CN117361886A - Microcrystalline glass, reinforced microcrystalline glass, preparation method and application thereof - Google Patents
Microcrystalline glass, reinforced microcrystalline glass, preparation method and application thereof Download PDFInfo
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- CN117361886A CN117361886A CN202311533644.2A CN202311533644A CN117361886A CN 117361886 A CN117361886 A CN 117361886A CN 202311533644 A CN202311533644 A CN 202311533644A CN 117361886 A CN117361886 A CN 117361886A
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- 239000011521 glass Substances 0.000 title claims abstract description 158
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 98
- 239000013078 crystal Substances 0.000 claims abstract description 26
- 229910004283 SiO 4 Inorganic materials 0.000 claims abstract description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 10
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims description 84
- 239000006064 precursor glass Substances 0.000 claims description 24
- 238000002425 crystallisation Methods 0.000 claims description 22
- 230000008025 crystallization Effects 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 15
- 238000005496 tempering Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002834 transmittance Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000006058 strengthened glass Substances 0.000 claims description 7
- 230000009970 fire resistant effect Effects 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005328 architectural glass Substances 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 35
- 239000011734 sodium Substances 0.000 description 24
- 239000011701 zinc Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 17
- 239000011787 zinc oxide Substances 0.000 description 17
- 239000011159 matrix material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 7
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000002667 nucleating agent Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000005341 toughened glass Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 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 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000006112 glass ceramic composition Substances 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide 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
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 241000249820 Lipotes vexillifer Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 229940011037 anethole Drugs 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The application relates to the technical field of glass, in particular to microcrystalline glass, reinforced microcrystalline glass and a preparation method and application thereof. The glass ceramics comprises a glass parent phase and a crystal phase, wherein the crystal phase is dispersed in the glass parent phase in the form of particles, and the crystal phase comprises Zn 2 SiO 4 Crystalline phase and ZnAl 2 O 4 A crystalline phase. Wherein, the microcrystalline glass comprises the following components in percentage by mass: 48% -66% of SiO 2 18% -28% of Al 2 O 3 0.1% -3% of Li 2 O, 4% -18% of ZnO and 0% -5% of P 2 O 5 1.2% -7% of TiO 2 0-8% of Na 2 O and 0 to 8% of K 2 O, and the Na 2 O and the K 2 The sum of the mass percentages of O is not more than 8%.
Description
Technical Field
The application relates to the technical field of glass, in particular to microcrystalline glass, reinforced microcrystalline glass and a preparation method and application thereof.
Background
With the rapid development of the electronic information industry, electronic products such as mobile phones and tablet computers are becoming necessities in daily life. The electronic product comprises display screen glass and/or backboard protective glass. However, conventional glass is a brittle material and its actual strength is far lower than the theoretical strength due to the presence of surface cracks. The electronic products adopting the traditional glass as the display screen and/or the backboard have poorer performances such as drop resistance, scratch resistance and the like. Therefore, it is important to improve the strength of glass.
Microcrystalline glass is a material in which a crystal phase is precipitated inside glass by crystallizing conventional glass. The crystal phase can deflect the propagation path of the crack, so that the tip of the crack is passivated, and the strength of the glass is improved. However, the presence of the crystalline phase also reduces the ion exchange performance of the glass-ceramic, so that the ion exchange process of the glass-ceramic requires a higher temperature and longer time than conventional glass, which not only reduces the production efficiency, but also significantly increases the production cost. And the mechanical strength of the traditional glass ceramics is still to be improved. In addition, as the microcrystalline glass is not easy to generate ion exchange, the mechanical strength of the glass product obtained after the chemical tempering treatment is difficult to meet the requirements of practical application.
Therefore, how to improve the mechanical strength and ion exchange performance of glass ceramics is a problem to be solved.
Disclosure of Invention
Based on the above, the application provides the microcrystalline glass with higher mechanical strength and better ion exchange performance and the preparation method thereof. In addition, the application also provides reinforced microcrystalline glass with good mechanical strength, and a preparation method and application thereof.
In a first aspect, the present application provides a glass-ceramic comprising a glass matrix phase and a crystalline phase, the crystalline phase being in the form of particlesThe particles are dispersed in the glass mother phase, and the crystal phase comprises Zn 2 SiO 4 Crystalline phase and ZnAl 2 O 4 A crystalline phase;
wherein, the microcrystalline glass comprises the following components in percentage by mass:
SiO 2 48%~66%、
Al 2 O 3 18%~28%、
Li 2 O 0.1%~3%、
ZnO 4%~18%、
P 2 O 5 0~5%、
TiO 2 1.2%~7%、
Na 2 0-8% of O
K 2 O 0~8%；
And the Na is 2 O and the K 2 The sum of the mass percentages of O is not more than 8%.
