CN110117815B - Method and device for artificially synthesizing large-size fluorophlogopite - Google Patents
Method and device for artificially synthesizing large-size fluorophlogopite Download PDFInfo
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- CN110117815B CN110117815B CN201910542031.2A CN201910542031A CN110117815B CN 110117815 B CN110117815 B CN 110117815B CN 201910542031 A CN201910542031 A CN 201910542031A CN 110117815 B CN110117815 B CN 110117815B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/34—Silicates
Abstract
The invention discloses a method and a device for artificially synthesizing large-size fluorophlogopite, which comprises the following components in percentage by weightThe component composition of the amount is quartz Sand (SiO)2)100 parts of alumina powder (Al)2O3)29.1 parts of potassium carbonate (K)2CO3)28.3 parts of potassium nitrate (KNO)3)5.3 parts of fused magnesia (MgO) and 68.3 parts of potassium fluosilicate (K)2SiF6)37.9 parts, the temperature fields of the high-temperature area and the low-temperature area of the growth device are changed through the temperature equalizing body, so that the temperature in the furnace is more uniform, a large-size platinum crucible and a corundum crucible are designed, the long crystal is used as a seed crystal for transverse inoculation, the uniform transverse temperature field and the proper longitudinal temperature gradient are adjusted, the large-size and high-quality fluorophlogopite crystal is prepared, the large-size quality qualification rate of the synthetic mica can be greatly improved, the problem that materials are urgently needed in the fields of high-temperature insulation, high-frequency media, high-pressure corrosion resistance, biological research, high-energy physics and the like is solved, and the growth device has obvious economic benefits and social benefits and wide market application prospects.
Description
Technical Field
The invention relates to the technical field of crystal material growth or preparation, in particular to a method and a device for artificially synthesizing large-size fluorophlogopite.
Background
The artificially synthesized fluorophlogopite is artificial mica, and the molecular formula of its single crystal plate is KMg3(AlSi3O10)F2Belongs to monoclinic system, is a typical layered silicate material, and can resist the temperature of over 1200 ℃. It is a layered silicate crystal which is grown by chemical raw materials or mineral raw materials through strict process conditions and material proportion under a high temperature state, high temperature reaction, melting, cooling and forced crystallization. The artificially synthesized fluorophlogopite is of a book-shaped structure, has the advantages of high tensile strength and compression strength, capability of bearing high pressure, capability of being reasonably stripped, good flatness, difficult deformation and aging, strong acid and alkali corrosion resistance, no gas release in vacuum and the like, and has low high-frequency dielectric loss, good high-temperature insulation property and good light transmission from ultraviolet (0.2 mu m) to infrared (5 mu m) because the fluorophlogopite does not contain hydroxyl.
The fluorophlogopite is a high-temperature-resistant non-metallic insulating material with excellent performance due to high purity and stable performance, can be used in working environments such as electric insulation, high-frequency media, high-temperature vacuum, high-temperature high-pressure, strong acid and strong alkali and the like, is a core material in the application fields such as national defense science and technology, electronic communication, high-energy physics, aerospace, optical imaging, industrial detection, vacuum devices, biomedical research, electrical instruments and the like, and belongs to a high-technology material.
The artificially synthesized large-size fluorophlogopite solves the problem that materials are urgently needed in the fields of high-temperature insulation, high-frequency media, high-pressure corrosion resistance, biological research, high-energy physics and the like, and has obvious economic benefit and social benefit. Although many years of research is carried out, the preparation of large-size fluorophlogopite still faces huge challenges, the long-term industrial preparation of fluorophlogopite adopts an internal heating method for preparation, but due to the limitation of the process, the preparation of large-size fluorophlogopite has extremely low qualification rate and great difficulty, and the preparation of artificially synthesized fluorophlogopite by the internal heating method needs to carry out operations such as furnace body building, electrode mounting, crystallization, furnace dismantling, punching, blasting and the like, the process flow is long, the operation is complex, the quality and the finished product qualification rate are low, the operation conditions and the production process which need to be controlled in the production preparation process are complex, so that the synthesized mica has low purity, more impurities and small crystallization, and because the mica crystal belongs to a two-dimensional crystal, the directional growth of the mica needs to be controlled in a high-temperature melting state, the influence factors are too many, and the growth of the crystal is influenced by a little impurity, so that the effective control difficulty of the internal heating method is great, the large-size fluorophlogopite sheet is not easy to prepare, and the utilization value of the synthetic mica is reduced, so that the synthesis of the large-size fluorophlogopite is still a difficult problem in industrial production.
