CN117886609A - Silicon carbide ceramic material and preparation method and application thereof - Google Patents
Silicon carbide ceramic material and preparation method and application thereof Download PDFInfo
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- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 176
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 66
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- 238000005255 carburizing Methods 0.000 claims abstract description 32
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 30
- 238000001953 recrystallisation Methods 0.000 claims abstract description 24
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 27
- 239000000919 ceramic Substances 0.000 claims description 21
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- 238000001035 drying Methods 0.000 claims description 16
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- 238000001816 cooling Methods 0.000 claims description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention discloses a silicon carbide ceramic material, a preparation method and application thereof, belonging to the technical field of ceramic materials; in the preparation method of the silicon carbide ceramic material, firstly, a green body with a corresponding shape is obtained by extrusion molding, then is subjected to cold isostatic pressing secondary molding, is subjected to carburizing pretreatment after recrystallization and sintering, is subjected to high-pressure injection of resin under vacuum after the carburizing pretreatment is finished, and is finally embedded with silicon powder and then sintered; thus, the silicon carbide ceramic material with low porosity, excellent mechanical property, oxidation resistance and corrosion resistance at normal temperature and high temperature and long service life can be obtained; in addition, the preparation method of the silicon carbide ceramic material provided by the invention is simple to operate and is beneficial to actual production and application.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a silicon carbide ceramic material, and a preparation method and application thereof.
Background
The silicon carbide ceramic has excellent thermal shock resistance, high-temperature mechanical properties (high strength, creep resistance, high elastic modulus and the like), high-temperature stability, excellent oxidation resistance, thermal conductivity and the like, and can be applied to various high-temperature resistant bearing parts with high mechanical strength requirements. The high covalent bond characteristic and extremely low diffusion coefficient of silicon carbide lead to great sintering densification difficulty, and various sintering preparation technologies of silicon carbide are developed for the high covalent bond characteristic and extremely low diffusion coefficient of silicon carbide.
Depending on the formulation and sintering process, it is generally classified into reactive sintering, pressureless sintering, and recrystallization sintering systems. Different material systems obtain different performances, and the method can be applied to different working environments, such as low cost of reaction sintering silicon carbide ceramics, and the silicon is used as a second bonding phase, so that the method is suitable for being applied to the field of high-temperature kilns with the temperature below 1300 ℃; the pressureless sintered silicon carbide ceramic usually uses boron carbide and carbon as sintering aids, has good corrosion resistance, and is particularly suitable for being applied to the chemical field of strong acid and strong alkali; the recrystallized silicon carbide takes high-purity silicon carbide as a raw material, and the silicon carbide is subjected to evaporation-condensation recrystallization under the protection of atmosphere at a high temperature of more than 2000 ℃ and a certain pressure, so that particle symbiosis occurs at a particle contact position to form a high-purity silicon carbide product with certain strength. The recrystallized silicon carbide ceramic has relatively low metal impurities and good oxidation resistance because of no second phase, is particularly suitable for the field of high-temperature kilns with the temperature of more than 1300 ℃, and is an ideal candidate material for high Wen Yaoju, heat exchangers or combustion nozzles. In the field of semiconductors, particularly in the field of high-temperature heat treatment of high-purity silicon, the demand for recrystallized silicon carbide ceramics is large, but on one hand, the high porosity (10-20%) of the silicon carbide ceramics leads to lower bending strength, generally 50-70MPa, and affects the high-temperature bearing of the silicon carbide serving as a refractory material; on the other hand, the size of the silicon carbide ceramic also affects the difficulty of preparation and the mechanical property of the product, and the research on how to improve the compactness and mechanical property of large-size silicon carbide ceramic materials (such as silicon carbide ceramic rollers with the length of more than 100 cm) is less at present; therefore, it is necessary to find a silicon carbide ceramic with simple preparation process, low cost, easy mass production, large size, high strength and high compactness and a manufacturing method thereof.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the silicon carbide ceramic material which has the advantages of simple preparation process, low cost, easiness in large-scale preparation of large-size rollers, low open porosity, high volume density and high bending strength at normal temperature and high temperature, and the preparation method and application thereof.
To achieve the above object, in a first aspect of the present invention, there is provided a method for preparing a silicon carbide ceramic material, the method comprising the steps of:
(1) Extruding, forming, drying and cold isostatic pressing the silicon carbide pug to obtain a silicon carbide prefabricated green body;
(2) The prefabricated silicon carbide green body is subjected to recrystallization sintering for 0.5 to 15 hours at 2000 to 2600 ℃ in sequence, carburization pretreatment is carried out, then resin is injected under pressure under vacuum condition, and then the prefabricated silicon carbide green body is dried, so that a silicon carbide ceramic green body is obtained;
(3) Embedding silicon carbide ceramic blank with silicon powder, sintering at 1400-1800 ℃ for 0.5-12h, and cooling to obtain silicon carbide ceramic material;
the silicon carbide pug comprises the following components in percentage by mass (45-60): (15-25) a first silicon carbide powder having an average particle diameter of 50-400 μm and a second silicon carbide powder having an average particle diameter of 0.1-2 μm.
In the preparation method of the silicon carbide ceramic material, firstly, a green body with a corresponding shape is obtained by extrusion molding, then is subjected to cold isostatic pressing secondary molding, is subjected to carburizing pretreatment after recrystallization and sintering, is subjected to pressurized injection of resin under vacuum after the carburizing pretreatment is finished, and is finally embedded with silicon powder and then sintered; thus, the silicon carbide ceramic material with low porosity, excellent mechanical property at normal temperature and high temperature and excellent oxidation resistance can be obtained.
