CN117107397A - Preparation method of photo-curable rare earth doped type low-oxygen silicon carbide fiber - Google Patents
Preparation method of photo-curable rare earth doped type low-oxygen silicon carbide fiber Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 90
- 239000000835 fiber Substances 0.000 title claims abstract description 64
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 61
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 61
- 239000001301 oxygen Substances 0.000 title claims abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
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- 238000000034 method Methods 0.000 claims abstract description 24
- 238000002844 melting Methods 0.000 claims abstract description 21
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- 230000008018 melting Effects 0.000 claims abstract description 20
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 claims abstract description 15
- 238000002074 melt spinning Methods 0.000 claims abstract description 11
- 238000005336 cracking Methods 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
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- 125000001033 ether group Chemical group 0.000 claims description 5
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- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 claims description 3
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 claims description 3
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
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- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- ZCPSWAFANXCCOT-UHFFFAOYSA-N trichloromethanesulfonyl chloride Chemical compound ClC(Cl)(Cl)S(Cl)(=O)=O ZCPSWAFANXCCOT-UHFFFAOYSA-N 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000013078 crystal Substances 0.000 abstract description 9
- 239000000919 ceramic Substances 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 6
- 238000000016 photochemical curing Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
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- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 description 2
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- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
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Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Ceramic Products (AREA)
Abstract
The invention discloses a preparation method of a photo-curable rare earth doped type low-oxygen silicon carbide fiber, which comprises the following steps: preparing liquid sol A from rare earth metal organic complex and polydimethylsilane, evaporating solvent from the sol A, performing high-temperature cracking reaction to obtain a required polycarbosilane precursor B containing rare earth metal elements, performing blending reaction with unsaturated organic ether to obtain modified polycarbosilane, performing melt spinning on the modified polycarbosilane, performing non-melting treatment under the action of a photoinitiator by ultraviolet irradiation, and performing high-temperature sintering treatment to obtain the rare earth doped type silicon carbide fiber. The method introduces rare earth elements in the preparation of the precursor, uniformly disperses the rare earth elements in silicon carbide crystal lattices, and combines photocuring to perform infusible crosslinking treatment on silicon carbide precursor, thereby reducing SiC f The oxygen content can improve the crystal growth and electromagnetic property of the ceramic.
Description
Technical Field
The invention relates to the technical field of silicon carbide fibers, in particular to a preparation method of a photo-curable rare earth element doped type low-oxygen silicon carbide fiber.
Background
Silicon carbide ceramic fiber (SiC) f ) Is an advanced structural material with carbon and silicon as main components, which is superior in mechanical properties and stability, such as: high strength, high modulus, excellent oxidation resistance, corrosion resistance and the like, and becomes a key strategic material of the ultra-high temperature structural component in the high-end application fields of aerospace, aviation, military industry, nuclear energy and the like. In the developed silicon carbide fiber preparation process, the precursor preparation method is the current industrialized production of small-diameter SiC f The most common and mature method for preparing the process kitIncluding precursor preparation, melt spinning, non-melting crosslinking treatment and high-temperature sintering. However, in the precursor preparation method, if an economic air crosslinking method is adopted in the non-melting treatment process, a large amount of oxygen elements are easily introduced. SiC (SiC) f A large amount of oxygen exists in an amorphous state of SiCxOy, and is extremely easy to thermally decompose at high temperature, so that SiC f The performance drops drastically at high temperatures. Improving the fiber non-melting process and reducing SiC f Oxygen content in (C) to increase SiC f The high temperature performance is of great significance.
The rare earth elements are rich in variety, have unique physical and chemical properties in terms of electronic structure, light, electricity, magnetism, thermodynamics and the like, and are dopants commonly used in the development of various functional materials. In the preparation process of SiC ceramics, rare earth oxide is often used as a sintering aid and directly added into raw materials to improve the sintering resistance and compactness of the ceramics. However, the physical addition is difficult to ensure the uniform dispersion of the additive, the electromagnetic property modification effect on the ceramic is small, and the chemical method can be used for doping and uniformly dispersing rare earth elements in crystal lattices, but the research on preparing rare earth modified silicon carbide fibers by using the chemical doping method is still relatively lacking at present; next, the metal-doped SiC prepared by the chemical method reported heretofore f The crosslinking process of (a) is either difficult to control the oxygen content or depends on equipment and instrumentation, and thus a more simple, inexpensive, efficient process is desired to develop.
