CN114956577A - High-strength transparent microcrystalline glass and preparation method thereof - Google Patents
High-strength transparent microcrystalline glass and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 48
- 238000005342 ion exchange Methods 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000005728 strengthening Methods 0.000 claims abstract description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 35
- 150000003839 salts Chemical class 0.000 claims description 16
- 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 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000006121 base glass Substances 0.000 claims description 11
- 238000002834 transmittance Methods 0.000 claims description 9
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 claims description 7
- 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 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 229910052670 petalite Inorganic materials 0.000 claims description 7
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 abstract description 12
- 230000008018 melting Effects 0.000 abstract description 12
- 239000000919 ceramic Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000006058 strengthened glass Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 12
- 238000004031 devitrification Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000006112 glass ceramic composition Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000003103 lithium disilicate glass Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical class OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000003426 chemical strengthening reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000006136 disilicate glass ceramic Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- 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 high-strength transparent glass ceramics and the preparation method thereof comprise the following components by mass percent: SiO 2 2 68‑74%；Al 2 O 3 5‑9%；TiO 2 0‑1%；CaO 0‑1%；Li 2 O 9‑13%；Na 2 O 0.1‑1.5%；K 2 O 0.1‑1%；P 2 O 5 3‑6%；ZrO 2 1‑6%；BaO 0‑1%；MgO 0‑3%；ZnO 0‑2%；Sb 2 O 3 0 to 2 percent. The high-strength transparent microcrystalline glass is prepared by the following steps: preparing raw materials according to requirements, mixing and melting the raw materials to form a basic glass plate;crystallizing the basic glass plate through two-step heat treatment to prepare ion-exchangeable microcrystalline glass; and B, strengthening the ion-exchangeable glass ceramics prepared in the step B by adopting a two-step high-temperature ion exchange method to obtain the strengthened glass ceramics.
Description
Technical Field
The invention relates to the field of glass ceramic materials, in particular to high-strength transparent glass ceramic.
Background
Due to the severe impact of metal cover plates on signal reception, many current electronic devices employ glass materials as screen and/or back cover protective materials. However, with the large screen display of the mobile terminal, the problem that the glass screen is easily broken and scratched becomes more prominent. The mechanical property of the existing high-alumina glass cannot meet the development requirement of a mobile terminal, and the mechanical property of a glass protective layer of electronic equipment is to be further improved.
Since the 20 th century 50 s, corning corporation in the united states realized the controllable preparation of glass ceramics, the glass ceramics attracted the attention of related researchers. The crystallized glass has a crystal phase inside, and can have physical properties that cannot be obtained in glass. Because the presence of the crystalline phase can prevent further propagation of surface or internal microcracks or redirect microcracks from propagating. Compared with the original glass, the microcrystalline glass has the advantages of obviously improved mechanical strength, thermal shock resistance and chemical stability, adjustable thermal expansion coefficient and the like.
With lithium disilicate (Li) 2 Si 2 O 5 ) The glass ceramics having a main crystal phase are collectively called as lithium disilicate glass ceramics, Li 2 Si 2 O 5 The crystalline phase is orthorhombic, the shape of the crystal is flat or platy, the lithium disilicate crystalline phase is a random non-oriented interlocking microstructure in the microcrystalline glass, a path is bent when a crack passes through the crystal, so that the crack is prevented from expanding, the strength and the toughness of the microcrystalline glass are improved, and compared with the glass phase, the lithium disilicate crystalline phase has high thermal conductivity, so that the thermal conductivity of the microcrystalline glass is improved. The microcrystalline glass with lithium disilicate as main crystal phase has high machinability, transparency, strength and biological performance. Is widely applied to biomedical materials, in particular to oral repair materials. And because the refractive index of the crystal phase (1.55-1.58) is close to that of the glass matrix, the glass ceramics with high transparency can be manufactured. Nevertheless, the high brittleness and poor toughness are still the main problems of lithium disilicate glass-ceramic materials. Patent CN104108883A provides a high-strength lithium disilicate glass ceramic and a method for preparing the sameThe composition contains zirconia and magnesium aluminum silicate crystal phases, and microcrystalline glass with high transmittance is difficult to obtain.
