CN115057621A - Colorless transparent magnesium-aluminum-silicon microcrystalline glass and preparation method thereof - Google Patents
Colorless transparent magnesium-aluminum-silicon microcrystalline glass and preparation method thereof Download PDFInfo
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- C03C10/0045—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 containing SiO2, Al2O3 and MgO as main constituents
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Abstract
The invention relates to colorless transparent magnesium-aluminum-silicon microcrystalline glass and a preparation method thereof. The microcrystalline glass has MgAl as main crystal phase 2 Si 3 O 10 The base glass comprises the following components in percentage by mol: 55 to 62 percent of SiO 2 、17％～24％Al 2 O 3 13 to 20 percent of MgO and 5 to 8 percent of ZnO. The preparation method comprises the following steps: the raw materials of the basic glass are subjected to ball milling mixing, melting, molding, annealing and cooling to obtain the basic glass, and the obtained basic glass is subjected to nucleation and crystallization heat treatment under an optimized heat treatment process to obtain the microcrystalline glass. The method has the advantages of easily available raw materials, simple preparation process and low cost, and the prepared microcrystalline glass has excellent optical properties such as high transparency and low haze and has mechanical properties such as higher hardness.
Description
Technical Field
The invention belongs to the field of microcrystalline glass and preparation thereof, and particularly relates to colorless transparent magnesium-aluminum-silicon microcrystalline glass and a preparation method thereof.
Background
The microcrystalline glass is a multi-phase solid material obtained by controlled crystallization of a base glass having a specific composition under an appropriate heat treatment process. They are a composite consisting of a crystalline phase and a glassy phase and exhibit excellent physicochemical properties of thermal, mechanical, dielectric, corrosion resistance, etc. Since the first development of microcrystalline glass by doctor stookey s.d. of corning corporation in 1953, microcrystalline glass has become one of the hot spots for inorganic material research due to its special properties. When the refractive index of the precipitated microcrystalline phase in the glass is similar to that of the residual glass phase or the size of crystal grains is far smaller than that of visible light, the transparent microcrystalline glass can be obtained. Researchers have now developed transparent glass-ceramics in a variety of oxide, oxyfluoride glass systems, in which magnesium aluminum silicon (MgO-Al) 2 O 3 -SiO 2 MAS) system microcrystalline glass has low dielectric loss, high mechanical strength and adjustable thermal expansion coefficient, and has wide application prospect in the aspects of large astronomical telescopes, optical fiber amplifiers, liquid crystal displays, fireproof windows, high-grade kitchenware and the like.
In recent years, lithium aluminum silicon (Li) 2 O-Al 2 O 3 -SiO 2 LAS) system glass ceramics are widely used by virtue of their excellent thermal expansion properties, but with the outbreak of the new energy automobile market, the demand of the lithium battery industry for upstream raw materials has increased substantially, resulting in a rapid increase in the prices of lithium carbonate and lithium-containing minerals, increasing the production cost of LAS system glass ceramics. The MAS system microcrystalline glass is an important variety in oxide system transparent microcrystalline glass, and microcrystalline glass containing crystalline phases such as cordierite, spinel, mullite, sapphirine, forsterite, enstatite and the like can be obtained by adjusting basic glass components and a heat treatment process, so that the MAS system microcrystalline glass is suitable for different occasions. The MAS system microcrystalline glass has wide raw material source, low price and self advantages: the sapphire has high strength, hardness and chemical stability, excellent magnetic and dielectric properties, and has obvious transparency advantage in the middle infrared band (4.5-5.5 mu m) compared with sapphire, and can be applied to the fields of electronics, communication, optical elements and the like.
