CN108707234A - A kind of silicon boron azane ceramic forerunner polymer containing borazine, preparation method and applications - Google Patents
A kind of silicon boron azane ceramic forerunner polymer containing borazine, preparation method and applications Download PDFInfo
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- CN108707234A CN108707234A CN201810384994.XA CN201810384994A CN108707234A CN 108707234 A CN108707234 A CN 108707234A CN 201810384994 A CN201810384994 A CN 201810384994A CN 108707234 A CN108707234 A CN 108707234A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/589—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained from Si-containing polymer precursors or organosilicon monomers
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- 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
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Abstract
The silicon boron azane ceramic forerunner polymer that the invention discloses a kind of containing borazine, preparation method and applications.The structure feature of silicon boron azane ceramic forerunner polymer of the present invention containing borazine is to contain borazine and silazane structure in polymer molecular chain.The preparation method of the ceramic forerunner polymer is to divide three-step reaction to synthesize silicon boron azane ceramic forerunner polymer under inert gas protection using ammonium chloride, organic primary amine, boron trihalides, dichlorosilane and ammonia as primary raw material.Ammonium chloride or organic primary amine react synthesis trichlorine borazine with boron trihalides first, then the chloro borazine that alkyl replaces is obtained by the reaction in trichlorine borazine and alkyl magnesium bromide Grignard Reagent, then ammonolysis synthesis silicon boron azane ceramic forerunner polymer is total to dichlorosilane.The silicon boron azane ceramic forerunner polymer containing borazine of the present invention is colourless or thick pale yellow shape liquid, dissolves in common solvent, processing performance is excellent.Precursor polymer solidfied material can converting ceramics, ceramic yield is high, can be used for preparing silicon boron nitrogen ceramic matric composite.
Description
Technical field
It is poly- to also relate to the presoma for the present invention relates to a kind of silicon boron azane ceramic forerunner polymer containing borazine
Close the preparation method of object.
Background technology
Polymer precursor, which converts SiBCN ceramics and its ceramic matric composite, has excellent high temperature resistant, anti-oxidant, high
Warm mechanical property and wave transparent performance, make it have broad application prospects in aerospace field.Polymer precursor conversion pottery
The outstanding feature of porcelain, which is its microstructure and properties, to be designed by the variation of the molecular structure of presoma, before polymer
The chemistry for driving body conversion ceramics depends on the molecular structure of initial polymer precursor and molding process conditions with physical property.
The preparation of SiBCN ceramic forerunners is initially synthesized by boron modification polysilazane, and Jeon etc. is with 2,4,6- tri-
Methyl -2,4,6- trivinyls cyclotrisilazane (VSZ) and borazine are raw material, pass through the boron between vinyl and boron cyano
Hydrogenation obtains soluble gelatin polymer, and this polymer contains silicon azo-cycle and boron azo-cycle, polymer conversion Cheng Tao simultaneously
The yield of porcelain is 70%-75%.Hydroboration system occurred using borazine and dimethyl divinyl silane in they later
It is standby go out a kind of better boracic azo-cycle polymer of craftsmanship, synthetic yield 85%, in 200-600 DEG C of temperature-rise period, the later stage
Unreacted vinyl, boron azo-cycle can be crosslinked with the B-C methyl bridges among silicon and be reacted in the liquid polymers of synthesis, make to gather
It closes object and is transformed into a kind of insoluble solid, ceramic yield is about 40%.
Three-(trimethyl silicane amine) hydrogen silanes (TTS), the 1,1,3,3,5,5- hexamethyl cyclotrisilazanes such as Wideman
(HCT) the ceramic forerunner polymer of boracic azo-cycle is obtained with cyclosilazane copolycondensation respectively.
The ammonolysis methylpropenyl dichlorosilane such as Muller, obtains polymethyl base silazane, then passes through hydroboration
Synthesize [B(C3H6Si(CH3)NH)3]n.In addition monomer path elder generation hydroboration methylpropenyl dichlorosilane is used, ceramics precursor is obtained
Body, then carry out ammonolysis and same products also can be obtained.
