CN113562987B - Chemical strengthening method of microcrystalline glass, strengthened microcrystalline glass and protective piece - Google Patents
Chemical strengthening method of microcrystalline glass, strengthened microcrystalline glass and protective piece Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000003426 chemical strengthening reaction Methods 0.000 title claims abstract description 16
- 230000001681 protective effect Effects 0.000 title claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 96
- 238000005342 ion exchange Methods 0.000 claims abstract description 64
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 39
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 239000002241 glass-ceramic Substances 0.000 claims description 90
- 238000005728 strengthening Methods 0.000 claims description 47
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 44
- 239000000919 ceramic Substances 0.000 claims description 40
- 239000006058 strengthened glass Substances 0.000 claims description 40
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 34
- 235000010333 potassium nitrate Nutrition 0.000 claims description 22
- 239000004323 potassium nitrate Substances 0.000 claims description 22
- 235000010344 sodium nitrate Nutrition 0.000 claims description 17
- 239000004317 sodium nitrate Substances 0.000 claims description 17
- 230000007704 transition Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 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 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 230000002087 whitening effect Effects 0.000 claims description 7
- 238000013001 point bending Methods 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 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 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 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 3
- 229910052670 petalite Inorganic materials 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 2
- 238000005496 tempering Methods 0.000 claims 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical group [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical group [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 4
- 229910000500 β-quartz Inorganic materials 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000005345 chemically strengthened glass Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000005341 toughened glass Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006112 glass ceramic composition Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 lithium aluminum silicon Chemical compound 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- OBDHSIPFRQLZJA-UHFFFAOYSA-N [Si]([O-])([O-])(O)O[Si](O)(O)O.[Li+].[Si](O)(O)(O)O[Si](O)(O)O.[Li+] Chemical compound [Si]([O-])([O-])(O)O[Si](O)(O)O.[Li+].[Si](O)(O)(O)O[Si](O)(O)O.[Li+] OBDHSIPFRQLZJA-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007676 flexural strength test Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002344 surface layer 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The application discloses a chemical strengthening method of microcrystalline glass, the microcrystalline glass and a protective piece, wherein the chemical strengthening method of the microcrystalline glass comprises the following steps: providing first-stage strengthened microcrystalline glass, wherein the first-stage strengthened microcrystalline glass is subjected to at least one-stage ion exchange, and the first-stage ion exchange is realized by utilizing lithium ions in sodium ion exchange microcrystalline glass; and placing the first-stage strengthened microcrystalline glass in a second-stage strengthened salt bath to perform second-stage ion exchange to obtain the strengthened microcrystalline glass, wherein the second-stage strengthened salt bath comprises lithium salt. By the mode, the environment durability of the reinforced microcrystalline glass can be improved.
Description
Technical Field
The present application relates to the field of dielectric materials, and in particular, to a chemical strengthening method for glass ceramics, a strengthened glass ceramics, and a protective member.
Background
The glass ceramics are also called glass ceramics, are composite materials combining crystalline phases and glass, have the dual characteristics of glass and ceramics, and have excellent optical properties and physical and chemical properties of being capable of transmitting visible light, high in mechanical strength, excellent in electrical insulation property, stable in dielectric constant, wear-resistant, corrosion-resistant, adjustable in thermal expansion coefficient and the like, and are widely applied to various fields, such as protective cover plate materials of portable electronic equipment, automobile protective glass and the like.
Chemically strengthened glass is a glass with high mechanical strength; the method utilizes a high-temperature ion exchange process to enable large alkali metal ions to replace small alkali metal ions in glass in high-temperature molten salt, thereby generating exchange ion volume difference, generating high-to-low compressive stress on a certain surface layer of the glass, further preventing and delaying the expansion of glass microcracks, and achieving the purpose of improving the mechanical strength of the glass. When the glass-ceramic is chemically strengthened, the lithium component in the glass-ceramic is high, and the sodium ion content on the surface of the glass-ceramic after ion exchange is high, so that the environmental durability of the glass-ceramic is poor.
Disclosure of Invention
The technical problem that this application mainly solves is to provide a chemical strengthening method of microcrystalline glass, tempered microcrystalline glass and guard, can improve the environmental durability of tempered microcrystalline glass.
