CN106192078A - A kind of air curing is used to carry out method prepared by low oxygen content continuous SiC fiber - Google Patents
A kind of air curing is used to carry out method prepared by low oxygen content continuous SiC fiber Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
Abstract
The present invention provides a kind of and uses air curing to carry out method prepared by low oxygen content continuous SiC fiber, by being used in conjunction, Cryogenic air is non-fusible and heat cross-linking, the most existing preparation method adds thermal crosslinking treatment after air curing step, avoid only by the problem improving the fiber too high oxygen level that air curing treatment temperature causes, directly carry out fiber the problem of silk that Pintsch process causes simultaneously after it also avoid Cryogenic air cure treatment, thus prepare oxygen content at below 10wt% and the preferable continuous SiC fiber of fiber properties.
Description
Technical field
The present invention relates to continuous SiC fiber technical field, be specifically related to a kind of use air curing to carry out hypoxia to contain
Method prepared by amount continuous SiC fiber
Background technology
Continuous SiC fiber has high intensity, high-modulus, high temperature resistant, antioxidation, creep resistant, corrosion-resistant, ceramic matrix is compatible
Property a series of excellences such as good performance, be a kind of ideal reinforcing fiber, in space flight, weapons, boats and ships and nuclear industry etc.
A little high-tech sectors are with a wide range of applications, and are the strategic raw materials of weaponry and Aero-Space cause.Such as,
Carbon/silicon carbide ceramic matrix composite (the SiC strengthened by continuous SiC fiberf/ SiC), have that intensity is high, density is low, use temperature
High.Applied to high anharmonic ratio electromotor, notable loss of weight can be realized, be the optimal of the existing superhigh temperature heat-resisting alloy of replacement
Select.At present, SiCf/ SiC ceramic matrix composite material has been widely used in the heat-resistant part of Aero-Space electromotor, supersonic speed transport pushes away
Enter in the field such as system, nuclear reactor material.
Comprehensive document both domestic and external report [Bunsell, A.R.；Piant,A.A review of the development
of three generations of small diameter silicon carbide fibres,
J.Mater.Sci.2006,41,823 839. and Colombo, P.；Mera,G.；Riedel,R.；Sorarù,
G.D.Polymer-derived ceramics:40years of research and innovation in advanced
Ceramics.J.Am.Ceram.Soc.2010,93,1805-1837.] understand, using Polycarbosilane (PCS) as precursor, system
The method of standby continuous SiC fiber can be divided into three generations: the preparation of (1) first generation product uses air curing, Typical Representative
Nicalon NL202 fiber and company of Ube Industries Ltd. (Ube for carbon company of Japan (Nippon Carbon)
Industries) Tyranno LoxM fiber, Tyranno LoxM fiber in atmosphere 1000 DEG C time remain in that stable, but
Due in this fiber containing more oxygen and free carbon, in more than 1000 DEG C or inert atmosphere more than 1200 DEG C in atmosphere
Time, mushrooming out of significant decomposition reaction accompanying crystallization will be there is, thus cause the intensity of fiber to drastically reduce in this fiber,
Seriously limit the application on ceramic matric composite of this fiber.(2) for asking existing for first generation continuous SiC fiber
Topic, uses different technology paths, have developed the second filial generation SiC fiber of low oxygen content, and Typical Representative is that carbon company of Japan uses
Electron beam irradiation method substitutes the Hi-Nicalon fiber prepared after original air curing processes and Ube Industries Ltd. is public
The Tyranno ZE fiber of department, the fiber of this low oxygen content is energy in the air of 1300 DEG C or in the inert atmosphere of 1600 DEG C
Enough holding, stablizes.(3) subsequently, on this basis for making impurity oxygen in fiber, free carbon content reduce further, carbon silicon ratio connects
Near stoichiometric proportion, structure is also become highly crystalline state from original β-SiC microcrystalline state, moderate crystallization, thus is ground
Send the third generation continuous SiC fiber being resistant to higher temperature.Its Typical Representative is that the Hi-Nicalon S of carbon company of Japan is fine
Dimension, the Tyranno SA fiber of company of Ube Industries Ltd. and the Sylramic fiber of U.S. COI Ceramics.
From the point of view of the development of continuous SiC fiber, although the oxygen content of the second filial generation and third generation continuous SiC fiber lower and
Having higher heat resistance and high-temperature oxidation resistance, but its preparation condition is the harshest, device therefor is increasingly complex, such as
Second filial generation continuous SiC fiber needs to carry out cure treatment by electron beam irradiation, and third generation continuous SiC fiber then needs
It is sintered under the high temperature of more than 1700 DEG C waiting and processes.Therefore, by contrast, air curing is used to process, on 1200 DEG C of left sides
The first generation continuous SiC fiber that the right side prepares, preparation process is the simplest, preparation condition is the gentleest.But, at present will
PCS fibril processes at 200 DEG C of air curings carried out above, then fusion-free fibre is continued through pyrolysis in tubular furnace and obtains
Continuous SiC fiber oxygen content be up to about 20wt%.Even using air curing to process at present to commercially produce
Nicalon NL202 and Tyranno LoxM fiber in oxygen content be also up to about 12wt%.Too high oxygen level, can make fiber
In SiCxOyAcutely decompose more than 1200 DEG C, produce CO and SiO gas and escape from fiber, thus stay in the fibre
Large number of orifices hole defect, makes fibre strength drastically reduce, and has had a strong impact on gained fiber stability at high temperature.
Summary of the invention
It is an object of the invention to provide and a kind of use air curing to carry out side prepared by low oxygen content continuous SiC fiber
Method, this invention solves in the continuous SiC fiber that existing method prepares because of too high oxygen level, causes more than 1200 DEG C fibers
Mechanical strength acutely reduce；In existing preparation method, low oxygen content continuous SiC fiber preparation condition is harsh, to equipment requirements mistake
High technical problem.
The present invention provides a kind of and uses air curing to carry out method prepared by low oxygen content continuous SiC fiber, including with
Lower step: continuous P CS fibril is carried out under the first temperature conditions Cryogenic air cure treatment, prepares fusion-free fibre；
After gained fusion-free fibre carries out the heat cross-linking reaction of less than 500 DEG C, continue to burn till prepared 1000 DEG C of static state carried out above
Low oxygen content continuous SiC fiber；Wherein, the first temperature conditions is: Cryogenic air cure treatment is warming up in starting latter 1 hour
100 DEG C and be incubated 1～3 hour, it is incubated 0.5～5 after then rising to 140～190 DEG C with the programming rate of 2～15 DEG C/h little
Time.
Further, heat cross-linking reaction is carried out under the second temperature conditions, and the second temperature conditions is: start heat cross-linking reaction
After, it is warming up to 100 DEG C in 1 hour and is incubated 1～3 hour, being then warming up to 500 with the programming rate of 50～100 DEG C/h
℃。
Further, static state is burnt till and is carried out under the 3rd temperature conditions, and the 3rd temperature conditions is: with 100～200 DEG C/little
Time programming rate rise to 1000～1300 DEG C, be incubated and within 0.5～2 hour, complete static state and burn till.
Further, continuous P CS fibril prepares according to the following steps: heated by PCS polymer under inert atmosphere protection
It is warming up to 300～380 DEG C, after it is melted into improving uniformity of melt completely, under the pressure of 250～300 DEG C, 0.1～0.5MPa,
Carry out drawing-off spinning with the speed of 300～550m/ minute, and the PCS fibril spun is wound on cylinder, obtain continuous P CS
Fibril.
Further, the average diameter of continuous P CS fibril is 10～15um, and 500～1000/bundle, continuous length is
500～1000m.
Further, the softening point of PCS polymer is 180～250 DEG C.
Further, inert atmosphere refers to nitrogen, argon or helium.
Another aspect of the present invention additionally provides a kind of continuous SiC fiber, and continuous SiC fiber presses any of the above-described method system
For obtaining.
Further, the oxygen content of continuous SiC fiber is below 10wt%.
Hinge structure, the technique effect of the present invention:
1, the air curing that the present invention provides carries out method prepared by low oxygen content continuous SiC fiber, simple process, behaviour
Facilitating, it is easy to accomplish industrialized production, preparation cost are low, heat resistance and the mechanical property of gained continuous SiC fiber are preferable.
2, the air curing that the present invention provides carries out method prepared by low oxygen content continuous SiC fiber, equipment needed thereby letter
Single, the conventional equipment using fiber to prepare just can be implemented, it is easy to accomplish industrialized production, and continuous SiC fiber can be greatly lowered
Production cost.
3, method prepared by the air curing low oxygen content continuous SiC fiber that the present invention provides, empty by being used in conjunction low temperature
Gas is non-fusible and heat cross-linking, the most existing preparation method adds thermal crosslinking treatment after air curing step, it is to avoid only
By improving the problem of the fiber too high oxygen level that air curing treatment temperature causes, it also avoid Cryogenic air simultaneously and do not melt
Change directly carries out, after processing, fiber the problem of silk that Pintsch process causes, thus has prepared oxygen content at below 10wt% and fibre
The dimension preferable continuous SiC fiber of properties.