Disclosure of Invention
The invention aims to provide microcrystalline glass with high light transmittance and high strength and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the high-strength transparent glass-ceramic is characterized in that the crystalline phase of the glass-ceramic comprises lithium disilicate, petalite and aluminum metaphosphate, and the crystallinity of the glass-ceramic is 60-95%.
Preferably, the microcrystalline glass is in the crystalline phase: 30-60% of petalite, 25-45% of lithium disilicate and 1-5% of aluminum metaphosphate.
Preferably, the size of the overall crystal generated in the microcrystalline glass body is less than or equal to 60 nm.
Preferably, the microcrystalline glass composition comprises, in mass fraction: SiO 2 2 68-74%；Al 2 O 3 5-9%；TiO 2 0-1%；CaO 0-1%；Li 2 O 9-13%；Na 2 O 0.1-1.5%；K 2 O 0.1-1%；P 2 O 5 3-6%；ZrO 2 3-6%；BaO 0-1%；MgO 0-3%；ZnO 0-2%；Sb 2 O 3 0-2%。
Preferably, SiO 2 /Li 2 O is 5.5-8.5%; and/or ZrO 2 +P 2 O 5 +TiO 2 5 to 10 percent.
Furthermore, the size of the overall crystal generated in the microcrystalline glass body is less than or equal to 60 nm.
Furthermore, the transmittance of the microcrystalline glass with the thickness of 1mm is more than or equal to 88 percent in the visible light range.
Furthermore, the Vickers hardness of the microcrystalline glass is more than or equal to 900kgf/mm 2 。
Furthermore, the surface compressive stress of the microcrystalline glass is more than or equal to 300 MPa.
Furthermore, the depth of the microcrystalline glass potassium ion exchange layer is more than or equal to 6 mu m.
The preparation method of the high-strength transparent glass ceramics is characterized by comprising the following steps:
A. preparing a base glass sheet from raw materials having the composition and mass fraction of claim 4;
B. b, crystallizing the base glass plate prepared in the step A through two-step heat treatment to prepare ion-exchangeable microcrystalline glass;
C. and D, chemically strengthening the ion-exchangeable glass ceramics prepared in the step B by adopting a high-temperature ion exchange method to obtain the high-strength transparent glass ceramics.
Preferably, the crystallization processing step is: firstly, keeping the temperature at 600-640 ℃ for 3-5 h; and secondly, keeping the temperature for 2-6 hours at a second temperature of 700-760 ℃.
Preferably, the high temperature ion exchange process step is: firstly, placing the ion-exchangeable glass ceramics in NaNO 3 Keeping the temperature of the molten salt constant at 400-500 ℃ for 4-10 h to perform primary ion exchange; second, taking out the microcrystalline glass which has finished the first ion exchange, and placing the microcrystalline glass in KNO 3 And (3) in the molten salt, keeping the temperature of 350-420 ℃ for 1-3 h, and performing secondary ion exchange.
Preferably, the high temperature ion exchange process step is: placing the ion-exchangeable glass ceramics in KNO 3 /NaNO 3 And (4) keeping the temperature of the mixed molten salt at 400-480 ℃ for 1-8 h.
The invention has the beneficial effects that: the invention obtains the microcrystalline glass which is uniformly crystallized and has three crystal phases of lithium disilicate, petalite and aluminum metaphosphate by limiting the composition range of the components and controlling the crystallization temperature range. The transmittance of the microcrystalline glass in a visible light range is at least 88% after the microcrystalline glass is chemically strengthened, and the Vickers hardness of the surface of the microcrystalline glass is at least 900kgf/mm 2 . On the contrary, if it is out of the composition or heat treatment temperature range, other crystal phase compositions are easily obtained. The high-strength transparent microcrystalline glass provided by the invention can be suitable for a front cover and/or rear cover protection component in a cover plate material for a touch display product.
