CN115417679A - Silicified graphite ceramic crucible and preparation method thereof - Google Patents

Silicified graphite ceramic crucible and preparation method thereof Download PDF

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CN115417679A
CN115417679A CN202210952852.5A CN202210952852A CN115417679A CN 115417679 A CN115417679 A CN 115417679A CN 202210952852 A CN202210952852 A CN 202210952852A CN 115417679 A CN115417679 A CN 115417679A
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parts
temperature
ceramic crucible
graphite
powder
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CN115417679B (en
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薛喜利
薛明虎
张桥
薛明政
张锐琦
董浩宇
刘长青
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Jiangsu Jiaming Carbon New Material Co ltd
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Abstract

The invention discloses a silicified graphite ceramic crucible and a preparation method thereof, wherein the silicified graphite ceramic crucible comprises the following components in parts by weight: 80-95 parts of silicon carbide, 1.5-3 parts of graphite powder, 5-9 parts of vanadium molybdenum carbide powder, 0.5-2 parts of gypsum powder, 2-4 parts of white mud, 0.5-1.5 parts of hydroxypropyl methyl cellulose and 0.5-1.5 parts of modified starch. In the invention, the vanadium molybdenum carbide powder belongs to the unique formula of the invention, the addition of the vanadium molybdenum carbide powder improves the overall performance of the graphite silicide ceramic crucible, and mainly realizes that the crucible has certain toughness while having better hardness, thereby enhancing the durability of the crucible, greatly enhancing the corrosion resistance of the crucible and having great advantages compared with the ceramic crucible popular in the market.

Description

Silicified graphite ceramic crucible and preparation method thereof
Technical Field
The invention relates to the field of ceramic crucibles, in particular to a silicified graphite ceramic crucible and a preparation method thereof.
Background
The siliconized Graphite (SCGC for short) is also called Silicon Carbide coated Graphite or siliconized Graphite. The novel silicon carbide/graphite composite material is formed by deeply infiltrating silicon or silicon carbide into the surface or the surface of graphite serving as a matrix, wherein the silicon carbide/graphite composite material consists of silicon carbide, graphite and free silicon. The thickness of the silicon carbide layer is about 1-3mm, the silicon carbide layer is tightly combined with the carbon graphite matrix, and a certain amount of graphite is distributed in the silicon carbide layer. The silicified graphite integrates the characteristics of carbon and silicon carbide, not only has the self-lubricating property of the carbon graphite material, good electric and thermal conductivity and thermal shock resistance, but also has the advantages of high hardness, oxidation resistance, chemical corrosion resistance and the like of the silicon carbide, so that the silicified graphite material is more and more extensive, is particularly suitable for application in severe occasions such as heavy load, high temperature or large temperature impact and the like, and is widely applied to the fields of chemical industry, metallurgy, aerospace and nuclear industry.
The conventional method for manufacturing the siliconized graphite comprises a reaction sintering method, wherein the reaction sintering method is formed by mixing silicon carbide powder, carbon powder, a proper amount of binder and an activating agent according to a conventional powder metallurgy process, performing ball milling, pressing and performing high-temperature reaction sintering with silicon. Reactive sintering or reactive forming is a process in which a porous blank and a gas phase or a liquid phase undergo a chemical reaction to increase the mass of the blank and reduce pores, and the blank is sintered into a finished product with certain strength and dimensional accuracy. Compared with other sintering processes, the reaction sintering has the following characteristics: (1) the quality of the product is improved, and the sintered product is not shrunk and has unchanged size; (2) the reaction speed is high, and the mass transfer and heat transfer process runs through the whole sintering process. However, the graphite ceramic crucible prepared by the existing formula and the process method has insufficient high-temperature strength and is easy to corrode, so that the service life is short, and the crucible needs to be frequently replaced in the using process, so that the energy consumption, the cost and the labor intensity of workers are increased.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a siliconized graphite ceramic crucible and a preparation method thereof.
The purpose of the invention is realized by adopting the following technical scheme:
in a first aspect, the present invention provides a siliconized graphite ceramic crucible, comprising, in parts by weight:
80-95 parts of silicon carbide, 1.5-3 parts of graphite powder, 5-9 parts of vanadium molybdenum carbide powder, 0.5-2 parts of gypsum powder, 2-4 parts of white mud, 0.5-1.5 parts of hydroxypropyl methyl cellulose and 0.5-1.5 parts of modified starch.
