CN116332505A - Lithium aluminum silicon glass and repairing method for surface defects of glass after chemical strengthening of lithium aluminum silicon glass - Google Patents
Lithium aluminum silicon glass and repairing method for surface defects of glass after chemical strengthening of lithium aluminum silicon glass Download PDFInfo
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- CN116332505A CN116332505A CN202310338190.7A CN202310338190A CN116332505A CN 116332505 A CN116332505 A CN 116332505A CN 202310338190 A CN202310338190 A CN 202310338190A CN 116332505 A CN116332505 A CN 116332505A
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- 239000011521 glass Substances 0.000 title claims abstract description 136
- -1 Lithium aluminum silicon Chemical compound 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000007547 defect Effects 0.000 title claims abstract description 32
- 238000003426 chemical strengthening reaction Methods 0.000 title claims description 14
- 238000005728 strengthening Methods 0.000 claims abstract description 48
- 238000004140 cleaning Methods 0.000 claims abstract description 19
- 238000005498 polishing Methods 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 230000009477 glass transition Effects 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 5
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 13
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 230000002787 reinforcement Effects 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000002950 deficient Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 238000011056 performance test Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 229910001415 sodium ion Inorganic materials 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 230000008439 repair process Effects 0.000 description 7
- 239000005345 chemically strengthened glass Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013098 chemical test method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Ceramic Engineering (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention relates to the technical field of lithium aluminum silicon glass processing, and provides lithium aluminum silicon glass, which is prepared from the following raw materials in parts by weight: siO (SiO) 2 :60.2 to 68.3 portions of Al 2 O 3 :10.15 to 16.24 portions of Na 2 O:0.5 to 13.1 parts of K 2 O:0.1 to 1.1 parts of Li 2 O:6 to 12.5 parts of ZrO 2 :0.1-1.5 parts, B 2 O 3 :0.1 to 1.5 parts of P 2 O 5 :0.1 to 0.2 part by weight of MgO:2.0 to 4.5 portions; the method for repairing the surface defects of the chemically strengthened lithium aluminum silicon glass comprises the following steps: reverse strengthening, cleaning, grinding and polishing and thinning; wherein the reverse strengthening temperature is a high temperature greater than or equal to the glass transition temperature; it can effectively solve the problem of glass watch in the current repairing processSurface defects, dimensional shrinkage, and stress relief.
Description
Technical Field
The invention relates to the technical field of lithium aluminum silicon glass processing, in particular to a method for repairing surface defects of lithium aluminum silicon glass after chemical strengthening.
Background
Along with the popularization of chemically strengthened glass, more and more chemically strengthened glass is applied to aspects of life, in particular to lithium aluminum silicon glass, and the glass has excellent anti-falling performance, good acid and alkali resistance, is widely applied to the fields of mobile phone cover plates, computer screen protectors, touch electronic boards and the like, and the demand is continuously increased. Meanwhile, macroscopic defects such as edge jumping, scratching, microcracks and the like can be avoided for the reinforced lithium aluminum silicon glass, if the defective products are directly scrapped, the production cost is increased, and the concept of green and environment protection is not facilitated. Therefore, it is particularly important to repair the surface defects of the reinforced lithium aluminum silicon glass.
However, the conventional repair process may not be suitable for chemically strengthened glass (polishing or cutting), because the chemically strengthened glass may cause burst of glass sheets if directly polished or cut, and thus the internal stress of the glass needs to be removed before the cutting or polishing process is performed, based on which it is necessary to develop a new repair method for the surface defects of the chemically strengthened lithium aluminum silicon glass.
Disclosure of Invention
To solve the above-mentioned problems, a first object of the present invention is to provide a lithium aluminum silicon glass having excellent mechanical properties, particularly a low expansion ratio.
