CN109761610B - Silicon carbide fiber and preparation method and application thereof - Google Patents
Silicon carbide fiber and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a silicon carbide fiber and a preparation method and application thereof, wherein the method comprises the following steps: al nanoparticle-loaded metal organic framework material NH2Preparation of UIO-66(Hf) doped silicon carbide precursor, loading Al nanoparticle metal organic framework material NH2Melt spinning of UIO-66(Hf) doped silicon carbide fiber precursor, Al nanoparticle-loaded metal organic framework material NH2-sintering of UIO-66(Hf) doped silicon carbide fibres. According to the preparation method of the silicon carbide fiber, hafnium, aluminum and nitrogen elements are introduced into the precursor, and the N element is introduced again in the sintering process, so that the prepared silicon carbide fiber contains the hafnium and the aluminum, and is good in mechanical property and excellent in high-temperature resistance.
Description
Technical Field
The invention belongs to the technical field of material processing and preparation, and particularly relates to silicon carbide fibers and a preparation method and application thereof.
Background
The silicon carbide (SiC) fiber is a ceramic fiber with high strength, high modulus, oxidation resistance, wear resistance, corrosion resistance, small specific gravity and other excellent properties. Extensive research is carried out on the preparation of continuous SiC fibers in sequence in various countries in the world, and the continuous SiC fibers have extremely wide application prospects in high-end fields such as aviation, machinery, chemical engineering, aerospace, weapons and the like. At present, the strength of the SiC fiber can reach 3.0 +/-0.4 GPa, the modulus can reach 200 +/-20 GPa, and the use temperature can reach 1000 ℃. The SiC fiber has certain limitation on application due to low room temperature strength and insufficient toughness, and in order to improve the strength and the toughness of the silicon carbide material, the SiC fiber can be suitable for the strength and the toughness of reinforcing materials of different polymer-based, metal-based and ceramic-based composite materials through different interface treatments.
Currently, there are 4 main methods for preparing continuous SiC fibers: a precursor conversion method (PD), a chemical vapor deposition method (CVD), an activated carbon fiber conversion method, and an ultra-fine powder high-temperature sintering method, wherein only the precursor conversion method (PD) and the chemical vapor deposition method (CVD) are commercially available. The strength and modulus of the obtained fiber are not high by an active carbon fiber conversion method; the fiber prepared by the superfine micro powder sintering method is rich in carbon in a large amount, thick in wire diameter, low in strength and poor in oxidation resistance. The CVD method is prepared by using continuous carbon fibers and methyl silane compounds as raw materials, reacting on the surface of a glowing core wire under nitrogen flow, cracking into SiC, and depositing on the core wire. The continuous SiC fibers prepared by CVD process are relatively thick (>100 μm) in diameter, reinforcing the metal-based material mainly in the form of monofilaments. The PD method is a main method for preparing the fine-diameter continuous SiC fiber at present, and realizes industrial production, and the process route comprises four working procedures of synthesis of a precursor, melt spinning of the precursor, non-melting treatment of soluble and meltable original fiber, high-temperature sintering of the non-melting fiber and the like. The precursor method has the characteristics of thin fiber diameter, capability of preparing different cross-sectional shapes, low cost, great suitability for industrial production and the like, and makes up the defects that a CVD method is not easy to weave and is difficult to manufacture components with complex shapes. However, in the precursor conversion process, a large amount of oxygen is easily introduced if an economical air crosslinking method is adopted in the non-melting treatment process. A large amount of oxygen in the SiC fiber exists in an amorphous state of SiCxOy, and the SiC fiber is easy to thermally decompose at high temperature, so that the performance of the SiC fiber is rapidly reduced at high temperature. The improved fiber infusibility process reduces the oxygen content in the SiC fiber, and has important significance for improving the high-temperature performance of the SiC fiber.