Sneddon etc. reacts the poly- boron silicon nitrogen carbon pioneer of synthesis by polysilazane using dehydrogenation coupled reaction with borazine
Body, Dong Shaohua etc. are total to the poly- boron silicon nitrogen carbon matrix precursor of ammonolysis synthesis with methyl hydrogen dichlorosilane with trichlorine borazine, work as trichlorine
After the content of borazine increases to a certain amount, synthetic product meeting gel, polymer precursor is solid state, and processing is tired
It is difficult.
The boron silicon nitrogen carbon ceramics preceramic polymer of document report is mostly solid state, and can not be molten in big multi-solvent
Solution, processing performance is poor, and processing and forming is difficult;Or synthesizing liquid silicon boron azane ceramic forerunner, but ceramic yield is relatively low,
Influence the performance of ceramic matric composite.
The boron silicon nitrogen carbon ceramics precursor of the present invention is after an a kind of novel chlorine by trichlorine borazine replaces,
The ceramic precursor of the boracic azo-cycle of the chain of ammonolysis synthesis is total to dichlorosilane.Each element is uniform in the chain polymer of synthesis
The polymer of distribution, this liquid has good processing performance, and fine and close solidfied material is obtained after crosslinking curing with excellent
High temperature resistance and antioxygenic property, ceramic yield can reach 94%.
Invention content
An object of the present invention is to provide a kind of boron silicon nitrogen carbon ceramics precursor polymer with excellent processing performance.
The second object of the present invention is to provide a kind of boron silicon nitrogen carbon ceramics precursor polymer with high ceramic yield.
The third object of the present invention is to provide the preparation method of the silicon boron nitrogen carbon ceramics presoma, by Grignard Reagent with
Three halogen borazine part of boron halogen keys react, and are then total to ammonolysis with dichlorosilane, before the ceramics containing borazine are prepared
Drive body polymer.In order to reach this purpose, technical scheme of the present invention is specific as follows:
A kind of silicon boron azane ceramic forerunner polymer containing borazine provided by the present invention, it is described to contain borazine
Silicon boron azane ceramic forerunner polymer molecular structure in contain:
(1) single alkyl replaces borazine,
Or/and double alkyl replace borazine,
(2) silazane structure,
The silicon boron azane ceramic forerunner polymer formulae containing borazine is schematically as follows:
Wherein:R1, R2For hydrogen, methyl, vinyl;R3For hydrogen, ethyl, propargyl, allyl, phenyl;R4For methyl, second
Alkynyl;Degree of polymerization x, y=1~20.
The preparation method of silicon boron azane ceramic forerunner polymer of the present invention containing borazine and steps are as follows:
1) under inert gas protection, ammonium chloride or organic primary amine is mixed with boron trihalides in a solvent, then added
Reaction generates three halogen borazines under heat condition.
It synthesizes three halogen borazines reaction organic primary amine used and ethamine, propargyl amine, allyl amine, aniline, benzyl can be selected
Amine, boron trihalides are boron chloride and Boron tribromide;Benzene, toluene, chlorobenzene can be selected in reaction dissolvent;Reaction temperature is 90~150
DEG C, the reaction time is 2~20 hours.
2) and then addition alkyl Grignard Reagent reaction synthesis alkyl replaces halogenated borazine.
Synthesizing alkyl replaces halogenated borazine reaction alkyl Grignard Reagent used to select methyl-magnesium-bromide, methyl chloride
Magnesium, acetenyl magnesium bromide and acetenyl magnesium chloride, addition is 1-2 times of three halogen borazine molal quantitys, obtained by the reaction
Alkyl replaces halogenated borazine to be that single alkyl replaces borazine or/and double alkyl to replace borazine.
3) after dichlorosilane being added into the product of step (2), it is passed through ammonia in system and carries out total ammonolysis reaction, synthesis
Silicon boron azane Preceramic Polymers containing borazine.
