CN101319414A - Production method of silicon carbide fiber with high temperature tolerance - Google Patents
Production method of silicon carbide fiber with high temperature tolerance Download PDFInfo
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Abstract
The invention relates to a method for manufacturing silicon carbide fibre with high temperature resistance. Low molecular silane LPS is used as a raw material and has a reaction with an organic compound containing dense elements to synthesize AL, Y-containing polycarbosilane, namely PACS and PYCS; the PACS and PYCS are manufactured into continuous PACS and PYCS fibre by melt spinning; the PACS and PYCS fibre are subjected to infusible treatment to produce infusible fibre which can control the oxygen content; and the infusible fibre is calcinated and sintered at a high temperature under the protection of an inert atmosphere, thereby preparing SiC fibre with high crystallization and high temperature resistance. The method has the advantages of simple process, convenient operation, easy implementation by utilizing equipment for producing a common SiC fibre and low manufacturing cost; and a product produced by the method has the excellent characteristics of high strength, high temperature resistance, high oxidation resistance, etc. and is suitable for batch preparation in industry.
Description
Technical field
The present invention relates to a kind of manufacture method of silicon carbide fiber with high temperature tolerance.
Background technology
Carborundum (SiC) ceramic fibre has important use with its high strength, high-modulus, excellent properties such as high temperature resistant, anti-oxidant, corrosion-resistant in high-tech sectors such as Aeronautics and Astronautics, nuclear industry, weaponrys and is worth.Industrial, adopt organosilicon polymer-Polycarbosilane (PCS) precursor conversion method to realize the suitability for industrialized production of continuous SiC fiber.Its typical preparation flow is: reset Polycarbosilane PCS that polycondensation reaction obtains as precursor with organosilicon polymer through Pintsch process; make continuous P CS fiber through melt spinning; place air to carry out after oxidation reaction makes intermolecular cross-linking form fusion-free fiber (being called not melt processed) continuous P CS fiber; in high temperature furnace, carry out high temperature again under the inert atmosphere protection and burn till, transform with inorganicization through thermal decomposition and make the SiC fiber.With external two main manufacturers-emerging product company of Japanese carbon company and space portion is example, adopts this method to produce the continuous SiC fiber product of different performance characteristics, and comes into the market to sell with " Nicalon ", " Tyranno " trade name respectively.Compare with the carbon fiber that obtains extensive use, one of performance characteristics of SiC fiber is its high temperature tolerance non-oxidizability especially at high temperature.The non-oxidizability of general purpose grade SiC fiber improves a lot (the aerial serviceability temperature of carbon fiber is about 400 ℃) than carbon fiber at present, but because the rich carbon of its precursor PCS itself, and adopted not melt processed of air oxidation in the manufacture process, the SiC fiber that makes is a kind of rich carbon, the SiC fiber of oxygen containing non-stoichiometric, when serviceability temperature is higher than 1200 ℃, violent thermal decomposition takes place in impurity mutually, produce a large amount of gaseous state CO, SiO also is accompanied by crystalline growth rapidly, fiber produces a large amount of defectives, become open structure, the intensity of fiber sharply reduction loses usability, so the serviceability temperature of the SiC fiber of general purpose grade has only 1000 ℃.Therefore, in recent years, the SiC fiber of the high temperature tolerance of preparation high-purity near stoichiometric proportion becomes the emphasis of research and development.
By changing impurity oxygen, the carbon content in preparation method and the technology reduction fiber, be the effective way that improves the heat-resisting quantity of SiC fiber.In the present research and commercial development, the method for employing can be divided three classes: (1) by synthetic high polymer amount PCS, adopt dry method or wet spinning to make fibrillation after, burn till without the direct high temperature of melt processed not and to make low oxygen content SiC fiber.But this method requires height to the control of synthesis technique, and the spinning technique technical difficulty is big and have environmental pollution, also is difficult to obtain thin diameter SiC fiber; (2) electron beam or gamma-ray irradiation replace air oxidation to carry out not melt processed (as U.S. Pat 4220600, US4283367 and US4342712) under the employing inert atmosphere.Japan carbon company (MichioTakeda, Jun-ichi Sakamoto, Yoshikazu Imai, Hiroshi Ichikawa.Thermalstability of the low-oxygen-content silicon carbide fiber, Hi-Nicalon
TM.Comp.Sci.Technol., 1999,59:813-819.) adopt this technology to realize suitability for industrialized production, made low oxygen content SiC fiber-commodity Hi-Nicalon by name (oxygen content＜0.5wt%), and obtained the SiC fiber-Hi-NicalonS of near stoichiometric proportion through further carbonization treatment.These two kinds of fibers have high strength (2.6～2.8GPa), high-modulus (270～420GPa), high density, good crystallinity and high temperature tolerance; (3) in the preparation process of SiC fiber, mainly in precursor polymer PC S synthetic, introduce element boron (B), aluminium (Al) by chemical reaction, again through melt spinning, non-melt processed and more behind the sintering of high temperature, the decomposition reaction that utilizes impurity phase under the high temperature is to remove impurity oxygen and carbon, utilize above-mentioned densification element to promote the densification of fiber simultaneously, thereby make the high temperature tolerance SiC fiber of near stoichiometric proportion.(the Kumagawa K. of company of Ube Industries Ltd., Yamaoka H., Shibuya M., Yamamura T.Fabrication and Mechanical Properties of new lmprovedSi-M-C-(O) Tyranno Fiber.Ceramic Engineering and Science Proceedings, 1998,19 (3): 65-72.) adopt this method, with the PCS that contains Al is that precursor is through melt spinning, air not melt processed and 1300 ℃ burns till and has made the Si-Al-O-C fiber, and having made polycrystalline Si C fiber through 1800 ℃ of high temperature sinterings, commodity are called Tyranno-SA.