Disclosure of Invention
The invention aims to provide a preparation method of a photo-curable rare earth doped type low-oxygen silicon carbide fiber, which introduces rare earth elements into a precursor to uniformly disperse the rare earth elements in silicon carbide crystal lattices, adopts low-cost and high-efficiency photo-curing to carry out non-melting crosslinking treatment on silicon carbide precursor, and reduces SiC f The oxygen content can improve the crystal growth and electromagnetic property of the ceramic.
In order to achieve the above purpose, the technical scheme of the invention is as follows: a preparation method of a photo-curable rare earth doped type low-oxygen silicon carbide fiber comprises the following steps:
step one, rare earth doped PCS preparation:
adding rare earth metal organic complex and polydimethylsilane with the mass ratio of 1:30-200 into an organic solvent, and carrying out a mixing reaction for 2-5 h at 50 ℃ under a protective atmosphere to obtain sol A with uniformly dispersed rare earth metal doping elements; heating the sol A at 70-90 ℃ to volatilize an organic solvent, and then carrying out high-temperature cracking recombination reaction at 300-500 ℃ in a high-purity nitrogen atmosphere to obtain a polycarbosilane precursor B containing rare earth metal elements;
step two, unsaturated ether group modification:
dissolving the polycarbosilane precursor B obtained in the first step in an anhydrous organic solvent, adding a certain amount of organic sulfonyl chloride for chlorination treatment under the condition of ice water bath, stirring for 5-20 minutes, adding unsaturated organic ether and triethylamine, continuously stirring for 20-40 minutes, removing ammonium salt and redundant raw materials through high-speed centrifugation and acetonitrile extraction after the reaction is finished, then removing redundant anhydrous organic solvent through reduced pressure distillation, and finally drying in vacuum to obtain modified polycarbosilane;
step three, preparing silicon carbide fibers:
putting the modified polycarbosilane obtained in the second step into a melt spinning device, carrying out melting and defoaming treatment at 200-400 ℃ under high-purity nitrogen atmosphere, spinning at a speed of 50-200 m/min under a pressure of 0.2-0.6 MPa to obtain a precursor, immersing the precursor into a methanol solution containing a photoinitiator, taking out and drying, and carrying out non-melting treatment for 0.5-5 h under the irradiation of nitrogen, argon or a mixed gas thereof at 100-200 ℃ under the irradiation of ultraviolet irradiation intensity of 2-15 mW/cm < 2 >, thereby obtaining non-melting fibers; and then placing the unmelted fiber into a mixed gas of nitrogen, nitrogen and 1% hydrogen, and sintering at a high temperature of 1200-1500 ℃ for 1-6 hours, and obtaining the rare earth doped type low-oxygen silicon carbide fiber after the reaction is finished.
Further, in the first step, the mass ratio of the rare earth metal organic complex to the polydimethylsilane is 1: 50-150.
Further, in the first step, the mass ratio of the rare earth metal organic complex to the organic solvent is 1: 100-1000.
In the first step, the protective atmosphere is one of high-purity argon and nitrogen; the rare earth metal organic complex comprises rare earth acetylacetonate compound, rare earth oxalic acid compound and rare earth cyclopentadienyl compound; the organic solvent is any one of benzene, dimethylbenzene, dimethyl sulfoxide, N-dimethylformamide, dichloromethane, normal hexane and the like.
Further, the rare earth metal organic compound is rare earth acetylacetonate, and the metals mainly comprise yttrium, lanthanum, praseodymium, samarium, europium, erbium, ytterbium, cerium and the like.
Further, the organic solvent is any one of dimethylbenzene and N, N-dimethylformamide.
Further, in the second step, the input mass ratio of the polycarbosilane precursor B to the organic sulfonyl chloride is 1:0.1 to 0.5, wherein the mol ratio of the unsaturated organic sulfonyl chloride to the triethylamine is 1:1 to 5.
Further, the input mass ratio of the polycarbosilane precursor B to the organic sulfonyl chloride is 1:0.2 to 0.4; the molar ratio of the unsaturated organic sulfonyl chloride to the triethylamine is 1:2 to 3.