Synthesize the optional dihydridodichlorosilane of dichlorosilane, the first of the silicon boron azane Preceramic Polymers containing borazine
Base hydrogen dichlorosilane, methylvinyldichlorosilane, addition is halogenated borazine and dichlorosilane molar ratio is 1:8~
34, reaction temperature is -15~-5 DEG C, and the reaction time is 3~10 hours.
Silicon boron azane Preceramic Polymers of the present invention containing borazine are colourless or thick pale yellow shape liquid
Body, dissolves in common organic solvent, such as toluene, acetone, dichloroethanes, processing performance are excellent.The nitrogen of boron containing ring of the present invention
The silicon boron azane ceramic forerunner polymer of alkane can form compact curing object by thermal polymerization crosslinking curing, and solidfied material can thermal cracking
It is converted to ceramic of compact, ceramic yield is high, and ceramic yield can be used for preparing silicon boron nitrogen ceramic base composite wood up to 75% or more
Material.
Description of the drawings
Fig. 1 is the infrared spectrum of the boron silicon nitrogen carbon polymer of embodiment 1;
Fig. 2 is the DSC curve of the boron silicon nitrogen carbon polymer of embodiment 1;
Fig. 3 is the infrared spectrum of the solidfied material of the boron silicon nitrogen carbon polymer of embodiment 1;
Fig. 4 is the thermogravimetric curve of the solidfied material of the boron silicon nitrogen carbon polymer of embodiment 1;
Fig. 5 is the XRD spectrum of the solidfied material ceramic product of the boron silicon nitrogen carbon polymer of embodiment 1;
Fig. 6 is the SEM figures of the solidfied material ceramic product of the boron silicon nitrogen carbon polymer of embodiment 1.
Specific implementation mode
Silicon boron azane ceramic forerunner polymer containing borazine to the present invention and its preparation by the following examples
Method is specifically described, but embodiment is served only for that the present invention is further described, is not intended to limit the interest field of the present invention.
1 presoma PBSZ-1 of embodiment
In the 500ml four-hole boiling flasks equipped with nitrogen conduit, blender, thermometer and condenser pipe, by vacuumizing, lead to nitrogen
After gas circulating dehumidification deoxygenation several times, NH is added4Cl powder 32g (0.30mol) and toluene 300ml, and be vigorously stirred to be formed it is suspended
Liquid is slowly introducing BCl into four-hole boiling flask after being heated to 110 DEG C3Gas, and insulation reaction 10h.Then it is cooled to room
Temperature is filtered under nitrogen protection using shleck technologies, and filtrate removes solvent through vacuum distillation, is then obtained again through distillation colourless
Acicular crystal trichlorine borazine (TCB).
In the 2000ml four-hole boiling flasks equipped with nitrogen conduit, blender, thermometer and condenser pipe, by vacuumizing, leading to
After nitrogen circulating dehumidification deoxygenation several times, trichlorine borazine 9g and dichloromethane is added thereto under the protection of nitrogen
1400ml opens stirring, makes the dissolving of trichlorine borazine in methylene chloride, then at normal temperatures, with syringe to reactant
The methyl-magnesium-bromide Grignard Reagent 49ml of 1mol/L is slowly added dropwise in system, after being added dropwise, reaction system reacts 3h at normal temperatures,
Obtain methyl substituted borazine white solution.
Four-hole boiling flask is placed in -10 DEG C of low temperature bath, dichlorosilane 41.2g is then added thereto, finally to anti-
It answers and is passed through ammonia in system, start to react, until reaction system stops reaction, then filter in alkalinity, rotate, isopropyl is used in combination
Product washes clean is obtained colorless viscous shape liquid by ether, and product is finally made into the isopropyl ethereal solution that mass fraction is 60%,
It is placed in refrigerator-freezer storage.Its infrared spectrum such as Fig. 1, DSC curve such as Fig. 2, infrared spectrum such as Fig. 3 after solidification, the thermogravimetric after solidification
Curve such as Fig. 4.
Presoma PBSZ-1 heat cures in vacuum drying oven obtain fine and close poly- silicon boron azane solidfied material, curing cycle 60
DEG C/1 hour, 80 DEG C/1 hour, 100 DEG C/2 hours, 120 DEG C/2 hours, 140 DEG C/2 hours, 160 DEG C/2 hours, 180 DEG C/2 is small
When.Poly- silicon boron azane solidfied material carries out ceramic in tube furnace under nitrogen atmosphere, with 3 DEG C/min of heating rates from room temperature liter
To 1500 DEG C, 2 hours then are kept the temperature, it is 94% to measure ceramic yield.
Wherein Fig. 5 is the XRD spectrum of the solidfied material ceramic product of the boron silicon nitrogen carbon polymer of embodiment 1;Fig. 6 is embodiment
The SEM of the solidfied material ceramic product of 1 boron silicon nitrogen carbon polymer schemes.In Fig. 6, a) 700 DEG C of cracking temperature, amplification factor 5000
Times;B) 1500 DEG C of cracking temperature, 5000 times of amplification factor;C) 700 DEG C of cracking temperature, 20000 times of amplification factor;D) cracking temperature
1500 DEG C, 20000 times of amplification factor.
2 presoma PBSZ-2 of embodiment
In the 500ml four-hole boiling flasks equipped with nitrogen conduit, blender, thermometer and condenser pipe, by vacuumizing, lead to nitrogen
After gas circulating dehumidification deoxygenation several times, BCl is added3The toluene solution of (0.09mol) is cooled to -10 DEG C thereto slowly with salt ice
The mixed liquor of triethylamine 18.22g (0.18mol) and toluene (20mL) is added dropwise, allyl is added into system again after being added dropwise
System is slowly increased to 110 DEG C of heat preservation 6h later, is cooled to room temperature by base amine 5.14g (0.09mol) and toluene (10mL).Using
Shleck technologies filter under nitrogen protection, and filtrate is transferred in revolving bottle, and vacuum distillation removes solvent and obtains water white transparency liquid
Body triallyl trichlorine borazine (TV-TCB).
To the reaction system of the 2000ml four-hole boiling flasks equipped with tetrafluoro stirring rod, thermometer, syringe and nitrogen gas-guide tube
It after checking out air-tightness, toasts, vacuumize repeatedly, trichlorine is then added under the protection of nitrogen in reaction system thereto successively
Borazine 6.55g and dichloromethane 1400ml opens stirring, makes trichlorine borazine dissolving dispersion in methylene chloride, with
Afterwards, at normal temperatures, the methyl-magnesium-bromide Grignard Reagent 36ml of 1mol/L is slowly added dropwise into reaction system with syringe, drips
Bi Hou, reaction system react 3h at normal temperatures, obtain methyl substituted borazine white solution.
Four-hole boiling flask is placed in -10 DEG C of low temperature bath, dichlorosilane 60g is then added thereto, finally to reaction
It is passed through ammonia in system, starts to react, until reaction system stops reaction, then filter in alkalinity, rotates, isopropyl ether is used in combination
By product washes clean, colorless viscous shape liquid is obtained, product is finally made into the isopropyl ethereal solution that mass fraction is 60%, is set
In refrigerator-freezer.
3 presoma PBSZ-3 of embodiment
To the reaction system of the 2000ml four-hole boiling flasks equipped with tetrafluoro stirring rod, thermometer, syringe and nitrogen gas-guide tube
It after checking out air-tightness, toasts, vacuumize repeatedly, trichlorine is then added under the protection of nitrogen in reaction system thereto successively
Borazine 2.18g and dichloromethane 1400ml opens stirring, makes trichlorine borazine dissolving dispersion in methylene chloride, with
Afterwards, at normal temperatures, the methyl-magnesium-bromide Grignard Reagent 12ml of 1mol/L is slowly added dropwise into reaction system with syringe, drips
Bi Hou, reaction system react 3h at normal temperatures, obtain methyl substituted borazine white solution.Four-hole boiling flask is placed in -10
DEG C low temperature bath in, then thereto be added dichlorosilane 40g, ammonia is finally passed through into reaction system, starts to react, directly
To reaction system in alkalinity, stops reaction, then filter, rotate, be used in combination isopropyl ether by product washes clean, obtain colorless viscous
Product is finally made into the isopropyl ethereal solution that mass fraction is 60%, is placed in refrigerator-freezer by shape liquid.
