CN113526871A - Microcrystalline glass, preparation method thereof and chemically strengthened microcrystalline glass - Google Patents

Microcrystalline glass, preparation method thereof and chemically strengthened microcrystalline glass Download PDF

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CN113526871A
CN113526871A CN202110732398.8A CN202110732398A CN113526871A CN 113526871 A CN113526871 A CN 113526871A CN 202110732398 A CN202110732398 A CN 202110732398A CN 113526871 A CN113526871 A CN 113526871A
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glass
heat treatment
beta
znal
solid solution
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CN113526871B (en
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刘超
郭云岚
王静
韩建军
谢俊
阮健
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Wuhan University of Technology WUT
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    • 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
    • C03C10/0018—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 monovalent metal oxide as main constituents
    • C03C10/0027—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 monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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

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  • Engineering & Computer Science (AREA)
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  • Ceramic Engineering (AREA)
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Abstract

The application relates to microcrystalline glass, a preparation method thereof and chemically strengthened microcrystalline glass. The microcrystalline glass comprises the following components in percentage by mole: SiO 22:59.14‑69.48％；Al2O3:16.13‑22.47％；Li2O:5.38‑6.95％；ZnO:3.14‑6.98％；TiO2:1.15‑4.60％；ZrO21.12-2.30%; not less than 0 percent (MgO + CaO + BaO) not more than 4.55 percent. The invention realizes ZnAl2O4The nanocrystalline is preferentially crystallized in a glass substrate, and a beta-quartz solid solution is crystallized after the nanocrystalline; ZnAl with preferential crystallization2O4The nanocrystal has certain regulation and control effect on the size of the subsequent beta-quartz solid solution nanocrystal, and inhibitsThe generation of large-size beta-quartz solid solution nanocrystals and clusters thereof improves the transmittance of the microcrystalline glass.

Description

Microcrystalline glass, preparation method thereof and chemically strengthened microcrystalline glass
Technical Field
The invention belongs to the technical field of glass preparation, and particularly relates to ZnAl2O4A/beta-quartz solid solution sequential crystallization, a transparent glass ceramics which can be chemically strengthened at low temperature and a preparation method thereof.
Background
Compared with the traditional glass, the microcrystalline glass has better mechanical property and thermal stability and wide application. Among them, β -quartz solid solution glass ceramics have been widely paid attention and studied because of their low thermal expansion coefficient and high transmittance. In general, the chemical formula of a solid solution of β -quartz is LixAlxSi1-xO2Wherein x is more than or equal to 0 and less than or equal to 0.5. x is 0 to correspond to a high temperature beta-quartz structure, and x is 0.5 to correspond to a beta-eucryptite structure (beta-LiAlSiO)4). Beta-eucryptite has a hexagonal crystal structure, and as the temperature increases, beta-eucryptite expands in a direction perpendicular to the c-axis and contracts in a direction parallel to the c-axis. Therefore, the Coefficients of Thermal Expansion (CTE) in the a-axis and the c-axis are respectively αa＝+8.21×10-6/° C and αc＝-17.6×10-6V. C. The existence of the negative thermal expansion crystal enables the thermal expansion coefficient of the beta-quartz solid solution glass ceramics to be adjustable in a large range. When the thermal expansion coefficient of the beta-quartz solid solution is close to 0, the beta-quartz solid solution shows excellent thermal stability and has better thermal shock resistance. In addition, the glass has better transmittance, and has wide application prospect in the aspects of kitchen stoves, telescope panels, fireplace glass, display glass, vehicle windshields, protective glass and the like.
However, compared with some other microcrystalline glasses (such as spinel microcrystalline glass), the mechanical property of the beta-quartz solid solution is poor, and the use of the beta-quartz solid solution is limited. Although the strength can be further improved by the ion exchange method, the ion exchange temperature of the beta-quartz solid solution glass ceramics is generally higher; higher temperature ion exchange temperatures (>600 ℃) typically cause amorphous or crystalline transformations of the β -quartz solid solution, such as to cancrinite. The amorphous phase and the nepheline crystal phase on the surface of the glass can cause the increase of the thermal expansion coefficient, and the temperature reduction process enables the surface of the microcrystalline glass to be in a tensile stress state, so that cracks are generated, and the strength of the microcrystalline glass is finally influenced. Therefore, the development of novel beta-quartz solid solution glass ceramics with high mechanical properties and capable of performing efficient ion exchange at a lower temperature is a problem to be solved.