Back two kinds of methods have been successfully applied to industrial production in above-mentioned three kinds of methods, have obtained the continuous SiC fiber product of high temperature tolerance.Wherein the temperature tolerance of Hi-NicalonS fiber in air and inert atmosphere reach respectively 1400 ℃ with 1500 ℃, the temperature tolerance of Tyranno-SA fiber in air and inert atmosphere also reach respectively 1400 ℃ with 1800 ℃, show the reduction along with impurity oxygen, carbon content in the fiber, the temperature tolerance of continuous SiC fiber is significantly improved.
But; when adopting second method in the manufacture process of SiC fiber, to adopt electron beam irradiation to carry out not melt processed; need expensive electron accelerator; and need be higher than the high dosage irradiation of common chemical fibre irradiation far away; also need to consume a large amount of high-purity argon gas and dispel the heat and anoxybiotic, technical process is very complicated, causes the manufacturing cost of SiC fiber to increase substantially; with Hi-Nicalon is example, and its price is 7～8 times of general purpose grade Nicalon fiber.And when adopting the third method to prepare the SiC fiber, because the Al element of introducing is just producing densification more than 1600 ℃, the decomposition of impurity phase still brings great damage to fiber in the time of 1200-1600 ℃, when high temperature sintering, the intensity of fiber shows at 1200-1600 ℃ and reduces rapidly, changes at " saddle-shape " that go up more than 1600 ℃.If therefore introduce in the fiber production process impurity oxygen too much cause 1200-1600 ℃ of temperature section fibre strength loss excessive, even then there is densification also to be difficult to obtain having the SiC fiber product of superperformance.Therefore, when adopting the third method to prepare high temperature tolerance SiC fiber, how the impurity oxygen content in the controlling fiber is a problem that must solve.
Therefore, adopting simple and convenient, as to be easy to realize industrialized mass production method to prepare high temperature tolerance SiC fiber is needs very.
Summary of the invention
At the problem that exists in the above-mentioned prior art for preparation method, the technical problem to be solved in the present invention provide a kind of simple and convenient, be easy to realize industrialized mass production, just can make high temperature tolerance SiC fiber preparation method by common preparation technology and equipment.
Technical scheme of the present invention is as follows:
The low molecule silane LPS that generates with Polycarbosilane PCS or by poly-diakyl silane Pintsch process is as raw material; with the synthetic Polycarbosilane that contains Al, Y of the organic compound reaction that contains the densification element; below be designated as PACS, PYCS; make continuous P ACS, PYCS fiber through melt spinning again; place air and reactive atmosphere to carry out the fusion-free fibre that melt processed not obtains controlled oxygen content this fiber; fusion-free fibre placed carry out under the high temperature furnace inert atmosphere protection that high temperature burns till and sintering, make the SiC fiber.
Concrete preparation process is as follows:
(1) raw material PCS is dissolved in the dimethylbenzene altogether with the organic compound that contains densification element al, Y, continues 300-350 ℃ of reaction after distilling out dimethylbenzene being heated to while stirring under the high pure nitrogen protection, and under final temperature insulation reaction 2-10 hour; Or with raw material LPS with after the organic compound that contains Al, Y mixes, under the high pure nitrogen protection, be heated to 420-480 ℃ of reaction, and under final temperature insulation reaction 2-10 hour, crude product filters after xylene soluble, be heated to 300-360 ℃ again and carry out decompression distillation, obtain PACS or PYCS after the cooling with except that desolvating and a small amount of lower-molecular substance;
(2) above-mentioned PACS or PYCS are placed the spinning tube of melt spinning device, under the high pure nitrogen protection, heat up and be heated to 300-400 ℃, treat that its fine melt becomes even melt and removes remaining bubble is after deaeration is handled, at 250-350 ℃, 0.1-0.6MPa under the pressure, carry out melt spinning with 300-600m/min speed, obtain the continuous P CS fiber that diameter is 8-16um through boundling, receipts silk;
(3) above-mentioned PACS or PYCS fiber are placed the not advanced line space gas of melt processed device oxidation processes, promptly the programming rate by 10-20 ℃/hour is heated to 180-220 ℃ in air atmosphere, insulation oxidation processes 2-4 hour, then with after the high pure nitrogen displaced air, heat temperature raising also feeds active reaction atmosphere, be heated to 300-400 ℃ by 10-20 ℃/min programming rate from 100 ℃, and after this temperature insulation is handled 2-4 hour, be chilled to room temperature and make PACS or PYCS fusion-free fibre;
(4) above-mentioned PACS or PYCS fusion-free fibre are placed high temperature furnace, under the high pure nitrogen protection, be warming up to 1200-1300 ℃, and the SiC fiber that made unformed shape in 1-2 hour is handled in insulation under this temperature by 100-200 ℃/hour programming rate;
(5) the SiC fiber of above-mentioned unformed shape is placed the high temperature furnace of high-purity argon gas protection, be warming up to 1800 ℃, and after heat preservation sintering under this temperature is handled 1-2 hour, just can make high crystalline high temperature tolerance SiC fiber.
