CN104831419B - A kind of preparation method of SiBN fiber - Google Patents
A kind of preparation method of SiBN fiber Download PDFInfo
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- CN104831419B CN104831419B CN201510257406.2A CN201510257406A CN104831419B CN 104831419 B CN104831419 B CN 104831419B CN 201510257406 A CN201510257406 A CN 201510257406A CN 104831419 B CN104831419 B CN 104831419B
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Abstract
The preparation method of a kind of SiBN fiber, comprises the following steps: the preparation of (1) high activity Si N fiber.Polycarbosilane fusion-free fibre is placed in decarburization nitride system, evacuation, then with gas in nitrogen or argon exchange system to normal pressure, repeats at least three times；Being passed through high-purity ammonia, heat up, within 2 hours, be warming up to 500 DEG C, after 0.90～0.95 DEG C/min is warming up to 700 DEG C, insulation 0.5h, 100 DEG C/h are warming up to 800～1200 DEG C, are incubated 1～2h.Logical nitrogen/argon air cooling, to room temperature, obtains high activity Si N fiber；(2) boronation of high activity Si N fiber.2h is warming up to 400～450 DEG C, is passed through the borane compound gas at least containing a B H key, response time 24～36h in system, and logical nitrogen/argon air cooling is to room temperature；(3) nitridation of boronation fiber.Being passed through high-purity ammonia, heat up, 6h is warming up to 1300～1400 DEG C, is incubated 1～2h.Logical nitrogen/argon air cooling to room temperature,.Present invention process is easy, and low cost is not required to existing decarburization nitride system is done any change, is suitable to large-scale production.
Description
Technical field
The present invention relates to the preparation method of a kind of SiBN fiber, especially relate to a kind of conversion with polycarbosilane fiber and prepare SiBN
The method of fiber.
Background technology
SiBN ceramic fibre is a kind of novel high temperature resistant wave-permeable ceramic fibre.Composite principle based on material, SiBN pottery is fine
Dimension has Si3N4Advantage (the Si of ceramic fibre and BN ceramic fibre3N4Ceramic fibre has higher intensity and preferable antioxidation
Performance, but resistance to elevated temperatures, dielectric properties are the poorest；BN ceramic fibre dielectric constant is low, and high-temperature stability is good, but its stretching is strong
Spending low, high-temperature oxidation resistance is poor).Have high temperature resistant, antioxidation, high-performance (good dielectric properties, mechanical property) concurrently
SiBN fiber be the Main way of high temperature resistant wave-permeable fiber.SiBN ceramic fibre not carbon elements can cause electromagnetism to damage with other
The component of consumption and thing phase, integrate the advantages such as wave transparent, high temperature resistant, antioxidation, dielectric properties are adjustable, may replace quartz fibre
For refractory ceramics base wave-penetrating composite material, prepare that excellent in mechanical performance, resistance to higher temperature, ablating rate be lower, electrical property
More stable wave-penetrating composite material, is with a wide range of applications in the fields such as Aeronautics and Astronautics.
Organic precursor method conversion method is as raw material with organic polymer (mostly being organometallic polymer), utilizes it solvable, fusible
After realizing molding etc. characteristic, process through high temperature thermal decomposition, the method being allowed to be changed into inorganic ceramic material from Organic substance.This is organic
Polymer is known as organic precursor method or ceramic precursor (preceramic polymer, precursor).Organic precursor method conversion method
Prepare continuous ceramic fiber and there is following distinguishing feature: (1) can prepare continuously, fiber that diameter is less (< 20 μm), fiber
Stitchability good, it is easy to braiding becomes the prefabricated component of complicated shape；(2) relatively low preparation temperature (< 1500 DEG C)；(3) may be used
Precursor is carried out MOLECULE DESIGN, controls the composition of precursor, such as the preparation functionality ceramic fiber etc. containing different element；(4)
Being suitable for industrialized production, production efficiency is high.Therefore, to prepare continuous ceramic fiber ideal for organic precursor method conversion method
Method.At present, organic precursor method conversion method has become one of main method preparing high performance silicon base ceramic fibre.
Organic precursor method is the most typically used to convert preparation SiBN ceramic fibre.Organic precursor method conversion method prepares SiBN pottery
Fiber generally can be divided into following four step operations: (1) precursor synthesizes, and i.e. synthesizes with target ceramic element, as Si, B, N, C,
Polymer-PVDF hollow fiber membrane (PBSZ) precursor that H etc. are key component；(2) spinning, will be spun by melted by PBSZ
The method of silk prepares PBSZ fibril；(3) crosslinking, is converted into thermosetting by thermoplastic PBSZ fibril by proper method
The PBSZ cross filament of property, i.e. PBSZ fusion-free fibre；(4) high temperature burns till, and i.e. makes PBSZ fusion-free fibre under high temperature
Inorganic chemical conversion SiBN ceramic fibre.
PVDF hollow fiber membrane is the critical materials of SiBN fiber, and its synthetic yield is low, and it is big that molecular structure controls difficulty.Additionally, it is former
Material list body, PBSZ precursor are extremely sensitive to water, air, and Control for Oxygen Content difficulty is very big, require the highest to appointed condition, work
Skill controls the most difficult.
The Okamura of Japan Atomic Energy Research Institute etc. use Polycarbosilane (PCS) fiber conversion method to have developed Si-N fiber.Point
After PCS fiber not being carried out crosslinking with radiation and air curing respectively, then pass through NH at low temperatures3Nitridation removing carbon, with
Time introduce nitrogen element, high temperature just obtains Si after burning till3N4With SiNO fiber.The main deficiency of this method is to pass through PCS
Fiber converts the Si of preparation3N4Fibre fire resistant performance is relatively low, dielectric properties are poor, it is difficult to meet application demand.Draw in the fibre
Enter heterogeneous element, suppress crystallite growth at high temperature, be one of major measure improving fibre fire resistant performance.Research shows,
In Si-N fiber, introduce B element, be possible not only to be effectively improved its resistance to elevated temperatures, it is also possible to effectively regulate its dielectric properties.
At present, the incorporation way of B element mainly has 2 kinds: introduces B element in PCS, introduce B element in cross-linking process.
After introducing B element in PCS, B element content is the most relatively low, and adversely affects the spinnability of precursor.In crosslinking
During introduce B element time, BCl3Higher to equipment requirements Deng aggressive atmosphere, additionally, due to relate to removing HCl, methyl
Etc. process, the structure of fibril is caused relatively macrolesion.
Summary of the invention
The deficiency existed for prior art, it is an object of the invention to provide the preparation method of a kind of SiBN fiber.
The technical scheme is that, prepare high activity Si-N fiber initially with PCS fusion-free fibre conversion, then utilize height
Dehydrogenation coupled reaction between N-H and the borane compound containing B-H key had more than needed in activity Si-N fiber, it is achieved B element
Chemistry introduces, then nitrogenizes in ammonia, prepares SiBN fiber.
Specifically,
The preparation method of a kind of SiBN fiber, comprises the following steps:
(1) preparation of high activity Si-N fiber
A. Polycarbosilane fusion-free fibre is placed in decarburization-nitride system, evacuation, then with gas in nitrogen or argon exchange system
Body, to normal pressure, repeats at least three times；
B. in decarburization-nitride system, it is passed through high-purity ammonia, while being passed through high-purity ammonia, internal system is heated up, wherein heated up
Within Cheng Wei: 2 hours, being warming up to 500 DEG C, after 0.90～0.95 DEG C/min is warming up to 700 DEG C, insulation 0.5h, 100 DEG C/h are warming up to
800～1200 DEG C, it is incubated 1～2h；
C. in decarburization-nitride system, logical nitrogen/argon air cooling, to room temperature, obtains high activity Si-N fiber；
(2) boronation of high activity Si-N fiber
Decarburization-nitride system 2h is warming up to 400～450 DEG C, is passed through in decarburization-nitride system at least containing a B-H key
Borane compound gas, in the response time 24～36h, logical nitrogen/argon air cooling is to room temperature；
(3) nitridation of boronation fiber
Being passed through high-purity ammonia to decarburization-nitride system, while being passed through high-purity ammonia heat up internal system, 6h is warming up to
1300～1400 DEG C, be incubated 1～2h, logical nitrogen/argon air cooling to room temperature,.