In order to solve the technical problems, one technical scheme adopted by the application is as follows: the chemical strengthening method of the glass ceramics comprises the following steps: providing first-stage strengthened microcrystalline glass, wherein the first-stage strengthened microcrystalline glass is subjected to at least one-stage ion exchange, and the first-stage ion exchange is realized by utilizing lithium ions in sodium ion exchange microcrystalline glass; and placing the first-stage strengthened microcrystalline glass in a second-stage strengthened salt bath to perform second-stage ion exchange to obtain the strengthened microcrystalline glass, wherein the second-stage strengthened salt bath comprises lithium salt.
Wherein the content of lithium ions in the secondary enhanced salt bath is less than/equal to 200ppm.
Wherein the content of lithium ions in the secondary strengthening salt bath is more than or equal to 50ppm and less than or equal to 100ppm.
Wherein the temperature of the secondary ion exchange is 360-400 ℃ and the time is less than/equal to 30min.
Wherein the secondary strengthening salt bath comprises a mixture of potassium nitrate and lithium nitrate.
Wherein, before placing the first-stage strengthened microcrystalline glass in a second-stage strengthened salt bath for carrying out second-stage ion exchange, the method comprises the following steps: and (3) placing the first-stage strengthened microcrystalline glass in a transition salt bath to clean the first-stage strengthened microcrystalline glass, wherein the transition salt bath comprises potassium salt.
Wherein the cleaning temperature is less than or equal to 380 ℃, the time is less than or equal to 10min, and the lithium ion content in the transition salt bath in the cleaning process is less than or equal to 150ppm.
Wherein, before placing the first-stage strengthened microcrystalline glass in a second-stage strengthened salt bath for carrying out second-stage ion exchange, the method comprises the following steps: the primary reinforced microcrystalline glass is pretreated so that the amount of lithium ions remained on the surface of the treated primary reinforced microcrystalline glass cannot exceed a defined amount, wherein the defined amount is that when the primary reinforced microcrystalline glass is placed in a secondary reinforced salt bath, the amount of lithium ions brought by the primary reinforced microcrystalline glass cannot enable the content of lithium ions in the secondary reinforced salt bath to be more than 200ppm.
Wherein, provide first order and strengthen microcrystalline glass includes: placing the microcrystalline glass in a first-stage reinforced salt bath for first-stage ion exchange; the temperature of the primary ion exchange is 420-460 ℃ and the time is 0.5-11 h.
Wherein the primary enhanced salt bath comprises pure sodium nitrate; or the primary strengthening salt bath comprises a mixture of sodium nitrate and potassium nitrate, and the content of the sodium nitrate is greater than that of the potassium nitrate.
Wherein, provide first order and strengthen microcrystalline glass still includes: and placing the primary reinforced microcrystalline glass in a secondary salt bath for secondary ion exchange, wherein the secondary salt bath comprises potassium salt.
Wherein the secondary salt bath comprises pure potassium nitrate; or the secondary salt bath comprises a mixture of sodium nitrate and potassium nitrate, and the content of potassium nitrate is greater than the content of sodium nitrate.
In order to solve the technical problems, another technical scheme adopted by the application is as follows: provided is a tempered glass-ceramic, wherein the sodium content of the surface of the tempered glass-ceramic is less than/equal to 10mol%.
Wherein the main crystal phase of the reinforced microcrystalline glass is lithium disilicate.
Wherein, the secondary crystal phase of the reinforced microcrystalline glass comprises: lithium silicate, petalite, quartz, a combination of one or more of the solid solutions of quartz.
Wherein the crystallinity of the reinforced microcrystalline glass is more than or equal to 70 percent.
Wherein the lithium content in the reinforced microcrystalline glass is more than or equal to 15mol percent.
Wherein the strengthened glass ceramic has no erosion and the whitening degree is less than the second grade under the conditions that the temperature is 85 ℃ and the humidity is 85 percent.
Wherein the four-point bending strength B10 value of the reinforced microcrystalline glass is more than 650MPa; the falling ball strength is more than 0.4m.
In order to solve the technical problems, another technical scheme adopted by the application is as follows: there is provided a protective member comprising the strengthened glass ceramic of any one of the above.