The microcrystalline glass comprises SiO with specific mass percent 2 、Al 2 O 3 、Li 2 O、ZnO、P 2 O 5 、TiO 2 、Na 2 O and K 2 O，Na 2 O and K 2 The sum of the mass percentages of O is not more than 8%, and the glass parent phase comprises Zn 2 SiO 4 Crystalline phase and ZnAl 2 O 4 Crystalline phase, in which ZnAl 2 O 4 The crystalline phase itself has better mechanical properties, thus ZnAl 2 O 4 The introduction of the crystalline phase improves the mechanical strength of the glass ceramics. Further, compared with other crystal phases contained in the conventional glass ceramics, zn 2 SiO 4 Better ion exchange capacity of the crystalline phase, thus Zn 2 SiO 4 The introduction of the crystalline phase can improve the ion exchange performance of the whole glass ceramics, so that the tempered glass ceramics with higher mechanical strength can be obtained after tempering treatment. In the glass ceramic, znAl 2 O 4 Crystalline phase and Zn 2 SiO 4 The mechanical strength of the glass ceramics can be further improved by the cooperation of crystal phases.
In some embodiments, the glass ceramic satisfies at least one of the following (1) - (2):
(1) The crystallinity of the microcrystalline glass is 15% -50%;
(2) The average transmittance of the glass ceramics in the visible light wave band is more than or equal to 75 percent.
In some embodiments, the glass ceramic satisfies at least one of the following (1) - (2):
(1) The microcrystalline glass comprises the following components in percentage by mass 2 O 3 ZrO 0-6% 2 0-8% MgO;
(2) The microcrystalline glass also comprises SnO with the sum of the mass percent not more than 0.5 percent 2 、CeO 2 And Sb (Sb) 2 O 3 。
In some of these embodiments, the glass-ceramic composition further comprises MgO, and the crystalline phase further comprises Mg x Zn (1-x) Al 2 O 4 A crystalline phase, wherein 0 < x.ltoreq.1.
In some embodiments, the glass ceramic satisfies at least one of the following (1) - (7):
(1) The SiO is 2 The mass percentage of (2) is 50% -66%;
(2) The Al is 2 O 3 The mass percentage of the catalyst is 20% -25%;
(3) The Li is 2 The mass percentage of O is 0.1% -2%;
(4) The mass percentage of ZnO is 5% -14.7%;
(5) The P is 2 O 5 The mass percentage of the catalyst is 0-2.5%;
(6) The TiO 2 The mass percentage of (2-5%);
(7) The Na is 2 The mass percentage of O is 0.1% -4%.
In a second aspect, the present application provides a method for preparing glass ceramics, including the steps of:
weighing raw materials according to the components of the microcrystalline glass of the first aspect;
melting and shaping raw materials to prepare precursor glass;
and crystallizing the precursor glass to prepare the microcrystalline glass.
In some of these embodiments, na 2 O and K 2 O provides the starting material in the form of the corresponding nitrate and the other components provide the starting material in the form of the corresponding oxide.
In some embodiments, the crystallization treatment is performed at 600-800 ℃ for 30 min-20 h.
In a third aspect, the present application provides a tempered glass-ceramic, which is obtained by subjecting the glass-ceramic of the first aspect to chemical tempering treatment, wherein the vickers hardness of the tempered glass-ceramic is greater than 7.5 GPa.
In a fourth aspect, the present application provides a method for preparing a strengthened glass ceramic, where the glass ceramic of the first aspect is chemically tempered by one or two ion exchange steps.
In some of these embodiments, the one-step ion exchange comprises the steps of: ion exchange is carried out on the microcrystalline glass in first molten salt; the first molten salt comprises 40-60% KNO by mass percent 3 And 40% -60% NaNO 3 The ion exchange condition is that the ion exchange is carried out for 2 to 5 hours at 440 to 480 ℃.
In some of these embodiments, the two-step ion exchange comprises the steps of: performing first ion exchange on the microcrystalline glass in second molten salt, and performing second ion exchange on the microcrystalline glass subjected to the first ion exchange in third molten salt; the second molten salt comprises NaNO 3 The condition of the first ion exchange is that the ion exchange is carried out for 2 to 6 hours at 440 to 480 ℃; the third molten salt comprises KNO 3 The condition of the second ion exchange is that the ion exchange is carried out for 0.5 to 3 hours at the temperature of 400 to 440 ℃.
In a fifth aspect, the present application provides a tempered glass-ceramic of the third aspect or a tempered glass-ceramic produced according to the production method of the fourth aspect for use in producing a protective glass, a fire-resistant glass or a building glass.
Drawings
FIG. 1 is an X-ray diffraction chart of the glass ceramic obtained in example 1.
Detailed Description
In order to make the above objects, features and advantages of the present application more comprehensible, embodiments accompanied with the present application are described in detail below. In the following description, numerous specific details are set forth
The details are provided to facilitate a thorough understanding of the present application. This application is, however, susceptible of embodiment in many other forms than those described herein and similar modifications can be made by those skilled in the art without departing from the spirit of the application, and therefore the application is not to be limited to the specific embodiments disclosed below.
In the description of the present application, the meaning of "plurality" is at least two, such as two, three, etc., unless explicitly defined otherwise. As used herein, "at least one" refers to any one, any two, or any two or more of the listed items. As used herein, "above a certain number" should be understood to mean a range of numbers and greater than a certain number.
The term "and/or," "and/or" as used in this application includes any one of two or more of the listed items in relation to each other and also includes any and all combinations of the listed items in relation to each other, including any two or more of the listed items in relation to each other, or all combinations of the listed items in relation to each other.
