CN117534321A - Aluminosilicate glass, preparation method thereof and glass product - Google Patents
Aluminosilicate glass, preparation method thereof and glass product Download PDFInfo
- Publication number
- CN117534321A CN117534321A CN202311399267.8A CN202311399267A CN117534321A CN 117534321 A CN117534321 A CN 117534321A CN 202311399267 A CN202311399267 A CN 202311399267A CN 117534321 A CN117534321 A CN 117534321A
- Authority
- CN
- China
- Prior art keywords
- glass
- aluminosilicate glass
- treatment
- aluminosilicate
- sio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 200
- 239000005354 aluminosilicate glass Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 13
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 23
- 230000008018 melting Effects 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 15
- 238000005728 strengthening Methods 0.000 claims description 15
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 230000002787 reinforcement Effects 0.000 claims description 3
- 239000006058 strengthened glass Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 26
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 25
- 238000005342 ion exchange Methods 0.000 description 13
- 239000000395 magnesium oxide Substances 0.000 description 13
- 230000035882 stress Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 230000035515 penetration Effects 0.000 description 10
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 10
- 230000007547 defect Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 9
- 230000006750 UV protection Effects 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910001887 tin oxide Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- 238000000265 homogenisation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 229910019092 Mg-O Inorganic materials 0.000 description 3
- 229910019395 Mg—O Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000006025 fining agent Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000005496 tempering Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910001432 tin ion Inorganic materials 0.000 description 2
- 239000005341 toughened glass Substances 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229930003316 Vitamin D Natural products 0.000 description 1
- QYSXJUFSXHHAJI-XFEUOLMDSA-N Vitamin D3 Natural products C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C/C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-XFEUOLMDSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- NCXOIRPOXSUZHL-UHFFFAOYSA-N [Si].[Ca].[Na] Chemical compound [Si].[Ca].[Na] NCXOIRPOXSUZHL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging 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
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000005347 annealed glass Substances 0.000 description 1
- 239000005328 architectural glass Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 210000001808 exosome Anatomy 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- -1 lithium aluminum silicon Chemical compound 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000019166 vitamin D Nutrition 0.000 description 1
- 239000011710 vitamin D Substances 0.000 description 1
- 150000003710 vitamin D derivatives Chemical class 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- 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
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The application relates to aluminosilicate glass, a preparation method thereof and a glass product. The aluminosilicate glass comprises the following preparation raw materials in percentage by mass: 55% -70% SiO 2 、15%~25%Al 2 O 3 、5%～10%Na 2 O、2%~8%Li 2 O、0～3%ZrO 2 、0～4%B 2 O 3 、0~3%K 2 O、1%～8%MgO、0.1%～3％TiO 2 、0～2％CeO 2 、0.01%～3%SnO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, (Al 2 O 3 +RO+Li 2 O）/（B 2 O 3 +SiO 2 ）≥0.4。
Description
Technical Field
The application relates to the technical field of glass production, in particular to aluminosilicate glass, a preparation method thereof and a glass product.
Background
Ultraviolet rays are light rays having a wavelength of 400nm to 10nm in an electromagnetic spectrum, and are classified into UVA (wavelength of 400nm to 320 nm), UVB (wavelength of 320nm to 280 nm), UVC (wavelength of 280nm to 100 nm) and EUV (wavelength of 100nm to 10 nm), wherein the carcinogenicity of UVA is strongest. Although proper amount of ultraviolet rays can promote the synthesis of vitamin D and sterilization of human body when irradiating the human body, excessive exposure to ultraviolet rays for a long time can cause aging and relaxation of skin, generate black spots and even cause cancer.
The integrity of transparent structural members such as portholes, aircraft cabins, etc. is closely related to flight safety and passenger riding comfort. Current aerospace transparencies comprise both laminated glass and glass-plastic composites. Among them, glass-plastic composite members have impact resistance and light weight, and are mainly used for bulletproof glass, bird strike resistant glass or special applications. At present, sodium-calcium-silicon glass is adopted as a glass material in the glass-plastic composite part, and the strength is lower. After the aluminosilicate glass is chemically strengthened, the mechanical properties of the glass are improved, wherein the float process is the preferred process for preparing the ultra-thick glass for aviation transparent parts, and the ultra-thick lithium aluminum silicon glass prepared by the conventional float glass has the problems of poor ultraviolet radiation resistance, more glass bubbles, serious tin adhesion on the lower surface layer of the glass and the like.
Thus, the conventional technology has yet to be improved.
Disclosure of Invention
Based on the above, it is necessary to provide an aluminosilicate glass, a preparation method thereof and a glass product, and the aim is to improve the ultraviolet resistance and mechanical properties of the aluminosilicate glass and reduce the tin adhering defect on the surface of the glass.
The application is realized by the following technical scheme:
in one aspect, the present application provides an aluminosilicate glass, wherein the aluminosilicate glass comprises the following raw materials in percentage by mass:
55%~70% SiO 2 、15%~25% Al 2 O 3 、5%～10% Na 2 O、2%~8% Li 2 O、0～3% ZrO 2 、0～4% B 2 O 3 、0~3% K 2 O、1%～8% MgO、0.1%～3％TiO 2 、0～2％CeO 2 、0.01%～3% SnO 2 the method comprises the steps of carrying out a first treatment on the surface of the Wherein, (Al 2 O 3 +RO+Li 2 O）/（B 2 O 3 +SiO 2 ）≥0.4。
In some embodiments, the aluminosilicate glass comprises the following preparation raw materials in percentage by mass:
58%~65% SiO 2 、16%~22% Al 2 O 3 、6%～9% Na 2 O、3%~6% Li 2 O、0～0.5% ZrO 2 、0～2% B 2 O 3 、0~2% K 2 O、3%～8% MgO、0.1%～3％TiO 2 、0～2％CeO 2 、0.1%～2% SnO 2 。
in some of these embodiments, 0.3. Ltoreq. TiO 2 +CeO 2 ≤3。
In some embodiments, the glass has a thickness of 2mm to 12mm.
