CN109385693A - Preparation method of Si-B-N ceramic fiber - Google Patents
Preparation method of Si-B-N ceramic fiber Download PDFInfo
- Publication number
- CN109385693A CN109385693A CN201811241027.4A CN201811241027A CN109385693A CN 109385693 A CN109385693 A CN 109385693A CN 201811241027 A CN201811241027 A CN 201811241027A CN 109385693 A CN109385693 A CN 109385693A
- Authority
- CN
- China
- Prior art keywords
- atmosphere
- fiber
- polycarbosilane
- ceramic fibre
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Abstract
A preparation method of Si-B-N ceramic fiber is provided, which comprises the following steps: 1) carrying out electron beam irradiation crosslinking on the polycarbosilane fiber in a boron-containing atmosphere to obtain boron-containing polycarbosilane infusible fiber; 2) heating boron-containing polycarbosilane infusible fiber in an ammonia atmosphere, then converting the atmosphere into an inert atmosphere, and continuously heating up in the inert atmosphere to obtain the Si-B-N ceramic fiber. According to the method, polycarbosilane fiber is used as a raw material, boron is introduced in the process of not melting, and the Si-B-N ceramic fiber is prepared through subsequent nitridation and high-temperature sintering, wherein the boron content of the obtained Si-B-N ceramic fiber is adjustable and controllable, the oxygen content is lower than 2 wt%, the carbon content is lower than 1 wt%, the tensile strength is greater than 1.5GPa, and the Si-B-N ceramic fiber has excellent wave-transmitting performance and high-temperature resistance.
Description
Technical field
The present invention relates generally to ceramics and ceramic fibre field, is specifically related to a kind of preparation method of ceramic fibre.
Background technique
Si-B-N ceramic fibre is by BN fiber and Si3N4The excellent properties of fiber are combined together, good with heat resistance,
The characteristics of intensity is high and wave transparent is had excellent performance, can meet High Mach number aircraft High-temperature-reswave-transparent wave-transparent composite material to wave transparent fiber
Requirement, be the main direction of development of high temperature resistant wave-permeable ceramic fibre.
Si-B-N ceramic fibre generallys use precursor pyrolysis and hot pressing preparation.Common method is that first synthesis PVDF hollow fiber membrane is first
Body is driven, using it as raw material, prepares Si-B-N ceramic fibre by spinning, non-fusible and high temperature firing.As Japanese East Asia fuel is public
Department is (referring to patent US5030744 and document Synthesis of a polyborosilazane and its conversion
into inorganic compounds.Journal of the American Ceramic Society,1993,76:717-
723) low molecule methyl hydrogen polysilazane and borine hybrid reaction are obtained into PVDF hollow fiber membrane, PVDF hollow fiber membrane is then dissolved in two
In toluene, PVDF hollow fiber membrane xylene solution is adjusted to sticky and spins state, obtains PVDF hollow fiber membrane fibrinogen through dry spinning, it is former
Fiber is pyrolyzed under ammonia atmosphere to 600 DEG C, then 1700 DEG C plus the obtained Si-B-N ceramic fibre of firing in a nitrogen atmosphere, fine
Tieing up average diameter is 10 μm, tensile strength 3.2GPa, modulus 400GPa.Seyferth etc. is (referring to patent US 5171736
With document Borasilazane Polymeric Precursors for Borosilicon Nitride.Journal of
The American Ceramic Society, 1990,73:2131-2133) by 1,3,5- trimethyl cyclotrisilazane and borine
1h is reacted in reflux in toluene, PVDF hollow fiber membrane is obtained by silicon azo-cycle open loop, it is the fusible Pick Wire of the PVDF hollow fiber membrane, non-fusible
And high temperature pyrolysis prepares fixed length SiBN ceramic fibre.Jansen etc. is (referring to 7297649 B2 of patent US；Patent EP
0502399A2；Patent US 5233066 and document Ceramic fibers for matrix composites in high-
Temperature engine application.Science, 1999,285:699-703) control hexamethyldisilazane
(HMDZ) and silicon tetrachloride (SiCl4) reaction condition so that SiCl4In an only Si-Cl key reacted with HMDZ, then will be anti-
Answer product and BCl3Reaction has obtained two chloroborane (TADB) of trichlorine silicon substrate amino, and TADB can be had using different crosslinking agents
There is the PVDF hollow fiber membrane of different performance, ammonolysis obtains insoluble white solid, and the liquid that methylamine solution obtains dissolving in n-hexane is poly-
Object is closed, which obtains solid-state PVDF hollow fiber membrane in 240 DEG C of heat cross-linkings, and the group of PBSZ becomes
SiB1.1N4.2C3.6H12.5O0.04, which can be used for preparing SiBNC ceramic fibre.The National University of Defense technology is (referring to patent
CN200710035733.9；CN200710035734.3；CN 200810031253.X；CN 200810031251.0；CN
200910311781.5) with BCl3、HMeSiCl2It is raw material with hexamethyldisilazane, has synthesized polymerized boron silazane precursor, passes through
Melt spinning, non-fusible and high temperature firing are crossed, Si-B-N ceramic fibre is prepared for.Donghua University is (referring to CN
200710170513.7；CN 201110410000.5) use precursor pyrolysis and hot pressing to be also prepared for Si-B-N ceramic fibre.Due to
SiCl involved in the synthesis process of PVDF hollow fiber membrane4、BCl3Contour activated monomer, meanwhile, in the PVDF hollow fiber membrane of synthesis containing compared with
More Si-N, B-N isoreactivity keys, it is extremely sensitive to air, moisture, so that synthesis process is high to equipment, process conditions requirement, batch
Quantifying is standby difficult, while the cost for also resulting in polymerized boron silazane precursor and Si-B-N ceramic fibre is very high, limits the fibre
The application of dimension.
