CN115594511A - Method for preparing silicon nitride ceramic by reaction sintering - Google Patents
Method for preparing silicon nitride ceramic by reaction sintering Download PDFInfo
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- CN115594511A CN115594511A CN202211369247.1A CN202211369247A CN115594511A CN 115594511 A CN115594511 A CN 115594511A CN 202211369247 A CN202211369247 A CN 202211369247A CN 115594511 A CN115594511 A CN 115594511A
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000005245 sintering Methods 0.000 title claims abstract description 50
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000000919 ceramic Substances 0.000 title claims abstract description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 239000011230 binding agent Substances 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 12
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003085 diluting agent Substances 0.000 claims abstract description 9
- 238000000462 isostatic pressing Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 41
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 8
- 238000005452 bending Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 3
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 238000005056 compaction Methods 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000005121 nitriding Methods 0.000 description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910021426 porous silicon Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 101000687323 Homo sapiens Rabenosyn-5 Proteins 0.000 description 1
- 102100024910 Rabenosyn-5 Human genes 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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Abstract
The invention relates to a method for preparing silicon nitride ceramics by reaction sintering, which comprises the following steps: mixing silicon powder with different particle sizes, a diluent and a catalyst, adding alcohol for ball milling, and drying to obtain initial silicon powder; mixing carbon powder, polyvinyl butyral and polyethylene glycol to obtain carbon-based binder slurry; adding the initial silicon powder into the carbon-based binder slurry, heating and stirring in a water bath kettle, drying, and sieving to obtain silicon powder wrapped by carbon powder; carrying out isostatic pressing on the silicon powder wrapped by the carbon powder to obtain a ceramic blank; and performing reaction sintering on the ceramic blank to obtain the silicon nitride ceramic. The preparation method has the advantages of simple process, low raw material cost, short product firing period, high nitridation rate, complete nitridation under the nitrogen atmosphere, simplification of the sintering process and suitability for large-scale production.
Description
Technical Field
The invention belongs to the technical field of preparation of porous ceramic materials, and particularly relates to a method for preparing silicon nitride ceramic through reaction sintering.
Background
The reactive sintering method is one of the main preparation techniques for preparing porous silicon nitride ceramics. The reaction sintering silicon nitride ceramic (RBSN) takes silicon powder as a raw material and reacts with nitrogen at a lower temperature to sinter so as to generate the silicon nitride ceramic. The reaction sintered silicon nitride ceramic has the advantages of high temperature resistance, oxidation resistance, wear resistance, thermal shock resistance and the like, and has special use value in the working environment of high-temperature, high-speed and strong corrosive medium.
Preparation of Si by reaction sintering method 3 N 4 Has the following advantages: 1. the reaction sintering temperature is low, and the sintering can be completed at 1250-1450 ℃; 2. the sintering shrinkage is low, the appearance size of the sintered product is basically unchanged, a near-net-shape product is easily obtained, the post-processing cost is reduced, and the cracking probability of the product is reduced; 3. parts with large size, high precision and complex shape can be prepared; 4. the sintering can be finished without adding a sintering aid, and the high-temperature creep resistance is good.
Because the conventional reaction sintering silicon nitride ceramic has low nitridation rate and overlong nitridation time, the nitridation time is generally dozens of hours or more, and the internal nitridation of a sample is incomplete, the production efficiency is low, the sintering cost is improved, and the silicon flowing defect is easily generated in the product in the nitridation process, so that the service performance is reduced; on the other hand, hydrogen or mixed gas of helium, argon and the like is needed in the nitriding process, the sintering process is complex, the sintering cost is increased, and the method is not suitable for large-scale production.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing silicon nitride ceramics by reaction sintering, aiming at the defects in the prior art, the method can simplify the sintering process, the prepared silicon nitride ceramics has high nitridation rate and short nitridation time, can be completely nitrided in the atmosphere of pure nitrogen, does not need other mixed gases, and the prepared porous silicon nitride ceramics has excellent performance and low production cost and is suitable for large-scale production.
