CN115010369A - Chemically-strengthened spinel microcrystalline glass and preparation method and application thereof - Google Patents
Chemically-strengthened spinel microcrystalline glass and preparation method and application thereof Download PDFInfo
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- CN115010369A CN115010369A CN202210737448.6A CN202210737448A CN115010369A CN 115010369 A CN115010369 A CN 115010369A CN 202210737448 A CN202210737448 A CN 202210737448A CN 115010369 A CN115010369 A CN 115010369A
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- 239000011521 glass Substances 0.000 title claims abstract description 88
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 77
- 239000011029 spinel Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 79
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002241 glass-ceramic Substances 0.000 claims description 40
- 239000002994 raw material Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- 239000006064 precursor glass Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 7
- 230000006911 nucleation Effects 0.000 claims description 7
- 238000010899 nucleation Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 description 14
- 239000011734 sodium Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- -1 lithium-aluminum-silicon Chemical compound 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003426 chemical strengthening reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018516 Al—O 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019092 Mg-O Inorganic materials 0.000 description 1
- 229910019395 Mg—O Inorganic materials 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
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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
- 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
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses chemically-strengthened spinel microcrystalline glass and a preparation method and application thereof. The microcrystalline glass is prepared from the following components in percentage by mole: 40-55% SiO 2 、12～30％Al 2 O 3 、6～22％Na 2 O、0～1％K 2 O、4～8％MgO、0～2.2％CaO、1.8～3％ZnO、2.1～5％B 2 O 3 、1～4％ZrO 2 And 1 to 5% of P 2 O 5 (ii) a The main crystal phase is (Mg, Zn) Al 2 O 4 The secondary crystal phase is zirconium dioxide, and the grain sizes of the main crystal phase and the secondary crystal phase are both less than or equal to 50 nm. The microcrystalline glass prepared by the invention is colorless, and the melting temperature and the heat treatment temperature are lower than those of the common spinel microcrystalline glass, so that the production energy consumption is reduced. In addition, the microcrystalsThe glass can be chemically strengthened, the mechanical property of the glass is enhanced, and the application field of the glass is further widened.
Description
Technical Field
The invention belongs to the field of inorganic materials, and particularly relates to chemically-strengthened spinel glass ceramics as well as a preparation method and application thereof.
Background
The cover plate material adopted in the market at present is mainly a lithium-aluminum-silicon system, and compared with the shortage of lithium ore resources, the reserve amount of sodium and magnesium raw materials is much more abundant, and with the development of new energy industry, the price of the lithium raw material rises rapidly, so that the production cost is greatly increased. And the lithium-aluminum-silicon system needs to be chemically strengthened by adopting a two-step method, the process is complex, and the production cost is increased. The sodium-magnesium-aluminum-silicon system microcrystalline glass is an excellent candidate material, and the main crystal phase of the microcrystalline glass is spinel. Spinel is an oxide with cubic structure and has a chemical formula of AB 2 O 4 Wherein A is a divalent metal ion of Zn, Fe or Mg with tetrahedral coordination, B is a metal ion of A1, Cr or Fe with octahedral coordination, and belongs to Fd3m space group. Common magnesium aluminate spinel (MgAl) 2 O 4 ) As Al-O, Mg-O forms stronger ionic bonds, the crystal has firm structure, high hardness (8), high melting point (2135 ℃) and stable chemical properties. The controllable precipitation of spinel in glass can increase the mechanical property of spinel, and the transparent glass ceramics with good mechanical property can be obtained by controlling the heat treatment system of spinel.
However, microcrystalline glasses containing spinel are generally made of TiO 2 Nucleating agent to perform nucleation. A significant amount of TiO is generally required 2 Nucleating agents to produce internal nucleation (e.g., about 5-10 wt.%) in the spinel-containing glass-ceramic are sufficient to impart a yellow or amber color to the precursor glass (glass from which the glass-ceramic article is formed), limiting its use in the field of cell phone covers and other fields where transparency and color are particularly desirable. The spinel microcrystalline glass contains a large amount of MgO and a small amount of Na 2 O, which is difficult to be chemically strengthened, is an important consideration in the field of cover glass as to whether chemical strengthening is possible, and thus has natural disadvantages compared with the preparation of chemically strengthened glass ceramics.