Secondly, the preparation of beta-quartz solid solution microcrystalline glass, in most cases using TiO, is carried out2And the like nucleating agents; in the process of preparing the microcrystalline glass, the glass usually contains other crystal phases besides beta-quartz solid solution crystals. From TiO2The introduced Ti element is easy to generate valence change in the glass to form Ti3+Ions, and the like. Such a lower valence state Ti3+Ions are easy to stably exist in the formed crystalline phase, so that the microcrystalline glass is colored, the transmittance of the glass in a visible light region is reduced, and the application range and the use performance of the beta-quartz solid solution microcrystalline glass are restricted. Therefore, how to improve the transmittance of the beta-quartz solid solution microcrystalline glass is also an urgent problem to be solved.
Disclosure of Invention
The invention provides microcrystalline glass with better transmittance, thermal property and mechanical property, a preparation method thereof and chemically strengthened microcrystalline glass for solving the technical problems.
The technical scheme of the invention is as follows:
the microcrystalline glass comprises the following components in percentage by mol:
SiO2:59.14-69.48％；
Al2O3:16.13-22.47％；
Li2O:5.38-6.95％；
ZnO:3.14-6.98％；
TiO2:1.15-4.60％；
ZrO2:1.12-2.30％；
0≤(MgO+CaO+BaO)≤4.55％；
preferably, 9.09. ltoreq. Li2O+ZnO≤13.09；52.77％≤ZnO/Li2O≤120.14％。
Preferably, 25.71% ≦ 25.71 ≦ forAl2O3/SiO2≤36.36。
Preferably, (MgO + CaO + BaO)/ZnO. ltoreq. 66.72%.
Preferably, the microcrystalline glass further comprises a fining agent, wherein the fining agent comprises Sb2O3，As2O3， SnO2，NaNO3Or Na2SO4One or a mixture of several of them.
Preferably, the microcrystalline glass comprises ZnAl which is crystallized successively2O4Nanocrystals and beta-quartz solid solution nanocrystals; the ZnAl2O4The size of the nanocrystal is in the range of 5nm-20nm, and the size of the beta-quartz solid solution nanocrystal is in the range of 10nm-40 nm; the crystal phase is uniformly distributed in the microcrystalline glass.
The preparation method of the microcrystalline glass comprises the following steps: mixing raw materials corresponding to the components according to a ratio, melting, clarifying, homogenizing, forming and annealing to obtain a glass original sheet, and then carrying out heat treatment to crystallize the glass to obtain the microcrystalline glass; the melting temperature is 1550-.
Preferably, the heat treatment is a one-step heat treatment or a two-step heat treatment. When the one-step heat treatment is carried out, the heat treatment temperature ranges from 760 ℃ to 950 ℃ and the time ranges from 2 to 20 hours. When the two-step heat treatment is carried out, the temperature range of the first heat treatment is 700-760 ℃, and the time range is 0.5-10 h; the temperature range of the second step heat treatment is 760 and 950 ℃, and the time range is 1-10 h.
A chemically strengthened glass ceramics is prepared through ion exchange including Na-Li ion exchange and/or K-Na ion exchange.
Preferably, the temperature range of the Na-Li ion exchange is 380-460 ℃, and the temperature range of the K-Na ion exchange is 400-480 ℃.