Where the terms "comprising," "having," "including," and "containing" are used herein, it is intended to cover a non-exclusive inclusion, such that another element may be added, unless a specifically defined term is used, such as "consisting of … … only," etc. Unless mentioned to the contrary, singular terms may include plural and are not to be construed as being one in number.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
"content" as described herein is mass percent unless otherwise defined.
The microcrystalline glass is a multiphase material which is formed by crystallizing the traditional glass to uniformly separate out tiny crystals in the glass and simultaneously contains a compact crystal phase and a glass mother phase. The crystal phase has better mechanical properties, so that the mechanical properties such as hardness, strength, toughness and the like of the microcrystalline glass are obviously improved, and further, the product containing the microcrystalline glass has better scratch resistance, drop resistance and the like. However, the presence of the crystalline phase also reduces the ion exchange properties of the glass-ceramics, and therefore the glass-ceramics have higher ion exchange temperatures and longer time. Thus, not only the production efficiency is reduced, but also the manufacturing cost is increased.
The ion exchange performance of glass ceramics is affected by the composition and content of the glass matrix phase, the composition, content and size of the crystal phase, and other factors. Through the composition design and microstructure regulation of the microcrystalline glass, the ion exchange performance and the mechanical strength of the microcrystalline glass are improved, and the microcrystalline glass has important significance for improving mechanical properties such as the strength of products.
The research of the application finds that the poor ion exchange capability of the traditional microcrystalline glass is mainly because the progress of ion exchange is influenced by crystal phases such as lithium disilicate, spinel and the like contained in the traditional microcrystalline glass. In addition, for the traditional microcrystalline glass with higher lithium oxide content, the production cost is high, the devitrification tendency of spodumene can be enhanced, the product is devitrified, and the transmittance of the glass is reduced. For traditional microcrystalline glass with higher zinc oxide content, the zinc oxide in the glass prevents ion exchange, and the mechanical strength of the product is reduced.
One embodiment of the present application provides a glass ceramic comprising a glass matrix phase and a crystalline phase, the crystalline phase being dispersed in the glass matrix phase in the form of particles, the crystalline phase comprising Zn 2 SiO 4 Crystalline phase and ZnAl 2 O 4 A crystalline phase;
wherein, the microcrystalline glass comprises the following components in percentage by mass:
SiO 2 48%~66%、
Al 2 O 3 18%~28%、
Li 2 O 0.1%~3%、
ZnO 4%~18%、
P 2 O 5 0~5%、
TiO 2 1.2%~7%、
Na 2 0-8% of O
K 2 O 0~8%；
And Na is Na 2 O and K 2 The sum of the mass percentages of O is not more than 8%.
Microcrystalline glass is based on aluminosilicate glass and generally comprises SiO 2 、Al 2 O 3 And alkali metal elements (e.g., na and K). SiO (SiO) 2 As a skeleton component of a network structure in a glass parent phase, al 2 O 3 As an intermediate of a network structure in the glass parent phase, the alkali metal element is used as a network modifier. Zn is introduced into the microcrystalline glass of the application 2 SiO 4 Crystalline phase and ZnAl 2 O 4 The crystalline phase serves as a crystalline phase and is distributed within the network structure of the glass parent phase.
The microcrystalline glass comprises SiO with specific mass percent 2 、Al 2 O 3 、Li 2 O、ZnO、P 2 O 5 、TiO 2 、Na 2 O and K 2 O，Na 2 O and K 2 The sum of the mass percentages of O is not more than 8%, and the glass parent phase comprises Zn 2 SiO 4 Crystalline phase and ZnAl 2 O 4 A crystalline phase. Wherein ZnAl 2 O 4 The crystalline phase itself has better mechanical properties, thus ZnAl 2 O 4 The introduction of the crystalline phase improves the mechanical strength of the glass ceramics. Further, compared with other crystal phases contained in the conventional glass ceramics, zn 2 SiO 4 Better ion exchange capacity of the crystalline phase, thus Zn 2 SiO 4 The introduction of the crystalline phase can improve the ion exchange performance of the whole microcrystalline glass. In the glass ceramic, znAl 2 O 4 Crystalline phase and ZnAl 2 O 4 The mechanical strength of the glass ceramics can be further improved by the cooperation of crystal phases.
Zn in the form of a powder 2 SiO 4 Crystalline phase and ZnAl 2 O 4 The crystalline phases may be dispersed in the glass matrix phase independently of each other in the form of particles, and small amounts of linkages may also be present between the particles.
Further, by properly adjusting the components of the glass ceramics, particularly Al 2 O 3 、ZnO、P 2 O 5 And TiO 2 The adjustment of the relative content and the crystallization treatment condition can effectively control Zn 2 SiO 4 Crystalline phase and ZnAl 2 O 4 Formation of a crystalline phase to give a Zn-containing composition 2 SiO 4 Crystalline phase and ZnAl 2 O 4 Microcrystalline glass in a crystalline phase.
