CN116768635B - Modified silicon nitride composite material and preparation method thereof - Google Patents
Modified silicon nitride composite material and preparation method thereof Download PDFInfo
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- CN116768635B CN116768635B CN202310838887.0A CN202310838887A CN116768635B CN 116768635 B CN116768635 B CN 116768635B CN 202310838887 A CN202310838887 A CN 202310838887A CN 116768635 B CN116768635 B CN 116768635B
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical class N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 83
- 239000002070 nanowire Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 150000003376 silicon Chemical class 0.000 claims abstract description 31
- YGGJBIMSYKHGAW-UHFFFAOYSA-H [F-].[Lu+3].[Y+3].[F-].[F-].[F-].[F-].[F-] Chemical compound [F-].[Lu+3].[Y+3].[F-].[F-].[F-].[F-].[F-] YGGJBIMSYKHGAW-UHFFFAOYSA-H 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 29
- 238000000498 ball milling Methods 0.000 claims abstract description 28
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 238000009740 moulding (composite fabrication) Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005121 nitriding Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 19
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 14
- ANDNPYOOQLLLIU-UHFFFAOYSA-N [Y].[Lu] Chemical compound [Y].[Lu] ANDNPYOOQLLLIU-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002699 waste material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000009694 cold isostatic pressing Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
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- 229920000877 Melamine resin Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 239000011159 matrix material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910021426 porous silicon Inorganic materials 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- -1 sintering aid Substances 0.000 description 2
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- 241000531116 Blitum bonus-henricus Species 0.000 description 1
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- 235000008645 Chenopodium bonus henricus Nutrition 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
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- 238000002490 spark plasma sintering Methods 0.000 description 1
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- 238000010345 tape casting Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a modified silicon nitride composite material and a preparation method thereof, wherein silicon nanowires are used as raw materials, and gas phase permeation reaction is carried out in nitrogen atmosphere to obtain modified silicon nanowires; adding silicon nitride, zirconium nitride, lutetium yttrium fluoride and sodium fluoborate into absolute ethyl alcohol, ball milling, adding modified silicon nanowires, stirring, mixing uniformly, drying, forming and sintering to obtain a preform; and finally, sequentially carrying out nitriding treatment and annealing treatment on the preform to obtain the silicon carbide. The modified silicon nitride composite material obtained by the invention has good thermal conductivity, good toughness, excellent performance and good application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of silicon nitride composite materials, and particularly relates to a modified silicon nitride composite material and a preparation method thereof.
Background
Silicon nitride is a very important non-oxide engineering ceramic material, has good toughness, strength, corrosion resistance, abrasion resistance, high temperature resistance and other performances, and is widely applied to various fields of automobile engine parts, ceramic cutters, electronic communication, bulletproof armor, aerospace and the like.
In the prior art, the silicon nitride material is made into an electronic device, and can be used in various fields such as electric power storage, electric power transmission, electric automobiles, electric locomotives and the like. However, the development of high power and high integration of electronic devices brings about the problem of high heat of operation, and if the heat cannot be timely dissipated, the working performance and even the service life of the electronic devices are inevitably affected. Therefore, it is very necessary to develop a silicon nitride material having good heat conductive properties.
Patent application CN112159236a discloses a high thermal conductivity silicon nitride ceramic substrate, which is prepared by ball milling and mixing silicon nitride powder, sintering aid, carbon black, triethyl phosphate and solvent for one time; adding a binder and a plasticizer, and performing secondary ball milling to obtain slurry; vacuum defoamation treatment and tape casting to obtain flaky biscuit; and (5) performing high-temperature sintering after vacuum glue discharging to obtain the silicon nitride ceramic substrate. According to the invention, carbon black is introduced into the raw material proportion, and sintering is performed in two steps, so that oxygen impurities of the carbon black and silicon nitride fully react under proper temperature and atmosphere conditions, the lattice oxygen content of the silicon nitride ceramic is effectively reduced, and the thermal conductivity of the silicon nitride ceramic is improved.
However, silicon nitride has a large brittleness and limits its application, so that it is necessary to toughen and modify silicon nitride. The most commonly used method at present is second phase toughening, namely, reinforcing phases such as fibers, whiskers or particles are introduced into a matrix, but the reinforcing phases are easy to agglomerate, have poor binding force with the matrix and finally influence the toughening effect.
Patent application CN103011872a discloses a preparation method of silicon nitride toughened ceramic, which realizes toughening by utilizing the actions of silicon nitride whiskers and a sintering aid, wherein the sintering aid consists of aluminum oxide, magnesium oxide and yttrium oxide. The patent application realizes toughening through common sintering, and the problem of poor binding force is unavoidable, and the toughening effect is general.