The invention provides a microcrystalline glass which is prepared by mixing zinc aluminate spinel (ZnAl)2O4) The nanocrystalline is compounded with beta-quartz solid solution nanocrystalline to prepare the ZnAl-containing material2O4/β-Microcrystalline glass of quartz solid solution nanocrystals. Due to ZnAl2O4Has higher elastic modulus (240GPa) and higher hardness (16.3 GPa), ZnAl2O4The introduction of the beta-quartz crystal can obviously improve the mechanical property of the beta-quartz solid solution microcrystalline glass. In general, ZnAl is conventionally contained2O4Microcrystalline glass of nanocrystalline and beta-quartz solid solution nanocrystalline, ZnAl2O4The nanocrystalline and the beta-quartz solid solution nanocrystalline can be separated out simultaneously in the heat treatment process; it is also possible that the solid solution of beta-quartz decomposes at high temperature, ZnAl2O4Precipitated as a by-product of the decomposition; can not pass through ZnAl2O4The preferential precipitation of the nanocrystals realizes the regulation and control of the subsequent crystallization of the beta-quartz solid solution nanocrystals. The invention has the beneficial effect that the prepared microcrystalline glass is not ZnAl2O4The nanocrystalline and the beta-quartz solid solution nanocrystalline are simply compounded, but through reasonable component design, selection of a nucleating agent and cooperation of a subsequent heat treatment process, preferential precipitation of ZnAl is realized under the condition of lower heat treatment temperature2O4The beta-quartz solid solution nanocrystalline is further precipitated during the heat treatment at higher temperature, particularly in the two-step heat treatment process combining the first heat treatment at lower temperature and the second heat treatment at higher temperature; ZnAl precipitated at lower temperature heat treatment2O4The nanocrystalline has a regulating and controlling function on the subsequent crystallization of the beta-quartz solid solution nanocrystalline under a higher temperature condition, and is beneficial to obtaining the microcrystalline glass with better transmittance, thermal property and mechanical property. ZnAl2O4Preferential precipitation of the nanocrystals can inhibit the growth and clustering of the beta-quartz solid solution nanocrystals, compared with the method adopting one-step heat treatment process to precipitate ZnAl2O4Microcrystalline glass of nanocrystalline and beta-quartz solid solution nanocrystalline (in the one-step method, in the process of heating a glass sample, the glass sample undergoes the process of heating from low temperature to high temperature, and a certain amount of ZnAl can be formed at a lower temperature2O4A nanocrystal; due to its low content, the regulating effect on the beta-quartz solid solution nanocrystal is limited), ZnAl2O4Step-by-step formation of nanocrystals and beta-quartz solid solution nanocrystalsThe ordered crystallization can improve the transmittance of the microcrystalline glass.
The principles of the component design consideration of the microcrystalline glass mainly comprise three points: firstly, ZnAl is realized2O4Ordered crystallization of the nanocrystalline and the beta-quartz solid solution nanocrystalline is realized, so that the microstructure of the microcrystalline glass is adjusted; secondly, on the premise of realizing the above ordered crystallization, the ZnAl content in the glass ceramics is reduced2O4The content of the nanocrystalline is reduced, so that the color of the microcrystalline glass in a visible light wave band is reduced, and the transmittance of the microcrystalline glass is improved; thirdly is ZnAl2O4After nanocrystalline and beta-quartz solid solution nanocrystalline, the residual glass component is still beneficial to the subsequent ion exchange.
The microcrystalline glass of the invention is to realize ZnAl2O4The ordered crystallization of the nanocrystal and the beta-quartz solid solution nanocrystal has very critical component design, and especially the ZnO content has great influence on the glass crystallization. The invention properly increases the ZnO content and improves the ZnO content in SiO2，Al2O3Under the synergistic effect of the ZnAl and the nucleating agent, the ZnAl can be realized by combining the subsequent heat treatment process2O4The nanocrystals can be preferentially precipitated at low temperature. When the heat treatment temperature is continuously increased, the beta-quartz solid solution nanocrystalline can be separated out, thereby realizing the regulation and control of the microcrystalline glass microstructure. The average grain size of beta-quartz solid solution nanocrystals in the microcrystalline glass can be reduced, the agglomeration of the beta-quartz solid solution nanocrystals in the microcrystalline glass can be inhibited, and the transmittance of the microcrystalline glass is improved.
In particular, the microcrystalline glass of the invention is used for realizing ZnAl2O4Ordered crystallization of the nanocrystalline and the beta-quartz solid solution nanocrystalline needs to meet the requirement that the molar content of ZnO is 3.14-6.98%, and ZnO/Li is more than or equal to 52.77%2O is less than or equal to 120.14 percent. When the content of ZnO is too low, ZnAl2O4The nanocrystal is difficult to preferentially precipitate. However, the content of ZnO is not suitable to be too high, and the phase separation tendency of the glass is increased due to the too high content of ZnO, so that the glass is devitrified; meanwhile, when the content of ZnO is too high, ZnAl precipitated in the microcrystalline glass2O4High content of nano crystal, heavy glass color and high transmittance in visible light bandLower. In addition, too much ZnO causes Zn remaining in the glass phase2+The content increases, which adversely affects the subsequent ion exchange.