In another aspect, the present application also provides a method for preparing aluminosilicate glass, comprising the steps of:
mixing the preparation raw materials of the aluminosilicate glass, so as to prepare a mixture;
and sequentially carrying out melting treatment, forming treatment, annealing treatment and chemical strengthening treatment on the mixture.
In some embodiments, the melt processing step satisfies at least one of conditions (a) - (b):
(a) The temperature of the melting treatment is 1500-1700 ℃;
(b) The time of the melting treatment is 5-8 hours.
In some embodiments, the annealing process is performed at a temperature of 600 ℃ to 700 ℃.
In some of these embodiments, the step of chemically strengthening treatment comprises the steps of: placing the annealed product into first molten salt, and performing first strengthening treatment to obtain first strengthened glass; the first molten salt comprises the following components in percentage by mass (0-50): potassium nitrate and sodium nitrate of (50 to 100);
placing the first reinforced glass in second molten salt, and performing second reinforcement treatment to prepare aluminosilicate glass; the second molten salt comprises potassium nitrate and sodium nitrate with the mass ratio of (90-100) to (0-10).
In some embodiments, the step of chemically strengthening treatment satisfies at least one condition of (c) - (d):
(c) The temperature of the first strengthening treatment is 400-450 ℃ and the time is 8-24 hours;
(d) The temperature of the second strengthening treatment is 400-420 ℃, and the time is 2-8 hours.
The aluminosilicate glass comprises raw materials of specific types and proportions, wherein, tiO 2 Can improve the melting characteristic of glass, reduce the high-temperature viscosity of the glass, improve the acid resistance of the glass, have good effect on ultraviolet resistance and prevent the glassThe glass is dyed by radiation, so that the problem that the glass is invalid due to the reduction of the transmittance of high-strength glass in a use environment can be effectively avoided; the tin oxide can release a large amount of oxygen, so that the growth of residual bubbles in the glass liquid is promoted, and finally the bubbles are discharged, and the glass homogenization process is effectively promoted. Due to Mg 2+ Smaller radius (0.076 nm), mg in glass 2+ With O 2- The coupling capability is strong, so that the Mg-O bond is strong, and the Mg is slowed down and reduced 2+ With Sn 2+ Rate at which ion exchange occurs, and Mg 2 + Radius and Sn 4+ Radius is equivalent, it can occupy a large amount of suitable Sn 4+ The solder enters the holes of the glass, so that the solder permeation is effectively prevented; by simultaneous control (Al 2 O 3 +RO+Li 2 O）/（B 2 O 3 +SiO 2 ) More than or equal to 0.4, the components are coordinated and matched through a specific proportioning relationship, so that the glass surface has higher surface stress and hardness and simultaneously has ultraviolet resistance, and when the glass product is applied to the preparation of the glass product, the scratch resistance and scratch resistance of the surface of the glass product can be improved, the tin penetration depth of the glass can be reduced, and the surface quality of the glass product can be improved.
The application also provides a glass product, which comprises the aluminosilicate glass or the aluminosilicate glass prepared by the preparation method of the aluminosilicate glass.
Drawings
FIG. 1 is a graph showing the transmittance results after ultraviolet radiation resistance of the glass sample of example 18.
Detailed Description
In order to facilitate an understanding of the present application, a more complete description of the present application will be provided below, along with preferred embodiments of the present application. This application may, however, be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. The indefinite articles "a" and "an" preceding an element or component in this application are not limited to the requirements of the number of elements or components (i.e. the number of occurrences). Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise. The meaning of "a plurality of" means at least two, e.g., two, three, etc., unless explicitly defined otherwise.
In this application, reference is made to a numerical interval (i.e., a numerical range), where the optional numerical distribution is considered continuous, and includes two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range, and each numerical value between the two numerical endpoints, unless otherwise indicated. Where a numerical range merely refers to integers within the numerical range, including both end integers of the numerical range, and each integer between the two ends, unless otherwise indicated, each integer is recited herein as directly, such as where t is an integer selected from 1-10, and where t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Further, when a plurality of range description features or characteristics are provided, these ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The temperature parameter in the present application is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations within a range such as + -5 ℃, + -4 ℃, + -3 ℃, + -2 ℃, + -1 ℃.