Method prepared by the employing air curing low oxygen content continuous SiC fiber that 4, the present invention provides, can effectively reduce
The oxygen content of SiC fiber, the SiC fiber prepared not only has the mechanical property of excellence, and has higher high temperature resistant
Performance.
Specifically refer to the air curing that uses according to the present invention and carry out method prepared by low oxygen content continuous SiC fiber
Various embodiments described below, by apparent for the above and other aspect making the present invention proposed.
Accompanying drawing explanation
Fig. 1 is that the air curing that uses that the present invention provides carries out method flow prepared by low oxygen content continuous SiC fiber
Schematic diagram.
Detailed description of the invention
The accompanying drawing of the part constituting the application is used for providing a further understanding of the present invention, and the present invention's is schematic real
Execute example and illustrate for explaining the present invention, being not intended that inappropriate limitation of the present invention.
Air curing belongs to the technical term of SiC ceramic fiber preparation field herein, refer in air atmosphere
Under uniform temperature, precursor fibril reacts with the oxygen in air, makes the molecular structure of fiber cross-link.Institute herein
Cure treatment device be to be heated approximately to the stove of 300 DEG C, this device can accommodate one or several PCS fibrils
Dimension.
Seeing Fig. 1, what the present invention provided uses air curing process to carry out side prepared by low oxygen content continuous SiC fiber
Method, comprises the following steps:
Continuous P CS fibril is carried out Cryogenic air cure treatment under the first temperature conditions, prepares fusion-free fibre；
After gained fusion-free fibre carries out the heat cross-linking reaction of less than 500 DEG C, continue to burn till prepared 1000 DEG C of static state carried out above
Low oxygen content continuous SiC fiber；
Wherein, the first temperature conditions is: Cryogenic air cure treatment is warming up to 100 DEG C in starting latter 1 hour and is incubated 1
～3 hours, it is incubated 0.5～5 hour after then rising to 140～190 DEG C with the programming rate of 2～15 DEG C/h.
Heat cross-linking in the method can be carried out by existing method, it is only necessary to ensures that its programming rate can not too fast and heat be handed over
Connection temperature is less than 500 DEG C, and the temperature by controlling heat cross-linking ensures that the degree of cross linking of PCS fiber is to prevent fiber also simultaneously
Silk.In the method, continuous P CS fibril used can be that commercially available prod can also be for be prepared by PCS polymer by existing method
Obtain.It can be by existing method technique that static state is burnt till, it is only necessary to controls this firing temperature and carries out.
The method that the present invention provides, by carrying out air curing process under conditions of temperature is relatively low, controls PCS former
Oxygen content in fiber, uses the heat cross-linking of less than 500 DEG C simultaneously, thus ensure that the PCS fiber of low oxygen content has enough
The degree of cross linking and do not occur and silk, thus obtain the continuous SiC fiber with low oxygen content.
Especially, the temperature conditions that wherein air curing used processes, fiber can be entered too much by anti-block, can be again
Follow-up crosslinking provides safeguard.The moisture that can will be attached on PCS fiber is processed by carrying out air curing under the first temperature conditions
Remove by being incubated at 100 DEG C, can prevent because the too fast PCS caused that heats up is former with 2～15 DEG C/h of slow intensifications the most again
Fiber silk, after having heated up, again carry out insulation and can improve PCS fibril and be issued to enough crosslinkings at this target temperature,
Ready for follow-up heat cross-linking.
Preferably, heat cross-linking reaction is carried out under the second temperature conditions, and the second temperature conditions is: start heat cross-linking reaction
After, it is warming up to 100 DEG C in 1 hour and is incubated 1～3 hour, being then warming up to 500 with the programming rate of 50～100 DEG C/h
℃.Carry out heat cross-linking by this condition, can first pass through and remove, 100 DEG C of insulations, the moisture being attached on fiber, afterwards by being somebody's turn to do
The intensification of speed can make PCS fibril fully realize heat cross-linking before inorganization.Thus process not improving air curing
On the premise of temperature, prevent PCS fibril from occurring and silk.Thus while ensureing gained SiC fibre property, reduce therein
Oxygen content.Carrying out heat cross-linking by this condition can allow fiber have enough crosslinking degrees before organic-inorganic converts, and otherwise exists
In subsequent process, PCS fiber can occur and silk, it is impossible to obtains target product.
Preferably, static state is burnt till and is carried out under the 3rd temperature conditions, and the 3rd temperature conditions is: with 100～200 DEG C/h
Programming rate rise to 1000～1300 DEG C, be incubated and within 0.5～2 hour, complete static state and burn till.Burn till by this condition, can improve
The mechanical property of gained fiber product.
Preferably, continuous P CS fibril prepares according to the following steps: the heating of PCS polymer risen under inert atmosphere protection
Temperature is to 300～380 DEG C, after it is melted into improving uniformity of melt completely, under the pressure of 250～300 DEG C, 0.1～0.5MPa, with
300～the speed of 550m/ minute carry out drawing-off spinning, and the PCS fibril spun is wound on cylinder, obtains continuous P CS former
Fiber.The PCS fibril prepared in this way, can improve mechanical property and the resistance to elevated temperatures of end-product.
PCS polymer used herein refers to through cracking and be reset the poly-carbon silicon that conversion obtains by polydimethylsiloxane
Alkane, or by Polycarbosilane or polysilane and FeCl3、AlCl3、Al(AcAc)3、Al(OR)3、B(OR)3、Ti(OR)4、Zr
(OR)4、Zr(AcAc)4In (R=Me, Et, Pt, Bt or Ph) one or more compounds reaction prepare containing Fe, Al, B,
The Polycarbosilane of the heterogeneous elements such as Ti or Zr.Or other contains the preceramic polymer of SiC ceramic of Si and C element.When
So PCS polymer can also be this commercially available series products.
Preferably, the average diameter of continuous P CS fibril is 10～15um, and 500～1000/bundle, continuous length is 500
～1000m.The PCS fibril of this size, air curing and heat cross-linking is used more fully, thus to be easily achieved continuously
The industrialized production of SiC fiber.
Preferably, the softening point of PCS polymer is 180～250 DEG C.Use the fibre of the PCS polymer of this softening point
Dimension, can prevent it from PCS fibril silk occurring when follow-up air curing processes, also ensure that melt spinning process simultaneously
It is smoothed out.
Preferably, inert atmosphere refers to nitrogen, argon or helium.
What the present invention provided use air curing carries out method prepared by low oxygen content continuous SiC fiber specifically includes with
Lower step:
(1) PCS polymer is placed in the molten cylinder of melt spinning device, under inert atmosphere protection, is heated to 300
～380 DEG C, after it is melted into improving uniformity of melt completely, under the pressure of 250～300 DEG C, 0.1～0.5MPa, with 300～
The speed of 550m/ minute carries out drawing-off spinning, and is wound on cylinder by the PCS fibril spun, obtain average diameter be 10～
15um, 500～1000/bundle, continuous length be 500～1000m whole cylinder PCS fibril；
(2) whole cylinder PCS fibril is placed in cure treatment device, after Cryogenic air cure treatment starts 1 hour
Inside it is warming up to 100 DEG C and is incubated 1～3 hour, being incubated after then rising to 140～190 DEG C with the programming rate of 2～15 DEG C/h
0.5～5 hour, prepare fusion-free fibre；
(3) whole cylinder fusion-free fibre is placed in graphite furnace, is passed through inert atmosphere and protects, first make at a lower temperature
Fiber carries out heat cross-linking, and heat-crosslinking conditions is: after starting heat cross-linking reaction, be warming up to 100 DEG C and to be incubated 1～3 little in 1 hour
Time, then it is warming up to 500 DEG C with the programming rate of 50～100 DEG C/h.Then carry out static state to burn till, according to 100～200 DEG C/
Hour programming rate rise to 1000～1300 DEG C, be incubated 0.5～2 hour, prepare low oxygen content continuous SiC fiber.
In abovementioned steps (1) and (3), inert atmosphere refers to the one in nitrogen, argon or helium.
Another aspect of the present invention additionally provides a kind of continuous SiC fiber using said method to prepare.The method is led to
Cross and be used in conjunction that Cryogenic air is non-fusible and heat cross-linking effectively changes oxygen content in gained continuous SiC fiber so that it is internal each element
The internal structure of composition and this fiber there occurs change.Thus improve every mechanical property of gained continuous SiC fiber and resistance to
Warm nature energy.
Further, the oxygen content of continuous SiC fiber is below 10wt%.
Embodiment
In following example, material used and instrument are commercially available.
Embodiment 1
(1) by PCS polymer, (softening point is 223 DEG C, and number-average molecular weight is 1.76 × 103G/mol, molecular weight distribution system
Number is 3.43) it is placed in the molten cylinder of melt spinning device, under inert atmosphere protection, it is heated to 360 DEG C, treats that it is the most molten
Melt after becoming improving uniformity of melt, 300 DEG C, under the pressure of 0.5MPa, carry out drawing-off spinning with the speed of 450m/ minute, put down
The most a diameter of 12um, 1000/bundle, continuous length be the whole cylinder PCS fibril of 500m.
(2) whole cylinder PCS fibril is placed in air curing processing means carries out cure treatment, within 1 hour, rise to 100
DEG C and be incubated 2 hours, then rise to 160 DEG C with the programming rate of 5 DEG C/h, 160 DEG C insulation 5 hours after be down to room temperature system
Obtain fusion-free fibre.
(3) whole cylinder fusion-free fibre is placed in graphite furnace, is passed through nitrogen and protects, within 1 hour, rise to 100 DEG C and be incubated
1 hour, rise to 500 DEG C with the programming rate of 50 DEG C/h, then according to the programming rate of 100 DEG C/h rises to 1300 DEG C,
It is incubated 1 hour, prepares low oxygen content continuous SiC fiber.
The continuous SiC fiber Si content that the present embodiment prepares is 57.92wt%, and C content is 35.78wt%, and O content is
5.36wt%, average diameter is 11.1um, and hot strength is 2.59GPa, and Young's modulus is 225GPa.
By this fiber in nitrogen 1400 DEG C insulation 1 hour after be down to room temperature, recording its strength retention ratio is 85%.But
Retain with continuous SiC fiber (oxygen content is for 18.42%) its intensity at identical conditions of the elevated oxygen level of comparative example 1 preparation
Rate is only 23%.As can be seen here, the low oxygen content SiC fiber prepared by the present invention not only there is excellent mechanical property (to draw
Stretching intensity is 2.59GPa), and there is more preferable resistance to elevated temperatures.
Embodiment 2
The whole cylinder PCS fibril that embodiment 1 step (1) is obtained be placed in air curing processing means is carried out non-fusible
Process, within 1 hour, rise to 100 DEG C and be incubated 2 hours, then rising to 170 DEG C with the programming rate of 10 DEG C/h, 170 DEG C of insulations
It is down to room temperature after 2 hours and prepares fusion-free fibre.Whole cylinder fusion-free fibre is placed in graphite furnace, is passed through nitrogen and protects, 1
Hour rise to 100 DEG C and be incubated 1 hour, rising to 500 DEG C with the programming rate of 60 DEG C/h, then according to 120 DEG C/h
Programming rate rises to 1200 DEG C, is incubated 0.5 hour, prepares low oxygen content continuous SiC fiber.
The SiC fiber Si content that the present embodiment prepares is 56.23wt%, and C content is 33.09wt%, and O content is
7.18wt%, average diameter is 11.9um, and hot strength is 2.30GPa, and Young's modulus is 202GPa.
By this fiber in nitrogen 1400 DEG C insulation 1 hour after be down to room temperature, recording its strength retention ratio is 79%.But
Retain with continuous SiC fiber (oxygen content is for 18.42%) its intensity at identical conditions of the elevated oxygen level of comparative example 1 preparation
Rate is only 23%.As can be seen here, the low oxygen content SiC fiber prepared by the present invention not only there is excellent mechanical property (to draw
Stretching intensity is 2.30GPa), and there is more preferable resistance to elevated temperatures.
Embodiment 3
The whole cylinder PCS fibril that embodiment 1 step (1) is obtained be placed in air curing processing means is carried out non-fusible
Process, within 1 hour, rise to 100 DEG C and be incubated 3 hours, then rising to 180 DEG C with the programming rate of 15 DEG C/h, 180 DEG C of insulations
It is down to room temperature after 0.5 hour and prepares fusion-free fibre.Whole cylinder fusion-free fibre is placed in graphite furnace, is passed through argon and protects
Protect, within 1 hour, rise to 100 DEG C and be incubated 3 hours, rising to 500 DEG C with the programming rate of 80 DEG C/h, then according to 150 DEG C/little
Time programming rate rise to 1100 DEG C, be incubated 2 hours, prepare low oxygen content continuous SiC fiber.
The SiC fiber Si content that the present embodiment prepares is 56.35wt%, and C content is 32.34wt%, and O content is
9.21wt%, average diameter is 12.3um, and hot strength is 2.22GPa, and Young's modulus is 201GPa.