The second object of the invention is to provide a method for repairing the surface defect of the chemically strengthened lithium aluminum silicon glass, so as to effectively solve the problems of surface defect, size shrinkage, stress fade and the like of the glass in the existing repairing process; on the basis, the technical scheme adopts the high Wen Ni strengthening temperature which is more than or equal to the glass transition temperature.
The embodiment of the invention is realized by the following technical scheme:
in a first aspect, the invention provides lithium aluminum silicon glass, which is prepared from the following raw materials in parts by weight: siO (SiO) 2 :60.2 to 68.3 portions of Al 2 O 3 :10.15 to 16.24 portions of Na 2 O:0.5 to 13.1 parts of K 2 O:0.1 to 1.1 parts of Li 2 O:6 to 12.5 parts of ZrO 2 :0.1-1.5 parts, B 2 O 3 :0.1 to 1.5 parts of P 2 O 5 :0.1 to 0.2 part by weight of MgO:2.0 to 4.5 portions.
Further, the lithium aluminum silicon glass is prepared from the following raw materials in parts by weight: siO (SiO) 2 :60.2 to 65.3 portions of Al 2 O 3 :10.15 to 14.5 portions of Na 2 O:0.5 to 10.5 parts of K 2 O:0.1 to 0.8 part of Li 2 O:6 to 8 parts of ZrO 2 :0.1-1 part, B 2 O 3 :0.5 to 1 part of P 2 O 5 :0.1 to 0.2 part by weight of MgO:2.0 to 3 parts.
Further, the thickness of the lithium aluminum silicon glass can be 0.55mm, 0.60mm and 0.70mm.
In a second aspect, the invention provides a method for preparing lithium aluminum silicon glass, which comprises the following steps of performing chemical strengthening and testing various properties:
a1: preparing lithium aluminum silicon glass by adopting a melting-forming method;
a2: measuring the size of the lithium aluminum silicon glass prepared in the step A1 by using an imager;
a3: carrying out chemical strengthening on the lithium aluminum silicon glass prepared in the step A1 to obtain original strengthened lithium aluminum silicon glass;
a4: and (3) performing performance detection on the glass obtained after the step A3.
Further, the A1 specifically includes:
a1a: melting: uniformly mixing the raw materials in parts by weight at 1420-1600 ℃ and melting to prepare bubble-free molten glass liquid with uniform chemical composition so as to ensure that ions in the raw material composition are fully diffused;
a1b: and (3) forming: the bubble-free molten glass liquid with uniform chemical composition obtained in the step A1a is prepared into lithium aluminum silicon glass by a float forming method, and the thickness of the lithium aluminum silicon glass is between 0.5 and 1mm, preferably between 0.55,0.60 and 0.70mm.
Further, the A3 specifically includes: the secondary strengthening treatment process adopted in strengthening the original strengthened lithium aluminum silicon glass has the following treatment conditions:
a3a: preheating: preserving the temperature of the unreinforced glass at 350-390 ℃ for 10-30 min;
a3b: preliminary reinforcement: using KNO 3 And NaNO 3 The mixed solution lithium aluminum silicon glass of (2) is strengthened, and the KNO 3 And NaNO 3 KNO in a mixed solution of (a) 3 The content is 32-55wt%, the treatment temperature is 415-440 ℃, and the treatment time is 1.5-2.5 h.
A3c: and (5) re-strengthening: 100wt% KNO 3 The treatment temperature of the solution is 415-420 ℃, and the treatment time is 1.5-2.0 h.
A3d: and (3) annealing, namely dripping salt on the sample prepared in the step B1B for 10-15 min, and then annealing at 365-370 ℃ for 30-60 min.