The beneficial effects of this application are: in contrast to the situation of the prior art, the present application provides a chemical strengthening method of glass ceramics, in which a salt bath containing lithium is used to exchange ions of glass ceramics, so that sodium ions in the glass ceramics are exchanged by lithium ions in the salt bath, and the strengthened glass ceramics subjected to sodium-lithium exchange are subjected to lithium-sodium reverse strengthening, so as to reduce sodium ion components on the surface of the strengthened glass ceramics, and improve the environmental durability of the strengthened glass ceramics.
Drawings
FIG. 1 is a schematic illustration of a four-point flexural strength test of the present application;
FIG. 2 is a schematic illustration of the drop ball strength test of the present application;
FIG. 3 is a schematic illustration of ball drop points in the ball drop intensity test of the present application;
FIG. 4 is a schematic diagram of the tempered glass ceramic after high temperature and high humidity treatment in example 1 of the present application;
FIG. 5 is a schematic illustration of the tempered glass ceramic after high temperature and high humidity treatment in example 3 of the present application;
FIG. 6 is a schematic view of glass cracking of the strengthened glass ceramic of comparative example 3 of the present application;
FIG. 7 is a schematic view of the tempered glass ceramic of comparative example 7 after high temperature and high humidity treatment.
Detailed Description
In order to make the objects, technical solutions and effects of the present application clearer and more specific, the present application will be further described in detail below with reference to the accompanying drawings and examples.
The microcrystalline glass material is prepared by carrying out microcrystallization treatment on a glass substrate, so that small-size crystals uniformly grow in the glass substrate, and the structural strength of the material can be greatly improved. The content of each alkali metal in the glass ceramics can influence the generation of a crystal structure and the ion exchange performance of the glass ceramics; when the formula components of the glass ceramics are designed, the growth of the crystal structure is preferentially considered, the ion exchange performance is considered later, and the ion exchange is blocked by the crystal structure, so that the ion exchange performance of the glass ceramics is poor under the two factors. In order to balance crystallization performance and ion exchange performance, the content of lithium components in the finally designed glass ceramics formula is higher, and particularly compared with conventional lithium aluminum silicon glass, the content of lithium components in the glass ceramics is far higher than that of the lithium aluminum silicon glass, so that after ion exchange is carried out on the glass ceramics, the content of sodium ions on the surface of the glass ceramics is higher, and the environmental durability of the glass ceramics is further deteriorated.
Based on the above, the application provides a chemical strengthening process method of glass ceramics, which can adjust the alkali metal composition on the surface of the glass ceramics by adjusting the salt bath ratio, improve the chemical stability of the glass ceramics and avoid appearance defects. The method can be applied to strengthening of glass ceramics containing lithium silicate or lithium disilicate crystal phases, is not limited to the method, and can be also applied to chemical strengthening of other glass ceramics.
The chemical strengthening process of the glass ceramics is essentially to carry out lithium-sodium reverse strengthening on the strengthened glass ceramics with sodium-lithium exchange to reduce sodium ion components on the surface of the strengthened glass ceramics.
Specifically, the first-stage strengthened glass ceramic is placed in a second-stage strengthened salt bath for second-stage ion exchange, so that the strengthened glass ceramic is obtained. The first-stage strengthened glass ceramic is strengthened glass ceramic with sodium-lithium exchange completed, and the second-stage strengthened salt bath comprises lithium salt to realize lithium-sodium exchange.
In one embodiment, the content of lithium ions in the secondary strengthening salt bath is regulated to be less than or equal to 200ppm, so that the lithium-sodium reverse strengthening can be smoothly realized, and the monomer performance of the strengthened glass per se, the surface of the strengthened glass is free from crack defects and the like. This is because the lithium-containing salt bath can have a certain corrosion effect on glass, if the lithium ion content in the salt bath is too high, the glass-ceramic will be corroded and damaged, and the surface of the glass-ceramic will be tensile stress due to lithium-sodium exchange, and if the exchange amount is too large, the tensile stress will cause surface microcracks. If the content of lithium ions is too low, the lithium-sodium exchange is not thorough; therefore, strict regulation of lithium ion concentration in salt baths is required.