By this fiber in nitrogen 1400 DEG C insulation 1 hour after be down to room temperature, recording its strength retention ratio is 47%.But
Retain with continuous SiC fiber (oxygen content is for 18.42%) its intensity at identical conditions of the elevated oxygen level of comparative example 1 preparation
Rate is only 23%.As can be seen here, the low oxygen content SiC fiber prepared by the present invention not only there is excellent mechanical property (to draw
Stretching intensity is 2.22GPa), and there is more preferable resistance to elevated temperatures.
Embodiment 4
(1) by by the PCS polymer of Polycarbosilane and the synthesis of 3% aluminium acetylacetonate, (softening point is 191 DEG C, the equal molecule of number
Amount is 2970g/mol, and molecular weight distribution index is 1.76) it is placed in the molten cylinder of melt spinning device, under inert atmosphere protection
Be heated to 342 DEG C, after it is melted into improving uniformity of melt completely, 265 DEG C, under the pressure of 0.3MPa, with 420m/ minute
Speed carry out drawing-off spinning, obtain average diameter be 13um, 1000/bundle, continuous length be the whole cylinder PCS fibril of 1000m
Dimension.(2) whole cylinder PCS fibril is placed in air curing processing means carries out cure treatment, within 1 hour, rise to 100 DEG C also
It is incubated 2 hours, then rises to 190 DEG C with the programming rate of 12 DEG C/h, be down to room temperature after being incubated 1 hour at 190 DEG C and prepare not
Melting fiber.(3) whole cylinder fusion-free fibre is placed in graphite furnace, is passed through nitrogen and protects, within 1 hour, rise to 100 DEG C and protect
Temperature 2 hours, rises to 500 DEG C with the programming rate of 75 DEG C/h, then according to the programming rate of 180 DEG C/h rises to 1300
DEG C, it is incubated 1 hour, prepares low oxygen content continuous SiC fiber.
The SiC fiber Si content that the present embodiment prepares is 52.47wt%, and C content is that 33.24wt%, Al content is
0.26wt%, O content is 8.15wt%, and average diameter is 11.7um, and hot strength is 2.16GPa, and Young's modulus is 180GPa.
By this fiber in nitrogen 1400 DEG C insulation 1 hour after be down to room temperature, recording its strength retention ratio is 56%.But
Retain with continuous SiC fiber (oxygen content is for 18.42%) its intensity at identical conditions of the elevated oxygen level of comparative example 1 preparation
Rate is only 23%.As can be seen here, the low oxygen content SiC fiber prepared by the present invention not only there is the mechanical property of excellence, and
And there is more preferable resistance to elevated temperatures.
Embodiment 5
The whole cylinder PCS fibril that embodiment 4 step (1) is obtained be placed in air curing processing means is carried out non-fusible
Process, within 1 hour, rise to 100 DEG C and be incubated 2 hours, then rising to 150 DEG C with the programming rate of 2 DEG C/h, be incubated 3 at 150 DEG C
It is down to room temperature after hour and prepares fusion-free fibre.Whole cylinder fusion-free fibre is placed in graphite furnace, is passed through nitrogen and protects, 1
Hour rise to 100 DEG C and be incubated 1 hour, rising to 500 DEG C with the programming rate of 100 DEG C/h, then according to 165 DEG C/h
Programming rate rises to 1200 DEG C, is incubated 1 hour, prepares low oxygen content continuous SiC fiber.
The SiC fiber Si content that the present embodiment prepares is 57.11wt%, and C content is that 33.73wt%, Al content is
0.28wt%, O content is 5.73wt%, and average diameter is 11.5um, and hot strength is 2.08GPa, and Young's modulus is 195GPa.
By this fiber in nitrogen 1400 DEG C insulation 1 hour after be down to room temperature, recording its strength retention ratio is 82%.But
Retain with continuous SiC fiber (oxygen content is for 18.42%) its intensity at identical conditions of the elevated oxygen level of comparative example 1 preparation
Rate is only 23%.As can be seen here, the low oxygen content SiC fiber prepared by the present invention not only there is the mechanical property of excellence, and
And there is more preferable resistance to elevated temperatures.
Embodiment 6
Difference with embodiment 1 is: with the continuous fibril of commercially available PCS (specifically refer to by commercially available PCS by existing other
Method prepares) (softening point is 180 DEG C, and average diameter is 10um, 500/bundle, continuous length is 500m) be raw material,
Under the first temperature conditions, carry out Cryogenic air cure treatment, prepare fusion-free fibre；Gained fusion-free fibre is carried out 500
Heat cross-linking reaction below DEG C, proceeds static state and burns till prepared low oxygen content continuous SiC fiber.
Wherein the first temperature conditions is: Cryogenic air cure treatment is warming up to 100 DEG C in starting latter 1 hour and is incubated 1
Hour, it is incubated 0.5 hour after then rising to 140 DEG C with the programming rate of 2 DEG C/h.Heat cross-linking is that insulation 5 is little at 350 DEG C
Time.It is to be warming up at 950 DEG C with 100 DEG C/h of heating rates that static state is burnt till, and is incubated 2 hours.
The SiC fiber Si content that the present embodiment prepares is 59.73wt%, and C content is 33.24wt%, and O content is
4.58wt%, average diameter is 8.2um, and hot strength is 1.56GPa, and Young's modulus is 154GPa.
Embodiment 7
Difference with embodiment 6 is: with the continuous fibril of commercially available PCS (softening point is 250 DEG C, and average diameter is 15um,
1000/bundle, continuous length is 1000m) it is raw material, under the first temperature conditions, carry out Cryogenic air cure treatment, prepare
Fusion-free fibre；Gained fusion-free fibre is carried out the heat cross-linking reaction of less than 500 DEG C, proceeds static state and burn till prepared hypoxia
Content continuous SiC fiber.
Wherein the first temperature conditions is: Cryogenic air cure treatment is warming up to 100 DEG C in starting latter 1 hour and is incubated 3
Hour, it is incubated 5 hours after then the programming rate of 15 DEG C/h rises to 190 DEG C.
The SiC fiber Si content that the present embodiment prepares is 51.04wt%, and C content is 37.90wt%, and O content is
9.88wt%, average diameter is 12.6um, and hot strength is 2.19GPa, and Young's modulus is 183GPa.
Embodiment 8
Difference with embodiment 6 is:
1, heat cross-linking reaction condition is: after starting heat cross-linking reaction, be warming up to 100 DEG C and be incubated 3 hours, so in 1 hour
After be warming up to 500 DEG C with the programming rate of 100 DEG C/h.
2, static firing condition is: rise to 1300 DEG C with the programming rate of 200 DEG C/h, is incubated and within 2 hours, completes static burning
Become.
3, continuous P CS fibril used prepares according to the following steps:
Under inert atmosphere protection, PCS polymer is heated to 300 DEG C, treats that it is melted into improving uniformity of melt completely
After, 250 DEG C, under the pressure of 0.1MPa, carry out drawing-off spinning, and the PCS fibril volume that will spin with the speed of 300m/ minute
It is wound on cylinder, obtains continuous P CS fibril
The SiC fiber Si content that the present embodiment prepares is 54.27wt%, and C content is 34.48wt%, and O content is
4.77wt%, average diameter is 9.3um, and hot strength is 1.81GPa, and Young's modulus is 225GPa.
Embodiment 9
Difference with embodiment 6 is:
1, heat cross-linking reaction condition is: after starting heat cross-linking reaction, be warming up to 100 DEG C and be incubated 1 hour, so in 1 hour
After be warming up to 500 DEG C with the programming rate of 50 DEG C/h.
2, static firing condition is: rises to 1000 DEG C with the programming rate of 100 DEG C/h, is incubated and completes static state in 0.5 hour
Burn till.
3, continuous P CS fibril used prepares according to the following steps:
Under inert atmosphere protection, PCS polymer is heated to 380 DEG C, treats that it is melted into improving uniformity of melt completely
After, 300 DEG C, under the pressure of 0.5MPa, carry out drawing-off spinning, and the PCS fibril volume that will spin with the speed of 550m/ minute
It is wound on cylinder, obtains continuous P CS fibril
The SiC fiber Si content that the present embodiment prepares is 54.59wt%, and C content is 35.89wt%, and O content is
5.02wt%, average diameter is 9.0um, and hot strength is 1.71GPa, and Young's modulus is 143GPa.
Comparative example 1
Difference with embodiment 1 is:
1, the condition of air curing is: Cryogenic air cure treatment is warming up to 100 DEG C in starting latter 1 hour and is incubated
3 hours, after then the programming rate of 10 DEG C/h rises to 210 DEG C, it is incubated 2 hours.
2, firing condition is dynamic continuous burnt: with the speed of 0.5 m/min, fusion-free fibre is continued through 1300 DEG C
Tube furnace, high pure nitrogen protect under continuous burnt；A length of 0.5 meter of the flat-temperature zone of described tube furnace.
The SiC fiber Si content that this comparative example prepares is 56.32wt%, and C content is 25.13wt%, and O content is
18.42wt%, average diameter is 11.8um, and hot strength is 1.82GPa, and Young's modulus is 157GPa.
Those skilled in the art will understand that the scope of the present invention is not restricted to example discussed above, it is possible to carries out it
Some changes and amendment, the scope of the present invention limited without deviating from appended claims.Although oneself is through in accompanying drawing and explanation
Book illustrates and describes the present invention in detail, but such explanation and description are only explanations or schematic, and nonrestrictive.
The present invention is not limited to the disclosed embodiments.
By to accompanying drawing, the research of specification and claims, when implementing the present invention, those skilled in the art are permissible
Understand and realize the deformation of the disclosed embodiments.In detail in the claims, term " includes " being not excluded for other steps or element,
And indefinite article " " or " a kind of " are not excluded for multiple.Some measure quoted in mutually different dependent claims
The fact does not means that the combination of these measures can not be advantageously used.It is right that any reference marker in claims is not constituted
The restriction of the scope of the present invention.
Claims (9)
1. one kind uses air curing to carry out method prepared by low oxygen content continuous SiC fiber, it is characterised in that include following
Step:
Continuous P CS fibril is carried out Cryogenic air cure treatment under the first temperature conditions, prepares fusion-free fibre；To institute
After obtaining the heat cross-linking reaction that fusion-free fibre carries out less than 500 DEG C, continuation is burnt till prepared described 1000 DEG C of static state carried out above
Low oxygen content continuous SiC fiber；
Wherein, described first temperature conditions is: described Cryogenic air cure treatment is warming up to 100 DEG C also in starting latter 1 hour
It is incubated 1～3 hour, after then rising to 140～190 DEG C with the programming rate of 2～15 DEG C/h, is incubated 0.5～5 hour.
Employing air curing the most according to claim 1 carries out method prepared by low oxygen content continuous SiC fiber, and it is special
Levying and be, the reaction of described heat cross-linking is carried out under the second temperature conditions, and described second temperature conditions is: start described heat cross-linking anti-
Ying Hou, is warming up to 100 DEG C and is incubated 1～3 hour, being then warming up to 500 with the programming rate of 50～100 DEG C/h in 1 hour
℃。
Employing air curing the most according to claim 2 carries out method prepared by low oxygen content continuous SiC fiber, and it is special
Levying and be, described static state is burnt till and is carried out under the 3rd temperature conditions, and described 3rd temperature conditions is: with 100～200 DEG C/h
Programming rate rise to 1000～1300 DEG C, be incubated and within 0.5～2 hour, complete described static state and burn till.
4. carry out low oxygen content continuous SiC fiber according to the employing air curing according to any one of claims 1 to 3 to prepare
Method, it is characterised in that described continuous P CS fibril prepares according to the following steps:
Under inert atmosphere protection, PCS polymer is heated to 300～380 DEG C, treats that it is melted into improving uniformity of melt completely
After, under the pressure of 250～300 DEG C, 0.1～0.5MPa, carry out drawing-off spinning with the speed of 300～550m/ minute, and will spin
The PCS fibril obtained is wound on cylinder, obtains described continuous P CS fibril.
Employing air curing the most according to claim 4 carries out method prepared by low oxygen content continuous SiC fiber, and it is special
Levying and be, the average diameter of described continuous P CS fibril is 10～15um, 500～1000/bundle, continuous length be 500～
1000m。
Employing air curing the most according to claim 4 carries out method prepared by low oxygen content continuous SiC fiber, and it is special
Levying and be, the softening point of described PCS polymer is 180～250 DEG C.
Employing air curing the most according to claim 6 carries out method prepared by low oxygen content continuous SiC fiber, and it is special
Levying and be, described inert atmosphere refers to nitrogen, argon or helium.
8. a continuous SiC fiber, it is characterised in that described continuous SiC fiber is side as according to any one of claim 1～7
Method prepares.
Continuous SiC fiber the most according to claim 8, it is characterised in that the oxygen content of described continuous SiC fiber is
Below 10wt%.
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| CN109516808B (en) * | 2018-12-13 | 2021-06-15 | 湖南泽睿新材料有限公司 | Method for preparing beryllium-containing silicon carbide ceramic fiber through gallium bath |
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