An embodiment of the application provides aluminosilicate glass, which comprises the following preparation raw materials in percentage by mass:
55%~70% SiO 2 、15%~25% Al 2 O 3 、5%～10% Na 2 O、2%~8% Li 2 O、0～3% ZrO 2 、0～4% B 2 O 3 、0~3% K 2 O、1%～8% MgO、0.1%～3％TiO 2 、0～2％CeO 2 、0.01%～3% SnO 2 the method comprises the steps of carrying out a first treatment on the surface of the Wherein, (Al 2 O 3 +RO+Li 2 O）/（B 2 O 3 +SiO 2 ）≥0.4。
In some of these embodiments, 0.4.ltoreq.Al (Al 2 O 3 +RO+Li 2 O）/（B 2 O 3 +SiO 2 ）≤4。
It is to be understood that when a range of values is disclosed herein, the range is to be regarded as continuous, and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
SiO is used as a material for the reaction of 2 The minimum value and the maximum value of the range of 55% -70% can be taken when the value range is 55% -70%, and each value between the minimum value and the maximum value. Specific examples include, but are not limited to, the point values in the embodiments: 55%, 55.1%, 55.2%, 55.3%, 55.4%, 55.5%, 55.6%, 55.7%, 55.8%, 55.9%, 56%, 56.1%, 56.2%, 56.3%, 56.4%, 56.5%, 56.7%, 56.8%, 56.9%, 57%, 57.1%, 57.2%, 57.3%57.4%, 57.5%, 57.6%, 57.7%, 57.8%, 57.9%, 58%, 58.1%, 58.2%, 58.3%, 58.4%, 58.5%, 58.6%, 58.7%, 58.8%, 58.9%, 59%, 59.1%, 59.2%, 59.3%, 59.4%, 59.5%, 59.6%, 59.7%, 59.8%, 59.9%, 60%, 60.1%, 60.2%, 60.3%, 60.4%, 60.5%, 60.6%, 60.7%, 60.8%, 60.9%, 61%, 61.1%, 61.2%, 61.3%, 61.4%, 61.5%, 61.6%, 61.7%, 61.8%, 61.9%, 62.1%, 62.2%, 62.3%, 62.4%, 62.5%, 62.6%, 62.7%, 62.8%, 62.9%, 63%, 63.1%, 63.2%, 63.3%, 63.4%, 63.6%. 63.7%, 63.8%, 63.9%, 64% >, 64.1%, 64.2%, 64.3%, 64.4%, 64.5%, 64.6%, 64.7%, 64.8%, 64.9%, 65%, 65.1%, 65.2%, 65.3%, 65.4%, 65.5%, 65.6%, 65.7%, 65.8%, 65.9%, 66%, 66.1%, 66.2%, 66.3%, 66.4%, 66.5%, 66.7%, 66.8%, 66.9%, 67.1%, 67.2%, 67.3%, 67.4%, 67.5%, 67.6%, 67.7%, 67.8%, 67.9%, 68%, 68.1%, 68.2%, 68.3%, 68.4%, 68.5%, 68.6%, 68.7%, 68.8%, 68.9%, 69.1%, 69.2%, 69.3%, 69.4%, 69.5%, 69.6%, 69.7%, 69.8%, 69.9%, or 70%. Or a range of any two of these values, including, by way of example: 60% -65%.
SiO 2 For the necessary composition, the glass is surrounded by silicon oxygen tetrahedra [ SiO ] 4 ]In the form of network forming components forming glass, which are the most critical chemical components in glass, density is 2.32g/cm 2 . When SiO 2 When the content is increased, the glass has high mechanical strength and good chemical resistance and chemical stability. SiO (SiO) 2 1713-1730 ℃ when following SiO 2 The content is increased, the melting temperature of the glass is increased, the melting temperature and the clarifying temperature are required to be higher, the preparation difficulty is increased, the glass defects (such as bubbles) are obviously increased, the mechanical strength of the glass is reduced, meanwhile, the compressive stress of the glass is reduced, and the requirement of the ultra-thick glass on high strength cannot be met. Too low SiO in glass 2 Can lead to inadequate chemical resistance and mechanical properties (e.g. modulus of elasticity) of the glass, so that SiO 2 The content is 55% -70%, more preferably 58% -65%.
Al 2 O 3 The value range of (2) is 15-25%, and 15-25% can be obtainedMinimum and maximum values of a range, and each value between such minimum and maximum values. Specific examples include, but are not limited to, 15%, 15.1%, 15.2%, 15.3%, 15.4%, 15.5%, 15.6%, 15.7%, 15.8%, 15.9%, 16%, 16.1%, 16.2%, 16.3%, 16.4%, 16.5%, 16.6%, 16.7%, 16.8%, 16.9%, 17%, 17.1%, 17.2%, 17.3%, 17.4%, 17.5%, 17.6%, 17.7%, 17.8%, 17.9%, 18%, 18.1%, 18.2%, 18.3%, 18.4%, 18.5%, 18.6%, 18.8%, 18.9%, 19%, 19.1%, 19.2%, 19.3%, 19.4% >. 19.5%, 19.6%, 19.7%, 19.8%, 19.9%, 20%, 20.1%, 20.2%, 20.3%, 20.4%, 20.5%, 20.6%, 20.7%, 20.8%, 20.9%, 21%, 21.1%, 21.2%, 21.3%, 21.4%, 21.5%, 21.6%, 21.7%, 21.8%, 21.9%, 22%, 22.1%, 22.2%, 22.3%, 22.4%, 22.5%, 22.6%, 22.7%, 22.8%, 22.9%, 23%, 24% >, 24.1%, 24.2%, 24.3%, 24.4%, 24.5%, 24.6%, 24.7%, 24.8%, 24.9% or 25%, or a range of any two of these values, including, by way of example: 16% -20%.
Al 2 O 3 For the necessary composition, it is an intermediate oxide with a density of 3.97g/cm 3 . When the content of alkali metal oxide in the glass is enough, the non-bridging oxygen and Al introduced by alkali metal 3+ Formation of AlO tetrahedra [ AlO ] 4 ]Improving mechanical strength (e.g. elastic modulus) and chemical stability of glass, and simultaneously aluminum oxide tetrahedron is more silicon oxide tetrahedron [ SiO ] 4 ]The volume is larger, larger gaps can be generated in the glass structure, the ion exchange is facilitated, and finally, a product with better chemical tempering effect is obtained, so that the high-strength glass target is realized. But Al is 2 O 3 The melting point is about 2050 ℃, belongs to extremely refractory oxide, can quickly improve the viscosity of glass, and causes the glass to be melted and clarified and the forming difficulty to be obviously increased, so that the defect contents of bubbles, glass ribs and the like in the glass are obviously increased, and the mechanical strength of the glass is reduced. Thus, al in glass 2 O 3 The content is determined to be 15% -25%, more preferably 16% -22%.
Na 2 The value range of O is 5% -10%, namely the minimum value and the maximum value of the range of 5% -10% can be taken, and each value between the minimum value and the maximum value. Specific examples include but are notLimited to 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.8%, 8.9%, 9%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8%, 9.9% or 10%, or a range of any two of these values, as examples, including: 5% -8%.