Specifically, extrusion is adopted for one-step molding, and then cold isostatic pressing is adopted for two-step molding to obtain the silicon carbide prefabricated green body, so that the volume density and the breaking strength of the silicon carbide prefabricated green body can be improved. The silicon carbide prefabricated green body is recrystallized for a corresponding time within a specific temperature range, so that the material can be ensured to resist the pressure of the pressurizing injection resin link, and the mechanical property and the high density of the product at the low temperature and the high temperature are realized; specifically, in the recrystallization process, the first silicon carbide powder and the second silicon carbide powder with proper mass ratio can be subjected to evaporation-condensation recrystallization at the given recrystallization temperature, particle symbiosis occurs at the contact position of particles to form a high-purity silicon carbide product with certain mechanical strength, the silicon carbide ceramic after recrystallization sintering does not contain any second phase, and the metal impurities of the silicon carbide powder are relatively low, so that the prepared product has good oxidation resistance and high-temperature stability. The introduction of carburization pretreatment can help to realize the compactness of the final product. In the step of injecting resin under vacuum, the volume of the blank body is basically kept unchanged before and after the early recrystallization sintering, and only the mass is slightly reduced, so that the blank body after the recrystallization sintering has higher porosity (the porosity after the recrystallization sintering is found to be between 10 and 20 percent in experiments) and lower bending strength (the bending strength after the recrystallization sintering is found to be only 50 to 70MPa in experiments), and therefore, the blank body is firstly placed under vacuum after carburizing pretreatment, internal air is removed by utilizing negative pressure, and then the resin is injected into the corresponding open pores of the blank body under vacuum, so that the filling quantity of the resin in the pores can be effectively improved, and the compactness and mechanical property of a product are further improved. Finally, sintering is carried out by using a silicon powder embedded blank, and under the given sintering temperature and time, carbon generated by thermal decomposition of resin filled in open pores of the recrystallized silicon carbide ceramic reacts with liquid phase silicon generated at high temperature to generate silicon carbide, namely, the open pores of the original recrystallized sintered silicon carbide are filled with newly generated silicon carbide, so that densification of the silicon carbide ceramic structure is further promoted, and the aim of high strength and high density is achieved.
The preparation method of the silicon carbide material is not only suitable for preparing small-size ceramic materials, but also suitable for preparing large-size ceramic materials, such as preparing silicon carbide ceramic roller materials, wherein the length of the roller in the size is more than 20cm, the length is preferably between 20 and 300cm, and the diameter of the outer ring is 3 to 10 cm; in the size range of the large-size silicon carbide ceramic roller bar material, the obtained product has excellent compactness, mechanical property, high-temperature stability and oxidation resistance.
Illustratively, the temperature of the recrystallization sintering in the step (2) may be any point value or any two point range value within 2000-2600 ℃, such as 2000 ℃, 2050 ℃, 2100 ℃, 2150 ℃, 2200 ℃, 2250 ℃, 2300 ℃, 2350 ℃, 2400 ℃, 2450 ℃, 2500 ℃, 2600 ℃, etc.; the recrystallization sintering time may be any point value or any two point range value within 0.5 to 15 hours, such as 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours, 15 hours, etc.
Illustratively, the sintering temperature in step (3) may be any point value or any two point range value within 1400-1800 ℃, such as 1400 ℃, 1450 ℃, 1500 ℃, 1550 ℃, 1600 ℃, 1650 ℃, 1700 ℃, 1750 ℃, 1800 ℃, etc.; the sintering time can be any point value or any two point range value within 0.5-12h, such as 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, etc.
Illustratively, the average particle size of the first silicon carbide powder may be any point value or any two point range value between 50-400 μm, such as 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm, 250 μm, 260 μm, 270 μm, 280 μm, 290 μm, 300 μm, 310 μm, 320 μm, 330 μm, 340 μm, 350 μm, 360 μm, 370 μm, 380 μm, 390 μm, 400 μm, etc.; the average particle diameter of the second silicon carbide powder may be any point value or any two point range value between 0.1 and 2 μm, for example, may be 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2.0 μm, etc.
Illustratively, in the silicon carbide pug, the mass ratio of the first silicon carbide powder to the second silicon carbide powder may be (45-60): any point value or any two point range value between (15-25), such as may be 45:15, 45:18, 45:20, 45:22, 45:25, 48:15, 48:18, 48:20, 48:22, 48:25, 50:15, 50:18, 50:20, 50:22, 50:25, 52:15, 52:18, 52:20, 52:22, 52:25, 55:15, 55:18, 55:20, 55:22, 55:25, 58:15, 58:18, 58:20, 58:22, 58:25, 60:15, 60:18, 60:20, 60:22, 60:25, etc.).
As a preferred embodiment of the preparation method of the invention, the silicon carbide pug comprises the following components in parts by mass:
45-55 parts of first silicon carbide powder, 15-20 parts of second silicon carbide powder, 5-10 parts of binder, 0.01-0.1 part of dispersing agent and 15-35 parts of solvent.
The research of the invention shows that the silicon carbide pug can better help realize excellent mechanical strength and high density of the product at normal temperature and high temperature, and has excellent oxidation resistance. Specifically, through selecting suitable parts by mass of first silicon carbide powder and second silicon carbide powder, good evaporation phenomenon can take place for second silicon carbide powder in recrystallization sintering process, and the second silicon carbide powder after the evaporation can condense the deposit between the particle contact point of the first silicon carbide powder that can't evaporate, and then help realizing the excellent comprehensive properties of product.