Drawings
FIG. 1 is a Differential Scanning Calorimetry (DSC) curve of measurement example 1
FIG. 2 is a graph showing transmittance measured in example 1
FIG. 3 is an XRD spectrum measured for example 1
FIG. 4 shows a base glass plate obtained in example 1
FIG. 5 is the SEM morphology of the crystals after etching by HF of example 1
FIG. 6 is a line scan of the energy spectrum of potassium and sodium elements of the cross section of example 5
FIG. 7 is a line scan of the potassium sodium spectrum of the cross section of example 9
Detailed Description
The invention relates to a glass-ceramic containing both crystal phase and glass phase. Unlike amorphous solids, crystalline phases in microcrystalline glasses can be distinguished by X-ray diffraction analysis as well as by high-resolution transmission electron microscopy. The crystalline phase of the glass ceramics comprises two or more than two crystalline phases of lithium disilicate, petalite, aluminum metaphosphate and the like (figure 3).
The crystalline phase of the lithium disilicate is an orthorhombic crystal, the shape of the crystal is flat or plate-shaped, the crystalline phase of the lithium disilicate is a random non-oriented interlocking microstructure in the microcrystalline glass, a path is bent when a crack passes through the crystal, so that the crack is prevented from expanding, the strength and the toughness of the microcrystalline glass are improved, and compared with a glass phase, the crystalline phase of the lithium disilicate has high thermal conductivity, so that the thermal conductivity of the microcrystalline glass is improved.
Petalite Li [ AlSi ] 4 O 10 ]The glass is a monoclinic crystal, has the refractive index of 1.50-1.51, the Mohs hardness of 6-6.5 and a low expansion coefficient, and can be used for improving the heat resistance of the glass ceramics.
The aluminum metaphosphate crystal is uniformly precipitated in the glass body together with other crystal phases, so that the chemical property, the stability and the mechanical strength of the microcrystalline glass are improved.
The inventors of the present invention have made extensive experiments and studies, and have obtained a high-strength transparent glass ceramics of the present invention at a low cost by specifying the contents and content ratios of specific components constituting the glass ceramics to specific values and precipitating the three crystal phases.
The compositional ranges of the respective components of the glass ceramics of the present invention will be explained below. In the present specification, the contents of the respective components are all expressed in terms of weight percentage with respect to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when all of the oxides, complex salts, and the like used as the raw materials of the glass-ceramic composition component of the present invention are decomposed and converted to oxides at the time of melting, the total amount of the oxides is 100%.
SiO 2 Is an essential component for forming a network structure of the glass, and is also an essential component for constituting a crystal phase by heat treatment of the base glass. If the amount is less than 68%, the resulting glass is difficult to obtain a corresponding crystal phase and crystallinity. Thus, SiO 2 The lower limit of the content is preferably 68%; on the other hand, by using SiO 2 The content of (A) is 74% or less, and excessive increase in viscosity and decrease in meltability can be suppressed. Thus, SiO 2 The upper limit of the content is preferably 74%.
Al 2 O 3 Are also components capable of forming a glass network structure and are also essential components capable of constituting a crystal phase by heat treatment of the base glass. The glass is beneficial to stabilizing the glass structure, improving the chemical durability and further improving the thermal conductivity of the glass. But if Al is present 2 O 3 When the content is less than 5%, the preferable effect cannot be obtained, and therefore, Al 2 O 3 The lower limit of the content is 5%; on the other hand, due to Al 2 O 3 Has a high melting point (2050 ℃ C.), and if the content exceeds 9%, the meltability and devitrification resistance are not good, so that Al 2 O 3 The upper limit of the content is 9%.
TiO 2 Is an optional component which is helpful for reducing the melting temperature of the microcrystalline glass, improving the refractive index and chemical stability of the glass and increasing the absorption capacity of ultraviolet rays. At the same time, TiO 2 Has the function of a crystal nucleating agent and is beneficial to crystallization in the heat treatment process. TiO 2 2 The lower limit of the content is preferably more than 0; on the other hand, by making TiO 2 Is 1% or less, and can lower the melting temperature of the glass and control the degree of devitrification, and therefore, TiO 2 The upper limit of the content is preferably 1%.
CaO is an optional component which contributes to the improvement of the low-temperature melting property of the glass, and has the effects of increasing the chemical stability and mechanical strength of the glass and shortening the material property. However, CaO has an accumulation effect, and wollastonite crystals (CaO. SiO) are easily precipitated by introducing an excessive amount of CaO 2 ) Making the glass brittle. In the present invention, the upper limit of the CaO content is preferably 1%.
Li 2 O is an optional component for improving the low-temperature melting property and the formability of the glass, and is also an essential component capable of being a crystal phase composition by heat treatment of the starting glass. In addition, when chemical tempering is performed by ion exchange, if Li is contained in the glass ceramics 2 The O component is very effective in forming a deep compressive stress layer even with a high lithium content. In the present invention, if Li 2 When the O content is less than 9%, the effect of precipitating the corresponding lithium-containing crystal phase is not good, and the melting difficulty is increased, so that Li 2 The lower limit of the O content is preferably 9%; on the other hand, if Li is contained excessively 2 O tends to lower the chemical durability of the glass or to increase the average linear expansion coefficient, so Li 2 The upper limit of the O content is preferably 13%.
Na 2 O has a remarkable flux action, and Na2O is contained in the glass ceramics to make Na in the glass ceramics when chemical strengthening is performed by ion exchange + Ion and K + Ions are ion exchanged to form a compressive stress layer. However, too much introduction tends to increase the expansion coefficient of the glass-ceramic and reduce its thermal stability, chemical stability and mechanical strength. In the present invention, the lower limit of the content of Na2O is 0.1% and the upper limit is 1.5%.
K 2 O is an optional component contributing to the improvement of the meltability and formability of the glass, and acts on Na 2 And similar to O, the whiteness and the smoothness of the glass can be improved. Potassium contained in glass has the effect of increasing surface compressive stress and stress layer depth when chemically tempered by ion exchange. But if it contains K excessively 2 O, a decrease in chemical durability and an increase in average linear expansion coefficient are easily generated. Thus, in the present invention, K 2 The lower limit of the O content is preferably 0.1%, and the upper limit is preferably 1%.
P 2 O 5 Can act as a nucleating agent in the glass and can become an essential component of the crystal phase composition by heat treatment of the original glass. The glass melting temperature is reduced, and the dispersion coefficient, the ultraviolet transmittance and the light transmittance can be improved. But if it contains P excessively 2 O 5 The deterioration of devitrification resistance and phase separation of the glass are easily caused. In the present invention, P 2 O 5 The lower limit of the content is preferably 3% and the upper limit is preferably 6% because the content of the glass becomes an essential component constituting a crystal phase by heat treatment of the base glass.
ZrO2 helps to increase the refractive index and chemical stability of the glass, and reduces the ultraviolet light transmission capability of the glass. But if it contains ZrO excessively 2 In the present invention, ZrO2 is an essential component that can be a constituent crystal phase by heat treatment of the base glass, and the lower limit of the content is preferably 3% and the upper limit is preferably 6%.
BaO is an optional component which is helpful for improving the low-temperature melting property of the glass, and the BaO helps to melt when being small in amount, and has the effects of increasing the refractive index and density of the glass, enhancing the chemical stability, absorbing the radiation capacity and the like. However, too much BaO causes difficulties in fining and secondary bubbles, resulting in devitrification of the glass. In the present invention, the lower limit of the BaO content is preferably more than 0, and the upper limit is preferably 1%.
MgO contributes to lowering the viscosity of glass, suppresses devitrification of raw glass during molding, and has the effect of improving low-temperature fusibility. However, if the MgO content is too high, devitrification resistance may be deteriorated, and undesirable crystals are obtained after crystallization, resulting in deterioration of the performance of the glass ceramics. In the present invention, MgO is an optional component, and the lower limit of the content thereof is preferably more than 0, and the upper limit thereof is preferably 3%.
ZnO can improve the melting performance of the glass and improve the chemical stability of the glass, and is an optional component, and the lower limit of the ZnO content is preferably more than 0; on the other hand, the upper limit of the ZnO content is controlled to 2% or less, and the deterioration of the devitrification property can be suppressed.
Examples of the invention (table 1) were prepared by the following method:
1. weighing and mixing the components: selecting raw materials of oxides, hydroxides, carbonates, nitrates, hydroxides, metaphosphoric acid compounds and the like corresponding to various components, uniformly mixing the raw materials according to the component proportion range, and putting the uniform mixture into a platinum or alumina crucible.
