Glass-ceramics, method for the production thereof and glass article

Abstract

The application provides a kind of glass-ceramics and its preparation method, glass product.The glass-ceramics includes the following components by mass percentage:SiO2 55~66wt%, Al2O3 21~28wt%, Li2O 1~4wt%, MgO 1~5wt%, ZnO 0~1.9wt%, TiO2 0~4wt%, ZrO2 2~6wt%, P2O5 1~6wt% and B2O3 0~3wt%;Wherein, the mass percentage of TiO2 is a, the mass percentage of ZrO2 is b, the mass percentage of P2O5 is c, the mass percentage of B2O3 is d, and satisfies 4wt%≤a+b+c+d≤8wt%;The mass percentage of ZnO is x, the mass percentage of MgO is y, and satisfies x / y≤1.The glass-ceramics of the application has lower thermal expansion coefficient, higher transparency and higher mechanical properties.

Description

Technical Field

[0001] This application relates to the field of glass technology, and in particular to a microcrystalline glass and its preparation method, as well as glass products. Background Technology

[0002] Currently, most zero-expansion microcrystalline glass products use the lithium aluminum silicate system (Li2O-Al2O3-SiO2), whose main crystalline phases are transparent low-expansion β-quartz solid solution and milky white opaque low-expansion β-spodumene solid solution.

[0003] Transparent, zero-expansion glass can be achieved by adjusting the ratio of β-quartz solid solution to residual glass phase in glass-ceramics. However, the coefficient of thermal expansion of the precipitated β-quartz solid solution is significantly lower than that of the matrix glass, which creates circumferential tensile stress in the residual glass phase surrounding the β-quartz solid solution. This easily leads to stress concentration, significantly reducing the overall strength of the glass-ceramic, and in severe cases, even causing cracking. Traditional zero-expansion transparent glass-ceramics typically have matrix glasses with high coefficients of thermal expansion, generally exceeding 40 × 10⁻⁶ at temperatures ranging from 50℃ to 750℃. -7 / K, which leads to a significant reduction in the strength of the crystallized glass-ceramic, severely limiting its application range.

[0004] Therefore, traditional glass-ceramics still need improvement. Summary of the Invention

[0005] Based on this, one or more embodiments of this application provide a microcrystalline glass with low coefficient of thermal expansion, high transparency, and high mechanical strength, as well as a method for preparing the same and glass products. The technical solution includes:

[0006] According to a first aspect of the embodiments of this application, a microcrystalline glass is provided, comprising, by mass percentage, the following components:

[0007] SiO255wt%~66wt%, Al2O321wt%~28wt%, Li2O 1wt%~4wt%, MgO 1wt%~5wt%, ZnO 0~1.9wt%, TiO20~4wt%, ZrO22wt%~6wt%, P2O51wt%~6wt% and B2O30~3wt%;

[0008] Wherein, the mass percentage of TiO2 is a, the mass percentage of ZrO2 is b, the mass percentage of P2O5 is c, and the mass percentage of B2O3 is d, and the following conditions are met: 4wt%≤a+b+c+d≤8wt%;

[0009] Let x be the mass percentage of ZnO and y be the mass percentage of MgO, and let x / y ≤ 1.

[0010] In one embodiment, the microcrystalline glass satisfies 4.6wt%≤a+b+c+d≤9wt%.

[0011] In one embodiment, the microcrystalline glass satisfies x / y≤0.7.

[0012] In one embodiment, the microcrystalline glass comprises, by weight percentage, the following components:

[0013] SiO260wt%~66wt%, Al2O322wt%~26wt%, Li2O 1wt%~3wt%, MgO 1wt%~5wt%, ZnO 0~1.9wt%, TiO20~2wt%, ZrO22wt%~6wt%, P2O51wt%~4wt% and B2O30~2.5wt%.

[0014] In one embodiment, the crystalline phase of the glass-ceramic comprises a β-quartz solid solution.

[0015] In one embodiment, the microcrystalline glass satisfies at least one of the following conditions (1) to (2):

[0016] (1) The crystallinity of the β-quartz solid solution is greater than or equal to 47%; and

[0017] (2) The grain size of the β-quartz solid solution is 20 nm to 60 nm.

[0018] According to a second aspect of the embodiments of this application, a method for preparing microcrystalline glass is provided, comprising the following steps:

[0019] The raw materials are provided according to the above-described composition of the microcrystalline glass, and the raw materials are mixed to prepare a mixture;

[0020] The mixture is melted to prepare molten glass;

[0021] The molten glass is shaped and then subjected to nucleation and crystallization processes in sequence to obtain the microcrystalline glass.

[0022] In one embodiment, the nucleation treatment is performed at a temperature of 640°C to 800°C for a duration of 2 hours to 12 hours.

[0023] In one embodiment, the crystallization treatment temperature is 780℃~1000℃, and the treatment time is 0.5h~4h.

[0024] According to a third aspect of the embodiments of this application, a glass article is provided, including the microcrystalline glass as described above or the microcrystalline glass prepared by the method described above.

[0025] Compared with the prior art, the present application has the following beneficial effects:

[0026] The present application can make the raw materials cooperate with each other and synergistically act on each other by reasonable proportioning, so that the beta-quartz solid solution with fine and uniform grain size is precipitated, the expansion coefficient of the base glass is effectively reduced, and the stress concentration in the crystallization process is reduced, and finally the microcrystalline glass with low thermal expansion coefficient, high transparency and high mechanical properties is prepared. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the technical solutions in the specific embodiments or prior art of the present application, the drawings needed in the description of the specific embodiments or prior art will be briefly introduced. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0028] Figure 1 The XRD pattern of the microcrystalline glass prepared in Example 18 of the present application. DETAILED DESCRIPTION

[0029] In order to make the above-mentioned purposes, features and advantages of the present application more apparent and easy to understand, the specific embodiments of the present application will be described in detail. In the following description, a large number of specific details are set forth in order to fully understand the present application. However, the present application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the spirit of the present application, therefore the present application is not limited by the specific embodiments disclosed below.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application are only for the purpose of describing the specific embodiments and are not intended to limit the present application. Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by existing methods.

[0031] In the present application, "further", "further", "particularly" and the like are used for the purpose of description, indicating the difference in content, but should not be understood as limiting the scope of protection of the present application.

[0032] In the present application, "optionally", "optional" and "optional" mean optional, that is, selected from any one of the two parallel schemes of "yes" or "no". If there are multiple "options" in a technical solution, unless otherwise specified, and there is no contradiction or mutual restriction relationship, each "option" is independent.

[0033] In the present application, the technical features described in an open form include both a closed technical solution consisting of listed features and an open technical solution containing the listed features.

[0034] In the present application, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the optional numerical distribution within the numerical interval is considered to be continuous, and includes both numerical end points (i.e., the minimum value and the maximum value) of the numerical range and every numerical value between the two numerical end points. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, including both end point integers of the numerical range and every integer between the two end points, in this document, it is equivalent to directly listing each integer, such as t being an integer selected from 1-10, which means t is any one integer selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. In addition, when multiple ranges are provided to describe a feature or characteristic, these ranges can be combined. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all sub-ranges encompassed therein.

[0035] In the present application, unless otherwise specified, the temperature parameter allows both constant temperature treatment and variation within a certain temperature interval. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. It is allowed to fluctuate within a range such as ±5°C, ±4°C, ±3°C, ±2°C, ±1°C.

[0036] In the present application, %(w / w) and wt% both represent weight percentage, %(v / v) refers to volume percentage, and %(w / v) refers to mass volume percentage.

[0037] In a first aspect of the present application, a microcrystalline glass is provided, comprising the following components in mass percentage: SiO255wt%-66wt%, Al2O321wt%-28wt%, Li2O 1wt%-4wt%, MgO 1wt%-5wt%, ZnO 0-1.9wt%, TiO20-4wt%, ZrO22wt%-6wt%, P2O51wt%-6wt%, and B2O30-3wt%;

[0038] wherein the mass percentage of TiO2 is a, the mass percentage of ZrO2 is b, the mass percentage of P2O5 is c, and the mass percentage of B2O3 is d, and 4wt%≤a+b+c+d≤8wt% is satisfied;

[0039] The mass percentage of ZnO is x, the mass percentage of MgO is y, and x / y≤1 is satisfied.