As a preferred embodiment of the production method of the present invention, the first silicon carbide powder has an average particle diameter of 100. Mu.m.
As a preferred embodiment of the production method of the present invention, the second silicon carbide powder has an average particle diameter of 0.5. Mu.m.
The present inventors have found that when the average particle diameters of the first silicon carbide powder and the second silicon carbide powder are further selected within the above range, the overall properties of the obtained product are superior.
As a preferred embodiment of the preparation method of the present invention, the binder comprises at least one of carboxymethyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol, and polyvinylpyrrolidone;
and/or the dispersing agent comprises at least one of polyacrylic acid, sodium polycarboxylate, sodium humate, sodium polyphosphate and polyethylene glycol;
and/or the solvent is water.
Preferably, the binder is hydroxypropyl methylcellulose or polyvinylpyrrolidone; the dispersing agent is sodium humate or polyethylene glycol.
According to the invention, the type of the binder and the dispersing agent can influence the comprehensive performance of the product to a certain extent, and when the type of the binder and the dispersing agent is selected as the above substances, the product with higher density and better mechanical strength can be obtained.
As a preferred embodiment of the preparation method of the invention, the preparation method of the silicon carbide pug comprises the following steps: and ball-milling and uniformly mixing the first silicon carbide powder, the second silicon carbide powder, the binder, the dispersing agent and the solvent to obtain the silicon carbide pug.
As a preferred embodiment of the preparation method of the invention, the pressure of the cold isostatic pressing is 100-220MPa, and the time is 0.5-30min.
Illustratively, the pressure of the cold isostatic pressing may be any point value or any two point range value between 100-220MPa, such as 100MPa, 110MPa, 120MPa, 130MPa, 140MPa, 150MPa, 160MPa, 170MPa, 180MPa, 190MPa, 200MPa, 210MPa, 220MPa, etc.; the time can be any point value or any two point range value between 0.5-30min, such as 0.5min, 1min, 3min, 5min, 8min, 10min, 12min, 15min, 18min, 20min, 22min, 25min, 28min, 30min, etc.
Preferably, the cold isostatic pressing pressure is 200MPa and the time is 10min.
According to the invention, the forming is performed under the pressure and time of the cold isostatic pressing provided by the invention, so that the volume density and the breaking strength of the green body can be improved, and the comprehensive performance of the product can be improved.
As a preferred embodiment of the preparation method of the invention, the recrystallization sintering temperature is 2480-2520 ℃ and the time is 0.8-1.2h.
The temperature and time of recrystallization sintering can help the second silicon carbide powder to sufficiently evaporate into and subsequently condense at the contact point of the first silicon carbide powder particles, thereby helping the promotion of the mechanical strength of subsequent products, simultaneously helping the tolerance of the blank body to pressure in the process of pressurizing and injecting resin, further helping to promote the compactness of the products and reducing the porosity.
As a preferred embodiment of the preparation method of the invention, the carburizing pretreatment is carried out at a temperature of 800-950 ℃ for 30-120min.
Illustratively, the carburizing pretreatment temperature may be any point value or any two point range value between 800-950 ℃, such as 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, etc.; the time can be any point value or any two point range value between 30-120min, such as 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min, 90min, 95min, 100min, 105min, 110min, 115min, 120min, etc.
Preferably, the carburizing pretreatment is carried out at a temperature of 880-920 ℃ for 55-65min.
When the temperature and time of the carburizing pretreatment are selected within the above ranges, particularly within a further preferable range, a good penetration effect of the carburizing agent can be achieved, and the injection amount of the subsequent resin can be further improved.
As a preferred embodiment of the preparation method of the present invention, the carburizing pretreatment includes at least one of kerosene, benzene, methanol, and diethyl ether.
As a preferred embodiment of the preparation method of the present invention, the carburizing pretreatment process is as follows: and placing the recrystallized blank body in a carburizing furnace for carburizing treatment.
According to the invention, the hydrocarbon organic liquid substance is selected, and the carburization temperature and time in the invention are matched, so that the injection amount of the subsequent resin can be improved well.
As a preferred embodiment of the preparation method of the present invention, the step of injecting the resin under pressure under vacuum is as follows: maintaining the pressure for 10-250min under vacuum condition (-0.1) -0MPa, and then injecting resin at pressure of 50-150MPa for 5-70 min.
After recrystallization treatment, the porosity in the blank is higher, and more air remains in the pores, so that the air in the pores can be removed by maintaining the pressure for a period of time under the current certain negative pressure condition, and then the resin is continuously injected under the certain negative pressure condition, so that the filling amount of the resin can be improved.
Illustratively, the dwell time may be any point value or any two point values between 10-250min, such as 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min, 180min, 190min, 200min, 210min, 220min, 230min, 240min, 250min, etc.; the injection pressure can be any point value or any two point range value between 50 and 150MPa, such as 50MPa, 60MPa, 70MPa, 80MPa, 90MPa, 100MPa, 110MPa, 120MPa, 130MPa, 140MPa, 150MPa and the like; the injection time can be any point value or any two point range value between 5-70min, such as 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, etc.
Preferably, the step of injecting the resin under vacuum at high pressure comprises the following steps: the pressure was maintained for 240min under vacuum (-0.1) MPa, followed by injection of the resin at 100MPa for 60 min.