Silicon dioxide (SiO) 2 ) Is a framework component of a glass matrix phase in the glass ceramics, and can enhance the mechanical properties of the glass ceramics. SiO (SiO) 2 Has low thermal expansion coefficient, siO in glass system 2 The higher the content, the smaller the thermal expansion coefficient of the microcrystalline glass, and the higher the mechanical strength. But SiO 2 Has a higher melting point, if SiO 2 Too high a content of (c) increases the difficulty in melting the raw materials, resulting in difficulty in molding the glass. Based on this, siO 2 The content of (C) is 48% -66%, when SiO 2 When the content of the glass is less than 48%, the network space of the glass matrix phase is loose, and the mechanical property of the glass ceramics is reduced. When SiO 2 When the content exceeds 66%, the melting difficulty of the raw material is high.
Alumina (Al) 2 O 3 ) Is a component necessary for increasing the ion exchange capacity of the glass ceramics, and can improve the chemical stability and the elastic modulus of the glass ceramics. At the same time Al 2 O 3 Participated in ZnAl 2 O 4 In the crystallization process of the crystal phase, znAl in microcrystalline glass 2 O 4 The content of the crystalline phase has a certain influence. In addition to Al 2 O 3 The amount of (2) also affects the volume of network space in the glass matrix. Based on this, al 2 O 3 The content of (2) is 18% -28%, and specifically may be 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27% or 28%. When Al is 2 O 3 The content is less than 18%, the network space structure of the glass parent phase is loose, and the ion exchange efficiency is reduced. When Al is 2 O 3 The content of the glass is more than 28%, the high-temperature viscosity of the glass system is obviously increased, and the melting temperature is excessively high in the production process, so that the energy consumption is increased, and the control of the discharge of bubbles is not facilitated.
Lithium oxide (Li) 2 O) is an ideal flux and is also an essential component for ion exchange. Specifically, li + Can be combined with Na in molten salt + And/or K + Ion exchange is carried out, so that the product has more excellent mechanical impact resistance. In addition, due to Li + The polarization characteristic of the polymer can effectively reduce the high-temperature viscosity at high temperature. Based on this, li 2 The content of O is 0.1% -3%, and specifically can be 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5% or 3%. When Li 2 The content of O is higher than 3%, the spodumene in the system has too high crystallization tendency and is difficult to control, and the transparency of the product is further affected.
Zinc oxide (ZnO) is advantageous for reducing the high temperature viscosity of the glass system, modifying the structure of the glass matrix phase, and improving the strength and chemical stability of the product. At the same time, znO is Zn 2 SiO 4 Crystalline phase and ZnAl 2 O 4 The composition of the crystalline phase and the content of ZnO have a certain influence on the content of the crystalline phase in the microcrystalline glass. Based on the content, the ZnO content is 4% -18%, and specifically can be 4%, 8%, 15%, 16%, 17% or 18%. Since ZnO may hinder ion exchange, when the content of ZnO is more than 18%, the ion exchange performance of the glass-ceramic may be degraded.
When Al is 2 O 3 At a lower content of (2) introducing a certain amount of P 2 O 5 The glass enters a network structure of a glass parent phase, so that gaps of the network structure are increased, and the aim of enhancing the ion exchange capacity is fulfilled. In addition, P 2 O 5 The introduction of the glass ceramic can further improve the strain point of the glass ceramic, can alleviate the problem of stress relaxation in the ion exchange process, and can improve the surface compressive stress value after strengthening. P (P) 2 O 5 Is introduced into Zn 2 SiO 4 The formation of a crystalline phase is also promoted. Based on this, P 2 O 5 The content of (2) is 0-5%, specifically 0, 0.1%, 1%, 2%, 3%, 3.5%, 4%, 4.5% or 5%. When P 2 O 5 When the content of (C) is higher than 5%The viscosity of the glass system is increased, resulting in opacification of the glass during the fusion process.
Titanium dioxide (TiO) 2 ) Is a nucleating agent in glass, and because the ZnO content in the application is small, tiO needs to be added 2 To ensure Zn 2 SiO 4 Formation of a crystalline phase. Based on this, tiO 2 The content of (2) is 1.2% -7%, and can be 1.2%, 2%, 3%, 4%, 5%, 5.5%, 6%, 6.5% or 7%. When TiO 2 When the amount of the additive is too large, the product is easy to be black, and the transmittance of the product is affected.
Sodium oxide (Na) 2 O) and potassium oxide (K) 2 O) improves the melting properties of the glass system and is made by Na + And K + After the exchange, a compressive stress layer can be formed on the surface of the product, so that the chemical strength of the glass ceramics is enhanced. Further, na 2 O and K 2 The sum of the mass percentages of O is not more than 8%.
Alternatively, na 2 The mass percentage of O is 0-8%, specifically 0, 0.1%, 0.5%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8%. When Na is + When the content is too high, the strength of the compressive stress layer formed after ion exchange is lowered. In addition, due to Na + Does not participate in crystallization and thus leads to Na remaining in the glass matrix phase + Higher than Na in the raw materials + Is contained in the composition. Alternatively, K 2 The mass percentage of O is 0-8%, specifically 0, 0.1%, 0.5%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8%.