2. Preparing a base glass plate: according to the difficulty of melting of the glass composition, heating is carried out in an electric furnace at 1300-1450 ℃ for 10-30 hours to uniformly melt the glass, and then a base glass plate with a certain thickness is formed by an ingot cutting method or a rolling method (figure 4).
3. Crystallization heat treatment: the base glass sheet obtained in the above-described step was subjected to two-stage heat treatment (examples 1 to 9), to prepare ion-exchangeable glass ceramics. Wherein the heat treatment conditions of the first stage are recorded in the column of "nucleation process" in Table 1, the heat treatment conditions of the second stage are recorded in the column of "crystallization process" in Table 1, and the temperature and holding time of the heat treatment are as shown in the table.
4. Strengthening of the microcrystalline glass: and (4) cutting, grinding and polishing the ion-exchangeable glass ceramics prepared in the step (3), preparing the glass ceramics into sheets, and performing strengthening treatment. Wherein, the examples 1-8 adopt a two-step high-temperature ion exchange method for reinforcement, and the example 9 adopts a mixed molten salt one-step reinforcement method for reinforcement.
The two-step high-temperature ion exchange method comprises the following steps: firstly, placing the ion-exchangeable glass ceramics in NaNO 3 Keeping the temperature of the molten salt constant at 450 ℃ for 8 hours to perform primary ion exchange; second, taking out the microcrystalline glass which has finished the first ion exchange, and placing the microcrystalline glass in KNO 3 In the molten salt, the temperature was maintained at 400 ℃ for 1 hour, and a second ion exchange was carried out (examples 1 to 8).
The one-step strengthening method of the mixed molten salt comprises the following steps: placing the ion-exchangeable glass ceramics in NaNO 3 And KNO 3 Keeping the temperature of the mixed molten salt at 420 ℃ for 2 hours, wherein the proportion of the mixed molten salt is as follows: KNO 3 ：NaNO 3 = 4: 1 (example 9).
Strengthening of the ion-exchangeable glass ceramicsThe conditions are as follows: the microcrystalline glass can be immersed in NaNO molten at the temperature of 420-460 DEG C 3 In the salt bath, ion exchange is carried out for 5-16 hours, and in the embodiment, Na ions replace part of Li ions in the microcrystalline glass, so that a surface pressure stress layer is formed to enable the microcrystalline glass to have high mechanical property; or the microcrystalline glass can be immersed in KNO melted at the temperature of 380-450 DEG C 3 The salt bath is subjected to ion exchange for 1 to 6 hours, and the preferable time range is 2 to 4 hours.
In the embodiment of the present invention, two strengthening methods (two-step high-temperature ion exchange method and mixed molten salt one-step strengthening method) are adopted, but the strengthening conditions of the microcrystalline glass of the present invention are not limited to the strengthening conditions used in the embodiment.
In the crystal phases of the microcrystalline glass before high-temperature ion strengthening in examples 1 to 9, the corresponding crystal phases in the microcrystalline glass were obtained by analyzing with a standard PDF card using an X-ray diffractometer, and the corresponding degrees of crystallinity were obtained by calculation (table 1).
Average grain size: the surface treatment of the microcrystalline glass in HF acid, the gold spraying treatment of the surface of the microcrystalline glass, the surface scanning under the scanning electron microscope, the diameter of the particles, and the division of the average diameter size of all the crystal particles by the number of crystal particles in the image (FIG. 5) were performed.
Visible light transmittance: a polished glass sheet of 1mm thickness was tested using an ultraviolet-visible spectrophotometer (table 1).
Vickers hardness: the loading force was 200g and the loading time was 15s, measured using a Vickers hardness tester (Table 1).
CS: namely, the surface compressive stress, was measured by using a glass surface stress meter FSM-6000 (Table 1).
DOC: i.e., the sodium ion exchange layer depth, was measured using a glass surface stress meter SLP-1000 (Table 1) of the Japan Kikuchi Kogyo Co., Ltd.
DOL: namely, the depth of the potassium ion exchange layer was measured by FSM-6000, a glass surface stress meter manufactured by NIPPON CORPORATION, Inc. (Table 1).