Patent application CN110105082a discloses a preparation method of fiber-toughened porous silicon nitride ceramic, which uses carbon quantum dots as carbon precursors and supermolecular gel of melamine and silicon dioxide as carbon sources, nitrogen sources and silicon sources. Preparing melamine, formaldehyde, tetraethoxysilane, absolute ethyl alcohol, acid and deionized water into gel, drying, grinding, sieving, compression molding to form a green body, and sintering the green body for the first time in an argon atmosphere and sintering the green body for the second time in a nitrogen atmosphere to obtain the fiber-toughened porous silicon nitride ceramic. The patent application controls the porosity and the generation of silicon nitride fibers by selecting raw materials and a preparation method, but the toughness of the finally obtained product is very general.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a modified silicon nitride composite material and a preparation method thereof, and the modified silicon nitride composite material has good thermal conductivity and good toughness.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the modified silicon nitride composite material comprises the following specific steps:
(1) Firstly, taking a silicon nanowire as a raw material, and carrying out gas phase permeation reaction in a nitrogen atmosphere to obtain a modified silicon nanowire;
(2) Adding silicon nitride, zirconium nitride, lutetium yttrium fluoride and sodium fluoborate into absolute ethyl alcohol, ball milling, adding modified silicon nanowires, stirring, mixing uniformly, drying, forming and sintering to obtain a preform;
(3) And finally, sequentially carrying out nitriding treatment and annealing treatment on the preform to obtain the modified silicon nitride composite material.
Preferably, the specific method of the step (1) is as follows: and placing the silicon nanowire into a vacuum tube furnace, replacing air in the vacuum tube furnace with nitrogen, heating to 1180-1200 ℃, and preserving heat for 4-5 hours to perform gas phase permeation reaction to obtain the modified silicon nanowire.
More preferably, the heating is performed at a heating rate of 6 to 8 ℃/min.
Preferably, in the step (2), the mass ratio of silicon nitride, zirconium nitride, modified silicon nanowire, lutetium yttrium fluoride, sodium fluoborate and absolute ethyl alcohol is 1:0.1 to 0.2:0.1 to 0.15:0.05 to 0.07:0.1 to 0.2: 5-7, the grain diameter of the silicon nitride, the zirconium nitride and the lutetium yttrium fluoride is 30-40 nm, the wire body diameter of the modified silicon nanowire is 10-15 nm, and the length is 10-15 mu m.
Preferably, in the step (2), the silicon nitride is a mixture of α -silicon nitride and β -silicon nitride, and the mass ratio of the α -silicon nitride to the β -silicon nitride is 1:0.2 to 0.3.
Preferably, in the step (2), the ball milling process conditions are as follows: the mass ratio of the ball material is 20:1, the diameter of the grinding ball is 12mm, and the ball milling time is 30-35 hours.
Preferably, in the step (2), cold isostatic pressing is adopted, and the pressure is 300-350 MPa.
Preferably, in the step (2), spark plasma sintering is adopted, the temperature is 1700-1800 ℃ and the time is 15-20 minutes in nitrogen atmosphere.
Preferably, in step (2), the lutetium yttrium fluoride is prepared by the following method: firstly, crushing the waste material of the lutetium yttrium silicate scintillation crystal into powder with the grain diameter of 100-150 mu m, washing for 2-3 times, vacuum drying at the temperature of 700-800 ℃ for 20-22 hours, transferring into a reaction furnace, and introducing the volume ratio of 1: 7-9, reacting for 17-18 hours at 700-800 ℃, and naturally cooling to room temperature under the protection of argon to obtain the catalyst; wherein, the ratio of the hydrogen fluoride to the lutetium yttrium silicate scintillation crystal waste material in the mixed gas is 1mL: 6-8 g, and the partial pressure of hydrogen fluoride in the reaction furnace is 5-7 kPa.
Further preferably, tail gases such as gaseous silicon fluoride and water vapor generated in the reaction process are absorbed by 30mmol/L potassium hydroxide solution.
Preferably, in the step (3), decoupled plasma nitridation is adopted, and the process conditions are as follows: the radio frequency power is 2500-2700W, the nitrogen flow is 200-220 mL/min, and the treatment time is 50-60 s.
Preferably, in the step (3), the annealing treatment is performed under the following process conditions: the nitrogen flow is 20-25 mL/min, the temperature is 800-900 ℃ and the time is 20-25 s.