In a specific example, the crystallinity of the glass ceramic is 15% -50%. If the crystallinity is too small, the ZnO content in the glass body is higher, and if ZnO blocks ion exchange, the subsequent tempering leads to low ion exchange depth; the crystallinity is too large, the growth size of crystal grains is difficult to control, and microcrystalline glass with lower transparency is easy to form.
In a specific example, the average transmittance of the glass ceramics in the visible light band is more than or equal to 75 percent. It is understood that the above average transmittance is related to the particle size of the crystal phase in the glass-ceramic, and in particular, when the particle size of the crystal phase is too large, the average transmittance is lowered.
In one specific example, the grain size of the crystalline phase is 10 nm to 100 nm.
In a specific example, the microcrystalline glass further comprises 0-5% of B 2 O 3 ZrO 0-6% 2 And 0-8% MgO.
Boron oxide (B) 2 O 3 ) The flux can be used as a fluxing agent, and a space end network formed by the flux can slide in a certain range. When stress exists in the microcrystalline glass, larger deformation can be obtained for buffering, so that the generation of cracks is reduced, and the elastic modulus of the microcrystalline glass is reduced. But B is 2 O 3 When the content is too high, exceeding 5%, the ion exchange capacity of the glass ceramics is remarkably reduced. Based on this, B 2 O 3 The content of (2) is not more than 5%, and may be specifically 0, 0.1%, 1%, 2%, 3%, 4% or 5%.
Zirconia (ZrO) 2 ) Is a nucleating agent in microcrystalline glass. Proper amount of nucleating agent can reduce Zn 2 SiO 4 Crystalline phase and ZnAl 2 O 4 The crystallite size of the crystalline phase is such that the glass-ceramic remains transparent. In some embodiments, the nucleating agent is capable of forming the glass system into a crystalline phase without crystallization. Based on this, zrO 2 The content of (2) is not more than 5%, and may be specifically 0, 0.1%, 1%, 2%, 3%, 4% or 5%. Magnesium oxide (MgO) can reduce the viscosity of a glass system at high temperature and improve the forming property of glass. However, too high a magnesium oxide content results in a significant reduction in the depth of the compressive stress layer formed by the ion exchange. Based on this, the content of MgO does not exceed 8%, and specifically may be 0, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7% or 8%.
In a specific example, the glass-ceramic composition further comprises MgO, and the crystalline phase further comprises Mg x Zn (1-x) Al 2 O 4 A crystalline phase, wherein 0 < x.ltoreq.1. The glass ceramics of this example also contains Mg x Zn (1-x) Al 2 O 4 The crystalline phase can further improve the mechanical strength of the glass ceramics.
In a specific example, the microcrystalline glass also comprises the following components in percentage by massMore than 0.5% SnO 2 、CeO 2 And Sb (Sb) 2 O 3 。
Tin oxide (SnO) 2 ) Cerium oxide (CeO) 2 ) And antimony trioxide (Sb) 2 O 3 ) Can be used as clarifier. Due to TiO 2 Ti of (B) 4+ The valence state change can occur in the microcrystalline glass, which is easy to cause the microcrystalline glass to be black, so that a small amount of clarifying agent is added to ensure the oxidizing atmosphere in the melting process, and the transparency of the microcrystalline glass is increased. SnO (SnO) 2 、CeO 2 And Sb (Sb) 2 O 3 The sum of the mass percentages of (a) is not more than 0.5%, and may be specifically 0, 0.1%, 0.2%, 0.3%, 0.4% or 0.5%.
In a specific example, siO 2 The mass percentage of (a) is 50% -66%, and can be 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65% or 66%.
In a specific example, al 2 O 3 The mass percentage of (2) is 20% -25%, and can be specifically 20%, 21%, 22%, 23%, 24% or 25%.
In a specific example, li 2 The mass percentage of O is 0.1% -2%, and can be specifically 0.1%, 0.4%, 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 1.6% or 2%.
In a specific example, the ZnO is 5% -14.7% by mass, and may specifically be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 14.7%.
In one specific example, P 2 O 5 The mass percentage of (2) is 0-2.5%, and can be specifically 0, 0.1%, 0.5%, 1%, 1.5%, 2% or 2.5%.
In one specific example, tiO 2 The mass percentage of (2% -5%), specifically can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.
In a specific example, na 2 The mass percentage of O is 0.1% -4%, and can be specifically 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5% or 4%.
Further, the application also provides a preparation method of the microcrystalline glass, which comprises the following steps:
s100: weighing raw materials according to the components of the microcrystalline glass;
s200: melting and shaping raw materials to prepare precursor glass;
s300: and crystallizing the precursor glass to prepare the microcrystalline glass.
Accurately weighing raw materials, fully mixing the raw materials, heating and melting to form molten glass liquid, forming the glass liquid to obtain precursor glass, and crystallizing the precursor glass to obtain the microcrystalline glass. It will be appreciated that the skilled person can suitably select common glass raw materials such as oxides and nitrates and the like to give the glass ceramics a desired composition.
In a specific example, na 2 O is NaNO 3 For providing raw materials, K 2 O is KNO 3 Is provided for raw materials.