[0040] In the present application, the mass percentage of SiO2 is "55wt%-66wt%", that is, the minimum value and the maximum value in the range of 55wt%-66wt%, and every value between the minimum value and the maximum value. Specifically, it includes but is not limited to the point values in the examples and the following point values: 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt% or 66wt%; or a range composed of any two of these values, such as 58wt%-63wt%.

[0041] In some optional embodiments, the mass percentage of SiO2 is 60wt%-66wt%; further, the mass percentage of SiO2 is 60wt%-64.5wt%; still further, the mass percentage of SiO2 is 64.5wt%.

[0042] SiO2 is an important oxide for glass forming, which can be used to stabilize the glass and glass-ceramic network structure. In glass and glass-ceramics, SiO2 is one of the main oxides of the base glass forming glass and the main crystal phase, which can be used to stabilize the network structure of the glass and glass-ceramic and the generation of the β-quartz solid solution main crystal phase. Controlling the mass percentage of SiO2 in the above specific range can reduce the melting temperature of the glass-ceramic on the one hand, and reduce the production difficulty, unit energy consumption and carbon emissions; on the other hand, it is also conducive to the precipitation of β-quartz solid solution crystal phase.

[0043] In the present application, the mass percentage of Al2O3 is "21wt%-28wt%", that is, the minimum value and the maximum value in the range of 21wt%-28wt%, and every value between the minimum value and the maximum value. Specifically, it includes but is not limited to the point values in the examples and the following point values: 21wt%, 21.5wt%, 22wt%, 22.5wt%, 23wt%, 23.5wt%, 24wt%, 24.5wt%, 25wt%, 25.5wt%, 26wt%, 26.5wt%, 27wt%, 27.5wt% or 28wt%; or a range composed of any two of these values, such as 22.6wt%-26.8wt%.

[0044] In some optional embodiments, the mass percentage of Al2O3 is 22wt%-26wt%; further, the mass percentage of Al2O3 is 25wt%-26wt%; still further, the mass percentage of Al2O3 is 25.5wt%.

[0045] Al2O3 can also be used to stabilize the network structure of the glass, and can also improve the mechanical properties and chemical durability of the glass; meanwhile, Al2O3 is also one of the main oxides of the main crystal phase of the β-quartz solid solution, and the content thereof needs to be controlled in a specific range to ensure the generation and grain size of the main crystal phase. However, the melting temperature of Al2O3 is relatively high, and as a network intermediate, the content thereof can be adjusted to control the glass viscosity.

[0046] In the present application, the mass percentage of Li2O is “1wt%~4wt%”, that is, the minimum value and the maximum value in the range of 1wt%~4wt%, and every value between the minimum value and the maximum value. Specifically, it includes but is not limited to the point values in the examples and the following point values: 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt% or 4wt%; or a range formed by any two of these values, such as 1.5wt%~3.5wt%.

[0047] In some optional embodiments, the mass percentage of Li2O is 1wt%~3wt%; further, the mass percentage of Li2O is 1wt%~2wt%; still further, the mass percentage of Li2O is 1.3wt%.

[0048] The alkali metal oxide Li2O has the effects of reducing the melting temperature and improving the ion exchange capacity, and is also one of the components of the β-quartz solid solution crystal phase and is indispensable; meanwhile, it has the characteristics of small ionic radius and strong field, and is easy to play an accumulation role in the glass network structure, which is conducive to the nucleation and growth of the lithium-containing crystal phase. Controlling the content thereof in a specific range can provide sufficient driving force for the precipitation of the target crystal phase, and make the glass network structure dense, thereby reducing the thermal expansion coefficient of the base glass and enhancing the strength of the glass-ceramics.

[0049] In addition, lithium raw materials are expensive, and controlling the content of Li2O in a specific range can effectively reduce the raw material cost of the glass-ceramics.

[0050] In the present application, the mass percentage of MgO is "1wt%~5wt%", i.e. the minimum value and the maximum value in the range of 1wt%~5wt% and every value between the minimum value and the maximum value. Specifically, it includes but is not limited to the point values in the examples and the following point values: 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt%, 4wt%, 4.1wt%, 4.2wt%, 4.3wt%, 4.4wt%, 4.5wt%, 4.6wt%, 4.7wt%, 4.8wt%, 4.9wt% or 5wt%; or a range formed by any two of these values, such as 1.8wt%~4.5wt%.