Another preparation method nitrogenizes decarburization using Polycarbosilane fusion-free fibre as raw material, using under ammonia atmosphere, so
Afterwards in BCl3Borax treatment under atmosphere, then (referring to patent CN 201410173365.4) is made after high temperature firing.The technique road
Raw material used in line is Polycarbosilane, and for mature industrialization product, performance is relatively stable, and process route is relatively easy.But
It is to need all to replace the carbon in Polycarbosilane molecule with nitrogen in nitridation process, which can make to form a large amount of lack in fiber
It falls into, influences the mechanical property and heat resistance of fiber.In addition, atmosphere used in boronation process is the BCl of strong corrosive3Gas
Atmosphere, the requirement to production equipment are high, it is difficult to mass production.Moreover, the fiber-reactive after nitridation is lower, it is difficult to BCl3Deng
Gas reaction, the boron content for causing this method to introduce is lower (≤2wt%), limits the heat resistance of fiber.
Summary of the invention
It is strong for the above boronation raw material corrosivity existing in the prior art, boron introduction volume is low, complex process, it is at high cost,
The problems such as gained fiber heat resistance is insufficient, the present invention provides a kind of preparation method of Si-B-N ceramic fibre, this method institutes
More stable with boron source, the boron content of introducing is controllable within the scope of 1~15wt%, and processing step is less, and technique is simpler,
It is suitble to industrialized production；The method of the present invention prepare resulting Si-B-N ceramic fibre in an inert atmosphere 1700 DEG C processing after still have
The intensity of 1GPa is the ideal reinforcing fiber of High-temperature-reswave-transparent wave-transparent composite material.
The technical scheme is that a kind of preparation method of Si-B-N ceramic fibre, comprising the following steps:
1) polycarbosilane fiber is placed in device, boracic atmosphere is filled with after vacuumizing, then carry out electron beam irradiation friendship
Connection, obtains the Polycarbosilane fusion-free fibre of boracic；
2) the Polycarbosilane fusion-free fibre of boracic is first heated in ammonia atmosphere the first high temperature, then changes atmosphere
For inert atmosphere, continues to be heated to the second high temperature in an inert atmosphere, obtain Si-B-N ceramic fibre.
The method of the present invention, by being introduced directly into boron in cross-linking process, obtains boracic using polycarbosilane fiber as raw material
Polycarbosilane fusion-free fibre then passes through nitridation decarburization, obtains Si-B-N ceramic fibre.It is fine to solve current Si-B-N ceramics
Tieing up non-fusible, nitridation, boronation present in preparation process, the caused process route of progress is long step by step, and technique controlling difficulty is big, at
This high problem, it is to prepare height that in addition, also overcoming, prior art boronation atmosphere corrosion is big, boron content introduces low problem
The new method of performance Si-B-N ceramic fibre.
Further, above-mentioned steps 1) in polycarbosilane fiber be by softening point within the scope of 70~240 DEG C and oxygen content
Polycarbosilane lower than 1wt% is made through melt spinning, and the diameter of the polycarbosilane fiber is less than 30 μm.Polycarbosilane it is soft
If change point be lower than 70 DEG C, will lead in irradiation process it is meltable simultaneously, if be higher than 240 DEG C, will be unable to spinning and poly- carbon silicon be made
Alkane fiber.The diameter of polycarbosilane fiber is greater than 30 μm, will lead to subsequent ammonia nitridation and is not thorough, there is nitride fiber core
More carbon more than needed influences the wave transparent performance of final ceramic fibre.
Further, above-mentioned steps 1) in boracic atmosphere refer to containing B2H6、B4H10、B3N3H6One of gas, or
Refer to B2H6、B4H10、B3N3H6One of gas and inert gas mixed gas.B2H6、B4H10、B3N3H6In containing more
B-H active group easily reacts with the polycarbosilane fiber after irradiation, realizes the introducing of boron element.
It is also further, above-mentioned B2H6、B4H10、B3N3H6One of gas and polycarbosilane fiber mass ratio be (1~
50): 100.If the mass ratio of boron-containing gas and polycarbosilane fiber is lower than 1:100, finally obtained Si-B-N ceramic fibre
Middle boron content is lower than 1wt%, and fiber heat resistance is poor.If the mass ratio of boron-containing gas and polycarbosilane fiber is higher than 50:
100, boron-containing gas is excessive, can not be introduced into fusion-free fibre, cause environmental pollution.
Also further, above-mentioned steps 1) in electron beam irradiation condition are as follows: radiation dose rate 10~105Gy/s, irradiation
Accumulated dose is 5~40MGy.Dosage rate is lower than 10Gy/s, and polycarbosilane fiber can not generate enough free radicals and realize crosslinking, and
Low efficiency, dosage rate are higher than 105Gy/s, fusion-free fibre are molten simultaneously.Accumulated dose is lower than 5MGy, and fusion-free fibre crosslinking degree is not
It is enough, in subsequent sintering process and silk.Accumulated dose is higher than 40MGy, has no significant effect to the preparation of subsequent ceramic fibre, but can waste spoke
According to dosage, fiber cost is improved.