Because the crystallization activation energy of the MAS system base glass is higher and is not beneficial to phase separation, nucleation and crystallization, TiO is usually introduced into the formula for preparing the magnesium-aluminum-silicon transparent glass ceramics 2 、ZrO 2 And the like. For example, J.Wang et al reported on Journal of Wuhan University of Technology-Mater.Sci.Ed.Vol.28(2013) pp.69-72 a spinel glass-ceramic incorporating a total of 8 wt% (TiO) 2 +ZrO 2 ) The method comprises the following steps of putting the batch materials into an alumina crucible, melting at 1600-1650 ℃, casting for forming, annealing at 600 ℃ to obtain base glass, and finally performing two-step heat treatment at 770-1000 ℃ to obtain the microcrystalline glass. Although the addition of these nucleating agents can improve the devitrification performance of MAS system base glasses to a great extent, there are many problems in practical applications, such as TiO 2 The addition of (2) may cause the glass to be in a yellow brown color due to 'ilmenite coloring', and the heat-treated microcrystalline glass is in a brown or light purple color, and the coloring phenomenon can reduce the value of a transparent microcrystalline glass product. And ZrO 2 Is a refractory oxide, and is difficult to dissolve when it exceeds 3 wt%, adversely affecting the melting and transparency of the glass, and in these cases, the use of the glass-ceramic as an optical material is extremely limited. Therefore, the development of a method for preparing the colorless and transparent magnesium-aluminum-silicon glass-ceramic with good mechanical properties without adding a nucleating agent is of great significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing the colorless transparent magnesium aluminum silicon glass ceramic and the preparation method thereof, which need not to add a nucleating agent, and obtains the colorless magnesium aluminum silicon glass ceramic with higher visible light transmittance by regulating and controlling nucleation and crystallization heat treatment processes, so as to overcome the defects that the nucleating agent is needed to be added in the preparation of the glass ceramic in the prior art, so that the glass ceramic is colored, the transmittance is reduced, and the like.
The invention provides colorless transparent magnesium-aluminum-silicon glass-ceramic, the main crystalline phase of which is MgAl 2 Si 3 O 10 The base glass of the microcrystalline glass comprises the following components in percentage by mol: 55 to 62 percent of SiO 2 、17％～24％Al 2 O 3 13 to 20 percent of MgO and 5 to 8 percent of ZnO, wherein the sum of the mole percentages of the components is 100 percent.
Preferably, the total mole percentage of MgO and ZnO is 20% -25%.
The invention also provides a preparation method of the colorless transparent magnesium-aluminum-silicon microcrystalline glass, which comprises the following steps:
(1) carrying out ball milling and mixing on raw materials of base glass, uniformly mixing, placing the mixture in a high-temperature furnace for melting, forming the obtained glass liquid, then annealing (stress is eliminated by annealing treatment), and cooling to room temperature to obtain the base glass, wherein the base glass comprises the following components in percentage by mole: 55 to 62 percent of SiO 2 、17％～24％Al 2 O 3 、13％～20％MgO、5％～8％ZnO；
(2) And (3) sequentially carrying out nucleation heat treatment and crystallization heat treatment on the base glass in the step (1) to obtain colorless transparent magnesium aluminum silicon microcrystalline glass.
Preferably, SiO in the step (1) 2 、Al 2 O 3 MgO and ZnO are respectively introduced by silicon dioxide, aluminum hydroxide, basic magnesium carbonate pentahydrate and zinc oxide.
Preferably, the molar percentage of the raw materials of the base glass in the step (1) is in accordance with the molar percentage of each component of the base glass.
Preferably, the melting temperature in the step (1) is 1550-1620 ℃, and the melting time is 2-4 hours.
Preferably, the step (1) is performed by molding: and pouring the molten glass into a preheated mold for molding, wherein the temperature of the preheated mold is kept at 260-350 ℃.
Preferably, the annealing temperature in the step (1) is 650-730 ℃, and the annealing time is 2-4 hours.
Preferably, the temperature of the nucleation heat treatment in the step (2) is 800-850 ℃, the time of the nucleation heat treatment is 3-6 hours, and the temperature rise rate is 2-10 ℃/min.
Preferably, the temperature of the crystallization heat treatment in the step (2) is 900-1050 ℃, the time of the crystallization heat treatment is 1-2 hours, and the temperature rise rate is 2-10 ℃/min.
The invention also provides application of the colorless transparent magnesium-aluminum-silicon microcrystalline glass in terminal display equipment or cover plate materials.
The forming mechanism of the microcrystalline glass comprises two processes of nucleation and growth, the invention can change the variety of crystalline phases precipitated in the glass and the size and the number of crystal grains by adjusting the formula of the basic glass and the time and the temperature of nucleation or crystallization heat treatment, thereby realizing the precipitation of a nano-sized magnesium-aluminum-silicon crystal phase in the magnesium-aluminum-silicon basic glass, and the unique structure can effectively improve the mechanical properties such as microhardness and the like of the material on the premise of ensuring good transparency.
Advantageous effects
(1) The invention designs the components of the basic glass, does not need to add nucleating agent, carries out nucleation and crystallization on the basic glass under the optimized heat treatment process, and can successfully control the precipitation of MgAl 2 Si 3 O 10 A crystalline phase, which is helpful for obtaining a colorless and transparent microcrystalline glass product;
(2) the magnesium-aluminum-silicon microcrystalline glass prepared by the method is colorless, good in transparency, low in haze, high in hardness and excellent in comprehensive performance;
(3) the invention has the advantages of easily obtained raw materials, simple preparation process, low cost, contribution to large-scale production and industrial application prospect in the aspects of terminal display equipment and cover plate materials.
Drawings
FIG. 1 shows a DSC curve of a base glass of magnesium aluminum silicon prepared in examples 1 to 3 of the present invention.
FIG. 2 is an X-ray diffraction pattern of a glass-ceramic of Mg-Al-Si prepared in example 1 of the present invention, wherein the inset is a digital photograph of the glass-ceramic obtained.
FIG. 3 is an X-ray diffraction pattern of a glass-ceramic of Mg-Al-Si prepared in example 2 of the present invention, wherein the inset is a digital photograph of the glass-ceramic obtained.
FIG. 4 is an X-ray diffraction pattern of a glass-ceramic of Mg-Al-Si prepared in example 3 of the present invention, wherein the inset is a digital photograph of the glass-ceramic obtained.
FIG. 5 is an X-ray diffraction pattern of a magnesium aluminum silicon glass-ceramic prepared in comparative example 1 of the present invention, wherein the inset is a digital photograph of the resulting glass-ceramic.
FIG. 6 is an X-ray diffraction pattern of a magnesium aluminum silicon microcrystalline glass prepared by comparative example 2 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Those skilled in the art will recognize that specific techniques or conditions are not described in the examples, and that the techniques or conditions may be performed according to the techniques or conditions described in the literature in the art. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The light transmittance, the haze and the Vickers hardness of the microcrystalline glass are tested by adopting the following methods:
light transmittance: processing the sample into a circular sheet with the thickness of 2mm, polishing the two surfaces, and measuring the average light transmittance in the wavelength range of 380-780 nm by using a Hitachi U-3310 type ultraviolet-visible spectrophotometer.
Haze: the haze of a microcrystalline glass sample with the thickness of 1mm is tested by adopting a Shanghai apparatus electro-optic WGW electro-optic haze meter according to a GB2410-80 test method.
Vickers hardness: and testing the hardness of the microcrystalline glass by adopting an indentation method. The sample was ground flat and polished, and tested with a Vickers hardness tester model FV-700 manufactured by Future-tech, Japan, and a load of 29.4N was applied to the surface of the sample with a Vickers indenter for 10 seconds, and the Vickers hardness of the material was calculated according to the following formula after indentation:
wherein H V Vickers hardness in GPa; f is applied load, and the unit is N; d is the mean pressureTrace length in mm.
Example 1
(1) The base glass was composed of 58% SiO in mol percent 2 、21％Al 2 O 3 15% of MgO and 6% of ZnO (wherein SiO is weighed out 2 The corresponding raw materials are silicon dioxide and Al 2 O 3 The corresponding raw material is aluminum hydroxide, the raw material corresponding to MgO is basic magnesium carbonate pentahydrate, the raw material corresponding to ZnO is zinc oxide), the raw materials are put into a mixer for ball milling after being prepared, the mixed batch is poured into a corundum crucible and placed into a high-temperature electric furnace, melting is carried out for 2.5 hours at 1620 ℃, then the molten high-temperature glass liquid is poured into a 350 ℃ mould for forming, the formed glass is rapidly moved into a 730 ℃ muffle furnace for annealing for 3 hours, and cooling is carried out to room temperature to obtain the base glass.
(2) Carrying out thermal analysis on the base glass by adopting Differential Scanning Calorimetry (DSC), and carrying out nucleation and crystallization heat treatment on the annealed base glass in a high-temperature furnace according to a certain heat treatment process by referring to the glass transition temperature and the crystallization peak temperature obtained by a DSC curve in figure 1, wherein the specific heat treatment parameters are as follows: raising the temperature from room temperature to 840 ℃ and preserving heat for 5 hours for nucleation, then continuing raising the temperature to 1030 ℃ and preserving heat for 1 hour for crystallization, wherein the temperature raising rate is 5 ℃/min, and cooling to room temperature after microcrystallization heat treatment to obtain the colorless and transparent magnesium-aluminum-silicon microcrystalline glass.
FIG. 1 is a DSC curve of a base glass prepared in this example, wherein T g Is the glass transition temperature, T p1 Is the first crystallization peak temperature, T p2 The second crystallization peak temperature.
As can be seen from FIG. 2, the obtained glass-ceramic is colorless and transparent, and the contrast of standard X-ray diffraction pattern shows that the main crystal phase is MgAl 2 Si 3 O 10 Corresponding to standard card PDF 25-0511; the size of the grain size is approximately 30nm as calculated by Jade 6.
Through testing, the average light transmittance of a sample with the thickness of 2mm in a wavelength range of 380-780 nm is 76%; the haze of a 1mm thick sample was 0.62%; the Vickers hardness was 9.64 GPa.
Example 2
(1) The base glass is composed of 60% SiO according to mol percentage 2 、19％Al 2 O 3 16% MgO and 5% ZnO (wherein SiO is measured out 2 The corresponding raw materials are silicon dioxide and Al 2 O 3 The corresponding raw material is aluminum hydroxide, the raw material corresponding to MgO is basic magnesium carbonate pentahydrate, the raw material corresponding to ZnO is zinc oxide), the raw materials are put into a mixer for ball milling after being prepared, the mixed batch is poured into a corundum crucible and placed into a high-temperature electric furnace, melting is carried out for 3 hours at 1580 ℃, then the molten high-temperature glass liquid is poured into a mold at 300 ℃ for molding, the molded glass is rapidly moved into a 680 ℃ annealing furnace for annealing for 2 hours, and cooling is carried out to room temperature to obtain the base glass.
(2) With reference to the glass transition temperature and crystallization peak temperature obtained from the DSC curve in fig. 1, the annealed base glass is subjected to nucleation and crystallization heat treatment in a high-temperature furnace according to a certain heat treatment process, and the specific heat treatment parameters are as follows: and (3) at the heating rate of 8 ℃/min, heating from room temperature to 830 ℃ and preserving heat for 4 hours for nucleation, then at the heating rate of 5 ℃/min, continuously heating to 980 ℃ and preserving heat for 1.5 hours for crystallization, and cooling to room temperature after microcrystallization heat treatment to obtain the colorless transparent magnesium-aluminum-silicon microcrystalline glass.
As can be seen from figure 3, the obtained microcrystalline glass is colorless and transparent, and the main crystal phase is MgAl according to the standard X-ray diffraction spectrum 2 Si 3 O 10 And also contains a small amount of cordierite; the grain size is less than 20nm as calculated by Jade 6.
Through testing, the average light transmittance of a sample with the thickness of 2mm in a wavelength range of 380-780 nm is 81 percent; the haze of a 1mm thick sample was 0.49%; the Vickers hardness was 8.41 GPa.
Example 3
(1) The base glass was composed of 57 mol% SiO 2 、20％Al 2 O 3 17% MgO and 6% ZnO (wherein SiO is measured out 2 The corresponding raw materials are silicon dioxide and Al 2 O 3 The corresponding raw material is aluminum hydroxide, the raw material corresponding to MgO is basic magnesium carbonate pentahydrate, and the raw material corresponding to ZnOZinc oxide is used as a raw material), ball milling is carried out on the raw material in a mixer after the raw material is prepared, the mixed batch is poured into a corundum crucible and is placed in a high-temperature electric furnace, melting is carried out for 4 hours at 1550 ℃, then the molten high-temperature glass liquid is poured into a mold at 260 ℃ for molding, the molded glass is rapidly moved into an annealing furnace at 650 ℃ for annealing for 4 hours, and cooling is carried out to room temperature to obtain the basic glass.
(2) With reference to the glass transition temperature and crystallization peak temperature obtained from the DSC curve in fig. 1, the annealed base glass is subjected to nucleation and crystallization heat treatment in a high temperature furnace according to a certain heat treatment process, with specific heat treatment parameters as follows: and (3) raising the temperature from room temperature to 810 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 6 hours for nucleation, then continuing raising the temperature to 950 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours for crystallization, carrying out microcrystallization heat treatment, and cooling to room temperature to obtain the colorless and transparent magnesium-aluminum-silicon microcrystalline glass.
FIG. 4 shows that the obtained glass-ceramic is colorless and transparent, and the contrast of standard X-ray diffraction pattern shows that the main crystal phase is MgAl 2 Si 3 O 10 (ii) a The grain size was less than 20nm as calculated by Jade 6.
Through testing, the average light transmittance of a sample with the thickness of 2mm in the wavelength range of 380-780 nm is 84%; the haze of a 1mm thick sample was 0.45%; the Vickers hardness was 8.04 GPa.
Comparative example 1
(1) The base glass is composed of 60% SiO according to mol percentage 2 、19％Al 2 O 3 16% MgO and 5% ZnO (wherein SiO is measured out 2 The corresponding raw materials are silicon dioxide and Al 2 O 3 The corresponding raw material is aluminum hydroxide, the raw material corresponding to MgO is basic magnesium carbonate pentahydrate, the raw material corresponding to ZnO is zinc oxide), the raw materials are put into a mixer for ball milling after being prepared, the mixed batch is poured into a corundum crucible and placed into a high-temperature electric furnace, melting is carried out for 3 hours at 1580 ℃, then the molten high-temperature glass liquid is poured into a mold at 300 ℃ for molding, the molded glass is rapidly moved into a 680 ℃ annealing furnace for annealing for 2 hours, and cooling is carried out to room temperature to obtain the base glass.
(2) Carrying out nucleation and crystallization heat treatment on the annealed base glass in a high-temperature furnace according to a certain heat treatment process, wherein the specific heat treatment parameters are as follows: raising the temperature from room temperature to 830 ℃ at the heating rate of 8 ℃/min, preserving the heat for 4 hours for nucleation, then continuing raising the temperature to 1060 ℃ at the heating rate of 5 ℃/min, preserving the heat for 1 hour for crystallization, carrying out microcrystallization heat treatment, and then cooling to room temperature to obtain the microcrystalline glass.
As can be seen from FIG. 5, the obtained glass-ceramic has been completely devitrified, and the main crystal phase is MgAl as can be seen by contrast with the standard X-ray diffraction pattern 2 Si 3 O 10 And cordierite, compared with the microcrystalline glass obtained in the example 2, the magnesium-aluminum-silicon microcrystalline glass contains more cordierite; the grain size is about 158nm through Jade 6 calculation; the Vickers hardness was 7.86 GPa.
Comparative example 2
(1) The base glass was composed of 57 mol% SiO 2 、16％Al 2 O 3 、21％MgO、2％ZnO、4％TiO 2 The raw material batch (wherein SiO) is weighed out 2 The corresponding raw materials are silicon dioxide and Al 2 O 3 The corresponding raw materials are aluminum hydroxide, MgO corresponding raw material is basic magnesium carbonate pentahydrate, ZnO corresponding raw material is zinc oxide and TiO 2 The corresponding raw material is titanium dioxide), the raw materials are put into a mixer for ball milling after being prepared, the evenly mixed batch is poured into a corundum crucible and is placed into a high-temperature electric furnace, the corundum crucible is melted for 4 hours at 1550 ℃, then the melted high-temperature glass liquid is poured into a mold with the temperature of 260 ℃ for molding, the molded glass is quickly moved into an annealing furnace with the temperature of 650 ℃ for annealing for 4 hours, and the glass is cooled to the room temperature to obtain the basic glass.
(2) Carrying out nucleation and crystallization heat treatment on the annealed base glass in a high-temperature furnace according to a certain heat treatment process, wherein the specific heat treatment parameters are as follows: and (3) raising the temperature from room temperature to 810 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 6 hours for nucleation, then continuing raising the temperature to 950 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours for crystallization, carrying out microcrystallization heat treatment, and then cooling to room temperature to obtain the microcrystalline glass, wherein the microcrystalline glass presents obvious brown yellow.
FIG. 6 shows that the gain is obtainedThe main crystal phase of the microcrystalline glass is cordierite and MgAl 2 Si 3 O 10 (ii) a Through testing, the average light transmittance of a sample with the thickness of 2mm in a wavelength range of 380-780 nm is 70%; the haze of a 1mm thick sample was 0.81%; the Vickers hardness was 7.25 GPa.
Claims (10)
1. The colorless transparent magnesium-aluminum-silicon glass ceramic is characterized in that the main crystalline phase of the glass ceramic is MgAl 2 Si 3 O 10 The base glass of the microcrystalline glass comprises the following components in percentage by mol: 55 to 62 percent of SiO 2 、17％～24％Al 2 O 3 、13％～20％MgO、5％～8％ZnO。
2. The colorless transparent magnesium aluminosilicate microcrystalline glass according to claim 1, wherein the total molar percentage of MgO and ZnO is 20-25%.
3. A preparation method of colorless transparent magnesium-aluminum-silicon microcrystalline glass comprises the following steps:
(1) carrying out ball milling and mixing on raw materials of base glass, uniformly mixing, then placing the mixture in a high-temperature furnace for melting, forming the obtained glass liquid, then annealing, and cooling to obtain the base glass, wherein the base glass comprises the following components in percentage by mol: 55 to 62 percent of SiO 2 、17％～24％Al 2 O 3 、13％～20％MgO、5％～8％ZnO；
(2) And (3) sequentially carrying out nucleation heat treatment and crystallization heat treatment on the base glass in the step (1) to obtain colorless transparent magnesium aluminum silicon microcrystalline glass.
4. The method according to claim 3, wherein SiO in the step (1) 2 、Al 2 O 3 MgO and ZnO are respectively introduced by silicon dioxide, aluminum hydroxide, basic magnesium carbonate pentahydrate and zinc oxide; the raw material mole percentage of the base glass is according to the mole percentage of each component of the base glass.
5. The method according to claim 3, wherein the melting temperature in step (1) is 1550 to 1620 ℃ and the melting time is 2 to 4 hours.
6. The production method according to claim 3, wherein the step (1) is performed by molding: and pouring the molten glass into a preheated mold for molding, wherein the temperature of the preheated mold is kept at 260-350 ℃.
7. The method according to claim 3, wherein the annealing temperature in step (1) is 650 to 730 ℃ and the annealing time is 2 to 4 hours.
8. The preparation method according to claim 3, wherein the temperature of the nucleation heat treatment in the step (2) is 800-850 ℃, the time of the nucleation heat treatment is 3-6 hours, and the temperature rise rate is 2-10 ℃/min.
9. The method according to claim 3, wherein the temperature of the crystallization heat treatment in the step (2) is 900-1050 ℃, the time of the crystallization heat treatment is 1-2 hours, and the temperature rise rate is 2-10 ℃/min.
10. Use of the colorless transparent magnesium aluminum silicon glass-ceramic as claimed in claim 1 in a terminal display device or a cover plate material.
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