CN114875524A - Continuous SiBN fiber and preparation method and application thereof - Google Patents
Continuous SiBN fiber and preparation method and application thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 82
- 229910003697 SiBN Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000012298 atmosphere Substances 0.000 claims abstract description 22
- 238000002844 melting Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 17
- 229920003257 polycarbosilane Polymers 0.000 claims abstract description 17
- 238000002074 melt spinning Methods 0.000 claims abstract description 11
- 229920001400 block copolymer Polymers 0.000 claims abstract description 10
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000005261 decarburization Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000005046 Chlorosilane Substances 0.000 claims description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- -1 polydimethylsiloxane Polymers 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 230000008707 rearrangement Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 2
- 239000002243 precursor Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 238000010304 firing Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052796 boron Inorganic materials 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a continuous SiBN fiber and a preparation method and application thereof. Obtaining original fiber through melt spinning, adopting ammonia gas or boron trichloride atmosphere to carry out non-melting treatment on the original fiber, and then carrying out high-temperature decarburization and firing in the ammonia gas atmosphere to obtain the continuous SiBN fiber. According to the invention, the low-air-sensitivity polycarbosilane-polyborosilazane block copolymer is obtained by utilizing the thermochemical reaction between polyborosilazane and polycarbosilane, and the preparation of the continuous SiBN fiber with low oxygen content by a precursor conversion method is facilitated.
Description
Technical Field
The invention relates to the technical field of SiBN fibers, in particular to a continuous SiBN fiber and a preparation method and application thereof.
Background
The continuous 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, chlorosilane, boron trichloride, hexamethyldisilazane and the like are used as initial raw materials, and polyborosilazane is obtained by polycondensation under the action of ammonia gas or amine. The SiBN fiber is prepared by sintering the precursor in an ammonia atmosphere after melt spinning. 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 PCS fiber is treated by boron trichloride and then nitrided in an ammonia atmosphere or firstly nitrided in the ammonia atmosphere and then dipped in a boric acid solution, and finally the PCS fiber is converted into SiBN (O) fiber by 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 permeating boron element into the fiber surface by using an atmosphere boron source or a liquid boron source has limitation, and the content of the boron element in the fiber is difficult to increase.
Disclosure of Invention
The invention provides a continuous SiBN fiber, a preparation method and application thereof, which are used for overcoming the defects of high process control difficulty, high cost, high oxygen element content, low boron element content and the like in the fiber in the prior art.
In order to achieve the above object, the present invention provides a method for preparing a continuous SiBN fiber, comprising the steps of:
s1: weighing polycarbosilane and polyborosilazane according to the mass ratio of (2:10) - (30:10), dissolving into an organic solvent, and stirring and uniformly mixing to obtain a raw material solution;
s2: heating the raw material liquid, and then removing the solvent to obtain a polycarbosilane-polyborosilazane block copolymer;
s3: carrying out melt spinning on the polycarbosilane-polyborosilazane segmented copolymer to obtain fibrils;
s4: at NH 3 Or BCl 3 Performing non-melting treatment on the fibril under the atmosphere to obtain non-melting fibril;
s5: and decarburizing the non-melting fibril in an ammonia atmosphere, and heating and sintering in an inert atmosphere to obtain the SiBN fiber.
In order to achieve the above object, the present invention also provides a continuous SiBN fiber produced by the above production method.
In order to achieve the purpose, the invention also provides an application of the continuous SiBN fiber, and the SiBN fiber prepared by the preparation method or the SiBN fiber is applied to a high-speed aircraft radome.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the continuous SiBN fiber provided by the invention takes polycarbosilane and polyborosilazane as precursors, the two precursors are physically mixed according to a certain proportion and then are uniformly stirred, and then are heated for thermal cross-linking reaction, so that Si-H of polycarbosilane and N-H of polyborosilazane are fully bonded, and the polycarbosilane-polyborosilazane segmented copolymer is obtained. And carrying out melt spinning on the block copolymer to obtain fibril, carrying out infusible treatment on the fibril in an ammonia gas or boron trichloride atmosphere, and then carrying out high-temperature decarburization and firing in the ammonia gas atmosphere to obtain the continuous SiBN fiber. The invention utilizes the mixture of polyborosilazane and polycarbosilaneAnd performing thermochemical reaction to obtain the polycarbosilane-polyborosilazane block copolymer with low air sensitivity, which is beneficial to preparing the continuous SiBN fiber with low oxygen content by a precursor conversion method. The invention simplifies the preparation process of SiBN fiber, reduces the preparation cost of the fiber, and the prepared SiBN fiber is compared with Si 3 N 4 The fiber has better high temperature performance.
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 an SEM photograph of SiBN fiber obtained in example 1;
FIG. 2 shows XPS spectra of SiBN fibers obtained in examples 1 to 4.
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 continuous SiBN fiber, which comprises the following steps:
s1: weighing polycarbosilane and polyborosilazane according to the mass ratio of (2:10) - (30:10), dissolving into an organic solvent, and stirring and uniformly mixing to obtain a raw material solution;
s2: heating the raw material liquid, and then removing the solvent to obtain polycarbosilane-polyborosilazane block copolymer;
s3: carrying out melt spinning on the polycarbosilane-polyborosilazane segmented copolymer to obtain fibrils;
s4: at NH 3 Or BCl 3 Performing non-melting treatment on the fibril under the atmosphere to obtain non-melting fibril;
s5: and decarburizing the non-melting fibril in an ammonia atmosphere, and heating and sintering in an inert atmosphere to obtain the SiBN fiber.
Preferably, in step S1, the polycarbosilane is obtained by performing pyrolysis rearrangement conversion on polydimethylsiloxane; the polyborosilazane is prepared by performing condensation reaction on chlorosilane, boron trichloride and hexamethyldisilazane.
Preferably, in step S1, the organic solvent is one of xylene, toluene, tetrahydrofuran, and dimethylformamide. The polarity is moderate, which is beneficial to the dissolution of the precursor.
Preferably, in step S2, the temperature of the heating treatment is 150 to 210 ℃ and the time is 1 to 10 hours. And (3) heating to fully bond the polycarbosilane and the polyborosilazane. The temperature is lower than 150 ℃, and bonding does not occur; above 210 ℃, the resulting precursor is easily crosslinked, which is not conducive to subsequent fiber preparation.
Preferably, in step S2, the solvent removal is specifically:
and (4) carrying out reduced pressure distillation by using a mechanical pump at the temperature of the heat treatment.
Preferably, in step S3, NH is introduced into the non-melting process 3 The flow rate of the (B) is 2-10 ml/(min. g), and the temperature is 50-300 ℃. By utilizing the reactivity of ammonia gas, the fiber is fedPerforming non-melting treatment; on one hand, economic benefits are considered for controlling the flow, and on the other hand, the effectiveness of non-melting is considered; the temperature is lower than 50 ℃ and does not react, and the temperature is higher than 300 ℃, so that the fiber is melted before being melted, and the shape of the fiber is not favorably maintained.
Preferably, in step S3, BCl is introduced into the non-melting treatment 3 The flow rate of (A) is 1-5 ml/(min. g), and the temperature is 50-150 ℃. Boron trichloride is also a reactant for fiber crosslinking. Since boron trichloride is more reactive than ammonia, effective crosslinking can be achieved at lower flow rates and lower temperatures.
Preferably, in step S4, the flow rate of ammonia gas introduced into the decarburization treatment is 5 to 50ml/(min g), the temperature rise rate is 1 to 5 ℃/min, and the temperature is 200 to 1000 ℃. The fiber is decarburized and nitrided. The temperature and the flow are controlled on the premise of considering economic benefits, the carbon content of the fiber is completely removed, and the high-temperature wave-transparent application of the fiber is facilitated.
The sintering temperature is 1300-1500 ℃, and the time is 1-8 h. The mechanical strength of the fiber sintered in the temperature range is optimal.
The invention also provides a continuous SiBN fiber prepared by the preparation method.
The invention also provides an application of the continuous SiBN fiber, and the SiBN fiber prepared by the preparation method or the SiBN fiber is applied to a high-speed aircraft radome.
