CN109485388A - Preparation method of Si-C-O ceramic fiber with adjustable and controllable element composition - Google Patents
Preparation method of Si-C-O ceramic fiber with adjustable and controllable element composition Download PDFInfo
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Abstract
The invention discloses a preparation method of Si-C-O ceramic fiber with adjustable element composition, which comprises the following steps: s1: preparing a blended polymer of organic silicon resin and polycarbosilane; s2: heating and insulating the blended polymer obtained in the S1; s3: obtaining fibrils; s4: obtaining non-melting fibers; s5: obtaining the Si-C-O ceramic fiber. The method takes the blend of the cheap organic silicon resin and the polycarbosilane as a precursor, and prepares the Si-C-O ceramic fiber with smooth surface, compact fiber structure and adjustable element composition at lower cost. Compared with the existing ceramic fiber, the Si-C-O ceramic fiber provided by the invention has the advantages of low cost and excellent performance, the diameter of the Si-C-O ceramic fiber is 6.7-12.1 mu m, the oxygen content is 9.34-27.53%, the monofilament tensile strength is 0.87-1.31 GPa, the modulus is 100-137 GPa, and the carbon content is 22.62-38.42%.
Description
Technical field
The present invention relates to ceramic fibre technical field, especially a kind of element forms regulatable Si-C-O ceramic fibre
Preparation method.
Background technique
Si-C-O ceramic fibre has good service performance at 1200 DEG C, there is better heatproof compared with oxide fibre
Performance and acid-alkali-corrosive-resisting, with the advantage that preparation cost is cheap compared with SiC fiber.Si-C-O be it is a kind of between SiC and
SiO2Between intermediary, by three kinds of silicon, oxygen, carbon elements with covalent bond be connected tetrahedral structure form, in titanium dioxide
Si-C-O network is obtained just with the oxygen that the carbon of a tetravalence substitutes two divalent in silicon network.Si-C-O structure has both oxidation simultaneously
The characteristic of object ceramics and non-oxide ceramics, additionally have good mechanical property and inoxidizability, in recent years increasingly by
To extensive concern.
Sol-gal process is the main method for preparing Si-C-O fiber at present, however the fiber power being prepared with the method
It is poor to learn performance.Precursor pyrolysis and hot pressing can be used for preparation Si-C-O ceramic fibre.Si-C-O fiber is mainly with organosilicon at present
Resin is prepared by precursor.Existing polymer-derived method preparation Si-C-O fiber has the following problems: gained fibrous inner structure
There are the separation of apparent phase, and fibre structure is loose, substantially without service performance；Gained fiber is mainly by SiO2Phase composition, carbon content
Low, fiber oxygen content is too high, and containing compared with multiple hole and defect, Si-C-O fibrous mechanical property is poor.
Summary of the invention
The present invention provides the preparation method that a kind of element forms regulatable Si-C-O ceramic fibre, for overcoming existing skill
The defects of fibre structure is loose in art, carbon content is low and fibrous mechanical property is poor realizes that preparation cost is low and ceramics obtained
Fibre property is excellent.
To achieve the above object, the present invention provides the preparation side that a kind of element forms regulatable Si-C-O ceramic fibre
Method, comprising the following steps:
S1: the polymer blend of organic siliconresin and Polycarbosilane is prepared；
S2: it under an inert atmosphere, is kept the temperature after polymer blend obtained by step S1 is warming up to 100~300 DEG C；
S3: by step S2, treated that polymer blend carries out melt spinning under 0.1~0.5MPa pressure, obtains fibril
Dimension；
S4: the obtained fibrinogen of step S3 is crosslinked, fusion-free fibre is obtained；
S5: under an inert atmosphere, the fusion-free fibre that step S4 is obtained to 900~1300 DEG C and is protected from room temperature
Si-C-O ceramic fibre is made in temperature.
To achieve the above object, the present invention also provides a kind of Si-C-O ceramic fibres, and the Si-C-O ceramic fibre is in bright
Black, smooth surface；The diameter of the Si-C-O ceramic fibre be 6.7~12.1 μm, oxygen content be 9.34~
27.53%, monofilament tensile strength is 0.87~1.31GPa, and modulus is 100~137GPa, and carbon content is 22.62~38.42%.
