CN115321816A - High-aluminosilicate glass and preparation method and application thereof - Google Patents
High-aluminosilicate glass and preparation method and application thereof Download PDFInfo
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- 239000005354 aluminosilicate glass Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 113
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 37
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 17
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004327 boric acid Substances 0.000 claims abstract description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 15
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 15
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 15
- 239000004576 sand Substances 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 64
- 239000000843 powder Substances 0.000 claims description 64
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 31
- 238000002844 melting Methods 0.000 claims description 23
- 230000008018 melting Effects 0.000 claims description 23
- 239000000395 magnesium oxide Substances 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 16
- 239000011787 zinc oxide Substances 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 239000008187 granular material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000006060 molten glass Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 description 10
- 239000005368 silicate glass Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000004554 molding of glass Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- -1 therefore Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K5/00—Casings, cabinets or drawers for electric apparatus
- H05K5/02—Details
- H05K5/03—Covers
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to high-aluminosilicate glass and a preparation method and application thereof. The high-aluminosilicate glass comprises the following raw materials in percentage by mass: 48 to 59 percent of silica sand, 9.8 to 20.5 percent of alumina, 0 to 4.5 percent of aluminum hydroxide, 0.5 to 13.1 percent of lithium carbonate, 6 to 14.5 percent of soda ash, 6 to 14.5 percent of potassium carbonate, 1 to 4.5 percent of magnesium hydroxide, 0.2 to 4.5 percent of boric acid and water. Wherein the viscosity index S = (0.7 XM) Aluminum hydroxide +1×M Magnesium hydroxide +3×M Boric acid +1.1×M Lithium carbonate +1.8×M Soda ash +2.8×M Potassium carbonate ‑0.5×M Silica sand ‑0.3×M Aluminum oxide )/M Water (W) The high aluminosilicate glass satisfies: s is more than or equal to 2 and less than or equal to 4.
Description
Technical Field
The invention relates to the technical field of glass products, in particular to high-aluminosilicate glass and a preparation method and application thereof.
Background
High aluminosilicate glass generally refers to silicate glass with mass content of more than 6%, has the characteristics of high strength, good wear resistance, good permeability, chemical stability and the like, and is widely applied to various consumer electronics products as protective glass. In the traditional preparation method of the high-aluminosilicate glass, raw materials usually enter a melting furnace in a powdery state, but the powdery raw materials are easily blown up by flame and fly away, so that a regenerative chamber is blocked, refractory materials of the furnace can be corroded, and the service life of the furnace is shortened. In order to prolong the service life of the melting furnace, the mixing of the ultrafine powder in the raw materials is generally strictly limited, and the ultrafine powder in the raw materials is screened and removed before entering the melting furnace, so that high-cost glass raw materials such as lithium carbonate, soda ash, borax and the like are wasted, and the waste ultrafine powder of the raw materials can seriously pollute the environment.
Disclosure of Invention
Based on this, it is necessary to provide a high aluminosilicate glass which is easy to form and convenient to prepare, and a preparation method and applications thereof.
In one aspect of the invention, the invention provides high aluminosilicate glass, which comprises raw material powder and water; the raw material powder comprises the following components in percentage by mass:
wherein the viscosity index S = (0.7 XM) Aluminum hydroxide +1×M Magnesium hydroxide +3×M Boric acid +1.1×M Lithium carbonate +1.8× M Soda ash +2.8×M Potassium carbonate -0.5×M Silica sand -0.3×M Alumina oxide )/M Water (I) M represents the mass percentage of the corresponding raw materials in the high-aluminosilicate glass; the high aluminosilicate glass satisfies: s is more than or equal to 2 and less than or equal to 4.
In some of these embodiments, the feedstock powder further comprises magnesium oxide; the mass percentage of the magnesium oxide in the raw material powder is 0.6-4.5%.
In some embodiments, the raw material powder further comprises zinc oxide; the mass percentage of the zinc oxide in the raw material powder is not more than 2%.
In some embodiments, the raw powder further comprises zirconia; the mass percentage of the zirconia in the raw material powder is 0.2-4%.
In some of these embodiments, the feedstock does not contain a binder.
In some embodiments, the composition comprises, in mass percent based on oxides:
in some of these embodiments, the composition further includes ZrO based on the oxide 2 (ii) a In the high aluminosilicate glass, the ZrO 2 The mass percentage of the component (A) is 0.2-4%.
In some of these embodiments, the composition further comprises ZnO, on an oxide basis; in the high-aluminosilicate glass, the mass percentage of ZnO is not more than 2%.
In another aspect of the present invention, a method for preparing a high aluminosilicate glass is provided, which comprises the following steps:
mixing the raw materials of the high-aluminosilicate glass, pressing and preparing blocky granules;
melting the block-shaped granulation body to prepare glass liquid; and
and forming the molten glass, and carrying out annealing treatment to prepare the high-aluminosilicate glass.
In some of these embodiments, the bulk granulation satisfies at least one of the following conditions:
(1) The bulk density of the block-shaped granules is 1.9g/cm 3 ～2.1g/cm 3 ；
(2) The block-shaped granules have a crushing resistance of 35 to 42kgf.
In another aspect of the present invention, an electronic product is further provided, which includes a body and a glass cover plate embedded in the body, where the glass cover plate is the above-mentioned high aluminosilicate glass.
The raw materials of the high-aluminosilicate glass comprise aluminum hydroxide, lithium carbonate, soda ash, potassium carbonate, magnesium hydroxide, boric acid, water and the like, the viscosity index S is more than or equal to 2 and less than or equal to 4, the raw materials have better bonding effect after being hydrated and can be pressed into block-shaped materials, so that the use efficiency of the high-aluminosilicate glass raw materials can be improved, and the preparation is convenient. Moreover, the high-aluminosilicate glass has high transmittance, bright color and less bubbles, and is particularly suitable for cover plate glass of electronic products.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The present invention may 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 invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features. The terms "comprising" and "including" as used herein mean open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range and each value between the minimum and maximum values, unless otherwise specified. 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 describing 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 encompass any and all subranges subsumed therein.
The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-solid phase mixing, and volume percentages for liquid-liquid phase mixing.
The percentage concentrations referred to in the present invention refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system to which the component is added.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The invention provides high-aluminosilicate glass, which comprises raw material powder and water. The raw material powder comprises the following components in percentage by mass:
wherein the viscosity index S = (0.7 XM) Aluminum hydroxide +1×M Magnesium hydroxide +3×M Boric acid +1.1×M Lithium carbonate +1.8× M Soda ash +2.8×M Potassium carbonate -0.5×M Silica sand -0.3×M Aluminum oxide )/M Water (W) M represents the mass percent of corresponding raw materials in the high-aluminosilicate glass; the high aluminosilicate glass satisfies: s is more than or equal to 2 and less than or equal to 4.
Crystallization of soda ash and potassium carbonate with water produces R 2 CO 3 ·nH 2 And O, the hydration film covering the surface of the sodium carbonate is thinned to cause the increase of the surface tension, and the bonding effect of the calcined soda is continuously enhanced. The product of aluminum hydroxide and magnesium hydroxide with water becomes R (OH) m ·nH 2 O, which is a gel material, has the characteristics of fine granularity, large specific surface area and good adhesiveness.
The raw materials of the high-aluminosilicate glass comprise aluminum hydroxide, lithium carbonate, soda, potassium carbonate, magnesium hydroxide, boric acid, water and the like, the viscosity index S is more than or equal to 2 and less than or equal to 4, and the hydrated raw materials have good bonding effect; therefore, the raw materials have binding property and can be pressed into block materials, so that the use efficiency of the high-aluminosilicate glass raw materials can be improved, and the preparation is convenient. When S is more than 4, the water content in the raw materials is low, the raw materials are difficult to hydrate to generate better adhesive property, so that the raw materials are difficult to form, or the formed raw materials have low strength and are easy to crack. When S is less than 2, the water content in the raw materials is too large, so that the raw materials are easy to stick to a mold after being mixed, and the demolding is difficult, or the raw materials are high in strength after being mixed and difficult to melt and clarify, so that a certain amount of bubbles exist in the glass, and the quality of a glass finished product is influenced.
In addition, the raw materials of the high-aluminosilicate glass do not introduce impurities such as iron, sulfur and the like, so that the glass has transparent color and luster and excellent appearance quality.
The silica sand is used as SiO in silicate glass 2 One of the main raw materials of (1). In the embodiment of the invention, the raw material powder of the high aluminosilicate glass contains 48-59% of silica sand by mass percent. Optionally, the silica sand in the raw material powder of the high aluminosilicate glass is 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, or 59% by mass. Furthermore, in the raw material powder of the high aluminosilicate glass, the mass percent of the silica sand is 49-54.3% or 48.7-59%.
The alumina is used as Al in silicate glass 2 O 3 One of the main raw materials of (1). In the embodiment of the invention, the mass percent of alumina in the raw material powder of the high aluminosilicate glass is 9.8-20.5%. Alternatively, the mass percentage of alumina in the raw material powder of the high aluminosilicate glass is 9.8%, 10%, 12%, 14%, 15%, 16%, 18%, 20%, or 20.5%. Furthermore, in the raw material powder of the high aluminosilicate glass, the mass percent of alumina is 9.8-14.1% or 13.4-20.5%.
Aluminum hydroxide can also be used as Al in silicate glass 2 O 3 The raw material of (2) and the hydrated aluminum hydroxide can also form a gel material with a bonding effect, which is beneficial to the molding of glass raw material powder. In the embodiment of the present invention, the raw material powder of the high aluminosilicate glass contains 0 to 4.5 mass% of aluminum hydroxide. Alternatively, the raw material powder of the high aluminosilicate glass contains aluminum hydroxide in an amount of 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, or 4.5% by mass. Furthermore, the mass percent of the aluminum hydroxide in the raw material powder of the high aluminosilicate glass is 0-4.3% or 1.4-3.1%.
The magnesium hydroxide has the similar action as aluminum hydroxide, can be used as a raw material of MgO in silicate glass on one hand, and can also be hydrated to form a gel material with a binding effect in the preparation process on the other hand. In the embodiment of the invention, the raw material powder of the high aluminosilicate glass contains 1-4.5% by mass of magnesium hydroxide. Optionally, the raw material powder of the high aluminosilicate glass contains 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, or 4.5% by mass of magnesium hydroxide. Furthermore, in the raw material powder of the high aluminosilicate glass, the mass percent of magnesium hydroxide is 1.3-4.1% or 1.1-2.7%.
Lithium carbonate is used as Li in silicate glass 2 The main raw material of O also has better binding effect after hydration. In the embodiment of the present invention, the mass percentage of lithium carbonate in the raw material powder of the high aluminosilicate glass is 0.5% to 13.1%. Optionally, the mass percentage of lithium carbonate in the raw material powder of the high aluminosilicate glass is 0.5%, 1%, 2%, 4%, 5%, 6%, 8%, 10%, 12%, or 13.1%. Furthermore, the mass percent of lithium carbonate in the raw material powder of the high aluminosilicate glass is 4.8-11.9% or 0.5-9.8%.
The soda ash is used as Na in silicate glass 2 The main raw material of O also has better binding effect after hydration. In the embodiment of the invention, the raw material powder of the high aluminosilicate glass contains 6-14.5% of soda by mass. Alternatively, the raw material powder of the high aluminosilicate glass contains soda ash in an amount of 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 14.5% by mass. Furthermore, the mass percent of the soda ash in the raw material powder of the high aluminosilicate glass is 6.2-14.3% or 7.3-12.3%.
The potassium carbonate has similar action to soda ash, and can be used as K in silicate glass 2 The raw material of O has better binding effect after hydration. In the embodiment of the invention, the mass percent of potassium carbonate in the raw material powder of the high aluminosilicate glass is 0.9-6.5%. Optionally, the mass percentage of the potassium carbonate in the raw material powder of the high aluminosilicate glass is 0.9%, 1%, 2%, 3%, 4%, 5%, 6% or 6.5%. Furthermore, in the raw material powder of the high aluminosilicate glass, the mass percent of potassium carbonate is 0.9-5.7% or 4.1-6.2%.
Boric acid is B in silicate glass 2 O 3 The raw materials of (1). In the embodiment of the invention, the mass percent of boric acid in the raw material powder of the high aluminosilicate glass is 0.2-4.5%. Alternatively, the percentage by mass of boric acid in the raw material powder of the high aluminosilicate glass is 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, or 4.5%. Furthermore, in the raw material powder of the high aluminosilicate glass, the mass percent of boric acid is 1-4.1% or 0.2-2.6%.
Magnesium oxide may also be used as a source of MgO in silicate glasses. In some embodiments, the raw material powder of the high aluminosilicate glass further includes, by mass: 0.6 to 4.5 percent of magnesium oxide. Furthermore, in the raw material powder of the high aluminosilicate glass, the mass percent of magnesium oxide is 0.6-2.9% or 1.4-4.2%.
In some embodiments, the raw material powder of the high aluminosilicate glass further comprises zinc oxide not more than 2% by mass. Further, the raw material powder of the high aluminosilicate glass contains zinc oxide in an amount of 0 to 1.9% by mass or 0 to 1.2% by mass.
In some embodiments, the raw material powder of the high aluminosilicate glass further includes, by mass: 0.2 to 4 percent of zirconia. Furthermore, the raw material powder of the high aluminosilicate glass contains 0.2-2.5% of zirconia or 1-3.7% of zirconia by mass.
In some embodiments, the mass percentage of water in the raw material relative to the raw material powder is 3.5-8%. Optionally, the mass percentage of water in the raw material with respect to the raw material powder is 3.5%, 4%, 5%, 6%, 7%, or 8%. Furthermore, in the raw material, the mass percentage of water relative to the raw material powder is 3.5-6.5% or 4-8%.
In some of these embodiments, the feedstock does not contain a binder. The high-aluminosilicate glass contains lithium carbonate, soda ash, potassium carbonate, boric acid, aluminum hydroxide, magnesium hydroxide, water and other raw materials, and has a good bonding effect after hydration, so that the raw materials can be formed without adding an additional bonding agent, therefore, impurities can be further prevented from being introduced into the high-aluminosilicate glass, and the appearance quality of the high-aluminosilicate glass is good.
In some embodiments, the raw material powder of the high aluminosilicate glass comprises, by mass: 49 to 54.3 percent of silica sand, 13.4 to 20.5 percent of alumina, 1.4 to 3.1 percent of aluminum hydroxide, 4.8 to 11.9 percent of lithium carbonate, 7.3 to 12.3 percent of soda ash, 0.9 to 5.7 percent of potassium carbonate, 0.6 to 2.9 percent of magnesium oxide, 1.1 to 2.7 percent of magnesium hydroxide, 0 to 1.2 percent of zinc oxide, 0.2 to 2.5 percent of zirconium oxide and 1 to 4.1 percent of boric acid; the mass percentage of the water relative to the raw material powder is 3.5-6.5%.
In some embodiments, the raw material powder of the high aluminosilicate glass comprises, by mass: 48.7 to 59 percent of silica sand, 9.8 to 14.1 percent of alumina, 0 to 4.3 percent of aluminum hydroxide, 0.5 to 9.8 percent of lithium carbonate, 6.2 to 14.3 percent of soda ash, 4.1 to 6.2 percent of potassium carbonate, 1.4 to 4.2 percent of magnesium oxide, 1.3 to 4.1 percent of magnesium hydroxide, 0 to 1.9 percent of zinc oxide, 1 to 3.7 percent of zirconium oxide and 0.2 to 2.6 percent of boric acid; the mass percentage of the water relative to the raw material powder is 4-8%.
In some embodiments, the composition comprises, in mass percent based on the oxides:
the high-aluminosilicate glass prepared according to the composition ratio has the advantages of high transmittance, transparent glass color, less bubbles and good appearance quality.
Silicon dioxide (SiO) 2 ) Is an important glass-forming oxide and is an essential component for forming a glass skeleton. If SiO 2 When the mass percent of the glass is less than 55%, the mechanical property of the glass is poor and the weather resistance is poor; if the melting point exceeds 63%, the melting point is too high, and it is not preferable to produce a glass having no bubbles and excellent mechanical properties. Thus, in this embodiment, siO 2 The mass percentage of the components is 55 to 63 percent. Alternatively, siO 2 Is 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62% or 63% by mass.
Aluminum oxide (Al) 2 O 3 ) Is a component for improving weather resistance, can reduce crystallization tendency of glass, and can improve chemical stability, thermal stability, mechanical strength and hardness of glass, in high aluminosilicate glass, al 2 O 3 Can participate in the network to play the role of a network generation body. Due to [ AlO ] 4 ]The space of tetrahedra is greater than [ SiO ] 4 ]Tetrahedral space, so that the increased alumina content is beneficial for ion exchange. If Al is present 2 O 3 If the content of (b) is too high, the meltability is remarkably deteriorated. Therefore, in the present embodiment, al 2 O 3 The mass percentage of (A) is 15-25%. Alternatively, al 2 O 3 Is 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25% by mass.
Boron oxide (B) 2 O 3 ) In high-temperature melting of glass with [ BO ] 3 ]The glass has the advantages of reducing the melting point of the glass, improving the melting and refining efficiency of the glass, reducing the liquidus temperature and the expansion coefficient of the glass, and simultaneously improving the strain point and the chemical stability of the glass. However, boron oxide has a high volatility characteristic in high temperature melting, resulting in non-uniformity of glass composition or phase separation. Thus, in embodiments of the invention, B 2 O 3 The mass percentage of the component (A) is 0.2-5%. Alternatively, B 2 O 3 Is 0.2%, 0.5%, 1%, 2%, 3%, 4% or 5% by mass.
Lithium oxide (Li) 2 O) is an ideal flux, an essential component for ion exchange, due to Li + The high temperature viscosity can be effectively reduced at high temperature. In an embodiment of the present invention, li 2 The mass percent of O is 0.2-6%. Alternatively, li 2 The mass percentage of O is 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5% or 6%.
Sodium oxide (Na) 2 O) is another main fluxing agent and is a product of ionThe exchange of components necessary to significantly lower the melting temperature of the high alumino-silicate glass is also a component necessary for the ion exchange. If the content is too low, the melting performance of the glass is deteriorated, and the stress value of a formed K-Na ion exchange layer is smaller, so that the microhardness is poor, cracks are easy to generate, and the falling resistance is reduced; if the content is too high, the glass network structure is deteriorated, the stability of mechanical and thermal properties is reduced, and the chemical durability is deteriorated. Thus, in an embodiment of the present invention, na 2 The mass percent of O is 4-9.5%. Alternatively, na 2 The mass percentage of O is 4%, 5%, 6%, 7%, 8%, 9%, or 9.5%.
Potassium oxide (K) 2 O) nature and Na 2 O similarly improves the melting properties of the glass. In an embodiment of the invention, K 2 The mass percentage of O is 0.7-4.5%. Further, K 2 The mass percentage of O is 0.7%, 1%, 2%, 3%, 4%, or 4.5%.
Magnesium oxide (MgO) can reduce the high-temperature viscosity of the glass at high temperature, improve the uniformity, increase the hydrolyzability, promote the melting and clarification of the glass, improve the Young modulus and chemical resistance of the glass and reduce the density of the glass. MgO also stabilizes the glass, improves the durability of the glass, prevents the glass from crystallizing, improves the elastic modulus of the glass, and suppresses the occurrence of cracks. In the embodiment of the invention, the mass percent of MgO is 1.5% -7%. Optionally, the MgO is 1.5%, 2%, 3%, 4%, 5%, 6%, or 7% by mass.
Zirconium oxide (ZrO) 2 ) The chemical stability of the glass can be improved, the surface hardness of the glass can be increased, and the pressure required by the crack formation of the glass can be improved, so that the glass is more resistant to scratch and drop. But too much ZrO 2 The melting temperature of the glass is increased and the possibility of cracking of the glass from the indentation is increased. In some of these embodiments, the composition further includes ZrO based on the oxide 2 (ii) a ZrO in high aluminosilicate glasses 2 The mass percentage of the component (A) is 0.2-4%. Alternatively, zrO 2 The mass percentage of the components is 0.2 percent, 0.5 percent, 1 percent and 2 percent3% or 4%.
After zinc oxide (ZnO) is introduced into the glass as a network outer body, the strain point and the chemical stability of the glass are improved. Meanwhile, the glass has the effects of improving the strength and the hardness below the softening point and reducing the thermal expansion coefficient of the glass. However, too much ZnO lowers the strain point of the glass to a large extent. In some of these embodiments, the composition further comprises ZnO, on an oxide basis; in the high-aluminosilicate glass, the mass percentage of ZnO is not more than 2 percent. Optionally, the ZnO is present in an amount of 0, 0.5%, 1%, 1.5% or 2% by mass.
Another embodiment of the present invention also provides a method for preparing a high aluminosilicate glass, including the following steps S110 to S130.
Step S110: the raw materials of the high aluminosilicate glass are mixed and pressed to prepare the massive granules.
In some of the embodiments, the pressing process in step S110 is performed using a press forming machine. In some embodiments, the pressure of the pressing process is 4T to 10T.
In some of these embodiments, the bulk density of the agglomerate is 1.9g/cm 3 ～2.1g/cm 3 。
In some of these embodiments, the bulk granules have a crush resistance of 35kgf to 42kgf.
Step S120: the lumpy granules are melted to prepare molten glass.
In some of these embodiments, the temperature of the melting process is 1560 ℃ to 1600 ℃. The melting treatment time is 6-8 h.
Step S130: and (4) forming the molten glass, and annealing to prepare the high-aluminosilicate glass.
In some embodiments, the molding manner in step S130 is casting molding.
In some of these embodiments, the temperature of the annealing process is 610 ℃ to 645 ℃. The time of the annealing treatment is 6-8 h.
The preparation method of the high-aluminosilicate glass comprises the steps of pressing raw materials into blocky granules, and then carrying out melting treatment, forming and annealing treatment to prepare the high-aluminosilicate glass. Through at first pressing into the piece with the raw materials, can avoid the powder of glass raw materials to scatter in the melting furnace, lead to melting furnace life to reduce, can improve glass raw materials's utilization ratio simultaneously. In addition, as the contact area of each raw material particle in the formed granules is greatly increased, the volume density is greatly increased, the heat conductivity coefficient is improved, the cosolvents such as boric acid and soda ash can cover the surfaces of silica sand and alumina powder to play a role in fluxing, and the solid phase reaction speed is accelerated, thereby being beneficial to improving the melting efficiency and the homogenization degree of the glass liquid.
In another embodiment of the present invention, an electronic product is further provided, which includes a body and a glass cover plate embedded in the body, wherein the glass cover plate is the high aluminosilicate glass.
In some embodiments, the electronic products include, but are not limited to, mobile phones, tablet computers, notebook computers, displays, and smart watches.
The following are specific examples.
The high aluminosilicate glasses of examples 1 to 16 and comparative examples 1 to 4 were prepared as follows:
(1) The raw materials were weighed to 20kg according to the mass percentages of the high aluminosilicate glass raw materials in tables 1 to 3, and the raw materials were mixed in a mixer for 5min.
(2) And (3) feeding the uniformly mixed raw materials into a compression molding machine, controlling the molding pressure to be 5T, and pressing the raw materials into blocky granules with the size of 30mm.
(3) And putting the block-shaped granules into a platinum-rhodium crucible, and preserving heat for 8 hours at the temperature of 1560-1600 ℃ to perform melting, clarification and homogenization treatment to obtain molten glass.
(4) Pouring the glass liquid into a stainless steel mold for molding, annealing at the temperature of 610-645 ℃ for 8h, and then cooling to room temperature along with a furnace. Slicing the glass product by using a wire cutting machine, then grinding and polishing and finish machining, and finally respectively testing the physical and chemical properties of the glass sample, wherein the test results are recorded in tables 1-3.
The bulk density is measured from the mass-to-volume ratio of the granular particles in lump form, and the average value of 20 granular particles in lump form is taken. The crush resistance was determined with reference to HG/T2782-2011. The light transmission and the L, a and b color values were measured using an ultraviolet-visible spectrophotometer. Bubble quantity measuring method: the glass sheets obtained in the examples or the comparative examples were irradiated with a halogen lamp, the size was determined using a scale, and the number of bubbles was counted, whereby the number of bubbles with a bubble diameter of > 0.1mm per kg of glass was calculated quickly and accurately, and the number of bubbles with a bubble diameter of < 0.1mm was counted using a German Leica polarising microscope.
Tables 1 to 3 provide the glass composition ratios and the results of the physicochemical properties tests of examples 1 to 16 and comparative examples 1 to 4.
TABLE 1
Note: the mass percent of water in the table is relative to the mass percent of the raw material powder
TABLE 2
Note: the mass percent of water in the table is relative to the mass percent of the raw material powder
TABLE 3
Note: the mass percent of water in the table is relative to the mass percent of the raw material powder
As can be seen from the data in tables 1 to 3, the bulk density of the granulated masses prepared in examples 1 to 16 was 1.9g/cm 3 ～2.1g/cm 3 The crushing resistance is 35-42 kgf, the heat transfer is effectively improved, the melting, clarifying and homogenizing efficiency is greatly improved, and the glass with high transmittance, bright color and less bubbles is favorably obtained. The raw materials of examples 1 to 16 had a viscosity index of 2 to 4, and the raw materials of comparative examples 1 to 4 had a viscosity index out of the range of 2 to 4, and a comparison showed that the raw material of comparative example 1 had a viscosity index too high, and the resulting granulated block had a high bulk density, but had a low crushing resistance and a low strength. And the number of bubbles in the prepared glass is obviously more than that of the glass of the examples 1 to 16, and the quality of the finished glass product is influenced. The viscosity index of the raw materials of comparative examples 2 to 4 was too low, the bulk density and crushing resistance of the obtained agglomerated bodies were low, and the prepared glass had a large number of bubbles and poor quality.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the patent of the invention is subject to the content of the appended claims, and the description can be used for explaining the content of the claims.
Claims (11)
1. The high aluminosilicate glass is characterized in that raw materials comprise raw material powder and water; the raw material powder comprises the following components in percentage by mass:
wherein the viscosity index S = (0.7 XM) Aluminum hydroxide +1×M Magnesium hydroxide +3×M Boric acid +1.1×M Lithium carbonate +1.8×M Soda ash +2.8×M Potassium carbonate -0.5×M Silica sand -0.3×M Aluminum oxide )/M Water (W) M represents the mass percentage of corresponding raw materials in the high-aluminosilicate glass; the high aluminosilicate glass satisfies: s is more than or equal to 2 and less than or equal to 4.
2. The high aluminosilicate glass of claim 1, wherein the raw material powder further comprises magnesium oxide; the mass percentage of the magnesium oxide in the raw material powder is 0.6-4.5%.
3. The high aluminosilicate glass of claim 1, wherein the raw material powder further comprises zinc oxide; the mass percentage of the zinc oxide in the raw material powder is not more than 2%.
4. The high aluminosilicate glass of claim 1, wherein the raw material powder further comprises zirconia; the mass percentage of the zirconia in the raw material powder is 0.2-4%.
5. The high aluminosilicate glass of claim 1, wherein the starting material is free of a binder.
6. The high aluminosilicate glass according to any one of claims 1 to 5, which comprises, in mass percent on an oxide basis:
7. the high aluminosilicate glass of claim 6, wherein the composition further comprises ZrO based on oxides 2 (ii) a In the high aluminosilicate glass, the ZrO 2 The mass percentage of the component (A) is 0.2-4%.
8. The high aluminosilicate glass of any one of claim 6, wherein the composition further comprises, on an oxide basis, znO; in the high-aluminosilicate glass, the mass percentage of ZnO is not more than 2%.
9. A preparation method of high aluminosilicate glass is characterized by comprising the following steps:
mixing the raw materials of the high aluminosilicate glass according to any one of claims 1 to 8, and pressing to prepare a lump-shaped granule;
melting the massive granules to prepare glass liquid; and
and forming the molten glass, and annealing to prepare the high-aluminosilicate glass.
10. The method for producing a high aluminosilicate glass according to claim 9, wherein the bulk granulated body satisfies at least one of the following conditions:
(1) The bulk density of the block-shaped granules is 1.9g/cm 3 ～2.1g/cm 3 ；
(2) The block-shaped granules have a crushing resistance of 35 to 42kgf.
11. An electronic product comprising a body and a glass cover plate fitted to the body, wherein the glass cover plate is the high aluminosilicate glass according to any one of claims 1 to 8.
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