CN109608201A - Silicon carbide/boron nitride fiber and its preparation method and application - Google Patents
Silicon carbide/boron nitride fiber and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to silicon carbide/boron nitride fibers and its preparation method and application, and described method includes following steps: NH2Silicon carbide/preparation of boron nitride precursor body, NH of-UIO-66 (Zr) doping2The preparation of silicon carbide/boron nitride precursor body melt spinning of-UIO-66 (Zr) doping, NH2Silicon carbide/boron nitride fiber sintering of-UIO-66 (Zr) doping.Silicon carbide/boron nitride fiber preparation method of the invention introduces zirconium, boron and nitrogen in precursor, is introduced back into N element during the sintering process, zirconium is contained in silicon carbide/boron nitride fiber of preparation, mechanical property is good, and high temperature resistance is splendid.
Description
Technical field
The invention belongs to materials to process preparation technical field, and in particular to a kind of silicon carbide/boron nitride fiber and its preparation
Methods and applications.
Background technique
Silicon carbide (SiC) fiber is the ceramics of a kind of high-strength and high-modulus, the Optimalities such as anti-oxidant, wear-resisting, corrosion-resistant, specific gravity is small
Fiber.Extensive research has successively been carried out to preparing continuous SiC fiber in countries in the world, in aviation, machinery, chemical industry, space flight, weapon
Contour leading-edge field has extremely wide application prospect.Currently, the intensity of SiC fiber, up to 3.0 ± 0.4GPa, modulus is reachable
200 ± 20GPa, using temperature up to 1000 DEG C.Make its application by certain since its room temperature intensity is lower and toughness is insufficient
Limitation, in order to improve the intensity and toughness of carbofrax material, SiC fiber is applicable to different by different interface processings
Polymer matrix, Metal Substrate, the intensity and toughness of ceramic matric composite reinforcing material.
Currently, the main method for preparing continuous SiC fiber has 4 kinds: precursor pyrolysis and hot pressing (Polymer-Derived, PD),
Chemical vapour deposition technique (ChemicalVaporDeposition, CVD), activated carbon fiber conversion method and micropowders high temperature are burnt
Connection, wherein only precursor pyrolysis and hot pressing (PD) and chemical vapour deposition technique (CVD) realize commercialization preparation.Active carbon fiber
Conversion method is tieed up, the intensity and modulus of gained fiber is not high；The fiber of super fine sintering process preparation largely rich carbon, string diameter compared with
Slightly, intensity is lower, and inoxidizability is poor.CVD method is using continuous carbon fiber and methyl-monosilane class compound as raw material, in nitrogen
It flows down and is reacted on scorching hot core filaments surface, be cracked into SiC and be deposited in core filaments and be made.The continuous SiC of CVD method preparation is fine
It is relatively thick (> 100 μm) to tie up diameter, mainly enhances metal_based material in the form of monofilament.PD method is to prepare the continuous SiC fibre of thin diameter at present
The main method of dimension, has realized industrialized production, and process route includes the synthesis of precursor, the melt spinning of precursor, general
Solvable fusible fibrinogen carries out the four big processes such as the high temperature firing of cure treatment and fusion-free fibre.Polymer-derived method has fibre
Dimension diameter is thin, can prepare different cross section shape, is at low cost, being extremely suitable for the features such as industrialized production, and compensates for CVD method and be not easy
It weaves, be difficult to manufacture the deficiency of complex shaped components.But precursor pyrolysis and hot pressing is during cure treatment, according to economy
Air cross-linking method, be readily incorporated a large amount of oxygen elements.A large amount of oxygen exist in SiC fiber with the unformed shape of SiCxOy, under high temperature
It easily thermally decomposes, so that performance sharply declines under SiC fiber high temperature.Fiber curing process is improved, is reduced in SiC fiber
Oxygen content, to improve SiC fiber high temperature performance be of great significance.
SiC fiber containing B has good high-temperature behavior, and SiC crystal grain in high-temperature sintering process can be effectively suppressed in being introduced into for B
It grows up, ensure that the mechanical behavior under high temperature of fiber.Metal-organic framework materials (MOFs) are the one kind quickly grown nearly ten years
Coordination polymer has three-dimensional pore structure, has many potential properties, in new function material as selectivity is urged
Change, molecular recognition, invertibity Subjective and Objective molecule (ion) exchange, ultra-high purity separation, biological conductive material, photoelectric material, magnetic
Property the new materials such as material and chip exploitation in show tempting application prospect, new dawn is brought to porous material science.
Although SiC fiber has all been widely studied, its high-temperature behavior, thermal stability and knitting property etc. all some owe
It lacks, therefore urgently studies a kind of material that can optimize above-mentioned performance.
Summary of the invention
An object of the present invention is to provide a kind of preparation methods of silicon carbide/boron nitride fiber.
Silicon carbide/boron nitride fiber preparation method of the invention, includes the following steps: S101: by zirconium bromide and benzene first
Acid is (1~4.5) according to molar ratio: in 15 addition n,N-Dimethylformamide solution and being stirred by ultrasonic, and injects poly- boron silicon nitrogen
Alkane is then added into autoclave, and dimethyl silicone polymer is added, it is made to be covered on the zirconium bromide and the poly- boron
Then silazane surface is heated to 110 DEG C~130 DEG C, and insulation reaction 34h~38h with the first heating rate, is subsequently cooled to
Room temperature, then be centrifuged, it is then washed and is dried with anhydrous methanol, obtain NH2- UIO-66 (Zr) material, then
It is heated to 160 DEG C~200 DEG C under two heating rates, and keeps the temperature 1.5h~2.5h, then successively dissolved, filtered with dimethylbenzene,
Vacuum distillation, obtains metal-organic framework materials NH2Silicon carbide/boron nitride precursor body of-UIO-66 (Zr) doping；S102: will
The metal-organic framework materials NH that the step S101 is obtained2Silicon carbide/boron nitride precursor body of-UIO-66 (Zr) doping is placed in
In melt spinning cylinder, molten condition is then heated to third heating rate under atmosphere of inert gases, repressurization to 3MPa~
Then melt is obtained metal-organic framework materials NH followed by flowing out after strainer, spinneret by 5MPa2- UIO-66 (Zr) mixes
Miscellaneous silicon carbide precursor fibre bundle, then heat cross-linking, to carry out cure treatment；S103: the fibre that the step S102 is obtained
Dimension beam is put into sintering furnace, is then passed to ammonia, is heated to 450 DEG C~650 DEG C with the 4th heating rate, and keep the temperature 2h~4h,
It is heated to 880 DEG C~920 DEG C with the 4th heating rate again and keeps the temperature 1.5h~2.5h to carry out Pintsch process, then protect
1200 DEG C~1600 DEG C are heated to the 5th heating rate in gas atmosphere and keeps the temperature 0.5h~1h, are then cooled to room temperature, are obtained
To metal-organic framework materials NH2The silicon carbide fibre of-UIO-66 (Zr) doping.
Silicon carbide/boron nitride fiber preparation method of the invention introduces zirconium, boron and nitrogen in precursor, is burning
It is introduced back into N element during knot, zirconium is contained in silicon carbide/boron nitride fiber of preparation, mechanical property is good, high temperature resistance pole
It is good.Especially there are carbonitride of silicium nanometer, silicon carbide/boron nitride fiber room temperature of preparation in silicon carbide/boron nitride fiber interface
Lower intensity 3.6 ± 0.2GPa, 280 ± 30GPa of elasticity modulus.After handling 100 hours in 1100 DEG C of air environments, intensity retains
Rate remains to reach 89% or more, in high-performance fiber field, such as antenna windows and antenna house etc. the tool of electromagnetic wave permeable material
There are extensive practical value and application prospect.
In addition, silicon carbide/boron nitride fiber preparation method that the present invention is above-mentioned, can also have following additional technology
Feature:
Further, in the step S101, the first heating rate is 8 DEG C/min~12 DEG C/min；Described
In step S102, second heating rate is 18 DEG C/min~22 DEG C/min；In the step S102, the third heating
Rate is 0.3 DEG C/h~0.7 DEG C/h；In the step S103, the 4th heating rate is 100 DEG C/h~200 DEG C/h；?
In the step S103, the 5th heating rate is 40 DEG C/h~60 DEG C/h.
Further, in the step S102, the protective gas is argon gas, and the flow of the argon gas is 300mL/
Min~500mL/min.
Further, in the step S103, the flow of the ammonia is 100mL/min~200mL/min.
Further, in the step S101, the ratio of the benzoic acid and the n,N-Dimethylformamide solution
For 3mmol:(18mL~22mL)；The mass percent that the PVDF hollow fiber membrane accounts for the solution is 14%~16%；It is described poly-
The molar ratio of dimethyl siloxane and the benzoic acid is 3:(3.5~4.5).
Further, in the step S101, drying temperature is 75 DEG C~85 DEG C, and drying time is 10h~14h.
Further, in the step S102, it is heated to 320 DEG C~360 DEG C when carrying out heat cross-linking and keeps the temperature
4h~6h.
It is another object of the present invention to the silicon carbide fibres for proposing the method preparation.
Another object of the present invention is to propose the silicon carbide fibre in aviation, machinery, chemical industry, space flight and weapon
The application in field.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Specific embodiment
The embodiment of the present invention is described below in detail, the embodiment is exemplary, it is intended to it is used to explain the present invention, and
It is not considered as limiting the invention.
UIO series material in the present invention is the level structural unit [Hf by regular octahedron6O4(OH)4] with to stupid diformazan
Acid (H2BDC) ligand is connected, and obtains the three-dimensional cubic crystal structure of octahedra centre bore cage and tetrahedral angle cage.
Embodiment 1
Embodiment 1 proposes a kind of silicon carbide/boron nitride fiber, and preparation method includes the following steps:
It (1) is that 1:15 is added in n,N-Dimethylformamide solution and ultrasound is stirred according to molar ratio by zirconium bromide and benzoic acid
It mixes, and injects PVDF hollow fiber membrane, be then added into autoclave, and dimethyl silicone polymer is added, it is made to be covered on institute
Zirconium bromide and the PVDF hollow fiber membrane surface are stated, 110 DEG C, and insulation reaction are then heated to the heating rate of 12 DEG C/min
38h is then cooled to room temperature, then is centrifuged, and is then washed with anhydrous methanol and is dried 14h at a temperature of 75 DEG C, obtained
To NH2- UIO-66 (Zr) material, is then heated to 200 DEG C, and keep the temperature 1.5h under the heating rate of 18 DEG C/min, then with two
Toluene is successively dissolved, is filtered, is evaporated under reduced pressure, and metal-organic framework materials NH is obtained2The carbonization of-UIO-66 (Zr) doping
Silicon/boron nitride precursor body.Wherein, the ratio of the benzoic acid and the n,N-Dimethylformamide solution is 3mmol:22mL；
The mass percent that the PVDF hollow fiber membrane accounts for the solution is 14%；The dimethyl silicone polymer rubs with the benzoic acid
You are than being 1:1.5.
(2) the metal-organic framework materials NH for obtaining the step (1)2Silicon carbide/nitridation of-UIO-66 (Zr) doping
Boron precursor is placed in melt spinning cylinder, then in the case where flow is the argon atmosphere of 300mL/min with the heating rate of 0.7 DEG C/h
It is heated to molten condition, then melt it is organic to be obtained metal followed by flowing out after strainer, spinneret by repressurization to 3MPa
Framework material NH2The silicon carbide precursor fibre bundle of-UIO-66 (Zr) doping, then 4h heat cross-linking is kept the temperature at a temperature of 360 DEG C, with
Carry out cure treatment.
(3) fibre bundle that the step (2) obtains is put into sintering furnace, then passes to the ammonia that flow is 200mL/min
Gas is heated to 650 DEG C with the heating rate of 100 DEG C/h, and keeps the temperature 2h, then is heated to 880 DEG C simultaneously with the heating rate of 200 DEG C/h
It keeps the temperature 2.5h and carries out Pintsch process, be then heated to 1600 DEG C in protective gas atmosphere with the heating rate of 40 DEG C/h and keep the temperature
0.5h is then cooled to room temperature, and obtains metal-organic framework materials NH2The silicon carbide fibre of-UIO-66 (Zr) doping.
Embodiment 2
Embodiment 2 proposes a kind of silicon carbide/boron nitride fiber, and preparation method includes the following steps:
It (1) is that simultaneously ultrasound is added in n,N-Dimethylformamide solution in 1.5:3 according to molar ratio by zirconium bromide and benzoic acid
Stirring, and PVDF hollow fiber membrane is injected, it is then added into autoclave, and dimethyl silicone polymer is added, is covered on it
The zirconium bromide and the PVDF hollow fiber membrane surface, are then heated to 130 DEG C, and insulation reaction with the heating rate of 8 DEG C/min
34h is then cooled to room temperature, then is centrifuged, and is then washed with anhydrous methanol and is dried 10h at a temperature of 85 DEG C, obtained
To NH2- UIO-66 (Zr) material, is then heated to 160 DEG C, and keep the temperature 2.5h under the heating rate of 22 DEG C/min, then with two
Toluene is successively dissolved, is filtered, is evaporated under reduced pressure, and metal-organic framework materials NH is obtained2The carbonization of-UIO-66 (Zr) doping
Silicon/boron nitride precursor body.Wherein, the ratio of the benzoic acid and the n,N-Dimethylformamide solution is 1mmol:6mL；Institute
Stating PVDF hollow fiber membrane and accounting for the mass percent of the solution is 16%；Mole of the dimethyl silicone polymer and the benzoic acid
Than for 3:3.5.
(2) the metal-organic framework materials NH for obtaining the step (1)2Silicon carbide/nitridation of-UIO-66 (Zr) doping
Boron precursor is placed in melt spinning cylinder, then in the case where flow is the argon atmosphere of 500mL/min with the heating rate of 0.3 DEG C/h
It is heated to molten condition, then melt it is organic to be obtained metal followed by flowing out after strainer, spinneret by repressurization to 5MPa
Framework material NH2The silicon carbide precursor fibre bundle of-UIO-66 (Zr) doping, then 6h heat cross-linking is kept the temperature at a temperature of 320 DEG C, with
Carry out cure treatment.
(3) fibre bundle that the step (2) obtains is put into sintering furnace, then passes to the ammonia that flow is 100mL/min
Gas is heated to 450 DEG C with the heating rate of 200 DEG C/h, and keeps the temperature 4h, then is heated to 920 with the heating rate of the 100 DEG C/h
DEG C and keep the temperature 1.5h carry out Pintsch process, be then heated to 1200 DEG C simultaneously with the heating rate of 60 DEG C/h in protective gas atmosphere
1h is kept the temperature, then cools to room temperature, obtains metal-organic framework materials NH2The silicon carbide fibre of-UIO-66 (Zr) doping.
Embodiment 3
Embodiment 3 proposes a kind of silicon carbide/boron nitride fiber, and preparation method includes the following steps:
It (1) is in 3.26:15 addition n,N-Dimethylformamide solution and to surpass according to molar ratio by zirconium bromide and benzoic acid
Sound stirring, and PVDF hollow fiber membrane is injected, it is then added into autoclave, and dimethyl silicone polymer is added, makes its covering
In the zirconium bromide and the PVDF hollow fiber membrane surface, 120 DEG C then are heated to the heating rate of 10 DEG C/min, and is kept the temperature anti-
36h is answered, is then cooled to room temperature, then is centrifuged, 12h is then washed and dried at a temperature of 80 DEG C with anhydrous methanol,
Obtain NH2- UIO-66 (Zr) material, is then heated to 180 DEG C, and keep the temperature 2h under the heating rate of 20 DEG C/min, then with two
Toluene is successively dissolved, is filtered, is evaporated under reduced pressure, and metal-organic framework materials NH is obtained2The carbonization of-UIO-66 (Zr) doping
Silicon/boron nitride precursor body.Wherein, the ratio of the benzoic acid and the n,N-Dimethylformamide solution is 3:20；It is described poly-
The mass percent that borosilicate azane accounts for the solution is 15%；The molar ratio of the dimethyl silicone polymer and the benzoic acid is
3:4.
(2) the metal-organic framework materials NH for obtaining the step (1)2Silicon carbide/nitridation of-UIO-66 (Zr) doping
Boron precursor is placed in melt spinning cylinder, then in the case where flow is the argon atmosphere of 400mL/min with the heating rate of 0.5 DEG C/h
It is heated to molten condition, then melt it is organic to be obtained metal followed by flowing out after strainer, spinneret by repressurization to 4MPa
Framework material NH2The silicon carbide precursor fibre bundle of-UIO-66 (Zr) doping, then 5h heat cross-linking is kept the temperature at a temperature of 340 DEG C, with
Carry out cure treatment.
(3) fibre bundle that the step (2) obtains is put into sintering furnace, then passes to the ammonia that flow is 150mL/min
Gas is heated to 550 DEG C with the heating rate of 150 DEG C/h, and keeps the temperature 3h, then is heated to 900 with the heating rate of the 150 DEG C/h
DEG C and keep the temperature 2h carry out Pintsch process, be then heated to 1400 DEG C in protective gas atmosphere with the heating rate of 50 DEG C/h and protect
Warm 0.75h, then cools to room temperature, and obtains metal-organic framework materials NH2The silicon carbide fibre of-UIO-66 (Zr) doping.
Embodiment 4
Embodiment 4 proposes a kind of silicon carbide/boron nitride fiber, and preparation method includes the following steps:
Step 1: NH2Silicon carbide/boron nitride precursor body preparation of-UIO-66 (Zr) doping
Take the zirconium bromide (ZrBr of 1wt.%4, 1mmol, purity > 99%) and phthalic acid (15mmol) be dissolved in 100mL
In n,N-Dimethylformamide (DMF) solution, solution and PVDF hollow fiber membrane 15wt.% (purity > 99%, softening after ultrasonic agitation
Point (70 ± 5) DEG C, MW3536) it is transferred in 100mL autoclave, pure polydimethylsiloxane (PCS) is slowly injected into high pressure
Kettle, for uniform fold in zirconium bromide and PVDF hollow fiber membrane surface, the speed of 10 DEG C/min quickly heats up to 120 DEG C, reacts 36 hours,
After reaction kettle is cooled to room temperature, centrifuge separation is washed repeatedly with sewage methanol and removes DMF, and it is small that 12 are dried in vacuo at 80 DEG C
When, obtain NH2- UIO-66 (Zr) material.Surface, the speed of 20 DEG C/min quickly heat up to 180 DEG C, keep the temperature 2 hours, obtain thick
Material.Coarse fodder obtains metal-organic framework materials NH through xylene soluble, filtering, vacuum distillation2The carbonization of-UIO-66 (Zr) doping
Silicon/boron nitride precursor body fines.
Step 2: NH2The preparation of silicon carbide/boron nitride precursor body melt spinning of-UIO-66 (Zr) doping
Step 1 fines is placed in melt spinning cylinder, 0.5 DEG C/min is heated in the case where flow is the argon atmosphere of 300mL/min
To molten condition, it is then forced into 3MPa, melt flow is flowed out through filter screen, spinneret, obtains metal-organic framework materials NH2-
Silicon carbide/boron nitride precursor body fibre bundle of UIO-66 (Zr) doping.Then 320 DEG C of heat cross-linkings in the atmosphere of air, heat preservation 4
Hour, carry out cure treatment.
Step 3: NH2Silicon carbide/boron nitride fiber sintering of-UIO-66 (Zr) doping
Above-mentioned gained cross filament is placed in sintering furnace, through-current capacity is the ammonia of 300mL/min, with 100 DEG C/h of speed
Rate is warming up to 450 DEG C, keeps the temperature 2h；900 DEG C of Pintsch process are then warming up to identical rate, keep the temperature 2h；Finally in argon gas
1200 DEG C are warming up to 50 DEG C/h of rates in atmosphere, keeps the temperature 0.5 hour, furnace cooling obtains metal-organic framework materials
NH2Silicon carbide/boron nitride fiber of-UIO-66 (Zr) doping.
Metal-organic framework materials NH prepared by embodiment 42Silicon carbide/boron nitride fiber of-UIO-66 (Zr) doping exists
Intensity 3.6GPa under room temperature, elasticity modulus 290GPa.After handling 100h in 1100 DEG C of air environments, strength retention ratio is
90%, in high-performance fiber field, such as the antenna windows and antenna house etc. of electromagnetic wave permeable material have extensive practical valence
Value and application prospect.
Embodiment 5
Embodiment 5 proposes a kind of silicon carbide/boron nitride fiber, and preparation method includes the following steps:
Step 1: NH2Silicon carbide/boron nitride precursor body preparation of-UIO-66 (Zr) doping.
Take the zirconium bromide (ZrBr of 3wt.%4, 3mmol, purity > 99%) and phthalic acid (15mmol) be dissolved in 100mL
In n,N-Dimethylformamide (DMF) solution, solution and PVDF hollow fiber membrane 15wt.% (purity > 99%, softening after ultrasonic agitation
Point (70 ± 5) DEG C, MW3536) it is transferred in 100mL autoclave, pure polydimethylsiloxane (PCS) is slowly injected into high pressure
Kettle, for uniform fold in zirconium bromide and PVDF hollow fiber membrane surface, the speed of 10 DEG C/min quickly heats up to 120 DEG C, reacts 36 hours,
After reaction kettle is cooled to room temperature, centrifuge separation is washed repeatedly with sewage methanol and removes DMF, and it is small that 12 are dried in vacuo at 80 DEG C
When, obtain NH2- UIO-66 (Zr) material.Surface, the speed of 20 DEG C/min quickly heat up to 180 DEG C, keep the temperature 2 hours, obtain thick
Material.Coarse fodder obtains metal-organic framework materials NH through xylene soluble, filtering, vacuum distillation2The carbonization of-UIO-66 (Zr) doping
Silicon/boron nitride precursor body fines.
Step 2: NH2Silicon carbide/boron nitride precursor body melt spinning of-UIO-66 (Zr) doping
Step 1 fines is placed in melt spinning cylinder, 0.5 DEG C/min is heated in the case where flow is 200mL/min argon atmosphere
Molten condition is then forced into 3MPa, and melt flow is flowed out through filter screen, spinneret, obtains metal-organic framework materials NH2-UIO-
Silicon carbide/boron nitride precursor body fibre bundle of 66 (Zr) doping.Then 340 DEG C of heat cross-linkings in the atmosphere of air, heat preservation 5 are small
When, carry out cure treatment.
Step 3: NH2Silicon carbide/boron nitride fiber sintering of-UIO-66 (Zr) doping
Above-mentioned gained cross filament is placed in sintering furnace, through-current capacity is the ammonia of 400mL/min, with 150 DEG C/h of speed
Rate is warming up to 550 DEG C, keeps the temperature 4h；900 DEG C of Pintsch process are then warming up to identical rate, keep the temperature 2h；Finally in argon gas
1400 DEG C are warming up to 50 DEG C/h of rates in atmosphere, keeps the temperature 0.8 hour, furnace cooling obtains metal-organic framework materials
NH2Silicon carbide/boron nitride fiber of-UIO-66 (Zr) doping.
Metal-organic framework materials NH prepared by embodiment 52Silicon carbide/boron nitride fiber of-UIO-66 (Zr) doping exists
Intensity 3.7GPa under room temperature, elasticity modulus 295GPa.After handling 100h in 1100 DEG C of air environments, strength retention ratio is
91%, in high-performance fiber field, such as the antenna windows and antenna house etc. of electromagnetic wave permeable material have extensive practical valence
Value and application prospect.
Embodiment 6
Embodiment 6 proposes a kind of silicon carbide/boron nitride fiber, and preparation method includes the following steps:
Step 1: NH2Silicon carbide/boron nitride precursor body preparation of-UIO-66 (Zr) doping.
Take the zirconium bromide (ZrBr of 4.5wt.%4, 4.5mmol, purity > 99%) and phthalic acid (15mmol) be dissolved in
In 100mL n,N-Dimethylformamide (DMF) solution, solution and PVDF hollow fiber membrane 15wt.% (softening point (70 after ultrasonic agitation
± 5) DEG C, MW3536)) it is transferred in 100mL autoclave, pure polydimethylsiloxane (PCS) is slowly injected into autoclave,
It is even to be covered on zirconium bromide and PVDF hollow fiber membrane (purity > 99%, softening point (70 ± 5) DEG C, MW3536) surface, 10 DEG C/min's
Speed quickly heats up to 120 DEG C, reacts 36 hours, and after reaction kettle is cooled to room temperature, centrifuge separation is washed repeatedly with sewage methanol
DMF is washed away, is dried in vacuo 12 hours at 80 DEG C, obtains NH2- UIO-66 (Zr) material.The speed on surface, 20 DEG C/min is fast
Speed is heated to 180 DEG C, keeps the temperature 2 hours, obtains coarse fodder.Coarse fodder obtains the organic bone of metal through xylene soluble, filtering, vacuum distillation
Frame material NH2Silicon carbide/boron nitride precursor body fines of-UIO-66 (Zr) doping.
Step 2: NH2Silicon carbide/boron nitride precursor body melt spinning of-UIO-66 (Zr) doping
Step 1 fines is placed in melt spinning cylinder, 0.5 DEG C/min is heated in the case where flow is the argon atmosphere of 200mL/min
To molten condition, it is then forced into 5MPa, melt flow is flowed out through filter screen, spinneret, obtains metal-organic framework materials NH2-
Silicon carbide/boron nitride precursor body fibre bundle of UIO-66 (Zr) doping.Then 360 DEG C of heat cross-linkings in the atmosphere of air, heat preservation 6
Hour, carry out cure treatment.
Step 3: NH2Silicon carbide/boron nitride fiber sintering of-UIO-66 (Zr) doping
Above-mentioned gained cross filament is placed in sintering furnace, through-current capacity is the ammonia of 500mL/min, with 200 DEG C/h of speed
Rate is warming up to 650 DEG C, keeps the temperature 4h；900 DEG C of Pintsch process are then warming up to identical rate, keep the temperature 2h；Finally in argon gas
1600 DEG C are warming up to 50 DEG C/h of rates in atmosphere, keeps the temperature 01 hour, furnace cooling obtains metal-organic framework materials
NH2Silicon carbide/boron nitride fiber of-UIO-66 (Zr) doping.
Metal-organic framework materials NH prepared by embodiment 62Silicon carbide/boron nitride fiber of-UIO-66 (Zr) doping exists
Intensity 3.8GPa under room temperature, elasticity modulus 300GPa.After handling 100h in 1100 DEG C of air environments, strength retention ratio is
93%, in high-performance fiber field, such as the antenna windows and antenna house etc. of electromagnetic wave permeable material have extensive practical valence
Value and application prospect.
To sum up, the present invention introduces heterogeneous element zirconium in precursor, plays the role of a sintering aid；In non-fusible mistake
Low temperature precrosslink technique is used in journey, introduces suitable oxygen element in the early stage；A small amount of PVDF hollow fiber membrane is added simultaneously, is being burnt into
Fibrous inside oxygen is consumed in the process, the shrink defects during fiber sintering is made up, so as to improve the mechanical property of composite fibre
And high temperature resistance.Aluminum-containing silicon carbide fiber can effectively improve the densification of silicon carbide fibre in high temperature sintering.The introducing of B can have
Effect inhibits SiC crystal grain in high-temperature sintering process to grow up, and ensure that the mechanical behavior under high temperature of composite fibre.At ammonia
The reason stage generates fire sand nano material in silicon carbide/boron nitride fiber interface and provides excellent composite effect, simultaneously
Also the content of oxygen in fiber is reduced, and introduces the boron nitride of low elastic modulus to reduce the elasticity modulus of matrix.NH2-UIO-66
(Zr) remain to be stabilized in (boiling water, strong acid and strong base) in harsh environment, metal-organic framework materials have specific surface area it is high,
Aperture is adjustable, can functional modification, good thermal stability and the features such as chemical stability, can be good at and silicon carbide carries out
It is compound, keep ceramic base complex fiber material of the invention strong in the thermal-shock resistance of superhigh temperature, have good optical property and
Magnetic properties.3.6 ± 0.2GPa of intensity, 280 ± 30GPa of elasticity modulus under the silicon carbide of preparation/boron nitride fiber room temperature.?
After handling 100 hours in 1100 DEG C of air environments, strength retention ratio remains to reach 89% or more, in high-performance fiber field,
Such as the antenna windows and antenna house etc. of electromagnetic wave permeable material have extensive practical value and application prospect.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (9)
1. a kind of preparation method of silicon carbide/boron nitride fiber, which comprises the steps of:
S101: according to molar ratio be (1~4.5) by zirconium bromide and benzoic acid: 15 are added in n,N-Dimethylformamide solution simultaneously
Ultrasonic agitation, and PVDF hollow fiber membrane is injected, it is then added into autoclave, and dimethyl silicone polymer is added, covers it
It covers in the zirconium bromide and the PVDF hollow fiber membrane surface, is then heated to 110 DEG C~130 DEG C with the first heating rate, and protect
Temperature reaction 34h~38h, then cools to room temperature, then be centrifuged, is then washed and dried with anhydrous methanol, obtained
NH2- UIO-66 (Zr) material, is then heated to 160 DEG C~200 DEG C, and keep the temperature 1.5h~2.5h under the second heating rate, then
It is successively dissolved with dimethylbenzene, filters, is evaporated under reduced pressure, obtain metal-organic framework materials NH2The carbon of-UIO-66 (Zr) doping
SiClx/boron nitride precursor body；
S102: the metal-organic framework materials NH that the step S101 is obtained2Silicon carbide/boron nitride of-UIO-66 (Zr) doping
Precursor is placed in melt spinning cylinder, is then heated to molten condition under atmosphere of inert gases with third heating rate, then plus
It is depressed into 3MPa~5MPa, melt is then obtained into metal-organic framework materials NH followed by flowing out after strainer, spinneret2-
The silicon carbide precursor fibre bundle of UIO-66 (Zr) doping, then heat cross-linking, to carry out cure treatment；
S103: the obtained fibre bundle of the step S102 is put into sintering furnace, ammonia is then passed to, is added with the 4th heating rate
Heat keeps the temperature 2h~4h to 450 DEG C~650 DEG C, then is heated to 880 DEG C~920 DEG C with the 4th heating rate and keeps the temperature
1.5h~2.5h carries out Pintsch process, is then heated to 1200 DEG C~1600 DEG C in protective gas atmosphere with the 5th heating rate
And 0.5h~1h is kept the temperature, it then cools to room temperature, obtains metal-organic framework materials NH2The silicon carbide of-UIO-66 (Zr) doping
Fiber.
2. the preparation method of silicon carbide fibre according to claim 1, which is characterized in that in the step S101, institute
Stating the first heating rate is 8 DEG C/min~12 DEG C/min；In the step S102, second heating rate is 18 DEG C/min
~22 DEG C/min；In the step S102, the third heating rate is 0.3 DEG C/h~0.7 DEG C/h；In the step S103
In, the 4th heating rate is 100 DEG C/h~200 DEG C/h；In the step S103, the 5th heating rate is 40
DEG C/h~60 DEG C/h.
3. the preparation method of silicon carbide fibre according to claim 1, which is characterized in that in the step S102, institute
Stating protective gas is argon gas, and the flow of the argon gas is 300mL/min~500mL/min.
4. the preparation method of silicon carbide fibre according to claim 1, which is characterized in that in the step S103, institute
The flow for stating ammonia is 100mL/min~200mL/min.
5. the preparation method of silicon carbide fibre according to claim 1, which is characterized in that in the step S101, institute
The ratio for stating benzoic acid and the n,N-Dimethylformamide solution is 3mmol:(18mL~22mL)；The PVDF hollow fiber membrane accounts for
The mass percent of the solution is 14%~16%；The molar ratio of the dimethyl silicone polymer and the benzoic acid is 3:
(3.5~4.5).
6. the preparation method of silicon carbide fibre according to claim 1, which is characterized in that in the step S101, do
Dry temperature is 75 DEG C~85 DEG C, and drying time is 10h~14h.
7. the preparation method of silicon carbide fibre according to claim 1, which is characterized in that in the step S102,
Be heated to 320 DEG C~360 DEG C when heat cross-linking and keep the temperature 4h~6h.
8. the silicon carbide fibre of the described in any item method preparations of claim 1-7.
9. the described in any item silicon carbide fibres of claim 1-7 are in the application of aviation, machinery, chemical industry, space flight and weapon field.
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