Further, the present invention at least contains the borane compound gas R of a B-H key described in step (2)1R2BH, its
Middle R1、R2Saturated hydrocarbyl, unsaturated alkyl, aromatic radical or H for C atomic number≤10.
Further, purity >=99.9999% of high-purity ammonia of the present invention.
Further, purity >=99.99% of the borane compound gas at least containing a B-H key of the present invention.
Further, nitrogen of the present invention or purity >=99.999% of argon.
The Advantageous Effects of the present invention:
1, the present invention converts initially with PCS fusion-free fibre and prepares highly active Si-N fiber, then through boronation, nitridation reaction,
Preparation SiBN fiber.Under PCS precursor room temperature more stable, insensitive to empty gas and water under room temperature, it is not necessary to anhydrous and oxygen-free operates,
Simple to operate；PCS precursor synthetic technology is perfect, and domestic built vertical multiple stage set is produced the PCS precursor synthesis of more than 5 tons per year and is
System；PCS precursor melt spinning, crosslinking technological comparative maturity.It is therefore not necessary to the synthesis of existing PCS precursor, melt
Spinning, crosslinking process adjust, it is only necessary to adjust decarburization-nitriding process, can obtain high activity Si-N fiber；
2, reacted and follow-up nitridation reaction by the boronation of boron source compound with high activity Si-N fiber, it is achieved B element can
Control introduces.On the one hand the introducing of B element, can improve the stability of fiber, resistance to elevated temperatures, dielectric properties, on the other hand,
Compensate for the micropore of Si-N fiber, be conducive to improving the mechanical property of fiber；
3, in the preparation process of high activity Si-N fiber, it is different from existing conventional techniques employing single-rate and is warming up to target temperature
Degree, the present invention uses multistage temperature-raising method, it is to avoid because of organic and inorganic drastically convert, decarburization and formed in the fibre big micropore,
Crackle, and cause fibre property to deteriorate.Meanwhile, the present invention is with single high-purity ammonia as reaction gas, and the Si-N fiber of preparation is lived
Property higher, be more beneficial for the reaction of follow-up boronation.
4, during the boronation of high activity Si-N fiber, the present invention uses the borane compound gas at least containing a B-H key to make
For boron source compound, not having corrosivity, lower to equipment requirements, cost is lower.
5, during the boronation of high activity Si-N fiber, boronation reaction temperature of the present invention is less than 500 DEG C.
6, during the boronation of high activity Si-N fiber, owing to boronation reaction is gas-solid reaction, reactant is difficult to fibrous inside
Spreading, permeate, react, the shorter response time easily causes reaction not exclusively, and Boron contents is low, and at fiber ladder radially
Degree distribution, i.e. the uneven distribution of boron element.In the present invention response time 24～36h, the response time is longer, so boron element is permissible
Penetrate into fibrous inside, fiber Boron contents higher, fill up micropore, the crackle stayed at fibrous inside because of decarburization, improve
The consistency of fiber, fibre strength is higher；
7, high temperature vacuum pumping, has certain danger, the present invention boronation react before and after without high temperature vacuum pumping,
Simplify operation, it is to avoid dangerous.
8, the nitridation stage of boronation fiber, the present invention leads to ammonia to having reacted, and nitridation reaction is more thorough.
Compared to prior art, use the Boron contents of the SiBN fiber that the inventive method makes higher and be evenly distributed, nitrogen content
Higher, fibre strength is higher.The present invention is by N-H more than needed in high activity Si-N fiber and the borane compound containing B-H key
Between dehydrogenation coupling, it is achieved B element chemistry introducing.The Boron contents of the SiBN fiber that employing the inventive method is made is higher
And be evenly distributed, nitrogen content is higher, fibre strength is higher.The present invention has simple process, the advantage of low cost.With poly-borosilicate
Azane precursor route is prepared SiBN fiber and is compared, and the present invention prepares SiBN fiber and has bigger cost advantage.And be not required to right
Existing decarburization-nitride system does any equipment and changes, and is suitable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the x-ray photoelectron spectroscopy full figure (XPS) of the SiBN fiber of embodiment 1 preparation
Fig. 2 is the SiBN fiber radially B element x-ray photoelectron spectroscopy (XPS) of embodiment 1 preparation
Detailed description of the invention
Embodiment 1
Polycarbosilane fusion-free fibre is placed in decarburization-nitride system, evacuation, then with gas in nitrogen or argon exchange system
To normal pressure, repeat at least three times；Being passed through high-purity ammonia, heat up, temperature increasing schedule: 2h is warming up to 500 DEG C, 0.95 DEG C/min liter
After warm to 700 DEG C, insulation 0.5h, 1h are warming up to 800 DEG C, are incubated 2h.Logical nitrogen/argon air cooling, to room temperature, obtains high living
Property Si-N fiber；2h is warming up to 400 DEG C, is passed through borine, response time 24h, logical nitrogen/argon gas in decarburization-nitride system
It is cooled to room temperature；Being passed through high-purity ammonia, heat up, 6h is warming up to 1350 DEG C, is incubated 1～2h.Logical nitrogen/argon air cooling to room temperature,
?.
Fig. 1 is that the X-ray photoelectron of the SiBN fiber of preparation can be schemed (XPS).The peak at 100.5 electron-volts of (eV) places is
Si2p, the peak at 152.1eV is Si2s, the peak at 192.5eV is B1s, the peak at 283.8eV is C1s, 400.8eV is N1s,
Peak at 533.7eV is O1s.Owing to XPS can detect all elements in addition to H, and the absolute sensitivity of qualitative analysis
Height, therefore, the fiber prepared is elementary composition by Si, B, N, C, O.Elementary analysis shows, Si, 54.62wt%,
B, 5.25wt%, N, 39.02wt%, C, 0.09wt%, O, 1.02wt%.The filament strength of the fiber prepared is 2.26GPa,
Elastic modelling quantity is 127GPa.
Fig. 2 is SiBN fiber radially B element x-ray photoelectron spectroscopy (XPS), and in Fig. 2,0,1,2,3,4 refer to respectively
Fiber sheath, fiber radially 60,120,180,240nm place B spectrum, show that B has penetrated into fibrous inside and has been distributed relatively
Uniformly.
Embodiment 2
Polycarbosilane fusion-free fibre is placed in decarburization-nitride system, evacuation, then with gas in nitrogen or argon exchange system
To normal pressure, repeat at least three times；Being passed through high-purity ammonia, heat up, temperature increasing schedule: 2h is warming up to 500 DEG C, 0.90 DEG C/min liter
After warm to 700 DEG C, insulation 0.5h, 3h are warming up to 1000 DEG C, are incubated 1h.Logical nitrogen/argon air cooling, to room temperature, obtains high living
Property Si-N fiber；2h is warming up to 450 DEG C, is passed through dimethylaminoborane, response time 36h, logical nitrogen in decarburization-nitride system
Gas/argon is cooled to room temperature；Being passed through high-purity ammonia, heat up, 6h is warming up to 1400 DEG C, is incubated 1h.Logical nitrogen/argon air cooling
To room temperature,.
Preparation the X-photoelectron spectroscopy figure of SiBN fiber, radially B element x-ray photoelectron spectroscopy respectively with Fig. 1,2 bases
This is consistent.Fiber element consists of, Si, 54.74wt%, B, 5.13wt%, N, 39.08wt%, C, 0.09wt%, O, and 0.96
Wt%.The filament strength of fiber is 2.17GPa, and elastic modelling quantity is 126GPa.
The explanation of the preferred embodiment of the present invention contained above, this is the technical characteristic in order to describe the present invention in detail, is not intended to
Summary of the invention is limited in the concrete form described by embodiment, other amendments carried out according to present invention purport and change
Type is also protected by this patent.The purport of present invention is to be defined by the claims, rather than by the specific descriptions institute of embodiment
Define.
Claims (5)
1. the preparation method of a SiBN fiber, it is characterised in that comprise the following steps:
(1) preparation of high activity Si-N fiber
A. Polycarbosilane fusion-free fibre is placed in decarburization-nitride system, evacuation, then with gas in nitrogen or argon exchange system
Body, to normal pressure, repeats at least three times；
B. in decarburization-nitride system, it is passed through high-purity ammonia, while being passed through high-purity ammonia, internal system is heated up, wherein heated up
Within Cheng Wei: 2 hours, being warming up to 500 DEG C, after 0.90～0.95 DEG C/min is warming up to 700 DEG C, insulation 0.5h, 100 DEG C/h are warming up to
800～1200 DEG C, it is incubated 1～2h；
C. in decarburization-nitride system, logical nitrogen/argon air cooling, to room temperature, obtains high activity Si-N fiber；
(2) boronation of high activity Si-N fiber
Decarburization-nitride system 2h is warming up to 400～450 DEG C, is passed through in decarburization-nitride system at least containing a B-H key
Borane compound gas, in the response time 24～36h, logical nitrogen/argon air cooling is to room temperature；
(3) nitridation of boronation fiber
Being passed through high-purity ammonia to decarburization-nitride system, while being passed through high-purity ammonia heat up internal system, 6h is warming up to
1300～1400 DEG C, be incubated 1～2h, logical nitrogen/argon air cooling to room temperature,.
The preparation method of SiBN fiber the most according to claim 1, it is characterised in that: described in step (2) extremely
Borane compound gas R containing a B-H key less1R2BH, wherein R1、R2Saturated hydrocarbyl, no for C atomic number≤10
Saturated hydrocarbyl, aromatic radical or H.
The preparation method of SiBN fiber the most according to claim 1, it is characterised in that: the purity of described high-purity ammonia
>=99.9999%.
The preparation method of SiBN fiber the most according to claim 1, it is characterised in that: described at least containing a B-H key
Purity >=99.99% of borane compound gas.
5. according to the preparation method of the SiBN fiber described in claim 1,2,3 or 4, it is characterised in that: described nitrogen or
Purity >=99.999% of argon.
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| CN110820061B (en) * | 2019-11-27 | 2021-01-01 | 中国人民解放军国防科技大学 | SiBN fiber with radial gradient distribution of composition/structure and preparation method thereof |
| CN111039678B (en) * | 2019-12-25 | 2021-11-19 | 中国人民解放军国防科技大学 | Gradient double-atmosphere non-melting method for polysilazane (borazane) fiber |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830706A (en) * | 2010-05-28 | 2010-09-15 | 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 |
| CN103952796A (en) * | 2014-04-28 | 2014-07-30 | 中国人民解放军国防科学技术大学 | Preparation method of silicon-nitrogen-boron continuous ceramic fibers |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830706A (en) * | 2010-05-28 | 2010-09-15 | 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 |
| CN103952796A (en) * | 2014-04-28 | 2014-07-30 | 中国人民解放军国防科学技术大学 | Preparation method of silicon-nitrogen-boron continuous ceramic fibers |
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