CN113121109A - Blue-light-proof high-strength lithium aluminum silicon cover plate glass and preparation method and application thereof - Google Patents
Blue-light-proof high-strength lithium aluminum silicon cover plate glass and preparation method and application thereof Download PDFInfo
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- 239000005357 flat glass Substances 0.000 title claims abstract description 30
- -1 lithium aluminum silicon Chemical compound 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 22
- 230000008018 melting Effects 0.000 claims abstract description 22
- 238000003426 chemical strengthening reaction Methods 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 18
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 17
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 17
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 13
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims description 96
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 238000005728 strengthening Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- 238000005342 ion exchange Methods 0.000 claims description 17
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000005347 annealed glass Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000006060 molten glass Substances 0.000 claims description 4
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims description 4
- 229940111695 potassium tartrate Drugs 0.000 claims description 4
- 239000001472 potassium tartrate Substances 0.000 claims description 4
- 235000011005 potassium tartrates Nutrition 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000006059 cover glass Substances 0.000 claims 4
- 238000007517 polishing process Methods 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000005368 silicate glass Substances 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 230000002265 prevention Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 3
- 229910006735 SnO2SnO Inorganic materials 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 206010003694 Atrophy Diseases 0.000 description 1
- 101100220616 Caenorhabditis elegans chk-2 gene Proteins 0.000 description 1
- 208000002177 Cataract Diseases 0.000 description 1
- 239000006018 Li-aluminosilicate Substances 0.000 description 1
- 230000037444 atrophy Effects 0.000 description 1
- 210000000695 crystalline len Anatomy 0.000 description 1
- 208000002780 macular degeneration Diseases 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 210000001525 retina Anatomy 0.000 description 1
- 210000000844 retinal pigment epithelial cell Anatomy 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/02—Tempering or quenching glass products using liquid
- C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Theoretical Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the technical field of cover plate glass, in particular to blue-light-proof high-strength lithium aluminum silicon cover plate glass, which comprises the following raw materials in percentage by mass: SiO 2256％～70％，Al2O318％～23％，Li2O 2％～4％，Na2O 6％～15％，MgO 1％～10％，ZnO 0.5％～6％，ZrO21％～5％，CdS 0.05％～3％，CdSe 0.05％～2％，SnO20.6％～1.5％，K2O 0～8％，B2O30-5% of a reducing agent and 0.01-1% of a reducing agent. Also disclosesAccording to the preparation method, the blue-light-proof high-strength lithium aluminum silicate glass is prepared by mixing, melting, annealing, secondary color development and composite chemical strengthening, has a blue-light-proof effect, is suitable for screen protection materials of electronic equipment such as mobile phones and the like, and can effectively prevent the surface of a flat panel display product from being damaged by impact or scratch.
Description
Technical Field
The invention relates to the technical field of cover plate glass, in particular to blue-light-proof high-strength lithium aluminum silicon cover plate glass and a preparation method and application thereof.
Background
With the continuous improvement of the requirements of terminals on product performance, 3D and 3.5D glass processing technologies are nearly mature, the demand of high-end cover plate glass with strong anti-falling performance in the terminal market is continuously increased, and in addition, the expectation and the demand of consumers on 5G mobile phones, the demand of the market on glass with higher strength in the future is obviously increased. Meanwhile, with the rapid development of modern technologies, the use of various electronic screens in life adds a lot of brilliance to the life of people, but when people watch television, flat panel and mobile phone screens for a long time, fatigue and acerbity can be generated, because of the existence of too much short-wave blue light in the light source spectrum. Short-wave blue light with the wavelength of 400-450 nm has high energy, can penetrate through crystalline lens and directly reach retina, causes atrophy and even death of retinal pigment epithelial cells, and causes macular degeneration, cataract and the like.
To sum up, current electronic product, screen intensity is not high leads to easily appearing breakage, fish tail, influences life, and does not have and prevents blue light performance, consequently urgently needs to provide a prevent blue light high strength lithium aluminium silicon cover plate glass.
Disclosure of Invention
The invention aims to provide blue-light-proof high-strength lithium aluminum silicon cover plate glass and a preparation method thereof, and solves the problems that the existing glass is not enough in strength and does not have blue light prevention.
The invention also aims to provide application of the blue-light-proof high-strength lithium aluminum silicon cover plate glass.
The invention is realized by the following technical scheme:
the blue-light-proof high-strength lithium aluminum silicon cover plate glass comprises the following raw materials in percentage by mass:
SiO2 56％～70％，Al2O3 17％～23％，Li2O 2％～4％，Na2O 6％～15％，MgO 1％～10％，ZnO 0.5％～6％，ZrO2 1％～5％，CdS 0.05％～3％，CdSe 0.05％～2％，SnO2 0.6％～1.5％，K2O 0～8％，B2O30-5% of a reducing agent and 0.01-1% of a reducing agent.
Further, Li2O、Na2O and K2The total mass percentage of O is 8 to 23 percent.
Further, the reducing agent is at least one of carbon powder, potassium tartrate and long-chain fatty amine.
Further, ZrO2The mass percentage of (B) is 2-4%.
Furthermore, the surface compressive stress of the blue-light-proof high-strength lithium aluminum silicon cover plate glass is 725.4-890.2 MPa, the depth of an ion exchange layer is 110.8-130.1 um, and the falling-resistant height is 1.05-1.4 m.
Further, the raw materials comprise the following components in percentage by mass: SiO 22 70％，Al2O3 18％，Li2O 2％，Na2O 6％，B2O3 0.79％，MgO 1％，ZnO 0.5％，ZrO2 1％，CdS 0.05％，CdSe 0.05％，SnO20.6 percent and 0.01 percent of carbon powder.
The invention also discloses a preparation method of the blue-light-proof high-strength lithium aluminum silicon cover plate glass, which comprises the following steps:
(1) mixing materials: weighing the raw materials according to the weight ratio, and then fully mixing to form a batch;
(2) melting: heating a muffle furnace to 900-1300 ℃, adding the batch into a platinum crucible, then placing the platinum crucible into the muffle furnace, heating to 1500-1680 ℃, and preserving heat for 4-6 hours to obtain glass liquid;
(3) annealing: pouring molten glass into a mold, and after the glass is molded and demoulded, putting the glass into an annealing furnace for annealing, wherein the annealing temperature is controlled to be 550-650 ℃;
(4) secondary color development treatment: heating the annealed glass to 550-620 ℃, preserving heat for 2-5 hours, and then cooling to room temperature;
(5) and (3) pretreating the cooled glass, and then carrying out chemical strengthening to obtain the blue-light-proof high-strength lithium aluminum silicon cover plate glass.
Further, the pretreatment comprises slicing, CNC, grinding and polishing.
Further, the fused salt for the first chemical strengthening is 50 to 75 percent of NaNO3And 25 to 50 percent of KNO3The strengthening temperature of the prepared salt is 380-430 ℃, and the strengthening time is 120-240 min;
the molten salt for the second chemical strengthening is KNO with the concentration of 90-100 percent3And 0 to 10% of NaNO3The strengthening temperature of the prepared salt is 380-430 ℃, and the strengthening time is 30-60 min.
The invention also discloses application of the blue-light-proof high-strength lithium aluminum silicon cover plate glass as a screen protection material in preparation of a display screen.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses blue light prevention high-strength lithium aluminum silicon cover plate glass, which comprises the following raw materials of SiO2、Al2O3、Li2O、Na2O、MgO、ZnO、ZrO2、CdS、CdSe、SnO2、K2O and B2O3。SiO2Is an important glass network former oxide, the structure of the silicon-oxygen tetrahedron of which forms an irregular continuous network and forms the framework of the glass, if SiO2At lower contents, the stability of the glass is reduced, but SiO2Too high content leads to increase in viscosity of the glass, causes difficulty in melting and refining of the glass, and requires control of the content within a suitable range, and therefore SiO2The content of (A) is 56-70%; al (Al)2O3Is an intermediate oxide which participates in the formation of a glass network and plays a role of a network formation body, the intrinsic strength of the glass can be improved by increasing the content of the intermediate oxide, and the ion exchange is facilitated during the chemical strengthening, but the viscosity of the glass is increased by excessively increasing the content of the intermediate oxide, so that the glass is difficult to melt, therefore, Al2O3The content is controlled to be 17-23 percent; b is2O3Is a network-forming bulk oxide which can improve glassHas good fluxing property, can reduce the high-temperature viscosity of the glass, accelerate the melting and clarification of the glass, improve the chemical stability of the glass and simultaneously improve the mechanical property of the glass, but B2O3The content of more than 5% inhibits the ion exchange depth of the glass, so that B2O3The content is controlled below 5 percent; li2O、Na2O、K2O is a network exo-oxide, and can relax and break a network formed by silicon-oxygen tetrahedrons after being introduced, so that the glass viscosity is reduced, the melting temperature is reduced, and the glass can be used as a fluxing agent; meanwhile, the content of alkali metal oxide in the glass has great influence on ion exchange. Li2O is an exchange ion in the first step of chemical strengthening and can be mixed with Na with larger ionic radius in the molten salt+、K+Carrying out exchange; but too high Li2O disrupts the network structure of the glass, reduces the mechanical properties of the glass and increases the tendency of the glass to devitrify, so Li2The content of O is 2 to 4 percent; na (Na)2O content of less than 6% causes difficulty in melting glass and poor exchange effect, and Na2The O content increases and the thickness of the ion exchange layer increases, but Na2The content of O exceeds 15%, the chemical stability of the glass is lowered, and therefore Na2The content of O is 6 to 15 percent; k2O is a component for improving ion exchange performance, can effectively increase the thickness of the compressive stress layer, and can react with Na2O produces a "mixed base" effect, and in addition K2O also reduces the high temperature viscosity, improves the melting and formability of the composition, and reduces devitrification, but not too much, reduces the chemically strengthened CS, and thus K2The content of O is controlled below 8 percent. MgO and ZnO are network exo-oxides which play a role in breaking networks in a glass structure, and a certain amount of MgO is introduced to relax and break the network formed by silicon-oxygen tetrahedrons, so that the melting of the glass can be promoted, the melting temperature of the glass is reduced, when the mass percentage of MgO is not more than 10%, the melting point of the glass is reduced, the crystallization tendency and the crystallization speed of the glass can be reduced, and the chemical stability of the glass is improved. When MgO and ZnO are used in combination, they appear similar to a mixed baseThe law of soil effect is helpful for realizing ion exchange. ZrO (ZrO)2Is an intermediate oxide, can improve the chemical stability of the glass, increase the surface hardness of the glass, and resist the formation and propagation of cracks on the glass, thereby making the glass more resistant to scratches and dropping, but ZrO2When the content of (A) is too high, not only the tendency of crystallization of the glass is increased, but also the melting temperature of the glass is increased, so that ZrO2The content of (A) is 1 to 5 percent. According to the invention, the content of CdS is 0.05-3%, the content of CdSe is 0.05-2%, and the wavelength range of blue light prevention is regulated and controlled by controlling the mass ratio of the CdS to the CdSe; SnO2SnO is a main refining agent in the process of preparing glass2The content of (A) is designed to be 0.6-1.5%.
Further, Li2O、Na2O and K2The total mass percent of O is controlled to be 8-23%, the viscosity of the glass can be reduced, and the chemical strengthening ion exchange is facilitated.
The invention also discloses a preparation method of the blue-light-proof high-strength lithium aluminum silicon cover plate glass, which comprises the steps of mixing, melting, annealing, secondary color development treatment and composite chemical strengthening to prepare the blue-light-proof high-strength lithium aluminum silicon glass.
The blue light prevention high-strength lithium aluminum silicon cover plate glass disclosed by the invention has a blue light prevention effect, is suitable for screen protection materials of electronic equipment such as mobile phones and the like, and can effectively prevent the surface of a flat panel display product from being impacted or scratched and damaged.
Detailed Description
The invention discloses blue-light-proof high-strength lithium aluminum silicon cover plate glass which comprises the following raw materials in percentage by mass (wt%): SiO 22 56％～70％，Al2O3 18％～23％，Li2O 2％～4％，Na2O 6％～15％，MgO 1％～10％，ZnO 0.5％～6％，ZrO2 1％～5％，CdS 0.05％～3％，CdSe 0.05％～2％，SnO2 0.6％～1.5％，K2O 0～8％，B2O30-5% of a reducing agent and 0.01-1% of a reducing agent.
The reducing agent can adopt at least one of carbon powder, potassium tartrate and long-chain fatty amine.
The following discusses the specific contents and effects of the components in the above-mentioned lithium aluminosilicate glass, that is, the reason for limiting the content range of each component, the units are mass percentages.
SiO2Is an important glass network former oxide, and the structure of silicon-oxygen tetrahedron forms irregular continuous network to form the framework of the glass. If SiO2Lower content, reduced glass stability, SiO2The content of (A) can improve the mechanical strength, chemical stability and thermal stability of the glass; but SiO2Too high a content also leads to an increase in viscosity of the glass, which causes difficulty in melting and refining the glass, and the content thereof needs to be controlled within a suitable range, so that SiO2The content of (A) is 56-70%.
Al2O3Is an intermediate oxide which participates in the formation of a glass network and plays a role of a network formation body, the intrinsic strength of the glass can be improved by increasing the content of the intermediate oxide, and the ion exchange is facilitated during the chemical strengthening, but the viscosity of the glass is increased by excessively increasing the content of the intermediate oxide, so that the glass is difficult to melt, therefore, Al2O3The content is controlled to be 17-23%.
B2O3Is a network-generated oxide which can improve a series of properties of the glass, has good fluxing property, can reduce the high-temperature viscosity of the glass, accelerate the melting and clarification of the glass, improve the chemical stability of the glass and simultaneously improve the mechanical properties of the glass, but B2O3The content of more than 5% inhibits the ion exchange depth of the glass, so that B2O3The content is controlled to be 0-5%.
Li2O、Na2O、K2O is a network exo-oxide, and can relax and break the network formed by silicon-oxygen tetrahedron after being introduced, thereby being beneficial to reducing the viscosity of glass and lowering the melting temperature, and therefore, the O can be used as a fluxing agent. Meanwhile, the content of alkali metal oxide in the glass has great influence on ion exchange. Li2O is an exchange ion in the first step of chemical strengthening and can be mixed with Na with larger ionic radius in the molten salt+、K+Carrying out exchange; but too high Li2O disrupts the network structure of the glass, reduces the mechanical properties of the glass and increases the tendency of the glass to devitrify, so Li2The content of O is 2-4%. Na (Na)2When the O content is less than 6%, the glass is difficult to melt and the exchange effect is poor. Na (Na)2The O content increases and the thickness of the ion exchange layer increases, but Na2When the O content exceeds 15%, the chemical stability of the glass is lowered. K2O is a component for improving ion exchange performance, can effectively increase the thickness of the compressive stress layer, and can react with Na2O produces a "mixed base" effect. In addition K2O is also a component for lowering the high-temperature viscosity and improving the meltability and formability, and can lower the devitrification property, but cannot be added too much.
MgO and ZnO are network exo-oxides which play a role in breaking the network in the glass structure, and a certain amount of the oxides can relax and break the network formed by the silicon-oxygen tetrahedron, promote the melting of the glass and reduce the melting temperature of the glass. When the mass percentage of MgO is less than 10%, the melting point of the glass is reduced, the crystallization tendency and the crystallization speed of the glass can be reduced, and the chemical stability of the glass is improved. When MgO and ZnO are used in combination, the law similar to the 'mixed alkaline earth effect' appears between the MgO and ZnO, which is helpful for realizing ion exchange.
ZrO2Is an intermediate oxide, can improve the chemical stability of the glass, increase the surface hardness of the glass, and resist the formation and propagation of cracks on the glass, thereby making the glass more resistant to scratches and dropping, but ZrO2When the content of (A) is too high, not only the tendency of crystallization of the glass is increased, but also the melting temperature of the glass is increased, so that ZrO2The content of (A) is 1 to 5 percent.
According to the invention, the content of CdS is 0.05-3%, the content of CdSe is 0.05-2%, and the wavelength range of blue light prevention is regulated and controlled by controlling the mass ratio of the CdS to the CdSe.