Described raw material Polycarbosilane PCS is the organosilicon polymer that constitutes main chain with the Si-C key, and its molecular structure unit is:
Alkyl R wherein
1, R
2=H ,-CH
2-,-CH-, Me, Et, Pt, organic groups such as Bt, Ph, they can be the same or different.Concrete example is as resetting the Polycarbosilane that polycondensation obtains by poly dimethyl silane at high temperature pyrolysis.
The low molecule silane LPS of described raw material is for constituting the silane oligomer mixture of main chain with Si-Si key and a small amount of Si-C key, its structure is linearity or ring-type.LPS is that poly-diakyl silane is (as shown in the formula, R wherein
1, R
2=H, Me, Et, Pt, Bt,
Ph etc.) mixture of the oligomer compound of pyrolysis formation is transparent liquid under the room temperature, and boiling point is 60-300 ℃, and molecular weight is 100-600.
Described densification element is aluminium (Al) or yttrium (Y), and the described compound that contains the densification element is compound such as the aluminium acetylacetonate Al (acac) that contains Al, Y
3, acetylacetone,2,4-pentanedione yttrium Y (acac)
3And corresponding alkoxide compound such as Al (OR)
3, Y (OR)
3Wherein R=Me, Et, Pt, Bt, Ph etc.
Described containing in PACS or PYCS synthetic, when being raw material with PCS, the molecular weight of PCS is that number-average molecular weight Mn is 800-2000, with the quality proportioning of the compound that contains Al, Y, B be 1: 0.05-1: 0.15, synthesis temperature is 200-350 ℃, and when the PCS molecular weight was higher, synthesis temperature is low was advisable; Introduce under the higher situation of quality proportioning of compound that more densification element promptly containing Al, Y when needs, should use the PCS of lower molecular weight to be raw material; When being raw material with LPS, LPS is 1 with the quality proportioning that contains the compound of Al, Y: 0.05-1: 0.15, synthesis temperature is 400-500 ℃, synthesis temperature is low excessively, the structural rearrangement of LPS and polycondensation deficiency, synthesis temperature is too high, and the cross-linking reaction that the excessive polycondensation of then easy generation causes influences the rheological characteristic of product, and synthesis temperature preferably is 420-460 ℃.
In described PACS or PYCS synthetic, also can mix and introduce densification element such as Al and Y.When being raw material with PCS, PCS is 1 with the quality proportioning that contains the compound of Al, Y: 0.05-1: 0.15, and wherein, the quality proportioning that contains between the compound of Al, Y is 3: 1-1: 3, other synthesis condition is constant.Also be same proportioning when being raw material with LPS.
The active reaction atmosphere that is adopted in the not melt processed of described PACS or PYCS fiber, be the low boiling with ad hoc structure, volatile oxygen-free alkene, alkynes class organic compound, as alkynes such as alkene such as ethene, propylene, butylene, amylene, cyclohexene, butadiene and acetylene, propine, butine, pentyne, hexins.
Described PACS or the PYCS fiber not melt processed in air and reactive atmosphere, also can adopt air is mixed adding with reactive atmosphere, in mixed atmosphere, handle under the uniform temperature, but method preferably is described advanced line space gas oxidation processes, with feeding the mode that active reaction atmosphere is handled after the high pure nitrogen displaced air, help the control of oxygen content in the fusion-free fibre so again.By control treatment temperature and the time, make Control for Oxygen Content in the fusion-free fibre at 2-12wt%, too high oxygen level in the fiber, then the decomposition of impurity phase is violent in high-temperature sintering process, and fiber is impaired serious, is difficult to obtain superperformance; Oxygen content is low excessively in the fiber, and the decomposition that then can not utilize the impurity phase is difficult to obtain the SiC fiber of high-purity, near stoichiometric proportion to remove impurity oxygen and carbon.Control for Oxygen Content scope preferably is 3-8wt%.
In existing literature research, adopt non-oxygen activity atmosphere that the PCS fiber is carried out not melt processed, can in common not melt processed stove, realize non-oxide not melt processed (the hair red crowned crane of PCS fiber, Song Yongcai, Li Wei is by the crosslinked preparation low oxygen content of polycarbosilane fiber chemical gaseous phase silicon carbide fibre. silicate journal, 2006,34 (1): 16-20; The hair red crowned crane, Song Yongcai, Li Wei etc. the not melt processed research material research journal of polycarbosilane fiber in cyclohexene atmosphere, 2007,21 (2): 177-182).The present invention adopts air+reactive atmosphere that the PCS fiber is carried out not melt processed, regulate and control the oxygen content in the fiber thus, and this technology and the technology of introducing densification element (Al, Y) preparation SiC fiber by chemical reaction in PCS are combined the described high temperature tolerance SiC fiber of preparation.
Synthetic PACS of the present invention or PYCS, with it is precursor, after the process melt spinning makes precursor, adopts not melt processed control oxygen content of air+reactive atmosphere, burn till with sintering by high temperature again and prepare high temperature tolerance SiC fiber, following good effect is compared with prior art arranged:
The present invention adopt air+reactive atmosphere not the melt processed method carry out the not melt processed of PACS or PYCS fiber, can effectively control the oxygen content in the fusion-free fibre, with existing air oxidation not melting method compare, can significantly reduce the oxygen content of fiber; With existing electron beam irradiation not melting method compare, have that technology is simple, easy to operate, the characteristics of low cost of manufacture;
2. adopt the present invention to prepare the method for high temperature tolerance SiC fiber, utilized the purification that the impurity phase decomposition produces under the high temperature, compare the electron beam irradiation method, do not need to increase again decarbonization process;
3. the present invention compares the existing method of utilizing the densification element to prepare high temperature tolerance SiC fiber, because oxygen content is lower and controlled, can stably make high performance fiber product;
4. compare existing preparation method, it is comparatively simple that the present invention need not increase expensive equipment, technology, utilizes the production equipment of common SiC fiber just can implement, and therefore is more to be applicable to the method for preparation of industrialization in batches.