Microcrystalline glass, Al, according to the invention2O3Is a glass intermediate oxide and is also ZnAl2O4Source of Al in nanocrystals and beta-quartz solid solution nanocrystals. Due to ZnAl2O4And the crystallization of a solid solution of beta-quartz requires a certain consumption of Al2O3. In order to maintain a portion of Al in the residual glass phase2O3Is present to facilitate the subsequent ion exchange, and the composition should be designed to maintain Al2O3With a relatively high content. Al (Al)2O3The content is too low, which is not beneficial to the crystallization of glass and the improvement of subsequent ion exchange performance; the content is too high, the glass is difficult to melt, the product quality is poor, the glass is easy to generate calculus when being melted, and the economic benefit is low. Comprehensive consideration, Al is required to satisfy2O3The mol content of the Al is 16.13-22.47%, and the Al is more than or equal to 25.71%2O3/SiO2≤36.36％。
In the present invention, SiO2Is a glass network former and is also a source of Si in the beta-quartz solid solution nanocrystalline. Compared with the traditional beta-quartz solid solution microcrystalline glass, the invention aims to ensure ZnAl2O4The preferential crystallization of the component (A) is realized, and the content of ZnO in the component (B) is properly improved. In addition, ZnAl2O4The devitrification of (A) consumes Al in the composition2O3In order to favour the crystallization of solid solutions of beta-quartz and also in order to obtain a certain content of Al in the residual vitreous phase2O3So as to be beneficial to the subsequent ion exchange and properly improve Al in the components2O3The content of (a). Therefore, the invention properly reduces SiO by comprehensively considering the influence of various aspects2Content, in the examples of the invention, SiO2The content is controlled to be 59.14-69.48%.
In the present invention, Li2O is a network modifier and also is a raw material necessary for beta-quartz solid solution nanocrystalline crystallization, and the content of O directly influences the crystallization performance of the glass. Too low a content to be realizedThe crystallization of the beta-quartz solid solution nanocrystal or the crystallization amount is too low. However, the higher the content, the poorer the chemical stability of the glass, and the crystals are liable to grow up, affecting the transmittance, and increasing the economic cost. Li in the invention2The content of O is 5.38-6.95%.
In the present invention, a certain amount of alkaline earth metal oxide (MgO, CaO, BaO) may be contained. The glass mainly has the effects of reducing the coloring of glass and improving the transmittance of the microcrystalline glass. However, the content should not be too high, and the content is not favorable for ZnAl2O4The separation of the glass is also easy to cause phase separation of the glass, block glass network channels and influence the proceeding of ion exchange. In the present invention, the total amount of suitable alkaline earth metal ions is: not less than 0 and not more than 4.55 percent (MgO + CaO + BaO) and not more than 66.72 percent (MgO + CaO + BaO)/ZnO.
In order to ensure that the microcrystalline glass has higher crystallization amount, the microcrystalline glass provided by the invention needs to meet the condition that Li is more than or equal to 9.092O+ZnO≤13.09；Li2When the content of O + ZnO is too low, the crystallization degree of the glass is low, and the enhancement effect cannot be achieved; too high content, the glass stability becomes poor, and the glass is easily devitrified during the heat treatment. The invention also comprises certain TiO2And ZrO2Which mainly functions as a nucleating agent.
TiO of the invention2The content should not be too low, otherwise ZnAl is difficult to induce2O4Crystallizing the nanocrystals; the content should not be too high, otherwise the glass is seriously colored, and the transmittance is affected. TiO in the invention2The content is 1.15-4.60%.
ZrO2Has a high melting point and a low solubility in silicate, and therefore, the content is not preferably too high. ZrO in the invention2The content is 1.12-2.30%. TiO selected for use in the present invention2And ZrO2The nucleating agents can be used alone or in combination.
In the invention, in order to promote the elimination of bubbles in the molten glass and realize better melting effect, the glass melting furnace also comprises a certain clarifying agent, and the selected clarifying agent can be but is not limited to Sb2O3，As2O3，SnO2，NaNO3， Na2SO4And the clarifying agent can be selected from one or a plurality of compounds.
The invention has the beneficial effects that:
1) the invention realizes ZnAl2O4The nanocrystalline is preferentially crystallized in a glass substrate, and a beta-quartz solid solution is crystallized after the nanocrystalline; ZnAl with preferential crystallization2O4The nanocrystalline has a certain regulation and control effect on the size of the subsequent beta-quartz solid solution nanocrystalline, inhibits the generation of large-size beta-quartz solid solution nanocrystalline and clusters thereof, and improves the transmittance of the microcrystalline glass. Meanwhile, the invention realizes ZnAl2O4On the premise of nanocrystal and beta-quartz solid solution nanocrystal sequential crystallization, the invention further regulates and controls ZnAl in the glass by adjusting the glass composition in the range2O4The crystallization content of the nano-crystal effectively reduces low-valence Ti in the glass3+Ion is ZnAl2O4Doping with nanocrystals to reduce Ti3+The coloring degree of the ions to the microcrystalline glass improves the transmittance of the microcrystalline glass in a visible light wave band. The microcrystalline glass of the present invention has a stable transmittance (@550nm) of 80% or more.
2) The microcrystalline glass has high-efficiency low-temperature ion exchange performance; at a lower ion exchange temperature and a shorter exchange time, Na+The depth of the ion exchange layer can reach 388 mu m and above, K+The depth of the ion exchange layer can reach 17 μm or more. After ion exchange, the hardness of the microcrystalline glass is obviously improved, and the main reason is that the ion exchange forms higher compressive stress on the surface of the microcrystalline glass through a plug squeezing effect, so that the deformation resistance of the microcrystalline glass is improved, and the hardness is improved; after the microcrystalline glass is chemically strengthened, the Vickers hardness of the microcrystalline glass can reach 8.23GPa, which is improved by 29 percent compared with the original glass.
3) The microcrystalline glass of the present invention has higher hardness than glass which is not heat treated, and the main reasons are as follows: firstly, the precipitated crystal phase is especially ZnAl2O4The nanocrystalline has higher hardness; secondly, along with the crystallization of the glass, the network extraplast in the glassIons (e.g. Zn)2+And Li+) And the crystallization is participated, so that the relative content of alkali metal ions in the residual glass phase is reduced, the non-bridge oxygen content is reduced, the density of the glass structure is increased, and the hardness is increased. The Vickers hardness of the microcrystalline glass can reach 7.53GPa, which is improved by 17 percent compared with the original glass.
Drawings
FIG. 1 is an XRD pattern of a one-step heat treatment using a glass having the composition described in example 1 of the present application. The temperatures and times in the figure represent the temperatures and times used for the one-step heat treatment.
FIG. 2 is an SEM image of a crystallized glass formed after heat treatment at 800 ℃ for 10 hours using a glass having the composition described in example 1 of the present application. ZnAl is simultaneously precipitated in the microcrystalline glass at the heat treatment temperature2O4Nanocrystals and beta-quartz solid solution nanocrystals, in which ZnAl is present2O4The average particle size of the nanocrystals was 12.4 + -2.7 nm, and the average particle size of the β -quartz solid solution nanocrystals (brighter nanoparticles in the figure) was 31.6 + -3.2 nm.
FIG. 3 is an SEM image of a glass-ceramic formed after a two-step heat treatment of a glass having a composition described in example 1 of the present application. ZnAl is firstly precipitated in the microcrystalline glass at the first heat treatment temperature2O4Nanocrystals of ZnAl at the temperature of the second heat treatment2O4Beta-quartz solid solution nanocrystalline is precipitated on the basis of the nanocrystalline. In the two-step heat treatment conditions, the first heat treatment temperature is 750 ℃ and the time is 10 hours, and the second heat treatment temperature is 800 ℃ and the time is 10 hours. Wherein ZnAl is2O4The average particle size of the nanocrystals was 8.4 + -1.3 nm, and the average particle size of the β -quartz solid solution nanocrystals (brighter nanoparticles in the figure) was 22.1 + -2.2 nm.
Fig. 4 is a transmittance chart of example 1 of the present application. Wherein the solid square plot represents the transmittance curve of the original sample (not heat treated); the solid circular curve indicates that only ZnAl is precipitated after heat treatment at 750 ℃ for 10h2O4A transmittance curve of nanocrystalline glass-ceramic; the curve of the hollow square graph shows that ZnAl is simultaneously precipitated after the heat treatment for 10 hours at 800 DEG C2O4Nanocrystal andthe transmittance curve of the microcrystalline glass of the beta-quartz solid solution nanocrystal; the curve of the hollow circular icon shows that ZnAl is firstly separated out after heat treatment for 10h at 750 ℃ and then heat treatment for 10h at 800 DEG C2O4And (4) separating out the beta-quartz solid solution nanocrystalline, wherein the transmittance curve of the microcrystalline glass is obtained.
