CN110846742B - SiBN fiber preparation method with adjustable boron content and SiBN fiber thereof - Google Patents
SiBN fiber preparation method with adjustable boron content and SiBN fiber thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing SiBN fiber with adjustable boron content and the SiBN fiber, wherein the method for preparing the SiBN fiber comprises the steps of carrying out ammonia gas atmosphere treatment on polycarbosilane fiber, decarbonizing and introducing active amino; carrying out boron trichloride atmosphere treatment, and introducing boron element; carrying out post-treatment in an ammonia atmosphere, dechlorinating and introducing active amino; repeating the processes of boron trichloride atmosphere treatment and ammonia gas atmosphere post-treatment for a plurality of times, and then performing high-temperature sintering to obtain SiBN fiber; the SiBN fiber contains 3.50-8.50 wt% of boron, has the strength of 1.05-1.45 GPa, has the strength retention rate of 60-112% after being treated in a nitrogen atmosphere at 1600 ℃, has the dielectric constant of 3.24-5.07 at 8-18 GHz and has the dielectric loss of 0.0050-0.0096 at 8-18 GHz. The preparation method provided by the invention realizes the regulation and control of the boron content in the SiBN fiber through the alternate treatment of the ammonia gas atmosphere and the boron trichloride atmosphere, and meanwhile, the preparation method has simple process and low cost; the SiBN fiber provided by the invention has excellent mechanical property, high temperature resistance and dielectric property.
Description
Technical Field
The invention relates to the technical field of SiBN fiber preparation, in particular to a SiBN fiber preparation method with adjustable boron content and a SiBN fiber thereof.
Background
The SiBN fiber has excellent high-temperature performance and very low dielectric constant and dielectric loss, is an ideal reinforcement for preparing a high-performance wave-transparent ceramic matrix composite, and has very important application prospects in systems of hypersonic aircraft communication, remote control, guidance, detonation and the like.
At present, the preparation of SiBN fiber is mainly realized by synthesizing a polyborosilazane precursor which can be melt-spun. For example, Jansen et al, using chlorosilane, boron trichloride, hexamethyldisilazane, etc. as starting materials, polycondensed under the action of ammonia gas or amine to obtain polyborosilazane (U.S. Pat. No. 3, 5834388; U.S. Pat. No. 5885519; U.S. Pat. No. 3, 5968859; U.S. Pat. No. 2004/0019230, 1). The precursor was melt-spun and then fired in an ammonia atmosphere to obtain SiBN fiber (Science 1999,285: 699). SiBN fibers with excellent performance are prepared by national defense science and technology university through a similar method (chem.Eur.J.2010,16: 6458; Mater.Lett.2012,78: 1). However, this method requires a completely oxygen-free and water-free environment to avoid the degradation of the fiber performance caused by oxygen absorption of the high-activity polyborosilazane precursor. This makes process control of fiber manufacture difficult and costly. In order to avoid the use of a high-activity precursor, the national defense science and technology university starts from the fact that PCS fiber is not melted in air, boron trichloride is adopted for treatment and then nitrogen treatment is carried out in an ammonia gas atmosphere, or the fiber is firstly nitrogen treated in the ammonia gas atmosphere and then dipped in boric acid solution, and finally the PCS fiber is converted into SiBN (O) fiber (CN 101830706.A) through high-temperature treatment. However, the fiber itself contains more oxygen element, which is not good for the high temperature performance of the fiber. Meanwhile, the method of only adopting a single atmosphere boron source or a liquid boron source to permeate boron elements through the surface of the fiber has limitation, and the content of the boron elements in the fiber is difficult to increase.
Disclosure of Invention
The invention provides a preparation method of SiBN fiber with adjustable boron content and the SiBN fiber, which are used for overcoming the defects of high process difficulty, high cost, poor temperature resistance caused by high oxygen content of the prepared fiber, low boron element content of the fiber and the like in the prior art, realizing simple process and low preparation cost, simultaneously realizing controllable introduction of boron element, and the prepared fiber has excellent mechanical property, dielectric property and better temperature resistance.