A method for preparing silicon nitride ceramics by reaction sintering comprises the following steps: mixing silicon powder with different particle sizes, a diluent and a catalyst, adding alcohol for ball milling, and drying to obtain initial silicon powder; mixing carbon powder, polyvinyl butyral and polyethylene glycol to obtain carbon-based binder slurry; adding the initial silicon powder into the carbon-based binder slurry, heating and stirring in a water bath kettle, drying, and sieving to obtain silicon powder wrapped by carbon powder; carrying out isostatic pressing on the silicon powder wrapped by the carbon powder to obtain a ceramic blank; and performing reaction sintering on the ceramic blank to obtain the silicon nitride ceramic.
Preferably, the particle size of the silicon powder comprises 75 μm, 20 μm and 10 μm, and the corresponding mass ratio is (50-75): (1-6): (24 to 44).
Preferably, the diluent is one or a mixture of submicron silicon powder and silicon nitride powder, and the addition content is 5-10% of the total mass of the silicon powder; the catalyst is one or a mixture of iron oxide, barium fluoride or calcium fluoride, and the addition content is 1-5% of the total mass of the silicon powder.
Preferably, the mass ratio of the silicon powder to the alcohol is 1: (0.6-0.8) and the ball milling time is 6-8 h.
Preferably, the particle size of the carbon powder is 0.8 μm, and the mass of the carbon powder is 6-10% of the total mass of the initial silicon powder.
Preferably, the method for preparing the carbon-based binder slurry includes the steps of:
and adding polyvinyl butyral accounting for 30-40% of the total mass of the carbon-based binder slurry and polyethylene glycol accounting for 5-10% of the total mass of the carbon-based binder slurry into alcohol accounting for 55-60% of the total mass of the carbon-based binder slurry, stirring, adding carbon powder after the polyvinyl butyral and the polyethylene glycol are completely dissolved, and uniformly mixing to obtain the carbon-based binder slurry.
Preferably, the initial silicon powder is added into the carbon-based binder slurry, the mass ratio of the initial silicon powder to the carbon-based binder slurry is 1 (0.6-0.8), the heating temperature of the water bath is 75 ℃, after the alcohol is completely evaporated, the silicon powder is taken out and dried, the drying temperature is 75-80 ℃, and the silicon powder wrapped by the carbon powder is obtained after drying and passing through a 80-mesh sieve.
Preferably, the isostatic compaction pressure is 120 to 150MPa.
Preferably, the maximum temperature of the reaction sintering is 1400-1420 ℃, and the reaction sintering process comprises the following steps:
repeatedly vacuumizing and filling nitrogen in the temperature rising process when the temperature is 0-100 ℃, and repeating the step for 3-5 times; at 100-600 ℃, keeping the vacuum state in the furnace, and keeping the gauge pressure at-0.1 MPa; when the temperature of the furnace rises to 600 ℃, high-purity nitrogen is filled, and the furnace pressure is kept at 0.1MPa; when the temperature of the furnace rises to 1000 ℃, preserving the heat for 2 hours; when the temperature of the furnace rises to 1150-1170 ℃, preserving the heat for 2-3 h; when the temperature of the furnace rises to 1230-1250 ℃, preserving the heat for 1.5-2 h; when the temperature of the furnace rises to 1300-1320 ℃, preserving the heat for 1-1.5 h; when the temperature of the furnace rises to 1350-1380 ℃, preserving the heat for 2-3 h; when the temperature of the furnace rises to 1400-1420 ℃, preserving the heat for 4-6 h, cooling to 1000 ℃, and then cooling to room temperature along with the furnace; wherein the temperature range of 1000-1250 ℃, the heating rate is 4 ℃/min, the temperature range of 1250-1400 ℃, the heating rate is 2 ℃/min; when the heat preservation is carried out each time, the furnace pressure is ensured to be 0.1MPa.