[0051] In some optional embodiments, the mass percentage of MgO is 2wt%~5wt%; further, the mass percentage of MgO is 2wt%~4wt%; further, the mass percentage of MgO is 3.5wt%.

[0052] In the present application, the mass percentage of ZnO is "0~1.9wt%", i.e. the minimum value and the maximum value in the range of 0~1.9wt% and every value between the minimum value and the maximum value. Specifically, it includes but is not limited to the point values in the examples and the following point values: 0wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt% or 1.9wt%; or a range formed by any two of these values, such as 0.5wt%~1.5wt%.

[0053] In some optional embodiments, the mass percentage of ZnO is 0~1.5wt%; further, the mass percentage of ZnO is 0.2wt%~1wt%; further, the mass percentage of ZnO is 0.6wt%.

[0054] It is understandable that adding appropriate alkaline earth metal oxides MgO and ZnO in the glass component is conducive to reducing the high temperature viscosity of the base glass, modifying the glass structure, and improving the strength and chemical stability of the base glass. Controlling the content of MgO in the above specific range can reduce the high temperature viscosity of the base glass melt, thereby reducing the difficulty of melting; and it is not easy to precipitate periclase and other impurities, thereby increasing the transparency of the glass-ceramic and reducing the thermal expansion coefficient. ZnO ions have a high field accumulation effect in the glass melt, and a small amount of addition is beneficial to the precipitation of target crystal phases.

[0055] In the present application, the mass percentage of TiO2 is "0~4wt%", that is, the minimum value and the maximum value in the range of 0~4wt%, and every value between such minimum value and maximum value. Specifically including but not limited to the point values in the examples and the following point values: 0wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt% or 4wt%; or a range formed by any two of these values, such as 0.5wt%~3.5wt%.

[0056] In some optional embodiments, the mass percentage of TiO2 is 0~2wt%; further, the mass percentage of TiO2 is 0~1wt%; still further, the mass percentage of TiO2 is 0.2wt%.

[0057] In the present application, the mass percentage of ZrO2 is "2wt%~6wt%", i.e. the minimum value and the maximum value in the range of 2wt%~6wt%, and every value between the minimum value and the maximum value. Specifically, it includes but is not limited to the point values in the examples and the following point values: 2wt%, 2.2wt%, 2.4wt%, 2.6wt%, 2.8wt%, 3wt%, 3.2wt%, 3.4wt%, 3.6wt%, 3.8wt%, 4wt%, 4.2wt%, 4.4wt%, 4.6wt%, 4.8wt%, 5wt%, 5.2wt%, 5.4wt%, 5.6wt%, 5.8wt% or 6wt%; or a range formed by any two of these values, such as 2.7wt%~5.5wt%.

[0058] In some optional embodiments, the mass percentage of ZrO2 is 2wt%~4wt%; further, the mass percentage of ZrO2 is 2wt%~3wt%; further, the mass percentage of ZrO2 is 2.5wt%.

[0059] In the present application, the mass percentage of P2O5 is "1wt%~6wt%", i.e. the minimum value and the maximum value in the range of 1wt%~6wt%, and every value between the minimum value and the maximum value. Specifically, it includes but is not limited to the point values in the examples and the following point values: 1wt%, 1.2wt%, 1.4wt%, 1.6wt%, 1.8wt%, 2wt%, 2.2wt%, 2.4wt%, 2.6wt%, 2.8wt%, 3wt%, 3.2wt%, 3.4wt%, 3.6wt%, 3.8wt%, 4wt%, 4.2wt%, 4.4wt%, 4.6wt%, 4.8wt%, 5wt%, 5.2wt%, 5.4wt%, 5.6wt%, 5.8wt% or 6wt%; or a range formed by any two of these values, such as 2.7wt%~5.5wt%.

[0060] In some optional embodiments, the mass percentage of P2O5 is 1wt%~4wt%; further, the mass percentage of P2O5 is 1wt%~2.5wt%; further, the mass percentage of P2O5 is 1.6wt%.

[0061] TiO2, ZrO2 and P2O5 are added as nucleating agents, which can improve the crystallization ability of the glass and the liquidus temperature during the formation process, thereby improving the crystallization ability of the lithium-aluminum-silicon system base glass.

[0062] The β-quartz solid solution microcrystalline glass has a low crystallization tendency and a high crystallization barrier. In general, TiO2 or a large amount of ZrO2 or P2O5 needs to be added to greatly reduce the crystallization activation energy, promote the generation of uniform crystal nucleus in the base glass, and generate target crystal phase.

[0063] TiO2 has a strong coloring ability, which will make the base glass have a deeper color, and too much TiO2 is not suitable. Controlling the content of TiO2 within a certain range can reduce the thermal expansion coefficient of the base glass, improve the strength of the glass, make the growth process of the precipitated crystal phase easy to control, and reduce the generation of impurities, thereby improving the comprehensive performance of the microcrystalline glass.

[0064] ZrO2 has a low solubility in the glass body and a very high melting temperature, and too much ZrO2 is not suitable. Controlling the content of ZrO2 within a certain range can make the growth process of the precipitated crystal phase easy to control and reduce the generation of impurities.

[0065] Adding P2O5 while adding ZrO2 can effectively increase the solubility of ZrO2 in the glass liquid, which is beneficial to melting. On the other hand, P2O5 itself has the functions of phase separation, grain refinement, and promoting crystallization, which is beneficial to the regulation of the crystallization process of the base glass. At the same time, controlling the content of P2O5 within a certain range is also helpful to reduce the high-temperature viscosity of the glass.

[0066] In the present application, the mass percentage of B2O3 is "0-3wt%", that is, the minimum value and the maximum value in the range of 0-3wt%, and every value between the minimum value and the maximum value. Specifically, it includes but is not limited to the point values in the examples and the following point values: 0wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, or 3wt%; or a range formed by any two of these values, such as 2.7wt%-5.5wt%.

[0067] In some optional embodiments, the mass percentage of B2O3 is 0-2.5wt%; further, the mass percentage of B2O3 is 0wt%-1wt%; further, the mass percentage of B2O3 is 0.3wt%.

[0068] The addition of B2O3 in a specific content helps to reduce the melting temperature of the glass and the expansion coefficient of the base glass, and is conducive to improving the strength of the glass-ceramics; meanwhile, it plays an auxiliary role in the growth of crystal nucleus and grain refinement.

[0069] In the present application, the sum of the mass percentages of ZrO2, TiO2, P2O5 and B2O3 is "4wt%~8wt%", that is, the minimum value and the maximum value in the range of 4.6wt%~9wt%, and every value between the minimum value and the maximum value. Specifically, it includes but is not limited to the point values in the examples and the following point values: 4wt%, 4.2wt%, 4.4wt%, 4.6wt%, 4.8wt%, 5wt%, 5.2wt%, 5.4wt%, 5.6wt%, 5.8wt%, 6wt%, 6.2wt%, 6.4wt%, 6.6wt%, 6.8wt%, 7wt%, 7.2wt%, 7.4wt%, 7.6wt%, 7.8wt% or 8wt%; or a range formed by any two of these values, such as: 4.5wt%~7.7wt%.

[0070] In some optional embodiments, the sum of the mass percentages of ZrO2, TiO2, P2O5 and B2O3 is 4.6wt%~7.9wt%; further, the sum of the mass percentages of ZrO2, TiO2, P2O5 and B2O3 is 4.6wt%~5wt%; still further, the sum of the mass percentages of ZrO2, TiO2, P2O5 and B2O3 is 4.6wt%.

[0071] Understandably, the mass percentage ratio of ZnO and MgO can be every value between 0~1; for example, it can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.

[0072] In some optional embodiments, the mass percentage ratio of ZnO and MgO is less than or equal to 0.7, that is, it can take any value between 0~0.7.

[0073] In the present application, by limiting the sum of the mass percentages of ZrO2, TiO2, P2O5 and B2O3 within a specific range, and limiting the mass percentage ratio of ZnO and MgO within a specific range, the base glass can have a low expansion coefficient, and a large number of β-quartz solid solution crystal phases with uniform distribution and nanometer size can be precipitated, so that the product can finally achieve the performance of high strength, high transmittance and zero expansion.

[0074] Understandably, in order to accelerate the clarification speed of the above components during the melting process, one or more of the environmentally friendly clarifiers such as SnO2, NaCl, NaNO3, CeO2, etc. can also be added to the glass components.