In order to achieve the purpose, the invention provides a preparation method of SiBN fiber with adjustable boron content, which realizes the adjustment and control of the boron content in the SiBN fiber by alternately treating polycarbosilane fiber in ammonia gas atmosphere and boron trichloride atmosphere, and comprises the following steps:
s1: under inert atmosphere, the polycarbosilane fiber which is not melted is treated under ammonia atmosphere, and is cooled to room temperature, so that the fiber with active amino groups introduced is obtained;
s2: under an inert atmosphere, carrying out boron trichloride atmosphere treatment on the fiber introduced with the active amino group obtained in the step S1 to obtain a fiber introduced with a boron element;
s3: carrying out ammonia gas atmosphere post-treatment on the fiber introduced with the boron element obtained in the step S2 in an inert atmosphere;
s4: repeating the process from S2 to S3 for several times according to different requirements on the content of the boron element;
s5: the fiber subjected to S4 was fired in an inert atmosphere to obtain a SiBN fiber.
In order to achieve the purpose, the invention also provides the SiBN fiber, wherein the content of boron in the SiBN fiber is 3.50-8.50 wt%, the strength is 1.05-1.45 GPa, the strength retention rate is 60-112% after nitrogen atmosphere treatment at 1600 ℃, the dielectric constant is 3.24-5.07 at 8-18 GHz, and the dielectric loss is 0.0050-0.0096 at 8-18 GHz.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the SiBN fiber with the adjustable boron content, provided by the invention, most of carbon elements in the polycarbosilane fiber are removed through ammonia gas atmosphere treatment, and active amino is introduced; then introducing boron into the fiber through boron trichloride atmosphere treatment, wherein the boron can be introduced into the fiber due to the fact that amino can react with boron trichloride; removing chlorine element in the fiber by ammonia gas atmosphere post-treatment, and introducing active amino, wherein the boron element can further react with ammonia gas to remove chlorine atoms and introduce active amino simultaneously because the boron element is introduced in a form of B-Cl, so as to provide active sites for introducing the boron element in the next step; then controlling the amount of boron introduced into the fiber by different repetition times of the processes of boron trichloride atmosphere treatment and ammonia gas atmosphere post-treatment, thereby meeting different requirements on the SiBN fiber; finally, the SiBN fiber is obtained by high-temperature sintering. The preparation method provided by the invention does not need to use high-activity polyborosilazane as a precursor, so that the preparation conditions are not strict as completely oxygen-free and water-free, thereby obviously reducing the process difficulty and the preparation cost; meanwhile, the preparation method can effectively control the amount of the boron element introduced into the fiber by the alternate treatment of the ammonia gas atmosphere and the boron trichloride atmosphere, thereby meeting different requirements; in addition, the SiBN fiber obtained by the preparation method has excellent mechanical property, high temperature resistance and dielectric property.
2. The SiBN fiber provided by the invention has the boron content of 3.50-8.50 wt%, the strength of 1.05-1.45 GPa, the strength retention rate of 60-112% after nitrogen atmosphere treatment at 1600 ℃, the dielectric constant of 3.24-5.07 at 8-18 GHz and the dielectric loss of 0.0050-0.0096 at 8-18 GHz. The SiBN fiber has excellent mechanical property, high temperature resistance and dielectric property.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing SiBN fiber with adjustable boron content according to the invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The drugs/reagents used are all commercially available without specific mention.
The invention provides a preparation method of SiBN fiber with adjustable boron content, which realizes the adjustment and control of the boron content in the SiBN fiber by alternately treating polycarbosilane fiber in ammonia atmosphere and boron trichloride atmosphere, and comprises the following steps:
s1: under inert atmosphere, the polycarbosilane fiber which is not melted is treated under ammonia atmosphere, and is cooled to room temperature, so that the fiber with active amino groups introduced is obtained;
the fiber needs to be cooled to room temperature and then treated in boron trichloride atmosphere, because the fiber strength is too low after the boron element is introduced due to too high temperature, and the cooling process can remove residual ammonia gas, otherwise, the residual ammonia gas reacts with subsequent boron trichloride, and the loss of equipment is caused.
Preferably, the ammonia gas atmosphere treatment is specifically:
heating from room temperature to 600 ℃ at a heating rate of 5-10 ℃/min, and introducing ammonia gas at a flow rate of 4-40 ml/min/g when the temperature is in a range of 300-600 ℃. The temperature rising rate, the temperature range and the ammonia gas flow are controlled to remove carbon elements in the polycarbosilane fiber as much as possible and introduce active amino groups as much as possible.
S2: under an inert atmosphere, carrying out boron trichloride atmosphere treatment on the fiber introduced with the active amino group obtained in the step S1 to obtain a fiber introduced with a boron element;
preferably, the boron trichloride atmosphere treatment specifically comprises:
heating from room temperature to 600 ℃ at a heating rate of 5-10 ℃/min, and introducing boron trichloride flow of 1-20 ml/min/g when the temperature is in the range of 100-600 ℃. The temperature rising rate, the temperature and the flow are controlled to control the amount of the introduced boron element; the introduction of boron trichloride within the range of 100-600 ℃ is comprehensively considered in terms of the speed and amount of introduced boron, and in addition, the mechanical property of the final fiber is reduced due to overhigh temperature.
S3: carrying out ammonia gas atmosphere post-treatment on the fiber introduced with the boron element obtained in the step S2 in an inert atmosphere;
preferably, the ammonia gas atmosphere post-treatment specifically comprises:
and when the temperature of the boron-introduced fiber obtained in the step S2 is reduced to any temperature value within the range of 200-400 ℃, introducing 1-20 ml/min/g of ammonia gas flow, and keeping the temperature for 0.5-3 h at any temperature value within the range of 200-400 ℃. The reaction temperature of the step S3 does not need to be very high, and 200-400 ℃ is optimal under the condition of comprehensive fiber performance. The flow rate of the ammonia gas and the heat preservation are both used for ensuring the chlorine element to be completely removed, and a certain amount of active amino is introduced.
S4: repeating the process from S2 to S3 for several times according to different requirements on the content of the boron element;
preferably, the repetition frequency is 1-5 times. The repetition times are different, and the boron content in the finally prepared SiBN fiber is different; as the number of repetitions increases, the boron content of the SiBN fiber increases.
S5: the fiber subjected to S4 was fired in an inert atmosphere to obtain a SiBN fiber.
Preferably, the firing is specifically:
raising the temperature from the heat preservation temperature of S3 to 1300-1500 ℃ at a temperature raising rate of 2-10 ℃/h under nitrogen flow, and preserving the temperature for 0.5-3 h at 1300-1500 ℃. The fiber is sintered by high temperature treatment, so that the fibril which is subjected to S4 undergoes a series of physicochemical changes to form the expected phase composition and microstructure. With the gradual increase of the treatment temperature, the organic structure in the fibril is gradually changed into an inorganic structure, meanwhile, pores generated by the fibril due to pyrolysis are gradually reduced, the fiber is gradually densified until the density reaches a stable value, and the SiBN fiber with excellent performance is obtained.
Preferably, the inert gas in the S1, S2, S3 and S5 is nitrogen or argon, and the purity is more than or equal to 99.99%.
Preferably, the purity of the ammonia gas in the S1 and S3 is more than or equal to 99.9 percent.
Preferably, the purity of the boron trichloride in the S2 is more than or equal to 99.9%.
The higher the purity of the atmosphere used, the less impurities are introduced, and the more excellent the properties of the finally prepared SiBN fiber are.
The invention also provides the SiBN fiber, wherein the content of boron in the SiBN fiber is 3.50-8.50 wt%, the strength is 1.05-1.45 GPa, the strength retention rate is 60-112% after the SiBN fiber is treated in a nitrogen atmosphere at 1600 ℃, the dielectric constant is 3.24-5.07 under 8-18 GHz, and the dielectric loss is 0.0050-0.0096 under 8-18 GHz.
Example 1
The embodiment provides a preparation method of SiBN fiber with adjustable boron content, which comprises the following steps:
(1) placing 20 beams (about 2g) of electron beams to irradiate the crosslinked polycarbosilane fiber in a high-temperature furnace, vacuumizing, and replacing 3 times with nitrogen; heating from room temperature to 600 ℃ at a heating rate of 5 ℃/min, and introducing high-purity ammonia gas of 40ml/min/g when the temperature is in the range of 300-600 ℃;
(2) flushing a large amount of nitrogen to remove residual ammonia; after the fibers treated by the ammonia gas are cooled to room temperature, heating the fibers from the room temperature to 600 ℃ at the heating rate of 10 ℃/min, and introducing 15ml/min/g of high-purity boron trichloride gas when the temperature is in the range of 200-600 ℃ to introduce boron element;
(3) flushing a large amount of nitrogen to remove residual boron trichloride; when the fiber treated by the boron trichloride is cooled to 400 ℃, introducing high-purity ammonia gas of 20ml/min/g, and preserving the heat at 400 ℃ for 1h to remove chlorine elements in the fiber and simultaneously introduce active amino;
(4) flushing a large amount of nitrogen to remove residual ammonia gas, introducing high-purity nitrogen, heating from 400 ℃ to 1400 ℃ at the heating rate of 5 ℃/min, and preserving heat at 1400 ℃ for 1h to finally prepare the SiBN fiber.
The elemental composition, the mechanical property, the temperature resistance and the dielectric property of the SiBN fiber prepared in the embodiment are shown in Table 1, and it can be known from the Table that the boron element content of the SiBN fiber prepared in the embodiment is 3.56 wt%, and meanwhile, the mechanical property, the temperature resistance and the dielectric property of the SiBN fiber are excellent.
Example 2
The embodiment provides a preparation method of SiBN fiber with adjustable boron content, which comprises the following steps:
(1) placing 20 beams (about 2g) of electron beams to irradiate the crosslinked polycarbosilane fiber in a high-temperature furnace, vacuumizing, and replacing for 2 times by using nitrogen; heating from room temperature to 600 ℃ at the heating rate of 8 ℃/min, and introducing high-purity ammonia gas of 30ml/min/g when the temperature is in the range of 300-600 ℃;
(2) flushing a large amount of nitrogen to remove residual ammonia; after the fibers treated by the ammonia gas are cooled to room temperature, heating the fibers from the room temperature to 600 ℃ at the heating rate of 8 ℃/min, and introducing high-purity boron trichloride gas of 20ml/min/g when the temperature is in the range of 100-600 ℃ to introduce boron element;
(3) flushing a large amount of nitrogen to remove residual boron trichloride; after the fibers treated by the boron trichloride are cooled to 300 ℃, introducing high-purity ammonia gas of 10ml/min/g, and preserving the heat at 300 ℃ for 0.5h to remove chlorine elements in the fibers and simultaneously introduce active amino;
(4) repeating the processes of the steps (2) to (3) once;
(5) flushing a large amount of nitrogen to remove residual ammonia gas, introducing high-purity nitrogen, heating from 300 ℃ to 1300 ℃ at the heating rate of 10 ℃/min, and preserving heat at 1300 ℃ for 0.5h to finally prepare the SiBN fiber.
The elemental composition, the mechanical property, the temperature resistance and the dielectric property of the SiBN fiber prepared in the embodiment are shown in Table 1, and it can be known from the Table that the boron element content of the SiBN fiber prepared in the embodiment is 5.14 wt%, and meanwhile, the mechanical property, the temperature resistance and the dielectric property of the SiBN fiber are excellent.
Example 3
The embodiment provides a preparation method of SiBN fiber with adjustable boron content, which comprises the following steps:
(1) placing 20 beams (about 2g) of electron beams to irradiate the crosslinked polycarbosilane fiber in a high-temperature furnace, vacuumizing, and replacing for 2 times by using nitrogen; heating from room temperature to 600 ℃ at a heating rate of 10 ℃/min, and introducing high-purity ammonia gas of 10ml/min/g when the temperature is in the range of 300-600 ℃;
(2) flushing a large amount of nitrogen to remove residual ammonia; after the fibers treated by the ammonia gas are cooled to room temperature, heating the fibers from the room temperature to 600 ℃ at the heating rate of 5 ℃/min, and introducing 1ml/min/g of high-purity boron trichloride gas when the temperature is in the range of 200-600 ℃ to introduce boron element;
(3) flushing a large amount of nitrogen to remove residual boron trichloride; after the fibers treated by the boron trichloride are cooled to 200 ℃, introducing high-purity ammonia gas of 1ml/min/g, and preserving the heat at 200 ℃ for 3 hours to remove chlorine elements in the fibers and simultaneously introduce active amino;
(4) repeating the processes of the steps (2) to (3) twice;
(5) flushing a large amount of nitrogen to remove residual ammonia gas, introducing high-purity nitrogen, heating from 200 ℃ to 1400 ℃ at the heating rate of 8 ℃/min, and preserving heat at 1400 ℃ for 3 hours to finally prepare the SiBN fiber.
The elemental composition, the mechanical property, the temperature resistance and the dielectric property of the SiBN fiber prepared in the embodiment are shown in Table 1, and it can be known from the Table that the boron element content of the SiBN fiber prepared in the embodiment is 6.81 wt%, and meanwhile, the mechanical property, the temperature resistance and the dielectric property of the SiBN fiber are excellent.
Example 4
The embodiment provides a preparation method of SiBN fiber with adjustable boron content, which comprises the following steps:
(1) placing 20 beams (about 2g) of electron beams to irradiate the crosslinked polycarbosilane fiber in a high-temperature furnace, vacuumizing, and replacing for 2 times by using nitrogen; heating from room temperature to 600 ℃ at a heating rate of 5 ℃/min, and introducing high-purity ammonia gas of 4ml/min/g when the temperature is in the range of 300-600 ℃;
(2) flushing a large amount of nitrogen to remove residual ammonia; after the fibers treated by the ammonia gas are cooled to room temperature, heating the fibers from the room temperature to 600 ℃ at the heating rate of 10 ℃/min, and introducing 15ml/min/g of high-purity boron trichloride gas when the temperature is in the range of 100-600 ℃ to introduce boron element;
(3) flushing a large amount of nitrogen to remove residual boron trichloride; after the fibers treated by the boron trichloride are cooled to 400 ℃, introducing high-purity ammonia gas of 10ml/min/g, and preserving the heat at 400 ℃ for 2 hours to remove chlorine elements in the fibers and simultaneously introduce active amino;
(4) repeating the process of steps (2) to (3) four times;
(5) flushing a large amount of nitrogen to remove residual ammonia gas, introducing high-purity nitrogen, heating from 400 ℃ to 1500 ℃ at the heating rate of 2 ℃/min, and preserving heat at 1500 ℃ for 1h to finally prepare the SiBN fiber.
The elemental composition, the mechanical property, the temperature resistance and the dielectric property of the SiBN fiber prepared in the embodiment are shown in Table 1, and it can be known from the Table that the boron element content of the SiBN fiber prepared in the embodiment is 8.43 wt%, and meanwhile, the mechanical property, the temperature resistance and the dielectric property of the SiBN fiber are excellent.
Comparative example 1
This comparative example provides Si3N4A method of making a fiber comprising the steps of:
(1) placing 20 beams (about 2g) of electron beams to irradiate the crosslinked polycarbosilane fiber in a high-temperature furnace, vacuumizing, and replacing for 2 times by using nitrogen; raising the temperature from room temperature to 600 ℃ at the temperature raising rate of 5 ℃/min, and introducing 300ml/min of high-purity ammonia gas when the temperature is in the range of 100-600 ℃;
(2) flushing a large amount of nitrogen to remove residual ammonia; introducing high-purity nitrogen, heating from 600 ℃ to 1300 ℃ at the heating rate of 10 ℃/min, and preserving heat for 1h at 1300 ℃ to finally prepare Si3N4A fiber.
Table 1 is a comparison table of the element composition, the mechanical property, the temperature resistance and the dielectric property of the fiber obtained in the examples 1-4 and the comparative example 1, and it can be seen from the table that the content of the boron element in the SiBN fiber prepared by the method for preparing the SiBN fiber with adjustable boron content is controllable within the range of 3.56-8.43 wt%, and the mechanical property, the temperature resistance and the dielectric property of the SiBN fiber are excellent. While Si prepared in comparative example 13N4The fiber does not contain boron, the temperature resistance of the fiber is obviously poorer than that of the SiBN fiber provided by the invention, and the dielectric property of the fiber is also poorer than that of the SiBN fiber provided by the invention. Therefore, the proper amount of boron element is introduced into the fiber, so that the temperature resistance and the dielectric property of the fiber can be obviously improved, and the mechanical property of the fiber can be maintained.
TABLE 1 comparison table of elemental composition, mechanical properties, temperature resistance and dielectric properties of fibers obtained in examples 1-4 and comparative example 1
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. A preparation method of SiBN fiber with adjustable boron content is characterized in that the preparation method realizes the adjustment and control of the boron content in the SiBN fiber by alternately processing non-melting polycarbosilane fiber in ammonia gas atmosphere and boron trichloride atmosphere, and comprises the following steps:
s1: under inert atmosphere, the polycarbosilane fiber which is not melted is treated under ammonia atmosphere, and is cooled to room temperature, so that the fiber with active amino groups introduced is obtained; the ammonia gas atmosphere treatment specifically comprises the following steps: heating from room temperature to 600 ℃ at a heating rate of 5-10 ℃/min, and introducing ammonia gas with a flow rate of 4-40 ml/min/g when the temperature is in a range of 300-600 ℃;
s2: under an inert atmosphere, carrying out boron trichloride atmosphere treatment on the fiber introduced with the active amino group obtained in the step S1 to obtain a fiber introduced with a boron element; the boron trichloride atmosphere treatment specifically comprises the following steps: heating from room temperature to 600 ℃ at a heating rate of 5-10 ℃/min, and introducing a boron trichloride flow of 1-20 ml/min/g when the temperature is in a range of 100-600 ℃;
s3: carrying out ammonia gas atmosphere post-treatment on the fiber introduced with the boron element obtained in the step S2 in an inert atmosphere; the post-treatment in the ammonia atmosphere comprises the following specific steps: when the temperature of the boron-introduced fiber obtained in the step S2 is reduced to any temperature value within the range of 200-400 ℃, introducing 1-20 ml/min/g of ammonia gas flow, and keeping the temperature for 0.5-3 h at any temperature value within the range of 200-400 ℃;
s4: repeating the process from S2 to S3 for several times according to different requirements on the content of the boron element;
s5: the fiber subjected to S4 was fired in an inert atmosphere to obtain a SiBN fiber.
2. The method of claim 1, wherein the repetition number of the step S4 is 1 to 5.
3. The method of preparing SiBN fiber with adjustable boron content according to claim 1, wherein in S5, the firing is specifically as follows:
raising the temperature from the heat preservation temperature of S3 to 1300-1500 ℃ at the temperature raising rate of 2-10 ℃/min under the inert gas flow, and preserving the heat for 0.5-3 h at the temperature of 1300-1500 ℃.
4. The method of claim 1, wherein the inert gas in the S1, S2, S3 and S5 is nitrogen or argon, and the purity is not less than 99.99%.
5. The method of claim 1, wherein the purity of the ammonia gas in the S1 and S3 is greater than or equal to 99.9%.
6. The method of claim 1, wherein the purity of boron trichloride in S2 is greater than or equal to 99.9%.
7. SiBN fiber, which is prepared by the preparation method of any one of claims 1 to 6; the SiBN fiber contains 3.50-8.50 wt% of boron, has the strength of 1.05-1.45 GPa, has the strength retention rate of 60-112% after being treated in a nitrogen atmosphere at 1600 ℃, has the dielectric constant of 3.24-5.07 at 8-18 GHz and has the dielectric loss of 0.0050-0.0096 at 8-18 GHz.
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| CN112250874B (en) * | 2020-10-28 | 2022-02-18 | 浙江华茂航天科技股份有限公司 | Preparation method of polyborocarbosilane |
| CN115821428B (en) * | 2023-02-14 | 2023-06-16 | 山东工业陶瓷研究设计院有限公司 | Low-temperature preparation method of BN fiber and BN fiber |
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| CN101830706B (en) * | 2010-05-28 | 2012-02-15 | 中国人民解放军国防科学技术大学 | Method for continuously preparing Si-B-N-O fiber by using PCS (Polycarbosilane) fiber |
| CN102634868B (en) * | 2012-05-04 | 2013-09-11 | 中国人民解放军国防科学技术大学 | Preparation method of silicon carbide fiber with boron nitride structure surface layer |
| CN103952796B (en) * | 2014-04-28 | 2016-04-06 | 中国人民解放军国防科学技术大学 | A kind of preparation method of silicon nitrogen boron continuous ceramic fiber |
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