Preferably, the content of lithium ions in the secondary enhanced salt bath is greater than/equal to 50ppm and less than/equal to 100ppm, such as 53ppm, 58ppm, 62ppm, 69ppm, 75ppm, 84ppm, 90ppm, etc. In the ion exchange process, lithium is exchanged into the glass ceramic, and the concentration of lithium ions in the salt bath is reduced, so that the concentration of lithium ions in the salt bath can be controlled without monitoring the concentration of lithium ions in the ion exchange process, and the content of lithium ions in the salt bath can be controlled by regulating and controlling the initial concentration of lithium ions in the salt bath.
In one embodiment, the secondary enhanced salt bath includes a high concentration of potassium salt with a small amount of lithium salt added to the potassium salt to effect control of the lithium ion content in the salt bath. Specifically, the secondary strengthening salt bath can be a mixture of potassium nitrate and lithium nitrate, and lithium nitrate is added into the molten high-concentration potassium nitrate to prepare the secondary strengthening salt bath.
In one embodiment, the temperature of the secondary ion exchange is 360 to 400 ℃, preferably 370 to 390 ℃, for less than/equal to 30 minutes. The lithium-sodium exchange speed is high, so that the ion exchange time of the reverse reinforcement is not too long, otherwise, the surface performance of the glass ceramics is damaged. For example, the temperature may be 370 ℃, 374 ℃, 378 ℃, 383 ℃, 387 ℃, 390 ℃, etc., and the time may be 3min, 5min, 8min, 11min, 16min, 20min, 26min, 30min, etc.
In the embodiment, the sodium ion accumulation on the surface of the final strengthened glass ceramic can be reduced through counter-strengthening ion exchange, the integrity of the appearance of the strengthened glass is ensured, the durability and the yield of the glass are improved, and the glass is beneficial to the production, the application and the popularization of the glass ceramic.
In one embodiment, the first-stage strengthened glass ceramic may be pre-treated in advance or purchased directly, or may be obtained by ion exchange of glass ceramic in situ, i.e. sodium-lithium exchange strengthening and lithium-sodium exchange reverse strengthening of glass ceramic may be performed continuously, first performing first-stage ion exchange to perform chemical strengthening, and then performing second-stage ion exchange reverse strengthening. The glass ceramics strengthening process method comprises the following steps:
s110: providing microcrystalline glass.
The microcrystalline glass can contain one or more of crystal phases such as lithium silicate, lithium disilicate, petalite, quartz, beta-quartz solid solution and the like, and can be specifically lithium disilicate with high lithium content and microcrystalline glass made of lithium silicate, namely microcrystalline glass with the main crystal phase of lithium silicate or lithium disilicate. The crystallinity of the glass-ceramic may be greater than/equal to 70%. The glass ceramics may be glass ceramics having a lithium content of 15mol% or more, and the specific crystal phase component is not limited.
S120: and placing the microcrystalline glass in a first-stage strengthening salt bath for first-stage ion exchange.
The primary ion exchange is used for realizing chemical strengthening of the glass ceramics, alkali metal ions with large radius in a salt bath are used for exchanging alkali metal lithium ions with small radius in the glass ceramics, and the pressure stress is formed on the surface of the glass ceramics by utilizing the difference of the volume of the exchanged ions, so that the effect of strengthening the glass ceramics is achieved.
The primary ion exchange is mainly used for sodium-lithium exchange, and the sodium ions in the salt bath are used for exchanging lithium ions in the glass ceramic. Wherein the primary enhanced salt bath comprises pure sodium salt or a mixture of sodium salt and potassium salt. In particular, it may be a pure sodium nitrate melt; or a mixture of sodium nitrate melt and potassium nitrate melt. When a mixture of sodium nitrate melt and potassium nitrate melt is used in the salt bath, the sodium nitrate content in the salt bath should be greater than the potassium nitrate content, for example, the ratio of the two can be NaNO 3 :KNO 3 99:1, 98:2, 97:3, 95:5, etc. The temperature of sodium-lithium exchange is 420-460 ℃ and the time is 0.5-11 h. For example, the temperature can be 430 ℃, 450 ℃ and the like, and the time can be 1h, 3h, 5h, 8h, 10h and the like.