Further, the input mass ratio of the polycarbosilane precursor B to the organic sulfonyl chloride is 1:0.3 to 0.4.
Further, in the second step, the anhydrous organic solvent includes n-hexane, n-heptane, n-octane, etc.; the organic sulfonyl chloride comprises sulfoxide chloride, methylsulfonyl chloride, trichloromethane sulfonyl chloride, toluene sulfonyl chloride and the like; the unsaturated organic ether includes ethylene glycol vinyl ether, diethylene glycol vinyl ether, ethylene glycol monoallyl ether, 4-hydroxybutyl vinyl ether, and the like.
Further, in the third step, the photoinitiator is dissolved in a methanol solution, and the concentration of the photoinitiator is 0.5 to 2.5%.
Further, in the third step, the photoinitiator is one or two of benzophenone, 1-hydroxy-cycloethyl phenyl ketone, dibenzoyl and benzil derivatives I-651.
After the scheme is adopted, the gain effect of the invention is as follows:
according to the invention, the rare earth metal organic complex and the polydimethylsilane are blended to form the liquid sol A, the sol A is subjected to solvent evaporation and high-temperature reaction to obtain the rare earth element doped polycarbosilane precursor B, and the rare earth elements are uniformly dispersed in the sol, so that the rare earth elements are uniformly doped in silicon carbide crystal lattices, the doping content of the rare earth elements is adjusted by controlling the use amount of the rare earth metal organic complex, and the chemically doped rare earth elements can prevent the migration of reactive ions and reduce the migration rate of crystals, so that the effect of regulating the growth of the silicon carbide crystal lattices is achieved. Meanwhile, rare earth doped elements can exist in the form of oxide at high temperature, and sintering of SiC is realized at a lower temperature by playing the role of a sintering aid, so that SiC is improved f The sintering compactness, the high-temperature stability performance of the rare earth element is enhanced, and the unique electronic characteristics of the rare earth element can also change SiC f The dielectric property of the fiber is SiC f Provides the possibility of electromagnetic application, expands SiC f Is used in the application range of (a).
Compared with the prior art, the invention does not need expensive special equipment, has simple equipment, is convenient and easy to control, is suitable for industrial production, can effectively reduce cost and avoid the rise of oxygen content, and prepares the high-performance rare earth modified silicon carbide fiber.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The invention provides a preparation method of a photo-curable rare earth doped type low-oxygen silicon carbide fiber, which comprises the following steps:
step one, rare earth doped PCS preparation:
under the protection of high-purity argon or nitrogen, the rare earth metal organic complex and polydimethylsilane are mixed according to the mass ratio of 1: adding 30-200 into an organic solvent, and carrying out a mixing reaction for 2-5 hours at 50 ℃ to obtain sol A with uniformly dispersed rare earth metal doping elements; wherein, the mass ratio of the rare earth metal organic complex to the solvent is 1: 100-1000, wherein the rare earth metal organic complex comprises rare earth acetylacetonate compound, rare earth oxalic acid compound and rare earth cyclopentadienyl compound, the embodiment is preferably rare earth acetylacetonate compound, and the metals mainly comprise yttrium, lanthanum, praseodymium, samarium, europium, erbium, ytterbium, cerium and the like; the organic solvent is benzene, dimethylbenzene, dimethyl sulfoxide, N-dimethylformamide, dichloromethane, N-hexane and the like, and the preferred solvent in the embodiment is one of dimethylbenzene and N, N-dimethylformamide; the preferred mass ratio of rare earth metal organic complex to polydimethylsilane in this example is 1: 50-150;
heating the sol A containing rare earth metal elements at 70-90 ℃ to volatilize the solvent, wherein the heating temperature is preferably 80 ℃; then carrying out high-temperature cracking recombination reaction at 300-500 ℃ in high-purity nitrogen atmosphere to obtain the polycarbosilane precursor B containing rare earth metal elements.