FIG. 5 shows NaNO in example 1 of the present application3Na is obtained after ion exchange for 4 hours at 460 ℃ in molten salt+Electron Probe (EPMA) plot of ion concentration distribution. Wherein the solid square iconic curve represents Na of the original sample (not heat treated)+An ion concentration profile; the solid circular curve indicates that only ZnAl is precipitated after heat treatment at 750 ℃ for 10h2O4Na of nanocrystalline microcrystalline glass+An ion concentration profile; the curve of the hollow square graph shows that ZnAl is simultaneously precipitated after the heat treatment for 10 hours at 800 DEG C2O4Na of microcrystalline glass of nanocrystalline and beta-quartz solid solution nanocrystalline+An ion concentration profile; the curve of the hollow circular icon shows that ZnAl is firstly separated out after heat treatment for 10h at 750 ℃ and then heat treatment for 10h at 800 DEG C2O4Nanocrystalline, Na of microcrystalline glass of beta-quartz sosoloid nanocrystalline is precipitated+Ion concentration profile.
Fig. 6 is a vickers hardness chart of example 1 of the present application. Wherein "original" on the abscissa represents the original sample (non-heat treated, non-ion exchanged sample); the other numbers on the abscissa indicate the samples obtained after heat treatment at the corresponding temperature/time. The solid square plots in the figure represent the vickers hardness of the original sample before ion exchange and the microcrystalline glass sample after heat treatment; solid circle icons represent the original sample and the heat treated microcrystalline glass sample in pure NaNO3Vickers hardness after exchanging for 4 hours at 460 ℃ in the molten salt; open square icons representing the pure KNO of the original sample and the heat treated glass-ceramic sample3Vickers hardness after exchanging for 4 hours at 460 ℃ in the molten salt; open circle icons indicate that the original sample and the heat treated glass-ceramic sample were first purified NaNO3Exchanging in fused salt at 460 ℃ for 4h, and then purifying KNO3Vickers hardness after 4h of exchange at 460 ℃ in molten salt.
Detailed Description
The microcrystalline glass provided by the invention can effectively regulate and control the crystallization sequence of the glass by reasonably regulating and controlling the content ratio of each oxide in the glass components. Namely, ZnAl is precipitated at low temperature2O4Nanocrystalline, then beta-quartz solid solution nanocrystalline is precipitated at high temperature, thereby realizing the regulation and control of the microstructure of the microcrystalline glass; and by adjusting ZnAl2O4The crystallization content of the nanocrystalline effectively reduces the coloring degree of the glass and improves the transmittance of the microcrystalline glass in a visible light wave band; meanwhile, the glass composition is regulated and controlled, so that the microcrystalline glass of the system can be subjected to low-temperature ion exchange, and the strength of the microcrystalline glass is improved.
In the present invention, the ion exchange is known as chemical tempering. The main principle is that the ions with larger radius (such as K) in the molten salt are mixed+And Na+) With ions of smaller radius in the glass (e.g. Li)+) And exchanging, forming a layer of compressive stress on the surface through a squeezing effect, and forming a stress layer with a certain depth. Because the compressive strength of the glass is much higher than the tensile strength of the glass, when the glass is subjected to an external load, the load firstly needs to overcome the compressive stress on the surface to enable the glass to be in a tensile stress state and to be broken, thereby improving the strength of the glass.
The present invention will be further illustrated by the following examples, but the present invention is not limited to the following examples, and the examples should not be construed as limiting the present invention.
The preparation steps of the microcrystalline glass are as follows:
the raw materials corresponding to the components are mixed according to a proportion, a glass raw material is obtained after melting, clarification and homogenization, molding and annealing, and the glass raw material is crystallized through heat treatment to obtain the microcrystalline glass.
The microcrystalline glass comprises the following components in percentage by mole:
SiO2:59.14-69.48％；
Al2O3:16.13-22.47％；
Li2O:5.38-6.95％；
ZnO:3.14-6.98％；
TiO2:1.15-4.60％；
ZrO2:1.12-2.30％；
25.71％≤Al2O3/SiO2≤36.36％；
9.09≤Li2O+ZnO≤13.09；
52.77％≤ZnO/Li2O≤120.14％；
the invention also comprises a certain content of alkaline earth metal ions, wherein, calculated by mol percentage, the content of (MgO + CaO + BaO) is more than or equal to 0 and less than or equal to 4.55 percent, and the content of (MgO + CaO + BaO)/ZnO is less than or equal to 66.72 percent.
The invention also comprises a certain clarifying agent. The clarifying agent comprises Sb2O3，As2O3，SnO2， NaNO3Or Na2SO4One or a mixture of several of them.
