CN116002993A - Tempered glass and method for producing the same - Google Patents
Tempered glass and method for producing the same Download PDFInfo
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- CN116002993A CN116002993A CN202310066731.5A CN202310066731A CN116002993A CN 116002993 A CN116002993 A CN 116002993A CN 202310066731 A CN202310066731 A CN 202310066731A CN 116002993 A CN116002993 A CN 116002993A
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- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000005341 toughened glass Substances 0.000 title abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000011521 glass Substances 0.000 claims abstract description 80
- 239000000654 additive Substances 0.000 claims abstract description 74
- 230000000996 additive effect Effects 0.000 claims abstract description 62
- 150000002500 ions Chemical class 0.000 claims abstract description 45
- 238000005728 strengthening Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000006073 displacement reaction Methods 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 18
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 18
- 235000011152 sodium sulphate Nutrition 0.000 claims description 18
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkali metal bicarbonate Chemical class 0.000 claims description 14
- 239000002241 glass-ceramic Substances 0.000 claims description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- 239000006058 strengthened glass Substances 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 235000010333 potassium nitrate Nutrition 0.000 claims description 8
- 239000004323 potassium nitrate Substances 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 4
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 description 11
- 238000003426 chemical strengthening reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 238000005496 tempering Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
Images
Classifications
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- 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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- Surface Treatment Of Glass (AREA)
Abstract
Embodiments of the present disclosure provide a tempered glass and a method of preparing the same. The method comprises the following steps: the glass to be strengthened is placed in furnace water for strengthening treatment, an additive is placed in the furnace water, the additive comprises an active component, second ions in the active component are used for carrying out displacement reaction with first ions in the furnace water, and the active component is neutral. The method can prolong the service life of furnace water and improve the quality of the prepared reinforced glass.
Description
Technical Field
The present disclosure relates to the field of materials, and in particular to a tempered glass and a method of making the same.
Background
Tempered glass (or toughened glass) has been widely used for glass cover plates for electronic products such as cellular phones, because of its excellent surface hardness and mechanical strength. In recent years, with the development of chemical strengthening processes, strengthened glass ceramics have also been used for glass cover plates of electronic products. Glass ceramics are glass products containing a crystal phase and a glass phase, and general glass ceramics systems include lithium aluminum silicon systems and the like. Ion exchange can be carried out between the glass ceramics and the chemical strengthening furnace water through the chemical strengthening process, so that the mechanical property of the glass ceramics is improved. However, the chemical strengthening process, especially for glass ceramics, requires controlling the concentration of various ions in the furnace water to ensure the quality of chemical strengthening.
Accordingly, there is a need for improvements in the present tempered glass and methods of making the same.
Disclosure of Invention
Embodiments of the present disclosure provide a solution or alleviation of one or more technical problems of the related art.
As a first aspect of embodiments of the present disclosure, embodiments of the present disclosure provide a method of making a strengthened glass. The method comprises the following steps:
the glass to be strengthened is placed in furnace water for strengthening treatment, additives are placed in the furnace water,
the additive comprises an active component, wherein a second ion in the active component is used for carrying out a displacement reaction with a first ion in furnace water, and the active component is neutral.
In one embodiment, the glass to be strengthened comprises glass-ceramic.
In one embodiment, the additive is in a solid state.
In one embodiment, the additive includes one or more of an oxide, an alkali metal silicate, an alkali metal phosphate, an alkali metal sulfate, an alkali metal chloride, an alkali metal bicarbonate, and an alkali metal hydroxide.
In one embodiment, the first ions comprise lithium ions and the second ions comprise sodium ions.
In one embodiment, the active component is present in the additive in an amount of not less than 60%,
the active component is insoluble in furnace water.
In one embodiment, the active component comprises sodium sulfate.
In one embodiment, the method further comprises:
and after the strengthening treatment is finished, placing the next glass to be treated in furnace water and replacing the additive.
In one embodiment, the strengthening treatment meets at least one of the following conditions:
the mass ratio of the additive to the glass to be reinforced is (1-3): (2-25);
the lithium ion content of the furnace water is 10-20ppm;
the pH value of the furnace water is 6-9.8;
the temperature of the furnace water is 450-470 ℃;
the strengthening treatment time is 6-8 hours;
the furnace water comprises potassium nitrate and sodium nitrate, and the content of the potassium nitrate is higher than that of the sodium nitrate.
As a second aspect of the disclosed embodiments, the disclosed embodiments provide a strengthened glass. Tempered glass is produced by the method described above.
According to the method for preparing the tempered glass, disclosed by the disclosure, through improving chemical components of the additive and selecting the active components with neutral pH value, the negative influence on the pH value of the furnace water can be avoided while the first ion concentration in the furnace water is maintained, so that the pH value of the furnace water can be maintained within the standard range required by the tempering treatment within a certain period of time, the service life of the furnace water is prolonged, the phenomenon of whitening and fouling on the surface of the glass caused by the rise of the pH value of the furnace water is avoided, and the quality of the prepared tempered glass is improved.
The foregoing summary is for the purpose of the specification only and is not intended to be limiting in any way. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features of the present disclosure will become apparent by reference to the drawings and the following detailed description.
Drawings
In the drawings, the same reference numerals refer to the same or similar parts or elements throughout the several views unless otherwise specified. The figures are not necessarily drawn to scale. It is appreciated that these drawings depict only some embodiments according to the disclosure and are not to be considered limiting of its scope.
FIG. 1 is a process schematic diagram of a method of strengthening glass according to one embodiment of the present disclosure;
fig. 2 is a graph of the results of monitoring the pH of the furnace water of example 1 and comparative example 1 of the present disclosure.
Detailed Description
Hereinafter, only certain exemplary embodiments are briefly described. As will be recognized by those of skill in the pertinent art, the described embodiments may be modified in various different ways, and the different embodiments may be combined arbitrarily without conflict, without departing from the spirit or scope of the present disclosure. Accordingly, the drawings and description are to be regarded as illustrative in nature and not as restrictive.
In a first aspect of the disclosure, the disclosure provides a method of making a strengthened glass. The method comprises the following steps: and (3) placing the glass to be strengthened in furnace water for strengthening treatment, wherein the furnace water is provided with additives. The additive comprises an active component, wherein a second ion in the active component is used for carrying out a displacement reaction with a first ion in furnace water, and the active component is neutral.
According to the technical scheme, the second ions in the active component and the first ions in the furnace water undergo a displacement reaction, so that the content of the first ions in the furnace water can be controlled, and as the active component is neutral, the active component does not greatly influence the pH value of the furnace water, the glass surface is not whitened and dirty, the pH value of the furnace water is kept stable, the service life of the furnace water is prolonged, the phenomenon of whitening and dirty on the glass surface caused by the rise of the pH value of the furnace water is avoided, and the quality of the prepared reinforced glass is improved.
In one embodiment, the type of glass to be strengthened is not particularly limited and may include, for example, glass-ceramic. Glass ceramics are glass containing glass phase and microcrystalline phase, and comprise a lithium aluminum silicon system, a magnesium aluminum silicon system, a fluorine system and other series. In one embodiment, the glass to be strengthened may be a lithium aluminum silicon system glass ceramic. Since the microcrystalline glass has a crystalline phase and the grain size can be controlled in a smaller range, the chemical compositions of crystalline phase generated by crystallization and surrounding glass phase substances are more similar, the refractive index difference is small, and continuous numbering can be formed into sheets, so that the microcrystalline glass has higher light transmittance in the visible light range, and is suitable for being used as the cover plate glass of the display screen of electronic equipment such as mobile phones, tablet computers and the like. In addition, as the microcrystalline glass contains a large amount of crystalline phase substances, the mechanical strength is improved, and the requirements of the screen cover glass of electronic equipment such as mobile phones and the like on scratch resistance and scratch resistance can be met. In order to further improve the anti-drop performance of the glass ceramics, chemical strengthening treatment can be carried out on the glass ceramics so as to introduce a stress layer on the surface of the glass. Chemical strengthening treatment is a common method of obtaining strengthened (or tempered) glass by introducing the glass to be strengthened into furnace water having a specific chemical composition so that ion exchange occurs between the glass and the furnace water. The furnace water contains alkali metal cations, the alkali metal cations in the furnace water and the alkali metal cations on the surface of the glass are replaced, and the radius size of the alkali metal cations in the furnace water is larger, so that the size of the alkali metal cations entering the surface of the glass after replacement is larger than that of the alkali metal cations before replacement, thereby causing the production of a plug squeezing effect on the surface of the glass and further forming a stress layer with a certain depth on the surface of the glass. The stress layer can play a role in improving the surface hardness to a certain extent, preventing micro cracks from diffusing, counteracting external impact and the like.
For easy understanding, the principle by which the above advantageous effects can be achieved by the method is first briefly described below:
the method for preparing the strengthened glass comprises the steps of carrying out chemical strengthening on the glass to be strengthened, namely placing the glass to be strengthened in furnace water containing specific components, and carrying out ion exchange. Cations in the glass structure are exchanged with ions with larger ionic radius in the furnace water, so that a stress layer with a certain thickness is formed on the surface of the glass, a larger stress value is obtained, and the strength of the glass is improved. Thus, during chemical strengthening, the furnace water receives the first ions displaced from the glass surface, and as the strengthening process continues, the concentration of the first ions also continues to increase. In some cases, particularly when glass-ceramic is strengthened, too high or too low a concentration of the first ion can affect the properties of the strengthened glass produced. Therefore, it is necessary to control the concentration of the first ions in the furnace water. Although some additives are used in the related art to suppress the increase in the first ion concentration, the above additives often cause a change in the pH value of the furnace water, thereby adversely affecting the strengthening effect, resulting in a reduction in the life of the furnace water. The method can maintain the stable pH value of the furnace water on the premise of realizing the control of the first ion concentration by adopting the additive containing neutral active components, thereby prolonging the service life of the furnace water and improving the strengthening quality.
In the present disclosure, the order of adding the additives and the glass to be strengthened to the furnace water is not particularly limited, and may be selected by those skilled in the art according to actual circumstances. For example, the concentration of the first ions in the furnace water may be monitored and the additive may be added to displace the first ions before a certain amount of glass to be strengthened has been treated and the concentration of the first ions in the furnace water rises to an upper threshold value for the concentration of the first ions required for the strengthening treatment. The additive may be added together with the glass to be strengthened of the next batch, or the additive may be added in the furnace water in advance, followed by adding the glass to be strengthened. Alternatively, the glass to be strengthened may be added to the furnace water first, followed by the addition of the additive. Additives added to the furnace water may be placed in the vicinity of the glass to be strengthened to enhance the effect of displacing the first ions.
In one embodiment, after the strengthening treatment is completed, the next glass to be treated may be placed in the furnace water and the additives replaced. As previously described, the second ions in the additive and the first ions in the furnace water may be displaced, thereby acting to stabilize the concentration of the first ions in the furnace water. It will thus be appreciated that the displacement reaction described above is initiated after the additive has been placed in the furnace water. Since the furnace water subjected to strengthening treatment is mostly recycled in the actual process, after a certain amount of glass to be strengthened is treated, the furnace water already has a certain concentration of first ions displaced from the glass to be strengthened. Thus, after the glass to be strengthened of one batch is finished, if the glass to be strengthened of the next batch is continued without taking out the additive for replacement, the consumption of the second ions in the active component in the additive may result, resulting in a decrease in the ability of the additive to control the content of the first ions in the furnace water. Therefore, after the start of the addition of the additive to the furnace water, the new additive can be synchronously replaced each time a new treatment for the glass to be strengthened is performed.
In one embodiment, the additive and the glass to be strengthened may be placed in the furnace water simultaneously. For example, a storage tank for containing additives for tablets may be provided in a basket for placing glass to be strengthened, to facilitate the addition and replacement of additives. In one embodiment, the additive may be synchronized with the glass to be strengthened into and out of the furnace water. That is, the additive may be added during the addition of the glass to be strengthened, and after the strengthening treatment is completed, both the additive and the strengthened glass are taken out from the furnace water. The second ion in the active component of the additive is used to react with the first ion in the furnace water, so that as the immersion time of the additive in the furnace water increases, the content of the second ion in the additive also decreases. The additive and the glass to be strengthened are synchronously fed into and discharged from the furnace water, so that the capability of the additive to replace the first ions in the furnace water can be maintained.
In one embodiment, the additive is in a solid state. More specifically, the additive may be a solid tablet. Thus, the addition and replacement of the additive can be easily performed. For example, a plurality of storage slots may be provided symmetrically in the aforementioned means for accommodating glass to be strengthened, such as a basket, for accommodating additives for tablets. In one embodiment, the placement slots may be provided at the four corners and the center of the basket and the additive tablets may be placed. The object placing groove and the glass to be strengthened can keep a certain distance.
In one embodiment, the first ions comprise lithium ions and the second ions comprise sodium ions. That is, the additive contains Na element, and in the strengthening process, the additive and lithium ions in the furnace water undergo a displacement reaction to absorb lithium ions in the furnace water and release sodium ions into the furnace water.
The lithium ion concentration has an important influence on the strengthening effect of glass, particularly glass ceramics. When the concentration of lithium ions in the furnace water is too high, the extrusion resistance of the strengthened glass is reduced, and when the concentration of lithium ions in the furnace water is too low, the strengthened glass is easy to whiten in the whole surface in a high-temperature and high-humidity environment (for example, the temperature is 85 ℃ and above and the humidity is 85 ℃ and above). Therefore, the active component is adopted to regulate and control the concentration of lithium ions, so that the glass strengthening effect can be improved. The main strengthening salt in the furnace water contains sodium ions, so that the second ions exchanged by the active components are sodium ions, and the furnace water performance is hardly influenced.
In the method, the lithium ion concentration of the furnace water in the strengthening process can be controlled to be 10-20ppm by regulating and controlling the amount of the added active component. Thus, adverse effects due to too high or too low a lithium ion concentration can be avoided. For example, the mass ratio of the active component to be added to the furnace water to the glass to be strengthened may be ((1-3): (2-25). For example, the glass to be strengthened and the additive may be immersed in the furnace water in a ratio of 10-50g of the glass to be strengthened to 5-15g of the active component each time strengthening treatment is performed.
In one embodiment, the additive may include one or more of an oxide, an alkali metal silicate, an alkali metal phosphate, an alkali metal sulfate, an alkali metal chloride, an alkali metal bicarbonate, and an alkali metal hydroxide. In one embodiment, to better form a solid, easy to replace additive, the additive may contain one or more of the above materials to form a carrier for the active ingredient or to assist in the displacement, absorption of lithium ions. For example, the foregoing oxide may include at least one of silicon oxide, aluminum oxide, and alkali metal oxide. Wherein, the silicon oxide and the aluminum oxide can be used for forming a carrier, thereby facilitating the molding and the preparation of the additive. Alkali metal oxides, alkali metal silicates, alkali metal phosphates, alkali metal sulfates, alkali metal chlorides, alkali metal bicarbonates, and alkali metal hydroxides may be used to assist in the absorption or displacement of the first ions. In some embodiments, the additive may be selected from compounds that do not contain boron and phosphorus elements and have a certain stability at high temperatures. More specifically, the additive may include one or more of sodium oxide, potassium oxide, sodium hydroxide, potassium hydroxide, sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, trisodium phosphate, sodium sulfate, and potassium sulfate.
In one embodiment, the additive may include a carrier, and the carrier may be formed of silica, alumina or other materials, and may be provided with a plurality of holes for accommodating the active components, so as to perform a sufficient contact function, and prevent the reacted active components from falling into the furnace water, resulting in a decrease in transparency of the furnace water. The active ingredient filled in the carrier may include one or more selected from the above-mentioned compounds.
In one embodiment, the content of active component in the additive may be not less than 60% for better control of the concentration of lithium ions in the furnace water. In order to better maintain transparency of the furnace water, a substance insoluble in the furnace water may be selected as an active component. It should be noted here that the fact that the active ingredient is insoluble in the furnace water means that the solubility of the active ingredient in the furnace water is so low that the active ingredient does not fall into the furnace water due to dissolution during the strengthening treatment. For example, under conditions of enhanced treatment, the amount of active ingredient dissolved in each 100g of furnace water may be less than 0.01g.
In one embodiment, the active component may include sodium sulfate. The inventors found that sodium sulfate, which is a strong acid and strong base salt, has a neutral pH. In the furnace water subjected to the strengthening treatment, sodium sulfate can be kept in a solid state form and react with the furnace water by the following steps:
2Na + +SO 4 2- +2Li + ＝Li 2 SO 4 +2Na +
therefore, when the active component is sodium sulfate, the active component and a product after the first ion replacement in the furnace water are neutral substances, so that the pH value of the furnace water is not affected by the process. Therefore, the reduction of the service life of the furnace water caused by the increase or decrease of the pH value of the furnace water can be avoided, and the quality of the reinforced glass is prevented from being influenced.
It is specifically noted that in this disclosure, the term "neutral" should be construed broadly. For example, it may be indicated that the pH of the substance is around 7, such as pH 7.+ -. 0.5.
In one embodiment, the additive may be a sodium sulfate tablet. Referring to fig. 1, the additive may undergo a displacement reaction in the furnace water to form lithium sulfate to control the lithium ion concentration in the furnace water. After the strengthening treatment is finished, the additive tablet with the lithium ions replaced can be taken out from furnace water along with the strengthened glass, and when the next batch of glass to be strengthened is treated, a new sodium sulfate tablet is replaced as an additive. The sodium sulfate tablet not only has neutral pH value, but also can form additive in solid state in furnace water, thus being capable of reducing lithium ion concentration in the furnace water through displacement reaction well, and being removed from the furnace water and replaced simply through taking out. Therefore, on one hand, the powdery additive can be prevented from occupying the volume of the furnace water after being added into the furnace water, and on the other hand, the powder can be prevented from being mixed into the furnace water to cause turbidity of the furnace water.
In one embodiment, the composition of the furnace water is not particularly limited and may be selected and adjusted by one skilled in the art depending on the particular type of glass to be strengthened. In one embodiment, the bulk salt contained in the furnace water may include sodium nitrate and potassium nitrate, with the potassium nitrate being present in an amount greater than the sodium nitrate. For example, 30 parts by weight of ammonium nitrate, and 70 parts by weight of potassium nitrate may be contained.
In one embodiment, the specific operation of the strengthening treatment is not particularly limited, and one skilled in the art can adjust according to the specific condition of the glass to be strengthened. In one embodiment, the temperature of the furnace water during the strengthening treatment may be 450-470 ℃ and the time of the strengthening treatment may be 6-8 hours. In the strengthening treatment process, the pH value of the furnace water is monitored, and the pH value of the furnace water is kept between 6 and 9.8.
In one embodiment, the strengthening treatment may include the steps of preheating, tempering, and cooling. Firstly, furnace water and glass to be strengthened immersed in the furnace water can be preheated, and the temperature of the furnace water is increased to 280-320 ℃ within 40-60 min. The furnace water may then be raised to the strengthening treatment temperature described above to effect strengthening treatment. In the strengthening treatment process, parameters such as lithium ion concentration, pH value and the like in the furnace water can be monitored in real time, on one hand, the progress of strengthening treatment can be judged, on the other hand, the quality of the furnace water can be controlled, and the furnace water is correspondingly treated before a certain parameter (such as lithium ion concentration and pH value) reaches the upper limit of the requirement on the quality of the furnace water, so that the quality of the obtained strengthened glass is prevented from being influenced. After the ion exchange is finished, the furnace water and the materials immersed in the furnace water can be subjected to slow cooling treatment, and after the temperature is reduced to a certain value, the reinforced glass and the additives are taken out of the furnace water. The cooling time of the slow cooling treatment can be 20-30 minutes, and the furnace is discharged when the furnace water is cooled to about 100 ℃, such as 110 ℃.
As a second aspect of the disclosed embodiments, the disclosed embodiments provide a strengthened glass. Tempered glass is produced by the method described above. Therefore, the tempered glass has at least the advantages of the tempered glass obtained by the method and is not described in detail herein. In general, the reinforced glass has reliable mechanical properties, is not easy to whiten in high-temperature and high-humidity environments, has good glass transmittance, and has no whitening and dirt on the surface.
The methods used in the examples described below are conventional methods unless otherwise indicated, and the reagents used are commercially available reagents unless otherwise indicated.
Example 1
The sodium sulfate tablet is used as additive, the furnace water temperature is 450-470 ℃ during strengthening treatment, and the tempering time is 6-8 hours. The furnace water contained 30% sodium nitrate +70% potassium nitrate, with 10 + 2 g/tablet sodium sulfate added with the furnace.
The microcrystalline glass is put into the furnace before tempering, sodium sulfate sheet bodies with corresponding mass are prepared, the microcrystalline glass and the sodium sulfate are loaded by using a 316L stainless steel jig, the microcrystalline glass and the sodium sulfate are placed in the same basket jig and are placed at four corners and the central position of the basket, and each jig for loading the sodium sulfate sheet bodies is loaded with no more than 2Kg. And (3) moving the hanging basket into a toughening furnace for strengthening, taking out the sodium sulfate sheet body along with the furnace after strengthening treatment is finished, and scrapping the used sodium sulfate sheet body.
Comparative example 1
The procedure of example 1 was followed using an ion sieve functional ceramic containing sodium silicate as an additive.
The pH of the furnace water subjected to the strengthening treatment of example 1 and comparative example 1 was monitored, and the test results are shown in fig. 2: the pH standard value of the furnace water needs to be controlled to be not higher than 9.8, otherwise, white dirt on the surface of the reinforced glass is easy to appear. Example 1 using the additive of the present disclosure was able to stabilize the pH at 7.2 after 200k (20 ten thousand pieces) of glass was processed, whereas the pH of the furnace water reached the upper limit after 50k (5 ten thousand pieces) of glass was processed using the additive of comparative example 1.
In the description of the present specification, it should be understood that the terms "center," "thickness," "upper," "lower," "front," "rear," "horizontal," "top," "bottom," "inner," "outer," "axial," "radial," "circumferential," and the like indicate an orientation or a positional relationship based on that shown in the drawings, merely for convenience of description and to simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present disclosure.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present disclosure, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present disclosure, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; the device can be mechanically connected, electrically connected and communicated; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the terms in this disclosure will be understood by those of ordinary skill in the art as the case may be.
In this disclosure, unless expressly stated or limited otherwise, a first feature being "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other by way of additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is less level than the second feature.
The above disclosure provides many different embodiments or examples for implementing different structures of the disclosure. The components and arrangements of specific examples are described above in order to simplify the present disclosure. Of course, they are merely examples and are not intended to limit the present disclosure. Furthermore, the present disclosure may repeat reference numerals and/or letters in the various examples, which are for the purpose of brevity and clarity, and which do not themselves indicate the relationship between the various embodiments and/or arrangements discussed.
The above is merely a specific embodiment of the disclosure, but the protection scope of the disclosure is not limited thereto, and any person skilled in the art can easily think of various changes or substitutions within the technical scope of the disclosure, which should be covered in the protection scope of the disclosure. Therefore, the protection scope of the present disclosure shall be subject to the protection scope of the claims.
Claims (10)
1. A method of making a strengthened glass comprising:
the glass to be strengthened is placed in furnace water for strengthening treatment, the furnace water is placed with additives,
the additive comprises an active component, wherein a second ion in the active component is used for carrying out a displacement reaction with a first ion in the furnace water, and the active component is neutral.
2. The method of claim 1, wherein the glass to be strengthened comprises glass-ceramic.
3. The method of claim 2, wherein the additive is in a solid state.
4. A method according to claim 3, wherein the additive further comprises one or more of an oxide, an alkali metal silicate, an alkali metal phosphate, an alkali metal sulfate, an alkali metal chloride, an alkali metal bicarbonate, and an alkali metal hydroxide.
5. The method of claim 1, wherein the first ions comprise lithium ions and the second ions comprise sodium ions.
6. A method according to claim 3, wherein the content of the active ingredient in the additive is not less than 60%,
the active component is insoluble in the furnace water.
7. The method of claim 5 or 6, wherein the active component comprises sodium sulfate.
8. The method as recited in claim 1, further comprising:
and after the strengthening treatment is finished, placing the glass to be treated in the furnace water and replacing the additive.
9. The method of claim 1, wherein the strengthening treatment meets at least one of the following conditions:
the mass ratio of the additive to the glass to be strengthened is (1-3): (2-25);
the lithium ion content of the furnace water is 10-20ppm;
the pH value of the furnace water is 6-9.8;
the temperature of the furnace water is 450-470 ℃;
the time of the strengthening treatment is 6-8 hours;
the furnace water comprises potassium nitrate and sodium nitrate, and the content of the potassium nitrate is higher than that of the sodium nitrate.
10. A strengthened glass prepared by the method of any one of claims 1-9.
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