A modified silicon nitride composite material is obtained by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a modified silicon nitride composite material and a preparation method thereof, wherein silicon nanowires are used as raw materials, and gas phase permeation reaction is carried out in nitrogen atmosphere to obtain modified silicon nanowires; adding silicon nitride, zirconium nitride, lutetium yttrium fluoride and sodium fluoborate into absolute ethyl alcohol, ball milling, adding modified silicon nanowires, stirring, mixing uniformly, drying, forming and sintering to obtain a preform; and finally, sequentially carrying out nitriding treatment and annealing treatment on the preform to obtain the silicon carbide. The modified silicon nitride composite material obtained by the invention has good thermal conductivity, good toughness, excellent performance and good application prospect.
The silicon nitride raw material adopts the mixture of the alpha-silicon nitride and the beta-silicon nitride, has proper proportion, promotes sintering and ensures that the product has certain toughness. According to the invention, zirconium nitride, lutetium yttrium fluoride, sodium fluoroborate and modified silicon nanowires are added to participate in silicon nitride sintering, so that the toughness of the product is synergistically improved. The silicon nanowire has a certain toughening effect, and the silicon nitride coating layer is formed on the surface of the silicon nanowire through gas phase infiltration reaction, so that the obtained modified silicon nanowire has better compatibility with silicon nitride, and the toughness of a product is effectively improved.
The main reason for influencing the thermal conductivity of the silicon nitride material is that oxygen impurities are contained in the silicon nitride material, and in the sintering process of the invention, zirconium nitride and lutetium yttrium fluoride consume the oxygen impurities, so that the oxygen content of the material is reduced, and the thermal conductivity of the product is improved. The sodium fluoborate realizes the boronation of the material after sintering, and is also beneficial to the improvement of the toughness and the heat conductivity of the material.
According to the invention, the prefabricated body is further subjected to nitriding treatment and annealing treatment, so that the oxygen content of the material is further reduced, the thermal conductivity of the material is further improved, the microstructure of the material is optimized, and the toughness of the material is further improved.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
All goods in the invention are purchased through market channels unless specified otherwise.
Example 1
The preparation method of the modified silicon nitride composite material comprises the following specific steps:
(1) Firstly, placing the silicon nanowire into a vacuum tube furnace, replacing air in the vacuum tube furnace with nitrogen, heating to 1180 ℃ at a heating rate of 6 ℃/min, and preserving heat for 4 hours to perform gas phase permeation reaction to obtain a modified silicon nanowire;
(2) Adding 1kg of silicon nitride, 0.1kg of zirconium nitride, 0.05kg of lutetium yttrium fluoride and 0.1kg of sodium fluoborate into 5kg of absolute ethyl alcohol, ball milling, adding 0.1kg of modified silicon nanowire, stirring and uniformly mixing, drying, forming and sintering to obtain a preform;
(3) And finally, sequentially carrying out nitriding treatment and annealing treatment on the preform to obtain the modified silicon nitride composite material.
In the step (2), the grain diameters of the silicon nitride, the zirconium nitride and the lutetium yttrium fluoride are 30nm, the wire body diameter of the modified silicon nanowire is 10nm, and the length is 10 mu m.
The silicon nitride is a mixture of alpha-silicon nitride and beta-silicon nitride, and the mass ratio of the alpha-silicon nitride to the beta-silicon nitride is 1:0.2.
the ball milling process conditions are as follows: the mass ratio of the ball material is 20:1, the diameter of the grinding ball is 12mm, and the ball milling time is 30 hours.
Cold isostatic pressing is adopted for forming, and the pressure is 300MPa.
Sintering by spark plasma, nitrogen atmosphere, temperature 1700 ℃ and time 15 minutes.
The lutetium yttrium fluoride is prepared by the following method: firstly, crushing the waste material of the lutetium yttrium silicate scintillation crystal into powder with the grain diameter of 100 mu m, washing for 2 times, drying in vacuum at 700 ℃ for 20 hours, transferring into a reaction furnace, and introducing the powder into a reaction furnace with the volume ratio of 1:7, reacting the mixed gas of hydrogen fluoride and nitrogen at 700 ℃ for 17 hours, and naturally cooling to room temperature under the protection of argon to obtain the catalyst; wherein, the ratio of the hydrogen fluoride to the lutetium yttrium silicate scintillation crystal waste material in the mixed gas is 1mL:6g, the partial pressure of hydrogen fluoride in the reaction furnace is 5kPa. Tail gases such as gaseous silicon fluoride, water vapor and the like generated in the reaction process are absorbed by 30mmol/L potassium hydroxide solution.