Description of drawings
Fig. 1 prepares high temperature tolerance SiC fibre technology flow chart for the present invention;
Fig. 2 be embodiment 4, embodiment 5 with the unformed SiC fiber high temperature sintering process of embodiment 6 prepared different oxygens in the variation comparison diagram of tensile strength;
Fig. 3 is the variation comparison diagram of tensile strength in embodiment 4, embodiment 7 and the reference examples 1 prepared unformed SiC fiber high temperature sintering process;
Fig. 4 is embodiment 4, embodiment 7 and the temperature tolerance comparison diagram of reference examples 1, reference examples 2 prepared SiC fibers;
Fig. 5 is embodiment 4, embodiment 7 and the oxidative resistance comparison diagram of reference examples 1, reference examples 2 prepared SiC fibers;
The specific embodiment
The invention will be further described below in conjunction with accompanying drawing and embodiment.The present invention is not restricted to following examples.
Fig. 1 is the technological process that the present invention prepares near stoichiometric proportion high temperature tolerance SiC fiber.
The present invention prepares near stoichiometric proportion SiC fiber through five processing steps; that is: the low molecule silane LPS that generates with Polycarbosilane PCS or by poly-diakyl silane Pintsch process is as raw material; with synthetic PACS of the organic compound reaction that contains the densification element or PYCS; make continuous P ACS or PYCS fiber through melt spinning again; place air and reactive atmosphere to carry out PACS or PYCS fusion-free fibre that melt processed not obtains controlled oxygen content fiber; fusion-free fibre placed carry out under the high temperature furnace inert atmosphere protection that high temperature burns till and sintering, make high temperature tolerance SiC fiber.
Reference example 1.
Get poly dimethyl silane 1000g and place reactor, after the feeding high pure nitrogen displaced air, slowly be heated to 460 ℃, and heat preservation hot depolymerized 4 hours under this temperature.Crude product filters after being dissolved in dimethylbenzene, and filtrate is removed in about 200 ℃ of distillations and desolvated and decompression distillation to 350 ℃, obtains about 520g light yellow resin shape Polycarbosilane PCS after the cooling, and its number-average molecular weight Mn is 1840, and softening point is 210-225 ℃.
Embodiment 1.
Get poly dimethyl silane 1000g and place reactor, after the feeding high pure nitrogen displaced air, slowly be heated to 420 ℃, and heat preservation hot depolymerized 5 hours under this temperature.Crude product filters after being dissolved in dimethylbenzene, and filtrate is distilled to remove at about 200 ℃ and desolvated, and obtains about 550g light yellow resin shape product Polycarbosilane PCS after the cooling, and its number-average molecular weight Mn is 990, and softening point is 110-117 ℃.With PCS and aluminium acetylacetonate Al (acac)
3Be dissolved in altogether in the dimethylbenzene by 1: 0.08 mass ratio, be heated to 350 ℃ of reactions while stirring under high pure nitrogen protection, and 350 ℃ of insulation reaction 4 hours, obtain light yellow product PACS after micromolecule is removed in distillation, its Mn is 1704, and softening point is 205-218 ℃.
Embodiment 2.
Get poly dimethyl silane 1000g and place the distillation type reactor, after the feeding high pure nitrogen displaced air, slowly be heated to 400 ℃, and pyrolysis 4 hours under this temperature, catabolite is collected in the condensation of pyrolysis limit, limit, and product is the mixture (being designated as LPS) of low molecule silane, and the pyrolytic reaction yield is 74%.LPS at room temperature is a transparency liquid, and boiling point is 60-300 ℃, and number-average molecular weight is 100-600.With LPS and aluminium acetylacetonate Al (acac)
3After mixing by the dissolving of 1: 0.10 mass ratio, under the high pure nitrogen protection, add thermal response and be warming up to 450 ℃ gradually, 450 ℃ of insulation reaction 4 hours.Crude product filters after with xylene soluble, carries out decompression distillation to remove a small amount of lower-molecular substance at 320 ℃ after heating distilling off solvent again, obtains product P ACS after the cooling, and its Mn is 1680, and softening point is 196-209 ℃.
Embodiment 3.
Get poly dimethyl silane 1000g and place reactor, after the feeding high pure nitrogen displaced air, slowly be heated to 420 ℃, and heat preservation hot depolymerized 10 hours under this temperature.Crude product obtains about 520g PCS through dissolution filter and about 200 ℃ of distillation processing, and its number-average molecular weight Mn is 1224, and softening point is 135-144 ℃.With PCS and aluminium acetylacetonate Y (acac)
3Be dissolved in altogether in the dimethylbenzene by 1: 0.08 mass ratio, be heated to 320 ℃ of reactions while stirring under high pure nitrogen protection, and 320 ℃ of insulation reaction 4 hours, obtain bronzing product P YCS after micromolecule is removed in distillation, its Mn is 1639, and softening point is 195-205 ℃.
Embodiment 4.
The PACS that embodiment 1 is synthesized places melt spinning device, after heating under the high pure nitrogen protection and carrying out the deaeration processing, at 290 ℃; 0.4MPa under the pressure; carry out melt spinning with 500m/min speed, make continuous P ACS fiber, average fibre diameter is 12.5um.The PACS fiber is placed not melting furnace, in air, be heated to 140 ℃ in 1 hour, be heated to 180 ℃, insulation oxidation processes 2 hours with 10 ℃/hour programming rate from 140 ℃ again.After treating that temperature is reduced to about 100 ℃ in the stove, with the air in high-purity inert atmosphere displacement stove, and cyclohexene is blasted in the system as the flow velocity of carrier gas with 10ml/min/g with high pure nitrogen, continuing to be warming up to 350 ℃ with 20 ℃/hour programming rates, insulation was handled 2 hours.This fusion-free fibre is placed high temperature furnace; under the high pure nitrogen protection; be heat-treated to 1200 ℃ by 150 ℃/hour programming rates; be incubated and make the SiC fiber after 2 hours; it is unformed shape substantially that X-ray diffraction detects (XRD) its structure, and average fibre diameter is 10.8um, and tensile strength is 3.1GPa; Young's modulus is 205GPa, and the fiber oxygen content is 5.43%.This fiber is placed high temperature furnace; be warming up to 1800 ℃ under the high-purity argon gas protection, make the SiC fiber in insulation under this temperature after handling 1 hour, it is β-SiC that XRD detects its primary structure; also there is a small amount of α-SiC; β-SiC crystallite dimension is 20.4nm, is indicated as the SiC fiber of high-crystallinity, and fibrous middle O content is 0.84wt%; Al content is 1.08wt%; average fibre diameter is 10.2um, and tensile strength is 2.5GPa, and Young's modulus is 390Gpa.
Embodiment 5.
The PACS fiber that makes by melt spinning among the embodiment 4 is placed not melting furnace, in air, be heated to 140 ℃ in 1 hour, be heated to 200 ℃, insulation oxidation processes 4 hours with 10 ℃/hour programming rate from 140 ℃ again.After treating that temperature is reduced to about 130 ℃ in the stove, the condition identical with embodiment 4 carried out not melt processed in cyclohexene atmosphere.This fusion-free fibre is placed high temperature furnace; under the high pure nitrogen protection; be heat-treated to 1200 ℃ by 150 ℃/hour programming rates; be incubated the SiC fiber that makes unformed shape after 2 hours; its average diameter is 10.5um; tensile strength is 2.8GPa, and Young's modulus is 205GPa, and the fiber oxygen content is 9.59%.This fiber is placed high temperature furnace; under the high-purity argon gas protection, be warming up to 1800 ℃; after insulation is handled 1 hour under this temperature, make the SiC fiber of high-crystallinity; O content is 1.86wt% in fibrous; Al content is 1.02wt%; its average diameter is 10.0um, and tensile strength is 1.1GPa, and Young's modulus is 350Gpa.
Embodiment 6.
The PACS fiber that makes by melt spinning among the embodiment 4 is placed not melting furnace, in air, be heated to 140 ℃ in 1 hour, be heated to 220 ℃, insulation oxidation processes 2 hours with 10 ℃/hour programming rate from 140 ℃ again.After treating that temperature is reduced to about 130 ℃ in the stove, the condition identical with embodiment 4 carried out not melt processed in cyclohexene atmosphere.This fusion-free fibre is placed high temperature furnace; under the high pure nitrogen protection; be heat-treated to 1200 ℃ by 150 ℃/hour programming rates; be incubated the SiC fiber that makes unformed shape after 2 hours; its average diameter is 10.6um; tensile strength is 2.6GPa, and Young's modulus is 180GPa, and the fiber oxygen content is 13.18%.This fiber is placed high temperature furnace, under the high-purity argon gas protection, be warming up to 1800 ℃, make high-crystallinity SiC fiber after handling 1 hour in insulation under this temperature; O content is 2.24wt% in fibrous; Al content is 1.06wt%, but fiber is very fragile, and tensile strength and modulus can not be measured.
Embodiment 7.
The PYCS that embodiment 3 is synthesized places melt spinning device, after heating under the high pure nitrogen protection and carrying out the deaeration processing, at 280 ℃; 0.4MPa under the pressure; carry out melt spinning with 500m/min speed, make continuous P ACS fiber, average fibre diameter is 11.6um.The PACS fiber is placed not melting furnace, in air, be heated to 140 ℃ in 1 hour, be heated to 190 ℃, insulation oxidation processes 4 hours with 10 ℃/hour programming rate from 140 ℃ again.After treating that temperature is reduced to about 130 ℃ in the stove, the condition identical with embodiment 4 carried out not melt processed in cyclohexene atmosphere.This fusion-free fibre is placed high temperature furnace; under the high pure nitrogen protection; be heat-treated to 1200 ℃ by 150 ℃/hour programming rates; be incubated the SiC fiber that makes unformed shape after 2 hours; its average diameter is 10.2um; tensile strength is 2.8GPa, and Young's modulus is 198GPa, and the fiber oxygen content is 5.92%.This fiber is placed high temperature furnace; under the high-purity argon gas protection, be warming up to 1800 ℃; after insulation is handled 1 hour under this temperature, make the SiC fiber of high-crystallinity; it is 18.6nm that XRD detects its β-SiC crystallite dimension; O content is 0.86wt% in fibrous, and Y content is 1.04wt%, and average fibre diameter is 9.5um; tensile strength is 2.3GPa, and Young's modulus is 380Gpa.