The melting temperature of the invention is 1550-.
And carrying out heat treatment on the prepared microcrystalline glass, wherein the heat treatment can be one-step heat treatment or two-step heat treatment. Wherein the one-step heat treatment is carried out at the temperature of 760 and 950 ℃ for 2-20 h. Wherein the two-step heat treatment is carried out, wherein the temperature range of the first step heat treatment is 700-760 ℃, and the time range is 0.5-10 h; the temperature range of the second step heat treatment is 760 and 950 ℃, and the time range is 1-10 h.
The preparation method also comprises the step of chemically strengthening the glass ceramics by adopting an ion exchange process after the heat treatment.
The chemical strengthening method of the microcrystalline glass comprises the following steps:
immersing a clean and smooth microcrystalline glass sheet in ion exchange molten salt;
the ion exchange molten salt is NaNO3Molten salts, or KNO3Molten salts or a combination of both;
the ion exchange comprises Na-Li ion exchange and/or K-Na ion exchange; wherein the temperature range of Na-Li ion exchange is 380-460 ℃, and the temperature range of K-Na ion exchange is 400-480 ℃.
The preparation method of the microcrystalline glass provided by the invention is simple in process and suitable for industrial production.
The invention is further illustrated below in the context of a number of examples, which are shown in tables 1 and 2 for glass compositions and performance parameters of examples 1-8 and comparative examples 1-2, and in figures 1-6 for some of the properties of the examples.
TABLE 1
Figure RE-GDA0003266881790000091
Figure RE-GDA0003266881790000101
TABLE 2
Figure RE-GDA0003266881790000102
Figure RE-GDA0003266881790000111
In the embodiments 1-8 of the invention, through reasonably regulating and controlling the components and the proportion, ZnAl is orderly separated out from the interior of the glass through heat treatment and crystallization2O4Nanocrystals and beta-quartz solid solution nanocrystals.
As can be seen from the detection results of examples 1 to 8 in tables 1 and 2, compared with the original glass, the hardness of the microcrystalline glass is higher and can reach 7.41 +/-0.06-7.53 +/-0.10 GPa, which is improved by 11.39-17.24% compared with the original glass; by KNO3The Vickers hardness of the microcrystalline glass after ion exchange can reach 8.04 +/-0.12-8.13 +/-0.07 GPa, which is improved by 21.89-26.96 percent relative to the original glass (namely the glass which is not subjected to heat treatment); first pass through NaNO3Then passing through KNO3The Vickers hardness of ion exchange can reach 8.11 +/-0.10-8.23 +/-0.12 GPa, which is improved by 23.09-29.00 percent relative to the original sample. And through NaNO3After the exchangeThe Vickers hardness of (A) is not greatly improved, mainly due to K+-Li+The ion exchange can be caused by larger surface pressure stress.
It can also be seen from the test results of examples 1-8 in tables 1 and 2 that the glass-ceramics are in NaNO, relative to the original sample3And KNO3After ion exchange in the molten salt, Na+Ions and K+The diffusion layer depth of ions is obviously improved, and the main reasons are as described above three main points: firstly, with ZnAl2O4Devitrification of nanocrystals, Zn in glass matrix2+The relative content of (a) is reduced. Due to Zn in the glass as the outer body of the glass2+Has an ionic radius of
Figure RE-GDA0003266881790000112
Between
Figure RE-GDA0003266881790000113
And
Figure RE-GDA0003266881790000114
thus its role in glass is also similar to that of Mg2+And Ca2+Ions. The presence of alkaline earth metal ions in the glass hinders the diffusion of the ions and thus reduces the ion exchange performance. With ZnAl in the glass2O4Devitrification of nanocrystals, Zn in glass matrix2+The relative content of (A) is reduced, the inhibition effect on ion diffusion is reduced, and therefore the ion exchange performance is improved; second, the microcrystalline glass, part of Al3+Exist in a highly coordinated (5-and 6-coordinated) state with ZnAl2O4The crystallization of the nanocrystalline and the beta-quartz solid solution nanocrystalline reduces the content of high-coordination aluminum, increases the ionic radius of a glass network channel, and reduces the diffusion activation energy, so the ion exchange performance is improved; thirdly, after the glass is crystallized, the ion exchange process mainly occurs at the junction of the crystal phase and the glass phase, and the region is more favorable for the diffusion of ions, so that the ion exchange performance is improved.