Preferably, the silicon nitride product prepared by reaction sintering has the nitridation rate of more than or equal to 95 percent, the porosity of less than or equal to 18 percent and the volume density of more than or equal to 2.5g/cm 3 The bending strength is more than or equal to 150MPa.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for preparing the silicon nitride ceramic by reactive sintering, provided by the invention, the silicon powder is subjected to surface treatment to obtain the silicon powder wrapped by the carbon powder. The silicon powder is added with carbon powder, and carbon and silicon dioxide are subjected to oxidation-reduction reaction at high temperature, so that the silicon dioxide protective film on the surface of the silicon powder can be removed, and the nitridation reaction is promoted.
The diluent and the catalyst for promoting silicon powder nitridation are added into the silicon powder, and the nitridation reaction in the product can be promoted through the interaction of the catalyst and the diluent. The reaction of the silicon powder and the nitrogen is exothermic, so heat accumulation can be generated in the silicon powder nitriding process, a part of silicon nitride can be generated in advance by adding some diluents, the heat accumulation in the nitriding process is reduced, the generation of silicon flow defects can be prevented, the sintering process can be simplified, and mixed gas of nitrogen and hydrogen or argon is not required to be used in the sintering process; on the other hand, during the nitridation reaction, the reaction of silicon powder and nitrogen gas is carried out from the surface to the inside, the nitridation rate is reduced in the later reaction stage (especially for some wall thickness products), the nitridation time is multiplied, the nitridation reaction rate in the later stage can be increased by adding a catalyst, and the nitridation time is shortened.
By surface treatment of the silicon powder, the nitridation rate of the silicon powder is improved, the nitridation time is shortened, the silicon powder nitridation process is simplified, the technical threshold of reaction sintering of silicon nitride is reduced, and the porous silicon nitride ceramic prepared by the method has good performance.
Detailed Description
Example one
50g of silicon powder with the particle size of 75 mu m, 6g of silicon powder with the particle size of 20 mu m and 44g of silicon powder with the particle size of 10 mu m are weighed and added into a ball milling tank, 5g of silicon nitride powder and 5g of ferric oxide are weighed and added into 60g of alcohol for ball milling, the ball milling time is 6 hours, slurry is obtained, and the initial powder is obtained after drying at the temperature of 75 ℃.
Weighing 36g of alcohol, adding 18g of polyvinyl butyral and 6g of polyethylene glycol, dissolving, adding 6g of carbon powder, and uniformly stirring to obtain the carbon-based binder slurry.
Adjusting the heating temperature of a water bath to 75 ℃, adding initial silicon powder into the carbon-based binder slurry under a stirring state, stopping stirring after alcohol is evaporated, taking out, drying at 75 ℃, and then sieving by a 80-mesh sieve to obtain silicon powder wrapped by carbon powder.
And (3) carrying out isostatic pressing on the silicon powder wrapped by the carbon powder, wherein the forming pressure is 120MPa.
And (4) placing the molded blank into a graphite crucible, and sintering in a vacuum nitrogen furnace. Firstly, vacuumizing for 3 times, keeping the gauge pressure at-0.1MPa in a vacuum state, and heating to 600 ℃ at 5h; then filling high-purity nitrogen to gauge pressure of 0.1MPa, heating to 1000 ℃ in 3h, and preserving heat for 2h; then the temperature is raised to 1150 ℃ within 37.5min, and the temperature is kept for 3h; then the temperature is raised to 1230 ℃ within 20min, and the temperature is kept for 2h; then heating to 1300 ℃ for 35min, and preserving heat for 1.5h; then heating to 1350 ℃ in 25min, and preserving heat for 2h; and then heating to 1400 ℃ in 25min, preserving heat for 6h, cooling to 1000 ℃, and cooling to room temperature along with the furnace to obtain a reaction sintered silicon nitride product.
The obtained silicon nitride product had a nitriding rate of 97.2%, a porosity of 17.5%, a bulk density of 2.58g/cm3, and a bending strength of 163MPa.