In the step (3), decoupled plasma nitridation is adopted, and the process conditions are as follows: the radio frequency power is 2500W, the nitrogen flow is 200mL/min, and the treatment time is 50s.
In the step (3), the annealing treatment process conditions are as follows: the nitrogen flow is 20mL/min, the temperature is 800 ℃, and the time is 20s.
Example 2
The preparation method of the modified silicon nitride composite material comprises the following specific steps:
(1) Firstly, placing the silicon nanowire into a vacuum tube furnace, replacing air in the vacuum tube furnace with nitrogen, heating to 1200 ℃ at a heating rate of 8 ℃/min, and preserving heat for 5 hours to perform gas phase permeation reaction to obtain a modified silicon nanowire;
(2) Adding 1kg of silicon nitride, 0.2kg of zirconium nitride, 0.07kg of lutetium yttrium fluoride and 0.2kg of sodium fluoborate into 7kg of absolute ethyl alcohol, ball milling, adding 0.15kg of modified silicon nanowire, stirring and uniformly mixing, drying, forming and sintering to obtain a preform;
(3) And finally, sequentially carrying out nitriding treatment and annealing treatment on the preform to obtain the modified silicon nitride composite material.
In the step (2), the grain diameters of the silicon nitride, the zirconium nitride and the lutetium yttrium fluoride are 40nm, the wire body diameter of the modified silicon nanowire is 15nm, and the length is 15 mu m.
The silicon nitride is a mixture of alpha-silicon nitride and beta-silicon nitride, and the mass ratio of the alpha-silicon nitride to the beta-silicon nitride is 1:0.3.
the ball milling process conditions are as follows: the mass ratio of the ball material is 20:1, the diameter of the grinding ball is 12mm, and the ball milling time is 35 hours.
Cold isostatic pressing is adopted for forming, and the pressure is 350MPa.
Sintering by using spark plasma, and sintering in nitrogen atmosphere at 1800 ℃ for 20 minutes.
The lutetium yttrium fluoride is prepared by the following method: firstly, crushing the waste material of the lutetium yttrium silicate scintillation crystal into powder with the particle size of 150 mu m, washing 3 times, vacuum drying at 800 ℃ for 22 hours, transferring into a reaction furnace, and introducing the volume ratio of 1:9, reacting the mixed gas of hydrogen fluoride and nitrogen at 800 ℃ for 18 hours, and naturally cooling to room temperature under the protection of argon to obtain the catalyst; wherein, the ratio of the hydrogen fluoride to the lutetium yttrium silicate scintillation crystal waste material in the mixed gas is 1mL:8g, and the partial pressure of hydrogen fluoride in the reaction furnace is 7kPa. Tail gases such as gaseous silicon fluoride, water vapor and the like generated in the reaction process are absorbed by 30mmol/L potassium hydroxide solution.
In the step (3), decoupled plasma nitridation is adopted, and the process conditions are as follows: the radio frequency power is 2700W, the nitrogen flow is 220mL/min, and the treatment time is 60s.
In the step (3), the annealing treatment process conditions are as follows: the nitrogen flow rate is 25mL/min, the temperature is 900 ℃, and the time is 25s.
Example 3
The preparation method of the modified silicon nitride composite material comprises the following specific steps:
(1) Firstly, placing the silicon nanowire into a vacuum tube furnace, replacing air in the vacuum tube furnace with nitrogen, heating to 1200 ℃ at a heating rate of 6 ℃/min, and preserving heat for 4 hours to perform gas phase permeation reaction to obtain a modified silicon nanowire;
(2) Adding 1kg of silicon nitride, 0.2kg of zirconium nitride, 0.05kg of lutetium yttrium fluoride and 0.2kg of sodium fluoborate into 5kg of absolute ethyl alcohol, ball milling, adding 0.15kg of modified silicon nanowire, stirring and uniformly mixing, drying, forming and sintering to obtain a preform;
(3) And finally, sequentially carrying out nitriding treatment and annealing treatment on the preform to obtain the modified silicon nitride composite material.
In the step (2), the grain diameters of the silicon nitride, the zirconium nitride and the lutetium yttrium fluoride are 30nm, the wire body diameter of the modified silicon nanowire is 15nm, and the length is 10 mu m.