Reference examples 1.
The PCS that reference example 1 is synthesized places melt spinning device, after heating under the high pure nitrogen protection and carrying out the deaeration processing, at 300 ℃; 0.3MPa under the pressure; carry out melt spinning with 500m/min speed, make continuous P CS fiber, average fibre diameter is 14.3um.The PCS fiber is placed not melting furnace, and employing and embodiment 4 the same terms carry out the not melt processed in air and the cyclohexene atmosphere, and the Si-H key extent of reaction of PCS fiber is not 42% after the melt processed.This fusion-free fibre is placed high temperature furnace, under the high pure nitrogen protection, be heat-treated to 1300 ℃ by 150 ℃/hour programming rates, be incubated and make the SiC fiber after 2 hours, have β-SiC crystallite in the XRD detection fibers, crystallite dimension is 2.6nm.Average fibre diameter is 12.6um, and tensile strength is 2.8GPa, and Young's modulus is 210GPa, and the fiber oxygen content is 5.6%.This fiber is placed high temperature furnace; be warming up to 1800 ℃ under the high-purity argon gas protection, make the SiC fiber in insulation under this temperature after handling 1 hour, β in its structure-SiC crystallite dimension is 28.2nm; average fibre diameter is 11.8um, and tensile strength and modulus can not be measured.
Reference examples 2.
To place not melting furnace by the PCS fiber that reference examples 1 makes, in air, be heated to 140 ℃ in 1 hour, be heated to 210 ℃ with 8 ℃/hour programming rate from 140 ℃ again, insulation oxidation processes 6 hours, the Si-H key extent of reaction of handling back PCS fiber is 75%.This fusion-free fibre is placed high temperature furnace, under the high pure nitrogen protection, be heat-treated to 1300 ℃, be incubated and make the SiC fiber after 2 hours by 150 ℃/hour programming rates.The XRD detection architecture is β-SiC crystallite, and crystallite dimension is 2.1nm.Fibre diameter is 12.5um, and tensile strength is 2.5GPa, and Young's modulus is 180GPa, and the fiber oxygen content is 13.4%.
Below above embodiment is combined with reference examples and be analyzed, further specify characteristics of the present invention.
From embodiment 4, embodiment 5 and embodiment 6 as can be seen; adopting the identical Polycarbosilane PACS that contains Al that is synthesized by embodiment 1 is raw material; after the process melt spinning makes continuous P ACS fiber; place air and reactive atmosphere to carry out the PACS fusion-free fibre that melt processed not obtains controlled oxygen content the PACS fiber; fusion-free fibre is carried out high temperature at 1200 ℃ burn till under inert atmosphere protection, obtained the unformed SiC fiber of three kinds of different oxygens.By the not control of melt processed condition, the oxygen content of these three kinds of fibers is respectively 6.93%, 9.59%, 13.18%.As can be seen, reduce oxygen content, help to obtain high-intensity unformed SiC fiber.But the more important thing is that when this unformed SiC fiber was made the SiC fiber of high crystalline through 1800 ℃ of high temperature sinterings, the fiber of different oxygen showed different final performances.Wherein, as embodiment 4, the SiC fiber of low oxygen content is through having higher mechanical property behind the high temperature sintering, and when oxygen content is higher in the fiber such as embodiment 6, can not make the SiC fiber of high-temperature resistant.In order to be illustrated more clearly in this point, in unformed fiber high temperature sintering process, measure the variation of fiber tensile strength under the different temperatures, the results are shown in accompanying drawing 2, can know from the comparison of the change curve of three kinds of fiber tensile strength shown in the figure and to find out, three kinds of fibers are when high temperature burns till 1400 ℃, its tensile strength also slightly raises, but all raise and reduce rapidly at 1400-1600 ℃ along with sintering temperature, existing many studies show that this be since in this stage fiber impurity phase SiCxOy produce swift and violent decomposition and cause due to the damage of fiber.The impurity phase content that reduces in the fiber can suppress this adverse reaction, and this can realize by reducing the oxygen content that fiber do not introduce in the melt processed process.As can be seen from Figure, after the method for melt processed has not reduced the oxygen content in the fiber in air of the present invention and the reactive atmosphere, intensity reduction at 1400-1600 ℃ of fiber is suppressed, the more important thing is, under this condition, the densification element could produce effective densification.As shown in Figure 2, in fiber, contain under the situation of Al equally, when oxygen content is higher in the fiber (as embodiment 5 and embodiment 6), because it is excessive 1200-1600 ℃ of fibre strength loss, densification can not be brought into play, perhaps densification can not be offset the destruction that impurity phase SiCxOy decomposes generation, is difficult to obtain the SiC fiber of superperformance.And Control for Oxygen Content is then gone up owing to densification produces significant intensity after 1800 ℃ of processing to lower state (as embodiment 4) in fiber, can make the SiC fiber of the high crystalline with excellent mechanical performances.
From embodiment 4, embodiment 7 and reference examples 1 more as can be seen, though adopted the not method of melt processed of air+reactive atmosphere equally, at 1200-1300 ℃ of SiC fiber that burns till the unformed or crystallite that has made low oxygen content, and show excellent mechanical property, but introduced Al in the fiber of embodiment 4, introduced Y in the fiber of embodiment 7, and do not introduce the densification element in the reference examples 1, therefore behind 1800 ℃ of high temperature sinterings, preceding two kinds of fibers have the good mechanical performance, and reference examples 1 fails to obtain high crystalline SiC fiber.It is very necessary that the densification element is introduced in this explanation, and the simple oxygen content that reduces in the fiber that relies on can not obtain high-temperature resistant SiC fiber.Accompanying drawing 3 is the variations of tensile strength under the different temperatures in high-temperature sintering process of these three kinds of fibers, has illustrated that clearly the fiber of reference examples 1 does not have densification to produce in sintering process.
With embodiment 4, embodiment 7 and reference examples 1, reference examples 2 prepared four kinds of SiC fibers, measure its temperature tolerance (in high-purity argon gas atmosphere, detecting the variation of its tensile strength after the treatment of different temperature) under the same conditions as accompanying drawing 4, measure its oxidative resistance (in air atmosphere, detecting the variation of its tensile strength after the treatment of different temperature) as accompanying drawing 5.Can clearly be seen that, by the SiC fiber of embodiment 4 with embodiment 7 prepared high crystallines, compare the crystallite that usual method makes SiC fiber (reference examples 2) and by same air+reactive atmosphere not after the melt processed at the crystallite SiC of 1300 ℃ of low oxygen contents that burn till fiber (reference examples 1), its tensile strength still has higher conservation rate at 1800 ℃, then two kinds of fibers respectively 1000 ℃, just produce more than 1300 ℃ rapidly that intensity reduces; And in air atmosphere, the tensile strength of preceding two kinds of fibers can be maintained to 1500 ℃ basically, and then two kinds of fibers then can only be maintained to 1000 ℃, 1200 ℃ basically.Obviously, the high crystalline SiC fiber that adopts method of the present invention to make has more excellent high temperature tolerance and oxidative resistance.
As can be seen from the above results, the simple oxygen content that reduces in the fiber that relies on, be difficult to obtain the SiC fiber of high temperature tolerance, and simple dependence introduced the densification element and oxygen content in the non-controlling fiber, can not guarantee to make high temperature tolerance SiC fiber, have only two aspect technology are combined, could make high temperature tolerance SiC fiber effectively.Therefore, adopt and of the present inventionly in PCS, introduce densification element (Al, Y) by chemical reaction and obtain PACS and PYCS, through behind the melt spinning, PACS and PYCS fiber are carried out the not melt processed of controlled oxygen content with air+reactive atmosphere, and burn till technical method with sintering through high temperature, be the effective method of the described high temperature tolerance SiC fiber of preparation.
In sum, adopt the present invention can make the SiC fiber of high crystalline, this fiber has high strength (2.0-2.5GPa), high-modulus (350-400GPa), high temperature tolerance (reaching 1800 ℃) and non-oxidizability (reaching 1500 ℃).With existing adopt electron beam irradiation not the melting method technology for preparing low oxygen content SiC fiber compare, technology of the present invention have technology simple, easy to operate, need not increase expensive equipment, utilize the production equipment of common SiC fiber just can implement, the characteristics of low cost of manufacture, be more suitable in industrial prepared in batches.The prepared SiC fiber of the present invention owing to have excellent specific properties such as high strength, high temperature tolerance, high antioxidant concurrently, is suitable for preparing high-performance composite materials most, in fields such as Aeronautics and Astronautics, nuclear industry, high-performance weaponrys important application prospects is arranged.
Claims (9)
1; a kind of manufacture method of silicon carbide fiber with high temperature tolerance; it is characterized in that: the low molecule silane LPS that generates with Polycarbosilane PCS or by poly-diakyl silane Pintsch process is as raw material; with the synthetic Al that contains of the organic compound reaction that contains the densification element; the Polycarbosilane of Y is PACS; PYCS; make continuous P ACS through melt spinning again; the PYCS fiber; place air and reactive atmosphere to carry out the fusion-free fibre that melt processed not obtains controlled oxygen content this fiber; fusion-free fibre placed carry out under the high temperature furnace inert atmosphere protection that high temperature burns till and sintering, make the SiC fiber.
2, the manufacture method of a kind of silicon carbide fiber with high temperature tolerance according to claim 1 is characterized in that concrete preparation process is as follows:
(1) raw material PCS is dissolved in the dimethylbenzene altogether with the organic compound that contains densification element al, Y, continues 300-350 ℃ of reaction after distilling out dimethylbenzene being heated to while stirring under the high pure nitrogen protection, and under final temperature insulation reaction 2-10 hour; Or with raw material LPS with after the organic compound that contains Al, Y mixes, under the high pure nitrogen protection, be heated to 420-480 ℃ of reaction, and under final temperature insulation reaction 2-10 hour, crude product filters after xylene soluble, be heated to 300-360 ℃ again and carry out decompression distillation, obtain PACS or PYCS after the cooling with except that desolvating and a small amount of lower-molecular substance;
(2) above-mentioned PACS or PYCS are placed the spinning tube of melt spinning device, under the high pure nitrogen protection, heat up and be heated to 300-400 ℃, treat that its fine melt becomes even melt and removes remaining bubble is after deaeration is handled, at 250-350 ℃, 0.1-0.6MPa under the pressure, carry out melt spinning with 300-600m/min speed, obtain the continuous P CS fiber that diameter is 8-16um through boundling, receipts silk;
(3) above-mentioned PACS or PYCS fiber are placed the not advanced line space gas of melt processed device oxidation processes, promptly the programming rate by 10-20 ℃/hour is heated to 180-220 ℃ in air atmosphere, insulation oxidation processes 2-4 hour, then with after the high pure nitrogen displaced air, heat temperature raising also feeds active reaction atmosphere, be heated to 300-400 ℃ by 10-20 ℃/min programming rate from 100 ℃, and after this temperature insulation is handled 2-4 hour, be chilled to room temperature and make PACS or PYCS fusion-free fibre;
(4) above-mentioned PACS or PYCS fusion-free fibre are placed high temperature furnace, under the high pure nitrogen protection, be warming up to 1200-1300 ℃, and the SiC fiber that made unformed shape in 1-2 hour is handled in insulation under this temperature by 100-200 ℃/hour programming rate;
(5) the SiC fiber of above-mentioned unformed shape is placed the high temperature furnace of high-purity argon gas protection, be warming up to 1800 ℃, and after heat preservation sintering under this temperature is handled 1-2 hour, just can make high crystalline high temperature tolerance SiC fiber.
3, the manufacture method of a kind of silicon carbide fiber with high temperature tolerance according to claim 1 and 2 is characterized in that described raw material Polycarbosilane PCS for constitute the organosilicon polymer of main chain with the Si-C key, and its molecular structure unit is:
Alkyl R wherein
1, R
2=H ,-CH
2-,-CH-, Me, Et, Pt, organic groups such as Bt, Ph, they can be the same or different, and concrete example has by poly dimethyl silane resets the Polycarbosilane that polycondensation obtains at high temperature pyrolysis.
4, the manufacture method of a kind of silicon carbide fiber with high temperature tolerance according to claim 1, it is characterized in that the low molecule silane LPS of described raw material is for constituting the silane oligomer mixture of main chain with Si-Si key and a small amount of Si-C key, its structure is linearity or ring-type, LPS is a poly-diakyl silane, the mixture of the oligomer compound that pyrolysis forms, wherein R
1, R
2=H, Me, Et, Pt, Bt, Ph
Be transparent liquid under this mixture room temperature, boiling point is 60-300 ℃, and molecular weight is 100-600.
5, the manufacture method of a kind of silicon carbide fiber with high temperature tolerance according to claim 1 and 2, it is characterized in that described densification element is aluminium (Al) or yttrium (Y), the described compound that contains the densification element is the compound that contains Al, Y, comprises aluminium acetylacetonate Al (acac)
3, acetylacetone,2,4-pentanedione yttrium Y (acac)
3And corresponding alkoxide compound such as Al (OR)
3, Y (OR)
3, wherein R=Me, Et, Pt, Bt, Ph.
6, the manufacture method of a kind of silicon carbide fiber with high temperature tolerance according to claim 1 and 2, it is characterized in that in described PACS of containing or PYCS synthetic, when being raw material with PCS, the molecular weight of PCS is that number-average molecular weight Mn is 800-2000, with the quality proportioning of the compound that contains Al, Y, B be 1: 0.05-1: 0.15, synthesis temperature is 200-350 ℃, and when the PCS molecular weight was higher, synthesis temperature is low was advisable; Introduce under the higher situation of quality proportioning of compound that more densification element promptly containing Al, Y when needs, should use the PCS of lower molecular weight to be raw material; When being raw material with LPS, LPS is 1 with the quality proportioning that contains the compound of Al, Y: 0.05-1: 0.15, synthesis temperature is 400-500 ℃, synthesis temperature is low excessively, the structural rearrangement of LPS and polycondensation deficiency, synthesis temperature is too high, and the cross-linking reaction that the excessive polycondensation of then easy generation causes influences the rheological characteristic of product, and synthesis temperature preferably is 420-460 ℃.
7, the manufacture method of a kind of silicon carbide fiber with high temperature tolerance according to claim 1 and 2, it is characterized in that in described PACS or PYCS synthetic, also can mix and introduce densification element such as Al and Y, when being raw material with PCS, PCS is 1 with the quality proportioning that contains the compound of Al, Y: 0.05-1: 0.15, and wherein, the quality proportioning that contains between the compound of Al, Y is 3: 1-1: 3, other synthesis condition is constant, also is same proportioning when being raw material with LPS.
8, the manufacture method of a kind of silicon carbide fiber with high temperature tolerance according to claim 1 and 2, it is characterized in that the active reaction atmosphere that adopted in the not melt processed of described PACS or PYCS fiber, be the low boiling with ad hoc structure, volatile oxygen-free alkene, alkynes class organic compound, comprise alkene: ethene, propylene, butylene, amylene, cyclohexene, butadiene and alkynes: acetylene, propine, butine, pentyne, hexin.
9, the manufacture method of a kind of silicon carbide fiber with high temperature tolerance according to claim 1 and 2, it is characterized in that described PACS or the PYCS fiber not melt processed in air and reactive atmosphere, employing mixes adding with air with reactive atmosphere, in mixed atmosphere, handle under the uniform temperature, or advanced line space gas oxidation processes, again with feeding the mode that active reaction atmosphere is handled after the high pure nitrogen displaced air, by control treatment temperature and time, make Control for Oxygen Content in the fusion-free fibre at 2-12wt%, Control for Oxygen Content scope preferably is 3-8wt%.
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