In comparative example 1 in Table 2, the relative content of ZnO is higher, so that the phase separation of the glass is easily accelerated, and the color of the glass after heat treatment is higherDeep, easily opacified and low in transmittance. Comparative example 2, in which the ZnO content was too low, Li2Too high O content and inability to achieve ZnAl heat treatment2O4Is preferentially crystallized, but is ZnAl2O4And the beta-quartz solid solution is precipitated simultaneously. The crystal grains precipitated at this time have a large size and a wide size distribution, resulting in a significant decrease in transmittance.
ZnAl is clearly seen from FIG. 12O4The nanocrystalline is precipitated at low temperature, and the beta-quartz solid solution nanocrystalline is precipitated at high temperature, so that ZnAl is realized2O4Ordered crystallization of nanocrystals and β -quartz solid solution nanocrystals.
As can be seen from a comparison of FIGS. 2 and 3, ZnAl is simultaneously precipitated2O4The microcrystal glass crystal particles of the nanocrystalline and the beta-quartz solid solution nanocrystalline have obvious clusters and larger crystal diameters. This is mainly due to the rapid growth of solid solutions of β -quartz. And ZnAl is precipitated first2O4The nanocrystalline precipitates the beta-quartz solid solution nanocrystalline, and the crystallite glass has smaller grain size and uniform distribution. This is mainly due to the first step of precipitation of ZnAl2O4After nanocrystalline, due to ZnAl2O4The existence of the nanocrystal can inhibit the rapid growth of the beta-quartz solid solution nanocrystal, thereby avoiding the clustering of the nanocrystal. Accordingly, referring to FIG. 4, the ZnAl is used2O4The sequential crystallization of the nanocrystalline and the beta-quartz solid solution nanocrystalline reduces the grain size of the microcrystalline glass, thereby weakening the scattering effect on visible light and being beneficial to improving the transmittance.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention.

Claims (10)

1. The microcrystalline glass is characterized by comprising the following components in percentage by mol:
SiO2:59.14-69.48％；
Al2O3:16.13-22.47％；
Li2O:5.38-6.95％；
ZnO:3.14-6.98％；
TiO2:1.15-4.60％；
ZrO2:1.12-2.30％；
0≤(MgO+CaO+BaO)≤4.55％。
2. the glass-ceramic according to claim 1,
9.09≤Li2O+ZnO≤13.09；
52.77％≤ZnO/Li2O≤120.14％。
3. the glass-ceramic according to claim 1, wherein,
25.71％≤Al2O3/SiO2≤36.36。
4. the glass-ceramic according to claim 1, wherein,
(MgO+CaO+BaO)/ZnO≤66.72％。
5. the glass-ceramic according to claim 1, wherein the glass-ceramic further comprises a fining agent, the fining agent comprising Sb2O3，As2O3，SnO2，NaNO3Or Na2SO4One or a mixture of several of them.
6. The glass-ceramic according to claim 1, characterized in that it comprises ZnAl crystallized successively2O4Nanocrystals and beta-quartz solid solution nanocrystals; the ZnAl2O4The size of the nanocrystal is in the range of 5nm-20nm, and the size of the beta-quartz solid solution nanocrystal is in the range of 10nm-40nm(ii) a The crystal phase is uniformly distributed in the microcrystalline glass.
7. The method for preparing microcrystalline glass according to claim 1, wherein the method comprises: mixing raw materials corresponding to the components according to a ratio, melting, clarifying, homogenizing, forming and annealing to obtain a glass original sheet, and then carrying out heat treatment to crystallize the glass to obtain the microcrystalline glass; the melting temperature is 1550-.
8. The method of claim 7, wherein the heat treatment is a one-step heat treatment or a two-step heat treatment; when the one-step heat treatment is carried out, the heat treatment temperature range is 760-; when the two-step heat treatment is carried out, wherein the temperature range of the first step heat treatment is 700-760 ℃, and the time range is 0.5-10 h; the temperature range of the second step heat treatment is 760 and 950 ℃, and the time range is 1-10 h.
9. A chemically strengthened glass ceramics characterized in that the glass ceramics according to any one of claims 1 to 6 is ion-exchanged, and the ion exchange includes Na-Li ion exchange and/or K-Na ion exchange.
10. The chemically strengthened glass-ceramic according to claim 9, wherein the temperature range of the Na-Li ion exchange is 380-460 ℃ and the temperature range of the K-Na ion exchange is 400-480 ℃.
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