As a preferred embodiment of the preparation method of the invention, the mass ratio of the resin to the silicon carbide prefabricated green body is (0.1-0.4): 1.
illustratively, the mass ratio of the resin to the silicon carbide preform may be (0.1-0.4): any point value or any two point range value between 1, such as 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, etc.
Preferably, the mass ratio of the resin to the silicon carbide preform is 0.2:1.
according to the research of the invention, the mass ratio of the resin to the silicon carbide prefabricated green body can bring a certain influence to the comprehensive performance of the product, and when the mass ratio of the resin to the silicon carbide prefabricated green body is further selected to be (0.1-0.4): 1, in particular 0.2:1, excellent overall properties of the product can be achieved on the basis of as little material as possible.
As a preferred embodiment of the preparation method of the present invention, in the step (2), the drying temperature is 140-220 ℃ and the drying time is 0.5-3.5h.
Illustratively, the temperature of the drying may be any point value or any two point range value between 140-220 ℃, such as 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, etc.; the drying time can be any point value or any two point range value between 0.5 and 3.5 hours, such as 0.5 hours, 1 hour, 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, etc.
Preferably, in the step (2), the drying temperature is 150 ℃ and the drying time is 3 hours.
According to the research of the invention, the resin is injected and then dried within the temperature and time range, so that the resin can be prevented from being volatilized or thermally decomposed in advance due to the excessively high drying temperature.
As a preferred embodiment of the production method of the present invention, the viscosity of the resin is 2000 to 5000 mPa.s, and the resin comprises at least one of a phenolic resin, an epoxy resin and a polycarbonate.
The resin in the viscosity range is selected to ensure that the resin has certain fluidity, so that the injection and control are convenient; and the resins in the above range are simple and readily available.
Preferably, the resin is a phenolic resin.
As a preferred embodiment of the preparation method of the present invention, in the step (3), the sintering temperature is 1480-1520 ℃ and the sintering time is 5.5-6.5h.
According to the invention, the reaction of carbon generated by thermal decomposition of injected resin and silicon powder coated on the surface can be influenced by the sintering temperature and time, and when the sintering temperature and time are in the above ranges, the carbon and the silicon powder can be better reacted to form silicon carbide, so that the silicon carbide ceramic material is further densified, and the mechanical strength and the oxidation resistance of the product are improved.
As a preferred embodiment of the production method of the present invention, the average particle diameter of the silicon powder is 1 to 12. Mu.m.
The average particle diameter of the silicon powder may be any point value or any two point values between 1 and 12 μm, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, or the like, by way of example.
Preferably, the silicon powder has an average particle diameter of 10 μm.
According to the research of the invention, the average particle size of the silicon powder can influence the reaction efficiency of carbon generated in the sintering process and the thermal decomposition of resin, and when the average particle size of the silicon powder is further selected to be 1-12 mu m, especially 10 mu m, the obtained reaction efficiency is better, and the comprehensive performance of the final product is better.
As a preferred embodiment of the preparation method, the mass ratio of the silicon powder to the silicon carbide prefabricated green body is (0.05-0.25): 1.
illustratively, the mass ratio of silicon powder to the silicon carbide preform may be (0.05-0.25): any point value or any two point range value between 1, such as 0.05:1, 0.08:1, 0.1:1, 0.12:1, 0.15:1, 0.18:1, 0.2: 1. 0.22:1, 0.25:1, etc.
Preferably, the mass ratio of the silicon powder to the silicon carbide prefabricated green body is 0.1:1.
the mass ratio of the silicon powder to the silicon carbide prefabricated green body can influence the reaction of the subsequent sintering process and carbon generated by thermal decomposition of resin to a certain extent, so that the filling rate of open pores in the green body is influenced; when the mass ratio of the silicon powder to the silicon carbide prefabricated green body is further selected to be (0.05-0.25): 1, especially 0.1:1, can guarantee that the open air hole is filled to the maximum extent, and then promote densification of the product and promote mechanical strength and oxidation resistance of the product.
In a second aspect of the invention, the invention provides a silicon carbide ceramic material prepared by the preparation method of the invention.
The silicon carbide ceramic material provided by the invention can be used as any form, such as a roller form, and has excellent compactness and excellent mechanical property; specifically, the silicon carbide ceramic material prepared by the preparation method has the silicon carbide content of more than or equal to 99 weight percent, the apparent porosity of 5-10 percent and the bulk density of 3.08-3.15g/cm 3 The bending strength at normal temperature is more than or equal to 100MPa, and the bending strength at high temperature (1350 ℃) is more than or equal to 120MPa. The prepared silicon carbide ceramic material has low open porosity, and the oxidation behavior is not obvious in a high-temperature service environment, so that the thermal shock resistance and the service life of the product can be ensured; meanwhile, oxygen in a high-temperature working environment can be prevented from entering the product, so that good oxidation resistance of the product is ensured, and the service life of the product is further prolonged.
In a third aspect of the invention, the invention provides the use of the silicon carbide ceramic material in the semiconductor field.
Compared with the prior art, the invention has the beneficial effects that:
(1) In the preparation method of the silicon carbide ceramic material, firstly, a green body with a corresponding shape is obtained by extrusion molding, then is subjected to cold isostatic pressing secondary molding, is subjected to carburizing pretreatment after recrystallization and sintering, is subjected to pressurized injection of resin under vacuum after the carburizing pretreatment is finished, and is finally embedded with silicon powder and then sintered; thus, the silicon carbide ceramic material with low porosity, excellent mechanical property, oxidation resistance and corrosion resistance at normal temperature and high temperature and long service life can be obtained; the preparation method of the silicon carbide ceramic material is simple to operate and is beneficial to actual production and application;
(2) The silicon carbide ceramic material provided by the invention has excellent mechanical strength at normal temperature and high density, so that the silicon carbide ceramic material can be widely applied to the field of semiconductors; compared with the ceramic materials used in the semiconductor field in the prior art, the ceramic materials mostly adopt high-purity graphite surface chemical vapor deposition silicon carbide coating materials to solve the problem that the performance cannot meet the requirements, so that the cost is high; the invention can realize the preparation of the silicon carbide ceramic material with low cost on the basis of adopting a simple preparation mode and cheap and easily available raw materials.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The reagents, methods and apparatus employed in the present invention are those conventional in the art unless otherwise indicated.
Example 1
The embodiment of the invention provides a silicon carbide ceramic material, and the preparation method of the silicon carbide ceramic material comprises the following steps:
(1) Mixing 55 parts of first silicon carbide powder (with the average particle size of 100 mu m), 20 parts of second silicon carbide powder (with the average particle size of 0.5 mu m), 10 parts of binder (hydroxypropyl methylcellulose), 0.1 part of dispersing agent (sodium humate) and 15 parts of water, and performing wet ball milling to obtain a silicon carbide pug;
(2) Extruding the silicon carbide pug at room temperature (25 ℃) for 5min for molding, then drying at 60 ℃ for 24h, and then carrying out cold isostatic pressing treatment on the dried green body at 200MPa for 10min to obtain a silicon carbide prefabricated green body;
(3) Recrystallizing and sintering the silicon carbide prefabricated green body at 2500 ℃ for 1h;
(4) Placing the recrystallized and sintered blank in a carburizing furnace for carburizing pretreatment, wherein the carburizing temperature is 900 ℃, the carburizing time is 60min, and the carburizing agent is kerosene;
(5) Placing the blank subjected to carburizing pretreatment in an environment of-0.1 MPa for 240min, and then injecting phenolic resin (the viscosity of the phenolic resin is 3000 mPa.s, and the mass ratio of the phenolic resin to the silicon carbide prefabricated blank is 0.2:1) under the environment of-0.1 MPa at a pressure of 100MPa for 60min; drying at 150deg.C for 3 hr after injection;
(6) Embedding the dried green body in the step (4) by using silicon powder with the average particle size of 10 mu m (the mass ratio of the silicon powder to the prefabricated green body of silicon carbide is 0.1:1), then sintering at 1500 ℃ for 6 hours, and then cooling to room temperature to obtain the silicon carbide ceramic material.
Example 2
The embodiment of the invention provides a silicon carbide ceramic material, and the preparation method of the silicon carbide ceramic material comprises the following steps:
(1) Mixing 55 parts of first silicon carbide powder (with the average particle size of 100 mu m), 20 parts of second silicon carbide powder (with the average particle size of 0.5 mu m), 10 parts of binder (hydroxypropyl methylcellulose), 0.1 part of dispersing agent (sodium humate) and 15 parts of water, and performing wet ball milling to obtain a silicon carbide pug;
(2) Extruding the silicon carbide pug at room temperature for 5min for molding, then drying at 60 ℃ for 24h, and then carrying out cold isostatic pressing treatment on the dried green body at 150MPa for 30min to obtain a silicon carbide prefabricated green body;
(3) Recrystallizing and sintering the silicon carbide prefabricated green body at 2000 ℃ for 10 hours;
(4) Placing the recrystallized and sintered blank in a carburizing furnace for carburizing pretreatment, wherein the carburizing temperature is 800 ℃, the carburizing time is 110min, and the carburizing agent is kerosene;
(5) Placing the carburized and pretreated blank body in an environment of 0MPa for 20min, and then injecting phenolic resin (the viscosity of the phenolic resin is 3000 mPa.s, the mass ratio of the phenolic resin to the silicon carbide prefabricated blank body is 0.2:1) under the environment of 0MPa at a pressure of 140MPa for 10min; drying at 200deg.C for 1 hr after injection;
(6) Embedding the dried green body in the step (4) by using silicon powder with the average particle size of 10 mu m (the mass ratio of the silicon powder to the prefabricated green body of silicon carbide is 0.1:1), then sintering for 2 hours at 1800 ℃, and then cooling to room temperature to obtain the silicon carbide ceramic material.
Example 3
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that the step (1) is that:
45 parts of first silicon carbide powder (with the average particle size of 100 mu m), 15 parts of second silicon carbide powder (with the average particle size of 0.5 mu m), 5 parts of binder (polyvinylpyrrolidone), 0.01 part of dispersing agent (polyethylene glycol) and 35 parts of water are mixed and then ball-milled by a wet method, so that the silicon carbide pug is obtained.
Example 4
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that the step (1) is that:
60 parts of first silicon carbide powder (with the average particle size of 100 mu m), 25 parts of second silicon carbide powder (with the average particle size of 0.5 mu m), 10 parts of binder (hydroxypropyl methylcellulose), 0.1 part of dispersing agent (sodium humate) and 15 parts of water are mixed and then ball-milled by a wet method, so that the silicon carbide pug is obtained.
Example 5
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that in the first silicon carbide powder in the step (1), the silicon carbide powder with the average grain diameter of 100 μm accounts for 60% of the total mass of the first silicon carbide powder, and the silicon carbide powder with the average grain diameter of 50 μm accounts for 40% of the total mass of the first silicon carbide powder.
Example 6
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that in the first silicon carbide powder in the step (1), the silicon carbide powder with the average grain diameter of 320 mu m accounts for 60% of the total mass of the first silicon carbide powder, and the silicon carbide powder with the average grain diameter of 200 mu m accounts for 40%.
Example 7
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that in the first silicon carbide powder in the step (1), the silicon carbide powder with the average grain diameter of 60 μm accounts for 100 percent based on the total mass of the first silicon carbide powder.
Example 8
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that the average grain size of the second silicon carbide powder in the step (1) is 2 μm.
Example 9
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that in the step (5), the mass ratio of the phenolic resin to the silicon carbide prefabricated green body is 0.1:1.
Example 10
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that in the step (5), the mass ratio of the phenolic resin to the silicon carbide prefabricated green body is 0.4:1.
Example 11
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that in the step (5), the mass ratio of the phenolic resin to the silicon carbide prefabricated green body is 0.05:1.
Example 12
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that in the step (5), the mass ratio of the phenolic resin to the silicon carbide prefabricated green body is 0.5:1.
Example 13
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that in the step (6), the mass ratio of the silicon powder to the silicon carbide prefabricated green body is 0.05:1.
Example 14
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that in the step (6), the mass ratio of the silicon powder to the silicon carbide prefabricated green body is 0.25:1.
Example 15
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that in the step (6), the mass ratio of the silicon powder to the silicon carbide prefabricated green body is 0.01:1.
Example 16
The only difference between the preparation method of the silicon carbide ceramic material and the embodiment 1 is that in the step (6), the mass ratio of the silicon powder to the silicon carbide prefabricated green body is 0.35:1.
Comparative example 1
The comparative example of the present invention provides a silicon carbide ceramic material whose preparation method is the only difference from example 1 in that there is no carburizing pretreatment step of step (4).
Comparative example 2
The comparative example of the present invention provides a silicon carbide ceramic material whose preparation method is the only difference from example 1 in that there is no cold isostatic pressing treatment in step (2), namely, step (2) is: and extruding and molding the silicon carbide pug at room temperature for 5min, and then drying at 60 ℃ for 24h to obtain the silicon carbide prefabricated green body.
Comparative example 3
The comparative example of the present invention provides a silicon carbide ceramic material, the only difference between the preparation method of the silicon carbide ceramic material and the example 1 is that the step (5), the step (5) of the comparative example is:
placing the blank subjected to carburizing pretreatment in an environment of-0.1 MPa for 240min, and then injecting phenolic resin (the viscosity of the phenolic resin is 3000 mPa.s, and the mass ratio of the phenolic resin to the silicon carbide prefabricated blank is 0.2:1) in the environment of-0.1 MPa for 60min; after the injection was completed, the mixture was dried at 150℃for 3 hours.
Comparative example 4
The comparative example of the present invention provides a silicon carbide ceramic material, the only difference between the preparation method of the silicon carbide ceramic material and the example 1 is that the step (5), the step (5) of the comparative example is:
Injecting phenolic resin into the carburized and pretreated green body at a pressure of 100MPa (the viscosity of the phenolic resin is 3000 mPa.s, the mass ratio of the phenolic resin to the silicon carbide prefabricated green body is 0.2:1), and the injection duration is 60 minutes; after the injection was completed, the mixture was dried at 150℃for 3 hours.
Comparative example 5
The comparative example of the present invention provides a silicon carbide ceramic material, the only difference between the preparation method of the silicon carbide ceramic material and the example 1 is that the step (5), the step (5) of the comparative example is:
placing the carburized and pretreated blank body in a device containing phenolic resin for 60min (the viscosity of the phenolic resin is 3000 mPa.s, and the mass ratio of the phenolic resin to the silicon carbide prefabricated blank body is 0.2:1), placing the device in an environment of-0.1 MPa for maintaining the pressure for 240min, pressurizing with 100MPa gas, and keeping for 60min; and then dried at 150℃for 3 hours.
Comparative example 6
The comparative example of the present invention provides a silicon carbide ceramic material whose preparation method is the only difference from example 1 in that in step (3), a silicon carbide preform is recrystallized and sintered at 1800 ℃ for 1 hour.
Comparative example 7
The comparative example of the present invention provides a silicon carbide ceramic material whose preparation method is the only difference from example 1 in that in step (3), a silicon carbide preform is recrystallized and sintered at 3000 ℃ for 1 hour.
Comparative example 8
The comparative example of the present invention provides a silicon carbide ceramic material whose preparation method is the only difference from example 1 in that in step (6), it is sintered at 1200 c for 6 hours.
Comparative example 9
The comparative example of the present invention provides a silicon carbide ceramic material whose preparation method is the only difference from example 1 in that in step (6), it is sintered at 2000 c for 6 hours.
Comparative example 10
The comparative example of the present invention provides a silicon carbide ceramic material, which is prepared by mixing 55 parts of a first silicon carbide powder (average particle size of 20 μm), 20 parts of a second silicon carbide powder (average particle size of 0.5 μm), 10 parts of a binder (hydroxypropyl methylcellulose), 0.1 part of a dispersant (sodium humate) and 15 parts of water and wet ball milling in the step (1), thus obtaining a silicon carbide pug.
Comparative example 11
The comparative example of the present invention provides a silicon carbide ceramic material, which is prepared by mixing 55 parts of a first silicon carbide powder (average particle size 100 μm), 20 parts of a second silicon carbide powder (average particle size 10 μm), 10 parts of a binder (hydroxypropyl methylcellulose), 0.1 part of a dispersant (sodium humate) and 15 parts of water and wet ball milling in the step (1) to obtain a silicon carbide pug.
Comparative example 12
The comparative example of the present invention provides a silicon carbide ceramic material, which is prepared by mixing 20 parts of a first silicon carbide powder (average particle size of 100 μm), 55 parts of a second silicon carbide powder (average particle size of 0.5 μm), 10 parts of a binder (hydroxypropyl methylcellulose), 0.1 part of a dispersant (sodium humate) and 15 parts of water and wet ball milling in the step (1), thus obtaining a silicon carbide pug.
Comparative example 13
The comparative example of the present invention provides a silicon carbide ceramic material, which is prepared by mixing 75 parts of a first silicon carbide powder (average particle size 100 μm), 10 parts of a binder (hydroxypropyl methylcellulose), 0.1 part of a dispersant (sodium humate) and 15 parts of water and performing wet ball milling in the step (1), thus obtaining a silicon carbide pug.
Comparative example 14
The comparative example of the present invention provides a silicon carbide ceramic material, which is prepared by mixing 75 parts of second silicon carbide powder (average particle size of 0.5 μm), 10 parts of binder (hydroxypropyl methylcellulose), 0.1 part of dispersant (sodium humate) and 15 parts of water and wet ball milling to obtain silicon carbide pug, wherein the only difference between the preparation method and the example 1 is that in the step (1).
Effect example 1
The silicon carbide ceramic materials prepared in the examples and the comparative examples are proved to have the properties, wherein the silicon carbide ceramic materials prepared in the examples and the comparative examples are columnar hollow silicon carbide ceramic rollers with the outer diameter of 57mm, the length of 2500mm and the roundness deviation of the rollers within 0.1 mm; the test item includes the following parts:
1. flexural strength at room temperature: testing with reference to GB/T6569-86;
2. flexural strength at 1350 ℃): testing is performed with reference to FCRI/ZY/C522-H/B1601;
3. bulk density: test with reference to GB/T2413-1981;
4. open porosity: test with reference to GB/T2997-2015;
the results obtained from the test are shown in table 1;
TABLE 1
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As can be seen from Table 1, when the technical scheme of the invention is adopted, the obtained product has good compactness, lower open porosity and excellent normal temperature and high temperature mechanical properties, and particularly, the volume density of the obtained product is 3.00g/cm 3 The open porosity is below 9.8%, the bending strength at room temperature is above 100 MPa, and the bending strength at 1350 ℃ is above 115 MPa; in addition, the product prepared by the embodiment of the invention is placed at 1350 ℃ for 30 hours, and then the surface of the product is observed to have no oxidation defect (karst cave or peeling) and has no weight before and after the test The product provided by the invention has excellent oxidation resistance; meanwhile, after the product is placed in a boiled corrosion solution (concretely, formic acid and hydrochloric acid solution) for 48 hours, the defect that the surface of the product is not corroded is observed, and the product has excellent corrosion resistance after detection, wherein the bending strength is hardly changed at room temperature before and after corrosion test;
as can be seen from examples 1 and 4, the mass ratio of the first silicon carbide powder to the second silicon carbide powder in the silicon carbide pug can affect the performance of the product, and when the mass parts of the first silicon carbide powder and the second silicon carbide powder are more preferably within the range given by the invention, the comprehensive performance of the obtained product is better; it is further seen from example 1 and comparative example 12 that when the mass ratio of the first silicon carbide powder to the second silicon carbide powder is out of the range given by the present invention, the flexural strength of the obtained product at room temperature and at high temperature is significantly reduced, and the bulk density is also lowered while the open porosity is significantly increased; as can be seen from example 1 and comparative examples 13 to 14, when only any one of the silicon carbide powders was added, the resulting product could not achieve excellent flexural strength at normal temperature and at high temperature; it can be seen from examples 1 and 5 to 7 and examples 1 and 8 that the average particle size of the first silicon carbide powder and the second silicon carbide powder also affects the overall properties of the product to some extent; it is further seen from example 1 and comparative examples 10 to 11 that when the average particle diameter of the first silicon carbide powder or the second silicon carbide powder is out of the range given in the present invention, the prepared product has a higher open porosity, a lower bulk density, and a lower flexural strength at ordinary temperature and at high temperature;
As can be seen from example 1 and examples 9-12, the mass ratio of phenolic resin to silicon carbide preform during the preparation process also affects the product performance, when further selecting the mass ratio of phenolic resin to silicon carbide preform to be (0.1-0.4): 1, the overall properties of the resulting product are more excellent, in particular, the bulk density of the resulting product is 3.06g/cm 3 The porosity of the opening is below 7.4%, and the bending strength at room temperature is below 112 MPaThe bending strength at 1350 ℃ is above 127 MPa;
as can be seen from example 1 and examples 13-16, the mass ratio of silicon powder to the silicon carbide preform during the preparation process also affects the product performance, when further selecting the mass ratio of silicon powder to the silicon carbide preform to be (0.05-0.25): 1, the overall properties of the resulting product are more excellent, in particular, the bulk density of the resulting product is 3.02g/cm 3 The open porosity is below 8.6%, the bending strength at room temperature is above 104 MPa, and the bending strength at 1350 ℃ is above 119 MPa;
as can be seen from examples 1 and comparative examples 1 to 2, the steps in the preparation process are not indispensable, and when comparative example 1 is not subjected to carburizing pretreatment, the flexural strength of the prepared product at room temperature and at high temperature is reduced by 25.78% and 26.57% respectively, compared with example 1; when the cold isostatic pressing treatment is not performed in comparative example 2, the bending strength of the prepared product at room temperature and high temperature is respectively reduced by 33.60 percent and 33.57 percent;
As can be seen from examples 1 and comparative examples 3 to 5, the resin injection operation has a large influence on the properties of the product, whether the product is injected under no pressure in comparative example 3, or the product is not first placed under vacuum in comparative example 4, or the product is injected without injection in comparative example 5, the overall properties of the resulting product are significantly reduced compared with example 1, the flexural strength at room temperature is reduced by 25.78 to 30.47%, the flexural strength at 1350 ℃ is reduced by 26.57 to 30.07%, the bulk density is reduced by 7.94 to 10.16%, and the open porosity is increased by 106.00 to 126.00%;
it can be seen from example 1 and comparative examples 6 to 7 that the recrystallization temperature also affects the overall properties of the product, and when the recrystallization temperature in comparative examples 6 to 7 is outside the range given in the present invention, the obtained product exhibits a tendency of increasing the open porosity and a decrease in the bulk density, while also exhibiting a significant tendency of decreasing the flexural strength at room temperature and at high temperature; it can be seen from examples 1 and comparative examples 8 to 9 that the sintering temperature also has an effect on the overall properties of the product, and that when the sintering temperature in comparative examples 8 to 9 is out of the range given in the present invention, the overall properties of the obtained product show a significant tendency to decrease.
