CN113955950A - Method for strengthening lithium-aluminum-silicon glass - Google Patents
Method for strengthening lithium-aluminum-silicon glass Download PDFInfo
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- CN113955950A CN113955950A CN202111282030.2A CN202111282030A CN113955950A CN 113955950 A CN113955950 A CN 113955950A CN 202111282030 A CN202111282030 A CN 202111282030A CN 113955950 A CN113955950 A CN 113955950A
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- lithium
- aluminosilicate glass
- glass
- lithium aluminosilicate
- strengthening
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- 239000011521 glass Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 43
- -1 lithium-aluminum-silicon Chemical compound 0.000 title claims abstract description 31
- 238000005728 strengthening Methods 0.000 title claims abstract description 31
- 239000006018 Li-aluminosilicate Substances 0.000 claims abstract description 85
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000005368 silicate glass Substances 0.000 claims abstract description 38
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000012266 salt solution Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 18
- 238000005530 etching Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 230000007797 corrosion Effects 0.000 claims abstract description 14
- 238000005260 corrosion Methods 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 230000007547 defect Effects 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000005342 ion exchange Methods 0.000 abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000003426 chemical strengthening reaction Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910018125 Al-Si Inorganic materials 0.000 description 2
- 229910018520 Al—Si Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000006058 strengthened glass Substances 0.000 description 1
- 238000002834 transmittance Methods 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
-
- 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
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
Abstract
The application relates to a method for strengthening lithium aluminosilicate glass, which comprises the following steps: selecting lithium-aluminum-silicon glass; according to the mass ratio of 4-10 wt% of HF to 4-7 wt% of HNO3: mixing 85-95 wt% of water to obtain a corrosion mixed solution; putting the lithium-aluminum-silicon glass into the etching mixed solution; taking out the lithium aluminum silicate glass and washing; preheating lithium aluminum silicate glass; preparing a salt solution; placing the lithium-aluminum-silicon glass in a salt solution, and preserving heat for 12-36 hours at the temperature of 400-; taking out the lithium-aluminum-silicon glass, and dripping salt for 5-10 minutes; after the salt dripping is finished, air cooling is carried out; spraying a citric acid solution on the surface of the lithium aluminosilicate glass, and wiping the lithium aluminosilicate glass; and cleaning the lithium aluminum silicate glass. The glass strength can be greatly improved, the ion exchange time is shortened, the strengthening efficiency is increased, the service life of the saline solution is prolonged, and the saline solution is reducedThe replacement frequency greatly reduces the production cost.
Description
Technical Field
The application relates to a strengthening process, in particular to a strengthening method of lithium-aluminum-silicon glass.
Background
Silicate glass is an amorphous material and has excellent properties such as thermal stability, high strength, high hardness, high transmittance and the like. The product has wide application in the fields of electronic products, buildings, automobiles, rail transit, aviation, aerospace and the like. Meanwhile, the glass is a typical brittle material, the tensile strength of the glass is low, and a plurality of factors influencing the glass strength are generated in the processing process and the using process of a product, wherein the influence of surface microcracks on the glass strength is most obvious.
In order to meet the requirements of products on the strength and performance of glass and to improve the strength of glass, chemical strengthening technology is developed to improve the strength of glass. Please refer to fig. 4, which is a schematic view of fig. 4 illustrating ion exchange of a conventional lithium aluminosilicate glass; as shown in the figure, the chemical strengthening technology refers to a process of forming a surface compressive stress layer by immersing glass in a salt solution containing alkali ions with a radius larger than that of the alkali metal ions in the glass, performing ion exchange, and then utilizing the radius difference of the two alkali metal ions to cause the surface to generate a "jamming" effect.