Disclosure of Invention
The invention provides a method and a device for preparing large-size fluorophlogopite with excellent purity, less impurities, corrosion resistance and high temperature resistance after artificial synthesis by improving the process, optimizing the production conditions, innovating and improving the production technology and equipment, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for artificially synthesizing large-size fluorophlogopite comprises the following components in percentage by weight:
furthermore, the purity of the quartz sand is more than or equal to 99.9 percent, the oversize product with the particle size of 150 mu m is less than 1 percent, the undersize product with the particle size of 45 mu m is less than 30 percent, and the Fe content is higher than that of the quartz sand2O3The content is less than 0.01 wt%, the purity of alumina powder is more than or equal to 99.0%, and the average particle size is 50 μm), the purity of potassium carbonate is more than or equal to 99.0%, the average particle size is 50 μm, the purity of potassium nitrate is more than or equal to 99.0%, the average particle size is 50 μm, the purity of fused magnesite is more than or equal to 99.0%, the average particle size is 50 μm, the purity of potassium fluosilicate is more than or equal to 99.0%, and the average particle size is 50 μm.
Further, the method comprises the steps of:
s1: raw material treatment: burning and selecting raw materials for synthesizing fluorophlogopite and carrying out necessary iron removal treatment to remove redundant impurities, weighing and mixing the raw materials according to the specific weight percentage to obtain a batch mixture, uniformly mixing the batch mixture, and putting the batch mixture into a corundum crucible to be melted in a high-temperature furnace;
s2: raw material pressing: after the glass melt is melted, water quenching is carried out, ball milling treatment is carried out on the water quenched glass raw material, the ball milled glass powder is centrifuged, dehydrated and dried, and then the dried glass powder is pressed into a material ingot;
s3: primary crystallization: loading the pressed raw materials into a large-capacity quartz crucible, and then moving the quartz crucible into a high-temperature furnace at 1500 ℃ to heat for 3-5 hours; after the heating is finished, adding the ingot into the quartz crucible again and ensuring that the fused material in the quartz crucible does not overflow, and then placing the quartz crucible into a high-temperature furnace to continue heating for 2-4 hours; after heating is finished, taking out the quartz crucible in the high-temperature furnace, inverting the molten material in a high-density refractory brick mold for molding, and placing the molded molten material in a precise annealing furnace for cooling annealing cooling crystallization treatment according to a set program;
s4: crystal growth: taking out crystallized melt after the annealing furnace is cooled to room temperature, then crushing, grinding and screening to prepare small flakes, and purifying and cleaning the scaly fragments of the fluorophlogopite to obtain the synthetic crushed small crystal raw material of the fluorophlogopite; selecting a large-size fluorophlogopite sheet as a seed crystal, putting the seed crystal and prepared fluorophlogopite flake raw materials into a large-size cuboid platinum crucible, covering the platinum crucible with a platinum concave edge after the platinum crucible is filled with the materials, sealing the platinum crucible with a high-temperature adhesive, putting the platinum crucible into a large-size corundum pipe sleeve, filling alumina powder serving as a heat insulation material between the periphery of the platinum crucible and the corundum pipe sleeve, compacting the alumina powder by vibration filling, then moving the corundum crucible into a crystal growth device, raising the temperature of the corundum crucible to a high-temperature area in a furnace, raising the temperature of the corundum crucible, keeping the temperature of the corundum crucible, melting the crystal back, inoculating the seed crystal, controlling the vertical falling speed of the corundum pipe sleeve and the temperature gradient of a crystal growth interface to slowly fall to a low-temperature area so as to ensure the directional growth of; and after the crystal growth is finished, stopping descending, slowly cooling to room temperature according to a design program, cooling, and taking out the platinum crucible in the cooled corundum sleeve to obtain the large-size fluorophlogopite crystal.