Step two, unsaturated ether group modification:
dissolving the polycarbosilane precursor B containing the rare earth metal element obtained in the first step in an anhydrous organic solvent, adding a certain amount of organic sulfonyl chloride for chloridizing treatment under the condition of ice water bath, stirring for 5-20 minutes, adding unsaturated organic ether and triethylamine, continuously stirring for 20-40 minutes, removing ammonium salt and redundant raw materials through high-speed centrifugation and acetonitrile extraction after the reaction is finished, removing the redundant solvent through reduced pressure distillation, and finally carrying out vacuum drying to obtain modified polycarbosilane (the part which is not illustrated in the first step can be carried out according to the prior method, and the synthesis is referred to as Ceramics International,2020, 46, 28300-28307; the patent publication number is CN 110204730A); wherein the organic sulfonyl chloride comprises thionyl chloride, methylsulfonyl chloride, trichloromethane sulfonyl chloride, toluenesulfonyl chloride and the like, and the input mass ratio of the polycarbosilane precursor B to the organic sulfonyl chloride is 1:0.1 to 0.5; the unsaturated organic ether comprises ethylene glycol vinyl ether, diethylene glycol vinyl ether, ethylene glycol monoallyl ether, 4-hydroxybutyl vinyl ether and the like, and the input mass ratio of the polycarbosilane precursor B to the unsaturated organic ether is 1:0.2 to 0.5; the anhydrous organic solvent comprises n-hexane, n-heptane, n-octane and the like, and the molar ratio of the unsaturated organic sulfonyl chloride to the triethylamine is 1:1 to 5; in this embodiment, the mass ratio of the polycarbosilane precursor B to the organic sulfonyl chloride is preferably 1:0.2 to 0.4; in this embodiment, the ratio of the polycarbosilane precursor B to the unsaturated organic ether is preferably 1:0.3 to 0.4; in this embodiment, the molar ratio of the unsaturated organic sulfonyl chloride to the triethylamine is preferably 1:2 to 3.
Step three, preparing silicon carbide fibers:
putting the modified polycarbosilane obtained in the second step into a melt spinning device, carrying out melting and defoaming treatment at 200-400 ℃ under the protection of high-purity nitrogen, spinning at the speed of 50-200 m/min under the pressure of 0.2-0.6 MPa to obtain a precursor, immersing the precursor into methanol solution dissolved with a photoinitiator, wherein the concentration of the contained photoinitiator is 0.5-2.5%, taking out, drying, and carrying out non-melting treatment for 0.5-5 h under the irradiation of nitrogen, argon or a mixed gas thereof at the temperature of 100-200 ℃ and the ultraviolet irradiation intensity of 2-15 mW/cm < 2 >, thereby obtaining non-melting fibers; and then placing the unmelted fiber in a protective atmosphere of nitrogen, nitrogen and 1% hydrogen mixed gas, and performing high-temperature sintering treatment for 1-6 h in a high-temperature furnace at 1200-1500 ℃ to obtain the rare earth doped type low-oxygen silicon carbide fiber after the reaction is finished.
Wherein the photoinitiator is one or two of benzophenone, 1-hydroxy-cycloethyl phenyl ketone, dibenzoyl and benzil derivatives I-651.
The invention provides a preparation method of rare earth doped type low-oxygen silicon carbide fiber, which is characterized in that a liquid sol A is formed by blending rare earth metal organic complex and polydimethylsilane, the sol A is subjected to solvent evaporation and high-temperature reaction to obtain a rare earth doped polycarbosilane precursor B, the precursor B and unsaturated organic ether are subjected to chlorination treatment, cross-linkable unsaturated ether groups are introduced into the branched chains of the precursor, and are subjected to non-melting treatment under the action of a photoinitiator after melt spinning.
Example 1
40g of yttrium acetylacetonate and 4kg of polydimethylsilane are dissolved in 25L of N, N-dimethylformamide solution, and are heated and mixed for 3 hours at 50 ℃ under the nitrogen atmosphere to obtain sol with uniformly dispersed rare earth metal doping elements, then the sol is heated at 80 ℃ to volatilize the solvent, dried and then placed in a reaction furnace, and high-temperature pyrolysis and recombination reactions are carried out at 350 ℃ under the high-purity nitrogen atmosphere to obtain the yttrium-doped polycarbosilane precursor.