There is therefore a need in the art for transparent, colorless and chemically strengthenable microcrystalline glass articles containing spinel.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide chemically-strengthened spinel glass ceramics, and a preparation method and application thereof. The invention obtains the microcrystalline glass which has higher visible light transmittance, is colorless and can be chemically strengthened by glass component design and heat treatment process control, and the microcrystalline glass of the system contains more Na 2 O can be melted at a lower temperature, and because the component contains Na with a smaller radius + Therefore, the 'one-step method' of common aluminosilicate glass and K in potassium nitrate molten salt can be directly used + Ion exchange is carried out to realize chemical strengthening. Further enhancing the mechanical property.
The purpose of the invention is realized by the following technical scheme:
a spinel microcrystalline glass capable of being chemically strengthened is prepared from the following components in percentage by mole: 40-55% SiO 2 、12～30％Al 2 O 3 、6～22％Na 2 O、0～1％K 2 O、4～8％MgO、0～2.2％CaO、1.8～3％ZnO、2.1～5％B 2 O 3 、1～4％ZrO 2 And 1 to 5% of P 2 O 5 (ii) a The main crystal phase is (Mg, Zn) Al 2 O 4 The secondary crystal phase is zirconium dioxide, and the grain sizes of the main crystal phase and the secondary crystal phase are both less than or equal to 50 nm.
Preferably, the colorless transparent chemically-strengthened spinel glass ceramics are prepared from the following components in percentage by mole: 44-50.2% SiO 2 、18～21％Al 2 O 3 、13～18％Na 2 O、0～1％K 2 O、4～8％MgO、0～2.2％CaO、1.8～3％ZnO、2.1～5％B 2 O 3 、1.5～2％ZrO 2 And 2.7-3.8% of P 2 O 5 。
Preferably, the colorless transparent chemically-strengthened spinel microcrystalline glass is prepared from the following components in percentage by mole: 47% SiO 2 、19.3％Al 2 O 3 、15.7％Na 2 O、0％K 2 O、6.5％MgO、0％CaO、2％ZnO、5％B 2 O 3 、1.5％ZrO 2 And 3% of P 2 O 5 。
Preferably, the content of P is less than or equal to 3 percent (calculated by mol percent) 2 O 5 +ZrO 2 )≤7％。
Preferably, the mol percentage of the MgO and the ZnO is more than or equal to 6 percent and less than or equal to 11 percent.
The chemically-strengthened spinel microcrystalline glass prepared by the invention further comprises a compressive stress layer after being chemically strengthened, and the average compressive stress is more than 800 MPa.
The preparation method of the chemically strengthened spinel glass ceramics comprises the following steps:
(1) uniformly mixing all the raw materials according to the component proportion, performing heat preservation and melting at 1500-1650 ℃ for 2h to prepare precursor glass, then molding to obtain a plate blank, and annealing the plate blank at 500-600 ℃ for 3h to obtain a glass plate blank;
(2) and (2) heating the glass plate blank in the step (1) to a nucleation temperature (Tn) of 600-700 ℃ at a heating rate of 10 ℃/min, preserving heat for 2-8 h, then heating to a crystallization temperature (Tn) of 700-850 ℃ at a heating rate of 5-8 ℃/min, preserving heat for 2-10 h, and finally naturally cooling to room temperature to obtain the spinel glass ceramics.
Preferably, the molding in step (1) is cast molding.
Preferably, the glass mat of step (2) is heated to a nucleation temperature (Tn) of 700 ℃ at a heating rate of 10 ℃/min and held for 2 hours.
Preferably, in step (2), the mixture is heated to a crystallization temperature (Tn) of 800 ℃ at a heating rate of 5 ℃/min and incubated for 2 h.
The chemically strengthened spinel glass ceramics can be applied to the preparation of mobile phone cover plates and other glasses with special requirements on transparency and color.