The silicon nitride is a mixture of alpha-silicon nitride and beta-silicon nitride, and the mass ratio of the alpha-silicon nitride to the beta-silicon nitride is 1:0.3.
the ball milling process conditions are as follows: the mass ratio of the ball material is 20:1, the diameter of the grinding ball is 12mm, and the ball milling time is 30 hours.
Cold isostatic pressing is adopted for forming, and the pressure is 350MPa.
Sintering by spark plasma, nitrogen atmosphere, temperature 1700 ℃ and time 20 minutes.
The lutetium yttrium fluoride is prepared by the following method: firstly, crushing the waste material of the lutetium yttrium silicate scintillation crystal into powder with the particle size of 100 mu m, washing 3 times, drying in vacuum at 700 ℃ for 22 hours, transferring into a reaction furnace, and introducing the volume ratio of 1:7, reacting the mixed gas of hydrogen fluoride and nitrogen at 800 ℃ for 17 hours, and naturally cooling to room temperature under the protection of argon to obtain the catalyst; wherein, the ratio of the hydrogen fluoride to the lutetium yttrium silicate scintillation crystal waste material in the mixed gas is 1mL:8g, the partial pressure of hydrogen fluoride in the reaction furnace is 5kPa. Tail gases such as gaseous silicon fluoride, water vapor and the like generated in the reaction process are absorbed by 30mmol/L potassium hydroxide solution.
In the step (3), decoupled plasma nitridation is adopted, and the process conditions are as follows: the radio frequency power is 2700W, the nitrogen flow is 200mL/min, and the treatment time is 60s.
In the step (3), the annealing treatment process conditions are as follows: the nitrogen flow is 20mL/min, the temperature is 900 ℃, and the time is 20s.
Example 4
The preparation method of the modified silicon nitride composite material comprises the following specific steps:
(1) Firstly, placing the silicon nanowire into a vacuum tube furnace, replacing air in the vacuum tube furnace with nitrogen, heating to 1190 ℃ at a heating rate of 7 ℃/min, and preserving heat for 4.5 hours to perform gas phase permeation reaction to obtain a modified silicon nanowire;
(2) Adding 1kg of silicon nitride, 0.15kg of zirconium nitride, 0.06kg of lutetium yttrium fluoride and 0.15kg of sodium fluoborate into 6kg of absolute ethyl alcohol, ball milling, adding 0.12kg of modified silicon nanowire, stirring and uniformly mixing, drying, forming and sintering to obtain a preform;
(3) And finally, sequentially carrying out nitriding treatment and annealing treatment on the preform to obtain the modified silicon nitride composite material.
In the step (2), the grain diameters of the silicon nitride, the zirconium nitride and the lutetium yttrium fluoride are 40nm, the wire body diameter of the modified silicon nanowire is 12nm, and the length is 13 mu m.
The silicon nitride is a mixture of alpha-silicon nitride and beta-silicon nitride, and the mass ratio of the alpha-silicon nitride to the beta-silicon nitride is 1:0.25.
the ball milling process conditions are as follows: the mass ratio of the ball material is 20:1, the diameter of the grinding ball is 12mm, and the ball milling time is 33 hours.
Cold isostatic pressing is adopted for forming, and the pressure is 320MPa.
Sintering by using spark plasma, and sintering in nitrogen atmosphere at 1750 ℃ for 18 minutes.
The lutetium yttrium fluoride is prepared by the following method: firstly, crushing the waste material of the lutetium yttrium silicate scintillation crystal into powder with the particle size of 120 mu m, washing 3 times, vacuum drying at 750 ℃ for 21 hours, transferring into a reaction furnace, and introducing the volume ratio of 1:8, reacting the mixed gas of hydrogen fluoride and nitrogen at 750 ℃ for 18 hours, and naturally cooling to room temperature under the protection of argon to obtain the catalyst; wherein, the ratio of the hydrogen fluoride to the lutetium yttrium silicate scintillation crystal waste material in the mixed gas is 1mL:7g, the partial pressure of hydrogen fluoride in the reaction furnace is 6kPa. Tail gases such as gaseous silicon fluoride, water vapor and the like generated in the reaction process are absorbed by 30mmol/L potassium hydroxide solution.
In the step (3), decoupled plasma nitridation is adopted, and the process conditions are as follows: the radio frequency power is 2600W, the nitrogen flow is 210mL/min, and the treatment time is 55s.
In the step (3), the annealing treatment process conditions are as follows: the nitrogen flow rate was 22mL/min, the temperature was 850℃and the time was 22s.
Comparative example 1
The preparation method of the modified silicon nitride composite material comprises the following specific steps:
(1) Firstly, adding 1kg of silicon nitride, 0.1kg of zirconium nitride, 0.05kg of lutetium yttrium fluoride and 0.1kg of sodium fluoborate into 5kg of absolute ethyl alcohol, ball-milling, adding 0.1kg of silicon nanowire, stirring and uniformly mixing, drying, forming and sintering to obtain a preform;
(2) And then sequentially carrying out nitriding treatment and annealing treatment on the preform to obtain the modified silicon nitride composite material.
In the step (1), the grain size of the silicon nitride, the zirconium nitride and the lutetium yttrium fluoride is 30nm, the wire body diameter of the silicon nanowire is 10nm, and the length is 10 mu m.
The silicon nitride is a mixture of alpha-silicon nitride and beta-silicon nitride, and the mass ratio of the alpha-silicon nitride to the beta-silicon nitride is 1:0.2.
the ball milling process conditions are as follows: the mass ratio of the ball material is 20:1, the diameter of the grinding ball is 12mm, and the ball milling time is 30 hours.
Cold isostatic pressing is adopted for forming, and the pressure is 300MPa.
Sintering by spark plasma, nitrogen atmosphere, temperature 1700 ℃ and time 15 minutes.
The lutetium yttrium fluoride is prepared by the following method: firstly, crushing the waste material of the lutetium yttrium silicate scintillation crystal into powder with the grain diameter of 100 mu m, washing for 2 times, drying in vacuum at 700 ℃ for 20 hours, transferring into a reaction furnace, and introducing the powder into a reaction furnace with the volume ratio of 1:7, reacting the mixed gas of hydrogen fluoride and nitrogen at 700 ℃ for 17 hours, and naturally cooling to room temperature under the protection of argon to obtain the catalyst; wherein, the ratio of the hydrogen fluoride to the lutetium yttrium silicate scintillation crystal waste material in the mixed gas is 1mL:6g, the partial pressure of hydrogen fluoride in the reaction furnace is 5kPa. Tail gases such as gaseous silicon fluoride, water vapor and the like generated in the reaction process are absorbed by 30mmol/L potassium hydroxide solution.
In the step (2), decoupled plasma nitridation is adopted, and the process conditions are as follows: the radio frequency power is 2500W, the nitrogen flow is 200mL/min, and the treatment time is 50s.
In the step (2), the annealing treatment process conditions are as follows: the nitrogen flow is 20mL/min, the temperature is 800 ℃, and the time is 20s.
Comparative example 2
The preparation method of the modified silicon nitride composite material comprises the following specific steps:
(1) Firstly, placing the silicon nanowire into a vacuum tube furnace, replacing air in the vacuum tube furnace with nitrogen, heating to 1180 ℃ at a heating rate of 6 ℃/min, and preserving heat for 4 hours to perform gas phase permeation reaction to obtain a modified silicon nanowire;
(2) Adding 1kg of silicon nitride, 0.1kg of zirconium nitride and 0.1kg of sodium fluoborate into 5kg of absolute ethyl alcohol, ball-milling, adding 0.1kg of modified silicon nanowire, stirring and mixing uniformly, drying, forming and sintering to obtain a preform;
(3) And finally, sequentially carrying out nitriding treatment and annealing treatment on the preform to obtain the modified silicon nitride composite material.
In the step (2), the grain diameters of the silicon nitride, the zirconium nitride and the lutetium yttrium fluoride are 30nm, the wire body diameter of the modified silicon nanowire is 10nm, and the length is 10 mu m.
The silicon nitride is a mixture of alpha-silicon nitride and beta-silicon nitride, and the mass ratio of the alpha-silicon nitride to the beta-silicon nitride is 1:0.2.
the ball milling process conditions are as follows: the mass ratio of the ball material is 20:1, the diameter of the grinding ball is 12mm, and the ball milling time is 30 hours.
Cold isostatic pressing is adopted for forming, and the pressure is 300MPa.
Sintering by spark plasma, nitrogen atmosphere, temperature 1700 ℃ and time 15 minutes.
In the step (3), decoupled plasma nitridation is adopted, and the process conditions are as follows: the radio frequency power is 2500W, the nitrogen flow is 200mL/min, and the treatment time is 50s.
In the step (3), the annealing treatment process conditions are as follows: the nitrogen flow is 20mL/min, the temperature is 800 ℃, and the time is 20s.