Example 1
This embodiment provides a method for preparing continuous SiBN fibers, including the steps of:
(1) dissolving polycarbosilane and polyborosilazane into dimethylbenzene according to the mass ratio of 2:10, and fully and uniformly stirring by adopting a mechanical stirrer to obtain a uniformly dispersed mixed solution;
(2) heating the solution to 150 ℃, and preserving heat for 1h to ensure that polycarbosilane and polyborosilazane are fully bonded; distilling under reduced pressure at 150 ℃ by using a mechanical pump to remove the solvent to obtain polycarbosilane-polyborosilazane block copolymer;
(3) carrying out melt spinning on the obtained mixed precursor to obtain fibril;
(4) attaching fibrils to BCl 3 Performing non-melting treatment at 150 deg.C in atmosphere, introducing BCl 3 The flow rate is 5 ml/(min. g), the treatment time is 1h, and the infusible fibril is obtained;
(5) introducing ammonia gas into the non-molten fibril within the temperature range of 200-1000 ℃, wherein the flow rate of the ammonia gas is 5 ml/(min-g), and the heating rate is 5 ℃/min;
(6) and (3) after the temperature is increased to 1000 ℃, changing ammonia gas into nitrogen, continuously increasing the temperature to 1300 ℃, preserving the heat for 1h, and then cooling along with the furnace to obtain the continuous SiBN fiber, wherein the tensile strength is 1.2GPa, and the strength retention rate is 67% after the fiber is treated in the nitrogen atmosphere at 1600 ℃ for 1 h.
FIG. 1 is an SEM image of the SiBN fiber obtained in this example, which shows that the SiBN fiber obtained has a diameter of 12 μm and a smooth and dense micro-morphology.
Example 2
This example provides a method for preparing continuous SiBN fibers, comprising the steps of:
(1) dissolving polycarbosilane and polyborosilazane into dimethylbenzene according to the mass ratio of 10:10, and fully and uniformly stirring by adopting a mechanical stirrer to obtain a uniformly dispersed mixed solution;
(2) heating the solution to 170 ℃, and preserving heat for 2 hours to ensure that polycarbosilane and polyborosilazane are fully bonded; distilling under reduced pressure at 170 ℃ by using a mechanical pump to remove the solvent to obtain polycarbosilane-polyborosilazane block copolymer;
(3) carrying out melt spinning on the obtained mixed precursor to obtain fibril;
(4) placing the fibril in NH 3 Performing non-melting treatment at 200 deg.C in atmosphere, introducing NH 3 The flow rate is 10ml/(min g), the treatment time is 2h, and the infusible fibril is obtained;
(5) introducing ammonia gas into the non-molten fibril at the temperature of 200-1000 ℃, wherein the flow rate of the ammonia gas is 20 ml/(min-g), and the heating rate is 5 ℃/min;
(6) and (3) after the temperature is increased to 1000 ℃, changing ammonia gas into nitrogen, continuously increasing the temperature to 1400 ℃, preserving the heat for 2 hours, and then cooling along with the furnace to obtain the continuous SiBN fiber, wherein the tensile strength is 1.3GPa, and the strength retention rate is 72 percent after the fiber is treated in the nitrogen atmosphere at 1600 ℃ for 1 hour.
Example 3
This example provides a method for preparing continuous SiBN fibers, comprising the steps of:
(1) dissolving polycarbosilane and polyborosilazane into dimethylbenzene according to the mass ratio of 20:10, and fully and uniformly stirring by adopting a mechanical stirrer to obtain a uniformly dispersed mixed solution;
(2) heating the solution to 190 ℃, and preserving heat for 5 hours to ensure that polycarbosilane and polyborosilazane are fully bonded; distilling under reduced pressure at 190 ℃ by using a mechanical pump to remove the solvent to obtain polycarbosilane-polyborosilazane block copolymer;
(3) carrying out melt spinning on the obtained mixed precursor to obtain fibril;
(4) placing the fibril in NH 3 Non-melting treatment is carried out under the atmosphere, the treatment temperature is 150 ℃, and NH is introduced 3 The flow is 10 ml/(min. g), the treatment time is 5h, and the infusible fibril is obtained;
(5) introducing ammonia gas into the non-molten fibril within the temperature range of 200-1000 ℃, wherein the flow rate of the ammonia gas is 50 ml/(min-g), and the heating rate is 5 ℃/min;
(6) and (3) after the temperature is increased to 1000 ℃, changing ammonia gas into nitrogen, continuously increasing the temperature to 1500 ℃, preserving the heat for 1h, and then cooling along with the furnace to obtain the continuous SiBN fiber, wherein the tensile strength is 1.5GPa, and the strength retention rate is 65% after the fiber is treated in the nitrogen atmosphere at 1600 ℃ for 1 h.