Furthermore, the seed crystal is inoculated after being transversely placed by adopting large-size fluorophlogopite, the section where the longest side of the seed crystal is positioned is taken as an inoculation surface, and the interface form is stable.
Furthermore, the high-temperature area and the low-temperature area adopt temperature equalizing bodies to ensure that the high-temperature area and the low-temperature area have obvious temperature gradients and uniform and transverse temperature fields.
Further, the furnace temperature of the high temperature zone is controlled at 1450-1470 ℃, and the longitudinal temperature gradient of the low temperature zone is 50-100 ℃/cm.
Further, the lowering speed of the corundum crucible in the Bridgman-Stockbarge method was 0.3 mm/hr.
The invention provides another technical scheme: a device for artificially synthesizing large-size fluorophlogopite comprises a platinum crucible, a corundum pipe sleeve, a high-temperature-region temperature thermocouple, a silicon-molybdenum rod, a growth furnace heat-insulating layer A, a furnace body, a high-low-temperature-region temperature-blocking brick, a low-temperature-region thermocouple, a growth furnace heat-insulating layer B, a growth furnace heat-insulating layer C and a high-low-temperature-region temperature-equalizing body, a platinum crucible is arranged in the center of the furnace body, synthetic mica is filled in the platinum crucible, the platinum crucible is placed in the corundum pipe sleeve, both sides of the corundum pipe sleeve are provided with temperature equalizing bodies in high and low temperature regions, the side surfaces of the temperature equalizing bodies in the high and low temperature regions are provided with silicon-molybdenum rods which are arranged from top to bottom, the top end of the furnace body is inserted with a high-temperature-region temperature thermocouple, the interior of the furnace body is divided into a growth furnace heat-insulating layer A, a growth furnace heat-insulating layer B and a growth furnace heat-insulating layer C through a transversely-arranged high-temperature-region temperature-blocking brick, and the growth furnace heat-insulating layer C is internally provided with a low-temperature-region thermocouple.
Further, the wall thickness of the corundum pipe sleeve is 8-10mm, and the length of the corundum pipe sleeve is larger than the growth length of the fluorophlogopite.
Furthermore, the platinum crucible is a thin-wall platinum crucible, and the wall thickness of the platinum crucible is 0.1-0.2 mm.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a method and a device for artificially synthesizing large-size fluorophlogopite, which improves the purity of a synthetic mica raw material and the components of mica flexibility and stripping property by adding potassium nitrate, the temperature fields of the high temperature area and the low temperature area of the growth device are changed through the temperature equalizing body, so that the temperature in the growth device is more uniform, and a large-size platinum crucible and a large-size corundum crucible are designed, long crystals are used as seed crystals for transverse inoculation, a uniform transverse temperature field and a proper longitudinal temperature gradient are adjusted, a large-size and high-quality fluorophlogopite crystal is prepared, the large-size quality qualification rate of synthetic mica can be greatly improved, the problem that materials are urgently needed in the fields of high-temperature insulation, high-frequency media, high-pressure corrosion resistance, biological research, high-energy physics and the like is solved, and the preparation method has obvious economic and social benefits and wide market application prospects.
Drawings
FIG. 1 is a front view of the apparatus for growing large-sized fluorophlogopite crystals according to the present invention.