[0075] The microcrystalline glass composition of the present application does not contain toxic clarifying agent components such as arsenic and antimony, and is environmentally friendly.

[0076] In some embodiments, the microcrystalline glass comprises, by mass percentage, SiO2 60wt%-66wt%, Al2O3 22wt%-26wt%, Li2O 1wt%-3wt%, MgO 1wt%-5wt%, ZnO 0-1.9wt%, TiO2 0-2wt%, ZrO2 2wt%-6wt%, P2O5 1wt%-4wt%, and B2O3 0-2.5wt%.

[0077] In some embodiments, the microcrystalline glass comprises, by mass percentage, SiO2 60wt%-64.5wt%, Al2O3 22wt%-26wt%, Li2O 1wt%-4wt%, MgO 2wt%-4wt%, ZnO 0-1.9wt%, TiO2 0-1wt%, ZrO2 2wt%-4wt%, P2O5 1wt%-2.5wt%, and B2O3 0-3wt%.

[0078] In one specific example, the microcrystalline glass comprises, by mass percentage, SiO2 64.5wt%, Al2O3 25.5wt%, Li2O 1.3wt%, MgO 3.5wt%, ZnO 0.6wt%, TiO2 0.2wt%, ZrO2 2.5wt%, P2O5 1.6wt%, and B2O3 0.3wt%.

[0079] In some embodiments, the crystalline phase of the microcrystalline glass comprises a β-quartz solid solution.

[0080] In some specific embodiments, the β-quartz solid solution has a crystallinity greater than or equal to 47%.

[0081] In some specific embodiments, the β-quartz solid solution has a grain size of 20nm-60nm.

[0082] The microcrystalline glass of the present application, by reasonably matching the raw material components, the components cooperate with each other and synergistically act, and finally the microcrystalline glass prepared has a transmittance greater than or equal to 85% at a thickness of 4mm, a coefficient of thermal expansion (50℃-750℃) of 0±1×10 -7 / K, a 535g steel ball drop height greater than or equal to 90cm, and a ROR ring pressure strength greater than or equal to 2760N.

[0083] In a second aspect, the present application provides a preparation method of the glass-ceramic, comprising the following steps S10-S30.

[0084] S10: providing raw materials according to the components of the glass-ceramic, mixing the raw materials to prepare a mixture;

[0085] S20: melting the mixture to prepare a glass liquid;

[0086] S30: forming the glass liquid, and sequentially performing nucleation treatment and crystallization treatment to obtain the glass-ceramic.

[0087] In some embodiments, the melting temperature in step S20 is 1600-1700°C, and the melting time is 4-8h.

[0088] Understandably, the present application reduces the melting temperature of the glass by adjusting the components of the glass-ceramic, thereby reducing the production difficulty of the glass-ceramic.

[0089] In some embodiments, the nucleation temperature in step S30 is 640-800°C, and the treatment time is 2-12h.

[0090] In some embodiments, the crystallization temperature in step S30 is 780-1000°C, and the treatment time is 0.5-4h.

[0091] In a third aspect, the present application provides a glass product comprising the glass-ceramic as described above or prepared by the preparation method of the glass-ceramic as described above.

[0092] The glass product as described above can meet the high-strength protection requirements of the furnace panel of electromagnetic stoves, electric ceramic stoves and integrated stoves, and the high-temperature environment fireproof and heat insulation plate of fireplaces, ovens and other application fields.

[0093] The glass product of the present application can also be applied to the fields of astronomical telescopes, fireproof glass, heat-resistant furnace window glass, high-temperature devices, chemical industry, electronics, navigation, exploration and military.

[0094] The present application will be further described below in conjunction with specific examples and comparative examples, but should not be understood as limiting the scope of protection of the present application. The raw materials involved in the following specific examples can be sourced from the market if not otherwise specified, the instruments used can be sourced from the market if not otherwise specified, and the processes involved can be routinely selected by those skilled in the art if not otherwise specified.

[0095] Example 1:

[0096] The raw materials of the glass components described in Table 1 were mixed uniformly, melted in a platinum crucible at 1600-1700°C for 4-8h with platinum stirring paddle, and then cooled to 1500-1600°C, and held for 2h for homogenization. The glass was cast into an iron mold to form a glass block with a size of about 200mm x 200mm. The mold was preheated to 400°C before casting. The glass block was transferred to an annealing furnace immediately after hardening, and annealed for 2h, and then cooled to 140°C at a rate of 6h, and naturally cooled. The glass block was then removed and stored.

[0097] The glass components of Examples 2-22 and Comparative Examples 1-6 are shown in Table 1, and the specific preparation steps were the same as in Example 1.

[0098] Table 1

[0099]

[0100] In Table 1, " / " means that the component is not included.

[0101] The base glasses prepared in Examples 1-22 and Comparative Examples 1-6 above were cut into 200x200x4.3mm glass sheets using a Shenyang Kejing STX-1203 wire cutting machine, and then thinned and polished to about 4mm using a double-sided grinding and polishing machine. The edges were ground using a CNC engraving machine. The transmittance of the glass sheets was measured using a Lambda950 ultraviolet-visible spectrophotometer from PerkinElmer, and the coefficient of thermal expansion was measured using a NETZSCH DIL 402 dilatometer. The results are shown in Table 2.

[0102] Table 2

[0103]

[0104] The base glasses prepared in Examples 1-21 above were subjected to nucleation and crystallization treatment according to the parameters shown in Table 3. The treatment was performed using a Nabertherm crystallization furnace. After crystallization, the glass was cut, the cross section was ground and polished, and the glass was stored.

[0105] Table 3

[0106]

[0107] The sample prepared in each example was cut into 50 mm x 50 mm, and its crystal phase type was tested by a Bruker X-ray diffractometer Bruker D8 advance, and the proportion of different types of crystal phases and the proportion of amorphous phases were simulated and calculated by TOPAS software; the Lambda950 ultraviolet-visible spectrophotometer of the American PerkinElmer company was used to test the transmittance in the wavelength range of 380 nm to 780 nm; the thermal expansion coefficient (50°C to 750°C) was tested by the German Netzsch DIL 402 thermal dilatometer; the falling ball impact resistance height was tested by the Dongguan Posiet PT-706 falling ball tester; the ring pressure ROR strength (upper ring φ = 16 mm, lower ring φ = 32 mm) was tested by the PT-307A universal testing machine of Posiet; and the results are shown in Table 4.

[0108] Figure 1 The XRD pattern of the microcrystalline glass prepared in Example 18.

[0109] Table 4

[0110]

[0111] As can be seen from Tables 1 to 4, the components of Comparative Examples 1 to 6 and Example 13 are substantially the same, and the difference lies in that:

[0112] In Comparative Example 1, the sum of the mass percentages of P2O5, B2O3, ZrO2 and TiO2 is 3.4wt%, which is less than 4wt%, resulting in insufficient crystallization driving force of the sample, lower crystallinity of the sample, and inability to refine the crystal grains, so that the size of the precipitated crystal phase increases, the transmittance of the sample decreases, and finally the thermal expansion coefficient is too high.

[0113] In Comparative Example 2, the sum of the mass percentages of P2O5, B2O3, ZrO2 and TiO2 is 9.6wt%, which is greater than 8wt%, which on the one hand leads to an increase in the CTE of the matrix glass, and on the other hand makes it difficult to control the crystallization process and precipitates periclase impurities (crystallinity of 6%), and the crystal grain size of the crystal phase becomes larger, so that the transmittance of the microcrystalline glass after crystallization decreases significantly, the CTE increases, and finally the anti-falling ball impact and ring pressure performance of the microcrystalline glass are greatly reduced.

[0114] In Comparative Example 3, the mass percentage of ZnO is 2wt%, and the mass percentage ratio of ZnO and MgO is 1.33, which is greater than 1; the increase of ZnO content and the decrease of MgO content make the CTE of the matrix glass increase significantly, affect the generation of stress concentration in the crystallization process, and finally reduce the anti-falling ball impact and ring pressure performance of the microcrystalline glass.

[0115] The mass percentage of ZnO in Comparative Example 4 is 4wt%, which is greater than 1.9wt%. With the increase of the content of ZnO, the CTE of the base glass is significantly increased, which affects the generation of stress concentration in the crystallization process; at the same time, due to the high field strength of Zn 2+ , the spinel phase (crystallinity of 3%) is easily precipitated, which finally increases the CTE of the glass-ceramics, and reduces the resistance to ball impact and ring pressure.

[0116] The mass percentage of ZrO2 in Comparative Example 5 is 1wt%, which is less than 2wt%. With the decrease of the content of ZrO2, the crystallization tendency is reduced, and the refining effect on the grains in the crystallization process is weakened, which leads to the decrease of the crystallinity and the increase of the grain size, and finally reduces the transmittance of the glass-ceramics, increases the CTE, and reduces the resistance to ball impact and ring pressure.

[0117] The mass percentage of Li2O in Comparative Example 6 is 5wt%, which is greater than 4wt%. With the increase of the content of Li2O, the structure of the base glass is more loose, and the CTE is significantly increased; at the same time, the crystallization tendency of the β-spodumene phase (crystallinity of 17%) is increased, which greatly reduces the transmittance of the glass-ceramics, increases the CTE, and reduces the resistance to ball impact and ring pressure.

[0118] In summary, the glass-ceramics containing the above specific proportions have excellent comprehensive performance: the transmittance is ≥85% at a thickness of 4mm, the thermal expansion coefficient (50℃-750℃) is 0±1×10 -7 / K, the resistance to 535g steel ball impact is ≥90cm, and the ROR ring pressure is ≥2760N.

[0119] The technical features of the above-described embodiments can be combined in any manner. In order to make the description concise, all possible combinations of the technical features in the above-described embodiments are not described, but as long as the combinations of the technical features do not contradict, they should be considered as the scope of the description.

[0120] The above-described embodiments only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as limiting the scope of the patent. It should be pointed out that for ordinary skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the protection scope of the present application should be subject to the appended claims.

Claims

1. A microcrystalline glass, characterized in that, comprises the following components by mass percentage: SiO2 62wt%~66wt%, Al2O3 23wt%~25.5wt%, Li2O 1wt%~3.5wt%, MgO 1.1wt%~3.5wt%, ZnO 0.3~1.5wt%, TiO2 0~0.8wt%, ZrO2 2wt%~4.7wt%, P2O5 1.5wt%~2.3wt%, and B2O3 0~3wt%; wherein the mass percentage of TiO2 is a, the mass percentage of ZrO2 is b, the mass percentage of P2O5 is c, and the mass percentage of B2O3 is d, and 4.6wt%≤a+b+c+d≤7.6wt% is satisfied; the mass percentage of ZnO is x, and the mass percentage of MgO is y, and 0.17≤x / y≤0.68 is satisfied; the crystal phase of the glass-ceramic comprises a β-quartz solid solution, and the grain size of the β-quartz solid solution is 25nm~41nm.

2. The glass-ceramic according to claim 1, characterized in that, The glass-ceramic satisfies 4.6wt%≤a+b+c+d≤6wt%.

3. The glass-ceramic according to claim 1, characterized in that, The glass-ceramic satisfies x / y≤0.

4.

4. The glass-ceramic according to any one of claims 1 to 3, characterized in that, The glass-ceramic comprises the following components by mass percentage: SiO2 63wt%~65wt%, Al2O3 25wt%~25.5wt%, Li2O 1wt%~3wt%, MgO 3wt%~3.5wt%, ZnO 0.6~1.2wt%, TiO2 0~0.2wt%, ZrO2 2.5wt%~4.7wt%, P2O5 1.5wt%~2wt%, and B2O3 0~2.5wt%.

5. The glass-ceramic according to claim 1, characterized in that, The β-quartz solid solution has a crystallinity greater than or equal to 47%.

6. A method of making a microcrystalline glass, characterized by, The method comprises the following steps: providing raw materials according to the components of the glass-ceramic of any one of claims 1~5, mixing the raw materials to prepare a mixture; melting the mixture to prepare a glass liquid; shaping the glass liquid, and sequentially performing nucleation treatment and crystallization treatment to obtain the glass-ceramic.

7. The method of claim 6, wherein the glass-ceramic is prepared by the steps of: The nucleation treatment is performed at a temperature of 640°C~800°C for 2h~12h.

8. The method for preparing microcrystalline glass according to claim 6 or 7, characterized in that, The crystallization treatment is performed at a temperature of 780°C~1000°C for 0.5h~4h.

9. A glass article, characterized by, The glass-ceramic is prepared by the method of any one of claims 1~5 or the method of any one of claims 6~8.

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