In carrying out the present application, applicants have found that the salt solution selected for prior chemical strengthening typically has a composition of 70-95 wt% KNO31-13 wt% of KNO23-20 wt% of NaNO31-7 wt% NaNO2Due to the chemical strengthening mechanism, the strengthened glass has the defects of low glass strength, weak scratch resistance and tolerance, high purity requirement of molten salt, low utilization rate and serious decline of glass strengthening effect after ions and glass are exchanged for a period of time.
Disclosure of Invention
In order to solve the above problems in the prior art, embodiments of the present application provide a method for strengthening lithium aluminosilicate glass. The specific technical scheme is as follows:
in a first aspect, a method for strengthening lithium aluminosilicate glass is provided, which comprises the following steps:
(a) selecting lithium aluminum silicate glass, wherein the lithium aluminum silicate glass comprises the following components in percentage by mass:
silicon dioxide (SiO)2) 58-70% of aluminum oxide (Al)2O3) 13-20% of lithium oxide (Li)2O) is 3-7%, and sodium oxide (Na)2O) is 8-12%, potassium oxide (K)20.5-5% of O), 0.5-2% of magnesium oxide (MgO), 0.5-2% of calcium oxide (CaO), and 0.5-2% of iron oxide (Fe)2O3) 0.01% or less, and boron oxide (B) in balance2O3) Zinc oxide (ZnO), cerium oxide (CeO)2) And zirconium dioxide (ZrO)2) The sum is less than or equal to 4 percent;
(b) according to the mass ratio of 4-10 wt% of HF to 4-7 wt% of HNO3: mixing 85-95 wt% of water to obtain a corrosion mixed solution;
(c) putting the lithium-aluminum-silicon glass into the corrosion mixed solution, corroding microcracks and other defects on the surface of the lithium-aluminum-silicon glass, and removing vacancies and impurity ions at cavities on the surface of the lithium-aluminum-silicon glass;
(d) taking out the lithium aluminum silicate glass and washing;
(e) preheating lithium aluminum silicate glass;
(f) preparing a salt solution, wherein the proportion of the salt solution comprises: 70-90 wt% KNO3、1-8wt％
KNO of23-15 wt% of NaNO31-8 wt% of NaNO20.5-2 wt.% of K2H2Sb2O7.4H2O, 0.5-2 wt% of K2CO30.5-2 wt% of Na2H2Sb2O7.4H2O, 0.5-2 wt% of Na2CO30.1-0.5 wt% of KOH, 0.1-0.5 wt% of NaOH and 0.1-0.5 wt% of Al2O3；
(g) Placing the lithium aluminum silicate glass in a salt solution, and preserving heat for 12-36 hours at the temperature of 400-430 ℃ to improve the scratch resistance, scratch tolerance and strength of the lithium aluminum silicate glass;
(h) taking out the lithium-aluminum-silicon glass, and dripping salt for 5-10 minutes;
(i) after salt dripping is finished, the lithium-aluminum-silicon glass is placed in the air and is cooled in the air;
(j) after air cooling is finished, spraying a citric acid solution on the surface of the lithium aluminosilicate glass, and wiping the lithium aluminosilicate glass;
(k) and cleaning the lithium aluminum silicate glass.
In a first possible implementation manner of the first aspect, in the step (c), the method for placing the lithium aluminosilicate glass in the etching mixed solution for etching comprises the following steps:
heating the corrosion mixed solution to 30-60 ℃;
and placing the lithium aluminosilicate glass in the corrosion mixed solution, so that the lithium aluminosilicate glass is corroded by the corrosion mixed solution, micro cracks and other defects on the surface of the lithium aluminosilicate glass are corroded, the micro cracks and other defects between 0 and 30 mu m in depth on the surface of the lithium aluminosilicate glass are corroded, and impurity ions at the surface vacancy and the cavity of the lithium aluminosilicate glass are removed.
With reference to the first possible implementation manner of the first aspect, in a second possible implementation manner of the first aspect, the corrosion time of the lithium aluminosilicate glass is 50-90 minutes.
In a third possible implementation manner of the first aspect, in the step (d), the lithium aluminum silicate glass is washed by deionized water.