In the figure: 1. synthesizing mica; 2. a platinum crucible; 3. a corundum pipe sleeve; 4. a temperature thermocouple in a high temperature region; 5. a silicon-molybdenum rod; 6. a growth furnace heat-insulating layer A; 7. a furnace body; 8. temperature blocking bricks in high and low temperature areas; 9. a low temperature zone thermocouple; 10. a growth furnace heat-insulating layer B; 11. a growth furnace heat-insulating layer C; 12. the high-low temperature region is a temperature equalizing body.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A method for artificially synthesizing large-size fluorophlogopite comprises the following components in percentage by weight:
the raw material requirements for synthesizing the large-size fluorophlogopite are as follows: the purity of the quartz sand is more than or equal to 99.9 percent, the oversize product with the particle size of 150 mu m is less than 1 percent, the undersize product with the particle size of 45 mu m is less than 30 percent, and the Fe content is2O3Less than 0.01 wt%, alumina powder purity not less than 99.0%, average grain size 50 μm), potassium carbonate purity not less than 99.0%, average grain size 50 μm, potassium nitrate purity not less than 99.0%, average grain size 50 μm, fused magnesia purity not less than 99.0%, average grain size 50 μm, potassium fluosilicate purity not less than 99.0%, average grain size 50 μm, and Fe content in raw material2O3And carrying out strict control.
A method for artificially synthesizing large-size fluorophlogopite comprises the following steps:
step 1: raw material treatment: burning and selecting raw materials for synthesizing fluorophlogopite and carrying out necessary iron removal treatment to remove redundant impurities, weighing and mixing the raw materials according to the specific weight percentage to obtain a batch mixture, uniformly mixing the batch mixture, and putting the batch mixture into a corundum crucible to be melted in a high-temperature furnace;
step 2: raw material pressing: after the glass melt is melted, water quenching is carried out, ball milling treatment is carried out on the water quenched glass raw material, the ball milled glass powder is centrifuged, dehydrated and dried, and then the dried glass powder is pressed into a material ingot;
and step 3: primary crystallization: loading the pressed raw materials into a large-capacity quartz crucible, and then moving the quartz crucible into a high-temperature furnace at 1500 ℃ to heat for 3-5 hours; after the heating is finished, adding the ingot into the quartz crucible again and ensuring that the fused material in the quartz crucible does not overflow, and then placing the quartz crucible into a high-temperature furnace to continue heating for 2-4 hours; after heating is finished, taking out the quartz crucible in the high-temperature furnace, inverting the molten material in a high-density refractory brick mold for molding, and placing the molded molten material in a precise annealing furnace for cooling annealing cooling crystallization treatment according to a set program;
and 4, step 4: crystal growth: taking out crystallized melt after the annealing furnace is cooled to room temperature, then crushing, grinding and screening to prepare small flakes, and purifying and cleaning the scaly fragments of the fluorophlogopite to obtain the synthetic crushed small crystal raw material of the fluorophlogopite; selecting a large-size fluorophlogopite sheet as a seed crystal, wherein the seed crystal is inoculated after the large-size fluorophlogopite sheet is transversely placed, the section where the longest side of the seed crystal is located is taken as an inoculation surface, and the interface form is stable; putting seed crystals and prepared fluorophlogopite flake raw materials into a large-size cuboid platinum crucible 2, wherein the platinum crucible 2 is a thin-wall platinum crucible, and the wall thickness of the thin-wall platinum crucible is 0.15 mm; after the platinum crucible 2 is filled with materials, the platinum concave edge is covered and sealed by a high-temperature adhesive, and the platinum concave edge is placed in a large-size corundum pipe sleeve 3, wherein the wall thickness of the corundum pipe sleeve 3 is 9mm, and the length of the corundum pipe sleeve 3 is greater than the growth length of fluorophlogopite; alumina powder is filled between the periphery of the platinum crucible 2 and the corundum sleeve to serve as a heat insulation material and is tightly filled and compacted through vibration, then the corundum sleeve is moved into a crystal growth device, the corundum sleeve is heated and insulated after being heated to a high-temperature area in a furnace, so that crystals are melted back and inoculated with seed crystals, then the vertical descending speed of the corundum sleeve 3 and the temperature gradient of a crystal growth interface are controlled to slowly descend to a low-temperature area to ensure the directional growth of the crystals, and the precise temperature control of different gradients is carried out for 20-30 days, wherein a temperature equalizing body is adopted in the high-temperature area and the low-temperature area to ensure that the high-temperature area and the low-temperature area have obvious temperature gradients, uniform and transverse temperature fields are provided, and the temperature difference at different positions at the same level is extremely small; the furnace temperature of the high temperature zone is controlled at 1450-1470 ℃, and the longitudinal temperature gradient of the low temperature zone is 70 ℃/cm; the descending speed of the corundum crucible in the descending of the platinum crucible 2 is 0.3 mm/h; and after the crystal growth is finished, stopping descending, slowly cooling to room temperature according to a design program, cooling, cutting off a power supply, taking out the platinum crucible 2 in the cooled pipe sleeve, and stripping to obtain the large-size fluorophlogopite crystal.