Compared with prior art, the beneficial effects of the present invention are as follows:
1, the present invention prepares polymer blend using organic siliconresin and Polycarbosilane as raw material, is pioneer with polymer blend
Body, compared with SiC fiber, preparation precursor is blended with Polycarbosilane using cheap silicone resin by the present invention, has preparation cost
Cheap advantage；Compared with oxide fibre, there are better heat resistance and acid-alkali-corrosive-resisting；With merely using organosilicon tree
Rouge is that the standby Si-C-O ceramic fibre of precursor is compared, and constituent content may be implemented in Si-C-O ceramic fibre prepared by the present invention
Regulation, product has superior fibrous mechanical property.
2, precursor is obtained Si-C-O ceramic fibre by the present invention after melt spinning, crosslinking and calcination processing, is prepared
Simple process, obtained fiber surface is smooth, and fibre structure is fine and close, and carbon content is higher, and Si-C-O ceramics produced by the present invention are fine
Tieing up diameter is 6.7~12.1 μm, and oxygen content is 9.34~27.53%, and monofilament tensile strength is 0.87~1.31GPa, and modulus is
100~137GPa, carbon content are 22.62~38.42%, and Si-C-O ceramic fibre mechanical property produced by the present invention can reach reality
Border requirement.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
The structure shown according to these attached drawings obtains other attached drawings.
Fig. 1 is the INFRARED SPECTRUM of organic siliconresin used, Polycarbosilane and gained polymer blend in the embodiment of the present invention 1
Schematic diagram；
Fig. 2 is the TG figure of gained polymer blend in the embodiment of the present invention 1；
Fig. 3 is the SEM schematic diagram of gained Si-C-O ceramic fibre in the embodiment of the present invention 1；
Fig. 4 is the AES figure of gained Si-C-O ceramic fibre in the embodiment of the present invention 4；
Fig. 5 is the SEM figure of gained Si-C-O ceramic fibre in the embodiment of the present invention 5.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts it is all its
His embodiment, shall fall within the protection scope of the present invention.
It is to be appreciated that the directional instruction (such as up, down, left, right, before and after ...) of institute is only used in the embodiment of the present invention
In explaining in relative positional relationship, the motion conditions etc. under a certain particular pose (as shown in the picture) between each component, if should
When particular pose changes, then directionality instruction also correspondingly changes correspondingly.
In addition, the description for being such as related to " first ", " second " in the present invention is used for description purposes only, and should not be understood as
Its relative importance of indication or suggestion or the quantity for implicitly indicating indicated technical characteristic.Define as a result, " first ",
The feature of " second " can explicitly or implicitly include at least one of the features.In the description of the present invention, " multiple " contain
Justice is at least two, such as two, three etc., unless otherwise specifically defined.
In the present invention unless specifically defined or limited otherwise, term " connection ", " fixation " etc. shall be understood in a broad sense,
For example, " fixation " may be a fixed connection, it may be a detachable connection, or integral；It can be mechanical connection, be also possible to
Electrical connection can also be physical connection or wireless communication connection；It can be directly connected, the indirect phase of intermediary can also be passed through
Even, the connection inside two elements or the interaction relationship of two elements be can be, unless otherwise restricted clearly.For this
For the those of ordinary skill in field, the specific meanings of the above terms in the present invention can be understood according to specific conditions.
It in addition, the technical solution between each embodiment of the present invention can be combined with each other, but must be general with this field
Based on logical technical staff can be realized, it will be understood that when the combination of technical solution appearance is conflicting or cannot achieve this
The combination of technical solution is not present, also not the present invention claims protection scope within.
Unless otherwise instructed, the raw material in the embodiment of the present invention is bought by commercial sources.
