CN113754284A - Preparation method of glass ceramic and industrial microwave oven - Google Patents
Preparation method of glass ceramic and industrial microwave oven Download PDFInfo
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- CN113754284A CN113754284A CN202110942072.8A CN202110942072A CN113754284A CN 113754284 A CN113754284 A CN 113754284A CN 202110942072 A CN202110942072 A CN 202110942072A CN 113754284 A CN113754284 A CN 113754284A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—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 silica as main constituent
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/02—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating
- C03B5/023—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating by microwave heating
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
- C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
The invention provides a preparation method of glass ceramic and an industrial microwave oven, belonging to the technical field of metallurgy and inorganic non-metallic material preparation. The glass raw materials of the invention contain compounds with better high-temperature wave-absorbing performance, such as: fe2O3Effectively improves the microwave heating uniformity and further improves the structure uniformity of the glass ceramic. Meanwhile, the reasonable design of the components of the glass raw material combines the microwave thermal effect and the microwave non-thermal effect, so that the glass raw material is lowerUnder the stress annealing temperature, the nucleation temperature and the growth temperature, the glass ceramic with fine grains, uniform structure and better homogenization can be formed in a shorter time, so that the glass ceramic obtains better bending resistance. The data of the examples show that the resulting glass-ceramic has a flexural strength of 219MPa, an average pyroxene crystal width of 50nm and a high-temperature softening temperature of 1130 ℃.
Description
Technical Field
The invention relates to the technical field of metallurgy and inorganic non-metallic material preparation, in particular to a preparation method of glass ceramic and an industrial microwave oven.
Background
The glass ceramic technology is a polycrystalline solid material obtained by nucleating and crystallizing base glass with controlled specific components based on the controllable nucleation and crystallization of the glass, and combines the characteristics of the ceramic and the glass. Glass-ceramics have properties that other materials, such as ceramics, glass, metals, or organic polymers, do not have.
The process for preparing the high-entropy glass ceramic by the traditional electric furnace comprises the following steps: firstly, heating and melting basic glass at 1300 ℃ or even higher temperature for more than 2h, casting and molding, then putting the basic glass into an annealing kiln for annealing for 2-4 h, and finally putting the basic glass into a crystallization furnace for nucleation and crystallization, wherein each process can be completed within 2-5 h according to the geometric dimension of the material. However, the above process is time-consuming, energy-consuming, complex in production process, requires at least 3 times for the material discharging and charging processes, and it is difficult to control the size of the crystal grains.
The microwave sintering technology is known for rapid dense sintering of ceramic materials, and chinese patent CN201410221126.1 discloses that the nanocrystalline is prepared through a multi-step microwave heat treatment process, the operation process is complicated, and temperature control is difficult in actual operation.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing glass ceramic and an industrial microwave oven. The preparation method provided by the invention is simple to operate, and the prepared glass ceramic has excellent flexural strength.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of glass ceramic, which comprises the following steps:
melting and casting the glass raw material under the microwave thermal effect and the microwave non-thermal effect to obtain a base glass material;
under the microwave thermal effect and the microwave non-thermal effect, sequentially carrying out stress annealing, nucleation and growth on the base glass material to obtain glass ceramic;
the glass raw materials comprise the following main components in percentage by mass:
SiO235～45％，CaO 25～30％，MgO 2～5％，Al2O34～10％，Fe2O34～13％，Na20.3-1.5% of O and 1-2% of rare earth oxide.
Preferably, the microwave heating effect and the microwave non-heating effect are provided by an industrial microwave oven, and the inner side of a heat preservation cavity of the industrial microwave oven is partially coated with a silicon carbide coating; the thickness of the silicon carbide coating is 1-4 mm.
Preferably, the heat preservation cavity of the industrial microwave oven is a hollow cylinder; the inner side of the heat preservation cavity is divided into 12 parts on average along the axial direction of the hollow cylinder, wherein 6 parts are coated with the silicon carbide coating, and the 6 parts coated with the silicon carbide coating are not adjacent to each other.
