CN111302631A - Microcrystalline glass and preparation method and application thereof - Google Patents

Microcrystalline glass and preparation method and application thereof Download PDF

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Publication number
CN111302631A
CN111302631A CN201811519909.2A CN201811519909A CN111302631A CN 111302631 A CN111302631 A CN 111302631A CN 201811519909 A CN201811519909 A CN 201811519909A CN 111302631 A CN111302631 A CN 111302631A
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China
Prior art keywords
glass
weight
microcrystalline glass
hours
microcrystalline
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曹达华
万鹏
陈炜杰
何峰
施江
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Foshan Shunde Midea Electrical Heating Appliances Manufacturing Co Ltd
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Foshan Shunde Midea Electrical Heating Appliances Manufacturing Co Ltd
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Priority to CN201811519909.2A priority Critical patent/CN111302631A/en
Publication of CN111302631A publication Critical patent/CN111302631A/en
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
    • F24C7/00—Stoves or ranges heated by electric energy
    • F24C7/002—Stoves
    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
    • F24C3/00—Stoves or ranges for gaseous fuels
    • F24C3/008—Ranges

Abstract

The invention discloses microcrystalline glass and a preparation method and application thereof. Wherein the microcrystalline glass is Li2O‑Al2O3‑SiO2A system microcrystalline glass comprising 3.6 to 3.8 wt% of Li2And O, wherein the crystallite size of the microcrystalline glass is 50-150 nanometers. The microcrystalline glass can still keep a lower thermal expansion coefficient and a higher thermal shock resistance on the basis of using lower content of lithium oxide (3.6-3.8 wt%), improve the comprehensive performance of the microcrystalline glass, and simultaneously can reach the current microcrystalline glass (Li)2O is 3.9-4.2 wt%), and can greatly reduce the production cost of the microcrystalline glass, thereby reducing the raw material cost and simultaneously reducing the performance of the microcrystalline glassThe requirements of the panel of the induction cooker are met, and the economic benefit is improved.

Description

Microcrystalline glass and preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to microcrystalline glass and a preparation method and application thereof.
Background
The microcrystalline glass has the advantages of no impurities, no discoloration, low magnetic line damping coefficient, good heat insulation performance, high strength, large hardness and low coefficient of expansion with heat and contraction with cold, so that an electromagnetic oven adopting the panel has greatly improved heat efficiency, insulation and permeation prevention performance, working performance of products and long service life, and is very suitable for being used on the panel of the electromagnetic oven, and the microcrystalline panel has the low expansion coefficient because the glass contains β -quartz solid solution (LAS) or β -spodumene solid solution (LAS)2) Such solid solutions require the use of high levels of spodumene. At present, the high-content spodumene ores in China are few, most of the spodumene ores imported from Australia are adopted, and a large amount of spodumene ores are also needed along with the development of new energy automobiles, so that the spodumene ores are increasingly scarce in resources and expensive in price. Therefore, the development of the low-content spodumene glass ceramics has very important significance for the induction cooker industry.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a microcrystalline glass, a preparation method thereof and an application thereof, wherein the microcrystalline glass can maintain a low thermal expansion coefficient and a high thermal shock resistance on the basis of using a low content of lithium oxide (3.6-3.8 wt%), improve the comprehensive performance of the microcrystalline glass, and simultaneously can achieve the purpose of the existing microcrystalline glass (Li), and a preparation method thereof and an application thereof2O is 3.9-4.2 wt%), and the production cost of the microcrystalline glass can be greatly reduced, so that the requirements of the panel of the induction cooker are met while the raw material cost is reduced, and the economic benefit is improved.
In one aspect of the invention, a glass-ceramic is provided. According to an embodiment of the invention, the glass-ceramic is Li2O-Al2O3-SiO2The system microcrystalline glass comprises 3.6-3.8 wt% of Li2And O, wherein the crystallite size of the microcrystalline glass is 50-150 nanometers.
The microcrystalline glass provided by the embodiment of the invention uses lower content of lithium oxide (3)6-3.8 wt.%), lower thermal expansion coefficient and higher thermal shock resistance, and can raise the comprehensive performance of microcrystal glass and reach the performance of microcrystal glass (Li)2O is 3.9-4.2 wt%), and the production cost of the microcrystalline glass can be greatly reduced, so that the requirements of the panel of the induction cooker are met while the raw material cost is reduced, and the economic benefit is improved.
In some embodiments of the present invention, the above microcrystalline glass further comprises: 19 to 22 wt% of Al2O362 to 64% by weight of SiO22.5 to 2.8 wt% of TiO21.9 to 2.3% by weight of ZrO21.0 to 1.4% by weight of Na2O and 1.5 to 1.7% by weight of K2And O. Therefore, the microcrystalline glass can keep a lower thermal expansion coefficient and higher cold and hot shock resistance while ensuring lower production cost.
In some embodiments of the present invention, the above microcrystalline glass further comprises: 19.84 to 21.84 wt% of Al2O362.99-63.99 wt% SiO22.57 to 2.77 wt% of TiO21.98-2.28% by weight of ZrO21.2 to 1.4% by weight of Na2O and 1.55 to 1.7% by weight of K2And O. Therefore, the microcrystalline glass can keep a lower thermal expansion coefficient and excellent cold and hot shock resistance while ensuring lower production cost.