Preferably, the purity of the silicon carbide is higher than 98%, and the particle size distribution is: 8.2% for 3-5mm, 30.6% for 1-3mm, 33.0% for 100 μm-1mm, and 28.2% for 50 μm-100 μm.
Preferably, the graphite powder has a purity higher than 99.9% and a particle size of 20-30 μm.
Preferably, the particle size of the vanadium molybdenum carbide powder is 100-150nm.
Preferably, the gypsum powder has a purity higher than 98% and a particle size of 50-100 μm.
Preferably, the white mud has a particle size of 50-100 μm and comprises, by mass: 54.85% SiO 2 43.54% of Al 2 O 3 And other impurities.
Preferably, the purity of the hydroxypropyl methylcellulose is greater than 99%.
Preferably, the modified starch is obtained by modifying starch with dodecyl dimethyl benzyl ammonium chloride, and the preparation process comprises the following steps:
mixing corn starch with a sodium hydroxide solution with the mass fraction of 20%, stirring for 1-2h, adding dodecyl dimethyl benzyl ammonium chloride, heating to 55-65 ℃, stirring for 3-5h, pouring into acetone for precipitation, collecting the precipitate, and drying to obtain modified starch; wherein, the mass ratio of the corn starch, the dodecyl dimethyl benzyl ammonium chloride and the sodium hydroxide solution is 0.3-0.6.
Preferably, the preparation method of the vanadium molybdenum carbide powder comprises the following steps:
s1, mixing vanadium pentoxide, molybdenum trioxide, nano activated carbon and absolute ethyl alcohol in a ball mill, adding a certain amount of polyvinyl alcohol, carrying out ball milling treatment by using a steel ball, and injecting into a mold for drying and molding after the ball milling is finished to obtain a first mixed material;
s2, placing the molded first mixed material in a high-temperature graphite furnace, vacuumizing, heating to 1500 ℃ in a staged manner, carrying out heat treatment for 3-6h, and cooling to normal temperature to obtain a second mixed material;
s3, mixing the second mixed material with bismuth oxide, heating to 850-900 ℃, carrying out heat preservation treatment for 3-5h, cooling to normal temperature, collecting the product, putting the product into HCl solution, carrying out ultrasonic treatment for 0.5-1h, drying, heating to 300 ℃, carrying out heat preservation for 1-2h, continuously putting the product into HCl solution, carrying out sealed standing for 8-12h, filtering out solid substances, washing with distilled water until washing liquid is neutral, and carrying out drying treatment to obtain vanadium molybdenum carbide powder.
Preferably, in the step S1, the ball-material ratio is 5-7, the ball milling speed is 150-250rpm, the ball milling temperature is 25 ℃ at normal temperature, and the ball milling time is 8-12h.
Preferably, in the step S1, the mass ratio of vanadium pentoxide to molybdenum trioxide to nano-activated carbon to absolute ethyl alcohol is 1.82-3.64; the addition amount of the polyvinyl alcohol is 10 to 20 percent of the mass of the absolute ethyl alcohol.
Preferably, in step S2, vacuum is applied to a pressure of 10-20Pa.
Preferably, in step S2, the stepwise warming to 1500 ℃ comprises: the first stage is to heat from room temperature to 550 ℃, keep the temperature for 1-2h, the second stage is to heat from 550 ℃ to 950 ℃, keep the temperature for 1-2h, and the third stage is to heat from 950 ℃ to 1500 ℃, keep the temperature for 1-2h; the temperature rising speed of the first stage is 180-300 ℃/h, the temperature rising speed of the second stage is 180-300 ℃/h, and the temperature rising speed of the third stage is 120-160 ℃/h.
Preferably, in step S3, the ratio of the added mass of bismuth oxide to the mass of the second mixed material is 1.1 to 1.5.
Preferably, in step S3, the concentration of the HCl solution is 0.1mol/L.