The primary ion exchange may also include potassium-sodium exchange, with potassium ions in the salt bath being used to exchange sodium ions in the glass-ceramic. The first-stage strengthened microcrystalline glass is placed in a second-stage salt bath for secondary ion exchange. The secondary salt bath comprises pure potassium salt or a mixture of sodium and potassium salts. Specifically, it may be a pure potassium nitrate melt; or a mixture of sodium nitrate melt and potassium nitrate melt. When a mixture of sodium nitrate melt and potassium nitrate melt is used in the salt bath, the potassium nitrate content in the salt bath should be greater than the sodium nitrate content, e.g. the ratio of the two may be KNO 3 :NaNO 3 99:1, 98:2, 97:3, 95:5, etc. For example, when the glass ceramic contains a β -quartz solid solution crystalline phase, a secondary ion exchange is also required after the primary ion exchange. The temperature of potassium-sodium exchange is 420-460 ℃ and the time is 0And 5-11 h. For example, the temperature can be 430 ℃, 450 ℃ and the like, and the time can be 1h, 3h, 5h, 8h, 10h and the like.
S130: and (3) placing the first-stage strengthened microcrystalline glass in a transition salt bath for cleaning.
Wherein, the product taken out from the salt bath after the primary ion exchange treatment has more ions in the salt bath attached to the surface of the glass, and the direct next treatment is unfavorable for controlling the ion content in the salt bath, in particular for controlling the lithium ion content, so that the product needs to be cleaned before the secondary ion exchange. The first-stage strengthened glass ceramic is required to be pretreated so that the amount of lithium ions remained on the surface of the treated first-stage strengthened glass ceramic cannot exceed a defined amount, and the defined amount is that when the first-stage strengthened glass ceramic is placed in a second-stage strengthened salt bath, the amount of lithium ions brought by the first-stage strengthened glass ceramic cannot enable the content of lithium ions in the second-stage strengthened salt bath to be more than 200ppm.
On the one hand, the first-stage strengthened glass may be cooled, then subjected to water washing, ultrasonic washing, then dried to moisture, preheated to a temperature of the second-stage strengthening, and the like, and then placed in a second-stage strengthening salt bath. However, this method can prolong the process, and on the other hand, the sodium ion content of the glass ceramics surface is high after the primary ion exchange, and the glass ceramics surface is eroded in the water washing and drying processes.
In the process method provided by the application, the microcrystalline glass is cleaned by using the transition salt bath, and the salt used in the transition salt bath can be selected according to a salt bath system used in secondary ion exchange, and the salt bath which is the same as the main component of the secondary strengthening salt bath can be selected; this can have less effect on the next salt bath composition. In the application, the transition salt bath can be selected from potassium salt, and the main components of the transition salt bath are the same as those of the secondary strengthening salt bath, and meanwhile, potassium-sodium exchange can be realized.
Alternatively, the transition salt bath may be selected from pure potassium salts, such as pure potassium nitrate melt. In other embodiments, waste potassium salt may be selected, such as potassium salt used for potassium-sodium exchange, so that cost can be saved and resources can be fully utilized, but when waste potassium salt is selected, the content of components in waste potassium salt should be considered, and if lithium ions are too much, use is not recommended.
In one embodiment, the temperature of the wash is less than or equal to 380 ℃ for less than or equal to 10 minutes. The lithium ion content in the transition salt bath during the cleaning process can be monitored, and the cleaning process can be stopped when the lithium ion content in the transition salt bath is less than or equal to 150ppm. Alternatively, the ion exchange may be stopped when the lithium ion content in the transition salt bath does not affect the next ion exchange. The ion carried on the surface of the glass ceramic after cleaning can not affect the salt bath proportion of the ion exchange in the next step, and can be directly put into the salt bath for the ion exchange reaction in the next step.
S140: and placing the cleaned primary reinforced microcrystalline glass in a secondary reinforced salt bath for secondary ion exchange.
The temperature of the secondary ion exchange is 360-400 ℃, the time is less than or equal to 10min, and the content of lithium ions in the secondary enhanced salt bath is controlled to be more than or equal to 50ppm and less than or equal to 100ppm, and the specific reference is made to the above description, and the details are not repeated.
The reinforced microcrystalline glass can be obtained after the secondary ion exchange; the obtained glass ceramic has low sodium ion content on the surface and can improve the environmental durability of the glass ceramic surface.
In one embodiment, the surface sodium ion content of the strengthened glass ceramic may be less than/equal to 10 mole percent, such as 3%, 5%, 8%, etc., as measured by XRF.
In one embodiment, the durability test is performed on the tempered glass-ceramic in a high temperature and high humidity environment, for example, the tempered glass-ceramic is exposed to a high temperature of 85 ℃ and a humidity of 85%, no surface erosion phenomenon occurs within 10 days, and the whitening degree of the glass is 1-2 grade. The blushing degree is divided into 5 stages, and specifically comprises the following steps: no blushing, grade 1; slightly whitish, can be wiped, grade 2; moderately whitish, not erasable, grade 3; local severe blushing, grade 4; full severe blushing, grade 5.
In one embodiment, the strengthened glass ceramic has good mechanical properties. The surface edge part is irradiated by a strong light lamp and has no small cracks (the crack width is 1-5 microns is the small crack). Compared with the prior art, the bending resistance and the impact resistance of the sample prepared by the method are improved by 20-30% under the same material.
Referring to fig. 1, fig. 1 is a schematic diagram of a four-point bending strength test according to the present application. Four-point bending strength test is carried out on the chemically strengthened glass, and the four-point bending strength B10 value of the strengthened glass ceramics is larger than 650MPa.
Referring to fig. 2 to 3, fig. 2 is a schematic diagram of a ball drop strength test according to the present application, and fig. 3 is a schematic diagram of a ball drop point in the ball drop strength test according to the present application. Ball drop strength test is carried out on the chemically strengthened glass, and the ball drop strength of the strengthened glass ceramics is measured to be more than 0.4m.
The reinforced glass ceramic is applicable to electronic display equipment, particularly applicable to the field of cover plate protection of electronic display equipment, and also applicable to impact resistance glass such as aviation glass, automobile glass, high-speed rail glass and the like.
According to the embodiment, on the basis of considering the ion exchange performance, the microcrystalline glass material, particularly the microcrystalline glass made of lithium disilicate and lithium silicate with high lithium content, is guaranteed to have sufficient ion exchange and obtain high-level stress, and through the strengthening process design, the accumulation of sodium ions on the surface of a final strengthening sample is reduced, and the integrity of the strengthening appearance is guaranteed. Can ensure the strengthening mass production of the glass ceramics, improve the durability and yield of the glass ceramics, and is beneficial to the production, application and popularization of the glass ceramics.
The present application will be illustrated and explained by the following sets of specific embodiments, but should not be used to limit the scope of the present application.
The glass-ceramic composition raw materials of each example are respectively prepared, a glass-ceramic matrix is prepared according to the formula of the glass-ceramic composition in the examples, the glass-ceramic matrix is subjected to heat treatment to obtain a glass-ceramic preform, the components and the proportion of the obtained glass-ceramic preform are shown in Table 1, and the specific heat treatment process parameters are shown in Table 1. The obtained glass ceramic preform can be subjected to post-treatment, such as thinning by a chemical or physical thinning method, so as to adapt to different product requirements, and polishing treatment. Slicing the crystallized sample, performing flat grinding and CNC processing to prepare a sample with the specification of 150mm 65mm 0.7mm, and performing subsequent strengthening treatment; the glass ceramic preform after the treatment is subjected to strengthening treatment to obtain glass ceramic, and specific chemical strengthening treatment process parameters are shown in tables 2 and 3 and fig. 4-7. The obtained glass ceramics were subjected to various performance tests, the test results are shown in tables 2 and 3, and FIGS. 4 to 7.
Table 1 preparation process parameters and performance parameters of glass ceramics
| Glass 1 | Glass 2 | Glass 3 | Glass 4 | ||
| Component 1 | SiO 2 /mol％ | 70.0 | 68.5 | 71.0 | 66.5 |
| Component 2 | Al 2 O 3 /mol％ | 4.5 | 7.5 | 13.5 | 12 |
| Component 3 | P 2 O 5 /mol％ | 0.5 | 1.0 | 0.5 | 0.5 |
| Component 4 | MgO/mol％ | 0.0 | 1.0 | 0.0 | 3.0 |
| Component 5 | ZrO 2 /mol％ | 1.5 | 1.5 | 2.0 | 1.5 |
| Component 6 | Na 2 O/mol％ | 2.0 | 2.5 | 2.0 | 2.5 |
| Component 7 | Li 2 O/mol％ | 21.0 | 17.0 | 9.5 | 13.0 |
| Component 8 | TiO 2 /mol％ | 0.5 | 1.0 | 1.5 | 1.0 |
| Principal crystalline phase | Lithium disilicate | Lithium disilicate | Beta-quartz solid solution | Beta-quartz solid solution | |
| Secondary crystalline phase | Lithium silicate | Quartz | Spodumene and quartz | Spodumene | |
| Crystallinity/% | 90 | 85 | 70 | 60 |
TABLE 2 strengthening process parameters and performance parameters of glass ceramics
TABLE 3 preparation process parameters and Performance parameters of glass ceramics
As can be seen from examples 1 to 4, after the first-stage strengthening process and the second-stage strengthening process, the sodium on the surface of the glass-ceramic was reduced to less than 10mol%, and the glass-ceramic was excellent in the high-temperature high-humidity performance test, the maximum of which was only 2 stages, i.e., the glass-ceramic was free from corrosion at a temperature of 85 ℃ and a humidity of 85% and the whitening degree was less than two stages, and although the surface was slightly whitened, the glass-ceramic was erasable, as shown in fig. 4 and 5, fig. 4 is a schematic diagram of the glass-ceramic of example 1 after the high-temperature high-humidity treatment, and fig. 5 is a schematic diagram of the glass-ceramic of example 3 after the high-temperature high-humidity treatment, and the whitening degree was 1 stage, and the glass-ceramic was slightly whitened and erasable. And no micro cracks exist on the surface, so that the strong light flashlight observation glass is difficult to photograph and catch the cracks, and the monomer performance is excellent and meets the requirements.
As can be seen from the above comparison examples 1 to 4, if the lithium ions of the secondary strengthening salt bath are not strictly controlled, surface microcracks appear after strengthening, as shown in fig. 6, fig. 6 is a schematic diagram for glass crack detection of the strengthened glass ceramics of comparison example 3, and the cracks are obvious and the monomer strength is reduced.
As can be seen from the above comparison examples 5-8, if the secondary strengthening process is not performed, excessive sodium ions on the surface of the glass can cause serious erosion and whitening phenomenon to occur on the high-temperature and high-humidity result, as shown in FIG. 7, FIG. 7 is a schematic diagram of detection after the high-temperature and high-humidity treatment of the glass of comparison example 7, the whitening degree is 3, and the glass cannot be erased. This can lead to failure in AF evaporation and reduced ink adhesion.
According to the scheme, on the basis of considering the ion exchange performance, the microcrystalline glass material, particularly the microcrystalline glass made of lithium disilicate and lithium silicate with high lithium content, is guaranteed to have sufficient ion exchange and obtain high-level stress, and through the strengthening process design, the accumulation of sodium ions on the surface of a final strengthening sample is reduced, and the strengthening appearance integrity is guaranteed. Can ensure the strengthening mass production of the glass ceramics, improve the durability and yield of the glass ceramics, and is beneficial to the production, application and popularization of the glass ceramics.
The foregoing description is only of embodiments of the present application, and is not intended to limit the scope of the patent application, and all equivalent structures or equivalent processes using the descriptions and the contents of the present application or other related technical fields are included in the scope of the patent application.
Claims (18)
1. A chemical strengthening method for microcrystalline glass is characterized in that,
providing first-stage strengthened microcrystalline glass, wherein the first-stage strengthened microcrystalline glass is subjected to at least one-stage ion exchange, and the first-stage ion exchange is realized by utilizing lithium ions in sodium ion exchange microcrystalline glass;
placing the first-stage strengthened microcrystalline glass in a second-stage strengthened salt bath to perform second-stage ion exchange to obtain the strengthened microcrystalline glass, wherein the second-stage strengthened salt bath comprises lithium salt, and the second-stage ion exchange comprises the step of exchanging sodium ions in the microcrystalline glass by utilizing the lithium ions;
the content of lithium ions in the secondary strengthening salt bath is more than/equal to 50ppm and less than 100ppm.
2. The method of claim 1, wherein placing the first-stage strengthened glass-ceramic in a second-stage strengthened salt bath for second-stage ion exchange comprises:
the temperature of the secondary ion exchange is 360-400 ℃ and the time is less than/equal to 30min.
3. A chemical strengthening method for glass ceramics according to claim 1, wherein,
the secondary enhanced salt bath comprises a mixture of potassium nitrate and lithium nitrate.
4. The method of claim 1, wherein placing the first-stage strengthened glass-ceramic in a second-stage strengthening salt bath for second-stage ion exchange comprises:
the primary reinforced microcrystalline glass is pretreated so that the amount of lithium ions remained on the surface of the treated primary reinforced microcrystalline glass cannot exceed a defined amount, wherein the defined amount is that when the primary reinforced microcrystalline glass is placed in a secondary reinforced salt bath, the amount of lithium ions brought by the primary reinforced microcrystalline glass cannot enable the content of lithium ions in the secondary reinforced salt bath to be more than or equal to 100ppm.
5. The method for chemically strengthening glass ceramics according to claim 4, wherein the pre-treating the first-stage strengthened glass ceramics comprises:
and placing the first-stage strengthened microcrystalline glass in a transition salt bath to clean the first-stage strengthened microcrystalline glass, wherein the transition salt bath comprises potassium salt.
6. The method of chemically strengthening glass ceramics according to claim 5, wherein the step of placing the first-stage strengthened glass ceramics in a transition salt bath to clean the first-stage strengthened glass ceramics comprises:
the cleaning temperature is less than or equal to 380 ℃, the time is less than or equal to 10min, and the lithium ion content in the transition salt bath in the cleaning process is less than or equal to 150ppm.
7. The method for chemically strengthening glass ceramics according to claim 1, wherein the providing the first-stage strengthened glass ceramics comprises:
placing the microcrystalline glass in a first-stage strengthening salt bath for first-stage ion exchange;
the temperature of the primary ion exchange is 420-460 ℃ and the time is 0.5-11 h.
8. The method for chemically strengthening glass ceramics according to claim 7, wherein,
the primary enhanced salt bath comprises pure sodium nitrate; or (b)
The primary strengthening salt bath comprises a mixture of sodium nitrate and potassium nitrate, and the content of sodium nitrate is greater than that of potassium nitrate.
9. The method for chemically strengthening glass ceramics according to claim 1, wherein the providing the first-stage strengthened glass ceramics further comprises:
and placing the primary reinforced microcrystalline glass in a secondary salt bath for secondary ion exchange, wherein the secondary salt bath comprises potassium salt.
10. The method for chemically strengthening glass ceramics according to claim 9, wherein,
the secondary salt bath comprises pure potassium nitrate; or (b)
The secondary salt bath comprises a mixture of sodium nitrate and potassium nitrate, and the content of potassium nitrate is greater than the content of sodium nitrate.
11. A tempered glass-ceramic prepared by the chemical tempering method for glass-ceramic according to any one of claims 1 to 10, wherein the sodium content of the surface of the tempered glass-ceramic is less than/equal to 10mol%.
12. The strengthened glass ceramic of claim 11 wherein,
the main crystal phase of the reinforced microcrystalline glass is lithium disilicate.
13. The strengthened glass ceramic of claim 11 wherein,
the secondary crystal phase of the reinforced microcrystalline glass comprises: lithium silicate, petalite, quartz, a combination of one or more of the solid solutions of quartz.
14. The strengthened glass ceramic of claim 11 wherein,
the crystallinity of the reinforced microcrystalline glass is more than or equal to 70 percent.
15. The strengthened glass ceramic of claim 11 wherein,
the lithium content in the reinforced microcrystalline glass is more than or equal to 15mol percent.
16. The strengthened glass ceramic of claim 11 wherein,
the strengthened microcrystalline glass has no corrosion and the whitening degree is less than the second grade under the conditions that the temperature is 85 ℃ and the humidity is 85 percent.
17. The strengthened glass ceramic of claim 11 wherein,
the four-point bending strength B10 value of the reinforced microcrystalline glass is greater than 650MPa; the falling ball strength is more than 0.4 and m.
18. A protective member comprising the strengthened glass ceramic of any one of claims 11 to 17.
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