In some embodiments of the present invention, the above microcrystalline glass further comprises: 0 to 1 wt% CaO, 0 to 1 wt% MnO, and 0 to 1 wt% Fe2O31 to 3 wt% of BaO, 0 to 1 wt% of Sb2O30.5 to 2% by weight of ZnO and 0 to 1% by weight of P2O5. Therefore, the obtained microcrystalline glass can have excellent performance.
In some embodiments of the invention, the microcrystalline glass has a thermal expansion coefficient of 0.5 multiplied by 10 within a range of 30-500 degrees centigrade-6～1.0×10-6/K。
In some embodiments of the present invention, the temperature of the microcrystalline glass is 0 to 500 ℃.
In some embodiments of the present invention, the crystalline phase of the glass-ceramic is LiAlSi2O6。
In some embodiments of the invention, the Li2O is derived from at least one of spodumene, lepidolite, petalite, laponite, and lithium carbonate. This can significantly reduce the raw material cost of the glass ceramics.
In a further aspect of the invention, the invention proposes a method for preparing the above-mentioned glass-ceramic. According to an embodiment of the invention, the method comprises:
(1) mixing the raw materials for forming the microcrystalline glass according to the formula amount so as to obtain a raw material mixture;
(2) melting the raw material mixture, forming and annealing to obtain base glass;
(3) and carrying out nucleation and crystallization treatment on the base glass so as to obtain the microcrystalline glass.
According to the method for preparing the microcrystalline glass, the lower thermal expansion coefficient and the higher cold and heat shock resistance can be kept on the basis of using the lower content of lithium oxide (3.6-3.8 wt%), the comprehensive performance of the microcrystalline glass is improved, and meanwhile the existing microcrystalline glass (Li) can be achieved2O is 3.9-4.2 wt%), and the production cost of the microcrystalline glass can be greatly reduced, so that the requirements of the panel of the induction cooker are met while the raw material cost is reduced, and the economic benefit is improved.
In addition, the method for preparing the microcrystalline glass according to the embodiment of the invention may further have the following additional technical features:
in some embodiments of the present invention, in step (1), the mixing of the glass-ceramic forming raw materials in the formulated amount is performed by at least one of a ball milling process and a mixing process. Therefore, the materials are uniformly mixed.
In some embodiments of the present invention, in the step (2), the melting comprises raising the temperature from room temperature to 1500-1700 ℃ at a rate of 5-10 ℃ per minute, and maintaining the temperature for 0.5-5 hours. Therefore, the cost of power consumption is reduced while the melting material is fully melted.
In some embodiments of the present invention, in the step (2), the mold is preheated at 600 to 700 ℃ for 0.5 to 2 hours in advance before the molding.
In some embodiments of the present invention, in the step (2), the annealing treatment is performed in an annealing furnace at 600 to 700 degrees centigrade for 1 to 3 hours.
In some embodiments of the present invention, in the step (3), the nucleation is performed at 500 to 700 ℃ for 2 to 3 hours. Therefore, the microcrystalline glass can keep a lower thermal expansion coefficient and higher cold and hot shock resistance while ensuring lower production cost.
In some embodiments of the present invention, in the step (3), the crystallization is performed at 700 to 900 ℃ for 1 to 2 hours. Therefore, the microcrystalline glass can keep a lower thermal expansion coefficient and higher cold and hot shock resistance while ensuring lower production cost.
In some embodiments of the invention, the method further comprises: and carrying out post-treatment on the microcrystalline glass, wherein the post-treatment comprises at least one of deburring, polishing, chamfering and silk-screen printing. Therefore, the surface of the microcrystalline glass is smooth and flat, and the appearance is better.
In a third aspect of the invention, a panel is presented. According to an embodiment of the present invention, the panel is made of the above-mentioned glass ceramics or the glass ceramics obtained by the above-mentioned method. Therefore, the panel has lower production cost and still has lower thermal expansion coefficient and higher thermal shock resistance, and is particularly suitable for panels for induction cookers.
In a fourth aspect of the invention, a cooking appliance is presented. According to an embodiment of the invention, the cooking appliance has the panel. Therefore, the cooking utensil can remarkably reduce the production cost by using the panel. Specifically, the cooking appliance may be an induction cooker or a multi-head gas stove.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow chart of a method for producing a glass-ceramic according to an embodiment of the present invention;
FIG. 2 is an SEM photograph of a crystallized glass obtained in example 1;
FIG. 3 is an SEM photograph of a crystallized glass obtained in example 2;
FIG. 4 is an SEM photograph of a crystallized glass obtained in comparative example 1;
fig. 5 is an SEM image of the crystallized glass obtained in comparative example 2.
FIG. 6 is an XRD curve of the crystallized glasses obtained in examples 1 to 2 and comparative examples 1 to 2.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, a glass-ceramic is provided. According to an embodiment of the invention, the glass-ceramic is Li2O-Al2O3-SiO2A system glass ceramics comprising 3.6 to 3.8% by weight of Li2O, and the crystallite size of the microcrystalline glass is 50-150 nanometers. The inventors have found that in order to obtain a glass ceramic having a low thermal expansion coefficient and a high thermal shock resistance, it is necessary to control Li in the glass ceramic2The O content is 3.9 to 4.2 wt%. However, it is desired to obtain Li2The microcrystalline glass with the O content of 3.9-4.2 wt% needs to use high-content spodumene, and at present, the high-content spodumene ore in China is less, and most of the high-content spodumene ore is adoptedThe spodumene ore imported from australia also needs a large amount of spodumene ore along with the development of new energy automobiles, so that the resource of the spodumene ore is more and more scarce, and the price is more and more expensive. The inventors of the present application have made studies in view of the above-mentioned problems and found that O in R — O (R ═ Li) is stronger than Si — O covalent bond due to the ionic bond of R — O2-By central ion Si4+The non-bridging oxygen is generated by drawing, so if the content of Li element is excessive, excessive lithium oxide is attached outside the network forming body, and Li attached outside the network body2O will differentiate [ SiO4]Tetrahedra, resulting in new, discrete oligomers, thereby destroying SiO2The compactness of the formed network former leads to the increase of the thermal expansion coefficient, and the inventor of the application unexpectedly finds that the lithium oxide to SiO can be reduced by controlling the weight of the lithium oxide to be 3.6-3.8 percent2The Si-O in the formed network-forming body is cut off to thereby form SiO2The formed network forming body structure is more compact, the lithium oxide in the range can form β quartz solid solution with higher content, the grain size of the microcrystalline glass is controlled to be 50-150 nanometers, and the fine grains can be uniformly distributed in the microcrystalline glass, so that the lower thermal expansion coefficient and the higher cold and heat shock resistance of the microcrystalline glass are ensured, the comprehensive performance of the microcrystalline glass is improved, and the current microcrystalline glass (Li) can be achieved at the same time2O is 3.9-4.2 wt%), and the production cost of the microcrystalline glass can be greatly reduced, so that the requirements of the panel of the induction cooker are met while the raw material cost is reduced, and the economic benefit is improved. For example, Li in the crystallite ratio can be controlled2The content of O is 3.6 wt%, 3.61 wt%, 3.62 wt%, 3.63 wt%, 3.64 wt%, 3.65 wt%, 3.66 wt%, 3.67 wt%, 3.68 wt%, 3.69 wt%, 3.70 wt%, 3.71 wt%, 3.72 wt%, 3.73 wt%, 3.74 wt%, 3.75 wt%, 3.76 wt%, 3.77 wt%, 3.78 wt%, 3.79 wt%, 3.8 wt%, and the crystallite size of the glass-ceramics is controlled to be 50nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80nm, 85 nm, 90nm, 95 nm, 100nm, 105 nm, 110 nm115 nm, 120nm, 125 nm, 130 nm, 135 nm, 140 nm, 145 nm, 150 nm.
According to an embodiment of the present invention, the above-described glass ceramics further includes: 19 to 22 wt% of Al2O362 to 64% by weight of SiO22.5 to 2.8 wt% of TiO21.9 to 2.3% by weight of ZrO21.0 to 1.4% by weight of Na2O and 1.5 to 1.7% by weight of K2And O. The inventor finds that the Al in the microcrystalline glass can be removed2O3、SiO2、TiO2、ZrO2、Na2O and K2The contents of other components such as O and the like are regulated and controlled, so that the components can play a synergistic effect, and the microcrystalline glass has a low thermal expansion coefficient and a low thermal shock resistance by matching with a crystalline phase with fine and uniform grain size. Therefore, the obtained microcrystalline glass can be further ensured to have a lower thermal expansion coefficient and a cold and hot shock resistance. For example, Al can be controlled2O3Is 19, 19.1, 19.2, 19.3, 19.4, 19.5, 19.6, 19.7, 19.8, 19.84, 19.9, 20, 20.1, 20.2, 20.3, 20.4, 20.5, 20.6, 20.7, 20.8, 20.9, 21, 21.1, 21.2, 21.3, 21.4, 21.5, 21.6, 21.7, 21.8, 21.84, 21.9, 22,% by weight; SiO 22Is 62 wt%, 62.1 wt%, 62.2 wt%, 62.3 wt%, 62.4 wt%, 62.5 wt%, 62.6 wt%, 62.7 wt%, 62.8 wt%, 62.9 wt%, 62.99 wt%, 63 wt%, 63.1 wt%, 63.2 wt%, 63.3 wt%, 63.4 wt%, 63.5 wt%, 63.6 wt%, 63.7 wt%, 63.8 wt%, 63.9 wt%, 63.99 wt%, 64 wt%; TiO 22Is contained in an amount of 2.5 wt%, 2.51 wt%, 2.52 wt%, 2.53 wt%, 2.54 wt%, 2.55 wt%, 2.56 wt%, 2.57 wt%Amounts%, 2.58 wt%, 2.59 wt%, 2.6 wt%, 2.61 wt%, 2.62 wt%, 2.63 wt%, 2.64 wt%, 2.65 wt%, 2.66 wt%, 2.67 wt%, 2.68 wt%, 2.69 wt%, 2.70 wt%, 2.71 wt%, 2.72 wt%, 2.73 wt%, 2.74 wt%, 2.75 wt%, 2.76 wt%, 2.77 wt%, 2.78 wt%, 2.79 wt%, 2.80 wt%; ZrO (ZrO)2Is 1.9 wt%, 1.98 wt%, 2.0 wt%, 2.1 wt%, 2.2 wt%, 2.28 wt%, 2.3 wt%; na (Na)2The content of O was 1.0 wt%, 1.05 wt%, 1.1 wt%, 1.15 wt%, 1.2 wt%, 1.25 wt%, 1.3 wt%, 1.35 wt%, 1.4 wt%; k2The content of O was 1.5 wt%, 1.55 wt%, 1.6 wt%, 1.65 wt%, 1.7 wt%. Preference is given to controlling Al2O319.84 to 21.84 wt% of SiO262.99-63.99 wt% of TiO2ZrO in an amount of 2.57 to 2.77 wt%2Na in an amount of 1.98 to 2.28 wt% and 1.2 to 1.4 wt%2O, 1.55 to 1.7% by weight of K2O。
According to an embodiment of the present invention, the above-described glass ceramics further includes: 0 to 1 wt% CaO, 0 to 1 wt% MnO, and 0 to 1 wt% Fe2O31 to 3 wt% of BaO, 0 to 1 wt% of Sb2O30.5 to 2% by weight of ZnO and 0 to 1% by weight of P2O5. Therefore, the obtained microcrystalline glass can have excellent performance. For example, the content of CaO is 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%; the MnO content was 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%; fe2O3Is contained in an amount of 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%; content of BaO1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0 wt%; sb2O3Is contained in an amount of 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%; the content of ZnO was 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt%; p2O5The content of (b) is 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%.
According to the embodiment of the invention, the coefficient of thermal expansion of the microcrystalline glass in the range of 30-500 ℃ is 0.5 multiplied by 10-6～1.0×10-6and/K. The inventor finds that the microcrystalline glass has the thermal expansion coefficient within the range, so that the microcrystalline glass has excellent heat resistance and heat insulation performance and the service life is prolonged.
According to the embodiment of the invention, the temperature of the microcrystalline glass for resisting cold and hot impact is 0-500 ℃. The inventor finds that the microcrystalline glass has the temperature of resisting cold and hot impact within the range, so that the service strength and the heat resistance of the microcrystalline glass can be improved, and the service life of the microcrystalline glass can be prolonged.
According to an embodiment of the present invention, the crystalline phase of the microcrystalline glass is LiAlSi2O6. Therefore, the microcrystalline glass can be ensured to have excellent performance.
According to an embodiment of the present invention, Li in the above-mentioned glass ceramics2O is derived from at least one of spodumene, lepidolite, petalite, laponite, and lithium carbonate. Thus, the present application uses low cost raw materials as compared to the use of expensive high content spodumeneCan reach the prior microcrystalline glass (Li)2O is 3.9-4.2 wt%), thereby remarkably reducing the raw material cost of the microcrystalline glass.
In a further aspect of the invention, the invention proposes a method for preparing the above-mentioned glass-ceramic. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing the raw materials for forming the microcrystalline glass according to the formula amount
According to one embodiment of the invention, in this step, Li is added2O、Al2O3、SiO2、TiO2And ZrO2Mixing and batching are carried out according to the composition of the microcrystalline glass. According to an embodiment of the invention, CaO, MnO and Fe with the above formula can be further added in the process of mixing materials2O3、BaO、Sb2O3、ZnO、P2O5、Na2O and K2And O. Therefore, the obtained microcrystalline glass can have excellent performance. According to still another embodiment of the present invention, the mixing of the glass-ceramic forming raw materials in the formulated amounts is performed by at least one of a ball milling process and a material mixing process. Specifically, can add the ball mill after mixing the raw materials and carry out the ball-milling and handle, perhaps add the blendor after mixing the raw materials and carry out the compounding and handle, concrete ball mill or blendor model, operating condition technical personnel in the field can be selected according to actual conditions is nimble, as long as can make the raw materials misce bene can, and then do benefit to the performance that improves the microcrystalline glass who obtains.
S200: melting the mixed material obtained in the step S100, forming and annealing
In the step, specifically, the mixed material obtained in the step S100 is placed into an alumina crucible, the temperature is increased from room temperature to 1500-1700 ℃ at the rate of 5-10 ℃ per minute, the mixed material is subjected to heat preservation for 0.5-5 hours for melting, then the molten mixed material is rapidly poured onto a mold which is preheated at the temperature of 600-700 ℃ for 0.5-2 hours in advance, then the formed glass is placed into an annealing furnace at the temperature of 600-700 ℃ for annealing for 1-3 hours, and then the formed glass is cooled to room temperature along with the furnace and taken out, so that the base glass is obtained. The inventors have found that, with respect to the above-mentioned temperature rise rate, temperature and time ranges of the melting process, if the temperature rise rate is too slow, the production cycle is lengthened, and if the temperature rise rate is too fast, the cost of power consumption is increased; if the melting temperature is too high, a large amount of bubbles can be generated in the microcrystalline glass, and if the melting temperature is too low, the melting material can be insufficiently melted; if the melting heat preservation time is too long, the cost of power consumption is increased, and if the melting heat preservation time is too short, the melt is not uniformly mixed, and the component layering phenomenon occurs. Therefore, the melting processing conditions within the range of the application can ensure that the molten material is fully melted and reduce the power consumption cost. Meanwhile, the mold is preheated in advance before casting molding, so that the mold can be pressed and molded within the range of molding viscosity of basic glass, and if the preheating temperature is too high, the solution can splash, and the service life of the mold is shortened; if the preheating temperature is too low, the melt viscosity is too high, the material property is insufficient, and the pressing forming cannot be carried out. From this, adopt the condition of preheating of this application, can guarantee the smooth casting moulding of melt and improve the life of mould simultaneously. For example, the temperature rise rate of the melting treatment may be 5 degrees celsius/minute, 5.2 degrees celsius/minute, 5.4 degrees celsius/minute, 5.6 degrees celsius/minute, 5.8 degrees celsius/minute, 6.0 degrees celsius/minute, 6.2 degrees celsius/minute, 6.4 degrees celsius/minute, 6.6 degrees