During the melting process of the uniformly mixed material, excessive or insufficient synthetic mica materials can be caused by decomposition of carbonate, generation and volatilization of fluoride, uneven density of the material and internal temperature during the melting process, uncertain factors such as mixed crystals and the like can appear in the synthetic fluorophlogopite process to influence the synthetic quality of large-size fluorophlogopite, and particularly, the volatilization of the fluoride in a high-temperature melting state can cause loss of useful components of the synthetic mica 1 and influence the proportion of the useful components in a melt. In order to reduce the volatilization of fluoride in the batch, a platinum concave edge cover is used for covering when the platinum crucible 2 is crystallized, and the platinum concave edge cover is sealed by a high-temperature adhesive. The raw materials for preparing the synthetic fluorophlogopite provided by the invention have other functions besides being used for synthesizing fluorophlogopite, and the addition of fluorine elements can enable impurities in the raw materials, such as calcium and the like, to form fluoride to be volatilized; if the amount of the potassium element is insufficient, some impurity crystals can be generated, potassium carbonate and potassium fluosilicate are adopted because the potassium carbonate and the potassium fluosilicate are active in chemical property and are easy to react with other chemical substances, a good foundation is laid for forming synthetic mica, and the prepared fluorophlogopite is transparent and free of impurities and large in crystal size.
The fluorophlogopite finished product KMg prepared by the method3(AlSi3O10)F2In, SiO2The content of (B) is 42.1-43%, Al2O3The content of (B) is 12.0-12.5%, K2The content of O is 11.0-11.5%, the content of MgO is 28.5-29.0%, the content of F is 8.8-9.2%, and the impurity Fe2O3The content is less than 150PPm, the content of impurity TiO2 is less than 0.5 percent, the content of impurity CaO is less than 0.5 percent, and the content of impurity Na2The content of O is less than 0.1 percent, and the content of impurity ZnO is less than 0.1 percent.
SiO2The method is mainly characterized in that high-purity quartz sand is introduced, when the content of silicon oxide is introduced too much, the obtained fluorophlogopite crystal contains a large amount of transparent glass bodies, and crystal blocks are brittle and hard and are difficult to strip; al (Al)2O3Mainly through oxidationIntroduction of aluminum powder does not exclude the introduction of a part of foreign alumina components by erosion of the corundum crucible, and if the content of alumina is introduced excessively, magnesium aluminate spinel (MgO. Al) is easily formed with magnesium oxide2O3) Or with silica to form mullite (SiO)2·Al2O3) Miscellaneous crystals, which have an influence on the purity and quality of mica crystals; f is mainly introduced by potassium fluosilicate, but when the fluorine content is too high, granular small crystals such as KF are easily generated.