Example 4
This example provides a method for preparing continuous SiBN fibers, comprising the steps of:
(1) dissolving polycarbosilane and polyborosilazane into dimethylbenzene according to the mass ratio of 30:10, and fully and uniformly stirring by adopting a mechanical stirrer to obtain a uniformly dispersed mixed solution;
(2) heating the solution to 210 ℃, and preserving heat for 1h to ensure that polycarbosilane and polyborosilazane are fully bonded; distilling under reduced pressure at 210 ℃ by using a mechanical pump to remove the solvent to obtain polycarbosilane-polyborosilazane block copolymer;
(3) carrying out melt spinning on the obtained mixed precursor to obtain fibril;
(4) attaching fibrils to BCl 3 Performing non-melting treatment at 150 deg.C in atmosphere, introducing BCl 3 The flow rate is 5 ml/(min. g), the treatment time is 1h, and the infusible fibril is obtained;
(5) introducing ammonia gas into the non-molten fibril within the temperature range of 200-1000 ℃, wherein the flow rate of the ammonia gas is 30 ml/(min-g), and the heating rate is 5 ℃/min;
(6) and (2) after the temperature is increased to 1000 ℃, changing ammonia gas into nitrogen, continuously increasing the temperature to 1600 ℃, preserving the heat for 1h, and then cooling along with the furnace to obtain the continuous SiBN fiber, wherein the tensile strength is 1.6GPa, and the strength retention rate is 86% after the fiber is treated in the nitrogen atmosphere at 1600 ℃ for 1 h.
FIG. 2 is an XPS spectrum of SiBN fibers obtained in examples 1-4, which shows that the SiBN fibers are mainly composed of Si, N, B and small amounts of O and C.
Comparative example 1
This embodiment provides a method for preparing SiBN fiber, including the following steps:
(1) carrying out melt spinning on polyborosilazane to obtain fibril;
(4) attaching fibrils to BCl 3 Performing non-melting treatment at 150 deg.C in atmosphere, introducing BCl 3 The flow rate is 5 ml/(min. g), the treatment time is 1h, and the infusible fibril is obtained;
(5) introducing ammonia gas into the non-molten fibril at the temperature of 200-1000 ℃, wherein the flow rate of the ammonia gas is 30 ml/(min-g), and the heating rate is 5 ℃/min;
(6) and (2) after the temperature is increased to 1000 ℃, changing ammonia gas into nitrogen, continuously increasing the temperature to 1600 ℃, preserving the heat for 1h, and then cooling along with the furnace to obtain the continuous SiBN fiber, wherein the tensile strength is 0.8GPa, and the strength retention rate is 75 percent after the fiber is treated in the nitrogen atmosphere at 1600 ℃ for 1 h.
Table 1 shows the performance parameters of SiBN fibers prepared in examples 1-4 and comparative example 1, and it can be seen from Table 1 that the boron content of the SiBN fibers prepared by the invention can be controlled in a large range of 3.6-9.5 wt%, the tensile strength is 1.2-1.6 GPa, the strength retention rate after 1600 ℃ treatment is more than 60%, and the SiBN fibers have excellent mechanical strength and high temperature resistance.
TABLE 1 SiBN fibers prepared 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 (10)
1. A method for preparing continuous SiBN fiber is characterized by comprising the following steps:
s1: weighing polycarbosilane and polyborosilazane according to the mass ratio of (2:10) - (30:10), dissolving into an organic solvent, and stirring and uniformly mixing to obtain a raw material solution;
s2: heating the raw material liquid, and then removing the solvent to obtain polycarbosilane-polyborosilazane block copolymer;
s3: carrying out melt spinning on the polycarbosilane-polyborosilazane segmented copolymer to obtain fibrils;
s4: at NH 3 Or BCl 3 Performing non-melting treatment on the fibril under the atmosphere to obtain non-melting fibril;
s5: and decarburizing the non-melting fibril in an ammonia atmosphere, and heating and sintering in an inert atmosphere to obtain the SiBN fiber.
2. The method of claim 1, wherein in step S1, the polycarbosilane is obtained by subjecting polydimethylsiloxane to pyrolysis rearrangement conversion; the polyborosilazane is prepared by performing condensation reaction on chlorosilane, boron trichloride and hexamethyldisilazane.
3. The method of claim 1, wherein in step S1, the organic solvent is one of xylene, toluene, tetrahydrofuran, and dimethylformamide.
4. The method according to claim 1, wherein the heat treatment is performed at 150 to 210 ℃ for 1 to 10 hours in step S2.
5. The method according to claim 1, wherein in step S2, the solvent removal is specifically:
and (4) carrying out reduced pressure distillation by using a mechanical pump at the temperature of the heat treatment.
6. The method according to claim 1, wherein in step S3, NH is introduced into the infusible material 3 The flow rate of the (B) is 2-10 ml/(min. g), and the temperature is 50-300 ℃.
7. The method of claim 1, wherein in step S3, BCl is introduced into the infusible material 3 The flow rate of (A) is 1-5 ml/(min. g), and the temperature is 50-150 ℃.
8. The method according to claim 1, wherein in step S4, the flow rate of ammonia gas introduced into the decarburization treatment is 5 to 50 ml/(min-g), the temperature rise rate is 1 to 5 ℃/min, and the temperature is 200 to 1000 ℃;
the sintering temperature is 1300-1500 ℃, and the time is 1-8 h.
9. A continuous SiBN fiber produced by the production method according to any one of claims 1 to 8.
10. The application of the continuous SiBN fiber is characterized in that the SiBN fiber prepared by the preparation method of any one of claims 1 to 8 or the SiBN fiber prepared by the preparation method of claim 9 is applied to a high-speed aircraft radome.
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| JPH07126393A (en) * | 1993-10-28 | 1995-05-16 | Tonen Corp | Thermosetting copolymer containing silicon and boron and its production |
| CN102249684A (en) * | 2011-05-10 | 2011-11-23 | 中国人民解放军国防科学技术大学 | Preparation method of SiBN(C) ceramic fiber |
| CN102515771A (en) * | 2011-12-09 | 2012-06-27 | 东华大学 | Continuous preparation method of silicon boron nitrogen-based ceramic fiber |
| CN106521710A (en) * | 2016-11-25 | 2017-03-22 | 厦门大学 | Preparation method of titanium-boron-containing carbonizedsilicon base ceramic fiber |
| CN110698678A (en) * | 2019-10-24 | 2020-01-17 | 中国科学院宁波材料技术与工程研究所 | Liquid curable boron-containing polycarbosilane and preparation method thereof |
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| JPH07126393A (en) * | 1993-10-28 | 1995-05-16 | Tonen Corp | Thermosetting copolymer containing silicon and boron and its production |
| CN102249684A (en) * | 2011-05-10 | 2011-11-23 | 中国人民解放军国防科学技术大学 | Preparation method of SiBN(C) ceramic fiber |
| CN102515771A (en) * | 2011-12-09 | 2012-06-27 | 东华大学 | Continuous preparation method of silicon boron nitrogen-based ceramic fiber |
| CN106521710A (en) * | 2016-11-25 | 2017-03-22 | 厦门大学 | Preparation method of titanium-boron-containing carbonizedsilicon base ceramic fiber |
| CN110698678A (en) * | 2019-10-24 | 2020-01-17 | 中国科学院宁波材料技术与工程研究所 | Liquid curable boron-containing polycarbosilane and preparation method thereof |
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