R 2 O is a monovalent alkali metal oxide, generally referred to as comprising Li 2 O、Na 2 O、K 2 O and the like belong to network outer bodies, play a role in breaking a network in a glass structure, promote glass melting, and are favorable for preparing high-quality ultra-thick glass. Na (Na) 2 O is an essential component, na in the glass 2 O is through Na + K in ions and fused salts + Ion exchange, forming high surface compressive stress on the glass, improving the mechanical strength of the glass, such as impact strength, bending strength and the like; meanwhile, the glass structure is used as a network outer body, and plays a role in breaking the network; but too much Na 2 O causes the deterioration of a series of properties such as chemical resistance, mechanical properties and the like of the glass, na of the present application 2 The content of O is controlled to be 5-10%. Preferably 6 to 9%.
Li 2 The value range of O is 2% -8%, namely the minimum value and the maximum value of the range of 2% -8% can be taken, and each value between the minimum value and the maximum value. Specific examples include, but are not limited to, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6.6%, 6.9%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.8%, or any two of these values including as examples or any two of these ranges of values. 4% -6%.
Li 2 O is an essential component, can obviously reduce the melting and clarifying temperature of glass, li + Has stronger field intensity and is beneficial toThe chemical stability is improved. Li (Li) 2 O is the key composition of glass for chemical strengthening when the glass contains NaNO 3 Li in molten salt + Ion and Na + In ion exchange, the glass is required to have Li high enough 2 O component, creating conditions for obtaining glass with high DOL value; but too high Li 2 O will make the glass easy to devitrify and devitrify, li in this application 2 O2% to 8%, more preferably 3% to 6%.
K 2 The value range of O is 0-3%, namely the minimum value and the maximum value of the range of 0-3% can be taken, and each value between the minimum value and the maximum value. Specific examples include, but are not limited to, 0, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, or 3%, or ranges of any two of these values, including, as examples: 1% -2%.
K 2 O is an optional component, K 2 O and Li 2 O、Na 2 O produces a 'mixed alkali effect' to improve the chemical stability of the glass, but K 2 The O content is too high to hinder ion exchange, and it is difficult to form glass having high surface compressive stress. Application K 2 The O content is 0 to 3%, more preferably 0 to 2%.
The MgO has a value ranging from 1% to 8%, i.e., a minimum value and a maximum value ranging from 1% to 8%, and each value between the minimum value and the maximum value. Specific examples include, but are not limited to, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6.6%, 6.7%, 6.8%, 6.9%, 7.7%, 7.1%, 7.7%, 7.8%, 7.7%, or any two of these examples of these values including the values or the values as two of these values: 1% -4%.
RO is a divalent positive alkaline earth metal oxide, generally known as CaO, mgO, znO, srO, baO, and can improve the chemical stability of glass compared with alkali metal oxides.
CaO belongs to an unnecessary composition, and is not beneficial to preparing high-quality glass because of larger erosion to refractory materials; meanwhile, ion exchange is blocked, the mechanical strength of the glass is reduced, and the CaO content in the glass is 0-1wt%, more preferably 0-0.5%.
MgO belongs to a necessary composition, can improve the mechanical property of the glass, can obviously improve the surface stress value of the glass after chemical strengthening of the glass, and realizes high-strength glass. In addition, the glass forming performance and the material property can be improved, and the preparation of the ultra-thick glass is facilitated. However, mgO has a melting point of 2800 ℃, which is difficult to melt, and excessive MgO has a defect, which is unfavorable for preparing high-quality ultra-thick glass. The MgO content of the present application is 1% to 8%, more preferably 3% to 8%.
B 2 O 3 The value range of (a) is "0-4%", i.e., the minimum and maximum values of the range of 0-4%, and each value between such minimum and maximum values. Specific examples include, but are not limited to, 0, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, or 4%, or a range of any two of these values, including, as examples: 2% -4%.
B 2 O 3 Belongs to a glass network forming body, has the melting point temperature of 450 ℃, can quickly reduce the glass melting temperature, is beneficial to preparing high-quality ultra-thick glass, and can improve the mechanical property and the chemical stability. But B is 2 O 3 Belongs to volatile components, is extremely easy to cause non-uniformity of glass components in the glass melting process, is unfavorable for preparing high-uniformity ultra-thick glass, and therefore, 0-4% of B is introduced 2 O 3 Preferably 0 to 2% of B 2 O 3 。
ZrO 2 The value range of (2) is "0-3%", i.e. the minimum value of the range of 0-3%A maximum value, and each value between such minimum and maximum values. Specific examples include, but are not limited to, 0, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, or 3%, or ranges of any two of these values, including, as examples: 1% -3%.
ZrO 2 Zirconium oxide forms zirconium oxide octahedra in glass for optional composition, and can improve the mechanical strength and chemical stability of glass. The zirconia has a melting temperature of 2700 ℃ and is an extremely refractory oxide, and the composition density is 5.89g/cm 3 The uneven glass components are easy to cause, so that the glass is difficult to melt and clarify, defects in the glass are increased, and the method is unfavorable for manufacturing high-quality ultra-thick glass. ZrO in glass 2 After the content is increased, the crystallization tendency of the glass is increased, and crystallization may occur in the glass during the preparation of the ultra-thick glass, resulting in a decrease in mechanical strength of the glass. Thus ZrO in glass 2 From 0 to 3%, more preferably from 0 to 0.5%.
TiO 2 The value range of (a) is 0.1% -3% "namely, the minimum value and the maximum value of the range of 0.1% -3% can be taken, and each value between the minimum value and the maximum value can be taken. Specific examples include, but are not limited to, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, or 3%, or a range of any two of these values, including, as examples: 1% -3%.