2kg of prepared yttrium-containing doped polycarbosilane is dissolved in 15L of normal hexane solution, 400g of thionyl chloride is added under the condition of ice water bath for chlorination treatment, 600g of ethylene glycol vinyl ether and 800g of triethylamine are added after stirring reaction is carried out for 10 minutes, stirring reaction is carried out for 30 minutes, ammonium salt and redundant raw materials are removed through high-speed centrifugation and acetonitrile extraction after reaction is finished, redundant normal hexane is removed through reduced pressure distillation, and finally modified polycarbosilane is obtained through vacuum drying.
1kg of modified polycarbosilane is placed in a melt spinning device under the protection of high-purity nitrogen, is subjected to melting and defoaming treatment at 350 ℃, is spun at a speed of 100m/min under a pressure of 0.5MPa to obtain a precursor, the precursor is immersed in a methanol solution containing 1% of benzophenone and benzil derivative I-651, taken out and dried, and then is subjected to 10mW/cm in a nitrogen atmosphere 2 And (3) carrying out infusibility treatment for 2 hours at 200 ℃ under ultraviolet irradiation to obtain infusible fibers, carrying out cracking reaction on the infusible fibers in a mixed gas of nitrogen and 1% hydrogen in a high-temperature furnace at 1300 ℃ for 3 hours, and obtaining the yttrium doped type low-oxygen silicon carbide fibers after the reaction is finished. The fiber has the doped yttrium content of 1 percent, the oxygen content of 1.5 percent, the strength of 2.8GPa at normal temperature, the elastic modulus of 260GPa and the volume resistivity of about 3.6KΩ/cm.
Example 2
60g of yttrium acetylacetonate and 4.8kg of polydimethylsilane are dissolved in 30L of xylene solution, and the mixture is heated and mixed for 3 hours at 50 ℃ under the nitrogen atmosphere to obtain sol with uniformly dispersed rare earth metal doping elements. And then heating the sol at 80 ℃ to volatilize the solvent, drying, and then placing the sol in a reaction furnace, and carrying out high-temperature pyrolysis and recombination reaction at 450 ℃ in a high-purity nitrogen atmosphere to obtain the yttrium-doped polycarbosilane precursor.
2kg of prepared yttrium-containing doped polycarbosilane is dissolved in 20L of normal hexane solution, 800g of tosyl chloride is added for chlorination treatment under the ice water bath condition, 600g of ethylene glycol vinyl ether and 800g of triethylamine are added after stirring reaction is carried out for 10 minutes, stirring reaction is carried out for 30 minutes, ammonium salt and redundant raw materials are removed through high-speed centrifugation and acetonitrile extraction after the reaction is finished, redundant normal hexane is removed through reduced pressure distillation, and finally modified polycarbosilane is obtained through vacuum drying.
1kg of modified polycarbosilane is placed in a melt spinning device under the protection of high-purity nitrogen, is subjected to melting and defoaming treatment at 350 ℃, is spun at a speed of 100m/min under a pressure of 0.5MPa to obtain a precursor, the precursor is immersed in a methanol solution containing 2%1-hydroxycycloethyl phenyl ketone, and is taken out and dried, and then is subjected to nitrogen atmosphere of 10mW/cm 2 And (3) carrying out infusibility treatment for 2 hours at 200 ℃ under ultraviolet irradiation to obtain infusible fibers, carrying out cracking reaction on the infusible fibers in a mixed gas of nitrogen and 1% hydrogen in a 1300 ℃ high-temperature furnace for 3 hours, and obtaining the yttrium doped type low-oxygen silicon carbide fibers after the reaction is finished. The fiber has the doped yttrium content of 1.4%, the oxygen content of 1.8%, the strength of 2.5GPa at normal temperature, the elastic modulus of 245GPa and the volume resistivity of about 2.9KΩ/cm.
Example 3
60g of cerium acetylacetonate and 6kg of polydimethylsilane are dissolved in 30L of xylene solution, and the mixture is heated and mixed for 3 hours at 50 ℃ under the nitrogen atmosphere to obtain sol with uniformly dispersed rare earth metal doping elements. And then heating the sol at 80 ℃ to volatilize the solvent, drying, and then placing the sol in a reaction furnace, and carrying out high-temperature pyrolysis and recombination reaction at 450 ℃ in a high-purity nitrogen atmosphere to obtain the cerium-containing doped polycarbosilane precursor.