In a second aspect, the present invention provides a method for preparing a siliconized graphite ceramic crucible, comprising the steps of:
(1) The mixing process comprises the following steps: adding the raw materials into a stirring pot, stirring for 10-15min, and adding deionized water accounting for 5% -8% of the total weight of the raw materials into the stirring pot, and wet-stirring for 20-25min;
(2) The molding process comprises the following steps: after wet stirring is finished, sealing and standing the material for 60-90min, and then forming by a forming process;
(3) And (3) a drying process: drying the formed material for 20-30h to make the water content less than 1%;
(4) And (3) a sintering process: sintering at 1300-1500 deg.C for 16-20h.
Preferably, the molding process in step (2) includes any one of vibration molding, extrusion molding, isostatic pressing, and rotational molding.
The beneficial effects of the invention are as follows:
1. the invention prepares a graphite silicide ceramic crucible, and the used component raw materials comprise silicon carbide, graphite powder, vanadium molybdenum carbide powder, gypsum powder, white mud, hydroxypropyl methyl cellulose and modified starch; wherein, silicon carbide, graphite powder and vanadium molybdenum carbide powder are used as main raw materials, and gypsum powder, white mud, hydroxypropyl methyl cellulose and modified starch are used as auxiliary raw materials. The vanadium molybdenum carbide powder in the main raw material is prepared by the invention, the modified starch in the auxiliary raw material is also prepared by the invention, and the other materials can be purchased in the market. The silicified graphite ceramic crucible prepared by the invention has the advantages of uniform heat conduction, difficult corrosion and long service life.
2. In the invention, the modified starch is obtained by modifying and activating the starch by using the dodecyl dimethyl benzyl ammonium chloride with good slime stripping effect and certain dispersion and permeation effects, and the modified starch has better viscosity stability and thickening effect compared with the common starch.
3. In the invention, vanadium molybdenum carbide powder belongs to the unique formula of the invention, the addition of the vanadium molybdenum carbide powder improves the overall performance of the graphite silicide ceramic crucible, and the crucible has certain toughness while having better hardness, thereby enhancing the durability of the crucible, greatly enhancing the corrosion resistance of the crucible, and having great advantages compared with ceramic crucibles popular in the market.
4. The vanadium molybdenum carbide powder is prepared by a two-step method, wherein in the first step, vanadium and molybdenum oxides and nano activated carbon are mixed and subjected to wet ball milling, and then a ball-milled product is subjected to vacuum high-temperature treatment; and the second step is to remove redundant carbon elements in the system by high-temperature treatment of a bismuth oxide system of the product obtained by the first step, then remove bismuth compounds and simple substances by an acid liquor immersion mode, wherein the treatment at the temperature of 300 ℃ is to oxidize bismuth generated by carbon reduction into bismuth oxide, and finally obtain vanadium-molybdenum carbide powder meeting the requirements.
5. In the process of preparing the vanadium molybdenum carbide powder by the two-step method, a solid solution mode is used in the two steps, the first step is to utilize the solid solution effect of vanadium carbide and molybdenum carbide to ensure that the vanadium carbide can be partially solid-dissolved into the molybdenum carbide in the high-temperature synthesis process so as to form a isomorphous solid solution, the second step is to utilize a bismuth oxide system to be heated to a temperature higher than the melting point of the bismuth oxide system so as to be melted, so that the bismuth oxide system is used as a high-temperature solvent to be infiltrated into the isomorphous solid solution generated in the first step, the residual carbon element in the reaction process in the first step is removed, the formation speed of crystals is weakened, and the crystals are more uniformly grown.
6. Compared with the conventional method for directly melting the metal simple substance, the bismuth oxide system selected in the second step of the invention needs lower temperature (lower than 1000 ℃), can achieve better decarbonization effect and save more energy, and the grain size distribution of the vanadium molybdenum carbide powder obtained after decarbonization is more uniform, thus achieving the unexpected effect.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but the present invention should not be construed as being limited to the implementable scope of the present invention.
Vanadium carbide belongs to a sodium chloride type cubic crystal system structure, is high temperature resistant, acid and alkali resistant and high in hardness, and has the unique characteristic that the vanadium carbide can be partially solid-dissolved with other carbide metals with the same crystal form to obtain a solid solution, and the existence of the solid solution can change the property of a generated ceramic material, so that the property of the obtained product is different due to different solid solution contents and distribution.