Further, remove Na 2 O and K 2 The other components than O provide the starting materials in the form of the corresponding oxides. Illustratively, the feedstock includes SiO 2 、Al 2 O 3 、Li 2 O、ZnO、P 2 O 5 、TiO 2 、NaNO 3 And KNO 3 Etc.
In one specific example, the melting temperature is 1500 ℃ to 1650 ℃, and specifically may be 1500 ℃, 1550 ℃, 1600 ℃, or 1650 ℃.
Shaping is the process of converting a molten glass liquid into a shaped precursor glass. The precursor glass may be a glass plate or glass block. In one specific example, the shaping of the precursor glass may be performed by a float forming process, overflow downdraw, draw-up, flat draw, calendaring, and the like.
In one specific example, the molten glass is cast into a mold and annealed to provide a precursor glass. The annealing temperature is 450-620 ℃, and specifically can be 450 ℃, 500 ℃, 550 ℃, 600 ℃ or 620 ℃.
The crystallization treatment is a process for generating a crystal phase of glass, and has an important influence on the structure and performance of microcrystalline glass. The crystallization treatment may be one-step crystallization treatment or two-step crystallization treatment.
In a specific example, the crystallization process is performed at 600 ℃ to 800 ℃ for 30 min to 20 h, the specific temperature may be 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃, and the time may be 30 min, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h, 18 h, 19 h, or 20 h. When the crystallization treatment temperature is 600-800 ℃ and the time is 30 min-20 h, zn can be ensured 2 SiO 4 Crystalline phase and ZnAl 2 O 4 The formation of the crystalline phase and the crystallinity of the glass-ceramic and the average particle diameter of the crystalline phase can be controlled.
In addition, the application also provides reinforced glass ceramics obtained by carrying out chemical tempering treatment on the glass ceramics. The vickers hardness of the reinforced microcrystalline glass is more than 7.5 GPa.
Further, the application also provides a preparation method of the reinforced glass ceramics, and the glass ceramics is subjected to chemical tempering treatment through one-step ion exchange or two-step ion exchange.
In some of these embodiments, the one-step ion exchange comprises the steps of:
and carrying out ion exchange on the microcrystalline glass in the first molten salt.
In a specific example, the one-step ion exchange further comprises a cutting process of the precursor glass. The size and thickness of the glass sheet obtained by cutting can be adjusted according to actual requirements, the thickness range is 0.2 mm-1.1 mm, and the size range is 4 inches-20 inches.
In the ion exchange process, alkali metal ions on the surface of the glass ceramics are replaced by alkali metal ions with larger diameters to obtain the reinforced glass ceramics. Thus, the volume difference is formed on the surface of the reinforced microcrystalline glass, and then a compressive stress layer with a certain depth is formed on the surface of the reinforced microcrystalline glass, so that the mechanical strength of the reinforced microcrystalline glass is improved. The alkali metal ion on the surface of the glass ceramics comprises Na + And Li (lithium) + During ion exchange, li + With Na in molten salt + And/or K + Exchange takes place, na + With K in molten salt + The exchange occurs.
In one specific example, the first molten salt includes KNO of 40% -60% 3 And 40% -60% NaNO 3 . The ion exchange process includes Na + And Li (lithium) + Exchange of (C) and Na + And K + Is a function of the exchange of (a).
The time and temperature of ion exchange have an effect on the surface compressive stress of the strengthened glass ceramic. Based on the above, the ion exchange condition is that the ion exchange is carried out at 440-480 ℃ for 2-5 hours, the specific temperature can be 440 ℃, 450 ℃, 460 ℃, 470 ℃ or 480 ℃, and the time can be 2 h, 3 h, 4 h or 5 h.
The glass ceramics are subjected to one-step ion exchange, so that the prepared reinforced glass ceramics have better mechanical properties and stability.
In some of these embodiments, the two-step ion exchange comprises the steps of:
performing first ion exchange on the microcrystalline glass in the second molten salt;
and carrying out second ion exchange on the microcrystalline glass subjected to the first ion exchange in third molten salt.
In one specific example, the two-step ion exchange further comprises a cutting process of the precursor glass. The size and thickness of the glass sheet obtained by cutting can be adjusted according to actual requirements, the thickness range is 0.2 mm-1.1 mm, and the size range is 4 inches-20 inches.
In one particular example, the second molten salt includes NaNO 3 . The first ion exchange process uses Na + And Li (lithium) + Is mainly exchanged.
In one particular example, the third molten salt includes KNO 3 . The second ion exchange process uses Na + And K + Is mainly exchanged.
In a specific example, the first ion exchange is performed at 440-480 ℃ for 2-6 hours, the specific temperature may be 440 ℃, 450 ℃, 460 ℃, 470 ℃ or 480 ℃, and the time may be 2 h, 3 h, 4 h, 5 h or 6 h.
In one specific example, the second ion exchange is performed at 400 ℃ to 440 ℃ for 0.5 h to 3 h, the specific temperature may be 400 ℃, 410 ℃, 420 ℃, 430 ℃ or 440 ℃, and the time may be 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h or 3 h.