A device for artificially synthesizing large-size fluorophlogopite is structurally shown in figure 1 and comprises a platinum crucible 2, a corundum pipe sleeve 3, a high-temperature-region temperature thermocouple 4, a silicon molybdenum rod 5, a growth furnace heat-insulating layer A6, a furnace body 7, a high-low-temperature-region temperature-blocking brick 8, a low-temperature-region thermocouple 9, a growth furnace heat-insulating layer B10, a growth furnace heat-insulating layer C11 and a high-low-temperature-region temperature-equalizing body 12, wherein the platinum crucible 2 is arranged in the center of the interior of the furnace body 7, the platinum crucible 2 is a thin-wall platinum crucible, and the wall thickness of the platinum crucible is 0.1-0.2 mm. Synthetic mica 1 is filled in a platinum crucible 2, the platinum crucible 2 is placed in a corundum pipe sleeve 3, the wall thickness of the corundum pipe sleeve 3 is 8-10mm, the length of the corundum pipe sleeve 3 is larger than the growth length of fluorophlogopite, the platinum crucible 2 can slide down together with the corundum pipe sleeve 3, both sides of the corundum pipe sleeve 3 are provided with temperature equalizing bodies 12 in high and low temperature areas, the temperature equalizing bodies are respectively arranged in the high and low temperature areas, the furnace temperature of the high and low temperature areas can be ensured to be uniform and unchanged, the temperature difference is controlled within 0.5 ℃, the temperature equalizing bodies are not in direct contact with heating furnace wires, the side surfaces of the temperature equalizing bodies 12 in the high and low temperature areas are provided with silicon-molybdenum rods 5 which are arranged from top to bottom, the top end of a furnace body 7 is inserted with a temperature measuring zone 4 for measuring the temperature of the high temperature area in the furnace body 7, the interior of the furnace body 7 is divided into a growth furnace heat-preserving layer A6, a growth furnace heat-preserving layer B10 and a growth furnace heat-preserving layer C11 by a high and low temperature area heat-preserving layer heat-insulating brick 8 which is transversely arranged, and a low-temperature thermocouple 9 is also arranged in the growth furnace heat-insulating layer C11 and is used for measuring the temperature in the growth furnace heat-insulating layer C11.
The artificially synthesized fluorophlogopite sheet has hard and crisp texture and poor peeling performance due to the inclusion of impurities, so that the quality and the forming qualification rate of large-size fluorophlogopite are low.
The above results show that the large-size fluorophlogopite sheet prepared by the invention has the following characteristics:
1. the mica plate has large size, high purity and low impurity content.
2. High mechanical strength and easy peeling.
3. Has good thermal stability.
4. Has good chemical corrosion resistance and does not generate hydration reaction.
5. Has the characteristic of low vacuum abandon rate.
6. Has the advantages of high transmittance and good transparency, and the mica surface is flat and smooth.
In conclusion, the method and the device for artificially synthesizing the large-size fluorophlogopite, which are provided by the invention, improve the purity of the raw material of the synthetic mica and improve the components of the flexibility and the stripping property of the mica by adding potassium nitrate, the temperature fields of the high temperature area and the low temperature area of the growth device are changed through the temperature equalizing body, so that the temperature in the growth device is more uniform, and a large-size platinum crucible 2 and a large-size corundum crucible are designed, long crystals are used as seed crystals for transverse inoculation, a uniform transverse temperature field and a proper longitudinal temperature gradient are adjusted, a large-size and high-quality fluorophlogopite crystal is prepared, the large-size quality qualification rate of synthetic mica can be greatly improved, the problem that materials are urgently needed in the fields of high-temperature insulation, high-frequency media, high-pressure corrosion resistance, biological research, high-energy physics and the like is solved, and the method has obvious economic and social benefits and wide market application prospects.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (1)
1. The method for artificially synthesizing the large-size fluorophlogopite is characterized by comprising the following components in percentage by weight:
the method for artificially synthesizing the large-size fluorophlogopite is characterized in that the raw material requirements for synthesizing the large-size fluorophlogopite are as follows: quartz sand: purity is more than or equal to 99.9%, oversize product of 150 μm is less than 1%, undersize product of 45 μm is less than 30%, Fe2O3The content is less than 0.01 wt%; alumina powder: the purity is more than or equal to 99.0 percent, and the average grain diameter is 50 mu m; potassium carbonate: the purity is more than or equal to 99.0 percent, and the average grain diameter is 50 mu m; potassium nitrate: the purity is more than or equal to 99.0 percent, and the average grain diameter is 50 mu m; electric smelting of magnesia: the purity is more than or equal to 99.0 percent, and the average grain diameter is 50 mu m; potassium fluosilicate: the purity is more than or equal to 99.0 percent, and the average grain diameter is 50 mu m;
the method for artificially synthesizing the large-size fluorophlogopite is characterized by comprising the following steps of:
s1: raw material treatment: burning and selecting raw materials for synthesizing fluorophlogopite and carrying out necessary iron removal treatment to remove redundant impurities, weighing and mixing the raw materials according to the specific weight percentage to obtain a batch mixture, uniformly mixing the batch mixture, and putting the batch mixture into a corundum crucible to be melted in a high-temperature furnace;
s2: raw material pressing: after the glass melt is melted, water quenching is carried out, ball milling treatment is carried out on the water quenched glass raw material, the ball milled glass powder is centrifuged, dehydrated and dried, and then the dried glass powder is pressed into a material ingot;
s3: primary crystallization: loading the pressed raw materials into a large-capacity quartz crucible, and then moving the quartz crucible into a high-temperature furnace at 1500 ℃ to heat for 3-5 hours; after the heating is finished, adding the ingot into the quartz crucible again and ensuring that the fused material in the quartz crucible does not overflow, and then placing the quartz crucible into a high-temperature furnace to continue heating for 2-4 hours; after heating is finished, taking out the quartz crucible in the high-temperature furnace, inverting the molten material in a high-density refractory brick mold for molding, and placing the molded molten material in a precise annealing furnace for cooling annealing cooling crystallization treatment according to a set program;
s4: crystal growth: taking out crystallized melt after the annealing furnace is cooled to room temperature, then crushing, grinding and screening to prepare small flakes, and purifying and cleaning the scaly fragments of the fluorophlogopite to obtain the synthetic crushed small crystal raw material of the fluorophlogopite; selecting a large-size fluorophlogopite sheet as a seed crystal, putting the seed crystal and prepared fluorophlogopite scale raw materials into a large-size cuboid platinum crucible (2), covering the platinum crucible (2) with a platinum concave edge after the materials are filled, sealing the platinum crucible with a high-temperature adhesive, putting the platinum crucible into a large-size corundum pipe sleeve (3), filling alumina powder serving as a heat insulation material between the periphery of the platinum crucible (2) and the corundum pipe sleeve (3), compacting the alumina powder by vibration filling, then moving the corundum crucible into a crystal growth device, raising the temperature to a high-temperature region in a furnace, raising the temperature, keeping the temperature, melting the crystal back, inoculating the seed crystal, controlling the vertical descending speed of the corundum pipe sleeve (3) and the temperature gradient of a crystal growth interface to slowly descend to a low-temperature region to ensure the directional growth of the crystal, and controlling the precise temperature with different gradients within 20-30 days; after the crystal growth is finished, stopping descending, slowly cooling to room temperature according to a design program, and cooling, and taking out the platinum crucible (2) in the cooled corundum pipe sleeve (3) to obtain the large-size fluorophlogopite crystal;
the seed crystal is inoculated after the large-size fluorophlogopite is transversely placed, the section where the longest side of the seed crystal is located is taken as an inoculation surface, and the interface form is stable;
the high-temperature area and the low-temperature area adopt temperature equalizing bodies to ensure that the high-temperature area and the low-temperature area have obvious temperature gradients and uniform and transverse temperature fields;
the furnace temperature of the high temperature zone is controlled at 1450-1470 ℃, and the longitudinal temperature gradient of the low temperature zone is 50-100 ℃/cm;
the lowering speed of the corundum crucible in the Bridgman-Stockbarge method was 0.3 mm/hr.
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Address after: 101, building 17, jinhufang, No. 288, Xiongzhou South Road, Liuhe District, Nanjing, Jiangsu Province, 210000 Applicant after: Lumixing Special Glass Technology Co.,Ltd. Address before: 101, building 17, jinhufang, 288 Xiongzhou South Road, Liuhe District, Wuxi City, Jiangsu Province 210000 Applicant before: Lumixing Special Glass Technology Co.,Ltd. |
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