Example two
75 mu m of silicon powder 75g,20 mu m of silicon powder 1g and 10 mu m of silicon powder 24g are weighed and added into a ball milling tank, 10g of silicon nitride powder and 1g of ferric oxide are weighed and added with 60g of alcohol for ball milling for 6h to obtain slurry, and the slurry is dried at 75 ℃ to obtain initial powder.
Weighing 44g of alcohol, adding 32g of polyvinyl butyral and 4g of polyethylene glycol, dissolving, adding 10g of carbon powder, and uniformly stirring to obtain the carbon-based binder slurry.
Adjusting the heating temperature of a water bath to 75 ℃, adding initial silicon powder into the carbon-based binder slurry under a stirring state, stopping stirring after alcohol is evaporated, taking out, drying at 80 ℃, and then sieving by a 80-mesh sieve to obtain silicon powder wrapped by carbon powder.
And (3) carrying out isostatic pressing on the silicon powder wrapped by the carbon powder, wherein the forming pressure is 150MPa.
And (4) placing the molded blank into a graphite crucible, and sintering in a vacuum nitrogen furnace. Firstly, vacuumizing for 3 times, keeping the gauge pressure at-0.1MPa in a vacuum state, and heating to 600 ℃ at 5h; then filling high-purity nitrogen to gauge pressure of 0.1MPa, heating to 1000 ℃ in 3h, and preserving heat for 2h; then the temperature is raised to 1170 ℃ for 42.5min, and the temperature is kept for 2h; then raising the temperature to 1250 ℃ within 20min, and preserving the heat for 1.5h; then heating to 1320 ℃ within 35min, and preserving the heat for 1h; then heating to 1380 ℃ for 30min, and preserving the heat for 3h; and then heating to 1420 ℃ for 20min, preserving heat for 4h, cooling to 1000 ℃, and cooling to room temperature along with the furnace to obtain a reaction sintered silicon nitride product.
The obtained silicon nitride product has a nitridation rate of 98.3%, a porosity of 16.1% and a bulk density of 2.73g/cm 3 The bending strength was 187MPa.
EXAMPLE III
62g of silicon powder with the particle size of 75 microns, 3g of silicon powder with the particle size of 20 microns and 35g of silicon powder with the particle size of 10 microns are weighed and added into a ball milling tank, in addition, 7.5g of silicon nitride powder and 2.5g of ferric oxide are weighed and added with 70g of alcohol for ball milling, the ball milling time is 7 hours, slurry is obtained, and the initial powder is obtained after drying at the temperature of 78 ℃.
Weighing 40.25g of alcohol, then adding 24.5g of polyvinyl butyral and 5.25g of polyethylene glycol, dissolving, then adding 7g of carbon powder, and uniformly stirring to obtain the carbon-based binder slurry.
Adjusting the heating temperature of a water bath to 75 ℃, adding initial silicon powder into the carbon-based binder slurry under a stirring state, stopping stirring after alcohol is evaporated, taking out, drying at 78 ℃, and then sieving by a 80-mesh sieve to obtain silicon powder wrapped by carbon powder.
And (3) carrying out isostatic pressing on the silicon powder wrapped by the carbon powder, wherein the forming pressure is 130MPa.
And (4) placing the molded blank into a graphite crucible, and sintering in a vacuum nitrogen furnace. Firstly, vacuumizing for 3 times, keeping the gauge pressure at-0.1MPa in a vacuum state, and heating to 600 ℃ at 5h; then filling high-purity nitrogen to gauge pressure of 0.1MPa, heating to 1000 ℃ in 3h, and preserving heat for 2h; then heating to 1160 ℃ for 40min, and preserving heat for 2.5h; then the temperature is raised to 1240 ℃ for 20min, and the temperature is preserved for 1.5h; then heating to 1310 ℃ for 35min, and preserving heat for 1h; then raising the temperature to 1370 ℃ for 30min, and preserving the heat for 3h; and then heating to 1410 ℃ for 20min, preserving heat for 5h, cooling to 1000 ℃, and cooling to room temperature along with the furnace to obtain a reaction sintered silicon nitride product.