Metal organic framework Materials (MOFs) are coordination polymers which have been developed rapidly in the last decade, have three-dimensional pore structures, generally use metal ions as connection points, and organic ligand sites support to form space 3D extension, and are another important novel porous material besides zeolite and carbon nanotubes, and are widely applied to catalysis, energy storage and separation. The role of metal cations in the framework of MOFs is on the one hand to provide a backbone as a junction and on the other hand to form branches in the backbone, thereby enhancing the physical properties (e.g., porosity and chirality) of the MOFs. The specific surface area of the material is far larger than that of a molecular sieve with similar pore channels, and the material can still maintain the integrity of a framework after solvent molecules in the pore channels are removed. Therefore, MOFs have many potential special properties, show attractive application prospects in the development of novel functional materials such as selective catalysis, molecular recognition, reversible host-guest molecule (ion) exchange, ultrahigh-purity separation, biological conduction materials, photoelectric materials, magnetic materials, chips and other novel materials, and bring new eosin to porous material science.
Although SiC fibers have been widely studied, they are deficient in high temperature properties, thermal stability, weaving properties, and the like, and thus there is a need to develop a material capable of optimizing the above properties.
Disclosure of Invention
One object of the present invention is to provide a method for preparing silicon carbide fiber.
The preparation method of the silicon carbide fiber comprises the following steps: s101: hafnium chloride and 2-amino-1, 2-o-dibenzoic acid are mixed according to a molar ratio of (1-4.5): 8, adding the mixture into an N, N-dimethylformamide solution, ultrasonically stirring, adding the mixture into an autoclave, injecting polydimethylsilane to cover the surface of the hafnium chloride, heating to 110-130 ℃ at a first heating rate, carrying out heat preservation reaction for 44-52 h, cooling to room temperature, carrying out centrifugal separation, washing and drying to obtain NH2-UIO-66(Hf) material; wherein, the proportion of the 2-amino-1, 2-o-dibenzoic acid to the N, N-dimethylformamide solution is 4 mmol: (20 mL-30 mL); the molar ratio of the polydimethylsiloxane to the 2-amino-1, 2-o-dibenzoic acid is 3: (3-5); s102: then adding the metal organic framework material into the solution containing AlCl3·2H2Filling protective gas into dimethyl sulfoxide-ethanol suspension of O under the condition of keeping out of the sun for 0.5 h-1.5 h, then keeping for 1.5 h-2.5 h under the radiation of visible light, then adding the mixture into a reaction kettle for reaction for 15 h-17 h to obtain precipitate, and washing the precipitate with acetone or ethanol to obtain the metal-organic framework material NH loaded with Al nano particles2-UIO-66(Hf) doped silicon carbide precursor; s103: placing the silicon carbide precursor obtained in the step S102 in a melt spinning cylinder, heating to a molten state at a second heating rate in an inert gas atmosphere, pressurizing to 3-5 MPa, and enabling the melt to sequentially flow through a filter screen,The mixed solution flows out of a spinneret plate to obtain the metal organic framework material NH loaded with the Al nano particles2UIO-66(Hf) doped silicon carbide precursor fiber bundles, which are then thermally crosslinked for non-melting treatment; s104: putting the fiber bundle obtained in the step S103 into a sintering furnace, introducing ammonia gas, heating to 450-650 ℃ at a third heating rate, preserving heat for 2-4 h, heating to 880-920 ℃ at the third heating rate, preserving heat for 1.5-2.5 h for pyrolysis, heating to 1200-1600 ℃ at a fourth heating rate in a protective gas atmosphere, preserving heat for 0.5-1 h, and cooling to room temperature to obtain a metal organic framework material NH2UIO-66(Hf) doped silicon carbide fibers.
According to the preparation method of the silicon carbide fiber, hafnium, aluminum and nitrogen elements are introduced into the precursor, and the N element is introduced again in the sintering process, so that the prepared silicon carbide fiber contains the hafnium and the aluminum, and is good in mechanical property and excellent in high-temperature resistance. Particularly, the interface of the silicon carbide fiber is provided with silicon carbonitride nano, the strength of the prepared silicon carbide fiber at normal temperature is 3.6GPa +/-0.3 GPa, and the elastic modulus is 290 +/-30 GPa. After the fiber is treated for 100 hours in an air environment at 1100 ℃, the strength retention rate can still reach over 88 percent, and the fiber has wide practical value and application prospect in the field of high-performance fibers, such as antenna windows and antenna covers of electromagnetic wave transmission materials.
In addition, the method for preparing the silicon carbide fiber of the present invention may further have the following additional technical features:
further, in the step S101, the first temperature increase rate is 8 ℃/min to 12 ℃/min; in the step S103, the second heating rate is 0.3 ℃/min to 0.8 ℃/min; in the step S104, the third temperature rise rate is 100 ℃/h to 200 ℃/h, and the fourth temperature rise rate is 45 ℃/h to 55 ℃/h.