Compared with the prior art, the invention has the beneficial effects that:
compared with the traditional spinel microcrystalline glass, the invention does not contain TiO 2 Therefore, the obtained glass-ceramics are colorless and have a melting temperature and a heat treatment temperature lower than those of the glass-ceramicsThe common spinel microcrystalline glass reduces the energy consumption for production. The microcrystalline glass product disclosed by the invention can be subjected to chemical strengthening, the mechanical property of the microcrystalline glass product is enhanced, and the application fields of the microcrystalline glass product are further widened, such as a high-strength glass cover plate, a scratch-resistant rear cover and the like.
Drawings
FIG. 1 is a graph of example 2, in which the spinel microcrystalline glass is heated to 700 ℃ at a heating rate of 10 ℃/min and is kept warm for 4h, then heated to 800 ℃ at a heating rate of 5 ℃/min and is kept warm for 4h, and finally naturally cooled to room temperature to obtain the transmittance curve of the spinel microcrystalline glass at the wavelength of 300-700 nm.
FIG. 2 is a diffraction pattern of a sample of example 6, nucleated at 700 ℃ for 2 hours and then crystallized at 800 ℃ for 6 hours, measured by an XRD diffractometer.
FIG. 3 shows stress fringes measured by FSM-6000LE instrument for samples 2-3.
FIG. 4 shows the K measured by EPMA from the surface to the inside of 100 μm of samples 2 to 5 + And (5) distribution diagram.
FIG. 5 is a diagram of a matter of example 1, in which the spinel microcrystalline glass is prepared by heating to 700 ℃ at a heating rate of 10 ℃/min and maintaining for 2h, then heating to 800 ℃ at a heating rate of 5 ℃/min and maintaining for 2h, and finally naturally cooling to room temperature.
FIG. 6 is an SEM microscopic morphology of the spinel microcrystalline glass prepared in example 6 by heating to 700 ℃ at a heating rate of 10 ℃/min and holding for 2h, then heating to 800 ℃ at a heating rate of 5 ℃/min and holding for 2h, and finally naturally cooling to room temperature.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
A preparation method of a series of colorless transparent chemically-strengthened spinel microcrystalline glasses comprises the following steps:
(1) uniformly mixing all the raw materials according to the component proportion shown in the table 1, carrying out heat preservation melting at 1500 ℃ for 2h to prepare precursor glass, then forming to obtain a plate blank, and annealing the plate blank at 500 ℃ for 3h to obtain a glass plate blank;
(2) respectively carrying out the following heat treatment systems on the glass plate blank in the step (1):
a: heating to 700 ℃ at a heating rate of 10 ℃/min and preserving heat for 2h, then heating to 800 ℃ at a heating rate of 5 ℃/min and preserving heat for 2h, and finally naturally cooling to room temperature to obtain the spinel glass ceramics;
b, heating to 700 ℃ at a heating rate of 10 ℃/min and preserving heat for 2h, then heating to 820 ℃ at a heating rate of 5 ℃/min and preserving heat for 2h, and finally naturally cooling to room temperature to obtain the spinel glass ceramics;
c: heating to 700 ℃ at a heating rate of 10 ℃/min and preserving heat for 2h, then heating to 800 ℃ at a heating rate of 5 ℃/min and preserving heat for 6h, and finally naturally cooling to room temperature to obtain the spinel glass ceramics;
d: heating to 700 ℃ at a heating rate of 10 ℃/min and preserving heat for 4h, then heating to 800 ℃ at a heating rate of 5 ℃/min and preserving heat for 4h, and finally naturally cooling to room temperature to obtain the spinel glass ceramics;
e: heating to 700 ℃ at a heating rate of 10 ℃/min and preserving heat for 2h, then heating to 840 ℃ at a heating rate of 5 ℃/min and preserving heat for 2h, and finally naturally cooling to room temperature to obtain the spinel glass ceramics.