By carrying out two-step ion exchange on the glass ceramics, two layers of different compressive stress areas are formed in the prepared reinforced glass ceramics, so that the generation and the expansion of cracks in the product are effectively prevented, and the mechanical properties of the reinforced glass ceramics are further improved.
Finally, the application also provides application of the strengthened microcrystalline glass or the strengthened microcrystalline glass prepared by the preparation method in preparation of protective glass, fireproof glass or building glass.
The protective glass can be applied to the fields of electronic equipment, windows, semiconductor devices and the like. Electronic devices include, but are not limited to, cell phones, tablet computers, televisions, wearable devices, and other terminal devices. Such fire-resistant glass includes, but is not limited to, composite fire-resistant glass and monolithic fire-resistant glass. Such architectural glass includes, but is not limited to, flat glass, decorative glass, and safety glass.
In order to make the objects and advantages of the present application more apparent, the present application will be described in further detail with reference to examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
The preparation process and test method of the glass ceramics and the reinforced glass ceramics of examples 1 to 30 and comparative examples 1 to 2 are as follows:
(1) Preparation of precursor glass
Examples 1-30 and comparative examples 1-2 were formulated according to the composition ratios (mass percent) designed in tables 1-6, and those skilled in the art can appropriately select commonly used glass raw materials (e.g., oxides and nitrates) so that the resulting precursor glasses had the compositions shown in the tables. Weigh the ingredients with total mass greater than 1000 g, mix them thoroughly and place them in a platinum crucible with volume greater than 400 mL. Then, the platinum crucible is put into a silicon-molybdenum furnace to be melted on 8 h at 1600 ℃, homogenized and cast into a die, and precision annealing is carried out at an annealing temperature of 500 ℃ to obtain the precursor glass.
(2) Preparation of microcrystalline glass
The precursor glasses obtained in each example and comparative example were subjected to crystallization treatment to obtain microcrystalline glass, and specific tempering conditions are shown in tables 1 to 6. The obtained glass ceramics are cut into glass ceramics slices of 5 mm multiplied by 5 mm multiplied by 0.8 mm, and preparation is made for the subsequent chemical tempering treatment. The composition of the glass hardly changed before and after the crystallization treatment, and only a crystal phase was formed in the glass. In other words, the composition of the glass-ceramic is the same as the composition of the precursor glass.
(3) Preparation of reinforced microcrystalline glass
The glass ceramic sheets of examples 1 to 30 were subjected to two-step ion exchange, and specific tempering conditions are shown in tables 1 to 5. Since the precursor glasses obtained in comparative examples 1 and 2 had poor properties after crystallization treatment and were difficult to chemically temper, the tempered glass ceramics were not prepared in comparative examples 1 and 2. In addition, na in the glass ceramics of example 3 2 O、Li 2 O and K 2 Low O content, na capable of ion exchange + 、Li + And K + Since ion exchange is difficult, tempering is not performed.
(4) Performance test method
The thermal expansion curve of the precursor glass before crystallization treatment was tested at a temperature rising rate of 5 ℃/min using a thermal expansion instrument (NETZSCH-DIL 402PC, resistant to relaxation, germany) and with reference to the GB/T16920-2015 standard, and the coefficient of thermal expansion CTE and glass transition temperature Tg were obtained by self-contained software.
The vickers hardness of the precursor glass before crystallization treatment, the microcrystalline glass after crystallization treatment and the tempered microcrystalline glass after tempering treatment were tested using a vickers hardness tester (FALCON-400 of anethole) and referring to GB/T37900-2019 standard.
The transmittance (i.e., visible light transmittance) of crystallized glass ceramics in the wavelength range of 380 nm to 800 nm is tested by an ultraviolet-visible light spectrophotometer (Lambda 950 of Perkinelmer corporation, U.S.) and by referring to the GB/T40415-2021 standard.
The crystallinity and the composition of the crystalline phase of the crystallized glass ceramics were tested by an X-ray diffractometer (Empyrean, shanghai's baiji instrument systems, inc.), and the compositions of the crystalline phases of the precursor glasses of comparative examples 1 to 2 after crystallization were tested.
The ion exchange depth of the tempered glass ceramics after the chemical tempering treatment was tested by a surface stress instrument (FSM 6000UV of japan foldback).
The test results are shown in tables 1 to 6. And figure 1 shows the X-ray diffraction pattern of example 1.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
TABLE 6
As can be seen from the test results of tables 1 to 6, the glass ceramics of examples 1 to 30 include Zn 2 SiO 4 Crystalline phase and ZnAl 2 O 4 The crystalline phase has higher hardness after crystallization treatment, which means that the glass ceramics of the above embodiments have higher mechanical strength and higher visible light transmittance. In addition, the microcrystalline glass of examples 1 to 30 can obtain a stress layer with a larger ion exchange depth after the tempering treatment, which indicates that the microcrystalline glass has better ion exchange performance, and thus the tempered microcrystalline glass with higher hardness can be obtained.
Li in the glass composition of comparative example 1 2 Higher O content, excessive Li 2 O forms LiAl (SiO 3 ) 2 As is clear from the test results, the precursor glass of comparative example 1 is subject to cracking after crystallization treatment, and the obtained glass-ceramic is whitish and opaque, and is difficult to meet the requirements of practical applications. The glass composition of comparative example 2 does not satisfy the range of the present application, and ZnAl is not contained in the glass ceramic 2 O 4 A crystal phase having a hardness of only 6.1 GPa, which indicates Zn in the glass ceramics of the present application 2 SiO 4 Crystalline phase and ZnAl 2 O 4 The crystalline phase can improve the hardness of the glass ceramics, thereby achieving the purpose of improving the mechanical strength of the glass ceramics.
FIG. 1 is an X-ray diffraction chart of a glass-ceramic obtained in example 1, which shows that the glass-ceramic contains aluminum zinc spinel (ZnAl 2 O 4 ) Crystalline phase and willemite (Zn) 2 SiO 4 ) A crystalline phase.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples only represent a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the claims. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. The scope of the patent is, therefore, indicated by the appended claims, and the description may be used to interpret the contents of the claims.
Claims (10)
1. A glass ceramic is characterized by comprising a glass mother phase and a crystal phase, wherein the crystal phase is dispersed in the glass mother phase in the form of particles, and the crystal phase comprises Zn 2 SiO 4 Crystalline phase and ZnAl 2 O 4 A crystalline phase;
wherein, the microcrystalline glass comprises the following components in percentage by mass:
SiO 2 48%~66%、
Al 2 O 3 18%~28%、
Li 2 O 0.1%~3%、
ZnO 4%~18%、
P 2 O 5 0~5%、
TiO 2 1.2%~7%、
Na 2 0-8% of O
K 2 O 0~8%；
And the Na is 2 O and the K 2 The sum of the mass percentages of O is not more than 8%.
2. The glass-ceramic according to claim 1, wherein the glass-ceramic satisfies at least one of the following (1) to (2):
(1) The crystallinity of the microcrystalline glass is 15% -50%;
(2) The average transmittance of the glass ceramics in the visible light wave band is more than or equal to 75 percent.
3. The glass-ceramic according to claim 2, wherein the glass-ceramic satisfies at least one of the following (1) to (2):
(1) The microcrystalline glass comprises the following components in percentage by mass 2 O 3 ZrO 0-6% 2 0-8% MgO;
(2) The microcrystalline glass also comprises SnO with the sum of the mass percent not more than 0.5 percent 2 、CeO 2 And Sb (Sb) 2 O 3 。
4. The glass-ceramic according to claim 3, wherein the glass-ceramic further comprises MgO, and the crystal phase further comprises Mg x Zn (1-x) Al 2 O 4 A crystalline phase, wherein 0 < x.ltoreq.1.
5. The glass-ceramic according to any one of claims 1 to 4, wherein the glass-ceramic satisfies at least one of the following (1) to (7):
(1) The SiO is 2 The mass percentage of (2) is 50% -66%;
(2) The Al is 2 O 3 The mass percentage of the catalyst is 20% -25%;
(3) The Li is 2 The mass percentage of O is 0.1% -2%;
(4) The mass percentage of ZnO is 5% -14.7%;
(5) The P is 2 O 5 The mass percentage of the catalyst is 0-2.5%;
(6) The TiO 2 The mass percentage of (2-5%);
(7) The Na is 2 The mass percentage of O is 0.1% -4%.
6. The preparation method of the glass ceramics is characterized by comprising the following steps:
weighing raw materials according to the components of the glass ceramics according to any one of claims 1-5;
melting and shaping the raw materials to prepare precursor glass;
and crystallizing the precursor glass to prepare the microcrystalline glass.
7. The method for producing glass ceramics according to claim 6, wherein the Na is 2 O and the K 2 O provides the starting material in the form of the corresponding nitrate, and the other components provide the starting material in the form of the corresponding oxide;
and/or the crystallization treatment temperature is 600-800 ℃ and the time is 30 min-20 h.
8. A strengthened glass ceramic, characterized in that the glass ceramic is obtained by chemical tempering treatment of the glass ceramic according to any one of claims 1-5, and the vickers hardness of the strengthened glass ceramic is greater than 7.5 GPa.
9. A method for preparing strengthened glass ceramics, which is characterized in that the glass ceramics is subjected to chemical tempering treatment by one-step ion exchange or two-step ion exchange;
the one-step ion exchange comprises the steps of: ion exchange is carried out on the microcrystalline glass in first molten salt; the first molten salt comprises 40-60% KNO by mass percent 3 And 40% -60% NaNO 3 The ion exchange condition is that the ion exchange is carried out for 2-5 hours at 440-480 ℃;
the two-step ion exchange comprises the following steps: performing first ion exchange on the glass ceramics in second molten salt, and performing second ion exchange on the glass ceramics subjected to the first ion exchange in third molten salt; the second molten salt comprises NaNO 3 The condition of the first ion exchange is that the ion exchange is carried out for 2-6 hours at 440-480 ℃; the third molten salt comprises KNO 3 The condition of the second ion exchange is that the second ion exchange is carried out for 0.5-3 hours at 400-440 ℃.
10. Use of the strengthened glass ceramic of claim 8 or the strengthened glass ceramic produced by the method of claim 9 in the production of protective glass, fire-resistant glass or architectural glass.
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