CN116924699A - Chemical strengthening method for glass raw sheet, low-warpage value strengthened glass, cover plate glass and display - Google Patents
Chemical strengthening method for glass raw sheet, low-warpage value strengthened glass, cover plate glass and display Download PDFInfo
- Publication number
- CN116924699A CN116924699A CN202310951176.4A CN202310951176A CN116924699A CN 116924699 A CN116924699 A CN 116924699A CN 202310951176 A CN202310951176 A CN 202310951176A CN 116924699 A CN116924699 A CN 116924699A
- Authority
- CN
- China
- Prior art keywords
- glass
- ion exchange
- raw sheet
- glass raw
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000006058 strengthened glass Substances 0.000 title claims abstract description 11
- 238000003426 chemical strengthening reaction Methods 0.000 title abstract description 29
- 239000005357 flat glass Substances 0.000 title abstract description 14
- 238000005342 ion exchange Methods 0.000 claims abstract description 90
- 150000003839 salts Chemical class 0.000 claims abstract description 35
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 238000005728 strengthening Methods 0.000 claims description 6
- 239000006059 cover glass Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000005341 toughened glass Substances 0.000 claims description 4
- 238000005496 tempering Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000002474 experimental method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011734 sodium Substances 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 238000006124 Pilkington process Methods 0.000 description 5
- 239000005345 chemically strengthened glass Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 206010010356 Congenital anomaly Diseases 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 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
- 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
- C03B25/02—Annealing glass products in a discontinuous way
- C03B25/025—Glass sheets
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
Landscapes
- 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)
- Surface Treatment Of Glass (AREA)
Abstract
The application relates to the field of glass chemical strengthening, in particular to a chemical strengthening method of a glass raw sheet, strengthened glass with low warpage value, cover plate glass and a display. The application provides a chemical strengthening method of a glass raw sheet, which comprises the following steps: s1) placing the preheated glass raw sheet into molten salt for wet ion exchange; s2) carrying out dry ion exchange on the glass raw sheet subjected to the wet ion exchange in the step S1); s3) annealing the glass raw sheet subjected to the dry ion exchange in the step S2). Compared with the traditional method, the application adds the step of dry ion exchange, thereby leading the glass raw sheet not to be easy to bend in the chemical strengthening process and solving the problem that the glass is easy to warp in the existing production and manufacturing process of the strengthened glass. Experiments show that the surface compressive stress of the glass obtained by the method reaches the standard, and the warping value is reduced from 0.28mm to 0.15mm, which is reduced by nearly 50%.
Description
Technical Field
The application relates to the field of glass chemical strengthening, in particular to a chemical strengthening method of a glass raw sheet, strengthened glass with low warpage value, cover plate glass and a display.
Background
The chemical strengthening can improve the strength, scratch resistance, impact resistance and other performances of the ultrathin cover plate glass. The chemically strengthened ultrathin cover plate glass can meet the performance requirements of mobile displays such as mobile phones, tablet computers and the like.
The production process of the cover plate glass comprises an overflow method and a float method, and the investment amount of the overflow method is huge, so that the production of the cover plate glass raw sheet in the market mainly adopts the float method production process. The glass plate forming in the float process is to flow high temperature molten glass over molten tin, spread, polish, thin and cool, and leave the molten tin and enter the annealing kiln. The whole process is completed on the surface of the molten tin, one surface is contacted with the molten tin (called a tin surface), and the other surface is contacted with a shielding gas (called an air surface), so that unavoidable tin ions are diffused to the lower surface of the glass; finally, the glass finished product presents different chemical compositions of a tin surface and an air surface, which are different from the components of the glass body, and the difference of the chemical compositions of the tin surface and the air surface is a congenital problem of the cover plate glass produced by a float process. The chemical strengthening of cover glass produced by the float process means immersing the glass in a solution containing alkali metal ions from the glass at a temperature not higher than the glass transition point (Tg)In alkali metal ion fused salt (such as potassium nitrate) with large radius, ion exchange occurs between glass and fused salt, such as K in fused salt + Substitution of Na in glass + K with large ionic radius + (0.133 nm) with Na having a small ion radius + The vacated position (0.099 nm) causes the surface to generate a 'crowding' phenomenon due to the volume difference between the exchange ions, so as to form surface compressive stress, when external force acts on the surface, the compressive stress of the part must be counteracted first, thus improving the mechanical strength of the glass and achieving the purpose of strengthening the glass.