Further, the A4 specifically includes:
a4a, cleaning: sequentially carrying out citric acid washing, alkali liquor washing and pure water washing on the chemically strengthened lithium aluminum silicon glass, and then drying for later use;
a4b, detecting: the appearance condition of the chemically strengthened lithium aluminum silicon glass is checked, specifically, whether the chemically strengthened lithium aluminum silicon glass has surface defects is checked, and each performance of the secondarily repaired lithium aluminum silicon glass obtained after repair is tested, specifically, the method comprises the following steps: the chemically strengthened lithium aluminum silicon glass has good surface and no micro defects such as scratches, and the properties of the chemically strengthened lithium aluminum silicon glass comprise: the surface Compressive Stress (CS) is 823-923 MPa, the stress layer thickness (DOL) is 90-117 mu m, the compressive stress (CS_30) at the position 30 mu m away from the surface is 91-126 MPa, the potassium stress layer thickness is 4.7-7.0 mu m, and the size expansion of the sample compared with the sample before chemical strengthening.
Further, the cleaning step of the A4a specifically comprises the following steps:
a4a1, wherein the concentration of citric acid in the citric acid washing is 2-5%, the PH is 1-3, and the cleaning temperature is 60+/-2 ℃; a4a2, alkali liquor is washed to be NaOH with the concentration of 1-3 percent, the PH is 11-13, and the cleaning temperature is 45+/-2 ℃;
a4a3, pure water temperature is 45+/-3 ℃ and cleaning time is 10-35 min; the drying temperature is 40-55 ℃.
In a third aspect, the invention also provides a method for repairing the surface defect of the chemically strengthened lithium aluminum silicon glass, which specifically comprises the following steps:
s1: performing reverse strengthening treatment on the defective lithium aluminum silicon glass sample under the condition of above the glass transition temperature to remove the compressive stress in the glass;
s2: and (3) sequentially carrying out acid washing, alkali washing and water washing on the reversely reinforced glass obtained in the step (S1), and then drying for later use.
And S3, polishing and thinning the glass prepared in the step S2 to simulate the process of eliminating the defects on the surface of the glass.
S4: and (3) detection: the appearance condition of the lithium aluminum silicon glass after the reverse reinforcement is inspected, specifically, whether surface cracks exist on the lithium aluminum silicon glass after the chemical reinforcement and whether the glass is devitrified are inspected, and various performances of the lithium aluminum silicon glass obtained after the reverse reinforcement are tested, specifically, the method comprises the following steps: the chemically strengthened lithium aluminum silicon glass has good surface and no micro defects such as scratches, and the properties of the chemically strengthened lithium aluminum silicon glass comprise: whether the surface Compressive Stress (CS) completely faded, whether the stress layer thickness (DOL) was reduced, whether the compressive stress (cs_30) at 30 μm from the surface was reduced, whether the potassium stress layer thickness was reduced, and the dimensional expansion of the sample compared to before chemical strengthening.
Further, the specific process of reverse reinforcement in the B1 is as follows:
s1a, preheating: the chemically strengthened glass is kept at the temperature of 350 to 390 ℃ for 10 to 30 minutes;
s1b, reverse strengthening salt treatment: immersing the preheated glass in reverse reinforced salt, and preserving the temperature for 0.5-2 h at 550-650 ℃;
s1c, annealing: and (3) dripping salt on the sample prepared in the step (S1 b) for 10-15 min, and then annealing.
Further, in step S1b, the reverse strengthening salt is a single solution or a mixed solution of metal nitrate.
Further, the reverse strengthening salt is one or more of lithium nitrate, sodium nitrate or potassium nitrate.
Further, the reverse strengthening salt is mixed salt solution of 10-20% of lithium nitrate and 80-90% of sodium nitrate.
Further, the annealing temperature in S1c is 340-500 ℃ and the annealing time is 30-60 min.
Further, the step S2 of cleaning includes the following steps:
s2a, acid washing: citric acid with the concentration of 2-5% is adopted, and the PH is kept at 1-3, and the cleaning temperature is kept at 55-65 ℃;
s2, alkali washing: naOH with the concentration of 1-3% is adopted, and the PH is kept at 11-13, and the cleaning temperature is kept at 40-50 ℃;
s2c, washing: pure water with the temperature of 40-50 ℃ is adopted, and the cleaning time is 10-35 min.
