CN115286251A - Tempered glass, microcrystalline glass and preparation method and application thereof - Google Patents
Tempered glass, microcrystalline glass and preparation method and application thereof Download PDFInfo
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- CN115286251A CN115286251A CN202210955790.3A CN202210955790A CN115286251A CN 115286251 A CN115286251 A CN 115286251A CN 202210955790 A CN202210955790 A CN 202210955790A CN 115286251 A CN115286251 A CN 115286251A
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- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000005341 toughened glass Substances 0.000 title claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 31
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 30
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 30
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 18
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims description 26
- 229910052596 spinel Inorganic materials 0.000 claims description 18
- 239000011029 spinel Substances 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 10
- 239000006058 strengthened glass Substances 0.000 claims description 10
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- -1 magnesium aluminate Chemical class 0.000 claims description 7
- 229910052642 spodumene Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000002834 transmittance Methods 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 4
- 239000006060 molten glass Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000005496 tempering Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 230000009970 fire resistant effect Effects 0.000 claims 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 21
- 230000008025 crystallization Effects 0.000 abstract description 21
- 229910052708 sodium Inorganic materials 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000010899 nucleation Methods 0.000 abstract description 6
- 230000006911 nucleation Effects 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 16
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 16
- 229910001928 zirconium oxide Inorganic materials 0.000 description 16
- 235000019589 hardness Nutrition 0.000 description 15
- 239000006121 base glass Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 8
- 238000013001 point bending Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000156 glass melt Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910017976 MgO 4 Inorganic materials 0.000 description 2
- 229910003251 Na K Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052644 β-spodumene Inorganic materials 0.000 description 2
- 229910010100 LiAlSi Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
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- 239000006112 glass ceramic composition Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
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- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000004127 vitreous body Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/02—Tempering or quenching glass products using liquid
- C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt
Abstract
The invention provides microcrystalline glass which comprises the following components in percentage by mass: siO 2 2 30％～50％、Al 2 O 3 24％～40％、Li 2 O 0～5％、MgO 2％～8％、B 2 O 3 0～3.5％、Na 2 O 0～10％、ZnO5％～15％、BaO 0～5％、ZrO 2 2% -8% and TiO 2 0 to 8 percent; and SiO 2 And Al 2 O 3 The mass ratio of (A) to (B) is 0.86-1.7; zrO (ZrO) 2 And TiO 2 The sum of the mass percentages of the components is a, the mass ratio of the MgO to the ZnO is b, and the following components are satisfied: a is more than or equal to 5 and less than or equal to 10; b/a is more than or equal to 0.02 and less than or equal to 0.17. The glass-ceramic can realize rapid crystallization without heat treatment steps such as nucleation, crystallization and the like through reasonable proportioning of glass components, and has better mechanical properties.
Description
Technical Field
The invention relates to the technical field of glass products, in particular to tempered glass, glass ceramics and preparation methods and application thereof.
Background
The nucleated glass is also called glass ceramic, generally, it is made up by introducing nucleating agent into base glass formulation or regulating oxide proportion in the formulation, make the base glass form one or more crystalline phases in the subsequent heat treatment process, crystalline phase and glass phase coexist in vitreous body, form the heterogeneous crystal material, it has excellent performance of glass and ceramic at the same time, have important effects on improving the properties such as average hardness, fracture toughness, shock resistance and anti-falling of the glass.
However, the conventional glass ceramics usually need to be obtained through multiple steps of melting, annealing, nucleating, crystallizing and the like, and the preparation process is complex and energy-consuming and time-consuming.
Disclosure of Invention
Therefore, the microcrystalline glass which can be rapidly crystallized and the preparation process of the microcrystalline glass is simplified, and the preparation method and the application of the microcrystalline glass are needed to be provided.
In addition, the reinforced glass prepared by the microcrystalline glass is also provided.
The invention provides microcrystalline glass, which comprises the following components in percentage by mass:
and SiO 2 And Al 2 O 3 The mass ratio of (A) to (B) is 0.86-1.7; zrO (ZrO) 2 And TiO 2 The sum of the mass percentages of the components is a, the mass ratio of the MgO to the ZnO is b, and a is more than or equal to 5 and less than or equal to 10; b/a is more than or equal to 0.02 and less than or equal to 0.17.
In some embodiments, the crystalline phase of the glass-ceramic includes at least one of magnesium aluminate spinel, zinc aluminate spinel, and magnesium zinc spinel.