The process of strengthening the crystal by means of solid solution: in a complete crystal, solute atoms are randomly distributed, and when a stress field is generated by defects (dislocations), strain energy generated by the solute atoms is changed, and the generated stress field can interact with the dislocations. Solute atoms are distributed around the dislocation, so that the strain energy of the dislocation is reduced, the stability of the dislocation is increased, the crystal strength is improved, and the performance of the crystal is improved.
The vanadium molybdenum carbide powder prepared and produced by the method has a uniform nano-scale structure, and the particle size is distributed between 100 nm and 150nm. The reason for this is firstly that a large amount of gas is generated during the carbon removal process, so that the contact between the generated crystal grains is weakened, a larger block structure is not formed, the morphological structure of the raw material is more maintained, secondly, the property of the bismuth oxide melt is more stable, the temperature distribution is more uniform, the dispersion of the generated crystals is promoted, and the crystal growth is further influenced.
Sufficient carbon black is added in the first step of vanadium and molybdenum carbide powder synthesis so as to ensure the synthesis and solid solution of vanadium carbide and molybdenum carbide, and carbon black which does not participate in the reaction needs to be removed in the second step. In a conventional mode, metal simple substances are directly used for melting and decarbonizing, the temperature needs to be raised to 1000 ℃ or higher to achieve a good decarbonizing effect, however, higher temperature needs to consume more energy, and the simple substance metal is gradually vaporized closer to a boiling point, so that raw materials are wasted and a heating furnace is polluted. In the traditional melting decarbonization metal simple substances, calcium, aluminum and other substances are most commonly used, and although the substances can achieve a good decarbonization effect, the required temperature is high, the difference between the formation and growth speeds of the obtained vanadium carbide and molybdenum carbide crystals is large, and the uniformity of the crystal particle size is poor.
The invention is further described below with reference to the following examples.
Example 1
A silicified graphite ceramic crucible comprises the following components in parts by weight:
87 parts of silicon carbide, 2.3 parts of graphite powder, 7 parts of vanadium molybdenum carbide powder, 1 part of gypsum powder, 3 parts of white mud, 1 part of hydroxypropyl methyl cellulose and 1 part of modified starch.
The purity of the silicon carbide is higher than 98%, and the particle size distribution is as follows: 8.2% of 3-5mm, 30.6% of 1-3mm, 33.0% of 100 μm-1mm and 28.2% of 50 μm-100 μm.
The purity of the graphite powder is higher than 99.9%, and the particle size is 20-30 μm; the particle size of the vanadium molybdenum carbide powder is 100-150nm; the purity of the gypsum powder is higher than 98 percent, and the particle size is 50-100 mu m; the white mud has the particle size of 50-100 μm and comprises the following components in percentage by mass: 54.85% SiO 2 43.54% of Al 2 O 3 And other impurities; the purity of the hydroxypropyl methyl cellulose is higher than 99%.
The modified starch is obtained by modifying starch with dodecyl dimethyl benzyl ammonium chloride, and the preparation process comprises the following steps:
firstly, mixing corn starch with a sodium hydroxide solution with the mass fraction of 20%, stirring for 1.5h, then adding dodecyl dimethyl benzyl ammonium chloride, heating to 60 ℃, stirring for 4h, pouring into acetone for precipitation, collecting the precipitate, and drying to obtain modified starch; wherein the mass ratio of the corn starch, the dodecyl dimethyl benzyl ammonium chloride and the sodium hydroxide solution is (0.5).
The preparation method of the vanadium molybdenum carbide powder comprises the following steps:
s1, mixing vanadium pentoxide, molybdenum trioxide, nano activated carbon and absolute ethyl alcohol in a ball mill, adding a certain amount of polyvinyl alcohol, carrying out ball milling treatment by using a steel ball, and injecting into a mold for drying and molding after the ball milling is finished to obtain a first mixed material; wherein, the ball-material ratio is 6, the ball milling speed is 200rpm, the ball milling temperature is 25 ℃ at normal temperature, and the ball milling time is 8-12h; the mass ratio of vanadium pentoxide to molybdenum trioxide to nano activated carbon to absolute ethyl alcohol is 2.73; the addition amount of the polyvinyl alcohol is 15 percent of the mass of the absolute ethyl alcohol.
S2, placing the molded first mixed material in a high-temperature graphite furnace, vacuumizing until the pressure is 10-20Pa, and then, heating to 1500 ℃ in a staged manner, wherein the method comprises the following steps: the temperature is raised from room temperature to 550 ℃ in the first stage, the temperature is kept for 1.5h, the temperature is raised from 550 ℃ to 950 ℃ in the second stage, the temperature is kept for 1.5h, and the temperature is raised from 950 ℃ to 1500 ℃ in the third stage, and the temperature is kept for 1.5h; the heating rate of the first stage is 220 ℃/h, the heating rate of the second stage is 220 ℃/h, the heating rate of the third stage is 140 ℃/h, and then the temperature is reduced to the normal temperature to obtain a second mixed material;
s3, mixing the second mixed material with bismuth oxide, heating to 850 ℃, carrying out heat preservation treatment for 4 hours, cooling to normal temperature, collecting the product, putting the product into an HCl solution with the concentration of 0.1mol/L, carrying out ultrasonic treatment for 0.5 hour, drying, heating to 300 ℃, carrying out heat preservation for 1.5 hours, continuously putting the product into the HCl solution with the concentration of 0.1mol/L, carrying out sealed standing for 10 hours, filtering out solid matters, washing with distilled water until the washing liquid is neutral, and carrying out drying treatment to obtain vanadium molybdenum carbide powder; wherein the ratio of the added mass of the bismuth oxide to the mass of the second mixed material is 1.3.
The preparation method of the siliconized graphite ceramic crucible comprises the following steps:
(1) The mixing process comprises the following steps: adding the raw materials into a stirring pot, stirring for 10min, adding deionized water accounting for 6% of the total weight of the raw materials into the stirring pot, and stirring for 20min;
(2) The molding process comprises the following steps: after the wet stirring is finished, sealing and standing the materials for 80min, and then forming by a forming process; including any one of vibration molding, extrusion molding, isostatic pressing molding and rotational molding;
(3) And (3) a drying process: drying the formed material for 25h to ensure that the moisture content is less than 1%;
(4) And (3) a sintering process: sintering at 1400 ℃ for 18h.
Example 2
A graphite silicide ceramic crucible, which is different from example 1 in the preparation method of vanadium molybdenum carbide powder.
The preparation method of the vanadium molybdenum carbide powder comprises the following steps:
s1, mixing vanadium pentoxide, molybdenum trioxide, nano activated carbon and absolute ethyl alcohol in a ball mill, adding a certain amount of polyvinyl alcohol, carrying out ball milling treatment by using a steel ball, and injecting into a mold for drying and molding after the ball milling is finished to obtain a first mixed material; wherein the ball-material ratio is 5; the mass ratio of vanadium pentoxide to molybdenum trioxide to nano activated carbon to absolute ethyl alcohol is 1.82; the addition amount of the polyvinyl alcohol is 10 percent of the mass of the absolute ethyl alcohol.
S2, placing the molded first mixed material in a high-temperature graphite furnace, vacuumizing until the pressure is 10Pa, and then, heating to 1500 ℃ in a staged manner, wherein the method comprises the following steps: in the first stage, the temperature is increased from room temperature to 550 ℃, the temperature is kept for 1h, in the second stage, the temperature is increased from 550 ℃ to 950 ℃, the temperature is kept for 1h, in the third stage, the temperature is increased from 950 ℃ to 1500 ℃, and the temperature is kept for 1h; the heating rate of the first stage is 180 ℃/h, the heating rate of the second stage is 180 ℃/h, the heating rate of the third stage is 120 ℃/h, and then the temperature is reduced to the normal temperature to obtain a second mixed material;
s3, mixing the second mixed material with bismuth oxide, heating to 850 ℃, carrying out heat preservation treatment for 3 hours, cooling to normal temperature, collecting the product, putting the product into an HCl solution with the concentration of 0.1mol/L, carrying out ultrasonic treatment for 0.5 hour, drying, heating to 300 ℃, carrying out heat preservation for 1 hour, continuously putting the product into the HCl solution with the concentration of 0.1mol/L, sealing and standing for 8 hours, filtering out solid substances, washing with distilled water until the washing liquid is neutral, and carrying out drying treatment to obtain vanadium molybdenum carbide powder; wherein the ratio of the added mass of the bismuth oxide to the mass of the second mixed material is 1.1.