The obtained silicon nitride product had a nitriding rate of 97.7%, a porosity of 17%, a bulk density of 2.63g/cm3, and a bending strength of 172MPa.
Comparative example 1
50g of silicon powder with the particle size of 75 mu m, 6g of silicon powder with the particle size of 20 mu m and 44g of silicon powder with the particle size of 10 mu m are weighed and added into a ball milling tank, 60g of alcohol is added for ball milling, the ball milling time is 6 hours, slurry is obtained, and the initial powder is obtained after drying at the temperature of 75 ℃.
Weighing 36g of alcohol, adding 18g of polyvinyl butyral and 6g of polyethylene glycol, dissolving, adding 6g of carbon powder, and uniformly stirring to obtain the carbon-based binder slurry.
And adjusting the heating temperature of a water bath kettle to 75 ℃, adding initial silicon powder into the carbon-based binder slurry under a stirring state, stopping stirring after the alcohol is evaporated, taking out, drying at 75 ℃, and then sieving by a 80-mesh sieve to obtain the silicon powder wrapped by the carbon powder.
And carrying out isostatic pressing on the silicon powder wrapped by the carbon powder, wherein the forming pressure is 120MPa.
And (4) placing the molded blank into a graphite crucible, and sintering in a vacuum nitrogen furnace. Firstly, vacuumizing for 3 times, keeping the gauge pressure at-0.1MPa in a vacuum state, and heating to 600 ℃ at 5h; then filling high-purity nitrogen to gauge pressure of 0.1MPa, heating to 1000 ℃ in 3h, and preserving heat for 2h; then the temperature is raised to 1150 ℃ within 37.5min, and the temperature is kept for 3h; then the temperature is raised to 1230 ℃ within 20min, and the temperature is kept for 2h; then heating to 1300 ℃ for 35min, and preserving heat for 1.5h; then heating to 1350 ℃ in 25min, and preserving the heat for 2h; and then heating to 1400 ℃ in 25min, preserving heat for 6h, cooling to 1000 ℃, and cooling to room temperature along with the furnace to obtain a reaction sintered silicon nitride product.
The resulting silicon nitride product exhibits flow silicon defects.
No diluent is added, heat accumulation is generated in the product during nitridation, the nitridation reaction speed is too high, and the product is easy to have silicon flowing defects.
Comparative example No. two
50g of silicon powder with the particle size of 75 mu m, 6g of silicon powder with the particle size of 20 mu m and 44g of silicon powder with the particle size of 10 mu m are weighed and added into a ball milling tank, 5g of silicon nitride powder and 5g of ferric oxide are weighed and added into 60g of alcohol for ball milling, the ball milling time is 6 hours, slurry is obtained, and the initial powder is obtained after drying at the temperature of 75 ℃.
Weighing 36g of alcohol, adding 18g of polyvinyl butyral and 6g of polyethylene glycol, dissolving, adding 6g of carbon powder, and uniformly stirring to obtain the carbon-based binder slurry.
Adjusting the heating temperature of a water bath to 75 ℃, adding initial silicon powder into the carbon-based binder slurry under a stirring state, stopping stirring after alcohol is evaporated, taking out, drying at 75 ℃, and then sieving by a 80-mesh sieve to obtain silicon powder wrapped by carbon powder.
And (3) carrying out isostatic pressing on the spread and wrapped silicon powder, wherein the forming pressure is 120MPa.