Further, in step S2, the drying temperature is 40-55 ℃.
Further, the grinding, polishing and thinning in the step S3 comprises coarse grinding and fine grinding which are sequentially carried out; wherein the rough grinding comprises: concentration of polishing powder: 1.1-1.2 g/mL, polishing time: 9-25 min, rotating speed: less than or equal to 50r/min; the refining comprises the following steps: upper sweep and lower throw, LP: concentration of polishing powder: 1.1-1.2 g/mL, polishing time less than or equal to 8min, rotating speed: less than or equal to 50r/min.
Chemical strengthening is known in the art, in which glass is placed in molten mixed salt or pure salt (generally potassium nitrate) and kept at a certain temperature, so that alkali metal ions with larger radius in the molten salt exchange alkali metal ions with smaller radius in the glass, and a laminated stress strengthening layer is generated on the surface of the glass, thereby achieving the purpose of improving the mechanical properties of the glass, such as bending resistance, falling resistance and the like.
The inventor innovatively adopts theoretical research and numerous practical findings: in the structure of the glass, alkali metal ions are mainly located in network gaps of the glass or are in charge compensation with charged groups such as aluminum oxide tetrahedra, in addition, the network structure of the glass is different from crystals, generally, any ions can be exchanged with ions in the glass and stably exist as long as basic charge balance is met, and based on the theory, when chemical strengthening is carried out, large ions in molten salt enter the network gaps of the glass to be in ion exchange with sodium ions in the network gaps, so that a squeezing effect is formed on a glass network. On the other hand, when chemical strengthening is performed, the strengthening temperature is generally lower than Tg (glass transition temperature) of glass, and at this temperature, glass is in a brittle state, compressive stress is generated in a glass cross section, and deformation due to the compressive stress is resisted in a glass material, so that glass is generally not broken.
For reworked glass, the technical scheme adopts an inverse strengthening method under the condition of above glass transition temperature to remove the internal stress of the chemically strengthened glass. However, unlike chemical strengthening, reverse strengthening is to exchange alkali metal ions with larger ionic radius in the glass structure with alkali metal molten pure salt or mixed salt with smaller radius, thereby releasing the compressive stress on the glass surface. It is noted that the diffusion activation energy required for small ions is smaller, meaning that more small ions enter the glass network in the same time, and thus the time for reverse strengthening tends to require a shorter soak time than chemical strengthening. In addition, temperature is an important parameter in the reverse strengthening process, since the compressive stress in the glass is released in the reverse strengthening process, the network structure of the glass is often subjected to tensile stress, and the glass is a brittle material at a temperature lower than Tg and cannot resist excessive deformation caused by the tensile stress. Based on the above, the reverse strengthening temperature point is selected above the glass Tg point when the glass is reworked, so that the glass can display the plasticity as much as possible in the reverse strengthening process, namely the glass is strengthened in a plastic state, and thus the glass is prevented from being broken or the size of the glass is not up to standard in the strengthening process.
The technical scheme of the embodiment of the invention has at least the following advantages and beneficial effects:
1. the invention carries out reverse strengthening treatment on defective lithium aluminum silicon glass under the condition of above glass transition temperature, so that the glass is strengthened in a plastic state, thereby eliminating the compressive stress in the glass.
2. According to the invention, after the glass surface micro defects are subjected to reverse strengthening treatment, the lithium aluminum silicon glass with excellent performance can be obtained, in the repairing process, the defects on the glass surface are eliminated by grinding, polishing and thinning the glass after the reverse strengthening, and then the reverse strengthening is performed to the glass again, so that the performance of the lithium aluminum silicon glass after the repairing is recovered to the state before the repairing; the repairing method greatly reduces the production cost of enterprises, improves the resource utilization rate of the enterprises, and enhances the core competitiveness of the enterprises.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
A repairing method of surface defects of chemically strengthened lithium aluminum silicon glass comprises the following steps:
s1, reverse reinforcement: the lithium aluminum silicon glass with defects after chemical strengthening is subjected to heat preservation for 20min at the temperature of 360 ℃; immersing the preheated glass in a mixed salt solution of 17% lithium nitrate and 83% sodium nitrate, and preserving the temperature for 0.5h at 550 ℃; then annealing is carried out, wherein the annealing temperature is 400 ℃, and the annealing time is 30min;
s2, cleaning: sequentially carrying out acid washing, alkali washing and water washing on the reversely reinforced glass obtained in the step S1, and then drying for later use; acid washing: adopting citric acid with the concentration of 3%, and keeping the PH at 2 and the cleaning temperature at 60 ℃; when alkaline washing: naOH with the concentration of 2% is adopted, and the PH is kept at 12, and the cleaning temperature is kept at 45 ℃; when water washing, the method comprises the following steps: pure water at 45 ℃ is adopted, and the cleaning time is 20min.
S3, grinding, polishing and thinning: and (3) grinding, polishing and thinning the glass prepared in the step (S2).
The differences between examples 2-15 and example 1 are shown in Table 1:
TABLE 1 Heat treatment Process conditions for reverse strengthening of examples 1-15
| Reverse strengthening treatment condition | |
| Example 1 | Na + ：Li + ＝83％：17％/550℃/0.5h |
| Example 2 | Na + ：Li + ＝83％：17％/550℃/0.5h |
| Example 3 | Na + ：Li + ＝83％：17％/550℃/0.5h |
| Example 4 | Na + ：Li + ＝83％：17％/550℃/0.5h |
| Example 5 | Na + ：Li + ＝83％：17％/550℃/0.5h |
| Example 6 | Na + ：Li + ＝85％：15％/550℃/0.5h |
| Example 7 | Na + ：Li + ＝85％：17％/550℃/0.5h |
| Example 8 | Na + ：Li + ＝85％：15％/550℃/0.5h |
| Example 9 | Na + ：Li + ＝85％：15％/550℃/0.5h |
| Example 10 | Na + ：Li + ＝85％：15％/550℃/0.5h |
| Example 11 | Na + ：Li + ＝87％：13％/550℃/0.5h |
| Example 12 | Na + ：Li + ＝87％：13％/550℃/0.5h |
| Example 13 | Na + ：Li + ＝87％：13％/550℃/0.5h |
| Example 14 | Na + ：Li + ＝87％：13％/550℃/0.5h |
| Example 15 | Na + ：Li + ＝87％：13％/550℃/0.5h |
After the sample is reversely strengthened, further polishing treatment is needed to remove the defects on the surface of the glass, and the specific technological parameters of the polishing treatment are shown in the following table 2:
table 2 polishing thinning process parameters of examples 1-15
The polishing powder used in the polishing and thinning process in examples 1 to 15 was prepared according to the composition of example 1 of chinese patent publication No. CN 110564304B.
Comparative examples 1 to 10
The differences between this comparative examples 1-10 and example 1 are shown in Table 3:
TABLE 3 heat treatment process conditions for reverse strengthening of comparative examples 1-10
| Reverse strengthening treatment condition | |
| Comparative example 1 | Na+：Li+＝83％：17％/450℃/0.5h |
| Comparative example 2 | Na+：Li+＝83％：17％/450℃/0.5h |
| Comparative example 3 | Na+：Li+＝83％：17％/450℃/0.5h |
| ComparisonExample 4 | Na+：Li+＝83％：17％/450℃/0.5h |
| Comparative example 5 | Na+：Li+＝83％：17％/450℃/0.5h |
| Comparative example 6 | Na+：Li+＝85％：15％/450℃/0.5h |
| Comparative example 7 | Na+：Li+＝85％：17％/450℃/0.5h |
| Comparative example 8 | Na+：Li+＝85％：15％/450℃/0.5h |
| Comparative example 9 | Na+：Li+＝85％：15％/450℃/0.5h |
| Comparative example 10 | Na+：Li+＝85％：15％/450℃/0.5h |
Experimental example 1
The performance test results of the lithium aluminum silicon glass with surface defects provided in examples 1-15 of the present invention before reverse strengthening are shown in Table 4; the results of the performance test after the reverse reinforcement are shown in table 5; the performance test results of the polished samples after re-strengthening are shown in table 6;
the performance test results of the lithium aluminum silicon glass with surface defects provided by comparative examples 1 to 10 before repair are shown in Table 7; the results of the performance test after the reverse reinforcement are shown in table 8; the performance test results of the polished samples after re-strengthening are shown in table 9;
in addition, in the performance test described above, the partial test methods adopted in the present example and comparative example were as follows:
(1) 4PB (MPa) test method
The bending resistance of the glass was characterized by four-point bending values (i.e. 4 PB) by the test method:
four-point bending test is carried out on the glass sample by using a universal testing machine, and the test conditions are as follows: at least five samples were tested for average value, with up/down spans of 20/40mm, down speed of 10mm/min, rod diameter of 6mm.
(2) Expansion and shrinkage (%) test
And detecting the expansion rate of the external dimensions of the original reinforced lithium aluminum silicon glass, the reinforced lithium aluminum silicon glass and the repaired lithium aluminum silicon glass before and after chemical reinforcement by adopting a secondary measuring instrument.
The performance test results show that the original reinforced lithium aluminum silicon glass prepared by the method and the secondary reinforced lithium aluminum silicon glass obtained after surface defect repair are good in all performances, and the repaired size can be recovered.
(3) Stress test (CS_30, CS, DOL, DOL_K)
Adopting FSM and SLP stress meter test, wherein the test conditions are FSM: refractive index 1.528, photoelastic coefficient 27.4; SLP: refractive index 1.33, photoelastic coefficient 27.6.
(4) Warp test
The warpage data of examples 1-15 were tested by a flatness meter, specifically as follows:
the measured sample was placed with the air side facing upwards and tested for its warp value with a flatness meter. Product size: 155 x 73 x dmm (d product thickness), sample warpage +.0.30 mm.
TABLE 4 Performance test results of surface defective lithium aluminum silicon glasses of examples 1-15 before reverse strengthening
TABLE 5 results of Performance test of lithium aluminum silicon glasses after reverse strengthening of examples 1-15
The polished samples were re-strengthened and tested for performance, and specific performance data are shown in table 6:
TABLE 6 results of Performance test of lithium aluminum silicon glasses after re-strengthening of examples 1-15
TABLE 7 Performance test results of lithium aluminum silicon glasses with surface defects of comparative examples 1 to 10 before reverse strengthening
TABLE 8 results of Performance test of lithium aluminum silicon glasses after reverse strengthening of comparative examples 1-10
Table 9 results of Performance test of lithium aluminum silicon glasses after re-strengthening comparative examples 1 to 10
In summary, after the defective lithium aluminum silicon glass is subjected to reverse strengthening treatment under the condition of above glass transition temperature, the performances of bending resistance, expansion rate of external dimension, warping degree and the like of the glass are effectively improved and the glass is excellent; and after the reverse strengthening treatment, the lithium aluminum silicon glass with more excellent performance can be obtained by carrying out the strengthening again, so that the performance of the repaired lithium aluminum silicon glass is recovered to the state before the repair. And the glass subjected to reverse strengthening treatment under the condition of the glass transition temperature has poor performance parameters, even serious fragmentation occurs, the production cost of enterprises is seriously influenced, and the resource utilization rate of the enterprises is greatly reduced.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The lithium aluminum silicon glass is characterized by being prepared from the following raw materials in parts by weight: siO (SiO) 2 :60.2 to 68.3 portions of Al 2 O 3 :10.15 to 16.24 portions of Na 2 O:0.5 to 13.1 parts of K 2 O:0.1 to 1.1 parts of Li 2 O:6 to 12.5 parts of ZrO 2 :0.1-1.5 parts, B 2 O 3 :0.1 to 1.5 parts of P 2 O 5 :0.1 to 0.2 part by weight of MgO:2.0 to 4.5 portions.
2. The lithium aluminum silicon glass according to claim 1, wherein the lithium aluminum silicon glass is prepared from the following raw materials in parts by weight: siO (SiO) 2 :60.2 to 65.3 portions of Al 2 O 3 :10.15 to 14.5 portions of Na 2 O:0.5 to 10.5 parts of K 2 O:0.1 to 0.8 part of Li 2 O:6 to 8 parts of ZrO 2 :0.1-1 part, B 2 O 3 :0.5 to 1 part of P 2 O 5 :0.1 to 0.2 part by weight of MgO:2.0 to 3 parts.
3. The repairing method of the surface defect of the chemically strengthened lithium aluminum silicon glass is characterized by comprising the following steps of:
s1, reverse reinforcement: subjecting the lithium aluminum silicon glass defective sample of claim 1 or 2 to a reverse strengthening treatment under the condition of above the glass transition temperature to remove the compressive stress inside the glass;
s2, cleaning: sequentially carrying out acid washing, alkali washing and water washing on the reversely reinforced glass obtained in the step S1, and then drying for later use;
s3, grinding, polishing and thinning: and (3) grinding, polishing and thinning the glass prepared in the step (S2).
4. The method for repairing a surface defect of a chemically strengthened lithium aluminum silicon glass according to claim 3, wherein the reverse strengthening in the step S1 comprises the steps of:
s1a, preheating: the defective glass after chemical strengthening is kept at the temperature of 350 to 390 ℃ for 10 to 30 minutes;
s1b, reverse strengthening salt treatment: immersing the preheated glass in reverse reinforced salt, and preserving the temperature for 0.5-2 h at 550-650 ℃;
s1c, annealing: and (3) dripping salt on the sample prepared in the step (S1 b) for 10-15 min, and then annealing.
5. The method for repairing surface defects of chemically strengthened lithium aluminum silicon glass according to claim 4, wherein in the step S1b, the reverse strengthening salt is a pure salt solution or a mixed salt solution of metal nitrate.
6. The method for repairing a surface defect of a chemically strengthened lithium aluminum silicon glass according to claim 5, wherein the reverse strengthening salt is one or more of lithium nitrate, sodium nitrate and potassium nitrate.
7. The method for repairing surface defects of chemically strengthened lithium aluminum silicon glass according to claim 6, wherein the reverse strengthening salt is a mixed salt solution of 10-20% of lithium nitrate and 80-90% of sodium nitrate.
8. The method for repairing surface defects of chemically strengthened lithium aluminum silicon glass according to claim 4, wherein the annealing temperature in S1c is 340-500 ℃ and the annealing time is 30-60 min.
9. The method for repairing a surface defect of a chemically strengthened lithium aluminum silicon glass according to claim 3, wherein the cleaning in the step S2 comprises the steps of:
s2a, acid washing: citric acid with the concentration of 2-5% is adopted, and the PH is kept at 1-3, and the cleaning temperature is kept at 55-65 ℃;
s2, alkali washing: naOH with the concentration of 1-3% is adopted, and the PH is kept at 11-13, and the cleaning temperature is kept at 40-50 ℃;
s2c, washing: pure water with the temperature of 40-50 ℃ is adopted, and the cleaning time is 10-35 min.
10. The method for repairing a surface defect of a chemically strengthened lithium aluminum silicon glass according to claim 3, wherein in the step S2, the drying temperature is 40-55 ℃.
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