Preferably, the temperature of the stress annealing is 400-550 ℃, and the heat preservation time is 10-30 min.
Preferably, the nucleation temperature is 40-50 ℃ higher than the nucleation temperature obtained by DSC differential thermal analysis, and the temperature rise rate of the DSC differential thermal analysis is 5 ℃/min; the heat preservation time of the nucleation is 10-30 min.
Preferably, the growth temperature is a growth temperature obtained by DSC differential thermal analysis; the heat preservation time for growth is 10-30 min.
Preferably, when the base glass material is placed in an industrial microwave oven, the temperature of the industrial microwave oven is 350-450 ℃.
Preferably, the rate of raising the temperature from the temperature of the industrial microwave oven to the temperature of stress annealing is 1-5 ℃/min; the speed of raising the temperature from the stress annealing temperature to the nucleation temperature is 1-5 ℃/min; the rate of increasing from the nucleation temperature to the growth temperature is 1-5 ℃/min.
The invention also provides an industrial microwave oven, which comprises a heat preservation cavity 1, a thermocouple 2, a crucible 5 and a base 6, wherein the inner side of the heat preservation cavity 1 is partially coated with a silicon carbide coating 3.
Preferably, the heat preservation cavity 1 is a hollow cylinder; the inner side of the heat preservation cavity 1 is divided into 12 parts on average along the axial direction of the hollow cylinder, wherein 6 parts are coated with silicon carbide coatings, and the 6 parts coated with the silicon carbide coatings are not adjacent to each other.
The invention provides a preparation method of glass ceramic, which comprises the following steps: melting and casting the glass raw material under the microwave thermal effect and the microwave non-thermal effect to obtain a base glass material; under the microwave thermal effect and the microwave non-thermal effect, sequentially carrying out stress annealing, nucleation and growth on the base glass material to obtain glass ceramic; the glass raw materials comprise the following main components in percentage by mass: SiO 2235～45％，CaO 25～30％，MgO 2～5％，Al2O34～10％，Fe2O34～13％，Na20.3-1.5% of O and 1-2% of rare earth oxide.
The glass raw materials of the invention contain compounds with better high-temperature wave-absorbing performance, such as: fe2O3Effectively improves the microwave heating uniformity and further improves the structure uniformity of the glass ceramic. Meanwhile, the reasonable design of the components of the glass raw material combines the microwave thermal effect and the microwave non-thermal effect, so that the glass raw material can form glass ceramic with fine grains, uniform tissues and good homogenization in a short time at a lower stress annealing temperature, a lower nucleation temperature and a lower growth temperature, and the glass ceramic obtains better fracture resistance.
Furthermore, the preparation method provided by the invention has few production links, only needs to be taken out of the furnace once after smelting, and then the subsequent stress annealing, nucleation and growth are completed in the same industrial microwave oven.
The data of the embodiment shows that the glass ceramic obtained by the preparation method provided by the invention has the breaking strength of 219MPa, the average pyroxene crystal width of 50nm and the high-temperature softening temperature of 1130 ℃.
The invention also provides an industrial microwave oven, which comprises a heat preservation cavity 1, a thermocouple 2, a crucible 5 and a base 6, wherein the inner side of the heat preservation cavity 1 is partially coated with a silicon carbide coating 3. The industrial microwave oven provided by the invention has the advantages that the silicon carbide coating is partially coated on the inner side of the heat preservation cavity, so that the industrial microwave oven can have a microwave heat effect and a microwave non-heat effect at the same time.