In the process of chemically strengthening the float ultrathin alkali aluminum silicon glass, the components on two sides of the glass are inconsistent to influence the ion exchange rate, so that CS (surface compressive stress) and DOL (ion exchange depth) on two sides of the cover plate glass are inconsistent, the glass is bulged and warped towards one side of an atmosphere surface, and the warping seriously influences popularization of domestic ultrathin alkali aluminum silicon glass and use of downstream customers.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present application is to provide a chemical strengthening method for glass raw sheet, a low-warpage strengthened glass, a cover glass and a display.
The application provides a chemical strengthening method of a glass raw sheet, which comprises the following steps:
s1) placing the preheated glass raw sheet into molten salt for wet ion exchange;
s2) carrying out dry ion exchange on the glass raw sheet subjected to the wet ion exchange in the step S1);
s3) annealing the glass raw sheet subjected to the dry ion exchange in the step S2).
The dry ion exchange of the application is specifically: and completely taking out the glass raw sheet subjected to wet ion exchange from the molten salt, directly preserving the heat without any treatment, and continuously carrying out dry ion exchange on the glass raw sheet by the molten salt remained on the surface of the glass raw sheet. The application has no special limitation on the medium of the glass raw sheet when dry ion exchange is carried out, and the glass raw sheet is completely arranged outside the molten salt; in some embodiments of the application, after the wet ion exchanged glass raw sheet is directly taken out of the molten salt, the wet ion exchanged glass raw sheet is directly subjected to heat preservation in the air without any treatment, i.e. is subjected to dry ion exchange. The temperature of the dry ion exchange is 360-450 ℃, preferably 370-440 ℃, more preferably 380-430 ℃, and more preferably 400-420 ℃; the time of the dry ion exchange is 0.1 to 4 hours, preferably 0.3 to 3 hours, more preferably 0.5 to 2 hours, and still more preferably 1 to 1.5 hours.
The wet ion exchange is a method for carrying out ion exchange on glass by adopting molten salt in the chemical strengthening process of the glass, which is well known to a person skilled in the art, and the preheated glass raw sheet is placed in molten salt, specifically, the preheated glass raw sheet is completely placed in the molten salt. The temperature of the wet ion exchange is 360-450 ℃, preferably 370-440 ℃, more preferably 380-430 ℃; the time of the wet ion exchange is 0.5 to 8 hours, preferably 1 to 7 hours, more preferably 2 to 6 hours. The molten salt is selected from alkali metal ion molten salts. In some embodiments, the molten salt is selected from at least one or two of potassium nitrate molten salt, sodium nitrate, lithium nitrate. In other embodiments, the molten salt is selected from 99.8% kno by mass 3 And 0.2% NaNO 3 Is added to the molten salt mixture.
The inventor creatively discovers that the glass raw sheet subjected to wet ion exchange in the molten salt is directly placed outside the molten salt for dry ion exchange, and the wet ion exchange and the dry ion exchange are sequentially carried out to replace the traditional ion exchange, so that the glass raw sheet can have a lower warping value while having higher compressive stress after being strengthened. The application also optimizes the temperature and time during wet ion exchange and dry ion exchange, thereby further reducing the warp value of the glass. The temperature of the wet ion exchange is not lower than the temperature of the dry ion exchange; the wet ion exchange time is not less than the dry ion exchange time.
The method for chemically strengthening the glass raw sheet firstly places the preheated glass raw sheet in molten salt for wet ion exchange. Specifically, the method comprises the steps of firstly preheating a glass raw sheet to obtain a preheated glass raw sheet, and then completely placing the preheated glass raw sheet in molten salt for wet ion exchange. The preheating temperature is 360-450 ℃, preferably 370-440 ℃, more preferably 380-430 ℃; the preheating time is 1-3 h. The wet ion exchange of the present application is the same as that described above, and will not be described again.
The application carries out wet ion exchange on the preheated glass raw sheet, and then carries out dry ion exchange on the glass raw sheet subjected to wet ion exchange. The dry ion exchange of the present application is the same as that described above, and will not be described again.
The application carries out dry ion exchange on the glass raw sheet after wet ion exchange, and then anneals the glass raw sheet after dry ion exchange to finish chemical strengthening of the glass raw sheet. The annealing temperature is 360-450 ℃, preferably 370-440 ℃, more preferably 380-430 ℃; the annealing time is 2-4 h.
The application provides reinforced glass with low warpage value, which is obtained by reinforcing a glass raw sheet by the chemical reinforcing method. In certain embodiments of the present application, the low warp value tempered glass of the present application is 7 inches in size and is strengthened from 7 inch raw glass sheets. The thickness of the reinforced glass with the low warpage value is 0.1 mm-2 mm, and the thickness of the glass raw sheet is the same as that of the finally obtained reinforced glass with the low warpage value.
In certain embodiments of the present application, the low warp value strengthened glass of the present application has a size of 7 inches and a warp value of 0.10mm to 0.15mm; the surface Compressive Stress (CS) value of the low warp value reinforced glass is 450MPa to 1000MPa, preferably 500MPa to 900MPa, and more preferably 550MPa to 800MPa. The stress layer depth (DOL value) of the low warp value tempered glass of the present application is 8 μm to 60. Mu.m, preferably 10 μm to 55. Mu.m, more preferably 12 μm to 50. Mu.m. The reinforced glass with the low warpage value provided by the application can meet the use requirement of compressive stress and has a lower warpage value.
In some embodiments of the application, the composition of the raw glass sheet of the application comprises, in mass percent of oxides: 62 to 73 percent of SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 4% -13% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 0.5 to 7.8 percent of CaO;4% -11% MgO;10 to 16 percent of Na 2 O; and 0.5 to 3% K 2 O. In other embodiments of the present application, the composition of the raw glass sheet of the present application comprises, in mass percent of oxides: 58% -73% of SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 8% -18% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 0.2 to 3 percent of B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 4% -11% MgO;10 to 20 percent of Na 2 O; and 0.5 to 8% of K 2 O. In one embodiment, the composition of the raw glass sheet of the present application comprises, in mass percent of oxides: 69% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 5% Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 6.5% CaO;4.5% MgO;14% Na 2 O; and 1% K 2 O. In one embodiment, the composition of the raw glass sheet of the present application comprises, in mass percent of oxides: 58% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 16% Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 1% of B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 5% MgO;15% Na 2 O; and 5% K 2 O。
The application also provides cover plate glass which is prepared from the reinforced glass with low warpage value. The low-warpage-value reinforced glass has a low warpage value, so that the glass can be used as cover glass for displays of various devices such as mobile phones, tablet computers and televisions. The application provides a display, which is provided with the cover plate glass. The display of the present application includes, but is not limited to, one or more of a cell phone display, a tablet computer display, and a television display.
The application provides a chemical strengthening method of a glass raw sheet, low-warpage value strengthened glass, cover plate glass and a display. The application provides a chemical strengthening method of a glass raw sheet, which comprises the following steps: s1) placing the preheated glass raw sheet into molten salt for wet ion exchange; s2) carrying out dry ion exchange on the glass raw sheet subjected to the wet ion exchange in the step S1); s3) annealing the glass raw sheet subjected to the dry ion exchange in the step S2). Compared with the three steps of preheating, ion exchange and annealing in the traditional chemical strengthening production, the glass raw sheet strengthening method is additionally provided with a dry ion exchange, so that the glass is not easy to bend in the chemical strengthening process of the glass raw sheet, and the technical problem that the glass is easy to warp in the traditional chemical strengthening production process of the glass is solved. Experiments show that the glass surface compressive stress obtained by the chemical strengthening method can meet the demands of downstream customers, and the 7-inch glass warpage value is reduced from 0.28mm to 0.15mm, namely, the warpage value is reduced by nearly 50%.
Detailed Description
The application discloses a chemical strengthening method of a glass raw sheet, low-warpage value strengthened glass, cover plate glass and a display. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present application. While the methods and applications of this application have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the application can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the application.
The raw glass sheets to be chemically strengthened used in examples 1 to 3 and comparative examples 1 to 3 of the present application were 0.7mm thick and 7 inches in size, and the components thereof, in terms of mass percent of oxides, were:
69% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 5% Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 6.5% CaO; mgO of 4.5; 14% Na 2 O; and 1% K 2 O。
The raw glass sheets to be chemically strengthened used in example 4 and comparative example 4 of the present application, having a thickness of 0.7mm and a size of 7 inches, comprise, in mass percent of oxides:
58% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 16% Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 1% of B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 5% MgO;15% Na 2 O; and 5% K 2 O。
The application is further illustrated by the following examples:
example 1
(1) Preheating a glass raw sheet to be chemically strengthened by adopting a preheating furnace, wherein the temperature of the preheating treatment is 400 ℃ and the time is 2 hours;
(2) Completely immersing the glass raw sheet after the preheating treatment into molten salt (99.8 percent KNO) 3 +0.2％NaNO 3 ) Wet ion exchange is carried out at 400 ℃ for 2.5 hours;
(3) Taking out the glass raw sheet subjected to wet ion exchange from molten salt, and directly carrying out dry ion exchange without any treatment, namely preserving heat at 400 ℃ for 1.5 hours;
(4) And (3) annealing the glass raw sheet subjected to dry ion exchange at 400 ℃ for 2 hours to obtain the chemically strengthened glass.
Comparative example 1
(1) Preheating a glass raw sheet to be chemically strengthened by adopting a preheating furnace; the temperature of the preheating treatment is 400 ℃ and the time is 2 hours;
(2) Immersing the glass raw sheet after the preheating treatment into molten salt (99.8% KNO) 3 +0.2％NaNO 3 ) Wet ion exchange is carried out at 400 ℃ for 4 hours;
(3) And (3) annealing the wet ion-exchanged glass raw sheet at 400 ℃ for 2 hours to obtain the glass subjected to traditional chemical strengthening.
The glasses obtained in example 1 and comparative example 1 were subjected to performance test and warpage value test, as shown in table 1 in detail:
TABLE 1
The surface Compressive Stress (CS) and the depth of stress layer (DOL) of the two strengthening methods are similar, although the surface compressive stress of the chemically strengthened glass is slightly reduced, the chemical strengthened glass can completely meet the demands of downstream customers, and the 7 inch glass warp value is reduced from 0.28mm to 0.15mm, namely the warp value is reduced by nearly 50 percent, which is far better than the glass after the traditional chemical strengthening.
Example 2
(1) Preheating a glass raw sheet to be chemically strengthened by adopting a preheating furnace, wherein the temperature of the preheating treatment is 400 ℃ and the time is 2 hours;
(2) Completely immersing the glass raw sheet after the preheating treatment into molten salt (the mass percentage is 99.8 percent KNO) 3 +0.2％NaNO 3 ) Wet ion exchange is carried out at 420 ℃ for 3 hours;
(3) Taking out the glass raw sheet subjected to wet ion exchange from molten salt, and directly carrying out dry ion exchange without any treatment, namely preserving heat at 420 ℃ for 1 hour;
(4) And (3) annealing the glass raw sheet subjected to dry ion exchange at 400 ℃ for 2 hours to obtain the chemically strengthened glass.
Comparative example 2
(1) Preheating a glass raw sheet to be chemically strengthened by adopting a preheating furnace; the temperature of the preheating treatment is 400 ℃ and the time is 2 hours;
(2) Immersing the glass raw sheet after the preheating treatment into molten salt for wet ion exchange, wherein the temperature is 420 ℃ and the time is 4 hours;
(3) And (3) annealing the wet ion-exchanged glass raw sheet at 400 ℃ for 2 hours to obtain the glass subjected to traditional chemical strengthening.
The glasses obtained in example 2 and comparative example 2 were subjected to performance test and warpage value test, as shown in table 3 in detail:
TABLE 2
| Sample preparation | Comparative example 2 | Example 2 |
| Procedure | Traditional chemical strengthening | The application is chemically strengthened |
| Preheating temperature | 400℃/2hrs | 400℃/2hrs |
| Ion exchange/wet ion exchange conditions | 420℃/4hrs | 420℃/3hrs |
| Dry ion exchange conditions | Without any means for | 420℃/1hrs |
| Annealing temperature | 400℃/2hrs | 400℃/2hrs |
| Surface compressive stress/MPa | 723 | 642 |
| Depth of stress layer/μm | 14.8 | 14.3 |
| Warp value/mm | 0.35 | 0.18 |
Example 3
(1) Preheating a glass raw sheet to be chemically strengthened by adopting a preheating furnace, wherein the temperature of the preheating treatment is 400 ℃ and the time is 2 hours;
(2) Completely immersing the glass raw sheet after the preheating treatment into molten salt (the mass percentage is 99.8 percent KNO) 3 +0.2％NaNO 3 ) Wet ion exchange is carried out at 380 ℃ for 5 hours;
(3) Taking out the glass raw sheet subjected to wet ion exchange from molten salt, and directly carrying out dry ion exchange without any treatment, namely preserving heat at 380 ℃ for 1 hour;
(4) And (3) annealing the glass raw sheet subjected to dry ion exchange at 400 ℃ for 2 hours to obtain the chemically strengthened glass.
Comparative example 3
(1) Preheating a glass raw sheet to be chemically strengthened by adopting a preheating furnace; the temperature of the preheating treatment is 400 ℃ and the time is 2 hours;
(2) Immersing the glass raw sheet after the preheating treatment into molten salt for wet ion exchange, wherein the temperature is 380 ℃ and the time is 6 hours;
(3) And (3) annealing the wet ion-exchanged glass raw sheet at 400 ℃ for 2 hours to obtain the glass subjected to traditional chemical strengthening.
The glasses obtained in example 3 and comparative example 3 were subjected to performance test and warpage value test, as shown in table 3 in detail:
TABLE 3 Table 3
| Sample preparation | Comparative example 3 | Example 3 |
| Procedure | Traditional chemical strengthening | The application is chemically strengthened |
| Preheating temperature | 400℃/2hrs | 400℃/2hrs |
| Ion exchange/wet ion exchange conditions | 380℃/6hrs | 380℃/5hrs |
| Dry ion exchange conditions | Without any means for | 380℃/1hrs |
| Annealing temperature | 400℃/2hrs | 400℃/2hrs |
| Surface compressive stress/MPa | 742 | 671 |
| Depth of stress layer/μm | 13.5 | 13.0 |
| Warp value/mm | 0.30 | 0.16 |
Example 4
(1) Preheating a glass raw sheet to be chemically strengthened by adopting a preheating furnace; the temperature of the preheating treatment is 400 ℃ and the time is 2 hours;
(2) Immersing the glass raw sheet after the preheating treatment into molten salt (the mass percentage is 99.8 percent KNO) 3 +0.2％NaNO 3 ) Wet ion exchange is carried out at 420 ℃ for 4 hours;
(3) Taking out the glass raw sheet subjected to wet ion exchange from molten salt, and directly carrying out dry ion exchange without any treatment, namely preserving heat at 420 ℃ for 1 hour;
(4) And (3) annealing the glass raw sheet subjected to dry ion exchange at 400 ℃ for 2 hours to obtain the chemically strengthened glass.
Comparative example 4
(1) Preheating a glass raw sheet to be chemically strengthened by adopting a preheating furnace; the temperature of the preheating treatment is 400 ℃ and the time is 2 hours;
(2) Immersing the glass raw sheet after the preheating treatment into molten salt (the mass percentage is 99.8 percent KNO) 3 +0.2％NaNO 3 ) Wet ion exchange is carried out at 420 ℃ for 5 hours;
(3) And (3) annealing the wet ion-exchanged glass raw sheet at 400 ℃ for 2 hours to obtain the glass subjected to traditional chemical strengthening.
The glasses obtained in example 4 and comparative example 4 were subjected to performance test and warpage value test, as shown in table 4 in detail:
TABLE 4 Table 4
| Sample preparation | Comparative example 4 | Example 4 |
| Procedure | Traditional chemical strengthening | The application is chemically strengthened |
| Preheating temperature | 400℃/2hrs | 400℃/2hrs |
| Ion exchange/wet ion exchange conditions | 420℃/5hrs | 420℃/4hrs |
| Dry ion exchange conditions | Without any means for | 420℃/1hrs |
| Annealing temperature | 400℃/2hrs | 400℃/2hrs |
| Surface compressive stress/MPa | 842 | 801 |
| Depth of stress layer/μm | 43.3 | 42.8 |
| Warp value/mm | 0.25 | 0.13 |
The foregoing is only a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art, who is within the scope of the present application, should make equivalent substitutions or modifications according to the technical scheme of the present application and the inventive concept thereof, and should be covered by the scope of the present application.
Claims (10)
1. A method for chemically strengthening a glass raw sheet, comprising the steps of:
s1) placing the preheated glass raw sheet into molten salt for wet ion exchange;
s2) carrying out dry ion exchange on the glass raw sheet subjected to the wet ion exchange in the step S1);
s3) annealing the glass raw sheet subjected to the dry ion exchange in the step S2).
2. The method according to claim 1, wherein the temperature of the dry ion exchange in step S2) is 360 ℃ to 450 ℃ and the time of the dry ion exchange is 0.1h to 4h.
3. The method according to claim 1, wherein the wet ion exchange in step S1) is performed at a temperature of 360 ℃ to 450 ℃ for a time of 0.5h to 8h.
4. The method according to claim 1, wherein the temperature of the wet ion exchange in step S1) is not lower than the process temperature of the dry ion exchange in step S2);
the wet ion exchange treatment time in step S1) is not less than the dry ion exchange treatment time in step S2).
5. The method according to claim 1, wherein the preheating in step S1) is performed at a temperature of 360 ℃ to 450 ℃ for a period of 1h to 3h.
6. The method according to claim 1, wherein the annealing temperature in step S3) is 360 ℃ to 450 ℃ and the annealing time is 2h to 4h.
7. A low warp value tempered glass obtained by tempering a glass raw sheet by the chemical tempering method according to any one of claims 1 to 6.
8. The low warp value strengthened glass of claim 7, wherein the composition of the raw glass sheet comprises, in mass percent of oxides:
62 to 73 percent of SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 4% -13% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 0.5 to 7.8 percent of CaO;4% -11% MgO;10 to 16 percent of Na 2 O; and 0.5 to 3% K 2 O；
Alternatively, the composition of the raw glass sheet comprises, in mass percent of oxides:
58% -73% of SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 8% -18% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 0.2 to 3 percent of B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 4% -11% MgO;10 to 20 percent of Na 2 O; and 0.5 to 8% of K 2 O。
9. A cover glass prepared from the low warp value tempered glass of claim 7 or 8.
10. A display device having the cover glass of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310951176.4A CN116924699A (en) | 2023-07-31 | 2023-07-31 | Chemical strengthening method for glass raw sheet, low-warpage value strengthened glass, cover plate glass and display |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310951176.4A CN116924699A (en) | 2023-07-31 | 2023-07-31 | Chemical strengthening method for glass raw sheet, low-warpage value strengthened glass, cover plate glass and display |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116924699A true CN116924699A (en) | 2023-10-24 |
Family
ID=88384174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310951176.4A Pending CN116924699A (en) | 2023-07-31 | 2023-07-31 | Chemical strengthening method for glass raw sheet, low-warpage value strengthened glass, cover plate glass and display |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116924699A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015143160A (en) * | 2014-01-31 | 2015-08-06 | 日本電気硝子株式会社 | Method of tempered glass and tempered glass |
| WO2017018376A1 (en) * | 2015-07-30 | 2017-02-02 | 日本電気硝子株式会社 | Method for producing reinforced glass plate |
| CN108516702A (en) * | 2018-05-23 | 2018-09-11 | 河北视窗玻璃有限公司 | The method and reinforcing jig of warpage are generated in a kind of reduction chemically enhancing glass |
| CN111454001A (en) * | 2020-06-02 | 2020-07-28 | 醴陵旗滨电子玻璃有限公司 | Chemical strengthening method and chemically strengthened glass |
| CN112159120A (en) * | 2020-10-15 | 2021-01-01 | 中国洛阳浮法玻璃集团有限责任公司 | Process method for improving warping generated in ion strengthening of ultra-thin float glass |
| CN112313182A (en) * | 2018-06-21 | 2021-02-02 | 肖特玻璃科技(苏州)有限公司 | Chemically tempered glass product without optical orange peel and method for producing same |
-
2023
- 2023-07-31 CN CN202310951176.4A patent/CN116924699A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015143160A (en) * | 2014-01-31 | 2015-08-06 | 日本電気硝子株式会社 | Method of tempered glass and tempered glass |
| WO2017018376A1 (en) * | 2015-07-30 | 2017-02-02 | 日本電気硝子株式会社 | Method for producing reinforced glass plate |
| CN108516702A (en) * | 2018-05-23 | 2018-09-11 | 河北视窗玻璃有限公司 | The method and reinforcing jig of warpage are generated in a kind of reduction chemically enhancing glass |
| CN112313182A (en) * | 2018-06-21 | 2021-02-02 | 肖特玻璃科技(苏州)有限公司 | Chemically tempered glass product without optical orange peel and method for producing same |
| CN111454001A (en) * | 2020-06-02 | 2020-07-28 | 醴陵旗滨电子玻璃有限公司 | Chemical strengthening method and chemically strengthened glass |
| CN112159120A (en) * | 2020-10-15 | 2021-01-01 | 中国洛阳浮法玻璃集团有限责任公司 | Process method for improving warping generated in ion strengthening of ultra-thin float glass |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110316974B (en) | Alkali-containing aluminosilicate glass, product, strengthening method and application thereof | |
| CN101328026B (en) | Molten salt for glass chemistry toughening and chemical toughening method using the same | |
| JP6973959B2 (en) | Chemically strengthenable glass plate | |
| TWI743029B (en) | Chemically temperable glass sheet and uses thereof | |
| CN102320741B (en) | Hardened glass substrate and manufacture method thereof | |
| CN110240419B (en) | Lithium aluminum silicon glass, lithium aluminum silicon chemically strengthened glass, and preparation method and application thereof | |
| JP2021120344A (en) | Chemically temperable glass sheet | |
| KR20160138015A (en) | Chemically temperable glass sheet | |
| CN106986556B (en) | Fused salt for chemical strengthening of medium-aluminum and high-aluminosilicate glass and method for carrying out chemical toughening and strengthening by using fused salt | |
| CN110845153A (en) | Reinforced microcrystalline glass with high-pressure stress layer depth and preparation method thereof | |
| CN111875264B (en) | Cover plate glass strengthening process | |
| EP4282840A1 (en) | Low warping tempered microcrystalline glass, preparation method therefor and application thereof | |
| CN104284868A (en) | Method for producing tempered glass | |
| WO2015125584A1 (en) | Method for manufacturing tempered glass and tempered glass | |
| TWI756171B (en) | Glass sheet capable of having controlled warping through chemical strengthening | |
| WO2009157297A1 (en) | Toughened glass and method for producing the same | |
| CN110655304B (en) | Glass capable of effectively improving chemical strengthening warping property | |
| CN107298528A (en) | Aluminium borosilicate glass and its preparation method and application | |
| CN110963715A (en) | Chemical strengthening method for flexible ultrathin glass cover plate | |
| EP3322676B1 (en) | Method for chemically strengthening with controlled curvature | |
| JP2019502640A (en) | Glass substrate for chemical strengthening and chemical strengthening method with controlled curvature | |
| WO2018166139A1 (en) | Glass to be chemically strengthened and anti-break glass plate made of same | |
| CN110981220A (en) | Chemical toughening method for glass | |
| TWI692458B (en) | Glass sheet capable of having controlled warping through chemical strengthening | |
| CN112010552A (en) | Aluminosilicate glass and strengthening method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |