CN1410606A - Preparation method of high temperature resistant multi crystal silicon carbide fiber - Google Patents
Preparation method of high temperature resistant multi crystal silicon carbide fiber Download PDFInfo
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Abstract
The characteristics of the invention are that the spin finish aid of the organic polymer containing one or multiple of sintering auxiliary agents is in troduced before spinning. The sintering auxiliary agent is at least one of B, Al, Y, Mg, Ti, Zr. The sintering auxiliary agent can be contained in one organic polymer or different organic polymers. The organic polymer is the polymer in silazane class and silicone carbon hydride. The method improves the spinning quality. The fiber produced can bear temperature higher than 1500 deg.C with diameter less than 10 micros, possessing good antioxidation property and mechanical property, being as the new generation of the reinforcement fiber. The method is easy to realize the continuous production.
Description
Technical field
The present invention relates to a kind of anti-high temperature polycrystal carborundum fiber preparation method more than 1500 ℃.
Background technology
Many at present is that precursor is burnt till preparation SiC fiber by melt spinning, non-melt processed and high temperature with organosilicon polymer-Polycarbosilane (PCS).But, because what adopt usually in the process of melt processed not is that the method for air oxidation makes fiber crosslinked, so just in fiber, introduced a large amount of oxygen, because PCS is a kind of precursor of rich carbon, therefore the ceramic fibre that finally obtains is the SiC fiber of the non-chemical proportion of a kind of rich carbon, oxygen enrichment simultaneously.When serviceability temperature surpassed 1200 ℃, impurity oxygen just can be overflowed with gaseous state CO or SiO form, caused fiber to produce a large amount of holes because of weightless, and crystal grain is grown up rapidly, and intensity sharply descends.So its maximum operation (service) temperature has only about 1000 ℃.In addition, because the PCS degree of branching is higher, molecular weight is less, and spinnability is very poor, spin fibre diameter limited, and fibrillation brings very big challenge to post-order process too greatly because of fragility.
Impurity oxygen is the basic reason that causes SiC fiber poor heat stability, therefore can significantly improve SiC fiber resistance to elevated temperatures by reducing oxygen content, the improvement approach mainly contains three major types: the one, and make the molecular weight of precursor PCS enough high by changing synthesis condition, adopt dry spinning to make fiber, without melt processed not just directly high temperature burn till the SiC fiber that makes low oxygen content.But this method has not only proposed harsh requirement to synthesis condition, and adopts dry spinning also to bring environmental pollution problems.Another kind of is to adopt non-oxide crosslinked method to carry out not melt processed, this comprises chemical gaseous phase cross-linking method that the unsaturated gas of employing carries out and the crosslinking with radiation method (as US4220600, US4283376 and US4342712 etc.) that adopts electron beam or gamma-rays etc. to carry out.The reappearance of chemical gaseous phase cross-linking method is relatively poor, and is wayward; And the method for crosslinking with radiation increases several times because of the large-scale irradiation apparatus of needs makes the cost of fiber.The 3rd class methods then are to introduce sintering aids such as B or Al in the fiber production process, high temperature deoxidation and impel fiber densification under sintering temperature.Because the high temperature removal of oxygen more than needed and carbon, the SiC fiber that these class methods make is a kind of high modulus fiber of nearly stoicheiometry of polycrystalline.The concrete grammar of introducing sintering aid has: (1) is introduced in sintering process and (is being contained under the B atmosphere sintering as employing B
4C, BO
2Deng).US5071600, US5279780 and US5366943 have reported this method, its shortcoming is the serialization production that is unsuitable for fiber.(2) do not introducing (as NO in the fusion process
2/ BCl
3Melt processed method not).US5051215 and US5071600 have reported this method, and its shortcoming is that the B content of introducing is limited, and the uniformity that sintering aid distributes is undesirable.(3) in precursor, introduce.This method can realize the molecular level horizontal distribution of sintering aid.But usually need to adopt the compound (as polyborosiloxane, borazine, aluminium acetylacetonate etc.) that contain B or Al and organosilicon polymer to carry out the chemical reaction of long period, and the gained compound make the spinnability variation because of the degree of branching is higher.Introduced with polyborosiloxane and the preparation of poly dimethyl silane reaction as US4220600 and US4283376 and to have contained the B Polycarbosilane and to prepare the method for SiC fiber by it.US4604367 be in organosilicon polymer in Si: the B ratio is that 2: 1～200: 1 ratio adds that borazine carries out thermal decomposition and polycondensation obtains the target precursor, through spinning, do not melt with high temperature sintering and obtain resistant to elevated temperatures Si-C-B-N fiber.US5945362 at first makes by the US4220600 method to contain the B Polycarbosilane, and then carry out copyrolysis reaction with a kind of aluminum contained compound such as aluminium acetylacetonate and obtain the target precursor, again through spinning, do not melt with high temperature sintering and obtain the good Si-C-Al-B fiber of alkaline resistance properties.But the reaction condition of above-mentioned complexity and limited spinning properties are still needed and are improved.Add spin finish aid and can improve the spinning properties of precursor, add the spinning properties that the vinyl polysilazane can obviously improve precursor when the super high molecular weight PCS spinning as people such as Toreki.US4657991 adds in PCS＜the silicon-carbon polymer of a kind of linearity of 20wt%, and the spinnability of precursor improves, and the intensity of ceramic fibre also is improved.
But, though US5071600 mentions and can introduce in precursor by the method for boron-containing compound and PCS reaction or simple blend＞B of 0.2wt% prepares polycrystalline Si C fiber, but the purpose that adds boron-containing compound herein only is to introduce unique sintering aid B, can not introduce other sintering aids, and this compound is not carried out any explanation in the patent, also do not provide any embodiment, it is desirable that prepared silicon carbide fibre mechanical property, woven performance are still owed.
Summary of the invention
The object of the present invention is to provide a kind of anti-more than 1500 ℃, diameter is thinner, mechanical property and stitchability are better, be easy to realize technological transformation, be easy to the polycrystal carborundum fiber preparation method that realizes that serialization is produced.
Technical scheme of the present invention is as follows:
(1) be dissolved in Polycarbosilane and the organic polymer that contains sintering aid in the organic solvent by a certain percentage; mix; under the high pure nitrogen protection, steam solvent and obtain the blend precursor; again above-mentioned blend precursor is placed melt spinning device; under high pure nitrogen protection, be heated to 300-500 ℃ carry out deaeration and handle after, at 200-400 ℃, under the 2-10 atmospheric pressure; carry out melt spinning with 100-500r/min speed, make the fibrillation that diameter is 10-20 μ m.
(2) above-mentioned fibrillation is placed oxidation furnace, the programming rate by 10-30 ℃/h in oxidizing atmosphere is heated to 160-250 ℃, and insulation oxidation processes 1-10 hour obtains fusion-free fibre after being chilled to room temperature.
(3) high temperature furnace that above-mentioned fusion-free fibre is placed high pure nitrogen protect is warming up to 1200-1300 ℃, and makes the silicon carbide fibre of amorphous state after insulation is handled 0.5-4 hour under this temperature.
(4) silicon carbide fibre of above-mentioned amorphous state is placed the high temperature furnace of high-purity argon gas or helium protection, be warming up to more than 1600 ℃, and just can make the polycrystal carborundum fiber after handling 1-4 hour in insulation under this temperature.
Described Polycarbosilane construction unit is mainly following formula:
[SiR
1R
2-CR
3R
4-] R wherein
1, R
2, R
3, R
4=H, Me, Et, Pt, Bt, organic group or silylation such as Ph, they can be identical also can be different.Its preparation method normally adopts at least a chlorosilane and sodium metal to carry out the thermal condensation reaction and obtains poly-diakyl silane, again at 300-600 ℃, carry out the thermal decomposition rearrangement reaction under the 1-100 atmospheric pressure and make Polycarbosilane, remove micromolecular compound through decompression distillation then.Its fusing point is generally 190-250 ℃, molecular weight 1,000-2,000.
Described organosilicon polymer also can contain a certain amount of Si-Si key.They are that the conversion of poly-diakyl thermal decomposition of silane is incomplete and residual.
Described organic polymer is a linear structure, perhaps is nonlinear organization but have than better rheological property of above-mentioned Polycarbosilane and spinning property.Its fusing point is usually less than 180 ℃.
Described organic polymer comprises silicon-carbon alkanes polymer, contains following structural formula:
[MR
5-CR
6-SiR
7R
8-] R wherein
5, R
6, R
7, R
8=H, Me, Et, Pt, Bt, organic group and R such as Ph
5Also can be-OR
6Group, R
6Also can be silylation.M is a sintering aid.
Described organic polymer also comprises the silazane base polymer, contains following structural formula:
[MR
5-NR
6-SiR
7R
8-] R wherein
5, R
6, R
7, R
8=H, Me, Et, Pt, Bt, organic groups such as Ph, R
5Also can be-NR
6 2Group, R
6Also can be silylation.M is a sintering aid.
Described sintering aid is B, Al, and Y, Mg, Ti, at least a among the Zr.Several sintering aids can be included in in a kind of organic polymer, also can be included in separately in the different organic polymers.
The ratio of quality was 20 when described Polycarbosilane mixed with organic polymer: 1-20: 20, and preferred mass ratio is 20: 2-20: 6.
Described organic solvent is dimethylbenzene, toluene, benzene, n-hexane etc.
As required, in the not melt processed process of polycarbosilane fiber, can adopt air atmosphere also can adopt reacting gas such as other oxidizing atmospheres such as ozone, nitrogen dioxide, ammonia.Being heated to 2-10 hour heat cross-linking of 300-500 ℃ of insulation after perhaps adopting suitable oxidizing crosslinked again under inert atmosphere handles.
As required, can carry out in two steps when the Polycarbosilane fusion-free fibre burns till, also can burn till more than 1600 ℃ in a step.But adopt a step should use high-purity argon gas, high-purity helium when burning till, should not use nitrogen as protective gas.
The silicon carbide fibre that the present invention makes is made up of elements such as Si, C, O and sintering aids.Wherein, O content＜0.5wt%, carborundum mainly exist with β-SiC crystal form, also contain a spot of α-SiC.
The present invention compares with existing method, and following good effect is arranged:
Utilization of the present invention contains the organic polymer of sintering aid and makes spin finish aid, in spinning process, be incorporated into sintering aid in the polycarbosilane precusor, so both helped improving spinning properties, can realize the distribution of the molecular level level of sintering aid again, also keep the preparation process of original fiber substantially; The raising of spinning properties helps preparing the ceramic fibre of thinner diameter, and mechanical property and stitchability improve; This programme is based upon on the original continuous production technology basis, is convenient to technology and amplifies, and is easy to realize serialization production.
The silicon carbide fibre that adopts the inventive method to make not only has excellent heat resistance, antioxygenic property, but also has excellent mechanical property, is the good fortifying fibre of high-performance composite materials of new generation.
The specific embodiment
The invention will be further described by the following examples.
Reference example 1.
Get 200g dimethyldichlorosilane and 80g sodium metal and place the 2000ml there-necked flask that contains dimethylbenzene, constant temperature was 100 ℃ of stirring reactions 10 hours.Remove by filter precipitation, use methanol wash 5 times.100 ℃ of dried of vacuum promptly get white poly dimethyl silane.
Get poly dimethyl silane 100g and place synthesizer, under nitrogen protection, slowly be heated to 450 ℃, and heat preservation hot depolymerized 8 hours under this temperature.Synthetic product filters after xylene soluble, is heated to 300 ℃ again, carries out decompression distillation under 100mmHg, obtains Polycarbosilane (PCS) after the cooling.The Polycarbosilane number-average molecular weight that makes is 1450, and fusing point is 210-220 ℃, and the molecular weight coefficient of dispersion is 1.68, and reaction yield is 60.5wt%.
Reference example 2.
Get 50g diphenyl dichlorosilane, 70g methylene bromide, 30g phenyl dichloride boron and 50g sodium metal and place the 2000ml there-necked flask that contains dimethylbenzene, constant temperature was 100 ℃ of stirring reactions 10 hours.Remove by filter precipitation, use methanol wash 5 times.100 ℃ of dried of vacuum promptly obtain the poly-boron carbon silane (PBCS) of liquid state that 81g has linear structure.Its number-average molecular weight is 10300, and B content is 3.6wt%.
Reference example 3.
Get 168g dimethyldichlorosilane and 100g dimethyl dichlorosilane (DMCS) and place the 3000ml there-necked flask that contains dimethylbenzene, use ice-water bath constant temperature, feeding high-purity ammonia no HCl gas in reaction system while stirring is produced as and reacts completely, add the 10ml ethylenediamine and make the precipitation flocculation, filtration steams solvent and can get flaxen silazane oligomer.
Get 100g silazane oligomer and be dissolved in the dimethylbenzene, place the 3000ml flask, be heated to boiling, slowly feed the BCl of 0.3mol while stirring
3Gas.Steam solvent and can get the thick poly-borosilicate azane (PBSN) of brown.Be heated to 300 ℃ again, the insulation that refluxes can get the solid-state poly-borosilicate azane of fragility in 5 hours, and number-average molecular weight is 800, and fusing point is 100-110 ℃, and reaction yield is 95%.B content is 2.5wt%.
Get 100g silazane oligomer and be dissolved in the dimethylbenzene, place the 1000ml flask, add the aluminium acetylacetonate of 15g, be heated to boiling, reacted 4 hours.Steam solvent and can get the thick poly-aluminium silazane (PASN) of brown.Be heated to 350 ℃ again, the insulation that refluxes can get the solid-state poly-borosilicate azane of fragility in 3 hours, and number-average molecular weight is 920, and fusing point is 120-130 ℃, and reaction yield is 91%.Al content is 1.1wt%.
Embodiment 1.
Get in PCS in the 100g reference example 1 and the 10g reference example 2 the PBCS heating for dissolving in dimethylbenzene; mix; under the high pure nitrogen protection, steam solvent; above-mentioned blend precursor is placed melt spinning device; under high pure nitrogen protection, be heated to 330 ℃ and carry out deaeration and handle after, at 290 ℃, under 5 atmospheric pressure; carry out melt spinning with 400r/min speed, making former filament diameter is 13 μ m.Precursor is placed oxidation furnace, and the programming rate by 15 ℃/h in air atmosphere is heated to 190 ℃, and insulation was handled 4 hours, and the fiber weightening finish is not 9.5wt% after the melt processed.Fusion-free fibre is placed high temperature furnace, and the programming rate with 500 ℃/h under the high-purity argon gas protection is warming up to 1700 ℃, and insulation is handled after 1 hour and made the polycrystal carborundum fiber.Fibre diameter is 6.9 μ m, and tensile strength is 2.24GPa, and elastic modelling quantity is 320GPa, fibrously is: Si, 65.9wt%; C, 32.1wt%; O, 0.4wt%; B, 0.4wt%.SEM observes surperficial smoother, and XRD analysis learns that crystalline phase is mainly β-SiC, also has a spot of α-SiC, and average grain size is 25.3nm.Handle that strength retention ratio is 75% after 100 hours for 1000 ℃ in the gained fiber air, handle that strength retention ratio is 95% after 100 hours for 1500 ℃ in the high-purity argon gas.
Embodiment 2.
Get in PCS in the 100g reference example 1 and the 10g reference example 3 the PBSN heating for dissolving in dimethylbenzene; mix; under the high pure nitrogen protection, steam solvent; above-mentioned blend precursor is placed melt spinning device; under high pure nitrogen protection, be heated to 370 ℃ and carry out deaeration and handle after, at 290 ℃, under 5 atmospheric pressure; carry out melt spinning with 300r/min speed, making former filament diameter is 16 μ m.Precursor is placed oxidation furnace, and the programming rate by 15 ℃/h in air atmosphere is heated to 190 ℃, and insulation was handled 4 hours, and the fiber weightening finish is not 9.2wt% after the melt processed.Fusion-free fibre is placed high temperature furnace, under high pure nitrogen protection, be warming up to 1250 ℃ by the programming rate of 150 ℃/h, the insulation processing made the amorphous state silicon carbide fibre after 1 hour.Fibre diameter is 11.5 μ m, and tensile strength is 2.2GPa, and elastic modelling quantity is 210GPa, fibrously is: Si, 50.5wt%; C, 31.9wt%; O, 15.2wt%; N, 1.5wt%; B, 0.23wt%.Above-mentioned fiber programming rate with 500 ℃/h under the high-purity argon gas protection is warming up to 1700 ℃, and insulation is handled after 1 hour and is made the polycrystal carborundum fiber.Fibre diameter is 9.2 μ m, and tensile strength is 1.64GPa, and elastic modelling quantity is 290GPa, fibrously is: Si, 67.9wt%; C, 30.1wt%; O, 0.4wt%; N, 0.1wt%; B, 0.3wt%.SEM observes surperficial smoother, and XRD analysis learns that crystalline phase is mainly β-SiC, also has a spot of α-SiC, and average grain size is 42.4nm.Handle that strength retention ratio is 66% after 100 hours for 1000 ℃ in the gained fiber air, handle that strength retention ratio is 91% after 100 hours for 1500 ℃ in the high-purity argon gas.
Embodiment 3.
Get the PCS in the 100g reference example 1; PASN heating for dissolving in the 10g reference example 3 is in dimethylbenzene; mix; under high pure nitrogen protection, steam solvent, above-mentioned blend precursor placed melt spinning device, be heated under the high pure nitrogen protection 350 ℃ and carry out deaeration and handle after; at 300 ℃; under 4 atmospheric pressure, carry out melt spinning with 300r/min speed, making former filament diameter is 16 μ m.Precursor is placed oxidation furnace, and the programming rate by 15 ℃/h in air atmosphere is heated to 195 ℃, and insulation was handled 4 hours, and the fiber weightening finish is not 10.6wt% after the melt processed.Fusion-free fibre is placed high temperature furnace, under high pure nitrogen protection, be warming up to 1250 ℃ by the programming rate of 150 ℃/h, the insulation processing made the amorphous state silicon carbide fibre after 1 hour.Fibre diameter is 11.1 μ m, and tensile strength is 2.3GPa, and elastic modelling quantity is 221GPa, fibrously is: Si, 49.8wt%; C, 31.2wt%; O, 15.8wt%; N, 1.4wt%; Al, 0.1wt%.Above-mentioned fiber programming rate with 500 ℃/h under the high-purity argon gas protection is warming up to 1700 ℃, and insulation is handled after 1 hour and is made the polycrystal carborundum fiber.Fibre diameter is 9.1 μ m, and tensile strength is 1.71GPa, and elastic modelling quantity is 310GPa, fibrously is: Si, 68.5wt%; C, 31.0wt%; O, 0.4wt%; N, 0.1wt%; Al, 0.15wt%.SEM observes surperficial smoother, and XRD analysis learns that crystalline phase is mainly β-SiC, also has a spot of α-SiC, and average grain size is 42.6nm.Handle that strength retention ratio is 68% behind the 100h for 1000 ℃ in the gained fiber air, handle that strength retention ratio is 92% behind the 100h for 1500 ℃ in the high-purity argon gas.
Embodiment 4.
Get the PCS in the 100g reference example 1; PASN heating for dissolving in PBSN in the 10g reference example 2 and the 10g reference example 2 is in dimethylbenzene; mix; under high pure nitrogen protection, steam solvent, above-mentioned blend precursor placed melt spinning device, be heated under the high pure nitrogen protection 340 ℃ and carry out deaeration and handle after; at 285 ℃; under 5 atmospheric pressure, carry out melt spinning with 350r/min speed, making former filament diameter is 15 μ m.Precursor is placed oxidation furnace, and the programming rate by 15 ℃/h in the air atmosphere that contains 20vol% nitrogen dioxide is heated to 80 ℃, and insulation was handled 1 hour, and the fiber weightening finish is not 8.5wt% after the melt processed.Fusion-free fibre is placed high temperature furnace, under high pure nitrogen protection, be warming up to 1250 ℃ by the programming rate of 150 ℃/h, the insulation processing made the amorphous state silicon carbide fibre after 1 hour.Fibre diameter is 11.0 μ m, and tensile strength is 2.35GPa, and elastic modelling quantity is 215GPa, fibrously is: Si, 48.6wt%; C, 29.0wt%; O, 10.7wt%; N, 3.2wt%; Al, 0.1wt%; B, 0.2wt%.Above-mentioned fiber programming rate with 500 ℃/h under the high-purity argon gas protection is warming up to 1700 ℃, and insulation is handled after 1 hour and is made the polycrystal carborundum fiber.Fibre diameter is 8.5 μ m, and tensile strength is 1.82GPa, and elastic modelling quantity is 332GPa, fibrously is: Si, 68.7wt%; C, 29.5wt%; O, 0.5wt%; N, 0.2wt%; Al, 0.15wt%; B, 0.3wt%.SEM observes surperficial smoother, and XRD analysis learns that crystalline phase is mainly β-SiC, also has a spot of α-SiC, and average grain size is 32.3nm.Handle that strength retention ratio is 80% after 100 hours for 1000 ℃ in the gained fiber air, handle that strength retention ratio is 94% after 100 hours for 1500 ℃ in the high-purity argon gas.
Reference examples.
Press the method that US4220600 introduces, the boric acid of getting 250g diphenyl dichlorosilane and 70g drying places the 2000ml there-necked flask that contains dimethylbenzene, and constant temperature was 100 ℃ of stirring reactions 2 hours.Filter 100 ℃ of dried of final vacuum and promptly get the thickness polyborosiloxane.Get the poly dimethyl silane in 20g polyborosiloxane and the 100g reference example 1, place the 500ml there-necked flask, reflux to 350 ℃, and be incubated 2 hours, cool to room temperature adds the 10g aluminium acetylacetonate again, continue reflux to 450 ℃, and be incubated 4 hours, be cooled to 300 ℃ at last, under 100mmHg, carry out decompression distillation, obtain poly-aluminium boron carbon silane (PABCS) after the cooling, fusing point is 205-219 ℃, and the content of Al, B is respectively 1.0wt%, 0.8wt%.Place melt spinning device, under high pure nitrogen protection, be heated to 350 ℃ carry out deaeration and handle after, at 300 ℃, under 6 atmospheric pressure, carry out melt spinning with 200r/min speed, making the precursor fibre diameter is 20 μ m.Precursor is placed oxidation furnace, and the programming rate by 15 ℃/h in air atmosphere is heated to 190 ℃, insulation oxidation processes 4 hours, and the fiber weightening finish is not 11.2wt% after the melt processed.Fusion-free fibre is placed high temperature furnace, under high pure nitrogen protection, be warming up to 1250 ℃ by the programming rate of 150 ℃/h, the insulation processing made the amorphous state silicon carbide fibre after 1 hour.Fibre diameter is 13.5 μ m, and tensile strength is 1.85GPa, and elastic modelling quantity is 185GPa, fibrously is: Si, 51.2wt%; C, 32.5wt%; O, 16.1wt%; Al, 1.1wt%; B, 0.8wt%.Above-mentioned fiber programming rate with 500 ℃/h under high-purity argon gas protection is warming up to 1700 ℃, and insulation was handled after 1 hour, and fibre diameter is 10.8 μ m, and tensile strength is 0.85GPa, and elastic modelling quantity is 285GPa, fibrously was: Si, 68.1wt%; C, 31.0wt%; O, 0.8wt%, Al, 1.3wt%; B, 0.7wt%.SEM observation fiber is very coarse, and XRD analysis learns that crystalline phase is mainly β-SiC, and average grain size is 50.1nm.Handle that strength retention ratio is 51% after 100 hours for 1000 ℃ in the gained fiber air, handle that strength retention ratio is 69% after 100 hours for 1500 ℃ in the high-purity argon gas.
Claims (8)
1. high temperature resistant polycrystal carborundum fiber preparation method is characterized in that may further comprise the steps:
(1) with Polycarbosilane and the organic polymer that contains sintering aid by 20: 1-20: 20 mass ratio is dissolved in the organic solvent, mix, under the high pure nitrogen protection, steam solvent and obtain the blend precursor, again above-mentioned blend precursor is placed melt spinning device, under high pure nitrogen protection, be heated to 300-500 ℃ carry out deaeration and handle after, at 200-400 ℃, under the 2-10 atmospheric pressure, carry out melt spinning with 100-500r/min speed, make the fibrillation that diameter is 10-20 μ m;
(2) above-mentioned fibrillation is placed oxidation furnace, the programming rate by 10-30 ℃/h in oxidizing atmosphere is heated to 160-250 ℃, and insulation oxidation processes 1-10 hour obtains fusion-free fibre after being chilled to room temperature;
(3) high temperature furnace that above-mentioned fusion-free fibre is placed high pure nitrogen protect is warming up to 1200-1300 ℃, and makes the silicon carbide fibre of amorphous state after insulation is handled 0.5-4 hour under this temperature;
(4) silicon carbide fibre of above-mentioned amorphous state is placed the high temperature furnace of high-purity argon gas or helium protection, be warming up to more than 1600 ℃, and insulation was handled 1-4 hour under this temperature.
2. according to the high temperature resistant polycrystal carborundum fiber preparation method of claim 1, it is characterized in that described Polycarbosilane construction unit is mainly following formula:
[SiR
1R
2-CR
3R
4-] R wherein
1, R
2, R
3, R
4=H, Me, Et, Pt, Bt, organic group or silylation such as Ph, they can be identical also can be different, its fusing point is 190-250 ℃, molecular weight 1,000-2,000.
3. according to the high temperature resistant polycrystal carborundum fiber preparation method of claim 1, it is characterized in that described organic polymer is the silazane base polymer, contains following structural formula:
[MR
5-NR
6-SiR
7R
8-] R wherein
5, R
6, R
7, R
8=H, Me, Et, Pt, Bt, Ph; R
5Also can be-OR
6Group, R
6Also can be silylation, M is a sintering aid.
4. according to the high temperature resistant polycrystal carborundum fiber preparation method of claim 1, it is characterized in that described organic polymer is a silicon-carbon alkanes polymer, contains following structural formula:
[MR
5-CR
6-SiR
7R
8-] R wherein
5, R
6, R
7, R
8=H, Me, Et, Pt, Bt, Ph; R
5Also can be-OR
6Group, R
6Also can be silylation, M is a sintering aid.
5. according to claim 1 or 2 or 3 or 4 high temperature resistant polycrystal carborundum fiber preparation method, it is characterized in that described sintering aid is B, Al, Y, Mg, Ti, at least a among the Zr.
6. according to the high temperature resistant polycrystal carborundum fiber preparation method of claim 5, it is characterized in that described sintering aid is B, Al, Y, Mg, Ti, among the Zr at least two kinds, several sintering aids can be included in in a kind of organic polymer, also can be included in separately in the different organic polymers.
7.. according to claim 1 or 2 or 3 or 4 high temperature resistant polycrystal carborundum fiber preparation method, mass ratio is 20 when it is characterized in that described Polycarbosilane mixes with organic polymer: 2-20: 6.
8. high temperature resistant polycrystal carborundum fiber preparation method is characterized in that may further comprise the steps:
(1) with Polycarbosilane and the organic polymer that contains sintering aid by 20: 1-20: 20 mass ratio is dissolved in the organic solvent, mix, under the high pure nitrogen protection, steam solvent and obtain the blend precursor, again above-mentioned blend precursor is placed melt spinning device, under high pure nitrogen protection, be heated to 300-500 ℃ carry out deaeration and handle after, at 200-400 ℃, under the 2-10 atmospheric pressure, carry out melt spinning with 100-500r/min speed, make the fibrillation that diameter is 10-20 μ m;
(2) above-mentioned fibrillation is placed oxidation furnace, the programming rate by 10-30 ℃/h in oxidizing atmosphere is heated to 160-250 ℃, and insulation oxidation processes 1-10 hour obtains fusion-free fibre after being chilled to room temperature;
(3) high temperature furnace that above-mentioned fusion-free fibre is placed high-purity argon gas or helium protect is warming up to more than 1600 ℃, and insulation was handled 1-4 hour under this temperature.
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| CN1330805C (en) * | 2005-06-29 | 2007-08-08 | 中国人民解放军国防科学技术大学 | Process for preparing continuous silicon carbide fiber containing aluminium |
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| CN101830706A (en) * | 2010-05-28 | 2010-09-15 | 中国人民解放军国防科学技术大学 | Method for continuously preparing Si-B-N-O fiber by using PCS (Polycarbosilane) fiber |
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2002
- 2002-11-18 CN CNB021397627A patent/CN1168859C/en not_active Expired - Fee Related
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