Drawings
FIG. 1 is a schematic longitudinal sectional view of an industrial microwave oven according to the present invention;
FIG. 2 is a schematic cross-sectional view of an industrial microwave oven provided in accordance with the present invention;
FIG. 3 is a differential thermal analysis curve of the base glass material in example 1;
FIG. 4 is a temperature-raising program of the glass raw material in example 1;
FIG. 5 is a high power microscopic morphology and energy spectrum of the glass ceramic obtained in example 1;
FIG. 6 is a micrograph of a glass-ceramic obtained in comparative example 1;
FIG. 7 is a high power microscopic morphology and energy spectrum of the glass-ceramic obtained in comparative example 1;
FIG. 8 shows the three-dimensional surface topography (measured by confocal laser microscopy) of the bend port of the glass-ceramic sample obtained in example 1;
FIG. 9 shows the three-dimensional surface topography (measured by confocal laser microscopy) of the bend port of the glass-ceramic sample obtained in comparative example 1;
FIG. 10 is a graph showing the relationship between the surface roughness and the crystal grain size of the glass ceramic obtained in example 1, as observed by a confocal laser microscope;
in fig. 1 and 2, 1 is a heat preservation chamber, 2 is a thermocouple, 3 is a silicon carbide coating, 4 is a glass raw material, 5 is a crucible, and 6 is a base.
Detailed Description
The invention provides a preparation method of glass ceramic, which comprises the following steps:
melting and casting the glass raw material under the microwave thermal effect and the microwave non-thermal effect to obtain a base glass material;
and under the microwave thermal effect and the microwave non-thermal effect, sequentially carrying out stress annealing, nucleation and growth on the base glass material to obtain the glass ceramic.
The invention carries out melting and casting on the glass raw material under the microwave thermal effect and the microwave non-thermal effect to obtain the basic glass material.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
In the invention, the glass raw material comprises the following main components in percentage by mass:
SiO235～45％，CaO 25～30％，MgO 3～5％，Al2O35～10％，Fe2O34～11％，Na20.3-1.5% of O and 1-2% of rare earth oxide.
In the invention, the glass raw material comprises 35-45% of SiO in percentage by mass2Preferably 39 to 44%, and more preferably 40 to 43%.
In the invention, the glass raw material comprises 25-30% by mass of CaO, preferably 26-29%, more preferably 27-28%, and even more preferably 27%.
In the invention, the glass raw material comprises 2-5% by mass of MgO, preferably 3-4% by mass of MgO, and more preferably 3% by mass of MgO.
In the invention, the glass raw material comprises 4-10% of Al by mass2O3Preferably 5 to 8%.
In the invention, the glass raw material comprises 4-13% by mass of Fe2O3。
In the invention, the glass raw material comprises 0.3-1.5% of Na by mass2O。
In the invention, the glass raw material comprises 1-2% by mass of rare earth oxide, preferably 1.2-1.8%, more preferably 1.4-1.6%, and even more preferably 1.5%. In the present invention, the rare earth oxide is preferably one or more of cerium oxide and lanthanum oxide, and more preferably cerium oxide.
In the present invention, the glass raw material preferably comprises iron tailings; after measuring the mass percentage of the components in the iron tailings, when the components in the iron tailings do not meet the component composition of the glass raw material, additionally adding the deficient components.
In the invention, the microwave heating effect and the microwave non-heating effect are preferably provided by an industrial microwave oven, and the inner side of a heat preservation cavity of the industrial microwave oven is preferably partially coated with a silicon carbide coating; the local application of the silicon carbide coating is further preferably carried out in the following manner: the heat preservation cavity of the industrial microwave oven is preferably a hollow cylinder; the inner side of the heat preservation cavity is divided into 12 parts on average along the axial direction of the hollow cylinder, wherein 6 parts are coated with the silicon carbide coating, and the 6 parts coated with the silicon carbide coating are not adjacent to each other. In the present invention, fig. 1 is a longitudinal sectional view of an industrial microwave oven according to the present invention, fig. 2 is a cross-sectional view of the industrial microwave oven according to the present invention, and in fig. 1 and 2, 1 is a heat retaining chamber, 2 is a thermocouple, 3 is a silicon carbide coating, 4 is a glass raw material, 5 is a crucible, and 6 is a base. In the invention, the thickness of the silicon carbide coating is preferably 1-4 mm, and more preferably 3 mm. In the invention, when the industrial microwave oven heat preservation cavity partially coated with the silicon carbide coating is heated, the part coated with the silicon carbide coating provides microwave heat effect, and the part not coated with the silicon carbide coating provides microwave non-heat effect.
In the invention, the melting temperature is preferably 1300-1340 ℃, and the heat preservation time is preferably 0.5-2 h, and more preferably 1 h; the rate of raising the temperature from room temperature to the melting temperature is preferably 30 to 60 ℃/min, and more preferably 50 ℃/min.
In the invention, the casting temperature is preferably more than or equal to 1200 ℃; the casting is preferably performed in a metal mold, and the shape of the metal mold is not particularly limited in the present invention, and may be selected by those skilled in the art according to actual conditions.
After the base glass material is obtained, the invention sequentially carries out stress annealing, nucleation and growth on the base glass material under the microwave thermal effect and the microwave non-thermal effect to obtain the glass ceramic.
In the present invention, the microwave thermal effect and the microwave non-thermal effect are preferably provided by an industrial microwave oven, and the structure of the industrial microwave oven is consistent with the technical scheme, which is not described herein again.
In the invention, when the base glass material is placed in an industrial microwave oven, the temperature of the industrial microwave oven is preferably 350-450 ℃, and more preferably 400 ℃.
In the invention, the temperature of the stress annealing is preferably 400-550 ℃, and more preferably 550 ℃; the heat preservation time is preferably 10-30 min, and more preferably 20 min. In the present invention, the rate of raising the temperature from the temperature of the industrial microwave oven to the temperature of the stress annealing is preferably 1 to 5 ℃/min, and more preferably 3 ℃/min.
In the invention, the nucleation temperature is preferably 40-60 ℃ higher than the nucleation temperature obtained by DSC differential thermal analysis, more preferably 50 ℃, and the temperature rise rate of the DSC differential thermal analysis is preferably 5 ℃/min; the heat preservation time for nucleation is preferably 10-30 min, and more preferably 20 min. In the present invention, the rate of raising the temperature from the temperature of stress annealing to the temperature of nucleation is preferably 1 to 5 ℃/min, and more preferably 3 ℃/min.
In the present invention, the growth temperature is preferably a growth temperature obtained by DSC differential thermal analysis; the heat preservation time is preferably 10-30 min, and more preferably 20 min. In the present invention, the rate of raising the temperature from the nucleation temperature to the growth temperature is preferably 1 to 5 ℃/min, and more preferably 3 ℃/min.
The invention also provides an industrial microwave oven, which comprises a heat preservation cavity 1, a thermocouple 2, a crucible 5 and a base 6, wherein the inner side of the heat preservation cavity 1 is partially coated with a silicon carbide coating 3.
The industrial microwave oven provided by the invention comprises a heat preservation cavity 1, wherein the heat preservation cavity 1 is preferably a hollow cylinder; the inner side of the heat preservation cavity 1 is partially coated with the silicon carbide coating 3, and more preferably, the inner side of the heat preservation cavity 1 is divided into 12 parts along the axial direction of the hollow cylinder on average, wherein 6 parts are coated with the silicon carbide coating, and the 6 parts coated with the silicon carbide coating are not adjacent to each other. In the present invention, the thickness of the silicon carbide coating is preferably the same as that of the above technical solution, and is not described herein again.
The industrial microwave oven provided by the invention comprises a thermocouple 2, and the thermocouple 2 is preferably positioned at the top of the heat preservation cavity 1. The specific position of the thermocouple 2 on the top of the heat preservation cavity 1 is not particularly limited, as long as the temperature of the heat preservation cavity can be monitored.
The industrial microwave oven provided by the invention comprises a base 6. The base material of the present invention is not particularly limited, and the base material known to those skilled in the art may be used.
The industrial microwave oven provided by the invention comprises a crucible 5, wherein the crucible 5 is preferably arranged at the upper part of a base 6. The material of the crucible 5 is not particularly limited in the present invention, and the crucible material known to those skilled in the art may be used.
The industrial microwave oven provided by the invention has the advantages that the silicon carbide coating is partially coated on the inner side of the heat preservation cavity, so that the industrial microwave oven can have a microwave heat effect and a microwave non-heat effect at the same time.
The following will explain the method for producing a glass ceramic and an industrial microwave oven according to the present invention in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
This example was carried out in an industrial microwave oven having the silicon carbide coating shown in fig. 1 and 2, the thickness of which was 3 mm.
1. The glass raw material mainly adopts the bayunebo iron tailings, and the short components are matched according to the glass raw material composition shown in the table 1.
TABLE 1 glass raw material composition (wt%)
2. Placing the glass raw material in a heat preservation cavity of an industrial microwave oven, heating to 1340 ℃ at a speed of 50 ℃/min, preserving heat for 1h, and then casting into a metal mold for molding to obtain the basic glass material.
3. The base glass material was subjected to DSC differential thermal analysis (temperature rise rate of 5 ℃/min), and the differential thermal analysis curve of the obtained base glass material is shown in FIG. 3, and it can be seen from FIG. 3 that: the nucleation temperature of the base glass material is 640 ℃, and the growth temperature is 750 ℃; based on this, the microwave nucleation temperature is set to 690 ℃ and the growth temperature is set to 750 ℃.
4. Placing the basic glass material in a heat preservation cavity of an industrial microwave oven at 400 ℃, heating to 550 ℃ at a speed of 3 ℃/min for stress annealing, and preserving heat for 20 min; heating at 10 deg.C/min to microwave nucleation 690 deg.C, and maintaining for 20 min; heating to a growth temperature of 750 ℃ at a speed of 10 ℃/min, preserving the heat for 20min, and cooling along with the furnace to obtain the glass ceramic.
FIG. 4 is a temperature-raising program of the glass raw material in example 1.
Comparative example 1
The glass raw material in the embodiment 1 is placed in a common smelting furnace, heated to 1340 ℃, kept warm for 1h, and cast into a metal mold for molding to obtain the basic glass material.
Putting the base glass material into a muffle furnace at 550 ℃ for annealing for 2 h; then heating to form nuclei at a temperature of 3 ℃/min, and keeping the temperature for 20min at 690 ℃; then heating to the growth temperature of 800 ℃ at the speed of 3 ℃/min, and preserving the heat for 2h to obtain the glass ceramic.
The glass ceramics obtained in example 1 and comparative example 1 were tested for flexural strength by GB/T37781-; GB/T37781-; the high-temperature softening temperature of the glass ceramics obtained in example 1 and comparative example 1 was measured by SEM texture observation, and the results are shown in Table 2.
TABLE 2 results of property test of glass-ceramics obtained in example 1 and comparative example 1
As can be seen from table 2: the glass ceramic prepared by the preparation method provided by the invention has a fine structure, has high-temperature resistance, and has remarkably improved bending strength; the combined action of microwave non-thermal effect, rare earth strengthening elements and tissue refinement can not be separated.
And (3) comparing the efficacies: in comparative example 1, 5.3 hours were required from melting to the final glass ceramic product, whereas example 1 required only 2 hours.
FIG. 5 is a high power microscopic morphology map and an energy spectrum of the glass ceramic obtained in example 1, wherein the bar chart at the lower left corner is the energy spectrum data at the position of red dot in the map; as can be seen from the high power microtopography of fig. 5: the glass ceramic obtained in the example 1 has fine and more nanocrystals, which shows that the glass ceramic obtained in the example 1 has good grain refinement effect and high mechanical property; as can be seen from the energy spectrum in fig. 5: a small amount of rare earth Ce is detected at the position of the red spot, namely the rare earth element is detected in the crystal, which shows that the preparation method provided by the invention is beneficial to the rare earth element entering the crystal.
FIG. 6 is a micrograph of a glass-ceramic obtained in comparative example 1; as can be seen from fig. 6: the conventional heat treatment mode has the defects of connected crystal grains and large crystal grain size, so that the fracture resistance is poor.
FIG. 7 is a high power microscopic morphology map and an energy spectrum of the glass ceramic obtained in comparative example 1, wherein the bar chart in the lower left corner is the energy spectrum data at the position of red dot in the map; from the high power microtopography of FIG. 7, it can be seen that: the glass-ceramic obtained in comparative example 1 formed locally coarse crystals; as can be seen from the energy spectrum of fig. 7: the rare earth element can not be detected at the position of the red point, namely the rare earth element is not detected in the crystal, which indicates that the rare earth element still exists in the glass phase.
FIG. 8 shows the three-dimensional surface topography (measured by confocal laser microscopy) of the bend port of the glass-ceramic sample obtained in example 1; as can be seen from fig. 8: the glass ceramic obtained in the embodiment forms high-density and uniform bulges in a fracture matrix; the relatively fine and dispersed nanoparticles can uniformly resist shear forces in the amorphous matrix. The preparation method provided by the invention can promote the uniform growth of crystals.
FIG. 9 shows the three-dimensional surface topography (measured by confocal laser microscopy) of the bend port of the glass-ceramic sample obtained in comparative example 1; as can be seen from fig. 9: the fracture of the glass ceramic obtained in comparative example 1 was composed of low-density pits and singular bumps, and a stress concentration point was generated, which was not favorable for increasing the strength.
FIG. 10 is a graph showing the relationship between the surface roughness and the crystal grain size of the glass ceramic obtained in example 1, as observed by a confocal laser microscope; as can be seen from fig. 10: the surface roughness can effectively measure the grain size and the grain number density, thereby firming the texture structure of the material. The larger the roughness, the smaller the grain size, and the larger the grain density.
Comparative example 2
Industrial microwave oven similar to example 1, using SiO as the substrate2-CaO-MgO-Al2O3Glass material prepared by regulating rare earth oxide CeO2The performance test is carried out, the content of the rare earth oxide is increased by 5.35 percent in the test, and the specific components are shown in Table 3.
TABLE 3 glass raw material composition (wt%)
Placing the glass raw material in a heat preservation cavity of an industrial microwave oven, heating to 1340 ℃ at a speed of 50 ℃/min, preserving heat for 1h, and then casting into a metal mold for molding to obtain the basic glass material.
Placing the basic glass material in a heat preservation cavity of an industrial microwave oven at 400 ℃, heating to 550 ℃ at a speed of 3 ℃/min for stress annealing, and preserving heat for 20 min; heating at 10 deg.C/min to microwave nucleation 690 deg.C, and maintaining for 20 min; heating to a growth temperature of 750 ℃ at a speed of 10 ℃/min, preserving the heat for 20min, and cooling along with the furnace to obtain the glass ceramic.
Comparative example 3
This comparative example used a chamber that was entirely coated with a silicon carbide coating and the glass raw materials are shown in table 3.
Placing the glass raw material in a heat preservation cavity of an industrial microwave oven, heating to 1340 ℃ at a speed of 50 ℃/min, preserving heat for 1h, and then casting into a metal mold for molding to obtain the basic glass material.
Placing the basic glass material in a heat preservation cavity of an industrial microwave oven at 400 ℃, heating to 550 ℃ at a speed of 3 ℃/min for stress annealing, and preserving heat for 20 min; heating at 10 deg.C/min to microwave nucleation 690 deg.C, and maintaining for 20 min; heating to a growth temperature of 750 ℃ at a speed of 10 ℃/min, preserving the heat for 20min, and cooling along with the furnace to obtain the glass ceramic.
Comparative example 4
Using the same industrial microwave oven as in example 1, glass raw materials are shown in Table 3.
Placing the glass raw material in a heat preservation cavity of an industrial microwave oven, heating to 1340 ℃ at a speed of 50 ℃/min, preserving heat for 1h, and then casting into a metal mold for molding to obtain the basic glass material.
Placing the basic glass material in a heat preservation cavity of an industrial microwave oven at 400 ℃, heating to 550 ℃ at a speed of 3 ℃/min for stress annealing, and preserving heat for 20 min; heating at 10 deg.C/min to microwave nucleation 690 deg.C, and respectively maintaining the temperature for 10min and 30 min; heating to a growth temperature of 750 ℃ at a speed of 10 ℃/min, preserving the heat for 20min, and cooling along with the furnace to obtain the glass ceramic.
The fracture resistance of the glass ceramics obtained in the comparative examples 2-4 was tested by GB/T37781-2019, and the results are shown in Table 4.
Table 4 results of performance testing
As can be seen from table 4: comparing example 1 and comparative example 2, under the same microwave treatment process, the influence of the addition amount of rare earth on the performance is large, and the bending resistance is reduced from 219MPa to 148MPa due to excessive addition of rare earth (the content of rare earth oxide is 5.35%). Comparing with comparative example 2 and comparative example 3, the heat preservation cavities of different silicon carbide coating modes are adopted for carrying out microwave nucleation crystallization treatment on the base glass material with the same components, and after the treatment of partially coating the silicon carbide coating, good flexural strength is obtained under the action of microwave non-thermal effect. Comparing comparative examples 2 and 4, the performance is best after 20min of nucleation by respectively carrying out treatment for 10min, 20min and 30min according to the microwave nucleation time, the crystallization quantity is less due to the over-period nucleation time, and the crystal starts to swallow and grow up in the longer nucleation time.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the glass ceramic is characterized by comprising the following steps:
melting and casting the glass raw material under the microwave thermal effect and the microwave non-thermal effect to obtain a base glass material;
under the microwave thermal effect and the microwave non-thermal effect, sequentially carrying out stress annealing, nucleation and growth on the base glass material to obtain glass ceramic;
the glass raw materials comprise the following main components in percentage by mass:
SiO235～45％，CaO 25～30％，MgO 2～5％，Al2O34～10％，Fe2O34～13％，Na20.3-1.5% of O and 1-2% of rare earth oxide.
2. The method for preparing the microwave oven as claimed in claim 1, wherein the microwave heating effect and the microwave non-heating effect are provided by an industrial microwave oven, and the inner side of a heat preservation cavity of the industrial microwave oven is partially coated with a silicon carbide coating; the thickness of the silicon carbide coating is 1-4 mm.
3. The method according to claim 2, wherein the insulating cavity of the industrial microwave oven is a hollow cylinder; the inner side of the heat preservation cavity is divided into 12 parts on average along the axial direction of the hollow cylinder, wherein 6 parts are coated with the silicon carbide coating, and the 6 parts coated with the silicon carbide coating are not adjacent to each other.
4. The preparation method according to claim 1, wherein the temperature of the stress annealing is 400-550 ℃, and the holding time is 10-30 min.
5. The preparation method according to claim 1, wherein the nucleation temperature is 40-50 ℃ higher than that obtained by DSC differential thermal analysis, and the temperature rise rate of DSC differential thermal analysis is 5 ℃/min; the heat preservation time of the nucleation is 10-30 min.
6. The method according to claim 1, wherein the growth temperature is a growth temperature obtained by DSC differential thermal analysis; the heat preservation time for growth is 10-30 min.
7. The manufacturing method according to claim 2, wherein the temperature of the industrial microwave oven is 350 to 450 ℃ when the base glass material is placed in the industrial microwave oven.
8. The method according to claim 7, wherein the rate of raising the temperature from the temperature of the industrial microwave oven to the temperature of the stress annealing is 1 to 5 ℃/min; the speed of raising the temperature from the stress annealing temperature to the nucleation temperature is 1-5 ℃/min; the rate of increasing from the nucleation temperature to the growth temperature is 1-5 ℃/min.
9. An industrial microwave oven comprises a heat preservation cavity (1), a thermocouple (2), a crucible (5) and a base (6), and is characterized in that the inner side of the heat preservation cavity (1) is partially coated with a silicon carbide coating (3).
10. Industrial microwave oven according to claim 9, characterized in that the insulating cavity (1) is a hollow cylinder; the inner side of the heat preservation cavity (1) is divided into 12 parts on average along the axial direction of the hollow cylinder, wherein 6 parts are coated with silicon carbide coatings, and the 6 parts coated with the silicon carbide coatings are not adjacent to each other.
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| CN114262238A (en) * | 2021-12-27 | 2022-04-01 | 万卓（江苏）新材料有限公司 | Preparation method of efficient soft porcelain flexible facing brick |
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