CN115286251B - 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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- CN115286251B CN115286251B CN202210955790.3A CN202210955790A CN115286251B CN 115286251 B CN115286251 B CN 115286251B CN 202210955790 A CN202210955790 A CN 202210955790A CN 115286251 B CN115286251 B CN 115286251B
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- 239000011521 glass Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims description 16
- 239000005341 toughened glass Substances 0.000 title claims description 7
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 78
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 15
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 12
- 229910052596 spinel Inorganic materials 0.000 claims description 18
- 239000011029 spinel Substances 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 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
- 229910052642 spodumene Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002834 transmittance Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000009970 fire resistant effect Effects 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 18
- 239000006121 base glass Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000013001 point bending Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- -1 magnesium aluminate Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000006058 strengthened glass Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 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
- 229910000831 Steel Inorganic materials 0.000 description 2
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000155 melt 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
- 238000005498 polishing Methods 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
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- RUVINXPYWBROJD-ONEGZZNKSA-N trans-anethole Chemical compound COC1=CC=C(\C=C\C)C=C1 RUVINXPYWBROJD-ONEGZZNKSA-N 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
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940011037 anethole Drugs 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000006184 cosolvent 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
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000000227 grinding Methods 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
- 239000011159 matrix material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RUVINXPYWBROJD-UHFFFAOYSA-N para-methoxyphenyl Natural products COC1=CC=C(C=CC)C=C1 RUVINXPYWBROJD-UHFFFAOYSA-N 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
- 238000005036 potential barrier Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Dispersion Chemistry (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides microcrystalline glass, which comprises the following components in percentage by mass: siO (SiO) 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% of TiO 2 0-8%; and SiO 2 Al and Al 2 O 3 The mass ratio of (2) is 0.86-1.7; zrO (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a, the mass ratio of MgO to ZnO is b, and the following conditions 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 ceramics can realize rapid crystallization through reasonable proportioning of glass components without heat treatment steps such as nucleation, crystallization and the like, and the mechanical properties of the glass ceramics are better.
Description
Technical Field
The invention relates to the technical field of glass products, in particular to reinforced glass and microcrystalline glass as well as a preparation method and application thereof.
Background
The microcrystalline glass is also called glass ceramic, and is generally formed by introducing a nucleating agent into a matrix glass formula or adjusting the proportion of oxides in the formula, so that the base glass forms one or more crystalline phases in a subsequent heat treatment process, and the crystalline phases and the glass phases coexist in the glass body to form a multiphase crystal material which has the excellent properties of both glass and ceramic and plays an important role in improving the average hardness, fracture toughness, impact resistance, drop resistance and other properties of the glass.
However, the conventional glass ceramics generally need to be obtained through a plurality of steps such as melting, annealing, nucleating and crystallizing, and the preparation process is complex and consumes energy and time.
Disclosure of Invention
Based on the above, it is necessary to provide a glass ceramic which can be crystallized rapidly and simplify the preparation process, and a preparation method and application thereof.
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 Al and Al 2 O 3 The mass ratio of (2) is 0.86-1.7; zrO (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a, and the mass ratio of MgO to ZnO is b, wherein 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 of these embodiments, the crystalline phase of the glass-ceramic further comprises at least one of zirconia and spodumene.
In some of these embodiments, the crystal phase has a grain size of 50nm to 200 μm.
In some embodiments, the glass-ceramic has a crystallinity of 20% to 65%.
In some of these embodiments, the SiO 2 The mass percentage of (3) is 36-50%.
In some of these embodiments, the Al 2 O 3 The mass percentage of (2) is 25-36%.
In some embodiments, the MgO is 4% to 7% by mass.
In some embodiments, the ZnO is 5% to 11% by mass.
In some of these embodiments, the B 2 O 3 The mass percentage of (2) 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 percentage of O is 0-6%.
In some embodiments, the BaO is 0-1.7% by mass.
In some of these embodiments, the ZrO 2 The mass percentage of (2-6%).
In some of these embodiments, the TiO 2 The mass percentage of (2) is 1.4-8%.
In some embodiments, the average transmittance of the glass ceramics at 380 nm-780 nm is 0.1% -65%.
In some of these embodiments, the glass-ceramic has a haze of greater than 24%.
In some of these embodiments, the glass-ceramic has a Vickers hardness greater than 700kgf/mm 2 。
In another aspect of the present invention, there is also provided a method for preparing glass ceramics, comprising the steps of:
weighing raw materials according to the components of the microcrystalline glass;
melting the raw materials to prepare glass liquid;
and forming the glass liquid to prepare the microcrystalline glass.
In another aspect, the invention also provides a tempered glass prepared from the microcrystalline glass through chemical strengthening; wherein Li is 2 O and/or Na 2 The mass percentage of O is not zero.
In another aspect of the present invention, there is also provided a method for preparing the tempered glass described above, comprising the steps of:
and carrying out chemical strengthening treatment on the glass ceramics in molten salt.
In another aspect, the invention also provides application of the glass ceramics in preparing protective glass, photoelectric glass or fireproof glass.
The glass ceramics comprises SiO with specific proportion 2 、Al 2 O 3 、MgO、ZnO、ZrO 2 TiO (titanium dioxide) 2 Through reasonable proportion of glass components, the glass ceramics can realize rapid crystallization without heat treatment steps such as nucleation, crystallization and the like, and the glass ceramics has better mechanical properties.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of glass ceramics according to example 12 of the present invention;
FIG. 2 is an X-ray diffraction pattern (XRD) of glass-ceramic of example 18 of the present invention.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein 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 Al and Al 2 O 3 Mass ratio (SiO) 2 /Al 2 O 3 ) 0.86 to 1.7; zrO (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a, and the mass ratio (MgO/ZnO) of MgO and 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 glass ceramics comprises SiO with specific proportion 2 、Al 2 O 3 、MgO、ZnO、ZrO 2 TiO (titanium dioxide) 2 Through reasonable proportion of glass components, the glass ceramics can realize rapid crystallization without heat treatment steps such as nucleation, crystallization and the like, and the glass ceramics has better mechanical properties.
SiO 2 Is an oxide related to glass forming and can be used for stabilizing glass and microcrystalline glass network structures. Regarding viscosity and mechanical properties, viscosity and mechanical properties are affected by the glass composition. SiO in glass and glass ceramics 2 As a primary glass-forming oxide for base glass, and can be used to stabilize the network structure of glass and glass-ceramic. In an embodiment of the invention, siO 2 The mass percentage of (2) 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 (3) 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 Composition as spinel and spodumene crystalline phasesHigh Al content 2 O 3 There is a benefit to the formation of crystalline phases. Thus, in an embodiment of the present invention, al 2 O 3 The mass percentage of (2) 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 (2) is 25-36%.
In addition, the invention is realized by controlling Al 2 O 3 With SiO 2 The mass ratio of the catalyst to the catalyst is less than or equal to 0.86 (SiO) 2 /Al 2 O 3 ) The crystallization activation energy of the target crystalline phase can be reduced to a certain extent, the precipitation capacity of the target crystalline phase is enhanced, and the rapid precipitation of the target crystalline phase is facilitated. In addition, the residual glass phase contains Al 2 O 3 The ability of Li-Na and Na-K ion exchange can be enhanced. But Al is 2 O 3 The melting temperature of (2) is high, and Al can be regulated as a network intermediate 2 O 3 To control the viscosity if Al 2 O 3 Too high an amount of (c) 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 body, improving the strength and chemical stability of the base glass, and are also the constituent components of spinel crystal phases. In the embodiment of the invention, the mass percentage of MgO is 2-8% and the mass percentage of ZnO is 5-15%, so that the requirement of sufficient supporting the rapid crystallization of the composition component content of the target crystalline phase in the crystallization process can be fully ensured. In addition, due to Zn 2+ The addition of ZnO increases the crystallization tendency of the base glass and reduces the crystallization activation energy of the target crystalline phase due to the accumulation of high field intensity in the glass melt. When the MgO content is too high, the high-temperature viscosity of the melt is increased, and the melting difficulty is increased. The ZnO raw material is expensive, and if the content is too high, a large amount of ZnO remains in the glass phase, which can lower the glass performance and reduce the Li-Na and Na-K ion exchange capacity of the glass ceramic. Alternatively, the mass percent of MgO is 2%, 3%, 4%, 5%, 6%, 7% or 8%. Further, mass percent of MgOThe percentage is 4-7%. Alternatively, the mass percent of ZnO is 5%, 6%, 8%, 10%, 12%, 14% or 15%. Further, the mass percentage of ZnO is 5-11%.
In the glass ceramic of the present embodiment, tiO 2 ZrO (ZrO) 2 As a commonly used nucleating agent, the MgO-Al can be improved by remarkably improving the crystallization capacity of glass and the liquidus temperature in the forming process 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 potential barrier, and the TiO is generally required to be added 2 Or more ZrO 2 Greatly reduces crystallization activation energy, promotes uniform crystal nucleus precipitation in the base glass, and generates a target crystal phase. But TiO 2 The base glass has a very strong coloring capability, is provided with a darker color, and is not suitable for being excessively added; at the same time, a higher content of TiO 2 The crystal phase growth in the base 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 greatly reduced performance occur. ZrO (ZrO) 2 The solubility in the glass body is low, the melting temperature is extremely high, excessive addition is not suitable, and simultaneously, the ZrO is high 2 The crystal phase growth in the base glass is difficult to control, the abnormal growth is caused, and more impurity phases are generated. Thus, in an embodiment of the invention, zrO 2 2 to 8 percent of TiO 2 Is 0 to 8 mass percent and ZrO 2 TiO (titanium dioxide) 2 The sum a of the mass percentages of the components 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 (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 (2) is 1.4-8%.
Meanwhile, in the microcrystalline glass, the component MgO, znO, tiO influencing the precipitation of crystalline phase of the base glass is regulated and controlled 2 ZrO (ZrO) 2 Satisfies 0.02.ltoreq.b/a.ltoreq.0.17 (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a), and the mass ratio of MgO and ZnO is b), so that the base glass can realize rapid and controllable crystallization, and the nucleation and growth of crystalline phases can be rapidly completed in the melting and pouring process, and finally the glass ceramic block with target crystalline phases, high strength and integrity can be obtained.
Alkali metal oxide Li 2 O and Na 2 O is mainly used as a cosolvent and an ion exchange capacity enhancing component. At the same time Li 2 O can also be used as a crystalline phase component, which is beneficial to the precipitation of spodumene crystalline phase. 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, so in the embodiment of the present invention, li 2 The mass percentage of O is 0-5%; na (Na) 2 The mass percentage of O is 0-10%. 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 percentage 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 Promote the phase separation, nucleation and crystallization of the base glass and shorten the crystallization time of the base glass. In an embodiment of the invention, B 2 O 3 The mass percentage of (2) is 0-3.5%. Alternatively, B 2 O 3 Is 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% or/and 3.5% by mass. Further, B 2 O 3 The mass percentage of (2) is 0-1.7%.
BaO increases the refractive index of glass phase in glass ceramics and can be Ti in the melting process 4+ Providing an oxidizing environment, reducing Ti 3+ The presence of coloring ions. In the embodiment of the invention, the mass percentage of the BaO is 0-5%. Alternatively, the mass percent of BaO is 0, 1%, 2%, 3%, 4%, or 5%. Further, the mass percent of BaO0 to 1.7 percent.
In some embodiments, the glass ceramic comprises the following components in percentage by mass: siO (SiO) 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% of TiO 2 0 to 6 percent; and SiO 2 Al and Al 2 O 3 The mass ratio of (2) is 0.86-1.48; zrO (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a, the mass ratio of MgO to ZnO is b, and the glass ceramics satisfies the following conditions: 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 glass ceramic comprises the following components in percentage by mass: siO (SiO) 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% of TiO 2 0.5% -7%; and SiO 2 Al and Al 2 O 3 The mass ratio of (2) is 0.86-1.56; zrO (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a, the mass ratio of MgO to ZnO is b, and the glass ceramics satisfies the following conditions: 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 glass ceramic comprises the following components in percentage by mass: siO (SiO) 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% of TiO 2 1.4 to 8 percent; and SiO 2 Al and Al 2 O 3 The mass ratio of (2) is 1.07-1.67; zrO (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a, the mass ratio of MgO to ZnO is b, and the glass ceramics satisfies the following conditions: 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 glass-ceramic comprises, by mass percentThe meter comprises the following components: siO (SiO) 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 to 6.6 percent of TiO 2 2% -5%; and SiO 2 Al and Al 2 O 3 The mass ratio of (2) is 0.86-1.70; zrO (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a, the mass ratio of MgO to ZnO is b, and the glass ceramics satisfies the following conditions: 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. Spinel (magnesia-alumina, zincium-alumina, magnesia-zincium spinel) is of the general formula AB 2 O 4 And a cubic basic spinel structured crystalline oxide. The prototype spinel structure was magnesium aluminate (MgAl 2 O 4 ). In a basic spinel structure, O atoms fill face-centered cubic (FCC) array sites. Spinel has extremely high mechanical properties (Mohs hardness is more than 7.5), and is an ideal reinforced and toughened crystalline phase in microcrystalline glass.
In some of these embodiments, the crystalline phase of the glass-ceramic further includes at least one of zirconia and spodumene. Spodumene (LiAlSi) 2 O 6 ) SiO with co-angular connection forming an interconnecting ring 4 And Al 3 O 4 A tetrahedral framework structure, thereby forming channels containing Li ions. The microcrystalline glass with beta-spodumene crystal phase 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 toughening. In addition, glass ceramics based on solid solutions of β -spodumene have good thermal shock resistance. The zirconia crystal phase has extremely high mechanical properties and is an ideal reinforced and toughened crystal phase.
In some of these embodiments, the grain size of the crystalline phase is 50nm to 200 μm. Alternatively, the grain size of the crystalline phase is 50nm, 100nm, 500nm, 1 μm, 10 μm, 50 μm, 100 μm or 200 μm.
In some of these embodiments, the glass-ceramic has a crystallinity of 20% to 65%. Alternatively, the glass-ceramic has a crystallinity of 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, or 65%.
In some of these embodiments, the average transmission of the glass-ceramic is 0.1% -65% at 380 nm-780 nm. According to the different grain sizes and crystallinity of the microcrystalline glass, the average transmittance of the microcrystalline glass in the 380 nm-780 nm area is between 0.1% and 65%, and the appearance of the microcrystalline glass is semitransparent or opaque.
In some of these embodiments, the glass-ceramic has a haze of greater than 24%.
In some of these embodiments, the glass-ceramic has a Vickers hardness greater than 700kgf/mm 2 . Further, the glass ceramics has a Vickers hardness of more than 720kgf/mm 2 Or 750kgf/mm 2 。
The invention also provides a preparation method of the microcrystalline glass, which comprises the following steps S110 to S130.
Step S110: weighing raw materials according to the components of the microcrystalline glass.
Step S120: and melting the raw materials to prepare glass liquid.
In some embodiments, the melting temperature in step S120 is 1450-1650 ℃ and the melting time is 2-10 h.
Step S130: and (5) forming glass liquid to prepare microcrystalline glass.
The preparation method of the glass ceramics has simple procedures and lower preparation cost, does not need complicated heat treatments such as nucleation, crystallization and the like, and can quickly crystallize the glass component raw materials by melting and molding to obtain the glass ceramics.
The invention also provides a reinforced glass prepared from the microcrystalline glass through chemical reinforcement; wherein Li is 2 O and/or Na 2 The mass percentage of O is not zero.
The invention also provides a preparation method of the reinforced glass, which comprises the following steps:
and carrying out chemical strengthening treatment on the microcrystalline glass in molten salt.
In some of these embodiments, the chemical strengthening treatment is performed at a temperature of 420℃to 500 ℃. The time of the chemical strengthening treatment is 2-12 h.
The invention also provides an application of the glass ceramics in preparing protective glass, photoelectric glass or fireproof glass.
The following are specific examples.
The preparation process and test method of the glass ceramics and the tempered glass of examples 1 to 23 and comparative examples 1 to 9 are as follows:
the preparation method comprises the steps of mixing the components (in percentage by mass) in the design components in the following steps of 1-23 and 1-9 in the following steps of 1-6, fully and uniformly mixing, melting the components for 8 hours at 1450-1650 ℃ by using a platinum crucible, stirring the components by using a platinum stirring paddle, preserving heat for 2 hours for homogenization after the stirring paddle is pulled out, casting the components on an iron mold to form glass blocks with the size of 80-160 mm, preheating the glass blocks to 400 ℃ before casting, immediately transferring the glass blocks into an annealing furnace for annealing after hardening, preserving heat for 2 hours, cooling the glass blocks for 140 ℃ for 6 hours, naturally cooling, and taking the glass blocks out for later use.
The glass samples of examples 1-23 were cut into 50 x 0.7mm glass sheets by a STX-1203 wire cutter of Shenyang crystal, thinning and polishing by a Shenzhen Haide HD-640-5L double-sided grinding and polishing machine, the surface was then CNC edged and tested for transmittance over the 380-780nm wavelength range using a Dutch anethole FALCON400 durometer to test for surface Vickers hardness using a Lambda950 ultraviolet visible spectrophotometer from Perkinelmer, inc. of America. SUGA optical HZ-V3 haze meter test sample haze, bruker X-ray diffractometer Bruker D8 advance test its crystalline phase, crystallinity, grain size, etc.
The glass ceramics were immersed in a salt composed of at least one of sodium nitrate and potassium nitrate according to the strengthening process of tables 1 to 6, the samples were kept at 420 to 500 ℃ for 2 to 12 hours, then washed with pure water to obtain final chemically strengthened glass ceramics cover glass, the glass ceramics cover glass was subjected to a test for Li-Na exchange stress depth dol_0 (μm) by scanning with an SLP2000 surface stress meter from japan folding industry limited company in combination with an SEM spectrometer, four-point bending strength (upper press bar spacing 20cm, lower press bar spacing 40 cm) and ring pressure (upper ring 16mm, lower ring 32 mm) by using a mickey MK-9968, ball drop test was performed for the steel ball mass 64 g starting 5 points (drop point distance edge 10 mm), each time was lifted 5cm until breakage, and ball drop energy=0.064 kg x 10n/kg for h was calculated and recorded in tables 1 to 6.
TABLE 1 glass Components, treatments and Properties of examples 1-6
The microcrystalline glass of the examples 1 to 6 comprises the following components in percentage by mass: siO (SiO) 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% of TiO 2 0 to 6 percent; and SiO 2 Al and Al 2 O 3 The mass ratio of (2) is 0.86-1.48; zrO (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a, the mass ratio of MgO to ZnO is b, and the glass ceramics satisfies the following conditions: 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. The microcrystalline glasses of examples 1 to 6 had a Vickers hardness of 723kgf/mm 2 ～778kgf/mm 2 Has better mechanical strength. After the chemical strengthening, the Vickers hardness of the strengthened glass of examples 1 to 6 was 763kgf/mm 2 ～835kgf/mm 2 The four-point bending strength is 818 MPa-952 MPa, the ball falling energy is 0.52J-0.68J, the ring pressure strength is 781N-1241N, and the mechanical strength can be further improved.
TABLE 2 glass Components, treatments and Properties of examples 7-12
The microcrystalline glass of the examples 7-12 comprises the following components in percentage by mass: siO (SiO) 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% of TiO 2 0.5% -7%; and SiO 2 Al and Al 2 O 3 The mass ratio of (2) is 0.86-1.56; zrO (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a, the mass ratio of MgO to ZnO is b, and the glass ceramics satisfies the following conditions: 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 glass ceramics of examples 7 to 12 had a Vickers hardness of 712kgf/mm 2 ～777kgf/mm 2 Has better mechanical strength. After the chemical strengthening, the Vickers hardness of the strengthened glass of examples 7 to 12 was 800kgf/mm 2 ～820kgf/mm 2 The four-point bending strength is 812MPa to 922MPa, the ball falling energy is 0.50J to 0.66J, the ring pressure strength is 773N to 1211N, and the mechanical strength can be further improved.
Referring to FIG. 1, a Scanning Electron Microscope (SEM) picture of the glass-ceramic of example 12 shows that the glass-ceramic has a large number of crystal phases, and the average size of the crystal grains is 80nm.
TABLE 3 glass Components, treatments and Properties of examples 13-18
The microcrystalline glass of the examples 13 to 18 comprises the following components in percentage by mass: siO (SiO) 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% of TiO 2 1.4 to 8 percent; and SiO 2 Al and Al 2 O 3 The mass ratio of (2) is 1.07-1.67; zrO (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a, the mass ratio of MgO to ZnO is b, and the glass ceramics satisfies the following conditions: 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 glass ceramics of examples 13 to 18 had a Vickers hardness of 756kgf/mm 2 ～797kgf/mm 2 Has better mechanical strength. After the chemical strengthening, the Vickers hardness of the strengthened glass of examples 13 to 18 was 795kgf/mm 2 ～854kgf/mm 2 The four-point bending strength is 866 MPa-967 MPa, the ball falling energy is 0.56J-0.69J, the ring pressure strength is 1020N-1350N, and the mechanical strength can be further improved.
Referring to fig. 2, an X-ray diffraction pattern (XRD) of the glass-ceramic of example 18 shows that the glass-ceramic of example 18 has a spinel as a main crystal phase and includes a zirconia crystal phase.
TABLE 4 glass Components, treatments and Properties of examples 19-23
The microcrystalline glass of the embodiment 19 to the embodiment 23 comprises the following components in percentage by mass: siO (SiO) 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 to 6.6 percent of TiO 2 2% -5%; and SiO 2 Al and Al 2 O 3 The mass ratio of (2) is 0.86-1.70; zrO (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a, the mass ratio of MgO to ZnO is b, and the glass ceramics satisfies the following conditions: 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 glass ceramics of examples 19 to 23 had a Vickers hardness of 737kgf/mm 2 ～788kgf/mm 2 Has better mechanical strength. After the chemical strengthening, the Vickers hardness of the strengthened glass of examples 19 to 23 was 779kgf/mm 2 ～849kgf/mm 2 The four-point bending strength is 800 MPa-941 MPa, the ball falling energy is 0.50J-0.70J, the ring pressure strength is 800N-1322N, and the mechanical strength can be further improved.
TABLE 5 glass Components, treatments and Properties of comparative examples 1 to 5
As can be seen from the data in Table 5, the glass components of comparative examples 1 to 5 are not within the range of the glass-ceramic component of the present invention, and the glass-ceramic produced has poor overall properties. The glass of comparative example 1 has poor glass forming property, insoluble substances exist in glass liquid and a crucible, clarification and uniformity are difficult, and glass products are difficult to prepare. The glasses prepared in comparative examples 2 to 3 could not be crystallized to generate crystalline phases during the preparation process, and the mechanical strength of the glasses was poor; and the reinforced steel has poor properties such as Vickers hardness, four-point bending strength, ball falling energy, ring pressure strength and the like, and poor mechanical strength. The glass formula of comparative example 4 has higher zirconia content, a large amount of zirconia white insoluble matters float on the surface of the glass liquid in the preparation process, the uniformity of the glass liquid is poor, and qualified glass products are difficult to obtain. The comparative example 5 glass formulation had a higher titanium oxide content and the glass was severely colored.
TABLE 6 glass Components, treatments and Properties of comparative examples 6 to 9
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As can be seen from the data related to table 6, the compositions of the glass ceramics of comparative examples 6 to 9 are not in the composition range of the glass ceramics of the present invention, and the glass ceramics cannot be crystallized by melting, forming and annealing processes; and the corresponding crystal phase can be separated out after further conventional crystallization heat treatment.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that, based on the technical solutions provided by the present invention, those skilled in the art obtain technical solutions through logical analysis, reasoning or limited experiments, all of which are within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (10)
1. The microcrystalline glass is characterized by comprising the following components in percentage by mass:
SiO 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％、
ZnO 5％～15％、
BaO 0～5％、
ZrO 2 2% -8%
TiO 2 0～8％；
And SiO 2 Al and Al 2 O 3 The mass ratio of (2) is 0.86-1.56; zrO (ZrO) 2 TiO (titanium dioxide) 2 The sum of the mass percentages of MgO and ZnO is a, and the mass ratio of MgO to ZnO is b, wherein 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 crystalline phase of the microcrystalline glass comprises at least one of magnesia-alumina spinel, zinc-alumina spinel and magnesia-zinc spinel, and also comprises at least one of zirconia and spodumene; the haze of the microcrystalline glass is greater than 24%;
the preparation method of the microcrystalline glass comprises the following steps:
weighing raw materials according to the components of the microcrystalline glass;
melting the raw materials to prepare glass liquid;
and forming the glass liquid to prepare the microcrystalline glass.
2. The glass-ceramic according to claim 1, wherein the crystal phase has a grain size of 50nm to 200 μm.
3. The glass-ceramic according to claim 1, wherein the glass-ceramic has a crystallinity of 20% to 65%.
4. A glass-ceramic according to any one of claims 1 to 3, wherein the SiO 2 The mass percentage of (3) is 36-50%;
and/or the Al 2 O 3 The mass percentage of (2) is 25-36%;
and/or, the mass percentage of MgO is 4% -7%;
and/or, the mass percentage of the ZnO is 5-11%;
and/or, the B 2 O 3 The mass percentage of (2) is 0-1.7%;
and/or, the Li 2 The mass percentage of O is 0.5-3%;
and/or the Na 2 The mass percentage 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 (2-6 percent);
and/or, the TiO 2 The mass percentage of (2) is 1.4-8%.
5. A glass-ceramic according to any one of claims 1 to 3, wherein the glass-ceramic has an average transmittance of 0.1% to 65% at 380nm to 780 nm;
and/or the microcrystalline glass has a Vickers hardness greater than 700kgf/mm 2 。
6. The preparation method of the glass ceramics is characterized by comprising the following steps:
weighing raw materials according to the components of the microcrystalline glass according to any one of claims 1 to 5;
melting the raw materials to prepare glass liquid;
and forming the glass liquid to prepare the microcrystalline glass.
7. The method for producing glass ceramics according to claim 6, wherein the melting temperature is 1450 to 1650 ℃, and the melting time is 2 to 10 hours.
8. A tempered glass as claimed in any one of claims 1 to 5The microcrystalline glass is prepared through chemical strengthening; wherein Li is 2 O and/or Na 2 The mass percentage of O is not zero.
9. The method for producing a tempered glass according to claim 8, comprising the steps of:
and carrying out chemical strengthening treatment on the glass ceramics in molten salt.
10. Use of a glass ceramic according to any one of claims 1 to 5 for producing a protective glass, a photovoltaic glass or a fire-resistant glass.
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