Effect example 2
The small-size columnar hollow silicon carbide ceramic roller (with the outer diameter of 57mm, the length of 100mm and the roundness deviation of the roller within 0.1 mm) prepared by the preparation method in the embodiment 1 is tested, and the bending strength obtained by the test is 360MPa by referring to the test method of GBT_6569 2006/ISO 14704:2000 fine ceramic bending strength; the preparation method provided by the invention can be used for preparing silicon carbide ceramic materials with different sizes, and the prepared ceramic materials have excellent comprehensive properties.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, and that those skilled in the art will understand that changes can be made to the technical solutions of the invention or equivalents thereof without departing from the spirit and scope of the technical solutions of the invention.
Claims (16)
1. A method for preparing a silicon carbide ceramic material, which is characterized by comprising the following steps:
(1) Extruding, forming, drying and cold isostatic pressing the silicon carbide pug to obtain a silicon carbide prefabricated green body;
(2) The prefabricated silicon carbide green body is subjected to recrystallization sintering for 0.5 to 15 hours at 2000 to 2600 ℃ in sequence, carburization pretreatment is carried out, then resin is injected under pressure under vacuum condition, and then the prefabricated silicon carbide green body is dried, so that a silicon carbide ceramic green body is obtained;
(3) Embedding silicon carbide ceramic blank with silicon powder, sintering at 1400-1800 ℃ for 0.5-12h, and cooling to obtain silicon carbide ceramic material;
the silicon carbide pug comprises the following components in percentage by mass: 15-25 of first silicon carbide powder and second silicon carbide powder, wherein the average grain diameter of the first silicon carbide powder is 50-400 mu m, and the average grain diameter of the second silicon carbide powder is 0.1-2 mu m.
2. The preparation method according to claim 1, wherein the silicon carbide pug comprises the following components in parts by mass:
45-55 parts of first silicon carbide powder, 15-20 parts of second silicon carbide powder, 5-10 parts of binder, 0.01-0.1 part of dispersing agent and 15-35 parts of solvent.
3. The method of producing according to claim 1, wherein the first silicon carbide powder has an average particle diameter of 100 μm.
4. The method according to claim 2, wherein the binder comprises at least one of carboxymethyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol, and polyvinylpyrrolidone;
and/or the dispersing agent comprises at least one of polyacrylic acid, sodium polycarboxylate, sodium humate, sodium polyphosphate and polyethylene glycol;
and/or the solvent is water.
5. The method according to claim 1, wherein the cold isostatic pressure is 100-220MPa for 0.5-30min.
6. The method according to claim 1, wherein the recrystallization sintering is carried out at a temperature of 2480 to 2520 ℃ for a time of 0.8 to 1.2 hours.
7. The method according to claim 1, wherein the carburizing pretreatment is carried out at a temperature of 800-950 ℃ for a time of 30-120min.
8. The method according to claim 1, wherein the carburizing pretreatment comprises at least one of kerosene, benzene, methanol, and diethyl ether.
9. The method according to claim 1, wherein the step of injecting the resin under pressure under vacuum is: maintaining the pressure for 10-250min under the vacuum condition of-0.1-0 MPa, and then injecting resin at the pressure of 50-150MPa for 5-70 min.
10. The method of claim 1, wherein the mass ratio of resin to silicon carbide preform is 0.1-0.4:1.
11. the method according to claim 1, wherein in the step (2), the drying temperature is 140 to 220 ℃ and the drying time is 0.5 to 3.5 hours.
12. The method according to claim 1, wherein in the step (3), the sintering temperature is 1480 to 1520 ℃ for 5.5 to 6.5 hours.
13. A production method according to claim 1, wherein the average particle diameter of the silicon powder is 1 to 12 μm.
14. The method of claim 1, wherein the mass ratio of silicon powder to silicon carbide preform is 0.05-0.25:1.
15. a silicon carbide ceramic material prepared by the method of any one of claims 1 to 14.
16. Use of a silicon carbide ceramic material according to claim 15 in the semiconductor field.
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| DE4201240A1 (en) * | 1991-12-24 | 1993-07-01 | Schunk Ingenieurkeramik Gmbh | Reaction bonded silicon carbide article - made by silicon infiltration and recrystallisation |
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