Test examples
The composites obtained in examples 1 to 4 and comparative examples 1 and 2 were examined for toughness and thermal conductivity, respectively, by the following methods:
(1) Toughness: bending strength test is carried out by referring to GB/T6569-2006 Fine ceramic bending strength test method, specifically a three-point bending method is adopted, and the span is 40mm; the fracture toughness test was performed with reference to GB/T23806-2009 method Single side Pre-crack Beam (SEPB) method for Fine ceramic fracture toughness test, with a kerf width of 80 μm and a kerf depth of 300 μm.
(2) Thermal conductivity: the thermal conductivity test was carried out with reference to GB/T5990-2021 test method for thermal conductivity, specific heat capacity and thermal diffusion coefficient of refractory materials (Hot wire method).
The results are shown in Table 1.
TABLE 1 investigation of toughness and thermal conductivity of composite materials
| Flexural Strength (MPa.m) 1/2 ) | Fracture toughness (MPa) | Coefficient of thermal conductivity (W.m) -1 ·K -1 ) | |
| Example 1 | 980 | 12.3 | 193 |
| Example 2 | 982 | 12.6 | 195 |
| Example 3 | 985 | 13.5 | 199 |
| Example 4 | 990 | 14.2 | 205 |
| Comparative example 1 | 969 | 11.4 | 185 |
| Comparative example 2 | 960 | 10.3 | 177 |
As can be seen from Table 1, the composite materials obtained in examples 1 to 4 were high in flexural strength and fracture toughness, indicating good toughness of the product, and high in thermal conductivity, indicating good thermal conductivity of the product.
The silicon nanowire in comparative example 1 is not modified, lutetium yttrium fluoride is omitted in comparative example 2, the thermal conductivity and toughness of the obtained product are obviously deteriorated, and the composition of sintering components and the surface modification treatment of the silicon nanowire are synergistic, and the interaction of the components and the surface modification treatment of the silicon nanowire jointly improve the thermal conductivity and toughness of the product.
The technical idea of the present invention is described by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must be implemented depending on the above embodiments. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of individual raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (8)
1. The preparation method of the modified silicon nitride composite material is characterized by comprising the following specific steps:
(1) Firstly, taking a silicon nanowire as a raw material, and carrying out gas phase permeation reaction in a nitrogen atmosphere to obtain a modified silicon nanowire;
(2) Adding silicon nitride, zirconium nitride, lutetium yttrium fluoride and sodium fluoborate into absolute ethyl alcohol, ball milling, adding modified silicon nanowires, stirring, mixing uniformly, drying, forming and sintering to obtain a preform;
(3) Finally, sequentially carrying out nitriding treatment and annealing treatment on the preform to obtain the modified silicon nitride composite material;
in the step (2), the mass ratio of the silicon nitride to the zirconium nitride to the modified silicon nanowire to the lutetium yttrium fluoride to the sodium fluoborate to the absolute ethyl alcohol is 1:0.1 to 0.2:0.1 to 0.15:0.05 to 0.07:0.1 to 0.2: 5-7, wherein the grain diameters of the silicon nitride, the zirconium nitride and the lutetium yttrium fluoride are 30-40 nm, the wire body diameter of the modified silicon nanowire is 10-15 nm, and the length is 10-15 mu m;
in the step (2), the silicon nitride is a mixture of alpha-silicon nitride and beta-silicon nitride, and the mass ratio of the alpha-silicon nitride to the beta-silicon nitride is 1:0.2 to 0.3.
2. The preparation method according to claim 1, wherein the specific method of step (1) is as follows: and placing the silicon nanowire into a vacuum tube furnace, replacing air in the vacuum tube furnace with nitrogen, heating to 1180-1200 ℃, and preserving heat for 4-5 hours to perform gas phase permeation reaction to obtain the modified silicon nanowire.
3. The method according to claim 1, wherein in the step (2), the ball milling process conditions are as follows: the mass ratio of the ball material is 20:1, the diameter of the grinding ball is 12mm, and the ball milling time is 30-35 hours.
4. The method according to claim 1, wherein in the step (2), cold isostatic pressing is used, and the pressure is 300 to 350MPa;
sintering by spark plasma, nitrogen atmosphere, temperature 1700-1800 ℃ and time 15-20 minutes.
5. The method of claim 1, wherein in step (2), the lutetium yttrium fluoride is prepared by the following method: firstly, crushing the waste material of the lutetium yttrium silicate scintillation crystal into powder with the grain diameter of 100-150 mu m, washing for 2-3 times, vacuum drying at the temperature of 700-800 ℃ for 20-22 hours, transferring into a reaction furnace, and introducing the volume ratio of 1: 7-9, reacting for 17-18 hours at 700-800 ℃, and naturally cooling to room temperature under the protection of argon to obtain the catalyst; wherein, the ratio of the hydrogen fluoride to the lutetium yttrium silicate scintillation crystal waste material in the mixed gas is 1mL: 6-8 g, and the partial pressure of hydrogen fluoride in the reaction furnace is 5-7 kPa.