The present invention provides the preparation method that a kind of element forms regulatable Si-C-O ceramic fibre, comprising the following steps:
S1: the polymer blend of organic siliconresin and Polycarbosilane is prepared；
S2: it under an inert atmosphere, is kept the temperature after polymer blend obtained by step S1 is warming up to 100~300 DEG C；
S3: by step S2, treated that polymer blend carries out melt spinning under 0.1~0.5MPa pressure, obtains fibril
Dimension；
S4: the obtained fibrinogen of step S3 is crosslinked, fusion-free fibre is obtained；
S5: under an inert atmosphere, the fusion-free fibre that step S4 is obtained to 900~1300 DEG C and is protected from room temperature
Si-C-O ceramic fibre is made in temperature.
Preferably, in the step S1, the preparation of the polymer blend the following steps are included:
S11: 1:(0.5~4 in mass ratio) organic siliconresin and Polycarbosilane are weighed, it is completely dissolved in solvent later simultaneously
It stirs evenly；
S12: mixed liquor obtained by step S11 is subjected to solvent and is handled, the polymer blend is obtained.
It is described to go solvent processing to be evaporated under reduced pressure at 100~300 DEG C except removal solvent.
Preparing polymer blend using this step can be realized under the premise of not destroying precursor spinning properties, reduce first
Body oxygen content is driven, active Si -- H bond is introduced, is conducive to cross-linking process progress, while introducing Si-C key in main chain, is conducive to
Improve the performance of fiber.
Preferably, the organic siliconresin is using Si-O-Si key as the organosilicon polymer of main chain, molecular structure unit
Are as follows:
Wherein, alkyl R1、R2、R3Independently selected from H, C1~C3Alkyl, C1~C3Substituted hydrocarbon radical or substituted aryl, and
R1、R2、R3In at most there are two being H because Si is at least connected with the group containing C in side chain in organic siliconresin structure.Example
Such as R1、R2、R3Independently selected from Me, Ph ,-OCH3、-CH2,-CH- organic group, they can be the same or different.It is described
Organic siliconresin can be SR8803, YR3370, SR249, RSN6018 etc..
The Polycarbosilane is the organosilicon polymer that main chain is constituted with Si-C key, and side chain has-H and-CH3；
The solvent is all kinds of organic solvents that can dissolve the organic siliconresin and the Polycarbosilane, as benzene, toluene,
Dimethylbenzene, ethylbenzene, diethylbenzene or propyl benzene.
Preferably, in the step S2, the heating rate is 1~20 DEG C/min；The soaking time is 1~5h；Institute
Stating inert atmosphere is the nitrogen or argon gas that purity is 99.999%.Heating and thermal insulation is to keep entire spinning system temperature equal
It is even；Inert atmosphere is to react when organic siliconresin heats up in air in order to prevent with air.
Preferably, in the step S3, the receipts silk speed of the melt spinning is 300~600r/min.Silk speed is received in control
Degree is to guarantee that spinning process is continuous.
Preferably, in the step S4, the crosslinking is crosslinked using ultraviolet radioactive, and a length of 250nm of ultraviolet light wave used~
350nm, 10~80h of ultraviolet light time.
Curing process is crosslinked using ultraviolet radioactive, compared to the non-fusible technology of existing electron beam irradiation, has technique
It is simple and convenient to operate, the features such as preparation cost is low.
Preferably, the crosslinking is crosslinked using reactive atmosphere, the reactive atmosphere include inert atmosphere in step S1 and
Active gases, the volume ratio of the two are (0.5~10): 1.
Fibrinogen cross-linking process can successfully be realized by being passed through reactive atmosphere in this ratio, and introduce the members such as boron, titanium in the fibre
Element is conducive to improve fibre property when high temperature sintering.
Preferably, the active gases include: in dichloro methyl silane, silicon tetrachloride, boron chloride and titanium tetrachloride extremely
Few one kind.The active gases is with the low boiling point compared with high reaction activity, volatile organic or inorganic compound.It is only high
The atmosphere of reactivity could react completion crosslinking with fibrinogen, and low boiling point, volatile characteristic can guarantee the gas in system
Body content is sufficient.
Preferably, in the step S5, the heating rate is 50~100 DEG C/h；The soaking time is 1~2h.This
Place's control heating rate is to heat up too fast to cause to damage to sample and graphite furnace in order to prevent；Heat preservation is in order under target temperature
It is sufficiently inorganization.
The present invention also provides a kind of Si-C-O ceramic fibre, the Si-C-O ceramic fibre breaks in bright black, without lousiness, nothing
Head, smooth surface, and circular in cross-section；The diameter of the Si-C-O ceramic fibre is 6.7~12.1 μm, and oxygen content is
9.34~27.53%, monofilament tensile strength be 0.87~1.31GPa, modulus be 100~137GPa, carbon content be 22.62~
38.42%.
Monofilament tensile strength and modulus: Testometric Micro350 type instron, sample marking distance:
25mm, the Mean Speed of collet decline: 5mm/min, the test sample of each fiber sample: 25 monofilament；
Oxygen content: Japanese EMGA-320V2 type nitrogen oxygen analyzer；
Carbon element content: the Japanese infrared sulphur carbon analyzer of EMGA-820 type.
Embodiment one
Prepare Si-C-O ceramic fibre 1#
The present embodiment provides the preparation methods that a kind of element forms regulatable Si-C-O ceramic fibre, including following step
It is rapid:
S1: the polymer blend of organic siliconresin and Polycarbosilane is prepared；
S11: it weighs 20g organic siliconresin SR8803 and 10g Polycarbosilane and is dissolved in 150ml benzene and stirs evenly；
S12: mixed liquor obtained by step S11 is evaporated under reduced pressure at 150 DEG C, is removed solvent benzol, is obtained the blending polymerization
Object；
S2: it takes polymer blend obtained by 10g step S1 to be placed in the spinning cylinder of melt spinning device, is passed through at 60 DEG C pure
Degree carrys out displaced air for 99.999% nitrogen, then 130 DEG C are heated to from 60 DEG C with the rate of 10 DEG C/min, keeps the temperature 0.5h；
S3: it by step S2 treated polymer blend under 0.3MPa pressure, is carried out with the receipts silk speed of 600r/min
Melt spinning obtains fibrinogen；
S4: the obtained fibrinogen of step S3 is placed in the UV crosslinking instrument of launch wavelength 254nm, is irradiated 10h, is obtained not
Melting fiber；
S5: the obtained fusion-free fibre of step S4 being placed in graphite furnace furnace, is vacuumized, and being passed through purity is 99.999%
Nitrogen displaced air three times, then with the heating rate of 60 DEG C/h from room temperature to 1000 DEG C, and isothermal holding at such a temperature
1h obtains Si-C-O ceramic fibre 1#。
Fig. 1 is the infrared spectrum of organic siliconresin used in the present embodiment, Polycarbosilane and gained polymer blend.From figure
1 it is found that organic siliconresin in 3500cm-1Nearby there are Si-OH absorption peak, 1200cm-1~1000cm-1There are Si-O- in range
Si key absorption peak, 2900cm-1Corresponding C-H absorption peak nearby, 1260cm-1Place is Si-CH3Absorption peak, in 1650cm-1~
1450cm-1There is apparent phenyl absorption peak in range；Polycarbosilane is in 2900cm-1Nearby there are C-H absorption peak, 2100cm-1Place
Corresponding Si-H absorption peak, 1000cm-1It is nearby the absorption peak of Si-C-Si main chain.(the infrared spectroscopy of Nicolet Impact 360
Instrument, solid sample use potassium bromide (KBr) pressed disc method, and beam scanning range is 4000~400cm-1)
Illustrate that gained polymer blend includes organic siliconresin and all absorption peaks of Polycarbosilane, mixed process are simple
There is no chemical reactions under experimental temperature for physical blending, organic siliconresin and Polycarbosilane.
Fig. 2 is the TG (thermogravimetric curve) of gained polymer blend in the present embodiment.The test condition of the curve are as follows: in nitrogen
Polymer blend is heated under atmosphere to 1000 DEG C, the ceramic yield of gained polymer blend reaches 77.5%.Illustrate blending polymerization
Object is weightless less with temperature raising, is suitable as ceramic precursor and prepares ceramic fibre.(NETZSCH STA 449F3 type heat point
Analyzer, measurement atmosphere are nitrogen, gas flow rate 50mL/min, and temperature range is room temperature to 1400 DEG C, 10 DEG C/min of heating rate)
Fig. 3 is gained Si-C-O ceramic fibre 1 in the present embodiment#SEM (scanning electron microscope) figure.As can be seen from Figure 3,
Fiber surface is smooth, without apparent defect.(Hitachi S-4800 type field emission scanning electron microscope)
The present embodiment using the polymer blend of organic siliconresin and Polycarbosilane as raw material, by melt spinning, crosslinking and
Si-C-O ceramic fibre is obtained after calcination processing.This method simple process, cost of material are low, gained Si-C-O ceramic fibre 1#Directly
Diameter is 6.7 μm, and oxygen content 27.53%, monofilament tensile strength is up to 0.94GPa, and for modulus up to 111GPa, carbon content is reachable
22.62%；Fiber surface is smooth.Oxygen, carbon content illustrate that the regulation of constituent content may be implemented in the method using of the invention；Directly
Diameter, monofilament tensile strength and modulus illustrate that the product of preparation has preferable mechanical property.
By above-mentioned characterization it is found that ceramic fibre preparation method provided in this embodiment can improve gained Si-C-O ceramic fibre
Integrality, avoid fibrous inner structure from there is apparent mutually separation and fibre structure loose, obtain mechanical property it is more excellent, can be completely
The Si-C-O ceramic fibre of sufficient requirement.Meanwhile carbon oxygen content is effectively controlled in fiber.
Embodiment two
Prepare Si-C-O ceramic fibre 2#
The present embodiment provides the preparation methods that a kind of element forms regulatable Si-C-O ceramic fibre, including following step
It is rapid:
S1: the polymer blend of organic siliconresin and Polycarbosilane is prepared；
S11: it weighs 20g organic siliconresin SR8803 and 20g Polycarbosilane and is dissolved in 150ml benzene and stirs evenly；
S12: mixed liquor obtained by step S11 is evaporated under reduced pressure at 150 DEG C, is removed solvent benzol, is obtained the blending polymerization
Object；
S2: it takes polymer blend obtained by 10g step S1 to be placed in the spinning cylinder of melt spinning device, is passed through at 60 DEG C pure
Degree carrys out displaced air for 99.999% nitrogen, then 150 DEG C are heated to from 60 DEG C with the rate of 10 DEG C/min, keeps the temperature 0.5h；
S3: it by step S2 treated polymer blend under 0.4MPa pressure, is carried out with the receipts silk speed of 600r/min
Melt spinning obtains fibrinogen；
S4: the obtained fibrinogen of step S3 is placed in the UV crosslinking instrument of launch wavelength 254nm, is irradiated 20h, is obtained not
Melting fiber；
S5: the obtained fusion-free fibre of step S4 being placed in graphite furnace furnace, is vacuumized, and being passed through purity is 99.999%
Nitrogen displaced air three times, then with the heating rate of 60 DEG C/h from room temperature to 1000 DEG C, and isothermal holding at such a temperature
1h obtains Si-C-O ceramic fibre 2#。
Si-C-O ceramic fibre 2 made from the present embodiment#Fibre diameter is 8.2 μm, and oxygen content 19.42%, monofilament is drawn
Stretching intensity is 0.90GPa, modulus 108GPa, carbon content 29.59%.
Since Polycarbosilane is insensitive to ultraviolet light, when Polycarbosilane ratio improves, cross-linking effect declines, fiber
Performance decline.
Embodiment three
Prepare Si-C-O ceramic fibre 3#
The present embodiment provides the preparation methods that a kind of element forms regulatable Si-C-O ceramic fibre, including following step
It is rapid:
S1: the polymer blend of organic siliconresin and Polycarbosilane is prepared；
S11: it weighs 10g organic siliconresin SR8803 and 40g Polycarbosilane and is dissolved in 150ml benzene and stirs evenly；
S12: mixed liquor obtained by step S11 is evaporated under reduced pressure at 170 DEG C, is removed solvent benzol, is obtained the blending polymerization
Object；
S2: it takes polymer blend obtained by 10g step S1 to be placed in the spinning cylinder of melt spinning device, is passed through at 60 DEG C pure
Degree carrys out displaced air for 99.999% nitrogen, then 200 DEG C are heated to from 60 DEG C with the rate of 10 DEG C/min, keeps the temperature 0.5h；
S3: it by step S2 treated polymer blend under 0.3MPa pressure, is carried out with the receipts silk speed of 600r/min
Melt spinning obtains fibrinogen；
S4: the obtained fibrinogen of step S3 is placed in the UV crosslinking instrument of launch wavelength 254nm, is irradiated 30h, is obtained not
Melting fiber；
S5: the obtained fusion-free fibre of step S4 being placed in graphite furnace furnace, is vacuumized, and being passed through purity is 99.999%
Nitrogen displaced air three times, then with the heating rate of 60 DEG C/h from room temperature to 1000 DEG C, and isothermal holding at such a temperature
1h obtains Si-C-O ceramic fibre 3#。
Si-C-O ceramic fibre 3 made from the present embodiment#Fibre diameter is 10.1 μm, and oxygen content 11.43%, monofilament is drawn
Stretching intensity is 0.83GPa, modulus 100GPa, carbon content 38.42%.
Example IV
Prepare Si-C-O ceramic fibre 4#
The present embodiment provides the preparation methods that a kind of element forms regulatable Si-C-O ceramic fibre, including following step
It is rapid:
S1: the polymer blend of organic siliconresin and Polycarbosilane is prepared；
S11: it weighs 20g organic siliconresin YR3370 and 20g Polycarbosilane and is dissolved in 150ml benzene and stirs evenly；
S12: mixed liquor obtained by step S11 is evaporated under reduced pressure at 150 DEG C, is removed solvent benzol, is obtained the blending polymerization
Object；
S2: it takes polymer blend obtained by 10g step S1 to be placed in the spinning cylinder of melt spinning device, is passed through at 60 DEG C pure
Degree carrys out displaced air for 99.999% nitrogen, then 130 DEG C are heated to from 60 DEG C with the rate of 10 DEG C/min, keeps the temperature 0.5h；
S3: it by step S2 treated polymer blend under 0.4MPa pressure, is carried out with the receipts silk speed of 600r/min
Melt spinning obtains fibrinogen；
S4: in the fibrinogen quartz tube furnace that step S3 is obtained, vacuumizing, and is passed through the nitrogen that purity is 99.999% and sets
It ventilates three times, is heated to 60 DEG C, be passed through the gaseous mixture of nitrogen and boron chloride that the purity that volume ratio is 3:1 is 99.999%
Body, and 4h is kept the temperature at 70 DEG C, it is cooled to room temperature to obtain fusion-free fibre；
S5: the obtained fusion-free fibre of step S4 being placed in graphite furnace, is vacuumized, and is passed through the nitrogen that purity is 99.999%
Gas displaced air three times, then with the heating rate of 60 DEG C/h from room temperature to 1000 DEG C, and isothermal holding 1h at such a temperature,
Obtain Si-C-O ceramic fibre 4#。
Si-C-O ceramic fibre 4 made from the present embodiment#Fibre diameter is 8.6 μm, and oxygen content 20.63%, monofilament is drawn
Stretching intensity is 1.12GPa, modulus 119GPa, carbon content 31.24%.
Fig. 4 is gained Si-C-O ceramic fibre 4 in the present embodiment#AES (Auger electron spectroscopy) figure.As can be seen from Figure 4, exist
Completed in boron chloride atmosphere it is non-fusible during, fibrinogen is reacted with boron chloride active gases, and boron element is introduced into fiber
In.(AES analyzer is ULVAC PHI-700, uses high pressure for the coaxial electron gun of 5kV and CMA energy analyzer, energy point
Resolution 1 ‰, 30 ° of incidence angle, the vacuum degree of analysis room is better than 3.9 × 10-9Torr) embodiment five
Prepare Si-C-O ceramic fibre 5#
The present embodiment provides the preparation methods that a kind of element forms regulatable Si-C-O ceramic fibre, including following step
It is rapid:
S1: the polymer blend of organic siliconresin and Polycarbosilane is prepared；
S11: it weighs 10g organic siliconresin RSN6018 and 40g Polycarbosilane and is dissolved in 150ml benzene and stirs evenly；
S12: mixed liquor obtained by step S11 is evaporated under reduced pressure at 150 DEG C, is removed solvent benzol, is obtained the blending polymerization
Object；
S2: it takes polymer blend obtained by 10g step S1 to be placed in the spinning cylinder of melt spinning device, is passed through at 60 DEG C pure
Degree carrys out displaced air for 99.999% nitrogen, then 155 DEG C are heated to from 60 DEG C with the rate of 10 DEG C/min, keeps the temperature 0.5h；
S3: it by step S2 treated polymer blend under 0.4MPa pressure, is carried out with the receipts silk speed of 600r/min
Melt spinning obtains fibrinogen；
S4: in the fibrinogen quartz tube furnace that step S3 is obtained, vacuumizing, and is passed through the nitrogen that purity is 99.999% and sets
It ventilates three times, is heated to 60 DEG C, be passed through the gaseous mixture of nitrogen and silicon tetrachloride that the purity that volume ratio is 3:1 is 99.999%
Body, and 4h is kept the temperature at 70 DEG C, it is cooled to room temperature to obtain fusion-free fibre；
S5: the obtained fusion-free fibre of step S4 being placed in graphite furnace furnace, is vacuumized, and being passed through purity is 99.999%
Nitrogen displaced air three times, then with the heating rate of 60 DEG C/h from room temperature to 1000 DEG C, and isothermal holding at such a temperature
1h obtains Si-C-O ceramic fibre 5#。
Si-C-O ceramic fibre 5 made from the present embodiment#Fibre diameter is 12.1 μm, and oxygen content 9.34%, monofilament is drawn
Stretching intensity is 1.31GPa, modulus 137GPa, carbon content 37.63%.
Fig. 5 is gained Si-C-O ceramic fibre 5 in the present embodiment#SEM (scanning electron microscope) figure.As can be seen from Figure 5,
Fiber surface and section are substantially smooth, without apparent defect.
In the present invention, C1~C3、C3~C6Etc. referring both to carbon atom number included in group.
In the present invention, " alkyl " is to be formed by group by losing any one hydrogen atom on hydrocarbon molecules；Hydrocarbon
Class compound includes alkane compound (linear paraffin, branched paraffin and cycloalkane), olefin(e) compound, acetylene hydrocarbon compound and aromatic hydrocarbons
Compound.As toluene loses, the hydrogen atom that methyl aligns on phenyl ring is formed by p-methylphenyl or toluene loses methyl and takes up an official post
The benzyl etc. that a hydrogen atom of anticipating is formed.
In the present invention, " alkyl " is to be formed by group by losing any one hydrogen atom on alkane compound molecule.
In the present invention, " aryl " is to lose a hydrogen atom on aromatic rings on aromatic compound molecule to be formed by base
Group；P-methylphenyl is formed by as toluene loses the hydrogen atom that methyl aligns on phenyl ring.
In the present invention, the carbon atom of " substituted hydrocarbon radical ", " substituted arene base " is limited, refers to alkyl, aryl, heteroaryl
Contained carbon atom number itself, and it is non-substituted after carbon atom number.Such as C1~C3Substituted hydrocarbon radical, refer to carbon atom number be C1~C3
Alkyl on, at least one hydrogen atom is replaced by non-hydrocarbons substituent group.As a hydrogen quilt-C ≡ N replaces and to be formed on adamantyl
Containing carbon atom number be 11 group.
In the present invention, " non-hydrocarbons substituent group " refers to the change containing the other elements (such as halogen, S, O, P, N) in addition to H and C
Conjunction object loses any one hydrogen atom and is formed by group.
In the present invention, when substituent group is oxygen, refer to that two H atoms in group on any one C atom are substituted by O, forms C
=O key.
In the present invention, Me is writing a Chinese character in simplified form for methyl, and Ph is writing a Chinese character in simplified form for phenyl.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all at this
Under the inventive concept of invention, using equivalent structure transformation made by description of the invention and accompanying drawing content, or directly/use indirectly
It is included in other related technical areas in scope of patent protection of the invention.
Claims (10)
1. the preparation method that a kind of element forms regulatable Si-C-O ceramic fibre, which comprises the following steps:
S1: the polymer blend of organic siliconresin and Polycarbosilane is prepared；
S2: it under an inert atmosphere, is kept the temperature after polymer blend obtained by step S1 is warming up to 100~300 DEG C；
S3: by step S2, treated that polymer blend carries out melt spinning under 0.1~0.5MPa pressure, obtains fibrinogen；
S4: the obtained fibrinogen of step S3 is crosslinked, fusion-free fibre is obtained；
S5: under an inert atmosphere, the fusion-free fibre that step S4 is obtained to 900~1300 DEG C and being kept the temperature from room temperature, system
Obtain Si-C-O ceramic fibre.
2. a kind of element as described in claim 1 forms the preparation method of regulatable Si-C-O ceramic fibre, feature exists
In, in the step S1, the preparation of the polymer blend the following steps are included:
S11: 1:(0.5~4 in mass ratio) organic siliconresin and Polycarbosilane are weighed, it is completely dissolved in solvent and stirs later
Uniformly；
S12: mixed liquor obtained by step S11 is subjected to solvent and is handled, the polymer blend is obtained.
3. a kind of element as claimed in claim 2 forms the preparation method of regulatable Si-C-O ceramic fibre, feature exists
In the organic siliconresin is using Si-O-Si key as the organosilicon polymer of main chain, molecular structure unit are as follows:
Wherein, alkyl R1、R2、R3Independently selected from H, C1~C3Alkyl, C1~C3Substituted hydrocarbon radical or substituted aryl, and R1、
R2、R3In at most there are two being H；
The Polycarbosilane is the organosilicon polymer that main chain is constituted with Si-C key, and side chain has-H and-CH3；
The solvent is all kinds of organic solvents that can dissolve the organic siliconresin and the Polycarbosilane, such as benzene, toluene, diformazan
Benzene, ethylbenzene, diethylbenzene or propyl benzene.
4. a kind of element as described in claim 1 forms the preparation method of regulatable Si-C-O ceramic fibre, feature exists
In in the step S2, the heating rate is 1~20 DEG C/min；The soaking time is 1~5h；The inert atmosphere is
The nitrogen or argon gas that purity is 99.999%.
5. a kind of element as described in claim 1 forms the preparation method of regulatable Si-C-O ceramic fibre, feature exists
In in the step S3, the receipts silk speed of the melt spinning is 300~600r/min.
6. a kind of element as described in claim 1 forms the preparation method of regulatable Si-C-O ceramic fibre, feature exists
In in the step S4, the crosslinking is crosslinked using ultraviolet radioactive, a length of 250nm~350nm of ultraviolet light wave used, ultraviolet light
10~80h of irradiation time.
7. a kind of element as described in claim 1 forms the preparation method of regulatable Si-C-O ceramic fibre, feature exists
In the crosslinking is crosslinked using reactive atmosphere, and the reactive atmosphere includes inert atmosphere and active gases in step S1, the two
Volume ratio be (0.5~10): 1.
8. a kind of element as claimed in claim 7 forms the preparation method of regulatable Si-C-O ceramic fibre, feature exists
In the active gases includes: at least one of dichloro methyl silane, silicon tetrachloride, boron chloride and titanium tetrachloride.
9. a kind of element as described in claim 1 forms the preparation method of regulatable Si-C-O ceramic fibre, feature exists
In in the step S5, the heating rate is 50~100 DEG C/h；The soaking time is 1~2h.
10. a kind of Si-C-O ceramic fibre, which is characterized in that the Si-C-O ceramic fibre is in bright black, smooth surface；
The diameter of the Si-C-O ceramic fibre is 6.7~12.1 μm, and oxygen content is 9.34~27.53%, and monofilament tensile strength is
0.87~1.31GPa, modulus are 100~137GPa, and carbon content is 22.62~38.42%.
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| CN115595690A (en) * | 2022-11-01 | 2023-01-13 | 福建立亚新材有限公司（Cn） | Preparation method of low-cost high-strength high-modulus continuous silicon carbide fiber |
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