Also further, above-mentioned steps 2) in the method that is heated in ammonia atmosphere are as follows: according to the liter of 0.1~10 DEG C/min
Warm speed from room temperature to 500~1000 DEG C within the scope of the first high temperature, and in first 0.5~4h of soak.Heating speed
Degree is lower than 0.1 DEG C/min, influences to be burnt into efficiency.Heating rate is higher than 10 DEG C/min, and the small molecule in pyrolytic process can not be timely
Evolution, forms a large amount of defects in the fibre, influences Properties of Ceramic Fiber.Ammonia treatment temperature is lower than 500 DEG C, and nitridation reaction can not
It carries out, ceramic fibre carbon content is high.Ammonia treatment temperature is higher than 1000 DEG C, and the free radical that nitridation reaction generates can not inactivate, and makes pottery
Porcelain fiber oxygen content is high.Soaking time is lower than 0.5h, and nitridation reaction is incomplete, and ceramic fibre carbon content is high.Soaking time is higher than
4h, nitridation reaction is excessive, and the free radical that nitridation reaction generates can not inactivate, and ceramic fibre oxygen content is high.
Also further, above-mentioned steps 2) in ammonia atmosphere refer to the mixed gas of pure ammonia or pure ammonia and nitrogen,
When ammonia atmosphere is the mixed gas of pure ammonia and nitrogen, the concentration of pure ammonia is greater than 30vol% in mixed gas.Ammonia is dense
When degree is lower than 30vol%, nitridation reaction is not thorough, and the carbon content of ceramic fibre is high, influences the wave transparent performance of fiber.
Also further, above-mentioned steps 2) in method for continuing heating in an inert atmosphere are as follows: according to 1~30 DEG C/min's
Heating rate rises to the second high temperature within the scope of 1000~1700 DEG C from the temperature after transformation atmosphere from by temperature, and high second
0.5~4h of temperature heat preservation.Heating rate is lower than 1 DEG C/min, influences to be burnt into efficiency.Heating rate is higher than 30 DEG C/min, and fiber heat is steady
A large amount of defects are formed during fixed, influence Properties of Ceramic Fiber.Treatment temperature is lower than 1000 DEG C, and fiber composed structure is not up to steady
Determine state, influences the heat resistance of ceramic fibre.Treatment temperature is higher than 1700 DEG C, and ceramic fibre crystallization generates defect, influences fibre
The mechanical property of dimension.Soaking time is lower than 0.5h, and thermostabilization process does not complete, and influences the heat resistance of ceramic fibre.When heat preservation
Between be higher than 4h, ceramic fibre crystallization, generate defect, influence the mechanical property of fiber.
Also further, above-mentioned inert atmosphere refers to argon gas and helium.
The present invention also provides the resulting Si-B-N ceramic fibre of above-mentioned preparation method, the boron of the Si-B-N ceramic fibre contains
Amount is controllable between 1~15wt%, and oxygen content is lower than 2wt%, and carbon content is lower than 1wt%, and tensile strength is greater than 1.5GPa.
The solution have the advantages that:
The method of the present invention, by being introduced directly into boron in cross-linking process, obtains boracic using polycarbosilane fiber as raw material
Polycarbosilane fusion-free fibre then passes through nitridation decarburization, obtains Si-B-N ceramic fibre.Compared with the existing technology, of the invention
The reaction of non-fusible and boronation is realized that processing step is less, and technique is simpler in a processing step, boron source used is boron
Alkane and boron azane, gases, the property such as opposite boron chloride are more stable.In addition, under the conditions of electron beam irradiation, polycarbosilane fiber
In contain a large amount of free radical, easily reacted with borine, boron azane, so as to more large content of introducing boron element.Work of the present invention
Skill step is few, simple process, is suitble to industrialized production.The resulting Si-B-N Properties of Ceramic Fiber of the method for the present invention is excellent, lazy
Property atmosphere in still have the intensity of 1GPa after 1700 DEG C of heating, be the ideal reinforcing fiber of High-temperature-reswave-transparent wave-transparent composite material.
Detailed description of the invention
From the detailed description with reference to the accompanying drawing to the embodiment of the present invention, these and/or other aspects of the invention and
Advantage will become clearer and be easier to understand, in which:
Fig. 1 is the flow diagram of preparation method of the present invention；
Fig. 2 (a), (b) are the electron microscopics of the different amplification of Si-B-N ceramic fibre prepared by the embodiment of the present invention 1
Picture；
Fig. 3 is the X-ray diffractogram of Si-B-N ceramic fibre prepared by the embodiment of the present invention 1；
Fig. 4 is the infrared spectrogram of Si-B-N ceramic fibre prepared by the embodiment of the present invention 1；
Fig. 5 is the dielectric properties of Si-B-N ceramic fibre prepared by embodiment 1.
Specific embodiment
In order to make those skilled in the art more fully understand the present invention, with reference to the accompanying drawings and detailed description to this hair
It is bright to be described in further detail.