TiO 2 The glass belongs to a necessary composition, and belongs to network exosome oxide in silicate glass, so that the melting property of the glass can be improved, the high-temperature viscosity of the glass can be reduced, the components are not volatilized, and the acid resistance of the glass can be improved. The inventor finds out through a large number of experiments that the glass has good ultraviolet resistance, prevents glass from being dyed by radiation, and can effectively avoid the problem that the glass is invalid due to the reduction of the transmittance of high-strength glass in a use environment. But too high TiO content in the glass 2 Can lead to the coloring of the glass and reduce the glassTransmittance, tiO 2 The content is selected to be 0.1 to 3%, more preferably 0.3 to 2%.
CeO 2 The value range of (a) is "0-2%", i.e., the minimum and maximum values of the range of 0-2%, and each value between such minimum and maximum values. Specific examples include, but are not limited to, 0, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% or 2%, or a range of any two of these values, including, as examples: 1% -2%.
CeO 2 It is an unnecessary component and can prevent the glass from being colored by radiation. Too high CeO 2 Can color glass, reduce the transmittance of glass, thus CeO 2 The content is selected to be 0-2%.
SnO 2 The value range of (a) is 0.01% -3% "namely, the minimum value and the maximum value of the range of 0.01% -3% can be taken, and each value between the minimum value and the maximum value can be taken. Specific examples include, but are not limited to, 0, 0.01%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, or 3%, or a range of any two of these values, including, as examples: 1% -3%.
In some embodiments, fe in the glass 2 O 3 The content is less than 0.02%, more preferably less than 0.01%.
In some embodiments, the ion exchange layer depth of the glass is greater than 250 μm; the surface compressive stress of the glass is more than or equal to 850MPa.
In some embodiments, the ion exchange layer depth of the glass is greater than 300 μm; the surface compressive stress of the glass is more than or equal to 900MPa.
In some embodiments, the glass has a flexural strength of 750MPa or more.
The aluminosilicate glass comprises raw materials of specific types and proportions, wherein TiO 2 Can improve the melting property of glass, reduce the high-temperature viscosity of glass, improve the acid resistance of glass and resist ultravioletThe wire has good effect, prevents glass from being dyed by radiation, and can effectively avoid the problem that the glass is invalid due to the reduction of the transmittance of high-strength glass in the use environment; the clarifier can effectively discharge bubbles in glass, reduce glass defects, and release a large amount of oxygen by tin oxide, thereby promoting the growth of residual bubbles in glass liquid, finally discharging and effectively promoting the homogenization process of glass. Due to Mg 2+ Smaller radius (0.076 nm), mg 2+ Strong field, mg in glass 2+ And 0 to 2- The coupling capability is strong, so that the Mg-O bond is strong, and the Mg is slowed down and reduced 2+ With Sn 2+ Rate at which ion exchange occurs, and Mg 2 + Radius and Sn 4+ Radius is equivalent, it can occupy a large amount of suitable Sn 4+ The solder enters the holes of the glass, so that the solder permeation is effectively prevented; by simultaneous control (Al 2 O 3 +RO+Li 2 O）/（B 2 O 3 +SiO 2 ) Not less than 0.4, the components have higher surface stress and hardness and ultraviolet resistance through the coordination and coordination of specific proportioning relationship, and when the glass product is applied to the preparation of the glass product, the scratch resistance and scratch resistance of the surface of the glass product can be improved, the tin penetration depth of the glass can be reduced, and the surface quality of the glass product can be improved.
It will be appreciated that the glass of the present application contains a fining agent composition that is effective for removing bubbles from the glass and reducing glass defects, and that the fining agent composition includes tin oxide, stannous oxide or a mixture of the two, preferably the fining agent is stannous oxide. At low temperature, stannous oxide absorbs oxygen in the glass and becomes stannic oxide. Tin oxide SnO 2 Is a high-temperature oxidation-reduction clarifier, the tin oxide is gradually decomposed to generate stannous oxide at the temperature exceeding 1420 ℃, and is decomposed fully at the temperature of 1620-1680 ℃ and all oxygen is completely released, and the reaction equation is shown as the formula (1):
（1）
as can be seen from the formula (1), the molten glass is oxidized at 1620 to 1680 DEG CThe tin releases a large amount of oxygen, so that the growth of residual bubbles in the molten glass is promoted, and finally the bubbles are discharged, thereby effectively promoting the homogenization process of the glass. When the glass enters a tin bath for forming, the glass liquid spreads on the tin liquid, and finally forms glass sheets of 3 mm-8 mm. Studies have shown that MgO in aluminosilicate glasses has an effect on the depth of tin penetration in the glass tin bath. During the forming process of the glass tin bath, although N is introduced into the tin bath 2 And H 2 Shielding gas, but O 2 Inevitably enters, thereby causing Sn in the tin bath to be oxidized into Sn 2+ And Sn (Sn) 4+ Due to Sn 2+ Ratio Sn 4+ Has a large diffusion coefficient and Sn 2+ Alkaline earth metal ions (Ca) more readily associated with the surface of the glass melt 2+ 、Mg 2+ ) The plasma is ion exchanged, so that alkaline earth metal ions (Ca 2+ 、Mg 2+ ) And (3) transferring tin ions from the surface layer of the glass melt into the tin liquid, and diffusing tin ions from the tin liquid into the surface layer of the glass to form a tin-infiltrated layer on the surface of the glass. In the alkali metal oxide RO, due to Mg 2+ Smaller radius (0.076 nm), mg 2+ Strong field, mg in glass 2+ With O 2- The coupling capability is strong, so that the Mg-O bond is strong, and the Mg is slowed down and reduced 2+ With Sn 2+ Rate at which ion exchange occurs, thus Mg 2+ The diffusion capacity is relatively weak, ultimately leading to Sn 2+ The tin penetration depth is reduced. When Sn is 2+ Is easily oxidized into Sn after entering the glass body 4+ , Sn 4+ Smaller radius, sn 2+ To further enter the glass body, it is desirable to have suitable "holes" in the glass structure to provide ion exchange conditions. Mg of 2+ Radius and Sn 4+ Radius is equivalent, it can occupy a large amount of suitable Sn 4+ Enter the holes of the glass and effectively prevent the tin penetration. Therefore, the tin penetration depth of the surface layer of the glass is inhibited by increasing the content of magnesium oxide in the glass, and the tin adhesion of the surface of the glass is reduced. In addition, by introducing tin oxide, stannous oxide or a mixture of both into the glass, by increasing Sn in the glass 2+ And Sn (Sn) 4+ The content of tin liquid in the glass is reduced, and the tin liquid enters into the holes of the glass after being oxidized, so that the tin penetration depth of the glass is further inhibited, and the glass surface is reducedSurface tin sticking defects.
In some embodiments, the aluminosilicate glass comprises the following preparation raw materials in percentage by mass:
58%~65% SiO 2 、16%~22% Al 2 O 3 、6%～9% Na 2 O、3%~6% Li 2 O、0～0.5% ZrO 2 、0～2% B 2 O 3 、0~2% K 2 O、3%～8% MgO、0.1%～3％TiO 2 、0～2％CeO 2 、0.1%～2% SnO 2 。
in a specific example, the aluminosilicate glass comprises the following preparation raw materials in percentage by mass:
61.2% SiO 2 、19.5% Al 2 O 3 、4.8% Na 2 O、6.1% Li 2 O、1.5% B 2 O 3 、5.5% MgO、1%TiO 2 、0.4% SnO 2 。
in some of these embodiments, 0.3. Ltoreq. TiO 2 +CeO 2 ≤3。
In some embodiments, the aluminosilicate glass has a thickness of greater than or equal to 2mm.
An embodiment of the application also provides a preparation method of the aluminosilicate glass, which comprises the following steps S10-S20.
S10, mixing the preparation raw materials of the aluminosilicate glass to prepare a mixture.
And S20, sequentially carrying out melting treatment, forming treatment, annealing treatment and chemical strengthening treatment on the mixture to prepare the aluminosilicate glass.
In some of these embodiments, the temperature of the melt processing is 1500 ℃ to 1700 ℃.
In some embodiments, the time of the melting process is 5 h to 8h.
In some embodiments, the temperature of the annealing process is 600 ℃ to 700 ℃.
Optionally, the step of chemically strengthening treatment includes the following steps a, b:
step a: placing the annealed product into first molten salt, and performing first strengthening treatment to obtain first strengthened glass; the first molten salt comprises the following components in percentage by mass (0-50): potassium nitrate and sodium nitrate of (50 to 100);
step b: placing the first reinforced glass in second molten salt, and performing second reinforcement treatment to prepare aluminosilicate glass; the second molten salt comprises potassium nitrate and sodium nitrate with the mass ratio of (90-100) to (0-10).
In some embodiments, the temperature of the first strengthening treatment is 400 ℃ to 450 ℃ and the time is 8 hours to 24 hours.
In some embodiments, the temperature of the second strengthening treatment is 400-420 ℃ and the time is 2-8 hours.
In the preparation method of the aluminosilicate glass, the specific types and the proportions of the raw materials of the glass are regulated, wherein TiO is added 2 And CeO 2 Improving the ultraviolet radiation resistance of the glass; the tin oxide is added to release a large amount of oxygen, so that the growth of residual bubbles in the glass liquid is promoted, and finally the bubbles are discharged, and the glass homogenization process is effectively promoted; introduction of higher AL 2 O 3 And MgO, improve the mechanical strength of the glass, add SnO 2 And Li (lithium) 2 O, improving the melting and clarifying effects of the ultra-thick glass; by introducing high MgO and SnO 2 Effectively preventing tin penetration; simultaneous control (Al) 2 O 3 +RO+Li 2 O）/（B 2 O 3 +SiO 2 ) Not less than 0.4, the components have higher surface stress and hardness and ultraviolet resistance through the coordination and coordination of specific proportioning relationship, and when the glass product is applied to the preparation of the glass product, the scratch resistance and scratch resistance of the surface of the glass product can be improved, the tin penetration depth of the glass can be reduced, and the surface quality of the glass product can be improved.
An embodiment of the present application also provides a glass product, which includes the aluminosilicate glass described above or the aluminosilicate glass produced by the method for producing aluminosilicate glass described above.
When the aluminosilicate glass and the preparation method thereof are applied to preparing glass products, the aluminosilicate glass has excellent ultraviolet resistance and mechanical property, reduces the tin adhering defect on the surface of the glass, and can meet the use requirement of the glass products.
For the purpose of simplifying and clarifying the objects, technical solutions and advantages of the present application, the present application will be described with reference to the following specific examples, but the present application is by no means limited to these examples. The embodiments described below are only preferred embodiments of the present application and may be used to describe the present application and should not be construed as limiting the scope of the present application. It should be noted that any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application are intended to be included in the scope of the present application.
The present application is further illustrated below in conjunction with specific examples, which should not be construed as limiting the scope of the present application.
Example 1
(1) And (3) batching: the required raw materials are accurately weighed according to the glass component formula shown in table 1 and uniformly mixed to obtain a glass mixture.
(2) Melting: and (3) placing the mixture obtained in the step (1) in a platinum crucible, and placing the mixture in a 1650 ℃ condition for melting and clarifying for 6 hours.
(3) Shaping: the molten glass is poured into a forming table to form glass.