Example 2
A preparation method of a series of colorless transparent chemically-strengthened spinel microcrystalline glasses comprises the following steps:
(1) uniformly mixing all the raw materials according to the component proportion shown in the table 1, carrying out heat preservation melting at 1550 ℃ for 2 hours to prepare precursor glass, then forming to obtain a plate blank, and annealing the plate blank at 550 ℃ for 3 hours to obtain a glass plate blank;
(2) same as example 1
Example 3
A preparation method of a series of colorless transparent chemically-strengthened spinel microcrystalline glasses comprises the following steps:
(1) uniformly mixing all the raw materials according to the component proportion shown in the table 1, then carrying out heat preservation melting at 1650 ℃ for 2h to prepare precursor glass, then forming to obtain a plate blank, and annealing the plate blank at 500 ℃ for 3h to obtain a glass plate blank;
(2) the same as in example 1.
Example 4
A preparation method of a series of colorless transparent chemically-strengthened spinel microcrystalline glasses comprises the following steps:
(1) uniformly mixing all the raw materials according to the component proportion shown in the table 1, carrying out heat preservation melting at 1500 ℃ for 2h to prepare precursor glass, then forming to obtain a plate blank, and annealing the plate blank at 600 ℃ for 3h to obtain a glass plate blank;
(2) the same as in example 1.
Example 5
A preparation method of a series of colorless transparent chemically-strengthened spinel microcrystalline glasses comprises the following steps:
(1) uniformly mixing all the raw materials according to the component proportion shown in the table 1, carrying out heat preservation melting at 1500 ℃ for 2h to prepare precursor glass, then forming to obtain a plate blank, and annealing the plate blank at 550 ℃ for 3h to obtain a glass plate blank;
(2) the same as in example 1.
Example 6
A preparation method of a series of colorless transparent chemically-strengthened spinel microcrystalline glasses comprises the following steps:
(1) uniformly mixing all the raw materials according to the component proportion shown in Table 1, carrying out heat preservation melting at 1600 ℃ for 2h to prepare precursor glass, then forming to obtain a plate blank, and annealing the plate blank at 500 ℃ for 3h to obtain a glass plate blank;
(2) the same as in example 1.
Table 1 shows the raw material composition ratios of a series of colorless transparent chemically-strengthened spinel microcrystalline glasses described in examples 1 to 6. Table 2 shows the results of the crystal phase and hardness tests of a series of colorless transparent chemically-strengthened spinel microcrystalline glasses 1-6.
Table 1 examples 1 to 6 raw material composition ratio table
| Mol% of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| SiO 2 | 47 | 47.6 | 45 | 50.2 | 46 | 44 |
| Al 2 O 3 | 19.3 | 18.4 | 21 | 18 | 20 | 20 |
| Na 2 O | 15.7 | 14 | 18 | 16 | 13 | 15 |
| |
0 | 1 | 0 | 0 | 0 | 1 |
| MgO | 6.5 | 8 | 4 | 6 | 8 | 8 |
| |
0 | 0 | 0 | 0 | 2.2 | 0 |
| ZnO | 2 | 2 | 2 | 3 | 1.8 | 2 |
| B 2 O 3 | 5 | 4 | 5 | 2.1 | 4 | 4.2 |
| ZrO 2 | 1.5 | 2 | 1.7 | 2 | 2 | 2 |
| P 2 O 5 | 3 | 3 | 3.3 | 2.7 | 3 | 3.8 |
| Total of | 100 | 100 | 100 | 100 | 100 | 100 |
TABLE 2 comparative tables for crystal phase and hardness tests of examples 1-6
The crystalline phases in table 2 were determined by X-ray diffraction (XRD) analysis, as can be seen from fig. 2: the resulting glass-ceramic exhibits a crystalline phase aggregate comprising a spinel phase as the predominant crystalline phase and one or more minor phases comprising various combinations of zirconia or nepheline phases alone.