And (4) placing the molded blank into a graphite crucible, and sintering in a vacuum nitrogen furnace. Firstly, vacuumizing and cleaning for 3 times, keeping the gauge pressure at-0.1MPa in a vacuum state, and heating to 600 ℃ for 5h; then filling high-purity nitrogen to gauge pressure of 0.1MPa, and heating to 1000 ℃ during 3h; then the temperature is raised to 1150 ℃ within 37.5 min; then the temperature is raised to 1230 ℃ within 20 min; then heating to 1300 ℃ within 35 min; then heating to 1350 ℃ in 25 min; and then heating to 1400 ℃ in 25min, preserving heat for 6h, cooling to 1000 ℃, and cooling to room temperature along with the furnace to obtain a reaction sintered silicon nitride product.
The resulting silicon nitride product exhibits flow silicon defects.
The step of heat preservation is omitted, silicon powder nitridation is an exothermic reaction and is gradually carried out from low temperature to high temperature, and if the low-medium temperature nitridation is not thorough in the reaction process, the silicon powder enters the high-temperature nitridation, the nitridation reaction rate is faster and faster, and silicon flow is inevitably caused. If a continuous temperature rising system is adopted and the step-type heat preservation is not carried out, the silicon powder is not nitrided enough at low temperature, and the nitriding reaction is faster and faster along with the temperature rise to cause silicon flow.
Comparative example No. three
50g of silicon powder with the particle size of 75 mu m, 6g of silicon powder with the particle size of 20 mu m and 44g of silicon powder with the particle size of 10 mu m are weighed and added into a ball milling tank, and 5g of silicon nitride powder and 5g of ferric oxide are weighed and added into the mixture for ball milling for 6 hours to obtain initial powder.
The obtained powder was subjected to isostatic pressing at a molding pressure of 120MPa.
And (4) placing the molded blank into a graphite crucible, and sintering in a vacuum nitrogen furnace. Firstly, vacuumizing for 3 times, keeping the gauge pressure at-0.1MPa in a vacuum state, and heating to 600 ℃ at 5h; then filling high-purity nitrogen to gauge pressure of 0.1MPa, heating to 1000 ℃ in 3h, and preserving heat for 2h; then the temperature is raised to 1150 ℃ within 37.5min, and the temperature is kept for 3h; then the temperature is raised to 1230 ℃ within 20min, and the temperature is kept for 2h; then heating to 1300 ℃ for 35min, and preserving heat for 1.5h; then heating to 1350 ℃ in 25min, and preserving the heat for 2h; and then heating to 1400 ℃ in 25min, preserving heat for 6h, cooling to 1000 ℃, and cooling to room temperature along with the furnace to obtain a reaction sintered silicon nitride product.
The green strength after molding is poor, and the silicon nitride product obtained after sintering has 68 percent of nitridation rate, 30 percent of porosity, 2.23g/cm < 3 > of bulk density and 52MPa of bending strength.
The alcohol is not added for ball milling and mixing, so that the obtained initial powder is not uniformly mixed, the subsequent product physical property is poor, the C-based binder slurry cannot be prepared without adding the alcohol, the product nitridation rate is low, and the strength of the molded blank is poor.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive step, which shall fall within the scope of the appended claims.
Claims (10)
1. A method for preparing silicon nitride ceramics by reaction sintering is characterized by comprising the following steps:
mixing silicon powder with different particle sizes, a diluent and a catalyst, adding alcohol for ball milling, and drying to obtain initial silicon powder;
mixing carbon powder, polyvinyl butyral and polyethylene glycol to obtain carbon-based binder slurry;
adding the initial silicon powder into the carbon-based binder slurry, heating and stirring in a water bath kettle, drying, and sieving to obtain silicon powder wrapped by carbon powder;
carrying out isostatic pressing on the silicon powder wrapped by the carbon powder to prepare a ceramic blank;
and performing reaction sintering on the ceramic blank to obtain the silicon nitride ceramic.
2. The method of claim 1, wherein the silicon nitride ceramic is prepared by reaction sintering,
the particle size of the silicon powder comprises 75 microns, 20 microns and 10 microns, and the corresponding mass ratio is (50-75): (1-6): (24 to 44).