Embodiment 1
The preparation of Si-B-N ceramic fibre, according to flow diagram shown in FIG. 1: by softening point be 176 DEG C, oxygen content is
The polycarbosilane fiber that diameter is 16.7 μm is made through melt spinning in the Polycarbosilane of 0.44wt%.By 10g polycarbosilane fiber
It is placed in obturator, vacuumizes replacement of helium twice, be filled with 1gB after being subsequently vacuumed out into obturator2H6Gas, will be close
It closes device and is placed in cross-linking radiation under electron accelerator, step up dosage to irradiating accumulated dose according to predose rate 100Gy/s
Reach 15MGy, obtains the Polycarbosilane fusion-free fibre of boracic.The Polycarbosilane fusion-free fibre of boracic is then placed in firing
In furnace, vacuumizes displacement ammonia three times, temperature is then risen to 900 DEG C according to the speed of 1 DEG C/min under ammonia atmosphere and is protected
Warm 1h, replacement atmosphere are argon gas, and temperature is risen to 1600 DEG C according to the speed of 4 DEG C/min and keeps the temperature 1h, obtain Si-B-N ceramics
Fiber.
The tensile strength of gained Si-B-N ceramic fibre is 1.82GPa, boron content 7.20wt%, and oxygen content is
0.86wt%, carbon content 0.64wt%.Fig. 2 (a), the electronics that (b) is Si-B-N ceramic fibre different amplification obtained
Displaing micro picture, it can be seen that fiber surface is smooth, and cross section structure is fine and close, shows excellent mechanical property.Fig. 3 is gained Si-B-
The XRD diagram of N ceramic fibre, it can be seen that fiber is typical amorphous state.Fig. 4 is the infrared spectroscopy of Si-B-N ceramic fibre
Figure, it was demonstrated that Si-N and B-N structure is mainly contained in fiber.Fig. 5 is the dielectric properties of Si-B-N ceramic fibre, and dielectric constant is about
3.52, dielectric loss 10-3~10-4Magnitude, low dielectric constant and dielectric loss confirm the excellent wave transparent performance of fiber.
Embodiment 2
The preparation of Si-B-N ceramic fibre, according to flow diagram shown in FIG. 1: by softening point be 176 DEG C, oxygen content is
The polycarbosilane fiber that diameter is 16.7 μm is made through melt spinning in the Polycarbosilane of 0.44wt%.By 10g polycarbosilane fiber
It is placed in obturator, vacuumizes replacement of helium twice, be filled with 0.1gB after being subsequently vacuumed out into obturator2H6Gas, will
Obturator is placed in cross-linking radiation under electron accelerator, steps up dosage to irradiating total agent according to predose rate 100Gy/s
Amount reaches 15MGy, obtains the Polycarbosilane fusion-free fibre of boracic.The Polycarbosilane fusion-free fibre of boracic is then placed in burning
At displacement ammonia in furnace, is vacuumized three times, temperature is then risen to 900 DEG C simultaneously according to the speed of 1 DEG C/min under ammonia atmosphere
1h is kept the temperature, replacement atmosphere is argon gas, and temperature is risen to 1600 DEG C according to the speed of 4 DEG C/min and keeps the temperature 1h, obtains Si-B-N pottery
Porcelain fiber.
The tensile strength of gained fiber is 1.53GPa, boron content 1.32wt%, oxygen content 0.92wt%, carbon content
For 0.68wt%.
Embodiment 3
The preparation of Si-B-N ceramic fibre, according to flow diagram shown in FIG. 1: by softening point be 176 DEG C, oxygen content is
The polycarbosilane fiber that diameter is 16.7 μm is made through melt spinning in the Polycarbosilane of 0.44wt%.By 10g polycarbosilane fiber
It is placed in obturator, vacuumizes replacement of helium twice, be filled with 5gB after being subsequently vacuumed out into obturator2H6Gas, will be close
It closes device and is placed in cross-linking radiation under electron accelerator, step up dosage to irradiating accumulated dose according to predose rate 100Gy/s
Reach 15MGy, obtains the Polycarbosilane fusion-free fibre of boracic.The Polycarbosilane fusion-free fibre of boracic is then placed in firing
In furnace, vacuumizes displacement ammonia three times, temperature is then risen to 900 DEG C according to the speed of 1 DEG C/min under ammonia atmosphere and is protected
Warm 1h, replacement atmosphere are argon gas, and temperature is risen to 1600 DEG C according to the speed of 4 DEG C/min and keeps the temperature 1h, obtain Si-B-N ceramics
Fiber.
The tensile strength of gained fiber is 1.88GPa, boron content 14.85wt%, oxygen content 0.66wt%, carbon content
For 0.71wt%.
Embodiment 4
The preparation of Si-B-N ceramic fibre, according to flow diagram shown in FIG. 1: by softening point be 101 DEG C, oxygen content is
The polycarbosilane fiber that diameter is 14.2 μm is made through melt spinning in the Polycarbosilane of 0.37wt%.By 10g polycarbosilane fiber
It is placed in obturator, vacuumizes replacement of helium twice, be filled with 1gB after being subsequently vacuumed out into obturator3N3H6Gas, will
Obturator is placed in cross-linking radiation under electron accelerator, steps up dosage to irradiating total agent according to predose rate 100Gy/s
Amount reaches 15MGy, obtains the Polycarbosilane fusion-free fibre of boracic.The Polycarbosilane fusion-free fibre of boracic is then placed in burning
At displacement ammonia in furnace, is vacuumized three times, temperature is then risen to 900 DEG C simultaneously according to the speed of 1 DEG C/min under ammonia atmosphere
1h is kept the temperature, replacement atmosphere is argon gas, and temperature is risen to 1600 DEG C according to the speed of 4 DEG C/min and keeps the temperature 1h, obtains Si-B-N pottery
Porcelain fiber.