FIG. 1 is a graph of example 2, in which the spinel microcrystalline glass is heated to 700 ℃ at a heating rate of 10 ℃/min and is kept warm for 4h, then heated to 800 ℃ at a heating rate of 5 ℃/min and is kept warm for 4h, and finally naturally cooled to room temperature to obtain the transmittance curve of the spinel microcrystalline glass at the wavelength of 300-700 nm. As can be seen from fig. 1: the sample of example 2 exhibited greater than 80% transmission in the visible range (400nm-700nm) with 86% transmission at 550 nm.
FIG. 2 is a diffraction pattern of a sample of example 6, which was nucleated at 700 ℃ for 2 hours and then crystallized at 800 ℃ for 6 hours, as shown in FIG. 2, by an XRD diffractometer: example 6 the sample after X-ray diffraction shows diffraction peaks in the diffraction pattern, which indicates that there are some crystals in the glass, and these peaks correspond to ZrO 2 (JCPDF #50-1089) and spinel (JCPDF #21-1152), indicating the presence of ZrO in the sample 2 And a spinel phase.
In example 1, the spinel glass ceramics was prepared by heating to 700 ℃ at a heating rate of 10 ℃/min and holding for 2 hours, then heating to 800 ℃ at a heating rate of 5 ℃/min and holding for 2 hours, and finally naturally cooling to room temperature, and had the following color coordinates of 92, 0.23, and 0.18 in the CIE L, a, b colorimetric system, and when the color coordinates were (80-100, -5-5, -5-5), the sample was considered transparent, thereby proving that the sample was transparent.
Example 7
A preparation method of chemically strengthened spinel microcrystalline glass comprises the following steps:
(1) uniformly mixing all the raw materials according to the component proportion shown in the table 3, carrying out heat preservation melting at 1500 ℃ for 2h to prepare precursor glass, then forming to obtain a plate blank, and annealing the plate blank at 500 ℃ for 3h to obtain a glass plate blank;
(2) respectively carrying out the following heat treatment systems on the glass plate blank in the step (1):
heating to 700 ℃ at a heating rate of 10 ℃/min and preserving heat for 4h, then heating to 800 ℃ at a heating rate of 5 ℃/min and preserving heat for 2h, and finally naturally cooling to room temperature to obtain the spinel glass ceramics, wherein the spinel glass ceramics is marked as a sample 2-1.
Example 8
A preparation method of chemically strengthened spinel microcrystalline glass comprises the following steps:
(1) uniformly mixing all the raw materials according to the component proportion shown in the table 3, carrying out heat preservation melting at 1500 ℃ for 2h to prepare precursor glass, then forming to obtain a plate blank, and annealing the plate blank at 500 ℃ for 3h to obtain a glass plate blank;
(2) respectively carrying out the following heat treatment systems on the glass plate blank in the step (1):
heating to 700 ℃ at a heating rate of 10 ℃/min and preserving heat for 4h, then heating to 800 ℃ at a heating rate of 5 ℃/min and preserving heat for 8h, and finally naturally cooling to room temperature to obtain the spinel glass ceramics, wherein the spinel glass ceramics is marked as a sample 2-2.
Example 9
A preparation method of chemically strengthened spinel microcrystalline glass comprises the following steps:
(1) uniformly mixing all the raw materials according to the component proportion shown in the table 3, carrying out heat preservation melting at 1500 ℃ for 2h to prepare precursor glass, then forming to obtain a plate blank, and annealing the plate blank at 500 ℃ for 3h to obtain a glass plate blank;
(2) respectively carrying out the following heat treatment systems on the glass plate blank in the step (1):
heating to 700 ℃ at a heating rate of 10 ℃/min and preserving heat for 4h, then heating to 800 ℃ at a heating rate of 5 ℃/min and preserving heat for 6h, and finally naturally cooling to room temperature to obtain the spinel glass ceramics, wherein the spinel glass ceramics are marked as samples 2-3.