The preparation method of the siliconized graphite ceramic crucible comprises the following steps:
(1) The mixing process comprises the following steps: adding the raw materials into a stirring pot, stirring for 10min, adding deionized water accounting for 5% of the total weight of the raw materials into the stirring pot, and wet-stirring for 20min;
(2) The molding process comprises the following steps: after wet stirring is finished, sealing and standing the material for 60min, and then forming by a forming process; including any one of vibration molding, extrusion molding, isostatic pressing molding and rotational molding;
(3) And (3) a drying process: drying the formed material for 20h to ensure that the water content is less than 1%;
(4) And (3) a sintering process: sintering at 1300 deg.c for 16 hr.
Example 3
A graphite silicide ceramic crucible, which is different from example 1 in the preparation method of vanadium molybdenum carbide powder.
The preparation method of the vanadium molybdenum carbide powder comprises the following steps:
s1, mixing vanadium pentoxide, molybdenum trioxide, nano activated carbon and absolute ethyl alcohol in a ball mill, adding a certain amount of polyvinyl alcohol, carrying out ball milling treatment by using a steel ball, and injecting into a mold for drying and molding after the ball milling is finished to obtain a first mixed material; wherein, the ball-material ratio is 7; the mass ratio of vanadium pentoxide to molybdenum trioxide to nano activated carbon to absolute ethyl alcohol is 3.64; the addition amount of polyvinyl alcohol is 20% of the mass of absolute ethyl alcohol.
S2, placing the molded first mixed material in a high-temperature graphite furnace, vacuumizing until the pressure is 20Pa, and then, raising the temperature to 1500 ℃ in a staged manner, wherein the method comprises the following steps: in the first stage, the temperature is increased from room temperature to 550 ℃, the temperature is kept for 2h, in the second stage, the temperature is increased from 550 ℃ to 950 ℃, the temperature is kept for 2h, in the third stage, the temperature is increased from 950 ℃ to 1500 ℃, and the temperature is kept for 2h; the heating rate of the first stage is 300 ℃/h, the heating rate of the second stage is 300 ℃/h, the heating rate of the third stage is 160 ℃/h, and then the temperature is reduced to normal temperature to obtain a second mixed material;
s3, mixing the second mixed material with bismuth oxide, heating to 900 ℃, carrying out heat preservation treatment for 5 hours, cooling to normal temperature, collecting the product, putting the product into an HCl solution with the concentration of 0.1mol/L, carrying out ultrasonic treatment for 1 hour, drying, heating to 300 ℃, carrying out heat preservation for 2 hours, continuously putting the product into the HCl solution with the concentration of 0.1mol/L, sealing and standing for 12 hours, filtering out solid substances, washing with distilled water until the washing liquid is neutral, and carrying out drying treatment to obtain vanadium molybdenum carbide powder; wherein the ratio of the added mass of the bismuth oxide to the mass of the second mixed material is 1.5.
The preparation method of the siliconized graphite ceramic crucible comprises the following steps:
(1) The mixing process comprises the following steps: adding the raw materials into a stirring pot, stirring for 15min, adding deionized water accounting for 8% of the total weight of the raw materials into the stirring pot, and wet-stirring for 25min;
(2) The molding process comprises the following steps: after wet stirring is finished, sealing and standing the material for 90min, and then forming by a forming process; including any one of vibration molding, extrusion molding, isostatic pressing molding and rotational molding;
(3) And (3) a drying process: drying the formed material for 30h to ensure that the water content is less than 1%;
(4) The sintering process comprises the following steps: sintering at 1500 deg.c for 20 hr.
Example 4
A graphite silicide ceramic crucible is different from that of example 1 in the content of each component.
The composition comprises the following components in parts by weight:
80 parts of silicon carbide, 1.8 parts of graphite powder, 9 parts of vanadium molybdenum carbide powder, 0.5 part of gypsum powder, 4 parts of white mud, 0.5 part of hydroxypropyl methyl cellulose and 1.5 parts of modified starch.
Example 5
A graphite silicide ceramic crucible is different from that of example 1 in the content of each component.