In some embodiments, the crystalline phase of the glass-ceramic further includes at least one of zirconia and spodumene.
In some of these embodiments, the crystalline phase has a grain size of 50nm to 200 μm.
In some of these embodiments, the microcrystalline glass has a crystallinity of 20% to 65%.
In some of these embodiments, the SiO 2 The mass percentage of (B) is 36-50%.
In some of these embodiments, the Al 2 O 3 The mass percentage of (A) is 25-36%.
In some embodiments, the MgO is 4-7% by weight.
In some embodiments, the ZnO is present in an amount of 5% to 11% by weight.
In some of these embodiments, B 2 O 3 The mass percentage of the component (A) is 0-1.7%.
In some of these embodiments, the Li 2 The mass percentage of O is 0.5-3%.
In some of these embodiments, the Na 2 The mass percent of O is 0-6%.
In some embodiments, the BaO accounts for 0 to 1.7 percent by mass.
In some of these embodiments, the ZrO 2 The mass percentage of (B) is 2-6%.
In some of these embodiments, the TiO 2 Is prepared from the following components in percentage by mass1.4％～8％。
In some embodiments, the microcrystalline glass has an average transmittance of 0.1 to 65% at 380 to 780 nm.
In some of these embodiments, the microcrystalline glass has a haze of greater than 24%.
In some of these embodiments, the microcrystalline glass has a Vickers hardness greater than 700kgf/mm 2 。
In another aspect of the present invention, a method for preparing microcrystalline glass is also provided, which comprises the following steps:
weighing the raw materials according to the components of the microcrystalline glass;
melting the raw materials to prepare molten glass;
and forming the glass liquid to prepare the microcrystalline glass.
In another aspect of the invention, the invention also provides a strengthened glass, which is prepared by the above microcrystalline glass through chemical strengthening; wherein Li 2 O and/or Na 2 The mass percentage of O is not zero.
In another aspect of the present invention, a method for preparing the above strengthened glass is also provided, which comprises the following steps:
and carrying out chemical strengthening treatment on the microcrystalline glass in molten salt.
In another aspect of the invention, the application of the microcrystalline glass in preparing protective glass, photoelectric glass or fire-proof glass is also provided.
The microcrystalline glass comprises SiO with a specific proportion 2 、Al 2 O 3 、MgO、ZnO、ZrO 2 And TiO 2 2 Through the reasonable proportioning of the glass components, the microcrystalline glass can realize rapid crystallization without the heat treatment steps of nucleation, crystallization and the like, and the microcrystalline glass has better mechanical property.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) picture of a crystallized glass of example 12 of the present invention;
fig. 2 is an X-ray diffraction pattern (XRD) of the crystallized glass of example 18 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth 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.
The invention provides microcrystalline glass, which comprises the following components in percentage by mass:
and SiO 2 And Al 2 O 3 Mass ratio of (SiO) 2 /Al 2 O 3 ) 0.86 to 1.7; zrO (ZrO) 2 And TiO 2 The sum of the mass percent of a, the mass ratio of MgO to ZnO (MgO/ZnO) is b, and a is more than or equal to 5 and less than or equal to 10; b/a is more than or equal to 0.02 and less than or equal to 0.17.
The microcrystalline glass comprises SiO with a specific proportion 2 、Al 2 O 3 、MgO、ZnO、ZrO 2 And TiO 2 By reasonable proportioning of the glass components, the microcrystalline glass can realize rapid crystallization without heat treatment steps such as nucleation, crystallization and the like, and has better mechanical properties.
SiO 2 Is an oxide for glass forming, and can be used for stabilizing the network structure of glass and microcrystal glass. With respect to viscosity and mechanical properties, viscosity and mechanical properties are affected by the glass composition. In glasses and glass ceramics, siO 2 As a basis forThe glass mainly forms oxides of the glass and can be used to stabilize the network structure of the glass and the glass-ceramic. In an embodiment of the present invention, siO 2 The mass percentage of (B) is 30-50%. Alternatively, siO 2 Is 30%, 32%, 35%, 36%, 40%, 42%, 45%, 48% or 50% by mass. Further, siO 2 The mass percentage of (A) is 36-50%.
Al 2 O 3 The network may also be stabilized and also provide improved mechanical properties and chemical durability. At the same time, al 2 O 3 High Al content as a constituent of spinel and spodumene crystal phases 2 O 3 The presence favors the formation of crystalline phases. Therefore, in the embodiment of the present invention, al 2 O 3 The mass percentage of (B) is 24-40%. Alternatively, al 2 O 3 Is 24%, 25%, 28%, 30%, 32%, 35%, 36%, 38% or 40% by mass. Further, al 2 O 3 The mass percentage of (A) is 25-36%.
In addition, the invention controls Al 2 O 3 With SiO 2 The mass ratio of (SiO) is more than or equal to 0.86 2 /Al 2 O 3 ) Less than or equal to 1.7, can reduce the crystallization activation energy of the target crystalline phase to a certain extent, enhances the precipitation capability of the target crystalline phase, and is beneficial to the rapid precipitation of the target crystalline phase. In addition, al is present in the residual glass phase 2 O 3 The Li-Na and Na-K ion exchange capacity can be enhanced. However, al 2 O 3 Has higher melting temperature, can be used as a network intermediate and can regulate Al 2 O 3 In the case of Al to control the viscosity 2 O 3 Too high, also generally increases the viscosity of the melt.
The alkaline earth metal oxides MgO and ZnO are beneficial to reducing the high-temperature viscosity of the base glass, modifying the glass structure and improving the strength and chemical stability of the base glass, and are also the components of a spinel crystal phase. In the embodiment of the invention, the mass percent of MgO is 2-8% and the mass percent of ZnO is 5-15%, which can fully ensure that the content of the composition of the target crystal phase is enough to support rapid crystallization in the crystallization processThe requirements of (a). Furthermore, due to Zn 2+ The high field intensity accumulation in the glass melt, the addition of ZnO increases the crystallization tendency of the base glass, and reduces the crystallization activation energy of the target crystal phase. When the content of MgO is too high, the high-temperature viscosity of the melt is increased, and the melting difficulty is increased. ZnO is expensive as a raw material, and if the content of ZnO added is too high, a large amount of ZnO remains in the glass phase, which in turn degrades the glass properties and also degrades the Li-Na and Na-K ion exchange capacity of the glass ceramic. Optionally, the MgO is 2%, 3%, 4%, 5%, 6%, 7%, or 8% by mass. Furthermore, the mass percent of MgO is 4% -7%. Optionally, the ZnO is 5%, 6%, 8%, 10%, 12%, 14%, or 15% by mass. Furthermore, the mass percent of ZnO is 5-11%.
In the crystallized glass of the present embodiment, tiO 2 And ZrO 2 The addition of the nucleating agent can increase the crystallization capacity and liquidus temperature of the glass during the forming process to increase the MgO-Al content 2 O 3 -SiO 2 Devitrification ability of glass. Due to MgO-Al 2 O 3 -SiO 2 The glass has low crystallization tendency and high crystallization barrier, and TiO is required to be added in general conditions 2 Or more ZrO 2 So as to greatly reduce the crystallization activation energy, promote the uniform crystal nucleus to be precipitated in the base glass and generate the target crystal phase. But TiO 2 2 The glass has strong coloring capability, so that the basic glass has darker color and is not suitable for being added too much; at the same time, a higher content of TiO 2 The growth of the crystal phase in the basic glass is difficult to control, the abnormal growth is caused, more impurity phases are generated, the performance of the glass ceramic is difficult to control, and the phenomena of cracking and performance great reduction occur. ZrO (ZrO) 2 The solubility in the glass body is low, the melting temperature is extremely high, excessive addition is not suitable, and high ZrO content is ensured 2 Similarly, the growth of the crystal phase in the base glass is difficult to control, and the crystal phase grows abnormally, so that more impurity phases are generated. Thus, in the embodiment of the present invention, zrO 2 2-8 percent of TiO 2 Is 0 to 8 percent, and ZrO 2 And TiO 2 The sum a of the mass percentages of the components satisfies that a is more than or equal to 5 and less than or equal to 10.
Alternatively, zrO 2 Is 2%, 3%, 4%, 5%, 6%, 7% or 8% by mass. Further, zrO 2 The mass percentage of (B) is 2-6%. Alternatively, tiO 2 Is 0, 1%, 2%, 3%, 4%, 5%, 6%, 7% or 8% by mass. Further, tiO 2 The mass percentage of the component (A) is 1.4-8%.
Meanwhile, in the microcrystalline glass provided by the invention, the components of MgO, znO and TiO which influence the precipitated crystal phase of the base glass are regulated and controlled 2 And ZrO 2 B/a is not less than 0.02 but not more than 0.17 (ZrO) 2 And TiO 2 The sum of the mass percentages of a and b) is the mass ratio of MgO and ZnO, so that the base glass realizes rapid and controllable crystallization, nucleation and growth of a crystalline phase can be rapidly completed in the melting and pouring process, and a complete microcrystalline glass block with a target crystalline phase and high strength is finally obtained.
Alkali metal oxide Li 2 O and Na 2 O is mainly used as a cosolvent and a component for enhancing the ion exchange capacity. Meanwhile, li 2 O can also be used as a crystalline phase component, and is beneficial to the precipitation of the crystalline phase of spodumene. In addition, li + Also has stronger accumulation effect, and increases the crystallization capacity of the base glass to a certain extent. However, the cost of the lithium raw material is high, and therefore, in the embodiment of the present invention, li 2 The mass percent of O is 0-5%; na (Na) 2 The mass percentage of O is 0 to 10 percent. Alternatively, li 2 The mass percentage of O is 0, 1%, 2%, 3%, 4% or 5%. Na (Na) 2 The mass percentage of O is 0, 2%, 4%, 5%, 6%, 8% or 10%. Further, li 2 The mass percentage of O is 0.5-3%. Na (Na) 2 The mass percent of O is 0-6%.
B 2 O 3 Helping to provide a base glass with a low melting temperature. In addition, B is added to the base glass 2 O 3 The phase separation and nucleation of the base glass are promoted, and the crystallization time of the base glass is shortened. In the embodiment of the present invention, B 2 O 3 Is in the range of 0 to up to3.5 percent. Alternatively, B 2 O 3 Is 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% or/3.5% by mass. Further, B 2 O 3 The mass percentage of the component (A) is 0-1.7%.
BaO increases the refractive index of the glass phase in the glass-ceramic, and can also be Ti in the melting process 4+ Providing an oxidizing environment and reducing Ti 3+ The appearance of coloring ions. In the embodiment of the present invention, the mass percentage of BaO is 0 to 5%. Optionally, the mass percentage of BaO is 0, 1%, 2%, 3%, 4%, or 5%. Further, the mass percent of BaO is 0-1.7%.
In some embodiments, the microcrystalline glass comprises the following components in percentage by mass: siO 2 2 30％～44％、Al 2 O 3 26.5％～38.4％、Li 2 O 0～4％、MgO 2％～8％、B 2 O 3 0～2％、Na 2 O 0～4％、ZnO 6％～15％、BaO 0～4％、ZrO 2 2% -8% and TiO 2 0 to 6 percent; and SiO 2 And Al 2 O 3 The mass ratio of (A) to (B) is 0.86-1.48; zrO (ZrO) 2 And TiO 2 The sum of the mass percentages of the components is a, the mass ratio of MgO to ZnO is b, and the microcrystalline glass meets the following requirements: a is more than or equal to 5 and less than or equal to 10; b/a is more than or equal to 0.04 and less than or equal to 0.09.
In some embodiments, the microcrystalline glass comprises the following components in percentage by mass: siO 2 2 31.5％～44％、Al 2 O 3 25.2％～36.5％、Li 2 O 0～4.5％、MgO 3.2％～8％、B 2 O 3 0～3.5％、Na 2 O 0～9％、ZnO 5％～13％、BaO 0～5％、ZrO 2 2% -8% and TiO 2 0.5 to 7 percent; and SiO 2 And Al 2 O 3 The mass ratio of (A) to (B) is 0.86-1.56; zrO (ZrO) 2 And TiO 2 2 The sum of the mass percentages of the components is a, the mass ratio of MgO to ZnO is b, and the microcrystalline glass meets the following requirements: a is more than or equal to 5 and less than or equal to 9; b/a is more than or equal to 0.04 and less than or equal to 0.13.
In some embodiments, the microcrystalline glass comprises the following components in percentage by mass: siO 2 2 36％～49.5％、Al 2 O 3 24.8％～35.7％、Li 2 O 0.5％～2.8％、MgO 4％～8％、B 2 O 3 0～1.7％、Na 2 O 0～6％、ZnO 5％～11％、BaO 0～1.7％、ZrO 2 2% -6% and TiO 2 1.4% -8%; and SiO 2 And Al 2 O 3 The mass ratio of (A) to (B) is 1.07-1.67; zrO (ZrO) 2 And TiO 2 The sum of the mass percentages of the components is a, the mass ratio of MgO to ZnO is b, and the microcrystalline glass meets the following requirements: a is more than or equal to 5.2 and less than or equal to 10; b/a is more than or equal to 0.07 and less than or equal to 0.17.
In some embodiments, the microcrystalline glass comprises the following components in percentage by mass: siO 2 2 31.5％～47％、Al 2 O 3 25％～36.5％、Li 2 O 0～5％、MgO 3.2％～8％、B 2 O 3 0～3％、Na 2 O 0～10％、ZnO 5.8％～13％、BaO 0～4.5％、ZrO 2 3% -6.6%, and TiO 2 2% -5%; and SiO 2 And Al 2 O 3 The mass ratio of (A) to (B) is 0.86-1.70; zrO (ZrO) 2 And TiO 2 2 The sum of the mass percentages of the components is a, the mass ratio of MgO to ZnO is b, and the microcrystalline glass meets the following requirements: a is more than or equal to 5 and less than or equal to 9.6; b/a is more than or equal to 0.03 and less than or equal to 0.11.
In some of these embodiments, the crystalline phase of the glass-ceramic includes at least one of magnesium aluminate spinel, zinc aluminate spinel, and magnesium zinc spinel. The spinel (magnesium aluminum, zinc aluminum, magnesium zinc spinel) is of the general formula AB 2 O 4 And cubic substantially spinel structured crystalline oxides. The prototype spinel structure is magnesium aluminate (MgAl) 2 O 4 ). In the basic spinel structure, O atoms fill the face-centered cubic (FCC) array sites. Spinel has very high mechanical performance (Mohs hardness is more than 7.5) and is an ideal strengthening and toughening crystal phase in microcrystalline glass.
In some embodiments, the crystalline phase of the glass-ceramic further comprises at least one of zirconia and spodumene. Spodumene (LiAlSi) 2 O 6 ) With common-angle connections SiO forming interconnecting rings 4 And Al 3 O 4 A tetrahedral framework structure, thereby forming channels containing Li ions. Microcrystalline glass having beta-spodumene crystalline phaseThe glass can be chemically strengthened in molten salt, and Na is used in the chemical strengthening process + (and/or K) + ) Substitution of Li in beta-spodumene structure + Thereby generating surface compressive stress and playing a role in tempering. In addition, the microcrystalline glass based on a β -spodumene solid solution has good thermal shock resistance. The zirconia crystal phase has extremely high mechanical properties and is an ideal reinforcing and toughening crystal phase.
In some of these embodiments, the crystalline phase has a grain size of 50nm to 200 μm. Alternatively, the crystal phase has a grain size of 50nm, 100nm, 500nm, 1 μm, 10 μm, 50 μm, 100 μm, or 200 μm.
In some of these embodiments, the microcrystalline glass has a crystallinity of 20% to 65%. Optionally, the glass-ceramic has a crystallinity of 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, or 65%.
In some embodiments, the microcrystalline glass has an average transmittance of 0.1% to 65% at 380nm to 780 nm. According to the difference of the grain size and the crystallinity of the microcrystalline glass, the average transmittance of the microcrystalline glass in a 380 nm-780 nm region is 0.1% -65%, and the microcrystalline glass is semitransparent or opaque in appearance.
In some of these embodiments, the microcrystalline glass has a haze of greater than 24%.
In some of these embodiments, the microcrystalline glass has a Vickers hardness greater than 700kgf/mm 2 . Further, the Vickers hardness of the microcrystalline glass is more than 720kgf/mm 2 Or 750kgf/mm 2 。
Another embodiment of the present invention further provides a method for preparing microcrystalline glass, including the following steps S110 to S130.
Step S110: weighing the raw materials according to the components of the microcrystalline glass.
Step S120: melting the raw materials to prepare the molten glass.
In some embodiments, the melting temperature in step S120 is 1450 ℃ to 1650 ℃, and the melting time is 2h to 10h.
Step S130: and forming the glass liquid to prepare the glass ceramics.
The preparation method of the microcrystalline glass has simple working procedures and lower preparation cost, does not need complex heat treatment such as nucleation, crystallization and the like, and melts and molds the raw materials of the glass components to obtain the microcrystalline glass through rapid crystallization.
The invention also provides a strengthened glass which is prepared by chemically strengthening the microcrystalline glass; wherein Li 2 O and/or Na 2 The mass percentage of O is not zero.
The invention also provides a preparation method of the strengthened glass, which comprises the following steps:
the microcrystalline glass is chemically strengthened in molten salt.
In some of these embodiments, the temperature of the chemical strengthening treatment is 420 ℃ to 500 ℃. The time of the chemical strengthening treatment is 2 to 12 hours.
The invention also provides application of the microcrystalline glass in preparation of protective glass, photoelectric glass or fireproof glass.
The following are specific examples.
The preparation processes and the test methods of the microcrystalline glass and the strengthened glass of the embodiment 1 to the embodiment 23 and the comparative embodiment 1 to the comparative embodiment 9 are as follows:
the preparation method comprises the steps of mixing the components (mass percent) of the examples 1-23 and the comparative examples 1-9 according to the design component ratios in the tables 1-6, fully and uniformly mixing, melting for 8 hours at 1450-1650 ℃ by using a platinum crucible, stirring by using a platinum stirring paddle, keeping the temperature for 2 hours for homogenization after the stirring paddle is pulled out, casting the mixture on an iron mold to form a glass block with the size of about 80 x 160mm, preheating the glass block to 400 ℃ before the mold casting, immediately transferring the glass block to an annealing furnace for annealing after the glass block is hardened, keeping the temperature for 2 hours, then cooling for 6 hours to 140 ℃, naturally cooling, and taking out for later use.
Glass samples of examples 1-23 were cut into 50 x 0.7mm glass pieces by a shenyangke STX-1203 wire cutter, polished by a HD-640-5L double side grinder polisher from shenzhen heider, CNC edged, tested for surface vickers hardness using a FALCON400 durometer from netherlands, and tested for transmittance in the 380-780nm wavelength range using a Lambda950 uv-vis spectrophotometer from PerkinElmer, usa. The haze of a sample is measured by an SUGA optical HZ-V3 haze meter, and the crystal phase, the crystallinity, the crystal size and the like of the sample are measured by an X-ray diffractometer Bruker D8 advance of Bruker.
The microcrystalline glass was subjected to the strengthening process according to tables 1 to 6, samples were immersed in a salt consisting of at least one of sodium nitrate and potassium nitrate, heat-preserved at 420 to 500 ℃ for 2 to 12 hours, and then washed with pure water to obtain a final chemically strengthened microcrystalline glass cover glass, li-Na exchange stress depth Dol _0 (μm) was measured using a SLP2000 surface stress meter of japan bending origin limited company in combination with SEM spectrometer line scanning, four-point bending strength (20 cm in upper press bar pitch, 40cm in lower press bar pitch) and ring pressure (16 mm in upper ring, 32mm in lower ring) were measured using a donggustet PT-307 universal tester, ball drop test was performed using michael MK-9968, steel ball mass was 64 g, 5 point ball drop test from 20cm (point drop distance 10mm from edge) was performed, 5cm was raised each time until breakage, and ball drop energy = 0.06kg 10n/kg/h was calculated and recorded in tables 1 to 6.
Table 1 glass compositions, processing and properties of examples 1-6
The microcrystalline glass of the embodiments 1 to 6 comprises the following components by mass percent: siO 2 2 30％～44％、Al 2 O 3 26.5％～38.4％、Li 2 O 0～4％、MgO 2％～8％、B 2 O 3 0～2％、Na 2 O 0～4％、ZnO 6％～15％、BaO 0～4％、ZrO 2 2% -8% and TiO 2 0 to 6 percent; and SiO 2 And Al 2 O 3 The mass ratio of (A) to (B) is 0.86-1.48; zrO (ZrO) 2 And TiO 2 The sum of the mass percentages of the components is a, the mass ratio of MgO to ZnO is b, and the microcrystalline glass meets the following requirements: a is more than or equal to 5 and less than or equal to10; b/a is more than or equal to 0.04 and less than or equal to 0.09. The microcrystalline glasses of examples 1 to 6 had a Vickers hardness of 723kgf/mm 2 ～778kgf/mm 2 And has better mechanical strength. After chemical strengthening, the strengthened glasses of examples 1 to 6 had Vickers hardness of 763kgf/mm 2 ～835kgf/mm 2 The four-point bending strength is 818MPa to 952MPa, the ball dropping energy is 0.52J to 0.68J, the ring pressure strength is 781N to 1241N, and the mechanical strength can be further improved.
Table 2 glass compositions, processing and properties of examples 7-12
The microcrystalline glass of the embodiments 7 to 12 comprises the following components by mass percent: siO 2 2 31.5％～44％、Al 2 O 3 25.2％～36.5％、Li 2 O 0～4.5％、MgO 3.2％～8％、B 2 O 3 0～3.5％、Na 2 O 0～9％、ZnO 5％～13％、BaO 0～5％、ZrO 2 2% -8% and TiO 2 0.5 to 7 percent; and SiO 2 And Al 2 O 3 The mass ratio of (A) to (B) is 0.86-1.56; zrO (zirconium oxide) 2 And TiO 2 The sum of the mass percentages of the components is a, the mass ratio of MgO to ZnO is b, and the microcrystalline glass meets the following requirements: a is more than or equal to 5 and less than or equal to 9; b/a is more than or equal to 0.04 and less than or equal to 0.13. The microcrystalline glasses of examples 7 to 12 had a Vickers hardness of 712kgf/mm 2 ～777kgf/mm 2 And has better mechanical strength. After chemical strengthening, the strengthened glasses of examples 7 to 12 had Vickers hardnesses of 800kgf/mm 2 ～820kgf/mm 2 The four-point bending strength is 812 MPa-922 MPa, the falling ball energy is 0.50J-0.66J, the ring pressure strength is 773N-1211N, and the mechanical strength can be further improved.
Referring to fig. 1, which is a Scanning Electron Microscope (SEM) picture of the crystallized glass of example 12, it can be seen that the crystallized glass has a large number of crystal phases and an average size of crystal grains of 80nm.
Table 3 glass compositions, processing and properties of examples 13-18
The microcrystalline glass of the embodiments 13 to 18 comprises the following components by mass percent: siO 2 2 36％～49.5％、Al 2 O 3 24.8％～35.7％、Li 2 O 0.5％～2.8％、MgO 4％～8％、B 2 O 3 0～1.7％、Na 2 O 0～6％、ZnO 5％～11％、BaO 0～1.7％、ZrO 2 2% -6% and TiO 2 1.4 to 8 percent; and SiO 2 And Al 2 O 3 The mass ratio of (A) to (B) is 1.07-1.67; zrO (zirconium oxide) 2 And TiO 2 The sum of the mass percentages of the components is a, the mass ratio of MgO to ZnO is b, and the microcrystalline glass meets the following requirements: a is more than or equal to 5.2 and less than or equal to 10; b/a is more than or equal to 0.07 and less than or equal to 0.17. The microcrystalline glasses of examples 13 to 18 had a Vickers hardness of 756kgf/mm 2 ～797kgf/mm 2 And has better mechanical strength. After chemical strengthening, the strengthened glasses of examples 13 to 18 had Vickers hardness of 795kgf/mm 2 ～854kgf/mm 2 The four-point bending strength is 866MPa to 967MPa, the ball drop energy is 0.56J to 0.69J, the ring pressure strength is 1020N to 1350N, and the mechanical strength can be further improved.
Referring to fig. 2, which is an X-ray diffraction pattern (XRD) of the glass-ceramic of example 18, it can be seen that the glass-ceramic of example 18 has a spinel as a main crystal phase and also includes a zirconia crystal phase.
Table 4 glass compositions, processing and properties of examples 19-23
The microcrystalline glass of the embodiments 19 to 23 comprises the following components by mass percent: siO 2 2 31.5％～47％、Al 2 O 3 25％～36.5％、Li 2 O 0～5％、MgO 3.2％～8％、B 2 O 3 0～3％、Na 2 O 0～10％、ZnO 5.8％～13％、BaO 0～4.5％、ZrO 2 3% -6.6%, and TiO 2 2% -5%; and SiO 2 And Al 2 O 3 The mass ratio of (A) to (B) is 0.86-1.70; zrO (zirconium oxide) 2 And TiO 2 The sum of the mass percentages of a and b is the mass ratio of MgO to ZnO, and the microcrystalline glass meets the following requirements: a is more than or equal to 5 and less than or equal to 9.6; b/a is more than or equal to 0.03 and less than or equal to 0.11. The microcrystalline glasses of examples 19 to 23 had a Vickers hardness of 737kgf/mm 2 ～788kgf/mm 2 And has better mechanical strength. After chemical strengthening, the strengthened glasses of examples 19 to 23 had a Vickers hardness of 779kgf/mm 2 ～849kgf/mm 2 The four-point bending strength is 800 MPa-941 MPa, the falling ball energy is 0.50J-0.70J, the ring pressure strength is 800N-1322N, and the mechanical strength can be further improved.
TABLE 5 glass compositions, treatment processes and Properties of comparative examples 1 to 5
As can be seen from the data in Table 5, the glass compositions of comparative examples 1 to 5 are out of the range of the glass-ceramic composition of the present invention, and the glass-ceramic obtained has poor combination properties. The glass of comparative example 1 has poor glass forming property, and insoluble substances exist in glass liquid and a crucible, so that the glass liquid and the crucible are difficult to clarify and uniform and are difficult to prepare into glass products. The glasses prepared in the comparative examples 2 to 3 cannot be crystallized to generate a crystal phase in the preparation process, and the mechanical strength of the glasses is poor; and the reinforced Vickers hardness, four-point bending strength, falling ball energy, ring pressure strength and other properties are poor, and the mechanical strength is poor. Comparative example 4 the glass formulation has a high zirconia content, a large amount of zirconia white insoluble matter floats on the surface of the glass melt during the preparation process, the uniformity of the glass melt is poor, and qualified glass products are difficult to obtain. Comparative example 5 the glass formulation had a high titanium oxide content and the glass was severely colored.
TABLE 6 glass compositions, treatment processes and Properties of comparative examples 6 to 9
As can be seen from the data associated with Table 6, the glass-ceramics of comparative examples 6 to 9 have compositions ratios outside the composition range of the glass-ceramics of the present invention, and are not crystallized by the melting, forming and annealing processes, and the glass body has no crystal phase; and the corresponding crystal phase can be precipitated after further conventional crystallization heat treatment.
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, which is convenient for specific and detailed understanding of the technical solutions of the present invention, but the present invention should not be construed as being limited to the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present 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 present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (11)
1. The microcrystalline glass is characterized by comprising the following components in percentage by mass:
and SiO 2 And Al 2 O 3 The mass ratio of (A) to (B) is 0.86-1.7; zrO (ZrO) 2 And TiO 2 The sum of the mass percentages of the components is a, the mass ratio of the MgO to the ZnO is b, and a is more than or equal to 5 and less than or equal to 10; b/a is more than or equal to 0.02 and less than or equal to 0.17.
2. The glass-ceramic according to claim 1, wherein the crystalline phase of the glass-ceramic comprises at least one of magnesium aluminate spinel, zinc aluminate spinel, and magnesium zincate spinel.
3. The glass-ceramic according to claim 2, wherein the crystalline phase of the glass-ceramic further comprises at least one of zirconia and spodumene.
4. The glass-ceramic according to claim 2, wherein the crystal grain size of the crystal phase is 50nm to 200 μm.
5. The glass-ceramic according to claim 1, wherein the glass-ceramic has a crystallinity of 20% to 65%.
6. The glass-ceramic according to any one of claims 1 to 5, wherein the SiO is SiO 2 In percentage by mass of36 to 50 percent;
and/or, said Al 2 O 3 The mass percentage of (A) is 25-36%;
and/or the MgO accounts for 4-7% by mass;
and/or, the ZnO accounts for 5-11% by mass;
and/or, said B 2 O 3 The mass percentage of the component (A) is 0 to 1.7 percent;
and/or, the Li 2 The mass percent of O is 0.5-3%;
and/or, said Na 2 The mass percent of O is 0-6%;
and/or the BaO accounts for 0 to 1.7 percent by mass;
and/or, the ZrO 2 The mass percentage of (A) is 2-6%;
and/or, the TiO 2 The mass percentage of the component (A) is 1.4-8%.
7. A crystallized glass according to any one of claims 1 to 5, wherein the crystallized glass has an average transmittance of 0.1 to 65% at 380 to 780 nm;
and/or the haze of the microcrystalline glass is more than 24%;
and/or the Vickers hardness of the microcrystalline glass is more than 700kgf/mm 2 。
8. The preparation method of the microcrystalline glass is characterized by comprising the following steps of:
weighing raw materials according to the components of the microcrystalline glass of any one of claims 1-7;
melting the raw materials to prepare molten glass;
and forming the glass liquid to prepare the microcrystalline glass.
9. A tempered glass produced by chemically tempering the glass ceramic according to any one of claims 1 to 7; wherein Li 2 O and/or Na 2 The mass percent of O is not zero。
10. The method for producing a strengthened glass according to claim 9, comprising the steps of:
and carrying out chemical strengthening treatment on the microcrystalline glass in molten salt.
11. Use of the glass-ceramic according to any one of claims 1 to 7 for the production of protective glass, photovoltaic glass or fire-resistant glass.
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