Further, in the step S102, AlCl is contained3·2H2AlCl in dimethyl sulfoxide-ethanol suspension of O3·2H2The ratio of O, dimethyl sulfoxide and ethanol is 5: (1.5-2.5): (2.8-3.2).
Further, in the step S102, the reaction temperature in the reaction kettle is 170 to 190 ℃.
Further, in the step S102, the protective gas is argon, and a flow rate of the argon is 100mL/min to 200 mL/min.
Further, in the step S104, the flow rate of the ammonia gas is 300mL/min to 500 mL/min.
Further, in the step S103, the temperature is 320-360 ℃ and the heat is preserved for 4-6 h when the thermal crosslinking is performed.
Further, in the step S101, absolute methanol is used for washing, the drying temperature is 75 to 85 ℃, and the drying time is 10 to 14 hours.
The invention also aims to provide the silicon carbide fiber prepared by the method.
It is a further object of the present invention to provide the use of the silicon carbide fibers in the aerospace, mechanical, chemical, and weaponry fields.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The UIO series material in the invention is composed of regular octahedral secondary structural unit [ Hf6O4(OH)4]Terephthalic acid (H)2BDC) ligands are connected to obtain three-dimensional cubic crystal structures of octahedral central hole cages and tetrahedral angle cages.
Example 1
Example 1 provides a silicon carbide fiber, the preparation method of which comprises the following steps:
(1) hafnium chloride and 2-amino-1, 2-o-dibenzoic acid are mixed according to a molar ratio of 1: 8 to the N, N-dimethylformamide solution and ultrasonically stirred, then it was added to the autoclave and polydimethylsilane was injected so as to cover the surface of the hafnium chloride, and thenHeating to 110 ℃ at the heating rate of 12 ℃/min, carrying out heat preservation reaction for 52h, then cooling to room temperature, carrying out centrifugal separation, then washing with anhydrous methanol, and then drying at the temperature of 75 ℃ for 14h to obtain NH2-UIO-66(Hf) material; wherein, the proportion of the 2-amino-1, 2-o-dibenzoic acid to the N, N-dimethylformamide solution is 4 mmol: 20 mL; the molar ratio of the polydimethylsiloxane to the 2-amino-1, 2-o-dibenzoic acid is 3: 5.
(2) then adding the metal organic framework material into the solution containing AlCl3·2H2Filling argon with the flow rate of 100mL/min into dimethyl sulfoxide-ethanol suspension of O under the condition of keeping out of the sun for 1.5 hours, then keeping for 1.5 hours under the radiation of visible light, then adding the mixture into a reaction kettle, heating to 190 ℃ and reacting for 15 hours to obtain precipitate, and washing the precipitate with acetone or ethanol to obtain the metal-organic framework material NH loaded with the Al nano particles2UIO-66(Hf) doped silicon carbide precursor. Wherein contains AlCl3·2H2AlCl in dimethyl sulfoxide-ethanol suspension of O3·2H2The ratio of O, dimethyl sulfoxide and ethanol is 5: 2.5: 2.8.
(3) placing the silicon carbide precursor obtained in the step (2) in a melt spinning cylinder, heating to a molten state at a heating rate of 0.8 ℃/min in an inert gas atmosphere, pressurizing to 3MPa, and flowing the melt out after sequentially flowing through a filter screen and a spinneret plate to obtain the Al nanoparticle-loaded metal-organic framework material NH2UIO-66(Hf) doped silicon carbide precursor fiber bundle, which was heated to 360 ℃ and thermally cross-linked for 4h for non-melting treatment.
(4) Putting the fiber bundle obtained in the step (3) into a sintering furnace, then introducing ammonia gas with the flow rate of 500mL/min, heating to 650 ℃ at the heating rate of 100 ℃/h, preserving heat for 2h, heating to 880 ℃ at the heating rate of 200 ℃/h, preserving heat for 2.5h for pyrolysis, heating to 1600 ℃ at the heating rate of 45 ℃/h in a protective gas atmosphere, preserving heat for 0.5h, and cooling to room temperature to obtain the metal organic framework material NH2UIO-66(Hf) doped silicon carbide fibers.