3. The method of claim 1, wherein the silicon nitride ceramic is prepared by reaction sintering,
the diluent is one or a mixture of submicron silicon powder and silicon nitride powder, and the addition content is 5-10% of the total mass of the silicon powder;
the catalyst is one or a mixture of iron oxide, barium fluoride or calcium fluoride, and the addition content is 1-5% of the total mass of the silicon powder.
4. The method of claim 1, wherein the silicon nitride ceramic is prepared by reaction sintering,
the mass ratio of the silicon powder to the alcohol is 1: (0.6-0.8) and the ball milling time is 6-8 h.
5. The method of claim 1, wherein the silicon nitride ceramic is prepared by reaction sintering,
the particle size of the carbon powder is 0.8 mu m, and the mass of the carbon powder is 6-10% of the total mass of the initial silicon powder.
6. The method of claim 1, wherein the silicon nitride ceramic is prepared by reaction sintering,
the preparation method of the carbon-based binder slurry comprises the following steps:
and adding polyvinyl butyral accounting for 30-40% of the total mass of the carbon-based binder slurry and polyethylene glycol accounting for 5-10% of the total mass of the carbon-based binder slurry into alcohol accounting for 55-60% of the total mass of the carbon-based binder slurry, stirring, adding carbon powder after the polyvinyl butyral and the polyethylene glycol are completely dissolved, and uniformly mixing to obtain the carbon-based binder slurry.
7. The method of claim 1, wherein the silicon nitride ceramic is prepared by reaction sintering,
and adding the initial silicon powder into the carbon-based binder slurry, wherein the mass ratio of the initial silicon powder to the carbon-based binder slurry is 1 (0.6-0.8), the heating temperature of the water bath is 75 ℃, taking out and drying after the alcohol is completely evaporated, the drying temperature is 75-80 ℃, and sieving with an 80-mesh sieve after drying to obtain the silicon powder wrapped by the carbon powder.
8. The method of claim 1, wherein the silicon nitride ceramic is prepared by reaction sintering,
the isostatic compaction pressure is 120-150 MPa.
9. The method of claim 1, wherein the silicon nitride ceramic is prepared by reaction sintering,
the reaction sintering highest temperature is 1400-1420 ℃, and the reaction sintering process comprises the following steps:
repeatedly vacuumizing and filling nitrogen in the temperature rising process when the temperature is 0-100 ℃, and repeating the step for 3-5 times;
at 100-600 ℃, keeping the vacuum state in the furnace, and keeping the gauge pressure at-0.1 MPa;
when the temperature of the furnace rises to 600 ℃, high-purity nitrogen is filled, and the furnace pressure is kept at 0.1MPa;
when the temperature of the furnace rises to 1000 ℃, preserving the heat for 2 hours;
when the temperature of the furnace rises to 1150-1170 ℃, preserving the heat for 2-3 h;
when the temperature of the furnace rises to 1230-1250 ℃, preserving the heat for 1.5-2 h;
when the temperature of the furnace rises to 1300-1320 ℃, preserving the heat for 1-1.5 h;
when the temperature of the furnace rises to 1350-1380 ℃, preserving the heat for 2-3 h;
when the temperature of the furnace rises to 1400-1420 ℃, preserving the heat for 4-6 h, cooling to 1000 ℃, and then cooling to room temperature along with the furnace;
wherein the temperature range of 1000-1250 ℃, the heating rate is 4 ℃/min, the temperature range of 1250-1400 ℃, the heating rate is 2 ℃/min;
when the heat preservation is carried out each time, the furnace pressure is ensured to be 0.1MPa.
10. The method of producing silicon nitride ceramics by reaction sintering according to any one of claims 1 to 9,
the silicon nitride product prepared by reactive sintering has the nitridation rate of more than or equal to 95 percent, the porosity of less than or equal to 18 percent, the volume density of more than or equal to 2.5g/cm < 3 > and the bending strength of more than or equal to 150MPa.
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