Example 10
A preparation method of chemically strengthened spinel microcrystalline glass comprises the following steps:
(1) uniformly mixing all the raw materials according to the component proportion shown in the table 3, carrying out heat preservation melting at 1500 ℃ for 2h to prepare precursor glass, then forming to obtain a plate blank, and annealing the plate blank at 500 ℃ for 3h to obtain a glass plate blank;
(2) respectively carrying out the following heat treatment systems on the glass plate blank in the step (1):
heating to 700 ℃ at a heating rate of 10 ℃/min and preserving heat for 4h, then heating to 800 ℃ at a heating rate of 5 ℃/min and preserving heat for 2h, and finally naturally cooling to room temperature to obtain the spinel glass ceramics, wherein the spinel glass ceramics are marked as samples 2-4.
Example 11
A preparation method of chemically strengthened spinel microcrystalline glass comprises the following steps:
(1) uniformly mixing all the raw materials according to the component proportion shown in the table 3, carrying out heat preservation melting at 1500 ℃ for 2h to prepare precursor glass, then forming to obtain a plate blank, and annealing the plate blank at 500 ℃ for 3h to obtain a glass plate blank;
(2) respectively carrying out the following heat treatment systems on the glass plate blank in the step (1):
heating to 700 ℃ at a heating rate of 10 ℃/min and preserving heat for 4h, then heating to 800 ℃ at a heating rate of 5 ℃/min and preserving heat for 2h, and finally naturally cooling to room temperature to obtain the spinel glass ceramics, wherein the spinel glass ceramics are marked as samples 2-5.
TABLE 3 ingredient ratio table for examples 7 to 11
The microcrystalline glasses obtained in examples 7 to 11 were immersed in KNO 3 Adding into molten salt, placing into ion exchange furnace (purchased from Ksl-1200X-J, Co., Ltd.) at a rate of 5 deg.C/min, heating to corresponding ion exchange temperature shown in Table 4, and placing the microcrystalline glass sample into KNO 3 In the molten salt, after the heat preservation for the corresponding time is carried out according to the ion exchange time described in table 4, the sample is taken out and cooled to room temperature along with the furnace, so as to obtain the ion-exchanged microcrystalline glass sample. Observing the sample by using FSM-6000LE surface stress instrumentThe surface compressive stress fringes and then the surface compressive stress and exchange depth of each sample were obtained by computer calculation (FSM6000 software). In addition, the K from the surface to the inside of the sample can also be measured by EPMA + The profile to obtain its exchange depth.
TABLE 4 summary of the exchange conditions for ion exchange of samples 2-1 to 2-5
| Sample (I) | Fused salt | Ion exchange temperature (. degree.C.) | Ion exchange time (h) |
| 2-1 | KNO 3 | 420 | 4 |
| 2-2 | KNO 3 | 440 | 4 |
| 2-3 | KNO 3 | 460 | 4 |
| 2-4 | KNO 3 | 440 | 6 |
| 2-5 | KNO 3 | 440 | 12 |
The performance indexes of the samples 2-1 to 2-5 after ion exchange are shown in the table 5.
TABLE 5 summary of various properties of samples 2-1 to 2-5 after ion exchange
From table 5 it can be seen that: after ion exchange, the microcrystalline glass has certain exchange depth and surface compressive stress, which shows that the glass can be subjected to ion exchange, and the hardness of the glass after being strengthened can be improved by 22 percent compared with that of the glass without being strengthened, which shows that the mechanical strength of the glass can be effectively improved by ion exchange.
FIG. 3 shows the stress fringes of samples 2-3 measured by FSM-6000LE instrument, as can be seen in FIG. 3: the interference fringes of the sample surface observed by FSM-6000LE indicate that the sample surface has stress difference, and indicate that the sample successfully carries out ion exchange and generates surface compressive stress.
FIG. 4 shows the K measured by EPMA from the surface to the inside of 100 μm of samples 2 to 5 + And (5) distribution diagram. As can be seen from fig. 4: k + Diffused into the surface of the glass after ion exchange and as the depth increases, K + The amount in the glass becomes smaller and smaller, and eventually to a depth of about 20 μm, no further diffusion occurs inwards.
FIG. 5 is a pictorial representation of a colorless, transparent, chemically-strengthened spinel microcrystalline glass prepared in accordance with example 1, showing that: the glass exhibits a colorless and transparent appearance.