SnO2SnO is a main refining agent in the process of preparing glass2The content of (A) is 0.6-1.5%.
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
The invention discloses a preparation method of blue-light-proof high-strength lithium aluminum silicon cover plate glass, which specifically comprises the following steps:
(1) weighing: in mass percent, according to SiO2 70％，Al2O3 18％，Li2O 2％，Na2O 6％，B2O30.79％，MgO 1％，ZnO 0.5％，ZrO2 1％，CdS 0.05％，CdSe 0.05％，SnO20.6 percent of carbon powder and 0.01 percent of carbon powder;
(2) mixing materials: accurately weighing the raw materials according to the weight ratio, and fully mixing the raw materials by using a mixer to form a batch;
(3) melting: heating a muffle furnace to 1300 ℃, adding the obtained batch into a platinum crucible with a platinum cover, then placing the platinum crucible into the muffle furnace, heating to 1680 ℃, and preserving heat for 6 hours to obtain glass liquid;
(4) annealing: pouring molten glass into a mold on a stainless steel plate, and annealing in an annealing furnace after the glass is formed and demolded, wherein the annealing temperature is controlled at 620 ℃;
(5) secondary color development treatment: and (3) carrying out secondary color development treatment on the annealed glass, namely reheating the glass to 620 ℃, preserving the heat for 3 hours, and then cooling the glass to room temperature along with the furnace after power failure.
(6) Carrying out chemical strengthening twice after the glass prepared in the step (5) is processed by slicing, CNC (computer numerical control), grinding, polishing and the like, wherein the molten salt for the first chemical strengthening is 75% of NaNO3And 25% KNO3The strengthening temperature of the prepared salt is 410 ℃, and the strengthening time is 140 min; the molten salt for the second chemical strengthening is KNO with the concentration of 100 percent3The strengthening temperature is 390 ℃, and the strengthening time is 30 min.
Proved by verification, the surface compressive stress of the blue-light-proof high-strength lithium aluminum silicon cover plate glass prepared by the embodiment is 890.2MPa, the depth of an ion exchange layer is 130.1um, and the falling-resistant height is 1.4 m.
Example 2
The invention discloses a preparation method of blue-light-proof high-strength lithium aluminum silicon cover plate glass, which specifically comprises the following steps:
(1) weighing: in mass percent, according to SiO2 56％，Al2O3 23％，Li2O 4％，Na2O 6％，K2O 0.5％，MgO 1.5％，ZnO 2％，ZrO2 3％，CdS 1％，CdSe 1％，SnO21 percent and 1 percent of potassium tartrate;
(2) mixing materials: accurately weighing the raw materials according to the weight ratio, and fully mixing the raw materials by using a mixer to form a batch;
(3) melting: heating a muffle furnace to 900 ℃, adding the obtained batch into a platinum crucible with a platinum cover, then placing the platinum crucible into the muffle furnace, heating to 1500 ℃, and preserving heat for 4 hours to obtain glass liquid;
(4) annealing: pouring molten glass into a mold on a stainless steel plate, and after the glass is molded and demoulded, putting the glass into an annealing furnace for annealing, wherein the annealing temperature is controlled at 550 ℃;
(5) secondary color development treatment: and (3) carrying out secondary color development treatment on the annealed glass, namely reheating the glass to 550 ℃, preserving the heat for 2 hours, and then cooling the glass to room temperature along with the furnace after power failure.
(6) Carrying out chemical strengthening twice after the glass prepared in the step (5) is processed by slicing, CNC (computer numerical control), grinding, polishing and the like, wherein the fused salt obtained by the first chemical strengthening is 50% of NaNO3And 50% KNO3The strengthening temperature of the prepared salt is 380 ℃, and the strengthening time is 120 min; the molten salt for the second chemical strengthening is KNO with the concentration of 90 percent3And 10% NaNO3The strengthening temperature is 380 ℃, and the strengthening time is 60 min.
Proved by verification, the surface compressive stress of the blue-light-proof high-strength lithium aluminum silicon cover plate glass prepared by the embodiment is 838.5MPa, the depth of an ion exchange layer is 121.4um, and the falling-resistant height is 1.25 m.
Example 3
The procedure was as in example 1, with the parameters used referring to the data in the table, as shown in table 1. The reducing agent is long-chain aliphatic amine.
The first-time chemical strengthening molten salt is 60 percent of NaNO3And 40% KNO3The strengthening temperature of the prepared salt is 430 ℃, and the strengthening time is 240 min; the molten salt for the second chemical strengthening is 95 percent KNO3And 5% NaNO3The strengthening temperature is 430 ℃ and the strengthening time is 30 min.
The remaining examples are the same as the procedure of example 1, with the parameters used being referred to the data in the table, as shown in table 1.
TABLE 1
Claims (10)
1. The blue-light-proof high-strength lithium aluminum silicon cover plate glass is characterized in that the glass comprises the following raw materials in percentage by mass:
SiO2 56％～70％，Al2O3 17％～23％，Li2O 2％～4％，Na2O 6％～15％，MgO 1％～10％，ZnO 0.5％～6％，ZrO2 1％～5％，CdS 0.05％～3％，CdSe 0.05％～2％，SnO2 0.6％～1.5％，K2O 0～8％，B2O30-5% of a reducing agent and 0.01-1% of a reducing agent.
2. The high-strength lithium aluminum silicon cover glass for preventing blue light according to claim 1, wherein Li2O、Na2O and K2The total mass percentage of O is 8 to 23 percent.
3. The blue-light-proof high-strength lithium aluminum silicon cover plate glass as claimed in claim 1, wherein the reducing agent is at least one of carbon powder, potassium tartrate and long-chain aliphatic amine.
4. The high-strength lithium aluminum silicon cover glass for preventing blue light according to claim 1, wherein ZrO 2 is present in the cover glass2The mass percentage of (B) is 2-4%.
5. The blue-light-proof high-strength lithium aluminum silicon cover plate glass according to claim 1, characterized in that the surface compressive stress of the blue-light-proof high-strength lithium aluminum silicon cover plate glass is 725.4-890.2 MPa, the depth of an ion exchange layer is 110.8-130.1 um, and the drop-resistant height is 1.05-1.4 m.
6. The blue-light-proof high-strength lithium aluminum silicon cover plate glass according to claim 1, characterized in that the raw materials comprise the following components in percentage by mass: SiO 22 70％，Al2O3 18％，Li2O 2％，Na2O 6％，B2O3 0.79％，MgO 1％，ZnO 0.5％，ZrO2 1％，CdS 0.05％，CdSe 0.05％，SnO20.6 percent and 0.01 percent of carbon powder.
7. The preparation method of the blue-light-proof high-strength lithium aluminum silicon cover plate glass as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
(1) mixing materials: weighing the raw materials according to the weight ratio, and then fully mixing to form a batch;
(2) melting: heating a muffle furnace to 900-1300 ℃, adding the batch into a platinum crucible, then placing the platinum crucible into the muffle furnace, heating to 1500-1680 ℃, and preserving heat for 4-6 hours to obtain glass liquid;
(3) annealing: pouring molten glass into a mold, and after the glass is molded and demoulded, putting the glass into an annealing furnace for annealing, wherein the annealing temperature is controlled to be 550-650 ℃;
(4) secondary color development treatment: heating the annealed glass to 550-620 ℃, preserving heat for 2-5 hours, and then cooling to room temperature;
(5) and (3) pretreating the cooled glass, and then carrying out chemical strengthening to obtain the blue-light-proof high-strength lithium aluminum silicon cover plate glass.
8. The method of claim 7, wherein the pre-treatment comprises slicing, CNC, grinding and polishing processes.
9. The preparation method according to claim 7, wherein the first-time chemically strengthened molten salt is 50-75% NaNO3And 25 to 50 percent of KNO3The strengthening temperature of the prepared salt is 380-430 ℃, and the strengthening time is 120-240 min;
the molten salt for the second chemical strengthening is KNO with the concentration of 90-100 percent3And 0 to 10% of NaNO3The strengthening temperature of the prepared salt is 380-430 ℃, and the strengthening time is 30-60 min.
10. The use of the blue-light resistant high-strength lithium aluminum silicon cover glass according to any one of claims 1 to 6 as a screen protection material in the preparation of a display screen.
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