In a fourth possible implementation manner of the first aspect, in the step (e), the lithium aluminum silicate glass is preheated by a preheating box of a chemical furnace, the preheating temperature is 250-.
In a fifth possible implementation form of the first aspect, in step (g), K in the salt solution is caused to be present﹢Replacing Na in 0-20 mu m of lithium aluminosilicate glass surface layer﹢And Li+Na in salt solution﹢Replacement of Li in 0-20 μm of Li-Al-Si glass surface layer+。
In a sixth possible implementation manner of the first aspect, in the step (j), the citric acid solution comprises deionized water and citric acid, and the mass ratio of the deionized water to the citric acid is 10: 1.
In a seventh possible implementation manner of the first aspect, in step (k), the step of cleaning the lithium aluminosilicate glass further includes:
washing the surface of the lithium-aluminum-silicon glass by using deionized water;
spraying a cleaning agent solution on the surface of the lithium aluminosilicate glass;
and washing the surface of the lithium-aluminum-silicon glass by using deionized water.
In combination with the seventh possible implementation manner of the first aspect, in an eighth possible implementation manner of the first aspect, the temperature of deionization is 30-50 ℃.
In a ninth possible implementation manner of the first aspect, the thickness of the lithium aluminosilicate glass is 1.5-12 mm.
Compared with the prior art, the application has the advantages that:
according to the strengthening method of the lithium-aluminum-silicon glass, most of microscopic defects on the surface of the glass are removed by using the corrosive mixed solution, so that guarantee is provided for further deep processing, strengthening and strengthening of the glass, and the strength of the glass can be greatly improved by strengthening after treatment by the method. Meanwhile, the method is also enhanced through the improved salt solution components, so that the ion exchange time is shortened, and the enhancement efficiency is increased. And this application salt solution not only can adsorb the foreign ion in the alkali metal salt itself, can also produce the reaction with Na + and Li + that exchange out from glass, adsorb Na + and Li +, and the Na + and Li + of exchanging out are mostly precipitated by the reaction, purify the salt solution, prolong the salt solution live time, have reduced the frequency that the salt solution was changed, greatly reduced manufacturing cost.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 is a schematic flow chart illustrating steps of a method for strengthening a lithium aluminosilicate glass according to an embodiment of the present disclosure;
FIG. 2 is a schematic representation of the surface structure of a lithium aluminosilicate glass according to an embodiment of the present disclosure before and after acid cleaning;
FIG. 3 is a schematic representation of the surface structure of a lithium aluminosilicate glass according to an embodiment of the present application before and after ion exchange;
FIG. 4 is a schematic diagram of ion exchange of a conventional lithium aluminosilicate glass.
Detailed Description
To make the objects, technical solutions and advantages of the present application more clear, embodiments of the present application will be described in further detail below with reference to the accompanying drawings.
Referring to fig. 1, a schematic flow chart of steps of a method for strengthening a lithium aluminosilicate glass according to an embodiment of the present application is shown; as shown, the strengthening method 1 of lithium aluminosilicate glass includes the following steps 101 to 111. Wherein:
step 101: lithium-aluminum-silicon glass is selected. The selected lithium aluminum silicate glass comprises the following components in percentage by mass: silicon dioxide (SiO)2) 58-70% of aluminum oxide (Al)2O3) 13-20% of lithium oxide (Li)2O) is 3-7%, and sodium oxide (Na)2O) is 8-12%, potassium oxide (K)20.5-5% of O), 0.5-2% of magnesium oxide (MgO), 0.5-2% of calcium oxide (CaO), and 0.5-2% of iron oxide (Fe)2O3) 0.01% or less, and boron oxide (B) in balance2O3) Zinc oxide (ZnO), cerium oxide (CeO)2) And zirconium dioxide (ZrO)2) The sum of the two is less than or equal to 4 percent.