Example 2
Embodiment 2 provides a silicon carbide fiber, and the preparation method thereof comprises the following steps:
(1) hafnium chloride and 2-amino-1, 2-o-dibenzoic acid in a molar ratio of 4.5: adding 8 into N, N-dimethylformamide solution, carrying out ultrasonic stirring, adding into an autoclave, injecting polydimethylsilane to cover the surface of the hafnium chloride, heating to 130 ℃ at the heating rate of 8 ℃/min, carrying out heat preservation reaction for 44 hours, cooling to room temperature, carrying out centrifugal separation, washing with anhydrous methanol, and drying at the temperature of 85 ℃ for 10 hours to obtain NH2-UIO-66(Hf) material; wherein, the proportion of the 2-amino-1, 2-o-dibenzoic acid to the N, N-dimethylformamide solution is 4 mmol: 30 mL; the molar ratio of the polydimethylsiloxane to the 2-amino-1, 2-o-dibenzoic acid is 1: 1.
(2) Then adding the metal organic framework material into the solution containing AlCl3·2H2Filling argon with the flow rate of 200mL/min into dimethyl sulfoxide-ethanol suspension of O under the condition of keeping out of the sun for 0.5h, then keeping for 2.5h under the radiation of visible light, then adding the mixture into a reaction kettle, heating to 170 ℃ and reacting for 17h to obtain precipitate, and washing the precipitate with acetone or ethanol to obtain the metal-organic framework material NH loaded with the Al nano particles2UIO-66(Hf) doped silicon carbide precursor. Wherein contains AlCl3·2H2AlCl in dimethyl sulfoxide-ethanol suspension of O3·2H2The ratio of O, dimethyl sulfoxide and ethanol is 5: 1.5: 3.2.
(3) placing the silicon carbide precursor obtained in the step (2) in a melt spinning cylinder, heating to a molten state at a heating rate of 0.3 ℃/min in an inert gas atmosphere, pressurizing to 5MPa, and flowing the melt out after sequentially flowing through a filter screen and a spinneret plate to obtain the Al nanoparticle-loaded metal-organic framework material NH2UIO-66(Hf) doped silicon carbide precursor fiber bundle, which was heated to 320 ℃ and thermally cross-linked for 6h to perform a non-melting treatment.
(4) Putting the fiber bundle obtained in the step (3) into a sintering furnace, and thenIntroducing ammonia gas with the flow rate of 300mL/min, heating to 450 ℃ at the heating rate of 200 ℃/h, preserving heat for 4h, heating to 920 ℃ at the heating rate of 100 ℃/h, preserving heat for 1.5h for pyrolysis, heating to 1200 ℃ at the heating rate of 55 ℃/h in a protective gas atmosphere, preserving heat for 1h, and cooling to room temperature to obtain the metal organic framework material NH2UIO-66(Hf) doped silicon carbide fibers.
Example 3
Example 3 provides a silicon carbide fiber, the preparation method of which comprises the following steps:
(1) hafnium chloride and 2-amino-1, 2-o-dibenzoic acid in a molar ratio of 2.75: 8, adding the mixture into an N, N-dimethylformamide solution, carrying out ultrasonic stirring, then adding the mixture into an autoclave, injecting polydimethylsilane to cover the surface of the hafnium chloride, heating to 120 ℃ at the heating rate of 10 ℃/min, carrying out heat preservation reaction for 48 hours, cooling to room temperature, carrying out centrifugal separation, washing with anhydrous methanol, and drying at the temperature of 80 ℃ for 12 hours to obtain NH2-UIO-66(Hf) material; wherein, the proportion of the 2-amino-1, 2-o-dibenzoic acid to the N, N-dimethylformamide solution is 4 mmol: 25 mL; the molar ratio of the polydimethylsiloxane to the 2-amino-1, 2-o-dibenzoic acid is 3: 4.
(2) then adding the metal organic framework material into the solution containing AlCl3·2H2Filling argon with the flow rate of 150mL/min into dimethyl sulfoxide-ethanol suspension of O under the condition of keeping out of the sun for 1 hour, then keeping for 2 hours under the radiation of visible light, then adding the mixture into a reaction kettle, heating to 180 ℃ and reacting for 16 hours to obtain precipitate, and then washing the precipitate with acetone or ethanol to obtain the Al nanoparticle-loaded metal-organic framework material NH2UIO-66(Hf) doped silicon carbide precursor. Wherein contains AlCl3·2H2AlCl in dimethyl sulfoxide-ethanol suspension of O3·2H2The ratio of O, dimethyl sulfoxide and ethanol is 5: 2: 3.
