CN117623624A - Aluminosilicate glass, reinforced glass, preparation method and application thereof - Google Patents
Aluminosilicate glass, reinforced glass, preparation method and application thereof Download PDFInfo
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- CN117623624A CN117623624A CN202311551897.2A CN202311551897A CN117623624A CN 117623624 A CN117623624 A CN 117623624A CN 202311551897 A CN202311551897 A CN 202311551897A CN 117623624 A CN117623624 A CN 117623624A
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- glass
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- beo
- aluminosilicate
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- 239000011521 glass Substances 0.000 title claims abstract description 178
- 239000005354 aluminosilicate glass Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 27
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 42
- 239000011734 sodium Substances 0.000 claims description 38
- 238000005728 strengthening Methods 0.000 claims description 36
- 229910001415 sodium ion Inorganic materials 0.000 claims description 27
- 229910052700 potassium Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000011591 potassium Substances 0.000 claims description 15
- 229910001414 potassium ion Inorganic materials 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 230000002787 reinforcement Effects 0.000 claims description 12
- 239000006058 strengthened glass Substances 0.000 claims description 9
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 6
- 238000002310 reflectometry Methods 0.000 abstract description 42
- 238000003426 chemical strengthening reaction Methods 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005342 ion exchange Methods 0.000 description 14
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000005341 toughened glass Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011800 void material Substances 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
- C03C3/089—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
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
- H04M1/02—Constructional features of telephone sets
- H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
- H04M1/026—Details of the structure or mounting of specific components
- H04M1/0266—Details of the structure or mounting of specific components for a display module assembly
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Theoretical Computer Science (AREA)
- Signal Processing (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides aluminosilicate glass, reinforced glass, a preparation method and application thereof, wherein the aluminosilicate glass comprises the following components in terms of oxide: siO (SiO) 2 、Al 2 O 3 、Li 2 O、Na 2 O、ZrO 2 And BeO; in terms of mass percent of oxides, li 2 The content of O is 4-7%; na (Na) 2 The content of O is 4-8%; zrO (ZrO) 2 The content of (2) is 0.5-2%; the content of BeO is 0.5-2%. Adding proper amount of ZrO into glass 2 And BeO reduces the reflectivity of the glass, provided the aluminosilicate glass has a thickness ofAt 1.3mm, the 550nm reflectance is less than 8.3%. Meanwhile, the aluminosilicate glass provided by the invention also contains Li 2 O and Na 2 O has good chemical strengthening performance, and further reduces the reflectivity of the glass after chemical strengthening and improves the scratch resistance of the glass. When the thickness of the reinforced aluminosilicate glass is 1.3mm, the reflectivity at 550nm is less than 8.1%, and the scratch width is less than 100 μm when the load is 1 kg.
Description
Technical Field
The invention belongs to the technical field of glass manufacturing, and particularly relates to aluminosilicate glass, reinforced glass, a preparation method and application thereof.
Background
Electronic devices with screens, such as mobile phones, tablet computers, car navigation, etc., are becoming popular in people's lives. However, when strong light irradiates, the display effect of the screen of the electronic equipment is greatly reduced by reflected light generated by the screen of the electronic equipment, and the use experience is affected.
In the prior art, a glass cover plate with low reflectivity is used to solve the problem. However, the reflectivity of the existing glass cover plate is still high, and the requirements are difficult to meet.
Disclosure of Invention
The invention mainly aims to provide aluminosilicate glass, reinforced glass, a preparation method and application thereof, and aims to solve the technical problem of how to provide aluminosilicate glass with low reflectivity, so that the aluminosilicate glass is more practical.
The aim and the technical problems of the invention are realized by adopting the following technical proposal. According to the aluminosilicate glass provided by the invention, the glass components comprise, in terms of oxidation: siO (SiO) 2 、Al 2 O 3 、Li 2 O、Na 2 O、ZrO 2 And BeO; in terms of mass percent of oxides, li 2 The content of O is 4-7%; na (Na) 2 The content of O is 4-8%; zrO (ZrO) 2 The content of (2) is 0.5-2%; the content of BeO is 0.5-2%.
The aim and the technical problems of the invention can be further realized by adopting the following technical measures.
In some embodiments, the aluminosilicate glass described above wherein the glass composition comprises, in mass percent on an oxide basis, zrO 2 ：BeO＝1：0.3-1.3。
In some embodiments, the aluminosilicate glass described above, wherein the glass composition comprises, in mass percent on an oxide basis: siO (SiO) 2 ：55-67％；Al 2 O 3 :16-25%; b, B 2 O 3 ：2-6％。
In some embodiments, the aluminosilicate glass described above, wherein the glass composition comprises, in mass percent on an oxide basis: k (K) 2 O:0-3%; mgO:0-3%; caO:0-1%; srO:0-2%; and, znO:0-2%; wherein K is 2 The contents of O, mgO, caO, srO and ZnO are not 0 at the same time.
In some embodiments, the aluminosilicate glass described above, wherein the glass component comprises, in mass percent on an oxide basis, a total alkali metal oxide content M:10-14%, alkaline earth metal oxide total content N:1% -5%.
In some embodiments, the aluminosilicate glass described above wherein the glass composition comprises 0.3.ltoreq.Li by mass percent on an oxide basis 2 O/M is less than or equal to 0.6, and (M+N)/Al is less than or equal to 0.5 2 O 3 ≤1，0.2≤BeO/N≤1。
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. According to the present invention, there is provided a tempered glass comprising:
a glass substrate, the glass substrate being any one of the aluminosilicate glasses described above;
the high-sodium reinforcement layer is arranged on the surface of the glass substrate; the material of the high-sodium reinforcement layer is based on a glass substrate, wherein part of lithium ions are exchanged with external sodium ions;
the high-potassium strengthening layer is arranged on the surface of the high-sodium strengthening layer; the material of the high-potassium reinforced layer is based on the high-sodium reinforced layer, wherein part of sodium ions are exchanged with external potassium ions.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. The preparation method of the reinforced glass provided by the invention comprises the following steps:
strengthening the glass substrate to exchange lithium ions in the glass substrate with external sodium ions, wherein the exchange depth is d 1 The sodium ions are exchanged with the external potassium ions, and the exchange depth is d 2 Obtaining strengthened glass; wherein d 1 ＞d 2 。
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. According to the screen cover plate provided by the invention, the screen cover plate comprises any glass.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. According to the electronic device provided by the invention, the electronic device comprises the screen cover plate.
By means of the technical scheme, the aluminosilicate glass, the reinforced glass and the preparation method and the application thereof have at least the following advantages:
the invention designs the aluminosilicate glass component by adding proper amount of ZrO into the glass 2 And BeO to reduce the reflectivity of the glass. The thickness of the aluminosilicate glass is 1.3mm, and the reflectivity at 550nm is less than8.3%. Meanwhile, the aluminosilicate glass provided by the invention also contains Li 2 O and Na 2 O has good chemical strengthening performance, can be strengthened by adopting an ion exchange mode of exchanging lithium ions with sodium ions and exchanging sodium ions with potassium ions, forms two strengthening layers with different gradient refractive indexes on the surface of the glass, further reduces the reflectivity of the glass and improves the scratch resistance of the glass. When the thickness of the reinforced glass is 1.3mm, the reflectivity of 550nm is less than 8.1 percent, and the reinforced glass has good scratch resistance, and the scratch width is less than 100 mu m when the reinforced glass is loaded with 1 kg.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
In order to more clearly illustrate the embodiments of the present disclosure or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present disclosure, and other drawings may be obtained according to these drawings without inventive effort to a person of ordinary skill in the art.
Fig. 1 is a schematic structural view of a tempered glass disclosed in an embodiment of the present disclosure.
Reference numerals illustrate:
1. a high potassium reinforcement layer; 2. a high sodium reinforcement layer; 3. a glass substrate.
Detailed Description
In order to further describe the technical means and effects adopted by the invention to achieve the preset aim, the following detailed description refers to an aluminosilicate glass, a reinforced glass, a preparation method thereof, a specific implementation mode, a structure, characteristics and effects thereof, which are provided by the invention, with reference to the accompanying drawings and the preferred embodiments. In the following description, different "an embodiment" or "an embodiment" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
Some embodiments of the present invention provide an aluminosilicate glass, the glass composition comprising, in terms of oxidation: siO (SiO) 2 、Al 2 O 3 、Li 2 O、Na 2 O、ZrO 2 And BeO; in terms of mass percent of oxides, li 2 The content of O is 4-7%; na (Na) 2 The content of O is 4-8%; zrO (ZrO) 2 The content of (2) is 0.5-2%; the content of BeO is 0.5-2%.
ZrO 2 The glass has the advantages that the transparency of the glass can be improved, the transmittance of the glass is increased, the reflectivity of a glass body is reduced, the compressive stress on the surface of the glass can be improved during chemical strengthening, and the scratch resistance is improved, but the content of the Zr crystal is too high, so that the glass melting temperature is increased, zr crystals are separated out during glass molding, and the glass quality is affected. Thus, zrO 2 The content of (2) is limited to 0.5-2%.
Be has very small atomic weight, but the oxide BeO of the Be has higher strength in all alkaline earth metal oxides, can reduce the melting temperature, the forming viscosity and the expansion coefficient of the glass, reduce the reflectivity of the glass and increase the transmittance, so the Be has unique advantages for seeking to reduce the reflectivity of the glass, and in addition, a certain amount of the Be can improve the annealing quality of the glass and increase the scratch resistance of the glass. However, beO also has a great disadvantage of having a high melting point, so adding too much BeO to the glass not only increases the production cost of the glass, but also increases the difficulty of the glass melting process, and thus the content of BeO is limited to 0.5-2%.
Li 2 O is an ion exchange component, and is particularly a component necessary for obtaining a deep stress depth by ion-exchanging Li ions contained in glass with Na ions in molten salt. In addition, li 2 O reduces the high-temperature viscosity of the glass and improves the Young's modulus. But when Li 2 When the O content is higher, the corrosion to the refractory material of the kiln is increased, the service life of the kiln is reduced, therefore, li in the invention 2 The O content is limited to 4-7%.
Na 2 O is an ion exchange component by ion-exchanging sodium to potassiumIons, thereby increasing the compressive stress on the glass surface, are also necessary components for forming layers of different refractive indices. In addition Na 2 O is a component that reduces the high-temperature viscosity to improve the meltability and moldability. If Na is 2 When the content of O is too small, the meltability is lowered and the ion exchange rate is lowered. Na (Na) 2 If the O content is too high, scratch resistance and surface compressive stress of the glass are remarkably reduced, and thus the content is limited to 4-8%.
In some embodiments, the aluminosilicate glass described above wherein the glass composition comprises, in mass percent on an oxide basis, zrO 2 ：BeO＝1：0.3-1.3。
The Applicant has found in the study that ZrO 2 And BeO to reduce the reflectivity of the glass, wherein the mass ratio of the BeO to the glass is ZrO 2 : beo=1: at 0.3-1.3, the glass exhibits a lower reflectivity.
In some embodiments, the aforementioned aluminosilicate glass comprises, in mass percent on an oxide basis: siO (SiO) 2 ：55-67％；Al 2 O 3 :16-25%; b, B 2 O 3 ：2-6％。
SiO 2 Is a network forming body of the material and is a main component of a glass framework. When SiO 2 When the content is too low, the strength of the formed glass is not high, the overall transmittance of the glass is reduced, and the reflectivity is increased; when SiO 2 When the content is too high, the glass is difficult to melt and mold. Thus, siO 2 At 55-67%, the glass has better mechanical properties and its reflectivity is also at a lower level.
Al 2 O 3 Can improve the heat resistance and chemical durability of the glass, and simultaneously improve the internal void ratio of the glass, so that alkali metal ions in the glass can freely move, the alkali metal ions in the glass can be conveniently exchanged, and the surface compressive stress of the glass after reinforcement is improved. When Al in glass 2 O 3 When the content is low, the durability and surface compressive stress of the glass become low, the scratch resistance becomes low, and when Al 2 O 3 When the content exceeds a certain amount, the viscosity of the glass melt increases, and clarification is difficult. Thus the inventionMing Zhong Al 2 O 3 The content is limited to 16-25%.
Al in glass provided by the invention 2 O 3 The content is 16-25%, resulting in an increase in glass melting temperature, thus introducing B 2 O 3 As a fluxing agent, the low temperature viscosity of the glass can be increased. And the scratch resistance and crack resistance of the glass are improved, the light transmittance of the glass is improved, and the reflectivity of the glass is reduced. But too much B 2 O 3 The toughness of the glass is greatly reduced, the ion exchange speed is reduced, and the performance of the glass after strengthening is reduced, therefore B 2 O 3 The content of (2) is limited to 2-6%.
In some embodiments, the aforementioned aluminosilicate glass comprises, in mass percent on an oxide basis: k (K) 2 O:0-3%; mgO:0-3%; caO:0-1%; srO:0-2%; and, znO:0-2%.
K 2 O is a component for reducing the high-temperature viscosity to improve the meltability and the formability, and its action and effect are as same as Na 2 O is substantially the same. Na (Na) 2 O and K 2 O can exist simultaneously or independently. Thus in the present invention, K 2 The content of O is limited to 0-3%.
Glass having too high MgO content increases devitrification, and thus, the MgO content is limited to 0 to 3%. Excessive CaO content increases brittleness of the glass, and is disadvantageous for potassium-sodium ion exchange, so that CaO content is limited to 0 to 1%. Too high a SrO content increases the density of the glass and increases the refractive index and reflectivity of the glass, and thus the SrO content is limited to 0-2%.
ZnO can improve the mechanical property of the glass and increase the Young modulus of the glass, and can reduce the high-temperature melting viscosity of the glass, so that the glass is easier to mold, and excessive ZnO can greatly improve the refractive index of the glass and increase the reflectivity of the glass, so that the content of ZnO is limited to 0-2%.
In some embodiments, the aforementioned aluminosilicate glass comprises the following components in percentage by mass of oxides, the total alkali metal oxide content M:10-14%, alkaline earth metal oxide total content N:1% -5%.
Oxidation of alkali metalsThe glass can reduce the high-temperature viscosity of the glass and improve the meltability and the formability of the glass. However, if the alkali metal oxide content M ([ Li) 2 O]+[Na 2 O]+[K 2 O]) Too high, the thermal expansion coefficient of the glass increases and the scratch resistance decreases. Thus, the alkali metal oxide content M is suitably in the range of 10-14%.
The addition of the alkaline earth metal oxide (BeO, mgO, caO, srO) can effectively reduce the high-temperature viscosity of the glass, thereby improving the meltability and formability of the glass and improving the scratch resistance of the glass. However, too much alkaline earth metal oxide increases the glass density, increases the refractive index, increases the reflectivity, and decreases the scratch resistance. Therefore, the total amount of alkaline earth metal oxides N is limited to 1-5%.
In some embodiments, the aforementioned aluminosilicate glass comprises, in mass percent on an oxide basis, 0.3.ltoreq.Li 2 O/M is less than or equal to 0.6, and (M+N)/Al is less than or equal to 0.5 2 O 3 ≤1，0.2≤BeO/N≤1。
The applicants have found in the study that when the alkali metal and alkaline earth metal satisfy 0.3.ltoreq.Li 2 O/M is less than or equal to 0.6, and (M+N)/Al is less than or equal to 0.5 2 O 3 When the ratio of BeO/N is more than or equal to 1 and less than or equal to 0.2 and less than or equal to 1, the glass has good melting property and scratch resistance and has lower reflectivity.
The present invention also provides a tempered glass, as shown in fig. 1, comprising: a glass substrate 3, the glass substrate 3 being any of the aluminosilicate glasses described above; a high sodium reinforcement layer 2 disposed on the surface of the glass substrate 3; the high-sodium reinforcement layer 2 is made of a glass substrate, wherein part of lithium ions in the glass substrate are exchanged with external sodium ions; the high-potassium reinforced layer 1 is arranged on the surface of the high-sodium reinforced layer 2, and the high-potassium reinforced layer is made of a material that part of sodium ions in the high-sodium reinforced layer 2 are exchanged with external potassium ions.
The invention also provides a preparation method of the reinforced glass, which is used for reinforcing the glass substrate, so that lithium ions in the glass substrate are exchanged with external sodium ions, and the exchange depth is d 1 The sodium ions are exchanged with the external potassium ions, and the exchange depth is d 2 Obtaining strengthened glass; wherein d 1 ＞d 2 。
In some embodiments, the glass substrate has a maximum optical path difference of less than 2, resulting in a relatively uniform reflectivity of the glass as a whole, thereby ensuring that the strengthening layer forms a graded index of refraction.
Strengthening glass can provide lower reflectivity and higher scratch resistance. The glass substrate 3 is strengthened by adopting a double ion exchange method, so that two different strengthening layers are formed on the surface of the glass, namely a high-potassium strengthening layer 1, a high-sodium strengthening layer 2 and the glass substrate 3 are sequentially arranged from outside to inside. The high-sodium reinforcement layer 2 is obtained by exchanging lithium ions in the glass substrate 3 with external sodium ions; the high-potassium reinforced layer 1 is obtained by exchanging sodium ions in the high-sodium reinforced layer 2 with external potassium ions. It should be noted that the influence of different elements in the glass on the refractive index is different, and the closer to the surface of the glass, the larger the concentration of exchange ions, the larger the influence on the refractive index; the closer to the glass substrate, the smaller the concentration of exchange ions, and the smaller the influence on the refractive index. Therefore, the high-sodium reinforced layer and the high-potassium reinforced layer are gradient refractive index reinforced layers, namely, the refractive indexes of the two reinforced layers are gradually changed along with the change of depth. And since the refractive index is graded, there is no distinct interfacial separation between the two strengthening layers and the glass substrate, and no interfacial reflection.
Among the glass elements, the refractive index order of Li, na, K is: k > Li > Na. In the high-potassium reinforced layer 1, the concentration of potassium ions gradually decreases from the outside to the inside, the concentration of sodium ions gradually increases, and the refractive index changes from high to low; in the high-sodium reinforcement layer 2, the sodium ion concentration gradually decreases from the outside to the inside, the lithium ion concentration gradually increases, and the refractive index changes from low to high. After the light is incident into the high-potassium reinforced layer 1, the gradual change structure of the refractive index from outside to inside, which changes the refractive index from high to low, enables the light to continuously repeatedly generate the refraction-reflection-refraction process in the gradual change structure until the light is emitted, and compared with a uniform medium, the reflection of the light is greatly reduced. After the light rays are incident into the high-sodium reinforced layer 2, the gradual change structure of the refractive index from outside to inside can enable the light rays incident at a larger angle to finally enter the substrate, so that the transmittance is greatly improved. By the combined action of the two different gradient refractive index reinforced layers, the reflectivity of the glass is further reduced, and the high-potassium reinforced layer 1 can greatly improve the hardness of the surface of the glass.
In some embodiments, d 1 In the range of 10-12 μm, d 2 In the range of 3-5 μm. Depth d of exchange of lithium ions in glass substrate 3 with sodium ions from the outside 1 Less than 10 μm has poor effect of reducing the reflectivity of the glass, and more than 12 μm greatly reduces the scratch resistance and the drop resistance of the prepared low-reflectivity glass, thus d 1 Is controlled to be in the range of 10-12 mu m. Depth d of exchange of sodium ion with external potassium ion 2 If the thickness of the high-potassium reinforced layer 1 is too thick and the high-sodium reinforced layer 2 is too thin, the effect of reducing the reflectivity of the glass is poor, and if the thickness of the high-potassium reinforced layer 2 is larger than 5 μm, the effect of reducing the reflectivity of the glass is poor, so d 2 Is controlled to be in the range of 3-5 μm.
In some embodiments, the method for strengthening the glass substrate comprises the following steps: immersing the glass substrate into NaNO at 400-470 DEG C 3 Soaking in molten salt for 1-5 hr, and soaking in KNO at 380-450deg.C 3 And (3) 0.25-3h in molten salt.
NaNO 3 The sodium ions and lithium ions are slowly exchanged and cannot reach the required depth when the temperature of the molten salt is lower than 400 ℃; naNO 3 The temperature of the molten salt is higher than 470 ℃, so that the tensile stress of the glass is increased, and the scratch resistance and the anti-drop performance of the glass are greatly reduced, so that the strengthening temperature of the sodium salt is controlled to be 400-470 ℃. NaNO 3 If the molten salt strengthening time is less than 1h, the sodium ion and lithium ion exchange cannot reach the required depth, and NaNO 3 When the molten salt strengthening time is more than 5 hours, the tensile stress of the glass is increased, and the scratch resistance and the anti-drop performance of the glass are greatly reduced, so that the sodium salt strengthening time is controlled to be 1-5 hours. KNO (KNO) 3 The potassium ions and sodium ions are slowly exchanged and cannot reach the required depth when the temperature of the molten salt is lower than 380 ℃; KNO (KNO) 3 The temperature of the fused salt is higher than 450 ℃, so that the tensile stress of the glass is increased, and the scratch resistance and the anti-drop performance of the glass are greatly reduced, so that the strengthening temperature of the potassium salt is controlled to be 380-450 ℃. KNO (KNO) 3 If the molten salt strengthening time is less than 0.25h, the potassium ion and sodium ion exchange cannot reach the required depth, KNO 3 Molten salt strengthIf the melting time is more than 3 hours, the potassium ion and sodium ion exchange depth is too deep, and the effect of reducing the reflectivity is poor, so that the potassium salt strengthening time is controlled to be 0.25-3 hours.
In some embodiments, the aforementioned glass substrate is immersed in NaNO at 400-450 DEG C 3 Immersing in the molten salt for 2-5 hr, and immersing in KNO at 380-435 deg.C 3 And (3) 0.25-1.5h in molten salt. The low-reflectivity glass prepared by adopting the temperature range and the time range has lower reflectivity and better scratch resistance.
In some embodiments, the method for strengthening the glass substrate includes: immersing the glass substrate into the mixed molten salt at 400-470 ℃ for 4-8h; the mixed molten salt comprises 3-10% KNO 3 And 90-97% NaNO 3 。
The object of the present invention can be achieved by either a two-shot strengthening method or a hybrid strengthening method. When the mixed molten salt is adopted to strengthen the glass substrate, the ion exchange depth is too shallow when the temperature is too low or the time is too short, and the tensile stress of the glass is increased when the temperature is too high or the time is too long, so that the scratch resistance and the drop resistance of the glass are greatly reduced, and the temperature of the mixed molten salt is controlled to be 400-470 ℃ and the time is controlled to be 4-8h. The mixed molten salt is prepared from 3-10% KNO 3 And 90-97% NaNO 3 Composition is prepared. The low-reflectivity glass produced in this range has a lower reflectivity.
In some embodiments, the glass substrate is immersed in the mixed molten salt at 420-450 ℃ for ion exchange for 4-6 hours. The low-reflectivity glass produced in this range has lower reflectivity.
In some embodiments, the aforementioned strengthened glass has a 550nm reflectance of less than 8.1% at a thickness of 1.3 mm; the scratch width is less than 100 μm when the reinforced glass is loaded with 1 kg.
The invention also provides a screen cover plate, which comprises any one of the glass. The screen cover plate can be used on display screens of various electronic devices.
The invention also provides electronic equipment, which comprises the screen cover plate. The electronic equipment is electronic equipment with a screen, such as a mobile phone, a tablet personal computer, a vehicle navigation device and the like.
The invention will be further described with reference to specific examples, which are not to be construed as limiting the scope of the invention, but rather as falling within the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will now occur to those skilled in the art in light of the foregoing disclosure.
Unless otherwise indicated, materials, reagents, and the like referred to below are commercially available products well known to those skilled in the art; unless otherwise indicated, the methods are all methods well known in the art. Unless otherwise defined, technical or scientific terms used should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Examples 1 to 8
According to the proportion of each component in the table, raw materials corresponding to each component (the mass of each component is converted into the mass of oxide) are calculated and weighed, fully stirred and then put into a melting furnace, and glass with the thickness of 1.3mm is prepared after the processes of melting, clarifying, forming, annealing, cutting and the like. Measuring reflectivity F of glass 1 The values measured are shown in Table 1.
And (3) performing primary strengthening and secondary strengthening on the prepared glass substrate to obtain the strengthened glass. The primary strengthening method comprises the following steps: preheating glass substrate and immersing in 100% NaNO 3 Molten salt; the temperature and time duration of the one-time strengthening of each example are shown in Table 1. The secondary strengthening method comprises the following steps: preheating the glass substrate and immersing the glass substrate in 100% KNO 3 Molten salt; the temperature and duration of the secondary strengthening of each example are shown in Table 1. Measurement of reflectivity F of tempered glass in each example 2 The measured values are shown in Table 1, together with the scratch width at a load of 1 kg.
TABLE 1 raw materials, experimental parameters and glass Performance measurements for examples 1-8
Examples 9 to 16
According to the proportion of each component in the table, raw materials corresponding to each component (the mass of each component is converted into the mass of oxide) are calculated and weighed, fully stirred and then put into a melting furnace, and glass with the thickness of 1.3mm is prepared after the processes of melting, clarifying, forming, annealing, cutting and the like. Measurement of the reflectivity F of glass at 550nm 1 The values measured are shown in Table 2.
And mixing and strengthening the prepared glass substrate to obtain the strengthened glass. The method for mixing and strengthening comprises the following steps: preheating glass substrate and immersing in NaNO 3 And KNO 3 Is added to the mixed molten salt of (2); various examples NaNO in mixed molten salts 3 With KNO 3 The ratio of (2) is shown in Table 2; the temperature and duration of the blend reinforcement for each example are shown in Table 2. Measurement of reflectivity F of tempered glass of 550nm in each example 2 The measured values are shown in Table 2, together with the scratch width at a load of 1 kg.
TABLE 2 raw materials, experimental parameters and glass Performance measurements for examples 9-16
As a result of experiments in examples 1 to 16, it was found that the glass substrates having a thickness of 1.3mm produced in examples 1 to 16 had a reflectance F of 550nm 1 Less than 8.3%; after strengthening the obtained glass substrate, the reflectivity F of the strengthened glass at 550nm 2 Less than 8.1%, F 2 –F 1 More than 0.2%, and the strengthened glass has good scratch resistance, and the scratch width under the load of 1kg is less than 100 mu m.
Comparative example 1
Comparative example 1 differs from example 7 in that the mass of BeO is 0g and the mass of MgO is 1.7g.
Comparative example 2
Comparative example 2 differs from example 7 in that ZrO 2 Is 0g of SiO 2 The mass of (2) was 56.6g.
Comparative example 3
Comparative example 3 differs from example 7 in that the mass of BeO is 0g, zrO 2 Is 0g, mgO is 1.7g, siO 2 The mass of (2) was 56.6g.
Comparative example 4
Comparative example 4 differs from example 7 in that the mass of BeO is 3g, siO 2 The mass of (2) was 54.5g.
Comparative example 5
Comparative example 5 differs from example 7 in that ZrO 2 Is 3g of SiO 2 The mass of (2) was 53.6g.
The glass components of comparative examples 1-5 are summarized in Table 3. Comparative examples 1 to 5 have a thickness of 1.3mm and a reflectance F of 550nm 1 See, below.
TABLE 3 measurement results of raw materials and glass Properties of comparative examples 1 to 5
As can be obtained from comparative examples 1 to 3, the alkali metal oxide was changed from BeO to MgO, or ZrO was not added to the glass composition 2 The reflectivity of the glass increases.
As can be seen from comparative examples 4 to 5, beO or ZrO 2 Too much addition can make the glass very refractory and difficult to melt uniformly.
The technical features of the claims and/or the description of the present invention can be combined in a manner not limited to the combination of the claims by the relation of reference. The technical scheme obtained by combining the technical features in the claims and/or the specification is also the protection scope of the invention.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way, but any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. An aluminosilicate glass, characterized in that,
the glass component comprises the following components in terms of oxide: siO (SiO) 2 、Al 2 O 3 、Li 2 O、Na 2 O、ZrO 2 And BeO;
the mass percentage of the oxide is calculated as,
Li 2 O：4-7％；
Na 2 O：4-8％；
ZrO 2 :0.5-2%; and
BeO：0.5-2％。
2. the aluminosilicate glass according to claim 1, wherein,
ZrO 2 ：BeO＝1：0.3-1.3。
3. the aluminosilicate glass according to claim 1, wherein,
SiO 2 ：55-67％；
Al 2 O 3 :16-25%; and
B 2 O 3 ：2-6％。
4. the aluminosilicate glass according to claim 1, wherein,
K 2 O：0-3％；
MgO：0-3％；
CaO：0-1％；
SrO:0-2%; the method comprises the steps of,
ZnO：0-2％；
K 2 the contents of O, mgO, caO, srO and ZnO are not 0 at the same time.
5. The aluminosilicate glass according to claim 1, wherein the glass component comprises, in mass percent on an oxide basis, a total alkali metal oxide content M:10-14%, alkaline earth metal oxide total content N:1% -5%.
6. The aluminosilicate glass according to claim 4, wherein 0.3.ltoreq.Li 2 O/M is less than or equal to 0.6, and (M+N)/Al is less than or equal to 0.5 2 O 3 ≤1，0.2≤BeO/N≤1。
7. A strengthened glass, comprising:
a glass substrate which is the aluminosilicate glass of any one of claims 1-6;
the high-sodium reinforcement layer is arranged on the surface of the glass substrate; the high-sodium reinforcement layer is glass which exchanges part of lithium ions in the glass substrate with external sodium ions;
the high-potassium strengthening layer is arranged on the surface of the high-sodium strengthening layer; the high-potassium strengthening layer is glass which exchanges part of sodium ions with external potassium ions in the high-sodium strengthening layer.
8. A method for preparing reinforced glass is characterized in that,
strengthening the glass substrate to exchange lithium ions in the glass substrate with external sodium ions, wherein the exchange depth is d 1 The sodium ions are exchanged with the external potassium ions, and the exchange depth is d 2 Obtaining strengthened glass; wherein d 1 ＞d 2 。
9. A screen cover comprising the glass of any of claims 1-6.
10. An electronic device comprising the screen cover of claim 9.
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