celsius/minute, 6.8 degrees celsius/minute, 7.0 degrees celsius/minute, 7.2 degrees celsius/minute, 7.4 degrees celsius/minute, 7.6 degrees celsius/minute, 7.8 degrees celsius/minute, 8.0 degrees celsius/minute, 8.2 degrees celsius/minute, 8.4 degrees celsius/minute, 8.6 degrees celsius/minute, 8.8 degrees celsius/minute, 9.0 degrees celsius/minute, 9.2 degrees celsius/minute, 9.4 degrees celsius/minute, 9.6 degrees/minute, 9.8 degrees celsius/minute, 10 degrees celsius/minute; the melting treatment temperature can be 1500 ℃, 1525 ℃, 1550 ℃, 1575 ℃, 1600 ℃, 1625 ℃, 1650 ℃, 1675 ℃ and 1700 ℃; the holding time of the melting treatment may be 0.5 hour, 0.75 hour, 1.0 hour, 1.25 hours, 1.5 hours, 1.75 hours, 2.0 hours, 2.25 hours, 2.5 hours, 2.75 hours, 3.0 hours, 3.25 hours, 3.5 hours, 3.75 hours, 4.0 hours, 4.25 hours, 4.5 hours, 4.75 hours, 5.0 hours. For example, the mold may preferably be a cast iron mold, a stainless steel mold; the preheating temperature of the mold can be 600 ℃, 625 ℃, 650 ℃, 675 ℃ and 700 ℃; the preheating time may be 0.5 hour, 0.75 hour, 1.0 hour, 1.25 hour, 1.5 hours, 1.75 hours, 2.0 hours. The temperature in the annealing treatment process can be 600 ℃, 625 ℃, 650 ℃, 675 ℃ and 700 ℃; the annealing time may be 1 hour, 1.1 hour, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2.0 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours, 3.0 hours.
According to the embodiments of the present invention, the mode of preheating the mold is not particularly limited, and in some specific embodiments of the present invention, the mold may be heated by the melted product, and generally the mold may be preheated to 600-700 ℃, at this time, no additional heating step is required, the cost is low, and the molding requirement of the glass ceramics can still be satisfied; in other embodiments of the present invention, the mold may be preheated by heating pipes, heating wires, etc., and the preheating temperature may be adjusted more flexibly.
S300: carrying out nucleation and crystallization treatment on the base glass
In the step, the microcrystalline glass obtained in the step is subjected to nucleation and crystallization treatment to obtain the microcrystalline glass. In the specific nucleation process, uniform and stable crystal nucleus can be formed in the glass phase, and TiO in the raw material2And ZrO2The nucleating agent is a nucleating agent in the non-uniform nucleating process, numerous crystal nuclei can be formed in glass at the nucleating temperature, too high temperature or too long heat preservation time can cause too fast nucleating and non-uniform nucleating, and too low temperature or too short heat preservation time can cause too high viscosity of the glass, high resistance and low nucleating density or even no nucleating, so that the nucleating treatment is carried out at 500-700 ℃ for 2-3 hours, and the uniform nucleating in the glass and high nucleating density distribution can be ensured. The crystallization treatment causes the crystal nucleus to grow up, the temperature is too high or the holding time is too long, the crystal grains grow up abnormally, the temperature is too low or the holding time is too short, the viscosity of the glass is too high,large resistance and insufficient crystallization capacity, even no crystallization. The crystallization treatment is carried out at 700-900 ℃ for 1-2 hours, and the uniform and fine crystal grain size can be ensured, so that the obtained microcrystalline glass has a lower thermal expansion coefficient and a higher thermal shock resistance, the comprehensive performance of the microcrystalline glass is improved, and the current microcrystalline glass (Li) can be achieved2O is 3.9-4.2 wt%), and the production cost of the microcrystalline glass can be greatly reduced, so that the raw material cost is reduced, the requirements of the panel of the induction cooker are met, and the economic benefit is improved. For example, the nucleation treatment temperature is 500 degrees celsius, 510 degrees celsius, 520 degrees celsius, 530 degrees celsius, 540 degrees celsius, 550 degrees celsius, 560 degrees celsius, 570 degrees celsius, 580 degrees celsius, 590 degrees celsius, 600 degrees celsius, 610 degrees celsius, 620 degrees celsius, 630 degrees celsius, 640 degrees celsius, 650 degrees celsius, 660 degrees celsius, 670 degrees celsius, 680 degrees celsius, 690 degrees celsius, 700 degrees celsius; the nucleation treatment time is 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours and 3.0 hours; the crystallization treatment temperature is 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃ and 900 ℃; the crystallization treatment time was 1 hour, 1.1 hour, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, and 2.0 hours.
According to an embodiment of the present invention, the method further includes: and carrying out post-treatment on the obtained microcrystalline glass piece, wherein the post-treatment comprises at least one of deburring, polishing, chamfering and silk screen printing. Therefore, the surface of the microcrystalline glass is smooth and flat, the appearance of the microcrystalline glass is better, meanwhile, the shape of the microcrystalline glass can be properly processed, the microcrystalline glass has a shape meeting the use requirement, the microcrystalline glass is convenient to use subsequently, in addition, the microcrystalline glass can be decorated, and the like, so that the microcrystalline glass meets the use appearance requirement.
In a third aspect of the invention, a panel is presented. According to an embodiment of the present invention, the panel is made of the above-mentioned glass ceramics or the glass ceramics obtained by the above-mentioned method. Therefore, the panel has lower production cost and still has lower thermal expansion coefficient and excellent cold and hot impact resistance, and is particularly suitable for panels for induction cookers. It is to be noted that the features and advantages described above in relation to the glass ceramic and the method of producing the glass ceramic are equally applicable to the panel and will not be described in further detail here.
In a fourth aspect of the present invention, an induction cooking range is provided. According to an embodiment of the present invention, the induction cooker has the above-mentioned panel. Therefore, the induction cooker can remarkably reduce the production cost of the induction cooker by using the panel. It should be noted that the features and advantages described above for the panel are also applicable to the induction cooker, and are not described herein again.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
The microcrystalline glass comprises the following components in formula: 3.6% by weight of Li2O, 19.84% by weight of Al2O363.99% by weight of SiO22.77% by weight of TiO21.98% by weight of ZrO 21% by weight of Na2O, 1.5% by weight of K2O, 0.5 wt% CaO, 1 wt% BaO, 2 wt% ZnO, 1 wt% P2O5And the balance unavoidable impurities.
The method for preparing the microcrystalline glass comprises the following steps: mixing the raw materials according to a formula, fully mixing the mixture by using a ball mill, putting the mixed material into an alumina crucible, heating the mixed material from room temperature to 1700 ℃ at the speed of 5 ℃ per minute, preserving heat for 3 hours, melting, quickly pouring the molten mixed material onto a cast iron mold preheated at 600 ℃ for 1 hour, putting the formed glass into an annealing furnace at 600 ℃ for annealing for 2 hours, cooling the formed glass to room temperature along with the furnace, taking out the cooled glass to obtain base glass, carrying out nucleation treatment on the obtained base glass at 580 ℃ for 2 hours, and finally carrying out crystallization treatment at 750 ℃ for 1.0 hour to obtain the microcrystalline glass B1. The SEM image of the crystal phase of the obtained microcrystalline glass is shown in figure 2, and the crystal grain size is 50-80 nm.
Example 2
The microcrystalline glass comprises the following components in formula: 3.8% by weight of Li2O, 21.84% by weight of Al2O362.99 wt% SiO22.57% by weight of TiO22.28% by weight of ZrO21.2% by weight of Na2O, 1.6% by weight of K2O, 0.5 weight% Fe2O31.2% by weight of BaO, 0.7% by weight of ZnO and the balance unavoidable impurities.
The method for preparing the microcrystalline glass comprises the following steps: mixing the raw materials according to a formula, fully mixing the mixture by using a ball mill, putting the mixed material into an alumina crucible, heating the mixed material from room temperature to 1500 ℃ at the speed of 10 ℃/min, preserving heat for 5 hours, melting, quickly pouring the molten mixed material onto a stainless steel mold preheated at 700 ℃ for 0.75 hour, putting the formed glass into an annealing furnace at 700 ℃ for annealing for 2 hours, cooling the formed glass to room temperature along with the furnace, taking out the cooled glass to obtain base glass, nucleating the obtained base glass at 620 ℃ for 3 hours, and finally crystallizing the obtained base glass at 790 ℃ for 2.0 hours to obtain the microcrystalline glass B2. The SEM image of the obtained microcrystalline glass is shown in FIG. 3, and the grain size is 120-150 nm.
Example 3
The microcrystalline glass comprises the following components in formula: 3.7% by weight of Li2O, 20% by weight of Al2O363.50% by weight of SiO22.6% by weight of TiO22.0% by weight of ZrO21.2% by weight of Na2O, 1.7% by weight of K2O, 0.6 wt% CaO, 1.2 wt% BaO, 0.5 wt% Sb2O31% by weight of ZnO, 0.5% by weight of P2O5And the balance unavoidable impurities.
The method for preparing the microcrystalline glass comprises the following steps: mixing the raw materials according to a formula, fully mixing the mixture, putting the mixed material into an alumina crucible, heating the mixed material from room temperature to 1650 ℃ at the speed of 7 ℃/min, preserving heat for 4 hours, melting, quickly pouring the molten mixed material onto a cast iron mold preheated at 625 ℃ for 1 hour, putting the formed glass into an annealing furnace at 625 ℃ for annealing for 3 hours, cooling the formed glass to room temperature along with the furnace, taking out the cooled glass to obtain base glass, carrying out nucleation on the obtained base glass at 500 ℃ for 2.2 hours, and finally carrying out crystallization at 900 ℃ for 1.2 hours to obtain microcrystalline glass, wherein the grain size of the microcrystalline glass is 80-100 nm.
Example 4
The microcrystalline glass comprises the following components in formula: 3.65 wt.% Li2O, 20.5% by weight of Al2O363.0% by weight of SiO22.7% by weight of TiO22.1% by weight of ZrO21.4% by weight of Na2O, 1.5% by weight of K2O, 1.5% by weight of BaO, 0.7% by weight of Sb2O31.2% by weight of ZnO, 0.6% by weight of P2O5And the balance unavoidable impurities.
The method for preparing the microcrystalline glass comprises the following steps: mixing the raw materials according to a formula, fully mixing the mixture, putting the mixed material into an alumina crucible, heating the mixed material from room temperature to 1550 ℃ at the rate of 8 ℃/min, preserving heat for 3 hours, melting, quickly pouring the molten mixed material onto a cast iron mold preheated at 650 ℃ for 1.5 hours, putting the formed glass into an annealing furnace at 650 ℃ for annealing for 2 hours, cooling the formed glass to room temperature along with the furnace, taking out the cooled glass to obtain base glass, carrying out nucleation on the obtained base glass at 700 ℃ for 2.4 hours, and finally carrying out crystallization at 700 ℃ for 1.4 hours to obtain microcrystalline glass, wherein the grain size of the microcrystalline glass is 60-90 nm.
Example 5
The microcrystalline glass comprises the following components in formula: 3.75% by weight of Li2O, 21.0 wt.% Al2O3、63.70Weight% SiO22.8% by weight of TiO22.2% by weight of ZrO21.3% by weight of Na2O, 1.6% by weight of K2O, 0.4 wt.% Fe2O32.2% by weight of BaO, 1% by weight of ZnO and the balance unavoidable impurities.
The method for preparing the microcrystalline glass comprises the following steps: mixing the raw materials according to a formula, fully mixing the mixture, putting the mixed material into an alumina crucible, heating the mixed material from room temperature to 1675 ℃ at the rate of 9 ℃/min, preserving heat for 5 hours, melting, quickly pouring the molten mixed material onto a cast iron mold preheated at 675 ℃ for 1.5 hours, putting the formed glass into an annealing furnace preheated at 675 ℃ for annealing for 2.5 hours, cooling the formed glass to room temperature along with the furnace, taking out the cooled glass to obtain base glass, carrying out nucleation on the obtained base glass at 600 ℃ for 2 hours, and finally carrying out crystallization at 820 ℃ for 1.8 hours to obtain the microcrystalline glass. The crystallite size of the obtained glass ceramics is 100-120 nm.
Comparative example 1
The microcrystalline glass comprises the following components in formula: 3.4% by weight of Li2O, 19.84% by weight of Al2O363.99% by weight of SiO22.77% by weight of TiO21.98% by weight of ZrO 21% by weight of Na2O, 1.5% by weight of K2O, 0.5 wt% CaO, 1 wt% BaO, 2 wt% ZnO, 1 wt% P2O5And the balance unavoidable impurities.
The method for preparing the microcrystalline glass comprises the following steps: mixing the raw materials according to a formula, fully mixing the mixture by using a ball mill, putting the mixed material into an alumina crucible, heating the mixed material from room temperature to 1700 ℃ at the speed of 5 ℃ per minute, preserving heat for 3 hours, melting, quickly pouring the molten mixed material onto a cast iron mold preheated at 600 ℃ for 1 hour, putting the formed glass into an annealing furnace at 600 ℃ for annealing for 2 hours, cooling the formed glass to room temperature along with the furnace, taking out the cooled glass to obtain base glass, carrying out nucleation treatment on the obtained base glass at 580 ℃ for 2 hours, and finally carrying out crystallization treatment at 750 ℃ for 1.0 hour to obtain the microcrystalline glass B3. The SEM image of the crystal phase of the obtained microcrystalline glass is shown in FIG. 4, and the crystal grain size is 50-150 nm.
Comparative example 2
The microcrystalline glass comprises the following components in formula: 3.9 wt.% Li2O, 21.84% by weight of Al2O362.99 wt% SiO22.57% by weight of TiO22.28% by weight of ZrO21.2% by weight of Na2O, 1.6% by weight of K2O, 0.5 weight% Fe2O31.2% by weight of BaO, 0.7% by weight of ZnO and the balance unavoidable impurities.
The method for preparing the microcrystalline glass comprises the following steps: mixing the raw materials according to a formula, fully mixing the mixture by using a ball mill, putting the mixed material into an alumina crucible, heating the mixed material from room temperature to 1500 ℃ at the speed of 10 ℃/min, preserving heat for 5 hours, melting, quickly pouring the molten mixed material onto a stainless steel mold preheated at 700 ℃ for 0.75 hour, putting the formed glass into an annealing furnace at 700 ℃ for annealing for 2 hours, cooling the formed glass to room temperature along with the furnace, taking out the cooled glass to obtain base glass, nucleating the obtained base glass at 620 ℃ for 3 hours, and finally crystallizing the obtained base glass at 790 ℃ for 2.0 hours to obtain the microcrystalline glass B4. The SEM image of the obtained glass ceramics is shown in FIG. 5, and the grain size is 150nm or more.
Evaluation:
1. the thermal expansion coefficient, the cold and hot shock properties and the crystal phase of the microcrystalline glasses obtained in examples 1 to 5 and comparative examples 1 to 2 were measured;
2. the test method comprises the following steps:
testing the thermal expansion coefficient: testing by using a NETZSCH thermal expansion coefficient instrument;
and (3) testing the cold and hot impact performance: putting the sample into a thermostat with the temperature of 500 ℃ for half an hour, taking out the sample, putting the sample into an ice-water mixture with the temperature of 0 ℃, and checking whether the sample cracks;
crystal phase test: the XRD graphs of examples 1-2 and comparative examples 1-2 are shown in FIG. 6, which is measured by an X-ray diffractometer (XRD).
The test results are shown in table 1:
TABLE 1
Figure BDA0001902965830000111
Figure BDA0001902965830000121
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (19)

1. The microcrystalline glass is characterized in that the microcrystalline glass is Li2O-Al2O3-SiO2A system microcrystalline glass comprising 3.6 to 3.8 wt% of Li2And O, wherein the crystallite size of the microcrystalline glass is 50-150 nanometers.
2. The glass-ceramic according to claim 1, characterized by further comprising:
19 to 22 wt% of Al2O3；
62 to 64 wt% of SiO2；
2.5 to 2.8% by weight of TiO2；
1.9 to 2.3% by weight of ZrO2；
1.0 to 1.4% by weight of Na2O；
1.5 to 1.7% by weight of K2O。
3. The glass-ceramic according to claim 1 or 2, characterized by further comprising:
19.84 to 21.84 wt% of Al2O3；
62.99-63.99 wt% SiO2；
2.57-2.77 wt% TiO2；
1.98-2.28% by weight of ZrO2；
1.2 to 1.4% by weight of Na2O；
1.55 to 1.7% by weight of K2O。
4. The glass-ceramic according to claim 3, characterized by further comprising:
0-1 wt% CaO;
0 to 1 wt% of MnO;
0 to 1 weight of Fe2O3；
1-3 wt% BaO;
0 to 1% by weight of Sb2O3；
0.5 to 2% by weight of ZnO;
0 to 1% by weight of P2O5。
5. The microcrystalline glass according to claim 1, wherein the microcrystalline glass has a thermal expansion coefficient of 0.5 x 10 in a range of 30 to 500 degrees centigrade-6～1.0×10-6/K。
6. The glass-ceramic according to claim 1, wherein the glass-ceramic has a thermal shock resistance temperature of 0 to 500 ℃.
7. The glass-ceramic according to claim 1, wherein the crystalline phase of the glass-ceramic is LiAlSi2O6。
8. The glass-ceramic according to claim 1, wherein the Li is Li2O is derived from at least one of spodumene, lepidolite, petalite, laponite, and lithium carbonate.
9. A method for producing a glass-ceramic according to any one of claims 1 to 8, comprising:
(1) mixing the raw materials for forming the microcrystalline glass according to the formula amount so as to obtain a raw material mixture; (ii) a
(2) Melting the raw material mixture, forming and annealing to obtain base glass;
(3) and carrying out nucleation and crystallization treatment on the base glass so as to obtain the microcrystalline glass.
10. The method according to claim 9, wherein in step (1), the mixing of the glass-ceramics-forming raw materials in the prescribed amount is performed by at least one of a ball-milling treatment and a mixing treatment.
11. The method of claim 9, wherein in step (2), the melting comprises raising the temperature from room temperature to 1500-1700 ℃ at a rate of 5-10 ℃ per minute and maintaining the temperature for 0.5-5 hours.
12. The method according to claim 9 or 11, wherein in the step (2), the mold is preheated at 600 to 700 degrees celsius for 0.5 to 2 hours in advance before the molding.
13. The method according to claim 9, wherein in the step (2), the annealing treatment is performed in an annealing furnace at 600 to 700 degrees centigrade for 1 to 3 hours.
14. The method according to claim 9, wherein in the step (3), the nucleation is performed at 500 to 700 ℃ for 2 to 3 hours.
15. The method as claimed in claim 9 or 14, wherein in the step (3), the crystallization treatment is performed at 700 to 900 ℃ for 1 to 2 hours.
16. The method of claim 9, further comprising: and carrying out post-treatment on the microcrystalline glass, wherein the post-treatment comprises at least one of deburring, polishing, chamfering and silk-screen printing.
17. A panel made of a glass-ceramic according to any one of claims 1 to 8 or obtained by the method according to any one of claims 9 to 16.
18. A cooking appliance having the panel of claim 17.
19. The cooking appliance of claim 18, wherein the cooking appliance is an induction cooker or a multi-head gas range.
CN201811519909.2A 2018-12-12 2018-12-12 Microcrystalline glass and preparation method and application thereof Pending CN111302631A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2657079A1 (en) * 1990-01-12 1991-07-19 Corning France GLASS PRECURSOR GLASSES, PROCESS FOR CONVERTING THESE GLASSES IN VITROCERAMIC GLASSES WITH VERY LOW OR ZERO DILATION AND VITROCERAMIC PRODUCTS OBTAINED.
CN1699230A (en) * 2005-01-20 2005-11-23 湖州大享玻璃制品有限公司 Li2O-Al2O3-SiO2 microcrystalline glass and microcrystalline glass and making process thereof
TWI297332B (en) * 2001-03-02 2008-06-01 Schott Ag Glass-ceramic
CN108117264A (en) * 2018-01-09 2018-06-05 湖州大享玻璃制品有限公司 Li2O-Al2O3-SiO2Based crystallized glass and its manufacturing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2657079A1 (en) * 1990-01-12 1991-07-19 Corning France GLASS PRECURSOR GLASSES, PROCESS FOR CONVERTING THESE GLASSES IN VITROCERAMIC GLASSES WITH VERY LOW OR ZERO DILATION AND VITROCERAMIC PRODUCTS OBTAINED.
TWI297332B (en) * 2001-03-02 2008-06-01 Schott Ag Glass-ceramic
CN1699230A (en) * 2005-01-20 2005-11-23 湖州大享玻璃制品有限公司 Li2O-Al2O3-SiO2 microcrystalline glass and microcrystalline glass and making process thereof
CN108117264A (en) * 2018-01-09 2018-06-05 湖州大享玻璃制品有限公司 Li2O-Al2O3-SiO2Based crystallized glass and its manufacturing method

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