6. The method of claim 1, wherein in step (3), decoupled plasma nitridation is used under the following process conditions: the radio frequency power is 2500-2700W, the nitrogen flow is 200-220 mL/min, and the treatment time is 50-60 s.
7. The method according to claim 1, wherein in the step (3), the annealing treatment is performed under the following process conditions: the nitrogen flow is 20-25 mL/min, the temperature is 800-900 ℃ and the time is 20-25 s.
8. A modified silicon nitride composite material characterized by being obtained by the production method according to any one of claims 1 to 7.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070013451A (en) * | 2005-07-26 | 2007-01-31 | 주식회사 한국반도체소재 | Method for fabrication of silicon-based ceramic nanowires using thermal reaction of silica powders |
| CN101224876A (en) * | 2008-01-28 | 2008-07-23 | 哈尔滨工业大学 | Method for preparing silicon nitride nano-wire and nano-strip |
| EP3412641A1 (en) * | 2017-06-05 | 2018-12-12 | Tallinn University of Technology | Fibrous networks of si3n4 with complex geometry and manufacturing thereof |
| CN110105082A (en) * | 2019-05-09 | 2019-08-09 | 西安航空学院 | A kind of preparation method of fiber reinforced porous silicon nitride ceramic |
| CN111146416A (en) * | 2019-12-19 | 2020-05-12 | 安普瑞斯（南京）有限公司 | Nitrogen-doped silicon-based material, preparation method thereof and application thereof in battery |
| CN112744854A (en) * | 2020-12-25 | 2021-05-04 | 中国科学院江西稀土研究院 | Rare earth fluoride and preparation method and application thereof |
| CN113307631A (en) * | 2021-05-13 | 2021-08-27 | 广东工业大学 | Method for preparing silicon nitride ceramic with high comprehensive performance through pressureless sintering |
| WO2022100249A1 (en) * | 2020-11-12 | 2022-05-19 | 广东工业大学 | Slurry and preparation method for high-performance aluminum nitride ceramic substrate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6806228B2 (en) * | 2000-06-29 | 2004-10-19 | University Of Louisville | Low temperature synthesis of semiconductor fibers |
| JP3698143B2 (en) * | 2003-01-21 | 2005-09-21 | 住友電気工業株式会社 | Porous Si3N4 for filter and manufacturing method thereof |
| CN110606747B (en) * | 2019-10-16 | 2021-09-07 | 西北工业大学 | Preparation method of isotropic ceramic nanowire preform |
-
2023
- 2023-07-10 CN CN202310838887.0A patent/CN116768635B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070013451A (en) * | 2005-07-26 | 2007-01-31 | 주식회사 한국반도체소재 | Method for fabrication of silicon-based ceramic nanowires using thermal reaction of silica powders |
| CN101224876A (en) * | 2008-01-28 | 2008-07-23 | 哈尔滨工业大学 | Method for preparing silicon nitride nano-wire and nano-strip |
| EP3412641A1 (en) * | 2017-06-05 | 2018-12-12 | Tallinn University of Technology | Fibrous networks of si3n4 with complex geometry and manufacturing thereof |
| CN110105082A (en) * | 2019-05-09 | 2019-08-09 | 西安航空学院 | A kind of preparation method of fiber reinforced porous silicon nitride ceramic |
| CN111146416A (en) * | 2019-12-19 | 2020-05-12 | 安普瑞斯（南京）有限公司 | Nitrogen-doped silicon-based material, preparation method thereof and application thereof in battery |
| WO2022100249A1 (en) * | 2020-11-12 | 2022-05-19 | 广东工业大学 | Slurry and preparation method for high-performance aluminum nitride ceramic substrate |
| CN112744854A (en) * | 2020-12-25 | 2021-05-04 | 中国科学院江西稀土研究院 | Rare earth fluoride and preparation method and application thereof |
| CN113307631A (en) * | 2021-05-13 | 2021-08-27 | 广东工业大学 | Method for preparing silicon nitride ceramic with high comprehensive performance through pressureless sintering |
Non-Patent Citations (1)
| Title |
|---|
| 硅纳米线的制备与生长机理;裴立宅, 唐元洪;材料科学与工程学报(第06期);第140-146页 * |
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