The composition comprises the following components in parts by weight:
95 parts of silicon carbide, 3 parts of graphite powder, 5 parts of vanadium molybdenum carbide powder, 2 parts of gypsum powder, 2 parts of white mud, 1.5 parts of hydroxypropyl methyl cellulose and 0.5 part of modified starch.
Example 6
A graphite silicide ceramic crucible is different from that of example 1 in the content of each component.
The composition comprises the following components in parts by weight:
84 parts of silicon carbide, 1.5 parts of graphite powder, 6 parts of vanadium molybdenum carbide powder, 1.6 parts of gypsum powder, 2.5 parts of white mud, 1.2 parts of hydroxypropyl methyl cellulose and 0.5 part of modified starch.
Comparative example 1
A graphite silicide ceramic crucible, differing from example 1 in that vanadium molybdenum carbide powder was replaced with commercially available vanadium carbide powder;
the composition comprises the following components in parts by weight:
87 parts of silicon carbide, 2.3 parts of graphite powder, 7 parts of vanadium carbide powder, 1 part of gypsum powder, 3 parts of white mud, 1 part of hydroxypropyl methyl cellulose and 1 part of modified starch.
Comparative example 2
A graphite silicide ceramic crucible, differing from example 1 in that vanadium molybdenum carbide powder was replaced with commercially available molybdenum carbide powder;
the composition comprises the following components in parts by weight:
87 parts of silicon carbide, 2.3 parts of graphite powder, 7 parts of molybdenum carbide powder, 1 part of gypsum powder, 3 parts of white mud, 1 part of hydroxypropyl methyl cellulose and 1 part of modified starch.
Comparative example 3
A graphite silicide ceramic crucible, which is different from the crucible in the embodiment 1 in that vanadium molybdenum carbide powder is completely replaced by graphite powder;
the preparation method comprises the following steps of:
87 parts of silicon carbide, 9.3 parts of graphite powder, 1 part of gypsum powder, 3 parts of white mud, 1 part of hydroxypropyl methyl cellulose and 1 part of modified starch.
In order to more clearly illustrate the present invention, the materials of the ceramic crucibles prepared in examples 1, 4, 5 and 6 according to the present invention and comparative examples 1, 2 and 3 were measured and compared, and the results are shown in the following table:
Figure BDA0003789952270000091
in the above table, the hardness test standard is referred to GB/T4340.1-2009 (unit conversion is 1gpa = 102.04hv); the detection reference standard GB/T38338-2019 of fracture toughness; the bending strength detection standard refers to GB/T39826-2021, the bending strength at room temperature is the bending strength detected at 25 ℃, and the bending strength at high temperature is the bending strength detected at 1400 ℃; the corrosion resistance is to detect the change rate of the mass of the corrosion resistance after the corrosion resistance is corroded in acid or alkali, namely the acid corrosion rate or the alkali corrosion rate, wherein the acid corrosion resistance is to soak in a sulfuric acid solution with the mass concentration of 20% for 48 hours, and the alkali corrosion resistance is to soak in a sodium hydroxide solution with the mass concentration of 20% for 48 hours.
As can be seen from the above table, the ceramic crucible prepared by the method of the embodiment of the invention has better comprehensive performance, and can simultaneously give consideration to the hardness, toughness, strength, high temperature resistance and corrosion resistance, which has important reference significance for the development and application in the field of ceramic crucible materials.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. A silicified graphite ceramic crucible is characterized by comprising the following components in parts by weight:
80-95 parts of silicon carbide, 1.5-3 parts of graphite powder, 5-9 parts of vanadium molybdenum carbide powder, 0.5-2 parts of gypsum powder, 2-4 parts of white mud, 0.5-1.5 parts of hydroxypropyl methyl cellulose and 0.5-1.5 parts of modified starch.
2. The siliconized graphite ceramic crucible according to claim 1, wherein the silicon carbide has a purity of greater than 98% and a particle size distribution of: 8.2 percent of 3-5mm, 30.6 percent of 1-3mm, 33.0 percent of 100 mu m-1mm and 28.2 percent of 50 mu m-100 mu m; the purity of the graphite powder is higher than 99.9%, and the particle size is 20-30 μm; the particle size of the vanadium molybdenum carbide powder is 100-150nm; the gypsum powder has a purity higher than 98% and a particle size of 50-100 μm.