FIG. 6 is an SEM microtopography of a colorless transparent chemically-strengthened spinel glass-ceramic prepared in example 6It can be seen that: (Mg, Zn) Al 2 O 4 The crystal grains are spherical and uniformly dispersed in the glass body, and the diameter of the crystal grains is about 20 nm.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A spinel microcrystalline glass capable of being chemically strengthened is characterized by being prepared from the following components in percentage by mole: 40-55% SiO 2 、12～30％Al 2 O 3 、6～22％Na 2 O、0～1％K 2 O、4～8％MgO、0～2.2％CaO、1.8～3％ZnO、2.1～5％B 2 O 3 、1～4％ZrO 2 And 1 to 5% of P 2 O 5 (ii) a The main crystal phase is (Mg, Zn) Al 2 O 4 The secondary crystal phase is zirconium dioxide, and the grain sizes of the main crystal phase and the secondary crystal phase are both less than or equal to 50 nm.
2. The chemically-strengthenable spinel glass-ceramic according to claim 1, characterized in that it is prepared from components comprising, in mole%: 44-50.2% SiO 2 、18～21％Al 2 O 3 、13～18％Na 2 O、0～1％K 2 O、4～8％MgO、0～2.2％CaO、1.8～3％ZnO、2.1～5％B 2 O 3 、1.5～2％ZrO 2 And 2.7-3.8% of P 2 O 5 。
3. The chemically-strengthenable spinel glass ceramic according to claim 2, wherein said colorless transparent chemically-strengthenable spinel glass ceramic is prepared from the following components in percentage by mole: 47% SiO 2 、19.3％Al 2 O 3 、15.7％Na 2 O、0％K 2 O、6.5％MgO、0％CaO、2％ZnO、5％B 2 O 3 、1.5％ZrO 2 And 3% of P 2 O 5 。
4. The chemically-strengthenable spinel glass-ceramic according to claim 1, wherein said glass-ceramic is present in a molar percentage of 3% to less than (P) 2 O 5 +ZrO 2 )≤7％。
5. A chemically strengthenable spinel glass-ceramic according to claim 1, wherein the molar percentage is between 6% and 11% (MgO + ZnO).
6. A method for preparing chemically strengthened spinel glass ceramics according to any of claims 1 to 5, characterized by comprising the steps of:
(1) uniformly mixing all the raw materials according to the component proportion, performing heat preservation and melting at 1500-1650 ℃ for 2h to prepare precursor glass, then molding to obtain a plate blank, and annealing the plate blank at 500-600 ℃ for 3h to obtain a glass plate blank;
(2) and (2) heating the glass plate blank in the step (1) to a nucleation temperature of 600-700 ℃ at a heating rate of 10 ℃/min, preserving heat for 2-8 h, then heating to a crystallization temperature of 700-850 ℃ at a heating rate of 5-8 ℃/min, preserving heat for 2-10 h, and finally naturally cooling to room temperature to obtain the spinel glass ceramics.
7. The method for preparing chemically strengthened spinel glass-ceramic according to claim 6, wherein the glass slab of step (2) is heated to a nucleation temperature of 700 ℃ at a heating rate of 10 ℃/min and is kept at the nucleation temperature for 2 h.
8. The method for preparing chemically strengthened spinel glass-ceramic according to any one of claims 6 to 7, wherein in the step (2), the glass-ceramic is heated to a crystallization temperature of 800 ℃ at a heating rate of 5 ℃/min and is kept warm for 2 hours.
9. The method for preparing chemically-strengthenable spinel glass-ceramic according to claim 8, wherein said forming of step (1) is a cast forming.
10. Use of the chemically strengthened spinel microcrystalline glass of any one of claims 1 to 5 in the preparation of mobile phone cover sheets and other glasses having specific requirements on transparency and color.
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| WO2024131064A1 (en) * | 2022-12-23 | 2024-06-27 | 重庆鑫景特种玻璃有限公司 | Microcrystalline glass, curved microcrystalline glass, and use thereof |
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