Dissolving 2kg of prepared cerium-containing doped polycarbosilane in 20L of n-octane solution, adding 400g of thionyl chloride for chlorination treatment under the condition of ice water bath, stirring for reaction for 10 minutes, adding 700g of 4-hydroxybutyl vinyl ether and 1.4kg of triethylamine, stirring for reaction for 30 minutes, removing ammonium salt and redundant raw materials through high-speed centrifugation and acetonitrile extraction after the reaction is finished, removing redundant n-hexane through reduced pressure distillation, and finally carrying out vacuum drying to obtain the modified polycarbosilane.
1kg of modified polycarbosilane is placed in a melt spinning device under the protection of high-purity nitrogen, is subjected to melting and defoaming treatment at 350 ℃, is spun at a speed of 150m/min under a pressure of 0.5MPa to obtain a precursor, the precursor is immersed in a methanol solution containing 2%1-hydroxycycloethyl phenyl ketone, taken out and dried, and is subjected to nitrogen atmosphere at 15mW/cm 2 And (3) carrying out infusibility treatment for 1h at 200 ℃ under ultraviolet irradiation to obtain infusible fibers, carrying out cracking reaction on the infusible fibers in a high-temperature furnace at 1350 ℃ in a mixed gas of nitrogen and 1% hydrogen, and obtaining the cerium doped type low-oxygen silicon carbide fibers after the reaction is finished for 5 h. The fiber has the doped yttrium content of 1.42%, the oxygen content of 1.3%, the strength of 2.6GPa at normal temperature, the elastic modulus of 270GPa and the volume resistivity of about 3.3KΩ/cm.
Example 4
45g of cerium acetylacetonate and 6kg of polydimethylsilane are dissolved in 30L of xylene solution, and the mixture is heated and mixed for 3 hours at 50 ℃ in a nitrogen atmosphere to obtain sol with uniformly dispersed rare earth metal doping elements. And then heating the sol at 80 ℃ to volatilize the solvent, drying, and then placing the sol in a reaction furnace, and carrying out high-temperature pyrolysis and recombination reaction at 450 ℃ in a high-purity nitrogen atmosphere to obtain the cerium-containing doped polycarbosilane precursor.
Dissolving 2kg of prepared cerium-containing doped polycarbosilane in 20L of n-octane solution, adding 400g of thionyl chloride for chlorination treatment under the condition of ice water bath, stirring for reaction for 10 minutes, adding 700g of 4-hydroxybutyl vinyl ether and 1.4kg of triethylamine, stirring for reaction for 30 minutes, removing ammonium salt and redundant raw materials through high-speed centrifugation and acetonitrile extraction after the reaction is finished, removing redundant n-hexane through reduced pressure distillation, and finally carrying out vacuum drying to obtain the modified polycarbosilane.
1kg of modified polycarbosilane is placed in a melt spinning device under the protection of high-purity nitrogen, and is melted and defoamed at 350 DEG CAfter that, spinning at a speed of 150m/min under a pressure of 0.5MPa to obtain a precursor, immersing the precursor in a methanol solution containing 2%1-hydroxycycloethyl phenyl ketone, taking out, drying, and then placing in a nitrogen atmosphere at a speed of 15mW/cm 2 And (3) carrying out infusibility treatment for 1h at 200 ℃ under ultraviolet irradiation to obtain infusible fibers, carrying out cracking reaction on the infusible fibers in a high-temperature furnace at 1350 ℃ in a mixed gas of nitrogen and 1% hydrogen, and obtaining the cerium doped type low-oxygen silicon carbide fibers after the reaction is finished for 5 h. The fiber has the doped yttrium content of 1.0%, the oxygen content of 1.1%, the strength of 2.7GPa at normal temperature, the elastic modulus of 280GPa and the volume resistivity of about 3.2KΩ/cm.
Comparative example 1
27g of titanium acetylacetonate and 6kg of polydimethylsilane are dissolved in 30L of dimethylbenzene solution, and are heated and mixed for reaction for 3 hours at 50 ℃ under nitrogen atmosphere to obtain sol with uniformly dispersed titanium doping elements, then the solution sol is heated at 80 ℃ to volatilize solvent, dried and then placed in a reaction furnace, and high-temperature cracking and recombination reactions are carried out at 450 ℃ under high-purity nitrogen atmosphere to obtain the titanium-containing doped polycarbosilane precursor.
2kg of the prepared titanium-containing doped polycarbosilane is dissolved in 20L of n-octane solution, 400g of thionyl chloride is added under the condition of ice water bath for chlorination treatment, 700g of 4-hydroxybutyl vinyl ether and 1.4kg of triethylamine are added after stirring reaction is carried out for 10 minutes, stirring reaction is carried out for 30 minutes, ammonium salt and redundant raw materials are removed through high-speed centrifugation and acetonitrile extraction after reaction is finished, redundant n-octane is removed through reduced pressure distillation, and finally modified polycarbosilane is obtained through vacuum drying.
1kg of modified polycarbosilane is placed in a melt spinning device under the protection of high-purity nitrogen, is subjected to melting and defoaming treatment at 350 ℃, is spun at a speed of 150m/min under a pressure of 0.5MPa to obtain a precursor, the precursor is immersed in a methanol solution containing 2%1-hydroxycycloethyl phenyl ketone, taken out and dried, and is subjected to nitrogen atmosphere at 15mW/cm 2 Non-melting treatment is carried out for 1h at 200 ℃ under the irradiation of ultraviolet light to obtain non-melting fiber, the non-melting fiber is subjected to cracking reaction in a high-temperature furnace at 1350 ℃ in a mixed gas of nitrogen and 1% hydrogen, the reaction time is 5h, and the reaction is finishedThus obtaining the titanium doped silicon carbide fiber. The doped titanium content in the fiber is 1.1%, the oxygen content is 2.1%, the strength at normal temperature is 2.3GPa, the elastic modulus is 250GPa, and the volume resistivity is about 3.8KΩ/cm.
The doped silicon carbide fibers prepared in examples 1 to 4 of the present invention and comparative example 1 were subjected to performance test, and the test results are shown in table 1.
Table 1 shows the performance parameters of the doped silicon carbide fibers of examples 1-4 and comparative example 1
From the data in the table, the molecular-grade introduction of rare earth metal in polycarbosilane is realized through the blending reaction of rare earth complex and polydimethylsilane, so that the rare earth element is uniformly distributed in silicon carbide fiber, the content is controllable, and the cross-linkable high-activity unsaturated ether group is introduced into the branched chain of the rare earth-containing polycarbosilane, so that the low-temperature photo-curing of the silicon carbide precursor is realized, the oxygen content in the fiber is controlled below 2%, and the crystal growth of the silicon carbide fiber can be effectively regulated and controlled by rich rare earth doping elements, so that the photoelectric and mechanical properties are improved. The photocuring crosslinking treatment measures can avoid the problems of the rise of oxygen content and high cost caused by high-energy electrons or ray radiation in the air heat treatment and curing process of the traditional metal doped precursor.
In addition, the high-temperature pyrolysis process of the precursor promotes the reduction and decomposition of the introduced organic components through 1% of hydrogen, and further controls the carbon and oxygen content in the product. The method is simple to operate, has low equipment requirement, and is suitable for industrial continuous production of continuous silicon carbide fibers with low oxygen content and high performance.
The above embodiments are only preferred embodiments of the present invention, and are not limited to the present invention, and all equivalent changes made according to the design key of the present invention fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a photo-curable rare earth doped type low-oxygen silicon carbide fiber is characterized by comprising the following steps of: the method comprises the following steps:
step one, rare earth doped PCS preparation:
adding rare earth metal organic complex and polydimethylsilane with the mass ratio of 1:30-200 into an organic solvent, and carrying out a mixing reaction for 2-5 h at 50 ℃ under a protective atmosphere to obtain sol A with uniformly dispersed rare earth metal doping elements; heating the sol A at 70-90 ℃ to volatilize an organic solvent, and then carrying out high-temperature cracking recombination reaction at 300-500 ℃ in a high-purity nitrogen atmosphere to obtain a polycarbosilane precursor B containing rare earth metal elements;
step two, unsaturated ether group modification:
dissolving the polycarbosilane precursor B obtained in the first step in an anhydrous organic solvent, adding a certain amount of organic sulfonyl chloride for chlorination treatment under the condition of ice water bath, stirring for 5-20 minutes, adding unsaturated organic ether and triethylamine, continuously stirring for 20-40 minutes, removing ammonium salt and redundant raw materials through high-speed centrifugation and acetonitrile extraction after the reaction is finished, then removing redundant anhydrous organic solvent through reduced pressure distillation, and finally drying in vacuum to obtain modified polycarbosilane;
step three, preparing silicon carbide fibers:
putting the modified polycarbosilane obtained in the second step into a melt spinning device, carrying out melting and defoaming treatment at 200-400 ℃ under high-purity nitrogen atmosphere, spinning at a speed of 50-200 m/min under a pressure of 0.2-0.6 MPa to obtain a precursor, immersing the precursor into a methanol solution containing a photoinitiator, taking out and drying, and carrying out non-melting treatment for 0.5-5 h under the irradiation of nitrogen, argon or a mixed gas thereof at 100-200 ℃ under the irradiation of ultraviolet irradiation intensity of 2-15 mW/cm < 2 >, thereby obtaining non-melting fibers; and then placing the unmelted fiber into a mixed gas of nitrogen, nitrogen and 1% hydrogen, and sintering at a high temperature of 1200-1500 ℃ for 1-6 hours, and obtaining the rare earth doped type low-oxygen silicon carbide fiber after the reaction is finished.
2. The method for preparing the photo-curable rare earth doped type low-oxygen silicon carbide fiber according to claim 1, which is characterized in that: in the first step, the mass ratio of the rare earth metal organic complex to the polydimethylsilane is 1: 50-150.
3. The method for preparing the photo-curable rare earth doped type low-oxygen silicon carbide fiber according to claim 1, which is characterized in that: in the first step, the mass ratio of the rare earth metal organic complex to the organic solvent is 1: 100-1000.
4. The method for preparing the photo-curable rare earth doped type low-oxygen silicon carbide fiber according to claim 1, which is characterized in that: in the first step, the protective atmosphere is one of high-purity argon and nitrogen; the rare earth metal organic complex comprises rare earth acetylacetonate compound, rare earth oxalic acid compound and rare earth cyclopentadienyl compound; the organic solvent is any one of benzene, dimethylbenzene, dimethyl sulfoxide, N-dimethylformamide, dichloromethane and N-hexane.
5. The method for preparing the photo-curable rare earth doped type low-oxygen silicon carbide fiber according to claim 1, which is characterized in that: the rare earth metal organic compound is rare earth acetylacetonate, and the metals mainly comprise yttrium, lanthanum, praseodymium, samarium, europium, erbium, ytterbium and cerium.
6. The method for preparing the photo-curable rare earth doped type low-oxygen silicon carbide fiber according to claim 1, which is characterized in that: the organic solvent is any one of dimethylbenzene and N, N-dimethylformamide.
7. The method for preparing the photo-curable rare earth doped type low-oxygen silicon carbide fiber according to claim 1, which is characterized in that: in the second step, the input mass ratio of the polycarbosilane precursor B to the organic sulfonyl chloride is 1:0.1 to 0.5, wherein the mol ratio of the unsaturated organic sulfonyl chloride to the triethylamine is 1:1 to 5.
8. The method for preparing the photo-curable rare earth doped type low-oxygen silicon carbide fiber according to claim 1, which is characterized in that: the input mass ratio of the polycarbosilane precursor B to the organic sulfonyl chloride is 1:0.2 to 0.4; the molar ratio of the unsaturated organic sulfonyl chloride to the triethylamine is 1:2 to 3.
9. The method for preparing the photo-curable rare earth doped type low-oxygen silicon carbide fiber according to claim 1, which is characterized in that: in the second step, the anhydrous organic solvent comprises n-hexane, n-heptane and n-octane; the organic sulfonyl chloride comprises sulfoxide chloride, methylsulfonyl chloride, trichloromethane sulfonyl chloride and toluene sulfonyl chloride; the unsaturated organic ether comprises ethylene glycol vinyl ether, diethylene glycol vinyl ether, ethylene glycol monoallyl ether and 4-hydroxybutyl vinyl ether.
10. The method for preparing the photo-curable rare earth doped type low-oxygen silicon carbide fiber according to claim 1, which is characterized in that: in the third step, the photoinitiator with the concentration of 0.5-2.5% is dissolved in the methanol solution.
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