In a preferred embodiment, the thickness of the lithium aluminosilicate glass is 1.5-12mm, for example, 1.5mm, 6mm, 8mm, 12mm, but not limited thereto. There is no special requirement for the length and width of the lithium aluminosilicate glass in the present application, and those skilled in the art can select the lithium aluminosilicate glass with the corresponding length and width according to the actual production requirement. The molecular structure of the lithium aluminosilicate glass disclosed in this embodiment is an alundum, but not limited thereto.
Specifically, on the basis of selecting the lithium aluminum silicon glass with the components meeting the requirements in percentage by mass, the lithium aluminum silicon glass with a defect-free surface is preferably selected, and the thickness of the lithium aluminum silicon glass is 1.5mm, 6mm, 8mm or 12 mm; if the lithium aluminosilicate glass is too long or too wide, the lithium aluminosilicate glass is cut into the required product size by a water jet numerical control cutting machine, for example, the lithium aluminosilicate glass is cut into the length of 250mm and the width of 120mm, but not limited thereto.
Preferably, the lithium aluminosilicate glass is further processed. Specifically, the edge of lithium aluminosilicate glass is chamfered through the numerical control edge grinding machine, and the numerical control edge grinding machine designs the notch shape of the grinding wheel according to the lithium aluminosilicate glass with different thicknesses, from rough grinding to fine grinding, the notch is gradually transited, after the edge grinding of the numerical control edge grinding machine, the chamfered angle of the lithium aluminosilicate glass is uniform, no burr is generated, the end surface has no scratch and white mark, however, the further processing mode of the lithium aluminosilicate glass is not limited to the mode, and the technical personnel in the field can select other suitable processing modes according to the teaching of the application.
Step 102: and preparing a corrosion mixed solution. According to the mass ratio of 4-10 wt% of HF to 4-7 wt% of HNO3: mixing 85-95 wt% of water to obtain the corrosion mixed solution.
Specifically, the weight ratio of the components is 4 wt% to 6 wt%: mixing 90 wt% to obtain the etching mixed solution, but not limited thereto, and those skilled in the art can select other corresponding mass ratios to mix proportionally according to actual etching requirements.
Step 103: and corroding the lithium aluminum silicate glass. Putting the lithium aluminum silicate glass into the etching mixed solution, etching away microcracks and other defects on the surface of the lithium aluminum silicate glass, and removing vacancies and impurity ions at cavities on the surface of the lithium aluminum silicate glass, wherein the change of the surface structure of the lithium aluminum silicate glass before and after acid cleaning is shown in fig. 2.
Specifically, the mixed etching solution is heated to 30-60 ℃, the temperature range (30-60 ℃) is the optimal reaction temperature, the mixed etching solution is etched most uniformly in the temperature range, the effect is optimal, and the surface of the etched lithium aluminosilicate glass has no deformation, and the temperature can be, for example, 30 ℃, 40 ℃, 50 ℃ and 60 ℃, but not limited thereto. And then placing the lithium aluminosilicate glass in the etching mixed solution, and allowing the etching mixed solution to etch the lithium aluminosilicate glass, wherein the etching time is 50-90 minutes, and may be, for example, 50 minutes, 70 minutes, or 90 minutes, but not limited thereto. To etch away micro-cracks and other defects between 0-30 μm deep on the surface of the lithium aluminosilicate glass, and remove the impurity ions at the vacancies and cavities on the surface of the lithium aluminosilicate glass, but not limited thereto.
Step 104: and (5) flushing. And taking out the lithium aluminum silicate glass and washing the glass clean.
Specifically, the lithium aluminum silicate glass is washed by deionized water, but the method is not limited thereto, and those skilled in the art can also select other suitable ways to wash the lithium aluminum silicate glass according to the teachings of the present application.
Step 105: and (4) preheating. Preheating the lithium aluminum silicate glass.
In a preferred embodiment, the lithium-aluminum-silicon glass is preheated by a preheating chamber of a chemical furnace, wherein the preheating temperature is 250 ℃ to 310 ℃, for example, 250 ℃, 280 ℃ and 310 ℃, but not limited thereto. The preheating time is 30-100 minutes, for example, 30 minutes, 60 minutes, 100 minutes, but not limited thereto, but the preheating method of the lithium aluminosilicate glass is not limited thereto, and those skilled in the art may select other suitable preheating methods according to actual needs.
Specifically, the lithium-aluminum-silicon glass is placed in a hanging basket, then the lithium-aluminum-silicon glass and the hanging basket are placed into a preheating box of a chemical furnace together, the preheating box is opened, the lithium-aluminum-silicon glass is preheated to 250 ℃, 280 ℃ or 310 ℃, and the preheating time is 30 minutes, 60 minutes or 100 minutes.
Step 106: and preparing a salt solution. The proportion of the prepared salt solution comprises: 70-90 wt% KNO31-8 wt% of KNO23-15 wt% of NaNO31-8 wt% of NaNO20.5-2 wt.% of K2H2Sb2O7.4H2O, 0.5-2 wt% of K2CO30.5-2 wt% of Na2H2Sb2O7.4H2O, 0.5-2 wt% of Na2CO30.1-0.5 wt% of KOH, 0.1-0.5 wt% of NaOH and 0.1-0.5 wt% of Al2O3。
Step 107: and (4) ion replacement. The lithium aluminum silicate glass is placed in the salt solution and is kept at the temperature of 400-.
In a preferred embodiment, K is in a salt solution﹢Replacing Na in 0-20 mu m of lithium aluminosilicate glass surface layer﹢And Li+Na in salt solution﹢Replacement of Li in 0-20 μm of Li-Al-Si glass surface layer+So that the scratch resistance and the scratch tolerance of the lithium aluminosilicate glass are obviously improved, and the bending strength reaches the maximum, but not limited to the maximum.
Specifically, after the preheating of the lithium aluminosilicate glass is completed, the basket and the lithium aluminosilicate glass can be lifted into the salt bath by the lifter, but the method is not limited thereto, and a person skilled in the art can select other suitable lifting modes according to actual production requirements. The salt solution prepared in the salt tank is loaded with the salt solution, the salt solution contains an exchanger, a catalyst and an adsorbent, KOH, NaOH and Al2O3 are used as the catalyst, and K2H2Sb2O7.4H2O、K2CO3、Na2H2Sb2O7.4H2O、Na2CO3As the adsorbent, besides adsorbing impurity ions in the alkali metal salt, the adsorbent can react with Na + and Li + exchanged from the glass to adsorb Na + and Li +, and at the same time, the exchange rate between ions can be effectively accelerated under high temperature, the exchange time can be shortened to half of that of the background art, and the strengthening efficiency is increased, as shown in FIG. 3.
Step 108: and (4) dropping salt. Taking out the lithium aluminum silicate glass, and dripping salt for 5-10 minutes.
Specifically, after the heat preservation is completed, the hanging basket and the lithium aluminum silicate glass can be lifted out of the salt tank by a lifter, but the method is not limited to this, and a person skilled in the art can select other suitable lifting modes according to actual production requirements. The salt is then dropped onto the lithium aluminosilicate glass for 5 minutes, 8 minutes, or 10 minutes, but not limited thereto. There may be no particular requirement for the choice of the salt dropping means in the present application, as is conventional for a person skilled in the art.
Step 109: and air cooling. And immediately placing the lithium aluminosilicate glass in the air after the salt dropping is finished, and carrying out air cooling to improve the surface stress of the lithium aluminosilicate glass.
In the present application, there is no particular requirement for the selection of the air cooling method for lithium aluminosilicate glass, and reference may be made to conventional selection by those skilled in the art.
Step 110: and spraying citric acid solution. And after air cooling is finished, spraying a citric acid solution on the surface of the lithium aluminosilicate glass, and wiping the lithium aluminosilicate glass.