(3) placing the silicon carbide precursor obtained in the step (2) in a melt spinning cylinder, and then heating at a speed of 0.5 ℃/min in an inert gas atmosphereHeating to a molten state, pressurizing to 4MPa, and flowing out the melt after sequentially flowing through a filter screen and a spinneret plate to obtain the Al nanoparticle-loaded metal organic framework material NH2UIO-66(Hf) doped silicon carbide precursor fiber bundle, which was heated to 340 ℃ and thermally cross-linked for 5h to perform a non-melting treatment.
(4) Putting the fiber bundle obtained in the step (3) into a sintering furnace, then introducing ammonia gas with the flow rate of 400mL/min, heating to 550 ℃ at the heating rate of 150 ℃/h, preserving heat for 3h, heating to 90 ℃ at the heating rate of 150 ℃/h, preserving heat for 2h for pyrolysis, heating to 1400 ℃ at the heating rate of 50 ℃/h in a protective gas atmosphere, preserving heat for 0.75h, and cooling to room temperature to obtain a metal organic framework material NH2UIO-66(Hf) doped silicon carbide fibers.
Example 4
Example 4 provides a silicon carbide fiber, the preparation method of which comprises the following steps:
the method comprises the following steps: al nanoparticle-loaded metal organic framework material NH2Preparation of UIO-66(Hf) doped silicon carbide fiber precursor
1 wt.% of hafnium chloride (HfCl) is taken41mmol, purity > 99%) and 2-amino-1, 2-o-dibenzoic acid (1.32g, 8.0mmol) are dissolved in 50mL of N, N-Dimethylformamide (DMF) solution, the solution is transferred to a 100mL autoclave after ultrasonic stirring, pure Polydimethylsilane (PCS) is slowly injected into the autoclave to uniformly cover the surface of hafnium chloride, the reaction is carried out at a speed of 10 ℃/min and quickly heated to 120 ℃ for 48 hours, the reaction kettle is cooled to room temperature, centrifugal separation is carried out, the DMF is repeatedly washed by sewage methanol to remove, and vacuum drying is carried out at 80 ℃ for 12 hours to obtain NH2UIO-66(Hf) material. Placing NH2-UIO-66(Hf) in AlCl-containing solution3·2H2And introducing nitrogen for 1h in a dimethyl sulfoxide (DMSO) -ethanol suspension of O in the dark, irradiating for 2h under visible light, and transferring the obtained suspension into a reaction kettle for reacting for 16 h. The resulting precipitate was washed with acetone and ethanol to remove residual DMSO. Obtaining metal organic framework material NH loaded with Al nano particles2-UIO-66(Hf) doped silicon carbide precursor fines.
Step two: al nanoparticle-loaded metal organic framework material NH2-melt spinning of UIO-66(Hf) doped silicon carbide fiber precursor
Placing the material obtained in the step one in a melting spinning cylinder, heating to a molten state at 0.5 ℃/min under an argon atmosphere with the flow rate of 100mL/min, pressurizing to 3MPa, and enabling the melt to flow out through a filter screen and a spinneret plate to obtain the Al nanoparticle-loaded metal organic framework material NH2UIO-66(Hf) doped silicon carbide fiber precursor fiber bundle. Then, the mixture was thermally crosslinked at 320 ℃ in an air atmosphere, and the mixture was kept at the temperature for 4 hours without melting.
Step three: al nanoparticle-loaded metal organic framework material NH2-sintering of UIO-66(Hf) doped silicon carbide fibres.
Putting the obtained cross-linked fiber in a sintering furnace, introducing ammonia gas with the flow rate of 300mL/min, heating to 450 ℃ at the speed of 100 ℃/h, and preserving heat for 2 h; then heating to 900 ℃ at the same speed for pyrolysis, and keeping the temperature for 2 h; finally, heating to 1200 ℃ at the speed of 50 ℃/h in the argon atmosphere, preserving the heat for 0.5 hour, and cooling along with the furnace to obtain the metal organic framework material NH2UIO-66(Hf) doped silicon carbide fibers.