The tensile strength of gained fiber is 1.54GPa, boron content 2.37wt%, oxygen content 0.47wt%, carbon content
For 0.59wt%.
Embodiment 5
The preparation of Si-B-N ceramic fibre, according to flow diagram shown in FIG. 1: by softening point be 213 DEG C, oxygen content is
The polycarbosilane fiber that diameter is 17.3 μm is made through melt spinning in the Polycarbosilane of 0.40wt%.By 10g polycarbosilane fiber
It is placed in obturator, vacuumizes replacement of helium twice, be filled with 1gB after being subsequently vacuumed out into obturator2H6Gas, will be close
It closes device and is placed in cross-linking radiation under electron accelerator, step up dosage to irradiating accumulated dose according to predose rate 100Gy/s
Reach 15MGy, obtains the Polycarbosilane fusion-free fibre of boracic.The Polycarbosilane fusion-free fibre of boracic is then placed in firing
In furnace, vacuumizes displacement ammonia three times, temperature is then risen to 900 DEG C according to the speed of 1 DEG C/min under ammonia atmosphere and is protected
Warm 1h, replacement atmosphere are argon gas, and temperature is risen to 1600 DEG C according to the speed of 4 DEG C/min and keeps the temperature 1h, obtain Si-B-N ceramics
Fiber.
The tensile strength of gained fiber is 2.14GPa, boron content 6.95wt%, oxygen content 0.65wt%, carbon content
For 0.55wt%.
Embodiment 6
The preparation of Si-B-N ceramic fibre, according to flow diagram shown in FIG. 1: by softening point be 176 DEG C, oxygen content is
The polycarbosilane fiber that diameter is 16.7 μm is made through melt spinning in the Polycarbosilane of 0.44wt%.By 10g polycarbosilane fiber
It is placed in obturator, vacuumizes replacement of helium twice, be filled with 1gB after being subsequently vacuumed out into obturator2H6Gas, will be close
It closes device and is placed in cross-linking radiation under electron accelerator, step up dosage to irradiating accumulated dose according to predose rate 100Gy/s
Reach 5MGy, obtains the Polycarbosilane fusion-free fibre of boracic.The Polycarbosilane fusion-free fibre of boracic is then placed in firing
In furnace, vacuumizes displacement ammonia three times, temperature is then risen to 900 DEG C according to the speed of 1 DEG C/min under ammonia atmosphere and is protected
Warm 1h, replacement atmosphere are argon gas, and temperature is risen to 1600 DEG C according to the speed of 4 DEG C/min and keeps the temperature 1h, obtain Si-B-N ceramics
Fiber.
The tensile strength of gained fiber is 1.55GPa, boron content 7.11wt%, oxygen content 0.81wt%, carbon content
For 0.54wt%.
Embodiment 7
The preparation of Si-B-N ceramic fibre, according to flow diagram shown in FIG. 1: by softening point be 176 DEG C, oxygen content is
The polycarbosilane fiber that diameter is 16.7 μm is made through melt spinning in the Polycarbosilane of 0.44wt%.By 10g polycarbosilane fiber
It is placed in obturator, vacuumizes replacement of helium twice, be filled with 1gB after being subsequently vacuumed out into obturator2H6Gas, will be close
It closes device and is placed in cross-linking radiation under electron accelerator, step up dosage to irradiating accumulated dose according to predose rate 1000Gy/s
Reach 15MGy, obtains the Polycarbosilane fusion-free fibre of boracic.The Polycarbosilane fusion-free fibre of boracic is then placed in firing
In furnace, vacuumizes displacement ammonia three times, temperature is then risen to 900 DEG C according to the speed of 1 DEG C/min under ammonia atmosphere and is protected
Warm 1h, replacement atmosphere are argon gas, and temperature is risen to 1600 DEG C according to the speed of 4 DEG C/min and keeps the temperature 1h, obtain Si-B-N ceramics
Fiber.
The tensile strength of gained fiber is 1.63GPa, boron content 7.05wt%, oxygen content 0.91wt%, carbon content
For 0.74wt%.
Embodiment 8
The preparation of Si-B-N ceramic fibre, according to flow diagram shown in FIG. 1: by softening point be 176 DEG C, oxygen content is
The polycarbosilane fiber that diameter is 16.7 μm is made through melt spinning in the Polycarbosilane of 0.44wt%.By 10g polycarbosilane fiber
It is placed in obturator, vacuumizes replacement of helium twice, be filled with 1gB after being subsequently vacuumed out into obturator2H6Gas, will be close
It closes device and is placed in cross-linking radiation under electron accelerator, step up dosage to irradiating accumulated dose according to predose rate 100Gy/s
Reach 15MGy, obtains the Polycarbosilane fusion-free fibre of boracic.The Polycarbosilane fusion-free fibre of boracic is then placed in firing
In furnace, vacuumizes displacement ammonia three times, temperature is then risen to 600 DEG C according to the speed of 1 DEG C/min under ammonia atmosphere and is protected
Warm 1h, replacement atmosphere are argon gas, and temperature is risen to 1600 DEG C according to the speed of 4 DEG C/min and keeps the temperature 1h, obtain Si-B-N ceramics
Fiber.