In a preferred embodiment, the citric acid solution includes deionized water and citric acid, and the mass ratio of the deionized water to the citric acid is 10:1, but not limited thereto, and those skilled in the art can select other suitable citric acid solutions according to actual production requirements.
Specifically, the citric acid solution is prepared according to the above proportion, and the citric acid solution is sprayed on the surface of the lithium aluminum silicate glass, wherein the spraying mode can be spraying in a spray can, but not limited thereto. And then wiping the glass with a scouring pad, but the method is not limited to this, and those skilled in the art can select other suitable wiping modes according to actual production requirements.
Step 111: and (4) cleaning. And cleaning the lithium aluminum silicate glass.
Specifically, deionized water at 30-50 ℃ is selected to wash the surface of the lithium aluminum silicate glass, for example, deionized water at 30 ℃, 40 ℃ or 50 ℃ is selected to remove stains and salinization on the surface of the glass optimally in the temperature range (30-50 ℃), then a detergent solution is sprayed on the surface of the lithium aluminum silicate glass, and after the surface of the lithium aluminum silicate glass is wiped clean, deionized water at 30-50 ℃ is selected to wash the surface of the lithium aluminum silicate glass.
The method 1 for strengthening lithium aluminosilicate glass utilizes HF and HNO3The mixed aqueous solution of (A) is corrosive to glass in terms of HF and HNO3And the water solution comprises (by mass ratio) 4-10 wt%: (85-95 wt%) and heating the mixed corrosive agent to 30-60 ℃ for reaction for 50-90 min to remove glassMost of microscopic defects on the surface of the glass provide guarantee for further deep processing, strengthening and strengthening of the glass, and the strengthening is carried out after the treatment by the method, so that the strength of the glass can be greatly improved.
Meanwhile, the method is also strengthened by the improved salt solution components, the exchange rate between ions can be effectively accelerated under the high-temperature condition, the exchange time can be shortened to a half compared with the prior art, and the strengthening efficiency is improved. And K in the salt solution of the present application2H2Sb2O7.4H2O、K2CO3、Na2H2Sb2O7.4H2O、Na2CO3As the adsorbent, impurity ions in alkali metal salt can be adsorbed, and the adsorbent can react with Na + and Li + exchanged from glass to adsorb Na + and Li +, most of the exchanged Na + and Li + are reacted and precipitated to purify a salt solution, prolong the service time of the salt solution, reduce the frequency of replacing the salt solution and greatly reduce the production cost.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
While the present embodiments have been described with reference to the accompanying drawings, it is to be understood that the invention is not limited to the precise embodiments described above, which are meant to be illustrative and not restrictive, and that various changes may be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The method for strengthening the lithium aluminosilicate glass is characterized by comprising the following steps:
(a) selecting lithium aluminum silicate glass, wherein the lithium aluminum silicate glass comprises the following components in percentage by mass: silicon dioxide (SiO)2) 58-70% of aluminum oxide (Al)2O3) 13-20% of lithium oxide (Li)2O) is 3-7%, and sodium oxide (Na)2O) is 8-12%, potassium oxide (K)20.5-5% of O), 0.5-2% of magnesium oxide (MgO), 0.5-2% of calcium oxide (CaO), and 0.5-2% of iron oxide (Fe)2O3) 0.01% or less, and boron oxide (B) in balance2O3) Zinc oxide (ZnO), cerium oxide (CeO)2) And zirconium dioxide (ZrO)2) The sum is less than or equal to 4 percent;
(b) according to the mass ratio of 4-10 wt% of HF to 4-7 wt% of HNO3: mixing 85-95 wt% of water to obtain a corrosion mixed solution;