Example 4 preparation of Al nanoparticle-loaded Metal organic framework Material NH2UIO-66(Hf) doped silicon carbide fiber strength 3.7GPa and elastic modulus 295GPa at normal temperature. After the fiber is treated for 100 hours in an air environment at 1100 ℃, the strength retention rate is 89%, and the fiber has wide practical value and application prospect in the field of high-performance fibers, such as antenna windows and antenna covers of electromagnetic wave transmission materials.
Example 5
Example 5 provides a silicon carbide fiber, the preparation method of which comprises the following steps:
the method comprises the following steps: al nanoparticle-loaded metal organic framework material NH2Preparation of UIO-66(Hf) doped silicon carbide fiber precursor.
Taking 3 wt.% of hafnium chloride (HfCl)43mmol, > 99% purity) and 2-amino-1, 2-dibenzoic acid (1.32g, 8.0mmol) were dissolved in 50mL of N, N-dimethylformylIn amine (DMF) solution, transferring the solution into a 100mL high-pressure kettle after ultrasonic stirring, slowly injecting pure Polydimethylsilane (PCS) into the high-pressure kettle, uniformly covering the surface of hafnium chloride, rapidly heating to 120 ℃ at the speed of 10 ℃/min, reacting for 48 hours, cooling the reaction kettle to room temperature, centrifuging, repeatedly washing with sewage methanol to remove DMF, and drying in vacuum at 80 ℃ for 12 hours to obtain NH2UIO-66(Hf) material. Placing NH2-UIO-66(Hf) in AlCl-containing solution3·2H2And introducing nitrogen for 1h in a dimethyl sulfoxide (DMSO) -ethanol suspension of O in the dark, irradiating for 2h under visible light, and transferring the obtained suspension into a reaction kettle for reacting for 16 h. Washing the obtained precipitate with acetone and ethanol, removing residual DMSO, and obtaining metal organic framework material NH loaded with Al nano particles2-UIO-66(Hf) doped silicon carbide precursor fines.
Step two: al nanoparticle-loaded metal organic framework material NH2-melt spinning of a UIO-66(Hf) doped silicon carbide precursor
Placing the fine material obtained in the first step into a melt spinning cylinder, heating to a molten state at 0.5 ℃/min under the argon atmosphere of 150mL/min, pressurizing to 4MPa, and enabling the melt to flow out through a filter screen and a spinneret plate to obtain the Al nanoparticle-loaded metal organic framework material NH2UIO-66(Hf) doped silicon carbide precursor fiber bundle. Then, the mixture was thermally crosslinked at 340 ℃ in an air atmosphere, and the mixture was kept at that temperature for 5 hours and then subjected to a non-melting treatment.
Step three: al nanoparticle-loaded metal organic framework material NH2-sintering of UIO-66(Hf) doped silicon carbide fibres.
Putting the obtained cross-linked fiber in a sintering furnace, introducing ammonia gas with the flow rate of 400mL/min, heating to 500 ℃ at the speed of 120 ℃/hour, and preserving heat for 3 hours; then heating to 900 ℃ at the same speed for pyrolysis, and keeping the temperature for 2 h; finally, heating to 1400 ℃ at the speed of 50 ℃/hour in the argon atmosphere, preserving the heat for 0.8 hour, and cooling along with the furnace to obtain the metal organic framework material NH loaded with the Al nano particles2UIO-66(Hf) doped silicon carbide fibers.
Example 5 preparation of Al nanoparticle-loaded Metal organic framework Material NH2-UIThe strength of the O-66(Hf) doped silicon carbide fiber at normal temperature is 3.8GPa, and the elastic modulus is 300 GPa. After the fiber is treated for 100 hours in an air environment at 1100 ℃, the strength retention rate is 91 percent, and the fiber has wide practical value and application prospect in the field of high-performance fibers, such as antenna windows and antenna covers of electromagnetic wave transmission materials.
Example 6
Example 6 provides a silicon carbide fiber, the preparation method of which comprises the following steps:
the method comprises the following steps: al nanoparticle-loaded metal organic framework material NH2Preparation of UIO-66(Hf) doped silicon carbide fiber precursor.
Taking 4.5 wt.% of hafnium chloride (HfCl)44.5mmol, purity > 99%) and 2-amino-1, 2-o-dibenzoic acid (1.32g, 8.0mmol) were dissolved in 50mL of N, N-Dimethylformamide (DMF) solution, the solution was transferred to a 100mL autoclave after ultrasonic stirring, pure Polydimethylsilane (PCS) was slowly injected into the autoclave to uniformly cover the hafnium chloride surface, rapidly heated to 120 ℃ at a speed of 10 ℃/min, reacted for 48 hours, centrifuged after the reactor cooled to room temperature, repeatedly washed with contaminated methanol to remove DMF, and vacuum dried at 80 ℃ for 12 hours to obtain NH2UIO-66(Hf) material. Placing NH2-UIO-66(Hf) in AlCl-containing solution3·2H2And introducing nitrogen for 1h in a dimethyl sulfoxide (DMSO) -ethanol suspension of O in the dark, irradiating for 2h under visible light, and transferring the obtained suspension into a reaction kettle for reacting for 16 h. Washing the obtained precipitate with acetone and ethanol, removing residual DMSO, and obtaining metal organic framework material NH loaded with Al nano particles2-UIO-66(Hf) doped silicon carbide precursor fines.
Step two: al nanoparticle-loaded metal organic framework material NH2-melt spinning of a UIO-66(Hf) doped silicon carbide precursor
Placing the fine material obtained in the first step into a melt spinning cylinder, heating to a molten state at 0.5 ℃/min under an argon atmosphere with the flow rate of 200mL/min, pressurizing to 5MPa, and allowing the melt to flow out through a filter screen and a spinneret plate to obtain the Al nanoparticle-loaded metal organic framework material NH2UIO-66(Hf) doped silicon carbide/silicon boron nitride precursorA fiber bundle. Then the mixture is thermally crosslinked at 360 ℃ in the atmosphere of air, and is subjected to heat preservation for 6 hours to be subjected to non-melting treatment.
Step three: al nanoparticle-loaded metal organic framework material NH2-sintering of UIO-66(Hf) doped silicon carbide fibres.
Putting the obtained cross-linked fiber in a sintering furnace, introducing ammonia gas with the flow rate of 500mL/min, heating to 550 ℃ at the speed of 200 ℃/h, and preserving heat for 3 h; then heating to 900 ℃ at the same speed for pyrolysis, and keeping the temperature for 2 h; finally, heating to 1600 ℃ at the speed of 50 ℃/hour in the argon atmosphere, preserving the heat for 1 hour, and cooling along with the furnace to obtain the metal organic framework material NH loaded with the Al nano particles2UIO-66(Hf) doped silicon carbide fibers.
Example 6 preparation of Al nanoparticle-loaded Metal organic framework Material NH2UIO-66(Hf) doped silicon carbide fiber strength 3.9GPa and elastic modulus 305GPa at normal temperature. After the fiber is treated for 100 hours in an air environment at 1100 ℃, the strength retention rate is 93 percent, and the fiber has wide practical value and application prospect in the field of high-performance fibers, such as antenna windows and antenna covers of electromagnetic wave transmission materials.
In conclusion, the invention introduces heterogeneous elements of hafnium and aluminum into the precursor to play a role of a sintering aid; the densification of the silicon carbide fiber can be effectively improved by sintering the aluminum-containing silicon carbide fiber at high temperature. In particular, the use of ammonia gas treatment to form nitrogen silicon carbide nanomaterials at the interface of the silicon carbide fibres provides excellent recombination effects while also reducing the oxygen content of the fibres. UIO-66(Hf) is one of the heat stable materials which can reach more than 500 ℃ at present, can still stably exist in harsh environments (boiling water, strong acid and strong base), and the metal organic framework material has the characteristics of high specific surface area, adjustable aperture, functional modification, good heat stability, good chemical stability and the like, and can be well compounded with silicon carbide, so that the ceramic matrix composite fiber material disclosed by the invention has strong thermal shock resistance at ultrahigh temperature and has good optical performance and magnetic property. The strength of the prepared silicon carbide fiber at normal temperature is 3.6 +/-0.3 GPa, and the elastic modulus is 290 +/-30 GPa. After the fiber is treated in an air environment at 1100 ℃ for 100 hours, the strength retention rate can still reach over 88 percent, and the fiber has wide practical value and application prospect in the field of high-performance fibers, such as antenna windows and antenna covers of electromagnetic wave transmission materials.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of silicon carbide fiber is characterized by comprising the following steps:
s101: hafnium chloride and 2-amino-1, 2-o-dibenzoic acid are mixed according to a molar ratio of (1-4.5): 8, adding the mixture into an N, N-dimethylformamide solution, ultrasonically stirring, adding the mixture into an autoclave, injecting polydimethylsiloxane to cover the surface of the hafnium chloride, heating the mixture to 110-130 ℃ at a first heating rate, carrying out heat preservation reaction for 44-52 h, cooling the mixture to room temperature, carrying out centrifugal separation, washing and drying to obtain NH2-UIO-66(Hf) material;
wherein, the proportion of the 2-amino-1, 2-o-dibenzoic acid to the N, N-dimethylformamide solution is 4 mmol: (20 mL-30 mL); the molar ratio of the polydimethylsiloxane to the 2-amino-1, 2-o-dibenzoic acid is 3: (3-5);
s102: then adding the metal organic framework material into the solution containing AlCl3·2H2Filling protective gas into dimethyl sulfoxide-ethanol suspension of O under the condition of keeping out of the sun for 0.5 h-1.5 h, then keeping for 1.5 h-2.5 h under the radiation of visible light, then adding the mixture into a reaction kettle for reaction for 15 h-17 h to obtain precipitate, and washing the precipitate with acetone or ethanol to obtain the metal-organic framework material NH loaded with Al nano particles2-UIO-66(Hf) doped silicon carbide precursor;
s103: placing the silicon carbide precursor obtained in the step S102 in a melting spinning cylinder, heating to a melting state at a second heating rate in an inert gas atmosphere, pressurizing to 3-5 MPa, and flowing the melt out after sequentially flowing through a filter screen and a spinneret plate to obtain the Al nanoparticle-loaded metal-organic framework material NH2UIO-66(Hf) doped silicon carbide precursor fiber bundles, which are then thermally crosslinked for non-melting treatment;
s104: putting the fiber bundle obtained in the step S103 into a sintering furnace, introducing ammonia gas, heating to 450-650 ℃ at a third heating rate, preserving heat for 2-4 h, heating to 880-920 ℃ at the third heating rate, preserving heat for 1.5-2.5 h for pyrolysis, heating to 1200-1600 ℃ at a fourth heating rate in a protective gas atmosphere, preserving heat for 0.5-1 h, and cooling to room temperature to obtain a metal organic framework material NH2UIO-66(Hf) doped silicon carbide fibers.
2. The method for producing a silicon carbide fiber according to claim 1, wherein in step S101, the first temperature increase rate is 8 to 12 ℃/min; in the step S103, the second heating rate is 0.3 ℃/min to 0.8 ℃/min; in the step S104, the third temperature rise rate is 100 ℃/h to 200 ℃/h, and the fourth temperature rise rate is 45 ℃/h to 55 ℃/h.
3. The method for producing a silicon carbide fiber according to claim 1, which comprisesCharacterized in that in the step S102, AlCl is contained3·2H2AlCl in dimethyl sulfoxide-ethanol suspension of O3·2H2The ratio of O, dimethyl sulfoxide and ethanol is 5: (1.5-2.5): (2.8-3.2).
4. The method for producing silicon carbide fiber according to claim 1, wherein in step S102, the reaction temperature in the reaction vessel is 170 to 190 ℃.
5. The method for producing silicon carbide fibers according to claim 1, wherein the protective gas is argon gas, and the flow rate of argon gas is 100 to 200mL/min in step S102.
6. The method for producing silicon carbide fibers according to claim 1, wherein the flow rate of the ammonia gas in step S104 is 300 to 500 mL/min.
7. The method of claim 1, wherein the thermal crosslinking is performed at a temperature of 320 to 360 ℃ for 4 to 6 hours in step S103.
8. The method of claim 1, wherein the silicon carbide fiber is washed with anhydrous methanol at 75 to 85 ℃ for 10 to 14 hours in step S101.
9. Silicon carbide fibers produced by the process of any one of claims 1 to 8.
10. Use of the silicon carbide fibers according to any one of claims 1 to 8 in the fields of aeronautics, mechanics, chemical engineering, aerospace and weapons.
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