4 presoma PBSZ-4 of embodiment
To the reaction system of the 2000ml four-hole boiling flasks equipped with tetrafluoro stirring rod, thermometer, syringe and nitrogen gas-guide tube
It after checking out air-tightness, toasts, vacuumize repeatedly, trichlorine is then added under the protection of nitrogen in reaction system thereto successively
Borazine 9g and dichloromethane 1400ml opens stirring, makes trichlorine borazine dissolving dispersion in methylene chloride, then,
At normal temperatures, the acetenyl magnesium bromide Grignard Reagent 49ml of 1mol/L is slowly added dropwise into reaction system with syringe, drips
Bi Hou, reaction system react 3h at normal temperatures, obtain the borazine white solution of acetenyl substitution.Four-hole boiling flask is placed in-
In 10 DEG C of low temperature bath, dichlorosilane 41.2g is then added thereto, ammonia is finally passed through into reaction system, starts anti-
It answers, until reaction system stops reaction, then filter in alkalinity, rotates, be used in combination isopropyl ether by product washes clean, obtain nothing
Product is finally made into the isopropyl ethereal solution that mass fraction is 60%, is placed in refrigerator-freezer by color viscous liquid.
5 presoma PBSZ-5 of embodiment
To the reaction system of the 2000ml four-hole boiling flasks equipped with tetrafluoro stirring rod, thermometer, syringe and nitrogen gas-guide tube
It after checking out air-tightness, toasts, vacuumize repeatedly, trichlorine is then added under the protection of nitrogen in reaction system thereto successively
Borazine 6.55g and dichloromethane 1400ml opens stirring, makes trichlorine borazine dissolving dispersion in methylene chloride, with
Afterwards, at normal temperatures, the acetenyl magnesium bromide Grignard Reagent 36ml of 1mol/L is slowly added dropwise into reaction system with syringe, is added dropwise
After, reaction system reacts 3h at normal temperatures, obtains the borazine white solution of acetenyl substitution.Four-hole boiling flask is set
In -10 DEG C of low temperature bath, dichlorosilane 60g is then added thereto, ammonia is finally passed through into reaction system, starts anti-
It answers, until reaction system stops reaction, then filter in alkalinity, rotates, be used in combination isopropyl ether by product washes clean, obtain nothing
Product is finally made into the isopropyl ethereal solution that mass fraction is 60%, is placed in refrigerator-freezer by color viscous liquid.
6 presoma PBSZ-6 of embodiment
To the reaction system of the 2000ml four-hole boiling flasks equipped with tetrafluoro stirring rod, thermometer, syringe and nitrogen gas-guide tube
It after checking out air-tightness, toasts, vacuumize repeatedly, trichlorine is then added under the protection of nitrogen in reaction system thereto successively
Borazine 2.18g and dichloromethane 1400ml opens stirring, makes trichlorine borazine dissolving dispersion in methylene chloride, with
Afterwards, at normal temperatures, the acetenyl magnesium bromide Grignard Reagent 12ml of 1mol/L is slowly added dropwise into reaction system with syringe, is added dropwise
After, reaction system reacts 3h at normal temperatures, obtains the borazine white solution of acetenyl substitution.Four-hole boiling flask is set
In -10 DEG C of low temperature bath, dichlorosilane 40g is then added thereto, ammonia is finally passed through into reaction system, starts anti-
It answers, until reaction system stops reaction, then filter in alkalinity, rotates, be used in combination isopropyl ether by product washes clean, obtain nothing
Product is finally made into the isopropyl ethereal solution that mass fraction is 60%, is placed in refrigerator-freezer by color viscous liquid.
Claims (10)
1. a kind of silicon boron azane ceramic forerunner polymer containing borazine, which is characterized in that the silicon containing borazine
Contain in the molecular structure of boron azane ceramic forerunner polymer:
(1) single alkyl replaces borazine,
Or/and double alkyl replace borazine,
(2) silazane structure,
The silicon boron azane ceramic forerunner polymer formulae containing borazine is schematically as follows:
Wherein:R1, R2For hydrogen, methyl or vinyl;R3For hydrogen, ethyl, propargyl, allyl or phenyl;R4For methyl or acetylene
Base;Degree of polymerization x, y=1~20.
2. the preparation method of the silicon boron azane ceramic forerunner polymer containing borazine as described in claim 1, feature
It is, includes the following steps:
(1) under inert gas protection, ammonium chloride or organic primary amine are mixed with boron trihalides in a solvent, then 90~
It is reacted 2~20 hours at 150 DEG C, generates three halogen borazines;
(2) and then addition alkyl Grignard Reagent reaction synthesis alkyl replaces halogenated borazine;
(3) after dichlorosilane being added into the product of step (2), it is passed through ammonia in system and carries out total ammonolysis reaction, synthesis contains
The silicon boron azane Preceramic Polymers of borazine.
3. preparation method as claimed in claim 2, which is characterized in that the organic primary amine described in step (1) is ethamine, propargyl
Amine, allyl amine or aniline.
4. preparation method as claimed in claim 2, which is characterized in that boron trihalides described in step (1) be boron chloride or
Boron tribromide.
5. preparation method as claimed in claim 2, which is characterized in that the solvent described in step (1) is benzene, toluene or chlorobenzene.
6. preparation method as claimed in claim 2, which is characterized in that the alkyl Grignard Reagent described in step (2) is methyl bromide
Change magnesium, methyl-magnesium-chloride, acetenyl magnesium bromide or acetenyl magnesium chloride.
7. preparation method as claimed in claim 2, which is characterized in that the addition of the alkyl Grignard Reagent described in step (2)
It is 1-2 times of three halogen borazine molal quantitys.
8. preparation method as claimed in claim 2, which is characterized in that the alkyl described in step (2) replaces halogenated borazine
Dichloro borazine or double alkyl is replaced to replace monochloro borazine for single alkyl.
9. preparation method as claimed in claim 2, which is characterized in that the dichlorosilane described in step (3) is dichlorosilane
Alkane, methyl hydrogen dichlorosilane or methylvinyldichlorosilane.
10. the application of the silicon boron azane ceramic forerunner polymer containing borazine as described in claim 1, is to pass through thermal polymerization
Crosslinking curing forms compact curing object, and solidfied material thermal cracking is converted to ceramic of compact, as preparing silicon boron nitrogen ceramic base composite wood
The application of material.
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CN112851363A (en) * | 2021-01-22 | 2021-05-28 | 哈尔滨工业大学 | Graphene oxide reinforced silicon-boron-carbon-nitrogen ceramic composite material and preparation method thereof |
CN114133575A (en) * | 2021-11-10 | 2022-03-04 | 中国科学院宁波材料技术与工程研究所 | Preparation method of high-boron-content polysilazane |
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CN109369918A (en) * | 2018-10-29 | 2019-02-22 | 航天材料及工艺研究所 | A kind of high boron content Si-B-C-N presoma and preparation method thereof |
CN112851363A (en) * | 2021-01-22 | 2021-05-28 | 哈尔滨工业大学 | Graphene oxide reinforced silicon-boron-carbon-nitrogen ceramic composite material and preparation method thereof |
CN112851363B (en) * | 2021-01-22 | 2022-03-22 | 哈尔滨工业大学 | Graphene oxide reinforced silicon-boron-carbon-nitrogen ceramic composite material and preparation method thereof |
CN114133575A (en) * | 2021-11-10 | 2022-03-04 | 中国科学院宁波材料技术与工程研究所 | Preparation method of high-boron-content polysilazane |
CN114133575B (en) * | 2021-11-10 | 2022-10-04 | 中国科学院宁波材料技术与工程研究所 | Preparation method of high-boron-content polysilazane |
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