The tensile strength of gained fiber is 2.08GPa, boron content 6.84wt%, oxygen content 0.55wt%, carbon content
For 0.96wt%.
Embodiment 9
The preparation of Si-B-N ceramic fibre, according to flow diagram shown in FIG. 1: by softening point be 176 DEG C, oxygen content is
The polycarbosilane fiber that diameter is 16.7 μm is made through melt spinning in the Polycarbosilane of 0.44wt%.By 10g polycarbosilane fiber
It is placed in obturator, vacuumizes replacement of helium twice, be filled with 1gB after being subsequently vacuumed out into obturator2H6Gas, will be close
It closes device and is placed in cross-linking radiation under electron accelerator, step up dosage to irradiating accumulated dose according to predose rate 100Gy/s
Reach 15MGy, obtains the Polycarbosilane fusion-free fibre of boracic.The Polycarbosilane fusion-free fibre of boracic is then placed in firing
In furnace, vacuumizes displacement ammonia three times, temperature is then risen to 900 DEG C according to the speed of 1 DEG C/min under ammonia atmosphere and is protected
Warm 1h, replacement atmosphere are argon gas, and temperature is risen to 1300 DEG C according to the speed of 4 DEG C/min and keeps the temperature 1h, obtain Si-B-N ceramics
Fiber.
The tensile strength of gained fiber is 1.64GPa, boron content 7.18wt%, oxygen content 0.95wt%, carbon content
For 0.66wt%.
Comparative example 1
By softening point is 176 DEG C, oxygen content is 0.44wt% Polycarbosilane through melt spinning, it is 16.7 μm that diameter, which is made,
Polycarbosilane fiber.10g polycarbosilane fiber is placed in obturator, vacuumizes replacement of helium twice, it then will be closed
Device is placed in cross-linking radiation under electron accelerator, steps up dosage to irradiation accumulated dose according to predose rate 100Gy/s and reaches
To 15MGy, Polycarbosilane fusion-free fibre is obtained.Then Polycarbosilane fusion-free fibre is placed in firing furnace, vacuumizes and sets
It changes ammonia three times, temperature is then risen to 900 DEG C according to the speed of 1 DEG C/min under ammonia atmosphere and keeps the temperature 1h, replace atmosphere
For nitrogen, temperature is risen to 1300 DEG C according to the speed of 4 DEG C/min and keeps the temperature 1h, obtains Si3N4Ceramic fibre.
The tensile strength of gained fiber is 1.13GPa, oxygen content 2.35wt%, carbon content 0.71wt%.
Embodiment 10
Fiber made from embodiment 1,2,3 and comparative example 1 is placed in firing furnace, according to 20 under argon atmosphere protection
DEG C/heating rate of min rises to 1300 DEG C, 1500 DEG C, 1700 DEG C and keeps the temperature 1h, the state and performance of fiber such as the following table 1,2 institutes
Show, table 1 is the appearance of sample after treatment of different temperature, and table 2 is the intensity of sample after treatment of different temperature.It can be with from table 1,2
Find out, the heat resistance of fiber and the boron content of introducing are related: being not introduced into the 1 gained fiber sample of comparative example of boron in 1300 DEG C of argons
It is only original half, fiber dusting after 1500 DEG C of processing, no intensity that 1h fibre strength is handled in gas；The embodiment of the present invention
In, with the increase of boron content, the heat resistance of Si-B-N ceramic fibre is more excellent, and wherein the sample of embodiment 3 passes through argon gas
In 1700 DEG C processing after intensity still can reach 1.51GPa.
The appearance of sample after 1 treatment of different temperature of table
The intensity of sample after 2 treatment of different temperature of table
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.Therefore, protection scope of the present invention is answered
This is subject to the protection scope in claims.
Claims (10)
1. a kind of preparation method of Si-B-N ceramic fibre, which comprises the following steps:
1) polycarbosilane fiber is placed in device, boracic atmosphere is filled with after vacuumizing, then carried out electron beam irradiation crosslinking, obtain
To the Polycarbosilane fusion-free fibre of boracic；
2) the Polycarbosilane fusion-free fibre of boracic is first heated to the first high temperature in ammonia atmosphere, it is lazy for then changing atmosphere
Property atmosphere, continues to be heated to the second high temperature in an inert atmosphere, obtains Si-B-N ceramic fibre.
2. the preparation method of Si-B-N ceramic fibre according to claim 1, which is characterized in that poly- carbon in the step 1)
Silane fiber be by softening point within the scope of 70~240 DEG C and oxygen content is made lower than the Polycarbosilane of 1wt% through melt spinning,
The diameter of the polycarbosilane fiber is less than 30 μm.
3. the preparation method of Si-B-N ceramic fibre according to claim 2, which is characterized in that boracic in the step 1)
Atmosphere refers to containing B2H6、B4H10、B3N3H6One of gas atmosphere, or refer to B2H6、B4H10、B3N3H6One of gas
The mixed gas of body and inert gas.
4. the preparation method of Si-B-N ceramic fibre according to claim 3, which is characterized in that the B2H6、B4H10、
B3N3H6One of the mass ratio of gas and polycarbosilane fiber be (1~50): 100.
5. the preparation method of Si-B-N ceramic fibre according to claim 4, which is characterized in that electronics in the step 1)
The condition of beam irradiation are as follows: radiation dose rate 10~105Gy/s, irradiation accumulated dose are 5~40MGy.