3. The siliconized graphite ceramic crucible according to claim 1, wherein the white mud has a particle size of 50-100 μm, and comprises, in mass percent: 54.85% SiO 2 43.54% of Al 2 O 3 And other impurities; the purity of the hydroxypropyl methylcellulose is higher than 99%.
4. The siliconized graphite ceramic crucible according to claim 1, wherein the modified starch is obtained by modifying starch with dodecyl dimethyl benzyl ammonium chloride by the following steps:
mixing corn starch with a sodium hydroxide solution with the mass fraction of 20%, stirring for 1-2h, adding dodecyl dimethyl benzyl ammonium chloride, heating to 55-65 ℃, stirring for 3-5h, pouring into acetone for precipitation, collecting the precipitate, and drying to obtain modified starch; wherein, the mass ratio of the corn starch, the dodecyl dimethyl benzyl ammonium chloride and the sodium hydroxide solution is 0.3-0.6.
5. The siliconized graphite ceramic crucible according to claim 1, wherein the preparation method of vanadium molybdenum carbide powder comprises the following steps:
s1, mixing vanadium pentoxide, molybdenum trioxide, nano activated carbon and absolute ethyl alcohol in a ball mill, adding a certain amount of polyvinyl alcohol, carrying out ball milling treatment by using a steel ball, and injecting into a mold for drying and molding after the ball milling is finished to obtain a first mixed material;
s2, placing the molded first mixed material in a high-temperature graphite furnace, vacuumizing, heating to 1500 ℃ in a staged manner, carrying out heat treatment for 3-6h, and cooling to normal temperature to obtain a second mixed material;
s3, mixing the second mixed material with bismuth oxide, heating to 850-900 ℃, carrying out heat preservation treatment for 3-5h, cooling to normal temperature, collecting the product, putting the product into HCl solution, carrying out ultrasonic treatment for 0.5-1h, drying, heating to 300 ℃, carrying out heat preservation for 1-2h, continuously putting the product into HCl solution, carrying out sealed standing for 8-12h, filtering out solid substances, washing with distilled water until washing liquid is neutral, and carrying out drying treatment to obtain vanadium molybdenum carbide powder.
6. The siliconized graphite ceramic crucible according to claim 5, wherein in step S1, the ball-to-material ratio is 5-7, the ball milling speed is 150-250rpm, the ball milling temperature is 25 ℃ at normal temperature, and the ball milling time is 8-12h.
7. The ceramic crucible of claim 5, wherein in step S1, the mass ratio of vanadium pentoxide to molybdenum trioxide to nano-activated carbon to absolute ethyl alcohol is 1.82-3.64; the addition amount of the polyvinyl alcohol is 10 to 20 percent of the mass of the absolute ethyl alcohol.
8. The siliconized graphite ceramic crucible according to claim 1, wherein in step S2, a vacuum is applied to a pressure of 10 to 20Pa; the staged heating to 1500 ℃ comprises: the first stage is to heat from room temperature to 550 ℃, keep the temperature for 1-2h, the second stage is to heat from 550 ℃ to 950 ℃, keep the temperature for 1-2h, and the third stage is to heat from 950 ℃ to 1500 ℃, keep the temperature for 1-2h; the temperature rising speed of the first stage is 180-300 ℃/h, the temperature rising speed of the second stage is 180-300 ℃/h, and the temperature rising speed of the third stage is 120-160 ℃/h.
9. The ceramic crucible of claim 1, wherein in step S3, the ratio of the added mass of bismuth oxide to the mass of the second mixed material is 1.1 to 1.5; the concentration of the HCl solution was 0.1mol/L.
10. A method of preparing a siliconized graphite ceramic crucible as claimed in any of claims 1 to 9, comprising the steps of:
(1) The mixing process comprises the following steps: adding the raw materials into a stirring pot, stirring for 10-15min, adding deionized water accounting for 5% -8% of the total weight of the raw materials into the stirring pot, and wet-stirring for 20-25min;
(2) The molding process comprises the following steps: after wet stirring is finished, sealing and standing the material for 60-90min, and then forming by a forming process;
(3) And (3) a drying process: drying the formed material for 20-30h to make the water content less than 1%;
(4) And (3) a sintering process: sintering at 1300-1500 deg.c for 16-20 hr.
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