(c) putting the lithium aluminosilicate glass into the corrosion mixed solution, corroding microcracks and other defects on the surface of the lithium aluminosilicate glass, and removing vacancies and impurity ions at cavities on the surface of the lithium aluminosilicate glass;
(d) taking out the lithium aluminum silicate glass and washing the lithium aluminum silicate glass;
(e) preheating the lithium aluminosilicate glass;
(f) preparing a salt solution, wherein the proportion of the salt solution comprises: 70-90 wt% KNO31-8 wt% of KNO23-15 wt% of NaNO31-8 wt% of NaNO20.5-2 wt.% of K2H2Sb2O7.4H2O, 0.5-2 wt% of K2CO30.5-2 wt% of Na2H2Sb2O7.4H2O、
0.5-2 wt% of Na2CO30.1-0.5 wt% of KOH, 0.1-0.5 wt% of NaOH and 0.1-0.5 wt% of Al2O3；
(g) Placing the lithium aluminosilicate glass in the salt solution, and preserving heat for 12-36 hours at the temperature of 400-430 ℃ so as to improve the scratch resistance, scratch tolerance and strength of the lithium aluminosilicate glass;
(h) taking out the lithium aluminum silicate glass, and dripping salt for 5-10 minutes;
(i) after salt dripping is completed, the lithium aluminum silicon glass is placed in the air and is cooled in the air;
(j) after air cooling is finished, spraying a citric acid solution on the surface of the lithium aluminosilicate glass, and wiping the lithium aluminosilicate glass;
(k) and cleaning the lithium aluminosilicate glass.
2. The method for strengthening lithium aluminosilicate glass according to claim 1, wherein in the step (c), the method for placing the lithium aluminosilicate glass in the etching mixed solution for etching comprises the following steps:
heating the etching mixed solution to 30-60 ℃;
and placing the lithium aluminosilicate glass in the corrosion mixed solution, enabling the corrosion mixed solution to corrode the lithium aluminosilicate glass, corroding microcracks and other defects on the surface of the lithium aluminosilicate glass, corroding the microcracks and other defects between 0 and 30 mu m in depth on the surface of the lithium aluminosilicate glass, and removing vacancies and impurity ions at cavities on the surface of the lithium aluminosilicate glass.
3. The method for strengthening lithium aluminosilicate glass according to claim 2, wherein the corrosion time of the lithium aluminosilicate glass is 50 to 90 minutes.
4. The method for strengthening lithium aluminosilicate glass according to claim 1, wherein in the step (d), the lithium aluminosilicate glass is rinsed by deionized water.
5. The method as claimed in claim 1, wherein in the step (e), the lithium-aluminum-silicon glass is preheated by a preheating chamber of a chemical furnace, the preheating temperature is 250-310 ℃, and the preheating time is 30-100 minutes.
6. The method for strengthening lithium aluminosilicate glass according to claim 1, wherein in the step (g), K in the salt solution is allowed to exist﹢Replacing Na in the surface layer of the lithium aluminosilicate glass with the diameter of 0-20 mu m﹢And Li+Na in the salt solution﹢Replacing Li in 0-20 μm of the surface layer of the lithium aluminosilicate glass+。
7. The method for strengthening lithium aluminosilicate glass according to claim 1, wherein in the step (j), the citric acid solution comprises deionized water and citric acid, and the mass ratio of the deionized water to the citric acid is 10: 1.
8. The method for strengthening lithium aluminosilicate glass according to claim 1, wherein in the step (k), the step of cleaning the lithium aluminosilicate glass further comprises:
washing the surface of the lithium-aluminum-silicon glass by using deionized water;
spraying a detergent solution on the surface of the lithium aluminosilicate glass;
and washing the surface of the lithium aluminum silicate glass by using deionized water.
9. The method for strengthening lithium aluminosilicate glass according to claim 8, wherein the temperature of the deionization is 30-50 ℃.
10. The method for strengthening lithium aluminosilicate glass according to claim 1, wherein the lithium aluminosilicate glass has a thickness of 1.5 to 12 mm.
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