Height of falling ball: both surfaces of a reinforced glass-ceramic plate having a length, width and height of 160X 70X 0.8mm were polished and fixed on a rubber mount, and 102g of a steel ball was dropped from a predetermined height to thereby obtain a maximum ball drop height at which the glass plate could withstand an impact without breaking (Table 1).
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
TABLE 1
Claims (10)
1. The high-strength transparent glass-ceramic is characterized in that the crystalline phase of the glass-ceramic comprises lithium disilicate, petalite and aluminum metaphosphate, and the crystallinity of the glass-ceramic is 60-95%.
2. The glass-ceramic according to claim 1, wherein the glass-ceramic has a crystalline phase: 30-60% of petalite, 25-45% of lithium disilicate and 1-5% of aluminum metaphosphate.
3. The glass-ceramic according to claim 1, wherein the size of the crystals formed in the glass-ceramic is 60nm or less.
4. A glass-ceramic according to any one of claims 1 to 3, characterized in that its composition comprises, in mass fractions: SiO 2 2 68-74%；Al 2 O 3 5-9%；TiO 2 0-1%；CaO 0-1%；Li 2 O 9-13%；Na 2 O 0.1-1.5%；K 2 O 0.1-1%；P 2 O 5 3-6%；ZrO 2 3-6%；BaO 0-1%；MgO 0-3%；ZnO 0-2%；Sb 2 O 3 0-2%。
5. Microcrystalline glass according to claim 4, characterised in that SiO 2 /Li 2 O is 5.5-8.5%; and/or ZrO 2 +P 2 O 5 +TiO 2 5 to 10 percent.
6. The glass-ceramic according to claim 5, wherein the glass-ceramic has a Vickers hardness of 900kgf/mm or more 2 The surface pressure stress is more than or equal to 300MPa, the depth of a potassium ion exchange layer is more than or equal to 6 mu m, and the transmittance of the microcrystalline glass with the thickness of 1mm is more than or equal to 88 percent in a visible light range.
7. The preparation method of the high-strength transparent glass ceramics is characterized by comprising the following steps:
A. preparing a base glass sheet from raw materials having the composition and mass fraction of claim 4;
B. crystallizing the basic glass plate prepared in the step A through two-step heat treatment to prepare ion-exchangeable glass ceramics;
C. and D, chemically strengthening the ion-exchangeable glass ceramics prepared in the step B by adopting a high-temperature ion exchange method to obtain the high-strength transparent glass ceramics.
8. The microcrystalline glass according to claim 7, wherein the crystallization treatment step is: firstly, keeping the temperature at 600-640 ℃ for 3-5 h; and secondly, keeping the temperature for 2-6 hours at a second temperature of 700-760 ℃.
9. The microcrystalline glass according to claim 7, wherein the high temperature ion exchange process step is: firstly, placing the ion-exchangeable glass ceramics in NaNO 3 Keeping the temperature of the molten salt at 400-500 ℃ for 4-10 h for primary ion exchange; second, taking out the microcrystalline glass which has finished the first ion exchange, and placing the microcrystalline glass in KNO 3 And (3) in the molten salt, keeping the temperature of 350-420 ℃ for 1-3 h, and performing secondary ion exchange.
10. According to the rightThe microcrystalline glass of claim 7, wherein the high temperature ion exchange process comprises: placing the ion-exchangeable glass ceramics in KNO 3 /NaNO 3 And (4) keeping the temperature of the mixed molten salt at 400-480 ℃ for 1-8 h.
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| CN115490428A (en) * | 2022-09-16 | 2022-12-20 | 四川虹科创新科技有限公司 | Transparent glass ceramics with ultrahigh drop strength and preparation method thereof |
| CN115745400A (en) * | 2022-11-22 | 2023-03-07 | 湖南旗滨微晶新材料有限公司 | Glass composition, reinforced microcrystalline glass, preparation method of reinforced microcrystalline glass and microcrystalline glass product |
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| WO2023086427A1 (en) * | 2021-11-12 | 2023-05-19 | Corning Incorporated | Glass-ceramic articles with improved mechanical properties and low haze |
| CN115490428A (en) * | 2022-09-16 | 2022-12-20 | 四川虹科创新科技有限公司 | Transparent glass ceramics with ultrahigh drop strength and preparation method thereof |
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