6. the preparation method of Si-B-N ceramic fibre according to claim 5, which is characterized in that in ammonia in the step 2)
The method heated in gas atmosphere are as follows: according to the heating rate of 0.1~10 DEG C/min from room temperature within the scope of 500~1000 DEG C
The first high temperature, and in first 0.5~4h of soak.
7. the preparation method of Si-B-N ceramic fibre according to claim 6, which is characterized in that the ammonia in the step 2)
Gas atmosphere refers to the mixed gas of pure ammonia or pure ammonia and nitrogen, when the mixed gas that ammonia atmosphere is pure ammonia and nitrogen
When, the concentration of pure ammonia is greater than 30vol% in mixed gas.
8. the preparation method of Si-B-N ceramic fibre according to claim 7, which is characterized in that lazy in the step 2)
Property atmosphere in method for continuing heating are as follows: according to 1~30 DEG C/min heating rate from by temperature from transformation atmosphere after temperature
The second high temperature within the scope of 1000~1700 DEG C is risen to, and in second 0.5~4h of soak.
9. the preparation method of Si-B-N ceramic fibre according to claim 8, which is characterized in that the inert atmosphere refers to argon
Gas and helium.
10. a kind of Si-B-N ceramic fibre, which is characterized in that its system described in any claim in -9 according to claim 1
Preparation Method obtains, and boron content is controllable between 1~15wt%, and oxygen content is lower than 2wt%, and carbon content is lower than 1wt%, stretches
Intensity is greater than 1.5Gpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811241027.4A CN109385693B (en) | 2018-10-24 | 2018-10-24 | Preparation method of Si-B-N ceramic fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811241027.4A CN109385693B (en) | 2018-10-24 | 2018-10-24 | Preparation method of Si-B-N ceramic fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109385693A true CN109385693A (en) | 2019-02-26 |
| CN109385693B CN109385693B (en) | 2021-02-05 |
Family
ID=65427933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811241027.4A Active CN109385693B (en) | 2018-10-24 | 2018-10-24 | Preparation method of Si-B-N ceramic fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109385693B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110820061A (en) * | 2019-11-27 | 2020-02-21 | 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 |
| CN110952170A (en) * | 2019-12-25 | 2020-04-03 | 中国人民解放军国防科技大学 | Nitride fiber thermal crosslinking assisted atmosphere non-melting method |
| CN111004035A (en) * | 2019-12-26 | 2020-04-14 | 中国人民解放军国防科技大学 | Under-beam irradiation device for polycarbosilane fiber and irradiation crosslinking method thereof |
| CN111039678A (en) * | 2019-12-25 | 2020-04-21 | 中国人民解放军国防科技大学 | Gradient double-atmosphere non-melting method for polysilazane (borazane) fiber |
| CN114560704A (en) * | 2022-01-24 | 2022-05-31 | 中国科学院过程工程研究所 | Boride-containing silicon carbide complex phase ceramic fiber and preparation method thereof |
| CN114957675A (en) * | 2021-11-29 | 2022-08-30 | 中国航空制造技术研究院 | Boron modified polycarbosilane powder and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6475521A (en) * | 1987-09-18 | 1989-03-22 | Daicel Chem | Electron beam-curable polycarbonate polymer |
| CN101734930A (en) * | 2009-12-18 | 2010-06-16 | 中国人民解放军国防科学技术大学 | Non-fusible treatment method of polysilazane or polyborosilazane fibres |
| 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 |
| CN102634868A (en) * | 2012-05-04 | 2012-08-15 | 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 |
| CN102674845A (en) * | 2012-05-07 | 2012-09-19 | 中国人民解放军国防科学技术大学 | Preparation method of silicon carbide fibers with silicon nitride surface layer |
| CN103046166A (en) * | 2013-01-25 | 2013-04-17 | 中国人民解放军国防科学技术大学 | Chemical gas-phase crosslinking method of polycarbosilane fibers |
| 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 |
| CN104846484A (en) * | 2015-05-20 | 2015-08-19 | 中国人民解放军国防科学技术大学 | Preparation method of silicon nitride fiber containing boron |
| CN106637915A (en) * | 2016-12-01 | 2017-05-10 | 中国人民解放军国防科学技术大学 | Auxiliary gas-phase cross-linking method of electron beams |
| CN107740205A (en) * | 2017-10-12 | 2018-02-27 | 中国科学院过程工程研究所 | A kind of compound organic precursor method prepares BN Si3N4The method of complex phase ceramic continuous fiber |
| CN107868998A (en) * | 2016-09-23 | 2018-04-03 | 中国科学院上海应用物理研究所 | A kind of silicon nitride fiber and preparation method thereof |
| CN108623812A (en) * | 2017-03-23 | 2018-10-09 | 中国科学院上海应用物理研究所 | Polycarbosilane and preparation method thereof containing heterogeneous element |
-
2018
- 2018-10-24 CN CN201811241027.4A patent/CN109385693B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6475521A (en) * | 1987-09-18 | 1989-03-22 | Daicel Chem | Electron beam-curable polycarbonate polymer |
| CN101734930A (en) * | 2009-12-18 | 2010-06-16 | 中国人民解放军国防科学技术大学 | Non-fusible treatment method of polysilazane or polyborosilazane fibres |
| 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 |
| CN102634868A (en) * | 2012-05-04 | 2012-08-15 | 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 |
| CN102674845A (en) * | 2012-05-07 | 2012-09-19 | 中国人民解放军国防科学技术大学 | Preparation method of silicon carbide fibers with silicon nitride surface layer |
| CN103046166A (en) * | 2013-01-25 | 2013-04-17 | 中国人民解放军国防科学技术大学 | Chemical gas-phase crosslinking method of polycarbosilane fibers |
| 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 |
| CN104846484A (en) * | 2015-05-20 | 2015-08-19 | 中国人民解放军国防科学技术大学 | Preparation method of silicon nitride fiber containing boron |
| CN107868998A (en) * | 2016-09-23 | 2018-04-03 | 中国科学院上海应用物理研究所 | A kind of silicon nitride fiber and preparation method thereof |
| CN106637915A (en) * | 2016-12-01 | 2017-05-10 | 中国人民解放军国防科学技术大学 | Auxiliary gas-phase cross-linking method of electron beams |
| CN108623812A (en) * | 2017-03-23 | 2018-10-09 | 中国科学院上海应用物理研究所 | Polycarbosilane and preparation method thereof containing heterogeneous element |
| CN107740205A (en) * | 2017-10-12 | 2018-02-27 | 中国科学院过程工程研究所 | A kind of compound organic precursor method prepares BN Si3N4The method of complex phase ceramic continuous fiber |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110820061A (en) * | 2019-11-27 | 2020-02-21 | 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 |
| 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 |
| CN110952170A (en) * | 2019-12-25 | 2020-04-03 | 中国人民解放军国防科技大学 | Nitride fiber thermal crosslinking assisted atmosphere non-melting method |
| CN111039678A (en) * | 2019-12-25 | 2020-04-21 | 中国人民解放军国防科技大学 | Gradient double-atmosphere non-melting method for polysilazane (borazane) fiber |
| CN110952170B (en) * | 2019-12-25 | 2022-04-19 | 中国人民解放军国防科技大学 | Nitride fiber thermal crosslinking assisted atmosphere non-melting method |
| CN111004035A (en) * | 2019-12-26 | 2020-04-14 | 中国人民解放军国防科技大学 | Under-beam irradiation device for polycarbosilane fiber and irradiation crosslinking method thereof |
| CN111004035B (en) * | 2019-12-26 | 2021-09-24 | 中国人民解放军国防科技大学 | Under-beam irradiation device for polycarbosilane fiber and irradiation crosslinking method thereof |
| CN114957675A (en) * | 2021-11-29 | 2022-08-30 | 中国航空制造技术研究院 | Boron modified polycarbosilane powder and preparation method thereof |
| CN114560704A (en) * | 2022-01-24 | 2022-05-31 | 中国科学院过程工程研究所 | Boride-containing silicon carbide complex phase ceramic fiber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109385693B (en) | 2021-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109385693A (en) | Preparation method of Si-B-N ceramic fiber | |
| CN103952796B (en) | A kind of preparation method of silicon nitrogen boron continuous ceramic fiber | |
| CN107419364B (en) | A kind of preparation method of the highly crystalline near stoichiometric proportion continuous SiC fiber of high temperature tolerance | |
| CN110629324B (en) | Boron-containing silicon carbide fiber and preparation method thereof | |
| CN1168859C (en) | Preparation method of high temperature resistant multi crystal silicon carbide fiber | |
| EP0438117B1 (en) | Preparation of substantially crystalline silicon carbide fibers from polycarbosilane | |
| US9045347B2 (en) | Stiochiometric silicon carbide fibers from thermo-chemically cured polysilazanes | |
| US8987402B2 (en) | Stoichiometric silicon carbide fibers from thermo-chemically cured polysilazanes | |
| CN108264352B (en) | Method for preparing Si-C-O ceramic fiber by organic silicon resin conversion | |
| CN109695071A (en) | A kind of durothermic method of raising continuous carbofrax fibre | |
| CN109402786B (en) | Preparation method of near-stoichiometric SiC fibers | |
| CN107640976A (en) | Three-dimensional carborundum fiber preform enhancing yttrium silicate composite and preparation method thereof | |
| CN106087112B (en) | A kind of preparation method of continuous SiC fiber of the surface with carbon-coating | |
| Narisawa et al. | Use of blended precursors of poly (vinylsilane) in polycarbosilane for silicon carbide fiber synthesis with radiation curing | |
| CN110105070A (en) | Continuous silicon carbide fiber with controllable electrical property and wide range and preparation method thereof | |
| CN104609892B (en) | Mullite fiber provided with SiBCN coating deposited on surface and preparation method of mullite fiber | |
| Pivin et al. | Ion irradiation of preceramic polymer thin films | |
| US20030057612A1 (en) | Process for producing microceramic tubes by radiation exposure of silicon-based polymers | |
| CN106995947A (en) | The gradual decarbonization method of nitride fiber | |
| JP2892849B2 (en) | Method for making a preceramic polymer infusible | |
| CN111039678B (en) | Gradient double-atmosphere non-melting method for polysilazane (borazane) fiber | |
| CN106916311A (en) | A kind of preparation method containing beryllium ceramic precursor | |
| CN115197430A (en) | Novel polycarbosilane ceramic precursor material and preparation method thereof | |
| CN109485388A (en) | Preparation method of Si-C-O ceramic fiber with adjustable and controllable element composition | |
| Hu | Preparation of silicon oxycarbide glass fibers from organically modified silicates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |