw materials enable the prepared microcrystalline glass to contain Li x Al x Si 1-x O 2 A solid solution;
preferably, the method further comprises chemically strengthening the microcrystalline glass after the microcrystallization treatment.
According to the disclosure, the components of the glass raw material comprise, in weight percent on an oxide basis, the following composition: siO 2 2 65-73％，Al 2 O 3 3-10％，Na 2 O 3-8％，K 2 O 2-4％，Li 2 O 4-10％，MgO 1-3％，CaO 0-2％，BaO 0-2％，ZrO 2 0-3％，ZnO 0-3％，P 2 O 5 2-5％，TiO 2 0-1％，SnO 2 0-1％。
According to the present disclosure, wherein the conditions of the melt homogenization include: heating to 1500-1560 deg.c and maintaining for 4-6 hr; the melt homogenization is carried out in a platinum crucible.
According to the present disclosure, wherein the annealing comprises two stages: the temperature of the first stage is 500-550 ℃ and the time is 1-3h; the temperature of the second stage is 400-450 deg.C, and the time is 0.5-1h.
According to the present disclosure, wherein the microcrystallization comprises two stages: the temperature of the first stage is 665-685 ℃, and the time is more than or equal to 4h; the temperature of the second stage is 760-790 ℃, and the time is more than or equal to 4h.
According to the present disclosure, wherein the process of chemical strengthening comprises two stages: in the first stage, the microcrystalline glass is placed in 100wt% of NaNO 3 Performing a first ion exchange in a molten salt; in the second stage, the microcrystalline glass after the first ion exchange is placed in KNO of 100wt% 3 And in the molten salt, carrying out second ion exchange.
The conditions of the first ion exchange include: the temperature is 350-400 ℃, and the time is 100-150min;
the conditions of the second ion exchange include: the temperature is 400-450 deg.C, and the time is 40-80min.
On the other hand, the disclosure also provides the microcrystalline glass prepared by the method.
On the other hand, the disclosure also provides application of the microcrystalline glass prepared by the method in electronic equipment and/or optical equipment.
By the technical scheme, the method for preparing the microcrystalline glass is provided, and the microcrystalline glass with high visible light transmittance, high strength, high hardness and high impact resistance is prepared by adjusting the composition design and the preparation process of the microcrystalline glass; the light transmittance of a sample with the thickness of 1mm of the microcrystalline glass exceeds 86 percent (the wavelength is 560 nm), and the Vickers hardness of the sample after being strengthened is more than 800kgf/mm 2 Surface stress value greater than 910MPa, stress layer depth greater than 80 μm, and fracture toughness greater than 1.6 MPa-mm 0.5 The microhardness is more than 8GPa.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 is an SEM test chart of the crystallized glass.
Fig. 2 is an XRD test pattern of the glass ceramics.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
In one aspect, the present disclosure provides a method for preparing a glass-ceramic, wherein the method comprises the following steps:
uniformly mixing glass raw materials, melting, homogenizing, forming, annealing and micro-crystallizing, wherein the glass raw materials enable the prepared microcrystalline glass to contain Li x Al x Si 1-x O 2 Solid solution.
Li as described in the present disclosure x Al x Si 1-x O 2 X in the solid solution is not limited, and only indicates that the main crystal phase in the prepared microcrystalline glass is a lithium aluminum silicate solid solution.
Preferably, the method further comprises chemically strengthening the microcrystalline glass after the microcrystallization treatment.
According to the disclosure, the components of the glass raw material comprise, in weight percent on an oxide basis, the following composition: siO 2 2 65-73％，Al 2 O 3 3-10％，Na 2 O 3-8％，K 2 O 2-4％，Li 2 O4-10％，MgO 1-3％，CaO 0-2％，BaO 0-2％，ZrO 2 0-3％，ZnO 0-3％，P 2 O 5 2-5％，TiO 2 0-1％，SnO 2 0-1％。
SiO 2 The network forming body of the base glass can be independently formed into glass, belongs to one of essential components, mainly forms a network main structure of the base glass and the microcrystalline glass, and endows the base glass (without microcrystallization) and the microcrystalline glass with better chemical stability, mechanical property and forming property. During the microcrystallization of the base glass, to form Li 2 Si 2 O 5 And LiAlSi 4 O 10 The crystalline phase provides SiO 2 Source of such that the base glass is encouraged to form a sufficient crystalline phase, siO, in the appropriate temperature range 2 If the content is too small, the phase of the prepared glass is easily separated and the chemical stability is poor, but SiO 2 At the same time, the melting temperature of the glass is raised, the glass is difficult to clarify and melt, and the content of SiO is too high in the micro crystallization process of the basic glass 2 Can promote the occurrence of quartz and quartz solid solution in the glass micro-crystallization processBulk, resulting in too high a melting temperature and difficulty in melting; thus, siO 2 The content is preferably at least 65% by weight and at most 73% by weight.
Al 2 O 3 Is one of the essential components of the base glass and belongs to the network intermediate oxide. There are two coordination states in glass, namely tetradentate [ AlO ] 4 ]And octadentate [ AlO ] 6 ]. Al in base glass 3+ Ion abstraction of non-bridging oxygen and charge balance with basic ions, so that most of aluminum oxide is prone to be [ AlO 4 ]And the broken network is reconnected, thereby forming a part of the glass network structure and achieving the purpose of improving the stability and the mechanical property of the glass. Al (aluminum) 2 O 3 The aluminum tetrahedron formed in the glass has larger volume than the silicon-oxygen tetrahedron in the glass, and the volume of the glass expands, thereby reducing the density of the glass, providing a strengthening channel for the glass in the ion strengthening process, and promoting the ion strengthening of the base glass and the microcrystalline glass, wherein Al in the base glass 2 O 3 The content is preferably at least 3wt%; however, al 2 O 3 The glass belongs to an extremely refractory oxide, and the high-temperature viscosity of the glass can be rapidly improved, so that the difficulty in clarifying and homogenizing the glass is increased, and the concentration of bubble defects in the glass is greatly increased; and also Al 2 O 3 The glass micro crystallization temperature can be obviously improved, and the production energy consumption is increased; inhibit the crystallization ability of the base glass, and is difficult to form lithium disilicate with fine-grain interlocking structure, resulting in LiAlSi in the crystallization process 4 O 10 Excessive formation of LiAlSi even in the base glass 2 O 6 A crystalline phase, so that the glass transmittance is reduced. Thus Al in the base glass 2 O 3 The content is preferably up to 10% by weight.
Na 2 The introduction of O as a very important network exosome can reduce the polymerization degree and the melting temperature of the network structure of the glass, improve the melting performance of the glass and simultaneously reduce the crystallization temperature of the glass. With TiO 2 When the Ti ions are introduced together, the coordination condition of the Ti ions can be effectively regulated and controlled. Simultaneous introduction of Li into glass composition 2 When O is used, the surface layer compressive stress value can be obtained by exchanging potassium ions in the molten salt in the chemical strengthening process of the glass ceramicsAnd diffusion depth. Therefore, the amount of incorporation thereof is preferably controlled to 3wt% or more. But excessive Na 2 O causes deterioration of chemical stability of the glass and influences formation of a desired main crystal phase during crystallization, so that it is preferable to control the amount of incorporation to 8wt% or less.
K 2 The O is used as a glass network outer body, and the introduction of the O can reduce the melting temperature of the glass, improve the melting quality and improve the optical performance of the glass. In addition, in Li 2 O and Na 2 In the case of co-introduction of O, K is introduced 2 O is beneficial to improving the ion exchange depth and the mechanical property and the optical property of the chemically reinforced microcrystalline glass. Thus K 2 The amount of O to be introduced is preferably controlled to 2wt% or more and 4wt% or less.
Li 2 O is one of essential components of the basic glass, belongs to network external components, can obviously reduce the viscosity of the glass, promote the clarification and the melting of the basic glass, simultaneously reduce the crystallization temperature of the glass rapidly, and has high Li 2 Li in the process of promoting basic microcrystallization by O concentration 3 PO 4 The formation is beneficial to forming a lithium disilicate crystal phase and a petalite crystal phase in the crystallization process; in order to achieve a microcrystallized glass with a high depth of ion strengthening, sufficient Li must be present in the base glass + In the chemical strengthening process with Na + Mutual strengthening occurs to reduce cracks on the surface of the crystallized glass and provide the mechanical strength function of the microcrystalline glass, and the content in the base glass is preferably at least 4wt%. Furthermore, but too high Li 2 O will make the viscosity of the base glass too low to obtain a chemically stable glass composition, and at the same time, will cause the compressive stress value during ion strengthening to be too low and increase the raw material cost, so Li in the base glass 2 O is preferably at most 10% by weight.
MgO is a glass network intermediate that improves glass melting under the control of the amount disclosed, li 2 O、Na 2 When O and ZnO are introduced together, the oxides support each other in function, the microstructure of the glass ceramics is adjusted, and the mechanical property of the glass is improved. For Li 2 O、Na 2 The microhardness of the chemical reinforced microcrystalline glass with O, mgO and ZnO existing simultaneously is more than 8GPa,the four-point bending strength is above 560MPa, the surface compressive stress value is above 800MPa, the stress depth value can reach above 70 mu m, and the fracture toughness is higher than 1.2 MPa.mm 0.5 . However, since the content of MgO is too high, which causes uncontrollable crystallization of the glass melt, the amount of MgO to be introduced is preferably controlled to 1wt% or more and 3wt% or less.
ZnO is a divalent metal oxide, can improve the melting of the glass and improve the optical performance of the glass, and is an unnecessary component of the basic glass. Zn 2+ Presence of hexa-coordinated [ ZnO ] 6 ]And tetra-coordinated [ ZnO ] 4 ]State in which the [ ZnO ] is hexacoordinated 6 ]The structure is compact and four coordinate [ ZnO4 ]]The structure is loose, and the four-coordination number is increased along with the increase of the alkali metal oxide. When four coordinate [ ZnO ] 4 ]When the content is more, the glass network is more loose, which is beneficial to the ion (Na) in the glass + ) The migration is carried out, so that the depth of an ion strengthening layer of the glass is improved, and the positive effects on improving the ion strengthening efficiency and strengthening depth of the glass and improving the surface strength of the glass are achieved; meanwhile, the chemical stability and the refractive index of the glass are improved, and the glossiness and the transmittance of the glass are increased. But it inhibits crystallization of the base glass, thereby causing the glass to be incapable of uniform crystallization, and therefore, the content thereof is preferably not more than 3wt%.
BaO is a divalent metal oxide, is an unnecessary component of basic glass, and can reduce the viscosity of the glass and improve the melting characteristic; the glass gloss and transmittance are increased, but too high a content results in too high a glass density, and thus the content thereof is preferably not more than 2wt%.
ZrO 2 Belongs to one of essential components of basic glass, can obviously improve the viscosity of the glass, and is also beneficial to reducing the size of crystal grains in the crystallization process, thereby improving the transmittance of the glass and quickly improving the chemical stability of the glass. ZrO (ZrO) 2 The crystallization capacity of the glass can be inhibited, and the fracture toughness and the bending strength of the glass are improved; and the crystal phase of the zirconia is transformed, so that stress induction can be generated, and the fracture toughness after crystallization is further improved. But ZrO 2 Belongs to a refractory component, quickly improves the viscosity of base glass and simultaneously has overhigh ZrO 2 The content may result in ZrO in the glass 2 The existence of unmelted material.At P 2 O 5 When co-introduced, zrO can be improved 2 Solubility in glass melt, improved glass forming performance and raised crystallized microcrystal glass strength. But ZrO 2 Too high an amount of the ZrO tends to cause difficulty in melting, and the glass melt tends to crystallize, affecting the forming process 2 The content is controlled to be 0-3wt%.
P 2 O 5 Is one of the network former components of the base glass, P 5+ The ions have larger field intensity, strong oxygen-capturing capability and small accumulation effect, and the phosphorus-oxygen network structure tends to be strong. Due to P 5+ The ionic field strength is greater than that of Si 4+ Ion, P 5+ Ions are easily combined with alkali metal ions to be separated from the network to form a crystal nucleus, so that the phase separation of the base glass is promoted, the nucleation activation energy is reduced, and the glass is the most effective nucleating agent in the base glass; when the base glass does not contain or has too low content, the surface of the base glass is atomized in the microcrystallization process, so that the base glass cannot be integrally crystallized and is difficult to crystallize into uniform microcrystalline glass; when there is sufficient P in the base glass 2 O 5 At the concentration, the base glass is firstly promoted to have phase separation and Li 3 PO 4 Aggregates, with increasing crystallization temperature, li 2 O and P 2 O 5 Reaction to form Li 3 PO 4 Crystal phase, thereby inducing Li in the glass 2 O and SiO 2 Reaction to form Li 2 SiO 3 And finally form Li 2 Si 2 O 5 A crystalline phase; furthermore, P 2 O 5 It is prepared from [ PO ] 4 ]The tetrahedrons are connected into a network, so that the glass network structure is in a loose state, and the network gaps are enlarged, thereby being beneficial to Na in glass + K in ions and molten salts + Ions are diffused mutually, the strengthening of the ions in the glass strengthening process is promoted, and the strengthening plays an important role in obtaining a higher compression stress layer, P 2 O 5 The content is preferably at least 2wt%; but P is 2 O 5 Too high content promotes the base glass to be difficult to form stable glass, and causes crystallization of the base glass, and crystallized glass with high transmittance is difficult to obtain; at the same time, the crystallization process will promote the precipitation of lithium metasilicate, resulting inToo little glass phase to form sufficient Li 2 Si 2 O 5 Crystalline phase and promoting the precipitation of a quartz phase, P 2 O 5 The content is preferably at most 5% by weight.
SnO 2 The glass refining agent is used as an important refining agent of glass, the introduction of the glass refining agent is beneficial to reducing the formation of gas defects in a glass melt, reducing the number of bubbles in the melt and improving the refining effect, and is vital to the preparation of microcrystalline glass which is in line with the use of a mobile terminal; the amount of the catalyst to be incorporated is preferably controlled to 0wt% or more and 1wt% or less.
According to the present disclosure, wherein the conditions of melt homogenization include: heating to 1500-1560 deg.c and maintaining for 4-6 hr; the melt homogenization is carried out in a platinum crucible.
According to the present disclosure, wherein the annealing comprises two stages: the temperature of the first stage is 500-550 ℃ and the time is 1-3h; the temperature of the second stage is 400-450 deg.C, and the time is 0.5-1h.
According to the present disclosure, wherein the microcrystallization comprises two stages: the temperature of the first stage is 665-685 ℃, and the time is more than or equal to 4h; the temperature of the second stage is 760-790 ℃, and the time is more than or equal to 4h.
According to the present disclosure, wherein the process of chemical strengthening comprises two stages: in the first stage, the microcrystalline glass is placed in 100wt% of NaNO 3 Performing a first ion exchange in a molten salt; in the second stage, the microcrystalline glass after the first ion exchange is placed in KNO of 100wt% 3 Carrying out second ion exchange in molten salt;
the conditions of the first ion exchange include: the temperature is 350-400 ℃, and the time is 100-150min;
the conditions of the second ion exchange include: the temperature is 400-450 deg.C, and the time is 40-80min.
On the other hand, the disclosure also provides the microcrystalline glass prepared by the method.
On the other hand, the disclosure also provides application of the microcrystalline glass prepared by the method in electronic equipment and/or optical equipment.
The present disclosure is further illustrated by the following examples. The raw materials used in the examples are all available from commercial sources.
Examples 1 to 5 and comparative example 1
Sample preparation: weighing glass raw materials according to a ratio, and uniformly mixing to obtain a batch mixture, wherein the glass raw materials and the ratio thereof are shown in Table 1; the batch was then transferred to an approximately 800mL platinum crucible, which was placed in a silicon molybdenum rod furnace at a temperature of 1550 ℃ for 5 hours to accelerate the expulsion of glass bubbles and homogenize the glass for elimination. After melting, pouring the molten liquid into a heat-resistant stainless steel mold for molding, then taking out the glass block, transferring the glass block into a box-type annealing furnace, carrying out heat treatment for 2 hours at 500 ℃, then reducing the temperature to 440 ℃ at the speed of less than 1 ℃/min, and naturally cooling to room temperature to obtain the base glass. And cutting and grinding the glass block to prepare a sample which accords with relevant tests. In order to obtain more stable measurement results, the compounding raw materials of the present disclosure are chemical-grade compounding raw materials.
Microcrystallization: heating the base glass to 670 ℃ (30 ℃ higher than the annealing point (640 ℃) for nucleation for 5 hours, and continuing to heat to 780 ℃ for crystallization at 5 hours, thereby obtaining the high-strength transparent glass ceramics.
Heating the micro crystallized glass to 350 ℃, preserving the temperature for 30min, and then carrying out a chemical strengthening process: the first stage is as follows: putting the microcrystalline glass into 100wt% of NaNO 3 In the molten salt, the ion exchange conditions were set as follows: keeping the temperature at 380 deg.C for 120min; and a second stage: taking out the glass and placing the glass in KNO with the weight percent of 100 3 In the molten salt, the ion exchange conditions were set as follows: keeping the temperature at 420 ℃ for 60min; placing the glass in a muffle furnace for rapid cooling; the chemically strengthened glass was tested by cleaning the surface residues with hot water.
Test examples 1 to 5 and comparative example 1
The physical properties of the crystallized glasses prepared in examples 1 to 5 and comparative example 1 were measured, and the results are shown in table 1.
The physical property symbols and the measurement method are defined as follows:
(1) Softening point, annealing strain point: the orton test is used.
(2) Refractive index Nd: the measurement was carried out using an Abbe refractometer at an ambient temperature of 20. + -. 0.5 ℃.
(3) Transmittance: and testing by using an ultraviolet-visible spectrophotometer.
(4) Vickers hardness: the loading force was 200g and the loading time was 15s, as measured using a HXD-3000 Vickers hardness tester.
(5) CS: the surface Compressive Stress is abbreviated as Compressive Stress, namely, a FSM-6000LE surface Stress meter of Japan bending original industry Co.
(6) DOL: the surface compression stress Layer Depth of Layer is abbreviated, and the FSM-6000LE surface stress meter of Japan bending original industry Co., ltd is adopted for testing.
(7) The Vickers hardness and fracture toughness of the obtained microcrystalline glass (before chemical strengthening) are detected by a conventional detection instrument, and the Vickers hardness, fracture toughness, surface tensile stress and stress depth of layer of the lithium aluminosilicate glass after chemical strengthening are detected.
(8) The SEM image and XRD image of the prepared microcrystalline glass are shown in figures 1 and 2 respectively.
The SEM image shows that the microcrystalline glass prepared by the method has the advantages of high crystal phase morphology and crystallization degree, high crystalline phase content and uniform crystal grain distribution, and the prepared microcrystalline glass has obvious granular crystals.
XRD pattern can see that the main crystalline phase in the microcrystalline glass prepared by the method is Li x Al x Si 1-x O 2 Solid solution, and the amorphous scattering characteristics in the sample are very weak, and mainly show the diffraction characteristics of the crystal, which indicates that the glass is easier to crystallize and has high crystalline phase content under the condition of microcrystallization heat treatment.
TABLE 1
The microcrystalline glass prepared by the method has the light transmittance of a 1mm thick sample of over 86 percent (the wavelength is 560 nm), and the Vickers hardness of over 800kgf/mm after being strengthened 2 Surface stress value greater than 910MPa, stress layer depth greater than 80 μm, and fracture toughness greater than 1.6 MPa-mm 0.5 The microcrystalline glass material with microhardness of more than 8GPa, high visible light transmittance, high strength, high hardness and high impact resistance is suitable for protecting components such as portable electronic equipment and optical equipment of a 5G mobile communication terminal.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. To avoid unnecessary repetition, the disclosure does not separately describe various possible combinations.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. A method for producing a glass-ceramic, characterized in that the method comprises the steps of:
uniformly mixing glass raw materials, melting, homogenizing, molding, annealing and micro-crystallizing, wherein the glass raw materials enable the prepared microcrystalline glass to contain Li x Al x Si 1-x O 2 A solid solution;
the method also comprises the step of chemically strengthening the microcrystalline glass after the microcrystallization treatment.
2. The method of claim 1, wherein the glass frit is composed of oxygenThe weight percentage of the compound is as follows: siO 2 2 65-73％，Al 2 O 3 3-10％，Na 2 O 3-8％，K 2 O 2-4％，Li 2 O 4-10％，MgO 1-3％，CaO 0-2％，BaO 0-2％，ZrO 2 0-3％，ZnO 0-3％，P 2 O 5 2-5％，TiO 2 0-1％，SnO 2 0-1％。
3. The method of claim 1, wherein the conditions of melt homogenization comprise: heating to 1500-1560 deg.c and maintaining for 4-6 hr; the melt homogenization is carried out in a platinum crucible.
4. The method of claim 1, wherein the annealing comprises two stages: the temperature of the first stage is 500-550 ℃, and the time is 1-3h; the temperature of the second stage is 400-450 deg.C, and the time is 0.5-1h.
5. The method according to claim 1, wherein the microcrystallization comprises two stages: the temperature of the first stage is 665-685 ℃, and the time is more than or equal to 4h; the temperature of the second stage is 760-790 ℃, and the time is more than or equal to 4h.
6. The method of claim 1, wherein the process of chemical strengthening comprises two stages: in the first stage, the microcrystalline glass is placed in 100wt% of NaNO 3 Performing first ion exchange in molten salt; in the second stage, the microcrystalline glass after the first ion exchange is placed in KNO with the weight percent of 100 3 And in the molten salt, carrying out second ion exchange.
7. The method of claim 6, wherein the conditions of the first ion exchange comprise: the temperature is 350-400 deg.C, and the time is 100-150min.
8. The method of claim 6, wherein the conditions of the second ion exchange comprise: the temperature is 400-450 deg.C, and the time is 40-80min.
9. A glass-ceramic obtainable by a process according to any one of claims 1 to 8.
10. Use of the glass-ceramic prepared by the method according to any one of claims 1 to 8 in electronic devices and/or optical devices.
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