(4) Annealing: and (3) annealing the formed glass product at 550-600 ℃ for 240min, and cooling to room temperature along with a furnace.
(5) Sample preparation: and cutting the annealed glass by using a wire cutting machine, and polishing the surface of the glass by using an automatic polishing machine.
(6) Strengthening: placing the glass sample at 420 ℃ NaNO 3 Chemically tempering in molten salt for 8 hours to obtain first reinforced glass; placing the first tempered glass at 400 ℃ KNO 3 And chemically tempering in molten salt for 2h to obtain a tempered glass sample.
(7) The physical and chemical properties of the prepared glass samples were tested, and specific performance tests were as follows.
1. The density of the glass samples prepared in the examples and the comparative examples is tested, and specifically GB/T14901-2008 glass density determination sink-float comparison method is adopted.
2. The elastic modulus of the glass samples prepared in the examples and comparative examples was tested by JC/T678-1997 (2017) test methods for elastic modulus, shear modulus and Poisson's ratio of glass materials.
3. The transmittance of the glass samples obtained in examples and comparative examples was measured using GB/T2680-1994 "determination of visible transmittance, solar direct transmittance, solar total transmittance, ultraviolet transmittance and related glazing parameters for architectural glass".
4. The surface compressive stress of the glass samples prepared in the examples and comparative examples was measured by a surface stress meter using the principle of photoelastic measurement.
5. The ion exchange layer depths of the glass samples prepared in the examples and comparative examples were tested, and a scattered light stress meter based on the principle of the scattered light elasticity method was specifically adopted.
6. The glass samples prepared in the examples and comparative examples were tested for flexural strength, with specific reference to BS EN-1288.5 standard.
The specific results are shown in tables 1 to 7.
Examples 2 to 10
Examples 2 to 10 are substantially the same as example 1, except that the raw material formulation in table 1 is used.
Other conditions and parameters are shown in Table 2, and specific test results are shown in tables 2 to 3.
Examples 11 to 12
Examples 11 to 12 are substantially the same as example 1, except that the raw material formulation in table 1 is used.
Other conditions and parameters are shown in Table 2, and specific test results are shown in tables 2 to 3.
Examples 13 to 20
Examples 13 to 20 are basically the same as example 1, except that the aluminosilicate glass has a different thickness.
Other conditions and parameters were the same as in example 1, and specific test results are shown in Table 4.
Comparative examples 1 to 2
Comparative examples 1 to 2 are basically the same as example 1 except that: the raw material formulations of the glasses in comparative examples 1 to 2 are shown in Table 5.
Other conditions and parameters are shown in Table 6, and specific test results are shown in Table 7.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
Comparative examples 1 to 2 and the results thereof are shown in tables 5 to 7 below:
TABLE 5
TABLE 6
TABLE 7
From the data in tables 1 to 7, the tests of the aluminosilicate glasses produced in examples 1 to 20 and comparative examples 1 to 2 showed that: the softening point is 848-895 ℃, the annealing point is 617-658 ℃, the strain point is 568-599 ℃, the elastic modulus is 82.6 GPa-84.8 GPa, the transmittance is 90.2-91%, the reduction value of the ultraviolet radiation resistance transmittance is 0-0.2%, the surface compressive stress is 933-1112 MPa, the ion exchange layer depth 289-489 mu m, and the bending strength is 860-968 MPa. Compared with the aluminosilicate glass prepared by the comparative example, the aluminosilicate glass prepared by the technical scheme reduces the glass tin penetration depth, and the prepared glass has excellent ultraviolet resistance and mechanical properties and can meet the practical application of products.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples only represent a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the claims. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.
Claims (10)
1. The aluminosilicate glass is characterized by comprising the following preparation raw materials in percentage by mass:
55%~70% SiO 2 、15%~25% Al 2 O 3 、5%～10% Na 2 O、2%~8% Li 2 O、0～3% ZrO 2 、0～4% B 2 O 3 、0~3% K 2 O、1%～8% MgO、0.1%～3％TiO 2 、0～2％CeO 2 、0.01%～3% SnO 2 the method comprises the steps of carrying out a first treatment on the surface of the Wherein, (Al 2 O 3 +RO+Li 2 O）/（B 2 O 3 +SiO 2 ）≥0.4。
2. The aluminosilicate glass of claim 1, wherein the aluminosilicate glass is prepared from the following raw materials in mass percent:
58%~65% SiO 2 、16%~22% Al 2 O 3 、6%～9% Na 2 O、3%~6% Li 2 O、0～0.5% ZrO 2 、0～2% B 2 O 3 、0~2% K 2 O、3%～8% MgO、0.1%～3％TiO 2 、0～2％CeO 2 、0.1%～2% SnO 2 。
3. the aluminosilicate glass according to claim 1, wherein 0.3 +. 2 +CeO 2 ≤3。
4. The aluminosilicate glass of any one of claims 1-3, wherein the aluminosilicate glass has a thickness greater than or equal to 2mm.
5. The preparation method of the aluminosilicate glass is characterized by comprising the following steps:
mixing the raw materials for preparing the aluminosilicate glass according to any one of claims 1 to 4 to prepare a mixture;
and sequentially carrying out melting treatment, forming treatment, annealing treatment and chemical strengthening treatment on the mixture.
6. The method of producing aluminosilicate glass according to claim 5, wherein the melting treatment step satisfies at least one of the conditions (a) to (b):
(a) The temperature of the melting treatment is 1500-1700 ℃;
(b) The time of the melting treatment is 5-8 hours.
7. The method for producing aluminosilicate glass according to claim 5, wherein the annealing treatment is performed at a temperature of 600 ℃ to 700 ℃.
8. The method for producing aluminosilicate glass according to any one of claims 5 to 7, wherein the step of chemically strengthening treatment comprises the steps of: placing the annealed product into first molten salt, and performing first strengthening treatment to prepare first strengthened glass; the first molten salt comprises the following components in percentage by mass (0-50): potassium nitrate and sodium nitrate of (50 to 100);
placing the first reinforced glass in second molten salt, and performing second reinforcement treatment to prepare aluminosilicate glass; the second molten salt comprises potassium nitrate and sodium nitrate with the mass ratio of (90-100) to (0-10).
9. The method for producing aluminosilicate glass according to claim 8, wherein the step of chemically strengthening treatment satisfies at least one of the conditions (c) to (d):
(c) The temperature of the first strengthening treatment is 400-450 ℃ and the time is 8-24 hours;
(d) The temperature of the second strengthening treatment is 400-420 ℃ and the time is 2-8 hours.
10. A glass article comprising the aluminosilicate glass of any one of claims 1-4 or the aluminosilicate glass produced by the aluminosilicate glass production method of any one of claims 5-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311399267.8A CN117534321A (en) | 2023-10-26 | 2023-10-26 | Aluminosilicate glass, preparation method thereof and glass product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311399267.8A CN117534321A (en) | 2023-10-26 | 2023-10-26 | Aluminosilicate glass, preparation method thereof and glass product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117534321A true CN117534321A (en) | 2024-02-09 |
Family
ID=89794861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311399267.8A Pending CN117534321A (en) | 2023-10-26 | 2023-10-26 | Aluminosilicate glass, preparation method thereof and glass product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117534321A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615610A (en) * | 2019-10-10 | 2019-12-27 | 清远南玻节能新材料有限公司 | Lithium-zirconium aluminosilicate glass, tempered glass, preparation methods of lithium-zirconium aluminosilicate glass and tempered glass, and display device |
| CN110615611A (en) * | 2019-10-10 | 2019-12-27 | 清远南玻节能新材料有限公司 | Aluminosilicate glass, tempered glass, preparation method of aluminosilicate glass and display device |
| CN115108721A (en) * | 2022-05-30 | 2022-09-27 | 河北光兴半导体技术有限公司 | Composition for preparing high-aluminosilicate glass, and preparation method and application thereof |
| US20230227346A1 (en) * | 2020-07-08 | 2023-07-20 | Nippon Electric Glass Co., Ltd. | Glass, strengthened glass, and method for manufacturing strengthened glass |
-
2023
- 2023-10-26 CN CN202311399267.8A patent/CN117534321A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615610A (en) * | 2019-10-10 | 2019-12-27 | 清远南玻节能新材料有限公司 | Lithium-zirconium aluminosilicate glass, tempered glass, preparation methods of lithium-zirconium aluminosilicate glass and tempered glass, and display device |
| CN110615611A (en) * | 2019-10-10 | 2019-12-27 | 清远南玻节能新材料有限公司 | Aluminosilicate glass, tempered glass, preparation method of aluminosilicate glass and display device |
| US20230227346A1 (en) * | 2020-07-08 | 2023-07-20 | Nippon Electric Glass Co., Ltd. | Glass, strengthened glass, and method for manufacturing strengthened glass |
| CN115108721A (en) * | 2022-05-30 | 2022-09-27 | 河北光兴半导体技术有限公司 | Composition for preparing high-aluminosilicate glass, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102609966B1 (en) | Microcrystalline glass product and microcrystalline glass for electronic equipment cover plate | |
| US8298972B2 (en) | Low iron high transmission glass with boron oxide for improved optics, durability and refining, and corresponding method | |
| KR102128490B1 (en) | Ion Exchangeable Li-Containing Glass Compositions For 3-D Forming | |
| KR102341851B1 (en) | Hybrid Soda-Lime Silicate and Aluminosilicate Glass Articles | |
| US6831030B2 (en) | High transmittance glass sheet and method of manufacturing the same | |
| US11746039B2 (en) | Glass composition, low inclusion content glass, preparation method therefor and application thereof | |
| CN109608047A (en) | A kind of high-crystallinity sodium nepheline transparent glass-ceramics and preparation method thereof | |
| JP7244804B2 (en) | Li2O-Al2O3-SiO2-based crystallized glass | |
| CN114195393B (en) | Glass composition, microcrystalline glass, and preparation method and application thereof | |
| KR102667262B1 (en) | Glass materials and methods for manufacturing the same and products made therefrom | |
| CN103524042A (en) | Environment-friendly type high-transmission high-refractivity crystalline glass and preparation method thereof | |
| CN114380496B (en) | Glass composition, alkaline lithium aluminosilicate glass and application thereof | |
| CN109320072B (en) | High-aluminum low-calcium glass capable of being chemically strengthened | |
| CN113683303B (en) | Alkali aluminosilicate glass and application thereof | |
| WO2007106274A2 (en) | Method of making glass including use of boron oxide for reducing glass refiting time | |
| CN112919802A (en) | High-strength flexible radiation-resistant glass and preparation method thereof | |
| CN117534321A (en) | Aluminosilicate glass, preparation method thereof and glass product | |
| WO2022054739A1 (en) | Li2O-Al2O3-SiO2-BASED CRYSTALLIZED GLASS | |
| CN105236736A (en) | Aluminosilicate glass and preparation method thereof | |
| CN116023025B (en) | Aluminoborosilicate glass for ion exchange, preparation method and application thereof | |
| WO2022255198A1 (en) | Crystallized glass manufacturing method | |
| EP4067317B1 (en) | Multicomponent oxide glass, optical element, optical fiber, and method of producing multicomponent oxide glass | |
| JP2004075498A (en) | Oxide-based glass and its manufacturing method | |
| JP4370704B2 (en) | Glass coloring method | |
| WO2023084935A1 (en) | Li2o-al2o3-sio2-based crystallized glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |