CN117800593A - Lithium silicon glass, reinforced glass, and preparation methods and applications thereof - Google Patents
Lithium silicon glass, reinforced glass, and preparation methods and applications thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 140
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 72
- 239000005368 silicate glass Substances 0.000 claims abstract description 72
- 239000002159 nanocrystal Substances 0.000 claims abstract description 32
- 238000002834 transmittance Methods 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 238000005728 strengthening Methods 0.000 claims abstract description 9
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003426 chemical strengthening reaction Methods 0.000 claims abstract description 7
- 239000005341 toughened glass Substances 0.000 claims description 31
- 239000011734 sodium Substances 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 230000009970 fire resistant effect Effects 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 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 6
- 239000006064 precursor glass Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052670 petalite Inorganic materials 0.000 claims description 5
- 229910052644 β-spodumene Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052637 diopside Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910018068 Li 2 O Inorganic materials 0.000 abstract description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 4
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000006058 strengthened glass Substances 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 238000005520 cutting process 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
- 238000005496 tempering Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QZRLETONGKUVFA-UHFFFAOYSA-N [K].[Cs] Chemical compound [K].[Cs] QZRLETONGKUVFA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 210000003918 fraction a Anatomy 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910003251 Na K Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 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
- 239000003345 natural gas Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Abstract
The invention relates to lithium silicon glass, reinforced glass, and a preparation method and application thereof. The lithium silicon glass comprises the following components in percentage by mass: siO (SiO) 2 69％～76％、Al 2 O 3 0～9％、K 2 O 0～4.5％、MgO 0～2％、Na 2 O 0～5％、Li 2 O 9％～16％、ZrO 2 0～5.2％、B 2 O 3 0～1％、P 2 O 5 2 to 4.5 percent, 0 to 4 percent of CaO and 0 to 3 percent of ZnO; the lithium silicate glass contains nanocrystal cores, and the crystal phase of the nanocrystal cores comprises lithium disilicate. Through reasonable proportion of components, the lithium silicon glass has higher visible light transmittance, higher softening temperature, higher elastic modulus and higher strengthening stress after being subjected to chemical strengthening, and has better fire resistance.
Description
Technical Field
The invention relates to the technical field of glass products, in particular to lithium silicon glass, reinforced glass, and a preparation method and application thereof.
Background
The fireproof glass has the main function of controlling the spread of fire or isolating smoke during fireproof, and is one fireproof material with fireproof effect evaluated in fireproof performance. The glass is special glass which is processed and treated by special technology and can keep the integrity and heat insulation in a specified fire resistance test. The main stream of monolithic fire-proof glass on the market comprises cesium potassium fire-proof glass, borosilicate fire-proof glass and microcrystalline fire-proof glass. Cesium potassium fireproof glass has higher strength, but is easy to burst when subjected to thermal shock; the borosilicate fireproof glass has low thermal expansion coefficient and good thermal shock resistance; but the strength of the glass is lower; the microcrystalline fireproof glass has higher strength and fire resistance, but lower visible light transmittance, and limits the application of the microcrystalline fireproof glass.
Disclosure of Invention
Based on the above, it is necessary to provide a lithium silicate glass with high transmittance and good fire resistance, a reinforced glass, and a preparation method and application thereof.
The invention provides lithium silicon glass, which comprises the following components in percentage by mass:
the lithium silicate glass contains nanocrystal cores, and crystal phases of the nanocrystal cores comprise lithium disilicate.
In some of these embodiments, the crystalline phase of the nanocrystal core further includes at least one of cristobalite, diopside, petalite, beta-spodumene, and wollastonite.
In some of these embodiments, the volume fraction a of the nanocrystal core satisfies: 0 < a < 1%.
In some of these embodiments, the lithium silicate glass satisfies at least one of the conditions (1) to (8):
(1) SiO in the lithium silicon glass 2 The mass percentage of (2) is 70-73%;
(2) Al in the lithium silicon glass 2 O 3 The mass percentage of (2.5-8 percent);
(3) K in the lithium silicon glass 2 The mass percentage of O is 0-1%;
(4) Na in the lithium silicon glass 2 The mass percentage of O is 0-4%;
(5) Li in the lithium silicon glass 2 The mass percentage of O is 9.8-13.4%;
(6) ZrO in the lithium silicate glass 2 The mass percentage of (2) is 1.5-4.8%;
(7) The mass percentage of CaO in the lithium silicon glass is 0-1.5%;
(8) The mass percentage of ZnO in the lithium silicon glass is 0-1.5%.
In some of these embodiments, the lithium silicate glass satisfies at least one of the conditions (1) to (4):
(1) The thermal expansion coefficient of the lithium silicon glass is 89 multiplied by 10 -7 /℃～107×10 -7 /℃；
(2) The softening temperature of the lithium silicon glass is 575-645 ℃;
(3) The elastic modulus of the lithium silicon glass is 78 GPa-85 GPa;
(4) The visible light transmittance of the lithium silicon glass is more than or equal to 90 percent.
In a second aspect, the invention also provides a preparation method of the lithium silicon glass, which comprises the following steps:
weighing raw materials according to the components of the lithium silicate glass in the first aspect;
mixing the raw materials, and preparing glass liquid by melting;
shaping and annealing the glass liquid to prepare precursor glass; and
And (3) carrying out heat treatment on the precursor glass to prepare the lithium silicon glass.
In a third aspect, the present invention also provides a tempered glass obtained by subjecting the lithium silicate glass of the first aspect to a chemical tempering treatment.
In some of these embodiments, the tempered glass satisfies at least one of the conditions (1) to (5):
(1) The surface stress value CS of the reinforced glass is 684 MPa-1058 MPa;
(2) The stress depth Dol-Na of the reinforced glass is 136-182 mu m;
(3) The softening temperature of the reinforced glass after being burnt by open fire is 865-940 ℃;
(4) The elastic modulus of the reinforced glass after firing by open fire is 92 GPa-102 Gpa;
(5) The fire-resistant time of the reinforced glass is more than or equal to 4 hours.
In a fourth aspect, the present invention also provides a method for preparing a tempered glass, comprising the steps of:
carrying out strengthening treatment on the lithium silicate glass in molten salt; the molten salt comprises 0-15% of sodium nitrate and 85-100% of potassium nitrate by mass percent.
In a fifth aspect, the present invention also provides the use of the tempered glass of the third aspect in the preparation of fire-resistant glass.
The lithium silicon glass component comprises silicon oxide, lithium oxide and phosphorus pentoxide in a specific content ratio, and contains nanocrystal cores, wherein crystal phases of the nanocrystal cores comprise lithium disilicate. Through reasonable proportion of components, the lithium silicon glass has higher transmittance, higher visible light transmittance, higher softening temperature, higher elastic modulus and higher strengthening stress after chemical strengthening, and better fire resistance.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. This invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used 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.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics. The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
In the present invention, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The percentage content referred to in the present invention refers to mass percentage for both solid-liquid mixing and solid-solid mixing and volume percentage for liquid-liquid mixing unless otherwise specified.
The percentage concentrations referred to in the present invention refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system after the component is added.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The invention provides lithium silicon glass, which comprises the following components in percentage by mass:
the lithium silicate glass contains nanocrystal cores, and crystal phases of the nanocrystal cores comprise lithium disilicate.
The lithium silicon glass component comprises silicon oxide, lithium oxide and phosphorus pentoxide in a specific content ratio, and contains nanocrystal cores, wherein crystal phases of the nanocrystal cores comprise lithium disilicate. The nanocrystal core refers to a crystal core with a particle size of less than or equal to 1 nm. The nanocrystal core has smaller particle size, and the lithium silicate glass still presents the property of glass phase, thus having higher transmittance. The nanocrystal core can be rapidly crystallized after being heated by fire, and the softening temperature and the mechanical strength of the glass are improved, so that the method is particularly suitable for preparing fireproof glass. Through reasonable proportion of components, the lithium silicon glass has higher visible light transmittance, higher softening temperature, higher elastic modulus and higher strengthening stress after being subjected to chemical strengthening, and has better fire resistance.
In some of these embodiments, the crystalline phase of the nanocrystal core further includes at least one of cristobalite, diopside, petalite, beta-spodumene, and wollastonite.
In some of these embodiments, the volume fraction a of nanocrystal cores satisfies: 0 < a < 1%. The volume ratio of the nanocrystal core is in the range, the volume ratio is smaller, and the lithium silicate glass mainly shows the property of glass phase and has higher visible light transmittance.
SiO 2 Is a network forming oxide, is an essential component for forming a glass skeleton, can improve the strength, chemical stability and the like of glass, can obtain higher strain points and lower thermal expansion coefficients of the glass. SiO (SiO) 2 Too low a content of (2) and too high a rise in thermal expansion coefficient, reduced molding and chemical resistance, and a tendency to crystallize; siO (SiO) 2 If the content of (c) is too high, the glass melting and refining temperatures will be higher, and the viscosity will increase, making it difficult to homogenize the glass, which is detrimental to the glass forming process. Thus, in an embodiment of the invention, siO 2 The mass percentage of (3) is 69-76%. Optionally, siO in lithium silicate glass 2 The mass percent of the composition is within the range of any of the following values: 69%, 70%, 71%, 72%, 73%, 74%, 75% or 76%. Further, siO in lithium silicate glass 2 The mass percentage of (2) is 70-73%.
Al 2 O 3 The network may also be stabilized and also provide improved mechanical properties and chemical durability. In an embodiment of the invention, al in lithium silicate glass 2 O 3 The mass percentage of (2) is 0-9%. Optionally, al in lithium silicate glass 2 O 3 The mass percentage of (a) is 0, 1%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8% or 9% in the range of any numerical composition. Further, al in lithium silicate glass 2 O 3 The mass percentage of (2.5-8%).
Li 2 O is one of the components forming the nanocrystal core phase and also acts as a co-solvent and as a component to enhance ion exchange capacity. In an embodiment of the invention, li in the lithium silicate glass 2 The mass percentage of O is 9-16%. Optionally Li in lithium silicate glass 2 The mass percentage of O is in the range of any of the following values: 9%, 9.8%,10%, 11%, 12%, 13%, 13.4%, 14%, 15% or 16%. Further, li in lithium silicate glass 2 The mass percentage of O is 9.8-13.4%.
Na 2 Action of O with Li 2 O is similar as a co-solvent and ion exchange enhancing component in lithium silicate glass. In an embodiment of the invention, na in the lithium silicate glass 2 The mass percentage of O is 0-5%. Optionally Na in lithium silicate glass 2 The mass percentage of O is in the range of any of the following values: 0. 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%. Further, na in lithium silicate glass 2 The mass percentage of O is 0-4%.
K 2 Action of O Na 2 O approaches, but K acts as a cosolvent in the glass 2 Too much O reduces the power of Na-K ion exchange. In an embodiment of the invention, K is in lithium silicate glass 2 The mass percentage of O is 0-4.5%. Alternatively, K in lithium silicate glass 2 The mass percentage of O is in the range of any of the following values: 0 to 4.5 percent. Further, K in lithium silicate glass 2 The mass percentage of O is 0-1%.
MgO is an external oxide of a network, and is helpful for reducing the melting point of glass, reducing the viscosity of the glass at high temperature, promoting the melting and clarification of the glass, enhancing the stability of the network space of the glass at low temperature and reducing the thermal expansion coefficient of the glass to a certain extent. In the embodiment of the invention, the mass percentage of MgO in the lithium silicon glass is 0-2%. Optionally, the mass percent of MgO in the lithium silicate glass is in the range of any of the following values: 0. 0.1%, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 1.6%, 1.8% or 2%.
ZnO has the function similar to MgO, is beneficial to reducing the high-temperature viscosity of glass, modifying the glass structure body and improving the strength and chemical stability of the glass. In the embodiment of the invention, the mass percentage of ZnO in the lithium silicon glass is 0-3%. Optionally, the mass percent of ZnO in the lithium silicate glass is in the range of any of the following values: 0. 0.5%, 1%, 1.5%, 2%, 2.5% or 3%. Further, the mass percentage of ZnO in the lithium silicon glass is 0-1.5%.
CaO acts similarly to MgO, and in the embodiment of the present invention, the mass percentage of CaO in the lithium silica glass is 0 to 4%. Optionally, the mass percentage of CaO in the lithium silicate glass is within the range of any of the following values: 0. 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5% or 4%. Further, the mass percentage of CaO in the lithium silicate glass is 0 to 1.5 percent.
ZrO 2 Added as a conventional nucleating agent. ZrO (ZrO) 2 The stability of lithium silicate glass systems can be improved by significantly reducing glass devitrification and liquidus temperature during formation. In an embodiment of the invention, zrO in lithium silicate glass 2 The mass percentage of (2) is 0-5.2%. Optionally, zrO in lithium silicate glass 2 The mass percent of the composition is within the range of any of the following values: 0. 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 4.8%, 5% or 5.2%. Further, zrO in lithium silicate glass 2 The mass percentage of (2) is 1.5-4.8%.
P 2 O 5 Can be used as a nucleating agent to promote glass nucleation. In an embodiment of the invention, P in lithium silicate glass 2 O 5 The mass percentage of (2-4.5%). Optionally, P in lithium silicate glass 2 O 5 The mass percent of the composition is within the range of any of the following values: 2%, 2.5%, 3%, 3.5%, 4% or 4.5%.
B 2 O 3 Helps to provide lithium silicate glass with a low melting temperature and can promote the formation of nanocrystal cores. In an embodiment of the invention, B in the lithium silicate glass 2 O 3 The mass percentage of (2) is 0-1%. Alternatively, B in lithium silicate glass 2 O 3 The mass percent of the composition is within the range of any of the following values: 0. 0.2%, 0.4%, 0.5%, 0.6%, 0.8% or 1%.
In some of these embodiments, the lithium silicate glass has a thermal expansion coefficient of 89X 10 at 50℃to 500 ℃ -7 /℃～107×10 -7 /℃。
In some of these embodiments, the softening temperature of the lithium silicate glass is 575 ℃ to 645 ℃.
In some of these embodiments, the modulus of elasticity of the lithium silicate glass is between 78GPa and 85GPa. The elastic modulus of the lithium silicate glass is in the above range, and the mechanical strength of the lithium silicate glass is preferable.
In some embodiments, the visible light (400 nm-800 nm) transmittance of the lithium silicate glass is greater than or equal to 90%. The visible light transmittance of the lithium silicate glass is within the above range, and the lithium silicate glass exhibits a transparent appearance.
The invention also provides a preparation method of the lithium silicon glass, which comprises the following steps S110 to S140.
S110: weighing raw materials according to the components of the lithium silicate glass.
S120: mixing the raw materials, melting, and preparing glass liquid.
In some of these embodiments, the temperature of the melting is 1500 ℃ to 1600 ℃; the melting time is 4-10 h.
S130: and forming and annealing the glass liquid to prepare the precursor glass.
In some of these embodiments, the forming process includes one of float forming, slot down-draw forming, overflow forming, down-draw forming, flat-draw forming, up-draw forming, and extended-press forming.
S140: and (3) performing heat treatment on the precursor glass to prepare the lithium silicon glass.
In some of these embodiments, the temperature of the heat treatment is from 560 ℃ to 680 ℃; the heat treatment time is 4-8 h. Further, the temperature of the heat treatment is 570-650 ℃; the heat treatment time is 4-8 h.
The invention also provides a reinforced glass which is obtained by the chemical reinforcing treatment of the lithium silicate glass.
The reinforced glass has good surface stress value and large stress depth, and has good thermal shock resistance.
In some of these embodiments, the strengthened glass has a surface stress value CS of 684MPa to 1058MPa. Further, the surface stress value CS of the tempered glass is 785MPa to 994MPa. The surface stress value CS of the tempered glass is within the range, so that the tempered glass has better thermal shock resistance and is prevented from being burst by heating.
In some of these embodiments, the strengthened glass has a stress depth Dol-Na of 136 μm to 182 μm. Further, the stress depth Dol-Na of the tempered glass is 153 μm to 178 μm. Stress depth Dol-Na of the tempered glass is within the range, the surface of the tempered glass is provided with a stress layer with proper thickness, and the tempered glass has good thermal shock resistance.
The reinforced glass is prepared by chemically reinforcing the lithium silicon glass, the glass body contains nanocrystal cores, and after the glass body is burnt by open fire, crystalline phases can be quickly separated out by heating the reinforced glass, so that the softening temperature and the elastic modulus of the reinforced glass can be further improved, and the reinforced glass has better fire resistance.
In some of these embodiments, the strengthened glass has a softening temperature of 865 ℃ to 940 ℃ after firing with an open flame. Further, the softening temperature of the tempered glass after firing by open fire is 872-934 ℃. The softening temperature of the tempered glass after firing by open fire is in the range, the softening temperature is higher, the tempered glass is not easy to soften and collapse under the firing for a longer time, and the fire resistance is better.
In some of these embodiments, the strengthened glass has an elastic modulus of 92GPa to 102GPa after firing with an open flame. Further, the elastic modulus of the reinforced glass after firing by open fire is 97GPa to 102GPa. The reinforced glass precipitates crystalline phases after being burned by open fire, and the elastic modulus of the reinforced glass is also improved, so that the reinforced glass has better mechanical strength.
In some of these embodiments, the fire time of the tempered glass is greater than or equal to 4 hours. Further, the fire-resistant time of the reinforced glass is more than or equal to 5 hours.
The invention also provides a preparation method of the reinforced glass, which comprises the following step S210.
S210: the lithium silicate glass is subjected to strengthening treatment in molten salt. The molten salt comprises 0-15% of sodium nitrate and 85-100% of potassium nitrate by mass percent.
In some of these embodiments, the temperature of the strengthening treatment is 380 ℃ to 420 ℃; the strengthening treatment time is 2-6 h.
In another embodiment, the invention also provides an application of the reinforced glass of the third aspect in preparing fireproof glass.
The following are specific examples.
The preparation method comprises the steps of mixing the components designed in the examples 1-12 and the comparative examples 1-6 according to the specifications shown in the tables 1-3, melting the components for 8 hours at 1500-1600 ℃ by using a platinum crucible, stirring the components by using a platinum stirring paddle, cooling to 1300-1400 ℃ after the stirring paddle is pulled out, preserving heat for 2H for homogenization, casting the components on an iron mold to form glass blocks with the size of 80 x 160mm, preheating the glass blocks to 450 ℃ before casting, immediately transferring the glass blocks into an annealing furnace for annealing after hardening, preserving heat for 2 hours, cooling to 140 ℃ after 6 hours, naturally cooling, and taking out the glass blocks for later use.
The glass sample is subjected to preccleation treatment by heat preservation for 4-8 h at 560-680 ℃, is cut into 140 x 6mm glass sheets by an STX-1203 wire cutting machine of Shenyang crystal, is thinned and polished by a Shenzhen Hold HD-640-5L double-sided grinding polisher, is tested for thermal expansion coefficient at 50-500 ℃ by a relaxation-resistant Classic 402PC thermal expansion instrument, and is measured for glass softening temperature according to the method of national standard GB/T-28195-2011. The Lambda950 ultraviolet-visible spectrophotometer of Perkinelmer Inc. of U.S.A. was tested for transmittance over the wavelength range of 400nm to 800 nm. The elastic modulus of glass was tested using JC/T687-1997 (2007) test method of elastic modulus, shear modulus and Poisson's ratio of glass material. The test results are recorded in tables 1 to 3.
And (3) immersing the glass sample subjected to the prenucleation treatment in a mixed solution of 0-15 wt% of sodium nitrate and 85-100 wt% of potassium nitrate at 380-420 ℃ for 2-6 hours for chemical strengthening treatment. The surface compressive stress CS (Mpa) and the stress depth Dol-Na (μm) were measured by a surface stress meter of SLP2000 and FSM-6000LE, japan, inc. The test results are recorded in tables 1 to 3.
Burning the central area of the reinforced glass by using a natural gas gun, measuring the temperature of the contact surface of flame and the glass at 900-950 ℃, observing the cracking or serious deformation degree of the glass after different times of burning, and recording the fire-resistant failure time; cutting a sample central area which is burnt for more than or equal to 3 hours into a sample with phi 5 mm, cutting the crystallization sample which is burnt and fire-resistant tested into a sample with phi 20mm, testing the crystal phase type of the sample by a Bruker X-ray diffractometer Bruker D8 advance, and testing the thermal expansion coefficient, softening temperature, transmittance and elastic modulus of the sample at 50-500 ℃ according to the testing method. The results are shown in tables 4 to 6.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
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TABLE 6
As can be seen from the data related to tables 1 to 6, the lithium silicate glasses of examples 1 to 6 comprise the following components in mass percent: siO (SiO) 2 69％～75.44％、Al 2 O 3 0～8.97％、K 2 O 0～4.39％、MgO 0～0.5％、Na 2 O 0～5％、Li 2 O 9％～15.4％、ZrO 2 0～5.2％、B 2 O 3 0～0.5％、P 2 O 5 2 to 4.37 percent, 0 to 3.75 percent of CaO and 0 to 2.92 percent of ZnO; the lithium silicate glass contains nanocrystal cores, and the crystal phase of the nanocrystal cores comprises lithium disilicate, and optionally at least one of cristobalite, spodumene, petalite, wollastonite and beta-spodumene. The lithium silicate glasses of examples 1 to 6 have a thermal expansion coefficient of 89.4X10 at 50 to 500 ℃ -7 ℃～107×10 -7 The softening temperature is 575-642 ℃, the elastic modulus is 79-84 GPa, and the visible light transmittance is 90.8-91%. The surface stress value CS of the reinforced glass prepared by the chemical reinforcing treatment of the examples 1 to 6 is 684MPa to 1058MPa, and the stress depth Dol-Na is 136 μm to 182 μm. The tempered glass of examples 1 to 6 has a thermal expansion coefficient of 80.4X10 at 50 to 500℃after firing -7 ℃～98.4×10 -7 The softening temperature is 865-962 ℃, the elastic modulus is 92-102 GPa, and the visible light transmittance is 78.6-90.2%. The fire-resistant failure time of the reinforced glass is more than or equal to 4 hours.
The lithium silicate glass of examples 7 to 12 comprises the following components in percentage by mass: siO (SiO) 2 70％～73％、Al 2 O 3 2.6％～8.4％、K 2 O 0～1.5％、MgO 0～2％、Na 2 O 0～4％、Li 2 O 9.8％～13.4％、ZrO 2 1.5％～4.8％、B 2 O 3 0～1％、P 2 O 5 2 to 4.4 percent, 0 to 1.5 percent of CaO and 0 to 1.5 percent of ZnO; the lithium silicate glass contains nanocrystal cores, and the crystal phase of the nanocrystal cores comprises lithium disilicate, and optionally at least one of cristobalite, petalite and beta-spodumene. The lithium silicate glasses of examples 7 to 12 have a thermal expansion coefficient of 89.5X10 at 50 to 500 ℃ -7 ℃～98.2×10 -7 The softening temperature is 583-635 ℃, the elastic modulus is 78-83 GPa, and the visible light transmittance is 90.9-91%. The surface stress value CS of the reinforced glass prepared by the chemical reinforcing treatment of examples 7 to 12 is 785MPa to 994MPa, and the stress depth Dol-Na is 153 μm to 178 μm. The tempered glass of examples 7 to 12 had a thermal expansion coefficient of 78.5X10 at 50 to 500℃after firing -7 ℃～88.1×10 -7 The softening temperature is 872-934 ℃, the elastic modulus is 97-102 GPa, and the visible light transmittance is 62.7-90.6%. The fire-resistant failure time of the reinforced glass is more than 5 hours.
The lithium silicate glass of comparative example 1 is different from example 11 in that it does not contain nanocrystal cores without being subjected to a pre-nucleation treatment; its thermal expansion coefficient at 50-500 deg.C is 90.8X10 -7 The performance of the lithium silica glass of example 11 was substantially identical to that of the glass having a softening temperature of 618℃and an elastic modulus of 82GPa and a visible light transmittance of 91 ℃. The surface stress value CS of the tempered glass prepared by the chemical tempering treatment of comparative example 1 was 785MPa, the stress depth Dol-Na was 153 μm, and the performance was substantially the same as that of the tempered glass of example 11. The tempered glass of comparative example 1 has a thermal expansion coefficient of 91.2X10 at 50 to 500℃after firing -7 The softening temperature is 615 ℃, the elastic modulus is 82GPa, and the visible light transmittance is 90.4%. The fire-resistant failure time of the reinforced glass is more than 5 hours, and the reinforced glass is softened and collapses under heating; this is probably because the tempered glass of comparative example 1 does not contain nanocrystal cores, and the tempered glass cannot be rapidly crystallized by burning and heating, so that the softening temperature of the tempered glass is increased, and the fire resistance is poor.
Comparative example 2 is different from example 11 in that the lithium silicate glass has not been subjected to strengthening treatment. The lithium silicate glass of comparative example 2 was burned to have a refractory failure time of less than 1 hour, and was cracked after burning; it can be seen that comparative example 2The lithium silicon glass is not subjected to chemical strengthening, and the heat shock resistance is poor. The lithium silicate glass of comparative example 2 has a thermal expansion coefficient of 87.9X10 at 50 to 500℃after firing -7 The softening temperature is 648 ℃, the elastic modulus is 86GPa, the visible light transmittance is 90.1%, and the softening temperature is not obviously improved, which is probably due to the fact that the glass is quickly burst when heated and is insufficient to form a large amount of crystal phases to improve the softening temperature.
Comparative example 3 does not contain P in the lithium silicate glass component 2 O 5 It is difficult to form nanocrystal cores. After the tempered glass subjected to chemical strengthening treatment is burned, a crystalline phase is difficult to separate out, the tempered glass is softened and collapses by heating, and the fire-resistant failure time is less than 0.1 hour.
The components of the lithium silicate glasses of comparative examples 4 to 6 are not within the scope of the present invention, and the tempered glasses of comparative examples 4 to 6 obtained by chemical tempering have inferior fire resistance to the tempered glasses of examples 1 to 12 in the fire resistance time after firing of not more than 3 hours.
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 of the invention should therefore be determined with reference to the appended claims, which are to be construed as in accordance with the doctrines of claim interpretation.
Claims (10)
1. The lithium silicon glass is characterized by comprising the following components in percentage by mass:
the lithium silicate glass contains nanocrystal cores, and crystal phases of the nanocrystal cores comprise lithium disilicate.
2. The lithium silicate glass according to claim 1, wherein the crystalline phase of the nanocrystal core further comprises at least one of cristobalite, diopside, petalite, β -spodumene and wollastonite.
3. The lithium silicate glass according to claim 1, wherein the volume ratio a of the nanocrystal cores satisfies: 0 < a < 1%.
4. The lithium silicate glass according to claim 1, wherein the lithium silicate glass satisfies at least one of the conditions (1) to (8):
(1) SiO in the lithium silicon glass 2 The mass percentage of (2) is 70-73%;
(2) Al in the lithium silicon glass 2 O 3 The mass percentage of (2.5-8 percent);
(3) K in the lithium silicon glass 2 The mass percentage of O is 0-1%;
(4) Na in the lithium silicon glass 2 The mass percentage of O is 0-4%;
(5) Li in the lithium silicon glass 2 The mass percentage of O is 9.8-13.4%;
(6) ZrO in the lithium silicate glass 2 The mass percentage of (2) is 1.5-4.8%;
(7) The mass percentage of CaO in the lithium silicon glass is 0-1.5%;
(8) The mass percentage of ZnO in the lithium silicon glass is 0-1.5%.
5. The lithium silica glass according to claims 1 to 4, wherein the lithium silica glass satisfies at least one of the conditions (1) to (4):
(1) The thermal expansion coefficient of the lithium silicon glass is 89 multiplied by 10 -7 /℃～107×10 -7 /℃；
(2) The softening temperature of the lithium silicon glass is 575-645 ℃;
(3) The elastic modulus of the lithium silicon glass is 78 GPa-85 GPa;
(4) The visible light transmittance of the lithium silicon glass is more than or equal to 90 percent.
6. The preparation method of the lithium silicon glass is characterized by comprising the following steps of:
the component weighing raw materials of the lithium silicate glass according to any one of claims 1 to 5;
mixing the raw materials, and preparing glass liquid by melting;
shaping and annealing the glass liquid to prepare precursor glass; and
And (3) carrying out heat treatment on the precursor glass to prepare the lithium silicon glass.
7. A reinforced glass obtained by subjecting the lithium silicate glass according to any one of claims 1 to 5 to a chemical strengthening treatment.
8. The tempered glass according to claim 7, wherein the tempered glass satisfies at least one of the conditions (1) to (5):
(1) The surface stress value CS of the reinforced glass is 684 MPa-1058 MPa;
(2) The stress depth Dol-Na of the reinforced glass is 136-182 mu m;
(3) The softening temperature of the reinforced glass after being burnt by open fire is 865-940 ℃;
(4) The elastic modulus of the reinforced glass after firing by open fire is 92 GPa-102 Gpa;
(5) The fire-resistant time of the reinforced glass is more than or equal to 4 hours.
9. A method for producing a tempered glass, comprising the steps of:
carrying out strengthening treatment on the lithium silicate glass in molten salt; the molten salt comprises 0-15% of sodium nitrate and 85-100% of potassium nitrate by mass percent.
10. Use of the tempered glass of claim 7 or 8 for the preparation of fire resistant glass.
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